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Method of producing highly filled polyvinyl chloride-based plastisol

Method of producing highly filled polyvinyl chloride-based plastisol
IPC classes for russian patent Method of producing highly filled polyvinyl chloride-based plastisol (RU 2412962):
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FIELD: chemistry.

SUBSTANCE: invention relates to processing polyvinyl chloride through dispersion, particularly to production of highly filled adhesive plastisols used in making protective coatings in motor-car construction, as anticorrosion protection of inner surfaces of metal structures. The method of producing highly filled plastisol based on polyvinyl chloride involves successive addition and mixture in a mixer of di(2-ethylhexyl)phthalate, triethylene glycol dimethacrylate, isopropylbenzene hydroperoxide, half of the given amount of kaolin, calcium strearate, polyvinyl chloride and the remaining amount of kaolin. Aliphatic silicon acrylate, diatomite and NGZ-4 phosphate hydraulic fluid are added before adding polyvinyl chloride, and after adding the remaining amount of kaolin, a polysulphide oligomer - liquid thiocol II with weight ratio of SH groups of 1.7-2.6% and molecular weight of 2100 is added.

EFFECT: high degree of restoration of the thixotropic structure, extrusion, fire resistance and tensile strength of the polyvinyl chloride plastisol and the hardened material.

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The invention relates to the processing of polyvinyl chloride (PVC) through the dispersion, in particular the production of highly filled plastisols used for the manufacture of protective coatings in the automotive industry, as anti-corrosion coating of internal surfaces of metal structures.

A method of obtaining PVC plastisol, including PVC, plasticizer, bentonite, stabilizer, polietilenglikolja derived oleic acid [A.S. USSR №804671, CL C08L 27/06, 1981].

The disadvantage of plastisol obtained in this way is a low adhesion to the metal surface.

A method of obtaining highly filled plastisol comprising emulsion PVC, di-2-ethylhexylphthalate, ether phosphoric acid, oligopyrroles, white spirit, kaolin, bentonite, oligoribonucleotide, Gidropress [RF Patent №2089572, MKI 6 C08L 27/06, SC 13/02 // (SC 13/02, 3:22, 3:24, 3:36, 5:01, 5:10, 5:14, 5:15, 5:205)].

The disadvantage of plastisol obtained in this method are the low rate of recovery of thixotropic structure after the application of shear deformation and extrusion of plastisol. While the vertical sections are formed nodules and streaks.

The closest is a method of obtaining highly filled plastisol PVC-based [RF Patent №2098437, MKI 6 C08L 27/06, K 13/02 // (SC 13/02, 3:22, 5:01, 5:098, 5:10, 5:14)]. Plastisol is obtained by mixing the following ingredients, parts by weight:

Polyvinyl chloride 100
Di(2-ethylhexyl)phthalate 80-100
Triethyleneglycoldinitrate 40-60
Of cumene hydroperoxide 0,4-1,2
White spirit 20-25
Kaolin 160-220
Calcium stearate 3-6

The disadvantage of plastisol obtained in this method are the low rate of recovery of thixotropic structure after the application of shear deformation and extrusion, as well as the lack of resistance. The presence of a solvent white spirit in the composition of the PVC plastisol leads to high pozarovzryvobezopasnost in the coating on the base.

The task of the invention is to develop a method of producing highly filled PVC plastisol coating, having a high degree of thixotropic recovery patterns after application change the type of deformation, extrusion, flame retardancy, tensile strength.

The technical result is to increase the degree of thixotropic recovery patterns after the application of shear deformation, extrusion, flame resistance, tensile strength PVC plastisol.

The technical result is achieved in that in a method of producing highly filled plastisol based on polyvinyl chloride, comprising the sequential introduction and mixing in a mixer di(2-ethylhexyl)phthalate, Triethylenetetramine, cumene cumene, half of a given amount of kaolin, calcium stearate, polyvinyl chloride and the remaining quantity of kaolin, before the introduction of polyvinyl chloride in the composition is optionally administered aliphatic siliconegel, diatomite and phosphate hydraulic fluid mark DALY-4, and after the remaining amount of the kaolin type polysulfide oligomer is a liquid Thiokol mark II with a mass fraction of SH-groups of 1.7 to 2.6% and molecular weight of 2100, the next the ratio of components, parts by weight:

Polyvinyl chloride 100
Di(2-ethylhexyl)phthalate 80-100
Triethyleneglycol the 10-20
Aliphatic siliconegel 30-40
Of cumene hydroperoxide 0,4-1,2
Kaolin 160-180
Calcium stearate 3-6
Polysulfide oligomer 1.5 to 2.5
Diatomite 3-5
Phosphate hydraulic fluid mark DALY-4 2-7

