SE435722B - COMPOSITION OF A PARTIALLY HYDRATED SEGMENT COPOLYMER, A POLYCAR CARBONATE AND ADDITIONAL A THERMOPLASTIC POLYMER, AND PREPARATION OF IT - Google Patents

Description

lß fi ïïßïJ-get 2 each has the desired properties) to obtain a material which exhibits the desired combination of properties. This approach has been successful in a limited number of cases, for example in improving the impact strength of thermoplastics, such as polystyrene, polypropylene and poly (vinyl chloride), using special blending techniques or special additives for this purpose. In general, however, blending of thermoplastics has not proved to be a successful way of combining in a single material the desired individual properties of two or more polymers. Instead, it has often been shown that such a mixture results in a combination of the worst features of each, with the result that a material with such poor properties is obtained that it has no practical or commercial value. The reasons for this are fairly well investigated and are partly based on the fact that thermodynamics teaches that most combinations of polymer pairs are immiscible, although a number of notable exceptions are known. What is more important is that most polymers adhere to each other very poorly. As a result, the interfaces between the components (as a result of their immiscibility) will represent om- are the reasons for severe weakness in the mixtures and therefore give natural blisters and cracks, which result in slight mechanical breakage. As a result, most polymers are considered "incompatible". In some cases, the term "combinability" is used synonymously with the term, "miscibility". However, in the present context, the term "combinability" is used more generally and indicates the ability of two polymers to combine together for favorable results and may, but not necessarily, denote miscibility .

One method that can be used to circumvent this problem in polymer blends is to make the two polymers combinable by blending a third component, often referred to as a "compatibility enhancer", which has a dual solubility function with respect to those intended for blending. the two polymers. Examples of this third component are obtained in block or graft copolymers. As a result of this property, this agent is located at the interface between the components and greatly improves the adhesion between the phases and therefore increases the stability against total phase separation.

In the present invention, an agent is intended to stabilize multipolymer blends, which agent is independent of the prior art compatibility promoting process and is not limited to the need to utilize limiting dual solubility properties. The materials used for this purpose are special block copolymers, which have the ability to undergo thermally reversible self-crosslinking. Their effect in the present invention is not that associated with the usual concept of promoting compatibility, which is evident from the general ability of these materials to act in a similar way for widely differing blending components, which is not in accordance with the solubility requirements which are associated with the previous concept. The present invention relates to a composition containing a partially hydrogenated block copolymer comprising at least two terminal polymer segments A of a monoalkenylar having an average molecular weight of 5,000-125,000 and at least one intermediate polymer segment B of a conjugated diene having an average molecular weight of 10,000 300,000, the terminal polymer segments A constituting 8-55% by weight of the block copolymer and not more than 25% of the arene double bonds in the polymer segments A and at least 80% of the aliphatic double bonds in the polymer segments B have been reduced by hydrogenation, the composition characterized in that it comprises in (a) 4-40 parts by weight of the partially hydrogenated block copolymer, (b) a polycarbonate having a melting point above 120 ° C and (c) 5-48 parts by weight of at least one different construction thermoplastic belonging to the group consisting of polyamides, polyolefins, thermoplastic polyesters, poly (aryl ethers), poly (aryl sulphones), acetal resins, thermoplastic polyurethanes halogenated thermoplastics and nitrile resins, J wherein the weight ratio of polycarbonate to different construction thermoplastics is greater than 1: 1, so that a polyblend is obtained, in which at least two of the polymers form at least partial, continuous interconnected networks with each other.

The block copolymer of the present invention effectively serves as a mechanical or structural stabilizer which interconnects the various polymer structural networks and prevents the necessary separation of the polymers during processing and subsequent use thereof. As will be explained in more detail 'ÄSßÉYFUàB _ r i. 4 below, the resulting structure of the polyblend (abbreviated to "polymer blend") is that of at least two partial, continuous interconnecting networks.This interconnected structure results in a dimensionally stable polyblend which is not delaminated by extrusion_and subsequent use. In order to produce stable blends, it is necessary that at least two of the polymers have at least partial, continuous networks, which are interconnected, preferably the block copolymer and at least one other polymer have partial, continuous interconnected network structures. In an ideal situation, all polymers would have complete, continuous networks interconnected, by "partial, continuous network" is meant that one part of the polymer has a continuous network phase structure, while the other part has Preferably, a major part (more than 50% by weight) of the partial, continuous annual network continuously. As will be readily appreciated, a wide variety of blend structures are possible, since the structure of the polymer in the blend may be completely continuous, completely dispersed, or partially continuous and partially dispersed. Furthermore, the dispersed phase of a polymer may be dispersed in a second polymer and not in a third polymer. In order to illustrate some of the structures, a list is given below of the various combinations of possible polymer structures, all structures being complete as opposed to partial structures. Three polymers (A, B and C) are included. Index "c" indicates a continuous structure, while index "d" indicates a dispersed_structure. Thus, the term "AcB" means that polymer A is continuous with polymer B, and the term "BdC" means that polymer B is dispersed in polymer C, etc.

AcB _ .. _ A09 'a BQC _.AdB I i AGC »-Beg A ° B- x' ^ °°, fa” 'ätíA' _ Acci v. _ Bdc 1 - _ _ AcB _ Ace. caff »~ A03 'f Ace cfgza i _ A03 I b A00 _ Håål WS 5 _f In the practice of the invention it is possible to improve one type of physical property of the compound mixture without causing any significant deterioration' of another physical property; This has not always been possible before. Thus, it has previously been expected that by adding an amorphous rubber such as an ethylene-propylene rubber to a thermoplastic polymer in order to improve the impact strength, a composite mixture with a significantly reduced heat distortion temperature (BDT) would necessarily be obtained. This is due to the fact that the amorphous guit forms separate particles in the mixture and the gum has by definition an extremely low BDT value around room temperature. According to the present invention, however, it is possible to significantly improve the silica solids while not lowering the heat distortion temperature. Even more surprising is the fact, as is apparent from the embodiments below, that in some cases the heat distortion temperature surprisingly increases as the amount of the present block copolymers increases, a phenomenon which is totally unexpected to those skilled in the art.

This possibility of "tailoring" polymer blends in order to achieve a much improved balancing of properties has not been previously revealed in the art. It is particularly surprising that even very small amounts of the block copolymer are sufficient to stabilize the structure of the polymer blend over a very wide range of relative concentration. For example, such a small amount of sm 4 parts by weight of the block copolymer is sufficient to stabilize a mixture of 5-90 parts by weight of polycarbonate with 90-5 parts by weight of a different construction thermoplastic.

In addition, it is also surprising that the block copolymers are useful for stabilizing polymers of so widely differing slag and with so widely differing chemical compositions. As will be explained in more detail below, the block copolymers have this ability to stabilize a wide variety of polymers over a wide range of concentrations, as they are oxidatively stable, exhibit essentially an infinite viscosity at shear load 0, and maintain network or area structure. in the melt.

Another important aspect of the invention is that the ease of processing and shaping the various polyblends is greatly improved by the use of the block copolymers as stabilizers. The block copolymers used in the composition according to the invention can exhibit widely differing geometric structures, since the invention is not based on the use of any specific geometric structure but rather on the chemical nature of each of the polymer segments. Thus, the block copolymers may be linear, radial or branched. Methods for preparing such polymers are known in the art. The structure of the polymers is determined by the polymerization method. Linear polymer is obtained e.g. by stepwise introduction of the desired monomers into the reaction vessel using such initiators as lithium alkyls or dilitiostilbene or by coupling a two-block copolymer with a difunctional coupling agent. Branched structures on the other hand can be obtained by using suitable coupling agents with a functionality of three or more with respect to the precursor polymers. The coupling can be effected with multifunctional coupling agents such as dihaloalkanes or alkenes and divinylbenzene, as well as certain polar compounds, such as silicon halides, siloxanes or esters of monohydric alcohols with carboxylic acids. The presence of any coupling agent residues in the polymer can be disregarded for an adequate description of the polymers which form part of the compositions of the present invention. Likewise, in a generic sense, the specific structures can be disregarded. The invention relates in particular to the use of selectively hydrogenated polymers with a configuration prior to hydrogenation of the following type polymers: f polystyrene-polybutadiene-polystyrene (SBS) In polystyrene-polyisoprene-polystyrene (SIS) poly (alpha-methylstyrene) polybutadiene-poly (alpha-methylstyrene) ) and poly (alpha-methylstyrene) polyisoprene-poly (alpha-methylstyrene).

Both polymer segments A and B can be either homopolymer segments or random copolymer segments, provided that each polymer segment is dominated by at least one class of the monomers that characterize the polymer segments. The polymer segment A may comprise homopolymers of a monoalkenylarene and copolymers of a monoalkenylarene with a conjugated diene, provided that the polymeric segment A is individually dominated by monoalkenylarene units. The term "monoalkenylarene" especially includes styrene and its analogs and homologues including alpha-methylstyrene and ring-substituted styrenes, especially ring-methylated styrenes. The preferred monoalkenyl arenes in 1: 1: su- s 7 are styrene and alpha-methylstyrene, with styrene being particularly preferred.

