Curable thermoplastic elastomer mix, method for its obtainment, and application

FIELD: chemistry.

SUBSTANCE: invention concerns curable thermoplastic elastomer mixes, their obtaining and application in production of items by cast or extrusion moulding. Curable thermoplastic elastomer mix includes: (a) 15 to 60 wt % of polymer or copolymer represented by complex polyalkylenephthalate polyether, and (b) 40 to 85 wt % of linked poly(met)acrylate or polyethylene/(met)acrylate curing resin combined with free radical peroxide initiation agent and organic diene co-agent in effective amount for linking the resin during extrusion or cast moulding of curable thermoplastic elastomer mix. After linkage the polymer or copolymer represented by complex polyalkylenephthalate polyether is present in the form of continuous phase, while the resin is present in dispersed phase. Such compositions are fit for production of rubber parts with excellent resistance to effect of oil lubricants and greases.

EFFECT: optimised residual compression deformation and Shore hardness, increased elastic constant during curing.

12 cl, 3 dwg, 2 tbl, 22 ex

 

The technical field

The present invention relates to a vulcanized thermoplastic elastomer mixtures, their preparation and application for the manufacture of products from rubber by means of injection-molding or extrusion molding. More specifically, but not in the order of limitation, the present invention relates to compounds(i)thermoplastic complex polyester (for example, polyalkyleneglycol, such as polyethylene - terephthalate, polybutylene terephthalate - pbtf was honored with, related copolymers, and the like) or a thermoplastic elastomer based on a complex of the polyester (for example, poliferation based esters and ethers, such as block copolymers, consisting of segments of polybutylene terephthalate and long-chain segments simple poliatilenglikola, and the like) and(ii)defunctionalizing, stitched polyacrylate or polyethylene/acrylate rubber vulcanizate (for example, elastomer, polyacrylate (ACM) type and elastomer polyethylene/acrylate (AEM) type) in combination with a peroxide free radical initiator and saagento diene type for stitching.

The level of technology

State of the art is known and accepted as a commercial practice, the use of a vulcanized polyacrylate elastomers for the production of parts from the Echuca high-performance, characterized by excellent resistance to lubricating oils and fats, which are therefore suitable for selected applications in the automotive industry and the like. Typically, the data production processes include the use of unfilled rubber compound and the crosslinking system of the presses that to get thermoeconomics molded parts requires, on the basis of rheological properties, carrying out physical mixing, direct pressing and subsequent vulcanization, where material, are molded in the distribution sprue, the remainder of the material in the Central sprue and other okrepkie not be shipped for recycling, which therefore increases the cost. In its category unfilled rubber compound refer either to the polyacrylate elastomer (ACM)obtained by copolymerization of monomers of esters of acrylic acid (for example, ethyl-, butyl - and ethoxyethylacetate, and, possibly with the inclusion of a certain amount of vinyl acetate), polyethylene/acrylate the elastomer (AEM)obtained by copolymerization of the monomer ethylene and monomers of esters of acrylic acid (for example, ethylene and methyl acrylate and the possible inclusion of other comonomers and grafted copolymer components, see, e.g., U.S. 2002/004568 A1), or polyphthalocyanine the elastomer (FPA), obtained by polymerization of a fluorinated monomer of ester of acrylic acid (for example, 1,1-dihydropyrrol-n-butyl acrylate). It is also known that the polyacrylate elastomer can be functionalitywith inclusion of a relatively small number of additional co monomer, such as greatprincely ester, maleic acid, or other co monomer having a reactive group, including acid, hydroxyl, epoxy, isocyanate, amine, oxazoline, chloracetate or diene. Data functionalityand polyacrylate elastomers after that you can profitably be vulcanized using vulcanizing of coagent containing functional groups that are covalently linked functionalized with reactive centers of the polyacrylate elastomer.

One of the problems associated with a vulcanized polyacrylate elastomers of the prior art, lies in the inherent rheological constraints expressed in their high viscosity and low melt flow in volcanoserver.com or partially volcanoserver.com condition. Therefore, to achieve acceptable properties usually need physical mixing with the next direct pressing and further vulcanization, instead of extrusion or injection molding with the direct production of finished parts (in accordance with the fact, as discussed above). However, in the European patent V and U.S. patent 4981908 describes the composition of thermoplastic elastomer containing a mixture of polyester resin on the basis of esters (including segmented polyamidoamine elastomers on the basis of simple and complex esters, commercially available under the trade name Hytrel® from E.I. DuPont de Nemours and Company) and dynamically vulcanized covalently crosslinked acrylate rubber (including ethylene/methylacrylate ternary copolymer containing about one mole percent of the co monomer having a functional group of a carboxylic acid, commercially available under the trade name Vamac® from E.I. du Pont de Nemours and Company). Covalent crosslinking in these descriptions is achieved by the use of functionalized polyacrylate elastomer in combination with a reactive bifunctional cross-linking agent. However, almost all data bifunctional cross-linking agents can also react with ester links in polyalkylacrylate (i.e. amine, hydroxyl group or carboxyl group will engage in the exchange reaction with the ester group and, as epoxy or acid groups will be joining terminal hydroxyl groups), which would entail the emergence of high viscosity and lack of reproducibility.

In an article entitled "Rubber-Thermoplastic Compositions. Part V. Selecting Polymers for Thermoplastic Vulcanizates"; A. Y. Coran, R. P. Patel, and D. Williams, " Rubber Chemistry Technology, Volume 55, pages 116-136 (1982), as a result of dynamic vulcanization has received approximately 100 songs of thermoplastic vulcanizates based on 9 types of thermoplastic resins and 11 types of rubbers (rubber, vulcanized during mixing with the molten plastic). On page 121 publication argues that ethylenevinylacetate rubber (EVA) must be vulcanized by the action of peroxide and unknown any sufficiently stable peroxide vulcanizer, suitable for use at high temperature required for mixing with the molten polybutylene terephthalate (called PTMT, polyethylenterephtalate). This article also describes the dynamic vulcanizer PTMT and rubber AFM (Elaprin® AR153), which was a commercially available mixture kauchukopodobnoe copolymer of ethyl acrylate/acrylic acid (99/1 mass parts) and 3 mass parts of a crosslinking agent in the form of dipyridamole ether of bisphenol a, see, for example, page 8 work EP 0095919 is 2.

