Compositions containing hydrogenated block copolymers and engineering thermoplastic resins
54 claims: 35 independent, 19 dependent
- 1Patentkrav 1. Komposition innehållande en partiellt hydrerad segmentsampolymer, som innefattar minst två ändstående polymersegment A av en monoalkenylaren med en medelmolekylvikt av 5 000 - 125 000 och minst ett mellanliggande polymersegment B av en konjugerad dien med en medelmolekylvikt av 10 000 - 300 000, varvid de ändstående polymersegmenten A utgör 8-55 vikt% av segmentsampolymeren och icke mer än 25 % av arendubbelbindningarna i polymersegmenten A och minst 80 % av de alifatiska dubbelbindningarna i polymersegmenten B har reducerats genom hydrering, kännetecknad därav, att den innefattar:(a) 4-40 viktdelar av den partiellt hydrerade segmentsampolymeren, (b) ett polykarbonat med en smältpunkt över 120°C och (c) 5-48 viktdelar av minst en olik konstruktionstermoplast tillhörande den grupp som utgörs av polyamider, polyolefiner, termoplastiska polyestrar, poly(aryletrar), poly (arylsulfoner)., acetalhartser, termoplastiska polyuretaner, halogenerade termoplaster och nitrilhartser, varvid viktförhållandet polykarbonat till olik konstruktionstermoplast är större än 1:1, så att en polyblandning bildas, vari minst två av polymererna bildar åtminstone partiella, med varandra sammanlänkade kontinuerliga nätverk. **
- 2Komposition enligt krav 1, kännetecknad därav, att polymersegmenten A har en talmedelmolekylvikt av 7 000 60 000 och att polymersegmenten B har en talmedelmolekylvikt av 30 000 - 150 000.
- 3Komposition enligt krav 1 eller 2, kännetecknad därav, att de ändstående polymersegmenten A utgör 10-30 vikt% av segmentsampolymeren.
- 4Komposition enligt något av föregående krav, kännetecknad därav, att mindre än 5 % av arendubbelbindningarna i polymersegmenten A och minst 99 % av de alifatiska dubbelbindningarna i polymersegmenten B har reducerats genom hydrering.
- 5Komposition enligt något av kraven 1-4, kännetecknad därav, att polykarbonatet har den.allmänna formeln 7W158-5 Ο II --éAr-A-Ar-O-C-O^j- I eller II --(Ar-O-C-Οή^- II vari Ar betecknar en fenylen- eller en alkyl-, aikoxi-, halogeneller nitro-substituerad fenylengrupp, A betecknar en kol-till-kol-bindning eller en alkyliden-, cykloalkyliden-, alkylen-, cykloalkylen-, azo-, imino-, svavel-, syre-, sulfoxid- eller sulfongrupp och n är minst 2.
- 6Komposition enligt något av kraven 1-5, kännetecknad därav, att den olika konstruktionstermoplasten har en skenbar kristallin smältpunkt överstigande 120°C.
- 7Komposition enligt krav 6, kännetecknad därav, att den olika konstruktionstermoplasten har en skenbar kristallin smältpunkt av mellan 150°C och 350°C.
- 8Komposition enligt något av kraven 1-7, kännetecknad därav, att den olika konstruktionstermoplasten är en polyolefin med en talmedelmolekylvikt över 10 000 och en skenbar kristallin smältpunkt över 100°C.
- 9Komposition enligt krav 8, kännetecknad därav, att polyolefinen är en homopolymer eller sampolymer, som härrör från en alfa-olefin eller 1-olefin med 2-5 kolatomer.
- 10Komposition enligt krav 8 eller 9, kännetecknad därav, att polyölefinens talmedelmolekylvikt är över 50 000.
- 11Komposition enligt något av kraven 8-10, kännetecknad därav, att polyolefinens skenbara kristallina smältpunkt ligger mellan 140°C och 250°C.
- 12Komposition enligt något av kraven 8-11, kännetecknad därav, att den innehåller en polyeten av hög densitet med en ungefärlig kristallinitet av över 75 % och en densitet av mellan 0,94 och 1,0 kg/liter.
- 13Komposition enligt något av kraven 8-11, kännetecknad därav, att den innehåller en polyeten av låg den7805150-5 sitet med en ungefärlig kristallinitet av över 35 % och en densitet av mellan 0,90 och 0,94 kg/liter.
- 14Komposition enligt något av kraven 8-13, kännetecknad därav, att den innehåller en polyeten med en talmedelmolekylvikt av 50 000 - 500 000.
- 15Komposition enligt något av kraven 8-11, kännetecknad därav, att den innehåller en isotaktisk polypropen.
- 16Komposition enligt något av kraven 8-11, kännetecknad därav, att polypropenen har en talmedelmolekylvikt överstigande 100 000.
- 17Komposition enligt något av kraven 8-11, kännetecknad därav, att den innehåller en polypropen, som är en sampolymer, vilken innehåller eten eller annan alfa-olefin såsom sammonomer i en mängd av 1-20 vikt%.
- 18Komposition enligt något av kraven 8-11, kännetecknad därav, att den innehåller poly(1-buten) såsom polyolefin.
- 19Komposition enligt något av kraven 8-11, kännetecknad därav, att den såsom polyolefin innehåller en homopolymer av 4-metyl-l-penten med en skenbar kristallin smältpunkt av mellan 240 och 250°C och en relativ densitet av mellan 0,80 och 0,85.
- 20Komposition enligt något av kraven 8-11, kännetecknad därav, att den såsom polyolefin innehåller en sampolymer av 4-metyl-l-penten och en alfa-olefin.
- 21Komposition enligt krav 20, kännetecknad därav, att den såsom polyolefin innehåller en sampolymer av 4-metyl-l-penten och en linjär alfa-olefin med 4-18 kolatomer, vilken linjära alfa-olefin är närvarande i en mängd av 0,5-30 vikt%.
- 22Komposition enligt något av kraven 1-7, kännetecknad därav, att den olika konstruktionstermoplasten är en termoplastisk polyester med en smältpunkt överstigande 120°C.
- 23Komposition enligt något av kraven 1-7 eller 22,.. kännetecknad därav, att den olika konstruktionstermoplasten är poly(etentereftalat), poly(propentereftalat) eller poly(butentereftalat). 780S150-5
- 24Komposition enligt krav 23, kännetecknad därav, att den olika konstruktionstermoplasten är poly(butentereftalat) med en medelmolekylvikt av 20 000 - 25 000.
- 25Komposition enligt något av kraven 1-7 eller 22, kännetecknad därav, att konstruktionstermoplasten är en cellulosaester.
- 26Komposition enligt något av kraven 1-7 eller 22, kännetecknad därav, att konstruktionstermoplasten är en homopolymer av pivalolakton.
- 27Komposition enligt något av kraven 1-7 eller 22, kännetecknad därav, att konstruktionstermoplasten är en sampolymer av pivalolakton med icke mer än 50 mol% av en annan beta-propiolakton.
- 28Komposition enligt krav 27, kännetecknad därav, att konstruktionstermoplasten är en sampolymer av pivalolakton med icke mer än 10 mol% av en annan beta-propiolakton.
- 29Komposition enligt något av kraven 26-28, kännetecknad därav, att konstruktionstermoplasten är en polypivalolakton med en medelmolekylvikt överstigande 20 000 och en smältpunkt överstigande 120°C.
- 30Komposition enligt något av kraven 1-7 eller 22, kännetecknad därav, att konstruktionstermoplasten är en polykaprolakton.
- 31Komposition enligt något av kraven 1-7, kännetecknad därav, att den olika konstruktionstermoplasten är en polyamid med en talmedelmolekylvikt över 10 000.
- 32Komposition enligt något av kraven 1-7, kännetecknad därav, att konstruktionstermoplasten är en homopolymer av formaldehyd eller trioxan.
- 33Komposition enligt något av kraven 1-7, kännetecknad därav, att konstruktionstermoplasten är en polyacetalsampolymer.
- 34Komposition enligt något av kraven 1-7, kännetecknad därav, att konstruktionstermoplasten är en homopolymer eller sampolymer härrörande från tetrafluoreten, klortrifluoreten, bromtrifluoreten, vinylidenfluorid eller vinylidenklorid.
- 35Komposition enligt något av kraven 1-7, känne 7805150-5 tecknad därav, att konstruktionstermoplasten är ett nitrilharts med en alfa, beta-olefiniskt omättad mononitrilhalt överstigande 50 vikt%.
- 36Komposition enligt krav 35, kännetecknad därav, att den alfa, beta-olefiniskt omättade mononitrilen har den allmänna formeln CH 0 =C-CN 2 .1 R vari R betecknar väte, en alkylgrupp med 1-4 kolatomer eller en halogen.
- 37Komposition enligt krav 35 eller'36, känneteckn a d därav, att nitrilhartset är en homopolymer, en sampolymer, en ymppolymer av en sampolymer på ett gunraisuhstrat eller en blandning av homopolymerer och/eller sampolymerer.
- 38Komposition enligt något av kraven 1-37, kännetecknad därav, att den innehåller segmentsampolymeren och den olika termoplasten i en mängd av 8-20 viktdelar respektive 10-35 viktdelar.
- 39Komposition enligt något av föregående krav, kännetecknad därav, att den innehåller en utdrygningsolja i en mängd av 0-100 viktdelar per 100 viktdelar segmentsampolymer.
