DE1494662A1 - Stabilizer mixture for spinnable polymers - Google Patents

Description

DR.-ING. BY KREISLER DR.-ING. BEAUTIFUL FOREST DR.-ING. TH. MEYER DR. FUES DIPL.-CHEM. ALEK VON KREISLER DIPL.-CHEM. CAROLA KELLER DR.-ING. KLDPSCH COLOGNE 1, DEICHMANNHAUS

Cologne, August 15, 1969 " KX / En

Montecatlnl Edison S.p.A.,

1-2 Largo Guido Doneganl, Malland (Italy) |

The invention relates to the manufacture of textile fibers and films, tapes, moldings and the like, in particular based on crystalline polyolefins, which by low pressure polymerization with the help of stereospecific catalysts and which are against the action of Heat and light as well as against aging are largely stabilized. In particular, the invention relates to manufacture of textile fibers stabilized in this way by spinning crystalline polyolefins together with stabilizing ones Mixtures of aliphatic thioesters, polyhydric phenols, nickel phenolates of alkylphenol monosulfides, Oxybenzotriazoles and metallic soaps.

The crystalline polyolefin used is preferably crystalline isotactic polypropylene, which is produced by stereospecific Polymerization of propylene was obtained. However, crystalline polyolefins of the general Formula R-CH = CHp, in which R is an alkyl or aryl radical or water

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hydrogen means, such as polyethylene, polybutene-1, polypentene-1, Polyhexene-1, poly-4-methylpentene-1, polyoctene-1, polystyrene and the like., are stabilized by the inventive method.

It is known that products based on polyolefins are degraded to a certain extent when processed in the heat, in particular in the presence of atmospheric oxygen. It is also known that manufactured goods based on crystalline Polyolefins are sensitive to light and heat are. This degrading effect can be achieved by adding special protective substances to the polymer, in particular during the manufacture of leads, films and the like will.

In general, small amounts of amines, phenolic compounds, aminophenols, triazole compounds, Phosphites, thiophosphites, thioesters and thioethers, chelates of transition metals, organotin compounds, oarbamates and thiocarbamates, oximes, polyquinolines and the like.

It has also already been proposed to stabilize polyolefins in particular against the action of light, with for for this purpose mixtures of an aliphatic thioester, a polyhydric phenol and an oxybenzotriazole compound, optionally in the presence of metal solvents.

In the patent (patent application P 12 95 184.7) is also a stabilization of polyolefins with a stabilizer mixture of an aliphatic thioester, a more- ^; valuable phenol, a alkyl phenolate of a bis-p-alkylphenol monosulfide, optionally with the addition of a metal soap,

J5 ° wrote.

9098.82 / 1653

BATH ORIGINAL

149466?

The invention now relates to a stabilizer mixture consisting of

a) aliphatic thioesters,

b) polyhydric phenols, which may contain sulfur,

c) Nickel phenolates of bis-p-alkylphenol monosulfides and

d) oxybenzotriazole compounds,

which shows a very high stabilizing effect when blended with crystalline olefin polymers in proportions of 5% or less. Such compositions can be spun into fibers or the like based on polyolefins with particular stability against the effects of heat and light as well as against aging.

The addition of a metallic soap, which acts as an acid scavenger, to the compositions prior to spinning them is improved the stability properties of the polymer blends.

Calcium stearate is particularly suitable as the metal soap; However, there are also zinc stearate, aluminum stearate, calcium laurate, Zinc laurate and aluminum laurate effective.

The stabilizing mixtures according to the invention are also used to stabilize compositions based on crystalline polyolefins and basic nitrogen polycondensates, which result in fibers with improved dyeability, effective.

They are also suitable for stabilizing compositions essentially based on crystalline polyolefins, which are obtained by adding organic or inorganic Color pigments for the polymer stabilizer mixture were colored before spinning or pressing.

