DE2035643A1 - Polyamides - Google Patents

Description

Polyamides

Priorities: 17 7 1969 and 7 ^ 0.1969 - Great Britain

The invention relates to synthetic polyamides and especially on synthetic fiber and film-forming polyamides which contain organic metal compounds

It has been found that the presence of certain organic metal compounds in the manufacture of synthetic polyamides and their presence in the final polymer has a wealth of beneficial effects. Thus, the rate of increase in the relative viscosity during the polymerization reaction is increased and the dyeability of the obtained polymer is improved.

The term "relative viscosity ^{11" means} the ratio of the viscosity of a solution of the polymer to the viscosity of the pure solvent.

009887/204?

Synthetic fiber and foaming polyamides on which The present invention can be used are both homo- and mixed polyamides, for example those derived from polyhexamethylene adipamide, polyhexamethylene superamide and polycaprolactam.

Organic compounds suitable for use according to the invention are, for example, those of the general Formula:

RO OR where M is a metal of IY. or T. group of

μ represents the periodic table and R is an alkyl

/ represents or aryl group; RO OR

R ¹ O 00OR wherein M represents a metal of group IV or V of the Periodic Table, R represents an alkyl group S and R ^{1 represents} an alkyl or axyl group R'O 00OR; and .

XIOO 000 where M is a metal of IV or V.

^ j. S \ represents group of the periodic tables

and R represents an alkyl or aryl group.

In particular, M can be titanium, zircon, hafnium, vanadium, niobium or tantalum.

Alternatively, polymeric derivatives of the above organic Connections are used, either separately or together with the monomer

Thus, according to the invention, a synthetic polyamide composition is proposed which contains 1 or more organic compounds of titanium, zirconium, hafnium, vanadium, niobium or tantalum .

009887/2047 V

■■■ - 3 -.

According to the invention there is also a method for increasing suggested the rate of increase in relative viscosity during a polyamidation reaction, which is carried out by one or more organic compounds of titanium, zircon, hafnium, vanadium, Niobium or tantalum adds.

Finally, according to the invention, a method for Improvement of the dyeability it proposed of synthetic polyamides, which is carried out that one before or one or more organic compounds of titanium, zircon, hafnium, vanadium, niobium or tantalum are added during the polyamidation reaction.

It can be up to 10 mol% organic metal compound or organic metal compounds can be added before or during the initial stages of polymerization, but it will preferably, 0.1 to 3 mol% of the metal compound or to add to the metal compounds

Preferably, the polyamide composition can be melt spun into continuous filaments, and preferably contains also an organic compound of titanium.

You organic metal compounds according to the invention used, result in the further advantage that different than conventional acidic polyamidation catalysts, which catalyze hydrolysis of the polyamide and thus the degradation of the polymer even under very mild hydrolytic conditions Conditions can promote these organic metal compounds are converted into inactive metal hydroxides, when the polyamide is briefly heated or the polymer is subjected to mild hydrolytic conditions. About that in addition, the usual acidic catalysts have the have an ionic character, often an undesirable one Coagulation effect on fine dispersions of pigments, matting agents and the like, which make up the polyamides can be added.

009887/2047

The organic metal compounds of the present invention are more compatible with these and other polymer additives.

The invention is illustrated by the following examples explained. Parts and percentages are expressed in weight.

example 1

The effect of tetraalkyl titanates on the rate of polymerization of hexamethylene adipamide.

After the titanate had been dried dry with hexamethylene diammonium adipate, the mixture was heated to 220 ° C. for 4 hours in a sealed tube in a nitrogen atmosphere. The polymerization rates were followed characterized in that the prepolymer was kept in a lab beaker at atmospheric pressure using steam at 290 ⁰ C.

The prepolymer was examined at different times, and its relative viscosity was determined. It has been found that alkyl titanates have a marked influence on the rate of amide polymerization, as can be seen from Table 1 can be seen.

Table 1

Time of treatment
with steam at 290 ^° C
(min) Relative viscosity Polyhexamethylene
adipamide + 1.4
Mol-56 Tetra-ieo-
propyl titanate 20th
30th
40
50
60 Polyhexamethylene
adipamid (comparison) 32
46
5 ^, 5
60
56 20th
34
42
46.5
50

009887/2047

Branched-chain alkyl titanates are more potent than their linear homologues. This is from Table 2 can be seen in which a comparison of the effect of tetra-n-butyl- and tetra-t-butyl titanate shown on the rate of polymerization of hexamethylene adipamide is. .

