JPH0325458B2 - - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to polyether polyamide resin compositions. Specifically, the present invention relates to a polyamide resin composition that provides a molded article having extremely high flexibility and impact resistance, as well as excellent appearance and color tone. In recent years, thermoplastic elastomers have been attracting attention as a material that fills the gap between rubber and plastics. Polyamide resins are in great demand as engineering plastics due to their excellent physical properties. Therefore, polyamide resin-based elastomers are also expected to be in great demand due to their excellent mechanical, thermal and chemical properties. Polyether polyamide resin elastomer is a copolymer of polyamide, which is a hard segment component, and polyether, which is a soft segment component.
133424). In order to improve the flexibility of an elastomer, it is possible to increase the ratio of the soft segment component to the hard segment component. The method has its limits. An alternative method is to add to the elastomer a polymer having active groups and rubber elasticity that can react with the polyether polyamide. In view of this point, the present inventors conducted extensive research and found that
The present invention was achieved by discovering that a specific modified ethylene copolymer is effective as a polymer to be added to polyether polyamide. That is, the gist of the invention is that the ether oxygen atoms have at least three ether oxygen atoms and these ether oxygen atoms form a linear chain of at least three carbon atoms or at least two carbon atoms between these atoms. a diamine comprising polyether blocks separated from each other by branched chains having carbon atoms;
Approximately equivalent amount of dicarboxylic acid and the weight proportion of the polyether block is 8% of the total polyether polyamide.
A polyether polyamide elastomer prepared by polycondensation with other polyamide-forming compounds in an amount such that the amount is ~60% by weight, and 1/10 to 2/3 times the weight of ethylene to the polyether polyamide elastomer. A crystallinity of 1 to 35%, obtained by grafting 0.05 to 1.5% by weight of an α,β-unsaturated carboxylic acid or an acid derivative thereof to the copolymer with an α-olefin having 3 or more carbon atoms, It consists of a polyether polyamide resin composition comprising a modified ethylene copolymer with a melt index of 0.01 to 50 g/10 min. The present invention will be described in detail below. The polyamide used as a raw material in the composition of the present invention has at least three ether oxygen atoms, and these ether oxygen atoms have at least a gap between these atoms. a diamine comprising polyether blocks separated from each other by linear chains of 3 carbon atoms or branched chains having at least 3 carbon atoms, approximately equivalent amounts of dicarboxylic acid, and the polyether blocks Polyether polyamide elastomers prepared by polycondensation with other polyamide-forming compounds in an amount such that the weight proportion of the total polyether polyamide is from 8 to 60% by weight of the total polyether polyamide, more particularly in JP-A-55-133424. This is a polyether polyamide elastomer with a structure detailed in the publication. Specifically, said diamine is advantageously 3 to 30
It has ether oxygen atoms. These oxygen atoms are preferably separated from each other by an aliphatic linear chain of preferably 3 to 4 C atoms. However, aliphatic, cycloaliphatic and araliphatic branched carbons between ether oxygen atoms are not excluded. Diamines therefore have the formula: H ₂ N—[(CH ₂ ) _o —O—] _n (CH ₂ ) _o —NH ₂ , where n is at least 3, advantageously from 3 to 4, m
represents 3 to 30, and repeated n can represent the same or different magnitude within the definition]
Preference is given to diamines of the form: The production of such diamines is known (for example, DE 2749972). A preferred diamine is known under the name "bis-(3-aminopropyl)-polytetrahydrofuran" (manufactured by BASF, Ludwigshalfen, West Germany) and has the formula I: _H2N- ( _CH2 ) _3- O- [(CH ₂ ) ₄ -O-] _p
( _CH2 ) ₃ - _NH2 , in which p is 2 to 30, preferably 6 to 3. Preferred dicarboxylic acids are terephthalic acid, isophthalic acid or mixtures of these two acids. Also, commercial mixtures of dimerized fatty acids having 36 C atoms [such products are referred to as “EMPOL dimer and trimer
Dimer and Trimer Acids” (Unilever, Emery, Netherlands)
] and “Diacid 1550” (Charleston, USA).
Manufactured by Westvaco], formula: It was found that the dicarboxylic acid represented by is extremely excellent. Suitable other polyamide-forming compounds are the customary nylon monomers (as the case may be, nylon oligomers and nylon precondensates) or derivatives of these monomers, in particular caprolactam, laurolactam, 11-aminoundecanoic acid, and the like. The proportion of other polyamide-forming compounds in the total polyether polyamide is 30% by weight or more and 80% by weight or less, preferably 40% by weight or more and 70% by weight or less.