The polymer segments B may comprise homopolymers of a conjugated diene, such as butadiene or isoprene, and copolymers of a conjugated diene with a monoalkenylarene, provided that the polymer segments B are dominated by conjugated diene units. When the monomer used is butadiene, it is preferred that 35-55 mol% of the condensed butadiene units in the butadiene polymer segment have 1,2-configuration. Thus, when such a segment is hydrogenated, the product obtained becomes or resembles a regular copolymer segment of ethylene and butene-1 (EB). If the conjugated diene used is isoprene, the hydrogenated product obtained is or is similar to a regular copolymer segment of ethylene and propylene (EP).

Hydrogenation of the precursor block copolymers is preferably carried out using a catalyst comprising the reaction products of an aluminum alkyl compound and nickel or cobalt carboxylates or alkoxides, under such conditions that at least 80% of the aliphatic double bonds but not more than 25% of the aromatic alkenylarene double bonds are substantially completely hydrogenated. Preferred block copolymers are those in which at least 99% of the aliphatic double bonds are hydrogenated while less than 5% of the aromatic double bonds are hydrogenated. _ The average molecular weights of the individual segments may vary within certain limits. The block copolymer present in the composition of the invention has at least two terminal polymer blocks A of a monoalkenylar having a number average molecular weight of 5,000-125,000, preferably 7,000 - 60,000, and at least one intermediate polymer block B of a conjugated diene having a number average molecular weight of 10,000 - 300,000, preferably 30,000 - 150,000. These molecular weights are most accurately determined by tritium intensity measurements or osmotic pressure measurements.

The proportion of the polymer segment A of the monoalkenylar should be between 8 and 55% by weight of the block copolymer, preferably between 10 and 30% by weight.

The polycarbonates present in the compositions of the invention are those of the general formulas 7sv1sn-s 8 r J 9 '. 0 i I and -é fl r-A-Ar-0-G-Q + - n S? . - {fi r-O-C-0è-- - II U. wherein Ar represents phenylene or an alkyl-, alkoxy-, halogen- or nitro-substituted phenylene group, A represents a carbon-to-carbon bond or an alkylidene-, cycloalkylidene-, alkylene-, cycloalkylene-, azo-, imino-, sulfur, oxygen, sulfoxide or sulfone group and n is at least 2.

The preparation of the polycarbonates is well known. A preferred. method of preparation is based on the reaction carried out by dissolving the dihydroxy component in a base such as pyridine and allowing phosgene to bubble through the stirred solution at the desired rate. Tertiary amines can be used to catalyze the reaction and to serve as acid acceptors during the reaction. Since the reaction is normally exothermic, the rate at which phosgene is added can be used to control the reaction temperature. The reactions generally utilize equimolar amounts of phosgene and dihydroxy reactant, but the molar ratios may vary depending on the reaction conditions.

In formulas I and II above, Ar and A are preferably p-phenylene and isopropylidene, respectively. This polycarbonate is produced by reacting para, para'-isopropylidene diphenol with phosgene and is marketed under the trade names LEXAN and MERLON. This commercial polycarbonate has a molecular weight of about 18,000 and a melting temperature of over 230 ° C.

Other polycarbonates can be prepared by reacting other dihydroxy compounds or mixtures of dihydroxy compounds with phosgene. The dihydroxy compounds may include aliphatic dihydroxy compounds, although aromatic rings are essential for achieving the best possible high temperature properties. The dihydroxy compounds may contain diurethane bonds in the structure. Some of the structure can also be replaced with siloxane bonds. The term "different construction thermoplastics" means construction thermoplastics which differ from the thermoplastics covered by the polycarbonates present in the compositions of the invention. 781331 50- 5 9 The term "construction thermoplastic" includes the various polymers listed in Table A below and defined in more detail below.

Table A l. Polyolefins 2. Thermoplastic polyesters 3. Poly (aryl ethers) and poly (aryl sulphones) 4. Polyamides 5. Acetal resins 6. Thermoplastic polyurethanes 7. Halogenated thermoplastics 8. Nitrile resins Preferably, these structural thermoplastics have glass transition temperatures or melting crystals as the temperature at which the low load modulus exhibits an aromatic decrease) of over 120 ° C, preferably between 200 ° C and 350 ° C, and is capable of forming a continuous network structure via a thermally reversible crosslinking mechanism. Such thermally reversible crosslinking mechanisms include crystal bonding, polar bonding, ionic bonding, lamellar bonding and hydrogen bonding. In a specific embodiment, where the viscosity of the block copolymer or blended block copolymer composition at the process temperature Tp and a shear rate of 100 sec.l is Q, the ratio of the viscosity of the structural thermoplastics or the mixture of structural thermoplastic with viscosity modifier and between 0.2 and 4.0, preferably between 0.8 and 1.2. The viscosity of the block copolymer, pores and structural thermoplastic in the present context refers to the "melt viscosity" measured using a piston driven capillary melt rheometer at a constant shear rate and at any suitable temperature above the melting point, e.g. 260 ° C. The upper limit (350 ° C) for apparent crystalline melting point or glass transition temperature has been chosen so that the resin can be processed in equipment using low or moderate shear rates at commercially used temperature levels of 350 ° C or below. * The construction thermoplastic also includes mixtures of different construction thermoplastics and mixtures with additional viscosity-modifying resins.

The different classes of construction thermoplastics are defined in more detail below. p fi x famn sn-s 10 The polyolefins which may be present in the composition according to the invention are crystalline or crystallizable.

They may be homopolymers or copolymers and may be derived from an alpha-olefin or 1-olefin having 2-5 carbon atoms. Examples of particularly useful polyolefins include low density polyethylene, 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 essential for the polymer to be able to form a continuous structure with the other polymers in the polymer blend of the invention. The number average molecular weight of the polyolefins may be above 10,000, and preferably above 50,000.

In addition, the apparent crystalline melting point may be above 100 ° C, preferably between 100 and 250 ° C and in particular between 140 ° C and 250 ° C. The preparation of these various polyolefins is well known and reference is generally made to "Olefin Polymers", vol. 14, Kirk-Othmer Encyclopedia of Chemical Technology, p. 217-335 (1967).

When using a high density polyethylene, it has an approximate crystallinity of over 75% and a density in kilograms per liter (kg / l) of between 0.94 and 1.0. If a low-density polyethylene is used, it has an approximate crystallinity of over 35% and a density of between 0.90 kg / l and 0.94 kg / l. The composition according to the invention may contain polyethylene with a number average molecular weight of 50,000 - 500,000.

When using a polypropylene, this is a so-called isotactic polypropylene as opposed to atactic polypropylene. The number average molecular weight of the polypropylene used can be over 100,000. The polypropylene can be produced using methods known in the art. Depending on the specific catalyst and the special polymerization conditions used, the polymer produced may contain atactic as well as isotactic and syndiotactic molecules or so-called stereo segment molecules. These can be separated by selective solvent extraction to obtain products with low content of atactic molecules, which crystallize more completely. The preferred commercial polypropylenes are generally prepared using a solid, crystalline hydrocarbon insoluble catalyst prepared from a titanium trichloride composition and an aluminum alkyl compound, e.g. tri-78031 50-5 5l of ethylaluminum or diethylaluminum chloride. If desired, the polypropylene used may be a copolymer containing minor (1 to 20% by weight) amounts of ethylene or another alpha-olefin as a comonomer.

Poly (1-butene) preferably has an isotactic structure. The catalysts used in the production of poly (1-butene) are preferably organometallic compounds, commonly referred to as Ziegler - Natta catalysts. A typical catalyst is the reaction product obtained by mixing equimolar amounts of titanium tetrachloride and triethylaluminum. The preparation process is normally carried out in an inert diluent, such as hexane. The manufacturing process is carried out at all stages of polymer formation in such a way as to exclude any presence of water, even in trace amounts.

A very suitable polyolefin is poly (4-methyl-1-pentene). Poly- (4-methyl-1-pentene) has an apparent crystalline melting point of between 240 and 250 ° C and a relative density of between 0.80 and 0.85. Monomer 4-methyl-1-pentene is manufactured commercially by alkali metal catalyzed dimerization of propylene. The homopolymerization-of-4-methyl-1--pentene with Ziegler-Natta catalysts is described in Kirk-Othmer En-CYCl0Peåää of Chemical Technology, supplement band, p. 789-792 (2nd edition, l97l). However, the isotactic homopolymer of 4-methyl-1-pentene has certain technical deficiencies, such as fragility and insufficient transparency. Therefore, the commercially available polymer poly (4-methyl-1-pentene) is in fact a copolymer with smaller proportions of other alpha-olefins and with the addition of suitable oxidation and melt stabilization systems. These copolymers are described in Kirk-Othmer, Encyclopedia of Chemical Technology, Supplementary Volume, p. 792-907 (2nd edition, 1971) and are available under the trade name TPX resin. Typical alpha-olefins are linear alpha-olefins having 4-18 carbon atoms. Suitable resins are copolymers of 4-methyl-1-pentene with 0.5-30% by weight of a linear alpha-olefin.

