KR810000694B1 - Poly olefin-based polymeric composition stabilized by organic poly amines - Google Patents

Abstract

A stabilized polyolefine-based polymeric compn. characterized in that it contains as stabilizer and a stabilizing amount of an organic polyamine having the following general formula(I) wherein R1,R2,R3 and R4 are equal to or different from each other and are an alkyl group havig from/to 4 carbon atoms; A is an alkylene group ranging from 2 to 10 carbon atoms B is a divalent aliphatic cycloaliphatic, aromatic or alkylaromatic radical which contains hereto atoms such as O, S, N and P either in the chain or as side substituents; and n is a whole number between 2 and 1000.

Description

Polyolefin Compositions Stabilized by Organopolyamines

The present invention relates to a polymer composition which is based on an α-olefin polymer and is stable to heat, light and aging, and relates to fibers, films, raffia and the like obtained using the same.

As is known in the art, polyolefins, in particular polypropylene, degrade heat treatment in the presence of oxygen in the atmosphere.

It is also known that products obtained using polyolefins as starting materials are sensitive to light, heat treatment and aging phenomena. The degradation of polyolefins can generally be limited by adding one or more protective materials to the polymer, especially when the polymer is transformed into a fiber, film or similar form of material. Generally, small amounts of amines, phenolic compounds, aminophenols, thiophosphorates, phosphites, thiophosphates, thioesters, chelating compounds of transition metals, organotin compounds, carbamate and thiocarbamate, Oximes, polyquinolines, and other analogues are used alone or in suitable combinations with one another.

Particularly suitable combinations of the above-mentioned compounds can give alpha-olefin polymers with practically good stability, but not all are satisfactory.

In the present invention, the polyamine compound represented by the following general formula acts as a polymer stabilizer, and in particular, the alpha olefin polymer prepared in the form of fibers, films, or other forms has a superior stabilizing effect compared to the conventional method of mixing various components. Found.

In the above formula, R ₁ , R ₂ , R ₃ and R ₄ are the same or different and are alkyl group having 1-4 carbon atoms, R ₅ is hydrogen or alkyl group having 1-4 carbon atoms, A is 2- 10 is alkylene, B is an aliphatic, cycloaliphatic, aromatic or alkyl-aromatic divalent functional group, and is a hetero atom such as oxygen, sulfur, nitrogen or phosphorus in a straight or branched chain substituent, n is an integer 2- Displays a number between 1000

It is preferable that the specificity (ηinh) in the polyamine compound of general formula (I) is 0.01-1dl / 1g (the viscosity is a value determined at 25 ° C. in chloroform as described in the Examples).

Contains less than 5% or the same weight in the polyamine compound and acts as a stabilizer against light, heat and aging before extrusion or during molding, making not only alpha-olefin polymers but also dyeable fibers. Effective for basic nitrogen condensation polymers and former polymers. The polyamines described above are also suitable for stabilizing compositions based on colored polyolefins by the addition of organic or inorganic dyes.

It is therefore an object of the present invention to provide a stable polyolefin comprising the polyamine represented by the general formula (I) described above as a stabilizer. It is recommended that the amount of polyamine added to the polyolefin be used in a weight of less than 5%, but in practice it is not so rigorous. Moreover, it was observed that even a small amount of polyamine of about 0.1% was effective in increasing the stability of the polyolefin. As polyolefin, polypropylene having an isotactic macromolecule is preferable, which is obtained by stereospecific polymerization of propylene. However, according to the invention also suitable polyolefins are prepared from monomers represented by the general formula R-CH = CH ₂ .

Wherein R is an alkyl or aryl group or a hydrogen atom, for example polyethylene, polybutene-1, methylpentene-1, poly-4-methylpentene-1, polystyrene, and the like.

Of the polyamines of general formula (I), R ₅ is preferably hydrogen, R ₁ , R ₂ , R ₃ and R ₄ are each methyl groups and A is selected from the group consisting of-(CH ₂ ) ₂ and-(CH ₂ ) _6-. B is selected from the following groups.

In this formula, R ₆ is an alkyl group representing 1 to 18 carbon atoms.

As the polyamine compound represented by the general formula (I), the compounds used to increase the stability of the polyolefin according to the present invention have the following repeating groups.

In the above formula, P is an integer between 2-10, R ₆ has already been described above.

The polyamine represented by general formula (II) is generally made by condensation of this functional amine compound.

