JPS6129985B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to compositions containing certain partially hydrogenated block copolymers. However,
The partially hydrogenated block copolymer used here is
at least two monoalkenyl arene-based terminal polymer blocks A having an average molecular weight of 5,000 to 125,000; and at least one conjugated diene-based intermediate polymer block B having an average molecular weight of 10,000 to 300,000; Polymer block A occupies 8 to 55% by weight of this block copolymer, and the arene double bonds of polymer block A are
It is a block copolymer in which not more than 25% and at least 80% of the aliphatic double bonds of the polymer block B have been reduced by hydrogenation. As used herein, the term "engineering thermoplastics" refers to a variety of heavy duty resins that have sufficient strength, stiffness, impact strength, and long-term dimensional stability so that they can be advantageously used as structural materials. It means union. Engineering thermoplastics are particularly preferred as materials to be used in place of metals. This is because it is lightweight and can often be advantageously used to reduce weight in automobiles and the like. In certain fields of use, the use of only one type of thermoplastic resin may result in its properties not fully satisfying the desired conditions. Therefore, it is important to try various methods to eliminate such dissatisfaction. One such approach is to create two polymers that have only some of the desired properties.
The idea is to mix one or more species to obtain a resin material with all of the desired properties. This attempt was successful only in certain technical fields, for example,
Success has been achieved in cases such as improving the impact resistance of thermoplastics (e.g. polystyrene, polypropylene, poly(vinyl chloride)), but in which case special blending techniques or additives have been used for this purpose. It was successfully used.
However, generally speaking, mixing multiple types of thermoplastic resins is never a "single substance that combines the good properties of each of two or more types of polymers."
It was not an advantageous way to obtain this.
In fact, it has often been found that such mixtures result in mixtures that combine the worst properties of each polymer, that is, mixtures that have no practical or commercial value. . The cause of this failure is relatively well understood; it is due in part to the fact that any two polymers are often not mutually miscible, as shown by thermodynamic considerations. (However, as is already well known,
There are some notable exceptions). More importantly, most polymers have poor adhesion to each other. As a result of this, the mutual miscibility of the component polymers in the polymer blend is poor and the domain boundaries are very weak areas where flaws and cracks naturally occur, resulting in mechanical defects. is likely to occur. Because of this situation, most "pairs of polymers" are said to have poor compatibility. Although the term "compatible" is sometimes used as a synonym for "miscible," as used herein, "compatible" has a more general meaning, meaning that two polymers cannot be combined. Refers to the compatibility of the two polymers when used with good results; therefore, "compatibility" in this case may or may not include "miscibility". It is also possible. One of the methods available for solving the above problems in polymer blends is to mix the two polymers with a third component to make the two polymers compatible with each other. The third component used here is "2" for the two polymers to be mixed.
It has a dual solubility nature and is often referred to as a ``compatibility-imparting agent.'' Examples of this third component include those obtained in the form of block or graft copolymers. Because this compatibilizer has the above-mentioned properties, it is located at the interface of the polymer components and greatly improves the interphase adhesion, thus increasing the stability and overall phase This prevents gross phase separation. The present invention provides a method for stabilizing multicomponent polymer blends that is completely independent of prior art compatibility imparting methods, and in no way does the present invention "exploit limited binary solubility properties." The method is not limited to the method that requires the following. Materials that can be used for this purpose are certain block copolymers that are capable of thermoreversible self-crosslinking. The above effects achieved according to the present invention are by no means to the extent that could be deduced from the ordinary concept of "imparting compatibility." This is because, even for a wide range of different blend components, which do not quite meet the solubility conditions required according to conventional concepts, the materials used according to the invention will generally equally achieve the above-mentioned desired effects. This is because a large amount of evidence has been found that it represents The present invention comprises at least two terminal polymer blocks A based on monoalkenyl arenes having an average molecular weight of 5,000 to 125,000, and at least one intermediate polymer block B based on conjugated dienes having an average molecular weight of 10,000 to 300,000. It is a partially hydrogenated block copolymer, in which the unterminated polymer block A accounts for 8 to 55% by weight of the block copolymer, and 25% of the allene double bonds in the polymer block A
In a composition comprising the following and a partially hydrogenated block copolymer in which at least 80% of the aliphatic double bonds of said polymer block B have been reduced by hydrogenation: (a) the above partially hydrogenated block copolymer; 4 to 40 parts by weight of block copolymer, (b) polyamide with a number average molecular weight of 10,000 or more, (c) polyolefin, thermoplastic polyester, poly(arylsulfone), polycarbonate,
5 to 48 parts by weight of at least one dissimilar engineering thermoplastic resin selected from the group consisting of acetal resins, thermoplastic polyurethanes, halogenated thermoplastics, and nitrile resins, wherein said polyamide to said dissimilar engineering thermoplastic resin. the weight ratio with the thermoplastic resin is greater than 1:1, whereby "at least two of the polymers form at least partially continuous interlocked networks." The present invention relates to a composition characterized in that it is capable of forming a polyblend such as The block copolymer used in the present invention is
Various polymer structure
networks) to each other to stabilize their mechanical properties or structure, and the mutual separation of each polymer in the blend occurs during processing or subsequent use. to ensure that prevention of As will be explained in more detail below, the polyblend (or polymer blend) thus obtained has at least two partially continuous interlocking networks. Due to the presence of this interlocking structure, the polyblend is dimensionally stable and will not delaminate during extrusion operations and subsequent use. In order to create a stable blend, at least two of the polymers used must have an at least partially continuous network structure that can be interlocked. Preferably, the block copolymer and "at least a portion of the other polymer" have a partially continuous interconnected network structure. Ideally, all polymers used have a completely continuous network structure that allows them to interlock. Here, "partially continuous network structure" means that only a part of the polymer has a continuous network phase structure, and the other part has a disperse phase structure.
This is a term that means having a phase structure. It is preferable that the majority (50% by weight or more) of this partially continuous network structure be uninterrupted. As can be easily understood,
Various types of blend structures can be formed. This is because the structure of the polymers in the blend can be completely continuous or completely dispersed or partially continuous and partially dispersed. For example, if there are three types of polymers, and each of them is a first polymer, a second polymer, and a third polymer, the dispersed phase of the first polymer is not in the third polymer, but in the third polymer. Dispersion in the dipolymer is also possible. A specific example of such a structure will be explained. The following table lists various polymer structure combinations. However, all structures in this case are complete structures rather than partial structures. Three polymers A, B and C will be considered here. Subscript "c" in the following table represents a continuous structure and "d" represents a distributed structure. Therefore, the symbol "AcB" means that polymer A and polymer B form a continuous phase, and "BdC"
means that polymer B is dispersed in polymer C. AcB AcC BcC AdB AcC BcC AcB AcC BdC BdA AcC BcC BdC AcB AcC CdA AcB AcC CdB AcB AcC By carrying out the present invention, polyblends with good properties can be produced, and the polyblends can be It has much better properties than the polymer itself. According to the invention, for example, large amounts of polyamide can be mixed with small amounts of relatively expensive engineering thermoplastics (e.g. poly(butylene terephthalate));
This results in a polyblend that retains most of the desirable properties of the relatively expensive engineering thermoplastics themselves. The price of this Voriblend is a fraction of the price of the engineering thermoplastic resin itself mentioned above.
