Impact-resistant, thermoplastic mixture of elastomers and thermoplastic materials
7 claims: 5 independent, 2 dependent
- 1Polymermischungen, enthaltend P1) 0.1-99.9 Gew. % eines kautschukelastischen Blockcopolymerisates aus 35 bis 85 Gew.-% an vinylaromatischen Monomer und 15 bis 65 Gew.-% Dien, wobei P1 α mindestens zwei Blöcke S, die einpolymerisierte Einheiten eines vinylaromatischen Monomeren und eine Glastemperatur über 25°C aufweisen und β mindestens einen, zwischen den blocken S befindlichen, elastomeren Block B/S, der sowohl einpolymerisierten Einheiten eines vinylaromatischen Monomeren (S) als auch eines Diens (B) enthält, mit statistischem Aufbau und einer Glastemperatur Tg von -50 bis +25°C, enthält, und wobei die im Festkörper aus den Blöcken S gebildete Hartphase 1 - 40 Vol.-%, und die aus den Blöcken B/S gebildete Weichphase 60 - 99 Vol.-% betragen, P2) 0.1 - 99.9 Gew.-% mindestens eines thermoplastisch verarbeitbaren oder duroplastischen Polymeren oder deren Mischungen und P3) 0 - 70 Gew.-% weiterer Zusatzstoffe und Verarbeitungshilfsmittel, wobei die Gewichtsprozente der Komponenten P1) bis P3) zusammen 100 % ergeben.
- 2Polymermischungen nach Anspruch 1, enthaltend:P1) 1 - 99 Gew.-% kautschukelastischen Blockcopolymerisats P1, P2) 1 - 99 Gew.-% eines thermoplastische verarbeitbaren Polymeren P2.
- 3Polymermischungen nach Anspruch 1 oder 2, in denen die T g der Hartphnase S des Blockcopolymerisats P1 über 50°C und T g der Weichphase B/S im Bereich von -50 bis +5°C liegt.
- 4Polymermischungen nach den Ansprüchen 1 bis 3, in denen das vinylaromatische Monomere des Blockcopolymerisats P1 ausgewählt ist aus Styrol, alpha-Methylstyrol, Vinyltoluol oder Diphenylethylen oder deren Mischungen und das Dien aus Butadien oder Isopren oder deren Mischungen ausgewählt ist.
- 5Polymermischungen nach den Ansprüchen 1 bis 4, in denen das Blockcopolymerisat nach den allgemeinen Formel (1) bis (11) aufgebaut ist (1) (S-B/S) n ;(2) (S-B/S) n -S;(3) B/S-(S-B/S) n ;(4) X-[(S-B/S) n ] m +1;(5) X-[(B/S-S) n ] m +1;(6) X-[(S-B/S) n -S] m +1;(7) X-[(B/S-S) n -B/S] m +1;(8) Y-[(S-B/S) n ] m +1;(9) Y-[(B/S-S) n ] m +1;(10) Y-[(S-B/S) n -S] m +1;(11) Y-[(B/S-S) n -B/S] m +1;wobei S einen vinylaromatischen Block, B/S einen statistischen Block aus Dien- und vinylaromatischen Einheiten, X den Rest eines n-funktionellen Initiators, Y den Rest eines m-funktionellen Kopplungsmittels und m,n natürliche Zahlen von 1 bis 10 bedeuten, mit der Maßgabe, daß in den Formeln (1), (3), (4) und (8) n mindestens 2 ist.
- 6Polymermischungen nach den Ansprüchen 1 bis 5, enthaltend ein Blockcopolymerisat der allgemeinen Formel S-B/S-S, X-[-B/ S-S] 2 oder Y-[-B/S-S] 2 .
- 7Polymermischungen nach den Ansprüchen 1 bis 6, enthaltend ein Blockcopolymerisat, dessen Weichphase unterteilt ist in Blöcke (12) (B/S) 1 [(B/S) 2 , (13) (B/S) 1 [(B/S) 2 [(B/S) 1 oder (14) (B/S) 1 [(B/S) 2 [(B/S) 3 , wobei die Indices 1,2,3 für unterschiedliche Strukturen in dem Sinne stehen, daß das Vinylaromat/Dien-Verhältnis in den einzelnen Blöcken B/S unterschiedlich ist oder sich innerhalb eines Blocks in den Grenzen (B/S) 1 (B/S) 2 kontinuierlich ändert, wobei die Glasübergangstemperatur T g jedes Teilblocks unter 25°C liegt.
Independent claims7
172 paragraphs, as filed
The invention relates to polymer mixtures containing<ul id="ul0001" list-style="none"><li>P1) 0.1-99.9% by weight of a rubber-elastic block copolymer composed of 35 to 85% by weight of vinylaromatic monomer and 15 to 65% by weight of diene, P1<ul id="ul0002" list-style="none"><li>α at least two blocks S, which have polymerized units of a vinyl aromatic monomer and a glass transition temperature above 25 ° C and</li><li>β at least one, located between the blocks S, elastomeric block B / S, which contains both polymerized units of a vinyl aromatic monomer (S) and a diene (B), with a statistical structure and a glass transition temperature Tg of -50 to + 25 ° C. ,</li></ul> contains, and wherein the hard phase formed from blocks S in the solid body is 1-40% by volume, and the soft phase formed from blocks B / S is 60-99% by volume,</li><li>P2) 0.1-99.9% by weight of at least one thermoplastically processable or thermosetting polymer or mixtures thereof and</li><li>P3) 0 to 70% by weight of further additives and processing aids, the weight percentages of components P1) to P3) together giving 100%.</li></ul>
The invention further relates to the use of the polymer mixtures according to the invention for the production of moldings of any kind and the moldings obtainable here.
Polymers, in particular thermoplastics, which contain rubber-elastic polymers have been known for a long time. In particular, block copolymers of vinyl aromatic polymers (eg styrene) and dienes (eg butadiene) are used here as so-called impact modifiers, it being possible for the diene portion of the block copolymer to be partially or completely hydrogenated.
Such impact modifiers for polyphenylene ether / polyamide blends are known, inter alia, from EP-A 234 063. From EP-A 236 593, PPE / PA blends are known which contain several impact modifiers, with either the polyamide or the PPE phase being impact modified.
Hydrogenated two-block rubbers made of polystyrene and hydrogenated polyisoprene blocks are known from WO 87/5311.
From DE-A 41 29 499 AB-A'-B 'block copolymers are known as impact modifiers.
Similar blends with other thermoplastics such as polyamide or polyester etc. are well known, with changes in the block copolymer of the blend essentially increasing the impact strength of the polymer blends. An increase in impact strength is also possible within certain limits by increasing the amount of impact modifier in the mixture, but other mechanical properties such as rigidity and strength are reduced.
Another disadvantage of the impact-modified polymer mixtures known hitherto is excessive shrinkage when processed to give shaped articles, ie the dimensions of the molded part change to an unreproducible extent after cooling.
In the more recent DE-A 44 20 952, novel block copolymers are proposed which exhibit rubber-elastic behavior and have maximum toughness with a low diene content. These are easy to manufacture on an industrial scale and, like thermoplastics, are easy to process on extruders, for example.
It was therefore an object of the present invention to provide impact-modified polymer mixtures which have improved mechanical properties such as better toughness, in particular while maintaining rigidity and strength.
When processing polymer mixtures of this type, the shrinkage of the moldings in particular is to be improved. At the same time, other essential properties such as the flowability of the melt or the heat resistance should be maintained or improved.
According to the invention, this object is achieved by the polymer mixtures defined at the outset.
Preferred embodiments can be found in the subclaims.
As component P1), the polymer mixtures according to the invention contain 0.1 to 99, preferably 1 to 99% by weight of a rubber-elastic block copolymer P1<ul id="ul0003" list-style="none"><li>P1) 0.1-99.9% by weight of a rubber-elastic block copolymer composed of 35 to 85% by weight of vinyl aromatic monomer and 15 to 65% by weight of diene, P1<ul id="ul0004" list-style="none"><li>α at least two blocks S, which have polymerized units of a vinyl aromatic monomer and a glass transition temperature above 25 ° C and</li><li>β at least one, located between the blocks S, elastomeric block B / S, which contains both polymerized units of a vinyl aromatic monomer (S) and a diene (B), with a statistical structure and a glass transition temperature Tg of -50 to + 25 ° C. ,</li></ul> contains, and the hard phase formed in the solid from blocks S is 1-40 vol.%, and the soft phase formed from blocks B / S is 60-99 vol.%.</li></ul>
In polymer mixtures according to the invention which contain thermoplastics as component P2), block copolymers P1 are preferably used as impact modifiers, the proportion of which can be up to 40% by weight, preferably up to 20% by weight, based on P1) to P3).
Depending on the application, however, any mixing ratios with component P2 are possible.
Block copolymers of vinyl aromatics (for example styrene) and dienes (for example butadiene) are copolymers of several polymer molecule regions (so-called blocks) which are lined up or linked in another form and which are more or less uniformly constructed. Depending on the structure and content of diene monomers, they can have a total of elastomeric, ie rubber-elastic properties or stiff, non-rubber-elastic properties, ie at a certain temperature to the outside, they behave either rubber-elastic, similar to a polydiene and are important, for example, as so-called SB rubber, or like transparent, impact-resistant styrene polymers. It is customary, based on the designations for impact-modified polystyrene, to designate those parts of the molecule which determine the rubber-elastic behavior as the soft phase and the rigid parts of the molecule (the pure polystyrene part) as the hard phase. SB rubber cannot be processed like thermoplastics, but has to be vulcanized for use like ordinary diene polymers, which severely limits their use.
The so-called Anionic polymerization leading to living polymers, in which the growth of a chain molecule takes place at one end of the chain, which theoretically lives as long as possible due to the lack of a spontaneous chain termination or transfer reaction (remains capable of polymerization), and offers the reaction of the living polymer with mono- or polyfunctional reaction partners as is well known, a versatile possibility for building block copolymers, although the choice of monomers is limited; in practice, only block copolymers of vinyl aromatic compounds, ie styrene and its descendants on the one hand and dienes, essentially butadiene or isoprene on the other, have gained importance. Block copolymers are obtained by polymerizing in each case to approximately the exhaustion of a monomer supply and then changing the monomer or monomers. This process can be repeated several times.
Linear block copolymers are described, for example, in U.S. Patents 3,507,934 and 4,122,134. Star-shaped block copolymers are known, for example, from US Pat. Nos. 4,086,298; 4,167,545 and 3,639,517.
The property profile of these block copolymers is essentially shaped by the content of polymerized diene monomers, ie length, arrangement and quantitative ratio of polydiene and polystyrene blocks. In addition, the type of transition between different blocks plays an important role: sharp and so-called tapered transitions are known, depending on whether the monomer change takes place abruptly or gradually. In the latter case, a more or less statistical sequence length distribution occurs.
