CS256179B1 - Blend for the production of polyvinylchloride pre-coating profiles - Google Patents

Abstract

A mixture for the production of translucent profiles made of polyvinyl chloride, containing 100 parts by weight of polyvinyl chloride with a K-value greater than 55, 3 to 25 parts by weight of chlorinated polyethylene with a chlorine content of 30 to 45%, stabilizers based on organotin gallate with and without sulfur) in an amount of 1 to 3 parts by weight of each type, preferably 1.5 to 1.6 parts by weight, 0.1 to 2.0 parts by weight, an ultraviolet* radiation absorber, 0.5 to 5.0 parts by weight of lubricant, optionally 0.1 to .5 parts by weight of epoxidized butyl ester of fatty acids of soybean or sunflower oil.

Description

256179

BACKGROUND OF THE INVENTION The present invention relates to a composition for the production of polyvinylchloride profiles suitable for lightening buildings, in particular extrusion technology.

It is known that the profiles on the backlighting panels can be made of a variety of plastics such as polymethylmethacrylate, polycarbonate, polyvinyl chloride (PVC), optionally polyolefins. In the use of polyvinyl chloride for the production of translucent profiles, it is necessary to provide an increase in the toughness of the aqueous, untreated PVC. The tenacity of the PVC can be increased in a number of ways, especially by the addition of a suitable polymeric material (e.g., acrylonitrile / butadiene / styrene, chlorinated polyethylene) , a copolymer of ethylene with vinyl acetate and the like) or cleavage of vinyl chloride into polymeric materials (e.g. ethylene / vinyl acetate copolymer, polyacrylates and p.). For processors, resp. Hence, there is a possibility for PPVC producers to use a grafted type of tough PVC, but to modify the basic PVC homopolymer with impact modifiers. From the relatively wide choice of modifiers, resp. The preparation of tough PVC is needed for the profiles in question, which will meet the requirements of application demands, but also the processing process itself. From an application point of view it is important to ensure the longest lifetime of the profiles in the environment of weather, industrial and civilization effects. Virtually all the toughness modifiers, as well as the grafted types of tough PVC, provide the products with mechanical properties that are satisfactory, as long as the amount of modifying component required is used. The greater problem is that the modifying additive does not cause too much deterioration of the optical properties. or the cause of a reduction in the life of the products in the outer environment.

For the process of preparing the homopolymeric PVC, as well as the modified PVC, it is necessary to use a mixture of various suitable combinations with special additives, ensuring in particular the stability of the products in the outer environment. The skylight profiles commonly available are made primarily using barium-cadmium-based stabilizers. When applied, PVC is relatively easy to process, but the light transmittance through PVC is reduced. Its disadvantage is its health defect.

On the basis of the literature data, the higher light transmittance values can be achieved by using organotin stabilizers. However, the extrusion of PVC with a stabilizing system of this type causes difficulties which result in increased machine pull, resistive high torques and an unlikely plasticization time, resulting in a reduction in toughness, light transmittance, thermal, light and weather stability of products. Furthermore, the disadvantage of tin stabilizers is their high cost compared to other conventional types of stabilizers, e.g. barium-cadmium, or equilibrium. For the above reasons, it is important to find such a dosage of tin stabilizers in combination with other additives that allow processing, specific extrusion, and also provide thermal and light application stability without the need for cost or quantity of stabilizers used.

The addition of phenolic antioxidants and UV absorbers is known in the literature to prolong the useful life of stabilized stannous stabilizers. The most widely used UV absorbers are benzotriazole abenzophenone. These additives are generally very expensive and for a variety of applications and technologies a suitable type and amount of additive is needed. In order to increase the thermal stability of PVC compositions based on stannous stabilizers, co-stabilizers, akonapr. organic phosphonates and epoxy compounds. The disadvantage of phosphonates is their certain health defect and reduced mechanical properties of the products. Thus, it is clear from the known facts that providing a process for extrusion of light transmissive profiles and achieving satisfactory application properties is associated with a whole range of material, economic and technological problems.

