DE2126251A1 - Polyacetal composition - Google Patents

Description

The invention "relates to a polyacetal composition with a good degree of whiteness and excellent heat resistance.

It is known that polyacetal resin (polyoxymethylene) can be produced by adding formaldehyde or its cyclic Oligomers (trioxane or tetraoxane or tetraoxymethylene) polymerized and then subjected the obtained polymer to various treatments for converting the end group will. A molding compound can be produced by mixing one

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Antioxidant, a heat stabilizer, or more other stabilizers can be made with the treated polymer.

In the production of the polyacetal resin, it is a necessary and important factor that, in addition to the conversion treatment various stabilizers are added to the terminal groups of the polyacetal resin, to improve the properties of the resin. Various suggestions have already been made for this purpose.

The aim of the invention is - a mass of high molecular weight To make available polyacetal resin, which has significantly improved whiteness and heat resistance.

Another object of the invention is a stabilizer, the polyacetal resin can be added to achieve a more stable composition than the conventional polyacetal resin compositions.

Other objects of the invention will be apparent from the more detailed description given below.

As a stabilizer for polyacetal resin have hitherto generally been phenolic compounds with a complicated structure, aromatic amines, dicyandiamides, ureas, hydrazines, sulfur compounds and polyamides are known. These were used to make a good industrial polyacetal composition

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2Q981S / 1634

Stabilizers were never used alone, they were usually in the form of a combination of two types of

Stabilizers are used, made from phenolic compounds as antioxidants and nitrogen compounds such as polyamides or dicyandiamines, as "hemestabilizer, passed"

Extensive studies of stabilizer combinations lie within the scope of the invention for polyacetal resin. As a result of these studies, the present invention has made a novel one Combination of stabilizers found which shows an excellent synergistic effect. It was in particular found that a polyetal mass with unexpected good heat resistance can be achieved if the third component is common with those already mentioned two types of stabilizers special! ^ hydroxydiphenyls or Bisphenols are used.

It is already well known that there are generally different Phenolic compounds can be used as a stabilizer for polyacetal resin. However, they are not always all types of Phenolic compounds suitable as stabilizers. Suitable phenol derivatives are disclosed in US Pat. No. 2,966,476 the following formula

R »R ¹

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7126251

described, in which R is a hydrogen atom or an alkyl group having 1 to 3 carbon atoms and R ^{1 is} an alkyl group having 1 'to 4 carbon atoms. The so-called sterically hindered phenols, for example 4,4'-butylidene-bis (3-methyl-6-tert-butylphenol) or 2,2'-methylene-bis (4,6-dimethylphenol) and the like, have been particularly recommended . These compounds are special bisphenols which are characteristic of their effects in protecting polyacetal resin against oxidation and discoloration. It is said that other phenolic compounds lack one or both of these properties.

It is also known that amine type stabilizers have an excellent antioxidant effect for polyacetal resin demonstrate; however, they cause "brown or black discoloration" when used (US Pat. No. 2,966,476). In addition, known antioxidants such as urea or hydrazines also lead to discolored products.

It is also well known that some species are more specific

Polyamides are very effective as a stabilizer for polyacetal resin because their effect as a heat stabilizer is quite reliable and sustained. However, not all types of polyamides are always effective. Among the polyamides, for example, according to American patent specification 2 993 025, the ^{terpolymers consisting of 35 σ} β> hexamethylene adipamide, 27 ° hexamethylene sebacamide and 38 % caprolactam have a good heat stabilizing effect.

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Even this copolyamide, which, as mentioned, is an excellent one Heat resistance still shows major disadvantages. One of the disadvantages is the discoloration. If this Copolyamide is mixed with polyacetal resin, the resulting resin composition changes color over time and with at high temperature such as the deformation temperature, remarkable discoloration occurs.

However, it has been found that the stabilizer combination according to the invention overcomes these disadvantages and an unexpected, remarkably good stabilizing effect can be obtained.

According to the invention, at least one compound is made from each of the following three classes of compounds selected and the compounds selected in this way for the preparation of the compounds according to the invention Polyacetal compound mixed with polyacetal resin:

Class 1: Hindered phenolic compounds; Class 2: nitrogen compounds; Class 3: Dihydroxydiphenyls or bisphenols

According to those described in US Pat. No. 2,966,476 Teachings dealing with the stabilization of polyacetal resin with the aid of a phenolic antioxidant cannot deal with all types sterically because of the poor stabilizing effect and the discoloration

209815 / 163A

Class 1 hindered phenolic compounds may be used in combination with a Class 2 terpolyamide. Representative examples of these sterically hindered phenols include 2,2'-methylenebis (4-methyl-6-tert-butylphenol), 2,2'-methylenebis (4-ethyl-6-tert.-butylphenol), 4,4'-methylenebis (2,6-di-1ert.-butylphenol), 2,2 * -butylidenebis (4-tert.-butyl-6-methylphenol) and compounds of the following formulas

wherein R represents an alkyl group having 1 to 5 carbon atoms.

However, it is surprising that the addition of dihydroxydiphenylene or their derivatives, which belong to the compound class 3, as a third component enables this class 1 belonging sterically hindered phenols to be used together with the compounds belonging to class 2.

The phenolic compounds or phenolic derivatives of class 1, which is one component of the stabilizers according to the invention are so-called sterically hindered phenols of the following formula (i)

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R ¹ R ¹ R

in which R denotes a hydrogen atom or an alkyl group with 1 Ms 3 carbon atoms and R 'denotes an alkyl group with 1 Ms carbon atoms. These include, for example, 4,4'-ethylidene-bis (2-methyl-6-tert.-butylphenol), 4,4'-butylidene-bis (3-methyl-6-tert.-butylphenol) or 2,2'- Methylene-Ms (3-methyl-6-isopropylphenol), 2,2'-methylene-Ms (4-methyl-6-tert. - "butylphenol), 2,2'-methylene-Ms (4-ethyl-6- tert .- "butylphenol), 4.4 ^! -Methylene-Ms (2,6-di-tert-butylphenol) and 2.2 ^! -Butylidene-bis (4-tert-butyl-6-methylphenol). These class 1 phenols also include compounds of the following formula (II)

(H) CH-CH2-CH-CH3

(in which R ^{1 is} an alkyl group with 1 to 5 carbon atoms

209815/16 3/1

"means" for example 1,1, 3-tris (2-methyl-4-hydroxy - 5- " tert-butylphenyl) "butane;

Compounds of the following formula (ill)

(CH ₃ )

I!

= C (III)

in which R is an alkyl group. 1 to 5 carbon atoms and χ is an integer from 1 to 6, preferably 2, for example pentaerythrityl tetra-2- (3,5-di-tert-butylphenyl) propionate;

Compounds of the following formula (IV)

HO R ¹

C (CH ₃ )

(IV)

OH

in which R is a hydrogen atom or a methyl group and R ' denotes a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, for example 1,3,5-tris- (3 ', 5'-di-

- 9

2 O 9 8 1 5/1 R 3/4

tert-butyl-4'-hydroxy "benzyl) 2,4,6-trimethylbenzene, Compounds of the following formula (V)

RHNH ₀ C Vr- -t CH ₀ NHR
/ from
< /
RHNH ₂ C. \
CH ₂ NHR

(V)

in which R is a hydrogen atom, an alkyl group with 1 to • 5 carbon atoms or an alkenyl group with 3 to 4 carbon atoms and R ^{1 is} an alkylidene group with 1 to 8 carbon atoms, for example 6,6'-methylenebis (ÖC, ÖC'-diamino-2 , 4-xylenol), 6,6'-ethylidene-bis (dC, dC ^f diamino-2,4-xylenol), 6,6 ^f -propylidene-bis (<? €, <£ · -diamino-2,4 -xylenol), 6,6'-butylidene-bis (<<, c <'-diamino-2,4-xylenol) and 4,4'-butylidene-bis (oC, (^ ¹ -diamino-2,4- xylenol); and compounds of the following formulas (VI), (VII) and

(VIII).