Block copolymers with sharply separated blocks are less viscous than those with a smeared block transition with identical molecular weight and diene content. If one wishes to obtain tougher block copolymers, block transitions with statistical sequence length distribution of diene and vinyl aromatics in the transition region will therefore be preferred (cf. US Pat. No. 4,122,134 and EP-A-0 316 671).
Morphological investigations of block copolymers show that the smeared block transition means that the sequence length of the pure diene phase is shifted compared to the polystyrene phase and thus the volume ratio in favor of the diene phase. The type of block transition can therefore increase the toughness of a polymer without the diene content having to be increased. This can be advantageous since the flowability of the melt and the thermostability of the polymers decrease with increasing diene content and the risk of crosslinking of the diene phase increases. In injection molding and extrusion processing, cross-linking is noticeable through so-called specks and cloudiness in the polymer.
The achievement of smeared block transitions by controlled change of the monomer addition is now technically complex and leads to a longer reaction time or a lower space-time yield, which increases the production costs. In the limit, the continuously controlled addition (cf. US Pat. Nos. 4,346,198 and 4,248,984) the reaction time increases extremely because of the unfavorable position of the copolymerization parameters of vinylaromatics and dienes and only polymers with inhomogeneous distribution of the diene and vinylaromatic units in the region of the block transition are obtained, which is how an increase in the number of transitions affects. This is made clear by a low glass temperature (T<sub>G</sub> below -50 ° C, cf. U.S. Patent 4,346,198, Example 1) and poor processing properties.
Especially materials with a diene content of over 35% by weight, which due to their property profile (toughness, transparency, gas permeability) would be suitable for medical applications such as infusion tubes, infusion drip chambers and stretch films, are very difficult to process by profile extrusion, injection molding or tubular film extrusion; despite stabilization with antioxidants and free radical scavengers, they are thermally very sensitive and tend to stickiness, so that additives have to be used with great effort. The so-called blocking (gluing of films and tubes on the roll) and poor demouldability can make processing by injection molding completely impossible.
The block copolymers P1 are distinguished by the fact that in a vinylaromatic-diene block copolymer consisting of blocks which form a hard phase (block type S) and those which form a soft phase, instead of a pure polydiene block as a soft phase, a block B / S composed of diene and vinyl aromatic units can occur, which has a statistical structure. The statistical average along the chain can be homogeneous or inhomogeneous.
Such a rubber-elastic block copolymer according to the invention is obtained by forming the soft phase from a statistical copolymer of a vinylaromatic with a diene within the scope of the above parameters; statistical copolymers of vinyl aromatics and dienes are obtained by polymerization in the presence of a polar cosolvent.
A block copolymer according to the invention can be represented, for example, by one of the general formulas 1 to 11: (1) (SB / S)<sub>n</sub>; (2) (SB / S)<sub>n</sub>-S; (3) B / S- (SB / S)<sub>n</sub>; (4) X - [(SB / S)<sub>n</sub>]<sub>m</sub>+1; (5) X - [(B / SS)<sub>n</sub>]<sub>m</sub>+1; (6) X - [(SB / S)<sub>n</sub>-S]<sub>m</sub>+1; (7) X - [(B / SS)<sub>n</sub>-B / S]<sub>m</sub>+1; (8) Y - [(SB / S)<sub>n</sub>]<sub>m</sub>+1; (9) Y - [(B / SS)<sub>n</sub>]<sub>m</sub>+1; (10) Y - [(SB / S)<sub>n</sub>-S]<sub>m</sub>+1; (11) Y - [(B / SS)<sub>n</sub>-B / S]<sub>m</sub>+1; in which<dl id="dl0001" compact="compact"><dt>S</dt><dd>for one vinyl aromatic block,</dd><dt>B / S</dt><dd>stands for the soft phase from a block statistically composed of diene and vinyl aromatic units,</dd><dt>X</dt><dd>the rest of an n-functional initiator,</dd><dt>Y</dt><dd>the rest of an m-functional coupling agent and</dd><dt>m, n</dt><dd>natural numbers from 1 to 10 mean.</dd></dl>
A block copolymer of one of the general formulas SB / SS, X - [- B / SS] is preferred<sub>2</sub> and Y - [- B / SS]<sub>2</sub> (Meaning of the abbreviations as above) and particularly preferably a block copolymer whose soft phase is divided into blocks (12) (B / S)<sub>1</sub>- (B / S)<sub>2</sub>; (13) (B / S)<sub>1</sub>- (B / S)<sub>2</sub>- (B / S)<sub>1</sub>; (14) (B / S)<sub>1</sub>- (B / S)<sub>2</sub>- (B / S)<sub>3</sub>; the indices 1, 2, 3 stand for different structures in the sense that the vinylaromatic / diene ratio in the individual blocks B / SA is different or within a block within the limits (B / S)<sub>1</sub>(B / S)<sub>2</sub> changes continuously, the glass transition temperature T<sub>G</sub> each sub-block is below 25 ° C.
A block copolymer which has several blocks B / S and / or S with different molecular weights per molecule is also preferred.
Preferred vinyl aromatic compound for the purposes of the invention is styrene and also α-methylstyrene and vinyltoluene or diphenylethylene and mixtures of these compounds. Preferred dienes are butadiene and isoprene, also piperylene, 1-phenylbutadiene and mixtures of these compounds.
A particularly preferred combination of monomers is butadiene and styrene. All of the weight and volume information below relates to this combination; when using the technical equivalents of styrene and butadiene, you may have to convert the information accordingly.
75-30% by weight of styrene and 25-70% by weight of butadiene are preferably used. A soft block particularly preferably has a butadiene content between 35 and 70% and a styrene content between 65 and 30%.
The proportion by weight of diene in the entire block copolymer is 15-65% by weight in the case of the styrene / butadiene monomer combination, and correspondingly that of the vinylaromatic component is 85-35% by weight. Butadiene-styrene block copolymers with a monomer composition of 25-60% by weight of diene and 75-40% by weight of vinyl aromatic compound are particularly preferred.
The block copolymers P1) can be obtained by anionic polymerization in a non-polar solvent with the addition of a polar cosolvent. There is an idea that the cosolvent acts as a Lewis base compared to the metal cation. Aliphatic hydrocarbons such as cyclohexane or methylcyclohexane are preferably used as solvents. Polar aprotic compounds such as ethers and tertiary amines are preferred as Lewis bases. Examples of particularly effective ethers are tetrahydrofuran and aliphatic polyethers such as diethylene glycol dimethyl ether. As tert. Amines include tributylamine and pyridine. The polar cosolvent is added to the non-polar solvent in a small amount, for example from 0.5 to 5% by volume. Tetrahydrofuran is particularly preferred in an amount of 0.1-0.3% by volume. Experience has shown that an amount of about 0.2% by volume is sufficient in most cases.
The copolymerization parameters and the proportion of 1,2 or 1,4 linkages of the diene units are determined by the dosage and structure of the Lewis base. The polymers according to the invention have, for example, a proportion of 15-40% of 1,2-linkages and 85-60% of 1,4-linkages based on all diene units.
The anionic polymerization is initiated using organometallic compounds. Compounds of alkali metals, especially lithium, are preferred. Examples of initiators are methyl lithium, ethyl lithium, propyllithium, n-butyllithium, sec.
Butyllithium and tert. Butyllithium. The organometallic compound is added as a solution in a chemically inert (inert) hydrocarbon. The dosage depends on the desired molecular weight of the polymer, but is generally in the range from 0.002 to 5 mol%, if it is based on the monomers.
The polymerization temperature can be between 0 and 130 ° C. The temperature range between 30 and 100 ° C. is preferred.
The volume fraction of the soft phase in the solid is of decisive importance for the mechanical properties. According to the invention, the volume fraction of the soft phase built up from diene and vinyl aromatic sequences is 60-99, preferably 70-90 and particularly preferably 80-90% by volume. The blocks A formed from the vinyl aromatic monomers form the hard phase, the volume fraction of which corresponds to 1-40, preferably 10-30 and particularly preferably 10-20% by volume.
It should be pointed out that there is no strict correspondence between the above-mentioned quantitative ratios of vinylaromatic compound and diene, the limit values of the phase volumes and the composition given above, which result from the ranges of the glass temperature according to the invention, since they are in full tens rounded numerical values. Rather, this could only happen accidentally.
The volume fraction of the two phases can be measured by means of contrasted electron microscopy or solid-state NMR spectroscopy. The proportion of the vinyl aromatic blocks can be determined by osmium breakdown of the polydiene fraction by precipitation and weighing. The future phase ratio of a polymer can also be calculated from the amounts of monomer used if it is allowed to polymerize completely each time.
In the sense of the invention, the block copolymer is clearly defined by the quotient of the volume fraction in percent of the soft phase formed from the B / S blocks and the fraction of diene units in the soft phase, which for the combination styrene / butadiene between 25 and 70 wt.% lies.
Due to the static incorporation of the vinyl aromatic compounds into the soft block of the block copolymer and the use of Lewis bases during the polymerization, the glass transition temperature (T.<sub>G</sub>) influenced. The glass transition temperature of the soft block is preferably -50 to + 25 ° C, preferably -50 to + 5 ° C.
The glass transition temperature of the hard phase S of the block copolymer P1 is above + 25 ° C, preferably above + 50 ° C.
The molecular weight of the block S is preferably 1000 to 200,000, particularly preferably 3,000 and 80,000 [g / mol]. S blocks can have different molecular weights within one molecule.
The molecular weight of the block B / S is usually from 2,000 to 250,000 [g / mol]; values of 5,000 to 150,000 [g / mol] are preferred.
Block B / S, like block S, can have different molecular weight values within one molecule.
The coupling center X is formed by the reaction of the living anionic chain ends with an at least bifunctional coupling agent. Examples of such compounds are found in U.S. Patents 3,985,830, 3,280,084, 3,637,554 and 4,091,053. For example, epoxidized glycerides such as epoxidized linseed oil or soybean oil are preferably used; divinylbenzene is also suitable. Dichlorodialkylsilanes, dialdehydes such as terephthalaldehyde and esters such as ethyl formate or benzoate are particularly suitable for dimerization.