These drawbacks are eliminated by the mixture, which consists in that it contains 100 wt. parts of polyvinyl chloride with a K value greater than 55, 3 to 25 wt. parts of chlorinated polyethylene containing 30 to 45% chlorine, stabilizers based on organotin compounds with a sulfur content and without a maximum of 1 to 3 wt. parts of each type, preferably 1.5 to 1.6 wt. parts, 0.1 to 2.0 wt. parts of an ultraviolet absorber, 0.5 to 5.0 wt. 0.1 to 3.0 wt. parts of the acrylic flow modifier and optionally 0.1 to 2.5 wt. parts of an epoxidized fatty acid butyl ester of soybean oil or sunflower oil. In the production of light profiles, the melt is fed to the spinning screws of the extruder embedded in a plasticizing chamber, optionally coated with a degassing zone, externally heated and controlled to a temperature of 20 to 220 ° C. through a heated extrusion head through a nozzle corresponding to the shape of the profile at a pressure of 20 to 60 MPa, and the shape of the film is stabilized by one or more water-calibrating calibers.

The composition for producing the light profiles according to the invention comprises a suspension or block-like PVC. Its molecular weight, expressed indirectly by the K-value, also has an effect on processing. The lower-molecular-weight, PVC-containing, lower molecular weight processing, with increasing molecular weight, is more difficult to process but has higher mechanical properties.

The chlorinated polyethylene is applied and preferably in the form of a PVC powder mixture containing 2 to 80% by weight. ; PVC.

It has been found that it is necessary to combine two types of stannous stabilizers (sulfur and sulfur-free) for the extrusion process. Sulfur-free organotin stabilizers are, for example, organotinic esters of malatine. In the form of sulfur-containing organotin stabilizers, organotin marcades can be applied. The organotin stabilizers are added in an amount of at least 1 wt. parts per 100 wt. Samples of blends with said amounts of stannous stabilizers exhibit, for example, thermal stability at a static thermal stress in the atmosphere of 180 C at a stabilimeter of about 81 minutes dynamic thermal stability at 180 ° C at a Brabender 39 mi-nut. Said thermal stability already permits the process of extrusion of light-permeable films. In order to ensure the operational reliability of the extrusion process, it is necessary to increase the dosage of the tin stabilizers to 1.5 to 1.6% by weight. parts / 100 wt. PVC parts. Samples prepared from mixtures containing 1.5 to 1.6 wt. d. Stannous stabilizers exhibit a static thermal stability of more than 100 minutes and a dynamic thermal stability of 50 minutes. When using a larger amount of a sulfur stannous stabilizer, from about 3 wt. d // 100 wt. Although PVC is capable of being handled by the actual extrusion process, such changes do not attain sufficient resistance to wind aging. Samples containing 3 wt. d. sulfur stannicostabilizer and 0.5 wt. d. UV absorberhenzotriazole type, exhibited in artificial weathering in the Xe-notest 1200 instrument, a change in the gray scale at about 1 00 h exposure to 1 to 2, with transparency decreasing from greater than 60% to 25%. Mixtures containing 1 wt. d. both stannous stabilizers and 0.3 wt. d. Henztriazole UV absorber for 100 wt. d. PVC showed a change in gray scale to 1-2 after 1500 hours exposure in the Xeno-test of 1200, while the transparency decreased to 30%. Samples from a mixture containing 1.5 to 1.6 wt. d. both stannous stabilizers and 0.3 to 0.5 wt. d. The benz-triazole UV absorber showed a change in the gray scale to 1-2, after 2,000 hours in the Xenoteste 1,200, while the transparency decreased to about 45 ° / o. Equal to Xenoteste 1,200 also contained mixtures containing 2 wt. d. both stannic stabilizers and 0.3 to 0.5 wt. d. henztriazole-type UV absorber per 100 wt. d.PVC. Increase in UV absorber over 0.5 wt. d. has not shown a marked change in Xenoteste 1200 stability. However, the higher dosage has a detrimental effect on cenuprofiles, due to the high UV, a-b-sorbers. Increasing the dosage of tin stabilizers above 2 wt. d./ΙΟΟ wt. d.PVC also has an adverse effect on the physico-mechanical properties of the samples, for example, Vicat's heat resistance has fallen below 70 ° C, the toothbrush injection hardness has dropped below 1a below 70N mm ”2 (after 30 sj. Regarding the high cost of both types of tin-based stabilizers, their high dosage would also not spit on the price of the light profiles.

