JPS6361040A - Thermoplastically deformable impact resistant polyamide alloy - Google Patents

Abstract

(57) [Abstract] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION Field of the Invention The present invention relates to thermoplastically deformable impact-resistant polyamide alloys consisting of copolyamides. Particularly low-viscosity polyamide alloys and their use that can be easily processed in injection molding or extrusion equipment, which are mainly composed of special low-viscosity amorphous copolyamides and special polyolefins, and in particular - It has high impact strength even at temperatures below 20°C, high rigidity, high thermal shape stability, and low oxygen permeability and water absorption.

Prior art U.S. Pat. No. 2,696,482 describes an amorphous polyamide made from bis(4-aminocyclohexyl)-methane and isophthalic acid, which has a very high viscosity and is difficult to process, for example in injection molding. It was not suitable for

German Patent Publication No. 1795464 describes the preparation of an amorphous copolyamide of a combination of alkyl-substituted hexamethylene diamine, isophthalic acid and terephthalic acid; It is expensive and difficult to process.

U.S. Pat. No. 3,597,400 (= German Patent Publication No. 1,933,395) describes an amorphous copolyamide composed of bis(4-aminocyclohexyl)-methane, hexamethylene diamine, isophthalic acid and terephthalic acid. is listed, and a high percentage of screws (
Combinations containing (4-aminocyclohexyl)-methane have a particularly high melt viscosity and are therefore disadvantageous during processing (e.g. injection molding) and are also difficult to produce large moldings at low diamine concentrations. This results in high viscosities that are difficult to control.

According to U.S. Pat. No. 436i9305, a copolyamide is prepared by combining certain proportions of iso- and terephthalic acids, a very low proportion of bis(4-aminocyclohexyl)-methane and the same in a special isomer mixture, i.e. trans /
at least 59 trans- or cis/trans-isomers
Shear stress 105 dyn/C when contained in weight%! I
With L2, a viscosity lower than 30,000 voids can be obtained at 280°C.

However, upon comparison, it became clear that the homologous composition of bis(4-aminocyclohexyl)-methane was responsible for the high viscosity and, moreover, the remarkable structural viscous behavior.

The state of the art as a whole does not provide any disclosure as to whether and to what extent the reactivity of the NF2 group, which influences the viscosity, can be adjusted by suitable substitutions in suitable positions of the cyclohexane ring. .

U.S. Pat. No. 4,536,541 discloses a special activated ethylene/propylene/diene ester containing a similarly low proportion of the bis(4-aminocyclohexyl)-methane isomer and based on succinic anhydride. polymer(
Amorphous copolyamides are described that have been impact-modified with EPDM).

However, for this type of impact strength modifier, ff I
Agents incorporated into J-amides can significantly increase the melt viscosity (US Pat. No. 4,174,358, DE 1,241,606) and therefore make the processing of such polyamides even more difficult. Are known.

Reducing the amount of bis(4-aminocyclohexyl)-methane in the amorphous copolyamide reduces thermal dimensional stability and worsens certain mechanical properties such as toughness and strength.

GB 998,439 describes the introduction of modified polyolefins and polyacrylates to modify the impact resistance of linear partially crystalline polyamides. Impact resistance modification with special reactive copolyolefins is also described in detail in DE 27 22 270, for polyamides PA6 and PA66. Since the partially crystalline PA type has a very low melt viscosity, the viscosity increase due to modification does not cause any problems when processing this one thermoplastic material.

US Pat. No. 4,339,555 describes the modification of conventional homopolyamides with certain copolyolefins containing urea derivatives in order to additionally improve the melting and mold release behavior.

Problem to be Solved by the Invention The present invention is directed to the problem of eliminating the above-mentioned disadvantages of polyamide and copolyamide alloys and of finding an alloy which is particularly easy to process, has low viscosity and has a high degree of use properties.

Means for Solving the Problem Solution to the Problem (2) A thermoplastically deformable impact resistant polyamide alloy according to the invention is made of: a) hexamethylene diamine and/or optionally dialkyl-substituted polyamide alloy; 80% by weight of hexamethylene diamine and bis(4-aminocyclohexyl)-methane homologs substituted adjacent to the amino group and optionally terephthalic acid and/or other aromatic or aliphatic dicarboxylic acids. .

