CS200061B1 - Products from polyvinyl chloride with stability against light and weathering - Google Patents

Description

Products made of polyvinyl chloride with increased stability to light and weathering

The present invention relates to polyvinyl chloride products, modified variants and mixtures thereof, for example, films, sheets, profiles, tubes, moldings, coated textiles and the like, with improved light and weathering stability, including but not limited to transparent, filled, pigmented and colored variants, hard, semi-soft and softened products, lightweight products, products with reduced tendency to electrostatic charge, products with non-flammable treatment, etc.

More than any other polymer, the production, processing and application of polyvinyl chloride, its modified variants and mixtures are inextricably linked to the use of stabilizing additives, which is directly related to the low activation energy of their thermal decomposition. Complex protection against light and weathering can only provide polyvinyl chloride products, copolymers and mixtures thereof with a combination of stabilizing agents capable of interfering with the major reactions of the destruction process.

For products and its outdoor applications, for example in construction and agriculture, there are basically three ways of stabilization with different protective effects:

1. Lead salt stabilization systems have the most common composition of phosphite oluva lead steerate chelator

UV absorber up to 5 wt. per 100 wt. of polymer 1.5

0.7 - * 0.1-to 0.5 - 200 061

They are relatively least effective, unsuitable for transparent products and for use in an industrial atmosphere due to the formation of colored sulfide. The combination of lead salts with barnate-cadmium soaps is a compromise that brings a slight improvement in the color fastness of the products, but does not eliminate the problems of critical pigment dosing and chalking on aging.

2. Organotin compounds based stabilization systems typically have a composition of tin carboxilate of 1 to 2 wt. per 100 rpm. tin mercaptide polymer 0.5 to 1 - ”UV absorber 0.1 to 0.5 - Sulfur-free compounds of this type satisfy the high light and weathering requirements of the products. The problem of the processing of e.g. unplasticized polyvinyl chloride stabilized by these compounds is solved by the selection of special lubricants or by combination with sulfur variants (tin mercaptides) at the expense of the resulting protective effect against harmful radiation.

3. Stabilization systems based on barium cadmium salts with a minimum content of 10% cadmium are represented by the classic triple combination with maximum light and weathering protection used in most outdoor applications:

barium cadmium complex solid 2.0 to 2.5 wt. per 100 w / w polymer chelator (org.phosphite) 0.5 to 1 - epoxidized oil 0.5 to 1.5 - UV absorber 0.1 to 0.5 - ”Their application meaning and range is determined, among other things also processing aspects;

The barium cadmium compounds are liquid, well dispersible under the processing conditions of the polymer blend and generally have their own lubricating effect.

The disadvantage of lead, barium and cadmium salt based systems is that they are unusable for transparent mixtures and wherever the toxicity of lead and cadmium is impaired. Due to their mechanism of protective action as action of hydrogen chloride and metal chloride producers, they are essentially unable to prevent degradation of the attacked surface layer of the products even in combination with ultraviolet absorbers or synergistic additives of the organic phosphite type. The present possibilities of stabilization of polyvinyl chloride products, its modified variants and mixtures by these systems can be derived from the durability guarantees, which in the Central European weather conditions are around five years.

Insufficient stability of the polyvinyl chloride products, their modified variants and mixtures with respect to light and weathering is increased according to the invention to the level desired by the consumer by containing a multi-component protective system consisting of an organotin compound of the dibutyl-oine-bis (alkyl) ester type of maleic acid of general formula

O-OC-CH-CH-CO-O-R

O-OC-CH * CH-CO-O-R wherein R - methyl-, ethyl-, propyl-, isopropyl-, butyl-, isobutyl-, octyl-, isooctyl- and the like and at least three other compounds from the group of additives of the type

1. ultraviolet absorbers from the group of substituted benztriazoles and / or benzophenones

for example!

2- (a-hydroxy-5-methylphenyl) benztriazoles,

2- (2-4-hydroxy-3,5-di-tert-butylphenyl) -benztriazoles,

2- (2-hydroxy-3-tert-butyl-5-methylphenyl) -benzotriazole,

2- (2-hydroxy-3-tert-butyl-5-methylphenyl) -5-chlorobenztriazole,

2- (2-hydroxy-3-5-di-tert-butylphenyl) -5-chlorobenztriazole,

2-hydroxy-4-methoxybenzophenone,

2-hydroxy-4,4-dimethoxibenzophenone,

2-hydroxy-4-n-octyloxibenzophenone,

2,2Adihydroxi-4-methoxybenzophenone,

2,2-dihydroxi-4,4-dimetoxibenzophenone,

2-hydroxy-5-chlorobenzophenone,

2,4-dohydroxibenzophenone,

2.2-dihydroxi-4-butyloxibenzophenone,

Of 2-hydroxy-4-dodecyloxibenzophenone.

