CS231209B1 - Polypropylene blend suitable for fiber or film production - Google Patents

Abstract

Polypropylene blend suitable for the production of fibers or films consisting of 85 to 99% by weight of isotactic polypropylene and 1 to 15% by weight of a vinyl statistical copolymer prepared by radical copolymerization of N, N-dialkyl-substituted omega-aminoalkyl esters of acrylic acid or methacrylic acid alkyl esters or the monomeric and optionally further vinyl monomer in the block or solution, wherein the copolymer exhibits an affinity for coloring to a photostabilizing effect.

Description

231Ž09 2

The invention relates to a polypropylene blend suitable for the preparation of shaped articles such as fibers and films with improved colorability to photostability.

Fibers and films of polypropylene may have in many directions advantageous physical and mechanical properties. Some limiting factor in their spread, especially in the textile industry, is their hydrophobicity. Due to this property, conventional staining procedures cannot be used. The weak interaction of polypropylene fibers or films with dyes makes it difficult to stain the darker shade with the desired light and wash stability.

In order to improve staining, procedures have been proposed based on blends of polypropylene with another polymer with good interaction with the colors. These are nitrogen-containing polymers such as polyamides, polyureas, polyaminotriazoles, acrylamide copolymers, vinylpyridine and the like. However, these polymers do not exhibit sufficient compatibility with poly-propylene, which is an obstacle to trouble-free spinning or results in workability of the fibers already produced.

Appropriate modification by some additives such as polyaminotriazoles according to the invention. No. 192,296, or a suitable composition of ethylene copolymers with N-vinylcarbosol, acrylate, or aminoalkyl acrylates, can improve the compatibility with polypropylene according to Japanese Patent Nos. 9696/1964 and 55594/1964. In some of the proposed polypropylene modifiers, we do not know the parameters characterizing spinning processability, fiber lengthening and dyeing parameters, and the stability of their washing and chemical dyeing.

The present invention relates to improving the polypropylene modification with a focus on enhancing the affinity of the polypropylene blends to the dye and optionally improving the light stability of the molded polypropylene articles. It is an object of the present invention to provide a polypropylene composition suitable for the production of fibers or films comprising 85 and 99% by weight of isotactic polypropylene and 1 to 15% by weight of a vinyl statistical copolymer prepared by free radical polymerization of Ν, Ν-dialkyl substituted amino alkyl acrylate. or methacrylic, alkyl esters of acrylic acid or methacrylic acid and optionally further vinyl monomer in block or solution, the copolymer having affinity for the dyes optionally having a photostabile effect, comprises repeating units of formula A · CH,

OO (A)

D "(CH 2) n" N (R> 2 J where R * is hydrogen or methyl, 2 of R denotes an alkyl group having 1 to 4 carbon atoms, and is an integer of 2 to 4, repeating units of formula B,

R

AND

- C-I

G = 0 30 -R 1 -CH x (B) wherein r 1 is hydrogen or methyl 3 231299 3? is an alkyl group having from 4 to 18 carbon atoms, optionally C units derived from a vinyl monomer selected from acrylonitrile, styrene, vinyl acetate, 4-acryloyloxy-2,2,6,6-tetramethylpiperidine, 4-methacryloyl-oxy - 2,2,6,6-tetremetylpiperidine, 4-acryloyloxy-1,2,2,6,6-pentamethylpiperidine or 4-methacryloxy-1,2,2,6,6-pentamethylpiperidine, wherein in the copolymer comprising units A and B is a proportion of A units of 25 to 70 mol% and in the ternary copolymer containing units A, B and C the proportion of units A is 20 to 60 56 mol and units of C1 to 20 56 mol.

According to the invention, a polypropylene blend comprising kop, Ν-dialkyl-ω-aminoalkyl acrylate and alkyl esters of orthophenyl or methacrylic is preferred, or the polypropylene blend comprises a copolymer of alkyl acrylate and Ν, Ν-dialkyl meth-amino-alkyl ester of methacrylic acid, or a ternary content Statistical copolymer containing, in addition to the aminoalkyl acrylic acid units and the alkyl acrylic ester, also units derived from a vinyl monomer selected from the group consisting of acrylonitrile, styrene, vinyl acetate, 2,2,6,6-tetramethyl-4- -piperidyl acrylate or methacrylate; and 1,2,2,6,6-pentamethyl-4-piperidylacrylate or methacrylate. The copolymers of the present invention are prepared, for example, on the basis of: Ν, Ν-dimethyl-2-aminoethyl ester of acrylic acid or methacrylic acid, N, N-diethyl-2-aminoethyl ether of acrylic acid or methacrylic acid, N, N- acrylic acid di-n-butyl-2-aminoethyl ester or methacrylic acid, N, N-di-n-butyl-4-aminobutyl acrylate, n-decylacrylate, n-dodecyl acrylate, n-dodecyl methacrylate, n-hexadecyl acrylate, n-octadecyl acrylate, n -octadecyl methacrylate, butyl acrylate, 2-ethylhexyl acrylate, 2-ethylhexyl methacrylate, n-octyl methacrylate, n-octyl acrylate.