- 40Komposition enligt krav 39, kännetecknad därav, att den innehåller en utdrygningsolja i en mängd av 5-30 viktdelar per 100 viktdelar segmentsampolymer.
- 41Komposition enligt något av föregående karav, k ä η n e tecknad därav, att den innehåller ett flödesbefrämjande harts såsom ytterligare harts i en mängd av 0-100 viktdelar per 100 viktdelar segmentsampolymer.
- 42Komposition enligt kray 41, kännetecknad därav, att den innehåller ett flödesbefrämjande harts såsom ytterligare harts i en mängd av 5-25 viktdelar per 100 viktdelar segmentsampolymer.
- 43Komposition enligt krav 41 eller 42, kännetecknad därav, att den innehåller ett ytterligare harts,· som tillhör den grupp som utgörs av ett alfa-metylstyrenharts, kumaronindenharts, vinyItoluen-alfa-metylstyrensampolymerer, polyinden- 750158-5 hartser och lågmolekylära polystyrenhartser.
- 44Förfarande för framställning av en komposition enligt något av kraven 1-43, kännetecknat därav, att man vid en processtemperatur Tp av mellan 150°C coh 400°C blandar (a) 4-40 viktdelar av en partiellt hydrerad segmentsampolymer, som innefattar minst två ändstående polymersegment A av en monoalkenylaren med en medelmolekylvikt av 5 000 - 125 000 och minst ett mellanliggande polymersegment B av en konjugerad dien med en medelmolekylvikt av 10 000 - 300 000, varvid de ändstående polymersegmenten A utgör 8-55 vikt% av segmentsampolymeren och icke mer än 25 % av arendubbelbindningarna i polymersegmenten A och minst 80 % av de alifatiska dubbelbindningarna i polymersegmenten B har reducerats genom hydrering, med (b) ett polykarbonat med en smältpunkt över 120°C och (c) 5-48 viktdelar av minst en olik konstruktionstermoplast, som tillhör den grupp som utgörs av polyamider, polyolefiner, termoplastiska polyestrar, poly(aryletrar), poly(arylsulfoner), acetalhartser, termoplastiska polyuretaner, halogenerade termoplaster och nitrilhartser, varvid viktförhållandet polykarbonat till olik konstruktionstermoplast är större än 1:1, så att en polyblandning bildas, vari minst två av polymererna bildar åtminstone partiella med varandra sammanlänkade kontinuerliga nätverk.
- 45Förfarande enligt krav 44, kännetecknat därav, att polymererna blandas vid en processtemperatur Tp av mellan 230°C och 300°C.
- 46Förfarande enligt krav 44 eller 45, kännetecknat därav, att polymererna upplöses i ett för samtliga polymerer gemensamt lösningsmedel och koaguleras genom blandning i ett lösningsmedel, vari ingendera polymeren är löslig.
- 47Förfarande enligt krav 44 eller 45, kännetecknat därav, att polymererna blandas såsom granuler och/eller pulver i en anordning, som åstadkommer skjuvkrafter.
- 48Förfarande enligt något av kraven 44-47, kännetecknat därav, att förhållandet mellan segmentsampolymerens viskositet och viskositeten hos polykarbonatet, den olika konstruktionstermoplasten eller blandningen av polykarbonat och olik kon7805150-5 struktionstermoplast är mellan 0,2 och4,o vid processtemperaturen Tp och en skjuvningshastighet av 100 s -1 .
- 49Förfarande enligt krav 48, kännetecknat därav, att förhållandet mellan segmentsampolymerens viskositet och viskositeten hos polykarbonatet, den olika konstruktionstermoplasten eller blandningen av polykarbonat och olik konstruktionstermoplast ligger mellan 0,8 och 1,2 vid processtemperaturen Tp och en skjuvningshastighet av 100 s \
- 50Förfarande enligt något av kraven 44-49, kännetecknat därav, att den olika konstruktionstermoplasten först blandas med ett viskositetsmodifieringsmedel innan den blandas med polykarbonatet och segmentsampolymeren.
- 51Förfarande enligt något av kraven 44-50, kännetecknat därav, att man såsom viskositetsmodifieringsmedel använder poly(2,6-dimetyl-l,4-fenylen)oxid eller en blandning av poly(2,6-dimetyl-l,4-fenylen)oxid med polystyren.
- 52Förfarande enligt krav 50 eller 51, kännetecknat därav, att viskositetsmodifieringsmedlet används i en mängd av 0-100 viktdelar per IO0 viktdelar kostruktionstermoplast.
- 53Förfarande enligt krav 52, kännetecknat därav, att viskositetsmodifieringsmedlet används i en mängd av 10-50 viktdelar per 100 viktdelar konstruktionstermoplast.
- 54Förfarande enligt något av kraven 44-53, kännetecknat därav, att segmentsampolymeren och den olika konstruktionstermoplasten används i en mängd av 8-20 viktdelar resp. 10-35 viktdelar.
Independent claims54
706 paragraphs in 23 sections, as filed
(54) Name: Composition of a partially hydrogenated block copolymer, a polycarbonate and a further thermoplastic polymer, and preparation thereof (56) Publications cited:
--—> - in Rnkstav within clamps indicates international document code.
<img file="SE435722B_D0001.tif" />
The present invention relates to a composition containing a partially hydrogenated block copolymer comprising at least two terminal polymer segment A of a monoalkenylar having an average molecular weight of 5000-125,000 and at least one intermediate polymer segment B of a conjugated diene having an average molecular weight of 10,000 - 300,000, wherein the terminal polymer segments A constitute 8-55% by weight of the block copolymer and no more than 25% of the eagle double bonds in polymer segments A and at least 80% of the aliphatic double bonds in polymer segments B have been reduced by hydrogenation.
Structural thermoplastics are a group of polymers that exhibit a balanced composition of properties including strength, stiffness, impact strength and long-term dimensional stability, which properties make them useful as structural materials. Structural thermoplastics are particularly attractive as substitutes for metals because of the weight reduction that can often be achieved, for example in engine designs.
For a particular application, perhaps a single thermoplastic ico may offer the desired combination of properties, and therefore there is an interest in being able to correct this deficiency. A particularly attractive way to go is to mix two or more polymers (which
Λ805150-5 each has the desired properties) to obtain a material exhibiting the desired combination of properties. This approach has been successful in a limited number of cases, for example, in improving the impact strength of thermoplastics, such as polystyrene, polypropylene and poly (vinyl chloride), using special blending techniques or special additives for this purpose. In general, however, blending of thermoplastics has not proven to be a successful way of combining in a single material the desired individual properties of two or more polymers. Instead, it has often been found that such a mixture results in a combination of the worst features of each, with the result that one obtains a material with such poor properties that it receives no practical or commercial value. The reasons for this are fairly well investigated and are based in part on the fact that thermodynamics teaches that most combinations of polymer pairs are not miscible, although a number of notable exceptions are known. What is more important is that most polymers adhere to each other very poorly. As a result, the interfaces between the components (as a result of their immiscibility) will represent areas of severe weakness in the blends and therefore produce natural blisters and cracks resulting in slight mechanical breakage. As a result, most polymers are considered non-combinable. In some cases, the term compatibility is used synonymously with the term miscibility. In the present context, however, the term combinability is used more generally and denotes the ability of two polymers to be combined together for favorable results and may, but not necessarily, denote miscibility.
One method that can be used to circumvent this problem in polymer blends is to make the two polymers combinable by admixture of a third component, which is often referred to as compatibility promoting agent and which exhibits a dual solubility function with respect to the two polymers intended for blending. Examples of this third component are obtained in segment or graft copolymers. As a result of this property, this agent is located at the interface between the components and greatly improves the adhesion between the phases and therefore increases the stability towards total phase separation.
The present invention relates to an agent for stabilizing multipolymer mixtures which is independent of the prior art.
50-5 combinability promoting process and is not limited to the need to utilize limiting dual solubility properties. The materials used for this purpose are special block copolymers which are capable of undergoing thermally reversible self-crosslinking. Their effect on the present invention is not that associated with the conventional compatibility-promoting concept, as evidenced by the general ability of these materials to act in a similar manner to the widely different blend component, which is not compatible with the solubility requirements associated with the former concept.
The present invention relates to a composition containing a partially hydrogenated block copolymer comprising at least two terminal polymer segment A of a monoalkenylene having an average molecular weight of 5000 - 125,000 and at least one intermediate polymer segment B of a conjugated diene having an average molecular weight of 10,000 to 300,000. , wherein the terminal polymer segments A constitute 8-55% by weight of the block copolymer and not more than 25% of the eagle double bonds in polymer segments A and at least 80% of the aliphatic double bonds in polymer segment B have been reduced by hydrogenation, the composition being characterized as comprising ( a) 4-40 parts by weight of the partially hydrogenated segregate copolymer, (b) a polycarbonate having a melting point above 120 ° C and (c) 5-48 parts by weight of at least one different construction thermoplastic, belonging to the group consisting of polyamides, polyolefins, thermoplastic polyesters, poly (aryl ethers), poly (arylsulfones), acetal resins, thermoplastic polyurethanes, halogenated thermoplastics and nitrile resins, the weight ratio of polycarbonate to different construction thermoplastics being 1 greater than 1: poly blend is obtained, wherein at least two of the polymers form at least partial, continuous interconnected networks.