It's nothing more than that. It is particularly surprising that the block copolymers can be used for structural stabilization of certain types of polyblends in which the relative concentration values of the component polymers vary over a very wide range. This means that it is sufficient to use a small amount of coalescence. For example, to stabilize a blend of 5 to 90 parts by weight of polyamide and 90 to 5 parts by weight of dissimilar engineering thermoplastic resin, it is sufficient to use only about 4 parts by weight of block copolymer. Furthermore, another surprise is that the block copolymers are also useful for stabilizing such a wide variety of polymer types and chemical make-up. It is a certain thing. As will be explained in more detail below, this block copolymer has the ability to stabilize different types of polymers present in different concentrations. This is because it is oxidatively stable, has an infinite viscosity at zero shear stress, and can possess a network or domain structure in the melt. Another important effect of the present invention is that by using the block copolymer as a stabilizer,
Processing and molding operations for various polyblends can be carried out more easily and effectively, ie, the efficiency of the operations can be greatly improved. The block copolymers used in the compositions according to the invention may have various geometric structures. This is because the effectiveness of the present invention does not depend on the specific geometrical structure of each polymer block, but rather on the chemical structure (composition). For example, the block copolymer may be linear, radial or branched. Methods for producing such block copolymers are well known in the art. The structure of this block copolymer will vary depending on the method of polymerization. For example, when certain monomers are sequentially introduced into a reactor using an initiator such as lithium-alkyl (i.e., alkyllithium) or dilithio-stilbene, or when a two-segment block copolymer is When coupled with a coupling agent, a linear block copolymer is obtained. On the other hand, copolymers with branched structures can be obtained by using coupling agents with appropriate functionality together with three or more precursor polymers. This coupling reaction can be carried out using polyfunctional coupling agents, and examples of such couplings include: dihaloalkanes or -
Alkenes, divinylbenzene, some polar compounds such as silicon halides, siloxanes, esters of monohydric alcohols and carboxylic acids. When describing the polymers that form part of the compositions according to the invention, the presence of residues from the coupling reaction may be ignored. Similarly, descriptions of specific structures may generally be ignored. In the present invention, partially hydrogenated (i.e., "selectively hydrogenated") polymers can be used, such as partially hydrogenated polymers having the following structure (however, for simplicity of description:
The structure of the polymer before hydrogenation is shown in the formula below). Polystyrene-polybutadiene-polystyrene (SBS) Polystyrene-polyisoprene-polystyrene (SIS) Poly(α-methylstyrene)-polybutadiene-poly(α-methylstyrene) Poly(α-methylstyrene)-polyisoprene-poly(α-methyl (styrene) Both polymer blocks A and B can be homopolymers or random copolymer blocks;
The multipolymer block must contain a large amount of "at least one type of monomer that characterizes the polymer block." The polymer blocks A may consist of a homopolymer of monoalkenyl arene or a copolymer of a monoalkenyl arene and a conjugated diene, each of the polymer blocks A containing a large amount of monoalkenyl arene units. It has to be something. The term "monoalkenyl arene" is a term that encompasses, for example, styrene and its analogues or homologs, such as alpha-methylstyrene and ring-substituted styrenes, especially ring-methylated styrenes. Preferred monoalkenyl arenes are styrene and alpha-methylstyrene, with styrene being particularly preferred. Polymer block B may consist of a homopolymer of a conjugated diene, such as butadiene or isoprene, or a copolymer of a conjugated diene and a monoalkenyl arene, although polymer block B may consist of a conjugated diene unit. It must contain a large amount of. When the monomer to be used is butadiene, it is preferred that from 35 to 55 mole percent of the condensed butadiene units in the butadiene polymer block be of the 1,2-configuration. The products obtained by hydrogenation of such blocks are regular copolymer blocks of ethylene and butene-1 (EB) or analogs thereof. When the conjugated diene used is isoprene, the resulting hydrogenation product is a regular copolymer block (EP) of ethylene and propylene or the like. Hydrogenation of the precursor block copolymer is preferably carried out as follows. that is, at least 80% of the aliphatic double bonds and 25% of the aromatic double bonds of alkenyl arenes using a catalyst comprising a reaction product of an aluminum alkyl compound and a nickel or cobalt carboxylate or alkoxide. Preferably, the process is carried out under conditions such that the following are substantially completely hydrogenated: Preferred block copolymers have at least 99% aliphatic double bonds.
is hydrogenated, and 5% or less of the aromatic double bonds are hydrogenated. The average molecular weight of the individual blocks can vary within certain limits. The block copolymers present in the composition according to the invention include at least two terminal polymer blocks A of the monoalkenyl arene series having a number average molecular weight of 5,000 to 125,000 (preferably 7,000 to 60,000) and a number average molecular weight of 10,000 to 300,000. (Preferably
at least one intermediate polymer block B based on a conjugated diene having a number average molecular weight of 30,000 to 150,000)
It has the following. This molecular weight can be measured most accurately by tritium counting, osmotic pressure measurement, or the like. The proportion of the monoalkenyl arene polymer block A in this block copolymer should be 8 to 55% by weight, preferably 10 to 30% by weight. The term "polyamide" means a condensation product containing repeating units having aromatic and/or aliphatic amide groups as an essential constituent of the polymer chain. Products of this type are commonly known as "nylons." Polyamide can be manufactured according to the following manufacturing method. That is, it can be prepared by polymerizing a monoamino-monocarboxylic acid or an internal lactam thereof having at least two carbon atoms between an amino group and a carboxylic acid group; It can be produced by performing a polymerization operation using substantially equimolar amounts of a diamine having a carbon atom and a dicarboxylic acid, or by performing a polymerization operation using substantially equimolar amounts of the above monoamino-monocarboxylic acid or its internal lactam. It can be produced by copolymerizing diamines and dicarboxylic acids. The dicarboxylic acids mentioned above may also be used in the form of their derivatives (eg esters). The terms "substantially equimolar amounts (of diamine and dicarboxylic acid)" are used in the strict sense of "equimolar amounts" and "a slightly less than equimolar ratio" (shifting this ratio means that the polyamide product (This is a commonly used technique used to stabilize viscosity.) Examples of the aforementioned monoamino-monocarboxylic acids or their internal lactams include compounds having 2 to 16 carbon atoms between the amino group and the carboxylic acid group (in the case of lactams, the carbon atoms are -
(combined with CO and NH- groups to form a ring). Examples of such aminocarboxylic acids and lactams include: ε-aminocaproic acid, butyrolactam, pivalolactam, caprolactam,
Caprylic-lactam, enantlactam, undecanolactam, dodecanolactam, 3- and 4-
-Aminobenzoic acid. Examples of the diamines include diamines of the general formula H ₂ N(CH ₂ ) _o NH ₂ , where n is an integer from 2 to 16, and specifically trimethylene diamine, tetramethylene diamine. ,
Mention may be made of pentamethylene diamine, octamethylene diamine, decamethylene diamine, dodecamethylene diamine, hexadecamethylene diamine, and especially hexamethylene diamine. Another example includes C-alkylated diamines such as 2,2-dimethylpentamethylene diamine, 2,2,4- and 2,4,4-trimethylhexamethylene diamine. Further examples of diamines include aromatic diamines such as p-phenylenediamine, 4,4'-diaminodiphenyl sulfone, 4,4'-diaminodiphenyl ether, 4,4'-diaminodiphenyl sulfone,・4′-diaminodiphenyl ether, 4・
4'-diaminodiphenylmethane: and cycloaliphatic diamines such as diaminodicyclohexylmethane. The dicarboxylic acids mentioned above may be aromatic, examples of which include isophthalic acid and terephthalic acid. Preferred dicarboxylic acids are those of the formula HOOC.Y.COOH (where Y represents a divalent aliphatic group having at least 2 carbon atoms), examples of which include: Contains: sebacic acid, octadecanedioic acid, suberic acid, azelaic acid, undecanedioic acid, glutaric acid, pimelic acid, and especially adipic acid. Oxalic acid is also a preferred acid. For example, the following polyamides can be incorporated into thermoplastic polyblends in accordance with the present invention. Polyhexamethylene adipamide (nylon 6:
6) Polypyrrolidone (nylon 4) Polycaprolactam (nylon 6) Polyheptolactam (nylon 7) Polycapryllactam (nylon 8) Polynonanolactam (nylon 9) Polyundecanolactam (nylon 11) Polydodecanolactam (nylon 12) Polyhexamethylene azelaamide (nylon 6:9) Polyhexamethylene sebacamide (nylon 6:
10) Polyhexamethylene isophthalamide (nylon 6: iP) Polymethaxylylene adipamide (nylon
MXD6) Polyamide of hexamethylene diamine and n-dodecane dioxic acid (nylon 6:12) Polyamide of dodecamethylene diamine and n-dodecane dioxic acid (nylon 12:12) Nylon copolymers can also be used, examples of which are: Examples include the following copolymers. Hexamethylene adipamide/caprolactam (nylon 6:6/6) Hexamethylene adipamide/hexamethylene-
Isophthalamide (nylon 6:6/6ip) Hexamethyleneadipamide/Hexamethylene-
Terephthalamide (nylon 6:6/6T) Trimethylhexamethylene oxamide/hexamethylene oxamide (nylon trimethyl-6:
2/6:2) Hexamethylene adipamide/hexamethylene-
Azelaamide (nylon 6:6/6:9) hexamethyleneadipamide/hexamethylene-
Azelaamide/Caprolactam (Nylon 6:
6/6:9/6) Nylon 6:3 is also useful. This polyamide is the reaction product of terephthalic acid dimethyl ester and trimethylhexamethylene diamine (a mixture of various isomers). Examples of preferred nylons include nylon 6:6/
6, 11, 12, 6/3 and 6/12 are listed. The number average molecular weight of these polyamides should be greater than 10,000. Term "Dissimilar Engineering Thermoplastics"
is a term denoting an engineering thermoplastic resin that is different (ie, "dissimilar") from the polyolefin present in the composition according to the invention. The term "engineering thermoplastic" is a term that encompasses various polymers of the type described in Table A below and in the description below. Table A 1 Polyolefin 2 Thermoplastic polyester 3 Poly(aryl sulfone) 4 Polycarbonate 5 Acetal resin 6 Thermoplastic polyurethane 7 Halogenated thermoplastic 8 Nitrile resin Glass transition temperature or apparent crystal melting point (modulus value is large under low stress) It is advantageous to use engineering thermoplastics which have a temperature at which the temperature decreases to 120° C. or higher (preferably from 150 to 350° C.) and which are capable of forming a continuous network structure by a thermoreversible crosslinking mechanism. Such thermoreversible crosslinking includes crystallite formation, polar aggregations, ionic aggregation, lamellae formation, hydrogen bond formation, and the like. Specifically, when the viscosity of the block copolymer or block copolymer mixed composition at the processing temperature (T _p ) and shear rate of 100 S ^-1 is η, the engineering thermoplastic resin or the The value of the ratio of viscosity to η of the mixture of thermoplastic resin and viscosity modifier can be from 0.2 to 4.0, preferably from 0.8 to 1.2. The "viscosity of block copolymers, polyamides, and engineering thermoplastics" described in this specification is "melt viscosity," and
This occurs at a certain temperature above the melting point (e.g.
