CS199474B1 - Composition for producing inflammable,tough and transparent materials - Google Patents

Description

SUMMARY OF THE INVENTION The present invention provides a composition for the production of flame-retardant, yet transparent, polyvinyl chloride (PVC) and / or vinyl chloride copolymers, formed by a suitable combination of individual component additives, providing optimum technical, aesthetic and utility properties of the final products.

Compositions based on PVC with high impact resistance, respectively, are known. Toughness with vinyl chloride, split (uninoculated) butyl rubber (Austrian Pat. No. 2 618 93), as an important component. PVC together with chlorine-containing polymers such as chloropran rubber, copolymers of vinyl chloride with chloroprene rubber and chlorinated polyethylenes [Chodkevič L., Michajlov M .: Vysokomolek. sojedin. 12. č. 10,722 (1970); austrálky pat. 294 9463 · Although the fire resistance of these materials is remarkable, the disadvantage is the low transparency. In contrast, a polymerization mixture prepared from homopolymers or copolymers of vinyl chloride and a styrene-alkyl acrylate copolymer (French Pat. No. 1,570,418) is in turn transparent, but less tough. Improved toughness of PVC is achieved by the addition of ethylene-vinyl acetate copolymer, with its amount increasing the toughness of fNaitoveove. H.: Plast. Technol. 21. No 8, 48 (1975); Ekepress infor. chim. those. pererab, high shear. Mater. No 47, 16 (1975); Ignateva G. F. et al. certifies. USSR 407 923], but

At the same time, the transparency decreases and in cases where lead and venous stearate are additionally used as stabilizer (Japanese Pat. Nos. 49-110 742 1974 and 50-043 149. (1975) 3), products made of this material are non-flammable. Flame retardancy and toughness are also achieved by a composition based on a vinyl chloride grafted (cleaved) ethylene-vinyl acetate copolymer containing 25 to 50% of vinyl acetate with the term vinyl chloride as a vinyl chloride copolymer. a terpolymer in which the polymer chains of vinyl chloride units, in addition chlorinated polyethylene and antimony trioxide (Japanese Pat. No. 49-015,741 (1974)) are attached to the macromolecular chain of the ethylene vinyl acetate copolymer as side branches, but also lacking in transparency. amounts of ethyl N - vinyl acetate copolymer, PVC alone, as a graft (grafted) vinyl chloride (Belgian Pat. file no. 828 724), in turn, low toughness of the material is achieved, and at higher levels, without regard to the type of stabilizers and lubricants, low transparency. The clear thermoplastic composition (NSR Pat. No. 2,152,366) can be prepared from 95 to 20 wt. parts of PVC, 5 to 80 wt. parts of a copolymer of L-methylstyrene with acrylonitrile and 3 to 30 wt. parts of the graft copolymer. However, its toughness and flame resistance are not sufficient for many technical applications. In the case of the preparation of PVC with good toughness, the method of slurry polymerization of a mixture containing wt. parts 100 of PVC, 3 to 8 acrylic monomer, 2 to 8 aromatic vinyl monomer and 3 to 8 diolefin in the presence of a free-radical initiator. However, due to the low rate of copolymerization or cleavage of PVC by said comonomers, low production, lower weather resistance and, at higher initiator concentrations, also higher thermal stability are achieved. Tough resin is further prepared [Japanese Pat. file no. 75 - 018 019 (1975) 3 by adding a coagulant and a water-insoluble (chloroform, petroleum ether) or soluble solvent (methanol, acetone) to a system consisting of rubber polydiene latex and PVC. The composition based on this resin, however, needs to be particularly stabilized with antioxidants and, in addition, its low transparency does not suit the application.

The advantages of the known compositions take advantage of and in addition by a suitable combination of the individual polymer components as well as the known additives, a higher effect is achieved both in toughness and in transparency, while maintaining flame retardancy, the composition and resp. a composition of the invention.