Preferred polymer structures are SB / SS, X - [- B / SS]<sub>2</sub> and Y - [- B / SS]<sub>2</sub>, whereby the statistical block B / S itself can be subdivided into blocks B1 / S1-B2 / S2-B3 / S3 -.... The statistical block preferably consists of 2 to 15 statistical sub-blocks, particularly preferably 3 to 10 sub-blocks. The division of the statistical block B / S into as many sub-blocks Bn / Sn as possible offers the decisive advantage that even with a composition gradient within a sub-block Bn / Sn, as is difficult to avoid under anionic polymerization under practical conditions (see below), the B / S block as a whole behaves like an almost perfect statistical polymer. It therefore makes sense to add less than the theoretical amount of Lewis base, which increases the proportion of 1,4-diene linkages, the glass transition temperature T<sub>G</sub> is lowered and the polymer's susceptibility to crosslinking is reduced. A larger or a smaller proportion of the sub-blocks can be equipped with a high proportion of diene. This means that the polymer retains its residual toughness even below the glass transition temperature of the predominant B / S blocks and does not become completely brittle.
The block copolymers according to the invention have a spectrum of properties which is very similar to that of soft PVC, but can be produced completely free of migratable, low molecular weight plasticizers. They are characterized by a high oxygen permeation P.<sub>O</sub> and water vapor permeation P<sub>w</sub> of over 2,000 [cm<sup>3</sup>· 100 µm / m<sup>2</sup>· D · bar] or over 10 [g 100 µm / m<sup>2</sup>· D · bar], where P<sub>O</sub> the amount of oxygen in cm<sup>3</sup> or P<sub>w</sub> indicates the amount of hydrogen in grams, which is by 1 m<sup>2</sup> Pass through film with a standard thickness of 100 µm per day and per bar partial pressure difference.
The polymerization is preferably carried out in several stages and, for example, with monofunctional initiation, the production of the hard block S is started. Some of the monomers are placed in the reactor and the polymerization is started by adding the initiator. In order to achieve a defined chain structure that can be calculated from the monomer and initiator metering, it is advisable to carry out the process up to a high conversion (over 99%) before the second monomer is added. However, this is not absolutely necessary.
The sequence of the monomer addition depends on the selected block structure. In the case of monofunctional initiation, for example, the vinylaromatic compound is either initially introduced or metered in directly. Then diene and vinyl aromatic should be added at the same time if possible. The statistical structure and the composition of the block B / S are determined by the quantitative ratio of diene to vinylaromatic compound, the concentration and chemical structure of the Lewis base and the temperature. According to the invention, the diene takes up a proportion by weight of 25% to 70% relative to the total mass, including vinyl aromatic compound. Block S can then be polymerized by adding the vinylaromatic. Instead, the required polymer blocks can also be connected to one another by the coupling reaction. In the case of bifunctional initiation, the B / S block is built up first, followed by the S block.
Further processing takes place according to the usual procedures. It is advisable to work in a stirred tank and to protonate the carbanions with an alcohol such as isopropanol, before further processing in the usual way with CO<sub>2</sub>/ To make the water slightly acidic, to stabilize the polymer with an oxidation inhibitor and a radical scavenger (commercially available products such as trisnonylphenyl phosphite (TNPP) or α-tocopherol (vitamin E) or products available under the trade name Irganox 1076 or Irganox 3052), the solvent after remove, extrude and granulate the usual procedures. Like other types of rubber, the granulate can be protected against sticking with an antiblocking agent such as Acrawax®, Besquare® or Aerosil®.
The molding compounds according to the invention contain, as an essential component, at least one thermoplastic or thermosetting polymer P2), the weight fraction of which, based on the total weight of the molding compositions, can be up to 99.9% by weight, preferably up to 5 to 99% by weight.
Basically, the advantageous effects of the mixtures according to the invention can be seen in plastics of all kinds. A list of suitable thermoplastics and thermosets can be found, for example, in the plastic paperback (Ed. Saechtling), edition 1989, where sources of supply are also mentioned. Methods for producing such thermoplastic or thermosetting plastics are known per se to the person skilled in the art. Some preferred types of plastic are explained in more detail below.
Polyoxymethylene homo- or copolymers are known per se to the person skilled in the art and are described in the literature.
In general, these polymers have at least 50 mol% of -CH repeating units<sub>2</sub>O- in the main polymer chain.
The homopolymers are generally prepared by polymerizing formaldehyde or trioxane, preferably in the presence of suitable catalysts.
In the context of the invention, polyoxymethylene copolymers are preferred, in particular those which, in addition to the repeating units —CH<sub>2</sub>O- up to 50, preferably 0.1 to 20 and in particular 0.3 to 10 mol% of repeating units<chemistry id="chem0001" num="0001"><img file="EP0800554B1_D0001.tif" /></chemistry> included, where R<sup>1</sup> to R<sup>4</sup> independently of one another a hydrogen atom, a C1 to C<sub>4</sub>-Alkylgruppe or a halogen-substituted alkyl group with 1 to 4 carbon atoms and R<sup>5</sup> a -CH<sub>2</sub>-, -CH<sub>2</sub>O-, a C<sub>1</sub>- to C<sub>4</sub>-Alkyl- or C<sub>1</sub>- to C<sub>4</sub>-Haloalkyl represent substituted methylene group or a corresponding oxymethylene group and n has a value in the range from 0 to 3. These groups can advantageously be introduced into the copolymers by ring opening of cyclic ethers. Preferred cyclic ethers are those of the formula<chemistry id="chem0002" num="0002"><img file="EP0800554B1_D0002.tif" /></chemistry> where R<sup>1</sup> to R<sup>5</sup> and n have the meaning given above. Examples include ethylene oxide, 1,2-propylene oxide, 1,2-butylene oxide, 1,3-butylene oxide, 1,3-dioxane, 1,3-dioxolane and 1,3-dioxepane as cyclic ethers and linear oligo- or polyformals such as polydioxolane or polydioxepane as comonomers.
Also suitable are oxymethylene terpolymers, for example by reacting trioxane, one of the cyclic ethers described above, with a third monomer, preferably a bifunctional compound of the formula<chemistry id="chem0003" num="0003"><img file="EP0800554B1_D0003.tif" /></chemistry> where Z is a chemical bond, -O-, -ORO- (R = C<sub>1</sub>- to C<sub>8</sub>-Alkylene or C<sub>2</sub>- to C<sub>8</sub>-Cycloalkylene) is produced.
Preferred monomers of this type are ethylene diglycide, diglycidyl ether and diether from glycidylene and formaldehyde, dioxane or trioxane in a molar ratio of 2: 1 and diether from 2 mol of glycidyl compound and 1 mol of an aliphatic diol with 2 to 8 carbon atoms, such as, for example, the diglycidyl ether of ethylene glycol, 1 , 4-butanediol, 1,3-butanediol, cyclobutane-1,3-diol, 1,2-propanediol and cyclohexane-1,4-diol, to name just a few examples.
Processes for the preparation of the homopolymers and copolymers described above are known to the person skilled in the art and are described in the literature, so that further details are unnecessary here.
The preferred polyoxymethylene copolymers have melting points of at least 150 ° C. and molecular weights (weight average) Mw in the range from 5000 to 200000, preferably from 7000 to 150,000.
End group-stabilized polyoxymethylene polymers which have CC bonds at the chain ends are particularly preferred.
Suitable polycarbonates are known per se. They can be obtained, for example, in accordance with the processes of DE-B-1 300 266 by interfacial polycondensation or in accordance with the process of DE-A-14 95 730 by reacting biphenyl carbonate with bisphenols. Preferred bisphenol is 2,2-di (4-hydroxyphenyl) propane, generally - as also hereinafter - referred to as bisphenol A.
Instead of bisphenol A, other aromatic dihydroxy compounds can also be used, in particular 2,2-di (4-hydroxyphenyl) pentane, 2,6-dihydroxynapthalene, 4,4'-dihydroxydiphenyl sulfone, 4,4'-dihydroxydiphenyl ether, 4,4'- Dihydroxydiphenyl sulfite, 4,4'-dihydroxydiphenylmethane, 1,1-di- (4-hydroxyphenyl) ethane or 4,4-dihydroxydiphenyl and mixtures of the aforementioned dihydroxy compounds.
Particularly preferred polycarbonates are those based on bisphenol A or bisphenol A together with up to 30 mol% of the aromatic dihydroxy compounds mentioned above.
The relative viscosity of these polycarbonates is generally in the range from 1.1 to 1.5, in particular from 1.28 to 1.4 (measured at 25 ° C. in a 0.5% strength by weight solution in dichloromethane).
Suitable polyesters are also known per se and are described in the literature. They contain an aromatic ring in the main chain, which comes from an aromatic dicarboxylic acid. The aromatic ring can also be substituted, for example by halogen such as chlorine and bromine or by C.<sub>1</sub>-C<sub>4</sub>-Alkyl groups such as methyl, ethyl, i- or n-propyl and n-, i- or tert-butyl groups.
The polyesters can be prepared in a manner known per se by reacting aromatic dicarboxylic acids, their esters or other ester-forming derivatives thereof with aliphatic dihydroxy compounds.
Preferred dicarboxylic acids are naphthalenedicarboxylic acid, terephthalic acid and isophthalic acid or mixtures thereof. Up to 10 mol% of the aromatic dicarboxylic acids can be replaced by aliphatic or cycloaliphatic dicarboxylic acids such as adipic acid, azelaic acid, sebacic acid, dodecanedioic acids and cyclohexanedicarboxylic acids.
Of the aliphatic dihydroxy compounds, diols having 2 to 6 carbon atoms, in particular 1,2-ethanediol, 1,4-butanediol, 1,6-hexanediol, 1,4-hexanediol, 1,4-cyclohexanediol and neopentyl glycol or mixtures thereof, are preferred.
Polyalkylene terephthalates derived from alkanediols having 2 to 6 carbon atoms are particularly preferred polyesters. Of these, polyethylene terephthalate, polyethylene naphthalate and polybutylene terephthalate are particularly preferred.
The viscosity number of the polyesters is generally in the range from 60 to 200 ml / g (measured in a 0.5% strength by weight solution in a phenol / o-dichlorobenzene mixture (weight ratio 1: 1 at 25 ° C.) ).
Poly (meth) acrylates include, in particular, polymethyl methacrylate (PMMA) and copolymers based on methyl methacrylate with up to 40% by weight of other copolymerizable monomers, such as those known under the names Lucryl® from BASF Aktiengesellschaft or Plexiglas® from Röhm GmbH are available.
Semi-crystalline, preferably linear polyamides such as polyamide-6, polyamide-6,6, polyamide-4,6, polyamide-6,12 and semi-crystalline copolyamides based on these components are suitable. Partly crystalline polyamides can also be used, the acid component of which consists entirely or partially of adipic acid and / or terephthalic acid and / or isophthalic acid and / or suberic acid and / or sebacic acid and / or azelaic acid and / or dodecanedicarboxylic acid and / or a cyclohexanedicarboxylic acid, and whose diamine component wholly or partly consists in particular of m and / or p-xylylenediamine and / or hexamethylenediamine and / or 2,2,4- and / or 2,4,4-trimethylhexamethylenediamine and / or isophoronediamine, and their compositions are known in principle (see Encyclopedia of Polymers, Vol. 11, p. 315 ff.).