260°C) at a constant shear rate using a piston-driven capillary melt rheometer. Having specified a preferred upper limit (350°C) for the apparent crystalline melting point or glass transition temperature, this resin can be used commercially at 350°C or below in equipment operated at low or moderate shear rates. Processing can be performed at a typical processing temperature. The engineering thermoplastic resin may be a mixture of various types of engineering thermoplastic resins or a mixture of these resins with a viscosity-adjusting resin as an additive. Definitions of these various types of engineering thermoplastics are provided below. The polyolefin present in the composition according to the invention may be crystalline or crystallizable. This may be a homopolymer or a copolymer and has 2 carbon atoms.
It may be derived from ~5 α-olefins or 1-olefins. Examples of particularly useful polyolefins include: low density polyethylene, high density polyethylene, isotactic polypropylene, poly(1-butene), poly(4-methyl-1-pentene);
Copolymer of 1-pentene and linear or branched α-olefin. In order to form a continuous structure together with other polymers in the polyblend (polymer blend) according to the present invention, it is an important condition that the above polymer has a crystalline structure or a crystallizable structure. It is. The number average molecular weight of the polyolefin is preferably 10,000 or more, more preferably 50,000 or more. Furthermore, its apparent crystal melting point is 100
The temperature is preferably 100-250°C, more preferably 140-250°C. The methods for producing these various polyolefins are well known, and for an overview please refer to, for example, Kirk-Othmer, ed., "Encyclopedia of Chemical Technology," Vol. 14, Vol.
“Orefin,” on pages 217 to 335 (1967).
Polymer” article. When using high-density polyethylene, its approximate crystallinity is about 75% or more and the density is 0.94.
It is preferable that it is ~1.0Kg/. When low density polyethylene is used, it is preferred that its approximate crystallinity is about 35% or more and its density is 0.90 to 0.94 Kg/. The composition according to the invention may contain a polyolefin having a number average molecular weight of 50,000 to 500,000. When polypropylene is used, it is preferred to use isotactic polypropylene, which has properties completely different from so-called atactic polypropylene. The number average molecular weight of the polypropylene used is preferably 100,000 or more. This polypropylene can be manufactured according to well-known manufacturing methods. Depending on the type of catalyst used and the polymerization conditions, polymer products are obtained which contain atactic molecules and isotactic, syndiotactic or so-called stereoblock molecules. These polymer molecules can be separated from each other by a selective solvent extraction procedure, which results in a relatively completely crystallized product with a low atactic content. Commercially available such preferred polypropylenes are generally produced using hydrocarbon-insoluble solid crystalline catalysts prepared from titanium trichloride compositions and aluminum alkyl compounds (e.g., triethylaluminum, diethylaluminum chloride). be. If desired, the polypropylene used may be in the form of a copolymer containing small amounts (for example 1 to 20% by weight) of ethylene or other alpha-olefins as comonomers. Preferably, the poly(1-butene) has an isotactic structure. The catalyst used in the production of poly(1-butene) is preferably an organometallic compound generally referred to as a Ziegler-Natsuta catalyst. A typical example of such a catalyst is an interacted product obtained by mixing equimolar amounts of titanium tetrachloride and triethylaluminum.
product). This process can generally be carried out in an inert diluent such as hexane. This manufacturing operation should be carried out under strict conditions to reliably prevent even trace amounts of moisture from entering throughout each polymer phase formation step. An example of a very suitable polyolefin is poly(4
-methyl-1-pentene). This poly(4-methyl-1-pentene) has an apparent crystalline melting point of 240 to 250°C and a relative density of 0.80 to 0.85. The monomer 4-methyl-1-pentene is produced industrially by dimerizing propylene in the presence of an alkali metal catalyst. 4- in the presence of Ziegler-Natsuta catalyst
The homopolymerization method of methyl-1-pentene is described in the following literature: "Encyclopedia of Chemical Technology", edited by Kirk Osmer, supplementary edition, pages 789-792 (2nd edition). , 1971
Year). However, isotactic homopolymers of 4-methyl-1-pentene have some drawbacks, such as morosa and insufficient transparency. Therefore, commercially available poly(4-methyl-1-
Pentene-1) is actually a copolymer with small amounts of other α-olefins, to which stabilizers are added to provide suitable oxidative and melt stability. There is. This type of copolymer is described in "Encyclopedia of Chemicals and Technology" edited by Kirk-Othmer, supplementary edition.
It is described on pages 792 to 907 (2nd edition, 1971). Commercial examples of this copolymer include “TPX
One example is one sold under the trade name "Resin" (registered trademark). Typical examples of α-olefins include linear α-olefins having 4 to 18 carbon atoms. A suitable resin is a copolymer of 4-methyl-1-bentene and 0.5 to 30% by weight linear alpha-olefin. If desired, the polyolefin may be a mixture of different polyolefins. However, a more preferred polyolefin is isotactic polypropylene. Optionally, the thermoplastic polyester disposed in the composition according to the invention is one which generally has a crystalline structure, has a melting point above 120° C., and is thermoplastic rather than thermosetting. . Examples of particularly useful types of polyesters include thermoplastic polyesters prepared by condensing dicarboxylic acids or their lower alkyl esters or acid halide or anhydride derivatives with glycols according to methods well known in the art. can give. Aromatic and aliphatic dicarboxylic acids suitable for preparing this polyester include: oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, suberic acid, azelaic acid, sebacic acid, terephthalic acid, , isophthalic acid, p-carboxyphenoacetic acid, p・p′-dicarboxydiphenyl, p・p′-dicarboxydiphenyl sulfone,
p-carboxyphenoxyacetic acid, p-carboxyphenoxypropionic acid, p-carboxyphenoxybutyric acid, p-carboxyphenoxyvaleric acid, p
-carboxyphenoxyhexanoic acid, p・p′-dicarboxydiphenylmethane, p・p-dicarboxydiphenylpropane, p・p′-carboxydiphenyloctane, 3-alkyl-4-(β-carboxyethoxy )-benzoic acid, 2,6-naphthalene dicarboxylic acid and 2,7-naphthalene dicarboxylic acid. Mixtures of dicarboxylic acids may also be used. Terephthalic acid is particularly preferred. Suitable glycols for preparing the polyesters include linear 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. A part or all of these glycols may be replaced with aromatic glycols. Suitable aromatic dihydroxy compounds include p-xylylene glycol, pyrocatechol, resorcinol, hydroquinone, or alkyl-substituted derivatives of these compounds. Other suitable glycols are 1.4
-cyclohexanedimethanol. More preferred glycols are straight chain alkylene glycols having 2 to 4 carbon atoms. Preferred polyesters are poly(ethylene terephthalate), poly(propylene terephthalate), and poly(butylene terephthalate). A more preferred polyester is poly(butylene terephthalate). Poly(butylene terephthalate), a crystalline copolymer, is 1.4
- can be prepared by polycondensation of butanediol with dimethyl terephthalate or terephthalic acid, and which has the general formula: (wherein n is 70 to 140). The molecular weight of poly(butylene terephthalate) is preferably 20,000 to 25,000. An example of commercially available poly(butylene terephthalate) is "Barox®"
Examples include those sold under the trade name "Thermoplastic Polyester". There are other commercially available polymers of this type, including products sold under the trade names ``Ceranetx'', ``Tenite'' and ``Bituf''. can give. Examples of other useful polyesters include cellulose esters. The thermoplastic cellulose ester that can be used here is a well-known material that can be molded,
It is currently widely used as a coating and film forming material. Examples of cellulose esters include: cellulose nitrate in the form of solid thermoplastic materials, cellulose acetate (e.g. cellulose diacetate, cellulose triacetate), cellulose butyrate, cellulose acetate butyrate, cellulose propionate. nate, cellulose tridecanoate, carboxymethyl cellulose, ethyl cellulose, hydroxyethyl cellulose, acetylated hydroxyethyl cellulose (Modern, Plastics, Encyclopedia, 1971-72 edition, pages 25-28 and therein) (See cited publications). Another useful polyester is polypivalolactone. Polypivalolactone is a linear polymer mainly having repeating ester structural units of the following formula: _-CH2 -C( _CH3 ) ₂ -C(O)O- (i.e., units derived from pivalolactone). Preferably, the polyester is
It is a homopolymer of pivalolactone. Other examples include pivalolactone and up to 50 mol%, preferably up to 10 mol% of other β-propiolactones (e.g. β-propiolactone, α·α-diethyl-β-propiolactone and α- Methyl-
There is a copolymer with α-ethyl-β-propiolactone). The term "β-propiolactone" refers to β
-Propiolactone (2-oxetanone) and β-propiolactone derivatives having no substituent on the β-carbon atom of the lactone ring. Preferred β-propiolactones are those having a tertiary or quaternary carbon atom in the α-position with respect to the carbonyl group. Particularly preferred are .alpha..alpha.-dialkyl-.beta.-propiolactones in which each of the alkyl groups independently has 1 to 4 carbon atoms. Examples of significant monomers are: α-ethyl-α-methyl-β-propiolactone, α-methyl-α-isopropyl-β-propiolactone, α-ethyl-α-n-butyl. -β-propiolactone, α-chloromethyl-α-methyl-β-propiolactone, α・α-bis(chloromethyl)-β-propiolactone, α・α-dimethyl-β-propiolactone ( pivalolactone). These polypivalolactones have a molecular weight of 20,000 or more and a melting point of 120°C or more. Another useful polyester is polycaprolactone. Preferred poly(ε-caprolactone) has the following formula: It is a substantially linear polymer having repeating units of . These polymers have similar properties to polypivalolactone and can be produced by similar polymerization methods. Another useful engineering thermoplastic
Examples include the following formula: -Ar-SO ₂ - where Ar is a divalent aromatic group, and this group is a unit in the polymer chain (to form various copolymers). Examples include aromatic polysulfones consisting of repeating units of [which can vary depending on the position of]. Thermoplastic poly(sulfone) has the following structure: (wherein Z is oxygen or sulfur, or an aromatic diol residue such as a 4,4-bisphenol residue). One example of such a poly(sulfone) is: has a repeating unit of , and another has the following formula: , and yet another has the following formula: repeating unit, or the following formula: and copolymerized units in various proportions. Thermoplastic poly(sulfone) also has the following formula: It may have repeating units.