Tin stabilizers have been found to have poor lubricating effects, so it is necessary to mix them with suitable lubricants. In the lubricant deposition, it is possible to use in particular the esters of mono- and dicarboxylic fatty acids with aliphatic mono- and polyfunctional alcohols, hydroxysulfuric acid, hydrocarbon waxes, paraffins or mixtures thereof.

The positive effect of epoxidized fatty acid esters, in particular, dynamic thermal stability, is shown. However, in the case of their high-yielding (from 1 wt.

In order to provide a sufficient consistency of the exit from the nozzle, the addition of an acrylate flow modifier is shown to be appropriate. The advantages are that the resulting profiles have mechanical and optical properties suitable for screening purposes. This is accomplished by cominating the composition of the composition and the extrusion technology of the present invention. The profiles prepared by the process according to the invention guarantee the following optical and mechanical properties:

Light transmittance recalculated to 1.5 mm thick - at a wavelength of 670 nra 60% - at a wavelength of 435 nm 30%

Wall transparency 60% Tensile impact strength at 23 ° C according to DIN 53448 Notched body 500 kj / m2. Example 1

In a high shear fluid mixer, a dry blend is prepared by mixing 100 parts by weight of suspension polyvinyl chloride to a value of 62, 15% by weight. parts of a mixture of chlorinated polyethylene containing 36% chlorine with 50% polyvinyl chloride, 1.6 parts by weight of a sulfur-free organometallic stabilizer, 1.6 wt. parts of a sulfur-butyric stabilizer, 1.5 wt. die-cast acrylic flow modifier, 0.5 wt. parts of a henztriazole-type ultraviolet radiation absorber, 1.5 wt. parts of a fatty acid ester containing aliphatic alcohols of hydrocarbon wax. The mixture is stirred at a temperature of 110 ° C (110 ° C) and the liquid additives are preferably added after the other components have been heated (with stirring) to a temperature of 70 ° C. After reaching a temperature of 110 ° C, the mixture is cooled to 40 ° C. From the prepared mixture, the profile is produced by dispensing the worm feed mixture onto the spinning screws of the extruder embedded in the outside chamber heated by the electric resistive bodies regulated by the regulators, wherein the individual zones starting from the hopper are 165, 166, 168 and 172 ° C. The mixture plasticized in these bands is extruded through an extrusion die constructed according to the profile shape and heated to 192 ° C into a water-cooled cooling stack.

The profile thus prepared is suitable for illuminating buildings and its optical and mechanical properties are as follows:

Light transmittance recalculated to 1.5 mm - 65.7% at 670 nm - 37.2% at 435 nm

Wall Transparency 66.3% Tensile impact strength at 23 ° C according to DIN 53 448 non-indented bodies 642.6 kj / m2. Example 2

In a high shear fluid mixer, a dry mixture is prepared by mixing 100 parts by weight of a K-value suspension of 63, 15 wt. parts of a powdered mixture of chlorinated polyethylene containing 38% chlorine with polyvinyl chloride in a ratio of 1: 1, 1.4 wt. parts of sulfur butyl tin-stabilizer, 1.6 wt. of sulfur-free organotin stabilizer, 0.5 wt. parts of epoxidized butyl ester fatty acids of soybean oil, 1.2 parts by weight of carboxylic acid esters with saturated aliphatic alcohols, 0.5 parts by weight of hydroxystearic acid, 0.5 parts by weight of high molecular weight multi-component esters, 0.3% by weight of soybean oil; parts of an ultra-violet absorber of the benztriazole type. The liquid additives are preferably added to the heating, with the other components having a temperature of 70 ° C. The mixture was stirred at 110 ° C and cooled to 40 ° C. The profile is mixed from the mixture as described in Example 1.