H- ,

(VI)

(VII) R.

(VIII) 5/1634 ORiQiNAL rNSPEC7H>

where R is an alkyl group with 1 "to 5 carbon atoms", for example 2,6-di-tert-butylphenol, 2,6-di-tert-butyl-4-methylphenol, 2 _t 6-di-tert-buty! hydroquinone and 2,6-di-tert-amylhydroquinone.

"In addition to these phenols, the formates of the compounds of formulas I to III and. V to "VII are used, for example 2,6-di-tert-butyl-4-methyl-1-formyloxybenzene, 4,4'-butylidene-bis (3-methyl-6-tert-butyl-1-formyloxybenzene and 1,1,3-tris (2-methyl-4-formyloxy-5-tert-butylphenol) butane.

The compounds of class 1 are so-called sterically hindered phenols, their antioxidant properties for various Polymers has already been well recognized, that is, phenol derivatives in which at least one hydrogen atom is in the ortho pitches to the hydroxyl group is substituted by alkyl groups.

In contrast to other polymers, it is necessary to use polyacetal resin with the aid of a nitrogen-containing compound to stabilize. Their stabilizing effect cannot be exactly explained; however, there is the hypothesis

- 11 -

that the nitrogen-containing compounds as an acceptor for monomeric brmaldehyde or for very small amounts of acid act that are present or formed in polyacetal resin.

The class 2 nitrogen compounds used as a component of the stabilizers of the invention include polyamides, for example terpolyamides consisting of hexamethylene adipamide, hexamethylene sebacamide and caprolactam (U.S. Patent 2,993,025), from caprolactam and hexamethylene sebacamide existing polyamides (J. Poly. Sci. 2_, 412,

(1947)), polyamides made from caprolactone and caprolactam

ester / (Japanese Patents 573,913 and 573,915), polyesteramides according to patent claim of the American patent 3 355 514, polycondensates, which from dicarboxylic acid dihydrazides or substances capable of forming a dicarboxylic acid dihydrazide, as well as urea and aliphatic diamines were formed (Dutch patent specification 6 818 620), Uracile, amidines, cyanoguanidines, polyurethanes, polyureas, polyamide-ureas, polyurethane-amides and polyaminotriazoles as well as copolymers or mixtures of these compounds.

According to the invention, nitrogen compounds are particularly suitable, which were produced by the polycondensation of dicarboxylic acid dihydrazide, urea and diamine.

The class 3 compounds used as a component of the stabilizers of the invention are dihydroxydiphenyls

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2Ü981S / 1R34.

or bisphenols which can be represented by the following formulas (IX) and (X), respectively

(IX)

in which R is a hydrogen atom or an alkyl group having 1 "to 5 carbon atoms, preferably a hydrogen atom means, and

R ■

HO-f \> - C— ζ V-OH (X)

R '^ ¹ X

R "

in which R and R 'have hydrogen atoms or alkyl groups 1 to 6 carbon atoms and can form a saturated alicyclic ring (homocyclic ring) and R "denotes a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, preferably a hydrogen atom. Such compounds are, for example, 4,4'-dihydroxydiphenyl, 4,4'-dihydroxydiphenylmethane, 4,4'-dihydroxydiphenyl-1,1-ethane, 4,4'-dihydroxydiphenyl-1,1-propane, 4,4'-dihydroxydiphenyl-1,1-n-butane, 4,4'-dihydroxydiphenyl-1,1-heptane, 4,4'-dihydroxydiphenyl-2,2-propane,

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2098LS / 1634

4,4 ^l -dihydroxydiphenyl-2,2-butane and 4,4'-dihydroxy- ^, 3-dimethylphenyl-2,2-propane.

The compounds of compound class 3 by themselves have no or only poor effectiveness as antioxidants. However, it has been found experimentally that by using the class 3 compounds simultaneously awarded with the phenolic compounds of class 1 and the aforementioned nitrogenous compounds of class 2 stabilized polyacetal compositions can be obtained in comparison with compositions with the two component stabilizers, which consist of compounds of class 1 and class 2 or class 1 and class 3 or class 2 and class 3.

It is surprising that the compounds of class 3 include phenol derivatives which are not so-called sterically hindered Are phenols, and that these compounds show a strong synergistic effect when taken together with Class 1 and Class 2 connections are used. The class 3 connections are different from the Class 1 phenols.

According to the invention phenol derivatives of class 1 in one Amount of 0.01 to 3 percent by weight, based on the weight of the polyacetal, applied. Using a great Amount of these phenolic compounds does nothing

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-H- _m 7126251

Disturbance of the stabilizer effect; however, from an economical point of view, 0.01 Ms 0.5% by weight of the phenolic compounds is preferably used. On the other hand, the nitrogen-containing compounds of class 2 are used in an amount of 0.1 to 10 percent by weight, preferably 0.1 to 3 percent by weight, based on the weight of the polyacetal. Furthermore, dihydroxydiphenyls or bisphenols of class 3 are used in an amount W of from 0.001 to 3 percent by weight, based on the weight of the polyacetal.

Polyacetals, the heat stability of which can be remarkably improved by the invention, include Polyoxymethylene homopolymer with a degree of polymerization. of 500 or more obtained by polymerization of formaldehyde or its cyclic oligomers and subsequent 'chain end closure of the polymer obtained, as by ^ ether or esterify, and polyoxymethylene copolymers having the same degree of polymerization mentioned above obtained by copolymerizing formaldehyde or its cyclic oligomers. with a comonomer that is used for copolymerization with formaldehyde or its cyclic oligomers is capable, and subsequent chain termination of the obtained Copolymers, such as by etherifying, esterifying or converting the unstable terminal oxymethylene units in units other than oxymethylene units by heat treatment or hydrolytic treatment

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■ were. Representative examples are polyoxymethylene diacetate, Polyoxymethylene dimethyl ether, polyoxymethylene diethyl ether, Copolymers of trioxane and dioxolane and copolymers of trioxane and styrene.

It is generally well known that the stabilizers for polyoxymethylene homopolymer are often wholly or almost entirely themselves prove unsuitable as stabilizers for polyoxymethylene copolymers and that the reverse pail often occurs. It is therefore very surprising that the novel Stabilizer combination has a strong synergistic effect for the stabilization of any polyoxymethylene homopolymers and polyoxymethylene copolymers shows *

The invention is illustrated below with the aid of examples, however, it is not intended to be limited to these examples.

