DE2343693A1 - THERMOPLASTIC POLYAMIDE MOLDING COMPOUNDS - Google Patents

Description

PARBWEFXi: HOECHST AG, formerly Master Lucius & Brüning File: - HOE 73 / F 266

Date: August 29, 1973 "

Thermoplastic polyamide molding compounds

Polyamides have recently become more and more important in the field of engineering plastics. Of particular interest are amorphous polyamides with glass transition points above 100 ⁰ C; they have very good heat resistance. Furthermore, many of these polyamides have very high hardnesses. It is precisely these hardnesses that are often bought at the price of poor toughness, a disadvantage that precludes the use of such materials in many technical areas. There are several ways to improve toughness. It is not possible to increase the toughness by changing the basic chemical structure, since it can generally only be bought with a reduction in the glass transition temperature and a deterioration in hardness. Mixing with other polymers can lead to an increase in toughness, but can result in a considerable reduction in other important mechanical properties, such as tensile and flexural behavior, hardness, etc.

509811/0933

It has now been found that unusually tough polyamide molding compositions are obtained which are characterized by high hardness, good elongation and stiffness properties when amorphous polyamides with glass transition temperatures of more than 100 ° C., with ionic copolymers of "d-olefins and" are used Salts of oC jβ-unsaturated carboxylic acids, which contain ions of mono- to trivalent metals, mixed, the amount of the ionic copolymer being 0.5 to 20 wt. ^ Of the total mixture.

Mixtures of

.Preferably 99 * 5 to 90 wt. ^,. A 99 * 5 to 8o wt. $ / At least one amorphous polyamide having a glass transition temperature of at least 100 C, preferably from 120 ⁰ C to l8o ° C, and

/ preferably 0.5 to 10% by weight , B 0.5 to 20% by weight of at least one ionic copolymer

a at least one << - 01efin and

b at least one, ions of a mono- to trivalent metal containing salt of an od, ß-unsaturated carboxylic acid or / and p £, ß-unsaturated dicarboxylic acid, and optionally

c at least one «L, ß-unsaturated carboxylic acid, and possibly

d at least one ester of a CO 3 -unsaturated carboxylic acid. ·

The amorphous polyamides are said to have a reduced specific viscosity (measured on a solution of 1 g of polyamide in 100 ml of phenol / tetrachloroethane in a weight ratio of 6o: 4o at 25 ° C) from 0.7 to 1.8 dl / g, preferably from 0.9 to 1.4 dl / g, they should be constructed linearly and on commercially available injection molding machines be processable. They are obtained by polycondensation of diamines, dicarboxylic acids and aminocarboxylic acids under customary conditions according to technically known processes. Amorphous polyamides to be used according to the invention are expedient

those that are derived from - 1> -

509811/0933

BATH ORIGINAL

cc) 5 to 50 mol, preferably 10 to 35 mol, 1,3-bis (aminomethyl) cyclohexane and / or 1,4-bis (aminomethyl) cyclohexane and / or 2,5 bis (aminomethyl ) bicyclo / 2,2, l7-heptane and / or 2,6-bis (aminomethyl) -bicyclo ^, 2, l / -heptane and / or at least one bis (4-aminocyclohexyl) derivative of an alkane with 1 to 6, preferably 1 to 3, carbon atoms,

C ^ ₂ ) 0 to 45 mol #, preferably 0 to 35 mol #, of at least one straight-chain or branched aliphatic diamine containing 4 to 20 carbon atoms, preferably 6 to 12 carbon atoms, the amino groups being replaced by at least 4 carbon atoms Atoms, preferably by at least 6 carbon atoms, are separated from one another,

β-) 5 to 50 mol $, preferably 10 to 55 mol $, at least an aromatic, in particular mononuclear, containing 7 to 20 carbon atoms, preferably 8 to 14 carbon atoms, in meta- or para-position carboxyl groups-bearing dicarboxylic acid,