The functional compound is, for example, dibromoethane, epichlorohydrin, P-xylenedichloride, diepoxy compound, and the like, which are suitable for forming a divalent functional group B. The condensation polymerization reaction is carried out by the conventional method by reacting this functional dihalogenation or diepoxy or halogen-epoxy compound with this functional amino compound, for example halogens obtained at temperatures higher than room temperature in the presence of alkaline hydrates. The acid is neutralized in the presence of alcohol. In particular, the molar ratio of the two reactants is preferably 1: 1, but may also be used in different ratios of 1: 0.5-1: 2. The condensation polymerized amino product of the present invention has resin-like properties and is soluble in methanol.

Compound (II) is obtained by reacting an aliphatic diamine H ₂ NA-NH ₂ with -2,2,6,6-tetraalkyl-substituted 4-piperidone under hydrogen in the presence of a hydrogenation catalyst such as platinum. The scheme is as follows.

Polyamines having formula (I) may be used alone or as known stabilizers such as oxybenzotriazoles, oxy-benzo-phenones, stabilizers containing Ni, metal soaps, phenol sulfates, phosphites, thioesters and other substances. Together with the mixture. Examples of the polyolefin composition having improved stability with a stabilizer are as follows.

a) polyolefin

b) The polyamine of general formula (I) as described above, in an amount of 0.1-5%.

c) phosphite compounds represented by the following general formula

Wherein X is oxygen sulfur and R ₇ , R ₈ and R ₉ are the same or different and are substituted by alkyl, aryl or alkyl aryl groups, in particular other functional groups such as -OH groups, with amounts ranging from 0.05-2% Used as.

d) phenol sulfates represented by the general formula

Wherein R ₁₀ and R ₁₂ are the same or different and are alkyl groups having 1-12 carbon atoms, and R ₁₁ is monovalent or multivalent selected from the group consisting of cycloalkyl, aryl, alkarylaryl groups which may contain hetero-atoms; The functional group of is displayed.

e) Mixing of compounds containing polyolefins in metal soaps, polyamines (I) or polyamines selected from stearates similar to calcium, zinc and magnesium is generally accomplished simply by stirring and mixing powdery additives into polyolefins.

However, it is also possible to add by other means, for example by mixing the stabilizer solution and the polyolefin in a suitable solvent and then evaporating the solvent or otherwise adding the stabilizer to the polyolefin after polymerization.

In addition, it is possible to increase the stability by impregnating the prepared product in the solution or by evaporating the solvent after dispersing the stabilizer, it shows that the stabilizer according to the present invention can be combined with the polyolefin in the molten state without contamination.

The mixture is granulated and then extruded in a melt spinning machine to have a spinneret length / diameter ratio of at least one. Granulation and spinning are preferably carried out in an inert gas atmosphere such as nitrogen and in the absence of oxygen.

In the course of the mixing, the polyolefin can be added with the stabilizer of the present invention and also with a matte and organic or inorganic dye. The filament obtained by extrusion is elongated at an elongation of 2-10 at a temperature of 80 ° -150 ° C., and the drawing apparatus is heated by a heating plate with liquid, steam or hot air. The stretched filaments are then subjected to dimensional stabilization at a temperature of 80-160 ° C. without shrinkage or in controlled condition.

The filament obtained by extruding the mixture obtained in the present invention may be a single filament or a double filament and is used for the production of knitting yarns, fabrics.

The composition of the present invention for spinning production is also used for the production of films, raffia fibers, and other commodities.

Modifications or changes in the practice of the invention may be made without departing from the scope of the invention.

In the following examples, the method of the present invention will be described in detail, but the present invention is not limited thereto.

Example 1

Preparation of N, N'-bis (2,2,6,6-tetramethyl-4-pimeryl) ethylenediamine; 162.75 g (1.05 mole) of 2,2,6,6-tetra dissolved in 200 cc of methanol 30 g (0.5 mol) of ethylenediamine and 0.5 g of platinum, dissolved in 40 cc of methyl-4-piperidone methanol, were put in a 1 liter autoclave and hydrogenated at a temperature of 80 at 50 asm for 2 hours. The catalyst was then removed and the residue was distilled off to give 155.5 g (92%) of product having a boiling point of 150-151 ° C./0.1 mmHg and a melting point of 80-81 ° C. with a nitrogen content of 16.51% (C ₂₀ H ₄₂ N ₄ = 16.56%; calculated).

[Production Method of Polyamine]

9.25 g (0.1 mole) epichloro in a solution of 33.8 g (0.1 mole) N, N'-bis (2,2,6,6-tetramethyl-4-piperidyl) ethyleneamine in 50 cc of methanol 4 g (0.1 mole) of sodium hydroxide (tablet) is added while the hydrin is mixed and the mixture is heated to reflux for 10 hours and later for 8 hours.

After the addition of NaOH, the mixture is heated to reflux for at least 2 hours to filter the resulting sodium chloride. The filtrate is first dried at 70-100 ° C. under atmospheric pressure to remove methanol, and then dried by heating at 120 ° C. under a pressure of 1 mmHg for 4 hours.