The following thing became clear and unexpected.

1. Instead of bis(4-aminocyclohexyl)-methane as an additional amine component, the adjacent position of the amino group,
i.e. when using homologues thereof which are alkyl substituted in the 3- and/or 5-positions, they can be easily processed from hexamethyldiamine, isophthalic acid and optionally cyterephthalic acid or other aliphatic dicarboxylic acids. An amorphous copolyamide is obtained. In this case, the effect on the viscosity due to the introduction of defined substituents and isomer mixtures could not be predicted; 2. From such copolyamides modified copolyolefins, e.g. -Butene-copolymers or mixtures thereof can be used to produce impact-resistant alloys that can be processed well; 3. The viscosity of these alloys can be well controlled, so that they can be manufactured over large areas, e.g. by injection molding. It can also be used in the production of molded articles or by extrusion method (it can also be used for thin products); The cicobolyamide viscosity is adjusted in a targeted manner; 5. The viscosity of the alloy according to the invention can also be influenced by the weight proportion of terephthalic acid.

Additional cycloaliphatic amines according to the invention include, for example, bis(4-amino-3-methyl-5-ethylcyclohexyl)-methane, bis(4-amino-3,5-diethylcyclohexyl)
-methane, bis(4-amino-3-methyl-5-isopropylcyclohexyl)-methane, bis(4-amino-3,5-diisoprogylcyclohexyl)-methane, bis(4-amino-3,5-dimethyl) cyclohexyl)
-methane, bis(4-amino-6-methylcyclohexyl)-methane, bis(4-amino-3-ethylcyclohexyl)-methane, bis(4-amino-3-isopropylcyclohexyl)
- diamines such as methane or mixtures thereof, or each of the aforementioned diamines or the cyclohexane ring has further alkyl substituents or optionally the -CH2- groups between the dicyclohexane rings are ethylene, propylene, isopropylene or certain isomeric mixtures of such cyamines which may be substituted for butylene.

The significantly reduced viscosity of the amorphous copolyamides P and copolyamide alloys prepared from them is clearly due to the steric effects of these diamines compared to unsubstituted diamines and the constant isomeric composition of the diamine homologs. It is in.

Other advantages when using such diamines in copolyamides or copolyamide alloys are: b) high stiffness even when conditioned; c) improved low temperature impact strength; and d) reduced water absorption. Similarly, bis(4-aminocyclohexyl)-methane-
caused by additional alkyl groups in the congeners.

Furthermore, the polyamide alloys according to the invention exhibit particularly low oxygen permeability.

The proportion of homologous diamine used in the copolyamide is varied to adjust a constant viscosity, but should be at least 2% by weight of the total diamine. Similarly, the viscosity of the polymer increases with increasing amount of terephthalic acid, with a significant upper limit of 10% by weight.

The copolyolefins for improving the impact resistance of polyamide alloys according to the invention include 1 maleic anhydride/acid or other ethylenically unsaturated dicarzenic acid or its anhydride (P)'0
．． 05-1.0 ft% grafted ethylene/
Copolyolefins of 1-butene or ethylene/propylene or preferably mixtures thereof are suitable, the amount used being from 0.01 to 80% by weight.

The theoretical composition of the polyamide alloy according to the invention is as follows: Hexamethylene diamine and derivatives 4&-20 mol %, in particular 4
5-25 mol% bis(4-aminocyclohexyl>-ts derivative 2-.30 mol%,
Especially 5-25 mol% isophthalic acid and others
50-40 mol% terephthalic acid o-1
0 mol % In practice, a slight excess of diamine is used for several reasons: due to volatility and impurity.

As is clear from the examples below, an excess of --NH2 end groups is advantageous due to better thermal stability and better bonding possibilities with --C0OH groups of the modifier.

The polyamide alloy according to the invention may contain other components such as fillers, reinforcing agents, pigments, dyes, heat stabilizers, antioxidants, UV protectants, plasticizers, nucleating agents, etc.

However, they may also be blended or mixed with other polyamide types or with different polymers.