Table 2

Time of treatment
with steam at 290 ⁰ O
(min) . '■.'
Relative viscosity of the sample minus
relative viscosity of the comparison sample 1.4 mol% Tetra-t-
butyl titanate 30th
40
50
60 1.4 mol% tetra-n-
butyl titanate "17.2
19.1
15th
7th 15.5
12.5
8.3
5

Example 2

The effect of tetraalkyl titanates on speed the polymerization of hexamethylene suberamide.

Polyhexamethylensuberamid prepolymers containing 0.67, 0.92 or 1.2 mol · # tetra-methyl-titanate contained were treated in a laboratory beaker at 290 ⁰ C under atmospheric pressure with steam at 290 ⁰ C. A comparative polyamide sample with no additive was simultaneously treated under the same conditions in a similar beaker. The relative viscosity of the 4 polymers after treatment is given in the table below. It can be seen that the presence of the alkyl titanate has a significant effect on the rate of amide polymerization.

009887/2047

- 6 Table 3

polymer Relative viscosity
after treatment Polyhexamethylene suberamide
(Comparison, no addition)
Polyhexamethylene sub-eramide
+ 0.67 mol- # tetra-methyl-
titanate
Polyhexamethylene suberamide
+ 0.92 mol- # tetra-methyl-
titanate
Polyhexamethyleneuberamid
+ 1.2 mol% tetra-methyl-
titanate 33.5
5 ^, 2
56.2
58

Example 3

Alkyl titanates not only increase the speed of the Polymerization of Haxamethylenadlpamid, but they result also base-stabilized polymers (i.e. polymers that contain more amine end groups than carboxylic acid end groups) as can be seen from the following Table 4. As expected, these polymers stained deeply. Venn out Yarns made from these polymers were dyed with Solway Blue at pH8 in the usual manner, then dyed it is deeper than a comparison yarn without an additive. The depth of coloration increased with increasing additional concentration until a limit was reached.

009887/2047

Table 4

Fully polymerized
Polyhexamethylene adipamide;
Concentration of the methyl titanate
in mol% Carboxylic acid end groups mig
only amine end groups per 10 g]
polyamide 0.1 11 0.2 6.5 0.5 -12.6 0.7 -28 0.9 -43 1.0 -47 1.1 -68

Example 4 ^

The base stabilization of the polyhexamethylene adipamide Invention can be counteracted by adding the desired amount of adipic acid. If this happens then the rate of polymerization is further increased, as can be seen in Table 5.

Tabel 5

Time of treatment
with steam at 290 ° 0
(min) Belative viscosity of the sample minus
relative viscosity of the comparison sample Polymer with excellent
weighed end groups
with 0.7 mol- # Te-
tra-methyl-titanate 20th
30th
40
50 base-stabilized
Polymer with 0.7 col-%
Tetra-methyl-titanate 15th
10.3
7.4
6.1 0.5
. 1 »3
2.7
3.7

009887 / 20A7

Effect of the tetra-aryl-titanate on the speed of the Polymerization of hexamethylene adipamide «

Example 1 was repeated, with the difference that the tetra-isopropyl titanate was replaced by tetra-phenyl titanate became.·

As can be seen from Table 6, tetra-phenyl titanate also has a marked effect on the rate of polymerization _β

Table 6

Time of treatment Helative viscosity Polyhexamethylene
adipamide +1.8
Mol% tetra-phenyl
titanate with steam at 290 ^° C
(min) Polyhexamethylene
adipamid (Yergl.) 21st 20th V 45.5 30th 50.6 50.9 40 40.8 55.9 50 46.1

Example 6

Example 1 was repeated, with the difference that the tetra-isopropyl titanate was replaced by tetra-n-butyl zirconate. As in Example 1, the presence of the zirconate had a significant effect on the rate of polymerization as seen in Table 7 zn .