If desired, the polyolefin is a mixture of different polyolefins. However, the most preferred polyolefin is isotactic polypropylene. Any thermoplastic polyesters present in the compositions of the invention have a generally crystalline structure and a melting point above 120 ° C and are thermoplastic plastics as opposed to thermosets. A particularly useful group of polyesters are the thermoplastic polyesters prepared by condensation of a dicarboxylic acid or a lower alkyl ester, acid halide or anhydride derivative thereof with a glycol according to methods well known in the art.

Among the aromatic and aliphatic dicarboxylic acids suitable for the preparation of polyesters are oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, suberic acid, azelaic acid, sebacic acid, terephthalic acid, isophthalic acid, β-carboriphenoacetic acid, β, β, β, β '-dicarboxydiphenylsulfone, β-carboxyphenoxyacetic acid, β-carboxyphenoxypropionic acid, β-carboxyphenoxybutyric acid, β--carboxyphenoxyvaleric acid, β-carboxyphenoxyhexanoic acid, β, β'-dicarboxylidiphenylmethane, β, p-p-carboxyphenoxyphenic acid , 3-alkyl-4- (beta-carboxyethoxy) benzoic acid, 2,6-naphthalenedicarboxylic acid and 2,7-naphthalenedicarboxylic acid. Mixtures of dicarboxylic acids can also be used. Terephthalic acid is especially preferred.

The glycols suitable for the preparation of the polyesters include straight chain alkylene glycols having 2 to 12 carbon atoms, such as, for example, 1,3-YkO1f 1,3-propylene glycol, 1,6-hexylene glycol, 1,10-decamethylene glycol and 1,12-dodecamethylene glycol. Aromatic glycols may be fully 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 1,4-cyclohexanedimethanol. Particularly preferred glycols are straight chain alkylene glycols having 2-4 carbon atoms. A preferred group of polyesters is poly (ethylene terephthalate), poly (propylene terephthalate fl and poly (butylene terephthalate). A particularly preferred polyester is poly (butylene terephthalate). Poly (butylene terephthalate), a crystalline copolymer, can be formed by polycondensation of 1,4 -butanediol and dimethyl terephthalate or terephthalic acid and has the general formula a 7sos1so-s 13 wherein n varies from 70 to 140. The average molecular weight of poly (butylene terephthalate) preferably ranges from 20,000 to 25,000.

Commercially available poly (butylene terephthalate) is available under the trade name VALOX thermoplastic polyester. Other commercial polymers include CELANEX TENITE and VITUF.

Other useful polyesters include cellulose esters. The thermoplastic cellulose esters used in the present context have extensive use as compression molding materials, coating materials and film-forming materials and are well known. These materials include the solid thermoplastic forms of cellulose nitrate, cellulose acetate (eg, cellulose diacetate, cellulose triacetate), cellulose butyrate, cellulose acetate butyrate, cellulose propionate, cellulose tride decanoate, carboxymethylcellulose, ethylcellulose and hydroxytylcellulose, hydroxytylcellulose . 25-28 in the Modern Plastics Encyclopedia, 1971-72, and the references given therein.

Another useful polyester is a polypivalolactone. Polypivalovactone is a linear polymer with recurring ester structural units having essentially the following formula: ---- CH2 ---- C (CH3) 2 --- C (0) 0 --- i.e. units derived from pivalolactone. The polyester is preferably a pivalolactone homopolymer. However, the copolymers of pivalolactone with up to 50 mol%, preferably not more than 10 mol% of other beta-propiolactones, such as beta-propiolactone, alpha, alpha-diethyl-beta-propiolactone and alpha-methyl-alpha-ethyl- beta-propiolactone.

The term "beta-propiolactones" refers to beta-propiolactone (2-oxetanone) and derivatives thereof which do not carry any substituents on the beta-carbon atom of the lactone ring. Preferred beta-propiolactones are those which contain a tertiary or quaternary carbon atom in the alpha position with respect to the carbonyl group. Particularly preferred are alpha, alpha-dialkyl-beta-propiolactones, wherein the alkyl groups each independently contain 1-4 carbon atoms. Examples of useful monomers are: alpha-ethyl-alpha-methyl-beta-propiolactone, alpha-methyl-alpha-isopropyl-beta-propiolactone, alpha-ethyl-alpha-n-butyl-beta-propiolactone, alpha-chloromethyl-alpha- methyl beta-propiolactone, alpha, alpha-bis (chloromethyl) -beta-propiolactone and alpha, alpha-dimethyl-beta-propiolactone (pivalolactone). i 7805-1513- 5 f '. These polypivalolactones have a molecular weight exceeding 20 ° C and a melting point exceeding 120 ° C. Another useful polyester is a polycaprolactone. Preferred poly1.E-caprolactones are substantially linear polymers with the repeating unit. _ o n. ll t. "E" * ° H2 "YH2- ° H2 ~ ° H2- ° H - ° r - .- ~ These polymers have properties similar to those of the polypivalolactones and can be prepared by a similar polymerization mechanism.

Various poly (aryl polyethers) are also useful as construction thermoplastics. The poly (aryl polyethers) contemplated in the present context include linear thermoplastic polymers consisting of recurring units of the formula --60 -G-oL-c-'ase 1 wherein G is the residue of a divalent phenol of formula I II I 'wherein R represents a bond between aromatic carbon atoms or -f- O - ~, --S -, --S --6 - or a divalent hydrocarbon group having 1 to 18 carbon atoms and G 'is the residue of a dibromo or diiodobenzenoid compound of the formula or vafosphose-s 1% wherein R 'represents a bond between aromatic carbon atoms, - O -, - S -, --VS - S - or a divalent hydrocarbon group having 1-18 carbon atoms, with the proviso that when R is --- O ---, the group R 'has a meaning other than --O--, when R' is --0--, the group R has a meaning other than --O--, when G is a group of formula II the group G 'is a group of formula V and when G' is a group of formula IV the group G is a group of formula III. Polyarylene polyethers of this type exhibit excellent physical properties as well as excellent thermal, oxidative and chemical stability. Commercial poly (aryl polyethers) are available under the tradename.ARYLON T polyaryl ethers having a melting temperature of between 280 ° C and 30 ° C.

Another group of useful construction thermoplastics includes aromatic poly (sulfones), which comprise recurring units of the formula Ar SO 2 wherein Ar is a divalent aromatic group, which may vary from unit to unit in the polymer chain (to form copolymers of various kinds). ). Thermoplastic poly (sulfones) generally contain at least some units with the structure á> ___ Z - <| U 2 SO 2 wherein Z is oxygen or sulfur or the residue of an aromatic diol such as 4,4'-bisphenol. An example of such a poly (sulfone) has recurring units of the formula soz ~ epl another example has recurring units of the formula: ;;:: ;;: - out SO2-; .- 3 rëx fl zmo-: s 16 and other examples have recurring units with the formula - @ - so2 - @ - o.-@_è3 “'-' ax. or copolymerized units in different proportions of the formula + ®- @ ~ ß ° 2- i i or i I * I I .'å. The thermuplastic poly (sulfones) may also contain recurring units of the formula "Poly (ether sulfones) having recurring units of structure are also useful as structural thermoplastics.

By polyamide is meant a condensation product which contains recurring aromatic and / or aliphatic amide groups as integrated parts of the main polymer chain. Such products are generically known as "nylons". A polyamide can be obtained by polymerizing YNIMSÛ-B 17 a monoaminomonocarboxylic acid or an inner lactam thereof having at least 2 carbon atoms between the amino and carboxylic acid groups or by polymerizing substantially equimolar amounts of a diamine containing at least 2 carbon atoms between amines and and a dicarboxylic acid or by polymerizing a monoaminocarboxylic acid or an internal lactam thereof, as defined above, together with substantially equimolar amounts of a diamine and a dicarboxylic acid. The dicarboxylic acid can be used in the form of a functional derivative thereof, e.g. and ester.

The term "substantially equimolar amounts" (of the diamine and of the dicarboxylic acid) is intended to cover both the strictly equimolar amounts and the slight deviations therefrom which occur in the conventional technique for stabilizing the viscosity of the resulting polyamides.

As examples of said monoaminomonocarboxylic acids or lactams thereof, there can be mentioned such compounds which contain 2-16 carbon atoms between the amino and carboxylic acid groups, the carbon atoms forming a ring with the -CO 2 NH group in the case of a lactam. Specific examples of aminocarboxylic acids and lactams include 5-amino-caproic acid, butyrolactam, pivalolactam, caprolactam, capryl-lactam, enantolactam, undecanolactam, dodecanolactam and 3- and 4-aminobenzoic acid.

Examples of said diamines are diamines of the general formula H 2 N (CH 2) n NH 2, wherein n is an integer from 2 to 16, such as trimethylenediamine, tetramethylenediamine, pentamethylenediamine, octamethylenediamine, decamethylenediamine, dodecamethylenediamine, hexadiaminediamine and hexadecamethylamine.