While diatomaceous earth increases the thixotropic properties of the compositions due to physical interaction with the polymer matrix. Improving the fire resistance of the cured PVC plastisol due to the fact that in the presence of diatomite when exposed to an open flame produces a larger volume of the coke mass, with the insulating barrier effect. The introduction of the PVC plastisol structuring additive - polysulfide oligomer can significantly reduce the amount of stains and provide ravnoudalennostj applied to protect the surface of the PVC plastisol. This is because the curing polysulfide oligomer with education is receiving stitched material begins at lower temperatures, than the gelatinization PVC-plastisol flowing at the temperature of 120-130°C. the Specified allows you to IntenseDebate the beginning of the process of structuring coatings methods airless spray. In addition, the interaction of cumene hydroperoxide with the polysulfide oligomer promotes education in the system of a large number of radicals, which leads to an increase in the degree of transformation in the polymer matrix of multicomponent plastisol. The presence in the composition of the PVC plastisol of Triethylenetetramine, aliphatic silicongate and polysulfide oligomer promotes the formation of interpenetrating nets and, as a consequence, leads to an increase in the content of gel-fraction. The presence in the composition of aliphatic silicongate can improve thermal and fire resistance of the cured PVC plastisol. Introduction to PVC-plastisol phosphate hydraulic fluid ngj-4, which is a mixture of alkyl - and arylphosphate with additives, allows to improve the fire resistance of materials. The absence in the PVC plastisol solvent white spirit greatly increases fire and explosion safety of the coating process.

When carrying out the claimed invention PVC-plastisol has a higher rate of recovery thixotropic structure and extrusion, as well as on sennou fire coverage.

As can be seen from the table, when the content of di(2-ethylhexyl)phthalate less than 80 parts by weight deteriorates the processability of the composition. The increase in the content of di(2-ethylhexyl)phthalate more than 100 parts by weight leads to a decline in the rate of recovery of thixotropic properties, tensile strength and oxygen index.

Using Triethylenetetramine at less than 10 parts by weight deteriorates the processability of the composition, reduces the adhesion strength of connection with the ground layer and the tensile strength. The increase in the content of Triethylenetetramine more than 20 parts by weight leads to a decline in the rate of recovery thixotropic properties and flow index.

The use of aliphatic silicongate fewer than 30 parts by weight deteriorates the processability of the composition, reduces the adhesion strength of connection with the ground layer and the tensile strength. The increase in the content of aliphatic silicongate more than 40 parts by weight leads to a decline in the rate of recovery thixotropic properties and flow index.

When the content of cumene hydroperoxide in quantities of less than 0.4 parts by weight of reduced depth transformation of the functional groups of the components involved in the formation of the polymer matrix. The use of cumene hydroperoxide in the amount of more than 1.2 parts by weight promotes integration of the operations intensification of processes of destruction of the cured PVC plastisol in conditions of atmospheric aging.

When the content of kaolin in fewer than 160 parts by weight of a reduced degree of recovery thixotropic properties, oxygen index and increases the runoff of the composition. The increase in the content of kaolin over 180 parts by weight leads to deterioration of processing AIDS compositions and increase extrusion process.

The use of calcium stearate in the amount of less than 3 parts by weight leads to a reduction in the degree of recovery of thixotropic properties. When the content of calcium stearate in the amount of more than 6 parts by weight increases the viscosity and extrusion, deteriorating the processability of the composition.

When using the content of polysulfide oligomer in an amount of less than 1.5 parts by weight of increased runoff PVC-plastisol when applied, decrease the degree of recovery of thixotropic properties and the index of the current songs. The increase in the content of polysulfide oligomer, more than 2.5 parts by weight causes a reduction in tensile strength and oxygen index.

The use of diatomaceous earth in the amount of less than 3 parts by weight leads to a decrease in flow, the degree of recovery of thixotropic properties and the oxygen index, the increase in runoff PVC plastisol. When the content of the diatomaceous earth in the amount of more than 5 parts deteriorates the processability of the composition, reduced oxygen index.

The use of phosphate hydraulic fluid markings-4 in the amount less than 2 parts by weight of leads to a decrease of the oxygen index. When using phosphate hydraulic fluid in the amount of more than 7 parts by weight increases microphase separation in PVC-plastisols and decreases the tensile strength of solidified materials.