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Contain polymer compositions stabilized against the effects of heat and light as well as against aging

a) a crystalline polyolefin, in particular polypropylene consisting essentially of isotactic macromolecules and

b) in proportions between 0.02 and 5 wt .- # of the composition, the stabilizer mixture according to the invention.

The stabilizer mixture can, together with pigments, colored substances and fillers are used -

As aliphatic thioesters, which are particularly suitable as components of a mixture, called selenium:

a) thioesters of thiodiethylene glycol, such as didodecoyl thiodiglycolate, octadecoyl thiodiglycolate and the like,

b) the thioesters of ß, ß'-thiodipropionic acid, such as lauryl thiodipropionate.

Particularly suitable polyhydric phenols are, for example, 4,4'-thiobie-6-tert.butylB> ethacreeol, polyphenols obtained by condensation of aldehydes and ketones with alkylphenols , ortho- hindered and para-substituted phenols, trishydroxyarylpropanes etc. '

The reaction products of alkylphenols with aldehydes (e.g. formaldehyde, acetaldehyde, etc.) or ketones (e.g. acetone) have the following general formula

ho - f \ S - c - r V - oh

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or

OH

where R is hydrogen or an alkyl radical (and at least one radical R in each ring is an alkyl radical) and R and R is hydrogen or an alkyl radical. Such compounds are in the Italian patents 6o6.8o4, 615 · Ml «536.250 and 623.440 and in British patent specification 571.943.

The compounds of Trls (hydroxyaryl) propane are in the Italian patent 632.726.

Among the particularly suitable nickel phenolates of the alkylphenol monosulphides, the following may be mentioned: alkylphenolates of bis-2-tert-butylphenol monosulphide, of QjO'-bisip-octylphenol) monosulphide and of OjO'-bisCp-araylphenol monosulphide.

As oxybenzotriazoles which can be used according to the invention, 2 ^l -oxy-3 ^l -tert.butyl-5 ^l -methylphenyl-5-chlorobenzotriazole and S ^ oxy-S'-tert.butylphenyl-S benzotriazole have proven to be particularly suitable proven.

The stabilizer mixture preferably contains 20 to 80 Nickel phenate and oxybenzotriazole.

This inventive stabilizing mixture is generally added to the polymers by simply mixing the stabilizer solution together in the form of

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Powders with the polyolefins in motion. The stabilizers however, they can be added by other methods, such as by mixing the polyolefins with a solution the stabilizers in a suitable solvent and subsequent evaporation of the solvent or by addition of the stabilizers to the polyolefins at the end of the polymerization.

Furthermore, you can achieve the stabilizing effect, by applying the stabilizing compounds to the objects, e.g. by immersing the latter in a Stabilizer solution or dispersion and subsequent evaporation of the solvent.

The stabilizers according to the invention are well tolerated with polyolefins in the melt state and effect no staining.

The stabilizer and polymer compositions are granulated and then in a melt spinning device, preferably as described in the applicant's Italian patent 614.043 1st, and preferably using spinnerets such as those in the Italian patent 600,248 of the applicant are described, which is a ratio from length to diameter over 1, pressed.

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

Optical fillers and organic fillers can also be used during the mixing of the polyolefins with the stabilizers according to the invention or inorganic color pigments are added.

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After spinning, the yarns are subjected to a drawing treatment with drawing ratios between 1: 2 and 1:10 at temperatures between 80 and 150 ^° C. in drawing devices which are operated with hot air, steam or the like. or heated by means of a heating plate.

The fibers can then be subjected to a dimensional stabilization treatment under free or restricted shrinkage conditions at 80 to 160 ° C., as described in the applicant's Italian patents 566,914 and 588,318. i

Compositions stabilized according to the invention are particularly suitable for the production of mono- and plurifils, continuous ones or staple fibers, bulky yarns and films, tapes, Pormkodies and the like.

The invention is illustrated in the following examples.