The block copolymer of the present invention effectively serves as a mechanical or structural stabilizer which links the various polymer structure networks and prevents the necessary separation of the polymers during processing and subsequent use thereof. As will be explained in more detail below, the resulting structure of the poly blend (shortening for polymer blend) is that of at least two partial, continuous interconnecting networks. This interconnected structure results in a dimensionally stable poly mixture which is not delaminated by extrusion and subsequent use.
In order to produce stable mixtures, it is necessary that at least two of the polymers have at least partial continuous networks which are interconnected. Preferably, the block copolymer and at least one other polymer have partial, continuous interconnected network structures. In an ideal situation, all polymers would have complete, continuous networks that are interconnected. By partial continuous network is meant that one part of the polymer has a continuous network phase structure, while the other part has a dispers phase phase structure. Preferably, a major portion (more than 50% by weight) of the partial continuous network is continuous. As will be readily appreciated, a wide variety of mixing structures are possible, since the polymer's structure in the mixture may be fully continuous, fully dispersed or partially continuous and partially dispersed. Furthermore, the dispersed phase of a polymer may be dispersed in a second polymer and not in a third polymer. In order to illustrate some of the structures, a list of the various combinations of possible polymeric structures is given below, where all structures are complete as opposed to partial structures. Three polymers (A, B and C) are included. Index c indicates a continuous structure, while index d indicates a dispersion structure. Thus, the designation AB means that the polymer A is contiguous to polymer B, and the designation B
<td>B is dispersion in polymer C,</td><td>etc.</td><td></td>
<td> ·' <sup>A</sup>c<sup>B</sup> .</td><td><sup>A</sup>c<sup>C</sup></td><td><sup>B</sup>° C</td>
<td></td><td><sup>A</sup>° C</td><td>A<sup>C</sup></td>
<td> ' <sup>A</sup>c<sup>B</sup> .</td><td><sup>A</sup>o °</td><td>.. a °</td>
<td><sup>B</sup>d<sup>A</sup></td><td></td><td></td>
<td>B<sub>d</sub>C</td><td><sup>A</sup>c<sup>B</sup></td><td><sup>A</sup>c<sup>C</sup></td>
<td>C<sub>d</sub>Ä.</td><td>A<sub>0</sub>B</td><td> ’ <sup>A</sup>c<sup>c</sup></td>
<td></td><td><sup>A</sup>O<sup>B</sup></td><td>V</td>
In practicing the invention, it is possible to improve one type of physical property of the composite blend without causing any significant deterioration of another physical property. This has not always been possible before. Thus, it has previously been expected that by adding an amorphous rubber such as an ethylene-propylene rubber to a thermoplastic polymer in order to improve impact strength it is necessary to obtain a composite mixture with a significantly reduced heat distortion temperature (HDT). This is attributable to the fact that the amorphous rubber forms separate particles in the mixture and, by definition, the rubber has an extremely low HDT value around room temperature. However, according to the present invention, it is possible to significantly improve the impact strength while not reducing the heat distortion temperature. Even more surprisingly, as is evident from the embodiments below, in some cases the heat distortion temperature increases surprisingly as the amount of the block copolymers present increases, a phenomenon which is totally unexpected to those skilled in the art.
This ability to tailor polymer blends in order to achieve a much improved balancing of properties has not previously been disclosed in the art. It is later surprising that even very small amounts of the block copolymer are sufficient to stabilize the structure of the polymer mixture over a very wide range of the relative concentration. For example, as little as 4 parts by weight of the block copolymer is sufficient to stabilize a mixture of 5-90 parts by weight of polycarbonate with 90-5 parts by weight of a different conc traction thermoplastic.
In addition, it is also surprising that the block copolymers are useful for stabilizing polymers of such a wide variety and with such widely different chemical compositions. As will be explained in more detail below, the block copolymers have this ability to stabilize a wide variety of polymers within a wide range of concentrations, since they are oxidatively stable, exhibit essentially an infinite viscosity at the shear load O. and maintain network or area .
Another important aspect of the invention is that the ease of machining and shaping of the various poly mixtures is greatly improved by the use of the block copolymers as stabilizers.
7805150-5
The block copolymers used in the composition of the invention may exhibit widely different geometric structures, since the invention is not based on the use of any specific geometric structure but rather on the chemical nature of each of the polymer segments. Thus, the block copolymers may be linear, radial or branched. Methods for preparing such polymers are known in the art. The structure of the polymers is determined by the polymerization method. Linear polymers are obtained e.g. by incrementally introducing the desired monomers into the reaction vessel using such initiators as lithium alkyls or dilitiostilbene or by coupling a two-segment copolymer with a difunctional coupling agent. Branched structures, on the other hand, can be obtained by using suitable coupling agents having a functionality of three or more with respect to the precursor polymers. The coupling can be effected with multifunctional coupling agents such as dihaloalkanes or alkenes and divinylbenzene, as well as certain polar compounds such as silicon halides, siloxanes or esters of benign alcohols with carboxylic acids. The presence of any coupling agent residues in the polymer may be left without regard to an adequate description of the polymers forming part of the compositions of the present invention. Similarly, in the generic sense, the specific structures can be left unanswered. The invention particularly relates to the use of selectively hydrogenated polymers having a configuration prior to hydration of the following type polymers:
polystyrene-polybutadiene-polystyrene (SBS) polystyrene-polyisoprene-polystyrene (SIS) poly (alpha-methylstyrene) polybutadiene-poly (alpha-methylstyrene) and poly (alpha-methylstyrene) polyisoprene-poly (alpha-methylstyrene).
Both polymer segments A and B can be either homopolymer segments or randomly constructed copolymer segments, provided that each polymer segment is dominated by at least one class of the monomers that characterize the polymer segments. Polymer segment A may comprise homopolymers of a monoalkenylar and copolymers of a monoalkenylar with a conjugated diene, provided that polymer segment A is individually dominated by monoalkenylar moieties. In particular, the term monoalkenylar includes styrene and its analogs and homologs including alpha-methylstyrene and ring-substituted styrenes, in particular ring-methylated styrenes. The preferred monoalkenyl arenes
7808150-5 is styrene and alpha-methylstyrene, with styrene being particularly preferred. The polymer segments B may comprise homopolymers of a conjugated diene, such as butadiene or isoprene, and copolymers of a conjugated diene with a monoalkenylene, provided that the polymer segments B are dominated by conjugated diene units. When the monomer used is butadiene, it is preferred that 35-55 mole% of the condensed butadiene units in the butadiene polymer segment have 1,2 configuration. Thus, when such a segment is hydrogenated, the resulting product becomes or resembles a regular copolymer segment of ethylene and butene-1 (EB). If the conjugated diene used is isoprene, the hydrogenated product obtained is or is similar to a regular copolymer segment of ethylene and propylene (EP).
Hydration of the precursor block copolymers is preferably carried out using a catalyst comprising the reaction products of an aluminum alkyl compound and nickel or cobalt carboxylates or alkoxides, under such conditions that at least 80% of the aliphatic double bonds but not more than 25% of the aromatic alkenylene hydrogenated. Preferred block copolymers are those wherein at least 99% of the aliphatic double bonds are hydrogenated while less than 5% of the aromatic double bonds are hydrogenated.
The average molecular weights of the individual segments may vary within certain limits. The block copolymer present in the composition of the invention has at least two terminal polymer segments A of a monoalkenylene having a number average molecular weight of 5000-125,000, preferably 7000 - 60,000. And at least one intermediate polymer segment B of a conjugated diene having a number average molecular weight of 10,000 300,000, preferably 30,000 - 150,000. These molecular weights are determined most accurately by means of tritium intensity measurements or measurements of the osmotic pressure.
The proportion of polymer segment A of the monoalkenylar should be between 8 and 55% by weight of the block copolymer, preferably between 10 and 30% by weight.
The polycarbonates present in the compositions of the invention are those of the general formulas
7805150-5
I 'I - (Ar – A – Ar – O – C – Ο) - and ·
Ο - (- Ar — 0 — C — Ο-) II η
wherein Ar represents phenylene or an alkyl, alkoxy, halogen or nitro-substituted phenylene group, A represents a carbon-to-carbon bond or an alkylidene, cycloalkylidene, alkylene, cycloalkylene, azo, imino, sulfur , oxygen, sulfoxide or sulfone group and n is at least 2.
The preparation of the polycarbonates is well known. A preferred method of preparation is based on the reaction carried out by dissolving the dihydroxy component in a base such as pyridine and allowing the phosgene to bubble through the stirred solution at the desired rate. Tertiary amines can be used to catalyze the reaction and to serve as acid acceptors during the reaction. Since the reaction is normally exothermic, the rate at which the phosgene is added can be utilized to control the reaction temperature. The reactions generally utilize equimolar amounts of phosgene and dihydroxy reactant, but the mole ratios may vary depending on the reaction conditions.
In formulas I and II above, Ar and A are preferably p-phenylene and isopropylidene, respectively. This polycarbonate is prepared by reacting para, para'-isopropylidene diphenol with phosgene and is marketed under the trade name LEXAN and MERLON. This commercial polycarbonate has a molecular weight of about 18,000 and a melting temperature of over 230 ° C. Other polycarbonates can be prepared by reacting other dihydroxy compounds or mixtures of dihydroxy compounds with phosgene. The dihydroxy compounds may comprise aliphatic dihydroxy compounds, although aromatic rings are essential for achieving the best possible high temperature properties. The dihydroxy compounds in the structure may contain diurethane bonds. Also, some of the structure can be replaced by siloxane bonds.