The copolymerization of a two-component mixture of said aminoacrylate or methacrylate compounds with alkyl acrylates or alkyl methacrylates, or tri-component sythems with the addition of acrylonitrile, or styrene, or vinyl acetate, or the marked vinyl derivatives of piperidine, using free-radical polymerization initiators, does not require demanding inclusion.

Compatibility with polypropylene in the increased content of alkyl acrylate or alkyl methacrylate structural cells in the copolymer is found in copolymers containing cells with longer alkyl substituents in the ester group. Copolymers containing less than 10 mole of 56 aminoalkyl acrylate or methacrylate compound do not exhibit the desired coloring effect of polypropylene when added to polypropylene in a range of up to 5% by weight. When added in larger concentrations, the products of these mixtures lose the required mechanical properties. Copolymers containing 20 to 70 moles. The% aainoacrylate or methacrylate compound has a viscosity number within the range of 0.2 to 2.5 dl / g, determined in benzene solution at 30 ° C.

Foil preparation mixtures may contain! up to 5% of a copolymer. For the preparation of the fibers, it is preferred that the copolymer-containing mixture is in an amount of 2 to 10% by weight. looking at the polypropylene, it is homogenized and granulated on an extruder prior to spinning after the addition of stabilizers and calcium stearate or sodium stearate. The homogenized mixture is then spun out of the melt on a spinning apparatus, preferably in an inert gas atmosphere of nitrogen. «

The fibers and films of the present invention are distinguished by good affinity, especially against acid dyes, and exhibit the desired distance under the effect of light. Coloring of fibers and films can be accomplished by conventional bathing procedures at 100 ° C for 1 hour. hours, in solutions containing 2-456 wt. dye, based on the weight of the dye; or foils, at a weight ratio of dyed product to bath or 1:50. When using acid dyes, coloring is preferably carried out in the presence of 1.5 56 wt. of surfactants based on the reaction products of ethylene oxide and alkylphenel, and also preferred with the addition of 2% ammonium acetate or potassium salicylate, the weight of which is 56% based on the weight of the linings or films. Before heating the dyeing bath, it is desirable to add 2% of the formic acid to the weight of the fibers or sheets. After staining, the fibers or foils are washed in water and optionally in an aqueous solution of saponets and conc. 0.1 to 2% and then in running water. The abrasion and washability of staining is very good.

The following examples are provided to illustrate the invention, but are not intended to be limiting. Example 1

120 g of n-octadecyl acrylate, 93 g of N, N-dimethyl-2-aminoethyl acrylate, 0.173 g of 2,2-azobisobutyronitrile and 170 ml of benzene were metered in after a 900 ml reactor. A nitrogen atmosphere was formed in the reactor and the reaction mixture was heated at 60 ° C for 90 h. After cooling, the copolymer cut into ethyl alcohol was filtered off and dried in a vacuum oven at room temperature. This gave 147 g of a powdered copolymer or yellowish color with a crush temperature of 34 to 36 ° C.

The dried pulp copolymer was added to Tatren HPF powdered polypropylene at 9% by weight. 0.9% w / w was added to the mixture. % dilauryl thiodipropionate, 0.29 wt. 2,4-bis- (n-octylthio) -6- (4-hydroxy-3,5-di-tert-butylanilino) -1,3,9-triazine and 0.1 wt. calcium stearate. The homogenized mixture was granulated on an extruder at 290 ° C.

The granulated mixture (flow rate 12.4 g / 10 min at 270 ° C) was spun at 270 ° C on la-boron spinning (screw diameter 16 mm, number of nozzle holes 20, diameter 0.9 mm), at a winding speed of 420 m / min. The tows were 1: 4.1 in length.