In contrast to the above dynamically vulcanised compositions of thermoplastic elastomers on the basis of a complex mixture of polyester, functionalized acrylate rubber and a crosslinking agent for the rubber phase operation GB 1208585 describes an example to be formed in the melt polymer compositions based on poly (ethylene terephthalate) mixed with koutsokoumnis ethylene copolymer (having or not having centers stitching) and polyisocyanate extension circuits, which in the preferred implementation also knits functionalized rubber.

In U.S. patent 4275180 describes a polymer composition comprising a crosslinked mixture of elastomer and thermoplastic polymer essentially containing no halogen. Examples specifically include kouchkovsky ternary copolymer functionalized ethylene/methacrylate (Vamac®), mixed with segmented polyetheramines copolymer-based esters and ethers (Hytrel®). In this reference, reported stitching using any commonly used method, which includes radiation or chemical crosslinking, such as the use of peroxide. However, in all examples, the use of high-intensity irradiation (for example, 12 Mrad) in the presence of coagent (cialiscanada). In published after this the patent application EP A reported halogen-free composition of thermoplastic elastomer, filled with aluminum trihydrate. In comparative examples 1 and 2 refer specifically to the ingredients and techniques of the examples in U.S. patent 4275180 and for stitching mixture Hytrel®/Vamac® in the presence of coagent of cialiscanada the same way as in working example 3, using the ionizing radiation dose of 15 Mrad. On page 7 of this reference States that in some cases, to facilitate the reaction of the crosslinking may be desirable to add a stitched polymer composition of coagent. Then it is reported that such coagency usually contain more than one unsaturated groups, which are believed to react with the initial radical is formed on the main polymer chain, with the more stable radical, for which the reaction mix with the formation of crosslinks is more effective than the reaction of destruction of the circuit. Treelistener received recognition as coagent. In contrast to the examples of the radiation-initiated crosslinking, all working examples that use peroxide vulcanizer (i.e. free radical initiator), did not contain cialiscanada or other coagent.

Description of the invention

At the present time discovered that a vulcanized thermoplastic elastomer mixture can be obtained by using the "afunctional the new" vulcanizate polyacrylate type in combination with a free radical peroxide initiator and cured saagento for stitching, regarding the type of diene or higher polyene. The other polymer component of the mixture represents polyalkylacrylate thermoplastic complex polyester and, in particular, thermoplastic polyetheramines elastomer-based esters and ethers, such as block copolymers, consisting of segments of polybutylene terephthalate and long-chain segments poliatilenglikola on the basis of simple esters. A vulcanized thermoplastic elastomer mixture of the present invention suitable for carrying out dynamic crosslinking during extrusion or injection molding of the original components with the obtained processed in the melt of a thermoplastic elastomer composition comprising crosslinked polyacrylate rubber as a dispersed phase and a polymer - polyalkylacrylate complex polyester as continuous phase. In addition, and in accordance with the illustration of examples of the present document, the selection of raw materials and the choice of free radical initiator in the best case lead to the achievement of the control morphology of the polymer in the resulting dispersed phase of rubber and in the resulting finished products.

Thus, according to the present invention features a vulcanized thermoplastic elastomer mixture containing:

(a) from 15 to 60 weight percent of the polymer or copolymer constituting polyalkylacrylate complex polyester; and

(b) from 40 to 85 weight percent of stitched poly(meth)acrylate or polyethylene/(meth)acrylate rubber vulcanizate in combination with an effective amount of peroxide free radical initiator and an organic diene of coagent for crosslinking the above-mentioned rubber during extrusion or injection molding mentioned vulcanized thermoplastic elastomer mixture.

In addition, according to the present invention features processed in the melt of thermoplastic elastomer composition containing:

(a) from 15 to 60 weight percent of the continuous phase polymer or copolymer, representing polyalkylacrylate complex polyester, and

(b) from 40 to 85 weight percent of the dispersed phase stitched poly(meth)acrylate or polyethylene/(meth)acrylate rubber vulcanizate, where the mentioned polyacrylate rubber sew under the action of a peroxide free radical initiator and an organic diene of coagent.

The present invention also features a method of making processed in the melt of thermoplastic elastomer composition, comprising the stage of:

(a) adding and mixing stitched poly(IU is)acrylate or polyethylene/(meth)acrylate rubber vulcanizate peroxide free radical initiator and an organic diene of coagent in the processing of the melt extruder or in the processing of the melt mixer at a temperature insufficient to stimulate the flow of stitching;

(b) adding polyalkylphenol closepreview polymer in the above-mentioned processing melt extruder or melt processing mixer and mixing mentioned polyalkylphenol closepreview polymer mentioned stitched poly(meth)acrylate or polyethylene/(meth)acrylate rubber vulcanizate prior to stitching;

(C) additional mixing mentioned stitched poly(meth)acrylate or polyethylene/(meth)acrylate rubber vulcanizate peroxide free radical initiator and an organic diene of coagent with the said polymer is polyalkylacrylate complex polyester, under conditions and at a temperature sufficient to stitch mentioned stitched poly(meth)acrylate or polyethylene/(meth)acrylate rubber vulcanizate; and

(d) extracting processed in the melt of thermoplastic elastomer composition containing from 15 to 60 weight percent of the above-mentioned polymer or copolymer, representing polyalkylacrylate complex polyester, is a continuous phase and from 40 to 85 weight percent mentioned poly(meth)acrylate or polyethylene/(meth)acrylate rubber vulcanizate crosslinked under the action mentioned peroxide free radical initiator and the above-mentioned organic diene of coagent, as the dispersed phase.