The polypropylene used in the examples has the following properties:

Viscosity limit / Ji ^ J 1.60
Ash content 0.029 %

Backlog after the
Heptane extraction

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Tabel

Eciopicl 0.5 2 3 Polypropylene Didodccoyl thiodiglycolate 0.5. Lauryl thiodipropionate 4.4 ^c -Thiobic-6_tcrt, butyl- mo thacrosol 0 ₅ 2 2'-oxy-5'ert "butylphenol- 5-chlorobensotriczole 2 ' -Oxy-3 ¹ -tcrt.butyl-5-nc- - ethylphenyl-5-chlorobenzotriazole 0.3 tfickolphenolat from Bic-p-tcrt ₀ 0.25 butylphenol monodulphide Henschel CaIc iuinst carat mixer 0.3 0.3 TiO ₂ 0.25 0.25 Making the 'mixture 250 Honschcl- Hensehe1- 250 miochcr mixer Spunbondings: 250 Screw temperature ° (a) 250 250 Head temperature 78 250 ^£ 2; o Sinus nozzle temperature 250 250 ' Spinneret type • 390 (a) (a) Maximum pressure (kg / cm) 130 67 73 Huiv / ickol ^ eschv / indigkeit steam (n / a IJinutc) 1: 5 390 390 SJtjcGjc ^ sQ ^ c ^ indungen:
Temperature °. 130 120 Toilet dium steam steam Stretch ratio 1: 5 1 ': 5

(a) = 60 / 0.8 · "16

(b) »40 / 0.8 _o 16

909 ·· 2/1 · §3

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4th I.
■ 0.5 5 6th 7th 8th 0.5 0.5 Honschol
mischor 0.5 0.5 250
250
250
(b)
65 0.5 390 Honochcl-
afterwards 0.5
0.3
0.25
Hiccup
nicchcr 0.3
0.25
Honschcl-
mixer Bony
mixer 120
steam
1: 5 250
250
250
(b)
40 250
250
250
(a)
73 250
250
250
(b)
60 250
250
250
(b)
60 390 390 350 350 130
steam
1: 5 130
steam
1: 5 130
steam
1: 5 130
steam
1: 5

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BAD OiMGiNAL

M)

9 10 11 12th 13th !
0.5 0.5 0.5 O ₇ 5 0.5 0.2 0.2 0.2 0.2 0.2 0.5 0.5 0.5 0.3
0.25
Henochol *
mixer 0; 3
0.25
Honcchol
mixer 0.3
0.25
Honschol
mixer 0.3
0.25
Honchcl-
miGchcr 0.3
0.25
Honochol
nicchcr 250
250
250
(a)
63 250
250
250
(a)
68 250
250
S 250
(a)
71 250
250
250
(a)
70 250
250
250
(a)
67 390 390 I 390 390 390 130
steam
1: '5 130
steam
1: 5 ! 130
ί steam
1: 5 130
steam
1: 5 130
Danpf
1: 5

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BAD OWGINAL

"Ι 15th • 0.5 16 0.5 0.5 0.5 0.5 0.3 0.2 0.2 0.25 0.2 Hanky- 0.5 0.5 inicchcr 0.5 250 0 _: 5 0.3 250 0.3 0.25 250 0.25 Bony (a), Hcncchol- nicchor 67 Diocher 250 390 250 250 130 250 250 steam 250 (a) 1: 5 (a) 75 71 390 390 130 130 steam steam 1: 5 1: 5

BAD OFMGiNAL

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Continuation of the table Bcicpicl 1 2 3 Ri / icnrschnftcn dor jjeotrodeten Paperη: 5r5 5.7 5.6 ougfcotigkcit (g / dcn) 25th 23 21 Strain (?") rhcminchor removal: 88 85 64 Percent rust limit viscosity / JbJ
according to AucprcDccn Stability ^ accelerated overhead
ter tlicrnir; chcr aging: brittle brittle Γ
brittle Percent withdrawal after
200 hours at 120 in one
! refrigerator with air circulation Stability f: ef: enover 'sunlight: Percent retraction efficiency after 300
Hours of exposure
ootsung nit SoKncroonr-cnlicJit bifj An
icruiiß deo 7th color in the StLT; -
lard blue-ükala,