The composition for the production of flame-retardant tough and transparent materials based on polyvinyl chloride and / or vinyl chloride copolymers by conventional processing technologies, mainly by rolling, extrusion, spraying or compression, consists of 2 to 40% by weight, preferably 10 to 30% by weight, of at least one copolymer of methacrylate-butadiene-styrene, acrylonitrile butadiene-styrene, acrylonitrile-methacrylate-butadiene-styrene and vinyl chloride-cleaved ethylene-vinyl acetate copolymer, -356 to 92% by weight, and preferably 64 to 84% by weight, and suspension and / or block polyvinyl. To a value of 55 to 75, preferably 60 to 68, and up to 8% by weight, and preferably 4 to 6% by weight. additives consisting of heat and light stabilizers, external and optionally internal lubricants, pigments, and optionally also antioxidants and abaorbers of ultraviolet radiation.

The advantage of the composition, respectively. composition according to the present invention is relatively high toughness, transparency and flame retardancy, simple toughness regulation by suitable choice of components, utilization of the synergistic effect of polyethylene additives, which is an effective external lubricant under working conditions and in addition to the inoculated ethylene / vinyl acetate copolymer Partially analogous effect is also achieved by the addition of partially eaterified polyhydric alcohols, resp. partially hydrolysed or saponified fats (triglycerides), which have the effect of both external and internal lubricants and furthermore increase the frost resistance of the products as well as the dynamic thermal stability. On the basis of these compositions it is possible to produce and with high productivity tough flame retardant and transparent materials, in which all of the above properties significantly increase the performance of products such as waveguide coverings, critical and decorative panels, containers and fittings exposed to chemicals and corrosive environments, car bodies, woodwork components and especially the furniture industry, etc.

Suspension or block PVC and K values of 55 to 75 are suitable as homopolymeric PVC for the preparation of the composition, as a rule a K value of 62 to 68 is generally best. A lower K value is easier to process, but generally has lower thermal stability and is more fragmented. . With a high K value, it is more difficult to process, requiring higher power consumption. Block PVC in terms of transparent properties is even more suitable than suspension PVC. Emulsion, except for product transparency would be satisfactory; therefore, it can only be used for compositions and articles where transparency and translucency are not required. In the case of the ethylene-vinyl acetate copolymer, the content of the second component should be in the range of 20 to 60%, preferably in the range of 35 to 50%. At less than 20% vinyl acetate, the composition is less transparent. The high vinyl acetate content in turn reduces the thermal stability. However, the stated vinyl acetate content limits do not limit the possibilities of using an ethylene-vinyl acetate copolymer in the compositions of the present invention. Similarly, vinyl chloride can be vaccinated, resp. cleave different types of ethylene-vinyl acetate copolymers, even though some optimal boundaries also apply. At low vinyl acetate content in vinyl chloride-grafted ethylene-vinyl acetate copolymer, its solubility in monomeric vinyl chloride decreases. In the case of vinyl chloride-cleaved ethylene-vinyl acetate copolymer it is a so-called. Tough PVC containing a copolymer component most often in the range of 4 to 12% by weight, and toughened PVC types with higher or lower content of split or at least dispersed ethylene-vinyl acetate copolymer cannot be excluded.

r For making compositions! and products according to the invention are particularly suitable, in addition to the base suspension PVC, e.g. o To a value of 62, a combination of vinyl chloride grafted ethylene - vinyl acetate copolymer with methacrylate - butadiene - styrene copolymer, which achieves a much higher than additive effect on toughness and good transparency. Relatively high toughness and transparency is achieved by a suitable choice of the relative weight ratio of the starting homopolymer and at least one, but usually two, elastomeric copolymer components, among the ternary copolymer methacrylate - butadiene - styrene, acrylonitrile - butadiene - styrene copolymer and ethylene chloride cleaved. In addition to conventional lubricants for preparing a composition, such as montan wax, it is suitable. apply polyethylene, which is a high-performance outer lubricant under process temperatures and, in addition, toughness and frost-resistance when applying the product.

However, when applied in an amount above 0.5% by weight, it already reduces transparency. Partially hydrolysed fats work not only as an external but also an internal lubricant and increase the frost resistance of the products. Similar eituation is when higher fatty acids are partially esterified with polyhydric alcohols such as ethylene glycol, diethylene glycol, polyethylene glycol, propylene glycol, polyether polyols, glycerol, trimethylolpropene, neopentyl glycol, pentaerythritol, sorbitol, dipentaerythritol, and dipentaerythritol.

