BE839775A - COMPOSITIONS OF STABILIZED POLYMERS BASED ON POLYPROPYLENE AND TEXTILE FIBERS OBTAINED THEREOF - Google Patents

Description

       

  "Polypropylene-based stabilized polymer compositions

  
and textile fibers obtained therefrom. "The present invention relates to compositions of

  
polymers, based on polymers of alpha-olefins, stabilized against heat, light and aging, as well as stabilized fibers, films, raffia and manufactured articles obtained from these polymer compositions.

  
 <EMI ID = 1.1>

  
polypropylene suffer from some degradation during heat treatment, particularly in the presence of atmospheric oxygen. Furthermore, it is known that the manufactured articles obtained starting from these polyolefins are sensitive to the action of light, to aging and to heat treatments.

  
the degradation action to which the polyolefins are subjected is generally limited by the addition, to the polymer, of one or more protective substances, in particular during the transformation of the polymer into fibers, films

  
or other similar shaped bodies.

  
In general, for this purpose, small amounts of amines, phenolic compounds, aminophenols, thioazole compounds, phosphites and thiophosphites, thioesters, thioethers, transition metal chelates, organotin compounds, carbamates and thiocarbamates, are used, oximes, polyquinolines and the like, these substances being used either singly or in suitable combinations with each other.

  
The above mentioned compounds, in particular when

  
they are used in a suitable combination with another, allow to obtain a stability of the polymers of alpha-olefins which, in practice, is acceptable but which is not entirely satisfactory.

  
It has now been found that the polyamines having the general formula:

  

 <EMI ID = 2.1>


  
 <EMI ID = 3.1>

  
 <EMI ID = 4.1>

  
hydrogen or an alkyl having 1 to 4 carbon atoms;

  
 <EMI ID = 5.1>

  
divalent aliphatic, cycloaliphatic, aromatic or alkyl-aromatic radical, containing, if so, atoms

  
 <EMI ID = 6.1>

  
side substituents and 'n' is an integer between 2 and 1000, exert a stabilizing action on polymers, in particular on alpha-olefin polymers, both as such and in the form of fibers, films

  
or other shaped articles the action of which is considerably greater than that of other compounds or mixtures of compounds heretofore suggested for this purpose.

  
Among the polyamines having the general formula (I)

  
in practice those having inherent viscosity are preferred

  
 <EMI ID = 7.1>

  
in chloroform at 25 [deg.] C according to the method indicated in the examples).

  
These polyamines which are incorporated into the polymer before or during its extrusion into shaped articles, in amounts equal to or less than 5% by weight, serve as a stabilizer against light, heat and aging not only relative to <EMI ID = 8.1 >

  
having improved dyeing characteristics. These polyamines are also suitable for stabilizing compositions essentially based on colored polyolefins by the addition of organic or inorganic pigments.

  
A subject of the present invention is therefore stabilized polymer compositions based on a polyolefin containing, as stabilizer, a polyamine having the general formula
(I) above indicated.

  
The amount of polyamine to be added to the polyolefin is not critical, although in practice it is preferred that this amount be kept at lower values.

  
 <EMI ID = 9.1>

  
quantities of polyamines, that is to say of the order of 0.1%,

  
are quite effective in stabilizing polyolefins.

  
As the polyolefin, a polypropylene is preferably used.

  
 <EMI ID = 10.1>

  
obtained by stereospecific polymerization of propylene.

  
However, polyolefins derived from monomers having the formula:

  

 <EMI ID = 11.1>


  
where R is an -alkyl or aryl group, or. a hydrogen atom, such as polyethylene, polybutene-1, polypentene-1,

  
 <EMI ID = 12.1>

  
also suitable for application according to the present invention.

  
Among the polyamines having general formula (I), we

  
 <EMI ID = 13.1>

  
 <EMI ID = 14.1>

  
selected from the group consisting of:

  

 <EMI ID = 15.1>


  
or. R6 is an alkyl containing 1 to 18 carbon atoms.

  
Some examples of polyamines having the general formula CI) and which can be used successfully

  
for the stabilization of polyolefins according to the present invention are those having the repeating unit:

  

 <EMI ID = 16.1>
 

  

 <EMI ID = 17.1>


  
where 'p' is an integer between 2 and 10 and

  
R6 has the value shown above.