C-alkylated diamines, e.g. 2,2-dimethylpentamethylenediamine and 2,2,4- and 2,4,4-trimethylhexamethylenediamine are further examples.

Other diamines which may also be mentioned by way of example are aromatic diamines, e.g. p-phenylenediamine, 4,4'-diaminodiphenylsulfone, 4,4'-diamaminodiphenyl ether and 4,4'-diaminodiphenylsulfone, 4,4'-diaminodiphenyl ether and 4,4'-diaminodiphenylmethane and cycloaliphatic diamines, e.g. diaminodicyclohexylmethane. Said dicarboxylic acids may be aromatic, e.g. isophthalic and terephthalic acids. Preferred dicarboxylic acids are those of the formula HOOC.Y.COOH, wherein Y represents a divalent aliphatic group containing (ß. 7305150-5 at least 2 carbon atoms, and examples of such acids are sebacic acid, octadecanedioic acid, suberic acid, azelaic acid, undecandic acid, glutaric acid, pimelic acid and especially adipic acid Oxalic acid is also a preferred acid.

In particular, the following polyamides can be incorporated into the thermoplastic polymer blends of the invention: polyhexamethylene adipamide (nylon 6: 6) polypyrrolidone (nylon 4) polycaprolactam (nylon 6) polyheptolactam (nylon 7) polycapryl lactam (nylon 8) polynonanolactam (nylon 9) ) polydodecanolactam (nylon 12) polyhexamethylene azelaamide (nylon 6: 9) polyhexamethylene sebacamide (nylon 6:10) polyhexamethylene isophthalamide (nylon 6: iP) polymethaxylylenadipamide (nylon MXD: 6) polyamide of hexamethylenediamine and n-dodecanediamine: and n-dodecanedioic acid (nylon 12:12).

Nylon copolymers can also be used, e.g. copolymers of the following; hexamethylene adipamide / caprolactam (nylon 6: 6/6) hexamethylene adipamide / hexamethylene isophthalamide (nylon 6: 6 / Gip) hexamethylene adipamide / hexamethylene terephthalamide (nylon 6: 6 / 6T) trimethylhexamethylene oxamide / hexamethylenoxamide / hexam 6: 2) = 'hexamethylene adipamide / hexamethylene azelaiamide (nylon 6: 6/6: 9) hexamethylene adipamide / hexamethylene azelaiamide / caprolactam (nylon me / ew / e). I 'Nylon 6: 3 is also useful. This polyamide is the product of the dimethyl ester of terephthalic acid and a mixture of isomer trimethylhexamethylenediamine.

Preferred nylons include nylon 6,6 / 6, 11, 12, e / s and 6/12. “The number average molecular weights of polyamides can be over 10,000.

The acetal resins used in the blends of the present invention include the high molecular weight polyacetal homopolymers prepared by polymerizing formaldehyde or trioxane; These polyacetal homopolymers are commercially available under the trade name DELRIN. A related polyether type resin is available under the trade name PENION and has the gunaci 'r' on --o - ca - structure. 2 I 2 _ - cnzci _. 4 n The acetal resin prepared from formaldehyde has a high molecular weight and a structure which can be illustrated in the following manner - X wherein terminal groups are derived from controlled amounts of water and x represents a large (usually 1500) number of bonded formaldehyde units. To increase the thermal and chemical resistance, the terminal groups are usually converted to esters or ethers. The term "polyacetal resins" also includes polyabethal copolymers. These copolymers include block copolymers of formaldehyde with monomers or prepolymers of other materials capable of providing active hydrogen atoms, such as alkylene glycols, polytiols, vinyl acetate-acrylic acid copolymers or reduced butadiene / acrylonitrile polymers.

Celanese commercially provides a copolymer of formaldehyde and ethylene oxide under the tradename CELCON, which is useful in the compositions of the present invention. These copolymers typically have a structure which includes recurring units of the formula m * CÄSLI: 7-8051 wherein R1 and R2 are independently hydrogen, 1-1 lower alkyl or lower halogen substituted alkyl and n is an entire Lal from O to 3, where n is e 0 in 85-99.9% of the recurring units.

Formaldehyde and trioxane can be copolymerized with other aldehydes, cyclic ethers, vinyl compounds, ketenes, cyclic carbonates, epoxides, isocyanates and ethers. These compounds include ethylene oxide, 1,3-dioxolane, 1,3-dioxane, 1,3-dioxpene, epichlorohydrin, propylene oxide, isobutyleneoxy and styrofoam oxide.

Polyurethanes, which are also known as isocyanate resins, can also be used as structural thermoplastics provided they are thermoplastics and not thermosets. So e.g. For example, polyurethanes formed from toluene diisocyanate (TDI) or diphenylmethane-4,4-diisocyanate (MDI) and a wide variety of polyols such as polyoxyethylene glycol, polyoxypropylene glycol, hydroxy-terminated polyesters and polyoxyethylene oxypropylene glycols are suitable.

These thermoplastic polyurethanes are available under the tradenames Q-THANE and PELLETHANE CPR.

Another group of useful construction thermoplastics includes halogenated thermoplastics having a substantially crystalline structure and a melting point in excess of 120 ° C. These halogenated thermoplastics include homopolymers and copolymers derived from tetrafluoroethylene, chlorotrifluoroethylene, bromotrifluoroethylene, vinylidene fluoride and vinylidene chloride.

Polytetrafluoroethylene (PTFE) is the name of completely fluorinated polymers with the basic chemical formula --4-CF2 - CF2- + š-, which contains 76% by weight of fluorine. These polymers are highly crystalline and have a crystalline melting point of over 300 ° C. Commercial PTFE is available under the brand names TEFLON and FLUON. Polychlorotrifluoroethylene (CTFE) and polyhromotrifluoroethylene (PBTFE) are also available in high molecular weights and can be used in accordance with the present invention.

Particularly preferred halogenated polymers are homopolymers and copolymers of vinylidene fluoride. Poly (vinylidene fluoride) homopolymers are partially fluorinated polymers of the chemical formula (CH2 CF2) n. These polymers are tough linear polymers with a crystalline melting point at 170 ° C. A commercial homopolymer is available under the trade name KYNAR. The term "poly (vinylidene fluoride)" as used herein means not only the normally solid homopolymers of vinylidene fluoride but also the normally solid copolymers of vinylidene fluoride containing at least 50 mole percent polymerized vinylidene fluoride units, preferably at least about 70 mole percent vinylidene fluoride and Suitable comonomers are halogenated olefins which contain up to 4 carbon atoms, eg dichlorodifluoroethylene, vinyl fluoride, vinyl chloride, vinylidene chloride, perfluoropropylene, perfluorobutadiene, chlorotrifluoroethylene, trichlorethylene and trichlorethylene. .

Another useful group of halogenated thermoplastics containing 22 phases are homopolymers and copolymers derived from vinylidene chloride. Crystalline vinylidene chloride copolymers are especially preferred. The normally crystalline vinylidene chloride copolymers useful in the present invention are those containing at least 70% by weight of vinylidene chloride plus 30% or less of a copolymerizable monoethylenic monomer. Examples of such monomers are vinyl chloride, vinyl acetate, vinyl propionate, acrylonitrile, alkyl and aralkyl acrylates with alkyl and aralkyl groups containing up to about 8 carbon atoms, acrylic acid, acrylamide, vinyl alkyl ethers, vinyl alkyl ketones, acrolein and other allyl ethers and chloropropylene. can also be used to advantage. Examples of such polymers are those which up to at least 70% by weight consist of vinylidene chloride, the known ternary composition being consisting of e.g. 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 vinyl ethyl and vinyl ethyl and vinyl ethyl vinyl chloride F Quarterly polymers of similar monomer composition can also be used. Particularly useful for the purpose of the present invention are copolymers with 70-95% by weight of vinylidene chloride, the remainder being vinyl chloride. Such copolymers may contain conventional amounts and types of plasticizers, stabilizers, nucleators and extrusion aids. It is also possible to use mixtures of two or more of such normally crystalline vinylidene chloride polymers as well as mixtures comprising such normally crystalline polymers in combination with other polymeric modifiers, e.g. copolymers of ethylene-vinyl acetate, styrene-maleic anhydride, styrene-acrylonitrile and polyethylene.

The nitrile resins useful as structural thermoplastics are thermoplastic materials having an alpha, beta-olefinically unsaturated mononitrile content of 50% by weight or more. These nitrile resins may be homopolymers, copolymers, graft polymers of copolymers on a rubber substrate or mixtures of homopolymers and / or copolymers. The alpha, beta-olefinically unsaturated mononitriles referred to in the present context have the structure CH ======== C '--- ~ CN IR fifl f fi f fi ß- 5 23 wherein R is hydrogen, an alkyl group having 1-4 carbon atoms or a halogen.

Such compounds include acrylonitrile, alpha-bromoacrylonitrile, alpha-fluoroacrylonitrile, methacrylonitrile and ethacrylonitrile. The most preferred olefinically unsaturated nitriles are acrylonitrile and methacrylonitrile and mixtures thereof.