In the following examples, all percentages and parts are percentages and parts by weight. R (fo) is the remaining percentage of Polyacetalmasse after the heat treatment of the Polyacetalmasse at 222 ⁰ C in air for 60 minutes and the light resistance ■ bsleutet the change after 300 hours continuous exposure, measured by the standard Pade-o-meter.

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209815/16, I / *

-16-. 7126251

The value Z means the whiteness of the polyacetal determined with the aid of a Hunter colorimeter. The value K ₂₂₂ shows the constant of the reaction rate of the thermal decomposition of the polymer, measured by the method described in US Pat. Nos. 2,964,500 and 2,998,409 "is described.

Examples 1 to 7

Fixed amounts of various stabilizers, which are given in Table 1, are added and mixed in polyoxymethylene diacetate, which was prepared by polymerizing formaldehyde and acetylating the polymer obtained with acetic anhydride (reduced viscosity, measured at 60 ° C in a solvent mixture of equal proportions of tetrachloroethane and p-chlorophenol: 2.00 and K ₂₂₂ ^: 0.05). The mixture is then mixed for 20 minutes using a conical mixing barrel (double cone mixer) ψ . The mixture obtained is vacuum dried at 60 ° C. for 6 hours. A molded plate with a thickness of 0.5 mm is then produced using a test hot press at a temperature of 190 ° C. and the heat resistance of this plate is measured. The results obtained are shown in Table 1 together with the results of comparative experiments.

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- 17 Table 1

example
* 2 Additive Amount of
additive
fabric, $> R ( , 3 Light be
constant
speed Comparison
attempt 1 3 4,4'-dihydroxydi-
phenyl-2,2-propane 0.1 85 , 0 no ver
modification It 4th 2,6-di-tert-butyl
4-methylphenol 0.5 89 , 0 It, Il 5 4,4'-butylidene-bis-
(3-methyl-6-tert.-
butylphenol) 0.5 89 , 2 It ti 6th 2,2'-methylene-bis-
(4-methyl-6-tert.-
butylphenol) 0.5 90 .0 weak
Red ti 7th 1,1,3-tris (2-methyl-
4-hydroxy-5-tert.
butylphenyl) butane 0.5 92 , 5 It Il 8th 1,3,5-trimethyl
2,4,6-tris- (3,5-di-
tert. -buty / l-4-h.ydroxy-
benzyl) benzene 0.5 89 ,8th W. η 9 2,2'-methylene-bis-
(4-methyl-6-tert.-
butylphenol) formate 0.5 91 , 5 It η 10 Terpolyamide (A) 1.0 86 , 5 weak
yellow η 11 Nitrogen compound
manure (B) 1.0 91 , 3 no ver
modification Il . 12th Polyester amide (0) 1.0 89 , 3 η η 13th Diphenylamine 0.1 90 , 5 changes
after brown ft 4,4'-dihydroxydiphe-
nyl-2,2-propane
Terpolyamide (A) 0.1
1.0 92 ,8th weak
yellow H Diphenylamine
Terpolyamide (A) 0.1
1.0 93 changes
after brown

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- 18 Tatelle 1 (continued) · '- 1 2 D 2 5 1

example

Additive

Amount of
Additive, $

Lightfastness

Comparative experiment 14

2, '6-I / i-ter t. -butyl 4-methylphenol

Terpolyamide (A)

0.5
1.0

96.0

weak gelfc

4.4 ^l -butylidene-bis- (3-methyl-6-tert.-

* Il 16 butylphenol;
Terpolyamide (A) 0.5
1.0 94, 9 no ver
modification Il 17th 2,6-di-tert-butyl
4-methylphenol
Nitrogen supply
bond (B) I.
0.5
1.0 96, 3 no ver
modification 4,4'-butylidene-bis-
(3-methyl-6-tert, -
butylphenol)
Nitrogen supply
bond (B) 0.5
1.0. 96, 4th It

2,6-di-tert-butyl

4-methylphenol 0.5

Polyester amide (G). 1.0

96.8

1, i, 3-tris (2-methyl-4-hydroxy-5-tert-butylphenyl) butane 0.5

Polyester amide (C) 1.0

96.5

ti 20th Diphenylamine 0.1 98.5 changes
after brown 4,4 -Butylidene-bis-
(3-methyl-6-tert.-
butylphenol)
Terpolyamide (A) 0.5
1.0 Il 21st N, N * -Difurfury1-
dithioxide 1.0 4,4 »-Butylidene-bis-
(3-never-thyl-6-th t.-
butylphenol) , 0.3 84.0 not
malleable Dilauryl ^^ '-
thiodipropionate 0.1

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example

Additive

Amount of
Additive, $

Lightfastness

Comparison K-vinyl pyrrolidone 1.5 93.0 changes attempt 22 vinyl acetate after yellow copolymer (70:30) 4,4 ^f -Butylidene-bis- 0.3 (3-methyl-6-tert.- butylphenol) 0.4 * Dilauryl-3.3 ¹ - thiodi-propionate

Ni complex salt of 1,2,3-benzotriazole

Bis (4-hydroxy-5-

tert-butyl-2-

methylphenyl) sulfide

Dioctadecyl disulfide

0.5
0.5 62, 5 not
malleable 0.25 0.13 0.13 87 6th not
malleable

Condensate of 3 moles of 3-methyl-6-tert-butylphenol and 1 Moles of crotonaldehyde

Hexamethylenediamine

ß, ß'-thiodipropionic acid

Terpolyamide (A) 1.5

2,2 -Methylene-bis- (4-methyl-6-tert, -butylphenol) 0.3

Dilauryl 3,3'-thiodipropionate 0.1 98.0

pale yellow

o-hydroxyacetanilide 0.5

2,2'-methylenebis (4-methyl-6-tert-butylphenol) 0.5

Polycaprolactam 1.0 96.3

pale yellow

N-cyanoacethydrazide 0.5

2,2'-methylenebis (4-methyl-6-tert-butylphenol) 0.5

Polycaprolactam 1.0 97.5

pale yellow

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■ - 20 - Table 1 ^ continued)

example

Additive

Amount of
Additive, %

Lightfastness

Comparative experiment 28

p-hydroxydiphenyl 0.1

2,2'-methylene-bis-0.5 (4-methyl-6-tert.-butylphenol)

Terpolyamide (A) 1.0

changed 97.8 to yellow

Il 29 4,4'-butylidene-bis-
(3-methyl-6-tert.-
butylphenol) 0.1 98 , 4 no ver
modification • 2,2'-methylene-bis-
(4-methyl-6-tert.-
butylphenol)
Terpolyamide (A) 0.5
1.0 ti 30th 2,6-di-tert-butyl
phenol 0 ₉ 1 97 , 6 changes
after yellow 2.2 * -Methylene-bis-
(4-methyl-6-tert.- 9>, o It 31 4.4 ^f -Thio-bis- (3-
methyl-6-tert.-
butylphenol) 0.1 2,6-di-tert-butyl
4-methylphenol 0.5 97 ,1 changes
after gray Nitrogen supply
bond (B) 1.0 H 32 4,4'-butylidene-bis-
(3-methyl-6-tert.-
butylphenol 0.1 2,6 "-di-tert-butyl-
4-methylphenol 0.5 98 ,8th no ver
modification Nitrogen supply
bond (B) 1.0 Il 33 2,6-di-tert-butyl
hydroquinone 0.1 2,6-di-tert-butyl
4-methylphenol 0.5 97 A. changes
after yellow Nitrogen supply
bond (B) 1.0

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- 21 Table 1 (continued)

example

Additive

Amount of additive, %

Lightfastness

Example ΐ

4,4'-dihydroxydiphenyl-2,2-propane

0.1

4,4'-butylidene-bis- 0.5 98.9 no ver (3-methyl-6-tert.- 1.0 modification butylphenol) Terpolyamide (A)

H 2 4,4'-dihydroxydi-
phenyl-2,2-propane 0.1 99.0 no ver
modification • 2,6-di-tert-butyl
4-methylphenol
Polyester amide (C) 0.5
1.0 3 4,4'-dihydroxydi-
phenyl-2,2-propane 0.1 2.2 -Methylene-bis-
(4-methyl-6-tert.-
butylphenol) 0.5 99.1 η Nitrogen supply
bond (B) 1.0

4,4'-dihydroxydiphenyl-2,2-propane

2,2 · -Methylene-bis- (4-methyl-6-tert-butylphenol) formate

Nitrogen compound (B).