The molecular weights M<sub>n</sub> (Number average) of the polyamides suitable as component P2 are preferably in the range between 5,000 and 100,000, particularly preferably between 10,000 and 80,000.
Semi-crystalline linear polyamides are suitable, for example with a relative viscosity of 2.2 to 4.5, measured in 0.5% solution (0.5 g / 100 ml) in 96% by weight sulfuric acid at 25 ° C. Preference is given to polyamides which are wholly or partly derived from lactams with 7 to 13 ring members, such as polycaprolactam, polycapryllactam or polylaurinlactam.
Also suitable are polyamides obtained by reacting dicarboxylic acids with one or more diamines. Suitable dicarboxylic acids are, for example, alkanedicarboxylic acids having 6 to 12, in particular 6 to 10, carbon atoms, in particular adipic acid. Suitable diamines are, for example, alkane or cycloalkane diamines having 4 to 12, in particular 4 to 8, carbon atoms; Hexamethylenediamine, m-xylylenediamine, bis (4-aminophenyl) methane, bis (4-aminocyclohexyl) methane or bis (4-aminophenyl) propane-2,2 or mixtures thereof are particularly suitable partners for the production of such polyamides. It may be advantageous to manufacture the polyamides mentioned and to use their mixtures.
Polyamide-6 (polycaprolactam), polyamide-6,6 (polyhexamethylene adipinamide) and polyamides, which contain at least 80% by weight of recurring units of the formula - [- NH- (CH<sub>2</sub>)<sub>4</sub>-NH-CO- (CH<sub>2</sub>)<sub>4</sub>-CO -] - are built. The latter polyamides can be obtained by condensing 1,4-diaminobutane with adipic acid. Suitable production processes for polyamides are described, for example, in EP-A-38 094, EP-A-38 582 and EP-A-39 524.
Also suitable are polyamides with a small proportion, preferably up to about 10% by weight, of other components which can be condensed in, in particular other amide formers, such as, for example, α, ω-amino acids or N-carboxylic acid anhydrides (lees anhydrides) of amino acids.
According to a preferred embodiment of the invention, the molding compositions according to the invention contain as component P2 a partially aromatic copolyamide with the structure described below.
Preferred partially aromatic copolyamides P2 contain as component P21: 40 to 90% by weight of units which are derived from terephthalic acid and hexamethylenediamine. A small proportion of terephthalic acid, preferably not more than 10% by weight of the total amount of aromatic dicarboxylic acids used, can be replaced by isophthalic acid or other aromatic dicarboxylic acids, preferably those in which the carboxyl groups are in the para position.
In addition to the units derived from terephthalic acid and hexamethylene diamine, the partially aromatic copolyamides contain units which are derived from ε-caprolactam (P22) and / or units which are derived from adipic acid and hexamethylene diamine (P23).
The proportion of units derived from ε-caprolactam is up to 50% by weight, preferably 20 to 50% by weight, in particular 25 to 40% by weight, while the proportion of units derived from adipic acid and derive hexamethylenediamine, is up to 60% by weight, preferably 30 to 60% by weight and in particular 35 to 55% by weight.
The copolyamides can also contain units of ε-caprolactam as well as units of adipic acid and hexamethylenediamine; in this case the proportion of units which are free from aromatic groups is preferably at least 10% by weight, preferably at least 20% by weight. The ratio of the units derived from ε-caprolactam and from adipic acid and hexamethylene diamine is not subject to any particular restriction.
The melting point of particularly suitable partially aromatic copolyamides is, for example, in the range from 260 to over 300 ° C., this high melting point also being associated with a high glass transition temperature of generally more than 75, in particular more than 85 ° C. Binary copolyamides based on terephthalic acid, hexamethylene diamine and ε-caprolactam have a melting point in the range of 300 ° C and a glass transition temperature of more than 110 at a content of about 70% by weight of units derived from terephthalic acid and hexamethylene diamine ° C.
Binary copolyamides based on terephthalic acid, adipic acid and hexamethylenediamine already reach a melting point of 300 ° C. and more at a content of approximately 55% by weight of units of terephthalic acid and hexamethylenediamine, the glass transition temperature not being quite as high as with binary copolyamides, which contain ε-caprolactam instead of adipic acid or adipic acid / hexamethylenediamine.
Suitable partially aromatic copolyamides can be prepared by the processes described in EP-A-129 195 and EP-A-129 196.
According to the invention, amorphous polyamides can also be used as component P2. Based on the monomers already mentioned, additional monomers, often provided with one or more side groups which hinder crystallization, are condensed in. The result is a generally transparent polyamide.
Examples of polymers which are suitable as component P2 of the molding compositions according to the invention are also partially crystalline polyolefins, preferably homo- and copolymers of olefins such as ethylene, propylene, butene-1, pentene-1, hexene-1, heptene-1, 3-methylbutene -1, 4-methylbutene-1, 4-methylpentene-1 and octene-1. Suitable polyolefins are accordingly, for example, polyethylene, polypropylene, polybutene-1 or poly-4-methylpentene-1. In general, a distinction is made between polyethylene (PE) and high-density PE (HDPE), low-density PE (LDPE) and linear-low-density PE (LLDPE).
Polyolefins which are preferably suitable as component P2 are polyethylene, polypropylene and poly-4-methylpentene-1, in particular polyethylene and polypropylene. In addition to the olefins, the polyolefins can also contain minor amounts of other monomers. For example, ethylene / octene copolymers or ethylene / hexene copolymers with a high proportion of octene or hexene (for example the commercial products Affinity® or Engage® from DOW Chemical Co.) are particularly suitable.
In another embodiment of the invention, component P2 is an ionomer. These are generally polyolefins, as described above, in particular polyethylene, which contain monomers with carboxyl groups in copolymerized form, for example acrylic acid, methacrylic acid and, if appropriate, further copolymerizable monomers. The acid groups are generally converted into ionic, possibly with the aid of metal ions such as Na, Ca, Mg and Al ions. converted ionically crosslinked polyolefins, but which can still be processed thermoplastically (see, for example, US Pat. Nos. 3,264,272; 3,404,134; 3,355,319; 4,321,337). However, it is not absolutely necessary to convert the polyolefins containing acid groups by means of metal ions. Also polyolefins containing free acid groups, which then generally have a rubber-like character and partly also contain further copolymerizable monomers, for example (Meth) acrylates are suitable as component P2 according to the invention.
Aromatic polyether ketones can also be used as component P2, as described, for example, in British Pat. No. 1,078,234, US Pat. No. 4,010,147, EP-A-135 938 and in the publication by CK Sham et. al., Polymer 29/6, 1016-1020 (1988). These polyether ketones can be obtained by reacting bisphenols with bis (halogenoaryl) ketones in polar aprotic solvents in the presence of alkali metal carbonates, for example lithium carbonate. A typical reaction product of this type is, for example, the product formed from hydroquinone and 4,4'-difluorobenzophenone.
Polyarylene sulfides, in particular polyphenylene sulfide, are also suitable as component P2. Its manufacture is described, for example, in US Pat. Nos. 3,354,129, 3,786,035 and EP-A-171 021.
Thermoplastic polyurethanes are also used as component P2 of the thermoplastic molding compositions according to the invention.
Thermoplastic polyurethanes and processes for their production are known and are described, for example, in DE-A-36 28 562.
Self-reinforcing crystalline polyarylates (LCP's = liquid crystalline polymers), linear polyimides, polybenzimidazoles, polyhydantoins, polypyrroles, polyphosphazenes, silicones are also suitable.
Of course, the thermoplastic elastomers P1 can also be incorporated in thermoset materials P2, such as, for example, in phenol, cresol, xylenol and resorcinol resins, urea and melamine resins, furan resins, crosslinked polymethacrylates, unsaturated polyester resins, phenoacrylate resins, epoxy resins, isocyanate resins (polyurethane precursors ) and so-called "hybrid" prepolymers from the groups mentioned above.
The following may also be mentioned as mixing partners P2: allyl ester resins; Polyurethanes, e.g. semi-hard RIM (Reaction Injection Molding) parts, hard and semi-hard integral foam RIM systems, hard and elastomeric polyurethane casting resins, hard to soft foams.
The thermoplastic elastomers P1 can also be used as a component in prepregs (sheet molding compounds, SMC); bulk molding compounds (BMC) with eg polyester, phenacrylate, diallyl phthalate or silicone resin matrix; still in glass fiber reinforced mats (GRP), semi-finished products and finished parts.
Non-crystalline copolymers such as methacrylate-acrylate-styrene polymers, acrylonitrile-butadiene-styrene polymers (ABS), acrylonitrile-styrene-acrylic ester polymers (ASA), methacrylate-butadiene polymers can also be used with particular advantage as component P2 of the mixture according to the invention. Styrene polymers (MBS), impact-resistant polystyrene (HIPS), but also homopolymers such as polystyrene, polymethyl methacrylate (PMMA), polyacrylonitrile, polymethacrylimide. Such polymers exist, for example in the case of ABS, ASA, MBS, but also in the case of impact-resistant polystyrene from two phases, a continuous (often referred to as a hard phase or matrix) and a disperse (usually referred to as a rubber or soft phase). The single-phase polymers usually lack the disperse soft rubber phase. Components P2 according to the invention are thus single-phase polymers consisting only of hard phase (such as polystyrene or PMMA), two-phase polymers (e.g. ABS, ASA, MBS, impact-resistant polystyrene), but also only the soft phases (e.g. the rubber contained in ABS, ASA, MBS, impact-resistant polystyrene) in ungrafted, grafted, pure or enriched form.
Impact-resistant polystyrenes and standard polystyrenes according to the invention, their production, structure and properties are described in the overview literature (A.Echte, F.Haaf, J.Hambrecht in Angew. Chem. (Int.Ed.Engl.) 20, 344-361, ( 1981), as well as Plastics Handbook, Volume Polystyrene, Carl Hanser Verlag (1968), and the impact-resistant polystyrenes used can also be modified by using special polybutadiene rubbers be structurally changed with a modified 1,4-cis or 1,4-trans portion or 1,2 and 1,4-linking portion compared to conventional rubbers. Furthermore, instead of polybutadiene rubber, other diene rubbers and elastomers of the ethylene-propylene-diene copolymer (EPDM rubber) type and hydrogenated diene rubbers can also be used. Suitable standard polystyrene is produced by the anionic or radical polymerization process. The nonuniformity of the polymer which can be influenced by the polymerization process is of minor importance. Standard polystyrene and impact-resistant polystyrene are preferred, the toluene-soluble portion of which has an average molecular weight M<sub>w</sub> from 50,000 to 500,000 g / mol and which are optionally also equipped with additives such as mineral oil, stabilizer, antistatic agents, flame retardants or waxes.
