CS230147B1 - Secondary softener for pvc mixture - Google Patents

Description

In general, the emollients are formulated as low volatile organic compounds, providing organic polymers with flexibility, ductility, and higher thermoplasticity. By their presence, they reduce the viscosity of the polymer melt during processing by reducing the so-called glass transition temperature (Tg) and the elastic modulus of the product. Their efficiency is particularly pronounced in the case of polymers in the glass state at normal temperature. Such polymers include, in particular, polyvinyl chloride. The principle of plasticizer action is based on an increase in the internal mobility of macromolecules and their effectiveness can be assessed in terms of the ability to lower the temperature Tg. This means that the plasticizer, as a liquid, has a larger free volume than the polymer itself, therefore by its presence it increases the free volume of the entire composition and allows Brown's micx * movement at lower temperatures than the Tg of the polymers themselves.

Plasticizers are divided into primary and secondary, respectively. extenders, which, by virtue of their properties and action, are essentially secondary plasticizers. While primary plasticizers are active solvents such as polyvinyl chloride, they already swell polymer particles at normal temperature and dissolve it at higher temperatures, secondary plasticizers are only partial solvents of polymers at higher temperatures.

Secondary plasticizers and extenders typically include aliphatic and aromatic hydrocarbons, their halogenated derivatives, alkylated aromatic hydrocarbons, and the like. These products are most widely used in polyvinyl chlorides of plasticized mixtures for the production of insulations and sheaths in the cable industry, inter alia improving their frost resistance, processability and reduce the price of finished products. They are generally dosed up to 10% by weight.

230,147 based on polyvinyl chloride. The basic quality requirements for these plasticizers are low viscosity, low volatility affecting the aging of polyvinyl chloride, high flash point, optimum electrical properties, low water content and low content of impurities, especially metal ions, whose presence reduces the thermal stability of polyvinyl chloride mixtures Properties. The decisive criterion for the application of secondary plasticizers is the evaluation of the plasticized polyvinyl chloride mixture and the properties of the final products.

In tab. I. An example of an evaluation of the physical, mechanical, and electrical properties of granulates softened by some of the currently used secondary plasticizers is given.

For the use of plasticized polyvinyl chlorides as insulating materials for electrical conductors, their electroinsulating properties are of decisive importance. The electrical insulating properties of mineral oil based plasticizers are a function of their chemical composition. Adverse, ie. the increase in conductivity, dielectric constant and decrease in electrical strength is manifested mainly by the presence of non-hydrocarbon polar constituents, inorganic salts and water. The chemical composition of the mineral oil, the so-called proportions of alkanes, cyclanes and aromatics and the structure within these groups, also play an important role.

The residual content of non-hydrocarbon polar substances which are very thoroughly removed from the crude oils for these purposes. conductivity values of 10 ”^ to 1Q ^-1 ^ oftm- ^ cm“! up to four orders of magnitude if alcoholic and peroxiaic groups predominate in the polar constituents. The negative contribution of carboxyl groups is not so pronounced, especially if the carboxyl group is bound to a large non-aromatic molecule, eg the conductivity of stearic acid at 80 ° C is 4.10 ^-1 ^ ohm ^ cm ^-1 , while benzoic acid has a conductivity at 125 ° G 5.10 ”^ Ohm '^ cm“ ^ ·. The presence of multiple bonds in the organic acid molecule also adversely affects the conductivity of oleic acid at 2 ° C to 2.10 "1θ ohm ~ ^ cm" ^. The presence of an aromatic nucleus in the polar molecule further increases conductivity, especially in combination with an active hydrogen proton, as in the case of

230 147 phenol / 20 ° C 1.7 · 10 ohm ¹ cm ^ · / or benzyl alcohol / 25 ° C 1.8 · 10 ”6 ohm” ^ cm '^ · /. The presence of water / conductivity 4x10 "® ohm" ^ cm "even at 18 ° C / reduces the electrical strength especially if the water present is in a dispersed state, i.e. at a higher concentration than the solubility.

In a similar way to conductivity comparisons, the adverse effect of polar substances can be documented by the value of the dielectric constant, which varies between 1.9 and 2.3 for pure hydrocarbon mixtures and is greatly increased by the presence of polar substances.

Very interesting and essential for the use of deeply refined mineral oils as secondary plasticizers of plastic is the influence of the hydrocarbon matrix on the electroinsulating properties of the oil. In general, saturated paraffinic, cyclanic and cyclanoparaffinic hydrocarbons are an ideal component of secondary softeners in terms of electroinsulating properties, while aromatic hydrocarbons have a negative effect.

