CS219592B1 - A method for producing dyed a) or filled polyolefin materials - Google Patents

Abstract

Colored a) or filled polyethylene, polypropylene, olefin copolymers, but also a) polystyrene using pigment and fillers, usually also stabilizers and auxiliaries, is produced in such a way that the pigment a) or filler, or mixtures of pigment and fillers, are dispersed in an amount of 1 to 80% by weight in a liquid medium of a mixture of at least two substances from the group: low molecular weight polyethylene with an average molecular weight of 500 to 20,000, low molecular weight polypropylene, optionally after hydrogenation, alkyl polyethoxymers (alkyl C8 to C30 and polyadated ethylene oxide in the molecule 2 to 30) and other nonionic and anionic surfactants, dialkyl esters of dicarboxylic acids and vegetable fats. Then, as a colored a) or filled concentrate, they are added to the colored a) or filled polyolefin or mixture of polyolefins, processed by further thorough homogenization at a temperature of 100 to 300 °C.

Description

219 592 [54) Production method for dyed a) or 1

The present invention relates to a substantial simplified process for the preparation of dyed a) or filled polyolefin materials, using technically available chemicals, simple devices and allowing the good dispersion of pigments and fillers and] in the final materials.

It is known [U.S. Pat. No. 3,226,353) dyeing polyethylene, polypropylene, and other plastics using dye concentrates prepared by dispersing the nanoscale pigments produced by the methyl methacrylate copolymer with 2-hydroxymethyl-5-eno-boronate. and esters of adipic acid, azelamium and sebaceous. More widely, we still use mixtures of polyisobutylene and paraffin in various proportions [jap. pat. 64 93 [1958], optionally, the pigment is mixed with a low molecular weight polyisobutylene, or a carrier for the presence of solvents (auto-conducting SSR 141 407), such as a solvent. isoamyl acetate (auto-certificated USSR 140 202). It is also known to color polyethylene with an aqueous dispersion of the dispersed pigment in the absence of an emulsifying agent at a temperature of 70 to 95 ° C (DAS1 028 377). The butadene-styrene copolymer (British Pat. No. 907 115) may also be used as the pigment carrier, the pigment dispersion being further improved by the addition of the admixed C12 to C20 acids. The dyeing of polyethylene or polypropylene in the mass can also be carried out with pigments dispersed in polypropylene wax (French Pat. No. 1,385,854), optionally a suspension or dispersion of a finely divided pigment and 5 to 60% by weight. . polyethylene oxide disperses in water and in organic solvents.

However, the disadvantage of these processes is that the preparation of the citrate and the dye itself is technically more complicated and, on the other hand, the addition of admixtures to the polyolefins, which are extracted, evaporate and possibly also smell the colored plastic. More noteworthy are the pigment carriers prepared by kneading 70 wt. parts of copolymer ethylene with propylene and 30 wt. parts of polypropylene wax at a temperature of about 80 ° C (DAS 1 082 045), in particular polyethylene, polypropylene or ethylene-propylene copolymers having a molecular weight of 500 to 30,000, depending on the molecular weight coloring matter, wherein the homogenization of the pigment with the carrier is carried out at a temperature of 25 to 200 ° C (U.S. Pat. No. 4,192,222).