  
The polyamines having the general formula (I) indicated above are generally obtained by polycondensation

  
 <EMI ID = 18.1>

  

 <EMI ID = 19.1>
 

  
with a bifunctional compound containing halogens and / or epoxy groups, suitable for the formation of a radical

  
 <EMI ID = 20.1>

  
and others.

  
Polycondensation is carried out by reacting

  
the bifunctional amine compound with the bifunctional dihalogenated or diepoxide or halogen-epoxide compound, according to conventional operating procedures, for example in the presence of a

  
 <EMI ID = 21.1>

  
obtained at a temperature above room temperature, and in the presence of alcohols as solvents for the reaction. It is better to use molar ratios between the two

  
 <EMI ID = 22.1>

  
 <EMI ID = 23.1>

  
1: 2. The polycondensed amino products according to the present invention have a resinous nature, and soluble in methanol.

  
As regards the compound (II), it is obtained by

  
 <EMI ID = 24.1>

  
tion as platinum according to the following reaction:

  

 <EMI ID = 25.1>
 

  
The polyamine having the general formula (I) can be used alone as well as in admixture with other known stabilizers such as oxy-benzotriazols, oxy-benzo-phenones, stabilizers containing nickel, metal soaps, anti-oxidant phenols, phosphites, thioesters and others.

  
By way of example, mention may be made of polyolefin compositions stabilized with a stabilizing mixture.

  
a) a polyolefin; . <EMI ID = 26.1> above, in amounts between 0.1% and 5%; c) a phosphite having the general formula:

  

 <EMI ID = 27.1>


  
 <EMI ID = 28.1>

  
possibly substituted with different functional groups,

  
 <EMI ID = 29.1> d) an antioxidant phenol having the general formula:

  

 <EMI ID = 30.1>


  
 <EMI ID = 31.1>

  
which may contain heterogeneous atoms; and e) a soap of a metal chosen from stearates of

  
 <EMI ID = 32.1>

  
the mixing of the polyamine (1) or of the mixture containing the polyamine, with the polyolefin, is generally carried out

  
by simply mixing the powder additives with the polyolefin with stirring.

  
However, it is possible to carry out the addition also with other methods, for example by mixing the polyolefins with a solution of stabilizers in a suitable solvent, followed by evaporation of the solvent, or by

  
 <EMI ID = 33.1>

  
polymerization.

  
On the other hand, it is possible to obtain the stabilizing action by applying the stabilizing compound or the stabilizing mixture, to the article of manufacture, for example.

  
by immersing this article in a solution or dispersion of stabilizers and then evaporating the solvent.

  
The stabilizers according to the present invention exhibit good compatibility with the polyolefin in the molten state, and have no messy action.

  
The blends are pelletized and then extruded on melt spinning equipment, preferably with dies having a length / diameter ratio greater than 1.

  
Granulation and spinning are carried out in the absence of oxygen, preferably in an atmosphere of inert gases.
(nitrogen).

  
In the course of the mixing, the polyolefins can be added, in addition to the stabilizers which are the subject of the present invention, also tarnishing agents and organic or inorganic coloring pigments.

  
The filaments obtained by extrusion are subjected to drawing with a drawing ratio of between 2 and 10, a

  
a temperature between 80 and 150 [deg.] C, on drawing devices heated with hot air or steam, or with a similar fluid, or provided with a heating plate.

  
The stretched filaments are then subjected to a dimensional stabilization treatment, with free shrinkage or <EMI ID = 34.1>

  
The filaments obtained by extrusion from the mixture forming the subject of the present invention can be either monofilaments or multifilaments, and they are used for the preparation of continuous yarns or fibers.

  
or for the preparation of textured or puffed yarns.

  
In addition to the preparation of yarns, the compositions according to the present invention can be used for the preparation of films, raffia, ribbons, shaped articles and the like.

  
Many variations or modifications can be introduced into the present invention without departing from the scope of the present invention.

  
Certain examples illustrating, without however limiting the present invention, are given below.

  
EXAMPLE n [deg.] 1

  
 <EMI ID = 35.1>

  
ethvlenediamine.