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4- 5 5 6th VJ, 7th 8th 5 ₉ 5 5.45 24 , 5 5.25 5.15 22nd , 5 25th 29 28.5 71 , 5 • ν 80 74 brittle 72 68 t chi « brittle 86 brittle brittle 67 ► ■■ · 65 62 56

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OHOlNM.

9 15th J ₅ O 10 18th 54 11 84 62 5.5 5.5 5: 2 25th 23 27 7β 76 76

1 2 1 3 -5, 2 • 5, 0 27 22nd 70 72 ♦ 1 82 69 60

90 9 882/1653 _owew al INSPECTED

HS4662

H 15th 16 - 5.3
21
80
85
89 5.2
20th
79
88
93 5.5
25th
83
78
82

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Claims (1)

Godfather η tans ρ back 1) Consisting of a stabilizer mixture for spinnable polymers the end a) aliphatic thioesters, b) polyhydric phenols, which optionally contain sulfur contain, c) alkylphenolates of alkylphenol monosulfides, d) Oxybenzotriazoles and e) Netallself, preferably calcium stearate. 2) Stabilizer mixture according to claim 1, characterized in that it is used for the production of "stabilized against the effects of heat and light and against aging" by extrusion of the melt and subsequent stretching as well as stabilized tapes, films, moldings and the like based on krlstallinen polyolefins, in particular substantially from existing leotaktischen macromolecules polypropylene, with crystalline polyolefins in amounts of 0.02 to 5 wt -% · is used. 3) Stabilizer mixture according to claims 1 and 2, characterized in that it contains 20 to 80 % nickel phenolate or oxybenzotriazole. In that it comprises 4) a stabilizer mixture according to claims 1 to 3, characterized in that the thioester as thioesters of thiodiethylene glycol or thioester of ß, ß-thiodipropionic acid ^f. 909882/1653 fM.7 §IAiJU l * U94662 4 * 5) Stabilizer solution according to claims 1 to 4, characterized in » that they are 4,4'-thiobis-6-tert.butylmethaoresol as polyhydric phenols or polyphenols, obtained by condensation of aldehydes and ketones with alkylphenols, Contains ortho-hindered and para-substituted phenols or tris-hydroxyarylpropanes. 6) Stabilizer mixture according to claims 1 to 5 * characterized in that « that it contains the nickel phenolate of bis-p-tert-butylphenol monosulfide as the nickel phenolate. 7) stabilizer mixture according to claims 1 to 6, characterized in that it as oxybenzotriazole 2 ^l -0xy-3 ^l -tert-butyl-S'-methylphenyl-S-chlorobenzotriazole or 2 ^f -0xy-5 ^f tert-butylphenyl-5 - contains chlorobenzotriazole. 8) stabilizer mixture according to claims 1 to 7, characterized in that that they with optical fillers and organic or inorganic color pigments to the polyolefin is added. 9) The use of stabilizer mixtures according to claims 1 to 8, characterized in that it is spun with the polyolefins duroh spinnerets that have a ratio from length to diameter over 1. 10) Method according to claim 9 » characterized in that spinning is carried out in the absence of oxygen. 11) Process according to claims 9 and 10, characterized in that the fibers and films after spinning and optionally after previous heat treatment in ratios between about 1: 2 and 1:10 at temperatures of about 8o to 150 ⁰ C in with hot air, steam or the like. heated 909882/1653 U94662 or stretching devices provided with a heating plate. 12) Method according to claims 9 to 11, characterized in that that the drawn fibers or films under free or hindered shrink conditions at temperatures of about 80 to 160 ° C are thermally stabilized. 909 8.8 2/1653