The polyamide alloy according to the invention can be used to provide more dimensionally stable equipment parts, in particular for the production of large-area or large-volume molded parts, such as those used, for example, in the production of automobile zedies or as machine parts or protection materials. It is a molding material which is particularly suitable for processing in extruders and injection molding machines for the production of wire rods and waveguide sleeves and other molded parts with negligible wall thickness and diameter dimensions. be.

EXAMPLES Next, the polyamide alloy according to the present invention and its production will be explained in detail with reference to examples.

Examples 1 to 5 illustrate the production of amorphous copolyamides and the types of polyamide alloys according to the invention. Comparative examples 6 and 9
showed that unsubstituted bis(4-aminocyclohexyl)-methane gives rise to a very high melt viscosity that is difficult to control and therefore its alloys can hardly be processed by injection molding methods. I have to.

Example 1 Isophthalic acid 376.5 g (47.7 mol%), 60
%-hexamethylenediamine solution 1395.5g (43,
0 mol%), bis(4-amino-3゜5-diethylcyclohexyl)-methane 11B, 0.9 (7.8 mol%
) and benzoic acid 8.7.9 (1.5 mol%) were metered into a reaction vessel and heated to 180°C and then to 250°C for 1 hour.
82.0 ml of the reaction liquid produced during the polycondensation was collected separately and heated under stirring and nitrogen blanketing, and the temperature was reduced to about 41.
The temperature was maintained at 285°C for 1 hour.

The resulting polymer was completely transparent, with a solution viscosity (0.5% in m-cresol) of 1.529 and a melt viscosity of 912.
Pa,s (270°G/122.6N). The lath transition Tg was 138°C.

The polymer thus produced was prepared using ethylene/propylene-ethylene/1-butene-grafted with maleic anhydride.
The copolymer mixture (melting point 49° C. to 70° C.) was mixed with 20 overlapping parts and extruded in a laboratory extruder NetStal 57.
The material was extruded in a 30/N 110 mold at a temperature of about 260°C.

The polymer strands quenched in water were ground and dried. Glass transition point is 138℃ and melt viscosity is 1342Pa
, 5 (270°C/122.6 N).

Example 2 Isophthalic acid 357.3 P (42, f3 mol%),
Benzoic acid 15. O? (2,4 mol%), terephthalic acid 40.0 P (4,8 mol%), bis(4-amino-
3-Methyl-5-ethylcyclohexyl)-methane 10
2.0 P (6.9 mol%) and hexamethylene diamine 254.0 ? (43.3 mol%) was charged into the reactor and gradually heated to 180'C under stirring and nitrogen blanketing.

After separation of the reaction water, the reaction mixture was heated to 285° C. for 3 hours and cooled.

The glass-like clear polycondensate has a solution viscosity ηrel = 1.6
28 and melt viscosity 1212 Pa, s (270'C/
122.6N). The glass transition point Ty was 152°C. After coextrusion with 2o% modifier as in Example 1, the melt viscosity was 1520 Pa, s (270
”C/122.6N)K rose.

T1 remained at 152°C.

The sample molded body produced from this had a water absorption rate of only 2.1% after being immersed in water for 3 months.

Example 3 Isophthalic acid 273.0 g (39.9 mol%), dodecanedicarboxylic acid 85.0 g (8.9 mol%), hexamethylene diamine 125.0 g (26.1 mol%)
, 333.09 (25.1 mol%) of bis(4-amino-3,5-diethylcyclohexyl)-methane at 285°C
Condensation polymerization was carried out. The relative viscosity of the transparent condensation product is 1.504
([), 5%-m-cresol), melt viscosity 680
Pa,s (270°G/122.6N) and the glass transition point 'rP was 165°C.

Ethylene/propylene/grafted with maleic anhydride
The viscosity of the alloy after extrusion with 20% by weight of the 1-butene-polyolefin mixture was 836 Pa,s (270
°G/122.6 N) and 72159°C.