  
162, 75g (1.05 mole) of 2, 2, 6,6-tetramethyl-4-piperidone dissolved in 200cm3 of methanol, 30g (0.5 mole) of ethylenedia-

  
 <EMI ID = 36.1>

  
removal of catalysts and solvent, the residue was distilled off, it was obtained. thus 155.5g (92%) of product, having a point of -

  
 <EMI ID = 37.1>

  
81 [deg.] C; an N content found by experiment of 16.51% (calculated for C20H42 N4 = 16.56%).

  
Polyamine preparation

  
 <EMI ID = 38.1>

  
9.25 g (0.1 mole) of epichlorohydrin were mixed and this mixture was heated under reflux for 10 hours, adding during the last 8 hours of heating, in small regular portions, 4 g (0.1 mole ) sodium hydrate in tablet form.

  
At the end of the addition of NaOH, the mixture was heated under reflux for a further 2 hours, then it was filtered to separate the sodium chloride formed in the reaction.

  
The filtrate was dried by removing methanol, first.

  
at atmospheric pressure at 70 [deg.] - 100 [deg.] C then heating

  
 <EMI ID = 39.1>

  
39g of a fragile and resinous product was thus obtained having a pale yellow color and an inherent viscosity of

  
 <EMI ID = 40.1>

  
Bischoff.

  
The operational process was as follows:

  
 <EMI ID = 41.1>

  
under constant stirring for 30 minutes. The solution thus obtained was introduced into the viscometer and the time

  
 <EMI ID = 42.1>

  
measures.

  
 <EMI ID = 43.1>

  
be calculated by the equation:

  

 <EMI ID = 44.1>


  
where c is the concentration expressed in g for <1> 00 cm of the solvent.

  
Stabilization tests <EMI ID = 45.1>

  
25g of the above polyamine were dissolved in

  
 <EMI ID = 46.1>

  
with: - 5 kg of polypropylene having an intrinsic viscosity <EMI ID = 47.1>

  
 <EMI ID = 48.1>
- 5g of calcium stearate.

  
This mixture was made into granules in an extruder.

  
 <EMI ID = 49.1>

  
spun under the following conditions:

  
Screw temperature: 250 [deg.] C Head temperature

  
extrusion 230 [deg.] C Die temperature 230 [deg.] C Maximum pressure 35 kg / cm.

  
 <EMI ID = 50.1>

  
and a length of 4mm.

  
The filaments coming out of the die were gathered

  
at a speed of 500 m / min and were drawn at 130 [deg.] C in a steam atmosphere, with a draw ratio of 3.3.

  
The filaments thus obtained showed the following characteristics:

  
Title 17 dtex

  
Tenacity 2.8 g / dtex. Elongation at break 85%

  
Tenacity after
1,400 hours of exposure to a

  
weathering

  
(or Weatherometer) 1.8g / dtex

  
(Having a Xenon arc lamp

  
of 6000 W, relative humidity

  
 <EMI ID = 51.1>

  
By way of comparison, it should be remembered that with the now known stabilizers, the toughness is reduced by half after approximately 500 hours of disposal. - Test n02
25g of the above-indicated polyamine were dissolved in 100 cc of methanol. the solution thus obtained

  
was mixed with:
- 5 kg of polypropylene having an intrinsic viscosity of 1.65 dl / g, a residue during extraction in heptane of 96.5% and 80 ppm of ash; <EMI ID = 52.1>
- 5 g of calcium stearate.

  
The mixture melted in a test tube at: 250 [deg.] 0 for
10 minutes had a light color.

  
The mixture was made into granules in an extruder, in an oxygen free atmosphere, at 180 [deg.] C, then was spun.

  
 <EMI ID = 53.1>

  
The filaments thus obtained showed the following characteristics:

  
Title: 17 dtex

  
Tenacity: 2.5 g / dtex Elongation at break: 90%

  
Tenacity above
1,400 hours of exposure <EMI ID = 54.1>

  
weatherproof: 2, Og / dtex

  
EXAMPLE n [deg.] 2

  
 <EMI ID = 55.1>

  
hexamethylenediamine.

  
162.75 g (1.05 mol) of 2, 2,6,6-tetramethyl-4-piperidone

  
 <EMI ID = 56.1>

  
 <EMI ID = 57.1> on carbon were introduced into a one liter autoclave,

  
 <EMI ID = 58.1>

  
during 2 hours.