By the term different structural thermoplastics "is meant structural thermoplastics which differ from those thermoplastics comprised by the polycarbonates present in the compositions of the invention.
7008450-5
The term construction thermoplastic includes the various polymers listed in Table A below and which are further defined below.
Table A
1st polyolefins
2nd Thermoplastic polyesters
3rd Poly (aryl ethers) and poly (aryl sulfones)
4th polyamides
5th acetal resins
6th Thermoplastic polyurethanes
7th Halogenated thermoplastics
Eighth nitrile
Preferably, these structural thermoplastics have glass transition temperatures or apparent crystalline melting points (defined as the temperature at which the low-load module exhibits a drastic reduction) of above 120 ° C, preferably between 150 ° C and 350 ° C, and are capable of forming a continuous network structure. via a thermally reversible cross-linking mechanism. Such thermally reversible crosslinking mechanisms include crystal bonding, polar bonding, ionic bonding, lamellar bonding and hydrogen bonding. In a specific embodiment, where the viscosity of the block copolymer or mixed block copolymer composition at the process temperature Tp and a shear rate of 100 sec.<sup>-1</sup> For example, the ratio between the viscosity of the structural thermoplastics or the mixture of structural thermoplastics with viscosity modifier should be between 0.2 and 4.0, preferably between 0.8 and 1.2. With the viscosity of the block copolymer, polycarbonates. and the construction thermoplastic, in the present context, refers to the melt viscosity measured using a piston-driven capillary melt rheometer at a constant shear rate and at any suitable temperature above the melting point, e.g. 260 ° C. The upper limit (350 ° C) for apparent crystalline melting point or glass transition temperature has been selected so that the resin can be processed in equipment utilizing low or moderate shear rates at commercially used temperature levels of 350 ° C or below.
The structural thermoplastic also includes mixtures of various structural thermoplastics and mixtures with additional viscosity modifying resins.
The different classes of structural thermoplastics are defined in more detail below.
www *
The polyolefins optionally present in the composition of the invention are crystalline or crystallizable. They may be homopolymers or copolymers and may be derived from an alpha-olefin or 1-olefin having 2-5 carbon atoms. Examples of particularly useful polyolefins include low density polyethylene, high density polyethylene, isotactic polypropylene, poly (1-butene), poly (4-methyl-1-pentene) and copolymers of 4-methyl-1-pentene with linear or branched alpha-olefins. A crystalline or crystallizable structure is essential for the polymer to form a continuous structure with the other polymers in the polymer blend of the invention. The number average molecular weight of the polyolefins may be above 10,000, and preferably above 50,000. In addition, the apparent crystalline melting point may be above 100 ° C, preferably between 100 and 250 ° C, and more preferably between 140 ° C and 250 ° C. The preparation of these various polyolefins is well known and reference is generally made to Olefin Polymers, vol. 14, Kirk-Othmer Encyclopedia of Chemical Technology, p. 217-335 (1967).
When using a high density polyethylene, it has an approximate crystallinity of over 75% and a density in kilograms per liter (kg / l) of between 0.94 and 1.0. Using a low density polyethylene, it has an approximate crystallinity of over 35% and a density of between 0.90 kg / l and 0.94 kg / l. The composition of the invention may contain polyethylene having a number average molecular weight of 50,000 - 500,000.
When using a polypropylene, this is a so-called isotactic polypropylene as opposed to atactic polypropylene. The number average molecular weight of the polypropylene used may be above 100,000. The polypropylene can be prepared using methods known in the art. Depending on the specific catalyst and the particular polymerization conditions employed, the polymer prepared may contain both atactic and isotactic and syndiotactic or so-called stereo segmental molecules. These can be separated by selective solvent extraction to obtain products with low content of atactic molecules which crystallize more fully. The preferred commercial polypropylenes are generally prepared using a solid crystalline hydrocarbon insoluble catalyst prepared from a titanium trichloride composition and an aluminum alkyl compound, e.g. triimty WM ·
7808150-5 ethyl aluminum or diethyl aluminum chloride. If desired, the polypropylene used may be a copolymer containing less (1-20 wt.%) Amounts of ethylene or another alpha-olefin such as comonomer.
Poly (1-butene) preferably has an isotactic structure. The catalysts used in the preparation of poly (1-butene) are preferably metallic organic compounds, commonly referred to as Ziegler - Natta catalysts. A typical catalyst is the reaction product obtained by mixing equimolar amounts of titanium tetrachloride and triethyl aluminum. The preparation process is normally carried out in an inert diluent such as hexane. The preparation process is carried out at all stages of polymer formation in such a way as to exclude any presence of water, even in trace amounts.
A very suitable polyolefin is poly (4-methyl-1-pentene). Poly (4-methyl-1-pentene) has an apparent crystalline melting point of between 240 and 250 ° C and a relative density of between 0.80 and 0.85. Monomer 4-methyl-1-pentene is commercially produced by alkali metal catalyzed dimerization of propylene. The homopolymerization of 4-methyl-1-pentene with Ziegler-Natta catalysts is described in the Kirk-Othmer Encyclopedia of Chemical Technology, Supplementary Band, p. 789-792 (2nd ed., 1971). However, the isotactic homopolymer of 4-methyl-1-pentene has certain technical defects, such as brittleness and insufficient transparency. Therefore, the commercially available polymer is poly (4-methyl-1-pentene), in fact, a copolymer with smaller proportions of other alpha-olefins and with the addition of suitable oxidation and melt stabilization systems. These copolymers are described in Kirk-Othmer, Encyclopedia of Chemical Technology, Supplementary Bands, p. 792-907 (2nd edition, 1971) and are available under the trade name TPX resin. Typical alpha olefins are linear alpha olefins having 4-18 carbon atoms. Suitable resins are copolymers of 4-methyl-1-pentene having 0.5-30% by weight of a linear alpha-olefin.
If desired, the polyolefin is a mixture of various polyolefins. However, the most preferred polyolefin is isotactic polypropylene.
Any thermoplastic polyesters present in the compositions of the invention have a generally crystalline structure and a melting point above 120 ° C and are thermoplastic resins as opposed to thermosetting resins.
78051 SO-5
A particularly useful group of polyesters are the thermoplastic polyesters produced by condensation of a dicarboxylic acid or a lower alkyl ester. kidney halide or anhydride derivatives thereof with a glycol according to methods well known in the art.
Among the aromatic and aliphatic dicarboxylic acids suitable for the production of polyesters are 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 , p-carboxyphenoxyacetic acid, p-carboxyphenoxy propionic acid, p-carboxyphenoxybutyric acid, p-carboxyphenoxyvaleric acid, p-carboxyphenoxyhexanoic acid, p, p'-dicarboxyphenylmethane, p, p-dicarboxyphenylpropane, p, p'-dicarboxy diphenyloctane, 3-alkyl-4- (beta-carboxyethoxy) benzoic acid, 2,6-naphthalene dicarboxylic acid and 2,7-naphthalene dicarboxylic acid. Mixtures of dicarboxylic acids can also be used. Terephthalic acid is particularly preferred.
The glycols suitable for preparing the polyesters include straight-chain alkylene glycols having 2 to 12 carbon atoms, such as ethylene glycol, 1,3-propylene glycol, 1,6-hexylene glycol, 1,10-decamethylene glycol and 1,12-dodecamethylene glycol. Aromatic glycols may be fully or partially substituted. Suitable aromatic dihydroxy compounds include p-xylylene glycol, pyrocatechol, resorcinol, hydroquinone or alkyl substituted derivatives of these compounds. Another suitable glycol is 1,4-cyclohexanedimethanol. Particularly preferred glycols are straight-chain alkylene glycols of 2-4 carbon atoms.
A preferred group of polyesters is poly (ethylene terephthalate), poly (propylene terephthalate) and poly (butylene terephthalate). A particularly preferred polyester is poly (butylene terephthalate). Poly (butylene terephthalate), a crystalline copolymer, can be formed by polycondensation of 1,4-butanediol. and dimethyl terephthalate or terephthalic acid and has the general formula
<img file="SE435722B_D0002.tif" />
Wherein n varies from 70 to 140. The average molecular weight of poly (butylene terephthalate) preferably ranges from 20,000 to 25,000.
Commercially available poly (butylene terephthalate) is available under the trade name VALOX thermoplastic polyester. Other commercial polymers include CELANEX TENITE and VITUF.
Other useful polyesters include cellulose esters. The thermoplastic cellulose esters used in the present context have widespread use as molding materials, coating materials and film-forming materials and are well known in the art. These materials include the solid thermoplastic forms of cellulose nitrate, cellulose acetate (e.g. cellulose diacetate, cellulose triacetate), cellulose butyrate, cellulose acetate butyrate, cellulose propionate, cellulose tridecanoate, carboxymethyl cellulose, ethyl cellulose, hydroxyethyl cellulose and acetylated hydroxyethyl cellulose as described. 25-28 in Modern Plastics Encyclopedia, 1971-72, and the references therein.