Suitable monomers for forming the hard phase can be selected, for example, from the monomers listed below: styrene and its substituted derivatives, such as, for example, α-methylstyrene, α-chlorostyrene, p-chlorostyrenes, 2,4-dichlorostyrene, p-methylstyrene, 3,4 -Dimethylscyrol, p-tert-butylstyrene, o- and p-divinylbenzene, p-methyl-α-methylstyrene and p-chloro-α-methylstyrene. Styrene and α-methylstyrene are preferred.
Acrylic and methacrylic compounds are understood to mean monomers such as, for example Acrylonitrile, methacrylonitrile, acrylic and methacrylic acid, methyl acrylate, ethyl acrylate, n- and isopropyl acrylate, n- and i-butyl acrylate, t-butyl acrylate, 2-ethylhexyl acrylate, methyl methacrylate, ethyl methacrylate, n- and i-propyl methacrylate, n- and i -Butyl methacrylate, t-butyl methacrylate, cyclohexyl methacrylate, isobornyl methacrylate, maleic anhydride and its derivatives, such as maleic esters, maleic diesters and maleimide, for example Alkyl and acrylic maleimides, such as methyl or phenyl maleimide, preferably acrylonitrile, methyl methacrylate, maleic anhydride and phenyl maleimide.
Examples of suitable homo- or Copolymers are polystyrene, polymethyl methacrylate, styrene-acrylonitrile copolymers, α-methylstyrene-acrylonitrile copolymers, styrene-maleic anhydride copolymers, styrene-phenylmaleimide copolymers, styrene-methyl methacrylate copolymers, methyl methacrylate-acrylonitrile-acrylonitrile copolymers, Copolymers, styrene-acrylonitrile-phenylmaleimide copolymers, α-methylstyrene-acrylonitrile-methyl methacrylate copolymers, α-methylstyrene-acrylonitrile-t-bucyl methacrylate copolymers, Styrene-acrylonitrile-t-butyl methacrylate copolymers.
Components P2 according to the invention are furthermore, for example, polycarbonate or mixtures of polycarbonate with several of the graft copolymers and thermoplastics described below. The proportion of polycarbonate is preferably between 5 and 95% by weight and the proportion of components B1 + B2 between 5 and 95% by weight. Such mixtures are already on the market, for example under the trade name Bayblend® (Bayer) or Terblend®s (BASF). These are mixtures of a polycarbonate with an ABS or ASA polymer.
Polycarbonate-polysiloxane block copolymers, polycarbonate-polyether block copolymers and polycarbonate-polyester block copolymers can also serve as thermoplastics P2.
According to the invention, aromatic polyester carbonates can also be used as thermoplastics. They consist of at least one aromatic bisphenol of the general formula (I) from at least one aromatic dicarboxylic acid and optionally of carbonic acid or its derivatives, such as phosgene, dialkyl and diaryl carbonate. Suitable aromatic dicarboxylic acids are, for example, orthophthalic acid, terephthalic acid, isophthalic acid, tert-butylisophthalic acid, 3,3'-diphenyldicarboxylic acid, 4,4'-diphenyldicarboxylic acid, 4,4'-benzophenonedicarboxylic acid, 3,4, -benzophenonedicarboxylic acid, 4,4'-diphenyletherdicarboxylic acid , 4, -Diphenylsulfone dicarboxylic acid, 2,2-bis (4-carboxyphenyl) propane, trimethyl-3-phenylindane-4,5-dicarboxylic acid.
Halogenated polymers such as polyvinylidene chloride, polyvinyl chloride (PVC) can also be used as the hard component according to the invention. Modified PVC is preferred. Low molecular weight plasticizers (eg dioctyl phthalate, dioctyl adipate) and / or polymeric compounds are used for the modification.
PVC can be produced by polymerisation in suspension, emulsion or bulk processes. Mixtures of PVC with plasticizers usually still contain processing stabilizers.
PVC that can be processed without a plasticizer is preferably produced by (suspension) graft polymerization of vinyl chloride onto an elastomer. The elastomer can consist of polybutadiene and / or polyacrylate rubber.
The following can also be used: chlorinated polyethylene, chlorinated polypropylene, polyisobutylene, polyvinyl acetate, polyvinyl alcohol, polyvinyl ether, polymethylpentene, polytetrafluoroethylene, tetrafluoroethylene-perfluoropropylene copolymers, copolymers of tetrafluoroethylene and perfluoroalkylvinylether, ethylene-tetrafluorethylene-polyethylene fluoride, polyethylene fluoride, polyethylene fluoride, polyethylene fluoride, polyethylene fluoride, polyethylene fluoride, polyethylene fluoride, polyethylenefluoride, Chlorotrifluoroethylene copolymers.
Cellulose derivatives such as cellulose acetate, cellulose propionate and cellulose acetobutyrate are also suitable.
Polyphenylene ethers P2 are known per se.
These are compounds based on substituted, in particular disubstituted, polyphenylene ethers, the ether oxygen of one unit being bound to the benzene nucleus of the adjacent unit. Polyphenylene ethers substituted in the 2- and / or 6-position relative to the oxygen atom are preferably used. Examples of substituents are halogen atoms such as chlorine or bromine and alkyl radicals having 1 to 4 carbon atoms, which preferably have no α-tertiary hydrogen atom, for example methyl, ethyl, propyl or butyl radicals. The alkyl radicals can in turn be substituted by halogen atoms such as chlorine or bromine or by a hydroxyl group. Further examples of possible substituents are alkoxy radicals, preferably having up to 4 carbon atoms or phenyl radicals optionally substituted by halogen atoms and / or alkyl groups. Copolymers of various phenols, such as copolymers of 2,6-dimethylphenol and 2,3,6-trimethylphenol, are also suitable.
Mixtures of different polyphenylene ethers can of course also be used.
Examples of polyphenylene ethers are poly (2,6-dilauryl-1,4-phenylene ether), poly (2,6-diphenyl-1,4-phenylene ether), poly (2,6-dimethoxy-1,4-phenylene ether), poly (2,6-diethoxi-1,4-phenylene ether), poly (2-methoxy-6-ethoxy-1,4-phenylene ether), poly (2-ethyl-6-stearyloxy-1,4-phenylene ether), poly ( 2,6-dichloro-1,4-phenylene ether), poly (2-methyl-6-phenyl-1,4-phenylene ether), poly (2,6-di-benzyl-1,4-phenylene ether), poly (2 -ethoxy-1,4-phenylene ether), poly (2-chloro-1,4-phenylene ether), Poly (2,5-dibromo-1,4-phenylene ether). Polyphenylene ethers in which the substituents are alkyl radicals having 1 to 4 carbon atoms, such as poly (2,6-dimethyl) -1,4-phenylene ether), poly (2,6-diethyl-1,4-phenylene ether), poly, are preferably used (2-methyl-6-ethyl-1,4-phenylene ether), poly (2-methyl-6-propyl-1,4-phenylene ether), poly (2,6-dipropyl-1,4-phenylene ether) and poly ( 2-ethyl-6-propyl-1,4-phenylene ether).
For the purposes of the invention, polyphenylene ethers are also to be understood as meaning those which have been modified with monomers such as fumaric acid, maleic acid or maleic anhydride.
Such polyphenylene ethers are described, inter alia, in WO 87/00540.
With regard to the physical properties of the polyphenylene ethers, preference is given to those which have an intrinsic viscosity of 0.2 to 0.7 dl / g, measured in chloroform at 30 ° C.
This intrinsic viscosity corresponds to an average molecular weight (weight average) <maths id="math0001" num=""><math display="inline"><mrow><mover accent="true"><mrow><mtext>M</mtext></mrow><mo>¯</mo></mover></mrow></math><img file="EP0800554B1_D0004.tif" /></maths><sub>w</sub> from 10,000 to 50,000, preferably 25,000 to 50,000 and in particular 40,000 to 50,000.
The following may be mentioned as preferred polymer mixtures with polyphenylene ethers P2:<ul id="ul0005" list-style="none" compact="compact"><li>P1) 1 to 80% by weight, preferably 2 to 60 and in particular 3 to 40% by weight</li><li>P2) 5 to 99% by weight, preferably 20 to 98 and in particular 30 to 97% by weight of a polyphenylene ether, which</li></ul> optionally up to 95 wt .-%, preferably up to 50 wt .-% can be replaced by a vinyl aromatic polymer and / or a polyamide.
A modified polyphenylene ether is preferably used in polyphenylene ether / polyamide mixtures<ul id="ul0006" list-style="none"><li>a) 59.95 to 99.95% by weight of an unmodified polyphenylene ether,</li><li>b) 0 to 40% by weight of a vinyl aromatic polymer,</li><li>c) 0.05 to 5% by weight of at least one compound from the group formed from</li><li>c<sub>1</sub>) an α, β-unsaturated dicarbonyl compound,</li><li>c<sub>2</sub>) a monomer containing amide groups with a polymerizable double bond and</li><li>c<sub>3</sub>) a monomer containing lactam groups with a polymerizable double bond,</li><li>d) 0 to 5% by weight of a radical initiator</li></ul> the percentages by weight based on the sum of a) to d) being obtainable in the course of 0.5 to 15 minutes at 240 to 375 ° C. in suitable mixing and kneading units such as twin-screw extruders.
Polymers which are structurally similar to component P1 can of course also be used as component P2. For example, these can be linear and / or star-shaped styrene-butadiene block copolymer materials such as Styrolux® from BASF, K-Resin® from Phillips Petroleum or Finaclear® from Fina.
Polymers which have a particularly long block S (generally polystyrene block S) and which therefore act as a kind of “compatibilizer” between component P1 and, for example, the above-mentioned linear and / or star-shaped styrene-butadiene block copolymer have also proven suitable. Materials, polystyrenes (crystal clear or impact resistant), etc. can serve.
The relevant customary rubbers can be used as the soft phase. For example, natural rubber, epichlorohydrin rubbers, ethylene-vinyl acetate rubbers, polyethylene chlorosulfone rubbers, silicone rubbers, polyether rubbers, diene rubbers, hydrogenated diene rubbers, polyalkenamer rubbers, acrylate rubbers, ethylene-propylene rubbers, fluoro-rubbers, fluoro-rubbers, and fluoro-rubbers become. Acrylate rubber, ethylene-propylene (EP -) rubber, ethylene-propylene-diene (EPDM-1 rubber, in particular butadiene-isoprene rubber, diene rubber or silicone rubber) is preferably used.