If the amount is less than 3% by weight, the properties of the resulting polyether polyamide resin composition as engineering plastics, such as heat resistance and chemical resistance, will deteriorate, and after the polymerization is completed, the polymer will be extracted from the polymerization vessel and pelletized. Sometimes the low melt viscosity makes handling extremely difficult. If the amount exceeds 80% by weight, the flexibility of the resulting polyether polyamide resin composition will be significantly reduced. Polycondensation is carried out in a conventional manner. In this case, the starting compounds according to the definition are, for example, reacted simultaneously to form a block polymer. Among the polyether polyamides according to the invention are:
In addition to polyether blocks having 3 to 30 ether oxygen atoms, polyamide chains of the conventional type (which are preferably homopolyamide blocks; but copolyamides are also possible and permissible) are present. In the composition of the present invention, in order to improve the flexibility and impact resistance of the polyether polyamide elastomer, a copolymer of ethylene and an α-olefin having 3 or more carbon atoms (hereinafter referred to as an unmodified ethylene copolymer) is used. Melt index (hereinafter referred to as MI
) 0.01 to 50 g/10 min of modified ethylene copolymer is used. The α-olefin having 3 or more carbon atoms which is a copolymerization component of the unmodified ethylene copolymer includes propylene, butene-1, hexene-1, dedecene-1, 4-methylbutene-1, 4-methylpentene-1, etc. Propylene and butene-1 are particularly preferred. The α,β-unsaturated carboxylic acids or acid derivatives thereof (hereinafter collectively referred to simply as α,β-unsaturated carboxylic acids) to be graft-polymerized to the unmodified ethylene copolymer include acrylic acid, methacrylic acid, and ethacrylic acid. Acids, maleic acid, fumaric acid, esters or acid anhydrides of the aforementioned acids, and the like can be mentioned. Among these, maleic anhydride is particularly preferred.
If the amount of α,β-unsaturated carboxylic acid graft-polymerized to the unmodified ethylene copolymer is too large or too small, it will not be effective in improving the flexibility and impact resistance of the polyether polyamide. Furthermore, if the amount is too large, there is a problem that the polyether polyamide is colored yellow to red when added to the polyether polyamide. Therefore, the amount to be graft-polymerized needs to be within the above range, preferably 0.1 to 1% by weight. Incidentally, graft polymerization here means that a part or all of the unmodified ethylene copolymer is chemically bonded to an α,β-unsaturated carboxylic acid monomer or polymer. On the other hand, the degree of crystallinity of the modified ethylene copolymer needs to be within the above range. Preferably 1-30
% range. If it is too high or too low than the above range, it is not effective to improve the flexibility and impact resistance of polyether polyamide. For the same reason, the MI of the modified ethylene copolymer needs to be within the above range, preferably 0.1 to 20.
g/10 minutes. Here, the crystallinity is a value measured by an X-ray method according to the description in Journal of Polymer Science, Volume 1955, pages 17 to 26. Also, MI is ASTMD−
123857T (measured at 190°C) shall be adopted. Such a modified ethylene copolymer can be obtained by adding α,β-unsaturated carboxylic acid to an unmodified ethylene copolymer having a crystallinity of 1 to 35% and a melt index of 0.01 to 50 g/10 min according to a conventional method. Added, usually 150~
It can be easily produced by melt-kneading at 300°C. A screw type extruder is often used for melt kneading. Of course, in order to efficiently cause graft polymerization, an organic peroxide such as α,α′-bis-t-butylperoxy-p-diisopropylbenzene is added to the unmodified ethylene copolymer.
It may be used in an amount of 0.001 to 0.05% by weight. Examples of unmodified ethylene copolymers having the crystallinity and MI that are raw materials for modified ethylene copolymers include:
Among Ziegler-Natsuta catalysts, a vanadium compound such as vanadium oxytrichloride or vanadium tetrachloride and an organoaluminum compound are used, and 50 mol% or more, preferably 80 to 95 mol% of ethylene and 50 mol% are used.