These nitrile resins can be divided into several classes based on their complexity. The simplest molecular structure is a random copolymer, mainly acrylonitrile or methacrylonitrile.

The most common example is a styrene-acrylonitrile copolymer. Block copolymers of acrylonitrile, in which long segments of polyacrylonitrile alternate with segments of polystyrene, or of polymethyl methacrylate are also known. Q e Simultaneous polymerization of more than two comonomers gives an interpolymer or, starting from three components, a terpolymer.

A large number of comonomers are known. These include lower alpha-olefins having 2-8 carbon atoms, e.g. ethylene, propylene, isobutylene, butene-1, pentene-1 and their halogen- and aliphatically substituted derivatives, such as vinyl chloride, vinylidene chloride; aromatic monovinylidene hydrocarbon monomers of the general formula R1 H2 O-_. wherein R 1 is hydrogen, chlorine or methyl and R 2 is an aromatic group having 6 to 10 carbon atoms, which may also contain substituents such as halogen and alkyl groups attached to the aromatic nucleus, e.g. styrene, alpha-methylstyrene, vinyltoluene, alpha-chlorostyrene, ortho-chlorostyrene, para-chloro-styrene, meta-chlorostyrene, ortho-methylstyrene, para-methylstyrene, ethylstyrene, isopropylstyrene, dichlorostyrene, vinylnaphthalene, etc. Especially preferred together is isobutylene and styrene, Another group of comonomers are vinyl ester monomers of the general formula I? Rao-9. wherein R 3 is hydrogen, an alkyl group having 1-10 carbon atoms, an aryl group having 6-10 carbon atoms comprising the carbon atoms in ring-substituted alkyl substituents, e.g. vinyl formate, vinyl acetate, vinyl propionate and vinyl benzoate. In Monomers, which are similar to those just mentioned and which are also useful, are vinyl ether monomers of the general formula H2c == cH-- o_1a4 a wherein R4 is an alkyl group having 1-8 carbon atoms, an aryl group having 6-10 carbon atoms or a monovalent aliphatic group having 2-10 carbon atoms, which aliphatic group may be hydrocarbon or sulfur containing, e.g. an aliphatic group having ether linkages, which may also contain other substituents, such as halogen and carbonyl. Examples of these monomeric vinyl esters include 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. - 7 Other comonomers are those which contain a mono- or dinitrile function. Examples include methylene glutaronitrile. (2,4-dicyanobutene-1), vinylidencyanide, crotonitrile, fumarodinitrile and maleodinitrile.

Other comonomers include the esters of olefinically unsaturated carboxylic acids, preferably the lower alkyl esters of alpha, beta-olefinically unsaturated carboxylic acids and in particular esters having structuring - ~ a '_ ° H2' '~ ==. ° -t-coone d' one, wherein 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 include methyl acrylate, ethyl acrylate, methyl methacrylate, ethyl methacrylate and methyl alpha-chloroacrylate. Particularly preferred are methyl acrylate, ethyl acrylate, methyl methacrylate and ethyl methacrylate.

Another class of nitrile resins are graft copolymers, which consist of a polymeric backbone, to which branches of another polymeric Bil-B 25 chain are attached or grafted. In general, the main chain 1 is a separate reaction. Polyacrylonitrile can be grafted with chains of styrene, vinyl acetate or methyl methacrylate to take a few examples. The main chain may consist of one, two, three or more components, and the grafted branches may consist of one, two, three or more comonomers.

The most promising products are the nitrile copolymers that are partially grafted onto a preformed rubber substrate. This substrate involves the use of a synthetic or natural rubber component, such as polybutadiene, isoprene, neoprene, nitrile rubbers, natural rubbers, acrylonitrile-butadiene copolymers, ethylene-propylene copolymers and chlorinated rubbers, which are used to reinforce the polymer. . This rubber component can be incorporated into the nitrile-containing polymer by any of the methods well known in the art, e.g. -direct polymerization of monomers, grafting of the acrylonitrile monomer mixture onto the rubber main chain or physical mixing of the rubber component. Particularly preferred are polymer blends which have been obtained by blending a graft copolymer of acrylonitrile and comonomer on the rubber backbone with another copolymer of acrylonitrile and the same comonomer. Acrylonitrile-based thermoplastics are usually polymer blends of a grafted polymer and an ungrafted homopolymer.

Commercial examples of nitrile resins include BAREX 210 resin, an acrylonitrile-based nitrile resin containing over 65% nitrile, and LOPAC resin containing over 70% nitrile, three quarters being derived from methacrylonitrile.

In order to harmonize the viscosity properties of the structural thermoplastic, porosity matrix and block copolymer, it is sometimes useful to first mix the various structural thermoplastics with a viscosity modifier before mixing the resulting mixture with the polo quohom and block copolymer. Suitable viscosity modifiers have a relatively high viscosity, a melting temperature of over 230 ° C and have a viscosity which is not particularly sensitive to temperature changes. Examples of suitable viscosity modifiers include poly (2,6-dimethyl-1,4-phenylene) oxide and mixtures of poly (2,6-dimethyl-1,4-phenylene) oxide with polystyrene.

The poly (phenylene oxides) included as possible viscosity modifiers can be illustrated by the following formula wherein R 1 is a monovalent substituent consisting of hydrogen, a hydrocarbon group containing no tertiary alpha carbon atom, a halogenated hydrocarbon group having at least two carbon atoms between the halogen atom and the phenolic nucleus and containing no tertiary alpha carbon atom, a hydrocarbonoxy group containing no aliphatic, tertiary alpha carbon atoms, or a halogenated hydrocarbonoxy group containing at least two carbon atoms between the halogen atom and the phenolic nucleus and which does not contain an aliphatic, tertiary alpha carbon atom, R1 has the same meaning as R1 and can also denote a halogen atom and m is an integer of at least 50, e.g. 50-800 and preferably 150-300.

Among the preferred polymers are polymers having a molecular weight of from 6,000 to 100,000, preferably 40,000. Preferably, the poly (phenylene oxide) is poly (2,0-dimethyl-1,4-phenylene) oxide.

Commercially, poly (phenylene oxide) is available as a mixture with styrene resin. These blends typically comprise between 25 and 50% by weight of polystyrene units and are provided under the tradename NORYL thermoplastic; When using a mixture of poly (phenylene oxide) and polystyrene, the preferred molecular weight is between 10 000 and 500 000, preferably around 30 000 g. The amount of viscosity modifier used depends mainly on the differences between the viscosities of the block copolymer and the structural thermoplastic at the temperature Tp. Typical amounts are 0-100 parts by weight of viscosity modifier per 100 parts by weight of construction thermoplastic, preferably 10-50 parts by weight per 100 parts by weight of construction thermoplastic.

There are at least two methods (apart from the absence of a delamination) by which the presence of an interconnecting network can be demonstrated.

In one method, an interconnecting network is shown when extruded or extruded articles, made from the blends of the present invention, are introduced into a refluxing solvent, remember-s 27 which quantitatively triggers the block copolymer and other soluble components, while the remaining polymer structure ( which comprise the construction thermoplastic and æpkgærumtüe fl x still have the shape and continuity of the extruded or extruded article and are structurally intact without crumbling or delamination, and the refluxing solvent does not contain any insoluble particulate material.If these criteria are fulfilled the both unlinked and continuous.The unextracted phase must be continuous because it is geometrically and mechanically intact.The extracted phase must have been continuous before the extraction, because quantitative extraction of a dispersed phase from an insoluble matrix is unlikely.

Finally, interconnecting networks must be present in order to have two simultaneous continuous phases. The continuity of the unextracted phase can also be confirmed by microscopic examination.

In the present mixtures, which contain more than two components, the interconnecting nature and continuity of each separate phase can be determined by selective extraction.

In the second method, a mechanical property, such as tensile modulus, is measured and compared with that expected in a given system where each continuous, isotropically distributed phase contributes to the mechanical response, which contribution is proportional to the volume fraction of the phase in the mixture. correspondence between the two values indicates the presence of an interconnecting network, while, if an interconnecting network is not present, the measured value differs from the calculated value.

An important aspect of the present invention is that the relative proportions of the various polymers in the blend can be varied within wide limits. The relative proportions of the polymers are given below in parts by weight (the total mixture comprises 100 parts by weight): Amount Preferred amount (parts by weight) (parts by weight) Different construction thermoplastics 5 - 48 10 - 35 4 - 40 8 - 20 Block copolymer fanvIs-rsn-s 28 The polycarbonate is present in an amount greater than the amount of the various construction thermoplastics, i.e. the weight ratio between polycarbonate and different construction thermoplastics is greater than 1: 1. Accordingly, the amount of polycarbonate may vary from 30 parts by weight to 91 parts by weight, preferably from 48 parts by weight to 70 parts by weight. It should be noted that the minimum amount of block copolymer required for the preparation of these blends may vary depending on the structural thermoplastic used. The various structural thermoplastics, polycarbonate and block copolymer can be mixed in any way that creates the interconnecting network. The construction thermoplastic, the polycarbonate and the block copolymer can e.g. dissolved in a solvent common to all components and cpagulated by mixing in a solvent in which neither polymer is soluble. However, a particularly preferred method is to intimately mix the polymers in the form of granules and / or powders in a high shear mixer. By "intimate mixing" is meant that the polymers are mixed under sufficient mechanical shear and heat energy to ensure that an interconnection of the various networks is achieved. Intimate mixing is usually achieved by using high shear extruders and thermoplastic extruders with an L / D ratio of at least 20: 1 and a compression ratio of 3 or 4: 1.