Another useful polyester is a polypivalolactone. Polypivalolactone is a linear polymer with recurring ester structure units having essentially the following formula:
--------- CH<sub>2</sub>--------- C (CH<sub>3</sub>) <sub>2</sub>------- C (O) O ------ ie units derived from pivalolactone. The polyester is preferably a pivalolactone homopolymer. However, the copolymers of pivalolactone also include at most 50 mol%, preferably at most 10 mol% of other beta-propiolactone, such as beta-propiolactone, alpha, alpha-diethyl-beta-propiolactone and alpha-methyl-alpha-ethyl-beta-propiolactone. The term beta-propiolactones refers to beta-propioactone (2-oxetanone) and derivatives thereof, which do not carry any substituents on the beta-carbon atom of the lactone ring. Preferred beta-propiolactones are those containing a tertiary or quaternary carbon atom in the alpha position with respect to the carbonyl group. Especially preferred are alpha, alpha-dialkyl-beta-propiolactones, wherein the alkyl groups independently each contain from 1 to 4 carbon atoms. Examples of useful monomers are: alpha-ethyl-alpha-methyl-beta-propiolactone, alpha-methyl-alpha-isopropyl-beta-propiolactone, alpha-ethyl-alpha-n-butyl-beta-propiolactone, alpha-chloromethyl-alpha methyl-beta-propiolactone, alpha, alpha-bis (chloromethyl) -beta-propiolactone, and alpha, alpha-dimethyl-beta-propiolactone (pivalolactone).
7805150-5 <sup>14</sup>
These polypivalolactones have a molecular weight exceeding 20,000 and a melting point exceeding 120 ° C.
Another useful polyester is a polycaprolactone.
Preferred poly (β-caprolactones) are essentially linear polymers: with the repeating unit
<img file="SE435722B_D0003.tif" />
These polymers have properties similar to those of the polypivalolactones and can be prepared by a similar polymerization mechanism.
Various poly (aryl polyethers) are also useful as construction thermoplastics. The poly (aryl polyethers) referred to in the present context comprise linear thermoplastic polymers consisting of repeating units of the formula
- (- 0 - G - - 0 Gr · / - wherein G is the residue of a divalent phenol of the formula
IN
<img file="SE435722B_D0004.tif" />
II or
<img file="SE435722B_D0005.tif" />
III wherein R represents a bond between aromatic carbon atoms
1-18 carbon atoms senoid compound
--- 1 --- s --- S --- or a divalent hydrocarbon group with and G is the residue of a dibromo or diode bone of the formula or
<img file="SE435722B_D0006.tif" />
in
IV
V
IN
Wherein R 'represents a bond between aromatic carbon atoms,
--- O ---, --- S ---, --- 'S --- S --- or a divalent hydrocarbon group having 1-18 carbon atoms, with the proviso that when R is ----- -O--, the group R 'is other than --- O ---, when R' is --- O ---, the group
R is other than --- 0 ---, when G is a group of formula II, group G 'is a group of formula V and when G' is a group of formula IV, group G is a group of formula III. Polyarylene polyethers of this type exhibit excellent physical properties as well as excellent thermal, oxidative and chemical stability. Commercial poly (aryl polyethers) are available under the trade name. ARYLON T polyaryl ethers with a melting temperature of between 280 ° C and 310 ° C.
Another group of useful structural thermoplastics include aromatic poly (sulfones) which comprise repeating units of the formula
--------<sub>Are</sub> -------- so<sub>2</sub> ------- wherein Ar is a divalent aromatic group, which may vary from unit to unit in the polymer chain (forming copolymers of various kinds). Thermoplastic poly (sulfones) generally contain at least some units of structure
<img file="SE435722B_D0007.tif" />
sO<sub>2</sub> wherein Z is oxygen or sulfur or the residue of an aromatic diol such as 4,4'-bisphenol. An example of such a poly (sulfone) has recurring units of the formula - yy - o - - ¢ 3<sup>-3</sup>°<sup>2</sup>— <sup>;</sup> another example has recurring units of the formula
<img file="SE435722B_D0008.tif" />
7805150-5 and other examples have recurring units of the formula
<img file="SE435722B_D0009.tif" />
or copolymerized units in various proportions of the formula
S 'or
<img file="SE435722B_D0010.tif" />
/ ** · The teiwplastic poly (sulfones) may also contain recurring units of the formula
<img file="SE435722B_D0011.tif" />
Poly (ether sulfones) with repeating units of structure
<img file="SE435722B_D0012.tif" />
and poly (ether sulfones) with repeating units of structure
<img file="SE435722B_D0013.tif" />
are also useful as structural thermoplastics.
By polyamide is meant a condensation product containing recurring aromatic and / or aliphatic amide groups such as integral parts of the main polymer chain. Such products are generically known as nylons. A polyamide can be obtained by polymerization of
4IIW l | Wool..
7W5150-S is a monoaminomonocarboxylic acid or an internal lactam thereof having at least 2 carbon atoms between the amino and carboxylic acid groups or by polymerization of substantially equimolar amounts of a diamine containing at least 2 carbon atoms between the amino groups and a dicarboxylic acid or by polymerization of a mono acid or inner lactam thereof, as defined above, together with substantially equimolar amounts of a diamine and a dicarboxylic acid. The dicarboxylic acid may be used in the form of a functional derivative thereof, e.g. an ester.
The expression essentially equimolar amounts (of the diamine and r * 'of the dicarboxylic acid) is intended to cover both strictly equimolar amounts and the minor deviations therefrom found in the conventional technique for stabilizing the viscosity of the polyamides obtained.
Examples of said monoaminomonocarboxylic acids or lactams thereof are those compounds which contain from 2 to 16 carbon atoms between the amino and carboxylic acid groups, the carbon atoms forming a ring with the -CO.NH group with respect to a lactam. Specific examples of aminocarboxylic acids and lactams include 6-aminocaproic acid, butyrolactam, pivalolactam, caprolactam, caprylic lactam, enantolactam, undecanolactam, dodecanolactam and 3- and 4-aminobenzoic acid.
Examples of said diamines are diamines of the general formula H HN (CH₂) NH_ wherein n is an integer from 2 to 16 such as trimethylΔZ XI a hexamethylene diamine.
C-alkylated diamines, e.g. 2,2-dimethylpentamethylenediamine and 2,2,4- and 2,4,4-trimethylhexamethylenediamine are further examples. Other diamines, which may also be mentioned by way of example, are aromatic diamines, e.g. p-phenylenediamine, 4,4'-diaminodiphenylsulfone, 4,4'-diaminodiphenyl ether and 4,4'-diaminodiphenylsulfone, 4,4'-diaminodiphenyl ether and 4.4<sup>></sup>-diaminodiphenylmethane and cycloaliphatic diamines, e.g. diaminodicyclohexylmethane.
Said dicarboxylic acids may be aromatic, e.g. isophthalic and terephthalic acids. Preferred dicarboxylic acids are those of the formula HOOC.Y.COOH, wherein Y represents a divalent aliphatic group containing * r
And at least 2 carbon atoms, and examples of such acids are sebacic acid, octadecanedioic acid, suberic acid, azelaic acid, undecanedioic acid, glutaric acid, pimellic acid and especially adipic acid. Oxalic acid is also a preferred acid.
In particular, the following polyamides can be incorporated with the thermoplastic polymer blends of the invention:
polyhexamethylene adipamide (nylon 6: 6) polypyrrolidone (nylon 4) polycaprolactam (nylon 6) polyheptolactam (nylon 7) polycaprylic lactam (nylon 8) polynonanolactam (nylon 9) polyundecanolactam (nylon 11) polydodecanolactam (nylon 12) polyhexamethylene amide (nylon 6:10) polyhexamethylene isophthalamide (nylon 6: iP) polymethoxylylene adipamide (nylon MXD: 6) polyamide of hexamethylenediamine and n-dodecandionic acid (nylon 6:12) (Nylon 12:12).
Nylon copolymers can also be used, e.g. copolymers of the following:
hexamethylene adipamide / caprolactam (nylon 6: 6/6) hexamethylene adipamide / hexamethylene isophthalamide (nylon 6: 6 / 6ip) hexamethylene adipamide / hexamethylene terephthalamide (nylon 6: 6 / 6T) trimethylhexamethylene oxamide / hexamethylene : 2) hexamethylene adipamide / hexamethylene-azalamide (nylon 6: 6/6: 9) hexamethylenadipamide / hexamethylene-azalamide / caprolactam (nylon 6: 6/6: 9/6). '
Nylon 6: 3 is also useful. This polyamide is the product of the dimethyl ester of terephthalic acid and a mixture of isomeric trimethylhexamethylenediamine.
Preferred nylons include nylon 6.6 / 6, 11, 12, 6/3 and. 6/12.
The number average molecular weights of the polyamides can be over 10,000.
The acetal resins used in the compositions of the present invention comprise the high molecular weight polyacetal homopolymers produced by polymerization of formaldehyde or trioxane. These polyacetal homopolymers are commercially available under vaw
50-5 run name DELRIN. A related polyether resin is available under the trade name PENTON and has the structure ch<sub>2</sub>c
0 --- CH<sub>2</sub>--- C --- oh<sub>2</sub>-CH<sub>2</sub>c
-. J<sub>n</sub>
The acetal resin prepared from formaldehyde has a high molecular weight and a structure which can be illustrated as follows —H-0 --- (- CH<sub>2</sub>- ~ 0 - CH<sub>2</sub>--04 .------ H
X wherein end groups are derived from controlled amounts of water and x represents a large (usually 1500) number of interconnected formaldehyde units. In order to increase the thermal and chemical resistance, the end groups are usually converted to esters or ethers.