βp) 0 to 45 mol $, preferably 0 to 35 mol $, at least one saturated, straight-chain or branched, aliphatic, containing 6 to 20 carbon atoms, preferably 6 to 12 carbon atoms Dicarboxylic acid, the carboxyl groups through at least 4 carbon atoms are separated from one another, and

/> c) 0 to 8o mol ^, preferably 0 to 50 mol $, at least one aliphatic aminocarboxylic acid with 2 to 20 carbon atoms, preferably 6 to 12 carbon atoms, in particular CO -aminocarboxylic acid,

where the MoI ^ sum of the components οΛ) and c < _o ) equal to those components ß.) and ßp),

509811/0933

BATH ORIGINAL

the mol ^ sum of all components' X ₁ ), ^ 2) » ^β χ)> ^ß 2 ^ ^and d * ~ ^ equal to 100 moljß,

the mol ^ sum of the components Pt ..) and ß ^) equals 20 to 95 , preferably 50 to 90

the mol ^ sum of components cX_ ₂ ), B ^) and ^ c) is equal to 5 to 80 mol, preferably 10 to 50 mol $, and

where all data in Mol # refer to the sum of all components), ^ ₂ ) * B ₁ ), ß ₂ ) and ^ t-).

In the case of bis (4-aminocyclohexyl) alkanes, the aromatic dicarboxylic acid can also be completely dispensed with, so that the proportion of aliphatic dicarboxylic acid is up to 50 mol $ can be.

The diamines 1,5-bis- (aminomethyl) -cyclohexane to be used for the production of the polyamide component A of the polyamide molding compositions according to the invention and 1,4-bis (aminomethyl) cyclohexane can through Hydrogenation of the corresponding xylylenediamines can be obtained. To produce the crystal-clear polyamides, trans-1,3> -bis (aminomethyl) -cyclohexane are used and mixtures of trans-1,5-bis (aminomethyl) -cyclohexane and trans-1,4-bis (aminomethyl) cyclohexane are particularly suitable. But it can also be. appropriate cis diamines or mixtures of cis and trans diamines are used will.

The diamines 2,5-bis- (aminomethyl) -bicyclo / 2,2,17heptane and 2,6-bis- (aminomethyl) -bicyclo _/ 2,2,17-heptane to be used for the production of the polyamide component A of the polyamide molding compositions according to the invention can be produced in a simple manner from cheap starting materials, as described, for example, in US Patents 2,666,748, 2,666,780 and 3 · 1 ^ 5,570. Mixtures of these diamines are preferably used, it also being possible to use the various stereoisomeric forms of the diamines.

_ 5 -509811/0933 ·.

The for the production of the polyamide component A according to the invention Polyamide molding compounds to be used bis (4-aminocyclohexyl) alkanes are made from many starting materials, namely phenol and aldehydes or ketones, using known processes. It will Bi5- (4-aminocyclohexyl) derivatives of alkanes with 1 to 6 carbon atoms, preferably 1 to 3 carbon atoms, in particular bis (4-aminocyclohexyl) methane and 2,2-bis (4-aminocyclohexyl) propane are used.

Straight- chain or branched aliphatic diamines oL ^) are suitable for producing the polyamide component A of the molding compositions according to the invention, those having 4 to 20 carbon atoms, preferably 6 to carbon atoms, especially hexamethylenediamine.

Further advantageous examples of aliphatic diamines c £ p), which are suitable for the production of the polyamide component A of the molding compositions according to the invention are tetramethylenediamine, pentamethylenediamine, 2-methylpentamethylene diamine, 2 «methyl hexamethylene diamine, 3-methyl-hexamethylenediamine, 3,4-dimethyl-hexamethylenediamine, 2,2,4-trimethylhexamethylenediamine, 2,4,4-trimethylhexamethylenediamine, Heptamethylenediamine, 2-methyl-4-ethylheptamethylenediamine, Octamethylenediamine, nonamethylenediamine, decamethylenediamine, Undecamethylene diamine and dodecamethylene diamine.