Structure of the following formula: poly(ether sulfone) with repeating units of and the structure of Poly(ether sulfones) having repeating units of are also useful as engineering thermoplastics. Examples of polycarbonates that can be used in the compositions of the invention include those with the general formula: and (In the formula, Ar is a phenylene group or an alkyl group,
alkoxy-, halogen- or nitro-substituted phenylene group; A is a carbon-carbon bond or alkylidene group, cycloalkylidene group, alkylene group,
Cycloalkylene group, azo group, imino group, sulfur,
and n is at least 2). The method of manufacturing polycarbonate is well known.
A preferred method of preparation is to dissolve the dihydroxy component in a base such as pyridine and carry out the desired reaction by bubbling phosgene into the stirred solution at the desired rate. Tertiary amines may be used during the reaction to facilitate the reaction and to act as an acid acceptor. This reaction is usually exothermic, so
The reaction temperature can be adjusted by adjusting the phosgene addition rate. In general, equimolar amounts of phosgene and dihydroxy reactant can be used in the reaction, but this molar ratio can be varied depending on the reaction conditions. In the above formulas () and (), Ar
It is preferable that is a p-phenylene group and A is an isopropylidene group. This polycarbonate is prepared by reacting p.p'-isopropylidene diphenol with phosgene and is commercially available under the trade names "Lexan" and "Merlon". This commercially available polycarbonate has a molecular weight of about 18,000 and a melting temperature in excess of 230°C. Other polycarbonates can be made by reacting other dihydroxy compounds, or mixtures of dihydroxy compounds, with phosgene. Examples of such dihydroxy compounds include aliphatic dihydroxy compounds, but the presence of an aromatic ring is essential for obtaining the best high temperature properties. Dihydroxy compounds may contain diurethane linkages therein. Further, a part of this structure may be replaced with a siloxane bond. Examples of acetal resins that can be used in the compositions of the invention include high molecular weight polyacetal homopolymers made by polymerization of formaldehyde or trioxane. These polyacetal homopolymers are commercially available under the trade name "Delrin" (registered trademark). Additionally, a polyether type resin is commercially available under the trade name "Pentone" (registered trademark), which has the following structure: It has the following. Acetal resins made from formaldehyde are of high molecular weight and have the following formula: -H-O(-
CH2 _- O-CH2 _- O) _-xH- [where the terminal groups are derived from a controlled amount of water and x represents a number ( Preferably, the formaldehyde unit has a structure of about 1500). To increase heat and chemical resistance, it is common practice to convert the terminal groups to ester or ether groups. The term polyacetal resin also includes polyacetal copolymers. Examples of these copolymers include monomers or prepolymers of formaldehyde and other substances capable of providing active hydrogen, such as alkylene glycols, polythiols, vinyl acetate-acrylic acid copolymers or reduced butadiene. / block copolymers with acrylonitrile polymers. Celanese, which can be advantageously used in the blends of the present invention, is a copolymer of formaldehyde and ethylene oxide and is commercially available under the trade name "Celcon"(R). This copolymer generally has the following formula: (In the formula, each R ₁ and R ₂ is a group selected from the group consisting of hydrogen, lower alkyl, and lower halogen-substituted alkyl, and n is an integer from 1 to 3. However, the repeating unit is 85 to 99.9 % has a structure consisting of repeating units (n is zero). Formaldehyde and trioxane can be copolymerized with other aldehydes, cyclic ethers, vinyl compounds, ketenes, cyclic carbonates, epoxides, isocyanates and ethers. Specific examples of these compounds include ethylene oxide, 1,3-dioxolane, 1,3-dioxane, 1,3-dioxopene, epichlorohydrin, propylene oxide, isobutylene oxide and styrene oxide. Polyurethanes, also known as isocyanate resins, can also be used as engineering thermoplastics as long as they are thermoplastic rather than thermosetting. For example, toluene diisocyanate (TDI) or diphenylmethane 4,4-diisocyanate (MDI) and a wide variety of polyols such as polyoxyethylene glycol, polyoxypropylene glycol, hydroxy-terminated polyesters, polyoxyethylene-oxypropylene glycol, etc. Manufactured polyurethane is suitable. These thermoplastic polyurethanes are commercially available under the trade names "Q-Tane" (registered trademark) and "Pentane-CPR" (registered trademark). Another practical engineering thermoplastic
One example has a substantially crystalline structure and a melting point of
Examples include halogenated thermoplastics with temperatures exceeding 120°C. Examples of these halogenated thermoplastics include homopolymers and copolymers derived from tetrafluoroethylene, chlorotrifluoroethylene, bromotrifluoroethylene, vinylidene fluoride and vinylidene chloride. Polytetrafluoroethylene (PTFE) is 76
It is the name given to fully fluorinated polymers of the basic chemical formula ( _-CF2 - _CF2 ) _-o containing % by weight of fluorine. This polymer is highly crystalline and has a crystalline melting point of over 300°C. Examples of commercially available PTFE include “Teflon” and “Fluon”
(Registered Trademark). Polychlorotrifluoroethylene (PCTFE) and polybromotrifluoroethylene (PBTFE) are also available in high molecular weight versions and can be used in the present invention. Particularly preferred halogenated polymers are homopolymers and copolymers of vinylidene fluoride. Poly(vinylidene fluoride) homopolymer is a partially fluorinated polymer having the formula ( _-CH2 - _CH2 ) _-o . This polymer is a tough linear polymer with a crystalline melting point of 170°C. Examples of commercially available homopolymers include those sold under the trade name "Kynar" (registered trademark). As used herein, the term "poly(vinylidene) fluoride" refers not only to normally solid vinylidene fluoride homopolymers, but also to poly(vinylidene) fluoride units containing at least 50 mole %, preferably at least 70 mole %, vinylidene fluoride units.
The term also refers to a normally solid vinylidene fluoride copolymer, more preferably containing 90 mol%.
Suitable comonomers are halogenated olefins having up to 4 carbon atoms, such as sym-dichlorodifluoroethylene, vinylfluoride, vinylidene chloride, perfluoropropene, perfluorobutadiene, chlorotrifluoroethylene, trichloroethylene and tetrafluoroethylene. Another useful example of halogenated thermoplastics includes homopolymers and copolymers derived from vinylidene chloride. Crystalline vinylidene chloride copolymers are particularly preferred. Normally crystalline vinylidene chloride copolymers useful in the present invention are those containing at least 70% by weight vinylidene chloride and 30% or less copolymerizable monoethylene monomer. Examples of such monomers are vinyl chloride, vinyl acetate, vinyl propionate, acrylonitrile,
Alkyl and -aralkyl acrylates having alkyl and aralkyl groups, respectively, having up to about 8 carbon atoms, acrylic acid, acrylamide, vinyl alkyl ethers, vinyl alkyl ketones, acrolein, aryl ethers and others, butadiene and chloropropene It is. Known ternary composition polymers may also be used advantageously. Examples of such polymers are at least 70% by weight of vinylidene chloride and the remaining amounts, such as 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 ester or ether and vinyl chloride, butadiene and vinyl acetate, vinyl propionate or vinyl chloride, vinyl ether and vinyl chloride.