And the present invention provides a shaped or molded article made from recyclable in the melt of thermoplastic elastomer composition containing:

(a) from 15 to 60 weight percent of the continuous phase polymer or copolymer, representing polyalkylacrylate complex polyester, and

(b) from 40 to 85 weight percent of the dispersed phase poly(meth)acrylate or polyethylene/(meth)acrylate rubber where the above-mentioned poly(meth)acrylate or polyethylene/(meth)acrylate rubber is stitched under the action of a peroxide free radical initiator and an organic diene of coagent.

Typically, the polymer or copolymer constituting polyalkylacrylate complex polyester, which are selected from the group consisting of polyalkylacrylate, polyalkylacrylate copolymer, polyetherketone on the basis of simple and complex esters derived from polyalkylacrylate, and polyetherketone on the basis of simple and complex esters derived from polyalkyleneglycol copolymer, and preferably is a block copolymer formed of segments of polybutylene terephthalate and segments of the simple poly(tetr Methylenebis)glycol. Typically, poly(meth)acrylate rubber is selected from the group consisting of polyacrylate elastomer and polyethylene/acrylate elastomer, and preferably is an elastomer, which represents an ethylene/methacrylate copolymer. In accordance with the present invention an organic diene coagent conveniently to choose from a group consisting of dietilenglikoluretan, diethylethylenediamine, N,N'-m-phenylenedimaleimide and triallylisocyanurate, and free radical initiator selected from the group consisting of 2,5-dimethyl-2,5-di(tert-BUTYLPEROXY)hexyne-3 and tert-butyl peroxybenzoate. The specific combination of block copolymer formed by segments of polybutylene terephthalate and segments of the simple poly(tetramethylene)glycol, acting as a continuous thermoplastic phase and the elastomer constituting the ethylene/methacrylate copolymer, a free radical initiator is 2,5-dimethyl-2,5-di(tert-BUTYLPEROXY)hexyne-3 or 2,5-dimethyl-2,5-di(tert-BUTYLPEROXY)hexane and coagent of diethylethylenediamine, leads to the production of highly dispersed phase of rubber with excellent properties.

Drawings

Figure 1 is made according to the method TEM photograph of the resulting product of the rubber (in the case of relatively high reaction rate for Svobodnoye the sexual initiator and the resulting morphology of the polymer with relatively large domains), the appropriate method of the present invention.

Figure 2 is made according to the method TEM photograph of the resulting product of the rubber (in the case of relatively low speed of reaction of free radical initiator and the resulting morphology of the polymer with a relatively high degree of dispersion of domains), a corresponding method of the present invention.

Figure 3 is a graph with overlapping dependencies, illustrating the linear decrease of the particle size of the rubber and the asymptotic reduction of residual deformation under compression when the increase in time required to reach maximum speed of vulcanization characteristic of the present invention.

Option(s) carrying out the invention

In the description of this invention and/or its application in the claims, the term "copolymer" is used to refer to polymers containing two or more Monomeric level, and, in the case of a polymer formed by the alternation of basic comonomers, such as polyalkylacrylate complex polyester and the like, the term "copolymer" is used to denote the presence of at least one additional monomer, different from the basic comonomers. The use of the term "ternary copolymer and/or Tr is Inoi comonomer" implies, that is a copolymer formed of at least three different comonomers. "Consisting essentially of" indicates that significant are these components, although they may be present and smaller amounts of other components, to the extent that they will not reduce the effectiveness of the present invention. The term "(meth)acrylic acid" refers to methacrylic acid and/or acrylic acid, inclusive. Similarly, the term "(meth)acrylate" means methacrylate and/or acrylate and poly(meth)acrylate" refers to a polymer resulting from polymerization of any of them, or a mixture of both appropriate types of monomers. The term "vulcanizer" and the phrase "rubber vulcanizer in accordance with their use in the present invention, as implied, are generic for vulcanized or partially vulcanized sewn or stitched rubber, and the stitching of the precursors of the cross-linked rubber, and as such, they include elastomers, unfilled rubber compound and the so-called soft vulcanizates, widely known at the present level of technology. The use of the phrase "organic diene coagent" involves the designation of organic saagento that contain two or more unsaturated double bonds. The phrase "rubber phase" and "phase thermoplastic" is consistent with their use in this document mean and refer to the phase with the corresponding morphology of the polymer, present in the resulting thermoplastic elastomer mixtures from the mixing and dynamic crosslinking of the source materials constituting the stitching acrylate rubber and polyalkylacrylate complex polyester, in accordance with the method of the present invention. For the purposes of the present invention an "effective amount" of peroxide free radical initiator and an organic diene of coagent in General refers to the selection and amounts necessary to achieve the low reaction rate and corresponding desirable big time required to achieve maximum speed G' (preferred options embodiments of the invention can be quantitatively described as the time required to achieve maximum speed G', level ≥3.9 minutes or more).

Obtaining a vulcanized thermoplastic elastomer blends of the present invention includes mixing a thermoplastic and rubber vulcanizate in the presence of an organic peroxide free radical initiator and an organic diene of coagent. Preferably, thermoplastic polymer or copolymer, representing polyalkylacrylate complex polyester, mixed with stitched poly(meth)acrylate is for polyethylene/(meth)acrylate of the vulcanizate. A vulcanized thermoplastic elastomeric compound corresponding to the present invention, is also characterized by the presence of a mixture of a certain type vulcanizing system. More specifically, the vulcanizer/vulcanizing system includes a combination of a free radical initiator and an organic diene of coagent. Presently discovered that without having to rubber vulcanizer was functionalized polymer, using a free radical initiator and a diene of coagent result in obtaining a vulcanized thermoplastic compound, which can be subjected to dynamic crosslinking during mixing in the melt and/or during formation in the melt. Thus, a vulcanized thermoplastic elastomer mixture is subjected to extrusion, injection molding the molding and the like, and a free radical initiator and diene coagent will act as a vulcanizer/vulcanizing system that allows the result to hold in a mixture of crosslinking of the rubber vulcanizate in situ.