The profile has the following optical and mechanical properties:

Light transmittance recalculated to 1.5 mm: - at 670 nm 74.5% - at 435 nm 48.3%

Wall Transparency 65.3% Tensile impact strength at 23 CC body notch according to DIN 53448 723 kj / m2. P ri 1 and d 3

In a high-speed fluid mixer, a dry mix is prepared by mixing 100 parts by weight of a K-value suspension of 61.8 wt. parts of powdered chlorinated polyethylene containing 37 percent chlorine with 2 percent polyvinyl chloride, 1.6 wt. parts of a sulfur butyl tin stabilizer, 1.6 wt. 0.5 parts by weight of an epoxidized fatty acid butyl ester of 1.5 wt. die-mass. parts of a mixed lubricant containing fatty acid esters and hydrocarbon waxes and 0.5 wt. parts of the ultraviolet radiation absorber of the benztriazole type. After heating the mixture to 70 ° C, liquid components are preferably added. The mixture was stirred at 120 ° C and cooled to 40 ° C. The Profilsa from the dry blend is produced by the procedure described in Example 1.

The extruded profile has the following mechanical and optical properties:

Light transmittance recalculated to 1.5 mm: - at 670 nm 64% - at 435 nm 33 ° / o

Wall transparency 64% Impact toughness at 23 ° C in accordance with DIN 53 448, bodies without notch 680 kj / m2. Example 4

In a high shear fluid mixer, a dry mixture is prepared by mixing 100 parts by weight of K-value suspension of 68.6 wt. parts of chlorinated polyethylene containing 58% chlorine mixed with 7% PVC, 1.5 wt. parts of an organo-non-sulfur stabilizer, 1.5 wt. parts of sulfur butyl tin dioxide stabilizer, 1 wt. parts of the acrylic flow modifier, 0.5 wt. parts of absorbent multilayer radiation of benztriazole type, 2.5 wt. parts of a lubricant containing fatty acid esters of aliphatic alcohols of a hydrocarbon wax. The mixture is stirred at a temperature of 110 ° C, preferably the liquid additive is added only after the other components have been heated to 70 ° C. After reaching a temperature of 110 ° C, the mixture is cooled to 40 ° C. The profile was made from the mixture as described in Example 1, with the temperature ranges set at 165, 170, 185, 180 ° C, respectively.

The profile has the following optical and mechanical properties: Light transmittance recalculated on the wall ridge 1.5 mm: - at a wavelength of 670 nm 32.6 ° / o - at a wavelength of 435 nm 62.2%

Wall Transparency: 62.9%

Tensile impact strength at 23 ° C according to DIN 53 448, bodies without notch 809 kj / m-2

Claims (2)

The subject of the invention can also be used in the construction, industry, agriculture, health care to illuminate buildings and halls in the form of walls and skylights. SUBJECT A composition for the production of polyvinyl chloride luminous profiles with improved thermal stability and weather resistance, by melt extrusion using a screw extruder, characterized in that it contains 100 wt. parts of polyvinyl chloride having a K-value greater than 55, 3 to 25 wt. parts of chlorinated polyethylene containing 30 to 45% of chlorine; organotin compound stabilizers with and without sulfur in an amount of 1 to 3 wt. parts of each type, preferably 1.5 to 1.6 wt. 0.1 to 2.0 wt. 0.5 to 5.0 parts by weight of lubricant, or 0.1 to 2.5 parts by weight of ultraviolet absorber; parts of epoxidized butyl ester of soybean or sunflower oil.