Quaternary polymers of similar monomer composition are also well known. Particularly useful for purposes of this invention are copolymers of 70 to 95 weight percent vinylidene chloride and the balance vinyl chloride. Such copolymers may include conventional amounts of conventional plasticizers, stabilizers, nucleators, and extrusion aids. Furthermore, a mixture of two or more of such normally crystalline vinylidene chloride polymers can also be used. Also, blends comprising mixtures of such normally crystalline polymers and polymeric modifiers (e.g., ethylene-vinyl acetate copolymer, styrene-maleic anhydride copolymer, styrene-acrylonitrile copolymer, polyethylene). can also be used. Nitrile resins useful as engineering thermoplastics are thermoplastics having an α,β-olefinically unsaturated mononitrile content of 50% or more by weight. These nitrile resins can be copolymers, grafted copolymers onto rubbery substrates, or mixtures of homopolymers and/or copolymers. The α/β-olefinic unsaturated mononitrile contained here has the structure of the following formula: (wherein R is hydrogen, an alkyl group having 1 to 4 carbon atoms, or a halogen). Examples of 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 classified into several types based on the complexity of their structure. What has the simplest molecular structure is a random copolymer mainly composed of acrylonitrile or methacrylonitrile. The most common example is styrene-acrylonitrile copolymer. Acrylonitrile-based block copolymers are also known in which long segments of polyacrylonitrile alternate with segments of polystyrene or polymethyl methacrylate. Simultaneous polymerization of more than two types of comonomers results in multicomponent copolymers (or terpolymers in the case of three components). Many comonomers are known. Examples of these include: carbon atoms from 2 to
8 lower α-olefins such as ethylene, propylene, isobutylene, butene-1, pentene-1; their halogen- and aliphatic group-substituted derivatives such as vinyl chloride, vinylidene chloride; general formula (wherein R ₁ is hydrogen, chlorine or methyl, R ₂
has 6 carbon atoms and may contain substituents such as halogen and alkyl groups attached to the aromatic nucleus.
~10 aromatic groups) monovinylidene aromatic hydrocarbon monomers such as styrene, α-methylstyrene, vinyltoluene, α-chlorostyrene, o-chlorostyrene,
p-chlorostyrene, m-chlorostyrene, o-
Methylstyrene, p-methylstyrene, ethylstyrene, isopropylstyrene, dichlorostyrene, vinylnaphthalene. Particularly preferred comonomers are isobutylene and styrene. Another example of this comonomer includes the general formula: (In the formula, R ₃ is a group selected from the group consisting of hydrogen, an alkyl group having 1 to 10 carbon atoms, and an aryl group having 6 to 10 carbon atoms including the carbon atom of the ring-substituted alkyl substituent. ) vinyl ester monomers such as vinyl formate, vinyl acetate, vinyl propionate and vinyl benzoate. Similar to the previous one, useful ones include the general formula: H ₂ C=CH-O-R ₄ [wherein R ₄ is an alkyl group having 1 to 8 carbon atoms, an aryl group having 6 to 10 carbon atoms] , or a monovalent aliphatic group having from 2 to 10 carbon atoms, which aliphatic group may have a hydrocarbon chain or an oxygen-containing chain (for example, an ether bond), and may also be a monovalent aliphatic group having from 2 to 10 carbon atoms. It is a vinyl ether monomer which may contain substituents such as halogen and carbonyl groups. Examples of these vinyl ether monomers 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 or p-chlorophenyl glycol. Another example of this comonomer is a comonomer containing a mono- or di-nitrile functionality. Specific examples include methyleneglutaronitrile, (2,4-dicyanobutene-1), vinylidene cyanide, crotonitrile, fumarodinitrile, maleodinitrile. Another example of this comonomer includes esters of olefinically unsaturated carboxylic acids, preferably lower alkyl esters of α,β-olefinically unsaturated carboxylic acids, more preferably of the structure: (In the formula, R ₁ is hydrogen, an alkyl group having 1 to 4 carbon atoms, or a halogen, and R ₂ is a hydrogen atom having 1 to 4 carbon atoms.)
(2) is an alkyl group. Examples of this type of compound include methyl acrylate, ethyl acrylate, methyl methacrylate,
Examples include ethyl methacrylate and methyl α-chloroacrylate. Most preferred are methyl acrylate, ethyl acrylate, methyl methacrylate and ethyl methacrylate. Another type of nitrile resin is a graft copolymer having a polymeric backbone with branches of other polymeric chains. Generally, this backbone is previously prepared in a separate reaction. Polyacrylonitrile can be grafted with styrene, vinyl acetate or methyl methacrylate, for example. The main chain may be composed of one, two, three or more components, and the grafted branches may also be composed of one, two, three or more components.
It may consist of three or more comonomers. The most promising products are graft copolymers in which a previously prepared rubbery substrate is partially grafted with a nitrile copolymer. The substrate is made of synthetic or natural rubber components used to strengthen polymers, such as polybutadiene, isoprene, neoprene, nitrile rubber, natural rubber, acrylonitrile-butadiene copolymers, ethylene-propylene copolymers, and chlorinated rubbers. could be. The rubbery component can be prepared by various methods well known to those skilled in the art, such as direct polymerization of the monomers, grafting of acrylonitrile monomer onto the rubbery backbone, or physical admixture) to the nitrile-containing polymer. Particularly preferred are polymers obtained by mixing a graft copolymer made by grafting acrylonitrile and a comonomer onto a rubbery backbone with another copolymer of acrylonitrile and the same comonomer as above. It's a blend. Typical examples of thermoplastics based on acrylonitrile include polymer blends consisting of grafted polymers and non-grafted homopolymers. Commercially available examples of nitrile resins include "Barex (registered trademark)-210 resin," which is a nitrile-rich resin based on acrylonitrile containing 65% or more of nitrile; 4 is derived from methacrylonitrile). In order to better match the viscosity properties of the dissimilar engineering thermoplastic resin, the polyamide, and the block copolymer, the dissimilar engineering thermoplastic resin is first mixed with a viscosity modifier, and this mixture is then mixed with the polyamide. and the block copolymer. Suitable viscosity modifiers have relatively high viscosities and
The modifier has a melting temperature above 230° C. and whose viscosity value is very insensitive to temperature changes. Examples of suitable viscosity modifiers include poly(2.6-
There are dimethyl-1,4-phenylene) oxide and mixtures of poly(2,6-dimethyl-1,4-phenylene) oxide and polystyrene. Poly(phenylene oxide) that can be used as a viscosity modifier has the following formula: (wherein R ₁ is hydrogen, a hydrocarbon group without a tertiary α-carbon atom, having at least two carbon atoms between the halogen atom and the phenol nucleus and a tertiary α
- halogenated hydrocarbon radicals without carbon atoms, aliphatic tertiary α-hydrocarbonoxy radicals without carbon atoms, and aliphatic tertiary α-hydrocarbonoxy radicals with at least two carbon atoms between the halogen atom and the phenol nucleus; is a monovalent substituent selected from the group consisting of hydrocarbonoxy groups without class α-carbon atoms; R ₁ ' is the same as R ₁ and may also be a halogen; m is at least 50, e.g. 50～
800, preferably an integer from 150 to 300). Among these polymers, preferred ones have a molecular weight of 6,000 to 100,000, preferably 40,000.
It is a polymer of Preferably, the poly(phenylene oxide) is poly(2,6-dimethyl-1,4-phenylene) oxide. Poly(phenylene oxide) is commercially available in a mixture with styrene resin. Examples of these mixtures include those containing 25 to 50% by weight polystyrene units, which are commercially available from General Electric Company under the trade name "Noryl(R) Thermoplastics." When a poly(phenylene oxide)/polystyrene mixture is used, its preferred molecular weight is between 10,000 and 50,000, more preferably about 30,000. The amount of viscosity modifier used depends primarily on the value of the difference between the viscosity of the block copolymer and the viscosity of the engineering thermoplastic at temperature T _p .
The amount used may be from 0 to 100 parts by weight of viscosity modifier per 100 parts by weight of engineering thermoplastic resin, preferably from 10 to 50 parts by weight of viscosity modifier per 100 parts by weight of engineering thermoplastic resin. There are at least two methods for confirming the presence of an interlocking network (although these methods are separate from methods for confirming the absence of delamination). One method consists of performing the following operations. Moldings or extrudates made from the blends of the invention,
The block copolymer and other soluble components are placed in a refluxing solvent that can be quantitatively dissolved. If an interlocking network is present, the polymer structure (composed of thermoplastic engineering resin and polyamide) remaining in the solvent will remain intact. That is, the shape ("continuity" of the shape) of the molded or extruded product is maintained as it is. Moreover, at this time, there is no sign of collapse or delamination, the original structure remains intact, and the refluxing solvent does not contain any fine powder consisting of the above-mentioned insoluble substances. If these conditions were completely satisfied at the time of observation, it can be considered that the extracted phase and non-extracted phase were in a continuous state of interlocking. This unextracted phase must be continuous. This is because it should be completely original and perfect in a geometrical and mechanical sense. The above-mentioned extraction phase should have been continuous in its original form before the extraction operation (ie the solvent immersion operation) was carried out.