Mixtures of two or more of the aliphatic Diamines are used.

As aromatic dicarboxylic acids,) for the production of the polyamide component A of the molding compositions according to the invention are those having 7 to 20 carbon atoms, preferably 8 to 14 carbon atoms. Particularly Mononuclear carboxyl groups in the meta or para position are suitable carrying dicarboxylic acids, especially isophthalic acid and terephthalic acid.

Further advantageous examples of aromatic dicarboxylic acids B ₁ ) which are suitable for the production of the polyamide component A of the molding compositions according to the invention are 2,6-pyridinedicarboxylic acid, 1,4-naphthalenedicarboxylic acid, 1,5-naphthalenedicarboxylic acid,

509811/0933 _ 6 -

2, β-naphthalenedicarboxylic acid and 4,4'-diphenylsulfonedicarboxylic acid.

It is also possible to use mixtures of two or more of the aromatic dicarboxylic acids, in particular mixtures of the Isophthalic acid with terephthalic acid.

Straight-chain or branched aliphatic dicarboxylic acids ßp) are suitable for producing the polyamide component A of Molding compositions according to the invention those having β to 20 carbon atoms, preferably 6 to 12 carbon atoms, especially adipic acid and decanedicarbons acid-1.10.

Further advantageous examples of aliphatic dicarboxylic acids ßp), which are suitable for the production of the polyamide component A of Suitable molding compositions according to the invention are 2,2,4-trimethyladipic acid, 2,4,4-trimethyladipic acid, pimelic acid, suberic acid, azelaic acid and sebacic acid.

Mixtures of two or more of the aliphatic Dicarboxylic acids are used, preferably mixtures of adipic acid and decanedicarboxylic acid-1,10.

) Are those preferably it is particularly advantageous to use £ aminocaproic acid having 2 to 20 carbon atoms, 6 to 12 C atoms, in particular (0 aminocarboxylic acids - for the preparation of the polyamide component A of the molding compositions according to the invention are suitable as aliphatic aminocarboxylic acids. ^.

Further advantageous examples of aliphatic aminocarboxylic acids which can be used for the production of the polyamide component A of the molding compositions according to the invention are aminopivalic acid, CO -aminoheptylic acid, CO -aminocaprylic acid, Cd -aminopelargonic acid, OJ -aminoundecanoic acid or 60-aminolauric acid.

- 7 - 509811/0933

Mixtures of two or more of the aliphatic aminocarboxylic acids can also be used, preferably mixtures of ε-aminocaproic acid and CO -aminolauric acid.

Instead of the aminocarboxylic acids, you can also use their lactams «

The polyamide component A of the molding compositions according to the invention is produced by known processes. Diamines, dicarboxylic acids and optionally aminocarboxylic acids) or. their lactam (s) are placed in a stainless steel autoclave, optionally with the addition of water. It's often expedient First produce a salt from the starting components, which then, optionally with the addition of water, in the steel autoclave is filled. The contents of the autoclave are heated to around 200 to 260 ° C. while stirring. Then water vapor is released and the Temperature increased to 25 to 500 ° C. At this temperature will condensation in a stream of nitrogen, optionally in vacuo, until the polyamide has the desired molecular weight has reached.

It is often advantageous to use an excess of up to 5 percent by weight, preferably 0.5 to 2 percent by weight, diamine (s) to use over the dicarboxylic acids in order to avoid losses To compensate for the distillation of diamine (s) during the polycondensation.

Polyamides with particularly high molecular weights and good mechanical properties are obtained when they are used in a stirred autoclave produced polyamides in a further process step, preferably in a twin screw extruder Vacuum, post-condensed.

In the manufacture of the polyamides, instead of the dicarbon

haemidogenic
acidic derivatives such as dicarboxylic acid halides, esters,

Use nitriles or amides by known processes.

