• 专利附录
  • 专利说明
  • 权利要求
  • 类似技术
  • 同族专利
  • 引用文献
  • 法律状态
  • 优先权
    • 专利摘要:
    PURPOSE: A polymer composition containing two or more different polymers for improving the impact strength of material by synergism except for polyamide as a matrix polymer is provided. Therefore, the molding composition has a low content of impact resistant modifiers, but excellent low-temperature impact strength. CONSTITUTION: This molding composition comprises: (i) 60 to 96.5 parts by weight of polyamide; (ii) 3 to 39.5 parts by weight of an impact-modifying component which contains anhydride groups; (iii) 0.5 to 20 parts by weight of a copolymer which contains units of the monomers: (a)C2-12 α-olefin, (b)one or more acrylic compounds, and (c)olefinically unsaturated epoxide, carboxylic anhydride, carboximide, oxazoline or oxazinone, wherein the total amount of components (i), (ii) and (iii) is 100 parts by weight, and the polyamide has more amino end groups than carboxyl end groups.
    公开号:KR20020000214A
    申请号:KR1020010035830
    申请日:2001-06-22
    公开日:2002-01-05
    发明作者:바르츠빌프리드；바우만프란츠-에리히；슈미츠구이도；오엔브린크게오르크；헤거하랄트
    申请人:페터스,슈베르트페거；데구사-휠스 악티엔게젤샤프트；
    IPC主号:
    专利说明:

    Polymer blend having good low-temperature impact strength
    [1] The present invention relates to a material having excellent low temperature impact strength, in addition to polyamide (PA) as a matrix polymer, comprising at least two other polymers which synergize to enhance the impact strength of the material. The invention also relates to shaped articles made from such materials.
    [2] Engineering components, such as those used in the automotive industry, for example, fuel lines, tubes with one or more layers, meet the very stringent requirements associated with low temperature impact strength today. To this end, tests are carried out using a variety of methods, for example, at a test temperature of −40 ° C.
    [3] Polyamides often used in engineering members of this type, for example nylon-4,6, nylon-6,6, nylon-4,12, nylon-6,12, nylon-6, nylon-11 or nylon- When a plasticizer is added to 12, the low temperature impact strength of the material becomes poor, and it is therefore essential to appropriately modify such material.
    [4] WO 95/22579 describes a method for improving the impact resistance of polyamides using two impact modifiers, wherein one of the impact modifiers used is a modified EPM rubber or a modified EPDM rubber, while Other impact modifiers are terpolymers prepared from ethylene, acrylic esters and glycidyl (meth) acrylates. This publication does not mention the amino terminal group content of the polyamide. This is not surprising since the bonds between maleic anhydride-functionalized EPM rubber or maleic anhydride-functionalized EPDM rubber and polyamides are usually excellent even though the amino terminal groups are considerably lacking.
    [5] A method of using similar molding compositions as layer material in a tube having two or more layers is described in EP-A 0 731 308, which again does not mention the amino end groups of the polyamide.
    [6] It is an object of the present invention to provide molding compositions and shaped articles having a particularly high low temperature impact strength. It is another object of the present invention to provide molding compositions and articles having a low impact resistance modifier as low as possible but low temperature impact strength so that the influence on other important properties is as small as possible. Finally, it is an object of the present invention to find a means to counteract the effect of plasticizers on reducing cold impact strength in plasticized polyamide molding compositions.
    [7] This purpose,
    [8] 60 to 96.5 parts by weight of polyamide (I),
    [9] 3 to 39.5 parts by weight of impact resistance improving component (II) containing an anhydride group selected from the group consisting of ethylene / α-olefin copolymers and styrene-ethylene / butylene block copolymers; and
    [10] 20 to 94.5 weight percent of at least one α-olefin (a) having 2 to 12 carbon atoms, acrylic acid and methacrylic acid and salts thereof, esters of acrylic acid and / or methacrylic acid with a C 1 -C 12 alcohol, wherein the ester is Optionally comprising free hydroxyl or epoxide functional groups), 5-79.5% by weight of one or more acrylic acid compounds (b) selected from the group consisting of acrylonitrile and methacrylonitrile and acrylamide and methacrylamide and olefinically unsaturated epoxides A molding composition comprising 0.5 to 20 parts by weight of copolymer (III) containing units of monomers consisting of 0.5 to 50% by weight of the side, carboxylic anhydride, carboximide, oxazoline or oxazinone (c), wherein The total amount of components (I), (II) and (III) is 100 parts by weight, and the polyamide contains more amino terminal groups than carboxyl terminal groups. The.