The blend or process temperature (Tp) is selected with respect to the polymers to be blended. When you mix the polymers in melt instead of mixing them in solution, it is e.g. necessary to select a process temperature above the melting point of the highest melting polymer. In addition, as explained in more detail below, the process temperature can be selected so as to obtain an isovicous mixture of the polymers. The mixing or process temperature may be between 150 ° C and 400 ° C, preferably between 23 ° C and 300 ° C.

Another parameter which is important in melt blending to ensure the formation of interconnecting networks is to harmonize the viscosity of the block copolymer, polycarbonate and the various structural thermoplastics (isovicous blend) at the temperature and shear stress of the blending process. The better the dispersion of the structural thermoplastic and the strength of the block copolymer network, the greater the prospects for the formation of co-continuous, interconnecting networks upon subsequent cooling. Therefore, it has been found that when the block copolymer has a viscosity Yjpois at the temperature Tp and a shear rate of 100 s_l, it is preferable that the structural thermoplastic and / or the paper have such a viscosity at the temperature Tp and a shear rate of the ratio 100 l_l. between the viscosity of the block copolymer and the viscosity of the structural thermoplastic and / or polycarbonate is between 0.2 and 4.0, preferably between 0.8 and 1.2. Accordingly, by "iso-viscous mixture" in the present context is meant that the viscosity of the block copolymer divided by the viscosity of the other polymers or the polymer mixture at the temperature Tp and a shear rate of 100 s'l is between 0.2 and 4.0. It should also be noted that in an extruder there is a wide distribution of shear rates. Isovisic blending may therefore occur even 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 blended is critical. Accordingly, one can choose to mix the block copolymer with pdqmarbmr fl æm or another polymer first and then mix the resulting mixture with the different construction thermoplastics, or one can simply mix all the polymers at once. There are many variations in the order of blending that can be utilized, resulting in the multicomponent blends of the present invention.

It is also obvious that the mixing scheme can be used in order to better harmonize the relative viscosities of the different polymers.

The block copolymer or block copolymer blend may be selected to substantially adapt to the viscosity of the structural thermoplastic and / or çol fl eubom fi æm. Optionally, the block copolymer may be mixed with a rubber compounding oil or an additional resin, as described in more detail below, in order to change the viscosity properties of the block copolymer.

The special physical properties of the block copolymers are important for the formation of co-continuous, interconnecting networks. More specifically, the most preferred block film-free copolymers in the unmixed state do not normally melt with increasing temperature, since the viscosity of these polymers is extremely non-Newtonian and tends to increase without limitation as one approaches a shear stress of 0. The viscosity of these block copolymers is furthermore relatively insensitive to temperature. This rheological behavior and inherent thermal stability of the block copolymer enhances its ability to maintain its network structure in the melt, so that interconnecting and continuous networks are formed when the various blends are prepared.

On the other hand, the viscosity behavior of the construction thermoplastics and polycarbonates are more temperature sensitive than the viscosity behavior of the block copolymers. Consequently, it is often possible to select a process temperature Tp, at which the block copolymer and the various structural thermoplastics and / or the viscosities of the pdßßarbmrá fall within the range required for the formation of interconnecting networks. As described above, optionally a viscosity modifier may first be mixed with the construction tinplate or powder to achieve the required viscosity harmonization. The mixture of partially hydrogenated block copolymer, pdqka nat etc. nat and various structural thermoplastics can be compounded with an excipient oil of the type commonly used in the processing of rubber and plastics. Particularly preferred are the types of oil that are compatible with the elastomeric polymer segments of the block copolymer.

Although oils with a higher aromatic content are satisfactory, petroleum-based white oils with a low volatility and less than 50% aromatic content, measured by the clay gel method (ASTM method D 2007), are particularly preferred.

These oils preferably have an initial boiling point above 260 ° C.

The amount of oil used may vary from 0 to 100 parts by weight per 100 parts by weight of block copolymer, preferably from 5 to 30 parts by weight per 100 parts by weight of block copolymer.

The mixture of partially hydrogenated block copolymer, polyacionate and various construction thermoplastics can be further compounded with a resin. The additional resin may be a flow promoting resin, such as an alpha-methylstyrene resin, and an end block plasticizing resin. Suitable end-segment plasticizing resins include fs fifi ai-n-s 31 coumarone inner resins, vinyltoluene-alpha-methylstyrene copolymers, poly-indene resins and low molecular weight polystyrene resins.

The amount of the additional resin may vary from 0 to 100 parts by weight per 100 parts by weight of block copolymer, preferably from 5 to 25 parts by weight per 100 parts by weight of block copolymer. Furthermore, the composition may contain other polymers, fillers, reinforcing agents, antioxidants, stabilizers, fire protection agents, antiblocking agents and other rubber and plastic compounding ingredients.

Examples of fillers that can be used can be found in the 1971-1972 Modern Plastics Encyclopedia, p. 240-247. Reinforcing agents are also useful in the present polymer blends. A reinforcing agent can be defined as a material which is added to a resinous matrix in order to improve the strength of the polymer. Most of these reinforcing materials are high molecular weight inorganic or organic products. Examples of reinforcing agents are glass fibers, asbestos, boron fibers, carbon and graphite fibers, whiskers, quartz and silica fibers, ceramic fibers, metal fibers, natural organic fibers and synthetic organic fibers. Particularly preferred are reinforced polymer blends containing 2-80% by weight of glass fibers, based on the total weight of the reinforced blend obtained.

The polymer blends of the invention can be used as metal substitutes and in such areas where high performance is sought. The invention is further illustrated by the following embodiments, in which the temperature indications refer to degrees Celsius.

In the working examples and comparative example below, different polymer blends were prepared by mixing the polymers in a 3.125 cm Sterling extruder with a Kenics nozzle. The extruder had an L / D ratio of 24: 1 and a compression screw ratio of 3.8: 1. The various materials used in the blends were as follows: AP'-7a0š.1: sn- s 32 l) Block copolymer - a selectively hydrogenated block copolymer according to the invention with the structure S-EB-S. 2) Oil - TUFFLO 6056 rubber extension oil._ I 3) Nylon 6 - PLASKON 8207 polyamide. 4) Nylon 6-12 - ZYTEL 158 polyamide. 5) Polypropylene - a substantially isotactic polypropylene with a melt flow index of 5 (230 ° C / 2.16 kg). 6) Po1y (butene terephthalate) (PBT) - VALOX 310 resin. 7) Polycarbonate - MERLON M-40 polycarbonate. and 8) Poly (ether sulfone) - 200P. 9) Polyurethane - PELLETHANE 10) Polyacetal - DELRIN 500. ll) Poly (acrylonitrile co-styrene) - BAREXj 210. 12) Fluoropolymer - TEFZEL 200 poly (vinylidene fluoride) copolymer.

CPR.

In all mixtures containing an oil component, the block copolymer and the oil were mixed in advance before the other polymers were added.

Example 1 Various polymer blends were prepared according to the invention.

A mixture of two block copolymers with higher and lower molecular weights was used in certain polymer mixtures in order to better harmonize the viscosity with the polycarbonate and / or other different construction thermoplastics. In some mixtures, an oil was blended with block segments in order to better harmonize the viscosity.

Comparative mixtures were also prepared which did not contain any block copolymer, but these mixtures were not easy to mix. Mixture 110 containing polycarbonate and Nylon 6 showed, for example, melt fracture and extreme spray irregularities during mold swelling. In contrast, each polymer blend containing a block copolymer was easy to blend and the extrudate was homogeneous in appearance. Furthermore, the resulting polyblend containing block copolymer exhibited the desired continuous, interconnecting networks, which could be determined by the criteria set forth above.