009887/2047

_ 9 - Table 7

Time of treatment
öiit steam at 290 ⁰ O
(min) Helative viscosity Polyhexamethylene-
adipamit +0.86
Mol- $ tetra-n-
butyl airconate 20th
30th
40
50
60 Polyhexamethylene
adipamid (comparison) 33.2
44.1
53
54.2
54.9 26.6
31
45.6
46.4
50.3

Example 7 .

Effect of polyalkyl titanates on the rate of polymerization of Heiiaraethylene adipamide.

Example 1 was repeated with the difference that the Tetra-isopropyl-titanate replaced by poly-n-butyl-titanate It can be seen from Table 8 that poly-n-butyl-titanate / has a noticeable effect on the rate of polymerization owns.

Table β

Time of treatment with steam
at 290 ° C (min)

Helative viscosity

Polyhexamethylene adipaaid (comparison)

Polyhexamethylene adipamide
4- 1.1 Mbl-56
Poly-n-butyl titanate

Polyhexaethylene adipamide +1.5 mole percent poly-n-butyl titanate

30th
40

50

30.8 40.8 43.3

33.3
41.6
45.9

36.5 42.0 44.0

Example 8

Effect of dialkoxydiacyl titanates on the polymerisation

0098-87 / 20.47

- ίο -

t! gas velocity of hexamethylene adipamido

The procedure of Example 2 was repeated with the. Difference, that 0.6 mol = ^ di-isopropoxy-titanium distearate was used.

A similar beneficial effect was observed as this shown below 1st. .

Sabell © 9

Polymer ■ Helative viscosity Polyhexametbyleneadipamide (¥ © pgleiek ₉
no addition)
Polyhexamethylene adipaiid + 0j6 hol »°%
Di-isopropoxy-titaa-disteara-fe . 47
69 _t 6

009887/2047

Claims (11)

- 11. Patent claims 1 e synthetic polyamide composition, characterized in that that they contain one or more organic compounds of metals of group IV or V of the periodic table contains. 2. Polyamide composition according to claim 1, characterized in that that the organic compound has the general formula, .OR where M is a metal of group IV or V of the ^ M * .-. Means periodic table and B means an alkyl "OE" or aryl group. 3 «polyamide composition according to claim 1, characterized in that the organic compound is the general formula E ¹ O OOGS, in which M is a metal of IV. Or V * χ- s * group of the periodic table means E a X _{1 is an} alkyl group and E 'is an alkyl or E ^f 0 OOGR means aryl group. 4 »Polyamide composition according to claim 1, characterized in that that the organic compound has the general formula ,, GDCl 00G _v , in which M is a metal of the iv E ^ x / ^ or V group of the periodic table ^ COCT 00C- ^ means and E is an alkyl or aryl * group means. 5. Polyamide composition according to one of the claims 2 to A, characterized in that the organic compound is polymeric. 009887/2047 6. Polyamide composition according to one of the preceding Claims, characterized in that they are "up to -10 mol% contains organic metal compound » 7 · Statute of limitations to increase the rate of increase the relative viscosity during a polyamidation reaction, characterized in that one or more organic Compounds of metals of group IV or V of the periodic table added " 8. Process for improving the dyeability of synthetic Polyamides, characterized in that before or during the polyamidation reaction, one or more organic compounds of metals of group IV or V of the periodic table are added. 9 · Process according to claim 7 or 8, characterized in that the organic compound has the general formula. RO ^ OR, where M is a metal of the IV. Or V. S group of the periodic table and R ^ means an alkyl or aryl group. R-- 10. The method according to claim 7 or 8, characterized in that the organic compound has the general formula R ¹ O OOCR, wherein M is a metal of group IV or V of the periodic table; R. is an alkyl group and R 'is an alkyl R ¹ O OOCR or aryl group. 11. The method according to claim 7 or 8, characterized in that that the organic compound has the general formula 009887/2047 , GOO 0OG, in which M is a metal of IV. jj ^^ M R or V. Group of the Periodic Table "S. ■ y < \ S * means and E is an alkyl or aryl COO OOCr group means. 12. Method according to one of claims 9 to 11, characterized characterized in that the organic compound is polymeric. 13 · The method according to any one of claims 7 to 12, characterized characterized in that up to 10 mol% organic metal compound are present. 009887/2047