The acrylate rubbers are generally alkyl acrylate rubbers made from one or more C.<sub>4</sub>-C<sub>8</sub>- Alkyl acrylates, preferably at least partially butyl, hexyl, octyl or 2-ethylhexyl acrylate. These alkyl acrylate rubbers can contain up to 30% by weight of hard polymer-forming monomers such as vinyl acetate, (meth) acrylonitrile, styrene, substituted styrene, methyl methacrylate, vinyl ether in copolymerized form. The acrylate rubbers further contain up to 10% by weight, preferably 1 to 5% by weight, of crosslinking, polyfunctional monomers (crosslinking monomers). Examples of these are monomers which contain two or more double bonds capable of copolymerization.
Diene rubbers are, for example, homopolymers of conjugated dienes having 4 to 8 carbon atoms such as butadiene, isoprene, piperylene and chloroprene, copolymers of such dienes with one another and copolymers of such dienes with styrene, acrylic or methacrylic compounds (for example acrylonitrile, methacrylonitrile, acrylic acid, methacrylic acid, butyl acrylate) , Acrylic acid ethyl hexyl ester and methyl methacrylate). Particularly preferred diene rubbers are commercially available butadiene, butadiene-styrene, butadiene-methyl methacrylate, butadiene-acrylic acid butyl ester and buta diene-acrylonitrile rubbers (for example Cariflex® from Shell; Finaprene® from Fina; Tufprene® from Asahi; Exxellor® from Exxon; Europrene® der Enichem etc .; the above company names are abbreviated).
Suitable silicone rubbers can be, for example, crosslinked silicone rubbers composed of units of the general formulas R<sub>2</sub>SiO, RSiO<sub>3/2</sub>, R<sub>3</sub>SiO<sub>1/2</sub> and SiO<sub>2/4</sub> be, where R represents a monovalent radical. The amount of the individual siloxane units is such that 100 units of the formula R<sub>2</sub>SiO to 10 mol units of the formula RSiO<sub>3/2</sub>, up to 1.5 mol units of R<sub>3</sub>SiO<sub>1/2</sub> and up to 3 mol units of SiO<sub>2/4</sub> available. R can be either a monovalent saturated hydrocarbon radical having 1 to 18 carbon atoms, the phenyl radical or alkoxy radical or a group which is easily attackable by free radicals, such as the vinyl or mercaptopropyl radical. It is preferred that at least 80% of allradicals R are methyl; combinations of methyl and ethyl or phenyl are particularly preferred.
The soft component can also be a multi-stage polymer (so-called "core / shell structure", "core / shell morphology"). For example, a rubber-elastic core (glass temperature T<sub>G</sub> <5 ° C) from a "hard" shell (polymers with T<sub>G</sub> > 5 ° C) or vice versa.
The components P1 and P2 according to the invention can be produced in virtually any mixing ratio, for example from 0.1 to 99.9% by weight of P<sub>1</sub>, preferably 10 to 90 wt .-% P<sub>1</sub> and 0.1 to 99.9% by weight of P<sub>2</sub>, preferably 10 to 90 wt .-% P<sub>2</sub>.
As component P3), the polymer mixtures according to the invention can contain further additives and processing aids such as stabilizers, oxidation retardants, agents against heat decomposition and decomposition by ultraviolet light, lubricants and mold release agents, colorants such as dyes and pigments, fibrous and powdery fillers and reinforcing agents, nucleating agents, plasticizers, etc contain, the proportion of which is generally not more than 70% by weight, preferably not more than 40% by weight.
Halides of metals of group I of the periodic system, for example sodium, potassium and / or lithium halides, optionally in combination with copper (I) halides, for example chlorides, bromides, iodides, are sterically hindered as examples of oxidation retarders and heat stabilizers Phenols, hydroquinones, various substituted representatives of these groups and their mixtures in concentrations of up to 1% by weight, based on the weight of the thermoplastic molding composition.
Various substituted resorcinols, salicylates, benzotriazoles and benzophenones may be mentioned as UV stabilizers, which are generally used in amounts of up to 2% by weight, based on the molding composition.
Organic dyes such as nigrosine, pigments such as titanium dioxide, cadmium sulfide, cadmium selenide, phthalocyanines, ultramarine blue and carbon black can also be added as dyes, and fibrous and powdery fillers and reinforcing agents. Examples of the latter are carbon fibers, glass fibers, amorphous silica, asbestos, calcium silicate (wollastonite), aluminum silicate, magnesium carbonate, kaolin, chalk, powdered quartz, mica and feldspar. The proportion of such fillers and dyes is generally up to 50% by weight, preferably up to 35% by weight.
Talc, calcium fluoride, sodium phenylphosphinate, aluminum oxide, silicon dioxide and nylon 22 can be used as nucleating agents.
Lubricants and mold release agents, which can generally be used in amounts of up to 1% by weight, are, for example, long-chain fatty acids such as stearic acid or behenic acid, their salts (for example Ca or Zn stearate) or esters (for example stearyl stearate or pentaerythritol tetrastearate). and amide derivatives (eg ethylene bisstearylamide). For better film processing, amounts of up to 0.1% by weight of mineral-based antiblocking agents can be added to the molding compositions according to the invention. Examples include amorphous or crystalline silica, calcium carbonate or aluminum silicate.
Examples of plasticizers are phthalic acid dioctyl ester, phthalic acid dibenzyl ester, phthalic acid butyl benzyl ester, hydrocarbon oils, N- (n-butyl) benzenesulfonamide and o- and p-tolylethylsulfonamide.
To further improve the flame resistance, all flame retardants known for the respective thermoplastics can be added, in particular those based on phosphorus compounds or red phosphorus itself.
The molding compositions according to the invention can be produced by processes known per se. According to a preferred embodiment, the preparation is carried out by adding component P.<sub>1</sub>) and possibly P<sub>3</sub>) to melt component P<sub>2</sub>).
For this purpose, extruders are expediently used, for example single-screw or twin-screw extruders or other conventional plasticizing devices such as Brabender mills or Banbury mills.
The polymer mixtures according to the invention are notable for good mechanical properties (rigidity, toughness), good heat resistance and low shrinkage when processed into moldings of any kind.
As a result, they are suitable for the production of molded parts and semi-finished products of all kinds, such as rolled skins, bellows, rubber bellows, mats, blankets, floor coverings, shoe soles, carpet backs, synthetic leather, blow molded articles, profile extrudates, injection molded articles, pipe extrudates and 3-dimensional blow molded articles.
Examples
Component- P1
Components P 1-1 to P1-3 were produced in accordance with DE-A 44 20 952:
A heatable and coolable 50 1 stainless steel reactor, which was equipped with a crossbar stirrer, was prepared by flushing with nitrogen, boiling with a solution of sec-butyllithium and 1,1-diphenylethylene in cyclohexane (molar ratio 1: 1) and drying.
22.8 l of cyclohexane were then introduced and 42 ml of s-butyllithium as initiator, 65.8 ml of tetrahydrofuran and styrene (S) and butadiene (B) were added in the amounts (g) given in Table 1 below and according to the timing program indicated . The polymerization time t in minutes and the start and end temperatures T are also given<sub>A</sub> or T<sub>E</sub> (in ° C), it should be noted that the polymerization time was always long compared to the duration of the monomer feed.
The temperature of the reaction mixture was controlled by heating or cooling the reactor jacket. After the end of the reaction (consumption of the monomers), titration was carried out with ethanol until the mixture was colorless and the mixture was acidified with a 1.5-fold excess of formic acid. Finally, 34 g of a commercially available stabilizer 2-t-butyl-6- (3-t-butyl-2-hydroxy-5-methylbenzyl) -4-methylphenyl acrylate (Irganox® 3052; Ciba-Geigy, Basel) and 82 g of trisnonylphenyl phosphite were added .
The solution was worked up on a degassing extruder (three domes, forward and backward degassing) at 200 ° C. and granulated. The granules were mixed in a fluid mixer with 10 g bisstearylamide (Acrawax) as external lubrication.<tables id="tabl0001" num="0001"><img file="EP0800554B1_D0005.tif" /></tables>
Component P2
<dl id="dl0002"><dt>P2-1:</dt><dd>Linear styrene-butadiene-styrene three-block copolymer with sharply separated block transitions with a polybutadiene content of 26% by weight and M<sub>w</sub> of 90000 g / mol with an MVR 1200 ° C / 5 kg) of 25 ml / 10 '. (Styrolux® KR 2691, BASF AG)</dd><dt>P2.2:</dt><dd>ABS polymer:<ul id="ul0007" list-style="none" compact="compact"><li>70 % By weight of a styrene / acrylonitrile (SAN) copolymer (shell) (styrene / acrylonitrile: 67/33% by weight), VZ = 80 ml / g (measured 0.5% in toluene at 23 ° C.)</li><li>30th % By weight of a graft copolymer from (core)<ul id="ul0008" list-style="none" compact="compact"><li>60 % By weight of polybutadiene (crosslinked) grafted with</li><li>40 % By weight styrene / acrylonitrile copolymer (70/30)</li><li>(Terluran® 967 K, BASF AG)</li></ul></li></ul></dd><dt>P2-3:</dt><dd>High pressure polyethylene with a melt index MFI (190 ° C / 2.16 kg) of 1.5 g / 10 ', density: 0.919 g / cm<sup>3</sup> (Lupolen® 1800, BASF AG)</dd><dt>P2-4:</dt><dd>Polystyrene with a VZ of 74 ml / g (measured as a 0.5% solution in toluene at 23 ° C), MVR (200 ° C / 5 kg): 25 ml / 10 '(polystyrene 144C, BASF AG)</dd><dt>P2-5:</dt><dd>Impact-resistant polystyrene (HIPS) with a polybutadiene content of 8% by weight, cell particle morphology with an average particle size of the soft phase of 2.5 µm (VZ = 70 ml / g; 0.5% in toluene at 23 ° C; polystyrene 476L, BASF AG)</dd><dt>P2-6:</dt><dd>SAN copolymer (75/25) with a VZ of 60 ml / g (0.5% in toluene at 23 ° C) MVR (200 ° C / 21.6 kg) = 27 ml / 10 '(Luran® 358 N , BASF AG)</dd><dt>P2-7:</dt><dd>Polycarbonate (from bisphenol A) with a VZ of 62 ml / g (0.5% at 23 ° C in chloroform) MVR (260 ° / 5 kg) = 8 ml / 10 '(Makrolon® 2800, Bayer AG)</dd><dt>P2-8:</dt><dd>Polypropylene with a melting point of 162 ° C, melt index MVR (230 ° C / 2.16 kg): 2.4 ml / 10 ', density: 0.907 g / ml (Novolen® 1100, BASF AG)</dd><dt>P2-9:</dt><dd>Styrene / methyl methacrylate copolymer (70/30) with MVR (200 ° C / 5 kg) of 4 ml / 10 '</dd><dt>P2-10</dt><dd>polymethyl methacrylate with an MVR (230 ° C / 3.8 kg) of 2 ml / 10 ', (Lucryl® 688, BASF AG)</dd></dl>
Production of polymer blends
The mixtures of P1 and P2 were each compounded at 200 to 250 ° C. on a single-screw extruder, granulated and then sprayed into test specimens.