The compositions of the compositions and the test results are shown in Tables 1 and 2 below. The compositions are expressed in% by weight. 7iUÛàïTÉíÛ "5 m ~ ßH m_HN a; mm m ~ ßH mß m.Nm m.HN ß ~ mm mm mh m.Nm m ~ hH o.om Hwšæ fl omuo flfl m _ ^ G0Hæum | Edm | ~ fl uu«: o ~> uxm. > Hom amumomæ al if: muwudw al of A f ow fifl mumvmvw al if> .mw MSS uwnonumxæ fi if mH ~ m ~ w DE FR AEZ cmmoumæaom ¶.umHßuwuuuu = wuønv> Hom Hwuwâä fi ømâßmucmå lmmm o f m f O fl mswnw fifl o o.mH Hwuw f w f omämmuømš | MWM> m wn al c al nm f m o qw Ha al nm H flfl UMA access Hm _ QHH now Mo al COAM f m vísoísïïüsn -s 54 o_om o.m fl mm mb m ~ Nm o.om ß.mw o.mH mw ms m_Nm m.ßa uøäwaomno flfl m Acmnæumnëmmu flfl hu access no access huxmvæ al if Hmuouma al if: muwH fl> H0m ACOU fi ømuwumvmaøm> ~ mw MSS. umconumxæ fi if m Go al AZ al wmonmä al mH ~ m ~ Aum al muuwuwucwuønva fi if Hmuwäw fi omämmucmñ lmmm mum fi wßmsmnw fifi o Hmumäæ fl omimmucwš lmwm> m mc fi c fl cmam mm mm ßoa. wa mm mod Nm 1 |||||||||||||||| ^ .muuow. H anamma Hm mo fl HG m fifl dß fim hm hm =. 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H MHH. mH HuwaæHomHosHm mw w_mH m.HH o.m ~ m.w ~ HHH wHH_ ° ~>. «» HH Q H o ~ H .v. >. «H o. @ H m.>« W.wm ww ° ~ .o «~.« Om ^ uomHsw Hw 5 ~>.> Mw.> O. ~ «M.mH woH mH. ° mm.« mH | uwum.> Hom mm «wm ~ m.m. w °. «° Hm NNH m ~ _o> Hm H 0 HHH Hm.w ~ w.>>.« H m_oH mß m> .o H «.« ~ mH om ~ @ ~>. ~ m °. «H .oH m.mH mm mm.o ~ w. «HHH _ mH w coH> z Hw wm_ ° m>. ° w ~. ~ mm.H> HH> mo wm.« MHH Q ° HH »H wH mH HH HH. NH HH xx ° H uwa nu Uomwl Oomm lw fi omëmm m flfi ß wH> u0§ummmHHw & mmHm | w0NH | uGmEmmm w mmunwšhaom Iwcm fl m ^ .mUHOmv N AAHMGB 7sos1so-sa \ mxs .u mms. Xm. .wa \ mxa .ønoíwmwn .ma wo fi x ~ eo \ mx .Hamas .ß a \ maa .nam wßmo .wa ~ au \ mx .esa fl xms .w ~ ¶ M .uws fi uwsl flfl mšxoom .ma m flflflfi mu H fi wøucwuonm .mw .M0mH> N0. NE0 \ mx.m fl wumv »Hh .v @ .uwm Eu Hmm En .m | oH N .co fi mømmxm Hmmc fl n .HH wo fl N NEU \ mM .flfl uoäucmxwm .m OO _H fl umnmmäwuwno fl mHO # m flfl mEo> m flfl mEo> m. .N wo fi x ~ ao \ mx .Hsøoz .m ~ eu \ mx .wawwmuuounmmun .HN a fi wnmu w un> fi mumum øuøømxmmuæm xx w.mæ w.Nw fl o fl e.mß mm m fl. O æ «.v ewa om mm m. «M °. ~ M m.ow wo fi mm wH.o mm.w Hua ma nmuwusw fl om mm m.mæ> .wN m ~ ww ß.Næ ßw fl mA.o mß.w. wm fi o ßo fi o.oH> .ma m.æ ~ ~ .wN ßß mo.o om_v wma cm wa æ.oa «~.> m.mN H_ ~ fi ooa mH ~ o mo.m ßm fi ma fl muwomh fl om mm ßw. > mæ_w m @ .m mwxß QNH «Ho«>. «H« ~ 0 mo fl wa wa ma. va ma NH Ha xxo fi umë un lwaomëmm mc fi ø lucmšmmm w mmuumähaom nunnan ^ .muuowv N anamma venñfso-s 39 The experimental results for the above mixtures suggest unexpected properties of the present mixtures. By e.g. comparing mixture 109 with mixtures 91 and 92, it can be seen that at a polycarbonate to PBT ratio of 3: 1 the heat distortion temperature does not drop, as was to be expected, as the amount of segment component increases from 0-15-30%. In fact, the heat distortion temperature is higher for blends containing the block copolymer than in blend 109, which does not contain any block copolymer. Normally, when adding an amorphous rubber to a thermoplastic, one would expect a significant lowering of the heat distortion temperature, since the heat distortion temperature of the rubber is very low. It is also important to note that with increasing amounts of block copolymer, the Izod impact strength increases significantly while the heat distortion temperature is not significantly affected. This is drastically illustrated by comparing the ratio between the percentage increase in impact strength and the percentage change in heat distortion temperature. examine the relationship between the relative increase in Izod impact strength (at 23 ° C) and the relative decrease in heat distortion temperature of polymer blends as the percentage of block copolymer increases from 0 to 15% at a given polycarbonate to different construction thermoplastic ratio of 3 : 1, it can be stated that one obtains much greater values than was to be expected. Those skilled in the art would normally expect this value to be positive and less than 1. However, for mixtures containing Nylon 6, a fluorinated copolymer, a polyacetal and poly (butene terephthalate) the ratios are -144, -23, 28 and -37. The negative values are particularly outstanding, as these represent an increase in the heat distortion temperature as the content of the block copolymer increases.

Example 2 Various additional mixtures were prepared in a manner similar to Example 1. The various mixtures are shown in Table 3 below. In all cases, the polyblends containing a block copolymer exhibited the desired interconnecting network structure. 7mï51ïsn-s 40 A fi wuhumiämm a fl u fi co fl æuxm. »Då ._15 MÄN mih MÄN .ïmm måw» wconwßå fi om m_Nm ß_mw m coaæz Gwmoumæ fl cm m _ Nm ß _ S o _ mm m _ 3 Û fi mumwnmuaupsnv Éom cäm .ina ... om. <3 ... om 0: 3 »mñwsweon _ nmwm> m mn fi c fl nm fl m_ mm ßm vw wß Hm om H: mc fl cw fl mam m anamma ..-: .., ..; _, -..... _. _ 41 o.mN o.mß o ~ mH mm øm fi ^ .w »Homv m anamma ^ cwu» um | Emw u flfi uv fl no fl auxwvæ fl om ußcønumxäaom nmmoumm fl øm .pø fl mvumuwucøunnvm fi om Hwnwäæaoms w mGmGun mwun> mGun mwun ä

Claims (54)