0.5 1.0

99.0

4,4'-dihydroxydiphenyl 0.1

2,6-di-tert-butyl-4-

methylphenol 0.5

Nitrogen compound (B) 1.0

99.2

4,4'-dihydroxydiphenyl

methane 0.1

2,6-di-tert-butyl-4-

methylphenol 0.5

Nitrogen compound (B) 1.0

99.0

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Table 1 (continued)

Amount of R (5 *) Lighting Example additive additive constant- fabric it, # speed - Example 7 4,4'-dihydroxydi- 0.1 phenyl-2,2-propane 1,3,5-trimethyl . 2,4,6-tris- (3,5- di-tert-butyl) - 4-hydroxybenzyl) - 0.5 no ver "benzene 1.0 98.7 modification Polyester amide (C)

(A): The terpolyamide used is a copolymer of 35 ° i hexamethylene adipamide, hexamethylene sebacamide 27 ^ and 58 fo caprolactam.

(B): A polycondensation product from dicarboxylic acid dihydrazide, Hexamethylene diamine and urea. This product is a nitrogen-containing, colorless, transparent polycondensation product with a softening temperature of 140 to 160 ° C. 20 parts were required for its manufacture Sebaic acid dihydrazide, 20 parts of adipic acid dihydrazide, 15 parts of hexamethylenediamine and 60 parts of urea are placed in a 300 ml three-necked flask, the mixture at Melted 200 ° C in a stream of nitrogen with stirring to make it react for 120 minutes was heated for a long time. Thereafter, the reaction system was connected to a vacuum line of 0.5 mmHg and that Mix by further heating to 200 ° C for 240 Minutes further implemented.

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(C): A polyester amide with a melting point of about 200 ° C. Mol % ethylmagnesium bromide and 3 mol ⁰ Jo Ii-Acetyl ca per la c tarn as a catalyst (the amount of the catalyst is based on the monomers "), - ', vials of the white powder obtained with a 1 $ aqueous solution of hydrochloric acid , Repeating the water washing until the washing water was neutral and drying the powder obtained.

Example 8

129 parts of dodecanedicarboxylic acid dihydrazide (tetradecanoic acid dihydrazide), St & parts of hexamethylenediamine and 50 parts of urea are placed in a three-necked flask with a capacity

given a capacity of 500 cm and heated for 120 minutes reacted to 210 ° C in a stream of nitrogen. In another three-necked flask with a capacity 300 cm are 100 parts of sebacic acid dihydrazide, 25 parts of tetramethylenediamine and 40 parts of urea reacted by heating to 210 ° C in a stream of nitrogen and the resulting transparent molten product is added to the first flask. The mixture is during 300 minutes under reduced pressure of 0.5 mm Hg

209815/1634

Heated 210 ° C to complete the reaction, whereby a white, semi-transparent, nitrogen-containing polycondensation product is obtained.

The esterified to 7 used in Examples 1 polyoxymethylene homopolymer is reacted with 0.8 $> this nitrogen-containing polycondensates, 0.1 # 4,4'-dihydroxydiphenyl-2,2-propane, and 0.5 ° i 2,6-di -tert-butyl-4-methylphenol using a Henschel mixer with a fitting

like from 150 1 "mixed at 40 ° C for 10 minutes.

Tableting is then carried out with the aid of an extruder with a cylinder temperature of 200 ° C. The tablets have a value R (^) of 99.3 ^ and a value Z of 99. After repeating the tablet compression process four times under the same conditions, the value R (%) of the tablets is 98.7 ° and the value Z is 97.

For comparison purposes, on the other hand this polyoxymethylene homopolymer with 1.0 · fo terpolyamide (A), which consists of 35 f> Hexamethyle-nadipamid, 27 i> hexamethylene sebacamide and 33 ° i caprolactam, and 0.1 $> diphenylamine and 0.5 f> 4.4 ^! -Butylide, n-bis (3-methyl-6-tert.-butylphenol) mixed. It is then compressed into tablets in the manner described above. R (% ■) of the tablets is 98.5 ^ and Z is 98 fo. After repeating the tabletting process four times under the same conditions, the '· ■'. - 25 -

209815/1634

Tablets received a tfert R (#) of 97.0 ^c /> and Z of 92 #.

Example 9

About 0.1 g of gaseous boron trifluoride is poured into a -70 ° C held flask containing 55 ml of isobutylene. Anhydrous formaldehyde vapor is passed through the flask, while stirring the mixture for about 10 minutes. The product obtained is filtered and dried. The thus obtained Polyoxymethylene copolymers are acetylated by treating with anhydrous acetic acid in the presence of clay sodium acetate.

The esterified copolymer obtained is treated with 0.8% of a nitrogen-containing compound (B), 0.05 % of 4,4'-dihydroxydiphenyl-2,2-propane and 0.4 ^ 2,6-di-tert-butyl- 4-methylphenol is mixed and the mixture is then extruded from a small extruder at a cylinder temperature of 195 ° C to make tablets. The heat resistance R (^) of the tablets is 99.3%.

Example 10

A mixture of 500 parts of polyoxymethylene copolymer having a content of 3.1 i ° derived from dioxolane monomer, 1,000 parts of water and 150 parts of triethanolamine are in a sealed autoclave wä.hrend 2 1/4 hours at 140 bib 150 ° C heated. After this time, the autoclave is cooled to room temperature and

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21262S1

opened. The copolymer obtained is with acetone and washed several times with hot water and then dried.

The copolymer obtained is treated with 0.1 io dicyandiamide, 0.3 2.2'-methylenebis (4-methyl-6-tert.-butylphenol) formate and 0.08 io 4,4'-dihydroxydiphenyl-2,2 -propane mixed and the mixture thus obtained is then pulverized in a heating room for 45 minutes in a mixer equipped with Sigma blades. "At a temperature of 200 Ms 205 ° C. The heat resistance R {%) of the pulverized mass" is 99.4 io and the value of the degree of whiteness, Z, is 99 - ·. The value R (i °) of the mass of this example, which contains no '4,4'-dihydroxydiphenyl-2,2-propane, is 98.0 i °.