Example 4 Isophthalic acid 21.3 kg (42.42 mol%), terephthalic acid 3.4 kg (6.86 mol%), 60.4%
- 26.15 kg (45 kg) of hexamethylene diamine aqueous solution
mol%), bis(4-amino-3-methylcyclohexyl)-methane 3.58 kg (4.97 mol%), stearic acid 400,! 9 (0.74 mol%) and water 5
The mixture was heated to 260° C. with stirring in a 150 t-autoclave. After depressurizing the autoclave, the contents were polycondensed at 290° C. under nitrogen, and the polycondensate was passed through a water bath as strands and granulated. The granules are clear and lath-like with a solution viscosity of 1.589 (0.5% in m-cresol) and a melt viscosity of t.
158 Pa, q (270° (ml!/122.6 N
) and 'rP 143°C.

The molded bodies produced from the granules have an impact strength of O, B according to DIN 53453, are tough and have a notched impact strength of 1.9.
It had k J 7m2.

Bending E-elasticity according to DIN 53452 is 2754 N/
The limit bending stress was 153 N/mtn2. Water absorption rate is 2.9 after being stored in water at 25℃ for 30 days.
It was in %.

The amorphous copolyamide was mixed with 20% by weight of the copolyolefin mixture described in Example 3, extruded and granulated. The viscosity of the granules is 1410Pa,s (270'C/122.6N
), Ty was 142°C.

44, OkJ/m2 (at 23°C) and 16 kJ/m2 (
58.
It had an elongation of 7N/2 and an elongation at break of 150%. 2
After being stored in water at 5℃ for 30 days, the water absorption rate is only 2.5%.
Met.

Example 5 Isophthalic acid 2.8 kl? (41.1%), terephthalic acid 0.52 kl? (7,4 mol%), hexamethylene diamine 2.07 kg (33,4 mol%), bis(4-amino-3,5-diethylcyclohexyl)-methane 0.83 kg (7,1 mol%) and benzoin. acid 50
g (1 mol%) in a 20t autoclave at 285°C.
was polycondensed.

The polycondensate produced has a solution viscosity of 1.574 (0.5% in m-cresol) and a melt viscosity of 840 Pa, s and 72
It had a temperature of 140°C.

Test specimens made from this polycondensate had an impact strength of 0, B and a notch impact strength of 2.3 kJ/m" (DIN 5
3453), further bending E-elasticity (dry) 308ON/
II! , 2 (DIN 53457) and with condition adjustment 2
It had 334N/Tomo 2.

Copolyolefin mixture strength as described in Examples 3 and 4 30.
5 kJ/m” (dry) and 12 kJ at -40°C
/ m2, bending E-modulus' (dry) 236ON/
ffi+112 and condition adjusted 2400 N/m
A bending stress of 2 and a critical bending stress of 100 N/m2 were measured.

Comparative Example 6 Isomer distribution: 46 wt.% trans/trans, 45 wt.% 7s/trans, and 9 wt.% cis/cis bis(4-
Aminocyclohexyl)-methane was used.

Isophthalic acid 15.0 kg (44,14 mol%), terephthalic acid 1.6 oIc9 (4,7 mol%), hexamethylenediamine 10.3 to 9 (43,3% mol%), bis(4-aminocyclohexyl) - 3 kg of methane (6,
97 mol%) and benzoic acid 0.221e9 (0.89 mol%) were polycondensed in a 201-autoclave at 280°C.

The copolyamide taken out as transparent strand P was granulated. Solution viscosity 1.539 and high melt viscosity 2974 P
a,s (270"C/122.6N). After coextrusion with 20% by weight of the modified copolyolefin mixture described in Example 3, the viscosity was 5200 Pa,s (2
70°C/122.6N)K increased.

C0PA (no denaturing agent)' Ty
135℃ bending strength 165
N/Gate 2 Impact strength 60%
40% without destruction 35kJ/m2 Notch impact strength 1.6kJ
/m 2 songs GfE-elasticity 31
001N/f12 Tensile strength at break
50% 102N/WIn250% 7QN/1r
a2 COPA (after adding modifier): TL?
(130°C bending strength at break)
95 N/! 2 Impact strength
Without destruction / Tsuf? Iy'H strength
! 5.9kJ/m2 Bending E-elasticity
214ON/aIII2 tensile strength at break
The 57 N/w2 specimen was difficult to manufacture due to its melt viscosity and could not be manufactured satisfactorily.

