DE2558476A1 - MODIFICATION OF THE MODIFIED PREPARATION BASED ON A VINYL HALOGENIDE POLYMER WITH A MULTI-PHASE ACRYLIC COMPOSITE POLYMER - Google Patents

Description

Modification of the modified preparation based on a

Vinyl halide polymer with a multiphase acrylic composite polymer Addendum to the patent ... ,, I. (Patent application P 2135 024.3) Subject matter of the patent . (Patent application P 2135 024.3) is a modified preparation based on a Vinyl halide polymer with a multiphase acrylic composite polymer with a (A) first non-crosslinked phase with a molecular weight of up to 450,000, produced by polymerization from at least 25% by weight of at least one Alkyl acrylate with 1 to 18 carbon atoms in the alkyl group, 0 to 75% by weight of another acrylic monomer and 0 to 75% by weight of another copolymerizable Ethylenically unsaturated monomers containing monomer emulsion, solution or suspension and (B) a second hard, thermoplastic phase with a molecular weight from about 400,000 to 5 x 10 6, made by polymerization from about 35 up to 100% by weight of at least one monomer from which the methacrylates, the acrylates, the group of substances comprising styrene or the substituted styrenes, 0 to 65% by weight of another acrylic monomer and 0 to 65% by weight of another copolymerizable Ethylenically unsaturated monomers containing emulsion, solution or suspension.

This multi-phase acrylic composite polymer preferably contains 50 to 90% by weight of the first phase and 10 to 50% by weight of the second phase, the first Phase a molecular weight has between 7,500 and 50,000.

The present invention relates to a modification thereof Preparation containing the multiphase acrylic composite polymer of the above-mentioned Contains kind as a modifier.

The subject of the application is therefore a modified preparation, which is characterized in that it is used instead of the vinyl halide polymer Base contains another thermoplastic material.

As such thermoplastics contains the modified Preparation preferably based on a thermoplastic monomer at least one the monomers acrylonitrile, butadiene, styrene, methyl methacrylate, ethylene or propylene or polyethylene, polypropylene or polybutylene terephthalate or a thermoplastic Polyester, a thermoplastic polyurethane, a thermoplastic polycarbonate or a thermoplastic polycaprolactam.

In general, the amounts of thermoplastic material are range at about 50 to 99.9% by weight and preferably at about 75 to 99.9% by weight. The quantities of the multiphase acrylic composite polymer are usually 0.1 to 50% by weight and preferably from 0.1 to 25% by weight.

These thermoplastics are due to the modification with the initially specified multiphase acrylic composite polymer in their processing properties improved. This is because the modifying polymer is at room temperature is solid, are mixed with the thermoplastics in the dry state can and provides overall improved sliding and lubricating properties.

Mixtures or preparations of the multiphase copolymer or the acrylic composite polymer with the thermoplastic Plastic can be prepared in the usual way. Mixtures that can be used are e.g. on a mixing roll under appropriate conditions, e.g. at about 1770 C approximately Get 5 minutes or less of your time. Dry mix working methods can also be used, such as used with a mechanical mixer-blending device will. Such working techniques are when adding modifiers and Additives to thermoplastics are well known in the art. The powder mixes can, if desired, in a commercially available extruder at various types Conditions are established.

The preparations according to the invention include their thermoplastic Basic plastics also the so-called ABS polymers (acrylonitrile-butadiene-styrene plastics) with one in which styrene-acrylonitrile copolymers grafted onto and / or with butadiene, Butadiene-styrene or butadiene-acrylonitrile copolymers are mixed. Such Preparations have better processing properties than ABS polymers without the named modifiers, because these preparations e.g. extend the time, until sticking or sticking to the rollers occurs, the gloss and that continue Improve external appearance in a beneficial manner and reduce the period of time extend before sustained by deposition of the polymer on the injection molding device Effects on the molded parts occur. Similar effects are achieved with comparable thermoplastics observed, e.g. those modified with rubber Polystyrene or with impact-resistant polystyrene, with polystyrene, with polymethyl methacrylate, for so-called barrier resins based on acrylonitrile copolymers, in the case of cellulose acetobutyrate, in the case of polypropylene, in the case of high-density polyethylene, just to name a few to name a few thermoplastics.

A second group of thermoplastics used in the Preparations according to the invention can be present are the polyester and polyamide plastics, which usually higher processing temperatures and more tightly regulated temperature conditions require. Examples are polyethylene terephthalate and polycaprolactam. the Preparations according to the invention allow this group of substances, in particular im With regard to further processing into corresponding fibers, lower processing temperatures without any detrimental effect on the fiber properties.