- 8 -509811/0933

The ionic copolymers used in the molding compositions according to the invention are copolymers of c ^ -olefins with oi. , ß-unsaturated carboxylic acids, the metal ions of mono- to trivalent metals are used. They are copolymers of the general formula

- (- CH ₀ - CH);

- C

C = O ΙΟ

M "m +

wherein FL = H, CH, to ^c i2 ^H 25 ' ^C 6 ^Ht 5' preferably H, CH- ,,

m +

= H, CH

C ₆ H ₅ ,

Γ% DD

especially H, CH ,, . and

= Ions of an m-valent (with m = 1 to mean

Metal

and where x, y and η represent integers.

It is also possible to use ionic copolymers of cC-olefins with cL _f ß-unsaturated dicarboxylic acids, such as, for example, copolymers of ethylene with maleic acid or copolymers of ethylene with itaeonic acid, which contain metal ions of monovalent to trivalent metals. Furthermore, graft polymers can also be used as ionic copolymers. Such copolymers can be obtained, for example, when oC , ß-unsaturated carboxylic acid esters are grafted onto polyolefins, saponified and then reacted with, for example, an alkali metal hydroxide.

Furthermore, compounds can be used as ionic copolymers that contain the following units:

509811/0933

a) f €

-EcH ₂ - c

C = O

c) -fCH _{2 -C}

C = O I

OH

d) fCH _o - C

C = O

wherein R ₁ = H, CH-, to C ₁₂ H ₂₁ -, ^c ^ c ^> preferably H, CH- ,, CgH ^ i

CgHj-, especially H, CH ^ ,,
R ₂ = H ,. CH ^, CgHj-,
R, = H, CH ₃ , C ₂ H and
R ^ = CH ₅ to C ₁₂ H ₂₅ , preferably CH ^ to CgH ₁ ^

and where x, y, ζ and w represent integers, and where Me has the above meaning.

/ ^a )
The olefin content / ionic copolymers should be at least 50 percent by weight: preference is given to using copolymers which contain an olefin content of 80 to 90 percent by weight. The sum of ionic proportion aind optionally Esteranteil d) should be at least 10 wt -.% Amount, the ionic component takes at least 5% of the total amount of ionic copolymer

509811/0933 ~ " ¹⁰ "

- ίο -

be. It is not absolutely necessary that all carboxyl groups are neutralized by metal ions, but at least 10 % of the carboxyl groups should be neutralized by metal ions.

The ionic copolymers B to be used according to the invention should have an average molecular weight> 5000, preferably> 50,000.

All metal ions listed in CA-PS 67 ^ .595 come as metal ions into consideration. Alkali metals, especially sodium ions, are preferred.

Products used with preference are ionic copolymers of ethylene and (meth) acrylic acid, the alkali metal ions, preferably Sodium ions.

The ionic copolymers are produced by known processes, for example by the process described in CA-PS 6 "Jk. 595.

To produce the molding compositions according to the invention, the amorphous polyamide A is mixed with the ionic copolyreeren B, for example in the form of granules and mixed directly into molded articles on an injection molding machine splashed. In order to achieve particularly good homogenization, the two components can be used in an extruder melt together, quench the stripped strand in a water bath, granulate and only after this homogeneous granulate Send drying to the processing machine.

The compounds (mixtures) according to the invention have surprisingly good mechanical properties. You stand out unusual toughness and at the same time high hardness, good elongation and stiffness properties. Particularly noteworthy is that the polymer alloys at bending and breaking points

- Il 509811/0933

neither splicing show nooh stress whitening. The surfaces of the moldings are very uniform, even with complex parts, the good flow behavior of the melt allows even workpieces to be produced flawlessly over long and complicated flow paths. The compounds can be used on extrusion and injection molding machines process, so not only technical parts but also foils, plates and tubes can be produced.

If necessary, the products can also contain additives, e.g. antistatic agents, flame retardants, heat and light stabilizers, Plasticizers, pigments and fillers such as asbestos fibers, glass fibers, carbon black, metals or metal oxides.