The heat resistance (Vicat B according to ISO 306), elongation at break (tensile test according to ISO 527) and the Charpy (notch) impact strength according to ISO 179/1 eU were measured on 4 mm thick tensile bars, and the melt flow index MVR according to ISO 1133 was also determined.
The compositions of the mixtures and the results are shown in Table 2.<tables id="tabl0002" num="0002"><img file="EP0800554B1_D0006.tif" /></tables><tables id="tabl0003" num="0003"><img file="EP0800554B1_D0007.tif" /></tables>
Polyphenylene ether mixtures
Components P1-1 to P1-3 corresponded to Examples 1-15.
Component P2
<dl id="dl0003"><dt>P2-11:</dt><dd>Polyamide 66 with a number average molecular weight of 22000 g / mol (Ultramid® A3, BASF AG) relative viscosity = 2.6 (measured as a 1% solution in concentrated sulfuric acid at 25 ° C).</dd><dt>P2-12:</dt><dd>Poly (2,6-dimethyl-1,4-phenylene ether) with an M<sub>w</sub> of 40,000 g / mol</dd><dt>P2-13</dt><dd>a modified polyphenylene ether made from: 90% by weight poly (2,6-dimethyl-1,4-phenylene ether) with a reduced specific viscosity of 0.6 dl / g (measured as a 1% chloroform solution at 25 ° C.) , 8 wt .-% polystyrene (MFI at 200 ° C / 5 kg load = 24 g / 10 min), 1.95 wt .-% fumaric acid and 0.05 wt .-% 3,4-dimethyl-3,4-diphenylhexane were in a twin-screw extruder (ZSK 30, Fa. Werner & Pfleiderer) dosed, implemented in a first part using kneading elements at 280 ° C and then degassed in a degassing zone at 300 ° C in a vacuum. The average residence time in the extruder was 1.5 minutes.</dd><dt>P2-14</dt><dd>Impact-resistant polystyrene with 9% by weight polybutadiene and cell particle morphology, average particle size of the soft component of 1.9 µm. The VZ of the hard matrix was 80 ml / g (0.5% in toluene at 23 ° C).</dd><dt>P2-15</dt><dd>Impact-resistant polystyrene with 17% by weight polybutadiene and cell particle morphology. The mean particle size of the soft component was 3.5 μm, the VZ of the hard matrix was 80 ml / g (0.5% in toluene at 23 ° C.).</dd><dt>P2-16</dt><dd>Impact-resistant polystyrene with 9% by weight polybutadiene, VZ: 79 ml / g (0.5% in toluene at 23 ° C.) The mean particle size of the soft component was 1.0 μm.</dd><dt>P2-17</dt><dd>(Comparative component according to DE-A 41 29 499): styrene-butadiene block rubber (Tufprene®A ', Asahi) with the block sequence SB-S'-B', a styrene content of 41% by weight and a Shore A hardness of 87 (DIN 53505)</dd><dt>P2-18</dt><dd>(Comparative component according to WO 87/5311): styrene-butadiene block rubber (Cariflex® TR 1101, Shell) with the block sequence SBS, a styrene content of 31% by weight and a Shore A hardness of 72 (DIN 53505)</dd><dt>P2.19</dt><dd>Styrene-butadiene star polymer with a styrene content of 68% by weight (Styrolux KR 2686, BASF AG)</dd></dl>
Component P3
<dl id="dl0004" compact="compact"><dt>P3-1</dt><dd>Carbon black batch 15% by weight in polystyrene Carbon black type: Black Pearls 880 from Cabot</dd></dl>
Production of molding compounds:
The components P1 to P3 were mixed on a twin-screw extruder (ZSK 30, W&P) at a cylinder temperature of 290 ° C. and processed to a homogeneous melt. Component P1 was added cold to the melt of P2 and P3 using a stuffing screw. The polymer melt was degassed, extruded, passed through a water bath, granulated and dried. The material was then sprayed at 280/80 ° C (melt temperature / mold surface temperature) to the desired test specimens.
material testing
Free shrinkage was determined on 110 x 110 x 2 mm injection molded panels with a central sprue. The free shrinkage is calculated by comparing the dimensions of the mold and those of the plate one hour after the injection molding process.
The damage work W<sub>total</sub> (Round disks) was determined according to DIN 53 443 at 23 ° C.
The heat resistance of the samples was determined using the Vicat softening temperature. The Vicat softening temperature was determined according to DIN 53 460, with a force of 49.05 N and a temperature increase of 50 K per hour, on normal small bars.
The notched impact strength of the samples was determined in accordance with ISO 179 1eA on ISO test specimens.
The tensile strength of the samples was determined according to DIN 53 455 on shoulder bars.
The compositions of the molding compositions and the results of the measurements are shown in Tables 3 and 4. <tables id="tabl0004" num="0004"><table frame="all"><title>Table 3</title><tgroup cols="5" colsep="1" rowsep="1"><colspec colnum="1" colname="col1" colwidth="31.50mm" /><colspec colnum="2" colname="col2" colwidth="31.50mm" /><colspec colnum="3" colname="col3" colwidth="31.50mm" /><colspec colnum="4" colname="col4" colwidth="31.50mm" /><colspec colnum="5" colname="col5" colwidth="31.50mm" /><thead valign="top"><row><entry namest="col1" nameend="col1" align="left">E.g.</entry><entry namest="col2" nameend="col2" align="left">Component P2-11 [wt:%]</entry><entry namest="col3" nameend="col3" align="left">Component P2-13 [% by weight]</entry><entry namest="col4" nameend="col4" /><entry namest="col5" nameend="col5" align="left">Shrinkage [%]</entry></row></thead><tbody valign="top"><row><entry namest="col1" nameend="col1" align="left">16</entry><entry namest="col2" nameend="col2" align="center">50</entry><entry namest="col3" nameend="col3" align="center">40</entry><entry namest="col4" nameend="col4" align="left">10th P1-1</entry><entry namest="col5" nameend="col5" align="left">0.64/0.71</entry></row><row><entry namest="col1" nameend="col1" align="left">17</entry><entry namest="col2" nameend="col2" align="center">50</entry><entry namest="col3" nameend="col3" align="center">40</entry><entry namest="col4" nameend="col4" align="left">10th P1-3</entry><entry namest="col5" nameend="col5" align="left">0.68/0.70</entry></row><row><entry namest="col1" nameend="col1" align="left">V1</entry><entry namest="col2" nameend="col2" align="center">50</entry><entry namest="col3" nameend="col3" align="center">40</entry><entry namest="col4" nameend="col4" align="left">10th P2-17</entry><entry namest="col5" nameend="col5" align="left">0.95/1.03</entry></row><row rowsep="1"><entry namest="col1" nameend="col1" align="left">V2</entry><entry namest="col2" nameend="col2" align="center">50</entry><entry namest="col3" nameend="col3" align="center">40</entry><entry namest="col4" nameend="col4" align="left">10th P2-18</entry><entry namest="col5" nameend="col5" align="left">0.97/1.05</entry></row></tbody></tgroup></table></tables><tables id="tabl0005" num="0005"><table frame="all"><title>Table 4</title><tgroup cols="10" colsep="1" rowsep="1"><colspec colnum="1" colname="col1" colwidth="15.75mm" /><colspec colnum="2" colname="col2" colwidth="15.75mm" /><colspec colnum="3" colname="col3" colwidth="15.75mm" /><colspec colnum="4" colname="col4" colwidth="15.75mm" /><colspec colnum="5" colname="col5" colwidth="15.75mm" /><colspec colnum="6" colname="col6" colwidth="15.75mm" /><colspec colnum="7" colname="col7" colwidth="15.75mm" /><colspec colnum="8" colname="col8" colwidth="15.75mm" /><colspec colnum="9" colname="col9" colwidth="15.75mm" /><colspec colnum="10" colname="col10" colwidth="15.75mm" /><thead valign="top"><row><entry namest="col1" nameend="col1" align="left">Example component [% by weight]</entry><entry namest="col2" nameend="col2" align="left">V3</entry><entry namest="col3" nameend="col3" align="left">V4</entry><entry namest="col4" nameend="col4" align="left">18</entry><entry namest="col5" nameend="col5" align="left">19</entry><entry namest="col6" nameend="col6" align="left">20</entry><entry namest="col7" nameend="col7" align="left">21</entry><entry namest="col8" nameend="col8" align="left">22</entry><entry namest="col9" nameend="col9" align="left">23</entry><entry namest="col10" nameend="col10" align="left">24</entry></row></thead><tbody valign="top"><row><entry namest="col1" nameend="col1" align="left">P2-12</entry><entry namest="col2" nameend="col2" align="left">35</entry><entry namest="col3" nameend="col3" align="left">35</entry><entry namest="col4" nameend="col4" align="left">35</entry><entry namest="col5" nameend="col5" align="left">35</entry><entry namest="col6" nameend="col6" align="left">35</entry><entry namest="col7" nameend="col7" align="left">35</entry><entry namest="col8" nameend="col8" align="left">35</entry><entry namest="col9" nameend="col9" align="left">35</entry><entry namest="col10" nameend="col10" align="left">36</entry></row><row><entry namest="col1" nameend="col1" align="left">P2-14</entry><entry namest="col2" nameend="col2" align="left">52</entry><entry namest="col3" nameend="col3" align="left">52</entry><entry namest="col4" nameend="col4" align="left">52</entry><entry namest="col5" nameend="col5" align="left">52</entry><entry namest="col6" nameend="col6" align="left">52</entry><entry namest="col7" nameend="col7" align="left">52</entry><entry namest="col8" nameend="col8" align="left">49</entry><entry namest="col9" nameend="col9" align="left">49</entry><entry namest="col10" nameend="col10" align="left">-</entry></row><row><entry namest="col1" nameend="col1" align="left">P2-15</entry><entry namest="col2" nameend="col2" align="left">-</entry><entry namest="col3" nameend="col3" align="left">-</entry><entry namest="col4" nameend="col4" align="left">-</entry><entry namest="col5" nameend="col5" align="left">-</entry><entry namest="col6" nameend="col6" align="left">-</entry><entry namest="col7" nameend="col7" align="left">-</entry><entry namest="col8" nameend="col8" align="left">3</entry><entry namest="col9" nameend="col9" align="left">3</entry><entry namest="col10" nameend="col10" align="left">-</entry></row><row><entry