Example 11

230 parts of sebacic acid dihydrazide are placed in a three-necked flask with a capacity of 1000 ml and * the contents with stirring in a nitrogen stream to 200 ° C heated to melt. Then 30 parts of urea and 116 parts of hexamethylenediamine are added and done Heating for minutes at a reaction temperature of 190 ° C implemented. The colorless, transparent reaction solution has a gradually increased viscosity and in the At the end of the reaction, the solution becomes cloudy and changes into a semi-transparent, viscous solution. Then it will be the reaction system was brought under a vacuum of 1 mm.Hg

209815/1634

and the reaction temperature increased to 200 ° C. The reaction is then completed by further heating for 300 minutes, whereby 220 parts of a white block polycondensate are obtained, the thermal analysis of which gives a carbon value of $ 53.71, a hydrogen value of 7.69% and a nitrogen value of 24.55% .

The polycondensate obtained softens and melts "at about 195 ° C and by compression molding with the help of a hot press, a transparent, colorless, good sheet or plate can be made from it getting produced. The polycondensate can also be thylsulf oxy d by dissolving in Diine or methanol and evaporating of the solvent to be transferred to dryness in a film. Furthermore, the polycondensate can be poured into a Non-solvents, such as dioxane, can be converted into a fine powder. The specific measured at 30 ° C in methanol The viscosity of the polycondensate is 0.30.

Polyoxymethylene diacetate with an intrinsic viscosity of 2.10 and a value K ₂₂₂ ^of ° »° 3 is mixed with 0.8% of this finely divided polycondensate powder, 0.5 % 4,4'-butylidene-bis (3-methyl-6-tert .-Butylphenol) formate, 0.1 i » 4.4 ^f -dihydroxydiphenyl-2,2-propane and 0.2 ^ titanium white (rutile) are mixed and the polyacetal mass obtained is subjected to injection molding at 190 ° C. On. in this way a thin plate with a thickness of 3 mm is made.

• - 28 -

209815/1634

-28- 7126251

The plate is subjected to a heat treatment in the air at 222 ° C. for 120 minutes. As a result, there is a weight loss of 1.3 % . The whiteness value, Z, is 97 after the heat treatment, while it was 99 before the heat treatment.

The molded plate is pulverized and re-injection molded into a plate. Even with viermali-P after repeating this process, no discoloration is observed.

Examples 12 to 24

A mixture of urea, adipic acid dihydrazide and hexamethylenediamine of the composition shown in Table 2 is placed in a three-necked flask with a capacity of 300 ml provided with an effective stirrer and melted by heating to 200 ° C. in a stream of nitrogen. W The reaction temperature is lowered to 170 ° C. and the reaction is continued at 170 ° C. for 300 minutes. The reaction mixture turns into a colorless, semi-transparent, highly viscous solution.

Then the reaction system is connected to a vacuum line of 1 mm Hg and under for a further 90 minutes Heating to 200 ° 0 implemented. In this process, nitrogen-containing polycondensates of different compositions are produced obtain. ■

- 29 209815/1634

- 29 - 7126251

Polyoxymethylene diacetate with an intrinsic viscosity of 1.60 and a value of Kp2? ^From Ot03, 1.0 $ of each of these nitrogen-containing polycondensates, 0.2 ^ 2.2'-methylenebis (4-methyl-6-tert.-butylphenol) and 0.2 $ 4,4'-dihydroxydiphenyl-2, 2-propane mixed and. the polyacetal composition obtained is injection molded at 195.degree. Test specimens are produced on which the heat resistance is measured. The results are shown in Table 2.

209815/1634

- 30 Table 2

Examples Reaktapten (g) Adipine
acidic
hydrazide Urine·
fabric: Hexamethylene
t leniamine R (YO Whiteness,
Z 12th 43 30th 29 99.36 98 13th 46 32 24 99.30 98 14 * 48 34 19th 99.25 98 15th 50 35 14th 99.00 97 .16 55 37 7th 99.00 97 17th 62 21st 33 99.40 99 • 18th 67 23 26th 99.25 98 19th 72 25th 21st 99.30 99 20th 79 27 11 99.10 98 21st 25th 42 16 99.28 99 .22 35 36 25th 99.38 98 23 121 12th 11 99.00 98 24. 139 6th 11 ■ 99.08 98

Example 25

A mixture of 258 parts of tetradecanedioic acid dihydrazide, 276 parts of 3,9-3is (3-aminopropyl) -2,4,8,10-tetraoxaspiro - / ^, 5J ⁷ -undecane and 60 parts of urea is stirred in a 1000 ml three-necked flask heated to 190 ° C. The reaction mixture gradually becomes viscous with evolution of gas

- 31 -

209815/1634

molten solution over. Then the reaction system is brought under reduced pressure of 1 mmHg and the reaction ' carried out at 210 ° 0 for 120 minutes to complete the reaction. Thereby 360 parts of a white and semi-transparent, nitrogen-containing polycondensate.

Polyoxymethylene diacetate with an intrinsic viscosity of 1.80 and a value of Kpo? ^From 0-02, 1 fo of the resulting polycondensate of tetradecanedioic acid hydrazide and 3, 9-bis (3-aminopropyl) -2,4,8, iO-tetraoxaspiro - / "5.57" -undecane, 0.3 $ 2,6-Di-tert-butyl-4-methylphenol and 0.1 $ 4,4'-dihydroxydiphenyl-2,2-propane were mixed well and the mixture was injection molded at 190 °. A shaped body with a good degree of whiteness is achieved. The heat resistance of the molding is 99.36,

Examples 26 to 38

174 parts of adipic acid dihydrazide are placed in a 1000 ml three-necked flask and heated to 200 ° G with stirring in a stream of nitrogen to melt it. Then will Parts of urea and 116 parts of hexamethylenediamine are added, the reaction temperature is lowered to 170 ° C. and the reaction is carried out carried out for 5 hours with stirring.

- 32 -

209815/1634

The obtained precondensate is divided into 12 parts and then each part under reduced pressure of 1 mm Hg under

further heated under the conditions shown in Table 3. The so The results obtained are shown in Table 3.

Polyoxymethylene diacetate with an intrinsic viscosity of 2.10 and a value K? 22 ^of 0> 03 is made with 0.8 % of each of the nitrogen-containing polycondensates shown in Table 3, 0.2 % of 2,6-di-tert-butyl-4 methylphenol and 0.07 1 ° 4,4'-dihydroxydiphenyl-2,2-propane are mixed well and the resulting polyacetal composition is pelletized by extrusion at 195 ° C. The result is shown in Table 3.