The resulting dynamically cross-linked product corresponding to the present invention, will represent processed in the melt of thermoplastic elastomer composition. As such dynamically cross-linked product can be p durgati malleability and send for recycling. The resulting processed in the melt of thermoplastic elastomer will generally be more thermoplastic compared with which his component of the rubber phase in the absence of phase thermoplastic complex polyester, and it will be more elastic in comparison with the phase of thermoplastic complex of the polyester in the absence of the rubber phase. In addition, the resulting processed in the melt of thermoplastic elastomer will include a polymer or copolymer in the form of polyalkylphenol complex polyester is present as a continuous phase, while the crosslinked poly(meth)acrylate or polyethylene/(meth)acrylate rubber is present as the dispersed phase.

It was found that using an appropriate present invention vulcanizing system in the form of an organic peroxide and a diene of coagent leads to the achievement of better reproducibility and possibility of a better control of the morphology of the polymer and the physical properties of the resulting dynamically crosslinked thermoplastic elastomer composition. In selecting the appropriate quantities of reagents and, in particular, the type of the organic peroxide and coagent, you can perform the selection and the adjustment of the degree of dispersion (the average size of domains) to disperse dynamically school is the phase of the rubber. More specifically, and in accordance with what later will be illustrated in the examples, the use of organic peroxide and coagent that allow you to get a reduced rate of curing at relatively moderate or low initial temperature mixing in the melt leads to the achievement of enhanced mixing phase of thermoplastic polymer and phase of the unfilled rubber mixture to increase the temperature and flow of the stitching. This, in turn, results in the achievement of improved dispersion of the resulting phase stitched rubber, dispersed in a continuous phase of thermoplastic. An unexpectedly high degree of control and reproducibility makes it possible to optimize properties such as residual deformation under compression, shore hardness, high elastic modulus during vulcanization and the like. For example, in accordance with the present invention when the ratio of the components in the composition in the form of twenty-five weight percent of polyalkylacrylate attributable to seventy-five weight percent of the dispersed phase polyethylene/acrylate rubber can be obtained optimum residual deformation at compression level ≤ 40% at 100°C for 22 hours.

Thermoplastic component, suitable for this izaberete the Oia, in its category refers to any thermoplastic polyalkylphenol complex polyester or related to the copolymer. Typically such polymers and copolymers can be obtained by polymerization of one or more of the isomers of phthalic acid, anhydrous phthalic acid or the corresponding esters and one or more diol comonomers according to any one of the methods of polymerization, typically implemented in practice at the present level of technology. Preferably the predominant phtalates isomer is terephthalate, and the prevailing diola is either ethylene glycol or 1,4-n-butanediol. It is most preferable to use 1,4-n-butanediol, receiving polymer polybutylene terephthalate or a copolymer. In addition, as known at the present level of technology, you can use different comonomers. Thus, together with polyalkyleneglycol can best way to copolymerizate other dibasic carboxylic acids, anhydrides, dibasic carboxylic acids and their esters and other diols, and lactones, and the like. Such copolymers can be either statistical copolymers or block copolymers of PET or pbtf was honored with. One particularly preferred type of copolymer is undoubtedly preferability based esters and ethers, with the present essentially of segments of polybutylene terephthalate and long-chain segments simple poliatilenglikola, commercially available in the company E.I. du Pont de Nemours and Company of Wilmington, Delaware under the trade name Hytrel®.

Stitched polymer rubber vulcanizer, suitable for the present invention, refers undoubtedly to the acrylate rubber type. Typically, these vulcanizates are linear copolymers obtained by copolymerization of more than one complex ester of acrylic acid, or a complex ester of methacrylic acid or their mixtures, or get them in the copolymerization of ethylene and one or more representatives, chosen from a complex ester of acrylic acid or a complex ester of methacrylic acid, and mixtures thereof. In the case of acrylate rubber will contain the bulk of the units of ethylene, acrylate units may be only for 6.5% (mol), but for optimum low values of residual strain during compression acrylate links should be more than 20% (mol). For the purposes of this invention such poly(meth)acrylate and polyethylene/(meth)acrylates are essentially linear copolymers, which can be stapled when using the vulcanizing system in the form of an organic peroxide and an organic diene of coagent. As such, poly(meth)acrylate and polyethylene/(meth)acrylate copolymers do not require the presence of the link function is analizirovalo triple co monomer. However, it is envisaged that the mere presence of small amounts of links functionalized co monomer, intentionally added to achieve specific properties in the final version, use that falls within the scope of the present invention, provided that such functionality will not have a negative impact on the rate of vulcanization, which at the time of dynamic crosslinking with free radical initiation. In addition, it is envisaged that for the purposes of the present invention is equivalent to the rubber vulcanizate acrylate type should be considered the vulcanizates certain polyphthalocyanines type (FPA) based monomers such as 1,1-dihydropyrrol-n-butyl acrylate and fluorinated copolymers derived from vinylidenefluoride and hexaferrite. Most preferably, the stitching acrylate rubber is a copolymer of ethylene and one or more alilovic esters of acrylic acid, methacrylic acid or mixtures, where the relative amount of ethylene copolymerizing with esters of acrylic acid (i.e. alkylacrylate), is less than 60 mass%, and alkylacrylate is more than 40 weight percent of the copolymer.