Despite many advantages, the disadvantage of these processes is the relatively complicated and slow preparation of the concentrates also by making them at a relatively low temperature. Increasing the temperature and thereby reducing the viscosity can reduce the stability of the concentrate dispersion of the filled polyolefin materials 2, especially in the case of hydrophilic pigment or fillers. The pigment dispersion for the dyeing of polyolefins in the mass consisting of pigment and carrier, the carrier being a mixture of polyglycols and arylphosphates (U.S. Pat. No. 4,810,181), improves the stability of the pigment dispersion on these carriers, but decreases in final coloring, mainly due to the insolubility of hydrophilic polyglycols in hydrophobic polyolefins. Migration of these components from dyed polyolefins, e.g., foil, may be temporary, e.g., to improve the aesthetics of such products, the alumina of the other may cause "cracking" of the fibers and the like. From this point of view, the pigment paste for dyeing is a polyolefin mass, especially for the dyeing of fiber-forming polymers consisting of a pigment and a carrier consisting of an alkyl or arylphosphite and a petrolatum, possibly polypropylene oil (U.S. Pat. in addition, as a dispersant, it uses soybean oil (Pat. CSSR 146 105), especially when linear linear polymers, such as polyesters, are present in the mass. However, the disadvantage is the poor adhesion of polyolefins to polar polymers as well as polyolefins to polepepments or fillers. In other ways (GDR Pat. No. 124,055, German Pat. No. 2,309,210), water-soluble nonionic or weakly cationic active agents with a water-soluble solvent are included in the dye preparation. These premixes also allow the application of liquid systems of pasty dyes and colorant concentrates (Muller P. and others: Plaste und Kautschuk 23,831 (1976); Nauge PA, Wyart D .: Plast.Moid. Elaistomeres 28, No. 7, 80 (1976) Brit. Plastic. Rubber 1977, No. 11, 26) when the efficiency of dispersing the pigments or fillers is relatively low. Thus, the advantages of the known methods of use and the drawbacks of the present invention are eliminated.

SUMMARY OF THE INVENTION The present invention relates to the preparation of colored a) or filled polyolefinic materials, mainly dyed a) or filled polyethylene, polypropylene or polystyrene and olefin copolymers using inorganic a) or organic pigments a) or fillers, generally also stabilizers and auxiliaries. in that the pigment (a) or filler (s) of pigments (a) or mixtures of fillers are dispersed in an amount of 1 to 80% by weight in the liquid medium of the mixture of at least two low low molecular weight polyethylene polyethylene; a molecular weight of 500 to 20,000; a low molecular weight polypropylene having a molecular weight of 400 to 5,000; a hydrogenated molecular weight polypropylene having a molecular weight of 400 to 5,000; a mineral oil of 219,392 having an average molecular weight of 350 to 600; with a weight of from 300 to 1500, alkylpolyethoxamers having a carbon number in the alkyl of 8 to 30 and a polyaddinedethylene oxide in a molecule of 2 to 30, non-ionic surfactants based on vegetable fats and fatty acids C8 to C20 and ethylene oxide, dialkyl esters of dibasic carboxylic acids acids, doidecylbenzenesulfonic acid and its salts, vegetable fats, and then being added to the dyed a) or the filled polyolefin or a mixture of polyolefins, treated with further evidence of homogenization at 100-300 ° C as a colored or filled concentrate. C, in an amount dependent on the concentration of the pigments a] or the fillers in the fin are miscible product. An advantage of the process according to the invention is the high-production preparation of pigment concentrates, respectively. toners, the possibility of conducting expanded concentrates, or toners, even directly into extruders, one or more coils, together with feed polyolefins, or to make them into stock, etc., high dispersion and stability of the dispersion of pigments and fillers not only in toners, respectively. Furthermore, the very good solubility of the pigment carriers, dyed or filled with polyolefins, as well as the good adhesion of the pigment filler to the polyolefins, does not result in their imigration, the possibility of simultaneous dosing and to ensure perfect homogenization of at least a substantial portion of the components as well as to complete the process of producing the dyed or filled polyolefins. Last but not least, the advantage is the availability of the required reagents and, as a rule, their synergistic effect, by improving other physico-mechanical and utility properties, whether intermediate or final products, such as improved static properties, which is particularly important in the case of fibers and foils, removing, , dustiness, flame retardancy, prolonged service life or vice versa, achieve a similarly regulated end product life.