4lkaný, Cyclanes and cyklanoparafíny feature conductivity interval IO ¹ to IO · ^ ^"18 ohm" cm ^ _"^} which are values in terms elektroisolačních very favorable properties.

For linearly annealed hydrocarbons, naphthalene, anthracene, benzanthracene, etc., the conductivity value is in the range of 2 to 6.10 " ohms ". However, the unfavorable and exceptional position of benzene as a molecule with a relatively high conductivity is compensated by an alkylac which strongly suppresses the conductivity. Already in the simple alkylated series benzene, toluene, xylene, a significant decrease in conductivity is apparent: 7.6.10 ^-8 (25 ° C); 1.10 ” ¹ * / 25 ° C; I.IO ^'1 ^ / 25 ° C / ohm-cm ^ "^ ·, so that the conductivity of xylene is already at the level of n-alkanes and alkylation of long chain alkyl fold this value falls further.

The value of the dielectric constant for aromatics increases with the number of aromatic rings, e.g. in the series benzene, naphthalene, phenanthrene increases as follows: 2.39; 2.52; 2.80.

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Furthermore, it has been shown experimentally that at a certain alkanocyclanomonoaromatic hydrocarbon content in the cyclanoparaffinic base, the electroisolating ability of the mixture is highest, but this value is further influenced by the ratio of unsubstituted cyclanic hydrocarbons to other saturated hydrocarbons in the oil base.

The prior art mineral oils with improved electrical properties, such as electroinsulating oils, do not fully satisfy as secondary plasticisers of plastics for electroinsulating purposes. Their electrical properties are usually within the limits specified in Tab. I., because in their manufacture / refining, particular consideration is not given to optimizing the composition suitable for this purpose.

The same disadvantage is also found in other currently used mineral oil based plasticizers. From tab. It can be seen that the specific resistivity, loss factor tg and dielectric constant of the PVC granules softened by said plasticizer types are in close proximity to the desired values and in some cases even do not reach the required parameters.

The above-mentioned drawbacks are solved by a plasticizer for the polyvinyl chloride compositions according to the invention, which contains 85 to 85%

99.5% wt. % of saturated hydrocarbons and alkylated monoaromatics and 0.5 to 15 wt. aromatic hydrocarbon fractions, wherein the saturated hydrocarbons consist of alkanes and cyclanes in a weight ratio of 1: 1 to 1: 4 relative to each other, and the weight ratio of saturated hydrocarbons / cyclanes + alkanes / to alkylated monoaromatics is at most 1: 1, preferably 1: 0.1 to In the aromatic hydrocarbon fraction, the monoaromatics to the two and polynuclear aromatics are present in a weight ratio of 4: 1 to 1: 1, preferably 2: 1 to 3: 1.

Due to the method of preparation of the composition, the amount of polar components carrying oxygen, sulfur and nitrogen heteroatoms should be adjusted to a maximum of 1% by weight, preferably 0.1% by weight, and a water content of no more than 0.005% by weight.

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The kinematic viscosity of the composition of the invention is in the range of 13 to 30 mm 2. s 50 at 50 ° C, depending on the application and the specific internal resistance at 23 ° C is at least 5.I0II Qhm.m.

By optimizing its composition in terms of individual hydrocarbon types, which is achieved by a suitable combination of accelerating technological operations and working conditions during these operations, a significant synergistic effect in the effect of individual components on the electroinsulating properties of the mixture has been achieved. heteroatoms and highly efficient water removal.

Table XI summarizes some of the application properties of the three different variations of this composition found with plasticized PVC granulates.

The composition of the composition according to the invention is explained in more detail in the following examples.

Example 1

The emollient is an oil obtained by high pressure hydrogenation of a light vacuum petroleum distillate at a pressure of 15 to 20 MPa under temperature conditions where slight hydrocracking occurs. Alternatively, an appropriate distillation slice from the redistillation of a hydrogenated medium or heavy oil distillate or a hydrotreated refined propane deasphaltizate may be used for the hydrogenation. After removal of the n-paraffins by solvent dewaxing, respectively. by catalytic dewaxing, the oil is refined with about 1 wt. contact clays at 105 to 180 ° C.