Vulcanizing system suitable for the present invention, includes itiator free radical polymerization, which quickly decomposes at a temperature of dynamic crosslinking, but not when the temperature of the melt during mixing. These include, for example, 2,5-dimethyl-2,5-di(tert-BUTYLPEROXY)hexyne-3, tert-butyl peroxybenzoate, 2,5-dimethyl-2,5-di(tert-BUTYLPEROXY)-2,5-dimethylhexane, dicumylperoxide, α,αbis(tert-BUTYLPEROXY)-2,5-dimethylhexane and the like. Preferably the free radical initiator is a 2,5-dimethyl-2,5-di(tert-BUTYLPEROXY)hexyne-3; 2,5-dimethyl-2,5-di(tert-BUTYLPEROXY)hexane or tert-butyl peroxybenzoate.

In accordance with what is known at the present level of technology, a crosslinking coagent, suitable for the present invention is an organic diene. Saagento, for example, may be dietilenglikoluretan, detranscendentalized, N,N'-m-phenylenedimaleimide, triallylisocyanurate, trimethylolpropane, tetraallyloxyethane, treelistener, tetramethylaniline, polietilenglikolmonostearat and the like. Preferably, saagento is either dietilenglikoluretan or detranscendentalized, or N,N'-m-phenylenedimaleimide or triallylisocyanurate.

The actual mixing of the components and subsequent dynamic binding, in principle, can be carried out either in periodic mode, libow continuous mode when using conventional equipment for mixing in the melt in accordance with the that is generally implemented in practice at the present level of technology. Preferably, the method is realized in the continuous mode in the processing of the melt extruder or the apparatus for injection moulding. The critical moment is to carry out the stages in such a way as to take advantage of the low-speed vulcanization at low temperatures, thus achieving a significant degree of mixing and dispersion to flow stitching. In this approach, the subsequent higher temperature will lead to crosslinking of the rubber phase after you have ensured the achievement of high level of dispersion.

Dynamically crosslinked thermoplastic elastomer composition corresponding to the present invention, in the best case can be modified by adding different types of fillers, pigments, stabilizers, antioxidants and the like, which in General is known at the present level of technology. Preferably processed in the melt of thermoplastic elastomer composition stabilized using a combination of polyamide and antioxidant, as reported in U.S. patent No. 3896078.

The following examples are presented to more fully demonstrate and further illustrate various aspects and features nastojasih the invention. As such demonstrate the options are intended to further illustrate the differences and advantages of the present invention, but they do not provide for the introduction of undue restrictions.

Examples 1-16

Was obtained and evaluated in a series of sixteen different mixtures of the present invention. Used thermoplastic represented polyetheramines block-copolymer-based esters and ethers characterized by the rate of flow of the melt (ISO 133) 18 g/10 minutes, melting point (ISO 3146C) 203°and density (ISO 1183) 1.19 g/cm3. Polyetheramines block copolymer esters and ethers consisted of a hard (crystalline) segment of polybutylene terephthalate and a soft (amorphous) segment based on long-chain simple polietilenglikoli, and was commercially available under the name Hytrel® E.I. DuPont de Nemours and Company of Wilmington, Delaware. Used polyacrylate rubber was a polyethylene/acrylate elastomer (related to the type of unfilled rubber compound)obtained by copolymerization of ethylene and 63% (wt.) of methyl acrylate, which is commercially available under the name Vamac® E.I. DuPont de Nemours and Company of Wilmington, Delaware. A mixture was obtained when using various free is nomadically the initiators of the peroxide type in combination with selected diene Saganami at various concentrations, as it is described in detail in the following following table 1. Peroxides are additionally given in table 1 for typical elevated temperature corresponding to the half-life with the formation of free radicals duration of one hour.

To determine the speed of vulcanization of the elastomer under specified peroxide and coagent on the Brabender mixer at the maximum temperature of the mixture, approximately 90°With, for about 2 minutes preparing a mixture of unfilled rubber compound, organic peroxide and coagent. These conditions corresponded to the level, much lower than the temperature and time that will be any significant reaction staple for specific combinations of peroxide and coagent that were used. After that, for these mixtures was determined by the speed of vulcanization when the device is used, Alpha Technologies Advanced Polymer Analyzer APA 2000 head with parallel plates, slit head 2,583 mm 100,0 frequency counts per minute deformation 0,500 degrees, 180°C. the Cured samples was performed in the analyzer ARA, just over 16 minutes, and monitored various characteristics related to the viscosity. To characterize the rate of vulcanization of the elastomer used, the time required to achieve maximum is Noah speed G' minmin (i.e. time, elapsed during the vulcanization process, after which to the elastic modulus showed the highest rate of increase, expressed in decimal minutes), and it is shown in table 1. This option appears to be most closely correlated with the conditions of dynamic vulcanization in the actual process of extrusion mixing a thermoplastic/elastomer.

After that, in the presence of phase thermoplastic spent dynamic mixing and crosslinking the composition, which is a natural development of previous compositions (that is, when the same concentrations of peroxide and coagent in phase elastomer, as used in the experiments to determine the rate of vulcanization of elastomers). These samples were mixed on a twin screw extruder Berstorff 25 mm In this activity, mixing unfilled rubber compound was dosed out in the cylinder of the extruder 1 at a controlled rate using a feeder for feeding elastomer related to the type of screw conveyor, maintained at a temperature of approximately 100°C. In zones 1 through 3 in a twin-screw extruder also withstand temperatures of 100°C. Liquid coagent pump filed in the barrel 2 of the extruder, and peroxide in the cylinder 3, and the liquid was mixed into to the unfilled rubber mixture of the ri using gear mixers. In those cases, when coagent pump was impossible, he was crushed by mixing with unfilled rubber mixture before loading in the feeder for feeding elastomer related to the type of screw conveyor, but peroxide in the cylinder 3 of the extruder was filed pump in all cases. Feeder type screw conveyor and the cylinder 1 through 3 in a twin-screw extruder maintained at a low temperature in order to avoid vulcanization of the elastomer before it is filed with the phase of thermoplastic. The extruder cylinders from 4 to 8 kept at 225°C. the phase of thermoplastic in the form of poliferation block copolymer esters and ethers filed in the extruder cylinder 4 with a controlled speed when using the feeder, based on the decrease of the mass and the lateral hydraulic extrusion press of the extruder. After adding the phase of thermoplastic followed a high-performance module sequence of mixing. The mixing modules used for dispersion of the elastomer phase of thermoplastic and to increase the temperature so that started to leak vulcanization. For the reaction zone of the extruder followed the hole for the vacuum, which is used to remove any volatile products. The material leaves the extruder through a die with 4 holes for receiving the threads and evaluation of Halsa sharp cooled in water and cut to form pellets. The temperature of the melt at the exit of the head of the extruder was in the range of from 250 to 260°C.