209815/1634

Table 3

3example CondensationTDedingimgen duration
(H) Condensation product Elementary-
analysis
N o Appearance Polyacetal composition ■ Whiteness Z rn temperature
( ⁰ G) '. 1
I. yield
(*) 25.18 White,
ha Ib you rc hr-
sighted R W 97 26th 190 3 65 25.72 colorless,
by
sighted 99.30 98 27 190 63 25.99 colorless,
by
sighted 99.43 ■ 98 28 190 1 60 25.79 White,
halfway through
sighted 99.28 98 29 200 3 62 26.02 colorless,
by
sighted 99.20 99 30th 200 5 60 26.50 colorless,
by
sighted 99.21 99 31 200 0.5 59 25.20 White,
halfway through
sighted 99.05 32 ' 220 65 99.00

Table 3 (port setting)

example Condensation conditions duration
(H), ■ Condensation product Slementar
analysis
N " ° / o Appearance Polyacetal composition '/ ice-
degree Z temperature
( ⁰ C) 1 yield 25.98 colorless,
by
sighted 99 33 220 '. 3 63 . 25.88 colorless,
by
sighted 99.40 99 34 220 • ⁵ 58 25.73 colorless,
by
sighted 99.41 99 35 220 0.5 56 25.80 colorless,
by
sighted 99.36 99 36 240 1 53 25.78 colorless,
by
sighted 99.36 99 37 240 2 53 25.86. colorless,
by
sighted 99.48 99 38 240 51 99.49

Example 39

17.4 parts of adipic acid dihydrazide, 11.6 parts of hexamethylenediamine and 7.1 parts of biuret are placed in a hard glass ampoule and heated to 190 ° C. at atmospheric pressure for 240 minutes. The ampoule is then connected to a vacuum of 1 mm Hg and heated to 220 ° C. for a further 120 minutes. In this case, 22 parts are obtained of a white, nitrogen-containing polycondensates, whose elemental analysis values 50.55 ° 1 carbon, 7.20 / 0 hydrogen and $ 27.80> Nitrogen ", respectively.

Polyoxymethylene diacetate with a softening point of 175 ° C and an intrinsic viscosity of 2.10 is 0.8% of this polycondensate, 0.4% 2,6-di-tert-butyl-4-methylphenol and $ 0.1 4,4'-Dihydroxydiphenylmethane mixed and the resulting Polyacetal mass is produced at a cylinder temperature of 195 ° C and a mold temperature of 100 ° C under an injection pressure of 1000 kg / cm is injection molded into a thin plate with a thickness of 3 mm. The plate is used as a test specimen Subjected to heat treatment for 120 minutes at 220 ° C in the air, a weight loss of 1.7 5 ^ being achieved. Of the Whiteness Z is 99. After this heat treatment at 220 ° C the mass is shaped into a film with the aid of a test hot press at 190 ° C. under a pressure of 200 kg / cm. The degree of whiteness Z of the film obtained in this way is 98.

- 36 -

20981S / T634

Example 40

Polyoxymethylene diacetate with an intrinsic viscosity of 180. and a value of Kp ₂₂ of 0.04 is used with 0.7 fo of the nitrogen-containing polycondensate described in Example 3 ", 0.3 ^C A 2,2'-butylidene-bis (2-tert-butyl-4-methylphenol) and 0.1 fo 4,4'-dihydroxydiphenyl-2,2-propane are mixed and the resulting polyacetal mass is extruded for tableting with the aid of a small test extruder with an internal cylinder diameter of 20 mm at a cylinder temperature of 195 ° C. Then The polyacetal tablets thus obtained were subjected to heat treatment at 222 ° C. in air for 120 hours, with a weight loss of 1.0 $ but almost no discoloration. On the other hand, this polyoxymethylene homopolymer became 0.7 1 ° of the same nitrogen-containing polycondensate, 0,3 ^ 2,2'-butylidene-bis- (2-tert-butyl-4-methylphenol) and 0.1 % 4,4'-dihydroxy-3,3'-dimethyldiphenyl-2,2 -propane mixed and the polyacetal mass obtained is extruded in the manner described above en is 1.9 ^.

Examples 41 to 51

Various dicarboxylic acid dihydrazides, diamines and urea or urea derivatives listed in Table 4, are according to the method described in Example 1 for the reaction brought and synthesized the corresponding nitrogen-containing condensates.

20 981S / 163 4

rf

Polyoxymethylene acetate with an intrinsic viscosity of 2.10 and a value K? 22 ^of 0.02 'is 0.7% for each of these nitrogen-containing polycondensates, 0.4 % 2,6-di-tert-butyl-4-methylphenol and 0.05 f ° 4.4 ^! -Dihydroxydiphenyl mixed well and the polyacetal mass obtained is tabletted by extrusion at a cylinder temperature of 190 ° C. The tablets obtained are subjected to the heat resistance test, the results of which are shown in Table 4.

209815/1634

Table 4

at Reactants (mol $>) Diamine urea
or urine
stoffde
rivat the end Softening Appearance Polyacetal composition v / ice-
degree Z game Dicarboxylic acid
dihydrazide Bis (amino-
propyl) -
ether 25 urine
fabric 50 prey
M. Point
( ⁰ C) 99 41. Sebacic acid
dihydrazide 25 Hexamethy
lenediamine
20th urine
fabric 50 62 100-130 colorless,"
by
sighted 99.20 99 42 Suberic acid
dihydrazide 30 Penta
methylene
diamine 20 urine
fabric 40 64 140-160 colorless,
by
sighted 99.38 _L. 98 43 Oxadivalerian
acid dihydra
zid 40 Hexamethy
lenediamine
20, urine
fabric 45 67 160-180 colorless,
by
sighted 99.00 98 44 Cyclohexanedi-
carboxylic acid
dihydrazide 35 Hexamethy
lenediamine
25th Ethylene
urine
fabric 45 60 140-160 colorless,
half-
by
sighted 99.10 99 45 Sebacic acid
dihydrazide 30 Hexa
methylene
diamine 25 Siuret 50 62 170-180 colorless,
by
sighted 99.20 .98 46 Adipic acid
dihydrazide 25 Te triethy
lenediamine
25th Methylene
bisharn-
fabric * 45 59 180-190 colorless,
by- .
sighted 99.31 99 47 Sebacic acid.
dihydrazide 30 60 140-160 colorless,
by
sighted 99.00

* { Methylene biuret;

Table 4 (! Continued)

O CO OO

cn

C-O

at Reactants (mol ° />) Diamine urea
or urine
material
derivative the end Softening Appearance Polyacetal composition V / ice
A'rad Z game Dicarboxylic acid
dihydrazide Hexa
methylene
diamine 20 urine
fabric 40 prey Point
( ⁰ C) - colorless,
by
sighted R W- 99 48 Azelaic acid
dihydrazide 40 Non-
methylene
.diamin 20 Thiourine
fabric 47 59 140-180 White,
half-
by
sighted 99.30 97 49 Suberic acid
dihydrazide 33 Non-
methylene
diamine 20 Ethylene
thiourine
fabric 45 62 160-190 White,
half-
by
sighted 99.10 97 50 Adipic acid
dihydrazide 35 Hexa
methylene
diamine 25 Urine * - ■
fabric 50 58 180-200 easy
yellow,
by
sighted 99.08 97 51 Dimeric acid
dihydra ζ id 25 60 70-120 99.00

VjI VO

Example 52

7.5 parts of oxalic acid dihydrazide, 8.6 parts of decamethylenediamine • and 6 parts of urea are placed in a hard glass ampoule and heated to 210 ° G for 120 minutes in a stream of nitrogen to carry out the reaction. After that, the ampoule connected to a vacuum line of 0.5 mm Hg, the reaction temperature increased to 240 ° C and the ampoule during further Heated for 180 minutes. First, the reaction mixture is in .Form of a white block before, but after a reaction time of 120 minutes begins to melt under reduced pressure and turns into a colorless, transparent and very viscous mixture. Finally, 13 parts of a colorless, transparent, Nitrogen-containing polycondensates obtained. According to analysis, the nitrogen content of the polycondensate is 21, O8; &, The obtained polymer can be obtained by pressing with the help of a test hot press be deformed under a pressure of 250 kg / cm at 200 ° C to a very good polish.