    [11] In a preferred embodiment, such molding compositions are
    [12] 60 to 96.5 parts by weight of polyamide (I), particularly preferably 70 to 85 parts by weight,
    [13] 5 to 30 parts by weight, preferably 6 to 25 parts by weight, particularly preferably 7 to 20 parts by weight of the impact resistance improving component (II) and
    [14] 30-80% by weight of α-olefin (s) (a), 7-70% by weight of acrylic acid compound (s) (b), particularly preferably 10-60% by weight and olefinically unsaturated epoxides, carboxylic anhydrides, carboxes 0.6-15 parts by weight of copolymer (III), particularly preferably containing units of monomers consisting of 1 to 40% by weight, particularly preferably 5 to 30% by weight of mead, oxazoline or oxazinone (c) 0.7 to 10 parts by weight.
    [15] Polyamides which can be used are mainly aliphatic homocondensates or co-condensates, for example nylon-4,6, nylon-6,6, nylon-6,8, nylon-6,10, nylon-6,12 , Nylon-4,10, Nylon-8,10, Nylon-10,10, Nylon-4,12, Nylon-10,12, Nylon-12,12, Nylon-6, Nylon-7, Nylon-8, Nylon -9, nylon-10, nylon-11 and nylon-12 (the names of the polyamides correspond to international standards where the first number represents the number of carbon atoms of the starting diamine and the last number represents the number of carbon atoms of the dicarboxylic acid). If only one number is specified, it means that the starting material is α, ω-aminocarboxylic acid or lactam derived therefrom. See, for example, H. Domininghaus, Die Kunststoffe und ihre Eigenschaften [Plastics and their Properties], pp. 272 et seq. VDI-Verlag, 1976.
    [16] When using copolyamides, they contain adipic acid, sebacic acid, suberic acid, isophthalic acid, terephthalic acid and naphthalene-2,6-dicarboxylic acid as coacids and bis (4) as imitation diamines. -Aminocyclohexyl) methane, trimethylhexamethylenediamine, hexamethylenediamine and the like. Lactams, such as caprolactam or laurolactam, and aminocarboxylic acids, such as ω-aminoundecanoic acid, may also be incorporated as ingredients.
    [17] Methods for preparing these polyamides are known from D. B. Jacobs, J. Zimmermann, Polymerization Processes, pp. 424-467, Interscience Publishers, New York, 1977 and DE-B 21 52 194.
    [18] Other suitable polyamides include US Pat. Nos. 2 071 250, 2 071,251, 2 130 523, 2 130 948, 2 241 322, 2 312 966, 2 512 606 and 3 393 210 and (see Kirk-Othmer, Encyclopedia of Chemical Technology, 3rd edn., Vol. 18, pp. 328 et seq. And 435 et seq., Wiley & Sons, 1982). Same mixed aliphatic / aromatic polycondensates.
    [19] Suitable as preferred ethylene / α-olefin copolymers of component (II) are
    [20] Ethylene / C 3 -C 12 α-olefin copolymers containing 20 to 96% by weight, preferably 25 to 85% by weight of ethylene. Examples of C 3 -C 12 α-olefins used are propene, 1-butene, 1-pentene, 1-hexene, 1-octene, 1-decene or 1-dodecene. Typical examples of such materials are ethylene-propylene rubber and LLDPE and VLDPE.
    [21] 20 to 96% by weight of ethylene, preferably 25 to 85% by weight and non-conjugated dienes (for example bicyclo [2.2.1] -heptadiene, 1,4-hexadiene, dicyclopentadiene, in particular 5 Ethylene / C 3 -C 12 α-olefin / nonconjugated diene terpolymer containing up to about 10% by weight. Examples of suitable C 3 -C 12 α-olefins are propene, 1-butene, 1-pentene, 1-hexene, 1-octene, 1-decene or 1-dodecene.
    [22] Methods of preparing such copolymers or terpolymers using Ziegler-Natta catalysts are prior art.
    [23] The styrene-ethylene / butene block copolymers preferably used are styrene-ethylene / butylene-styrene block copolymers (SEBS) which can be obtained by hydrogenating a styrene-butadiene-styrene block copolymer. However, a deblocking system (SEB) or a multiblock system may be used. Block copolymers of this type are prior art.