  
After removal of the catalyst and the solvent, the residue was distilled off, thus obtaining 177g (90%) of a product having

  
 <EMI ID = 59.1>

  
Preparation of polyamine.

  
By operating according to Example 1, to a solution of 39.4 g
(0.1 mol) of N, N'-bis- (2,2,6,6-tetramethyl-4-piperidyl) hexamethylenediamine in 50 cm of methanol, mixed

  
 <EMI ID = 60.1>

  
 <EMI ID = 61.1>

  
brittle, having an inherent viscosity of 0.18 dl / g and a nitrogen content of 12.01%.

  
Stabilization Tests <EMI ID = 62.1>

  
in the same quantities as indicated in test n [deg.] 2. The mixture was made into granules and extruded into the same

  
 <EMI ID = 63.1>

  
The filaments obtained after steam drawing at 13000 with a draw ratio of 3, 3, had the following characteristics:

  
Title: 17 dtex

  
Toughness 2.4 g / dtex Elongation at break 94%

  
Residual toughness

  
after 1,400 hours

  
exposure to the device

  
weathering: 1.8 g / dtex -Test_ [pound] ^ 4_
25g of the above mentioned polyamine were dissolved

  
 <EMI ID = 64.1>

  
with
- 5 kg of polypropylene having an intrinsic viscosity <EMI ID = 65.1>

  
and an ash content equal to 80 ppm;
- 5 g of calcium stearate.

  
This mixture was made into granules and extruded into

  
the same conditions as test n [deg.] 1.

  
The filaments leaving the spinneret were collected at a speed of 500 m / min, then were stretched in an atmosphere

  
 <EMI ID = 66.1>

  
The filaments thus obtained exhibited the following characteristics:

  
Title 17 dtex

  
Toughness 2.6 g / dtex

  
 <EMI ID = 67.1>

  
Tenacity after 1.400

  
hours of exposure to

  
aging device

  
weatherproof 1.7 g / dtex

  
 <EMI ID = 68.1>

  
Polyamine preparation

  
The conditions of example <1> were repeated but in

  
 <EMI ID = 69.1>

  
of tablets.

  
121 g of a pale yellow, solid and flexible product were obtained having an inherent viscosity of 0.15 dl / g and a nitrogen content of 10.45%.

  
Stabilization tests

  
With the polyamine indicated above, was prepared.

  
 <EMI ID = 70.1>

  
transformed into granules and spun, the filaments thus obtained were drawn by operating under the same conditions as what is specified in test 1.

  
The filaments exhibited the following characteristics:

  
Title 17dtex

  
Tenacity 2.4 g / dtex

  
 <EMI ID = 71.1>

  
Residual toughness at the end

  
1,400 hours of exposure

  
to a weathering apparatus 1; 5g / dtex

  
EXAMPLE N [deg.] 4

  
Polyamine preparation

  
 <EMI ID = 72.1> were heated under reflux for 8 hours.

  
The solvent was then removed by heating first at atmospheric pressure to 100 [deg.] C then at 120 [deg.] C for two hours at 1 mmHg. 67 g of a fragile and resinous light yellow product were obtained, having an inherent viscosity

  
 <EMI ID = 73.1>

  
Stabilization tests

  
The above polyamine was mixed with the same compounds, in the same amounts as for test 2.

  
The mixture was then transformed into granules and extruded,

  
i the filaments thus obtained were drawn under the same conditions as what was indicated in test 1.

  
The filaments exhibited the characteristics

  
 <EMI ID = 74.1>

  
Title 17 dtex Tenacity: 2. 6 g / dtex

  
 <EMI ID = 75.1>. Exposure time to weathering device to reduce

  
half the initial toughness 1.200 Hours

  
 <EMI ID = 76.1>

  
for 20 hours, adding during the last 16 hours of heating, in small regular portions, 16 g (0.4 mol) of NaOH tablets.

  
 <EMI ID = 77.1>

  
under reflux for a further 4 hours, and the reaction mixture was then diluted with 150 cm 3 of benzene, and then filtered to separate the obtained sodium bromide.

  
The filtrate was brought to dryness by heating it first to 100 [deg.] C at atmospheric pressure, and subsequently under vacuum (for 2 hours at 120 [deg.] C at 1 mmHg.).