namest="col1" nameend="col1" align="left">P2-16</entry><entry namest="col2" nameend="col2" align="left">-</entry><entry namest="col3" nameend="col3" align="left">-</entry><entry namest="col4" nameend="col4" align="left">-</entry><entry namest="col5" nameend="col5" align="left">-</entry><entry namest="col6" nameend="col6" align="left">-</entry><entry namest="col7" nameend="col7" align="left">-</entry><entry namest="col8" nameend="col8" align="left">-</entry><entry namest="col9" nameend="col9" align="left">-</entry><entry namest="col10" nameend="col10" align="left">44</entry></row><row><entry namest="col1" nameend="col1" align="left">P1-1</entry><entry namest="col2" nameend="col2" align="left">-</entry><entry namest="col3" nameend="col3" align="left">-</entry><entry namest="col4" nameend="col4" align="left">9,7</entry><entry namest="col5" nameend="col5" align="left">-</entry><entry namest="col6" nameend="col6" align="left">4,9</entry><entry namest="col7" nameend="col7" align="left">4,9</entry><entry namest="col8" nameend="col8" align="left">9,7</entry><entry namest="col9" nameend="col9" align="left">-</entry><entry namest="col10" nameend="col10" align="left">-</entry></row><row><entry namest="col1" nameend="col1" align="left">P1-3</entry><entry namest="col2" nameend="col2" align="left">-</entry><entry namest="col3" nameend="col3" align="left">-</entry><entry namest="col4" nameend="col4" align="left">-</entry><entry namest="col5" nameend="col5" align="left">9,7</entry><entry namest="col6" nameend="col6" align="left">-</entry><entry namest="col7" nameend="col7" align="left">-</entry><entry namest="col8" nameend="col8" align="left">-</entry><entry namest="col9" nameend="col9" align="left">9,7</entry><entry namest="col10" nameend="col10" align="left">-</entry></row><row><entry namest="col1" nameend="col1" align="left">P1-2</entry><entry namest="col2" nameend="col2" align="left">-</entry><entry namest="col3" nameend="col3" align="left">-</entry><entry namest="col4" nameend="col4" align="left">-</entry><entry namest="col5" nameend="col5" align="left">-</entry><entry namest="col6" nameend="col6" align="left">-</entry><entry namest="col7" nameend="col7" align="left">-</entry><entry namest="col8" nameend="col8" align="left">-</entry><entry namest="col9" nameend="col9" align="left">-</entry><entry namest="col10" nameend="col10" align="left">20</entry></row><row><entry namest="col1" nameend="col1" align="left">P2-18</entry><entry namest="col2" nameend="col2" align="left">9,7</entry><entry namest="col3" nameend="col3" align="left">-</entry><entry namest="col4" nameend="col4" align="left">-</entry><entry namest="col5" nameend="col5" align="left">-</entry><entry namest="col6" nameend="col6" align="left">4,8</entry><entry namest="col7" nameend="col7" align="left">-</entry><entry namest="col8" nameend="col8" align="left">-</entry><entry namest="col9" nameend="col9" align="left">-</entry><entry namest="col10" nameend="col10" align="left">-</entry></row><row><entry namest="col1" nameend="col1" align="left">P2-19</entry><entry namest="col2" nameend="col2" align="left">-</entry><entry namest="col3" nameend="col3" align="left">9,7</entry><entry namest="col4" nameend="col4" align="left">-</entry><entry namest="col5" nameend="col5" align="left">-</entry><entry namest="col6" nameend="col6" align="left">-</entry><entry namest="col7" nameend="col7" align="left">4,8</entry><entry namest="col8" nameend="col8" align="left">-</entry><entry namest="col9" nameend="col9" align="left">-</entry><entry namest="col10" nameend="col10" align="left">-</entry></row><row><entry namest="col1" nameend="col1" align="left">P3-1</entry><entry namest="col2" nameend="col2" align="left">3,3</entry><entry namest="col3" nameend="col3" align="left">3,3</entry><entry namest="col4" nameend="col4" align="left">3,3</entry><entry namest="col5" nameend="col5" align="left">3,3</entry><entry namest="col6" nameend="col6" align="left">3,3</entry><entry namest="col7" nameend="col7" align="left">3,3</entry><entry namest="col8" nameend="col8" align="left">3,3</entry><entry namest="col9" nameend="col9" align="left">3,3</entry><entry namest="col10" nameend="col10" align="left">-</entry></row><row><entry namest="col1" nameend="col1" align="left">W<sub>s</sub> [Nm]</entry><entry namest="col2" nameend="col2" align="left">35</entry><entry namest="col3" nameend="col3" align="left">36</entry><entry namest="col4" nameend="col4" align="left">36</entry><entry namest="col5" nameend="col5" align="left">36</entry><entry namest="col6" nameend="col6" align="left">34</entry><entry namest="col7" nameend="col7" align="left">32</entry><entry namest="col8" nameend="col8" align="left">35</entry><entry namest="col9" nameend="col9" align="left">35</entry><entry namest="col10" nameend="col10" align="left">-</entry></row><row><entry namest="col1" nameend="col1" align="left">Vicat B [° C]</entry><entry namest="col2" nameend="col2" align="left">125</entry><entry namest="col3" nameend="col3" align="left">125</entry><entry namest="col4" nameend="col4" align="left">127</entry><entry namest="col5" nameend="col5" align="left">128</entry><entry namest="col6" nameend="col6" align="left">127</entry><entry namest="col7" nameend="col7" align="left">126</entry><entry namest="col8" nameend="col8" align="left">126</entry><entry namest="col9" nameend="col9" align="left">127</entry><entry namest="col10" nameend="col10" align="left">107</entry></row><row><entry namest="col1" nameend="col1" align="left">a<sub>k</sub> [kJ / m<sup>2</sup>]</entry><entry namest="col2" nameend="col2" align="left">22,7</entry><entry namest="col3" nameend="col3" align="left">22,7</entry><entry namest="col4" nameend="col4" align="left">23,0</entry><entry namest="col5" nameend="col5" align="left">2,0</entry><entry namest="col6" nameend="col6" align="left">23,0</entry><entry namest="col7" nameend="col7" align="left">21,1</entry><entry namest="col8" nameend="col8" align="left">24</entry><entry namest="col9" nameend="col9" align="left">24,7</entry><entry namest="col10" nameend="col10" align="left">-</entry></row><row><entry namest="col1" nameend="col1" align="left">Tensile strength [N / mm<sup>2</sup>]</entry><entry namest="col2" nameend="col2" align="left">48</entry><entry namest="col3" nameend="col3" align="left">48</entry><entry namest="col4" nameend="col4" align="left">55</entry><entry namest="col5" nameend="col5" align="left">55</entry><entry namest="col6" nameend="col6" align="left">53</entry><entry namest="col7" nameend="col7" align="left">55</entry><entry namest="col8" nameend="col8" align="left">54</entry><entry namest="col9" nameend="col9" align="left">54</entry><entry namest="col10" nameend="col10" align="left">-</entry></row><row rowsep="1"><entry namest="col1" nameend="col10" align="justify">V = comparative tests</entry></row></tbody></tgroup></table></tables>
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| Change of applicant/patenteeR081 | R081 | DE | |
| Change of representativeR082 | R082 | DE | |
| Annual fee paid to national office [announced via postgrant information from national office to epo]GrantedPGFP | PGFP | EP | |
| Annual fee paid to national office [announced via postgrant information from national office to epo]GrantedPGFP | PGFP | EP | |
| Change of representativeR082 | R082 | DE | |
| European patent in force as of 2002-01-01IF02 | IF02 | GB | |
| No opposition filedOpposition26N | 26N | EP | |
| No opposition filed within time limitOppositionORIGINAL CODE: 0009261PLBE | PLBE | EP | |
| Information on the status of an ep patent application or granted ep patentGrantedSTATUS: NO OPPOSITION FILED WITHIN TIME LIMITSTAA | STAA | EP | |
| Fr: translation filedET | ET | EP | |
| Definitive protectionFG2A | FG2A | ES | |
| It: translation for a ep patent filedITF | ITF | EP | |
| It: translation for a ep patent filedITF | ITF | EP | |
| Gb: translation of ep patent filed (gb section 77(6)(a)/1977)GBT | GBT | EP | |
| Corresponds to:REF | REF | EP | |
| Designated contracting statesAK | AK | EP | |
| (expected) grantORIGINAL CODE: 0009210GRAA | GRAA | EP | |
| Despatch of communication of intention to grant a patentORIGINAL CODE: EPIDOS IGRAGRAH | GRAH | EP | |
| Despatch of communication of intention to grantORIGINAL CODE: EPIDOS AGRAGRAG | GRAG | EP | |
| Despatch of communication of intention to grant a patentORIGINAL CODE: EPIDOS IGRAGRAH | GRAH | EP | |
| Despatch of communication of intention to grantORIGINAL CODE: EPIDOS AGRAGRAG | GRAG | EP | |
| Despatch of communication of intention to grantORIGINAL CODE: EPIDOS AGRAGRAG | GRAG | EP | |
| First examination report despatched17Q | 17Q | EP | |
| Request for examination filed17P | 17P | EP | |
| Designated contracting statesAK | AK | EP | |
| Public reference made under article 153(3) epc to a published international application that has entered the european phaseORIGINAL CODE: 0009012PUAI | PUAI | EP |
Numbers
- Publication
- 0800554
- Publication, DOCDB
- 0800554
- Publication, EPODOC
- EP0800554
- Application
- 95941725
- Application, DOCDB
- 95941725
- Application, EPODOC
- EP19950941725
Titles3
- German
- SCHLAGZÄHE, THERMOPLASTISCH VERARBEITBARE MISCHUNG AUS ELASTOMEREN UND THERMOPLASTEN
- English
- IMPACT-RESISTANT, THERMOPLASTIC MIXTURE OF ELASTOMERS AND THERMOPLASTIC MATERIALS
- French
- MELANGE THERMOPLASTIQUE D'ELASTOMERES ET DE MATIERES THERMOPLASTIQUES RESISTANT AUX CHOCS
Classification
- CPC, 6
- B32B27/08
- B32B27/302
- B32B27/32
- B32B27/34
- B32B27/36
- C08L53/02
- IPC, 5
- C08L51 00
- B32B27 08
- C08L53 02
- C08L55 02
- C08L69 00
Designated states1
- Contracting states, 1
- Netherlands (Kingdom of the)