Of the thermal stabilizers, known organotin stabilizers can be applied, such as dialkyl tin maleate, especially dibutyltin maleate, dibutiltin dilaurate, then dialkyl thiopropionate, and more particularly, especially two-component stabilizers of a sulfur-containing organotin compound, e.g. type

R '

I

R '-S-Sn-0-CO' l I

R ' »simply belongs monobutyltin-S, ^S, S-tris-isooctyl mercaptoacetate, butyltin tris-lauryl, tributyltin S-isooctylmercaptoacetate, trifenylcinlaurylmerkaptid. triphenyltin thiophenate, thibutoglycolic dibutyltin ester and the like. and a sulfur-free organotin compound, e.g. Type R ^of ₂ ® '2® ⁿ * Further include calcium, zinc and cadmium salts of higher fatty acids, mixed salts of these elements with higher fatty acids, as well as mixed salts. Lead and barium-based stabilizers cannot be applied as they significantly reduce transparency. In addition, known light stabilizers β 2 -hydroxy-4-n-octoxybenzophenol, 2- (2H-benzotriazol-2-yl) -phenol and pigments, in particular organic athioxydans, e.g. 2,6-di-tert. butyl-4-methylphenol, 4,4-thiobis-tert-butyl-m-cresol, and other generally known additives, depending on the intended application of the material.

Further details of the invention, as well as advantages, are apparent from the examples.

Example 1

To prepare the composition! listed in Table 1 will be used! the following raw materials:

S-PVC (Type 622) with a K value of 62, a bulk density of 615 g / dm and a viscosity number of 95 cnr / g; the volatile substances make up 0.3% by weight; kraft ash 0.04% by weight; The absorption of plasticizer at 75 ° C in a 10 x 100 mm tube is 24 min; by sieve analysis on a 0.250 mm sieve, the determined residue is 1% and on a 0.063 mm sieve 96%.

Vinyl vinyl acetate ethylene vinyl acetate copolymer - tough PVC (type KH 081) having a K value of 68, a viscosity number of 115 cm @ 2 / g and a bulk density of 645 g / dm @ 2; determined chlorine content - 52.4% by weight by sewing analysis - sieve residue 0.250 mm = 1.2%; sieve residue 0,063 mm - 64%.

The wax is predominantly an outer lubricant, type E wax consisting of esters of montanic acids with glycol and / or 1,3-butanediol having a saponification number of 142, an acid number of 17 mg KOH / g and a melting point of 78 ° C.

A stabilizer consisting of a mixture of dibutyltin tin ester of thioglycolic acid and dibutyltin tin monoester of maleic acid.

Acetic acid with admixtures of palmitic acid in an amount of 5,5% by weight.

Preparation of compositions no. 1 to 5 in tab. are stabilized in a hot mixer at a temperature of 90 ° C and at a speed of 2800 rpm until the temperature of the stabilized mixture automatically rises to 128 ° C. The powder mixture is then rolled (calendered) on a twin-roll roller with a relative rotation of 1.25: 1 for 3 min at 180 ° C to a thickness of 0.8-1 mm. A 4 mm depth plate is then pressed from the sheets on a press at 180 ° C. The board is cut by sawing, grinding and notching into bodies with dimensions 4x6x50 mm and measured and their notch toughness according to ČSN 64 0612.

A further proportion of rolled foils is pressed to a valid depth of 1 mm and their transparency determined according to DIN 50 31. The composition of the compositions as well as the results of their toughness and transparency are shown in Table 1.