This is because it is almost impossible for a dispersed layer to be quantitatively extracted from an insoluble matrix. Furthermore, an interlocking network must exist for multiple continuous phases to influence simultaneously. It is also possible to confirm whether the non-extracted phase has continuity by microscopic observation. In blends of the invention containing more than two constituents, the interlocking structure and continuity of the phases can be confirmed by selective extraction operations as described above. For example, in the case of a blend containing a block copolymer, polypropylene, and nylon 6, the block copolymer can be extracted first by refluxing toluene, while the polypropylene phase and the nylon phase remain. The nylon can then be extracted by using hydrochloric acid,
On the other hand, the polypropylene phase remains. Alternatively, it is possible to first extract the nylon and then extract the block copolymer. After each extraction operation, the continuity of the phases and the interconnection of the holes can be investigated by microscopic observation. The second method is performed as follows. Mechanical properties such as tensile modulus are measured and the measured values are compared to calculated values. This calculated value indicates that each of the multiple isotropically distributed continuous phases "contributes" to a part of the mechanical response (for example, tensile modulus), and that "contribution" is determined by the volume (volume) occupied by each phase. This is a value calculated based on the assumption that it is proportional to If these two values (i.e. the measured value and the calculated value above) match, then
This suggests the existence of an interlocking network structure. On the other hand, if an interlocking network were not present, the measured value would be different from the calculated value. One of the important advantages of the present invention is that the proportions of each polymer in the blend can be varied over a wide range. The relative proportions (amounts used) of each polymer are shown in the following table (expressed in parts by weight; the total amount of the blend is 100 parts).

[Table] The polyamide can be used in an amount greater than the amount of the dissimilar engineering thermoplastic resin. That is, the weight ratio of the polyamide to the dissimilar engineering thermoplastic resin may be greater than or equal to 1:1. That is, the amount of polyamide may be 30-91 parts by weight, preferably 48-70 parts by weight. In addition,
Note that the minimum amount of block polymer required to form this blend can vary depending on the type of engineering thermoplastic. dissimilar engineering thermoplastics as described above;
The polyamide and block copolymer may be mixed using any mixing method that produces an interlocking network. For example, engineering resins, polyamides, and block copolymers can be aggregated by dissolving them all in a common solvent and mixing with a solvent that does not dissolve any of the polymers. However, a particularly useful method is to intimately mix these polymers in granulate and/or powder form in a high shear mixer. "Intimately mixing" means mixing the polymers using sufficient mechanical shear and thermal energy;
This means ensuring that the various network structures are interlocked. Intimate mixing (making blends)
can be carried out, for example, using high shear extruders (eg twin screw mixing extruders and thermoplastic resin extruders; L/D ratio at least 20:1; compression ratio 3:1 or 4:1). Mixing temperature or processing temperature (T _p )
can be appropriately selected depending on the type of each polymer for blend formation. For example, if the polymers are mixed according to a melt mixing method rather than a solution mixing method, the processing temperature should be selected from a temperature higher than the melting point of the "highest melting point polymer." Furthermore, as will be explained in more detail below, the processing temperature is preferably such that isoviscous mixing of each polymer can be achieved. The mixing temperature or processing temperature is 150-400℃, preferably 230-300℃.
It can be ℃. Another important condition for ensuring the formation of an interlocking network in a melt mixing operation is that under the operating temperature and shear stress of this mixing process, block copolymers, polyamides and dissimilar engineering thermal It is to harmonize the viscosity of the plastic resin (equal viscosity mixing). The better the degree of interdispersion of the engineering resin and polyamide into the block copolymer network, the better the continuous interlocking network will be during the subsequent cooling process. It will definitely happen. When the viscosity of the block copolymer at a temperature T _p and a shear rate of 100 s ^-1 is η poise, the value of the viscosity ratio of "block copolymer" to "engineering thermoplastic resin and/or polyamide" is 0.2 to 4.0 (preferably 0.8 to
1.2) The viscosity of the engineered thermoplastic and/or polyamide (temperature T
_p , viscosity under a shear rate of 100 s ^-1 ) was found to be advantageous (alternatively, using engineering thermoplastics and/or polyolefins with viscosity values satisfying the above conditions). ). Therefore, the term "isoviscosity mixing" as used herein means that the viscosity ratio of the block copolymer to the other polymer or the mixture of the other polymers is such that the viscosity ratio of the block copolymer to the other polymer or the mixture of the other polymers is at a temperature T _p and a shear rate of 100 s ^-1 . This means performing a mixing operation so that the ratio is between 0.2 and 4.0. In the extruder, the value of shear rate is different at each location,
There are large variations. Therefore, even if the viscosity curves of two polymers meet at a certain shear rate value,
There may be cases in which equal viscosity mixing can be carried out. In some cases, the order in which each polymer is mixed will be a critical condition. Therefore, it may be possible to first mix the block copolymer with the polyamide and other polymers and then mix the resulting mixture with a dissimilar engineering thermoplastic, or alternatively, each polymer may be mixed at the same time. Since there are cases where mixing is possible (simple mixing), a mixing order suitable for each case can be selected each time. When deciding the mixing order of each polymer when making the polyblend (multi-component blend) according to the present invention, it must be determined in consideration of many conditions in that case.
Furthermore, in order to suitably harmonize the relative viscosities of each polymer, it is necessary to select an appropriate mixing order, which will be easily understood. The block copolymer (or mixture of block copolymers) can be selected to substantially match the viscosity of the engineering thermoplastic and/or polyamide. If desired, the block copolymer can be mixed with a rubber compounding oil or replenishing resin (see below) to modify the viscosity properties of the block copolymer. The individual physical properties of this block copolymer are
It is an important factor for the formation of a continuous interlocking network. The most preferred block copolymers mentioned are those that do not melt (in the conventional sense) at elevated temperatures before being incorporated into a blend. This is because the viscosity of the copolymer is very non-Newtonian and tends to increase indefinitely as the value of shear stress approaches zero. Since this block copolymer has the above-mentioned rheological properties and thermal stability (which are inherent properties),
It tends to strongly retain its network structure (domain structure) even in the melt state, so when it is used to make various blends, a continuous interlocking network is formed in the blend. The structure is reliably formed. On the other hand, the viscosity properties of the dissimilar engineering thermoplastics and polyamides are generally more temperature sensitive than the block copolymers. Therefore, processing temperatures (i.e. operating temperatures) such that the viscosity of the block copolymer and the dissimilar engineering thermoplastic and/or polyamide are within the desired range of viscosity values necessary to form an interlocking network. It is often possible to choose T _p . If desired, the viscosity modifiers described above can be mixed first with engineering thermoplastics or polyamides to effect the necessary viscosity adjustment. Blends of partially hydrogenated block copolymers, polyamides, and dissimilar engineering thermoplastics may be mixed with extender oils commonly used in rubber and plastic processing. Extending oils of the type that are miscible with the elastomeric blocks of the block copolymers are particularly preferred. Bulking oils with relatively high aromatic content are preferred. Particularly preferred, however, are petroleum-based, low-volatility white oils with an aromatic content of 50% or less, determined by the clay gel method (ASTM test method D2007). It is desirable to use bulk oil with an initial boiling point of 260℃ or higher. The amount of extender oil used is 0 to 100 phr (phr = "parts by weight" per 100 parts by weight of block copolymer), preferably 5 to 30 phr. Blends of partially hydrogenated block copolymers, polyamides, and dissimilar engineering thermoplastics can be further mixed with other resins. Examples of such supplemental resins include flow promoting resins (eg alpha-methylstyrene resins) and end block plasticizing resins. Examples of suitable end block plasticized resins include coumaron-indene resins, vinyltoluene-α-methylstyrene copolymers, polyindene resins, and low molecular weight polystyrene resins. The amount of additional resin is 0 to 100 phr, preferably 5
It can be ~25 phr. Additionally, the composition may contain other polymers, fillers, reinforcing agents, antioxidants, stabilizers, flame retardants, antiblocking agents, and other rubber or plastic compounding ingredients. can. Specific examples of fillers that can be used include “Modern, Plastics, Encyclopedia”;
1971-72 edition, pages 240-247. Polyblend (polymer blend) according to the present invention
It is also useful to add reinforcing agents. The term "reinforcing agent" herein refers to a substance added to a resinous matrix to improve the strength of the polymer. Most reinforcing agents are high molecular weight inorganic or organic materials. Examples of reinforcing agents include: glass fibers, asbestos, boron fibers, carbon (or graphite) fibers, whiskers, quartz and silica fibers, ceramic fibers, metal fibers,
Natural organic fibers, synthetic organic fibers. Glass fiber 2-
Particularly preferred are reinforced polymer blends (ie, reinforced polymer blends) comprising 80% by weight (based on the total weight of the reinforced polymer blend). The polymer blend according to the invention can be advantageously used in areas where high performance materials are required;
It can also be used as a metal substitute. In the Examples and Comparative Examples shown below, various polyblends were made by mixing the polymers using a 3.125 cm Stirling extruder with a Kenics nozzle. The L/D ratio of this extruder is 24:1, and the screw is
It was a 3.8:1 compression ratio screw. The materials used in these blends are listed below. (1) Block copolymer - A selectively hydrogenated block copolymer of the present invention having an S-EB-S structure and a block molecular weight of 7500-38000-7500. (2) Bulking oil [Taflo, a commercially available rubber bulking oil.