    [24] Component (II) is introduced by known methods by thermal or free radical reaction of the main chain polymer with unsaturated dicarboxylic anhydrides, unsaturated dicarboxylic acids or unsaturated monoalkyl dicarboxylates, and at a concentration sufficient to ensure good binding to the polyamide. It contains an anhydride group introduced into. Examples of suitable formulations are maleic acid, maleic anhydride, monobutyl maleate, fumaric acid, aconic acid or itaconic anhydride. When using this method, it is preferable to graf the 0.1-4 weight% of unsaturated anhydrides to the impact resistance improvement component (II). As in the prior art, it is also possible to graf other unsaturated monomers such as styrene, α-methylstyrene or indene with unsaturated dicarboxylic anhydrides or precursors thereof.
    [25] Examples of monomers used to prepare the copolymer of component (III) include, but are not limited to:
    [26] (a) α-olefins such as ethylene, propene, 1-butene, 1-pentene, 1-hexene, 1-octene, 1-decene or 1-dodecene,
    [27] (b) acrylic acid, methacrylic acid, or a salt thereof comprising Na + or Zn 2+ as a counterion; Methyl acrylate, ethyl acrylate, n-propyl acrylate, n-butyl acrylate, isobutyl acrylate, n-hexyl acrylate, n-octyl acrylate, 2-ethylhexyl acrylate, isononyl acrylate, dode Sil acrylate, methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, 2-ethylhexyl methacrylate, hydroxy-ethyl methacrylate, 4-hydroxybutyl methacrylate, glycidyl acrylate, glycidyl methacrylate, acrylonitrile, methacrylonitrile, acrylamide, N-methyl-acrylamide, N, N-dimethylacrylamide, N -Ethylacrylamide, N-hydroxyethylacrylamide, N-propylacrylamide, N-butylacrylamide, N- (2-ethylhexyl) acrylamide, methacrylamide, N-methylmeth Tacrylamide, N, N-dimethylacrylamide, N-ethyl methacrylamide, N-hydroxyethyl methacrylamide, N-propyl methacrylamide, N-butyl methacrylamide, N, N-dibutyl methacryl Amides, N- (2-ethylhexyl) methacrylamide;
    [28] (c) vinyloxirane, allyloxirane, glycidyl acrylate, glycidyl methacrylate, maleic anhydride, aconic acid anhydride, itaconic anhydride, and di produced from these anhydrides by reaction with water. Carboxylic acid; Maleimide, N-methylmaleimide, N-ethylmaleimide, N-butylmaleimide, N-phenylmaleimide, aconitimide, N-methyl-aconitimide, N-phenylaconitimide, itaciconimide , N-methyl itaconimide, N-phenyl itaconimide, N-acryloyl caprolactam, N-methacryloyl caprolactam, N-acryloyl laurolactam, N-methacryloyllau Rolactam, vinyloxazoline, isopropenyloxazoline, allyloxazoline, vinyloxazinone or isopropenyloxazinone.
    [29] When using glycidyl acrylate or glycidyl methacrylate, they simultaneously act as acrylic acid compound (b), so if the amount of glycidyl (meth) acrylate is sufficient, there is no need for other acrylic acid compounds to be present. In this particular embodiment, the copolymer contains the following monomer units, wherein the total amount of component (b) and component (c) is at least 5.5% by weight:
    [30] (a) 20 to 94.5 weight percent of at least one α-olefin having 2 to 12 carbon atoms,
    [31] (b) one selected from the group consisting of acrylic acid and methacrylic acid and salts thereof, esters of acrylic acid and / or methacrylic acid with C 1 -C 12 alcohols, acrylonitrile and methacrylonitrile, acrylamide and methacrylamide 0 to 79.5% by weight of the above acrylic acid compound,
    [32] (c) 0.5 to 80% by weight ester of acrylic or methacrylic acid, where the ester contains an epoxy group.
    [33] Copolymers of component (III) may contain small amounts of other copolymerized monomers, such as dimethyl maleate, dibutyl fumarate, diethyl itaconate or styrene, as long as they do not significantly detrimentally affect properties. Can be.
    [34] Processes for the preparation of this type of copolymer are prior art. For example, a wide range of types are commercially available, such as LOTADER R (Elf Atochem; ethylene / acrylate / tercomponent or ethylene / glycidyl / methacrylate).
    [35] The polyamides of component (I) have excess amino terminal groups usually caused by using diamines as molecular weight regulators during the preparation of the polyamides. Excess amino terminal groups can also be achieved by mixing polyamides with a low amino group content and high molecular weight polyamides with a high amino group content. The ratio of amino end groups to carboxyl end groups should be at least 51:49, preferably at least 55:45, particularly preferably at least 60:40 and most preferably at least 70:30.