Then the material was dried for 16 hours in a drying Cabinet at 80°and were subjected to injection molding to molding to obtain plates with dimensions of 3 inches by 3 inches by 1/8 inch and 1/8-inch standard samples for microbacteria. The temperature of the cylinder when the injection molding was kept equal to 225°C. the Time and the injection pressure was chosen so as to achieve the duly completed forms for details.

The samples then were subjected to the test for determining residual stresses in compression in accordance with ASTM D395-89, Test Method B - Compression Set Under Constant Deflection in Air. Conditions were a 100°C for 22 hours. Before conducting the test plate was subjected to annealing at 120°C for 16 hours so that in the moment when the sample will be in terms of conducting tests to determine the residual strain during compression, the occurrence of crystallization in a continuous phase of thermoplastic polyetherketone on the basis of simple and complex esters had no effect on the result of determination of permanent deformation under compression. Using a stamp from the plates 3" × 3" × 1/8" carved disks with the proper diameter (1,14"±0,02") for tests on determination of residual deformation when compressed the AI and they were bonded to obtain the proper height (0,49"± 0,02"). For analysis of particle size by the method TEM of records deleted part of each sample in a direction transverse to the flow direction. When using cryoultramicrotomy Reichert-Jung and a diamond knife at a temperature that is installed approximately at 90°received slices with a thickness of 90 nanometers. Sections were collected on copper braided meshes and within 2 hours was subjected to vapors RUO Li4(for contrasting complex polyester). Images were obtained using a transmission electron microscope JEOL 1200EX, operating at 120 kV, and register them on large format film. After this is done according to the method of TEM pictures were visually evaluated and received a subjective assessment of typical size for the rubber phase. The hardness And the shore was determined in accordance with ASTM D 2240-5.

The respective compositions and the resulting data are presented in table 1. In figure 3 the resulting value is expressed as percentage of residual deformation under compression and an average particle size of rubber are presented in graphical form based on the time required to reach maximum speed of vulcanization. The results indicate that the desired low values of residual strain during compression is achieved when the time required is o maximum speed G', will be great that testifies to the passing of slower vulcanization during the dynamic vulcanization in comparison with samples with higher values of residual deformation under compression. Figures 1 and 2 correspond to made according to the method of TEM photographs for the resulting products of rubber (in the case of relatively high speed of reaction of free radical initiator and the resulting morphology of the polymer with relatively large domains), and (in the case of relatively low speed of reaction of free radical initiator and the resulting morphology of the polymer with a relatively high degree of dispersion of domains, where they both correspond to the method of the present invention. Collectively, the data indicate that in accordance with the present invention the residual strain at compression level ≤ 46 at 100°With time and 22 hours, along with hardness And shore-level ≥59, is achieved when using peroxides with a half-life equal to one hour at 125°and preferably 140°or even 152°C. This is particularly evident when the choice of peroxide, coagent and elastomer allows you to get a great time necessary to achieve a maximum speed of vulcanization (the time required forachieve maximum speed G', in decimal minutes), level ≥ 3.9 minutes (and preferably closer to 8 minutes or more).

Examples 17-20

According to the method similar to the method of examples 1-16, received a series of four additional mixtures poliferation block copolymer esters and ethers and polyethylene/acrylate elastomer and gave them a rating. Four different coagent was characterized by half-lives longer than one hour at relatively high temperatures 152°and 140°and, therefore, relatively low speed of vulcanization, as evidenced by the relatively long time required to achieve maximum speed G'. In addition, the results presented in table 2 demonstrate that the desirable low values of residual strain during compression is achieved when the time required to achieve maximum speed G', high, indicating a slower vulcanization during the dynamic vulcanization in comparison with samples with higher values of residual deformation under compression.

td align="left">  
Table 1
No. AveRubber E/MA (ethylene/methyl acrylate)Phase thermo-PlastHytrel®, % (1)The type of peroxide/td> Peroxide, wt.% in the calculation of the E/MAT1/2 (the temperature of the half-life of the peroxide 1 hour), °Type of coagentCoagent,% (based on rubber E/MAHardness And shore when the injection moldingResidual deformation during injection molding (compression at 100°, 22 hours for the annealed sample), %Vulcanization of the elastomer: time to reach maximum speed G', minminTypical particle size, microns
1E/MHytrel® 5526252,5-dimethyl-2,5-di(tert-butyl-peroxy)hexyne-32152Dietilen-glycol-diacrylate3,8559410,64,0
2E/MHytrel® 5526252,5-dimethyl-2,5-di(tert-butyl-peroxy)hexyne-32,5152Dietilen-glycol-diacrylate5,6663410,56,0
3E/MHytrel® 552625Tert-butyl-peroxybenzoate0,75125Dietilen-glycol-diacrylate3,850,5
4E/MHytrel® 552625Tert-butyl-peroxybenzoate1,5125Dietilen-glycol-diacrylate5,6663460,56,0
5E/MHytrel® 5526252,5-dimethyl-2,5-di(tert-butyl-peroxy)hexyne-32152Dietilen glycol dimethacrylate3,8560318,51,5
6E/MHytrel® 5526252,5-dimethyl-2,5-di(tert-butyl-peroxy)hexyne-32,5152Dietilen glycol dimethacrylate5,6662308,31,0
7E/MHytrel® 552625Tert-butyl-peroxybenzoate0,75125Dietilen glycol dimethacrylate3,850,9
8E/MHytrel® 552625Tert-butyl-peroxybenzoate1,5125Dietilen-glycol-timetake is at 5,660,8
9E/MHytrel® 5526252,5-dimethyl-2,5-di(tert-butyl-peroxy)hexyne-32152N,N'-m-phenylene-timelimit1,9665410,77,0
10E/MHytrel® 552625Tert-butyl-peroxybenzoate0,75125N,N'-m-phenylene-timelimit1,9664460,46,0
11E/MHytrel® 5526252,5-dimethyl-2,5-di(tert-butyl-peroxy)hexyne-32,5152N,N'-m-phenylene-timelimit3,8565390,73,0
12E/MHytrel® 552625Tert-butyl-peroxybenzoate1,5125N,N'-m-phenylene-timelimit3,8569440,46,0
13E/MHytrel® 5526252,5-dimethyl-2,5-di(tert-butyl-peroxy)hexyne-3 2152Triallyl-isocyanurate1,9666364,25,0
14E/MHytrel® 552625Tert-butyl-peroxybenzoate0,75125Triallyl-isocyanurate1,960,8
15E/MHytrel® 5526252,5-dimethyl-2,5-di(tert-butyl-peroxy)hexyne-32,5152Triallyl-isocyanurate3,856936a 3.95,0
16E/MHytrel® 552625Tert-butyl-peroxybenzoate1,5125Triallyl-isocyanurate3,8568420,87,0
(1) % (wt.) in the calculation only on the weight of the E/MA plus Hytrel®.