6056” was used]. (3) Nylon-6 [Plascon (registered trademark), a commercially available polyamide manufactured by Allied Chemical Co.
−8207” was used. This is polyamide for injection molding]. (4) Nylon 6-12 ("Zytel (registered trademark)-158", a commercially available polyamide manufactured by DuPont) was used. This is a polyamide generally suitable for injection molding, and its crystalline melting point is 219°C]. (5) Polypropylene [substantially isotactic polypropylene with melt flow index = 5 (230°C/2.16 Kg] was used]. (6) Poly(butylene terephthalate) [abbreviation "PBT": General Electric Company's polypropylene]. From the plastic part, we used a product commercially available under the trade name "Barox" (registered trademark)]. (7) Polycarbonate ["Mellon (registered trademark)", a commercially available polycarbonate manufactured by Mobay Co., Ltd.
M-40'' was used. This is generally a polycarbonate suitable for injection molding and extrusion. (8) Poly(ether sulfone)-200P. (9) Polyurethane [Polyurethane commercially available under the trade name "Pellethane (registered trademark)-CPR" from the CPR division of Appdition Co., Ltd. was used. This is polyurethane for injection molding.] (10) Polyacetal [Polyacetal commercially available from DuPont under the trade name "Delrin (registered trademark)-500" was used. It is a polyacetal homopolymer that can be used for injection molding and other general applications and has a crystalline melting point of 175
℃] (11) Poly[acrylonitrile-co-styrene (co
-styrene)] [Baretsux (registered trademark) - from Standard Oil Company of Ohio, USA.
210, which is commercially available]. (12) Fluoropolymer [A poly(vinylidene fluoride) copolymer commercially available from Dupont under the trade name Tefzel (registered trademark)-200 was used]. These engineering thermoplastic resins are
It had an apparent crystalline melting point of over 120°C. The properties of some of these resins are shown in Table A below.

Table: In all blends containing extender oil, the block copolymer and extender oil were premixed before adding the other polymers. EXAMPLES Various polyblends were prepared in accordance with the present invention, in each case the polyblends were easily mixed and
And the extrudate had a uniform appearance. Moreover, in each case, the resulting polyblend had the desired continuous interlocking network structure as determined by the aforementioned criteria. The composition, conditions and test results are shown in the table below. Compositions are expressed in weight percentages. In addition, in the polyblends listed in Table 1,
Blends 97-113 were prepared according to the present invention. On the other hand, Blends 14-82 and Blends 177 and 178 are control samples outside the scope of the present invention and are therefore marked *.

【table】

【table】

[Table] Example 3 (Comparative Example) Blend of example blend number 52 (control sample) by melt blending glass fibers with polyblend at a temperature of 240° C. in an extruder.
100 parts by weight PPG0.625cm glass fiber twine 65.6
Reinforced with heavy weight parts. The resulting composition had the following properties. Young's modulus × 10 ³ , kPa 7431 Yield point, kPa 50188 Breaking tension, kPa 50188 Ultimate elongation at break, % 1.58 Flexibility coefficient × 10 ³ , kPa 6081 Notched Izot impact strength, J/cm 0.69 Example (Comparative example) ) A glass-reinforced blend similar to the blend prepared in the example was prepared, except that instead of first preparing the polyblend and then adding the glass fibers, all four major components and the glass fibers were dry blended at the same time. Various compositions, conditions and test results are shown in the table below. In each case, the resulting polyblend (control sample) had an interlocking network.

【table】

Table: Examples (Comparative Examples) Various polyblends containing nylon 6 were prepared. This comparative example shows that the presence of a block copolymer is essential to the success of the present invention. All blends were prepared by mixing in an extruder at 230°C. The respective compositions are shown in the table below (note that some are the same as shown in the table). Blends 18, 12 and 41 contain only nylon 6 or nylon 6 and polypropylene, whereas blends 14-17 and 43 contain at least 2
Figure 3 shows a blend having a continuous interlocking network of 1,000,000 pieces.

[Table] The presence (or absence) of a continuous interlocking network was investigated by selective sampling. In this method, the polyblend was subjected to Soxhlet extraction with hot refluxing toluene for 16 hours. Ideally, hot toluene extracts the block copolymer and bulking oil, but does not dissolve the PBT or nylon. The unextracted portion of the blend is then placed in a container containing 6 molar hydrochloric acid (HCl) and shaken at room temperature for about 20 hours. The HCl dissolves the nylon 6 but not the polypropylene or PBT. Weigh the unextracted portion of the bundle remaining after each extraction;
The weight loss was compared with the predicted value (calculated value). In Blend 18, nylon 6 dissolved 1.2% in hot toluene compared to the predicted value of 0% (which is well within the accuracy of the above method). The rest of the polymer
Completely dissolved in HCl. Extraction of blends 12 and 41 without the claimed block copolymer shows the absence of a continuous interlocking network. Blend 12 had 3.7% of the blend dissolved in hot toluene versus the predicted value of 0%, which is also well within the accuracy of the method described above. however,
Only 17.8% of the extracted blend was dissolved in HCl compared to the predicted value of 50%. This indicates that most of the nylon is wrapped in polypropylene and is therefore inaccessible to HCl, that is, there is no continuous network structure of nylon that is accessible to HCl. For blend 41, 0.4% of the blend of PBT and nylon 6 dissolved in hot toluene compared to 0% of theory. However, only 2.3% of the extracted blend was dissolved in HCl compared to the predicted value of 50%, which means that only a small portion of the nylon was dissolved in HCl.
It is thought that it could not be approached, indicating the lack of a continuous interlocking network. Contrary to the results for blends 12 and 41, this extraction method
~17 and 43 indicating the presence of a continuous interlocking network. For example, Blend 14 uses 4.2 parts by weight of block copolymer. Toluene extracted 4.9% against the predicted value of 5%, and
The most important point is that HCl is extracted at 47.5% compared to the predicted value of 45.0%, and all of these are within the accuracy of the present extraction method. This indicates that the nylon exists as a continuous network, as all the nylon would be accessible to HCl, as expected from a completely connected phase. Furthermore, similar results were obtained with other polyblends. Comparative Examples In this comparative example, various blends of nylon 6 and other engineering thermoplastics were prepared without the presence of the block copolymer. Various blends are shown in the table below along with individual notes on the blends.

【table】

Claims (1)

[Claims] 1. At least two monoalkenyl arene-based terminal polymer blocks A having an average molecular weight of 5,000 to 125,000, and at least one conjugated diene-based intermediate polymer having an average molecular weight of 10,000 to 300,000. A partially hydrogenated block copolymer having a block B, wherein the terminal polymer block A accounts for 8 to 55% by weight of the block copolymer, and the arene double bond of the polymer block A (a) in which at least 80% of the aliphatic double bonds of the polymer block B have been reduced by hydrogenation; 4 to 40 parts by weight of partially hydrogenated block copolymer, (b) polyamide with a number average molecular weight of 10,000 or less, (c) polyolefin, thermoplastic polyester, poly(arylsulfone), polycarbonate,
5 to 48 parts by weight of at least one dissimilar engineering thermoplastic selected from the group consisting of acetal resins, thermoplastic polyurethanes, halogenated thermoplastics, and nitrile resins; a weight ratio of greater than 1:1, thereby forming a polyblend such that at least two of the polymers form an at least partially continuous interlocking network with each other. A composition characterized in that it is capable of: 2. Polymer block A has a number average molecular weight of 7,000 to 60,000, and polymer block B has a number average molecular weight of 30,000 to 150,000.
The composition according to claim 1, having a number average molecular weight of . 3 The terminal polymer block A is a block copolymer.
3. A composition according to claim 1 or 2, comprising from 10 to 30% by weight. 4. According to any one of claims 1 to 3, 5% or less of the allene double bonds of polymer block A and at least 99% of the aliphatic double bonds of polymer block B have been reduced by hydrogenation. Composition of. 5 Dissimilar engineering thermoplastic resins are 120
5. The composition according to any one of claims 1 to 4, having an apparent crystalline melting point of 0.degree. C. or higher. 6 Dissimilar engineering thermoplastic resins are 150
6. The composition of claim 5, having an apparent crystalline melting point of between 350<0>C and 350<0>C. 7 Dissimilar engineering thermoplastics
The composition according to any one of claims 1 to 4, which is a polyolefin having a number average molecular weight of 10,000 or more and an apparent crystalline melting point of more than 100°C. 8. A composition according to claim 7, wherein the polyolefin is a homopolymer or copolymer derived from α-olefin or 1-olefin having 2 to 5 carbon atoms. 9. The composition according to any one of claims 7 to 8, wherein the polyolefin has a number average molecular weight of 50,000 or more. 10 The apparent crystal melting point of polyolefin is 140
10. The composition according to any one of claims 7 to 9, which has a temperature of .degree. C. to 250.degree. 11. The composition of any of claims 7 to 10, wherein the composition comprises high density polyethylene having an approximate crystallinity of about 75% or more and a density of 0.94 to 1.0 Kg/. 12. The composition of any of claims 7 to 10, wherein the composition comprises low density polyethylene having an approximate crystallinity of about 35% or more and a density of 0.90 to 0.94 Kg/. 13. Claim 7, wherein the composition comprises polyethylene having a number average molecular weight of 50,000 to 500,000.