509811/0933 -12-

Examples

In the following examples, the viscosity ^{measurements were carried out at 25 °} C. on solutions of 1 g of polyamide or polyamide mixture in 100 ml of phenol-tetrachloroethane (3 + 2 parts by weight).

The glass transition temperature (Tg) was determined by Differential thermal analysis at a heating rate of 4 ° C / min.

The ball indentation hardness was according to DIN 53 ^ 56 with a load of 50 kp, a ball diameter of 5 mm and a measuring time of 10 see. certainly,

the Ε module from the bending test according to DIN 53 4-52 with a Standard small rod received,

the elongation at break according to DIN 53 455 on a standard small rod and the

Notched impact strength according to DIN 53 ² 1 · 53 measured on an injection-molded standard small rod.

To determine the toughness properties, we applied a drop test to our samples, which allows good differentiation even with very tough products. Injection plates measuring 6 cm × 6 cm × 0.2 cm are placed on a firm surface in which there is a hole 2.6 cm in diameter under the center of the plate. A weight of 9 ^ 0 g, at the lowest point of which a steel ball with a diameter of 0.9 cm is attached, falls concentrically onto the plate to be tested. The "mean height of fall" in cm is given as a measure of the toughness. This means the height from which the weight must fall on the injection-molded panels to be tested so that on average 50 $ of the panels tested burst. The measurements are made after five days storage of the spray plates in air at 20 ⁰ C.

- 13 509811/0933

- 13 starting products:

A polyamide: Naoh usual condensation process (described for example in DT-OS 2.0β0.702, especially in the examples) made from 3 * 32 kg terephthalic acid, 2.90 kg bisaminomethylcyclohexane (70 % 1.3 and 30 % \ _t h Isomer, mainly present in the trans form) and 2.20 kg of hexamethylenediamine adipate (AH-SaIz). Reduced specific viscosity (RSV) = 1.27 dl / g. Tg = 150 ° C.

B Ion-internal copolymer: Manufactured according to CA-PS 67 ^ .595 from 90 parts by weight of ethylene and 10 parts by weight of methacrylic acid, the carboxyl groups of which were 18 % neutralized with sodium ions, with a melt index of less than 0.1 g / 10 minutes according to ASTM-D -I238-57 T.

The dry products A and B were mixed, in one Extruder homogenized at 280 C, after stripping and cooling in a water bath, granulated, dried and then in a Screw injection molding machine with a cylinder temperature of 270 to 28o ° C injected into molded and test specimens.

- 14 509811/0933

Example e 1 to 5

cn ο (O oo

(D (a> u>

example Summary
(Wt. %)
AWAY 0 RSV Elongation at break
31 Notch impact
toughness a.
/ kpcm / ern _ / ^K Hardness ^
/ kp / cmy Modulus of elasticity
/ kp / cnC7 Medium height of fall
/cm/ 1 100 1 1.27 62 3.8 1730 2.97 31 2 99 2.5 1.28 76 4.5 I69O 2.97 74 3 97.5 5 1.26 145 5.8 I68O 2.97 97 4th 95 10 1.27 165 8.9 1590 2.84 195 VJl 90 1.25 155 8.7 1470 2.65 198

I- »

VJI I

4> CO CO CD CO

Claims (8)