    [36] In one advantageous embodiment, part of the polyamide of component (I) is in the form of a polyamine-polyamide copolymer, specifically 0.1 to 10 parts by weight, preferably 0.2 to 5 parts by weight, particularly preferably 0.25 to 3 parts by weight It is wealth. Polyamine-polyamide copolymers are prepared using the following monomers:
    [37] (a) four nitrogen atoms present in an amount of 0.5 to 25% by weight, preferably 1 to 20% by weight, particularly preferably 1.5 to 16% by weight, based on the polyamine-polyamide copolymer At least 8, particularly preferably at least 11 and polyamines having a number average molecular weight (Mn) of at least 146 g / mol, preferably at least 500 g / mol and particularly preferably at least 800 g / mol and
    [38] (b) a polyamide forming monomer selected from the group consisting of lactams, ω-aminocarboxylic acids and / or equimolar combinations of diamines and dicarboxylic acids.
    [39] In one preferred embodiment, the concentration of amino groups in the polyamine-polyamide copolymer is between 100 and 2500 mmol / kg.
    [40] Examples of components that can be used as polyamines are as follows:
    [41] Polyvinylamine (see literature; Rompp Chemie Lexikon [Rompp's Chemical Encyclopedia], 9th edition, Vol. 6, p. 4921, Georg Thieme Verlag Stuttgart, 1992),
    [42] Polyamines prepared from alternating polyketones (see DE-A 196 54 058),
    [43] -((H 2 N- (CH 2 ) 3 ) 2 N- (CH 2 ) 3 ) 2 -N (CH 2 ) 2 -N ((CH 2 ) 2 -N (((CH 2 ) 3 -NH 2 ) 2 ) 2 (see DE-A No. 196 54 179) or tris (2-aminoethyl) amine, N, N-bis (2-aminoethyl) -N ', N'-bis [2- [bis ( 2-aminoethyl) amino] ethyl] -1,2-ethanediamine, 3,15-bis (2-aminoethyl) -6,12-bis [2- [bis (2-aminoethyl) amino] ethyl]- 9- [2- [bis [2- [bis (2-aminoethyl) amino] ethyl] amino] ethyl] -3,6,9,12,15-pentazaheptadecane-1,17-diamine (see literature) Dendrimers such as JM Warakomski, Chem.Mat. 1992, 4, 1000-1004),
    [44] Straight chain polyethyleneimines that can be prepared by polymerizing and then hydrolyzing 4,5-dihydro-1,3-oxazole (see literature; Houben-Weyl, Methoden der Organischen Chemie [Methods in organic chemistry], Vol. E20) , pp. 1482-1487, Georg Thieme Verlag Stuttgart, 1987),
    [45] Aziridine (see literature; Houben-Weyl, Methoden der Organischen Chemie [Methods in organic chemistry], Vol. E20, pp. 1482-1487, Georg Thieme Verlag Stuttgart, 1987) and is generally obtained as Branched polyethyleneimines having an amino group distribution of amino groups 25 to 46%, secondary amino groups 30 to 45% and tertiary amino groups 16 to 40%.
    [46] If preferred, the number average molecular weight (Mn) of the polyamine is 20000 g / mol or less, particularly preferably 10000 g / mol or less, more particularly preferably 5000 g / mol or less.
    [47] The lactam or ω-aminocarboxylic acid used as the polyamide-forming monomer has 4 to 19 carbon atoms, in particular 6 to 12 carbon atoms. It may be particularly preferred to use ε-caprolactam, ε-aminocaproic acid, caprylolatam, ω-aminocaprylic acid, laurolactam, ω-aminododecanoic acid and / or ω-aminoundecanoic acid.
    [48] Examples of combinations of diamines with dicarboxylic acids include hexamethylenediamine / adipic acid, hexamethylenediamine / dodecanedioic acid, octamethylenediamine / sebacic acid, decamethylenediamine / sebacic acid, decamethylenediamine / dodecanedioic acid, dodeca Methylenediamine / dodecanedioic acid and dodecamethylenediamine / 2,6-naphthalenedicarboxylic acid. However, in addition to these, decamethylenediamine / dodecanedioic acid / terephthalic acid, hexamethylenediamine / adipic acid / terephthalic acid, hexamethylenediamine / adipic acid / caprolactam, decamethylenediamine / dodecanedioic acid / ω-aminoundecanoic acid, Other combinations such as decamethylenediamine / dodecanedioic acid / laurolactam, decamethylenediamine / terephthalic acid / laurolactam or dodecamethylenediamine / 2,6-naphthalenedicarboxylic acid / laurolactam may also be used.