The term polyacetal resins also includes polyacetal copolymers. These copolymers include block copolymers of formaldehyde with monomers or prepolymers of other materials capable of providing active hydrogen atoms, such as alkylene glycols, polytiols, vinyl acetate acrylic acid copolymers or reduced butadiene / acrylonitrile polymers.
Celanese commercially provides a copolymer of formaldehyde and ethylene oxide under the trade name · CELCON, which is useful in the compositions of the present invention. These copolymers typically have a structure which includes repeating units of the formula
<img file="SE435722B_D0014.tif" />
* rw
7805150-5 wherein and R<sub>2</sub> independently of each other is hydrogen, 1-lower alkyl or lower halogen-substituted alkyl and n is a whole Lal from 0 to 3, where n is 0 in 85-99.3% of the recurring units.
Formaldehyde and trioxane can be copolymerized with other aldehydes, cyclic ethers, vinyl compounds, ketens, cyclic carbonates, epoxides, isocyanates and ethers. These compounds include ethylene oxide, 1,3-dioxolane, 1,3-dioxane, 1,3-dioxane, epichlorohydrin, propylene oxide, isobutylene oxide and styrene oxide.
Polyurethanes, also known as isocyanate resins, can -IPWU can also be used as structural thermoplastics provided that they are thermoplastics and non-thermosets. So e.g. polyurethanes formed from toluene diisocyanate (TDI) or diphenylmethane-4,4-diisocyanate (MDI) and a large number of polyols such as polyoxyethylene glycol, polyoxypropylene glycol, hydroxy terminated polyesters and polyoxyethylene oxypropylene glycols are suitable.
These thermoplastic polyurethanes are available under the trade names Q-THANE and PELLETHANE CPR.
Another group of useful structural thermoplastics includes halogenated thermoplastics having a substantially crystalline structure and a melting point exceeding 120 ° C. These halogenated thermoplastics include homopolymers and copolymers derived from tetrafluoroethylene, chlorotrifluoroethylene, bromine trifluoroethylene, vinylidene fluoride and vinylidene chloride.
Polytetrafluoroethylene (PTFE) is the term for fully fluorinated polymers of the basic chemical formula --- (- CF<sub>2</sub>---- CF<sub>2</sub>Containing 76 wt% fluorine. These polymers are highly crystalline and have a crystalline melting point above 300 ° C. Commercial PTFE is available under the trade names TEFLON and FLUON. Polychlorotrifluoroethylene (PCTFE) and polybromotrifluoroethylene (PBTFE) are also available with high molecular weights and can be used according to the present invention.
Particularly preferred halogenated polymers are homopolymers and copolymers of vinylidene fluoride. Poly (vinylidene fluoride) homopolymers are partially fluorinated polymers of the chemical formula ---- (- CH<sub>2</sub> ---- CF<sub>2</sub> ---) - ^ -. These polymers are tough linear polymers with a crystalline melting point at 170 ° C. A commercial homopolymer is available under the trade name KYNAR. As used herein, the term poly (vinylidene fluoride) refers not only to the normally solid homopolymers of vinylidene fluoride but also to the normally solid copolymers of vinylidene fluoride containing at least 50 mole% polymerized vinylidene fluoride units, preferably at least about 70 mole% vinylidene fluoride %. Suitable comonomers are halogenated olefins containing up to 4 carbon atoms, e.g. sym. dichlorodifluoroethylene, vinyl fluoride, vinyl chloride, vinylidene chloride, perfluoropropene, perfluorobutadiene, chlorotrifluoroethylene, trichlorethylene and tetrafluoroethylene.
Another useful group of halogenated thermoplastics includes homopolymers and copolymers derived from vinylidene chloride. Crystalline vinylidene chloride copolymers are particularly preferred. The normally crystalline vinylidene chloride copolymers useful in the present invention are those containing at least 70% by weight vinylidene chloride plus 30% or less of a copolymerizable monoethylenic monomer. Examples of such monomers are vinyl chloride, vinyl acetate, vinyl propionate, acrylonitrile, alkyl and aralkyl acrylates with alkyl and aralkyl groups containing up to about 8 carbon atoms, acrylic acid, acrylamide, vinyl alkyl ethers, vinyl alkyl ketones., Acrolein, allyl ethers and allyl ethers. Known ternary compositions can also be used advantageously. Examples of such polymers are those consisting of at least 70% by weight of vinylidene chloride, the remainder being e.g. acrylonin and vinyl chloride, acrylic acid and acrylo'G 'nitrile, alkyl acrylates and alkyl methacrylates, acrylonitrile and butadiene, acrylonitrile and itaconic acid, acrylonitrile and vinyl acetate, vinyl propionate or vinyl chloride, allyl esters or ether and ether and vinyl chloride, Quaternary polymers of similar monomer composition may also be used. Especially useful for sieve. The present invention is copolymers having 70-95 wt% vinyl. lithium chloride, the remainder being vinyl chloride. Such copolymers may contain conventional amounts and types of plasticizers, stabilizers, nucleators and extrusion aids. Further, mixtures of two or more of such normally crystalline vinylidene chloride polymers as well as mixtures comprising such normally crystalline polymers in combination with other polymeric modifiers, e.g. copolymers of ethylene-vinyl acetate, styrene-maleic anhydride, styrene-acrylonitrile and polyethylene.
The nitrile resins useful as structural thermoplastics are thermoplastic materials having an alpha, beta-olefinically unsaturated mononitrile content of 50% by weight or more. These nitrile resins may be homopolymers, copolymers, graft copolymers on a rubber substrate or mixtures of homopolymers and / or copolymers.
The alpha, beta-olefinically unsaturated mononitriles referred to in the present context have the structure ch a C -.
R
- CN msTso-wherein R is hydrogen, an alkyl group of 1-4 carbon atoms or a halogen. Such compounds include acrylonitrile, alpha-bromoacrylonitrile, alpha-fluoroacrylonitrile, methacrylonitrile and etacrylonitrile. The most preferred olefinically unsaturated nitriles are acrylonitrile and methacrylonitrile and mixtures thereof.
These nitrile resins can be divided into several classes based on their complexity. The simplest molecular structure is a randomly constructed copolymer, mainly acrylonitrile or methacrylonitrile. The most common example is a styrene-acrylonitrile copolymer. Segment copolymers of acrylonitrile, wherein long segments of polyacrylonitrile alternate with segments of polystyrene, or of polymethylmethacrylate are also known.
Simultaneous polymerization of more than two comonomers yields an interpolymer or, based on three components, a terpolymer. A large number of comonomers are known. These include lower alpha olefins of 2-8 carbon atoms, e.g. ethylene, propylene, isobutene, butene-1, pentene-1 and their halogenated and aliphatic substituted derivatives such as vinyl chloride, vinylidene chloride; aromatic monovinylidene hydrocarbon monomers of the general formula
<img file="SE435722B_D0015.tif" />
wherein R, is hydrogen, chlorine or methyl and R 6 is an aromatic group of 6-10 carbon atoms which may also contain substituents such as halogen and alkyl groups attached to the aromatic nucleus, e.g. styrene, alpha-methylstyrene, vinyltoluene, alpha-chlorostyrene, ortho-chlorostyrene, para-chlorostyrene, meta-chlorostyrene, ortho-methylstyrene, para-methylstyrene, ethylstyrene, isopropylstyrene, dichlorostyrene, vinyl naphthalene, etc.
Another group of comonomers are vinyl ester monomers of the general formula
H i 0 0 = 0 wherein R<sub>3</sub> is hydrogen, an alkyl group having 1-10 carbon atoms, an aryl group having
6-10 carbon atoms comprising the carbon atoms of ring-substituted alkyl substituents, e.g. vinyl formate, vinyl acetate, vinyl propionate and vinyl benzoate.
Monomers, similar to the ones mentioned and which are also useful, are vinyl ether monomers of the general formula
<img file="SE435722B_D0016.tif" />
<img file="SE435722B_D0017.tif" />
<img file="SE435722B_D0018.tif" />
wherein R<sub>4</sub> is an alkyl group of 1-8 carbon atoms, an aryl group of 6-10 carbon atoms or a monovalent aliphatic group of 2-10 carbon atoms, which aliphatic group may be hydrocarbon- or sulfur-containing, e.g. an aliphatic group with ether bonds, and which may also contain other substituents such as halogen and carbonyl. Examples of these monomeric vinyl esters include vinyl methyl ether, vinyl ethyl ether, vinyl n-butyl ether, vinyl 2-chloroethyl ether, vinyl phenyl ether, vinyl isobutyl ether, vinyl cyclohexyl ether, p-butyl cyclohexyl ether, vinyl ether and p-chlorophenyl glycol.
Other comonomers are those containing a mono- or dinitrile function. Examples of this include methylene glutaronitrile. (2,4-dicyanobutene-1), vinylidency cyanide, crotonitrile, fumarodinitrile and maleodinitrile.
Other comonomers include the esters of olefinically unsaturated carboxylic acids, preferably the lower alkyl esters of alpha, beta-olefinically unsaturated carboxylic acids and, in particular, esters of the structure
CH<sub>2</sub>= R Q is hydrogen, an alkyl group of 1-4 carbon atoms or a halogen and R R<sub>2</sub> is an alkyl group of 1-2 carbon atoms. Compounds of this type include methyl acrylate, ethyl acrylate, methyl methacrylate, ethyl methacrylate and methyl alpha-chloro acrylate. In particular, methyl acrylate, ethyl acrylate, methyl methacrylate and ethyl methacrylate are preferred.