_Claims : H0E b at least one, ions of a mono- to trivalent metal containing salt of a pd, ß-unsaturated Carboxylic acid and / or e £, ß-unsaturated dicarboxylic acid, and if necessary c at least one cK. , ß-unsaturated carboxylic acid, and possibly d at least one ester of a C ^, ß-unsaturated · carboxylic acid . 2. Thermoplastic molding composition according to claim 1, characterized in that the polyamide (s) A is derived (derived) from OC ₁ ) 5 to 50 mol, preferably 10 to 35 mol #, 1,3-bis (aminomethyl) cyclohexane and / or 1,4-bis (aminomethyl) cyclohexane and / or 2.5 bis ( aminomethyl) bicyclo / 2.2 _J 17-heptane and / or 2,6-bis- (aminomethyl) -bicyclo / 2,2,3 _ / - heptane and / or at least one bis- (4-aminocyclohexyl) ™ Der. tvat of an alkane with 1 to 6, preferably 1 to 3, C atoms, ■ ... 509811/0933 _ _l6 _ c ^ ₂ ) 0 to 45 moles, preferably 0 to 35 moles, at least a straight or branched aliphatic diamine containing 4 to 20 carbon atoms, preferably 6 to 12 carbon atoms, the amino groups being ^{separated from one another by at least 4 carbon atoms, preferably by 1} at least 6 carbon atoms. . are separated β,) 5 to 50 mol $, preferably 10 to 35 mol $, at least an aromatic, in particular mononuclear, containing 7 to 20 carbon atoms, preferably 8 to 14 carbon atoms, in meta- or para-position carboxyl groups bearing dicarbon acid ß ₂ ) 0 to 45 MoI ^, preferably 0 to 35 MoIJw, at least one saturated, straight-chain or branched, aliphatic, 6 to 20 carbon atoms, preferably 6 to 12 carbon atoms, containing dearboxylic acid, the carboxyl groups by at least 4 C. -Atoms are separated from each other, and 2 ^) 0 to 8o MoI ^, preferably 0 to 50 MoI ^, at least one aliphatic aminocarboxylic acid with 2 to 20 carbon atoms, preferably 6 to 12 carbon atoms, in particular CO -aminocarboxylic acid, where the Mol # sum of the components οΛ) and c < _o ) equals coarse J- ^ those'components B ₁ ) and B ^) * · the mol ^ sum of all components -.? (,), PC ₂ ) * ^Q \)> ^ß p) ^and ^ equals 100 the mol ^ sum of components Pi ₁ ) and B ₁ ) equal to 20 to 95, preferably 50 to 90 mol, - 17 509811/0933 17 - HOE 73 / F 266 the MoI ^ sum of components ei ₂ ) , B ₂ ) and ^) is equal to 5 to 80 Mo 1 $, preferably 10 to 50 mol $, and where all data in MoI ^ refer to the sum of all components OC ₁ ), <λ ₂ )> ^ß i) ' ^ß 2 ^ ^and ^ H. " J5. Thermoplastic standard mass according to claim 2, characterized in that the aliphatic diamine among ^ ₂ ) is hexamethylene diamine. 4. Thermoplastic molding composition according to claim 2, characterized in that the aromatic dicarboxylic acid (s) under B ₁ ) is / are terephthalic acid and / or isophthalic acid. 5. Thermoplastic molding compound according to claim 2, characterized in that the aliphatic dicarboxylic acid (s) under β ~ adipic acid and / or decanedicarboxylic acid-1.10 is / are. 6. Thermoplastic molding composition according to claim 2, characterized in that the aliphatic (s) aminocarboxylic acid (s) under ft ~) L · -aminocaproic acid and / or 00 -aminolauric acid is / are. 7. Thermoplastic molding composition according to claim 1, characterized in that that the ionic copolymer B is a copolymer of the general formula ? 1? 2 4CH ₂ - CH) ^ f CH ₂ - C-4 ^ C = O η 0 ~ m ^e where R ₁ = H, CH, to C ₁₂ H ₂₅ , CgH ^, preferably H, CH ,, C ₃ H ₁ -, CgHc *, especially H, CH. ,, - 18 509811/0933 - 18 - HOE 7JJ / F H, CH. ,, C ₂ Hj- and Me ^m = ions of an m-valent (with m = 1 to J5) metal and wherein x, y and η represent integers. 8. The thermoplastic molding composition according to claim 1, characterized in that the ionic copolymers B ^ preferably> 50,000, having a weight average molecular weight 5000 ^ ^7. 9 · Thermoplastic molding compound according to claim 1, characterized in that that the ionic copolymer B selected is a copolymer containing alkali metal ions, preferably sodium ions Ethylene and (meth) acrylic acid are used. 509811/0933