2. organic compounds derived from phosphorous acid in which the organic radical is bound to phosphorus via oxygen of the type

OR 0-R-0 / \

P - OR; R-O-P P-O-R; respectively.

OR \ -R-0 ^Z

Az ° \

Wherein R is an organic radical such as alkyl-, aryl-, aralkyl- and the like.

3. Nickel salts of phosphorous acid containing at least one substituent with a phenolically bonded hydroxyl group of the general formula:

P - O - R resp

R-O-P-O-Ni jol

AND

Wherein R may further be hydrogen, alkyl, aryl, aralkyl, alkenyl, cycloalkyl, phenyl, alkylated phenyl, and the like.

4. epoxidized oils or esters of higher fatty acids such as soybean and tall oil, alkyl esters of these acids and the like;

5. phenolic antioxidants, in particular alkylated phenols of the general formula

OH wherein R is hydrogen or an organic radical for example

2,6-di-tert-butyl-4-methylphenol,

2,4-dimethyl-6- (1-methylcyclohexyl) phenol,

2,2-methylene-bis- (4-methyl-6-tert-butylphenol),

4,4-Butylidene-bis (trimethyl-6-tert-butylphenol)

2,2-10-bis- (4-methyl-6-1-tert-butylphenol), beta- (3,5-di-tert-butyl-4-hydroxyphenyl) -propionic acid ester, styrene phenol, mixtures alkylated phenols and

1,1,3-tris- (2-methyl-4-hydroxy-tert-butylphenol).

6. aliphatic alcohols with at least six backbone carbon atoms, for example

2-ethylhexyl alcohol, decyl alcohol, cetyl alcohol, stearyl alcohol and the like.

Products of polyvinyl chloride, its modified variants and mixtures, containing the described multi-component stabilization systems, are in particular substantially more stable during irradiation and during weather aging than all previously known products with stabilization systems based on lead and barium-cadmium compounds. properties such as color and gloss of the exposed surface, transparency, etc., but also mechanical properties such as tensile strength, ductility, impact resistance, etc. All components of said combinations of stabilizing additives are harmless to health and therefore harmless both in the processing of mixtures and in use products. They do not react with sulfur oxides to form colored compounds and are therefore suitable for industrial applications. The protective system according to the invention is particularly advantageous for transparent mixtures of polyvinyl chloride and its copolymers with controllable transmittance in the ultraviolet and visible light regions and for special applications of products with the required extremely long lifetime in weather conditions.

The frequency and choice of components of the protective system may vary according to the nature, intended use and material composition of the products. For example, softened polyvinyl chloride wallpapers do not necessarily contain phosphorous acid-derived compounds and their nickel salts, epoxidized oils or esters, or higher aliphatic alcohols, since they are mainly of the so-called middle category applications in terms of environmental aggressiveness and long-term stability requirements. properties and, moreover, combinations with plasticizers, which do not cause any problems with processing. On the other hand, for example, façade cladding elements will comprise a protective system consisting of all components which, by themselves, whose interactions favorably influence both the swellability of the polymer blend and, in particular, the durability of the finished products in their outdoor applications. areas such as construction will be optimal and economic stabilization will always stabilize maximum.

Some typical products and corresponding composition of their protective systems according to the invention are given in the following examples:

EXAMPLE 1 Chamfered pyramid-shaped façade cladding elements made of suspension polyvinyl chloride filled with precipitated calcium carbonate and titanium white, containing a multi-component stabilizer system in an amount of 5.5% by weight. per 100 wt. a polymer consisting of 20% dibutyltin-bis- (isopropyl-) maleinate,% 2- (2H-hydroxy-3-tert-butyl-5-methylphenyl) -5-chlorobenzotriazole,

10% nickel salt of 3,5-di-tert-butyl-4-hydroxibenzylphosphoric acid monoethyl ester,% epoxidized soybean oil,% 2,6-di-tert-butyl-4-methylphenol and 20% 2-ethylxyl alcohol.