  
81 g of a brittle, resinous pale yellow solid was obtained having an inherent viscosity of 0.12 dl / g and a nitrogen content of 12.95%.

  
Stabilization tests

  
The above polyamine was mixed, in the same amounts and with the same substances as indicated

  
 <EMI ID = 78.1> granulated product which was then extruded under exactly the same conditions as in test 1 ..

  
The filaments, drawn in an atmosphere of steam to
130 [deg.] C with a draw ratio of 3, 3, exhibited the following characteristics:

  
Title 17 dtex

  
Tenacity 2.5 g / dtex

  
 <EMI ID = 79.1>

  
Residual toughness at the end

  
from 1,400 hours of exposure to the weathering device: 1.7 g / dtex

COMPARISON EXAMPLE N [deg.] 6

  
 <EMI ID = 80.1>

  
The filaments obtained, drawn with steam at 130 [deg.] C,

  
with a draw ratio of 3, 3, exhibited the following characteristics:

  
Title 17 dtex

  
Tenacity 2.4 g / dtex

  
 <EMI ID = 81.1>

  
Exposure time to

  
the aging device

  
weatherproofing necessary. to decrease by

  
half the initial tenacity: 150 hours

  
Of course, the invention is in no way limited to the embodiments described and shown which have been given only by way of example. In particular, it comprises all the means constituting technical equivalents of the means described, as well as their combinations, if these are carried out according to its spirit and implemented within the scope of the following claims. ,

CLAIMS

  
 <EMI ID = 82.1>

  
1. Polymer compositions stabilized based on polyolefins, characterized in that they contain, as stabilizer, a polyamine having the general formula:

  

 <EMI ID = 83.1>


  
 <EMI ID = 84.1> carbon, <EMI ID = 85.1> tick or alkylaromatic, which may contain heterogeneous atoms like O, S, N and P either in the chain or as side substituents, and
- n is an integer between 2 and 1000.


    

Claims (1)

2. Compositions according to claim 1, characterized in that the polyamine of general formula (I) above has an inherent viscosity of between 0.01 and 1 dl / g. 3. Compositions according to any one of claims <EMI ID = 86.1> <EMI ID = 87.1> 4. Compositions according to any one of the preceding claims characterized in that the amount of the polyamine of general formula (I) above is either equal <EMI ID = 88.1> 5. Compositions according to claim ^, characterized in that the amount of the aforementioned polyamine is included <EMI ID = 89.1> 6. Compositions according to any one of the preceding claims, characterized in that the polyamines of general formula (I) are used as a mixture with other stabilizers such as oxy-benzo-triazols, oxy-benzo-phenones, stabilizers containing , With nickel, and metal soaps, and with anti-oxidants such as phenol, phosphite and thioesters. 7. Compositions according to any one of the preceding claims, characterized in that they are given the form of fibers, filaments, films and other shaped articles. <EMI ID = 90.1> rised in that their general formula: <EMI ID = 91.1> <EMI ID = 92.1> are an alkyl having 1 to 4 carbon atoms, - It is hydrogen or an alkyl containing from 1 to 4 carbon atoms, <EMI ID = 93.1> or aromatic or alkyl-aromatic, which may contain heterogeneous atoms such as O, N, S or P, either in the chain or in the form of side substituents, and n is an integer between 2 and 1000. 9. Poly (2,2,6,6-tetra-alkyl-4-piperidyl) amines according to <EMI ID = 94.1> <EMI ID = 95.1> 10. Bifunctional amines characterized in that they have the general formula: <EMI ID = 96.1> <EMI ID = 97.1> <EMI ID = 98.1> <EMI ID = 99.1> <EMI ID = 100.1> <EMI ID = 101.1> according to claim 10, .characterized in that it consists <EMI ID = 102.1> in position 2,2,6,6: <EMI ID = 103.1> <EMI ID = 104.1> pressure, in the presence of a hydrogenation catalyst. 12. Process for the preparation of poly (2,2,6,6 -tetra-alkyl-4piperidyl) amines according to any one of claims 8 or 9, characterized in that it consists in condensing the aforementioned bifunctional amines according to claim. 10 <EMI ID = 105.1> epoxy groups, which can form a bivalent radical B.