The fillers can also be not only inorganic, most often in the form of a powder, particularly micronized, possibly fibers, etc., silicon dioxide, magnesium oxide, calcium carbonate, magnesium calcium carbonate, aluminosilicates, especially natural or synthetic zeolites , natural glasses, especially expanded, such as perlite, alkaline earth sulphates such as barium sulphate, powdered metals, metal carbides, metal oxides, solid acids, graphite etc., but also organic, such as reactive carbon, coke , black or brown coal, pyroole distillation residues, as well as other homopolymers and copolymers such as polyvinyl chloride, vinyl chloride-olefin copolymer, phenol formaldehyde resins and the like. Often, the pigment may have the function of a filler and the opposite, such as tannic white, may be simultaneously a white pigment, a calcium carbonate-like filler and a barium sulfate, zinc oxide. In the production of black carbon black foils, even coke powder powder can also fulfill functions. In the case of the production of fibers as well as thin films, it is necessary to pay attention to the fineness, both of the pigment of the dyes and of the fillers and auxiliaries. Stabilizers are substances which prevent undesired decomposition of polyolefins, optionally fillers, pigments and other media. Thus, they are known antioxidants, antiozonants, effective against oxygen-related degradation, respectively. with air, ozone-free, and often with other oxidizing agents, thermal stabilizers to increase thermal stability, especially at normal and elevated temperatures. The adjuvants or additives are substances that enhance the further physico-chemical and mechanical properties of the intermediate products and the final products. Such pigment carriers, surface colorants, antistatic agents, dispersants, and surfactants at all, brighteners, surfactants, bactericides, antiinfectives, fumigants, and the like.

The liquid medium in which the pigments a) or fillers are dispersed consists of at least a mixture of two substances, with the surfactant being at least one of the substances being at least one of the substances being dispersed, and not only the rapid dispersion of the heterogeneous particles but also the concentration stability. The presence of both hydrophobic and hydrophilic portions of surfactant molecules will allow for thorough homogenization of not only pigments but also fillers. The low molecular weight polyethylene constitutes essentially byproducts, generally low-tech-economically utilized from the production of polyethylene. low molecular weight polymers of olefins C2 to C5, for example by cationic polymerization or copolymerization. In the case of alkylpolyethoxyamers, important for stability in the final product, so that the alkyl and hydrophobic moiety moieties are long enough to direct the polyolefin, thereby also providing good "compatibility", the migration of hydrophilic components is largely prevented in the hydrophobic environment, ie also dust and foil. It should also be noted that from the end of the finished properties of the dyed or filled polyolefins of the products, it is preferable to prepare the concentrates, the toers and the polymers, respectively. premixes with a sufficiently high viscosity (at least greasy) at temperatures up to 30 ° C. Also, unlike qualities at room temperature, it is necessary, for example, to temper the routes into pump dispensers, etc., but the quality of the dyed or filled materials is substantially higher; Auxiliary ingredients do not smell from finished 219 592 robots, do not evaporate, retain better shape stability and physico-mechanical properties.

Further advantages, as well as details of the practice of the present invention, are apparent from the examples. Example 1

150 g of cetylpolyethoxamer (20 to 22 moles of content of bound ethylene oxide) are added to the mixing tank with a volume of 2.0 dm3 fitted with an anchor stirrer (150 rpm) and a tempering jacket with hot water and drain at the bottom together with a shut-off valve and gear pump. per mole of cetyl alcohol, surface treatment 1 g / dm 3 in water 42 mN / m). 450 g of molecular weight polyethylene having an average molecular weight of 2111 (dynamic viscosity at 80 ° C = 1322 mPa · s and 90 ° C = 725 mPa · s; bromine number = 2.03 gBr 2/100 g; ash = 0.0034% The product of the low density polyethylene and 400 g of live pigment (Irgarin gelb 3R LTN) was heated to 80 ° C and stirred for 8 min at this temperature. the bottom pipe is discharged and the cooled pipe and the extruded toner are cut through the roller pump (toner I), and 1.96 g is weighed out of the thus prepared toner and mixed with 250 g of granulated low strength polyethylene with a melt index 2 g / 10 min; Density at 20 ° C 920 kg / m², tensile strength 13 MPa, load capacity 500% and point of shrinkage (Vicat) 90 ° C (type RA 2-19) processed on double cylinder kneader 150 ° C for 8 min The plate is pressed by pressing for 8 min at 8 MPa at an upper temperature of 175 ° C and lower at 185 ° C. It is then cooled at 15 MPa and 25 ° C. The prepared platelet strength of 819 MPa, elongation at 480%, and pigment dispersion 11/2 (i.e., 9 in agglomerate 2 in background). Example 2