* Samples for which values of residual strain in compression is not given, it was impossible to expose the injection molding, because the composition differed excessive stickiness in order to pelletize and serve in the equipment for injection moulding.

Table 2
No. AveRubber E/MA (ethylene/methyl acrylate)Phase thermo-PlastHytrel®, % (1)The type of peroxidePeroxide, wt.% in the calculation of the E/MAT1/2 (the temperature of the half-life of the peroxide 1 hour), °Type of coagentCoagent,% (based on rubber E/MAHardness And shore when the injection moldingResidual deformation during injection molding (compression at 100°, 22 hours for the annealed sample), %Vulcanization of the elastomer: time to reach maximum speed G', minminTypical particle size, microns
17Hytrel® 5526252,5-dimethyl-2,5-di(tert-butyl-peroxy)hexyne-32,5152Ethylene-glycol-dimethacrylate2,96433˜ 6,6
18Hytrel® 5526252,5-dimethyl-2,5-di(tert-butyl-peroxy)hexyne-32,5152Dietilen glycol dimethacrylate3,56532˜ 7
19Hytrel® 5526252,5-dimethyl-2,5-di(tert-butyl-peroxy)hexyne-32,5152Dimethacrylate, politi-langille (200)4,86433˜ 7,5
20Hytrel® 5526252,5-dimethyl-2,5-di(tert-butyl-peroxy)hexane2,5140Dietilen glycol dimethacrylate3,56440˜ 3,2
(1) % (wt.) in the calculation only on the weight of the E/MA plus Hytrel®.

Examples 21 and 22

Using the methods described in examples 1 to 16 was obtained and subjected to crosslinking of the next pair of phases dynamically mixed elastomers, when the phase of thermoplastic in the received thermoplastic mixture.

tr>
MixtureAndIn
VCX-1012 (elastomer made from ethylene/63% methyl acrylate)46,5 %69,8 %
Hytrel® 5556 (butylene/poly(alkalinity)phthalate on the basis of simple esters)50 %25 %
Royal blend antioxidant *2 %2 %
Peroxide Aztec® viewport downward2,9 %(1)2,9 %(1)
Sartomer® SR231 ***4,3 %(1)4,3 %(1)
Licolub® WE40**** (lubricant)0,5 %
(1)The percentage in the calculation of the E/MA.

* Uterine mixture of antioxidants consisting of:

10 % Irganox® 565; 2,6-di-tert-butyl-4-(4,6-bis(octylthio)-1,3,5-triazine-2-ylamino)phenol,

15 % Ultranox® 626; bis(2,4-di-tert-butylphenyl)pentaerythrityl,

75 % Hytrel® 5556.

** Aztec® viewport downward (CAS 1068-27-5): peroxide vulcanizer; 2,5-dimethyl-2,5-di(tert-BUTYLPEROXY)hexyne-3.

*** "Sartomer® SR231" (CAS 2358-84-1): detranscendentalized, coagent.

**** "Licolub® WE40": "complex ester Antanovich acids", lignite wax, used as anti-adhesive grease.

1. A vulcanized thermoplastic elastomer mixture containing

(a) from 15 to 60 wt.% polymer or copolymer, representing polyalkylacrylate complex polyester; and

(b) from 40 to 85 wt.% stitched poly(meth)acrylate or polyethylene/(meth)acrylate vulcanizing rubber in combination with a peroxide free radical initiator and the organic diene saagento in number, effective for crosslinking the above-mentioned rubber during extrusion or injection molding mentioned vulcanized thermoplastic elastomer mixture which, after crosslinking the polymer or copolymer constituting polyalkylacrylate complex polyester, is present as a continuous phase and the rubber is present as the dispersed phase.

2. The mixture according to claim 1, where the stitching poly(meth)acrylate or polyethylene/(meth)acrylate vulcanizing rubber in combination with an effective amount of peroxide free radical initiator and an organic diene of coagent for crosslinking the above-mentioned rubber, characterized by the time required to achieve maximum speed G', level ≥3.9 minutes, when determining with the use of the instrument by Alpha Technologies Advanced Polymer Analyzer ARA 2000, with the head parallel plates, slit head 2,583 mm 100,0 frequency counts per minute deformation 0,500° 180°C.