The final product with a kinematic viscosity of 13 to 18 mm ^. s ¹ at 50 ° C, specific gravity 860 kg.m ”\ flash point 192 ° C, pour point -8 ° C, water content max. and max ·% wt. of polar substances is especially suitable as secondary substances

230 147 polyvinyl chloride plasticizer for cable use. The characteristics of this product are shown in Tab. II - type 1.

The composition of the product is as follows: 17.6 wt.% Of alicanes, 57.5 wt.% Of cyclanes, 20.9 wt.% Of alkylated monoaromatics, 2 wt.% Monoaromatics, 1 wt.% Of double and polynuclear aromatics.

Example 2

The composition of Example 1 is further refined with 5 wt. contact clays activated for 3 hours at a temperature of 350 to 400 ° 0, at a reatination temperature of 180 ° 0. After rinsing and filtering on the filter press, the content of polar components in the plasticizer is below 0.5% by weight. The composition is particularly suitable as a plasticizer for cable insulation, which is used for the production of very thin cable insulation films.

The composition of the product is as follows: 20.1 wt.% Alkanes, 58.1 wt.% Cyclanes, 19.0 wt.% Alkylated monoaromatics, 1.8 wt.% Monoaromatics, and 0.5 wt.% Bivalent and polynuclear aromatics. The characteristic properties of this composition are summarized in Tab. II - type 2.

Example 3

The plasticizer is a mixture of oil obtained by high pressure hydrogenation of the medium vacuum distillate of oil and oil of Example 1 in a 1: 1 by volume ratio. The resulting kinematic viscosity of the mixture is 27-30 at 50 ° C. The composition confers advantageous mechanical properties on polyvinyl chloride insulation materials permanently exposed to temperatures up to 40 to 60 ° C.

The composition of the composition is as follows: 27.0% by weight of alkanes,

29.1 wt.% Cyclanes, 28.9 wt.% Alkylated monoaromatics, 11.2 wt.% Monoaromatics, and 0.5 wt. two- and multi-core aromatics.

Example 4

The composition of Examples 1 is further refined with a mixture of H 2 SO 4 and olea such that the content of aromatic components is reduced to 0.5% <230 147 wt. and the content of polar constituents carrying the O, S, N heteroatoms is about 0.1 wt%. Because of these parameters and the low water content, which ranges from 0.002 to 0.005% by weight, my plasticizer thus produced having a kinematic viscosity of 12 to 16 mm? .s ^-1 at 50 ° C, outstanding electrical properties / Resistivity at 23 ° C «^ 6,5.10 ohm m; loss factor tg at 23 ° C 0,00 0.00002; dielectric constant 2.08 / and can be used in insulating materials of electric cables, where high resistance against electric breakdown is particularly important.

The composition is as follows: 18.4 wt% alkanes, 72, G _HM Cyclanes, 9.1 wt% of alkylated monoaromatics, 0.3 wt% and 0.1 & monoarornátů wt two- and more nuclear aromatics.

Example 5

The composition of Example 1 is further dried by the addition of 2 wt. of anhydrous sodium sulphate, activated for 24 hed »at 150 to 170 ° C. Their properties and composition are close to that of the plasticizer of Example 2, wherein the desiccant present can be removed by filtration very quickly and easily. The qualitative parameters of this agent are shown in Tab. II - type 3.

Example 6

The plasticizer composition of Example 1 is further refined by the addition of 3 wt. contact clays pre-activated at 350 to 400 ° C for 3 heebs to which 1 wt. (based on clay weight) of a dehydrated partially neutralized ethylenediaminotetraacetic acid complexing agent. With this contact, the composition is heated to 90 ° C for 20 to 30 min and then filtered in a filter press as usual. This agent is perfectly free of trace heavy metal cations and is therefore particularly suitable for the production of insulating parts of coaxial cables used in computer and control technology. The composition has the same composition as that of Example 2.

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Claims (1)

Secondary plasticizer for polyvinyl chloride mixtures characterized in that it contains 85 to 99.5 wt. % saturated hydrocarbons and alkylated monoaromatics and 0.5 to 15 wt. aromatic hydrocarbon fractions, wherein the saturated hydrocarbons consist of alkanes and cyclanes in a weight ratio of 1: 1 to 1: 4 relative to each other and the weight ratio of saturated hydrocarbons to alkylated monoaromatates is at most 1: 1, preferably 1: 0.1 to 1: 0, In the aromatic hydrocarbon fraction, monoaromatics to bivalent and polynuclear aromatics are present in a weight ratio of from 4: 1 to 1: 1, preferably 2: 1 to