Another class of nitrile resins are graft copolymers consisting of a polymer backbone to which branches of another polymer backbone are attached or grafted. Generally, the main chain is modeled in a separate reaction. Polyacrylonitrile can be inoculated with chains of styrene, vinyl acetate or methyl methacrylate to take some examples. The main chain may consist of one, two, three or more components, and the grafted branches may consist of one, two, three or more comonomers.
The most promising products are the nitrile copolymers which are partially grafted onto a pre-formed rubber substrate. This substrate includes the use of a synthetic or natural rubber component such as polybutadiene, isoprene, neoprene, nitrile rubbers, natural rubbers, acrylonitrile-butadiene copolymers, ethylene-propylene copolymers and chlorinated rubbers used to strengthen the polymer. This rubber component can be incorporated with the nitrile-containing polymer by any of the methods well known in the art, e.g. direct polymerization of monomers, grafting of the acrylonitrile monomer mixture on the rubber backbone, or physical mixing of the rubber component. Particularly preferred are polymer blends which have been obtained by mixing a graft copolymer of acrylonitrile and comonomer on the rubber backbone with another copolymer of acrylonitrile and the same comonomer. Acrylonitrile-based thermoplastics are usually polymer blends of a grafted polymer and a grafted homopolymer.
Commercial examples of nitrile resins include BAREX 210 resin, an acrylonitrile-based nitrile resin containing over 65% nitrile, and LOPAC resin containing over 70% nitrile, three quarters derived from methacrylonitrile.
In order to denote the viscosity properties of the structural thermoplastic, polycarbonate and block copolymer, it is sometimes useful to first mix the various structural thermoplastics with a viscosity modifier before mixing the resulting mixture with the polycarbonate and block copolymer. Suitable viscosity modifiers have a relatively high viscosity, a melting temperature of over 230 ° C and exhibit a viscosity which is not particularly sensitive to temperature changes. Examples of suitable viscosity modifiers include poly (2,6-dimethyl-1,4-phenylene) oxide and mixtures of poly (2,6-dimethyl-1,4-phenylene) oxide with polystyrene.
The poly (phenylene oxides) included as possible viscosity modifiers can be illustrated by the following formula
<img file="SE435722B_D0019.tif" />
wherein R 2 is a monovalent substituent consisting of hydrogen, a hydrocarbon group containing no tertiary alpha carbon atom, a halogenated hydrocarbon group having at least two carbon atoms between the halogen atom and the phenolic nucleus and containing no tertiary alpha carbon atom, a hydrocarbon oxy group containing no aliphatic, tertiary alpha carbon atoms, or a halogenohydrocarbonoxy group containing at least two carbon atoms between the halogen atom and the phenolic nucleus and containing no aliphatic, t is the same meaning as R 2 and may additionally denote a halogen atom and m is an integer of at least 50, e.g. 50-800 and preferably 150-300. Among the preferred polymers are polymers having a molecular weight of from 6,000 to 100,000, preferably 40,000. Preferably, poly (phenylene oxide) is poly (2,6-dimethyl-1,4-phenylene) oxide.
Commercially, poly (phenylene oxide) is available as a blend with styrene resin. These blends usually comprise between 25 and 50% by weight polystyrene units and are provided under the trade name NORYL thermoplastic. When using a mixture of poly (phenylene oxide) and polystyrene, the preferred molecular weight is between 10,000 and 50,000, preferably around 30,000.
The amount of viscosity modifier used is mainly due to the differences between the viscosities of the block copolymer and the construction thermoplastic at the temperature Tp. Typical amounts are from 0-100 parts by weight of viscosity modifier per 100 parts by weight of structural thermoplastic, preferably 10-50 parts by weight per 100 parts by weight of structural thermoplastic.
There are at least two methods (besides the absence of a delamination) by which the presence of a interconnecting network can be shown.
In one method, an interconnecting network is shown when molded or extruded articles made from the blends of the present invention are introduced into a refluxing solvent.
7805150-5 which quantitatively triggers the block copolymer and other soluble components, while the remaining polymer structure (comprising the structural thermoplastic and polycarbonate) still has the shape and continuity of the molded or extruded article and is structurally intact without crumbing or delamination, and the refluxing solvent does not contain insoluble particulate material. If these criteria are met, the unextracted and extracted phases are both interconnected and continuous. The unextracted phase must be continuous as it is geometrically and mechanically intact. The extracted phase must have been continuous prior to extraction, since quantitative extraction of a dispersed phase from an insoluble matrix is unlikely. Finally, interconnecting networks must be present in order to have two simultaneous continuous phases. The continuity of the unextracted phase can also be confirmed by microscopic examination. In the present mixtures containing more than two components, the interconnecting nature and continuity of each separate phase can be determined by selective extraction.
In the second method, a mechanical property, such as tensile modulus, is measured and compared with that expected in a given system where each continuous, isotropically distributed phase contributes to the mechanical response, which contribution is proportional to the volume volume of the mixture, consistent with the two values indicate the presence of a interconnecting network, whereas, if a interconnecting network is not present, the measured value differs from the calculated value.
An important aspect of the present invention is that the relative proportions of the various polymers in the mixture can be varied within wide limits. The relative proportions of the polymers are given below in parts by weight (the total mixture comprises 100 parts by weight):
Different construction thermoplastics
block copolymer
Quantity (parts by weight)
5-48
4-40
Preferred amount (parts by weight)
- 35
8-20
7805150-5
The polycarbonate is present in an amount which is greater than the amount of the different structural thermoplastics, ie. the weight ratio of polycarbonate to different structural thermoplastics is greater than 1: 1. Accordingly, the amount of polycarbonate can vary from 30 parts by weight to 91 parts by weight, preferably from 48 parts by weight to 70 parts by weight. It should be noted that the minimum amount of block copolymer necessary to prepare these mixtures may vary depending on the construction thermoplastic used.
The various structural thermoplastics, polycarbonates and block copolymers can be blended in any way that creates the interconnecting network. The construction thermoplastic, polycarbonate and block copolymer can be e.g. is dissolved in a solvent common to all components and coagulated by mixing in a solvent in which neither polymer is soluble. However, a particularly preferred method is to intimately mix the polymers in the form of granules and / or powders in a high shear mixer. By intimate mixing is meant that the polymers are mixed under sufficient mechanical shear and thermal energy to ensure that interconnection of the various networks is achieved. Intimate mixing is usually achieved by using high shear extruders and thermoplastic extruders with an L / D ratio of at least 20: 1 and a compression ratio of 3 or 4: 1.
The mixing or process temperature (Tp) is selected with respect to the polymers to be blended. When mixing the polymers in melt instead of mixing them in solution, it is e.g. necessary to select a process temperature above the melting point of the most highly melting polymer. In addition, as explained in more detail below, the process temperature can be selected so as to obtain an isoviscous mixture of the polymers. The mixing or process temperature may be between 150 ° C and 400 ° C, preferably between 230 ° C and 300 ° C.
Another parameter osm is important when mixing in the melt to provide the formation of interconnecting networks is to harmonize the viscosity of the block copolymer, polycarbonate and the various
7WS1W-5 construction thermoplastic (isoviscous mixture) at the mixing process temperature and shear stress. The better the dispersion of the structural thermoplastic and polycarbonate in the block copolymer network, the greater the prospects of forming co-continuous, interconnecting networks upon subsequent cooling. Therefore, it has been found that when the block copolymer has a viscosity Y1 pois at the temperature Tp and a shear rate of 100 s *, it is preferred that the construction thermoplastic and / or polycarbonate have such a viscosity at the temperature Tp and a shear rate of 100 s.<sup>1</sup> that the ratio of the viscosity of the block copolymer to the viscosity of the structural thermoplastic and / or polycarbonate is between 0.2 and 4.0, preferably between 0.8 and 1.2. Accordingly, in the present context, by isoviscous blending, it is meant that the viscosity of the block copolymer divided by the viscosity of the other polymers or polymer blend at the temperature Tp and a shear rate of 100 sec is between 0.2 and 4.0. It should also be noted that in an extruder there is a wide distribution of shear rates. Isoviscous mixing can therefore occur even if the viscosity curves of the two polymers differ at some of the shear rates. In some cases, the order in which the polymers are mixed is of critical importance. Accordingly, one may choose to mix the block copolymer with the polycarbonate or other polymer first and then mix the resulting mixture with the various structural thermoplastics, or simply mix all polymers at once. There are many variations in the blending order that can be utilized, resulting in the multi-component blends of the present invention. It is also obvious that the blending scheme can be utilized to better harmonize the relative viscosities of the various polymers.
The block copolymer or block copolymer mixture can be selected to be substantially adapted to the viscosity of the structural thermoplastic and / or polycarbonate. Optionally, the block copolymer may be blended with a rubber compound oil or additional resin, as described further below, in order to alter the viscosity properties of the block copolymer.
The special physical properties of the block copolymers are important for the formation of continuous, interconnecting networks. Specifically, the most preferred segment polymers in the admixed state do not normally melt with increasing temperature, since the viscosity of these polymers is extremely non-Newtonian and tends to increase without limitation as a shear stress of 0 approaches. Furthermore, the viscosity of these block copolymers is relatively temperature insensitive. This rheological behavior and inherent thermal stability of the block copolymer enhance its ability to maintain its network structure in the melt, so that interconnected and continuous networks are formed as the various mixtures are prepared.