To the thermoplastics contained in the preparations also include within the scope of the invention the polycarbonates, which in their lubricating or lubricity and in their processing properties due to the admixed Modifiers are improved.

The preparations mentioned can also contain polyurethanes. The modifier improves their processability, both than thermoplastic plastic, where better detachment from the surfaces of the Processing facilities is achieved, as well as in the injection molding of polyurethanes, in which the polymer is foamed and shaped during the process.

In the following, for a better understanding of the invention, first a general method of working is described, which is then followed by the following examples To refer to. The parts and percentages mentioned are, unless otherwise stated will, parts by weight and percentages by weight.

A modifier is used in the preparation according to the invention used multi-phase acrylic composite polymer, e.g. one of 40% by weight Butyl acrylate and 60% by weight of styrene and a first phase consisting of 90% by weight of methyl methacrylate and 10 wt.% Ethyl acrylate consisting of the second phase, the ratio of both phases in the composite polymer is 1: 1.

2 parts are stirred in 881 parts of distilled water under nitrogen a 5% aqueous acetic acid solution, sets the temperature of the mixture to 400 C and uses 82 parts of 5 parts of a 5% aqueous acetic acid solution, 3.5 parts of a 20% strength aqueous sodium lauryl sulfate solution, 1.5 parts of an 80% strength aqueous concentrate of the primary phosphate of Octylphenoxypolyäthoxyäthanols, 170 parts of distilled water, 15 parts of n-dodecyl mercaptan, 200 parts of n-butyl acrylate, 300 parts of styrene and 5 parts of cumene hydroperoxide consisting of a monomer mixture and then 26 parts of a solution of 1 part of sodium sulfoxylate formaldehyde in 25 parts distilled water, whereupon the nitrogen flow is weakened. Then you bet in the course of 1.5 hours a further 618 parts of the monomer mixture.

After the reaction has ended, the product obtained is filtered off and allow the emulsion to evaporate in a vacuum oven at 609 ° C. for 2 to 3 days. You get a semi-solid material with an intrinsic molar viscosity number 0.11 in acetone i3 acetone = 0.11).

Mix 484 parts of distilled water and 796 parts of an emulsion of the polymer prepared as described, which contains 250 parts of solids, under Nitrogen, adjusts the temperature of the mixture to 44 to 450 C and sets 26 Parts of a solution of 1 part of sodium sulfoxylate formaldehyde in 25 parts of distilled Water followed by 359.6 parts of 1.25 parts over about 1 hour an 80% aqueous concentrate of the primary phosphate of octylphenoxypolyethoxyethanol, 108 parts of distilled water, 225 parts of methyl methacrylate, 25 parts of ethyl acrylate and 0.38 parts of cumene hydroperoxide to the existing monomer mixture. You cool that from 20% by weight butyl acrylate, 30% by weight styrene, 45% by weight methyl methacrylate and 5% by weight Product consisting of ethyl acrylate, filter it through cheesecloth and evaporate aliquots of the resulting emulsion in a vacuum oven for 2 to 3 days 600 C a. A solid with the intrinsic molar viscosity is obtained 0s78 in acetone (27 acetone = 0.78). The non-evaporated part of the Emulsion with good yield and a good product / dust ratio by spraying, Example 1 Two multiphase acrylic composite polymers were prepared according to the above general procedure: (a) A polymeric modifier made from 50 Parts of butyl acrylate as the first phase and one of 45 parts of methyl methacrylate and 5 parts of ethyl acrylate existing mixture as the second phase; and (b) another polymeric modifier composed of 23 parts of butyl acrylate, 34.5 parts of styrene, 2.16 Parts of methyl methacrylate and 0.24 parts of ethyl acrylate as the first phase and 0.64 parts Butyl acrylate, 0.96 parts of styrene, 34.6 parts of methyl methacrylate and 3.8 parts of ethyl acrylate as the second phase.

Both modifiers were spray dried from the emulsion isolated. 2 parts per hundred (2 phr) modifiers were hand mixed with a Commercially available ABS plastic intended for extrusion and mixed at 1900 C rolled on a steam-heated laboratory two-roll mixer, with the speed the start roller 26 rpm and that of the end roller 20 rpm. was until a heavy one Sticking or discoloration has occurred. A similar attempt was made with an Injection molding certain, commercially available ABS plastic carried out.