In this way, a brittle, light resinous material 39 is obtained, which is pale yellow, having an intrinsic viscosity of 0.14 dl / g and a nitrogen content of 13.6 g. Intrinsic viscosity is the value determined at 25 ℃ ± 0.1 ℃ in 0.5% chloroform solution using Desreux-Bischoff Viscometer.

The viscosity measurement procedure is as follows;

Add 0.1 g of sample to 20 cc of solvent and keep stirring for 30 minutes. The resulting solution was placed in a viscometer and the flow time (ts) of the solution and the flow time (to) of the pure solvent were measured. Then, the relative viscosity was obtained from the formula ts / to, and the intrinsic viscosity (ηinh) was obtained from the following formula. Calculate

Where C is the concentration and the unit is g / (100 cc solvent).

[Stability test]

[Exam 1]

25 g of the polyamine described above is dissolved in 100 cc of methanol and then mixed with the following compound in this solution.

5 kg of polypropylene having an intrinsic viscosity of -1.65 dl / g, 96.5% of heptane extract, 80 p.p.m of ash and 5 g of calcium stearate are mixed. This mixture is granulated in 180 coral-free atmosphere and spun under the following conditions.

The spinning nozzle used had 40 holes with a diameter of 0.8 mm and a length of 4 mm. The filaments from the spinning nozzle are collected at a rate of 500 mt / min and elongated at an elongation of 3.3 at 130 ° C. under a steam atmosphere.

The characteristics of the filament thus obtained are as follows.

Intensity after exposure to weatherability tester for 1400 hours; 1.8 g / dtex (This tester has a 6000-watt xenon-amplifier with a relative humidity of 30.5% and a black panel temperature of 63 ° ± 3 °).

In the case of using a known stabilizer, the strength was halved after about 500 hours of exposure.

[Exam 2]

25 g of the aforementioned polyamine is dissolved in 100 cc of methanol and the following materials are mixed in this solution.

-5 kg polypropylene with a specific viscosity of 1.65 dl / g, residue of heptane extract 96.5%, 80 ppm ash.

5 g of penta-erythritol tetrakis {3 (3.5-di-butyl-4-hydroxyphenyl) -propionate}, 12.5 g of tri-n-dodecyl-phosphite, 5 g of calcium stearate.

The mixture was melted in a test tube at 250 ° C. for 10 minutes to give bright light. The mixture was granulated by extrusion at 180 ° C. in an oxygen-free atmosphere and spun under the same conditions as in Test 1.

The filament thus obtained has the following characteristics.

Intensity 2.0 g / dtex after 1400 hours of exposure to weatherability meter [Example 2]

Preparation of N, N ¹ -bis (2,2,6,6-tetramethyl-4-piperidyl) hexamethylenediamine.

162.75 g (1.05 mole) of 2,2,6,6-tetramethyl-4-piperidone dissolved in 200 cc of methanol and 5 g (0.5 mole) of hexamethylenediamine dissolved in 70 ° cc of methanol, 0.5 g of platinum 10% coated in a 1L autoclave and hydrogenated at 50 atm, 80 ° C for 2 hours.

The catalyst and solvent were removed and the residue was distilled to give 177 g (90%) of the product, the boiling point of this compound was 180-181 ° C./0.1 mmHg, the melting point was 61-62 ° C., and the N content was 14.26%. (Theoretical value for C ₂₄ H ₅₀ N ₄ is 14.21%).

[Production method of polyamine]

Operating according to Example 1, 9.25 g (0.1 mole) was added to 50 cc of methanol solution of 39.4 g (0.1 mole) of N, N ¹ -bis (2,2,6,6-tetramethyl-4-piperidyl). Mix epichlorohydrin. As a result, 43 g of a pale yellow product, which is easily crushed, is obtained, and its intrinsic viscosity is 0.18 dl / g and the nitrogen content is 12.01%.

[Stability test]

[Exam 3]

25 g of the polyamine described above was dissolved in 100 cc of methanol and the same product as in Test 2 was mixed in the same amount, then granulated and extruded under the same conditions as Test 1. The properties of the filaments obtained by elongation at 3.3 in water vapor at 130 ° C. are as follows.

Name 17dtex

Strength 2.4g / dtex

Elongation at Break 94%

1.8g / dtex after 1400 hours exposure

[-Test 4]

25 g of the polyamine described above was dissolved in 100 cc of methanol, and 5 kg of polypropylene having an intrinsic viscosity of 1.65 dl / g, 86.5% of heptane extract, 80 ppm of ash, and 5 g of calcium stearate were mixed and hardened. The filament roll extruded under the condition of elongation at a rate of 500 mt / min from the spinning nozzle was elongated at an elongation of 3.3 in a steam atmosphere at 130 ° C. The filaments obtained had the following characteristics.