110 g of oleyl-polyethoxamer (prepared by the polymorph of 22 moles of ethylene oxide per mole of oleic acid), 120 g of dioctyl phthalate, 119 g of rope oil, 120 g of low molecular weight polypropylene of the average molecular weight 612 (weighed 120 g) were weighed into the mixing container specified in Example 1. density 20 ° / 4 ° C = 846 kg / m 3; nD 2 O = 1,400; dyn viscosity at 20 ° C = 504.1 mPa · s at 50 ° C == 63.7 mPa · s at 80 Bromine number = 57.1 g Br 2 100 g; ash = 0.002% by weight) commercially available under the formula "PropylBll K 1000", 120 g of low molecular weight polyethylene specified in Example 1 and 400 g of brownish-red plgmnet (iron oxide) and the entire contents of the mixing container were heated to 90 ° C and maintained for 5 minutes at room temperature while stirring, followed by 2,001 g of this amount of toner (toner II). with 200 g of the polyethylene granulate specified in Example 1, the sludge is agglomerated in the temperature of 165 DEG C. for 5 minutes. The dyed polyethylene prepared in this way is pressed at a pressure of 8 MPa, a temperature of 175 DEG C. and a lower 185 DEG C. for 2 minutes and then cooled to a pressure of up to 15 MPa. temperature 25 ° C. The strength of the thus prepared sample of dyed polyethylene is 11.7 MPa, 500% strength and 10/2 pigment dispersion. Example 3 In a mixing tank specified in Example 1, a Ctoner similar to Example 2 was prepared at 70 ° C from 170 g of laurylpolyethoxamer prepared by the polyaddition of 3 to 4 moles of ethylene oxide per. 1 mole of lauryl alcohol (surface tension 1 g / dm 3 in water is 31 mN / m), 100 g of low molecular weight polypropylene specified in Example 2, 70 g of hydrogenated low molecular weight polypropylene giant. 0.2 g Br / 100 g; 340 g of low molecular weight polyethylene specified in Example 1 and 320 g of pigment (red pigment Chromopthal Scharlach RN). From this toner (toner III), 2.007 g and 200 g of low-strength polyethylene were prepared on the pre-dyed polyethylene of the specified Example 1. The strength of the prepared sample was 12.36 MPa; elongation 520% and pigment dispersion 9/2. Example 4

It is similar to Example 3, except that only 5 g of laurylpoilyethoxamer prepared by polyaddition of 3 to 4 moles of ethylene oxide per mole of lauryl alcohol are used instead of 170 g (1 g / dm 3 in water is 31 mN / m) and instead of 100 g of low molecular weight polypropylene, 200 g and 65 g of mineral oil are used. Using this toner (or IV), the strength of the dyed polyethylene sample is 11.6 MPa; elongation 535% and pigment dispersion 9/2. Example 5

150 goleyl polyethoxamer (prepared by polyaddition of 22 moles of ethylene oxide per mole of acidic acid), 150 g of low molecular weight polyethylene as specified in Example 2, and 300 g of low molecular weight polyethylene as specified in Example 2 are weighed into a mixing container specified in Example 1 and heated to a temperature of 85 g. In addition, 180 g of anti-monoxide powder, 180 g of suspension copolymervinyl chloride / propylene containing 4.1% by weight of copolymerized propylene (chlorine content = 54.4% w / w; bulk density; = 559.5 g / dm3; absorber absorption 11 min; thermal stability = 13 min) and 2% dibutyltin maleate as stabilizer and 40 g of white pigment (Verzálmodmoder BG). After stirring for 10 min, 60 g of this color mixture is removed and added to 1000 g of low density polyethylene specified in Example 1 and calendered on a double cylinder calender for 7 min at 65 ° C. The dyed applied polyethylene is then prepared by pressing for 2 min at 8 MPaa at 175 ° C upper and 185 ° C lower. It is then cooled at a pressure of up to 15 MPa and a temperature of 25 ° C. The material has a strength of 20 MPa, a ductility of 320% and a dispersion of 12/2. The 200-cyclic plate is charged at 12.5 kV / cm, the charge half-dispersion time is 2 min, while the prepared polyethylene has a half-life of more than 10 min. Example 6