Also, the prepared fibers of 122.8 dtex were stained in a water bath containing 2% Suminol fast blue PR, 2% Slovagen SMK surfactant, and 2% acidic for fiber weight. After 1 h at 100 ° C, the dye was completely pumped out of the bath. The saturated uniform dyeing of the fibers remained unchanged in 0.2% by weight. solution of T1X detergent for 1 hour at 60 ° C. Example 2

13 g of n-octadeoyl methacrylate, 6.3 g of N, N-diethyl-2-aminoethyl methacrylate, 0.09 g of 2,2-azobisobutyronitrile and 20 ml of benzene were added to a 100 ml reaction flask. Under nitrogen, the reaction mixture was heated at 60 ° C for 47 h. The resulting polymer was isolated from the reaction mixture in a manner similar to that described in Example 1. 13.6 g of a light yellow powder powder copolymer were obtained. The dried 0.9 g copolymer was mixed with 9.1 g of isotactic. polypropylene Tatren HPF and 0.01 g 2,6-ditero-butyl-4-methylphenol. The mixture was homogenized in the melt at 220 ° C under an inert nitrogen atmosphere. From this modified polypropylene, presses at 220 ° C prepared sheets of 0.1-1.13 mm thick, which were stained at 100 ° C in a bath containing 2% dye Midor-Blue ER, 2 55 surfactant Slovagen SieK and 2% morph acid with respect to the film weight. Pe 49 min. staining at 100 ° C, the foils were stained with a rich shade when the dye was completely exhausted from the bath. For dyed films, dye scrubbing stability in aqueous solution at a concentration of 0.4% by weight was achieved. at 60 ° C for 1 hour. Example 3

A solution containing 88 g of benzene, 98.4 g of n-octayl deoxy acrylate, 2.7 g of butyl acrylate, 29.7 g of N, N-diethyl-2-aminoethyl acrylate, 10.6 g of 4, 4 g of n, N-diethyl 2-aminoethyl acrylate were added to a 900 ml reactor. -acryloyl oxy-2,2,6,6-tetramethylpiperidine and 0.2 g 2,2-azobisobutyronitrile. After nitrogen nitrogen formation in the reactor, the reaction mixture was heated at 60 ° C for 47 hours. The precipitated copolymer was isolated from the reaction mixture similar to Example 1, yielding 73.4 g of a slightly yellow powdered copolymer. The dried copolymer was used at 9.9% by weight. in Tatren HPF polypropylene for the preparation of fibers according to the procedure of Example 1. 5 231209

The dyeing of the fibers was uniform from the dye distribution hill and the rich dyeings showed the desired wash resistance in detergent detergents. Attaches

5.9 g of K, N-dimethyl-2-aminoethyl methacrylate, 14.6 g of n-octadecyl acrylate, 1.1 g of 2-ethylhexyl acrylate, 3.2 g of 4-methacryloyloxy were successively metered into the reaction flask / 100 ml reactor. -1,2,2,6,6-pentamethylpiparidine and 0,15 g dibenzoyl peroxide. After purging the reactor with nitrogen, the reaction mixture was homogenized with gradual heating to a polymerization temperature of 70 ° C and a moderate nitrogen flow was maintained throughout the reaction. The polymerization was stopped after 32 hours. After cooling, the reaction product was dissolved in benzene, the copolymer precipitated into ethyl alcohol, dried to give 19.5 g of copolymer. According to the procedure of Example 2, a blend of 9% copolymer film having a thickness of 0.07 to 0.12 mm, which exhibited very good dyeability, was prepared for staining and irradiation stability. Example 5

2.26 gn-dodecyl methacrylate, 3.91 g of n-dodecyl acrylate, 0.64 g of butyl methacrylate, 2.87 g of N, K-dibutyl-2-aminoethyl acrylate, 0.07 g of N, K-dibutyl-2-aminoethyl acrylate were weighed into a reaction flask equipped with a nitrogen inlet and a stirrer. , 01 g of 2,2-azobisobutyronitrile and 8.8 g of benzene. By spraying the treatment with pure nitrogen, an inert atmosphere was provided above the reaction mixture. After 26 hours of polymerization at 60 ° C, a solution containing 0.75 g of n-dodecyl methacrylate, 1.44 g of n-dodecyl acrylate, 0.01 g of 2,2-azobisobutyronitrile and 10 ml of benzene and polymerization were added. was allowed to continue for a further 26 hours. The resulting copolymer was isolated from the reaction mixture similar to Example 1. 10.2 g of a slightly yellowish color copolymer with a soak temperature of 31-33 ° C was obtained. As used in Example 2, 12 wt. a 0.12 mm rake copolymer film which exhibits a better dyeability. The used Midlon Blue ER dye from the bath (containing 2% by weight of the dye to the weight of the foils) was used with an efficiency of about 65% for foil staining. In an inert nitrogen atmosphere, a mixture of 6.5 g of n-hexadecyl methacrylate, 2.8 g of N was polymerized. , K-dibutyl-4-aminobutyl acrylate and 0.4 g of acrylonitrile in a solution of 10 ml of benzene with the initiation of 0.02 g of 2,2-azobisobutyronitrile at 64 ° C, after 38 hours of polymerization, the reaction mixture is isolated after precipitation into ethanol of 7.4. g of a copolymer with a soak temperature of about 31 ° C. Polypropylene films containing 9% of the copolymer showed comparable staining in Example 2 using Suminol fast blue PR in an aqueous hood containing 2% by weight of copolymer. dyes from the weight of the films. Example 7