Comparative Example 7 In this example, the following isomer mixture bis(4-aminocyclohexyl)-meta/ was used.
cis 6% by weight.

Isophthalic acid 2.98 to 9 (44,0%#%), f-phthalic acid 0.3411C9 (5,0 mol%), hexamethylenediamine y2.071c9 (43,7 mol%), bis(4-amino cyclohexyl)-methane 0゜55kg (
6,5 mol%) and benzoin #R40P (0°8 mol%)
was polycondensed to a transparent copolyamide P in a 201-autoclave.

The viscosity rose very quickly and it was difficult to empty the autoclave. Relative solution viscosity [11.68 (0.5% in m-cresol), melt viscosity 7640 Pa, s
(270'C/122.6N).

After extrusion with 20% by weight of the copolyolefin mixture described in Example 3, a highly viscous polymer alloy is obtained whose melt viscosity is 10000 Pa, 5 (270°C/122.6
N) It was higher. Since it could not be filled into powder molds, it was not possible to produce useful injection molded articles.

Comparative Example 8 Polycondensation was carried out at 280° C. as in Example 5: IPA
2.905 to 9 (35 mol%”) TP
A 1.240PC9 (15 mol%
) HMD 2.800 to 9 (48 mol%) bis(4-aminocyclohexyl) yt Ty 0.220 to 9 (2% to %
) Stearic acid 0.005Iai (0.03 mol%) Solution viscosity 1.512 Melt viscosity 3240Pa, s (270C/12
2.6N)T, 126°C A test specimen could not be produced and could not be blended due to increased viscosity.

Comparative example 9 Polycondensation was carried out analogously to Example 8.

IPA 4.780 to 9 (42%#%
)TPA O,9101? (8%#
%) HMD 3.600Tc9(4
5% #%) bis(4-aminocyclohexyl) meta y 0.720 to 9 (5% le%) stearic acid 0.030 to 9 (0.15 mol%) Solution viscosity 1.47 Melt viscosity 2900 Pa, 5 ( 270℃/122
．． 6N)T, 133°C It was not possible to produce a test specimen, and the viscosity increased, so it could not be blended.

Procedural amendment (lffl effect) November 2ζ, 1986

Claims (1)

[Claims] 1. a) Hexamethylene diamine and/or hexamethylene diamine optionally substituted with alkyl and bis(4-amino-cyclohexyl)-methane congeners substituted at positions adjacent to the amino group and terephthalic acid and/or
or b) 20 to 99.99% by weight of an amorphous copolyamide consisting of isophthalic acid which may be replaced by other aromatic or aliphatic dicarboxylic acids, and b) 0.01 to 80% by weight of a modified copolyolefin. Thermoplastically deformable impact resistant polyamide alloy. 2. Bis(4-amino-cyclohexyl)-methane homologs substituted adjacent to the amino group have an alkyl group at the 3- and/or 5-position of the cyclohexane ring, and optionally at other positions. and the alkyl group is R=C_1~C_
8, especially R=C_1 to C_4, especially methyl-, ethyl-
The polyamide alloy according to claim 1, which is an isomer mixture of , propyl, and isopropyl groups, in which a combination of a methyl group and an ethyl group or an isopropyl group is particularly advantageous. 3. A polyamide according to claim 1, in which the proportion of alkyl-substituted diamines in the total diamine content of the copolyamide is at least 2% by weight and in particular consists of a mixture of trans/trans and cis/trans isomers. Alloy. 4. The polyamide alloy according to claim 1, wherein the proportion of terephthalic acid in the amorphous copolyamide is from 0 to 10% by weight, as the case may be. 5. The modified copolyolefin is a copolymer of ethylene and an α-olefin having 3 to 16 carbon atoms, which is grafted with an ethylenically unsaturated dicarboxylic acid or anhydride thereof.Claim 1 Polyamide alloy as described in section. 6. Hexamethylene diamine or its derivatives 48-20 mol%, especially 45-25 mol% Bis(4-aminocyclohexyl)-derivatives 2-30 mol%, especially 5-25 mol% Isophthalic acid and others 50-40 The polyamide alloy according to claim 1, comprising 0 to 10 mol% terephthalic acid.