-6 TabuTka 1 ·

OznaSenie Composition and properties of mater iálu composition récepture (mass parts? toughness CkJ. m ^-2 ) Transparencia (T,%) and b C D 1 100 S-PVC 622. 3 stabilizer 0,3 wax E 0,2 kys. stearic 2.9 75.0 2 95 S-PVC 621 5 PVC-KH 081 3 stabilizer for 0.3 wax E 0,2 kys. stearic 3,4- 77.8 3 90 S-PVC 623 10 PVC-KH 081 3 stabilizer 0.3 wax E 0,2 kys. stearic 3.9 79.7 4 85 S-PVC 623 16 PVC-KH 081 3 stabilizer 0.3 wax E 0,2 kys. stearic 4.0 79.4 5 80 S-PVC 623 20 PVC-KH 081 3 stabilizer 0.3 wax E 0,2 kys. stearic 4,1 · 77.4

Example 2

In addition to the components specified in Example 1 as additional additives ¹ (heat and light stabilizers, mainly ultraviolet stabilizers, antioxidants and lubricants), the following substances and mixtures are applied to prepare the compensations:

Calcium - zinc soaps (Ca - Zn soap); as a heat stabilizer for high-transparency and color mixtures.

Tris- (nonylphenyl) phosphite (label - chelator).

Diesters of dicarboxylic acids and saturated alcohols, drop temperature. 45 ° C (dicarboxylic acid designation).

»7

- 7 - -.

fipoxidized soybean oil (thermal stabilizer and current secondary softener), abbreviated epoxy, oil.

2- (2H-benzotriazol-2-yl) phenol, m.p. 131 DEG C. (UV absorber).

The procedure for the preparation of the compositions is similar to that of Example 1, except that only the components and components are changed. recipe and time. želatirtizáeie.

The composition of the compositions, the gelatinization time as well as the properties of the compositions, respectively. materials thereof are characterized in Table 2.

Table 2

Labeling of compositions i e Material composition and properties recipe (mass parts) gelation time, (min). notched húževna- weight the (KJ. M ~ 2) transparent Renca T,% and · b C d - - e 6 100 · S-PVC 622 4 Ga-Zn soaps 2 chelator 2 epox.oil 0,5 dicarb. acid. 0,5 wax E 0.2 UV absorber 12.8 2.6 67.7 7 95 S-PVC 621 5 PVC-KH 081 4 Ca-Zn soaps 2 chelator 2 epoxy, oil 0,5 dicarb. acid. 0,5 wax E 0.2 UV absorber 23 ‘ 2.8 . 68.3 - ⁸ 90 S-PVC 623 8 PVC-KH 081 4 Ca-Zn soaps 2 chelator 2 epoxy, oil 0,5 dicarb. · acid 0,5 wax E 0.2 UV absorber 12 4.6 67.6

Continued tables 2

and b C ' and e 9 85 S-PVC 623 16 PVC-KH 081 4 Ca-Zn mydia 2 chelétor 2 epoxy, oil 0,5 dicarb. acid. 0,5 wax E 0.2 UV absorber 9 5.6 67.3 10 80 S-PVC 623 20 PVC-KH 081 4 Ca-Zn soaps 2 chelator 2 epoxy, oil 0,5 dicarb. acid, 0,5 wax E 0.2 UV absorber 7.8 ...... 8.5 62.

Example 3

Using the raw materials specified in Examples 1 and 2 and additional components, the following mixture (by weight) is prepared:

86,5 With PVC 622;

PVC-KH 081;

3,8 methacrylate - butadiene - styrene copolymer (MBS);

dibutyltin tin ester thioglycol (stabilizer 2);

a stabilizer;

0.3 wax E;

0.7 calcium stearate;

0.3 polyethylene having a melting point of 65 ° C and a melt index of 200;

0,2 partial acid. stearic esterified glycerol. respectively. partially saponified animal fat (monoglyceride content = 25% by weight; acid value = 6 mg KOH / g; melting point 38 ° 0; water content 0.6% by weight);

0.2 tfv absorber.

Then, 2 kg of this mixture was stabilized at 90 ° C in a hot mixer at a speed of 2800 rpm until the mass temperature spontaneously rose to 128 ° C. The stabilized mixture is extruded in a single screw machine (D = 22 mm; L = 25 JD) with a compression ratio of 1: 2 at 50 rpm and a temperature mode of the zones - t, = 137 ° C. * 2 ^s ^ 3 C, t ^ = 188 C, via adjustable nozzle 1.5x80 mm and temperature 194.5 ° C.

- 9 The fabric produced has a transparency of 81% / mm depth. The web is formed by pressing, sawing and grinding into standardized bodies 4x6x50 mm for the measurement of notch toughness. The determined impact strength is 10.6 kJ.m.