In the composition of the plastisols according to the invention uses the following components: polyvinyl chloride (GOST 14039-78); di(2-ethylhexyl)phthalate (GOST 8728-88); triethyleneglycoldinitrate TGM-3 (TU-6-16-2010-82); aliphatic siliconegel - product manufactured by Sartomer No. CN-9800 viscosity 54,7 PA·s at 25°C. and a density at 25°C 1,09 g/ml of cumene hydroperoxide PIPERIS (TU 34.402.62-121-90); calcium stearate C-17 (TU 6-09-4104-75); polysulfide oligomer is a liquid Thiokol mark P (GOST 12812-80) with a mass fraction of SH-groups of 1.7 to 2.6% and molecular weight of 2100; diatomite (TU 5761-001-25310144-99) is a light, porous rocks from white to yellowish-gray with medium density, varying from 0.15 to 0.6 g/cm3. Diatomite 96% consists of water silica (opal) General formula SiO2·nH2O; phosphate hydraulic fluid (composition: dibutyltin 9-19%, tributyl phosphate 1.0 to 1.5%additive 2N 0,5-1,0, polybutylmethacrylate 5-7%) with the following characteristics: flash - 168-174°C, acid number, KOH/1 g - 0,10-0,17 mg, density at 20°C of 1.05-1.07 g/cm3, kinematic viscosity at 20°C - 5,2-65 cSt, the refractive index 1,4592-1,4599.

Rheological properties of PVC-plastisol determine the device "Polymer - RPE. 1M in the range of shear rates of 0.35-91,3 with-1at 23±2°C.

The degree of recovery of thixotropic structure is determined as follows. Plastisol directly in the working node viscometer dispersed for 15 min at a shear rate of 91.3-1. Then for 30 min plastisol is at rest, then determine the index of the stream.

The rate of extrusion is determined on the installation firm "Willow" by fixing the time of the expiration of 60 g plastisol under a pressure of 1.4 bar through a round hole with a diameter of 2.4 mm

Adhesive ability assessed by the plastisol film after gelatinization at 130°C 30 min on the surface of the metal plate, covered with soil EP-00228. Determine the nature of the detachment of the film: adhesive detachment of material from the substrate; cohesion - the destruction of the material without separation from the substrate.

Runoff is determined as follows. On a plate, covered with soil EP-0228, using the template h mm put the plastisol layer with a thickness of 1 mm, after which the plate is placed in a vertical position and incubated at room temperature for 30 minutes, Measure the length of the path traveled by the border of the plastisol.

The tensile strength determine who and the bursting machine with the speed of movement of the lower clamp 100 mm/min for samples in the form of a double-sided blades.

The oxygen index was determined in accordance with GOST 21793-76.

The composition of the PVC plastisols and properties of materials obtained by the proposed method are given in the table.

Example 1 (invention).

In a mixer with anchor stirrer download di(2-ethylhexyl)phthalate, triethylammonium, of cumene hydroperoxide, half of a given amount of kaolin, calcium stearate, aliphatic siliconegel, diatomite and phosphate hydraulic fluid mark DALY-4. The mixing is carried out for 30 minutes, after which the paste is introduced polyvinyl chloride. After stirring for 30 min batch upload the remaining part of kaolin and continue mixing for another 60 minutes and Then the reaction mass is added polysulfide oligomer and mix for 5 minutes the PVC plastisol is applied to protect the base and utverjdayut at a temperature of 130°C for 30 minutes.

Thus, the claimed method of obtaining highly filled PVC plastisol coating ensures compositions and materials with high degree of thixotropic recovery patterns after shear deformation, extrusion, fire resistance and tensile strength. In addition, increased explosion safety when applying structured coating.

The way the floor is to be placed highly filled plastisol PVC-based, including sequential introduction and mixing in a mixer di(2-ethylhexyl)phthalate, Triethylenetetramine, cumene cumene, half of a given amount of kaolin, calcium stearate, polyvinyl chloride and the remaining quantity of kaolin, characterized in that before the introduction of polyvinyl chloride in the composition is optionally administered aliphatic siliconegel, diatomite and phosphate hydraulic fluid mark DALY-4, and after the remaining amount of the kaolin type polysulfide oligomer is a liquid Thiokol mark II with a mass fraction of SH-groups of 1.7 to 2.6% and molecular weight of 2100, in the following ratio of components, parts by weight:

polyvinyl chloride 100
di(2-ethylhexyl)phthalate 80-100
triethyleneglycoldinitrate 10-20
aliphatic siliconegel 30-40
of cumene hydroperoxide 0,4-1,2
kaolin 160-180
calcium stearate 3-6
polysolve the hydrated oligomer 1.5 to 2.5
diatomite 3-5
phosphate hydraulic fluid mark DALY-4 2-7

 

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