    [49] In one preferred embodiment, the polyamine-polyamide copolymer is selected from the group consisting of 0.015 to about 3 mole percent dicarboxylic acid and 0.01 to about 1.2 mole percent tricarboxylic acid, based on the total amount of the other polyamide-forming monomers, respectively. Prepared using further carboxylic acid. In calculating this ratio, the respective monomers are included in consideration of the combination of the equivalents of diamine and dicarboxylic acid. When using dicarboxylic acids, it is preferably added in an amount of 0.03 to 2.2 mol%, particularly preferably 0.05 to 1.5 mol%, very particularly preferably 0.1 to 1 mol%, especially 0.15 to 0.65 mol%. When using tricarboxylic acid, preferably 0.02 to 0.9 mol%, particularly preferably 0.025 to 0.6 mol%, very particularly preferably 0.03 to 0.4 mol%, in particular 0.04 to 0.25 mol%. Incidental use of oligocarboxylic acids significantly improves resistance to solvents and fuels, in particular to hydrolysis and to alcoholic degradation.
    [50] The oligocarboxylic acids used are preferably di- or tri-carboxylic acids having 6 to 24 carbon atoms, for example adipic acid, suberic acid, azelaic acid, sebacic acid, dodecanedioic acid, isophthalic acid, 2,6-naphthalene Dicarboxylic acid, cyclohexane-1,4-dicarboxylic acid, trimesic acid and / or trimellitic acid.
    [51] If desired, aliphatic, cycloaliphatic, aromatic, aralkyl and / or alkylaryl-substituted monocarboxylic acids having 3 to 50 carbon atoms, such as lauric acid, unsaturated fatty acids, acrylic acid or benzoic acid, may also be used as modifiers. Such modulators can be used to lower the concentration of amino groups without changing the molecular structure. This method can also be used to introduce functional groups such as double bonds, triple bonds, and the like. However, it is preferred that the polyamine-polyamide copolymer comprise a significant proportion of amino groups. The concentration of amino groups in such copolymers is preferably 150 to 1500 mmol / kg, particularly preferably 250 to 1300 mmol / kg, very particularly preferably 300 to 1100 mmol / kg. In the case of the present invention, the amino groups described above and below are all secondary or tertiary amine functional groups which may be present in the polyamine as well as amino terminal groups.
    [52] The polyamine-polyamide copolymer of the present invention can be produced by various processes.
    [53] One method is to take only lactams and separate the omega-aminocarboxylic acids and polyamines together to effect polymerization or polycondensation. Oligocarboxylic acids can be added at the beginning of the reaction or during the course of the reaction.
    [54] However, one preferred method is to first perform lactam cleavage and prepolymerization (in the alternative, taking only the appropriate ω-aminocarboxylic acid, alternatively taking diamine and dicarboxylic acid together and directly using prepolymerization), and second In the step, it is a two-step process in which the metering portion is added before, during or after the prepolymerization of the oligocarboxylic acid used incidentally with the addition of the polyamine. The pressure is then released at a temperature of 200 to 290 ° C. and the polycondensation is carried out in a nitrogen stream or in vacuum.
    [55] Another preferred method is to hydrolyze the polyamide to give a prepolymer which is simultaneously or subsequently reacted with the polyamine. Preference is given to using polyamides in which all of the oligocarboxylic acids with an end group difference of almost zero or incidentally used are previously incorporated by polycondensation. However, oligocarboxylic acids can also be added at the start of the decomposition reaction or during the progress of the reaction.
    [56] Such methods can be used to produce highly branched polyamides having an acid value of 40 mmol / kg or less, preferably 20 mmol / kg or less, particularly preferably 10 mmol / kg or less. The reaction is carried out at a temperature of 200 to 290 ° C. for 1 to 5 hours to almost complete conversion.
    [57] If desired, a vacuum step that lasts for several hours can be added as another processing step. This step lasts at least 4 hours, preferably at least 6 hours and particularly preferably at least 8 hours at 200 to 290 ° C. After several hours of induction, an increase in melt viscosity was observed, probably due to the removal of ammonia and chain linkages as the amino end groups reacted with each other. It also increases the molecular weight, which is particularly advantageous for molding compositions for extrusion.
    [58] In addition, if it is not desired to complete the reaction in the molten state, the polyamine-polyamide copolymer may be solid-phase post-condensed as in the prior art.
    [59] The polyamine-polyamide copolymer can be used to adjust the ratio of amino end groups to carboxylic acid end groups in component (I). On the one hand, the interaction between component (I) and on the other hand component (II) and (III) is further improved, which further improves the low temperature impact strength. At the same time, the addition of these copolymers lowers the melt viscosity, so this type of molding composition is easier to process. This finding is surprising because there is generally an inverse correlation between melt viscosity and impact strength.