Example 4

Using the raw materials specified in Examples 1 to 3 and in addition dioctyl adipate as internal lubricant, the following mixture (mass parts) is prepared:

100 PVC-KH 081;

MBS · stabilizer 2;

a stabilizer;

0.55 wax E;

0.2 stearic acid;

0,3 partial acid. stearic esterified glycerol;

1,5 dioctyladipate;

1.5 epoxide, oil;

0.2 t absorber.

Then 2 kg of this mixture is stabilized at a temperature of 90 ° C similar to Example 3.

Further processing, strip extrusion and determination of parameters are performed similar to Example 3. Transparency of the sample is 53.6% / mm depth and the notch toughness of the manufactured bodies is 34.5 kJ.m.

Example 5

The formulation composition and production method ^- similar to that in Example 4, with the only difference that instead of 100 wt. parts of PVC-KH 081 used only 95 wt. parts, but additionally 5 wt. % by weight of parts of a 58.5 wt.% vinyl chloride-propylene suspension copolymer with 3.8 wt. propylene. The flow properties of the composition in comparison with the composition of Example 4 are improved. The sample transparency reaches 62.5% / mm depth and the notch toughness is 33 kJ · m 2. The material is practically non-flammable (oxygen number = 34).

Example 6

Similar to Examples 1 and 2, using the ingredients specified in the other examples, the compositions and materials thereof are prepared. The formulations of the preparation as well as the results characterizing the properties of the compositions and the samples prepared therefrom are given in Table 3.

- 10 TABLE 3

Identification of the composition

Composition a material properties formula notched Transparency, (w . section) toughness. (kJ.m ² ) ’Γ (% / mm? 86.5. S-PVC 622 10 PVC-KH 081 3.8 MBS 2 stabilizer  2 ' stabilizer 2 0.3 wax E 0.7 Stearate Lime- stearate 10.6 1 82.2 0.2 steam. hydrolysed an animal, grease 0.3 polyethylene 0.2 UV absorber 86 S-PVC 622 10 PVC-KH 081 5 MBS 2 stabilizer .1 2 stabilizer 2 0.3 wax E 0.7 stearan -ápe- stearate 17 80.6. 0.2 steam. hydrolysis, - '  - animal. grease 0.3 polyethylene · 0.2. UV absorber -

Object of the invention

Claims (3)

Object of the invention 1. Composition for production. non-combustible tough and transparent materials based on polyvinyl chloride and / or vinyl chloride copolymers by conventional processing techniques, in particular by rolling, extrusion, spraying or pressing, characterized in that it consists of: 2. The composition according to claim 1, characterized in that a copolymer of methacrylate-butadiene-styrene and vinyl chloride-cleaved ethylene-vinyl acetate copolymer are added as a copolymer in an amount of 2 to 40% by weight, preferably 10 to 30% by weight. 1: 20 to 3: 1, preferably 1: 10 to 1 with 2. 2 to 40% by weight, preferably 10 to 30% by weight, of at least one copolymer from the group of methacrylate-butadiene-styrene, acrylonitrile-butadiene-styrene, acrylonitrile-methacrylate-butadiene-styrene and vinyl chloride-cleaved ethylene-vinyl acetate copolymer, 11 56 to 92% by weight, preferably 64 to 84% by weight, of a suspension and / or block polyvinyl chloride having a K value of 55 to 75, preferably 60 to 68, and 3 to 8% by weight, preferably 4 to 6% by weight, of additives consisting of heat and light stabilizers, external and optionally internal lubricants, pigments and optionally also an antioxidant. · Ultraviolet radiation absorbers and absorbers. 3. Compositions according to claim 1 and / or 2, characterized in that 0.1 to 1% by weight, preferably 0.3 to 0.5% by weight, of polyolefin, preferably polyethylene, are added as additives in the additives. with a melt temperature of up to 75 ° C, optionally partially hydrolysed fats and / or partially esterified polyhydric alcohols and as thermal and light stabilizers two-component sulfur and sulfur-free organotin stabilizers in a total amount of 0.3 to 5.5% by weight, preferably 2 to 4 wt. .