The procedure is similar to that of Example 5, except that 6 g of the blended mixture is taken directly from the container into a la-boron mixer to which 100 g of polyethylene powder is added, followed by granulation of the material thus obtained on a single-screw lab extruder operating at temperature -175 ° C. From the granulate thus prepared, the plate is compressed for 3 minutes under similar conditions as in Example 5. The strength of the material is 20 MPa, a gravity of 320% and a dispersion of 11/2. Example 7

150 g of dioctyl phthalate, 150 g of wound oil, 150 g of low molecular weight polypropylene oil as specified in Example 2 and 150 g of low-molecular polyethylene specified in Example 1 are weighed into a mixing container specified in Example 1, heated to a temperature of Further, 180 g of powdered antimony trioxide, 180 g of stabilized vinyl chloride / propylene foam copolymer specified in Example 5, and 40 g of powdered brown pigment (iron oxide powder) were added to 94 ° C and stirred vigorously. The following procedure is similar to that of Examples 6 and 7. The obtained brown filled polyethylene has a strength of 10MPa, a ductility of 500% and a dispersion of 11/2. Example 8

Toner I, prepared as described in Example 1, is used for dyeing in a isotactic polypropylene film having a melt index of 10.5 g / 10 min by adding 1 g of said toner to the dio 100 g powdered polypropylene and preparing (after addition of stabilizers) using a twin screw at 220 ° C. Very good coloristic properties of the thus prepared polypropylene color composition are obtained, such as dispersion (11/2). It may be foil or extruded polypropylene fibers. Example 9

The procedure is similar to that of Example 1, with only the actual pigment carrier, which is 600 g of 60% by weight. low molecular weight polyethylene as a byproduct from the production of high pressure polyethylene, 39 wt. polypropylene oil (Propyloil to 1000) and 1 wt. of the ethylpolyethoxamer to which 400 g of pigment "Verzal blue BG" has been added with stirring. Using the thus prepared tester, the colored polyethylene prepared by coloring for 7 min has a ductility of 433%, a tensile strength of 8, 4 MPa and a pigment dispersion of 13/2. Example 10

The procedure is similar to that of Examples 1 and 8, but the toner preparation carrier consists of 75 wt. by-product of high pressure polyethylene and 25 wt. partially saponified polyethoxylated (3 moles of ethylene oxide and 1 mole of partially saponified palm oil) of palm oil. In toner, 40% by weight. The prepared polypropylene color composition has a titanium dioxide dispersion 11 / 3a and is suitable for the production of films and fibers. Example 11

Toner I prepared according to the procedure described in Example 1, except that a low molecular weight polyethylene is used with an average molecular weight of 17,680 for the preparation of an isotactic polypropylene fiber dyed in mass of 6.0 g / 10 min. by adding 1.9 g of said toner to a 200 g powdered polypropylene and a colored polyolefin (prepared (after addition of stabilizers) by means of a twin screw at 230 ° C. and concluding the formation of a fibrillar structure in the polypropylene fiber.

Claims (1)

OBJECT OF THE INVENTION A method of producing dyed a) or filled polyethylene, mainly dyed a) or filled polyethylene, polypropylene or polystyrene and olefin copolymers, using inorganic or organic pigments a) and fillers, generally also stabilizers and wherein the pigment (a) or the filler or mixture of pigments (a) or the filler mixture is dispersed in an amount of 1 to 80% by weight. in a liquid medium a mixture of at least two low molecular weight polyethylene groups having a molecular weight of 500 to 20,000, a low molecular weight polypropylene having a molecular weight of 400 to 5000, a hydrogenated low molecular weight polypropylene having a molecular weight of 400 to 5000, mineral oils of average molecular weight 350 to 600, low molecular weight copolymers of C2 to C5 alkenes of an average molecular weight of 300 to 1500, alkyl polyethoxamers having carbon alkyl numbers of 8 to 30, and polyaddated ethylene oxide at 2 to 30, non-ionic surfactants include vegetable fats and fatty acids C8 to C20 and ethylene oxide, dialkyl esters of dibasic carboxylic acids, dodecylbenzenesulfonic acid and its salts, vegetable oils, and then are added as colored (a) or filled polyolefin or a mixture of polyolefin or a mixture of polyolefins, processed by by the other evidence of homogenisation 100 to 300 ° C, depending on the need for the concentration of pigments and] or fillers in the final product.