    [60] In addition to components (I) to (III), the molding composition may also comprise relatively small amounts of additives necessary to achieve certain properties. Examples thereof include plasticizers, pigments or fillers (e.g. carbon black, titanium dioxide, zinc sulfide, silicates or carbonates), processing aids (e.g. waxes, zinc stearate or calcium stearate), flame retardants (e.g. For example, magnesium hydroxide, aluminum hydroxide or melamine cyanurate), glass fibers, antioxidants, UV stabilizers, and additives that provide antistatic properties or electrical conductivity to the product (eg, carbon fiber, graphite fibrils, stainless steel) Steel fibers or conductive black).
    [61] In one preferred embodiment, the molding composition comprises plasticizer in an amount of 1 to 25% by weight, preferably 2 to 20% by weight, particularly preferably 3 to 15% by weight.
    [62] Plasticizers and their use in polyamides are known. A general overview of suitable plasticizers for polyamides can be found in Gachter / Muller, Kunststoffadditive [Plastics additives], C. Hanser Verlag, 2nd edition, p. 296.
    [63] Examples of typical compounds suitable as plasticizers are esters of p-hydroxybenzoic acid having 2 to 20 carbon atoms in the alcohol component or amides of arylsulfonic acid having 2 to 12 carbon atoms in the amine component, preferably amides of benzenesulfonic acid.
    [64] Examples of plasticizers that can be used are ethyl p-hydroxybenzoate, octyl p-hydroxybenzoate, isohexadecyl p-hydroxybenzoate, Nn-octyltoluenesulfonamide, Nn-butylbenzenesulfonamide or N-2 Ethylhexylbenzenesulfonamide.
    [65] The molding compositions of the invention are used, for example, in the manufacture of molded articles for mechanical engineering products or sporting goods, and in particular for the manufacture of molded articles for the production of industrial parts in the automotive industry. It is generally a tube, a filler neck or a container, especially for moving or storing liquids or gases. This type of tube may be straight or corrugated in shape, or only a portion of it may be corrugated. Since the corrugated tube is a prior art (eg US Pat. No. 5 460 771), there is no need to further discuss this topic. Important uses are as fuel lines, tank-fill pipes, steam lines (porridges, lines for moving fuel vapors, eg ventilation lines), coolant-fluid lines, air-conditioning system lines or fuel tanks. Molding compositions include quick connectors, pump housings, fuel-filter housings, activated carbon canisters, valve housings, anti-sludge cups, connectors to plastic fuel tanks, tank charger necks, cable coatings for electrical cables, housings for hydraulic cylinders, windshields- It is also advantageously used for cleaning system lines, clutch lines, pressure reducing lines, ventilation lines, hydraulic lines or air-brake lines.
    [66] The molding compositions of the invention are also used to produce fuel-pump lines or water-feed lines.
    [67] All such moldings consist solely of the molding composition of the invention or, for example, one of two or more layers, for example a reinforcing outer or inner layer, in a tube having two or more layers or a container having two or more layers. As a molding composition of the present invention may be included.
    [68] The molded article of the present invention can be produced by conventional prior art methods such as extrusion, coextrusion, blow molding or injection molding.
    [69] Example
    [70] The following materials are used for the experiment:
    [71] PA1: commercially available nylon-6,12 having an excess carboxyl end group (acid value: 60 mmol / kg; amino end group concentration: 11 mmol / kg); η rel = 2.2; VESTAMID R D22 (manufactured by DEGUSSA-HULS AG)
    [72] PA2: nylon-6,12 having an excess amino terminal group (acid value: 27 mmol / kg; amino terminal group concentration: 48 mmol / kg); η rel = 2.2
    [73] EXXELOR R VA 1803: Maleic anhydride-grafted ethylene / propylene rubber as impact resistance improving component (EXXON Chemicals)
    [74] LOTADER R AX 8900: Random terpolymer (ATOCHEM) made from ethylene, about 32% by weight of acrylate and about 7-9% by weight of glycidyl methacrylate
    [75] BBSA: N-butylbenzenesulfonamide (plasticizer).
    [76] Comparative Example 1
    [77] 100 parts by weight of PA1, 10 parts by weight of BBSA, 10 parts by weight of Excelror R VA 1803 and 1 part by weight of Rotader R AX 8900 are mixed and extruded using a Berstorff ZE 25 33D twin screw kneader. Pelletize at a treatment rate of 10 kg / h at 200 rpm. These pellets are then used to produce extruded monotubes of size 8 × 1 mm (ie, outer diameter 8 mm, wall thickness 1 mm). The impact test results are shown in Table 1.