l vtcsknën1cjsn-s 42 Patent claims A composition comprising a partially hydrogenated block copolymer comprising at least two terminal polymer blocks A of a monoalkenylene having an average molecular weight of 5,000 to 125,000 and at least one intermediate polymer block B of a conjugated diene having an average molecular weight of 10,000 to 300,000. 000, the terminal polymer segments A constituting 8-55% by weight of the block copolymer and not more than 25% of the arene double bonds in the polymer segments A and at least 80% of the aliphatic double bonds in the polymer segments B having been reduced by hydrogenation, characterized wherein it comprises: (a) 4-40 parts by weight of the partially hydrogenated block copolymer, '(b) a polycarbonate having a melting point above 12000 and (c) 5-48 parts by weight of at least one different construction thermoplastic belonging to the group constituted of polyamides, polyolefins, thermo-plastics, thermoplastic polyurethanes, halogenated thermoplastics and nitrile resins, the holding polycarbonate to different construction thermoplastics is greater than 1: 1, so that a polyblend is formed, wherein at least two of the polymers form at least partial, interconnected continuous networks. 2. A composition according to claim 1, characterized in that the polymer segments A have a number average molecular weight of 7,000 - 60,000 and that the polymer segments B have a number average molecular weight of _30,000 ~ 150,000. 3. A composition according to claim 1 or 2, characterized in that the terminal polymer segments A constitute 10-30% by weight of the block copolymer. '- Composition according to any one of the preceding claims, characterized in that less than 5% of the arene double bonds in the polymer segments A and at least 99% of the aliphatic double bonds in the polymer segments B have been reduced by hydrogenation. 5. A composition according to any one of claims 1-4, characterized in that the polycarbonate has the general formula - in the H1SWSES 4.3 H - + Ar-A-Ar-O-C-O + E- I or -H - (- Ar-oc-o + n- _ g II wherein Är represents a phenylene or an alkyl, alkoxy, halogen- or nitro-substituted phenylene group, A represents a carbon-to carbon bond or an alkylidene, cycloalkylidene, alkylene, cycloalkylene, azo, imino, sulfur, oxygen, sulfoxide or sulfone group and n is at least 2. 6. A composition according to any one of claims 1-5, characterized in that the different construction thermoplastic has an apparent crystalline melting point exceeding 120 ° C. 7. A composition according to claim 6, characterized in that the different construction thermoplastic has an apparent crystalline melting point of between 150 ° C and 35000. ' Composition according to any one of Claims 1 to 7, characterized in that the different construction thermoplastic is a polyolefin with a number average molecular weight above 10,000 and an apparent crystalline melting point above: Loo ° c. 9. A composition according to claim 8, characterized in that the polyolefin is a homopolymer or copolymer derived from an alpha-olefin or 1-olefin having 2-5 carbon atoms. 10. l0. Composition according to Claim 8 or 9, characterized in that the total molecular weight of the polyolefin is more than 50,000. 11. ll. Composition according to any one of claims 8 to 10, characterized in that the apparent crystalline melting point of the polyolefin is between 14,000 and 250 ° C. Composition according to any one of Claims 8 to 11, characterized in that it contains a high density polyethylene having an approximate crystallinity of more than 75% and a density of between 0, 94 and 1.0 kg / liter. 13. A composition according to any one of claims 8 to 11, characterized in that it contains a polyethylene of low den- ¿I \ ivüisafsísn-ss i i. 44 site with an approximate crystallinity of over 35% and a density of between 0.90 and 0.94 kg / liter. A composition according to any one of claims 8 to 13, characterized in that it contains a polyethylene having a number average molecular weight of 50,000 - 500,000. Composition according to one of Claims 8 to 11, characterized in that it contains an isotactic polyprocene n e - k e n n e - pen. Composition according to any one of Claims 8 to 11, characterized in that the polypropylene has a number average molecular weight in excess of 100,000. 17. A composition according to any one of claims 8-11, characterized in that it contains a polypropylene which is a copolymer which contains ethylene or other alpha-olefin as known as a comonomer in an amount of 1 to 20% by weight. 18. l8. Composition according to any one of Claims 8 to 11, characterized in that it contains poly (1-butene) such as polyolefin. Composition according to any one of Claims 8 to 11, characterized in that it contains as polyolefin a homopolymer of 4-methyl-1-pentene with an apparent crystalline melting point of between 240 DEG and 250 DEG C. and a relative density of between 0 DEG. 80 and 0.85. Composition according to any one of Claims 8 to 11, characterized in that it contains, as polyolefin, a copolymer of 4-methyl-1-pentene and an alpha-olefin. 21. A composition according to claim 20, characterized in that it contains as polyolefin a copolymer of 4-methyl-1-pentene and a linear alpha-olefin having 4-18 carbon atoms, which linear alpha-olefin is present in an amount of 0.5-30% by weight. 22. A composition according to any one of claims 1-7, characterized in that the different construction thermoplastic is known - a thermoplastic polyester with a melting point exceeding 120 ° C. 23. A composition according to any one of claims 1 to 7 or 22, characterized in that the different construction thermoplastic is poly (ethylene terephthalate), poly (propylene terephthalate) or poly (butene terephthalate). Yâf fl lš fl B fl e-B 45 Composition according to Claim 23, characterized in that the different construction thermoplastic is poly (butene terephthalate) with an average molecular weight of 20,000 - 25,000. 25. A composition according to any one of claims 1-7 or 22, characterized in that the construction thermoplastic is a cellulose ester. 26. A composition according to any one of claims 1-7 or 22, characterized in that the construction thermoplastic is a homopolymer of pivalolactone. 27. A composition according to any one of claims 1-7 or 22, characterized in that the construction thermoplastic is a copolymer of pivalolactone with not more than 50 mol% of another beta-propiolactone. * 28. A composition according to claim 27, characterized in that the construction thermoplastic is a copolymer of pivalolactone with not more than 10 mol% of another beta-propiolactone. 29. A composition according to any one of claims 26-28, characterized in that the construction thermoplastic is a polypivalolactone having an average molecular weight exceeding 20,000 and a melting point exceeding 120 ° C. 30. A composition according to any one of claims 1 to 7 or 22, characterized in that the construction thermoplastic is a polycaprolactone. 31. A composition according to any one of claims 1-7, characterized in that the different construction thermoplastic is a polyamide with a number average molecular weight of more than 10,000. A composition according to any one of claims 1 to 7, characterized in that the construction thermoplastic is a homopolymer of formaldehyde or trioxane. Composition according to any one of claims 1 to 7, characterized in that the construction thermoplastic is a polyacetal copolymer. Composition according to any one of Claims 1 to 7, characterized in that the construction thermoplastic is a homopolymer or copolymer derived from tetrafluoroethylene, chlorotrifluoroethylene, bromotrifluoroethylene, vinylidene fluoride or vinylidene chloride. ' 35. A composition according to any one of claims 1-7, characterized in that the construction thermoplastic is a nitrile resin having an alpha, beta-olefinically unsaturated mononitrile content in excess of 50% by weight. _ 36. A composition according to claim 35, characterized in that the alpha, beta-olefinically unsaturated mononitrile has the general formula caffe-CN .I - R wherein R represents hydrogen, an alkyl group having 1-4 carbon atoms or a halogen. 37. A composition according to claim 35 or 36, characterized in that the nitrile resin is a homopolymer, a copolymer, a graft polymer of a copolymer on a gum composition or a mixture of homopolymers and / or copolymers. Oh 38. A composition according to any one of claims 1-37, characterized in that it contains the block copolymer and the various thermoplastics in an amount of 8-20 parts by weight and 10 parts by weight, respectively. Composition according to any one of the preceding claims, characterized in that it contains an excipient oil in an amount of 0-100 parts by weight per 100 parts by weight of block copolymer. 40. '40. Composition according to Claim 39, characterized in that it contains an excipient oil in an amount of 5-30 parts by weight per 100 parts by weight of block copolymer. 0 41. A composition according to any one of the preceding caravas, characterized in that it contains a flow-promoting resin as an additional resin in an amount of 0-100 parts by weight per 100 parts by weight of block copolymer. a 42. A composition according to claim 41, characterized in that it contains a flow-promoting resin as an additional resin in an amount of 5-25 parts by weight per 100 parts by weight of block copolymer. Composition according to Claim 41 or 42, characterized in that it contains an additional resin which belongs to the group consisting of an alpha-methylstyrene resin, coumarone-indene resin, vinyltoluene-alpha-methylstyrene copolymers, polyindene-1α-alkano 47 resins and low molecular weight polystyrene resins. Process for preparing a composition according to any one of claims 1 to 43, characterized in that at a process temperature Tp of between 150 ° C and 400 ° C, (a) 4-40 parts by weight of a partially hydrogenated block copolymer are mixed. more, comprising at least two terminal polymer segments A of a monoalkenylar having an average molecular weight of 5,000 - 125,000 and at least one intermediate polymer segment B of a conjugated diene having an average molecular weight of 10,000 - 300,000, the terminal polymer segments A being 8-55 % by weight of the block copolymer and not more than 25% of the arene double bonds in the polymer segments A and at least 80% of the aliphatic double bonds in the polymer segments B have been reduced by hydrogenation, with (b) a polycarbonate with a melting point above 120 ° C and (c) 5- 48 parts by weight of at least one different construction thermoplastic, belonging to the group consisting of polyamides, polyolefins, thermoplastic polyesters, poly (aryl ethers), poly (aryl sulphones), acetal resins, thermoplastic elastic polyurethanes, halogenated thermoplastics and nitrile resins, the weight ratio of polycarbonate to different construction thermoplastics being greater than 1: 1, so that a polyblend is formed, in which at least two of the polymers form at least partial interconnected continuous networks. Process according to Claim 44, characterized in that the polymers are mixed at a process temperature Tp of between 23 ° C and 300 ° C. 46. A process according to claim 44 or 45, characterized in that the polymers are dissolved in a solvent common to all polymers and coagulated by mixing in a solvent in which neither polymer is soluble. A method according to claim 44 or 45, characterized in that the polymers are mixed as granules and / or powders in a device which produces shear forces. 48. A method according to any one of claims 44-47, characterized in that the ratio between the viscosity of the block copolymer and the viscosity of the polycarbonate, the different construction thermoplastic or the mixture of polycarbonate and different construction thermoplastics is between 0.2 and 4.0 at the process temperature Tp and a shear rate of 100 s'l. A method according to claim 48, characterized in that the ratio between the viscosity of the block copolymer and the viscosity of the polycarbonate, the different construction thermoplastic or the mixture of polycarbonate and different construction thermoplastics is between 0.8 and 1.2 at the process temperature Tp and a shear rate of 100 sql. 0 0 A method according to any one of claims 44-49, characterized in that the different construction thermoplastic may first be mixed with a viscosity modifier before being mixed with the polycarbonate and the block copolymer. Process according to one of Claims 44 to 50, characterized in that poly (2,6-dimethyl-1,4-phenylene) oxide or a mixture of poly (2,6-dimethyl-) is used as the viscosity modifier. 1,4-phenylene oxide with polystyrene. 52. A method according to claim 50 or 51, characterized in that the viscosity modifier used in an inlet of 0-100 parts by weight gives 100 parts by weight of construction thermoplastic. 53.; A method according to claim 52, characterized in that the viscosity modifier is used in an amount of 10-50 parts by weight per 100 parts by weight of construction thermoplastic. 54. A method according to any one of claims 44-53, characterized in that the block copolymer and the different construction thermoplastic are used in an amount of 8-20 parts by weight resp. 10-35 parts by weight.