12. The composition according to any one of 12 to 12. 14. The composition according to any one of claims 7 to 10, wherein the composition comprises isotactic polypropylene. 15. The composition according to claim 14, wherein the polypropylene has a number average molecular weight of 100,000 or more. 16 The composition contains 1 to 20% by weight as comonomer
11. A composition according to any of claims 7 to 10, comprising polypropylene in the form of a copolymer containing an amount of ethylene or other alpha-olefins. 17 The composition contains poly(1-
11. The composition according to any one of claims 7 to 10, comprising: 18 The composition, as a polyolefin, 240~
11. A composition according to any of claims 7 to 10, comprising a homopolymer of 4-methyl-1-pentene having an apparent crystalline melting point of 250<0>C and a relative density of 0.80 to 0.85. 19. The composition according to any one of claims 7 to 10, wherein the composition contains a copolymer of 4-methyl-1-pentene and α-olefin as the polyolefin. 20 The composition is polyolefin, 4 to 18
Linear α-olefin with 0.5 carbon atoms
4-Methyl-1- present in an amount of ~30% by weight
20. The composition of claim 19, comprising a copolymer of pentene and the linear α-olefin. 21 Dissimilar engineering thermoplastics
A composition according to any one of claims 1 to 4, which is a thermoplastic polyester having a melting point of 120°C. 22 Claims 1-4 and 2 in which the dissimilar engineering thermoplastic resin is poly(ethylene terephthalate), poly(propylene terephthalate) or poly(butylene terephthalate)
1. The composition according to any one of 1. 23 Dissimilar engineering thermoplastics
Claim 22 is poly(butylene terephthalate) having an average molecular weight of 20,000 to 25,000.
Compositions as described. 24. The composition according to any one of claims 1 to 4 and 21, wherein the engineering thermoplastic resin is a cellulose ester. 25 Claims 1 to 25, wherein the engineering thermoplastic resin is a homopolymer of pivalolactone.
22. The composition according to any one of 4 and 21. 26 The engineering thermoplastic resin contains pivalolactone and 50 mol% or less of other β. 22. The composition according to any one of claims 1 to 4 and 21, which is a copolymer with propiolactone. 27. The composition of claim 26, wherein the engineering thermoplastic resin is a copolymer of pivalolactone and 10 mol% or less of other β-propiolactone. 28 Claims 25-2, wherein the engineering thermoplastic resin is polypivalolactone having an average molecular weight of 20,000 or more and a melting point of 120°C or more.
7. The composition according to any one of 7. 29. The composition according to any one of claims 1 to 4 and 21, wherein the engineering thermoplastic resin is polycaprolactone. 30. The composition according to any one of claims 1 to 4, wherein the engineering thermoplastic resin is a polycarbonate having the following general formula. or In the formula, Ar represents a phenylene group or an alkyl-, alkoxy-, halogen, or nitro-substituted phenylene group, and A represents a carbon-carbon bond or an alkylidene group, a cycloalkylidene group, an alkylene group, a cycloalkylene group, an azo group, represents an imino group, sulfur, oxygen, sulfoxide group or sulfone group, and n is at least 2. 31 The engineering thermoplastic resin is a homopolymer of formaldehyde or trioxane,
A composition according to any one of claims 1 to 4. 32. The composition according to any one of claims 1 to 4, wherein the engineering thermoplastic resin is a polyacetal copolymer. 33 Engineering thermoplastic resins include tetrafluoroethylene, chlorotrifluoroethylene,
Claims 1 to 3 are homopolymers or copolymers derived from bromotrifluoroethylene, vinylidene fluoride and vinylidene chloride.
4. The composition according to any one of 4. 34 Engineering thermoplastic resin is α・β−
Claims 1 to 4 are nitrile resins containing 50% by weight or more of olefinic unsaturated mononitrile.
The composition according to any one of. 35. The composition of claim 34, wherein the α/β-olefinically unsaturated mononitrile has the following general formula: In the formula, R represents hydrogen, an alkyl group having 1 to 4 carbon atoms or halogen. 36 The nitrile resin is a homopolymer, a copolymer, a graft copolymer obtained by grafting a copolymer onto a rubbery substrate, or a blend of a homopolymer and/or a copolymer, and the invention is described in claim 34 or 35. Composition of. 37. A composition according to any of claims 1 to 36, wherein the composition comprises the block copolymer and the dissimilar thermoplastic resin in amounts of 8 to 20 parts by weight and 10 to 35 parts by weight, respectively. 38. A composition according to any of claims 1 to 37, wherein the composition comprises bulking oil in an amount of 0 to 100 phr. 39. The composition comprises bulking oil in an amount of 5 to 30 phr.
A composition according to claim 38. 40 A monoalkenyl arene-based terminal polymer block A having an average molecular weight of 5,000 to 125,000 and at least one conjugated diene-based intermediate polymer block B having an average molecular weight of 10,000 to 300,000. It is a partially hydrogenated block copolymer, in which the terminal polymer block A accounts for 8 to 55% by weight of the block copolymer, and 25% or less of the allene double bonds of the polymer block A and A composition comprising a partially hydrogenated block copolymer in which at least 80% of the aliphatic double bonds of polymer block B have been reduced by hydrogenation, the composition comprising: (a) the above partially hydrogenated block copolymer; 4 to 40 parts by weight of copolymer, (b) polyamide with a number average molecular weight of 10,000 or more, (c) polyolefin, thermoplastic polyester, poly(arylsulfone), polycarbonate,
5 to 48 parts by weight of at least one dissimilar engineering thermoplastic selected from the group consisting of acetal resins, thermoplastic polyurethanes, halogenated thermoplastics, and nitrile resins; Polyblends in which the weight ratio of the resins is greater than 1:1, whereby at least two of the polymeric pairs form an at least partially continuous interlocking network with each other. (a) a block A of at least two monoalkenyl arene-based terminal polymers having an average molecular weight of 5,000 to 125,000 and an average molecular weight of 10,000 to 300,000; a partially hydrogenated block copolymer having at least one conjugated diene intermediate polymer block B having the terminal polymer block A;
accounts for 8 to 55% by weight of this block copolymer, and less than 25% of the allene double bonds in the polymer block A and at least 80% of the aliphatic double bonds in the polymer block B are hydrogenated. Partially hydrogenated block copolymer 4-
40 parts by weight at an operating temperature T _p of 150° C. to 400° C. (b) a polyamide having a number average molecular weight of 10,000 or more, and (c) a polyolefin, thermoplastic polyester, poly(arylsulfone), polycarbonate,
5 to 48 parts by weight of at least one dissimilar engineering thermoplastic selected from the group consisting of acetal resins, thermoplastic polyurethanes, halogenated thermoplastics, and nitrile resins, in which said polyamide to said dissimilar The weight ratio of the engineering thermoplastic resin is greater than 1:1, such that at least two of the polymers form an at least partially continuous interlocking network with each other. A method for producing a composition containing a partially hydrogenated block copolymer, characterized in that a polyblend can be formed. 41. Process according to claim 40, characterized in that the polymers are mixed at an operating temperature T _p of between 230°C and 300°C. 42. Process according to claim 40 or 41, characterized in that the polymers are all dissolved in the same solvent and coagulated by mixing in a solvent in which these polymers do not dissolve. 43. The method according to claim 40 or 41, characterized in that the polymers are mixed in the form of granules and/or powder in a device that applies shearing force. 44 The ratio of the viscosity of the block copolymer divided by the viscosity of the polyamide, the dissimilar engineering thermoplastic resin, or the mixture of the polyamide and the dissimilar engineering thermoplastic resin is 0.2 to 4.0 at an operating temperature T _p and a shear rate of 100 S ^-1 44. The method according to any one of claims 40 to 43, characterized in that: 45 The ratio of the viscosity of the block copolymer divided by the viscosity of the polyamide, a dissimilar engineering thermoplastic, or a mixture of the polyamide and the dissimilar engineering thermoplastic is 0.8 to 1.2 at an operating temperature T _p and a shear rate of 100 S ^-1 45. A method according to claim 44, characterized in that: 46 block copolymer and dissimilar engineering thermoplastic resin, 8 to 20 parts by weight and 10 parts by weight, respectively.
46. Process according to any of claims 40 to 45, characterized in that it is used in an amount of ~35 parts by weight.