    [78] Example 1
    [79] 100 parts by weight of PA2, 10 parts by weight of BBSA, 10 parts by weight of Excelror R VA 1803 and 1 part by weight of Rotader R AX 8900, were added using a Berstorp ZE 25 33D twin screw kneader as in Comparative Example 1. Process with The impact test results are shown in Table 1.
    [80] Comparative Example 2
    [81] Same as Example 1 except that no Rotader R AX 8900 is used (see Table 1).
    [82] Impact strength at -40 ° C measured on an 8 × 1 mm tube StandardBreak ratio: Number of breaks per 10 test tubes Comparative Example 1Example 1Comparative Example 2 SAE J844 (shock weight 455 g)20One SAE J2260 (shock weight 912 g)000 VW / Audi (shock weight 500 g)506 DIN 73378000
    [83] The present invention provides molding compositions and molded articles having the same low impact resistance as possible but low temperature impact strength so that the influence on other important properties is as small as possible, and provides low temperature impact strength in plasticized polyamide molding compositions. It provides a means to counteract the effect of reducing plasticizers.
    权利要求:
    Claims (13)
    [1" claim-type="Currently amended] 60 to 96.5 parts by weight of polyamide (I),
    3 to 39.5 parts by weight of impact resistance improving component (II) containing an anhydride group selected from the group consisting of ethylene / α-olefin copolymers and styrene-ethylene / butylene block copolymers; and
    20 to 94.5 weight percent of at least one α-olefin (a) having 2 to 12 carbon atoms, acrylic acid and methacrylic acid and salts thereof, esters of acrylic acid and / or methacrylic acid with C 1 -C 12 alcohols, with acrylonitrile 5-79.5% by weight of methacrylonitrile and at least one acrylic acid compound (b) selected from the group consisting of acrylamide and methacrylamide and olefinic unsaturated epoxides, carboxylic anhydrides, carboximides, oxazolines or oxazinones (c) 0.5 to 20 parts by weight of copolymer (III) containing units of monomers comprised of 0.5 to 50% by weight, wherein the total amount of components (I), (II) and (III) is 100 parts by weight, polyamide A molding composition wherein the amino acid group contains more amino terminal groups than carboxyl terminal groups.
    [2" claim-type="Currently amended] The copolymer of claim 1 wherein the copolymer of component (III)
    20 to 94.5 weight percent of at least one α-olefin (a) having 2 to 12 carbon atoms,
    Acrylic and methacrylic acid and salts thereof,
    Esters of acrylic acid and / or methacrylic acid with C 1 -C 12 alcohols,
    Acrylonitrile and methacrylonitrile and
    0-79.5% by weight of at least one acrylic acid compound (b) selected from the group consisting of acrylamide and methacrylamide and
    Molding composition comprising 0.5 to 80% by weight of ester (c) of acrylic acid or methacrylic acid, wherein the ester contains an epoxy group.
    [3" claim-type="Currently amended] The method of claim 1 or 2, wherein the polyamide is nylon-4,6, nylon-6,6, nylon-6,8, nylon-6,10, nylon-6,12, nylon-4,10, nylon -8,10, nylon-10,10, nylon-4,12, nylon-10,12, nylon-12,12, nylon-6, nylon-7, nylon-8, nylon-9, nylon-10, nylon Molding composition selected from the group consisting of -11 and nylon-12.
    [4" claim-type="Currently amended] The polyamine monomer according to any one of claims 1 to 3, wherein, in component (I), 0.1 to 10 parts by weight in the polyamide has 4 or more nitrogen atoms and has a number average molecular weight (M n ) of 146 g / mol or more. (a) a polyamide-forming monomer selected from the group consisting of 0.5 to 25% by weight (based on the weight of the polyamine-polyamide copolymer) and an equimolar combination of lactam, ω-aminocarboxylic acid and / or diamine and dicarboxylic acid Molding composition in the form of a polyamine-polyamide copolymer prepared using (b).
    [5" claim-type="Currently amended] The molding composition according to any one of claims 1 to 4, which contains 1 to 25% by weight of a plasticizer.
    [6" claim-type="Currently amended] The molding composition according to any one of claims 1 to 5, wherein the molding composition is provided with antistatic property and / or electric conductivity.
    [7" claim-type="Currently amended] Molded article made from the molding composition according to claim 1.
    [8" claim-type="Currently amended] 8. The molded article according to claim 7, which is an engineering member in the automotive industry.
    [9" claim-type="Currently amended] The molded article according to claim 7 or 8, which is a tube, a charger neck or a container.