Extru- + 2 phr + 2 phr injection + 2 phr + 2 phr sion additive additive cast additive additive - ABS (a) (b) - ABS (a) (b) Min. to the slight- 0.5 47 108 1.5 2.0 2.5 gluing Min. To difficult gluing 11 47 108 18 31 35 example 2 The preparation with the modifier (b) and the ABS plastic was 5 minutes rolled long after softening at 1770 C; then the resulting foils were separated, folded and 0.032 cm thick panels at a pressure of 64,000 kg and at a Pressed temperature of 1770 C. The tests were then carried out according to ASTM methods, ASTM D-256 and ASTM D-648. There was only a minor one Decrease in important physical properties.

Properties Test- Extru- + 2 phr spray- + 2 phr method sions additive Casting additive - ABS (b) - ABS (b) Izod notched impact strength ASTM 230 C, kg cm / cm D-256 41.4 40.8 27.8 22.9 Deformation ASTM Temp. ° C D-648 88 88 83 85 Example 3 The formulation Example 2 was run in a 2.54 cm Killion laboratory extruder with a tubular die with a diameter of 1.27 cm and a two-stage compressor with high compression, L / D = 24/1 of the extruder screw with different Melting temperatures extruded. The preparation was at three melting temperatures (21nu C, 2210 C and 2320 C) with 2 parts of one hundred (2 phr) modifier of the unmodified control formulation for lack of surface roughness and for lack of extrusion marks and because of a larger one Shine superior.

Example 4 Modifiers (a) and (b) were added to 5 parts of Hundred (5 phr) along with thermoplastics listed below rolled: thermoplastic rolling temp. Modifier plastic (o c) none (a) (b) Chlorinated PVC * 193 Adhesive time Adhesive time Adhesive time 4 minutes 20 minutes 20 minutes cellulose aceto- 149 satisfy- --- good butyrate of peel peel Impact-resistant 160 satisfying-improving polystyrene of peeling tes peeling *) CPVC 100 parts, additive 2 parts, tin stabilizer 2 parts, lubricant 1 part Example 5 The modifier (b) was mixed with various amounts of polyester chips and at 2940 C and 2060 m / min. spun into a fiber. With an addition of 2.5 Modifier became a definite pressure drop in the extruder versus a control fiber found with no modifier; furthermore, such pressure drops were observed an addition of 5% and 7.5% modifier was observed. In both cases there was one increased screw speed necessary to achieve the desired yield obtain. The melting temperature could be lowered with the existing additive, to get the same effect, i.e. at 7.5% modifier brought a temperature decrease of 8 ° C brings the extruder pressure back to the desired level return.

A fiber with a denier similar to the control fiber with no modifier has been received. In non-extruded form, the fiber had a modifier only slightly weaker breaking strength values than the control fiber. The physical Properties of the extruded fiber were measured after being in a double knitted fabric had been processed. There were no significant unfavorable Effects on tissue properties noted. It actually became an improvement the wearing properties determined.

Example 6 A commercially available thermoplastic polyurethane (Cyanoprene 1880) was rolled for 3 minutes at 171 ° C.

The molten material formed a uniform film that was stretched out was very difficult to remove from the roller mixer. Once 2.5 parts of the modifier, which was prepared according to the general procedure had been added, neither the melting time nor the film quality was affected, but the The film now showed good peelability from the roller.

Claims (2)

Claims: 1. Modification of the modified preparation Based on a vinyl halide polymer with a multiphase acrylic composite polymer according to patent ....... (patent application P 2135 024.3) with (A) about 50 to 90% by weight a first, non-crosslinked phase with an average molecular weight from about 7,500 to 50,000, prepared by polymerization from at least one 25% by weight of at least one alkyl acrylate with 1 to 18 carbon atoms in the alkyl group, 0 to 75% by weight of another acrylic monomer and 0 to 75% by weight of another copolymerizable Ethylenically unsaturated monomers containing monomer emulsion, solution or suspension and with (B) 10 to 50% by weight of a second, hard, thermoplastic Phase with a molecular weight of about 400,000 to 5 x 10 6, prepared by Polymerization from about 35 to 100% by weight of at least one monomer from the the methacrylate, the acrylates, the styrene or the substituted styrenes Group of substances, 0 to 65% by weight of another acrylic monomer, and 0 to 65% by weight of one other emulsion containing copolymerizable ethylenically unsaturated monomers, Solution or suspension, which does not indicate that it is in place the vinyl halide polymer is based on another thermoplastic contains. 2. Preparation according to claim 1, d a d u r c h g e k e n n -z e i c h n e t that they are based on a thermoplastic monomer of at least one of the Monomers acrylonitrile, butadiene, styrene, methyl methacrylate, ethylene or propylene or polyethylene, polypropylene or polybutylene terephthalate or a thermoplastic Polyester, a thermoplastic polyurethane, a thermoplastic polycarbonate or contains a thermoplastic polycaprolactam.