The following is preferably 20 to 5 mol% α having 3 or more carbon atoms
- Examples include those obtained by copolymerizing with olefin. Particularly suitable as such unmodified ethylene copolymers are the series of polymers commercially available from Mitsui Petrochemical Industries, Ltd. under the trademark Tafmer, such as Tafmer A4085, Tafmer A4090, Tafmer A20090, etc. A series (ethylene-butene-1 copolymer); Tafmer P0280, Tafmer P0480, Tafmer P0680,
Examples include Tafmer P series (ethylene-propylene copolymers) such as Tafmer P0880. In the present invention, a polyether polyamide resin composition is produced by melt-mixing a modified ethylene copolymer as described above with a polyether polyamide. Melt mixing can be carried out according to conventional methods, using an extruder or similar equipment. The amount of the modified ethylene copolymer used is in the range of 1/10 to 2/3 times the weight of the polyether polyamide, preferably 15/85 to 30/70 times the weight of the polyether polyamide. If the amount of the modified ethylene copolymer used is greater than the above range, the resulting molded product will have poor chemical resistance and cannot be used for normal purposes. difficult to achieve. Of course, the polyether polyamide resin composition of the present invention may contain inorganic fillers, glass fibers, and various well-known additives in addition to the above-mentioned components, and these can be added at any stage according to conventional methods. can do. The present invention has been described in detail above, and the polyether polyamide resin composition of the present invention provides a molded article having extremely high flexibility and impact resistance, and excellent external color tone. Furthermore, the modified ethylene copolymer used can be manufactured more easily than the easily available unmodified ethylene copolymer. Next, the present invention will be explained in more detail with reference to examples, but the present invention is not limited to the following examples unless it exceeds the gist thereof. In addition, in the following examples, "parts" indicate "parts by weight." [Production of modified ethylene copolymer] Example 1 Ethylene-butene-1 copolymer 100 with crystallinity 20%, MI 3.6 g/10 min, butene-1 content 14 mol%
α,α′-bis− dissolved in a small amount of acetone
0.025 parts of t-butylperoxy-p-diisopropylbenzene and 0.5 parts of maleic anhydride were blended in a Henschel mixer. This blend was extruded into pellets at 230° C. using an extruder with an inner diameter of 4 mm and L/D=28 to obtain a modified ethylene copolymer [A]. After pulverizing a portion of the pellets, unreacted maleic anhydride was extracted with acetone using a Soxhlet extractor for 12 hours. After drying, this material was press-molded and the amount of maleic anhydride was determined using an infrared spectrum. It was found that 0.33% by weight of maleic anhydride had been graft-polymerized. Moreover, the crystallinity and MI were almost the same as those of the unmodified product. Example 2 Exactly the same as in Example 1 except that instead of the ethylene-butene-1 copolymer, an ethylene-propylene copolymer with a crystallinity of 5% and a propylene content of 18 mol% at an MI of 0.44 g/10 min was used. Thus, a modified ethylene copolymer [B] in which 0.3% by weight of maleic anhydride was graft-polymerized was obtained. Also, crystallinity and MI
was almost the same as the unaltered one. Examples 1 to 4 Comparative Examples 1 and 2 ε-caprolactam in a 1 volume autoclave
200g is dibasic acid EMPOL1014 (manufactured by Emery, EMPOL is a trademark) 63g and diamine.
JEFFAMINE D400 (manufactured by Jefferson Chemical Co., JEFFAMINE is a trademark) 38g and
48 g of JEFFAMINE D2000 and 0.7 g of JEFFAMINE T403, which is a triamine, were melted together. After raising the temperature to 260℃, increase the internal pressure to 15-2Kg/cm ²
Hold for 1.5 hours. Next, the pressure was released at 260°C within 1 hour, and the pressure was further reduced to 200 mmHg, followed by holding for 4 hours.
The melt was extruded into water and pelletized. The pellets were boiled in boiling water for 10 hours to extract unreacted substances, and then dried under reduced pressure. Modified ethylene copolymer ([A],
[B]) was added in the proportions shown in Table 1, melt-mixed at 220°C using a single screw extruder, cooled with water, and pelletized to produce a polyether polyamide resin composition. A test piece was molded using this pellet. After drying this test piece, the tensile and bending properties (JIS K6301 and ASTM D790) were measured at 20°C, and the Izod impact strength (ASTM D256) was measured at -20°C and -40°C. The results are shown in Table 1. Comparative Example 1 was prepared without adding the modified ethylene copolymer. Furthermore, as a modified ethylene copolymer, the crystallinity
52%, MI 3.5 g/10 min, density 0.921 g/cm ³ High pressure polyethylene was used, but in the same manner as in Example 1.
Comparative Example 2 was prepared by adding a graft polymer of 0.31% by weight of maleic anhydride (referred to as modified ethylene copolymer [C]) to the same pellets as in Example. Their mechanical strengths are shown in Table 1. 【table】

Claims (1)

[Scope of Claims] 1 Having at least 3 ether oxygen atoms and these ether oxygen atoms forming a linear chain of at least 3 carbon atoms or at least 2 carbon atoms between these atoms. a diamine containing polyether blocks separated from each other by branched chains having an approximately equivalent amount of dicarboxylic acid, such that the weight proportion of the polyether blocks is from 8 to 60% by weight of the total polyether polyamide. a polyether polyamide elastomer produced by polycondensation with an amount of another polyamide-forming compound, and 1/10 to 2/3 of the polyether polyamide elastomer.
Crystallinity 1-35% by weight, melt index
0.01-50g/10min ethylene and α with carbon number 3 or more
- Add α,β-unsaturated carboxylic acid or its acid derivative to the copolymer with olefin.
0.05-1.5wt% graft polymerized crystallinity 1
~35% of a modified ethylene copolymer with a melt index of 0.01 to 50 g/10 min. 2. The polyether polyamide resin composition according to claim 1, characterized in that the modified ethylene copolymer is obtained by graft polymerizing maleic anhydride to a copolymer of ethylene and butene-1. composition. 3. The polyether polyamide resin composition according to claim 1, wherein the modified ethylene copolymer is a copolymer of ethylene and propylene graft-polymerized with maleic anhydride. thing.