Name 17dtex

Strength 2.6g / dtex

Elongation at break 102%

1.7 / dtex after 1400 hours of exposure to weather resistance

Example 3

[Production method of polyamine]

The conditions of Example 1 were repeated, but 74 g (0.2 moles) of N-bis- (2-oxy-3-chloropropyl) -n-dodecylamine dissolved in 100 cc of methanol and 67.6 g of dissolved in 120 cc of methanol ( 0.2 mole) of N, N ¹ -bis (2,2,6,6-tetramethyl-4-piperidyl) -ethylenediamine was used. In addition, 16 g (0.4 mol) of sodium hydroxide are added in small portions during the last 8 hours of heating.

121 g of a pale pale yellow solid is obtained, in which the intrinsic viscosity is 0.15 dl / g and the nitrogen content is 10.45%.

[Stability test]

A mixture with polyamine is prepared in the same amount as described in Test 2, and treated and spun under the same conditions as Test 1 to obtain a filament. The filaments obtained have the following characteristics.

Name 17dtex

Strength 2.4g / dtex

100% elongation at break

Strength 1.5g / dtex after 1400 hours exposure to weatherability meter

Example 4

[Production method of polyamine]

N, N'-bis- (2,2,6,6-tetramethyl-4-piperidyl) -ethylenediamine 33.8 g (0.1 mol), 2,2-bis {4- (2,3-epoxypro 34 g (0.1 mole) of oxyphenyl) -propane and 100 cc of methanol were mixed and heated under reflux for 8 hours, first heated to 100 ° C. at atmospheric pressure to remove the solvent, and then heated at 120 ° C. for 2 hours at a pressure of 1 mmHg, and 67 g of flexibility was obtained. And a resinous pale yellow product is obtained, in which the intrinsic viscosity is 0.2 dl / g and the nitrogen content is 8.18%.

[Stability test]

As in Test 2, the filaments obtained by mixing polyamines in the same compound, in the same amount and spinning under the same conditions as in Test 1, have the following characteristics.

Name 17dtex

Strength 2.6g / dtex

Elongation at Break 90%

1,200 hours of exposure to weather gauge to halve original intensity

Example 5

[Production method of polyamine]

78.8 g (0.2 mol) N, N'-bis- (2,2,6,6-tetramethyl-4-piperidyl) -hexamethylenedimine, 37.6 g (0.2 mol) dml 1.2-dibromo Carbon and 130 cc of isopropanol were heated to reflux for 20 hours and 0.4 mol of NaOH 16g was added in small portions over the last 16 hours. After complete addition of NaOH, the mixture was heated to reflux for 4 hours and the reaction mixture was diluted with 150 cc of benzene and filtered to separate the resulting sodium bromide.

The filtrate is first heated to 100 ° C. at atmospheric pressure and dried first, and dried for 2 hours at 120 ° C. under vacuum of 1 mmHg to obtain 81 g of a resinous pale yellow solid. The specific viscosity is 0.12 dl / g and the nitrogen content is 12.95%.

Stability test

As indicated in Test 2, the same amount was added to the above-mentioned polyamine and mixed, and the mixture was spun under the same conditions as in Test 1 to obtain a filament, which was stretched to an elongation of 3.3 at 130 ° C. in the atmosphere of water vapor. The following characteristics are shown.

Name 17dtex

Strength 2.5g / dtex

95% elongation at break

Intensity after 1,400 hours exposure to weatherability meter; 1.7 g / dtex

Example 6

The filaments obtained by spinning the mixture in Test 2 without polyamine under the same conditions as Test 1 were spun at 3.3 elongation in water vapor at 130 ° C. to exhibit the following properties.

Name 17dtex

Strength 2.4g / dtex

Elongation at Break 95%

150 hours of exposure to weather resistance to halve the intensity

Claims (1)

As a stabilizer in preparing stabilized polyolefins based on polymer composition

(Wherein R ₁ , R ₂ , R ₃ , R ₄ are the same or different atomic groups from each other alkyl having 1-4 carbon atoms, R ₅ is hydrogen or alkyl having 1-4 carbon atoms, A is 2-10 Alkylene having carbon atoms, B contains divalent aliphatic, cycloaliphatic, aromatic or alkylaromatic groups in the chain structure or as heterocyclic atoms, such as O, S, N, P, and n Polyolefins stabilized by organopolyamines, using polyamines having a general formula of an integer between 2 and 1000, having an intrinsic viscosity of 0.01-1 dl / g and a content of not more than 5% by weight in the polymer composition. Composition.