Polyoxymethylene diacetate with an intrinsic viscosity of 2.30 and a value Kpoo of 0.07 is used with 0.8 fo this nitrogen-containing ^{polycondensate, 0.3 σ} β> 2,6-di-tert.-butylhydroquinone and 0, 2 ° / o 4,4'-dihydroxydiphenyl mixed and the Polyacetalmasse obtained is tableted with a small test-extruder having a cylinder inner diameter of 20 mm at a cylinder temperature of 195 ° C by extrusion. The polyacetal tablets thus obtained are then subjected to a heat treatment in air for 120 minutes

- 41 -209815 / 163A

~ 41 -

Subjected to 222 ° C, resulting in a weight loss of 1.2 is achieved but almost no discoloration occurs.

These polyacetal tablets are again tabletted five times under the same conditions of the cylinder by extrusion, The whiteness of the tablets obtained is also after, the fourth Repetition unchanged and all v / s Z are 98. Each of the fifth tableting, the fourth Z goes over to 97.

Example 53

17 parts of adipic acid dihydrazide, 16 parts of malonic acid dihydrazide, 40 parts of isophorondiaiain and 80 parts of biuret are placed in a three-necked flask equipped with a powerful stirrer with a capacity of 300 ml, heated in a stream of nitrogen to 200 ° C. and melted and heated to the same for 300 minutes Temperature further implemented. The reaction mixture solidifies with evolution of gas. Then the reaction system is connected to a vacuum line of 1 mm Hg and the mixture is heated to 230 ° C while. Subjected to further reaction for 120 minutes. The reaction mixture gradually melts and turns into a viscous, colorless, transparent, molten solution. Parts of a colorless, transparent, glass-like, nitrogen-containing polycondensate with a nitrogen analysis value of 20.68 % are obtained. Its softening point is

180 ° C.

- 42 -

209815/1634

Polyoxymethylendimethyläther with a Gxenzviskosität of 2.10 and a value ^of Kg22 ®> ® ^ is 0.9 fo this nitrogen-containing polycondensates, 0.4% of 2,2'-methylene-bis- ^ -methyl-ö-tert-butylphenol ) and 0.1 % 4,4'-dihydroxydiphenyl-2,2-propane "are mixed. The polyacetal composition obtained is tabletted by extrusion with the aid of a small test extruder with an internal cylinder diameter of 20 mm at a cylinder temperature of 195.degree Tablets are obtained with a degree of whiteness Z of 99. These tablets are then subjected to a heat treatment in air at 222 ° C. for 120 minutes, with a weight loss of 1.0%.

Examples. 54 to 57

The various polyoxymethylene copolymers shown in Table 5 are with 0.8 i <> of a nitrogen-containing polycondensate, 0.3 1 ° 2,2'-methylenebis (4-methyl-6-tert-butylphenol) and 0 , 1% 4,4'-dihydroxydiphenyl-2,2-propane mixed. The nitrogen-containing polycondensate used was synthesized dihydraζid in the manner described in Example 1 from adipic acid, hexamethylene diamine and urea and had elemental analyzes values of 56.12% carbon, 8.66 $> hydrogen and 20.34% nitrogen. The polyacetal mass obtained is tabletted by extrusion at a cylinder temperature of 185.degree. The tablets thus obtained are subjected to the heat resistance test.

- 43 -209815/1634

The results obtained are shown in Table 5. From these examples it can be seen that the inventive Heat stabilizers for both polyoxymethylene homopolymers as well as • polyoxymethylene copolymers are effective.

209815/1634

Tabel

at Production and properties of the polyoxymethylene
Copolymers Polyacetal composition Whiteness
Z game A mixture of trioxane and styrene was
treatment of Co ⁶⁰ at O ⁰ O in a dose of 1.2 χ 10 ^b <T
irradiated and then one at 50 ^° C. for 8 hours
Subjected to post-polymerization. A copoly-
get more. This was then treated with acetic acid
hydride acetylated. The copolymer had a styrene
content of about 3 $>, an intrinsic viscosity of 2.10 and
a value of K ₂₂ 2 ^of 0.06. Heat resistant
speed
R (fo), 90 min. 99 54 A mixture of trioxane and acrylamide was in one
Dosage of 1.2 χ 10 ° 2Γ with ^ "radiation from Co ° at
Irradiated 0 ⁰ C and then for 8 hours at 5O ⁰ C
post-polymerized. It became a copolymer with a
Intrinsic viscosity of 1.80 and a value of K ₂ 22 ^of 0.04
obtain. 99.00 99 55 Trioxane and dioxane were at 66 ^° C. for 4 hours
polymerized with the help of boron fluoride etherate. That so
Copolymers obtained were at 145 ⁰ C in benzyl alcohol
with a content of .10 % tributylamine dissolved to insta
to remove bile terminal units. The copolymer '
contained 2 </ <> ■ dioxolane and had an intrinsic viscosity
of 1.90 and a value of K ₂ 22 ^{From 0} » ⁰¹ * 99.10 99 56 One through copolymerization of formaldehyde and dioxolane
Copolyroeres obtained was stirred at 145 ⁰ C in benzyl alcohol
containing 10% tributylamine dissolved to insta
bile terminal units. to be removed. The copolymer
contained 1.1 mol -fo dioxolane and had an intrinsic viscosity
ity of 1.90 and a value K ₂ 02 ^{of 0} ^ * 99.00 99 57 99.18

Example 58

200 parts of dimethyl adipate, 200 parts of hydrazine hydrate (purity 90 $) and hexamethylenediamine and 600 parts of urea are placed in a stainless steel autoclave equipped with a stirrer and ^{reacted under the autogenous pressure for 180 minutes at 180 °} C. After the reaction, the autoclave is opened The autoclave is cooled to 70 ° C. and the temperature is gradually increased again while gaseous nitrogen is passed through the autoclave Heated to 210 ° C. in order to complete the reaction. This gives 580 parts of a colorless, transparent, nitrogen-containing polycondensate with a nitrogen analysis value of 25.36 % kg / cm can be shaped into a film with the aid of a test hot press.

Polyoxymethylene diacetate with an intrinsic viscosity of 1.80 and a value K ₂ 22 ~ ^of ° »° ^{4 we (3} · ^mi ' ^t ^» ° ^ of this nitrogen-containing polycondensate, 0.3 % 1,1,3-tris (2- methyl-4-formyloxy-5-tert-butylphenyl) butane and 0.1 fo 4,4 ^r -dihydroxydiphenyl-2,2-propane are mixed well. The polyacetal mass obtained is at 195 ° C under a pressure of 800 kg / A molded article with a good degree of whiteness and a glossy surface is obtained. The heat resistance R ($) of the molded article is 99.00 and the degree of whiteness Z is 99.

- 46 -

209815/1634

Examples 59 to 64

Different types of dicarboxylic acid dihydrazides, diainines and urea or urea derivatives shown in Table 6 are placed in individual hard glass ampoules and heated and melted at 180 G in a stream of nitrogen. The reaction is carried out at the same temperature, at 180.degree. C., wäh- ■ rend continued for 90 minutes. Then the ampoule is connected to a vacuum of 1 mm Hg and the further reaction during . Performed 180 minutes at the same temperature to avoid unreacted and to remove volatile products. A polycondensate containing nitrogen is achieved.