Said combination of stabilizing agents protects the products from the detrimental effects of weathering factors, in particular sunlight, its ultraviolet and infrared components, and oxygen, providing the products with long-term stability of properties including surface quality in excess of fifteen years, roughly three times the stability of similar products. protected against light and weathering by systems based on salts of lead, barium and cadmium.

Example 2

Pressed boards with a thickness of 1.5 mm usable as balcony fillings, consist of three layers. The base layer of the graft copolymer vinyl chloride (ethylene) vinyl acetate is filled with precipitated calcium carbonate and stabilized with lead stabilizers against degradation during processing. The central decorative layer of 0.2 mm thickness is of the same copolymer and contains, in addition to white fillers, colorants and a stabilizing system consisting of:

0,8% by weight of dibutyltin bis (2-ethylhexyl) maltinate,

0,3% by weight of 2,2,2-dihydroxi-4-ethylhexyloxibenzophenone,

2.2 wt. Of epoxidized soybean oil; and

0.2 w / w bis- (2-ethylhexyl-) pentaerithrityl diphosphite, per 100 w / w. polymer.

The transparent surface, the so-called barrier layer, is made of polyvinyl chloride. It has a thickness of 0.2 mm and contains a stabilization system with a composition of

1.7 wt. dibutyl tin bis (isopropyl) maleinate,

0,6 wt. 2- (2-hydroxy-5-methylphenyl) -benztriazole,

0.5 wt. bos- (3,5-di-tert-butyl-4-hydroxibenzyl-ethyl-phosphite-Ni),

1.5 wt. epoxidized soybean oil,

0.1 wt. 2,6-di-tert-butyl-4-methylphenol a

1.0 wt. 2-ethylhexyl alcohol, per 100 wt. polymer.

the durability of the products in the weather conditions of the Central European climate given by the stability of the color shade is higher than 10 years.

Example 3

Stabilized transparent foil made of softened polyvinyl chloride, suitable for applications in agriculture, horticulture or forestry, where it is necessary to protect plant crops from harmful weather effects, is made of a mixture of 63 wt. polyvinyl chloride and 32 wt. dioctyl phthalate, as a plasticizer, and further comprises a stabilizing system consisting of

1.5 wt. dibutyl tin bis (2-ethylhexyl) maleinate,

2.25 wt. epoxidized soybean oil,

1.0 wt. bis- (2-ethylhexyl) pentaerythrityl diphosphite a

0.25 wt. 2,2-dohydroxi-4-ethylhexyloxibenzophenone.

The stabilizing system provides the film with effective protection against light and weathering, which extends its lifetime from two to four to five years while maintaining the film's light transmission and mechanical properties without requiring special treatment.

Example 4

Window profiles of a blend of polyvinyl chloride modified with chlorinated polyethylene, with increased toughness and guaranteed resistance to light and weathering for 10 years, containing a stabilization system of composition (per 100wt polymer):

1.0 wt. dibutyl-tin-bis- (isopropyl) -maleinate,

0.6 wt. 2- (2,4-hydroxy-3-tert-butyl-5-methylphenyl) -5-chlorobenzotriazole

0.5 wt. nickel bis- (3,5-di-tert-butyl-4-hydroxibenzyl-ethyl-phosphorophosphine),

2.0 wt. epoxidized soybean oil,

1.0 wt. stearyl alcohol and

0.1 wt. n-octadecyl beta- (3,5-di-tert-butyl-4-hydroxiphenyl-) propionate.

Claims (1)

Products of polyvinyl chloride, its modified variants and mixtures, with increased light and weathering stability, characterized in that they contain a protective multi-component system consisting of 0.2 - 3 parts by weight of a organotin compound of the dibutyl-tin-bis- (alkyl) type - maleate and at least three other ultraviolet absorber type (1) compounds from the group of substituted benztriazoles and / or benzophenones, in an amount of 0.05 to 1.0 wt.%, (2) phosphorous acid-derived organic compounds in which the organic (3) nickel phosphorous acid salts containing at least one substituent with a phenolically bonded hydroxyl group in an amount of 0.05 to 0.8 wt. (4) epoxidized oils or higher fatty acid esters in an amount of 0.2 to 5.0 wt.%; (5) phenolic antioxidants in an amount of 0.01 to 0.35 wt. and finally (6) aliphatic alcohols having at least six carbon atoms of the backbone in an amount of 0.1 to 3.0 wt.%, based on the weight of the polymer.