3.25 g of n-octadecyl acrylate, 1.42 g of N, N-diethyl-2-aminoethyl acrylate and 0.3 g of styrene were weighed into a glass tube and 5 ml of benzene containing 0.01 g of 2.2- was added to the mixture of these monomers. azobisobutyronitrile. An inert atmosphere was formed in the flask by alternating evacuation and disturbance of the vacuum with pure nitrogen, and after sealing the tube, the tertiary was homogenized to a homogenized monomer mixture at 56 ° C for 42 h, 4.11 g of terpolymer was isolated with etching in ethanol. 32 ° C to 34 ° C. An analogous mixture was polymerized in the next pot, but styrene was replaced with 0.26 g of vinyl acetate. After 32 hours of copolymerization at 65 ° C, 3.82 g of a terpolymer with a pellet temperature of 32.5 to 35 ° C were isolated. Polypropylene films containing 7 wt. copolymers according to the procedure of Example 2. Using 2% Suminol fast blue PR, 2% surfactant Slovagen SMK and 2% acid. with regard to the weight of the films, dye depletion of about 80% was achieved in the aqueous dye for 1 hour at 100 ° C. The buffing bounces showed 0.4% wt. solution of tonic detergent at 60 ° C,

Claims (2)

THE FIELD OF THE INVENTION Polypropylene blend suitable for the production of fibers or foils, characterized in that it consists of 85 to 99% by weight of isotactic polypropylene and 1 to 15% by weight of vinyl random copolymer, obtainable by free-radical copolymerization of α, N-dialkyl-substituted aminoalkyl acrylic or methacrylic acid acrylic or methacrylic acid and optionally other vinyl monomer in block but in solution, the copolymer having a dye affinity or a photostabilizing effect contains repeating units of the general formula A C = 0 I I 2 (CH ₂ ) _n -N (R ² ) ₂ J where r 'is a hydrogen atom or a methyl group, R ² denotes an alkyl group having a carbon number 1 to 4, a is an integer of 2 to 4. repeating units of formula B, C = O (1) R ³ wherein R ¹ is a hydrogen atom or a methyl group, R ³ is an alkyl group having a carbon number of 4 to 18, optionally repeating units C, removed from the vinyl monomer selected from xc _; Stock »plrty. including acrylonitrile, styrene, vinyl acetate, 4-acryloyloxy-2,2,6, 4'-tetramethylpiperidine, 4-methacryloyloxy-2,2,6,6-tetramethylpiperidine, 4-aryloyloyloxy-1,2,6,6 , 6-pentamethylpiperidine or 4-methacryloyloxy-1,2,2,6,6-pentamethylpiperidine, wherein in the copolymer containing units A and B the proportion of units A is 29 to 70 mole% and in the dark copolymer containing units A, B and 0 is the proportion units A 20 to 60 mole% and units C 1 to 20 mole%. 2. Polypropylene mixture according to claim 1, characterized in that it contains a statistical copolymer of a base of Ν, dial-dialkyl-omega-aminoalkyl ester of acrylic acid and an alkyl ester of acrylic or methacrylic acid or a copolymer based on alkyl acrylate and N, N-dialkyl- omega-aminoalkyl methacrylic acid ester, or containing a ternary statistical copolymer containing, in addition to the aminoalkyl units of Brylic acid and alkyl acrylate, also units derived from a vinyl monomer selected from the group consisting of acrylonitrile, styrene, vinyl acetate, 2,2,6,6-tetramethyl-4 -piperidyl acrylate and methacrylate and 1,2,2,6,6-pentamethyl-4-piperidylacrylate and methacrylate.