The viscosity behavior of the structural thermoplastics and polycarbonates, on the other hand, is more temperature sensitive than the viscosity behavior of the block copolymers. Accordingly, it is often possible to select a process temperature Tp at which the block copolymer and the various structural thermoplastics and / or polycarbonate viscosities fall within the range required to form interconnecting networks. As described above, optionally a viscosity modifier may first be mixed with the structural thermoplastic or polycarbonate to achieve the required viscosity harmonization.
The mixture of partially hydrogenated block copolymer, polycarbonate and various structural thermoplastics can be compounded with an extender oil of the type commonly used in rubber and plastics processing. Particularly preferred are the types of oil which are compatible with the elastomeric polymer segments in the block copolymer. Although oils with higher aromatic content are satisfactory, especially the petroleum-based white oils which have low volatility and less than 50% aromatic content, measured by the clay gel method (ASTM method D 2007), are particularly preferred. These oils preferably have an initial boiling point above 260 ° C.
The amount of oil used can vary from 0 to 100 parts by weight per 100 parts by weight of block copolymer, preferably from 5 to 30 parts by weight per 100 parts by weight of block copolymer.
The mixture of partially hydrogenated block copolymer, polycarbonate and various structural thermoplastics can be further compounded with a resin. The additional resin may be a flow promoting resin, such as an alpha-methyl styrene resin, and an end segment plasticization resin. Suitable end segment plasticization resins include
Zemw-B coumarone indene resins, vinyltoluene-alpha-methylstyrene copolymers, polyindene resins and low molecular weight polystyrene resins.
The amount of the additional resin may vary from 0 to 100 parts by weight per 100 parts by weight of block copolymer, preferably from 5 to 25 parts by weight per 100 parts by weight of block copolymer.
Further, the composition may contain other polymers, fillers, reinforcing agents, antioxidants, stabilizers, fire protection agents, anti-blocking agents and other rubber and plastic compounding ingredients.
Examples of fillers that can be used are in the 1971-1972 Modern Plastics Encyclopedia, p. 240-247.
Reinforcing agents are also useful in the present polymer blends. A reinforcing agent may be defined as a material added to a resinous matrix in order to improve the strength of the polymer. Most of these reinforcing materials are inorganic or organic high molecular weight products. Examples of reinforcing agents are glass fibers, asbestos, boron fibers, carbon and graphite fibers whiskers, quartz and silica fibers, ceramic fibers, metal fibers, natural organic fibers and synthetic organic fibers. Particularly preferred are reinforced polymer blends containing 2-80 wt% glass fiber, based on the total weight of the resulting blended blend.
The polymer blends of the invention can be used as metal substitutes and in those areas where high performance is sought.
The invention is further illustrated by the following embodiments, wherein the temperature indications refer to degrees Celsius.
In the exemplary and comparative examples below, various polymer blends were prepared by blending the polymers into a 3.125 cm Sterling extruder with a Kenics nozzle The extruder had a L / D ratio of 24: 1 and a compression screw ratio of 3.8: 1.
The various materials used in the blends were as follows:
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7806180-5
1) Segment copolymer - a selectively hydrogenated block copolymer of the invention having the structure S-EB-S.
2) Oil - TUFFLO 6056 rubber extension oil.
3) Nylon 6 - PLASKON 8207 polyamide.
4) Nylon 6-12 - ZYTEL 158 polyamide.
5) Polypropylene - a substantially isotactic polypropylene having a melt flow index of 5 (230 ° C / 2.16 kg).
6) Poly (butene terephthalate) (PBT) - VALOX 310 resin.
7) Polycarbonate - MERLON
M-40 polycarbonate.
8) Poly (ether sulfone) - 200P.
9) Polyurethane - PELLETHANE CPR.
10) Polyacetal - DELRIN 500.
11) Poly (acrylonitrile co-styrene) - BAREX 210.
12) Fluoropolymer - TEFZEL 200 poly (vinylidene fluoride) copolymer.
In all mixtures containing an oil component, the block copolymer was mixed and the oil in advance before the other polymers were added.
Example 1
Various polymer blends were prepared according to the invention. A mixture of two block copolymers with higher and lower molecular weights was used in certain polymer blends in order to better harmonize the viscosity with the polycarbonate and / or other different structural thermoplastics. In some mixtures, an oil was mixed with the block copolymer in order to better harmonize the viscosity. Comparative mixtures were also prepared which did not contain any segment copolymer, but these mixtures were not easy to mix. For example, blend 110 containing polycarbonate and Nylon 6 exhibited melt fracture and extreme spray irregularities in mold swelling. In contrast, any polymer blend containing a block copolymer was easy to blend and the extrudate was homogeneous in appearance. Furthermore, the resulting poly mixture containing one. block copolymer the desired continuous interconnecting networks, which could be determined by the above criteria.
The compositions of the compositions and the experimental results are presented in Tables 1 and 2 below. The compositions are expressed in% by weight.
in CM
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7808150-5
The test results for the above mixtures indicate unexpected properties of the present mixtures. For example, Comparing Blend 109 with Blends 91 and 92, it can be seen that at a polycarbonate to PBT ratio of 3: 1 the heat distortion temperature does not decrease, as would be expected, as the amount of segment component increases from 0-15-30%. In fact, the heat distortion temperature is higher for blends containing the block copolymer than in blend 109 containing no block copolymer. Normally, when adding an amorphous rubber to a thermoplastic, a significant reduction in the heat dissipation temperature expectation would be expected, since the heat dissipation temperature of the rubber is very low.
It is also important to note that with increasing amounts of block copolymer the Izod impact strength increases significantly while the heat distortion temperature is not significantly affected. This is illustrated drastically by comparing the ratio of the percentage increase in impact strength to the percentage change in heat distortion temperature '. For example, Examine the relationship between the relative increase in Izod impact strength (at 23 ° C) and the relative decrease in heat distortion temperature for polymer blends as the percentage of block copolymer is increased from 0-15% at a given ratio of different polycarbonate to 3: 1 structural thermoplastics. note that you get much larger values than you would expect. The skilled person would normally expect. say that this value is positive and less than 1. However, for mixtures containing Nylon 6, a fluorinated copolymer, a polyacetal and poly (butene terephthalate), the ratios are -142, -23, 28, respectively. -37. The negative values are particularly outstanding, as they represent an increase in the heat distortion temperature as the content of the block copolymer increases.
Example 2
Various additional mixtures were prepared in a manner similar to Example 1. The various mixtures are presented in Table 3 below. In all cases, the poly mixtures containing a block copolymer exhibited the desired interconnecting network structure.
7805150-5
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WWW
WMwwhwwi <rrw ~ 7805T50-5
Contents23
49 sheets
Sheet 1 Sheet 2 Sheet 3 Sheet 4 Sheet 5 Sheet 6 Sheet 7 Sheet 8 Sheet 9 Sheet 10 Sheet 11 Sheet 12 Sheet 13 Sheet 14 Sheet 15 Sheet 16 Sheet 17 Sheet 18 Sheet 19 Sheet 20 Sheet 21 Sheet 22 Sheet 23 Sheet 24 Sheet 25 Sheet 26 Sheet 27 Sheet 28 Sheet 29 Sheet 30 Sheet 31 Sheet 32 Sheet 33 Sheet 34 Sheet 35 Sheet 36 Sheet 37 Sheet 38 Sheet 39 Sheet 40 Sheet 41 Sheet 42 Sheet 43 Sheet 44 Sheet 45 Sheet 46 Sheet 47 Sheet 48 Sheet 49
134 members in 14 offices
Priority claims4
| Document | Office | Kind | Date |
|---|---|---|---|
| 79419877 | United States of America | A | |
| 79419877 | United States of America | A | |
| 794198 | – | – | – |
| US19770794198 | – | – | – |
Members134
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2 legal events, as the office reported them to INPADOC
Over the term
Point at a mark for the eventEvents
| Event | Code | |
|---|---|---|
| Patent has lapsedLapsedNUG | NUG | |
| Patent in forceNAL | NAL |
Numbers
- Publication, DOCDB
- 435722
- Publication, EPODOC
- SE435722
- Application
- 7805150
- Application, DOCDB
- 7805150
- Application, EPODOC
- SE19780005150
Titles2
- Swedish
- KOMPOSITION AV EN PARTIELLT HYDRERAD SEGMENTSAMPOLYMER, ETT POLYKARBONAT OCH YTTERLIGARE EN TERMOPLASTISK POLYMER, SAMT FRAMSTELLNING HERAV
- English
- COMPOSITION OF A PARTIAL HYDRATED SEGMENT COPOLYMER, A POLYCAR CARBONATE AND ADDITIONALLY A THERMOPLASTIC POLYMER, AND PREPARATION OF IT
Classification
- CPC, 3
- C08L53/025
- C08L69/00
- C08L101/00
- IPC, 15
- C08L1 00
- C08L53 00
- C08L7 00
- C08L21 00
- C08L23 00
- C08L27 00
- C08L33 00
- C08L33 02
- C08L51 00
- C08L51 02
- C08L53 02
- C08L67 00
- C08L69 00
- C08L77 00
- C08L101 00