    [10" claim-type="Currently amended] The fuel line, the tank-fill pipe, the steam line, the fuel-pump line, the coolant-fluid line, the air-conditioning system line, the fuel container, the quick connector, the pump housing, Fuel-filter housings, activated carbon canisters, valve housings, anti-sludge cups, connectors to plastic fuel tanks, tank charger necks, cable coatings for electrical cables, housings for hydraulic cylinders, windshield-cleaning system lines, clutch lines, decompression lines Molded parts for ventilation lines, hydraulic lines, air-brake lines or water-supply lines.
    [11" claim-type="Currently amended] The molded article according to any one of claims 7 to 10, comprising the molding composition according to any one of claims 1 to 6 as one of two or more layers.
    [12" claim-type="Currently amended] The molded article according to claim 11, which is a tube having two or more layers.
    [13" claim-type="Currently amended] The molded article according to any one of claims 7 to 12, which is produced by extrusion, coextrusion, blow molding, or injection molding.
    类似技术:
    公开号 | 公开日 | 专利标题
    ES2288902T3|2008-02-01|Material composed of various layers of polyamide.
    KR100648878B1|2006-11-24|Transparent polyamide block and polyether block copolymers
    EP2670805B1|2017-11-08|Melt-blended thermoplastic composition
    JP4523342B2|2010-08-11|Polyamide-based multilayer tube for gasoline transportation
    ES2198381T3|2004-02-01|Multiple layer composite material based on polyamide / polyolefine.
    US8133561B2|2012-03-13|Multi-layer composite comprising an EVOH layer and a protective layer
    US6306951B1|2001-10-23|Polyphthalamide composition
    US4410661A|1983-10-18|Toughened polyamide blends
    AU780427B2|2005-03-24|Composite having two or more layers, including an EVOH layer
    KR101202602B1|2012-11-19|Multilayer composite having a polyester layer and a protective layer
    KR100972088B1|2010-07-22|Copolyamides
    KR100382092B1|2003-05-09|Multilayer structure and tank consisting of this structure, which has a barrier layer in direct contact with the fluid contained
    EP1065048B1|2004-08-04|Composite multilayer structure
    ES2624147T3|2017-07-13|Reactive polyamide resin and polyamide resin compositions
    JP3945686B2|2007-07-18|Molding material or injection molding material and molded product
    EP1877467B1|2019-04-17|Use of thermoplastic compositions for the thermal protection of substrates
    ES2437440T3|2014-01-10|Composition comprising a copolyamide and a crosslinked polyolefin
    TWI482817B|2015-05-01|Partially aromatic polyamide moulding compositions and their uses
    EP1797142B2|2020-04-29|Flexible semicrystalline polyamides
    JP3894445B2|2007-03-22|Polyamide compressed air hose
    EP2132030B1|2017-02-22|Flexible pipes for conveying crude oil or gas and flexible pipe using a polyamide composition
    JP3819288B2|2006-09-06|Molding material containing polyamine-polyamide-copolymer, use thereof and article containing the molding material
    US7232597B2|2007-06-19|Corrugated polyamide tube
    JP5867418B2|2016-02-24|Polyether polyamide elastomer
    JP5105563B2|2012-12-26|Polyamide and polyamide composition
    同族专利:
    公开号 | 公开日
    JP4662656B2|2011-03-30|
    CA2351152A1|2001-12-23|
    EP1170334A3|2003-01-29|
    JP2002069296A|2002-03-08|
    DE50113219D1|2007-12-20|
    EP1170334B1|2007-11-07|
    AT377629T|2007-11-15|
    KR100843503B1|2008-07-04|
    US20020019477A1|2002-02-14|
    US6579581B2|2003-06-17|
    MXPA01006398A|2002-08-06|
    BR0100937A|2002-02-13|
    EP1170334A2|2002-01-09|
    BR0100937B1|2010-09-21|
    CN1200974C|2005-05-11|
    CZ20012346A3|2002-02-13|
    DE10030716A1|2002-01-03|
    CN1330111A|2002-01-09|
    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    法律状态:
    2000-06-23|Priority to DE10030716.7
    2000-06-23|Priority to DE2000130716
    2001-06-22|Application filed by 페터스,슈베르트페거, 데구사-휠스 악티엔게젤샤프트
    2002-01-05|Publication of KR20020000214A
    2008-07-04|Application granted
    2008-07-04|Publication of KR100843503B1
    优先权:
    申请号 | 申请日 | 专利标题
    DE10030716.7|2000-06-23|
    DE2000130716|DE10030716A1|2000-06-23|2000-06-23|Low temperature impact resistant polymer alloy|
    [返回顶部]