Polyoxymethylene diacetate with an intrinsic viscosity of 2.00 and a value of Kp ₂ ? ^v n ° is 0.05 with 0.8 $ of this nitrogen-containing polycondensate, 0.1 fo 4,4'-dihydroxydiphenyl-2,2-propane, and 0.3% 2,6-Di-tert-butyl-4 -methylphenol mixed well and the Polyacetalmasse obtained using a small test extruder having a cylinder inner diameter of 20 mm at a cylinder temperature of 195 ⁰ C, to tablet the mass. The tablets obtained in this way are subjected to the test for marine stabilization. The results are shown in Table 6.

-Al-

209815/1634

Tabel

at Components (Reactants) of Diamine urea
or urine
stoffde
rivat the end Softening Appearance Polyacetal composition White game added condensate (mol %) Hexamethy
lenediamine
. .20 ' urine
fabric 50 prey Point colorless,
transparent - Degree
Z Dicarboxylic acid
dihydrazide Ethylene
diamine 20 Biuret 55 (ro ( ⁰ C) colorless,
transparent 98.90 98 59 Terephthalic
acid dihydric
drazid 30 Isophorone
diamine 33 urine
fabric 34 58 180-190 colorless,
transparent 98.80 98 60 Caphthalene
dicarboxylic acid
dihydrazide 25 Polyethy-
lenimin,
MG 600 20 urine
fabric 40 48 190-200 slightly yellow,
halfway through
sighted 99.40 99 61 Decamethylene
dicarboxylic acid
dihydrazide 33 Hexamethy
lenediamine
15 · urine
fabric 40 50 120-140 colorless,
transparent 98.62 98 · 62 Octadecane-1,18-
dicarboxylic acid
dihydrazide 40 Hexameth
lenediamine
. 20th Ethylene
urine
fabric 25
Thio
urea
25th 62 70-90 slightly yellow,
halfway through
sighted 98.89 99 63 Eicosan-1.20-
dicarboxylic acid
dihydrazide 45 60 40-85 98.73 21262t
00
cn 64 Sebacic acid
dihydrazide 30 61 110-135

Claims (17)

Claims 1. Polyacetal composition containing a polyacetal, 0.001 to 3 percent by weight, based on the weight of the polyacetal, of a sterically hindered phenol as an antioxidant and 0.1 "to 10 percent by weight, based on the weight of the polacetal, a nitrogen-containing" compound, characterized by the content of 0.001 to 3 percent by weight, based on the weight of the polyacetal, a dihydroxydiphenyl or bisphenol Formulas HO OH in which R is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, R " in which R "and R ¹ denote hydrogen atoms or alkyl groups with 1 to 6 carbon atoms or can form a saturated homocyclic ring and R" represents a hydrogen atom or an alkyl group with 1 to 4 carbon atoms, preferably a hydrogen atom, - 49 - 209815/163 2. polyacetal composition according to claim 1, characterized g e indicates that it is a sterically hindered phenol of the formula as an antioxidant • * OH OH R.
R ¹ R ¹ R 'R ¹ in which R is a hydrogen atom or an alkyl group having 1 "to 3 carbon atoms and R ^{1 is} an alkyl group having 1 to 5 carbon atoms. 3. Polyacetal composition according to claim 1, characterized in that it is used as an antioxidant a hindered phenol of the formula CII-CH ₀ -CH-CH- [II] I ι I OH R ¹ R ¹ OH '. contains, in which R ' denotes an alkyl group having 1 to 5 carbon atoms. - 50 -209815/1634 4. polyacetal composition according to claim 1, characterized in that that as an antioxidant they are a sterically hindered phenol of the formula HO [III] 4 · contains, in which R is an alkyl group with 1 "to 5 carbon atoms and χ is an integer from 1 "to 6, preferably 2". 5. polyacetal composition according to claim 1, characterized in that that they are a sterically hindered phenol of the formula as an antioxidant < ^CH 3> 3 ^C
no-f } -CH ₂ - 3 [IV] I.
R ¹ /
R. R.
• fSr ^CH 2-C • R "
CHo
A. JCX
TC (CH,),
OH ■ ' C (CH ₃ )
VOH R ¹ 3 contains, in which R is a hydrogen atom or a methyl group and R ^{1 is} a hydrogen atom or an alkyl group - 51 ■ 209815/1634 with 1 Ms 4 carbon atoms "means. 6. polyacetal composition according to claim 1, characterized g e ken.η draws that as an antioxidant it is a sterically hindered phenol of the formula RHNH ₂ C CH ₂ NHR ^ho ~ v3 ~ ^r .'hK-oh RHNH ₂ C CH ₂ NHR [V] contains, in which R is a hydrogen atom, an alkyl group with 1 Ms 5 carbon atoms or an alkenyl group with 3 Ms 4 carbon atoms and R '. an alkylidene group with 1 Ms 8 carbon atoms "means. 7. polyacetal composition according to claim 1, characterized in that it is used as an antioxidant a hindered phenol of one of the formulas tVI] - 52 2098157163A [VIII] Contains, in which B. an alkyl group with 1 to 5 carbon atoms "means. 8. Polyaoetal composition according to claim 1, characterized in that denotes that they als'Antioxydations- w medium is a formate of a sterically hindered phenol of formulas I, II, III ,. V, VI or VII according to one of the Claims 2, 3, 4, 6 or 7 contains. 9. Polyacetal composition according to claim 1 to 8, characterized in that it is used as nitrogen-containing Compound a polyamide, a polyester amide, a polycondensate from a dicarboxylic acid dihydrazide or one capable of forming a dicarboxylic acid dihydrazide Substance, urea and an aliphatic diamine, a ureaeil, amidine, cyanoguanidine, polyurethane, polyurea, Contains polyamide urea, polyurethane amide or polyaminotriazole. 10. Polyacetal composition according to claim 1 to 9, characterized in that it contains ^{4,4 f -dihydroxydiphenyl as dihydroxydiphenyl.} . "- 53 - 209815/1634 11. Polyacetal composition according to claim 1 "to 9, characterized characterized as being bisphenol 4,4'-dihydroxydiphenylmethane contains. 12. Polyacetal composition according to claim 1 to 9, d a d u. R c h characterized in that they are 4,4'-dihydroxydiphenyl-1,1-ethane as bisphenol contains. 13. Polyacetal composition according to claim 1 to 9, characterized characterized as being bisphenol 4,4'-dihydroxydiphenyl-1,1-propane contains. 14. Polyacetal composition according to claim 1 to 9, characterized in that it is 4,4'-dihydroxydiphenyl-1,1-butane as the bisphenol contains. 15. Polyacetal composition according to claim 1 to 9, characterized in that it is 4,4'-dihydroxydiphenyl-1,1-heptane as the bisphenol contains. 16. Polyacetal composition according to claim 1 to 9, characterized in that it ^{contains 4,4 f} -dihydroxydiphenyl-2,2-propane as bisphenol. 17. Polyacetal composition according to claim 1 to 9, characterized in that it is 4,4'-dihydroxydiphenyl-2,2-butane as the bisphenol contains. 209815/1634