3. The mixture according to claim 2, where the said polymer or copolymer constituting polyalkylacrylate complex polyester, is polyalkyleneglycol, a copolymer of polyalkylacrylate, poliferation on the basis of simple and complex esters derived from polyalkylacrylate or poliferation on the basis of simple and complex esters derived from the copolymer polyalkylene is retaliate; the said rubber is a polyacrylate elastomer or polyethylene/acrylate elastomer; mentioned coagent is dietilenglikoluretan, etilenglikolevykh, detranscendentalized, polietilenglikolmonostearat, N,N'-m-phenylenedimaleimide or triallylisocyanurate; and said initiator is a 2,5-dimethyl-2,5-di(tert-BUTYLPEROXY)hexyne-3, 2,5-dimethyl-2,5-di(tert-BUTYLPEROXY)hexane and tert-butyl peroxybenzoate.

4. The mixture according to claim 3 where the above-mentioned polymer or copolymer, representing polyalkylacrylate complex polyester, is a block copolymer formed of segments of polybutylene terephthalate and segments of the simple poly(tetramethylene)glycol, the said rubber is an elastomer, which represents an ethylene/methacrylate copolymer, said initiator is a 2,5-dimethyl-2,5-di(tert-BUTYLPEROXY)hexyne-3, and the aforementioned coagent is detranscendentalized.

5. Processed in the melt of thermoplastic elastomer composition containing (a) from 15 to 60 wt.% the continuous phase of the polymer or copolymer constituting polyalkylacrylate complex polyester, and (b) from 40 to 85 wt.% the dispersed phase poly(meth)acrylate or polyethylene/(meth)acrylate rubber where the above-mentioned rubber-rayed at the t dynamic crosslinking under the action of a peroxide free radical initiator and an organic diene of coagent, where the composition preferably has a residual deformation in compression at 100°and time of 22 h-level ≤46 when measured in accordance with ASTM D395-89,MethodB and hardness And shore-level ≥59.

6. The composition according to claim 5, where the said polymer or copolymer constituting polyalkylacrylate complex polyester, is polyalkyleneglycol, a copolymer of polyalkylacrylate, poliferation on the basis of simple and complex esters derived from polyalkylacrylate or poliferation on the basis of simple and complex esters derived from a copolymer of polyalkylacrylate mentioned rubber is a polyacrylate elastomer or polyethylene/acrylate elastomer, the said coagent is dietilenglikoluretan, etilenglikolevykh, detranscendentalized, polietilenglikolmonostearat, N,N1-m-phenylenedimaleimide or triallylisocyanurate, and said initiator is a 2,5-dimethyl-2,5-di(tertBUTYLPEROXY)hexyne-3, 2,5-dimethyl-2,5-di(tert-BUTYLPEROXY)hexane and tert-butyl peroxybenzoate.

7. The composition according to claim 6, where the said polymer or copolymer. representing polyalkylacrylate complex polyester, is a block copolymer formed of segments of polybutylene terephthalate and segments of the simple poly(tet is amerileather)glycol, the said rubber is an elastomer, which represents an ethylene/methacrylate copolymer, said initiator is a 2,5-dimethyl-2,5-di(tertBUTYLPEROXY)hexyne-3, and the aforementioned coagent is detranscendentalized.

8. A method of manufacturing processed in the melt of thermoplastic elastomer composition, which includes stages

(a) mixing stitched poly(meth)acrylate or polyethylene/(meth)acrylate vulcanizing rubber, peroxide free radical initiator and an organic diene of coagent in the processing of the melt extruder or in the processing of the melt mixer at a temperature sufficient to initiate crosslinking;

(b) adding the polymer is polyalkylacrylate complex polyester, in the above-mentioned processing melt extruder or melt processing mixer and mixing the above-mentioned polymer is polyalkylacrylate complex polyester, mentioned stitched poly(meth)acrylate or polyethylene/(meth)acrylate vulcanizing the rubber prior to stitching;

(c) additional mixing mentioned stitched poly(meth)acrylate or polyethylene/(meth)acrylate vulcanizing rubber, peroxide free radical and is itiator and organic diene of coagent with the said polymer, representing polyalkylacrylate complex polyester, under conditions and at a temperature sufficient to stitch mentioned stitched poly(meth)acrylate or polyethylene/(meth)acrylate vulcanizing rubber; and

(d) extracting processed in the melt of thermoplastic elastomer composition containing from 15 to 60 wt.% the above-mentioned polymer or copolymer, representing polyalkylacrylate complex polyester as continuous phase and from 40 to 85 wt.% mentioned poly(meth)acrylate or polyethylene/(meth)acrylate vulcanizing rubber, crosslinked under the action mentioned peroxide free radical initiator and the above-mentioned organic diene of coagent, as the dispersed phase.

9. The method of claim 8, where the mentioned stitched poly(meth)acrylate or polyethylene/(meth)acrylate vulcanizing rubber, in combination with a peroxide free radical initiator and an organic diene saagento for stitching specified rubber is characterized by the time required to achieve maximum speed G', level ≥3.9 minutes, when determining with the use of the instrument by Alpha Technologies Advanced Polymer Analyzer ARA 2000, with the head parallel plates, slit head 2,583 mm 100,0 frequency counts per minute deformation 0,500° 180°C.

10. The way pop, where each of the above-mentioned polymer or copolymer, representing polyalkylacrylate complex polyester, the above-mentioned rubber-mentioned organic diene of coagent and referred to the initiator is defined as indicated in claim 4 or 7.

11. The method according to claim 9, where the said polymer is polyalkylacrylate complex polyester, is a block copolymer formed of segments of polybutylene terephthalate and segments of the simple poly(tetramethylene)glycol, the said rubber is an elastomer, which represents an ethylene/methacrylate copolymer, said initiator is a 2,5-dimethyl-2,5-di(tert-BUTYLPEROXY)hexyne-3, and the aforementioned coagent is detranscendentalized.

12. A shaped or molded article made from the composition determined as described in one of claims 1 to 6 or 7.



 

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