RU2516643C1 - Coating composition - Google Patents

Abstract

FIELD: chemistry.

SUBSTANCE: coating composition contains oligobutadienediol, mineral filler, polymethylene polyphenyl polyisocyanate with 29.5-31.0 wt % isocyanate groups, an organotin catalyst, 2,4,6-tri-tert-butylphenol, ethylsilicate, zinc oxide, diatomite, a modifier - 1,1-bis(4-hydroxyphenol)-2,2,3,3,4,4,5,5,6,6,7,7-dodecafluoroheptane of the formula:

EFFECT: high sedimentation resistance of the composition at the treatment step, coupled with high thermal resistance and aggressive medium resistance of the material, while maintaining the level of dynamic and physical-mechanical properties of the coating.

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Description

The invention relates to methods for producing compositions intended for the manufacture of coatings for athletics treadmills, gyms, playgrounds, as well as heat- and aggressive-resistant, roofing and waterproofing coatings.

Known composition for coatings, including low molecular weight butadiene-piperylene rubber, calcium oxide, chalk, glycerin, polyisocyanate, a urethane formation catalyst and hydroxylated rubber crumb [RF Patent 2024564, C09D 109/00, 1994]. The disadvantage of coatings from such a composition is the low level of dynamic and elastic hysteresis indicators.

Known composition for coatings, including low molecular weight butadiene-piperylene rubber, polyisocyanate, urethane formation catalyst, plasticizer, mineral filler, trifunctional low molecular weight alcohol and 2,4,6-tri-tert-butylphenol [RF Patent 2131898, MKI C09D 109/00, 1990] . The disadvantage of coatings from this composition is low sedimentation stability, a low level of physical, mechanical, dynamic and elastic hysteresis parameters.

Closest to the proposed technical essence and the achieved result is a composition comprising: oligobutadiene diol, glycerin, mineral filler, polyisocyanate, organotin catalyst, 2,4,6-tri-tert-butylphenol, ethyl silicate, and it additionally contains a polysulfide oligomer - liquid thiols with a number average molecular weight of 1700-5500 and a viscosity at 25 ° C of 7.5-50 (Pa · s), zinc oxide, diatomite, a modifying additive - -1H, 1H, 11H-trihydroperfluorundecanoxy- (2H-hydroxyethyl) -oligo-2 methyl-1-oxylidene of the formula, pr the following component ratio, mass parts .:

Oligobutadiene diol one hundred Glycerol 5-20 Mineral filler 60-100 Polyisocyanate 14-24 Organotin catalyst 0.01-1.10 2,4,6-tri-tert-butylphenol 0.5-1.5 Ethyl silicate 0.8-1.6 Polysulfide oligomer 5-15 Zinc oxide 10-20 Diatomite 20-30 Modifying additive 0.2-0.4

[RF patent 2452755, IPC C09D 175/14, publ. 2012]. The disadvantage of the composition is the formation of a defective three-dimensional spatial network of chemical bonds during curing due to the use of a monofunctional, highly polar modifier containing secondary hydroxyl groups, which forms, along with glycerin, short-chain, low molecular weight units. As a result, the coating has a reduced thermal and aggressive resistance.

The objective of the invention is to obtain a material with high thermal and aggressive resistance, while maintaining the level of dynamic and physico-mechanical properties obtained from a composition having high sedimentation stability at the interface "oligomer-filler".

The technical result is to increase the sedimentation stability of the composition, with increased thermal and aggressive resistance of the material, while maintaining the level of dynamic and physico-mechanical properties of the coating.

The technical result is solved by using a composition comprising oligobutadiene diol, a mineral filler, polymethylene polyphenyl polyisocyanate with a content of isocyanate groups of 29.5-31.0 wt.%, An organotin catalyst and 2,4,6-tri-tert-butylphenol, ethyl silicate, zinc oxide, diatomite, the specified modifier -1,1-bis (4-hydroxyphenol) -2,2,3,3,4,4,5,5,6,6,7,7-dodecafluoroheptane, of the following formula:

in the following ratio of components, parts by weight:

Oligobutadiene diol one hundred Mineral filler 60-100 Polymethylene Polyphenyl Polyisocyanate 10-20 Organotin catalyst 0.01-1.10 2,4,6-tri-tert-butylphenol 0.5-1.5 Ethyl silicate 0.8-1.6 Zinc oxide 10-20 Diatomite 20-30 The specified modifier 2-3

The essence of the method of obtaining the composition is as follows. In the case of the use of several substances in the composition of the prototype composition (glycerol and 1H, 1H, 11H-trihydroperfluoroodecanoxy- (2H-hydroxyethyl) -oligo-2-methyl-1-oxylidene) containing hydroxyl groups (primary and secondary) when reacted with polymethylene polyphenyl polyisocyanate During the curing process, a series of parallel reactions occurring at different speeds. This fact inevitably leads to a violation of the regularity of the spatial network of transverse chemical bonds and, as a consequence, to a deterioration of the whole complex of properties of an elastic polydienurethane material. In this method of producing an elastic material, it was decided to abandon the use of glycerol (with different reactivity hydroxyl groups) and monofunctional 1Н, 1Н, 11Н-trihydroperfluorundecanoxy- (2Н-hydroxyethyl) -oligo-2-methyl-1- oxylidene) using instead of them the specified modifier - 1,1-bis (4-hydroxyphenol) -2,2,3,3,4,4,5,5,6,6,7,7-dodecafluoroheptane containing only primary hydroxyl groups . When the composition is cured, a network structure is formed containing fluorinated fragments (C-F) in the polymer backbone, which can effectively resist the damaging thermal and atmospheric effects on the “weak” sections of the polydienurethane chain. When mixing the components of the composition, this modifier (with a low surface tension) improves the wettability of the mineral filler with an oligomer, while being a chain extender in reactions with polymethylene polyphenyl polyisocyanate during the formation of a material based on polydienurethane. In addition, this modifier is not only a comonomer in the synthesis of polydienurethanes, but also acts as a reactive antioxidant for polydienurethane materials. The introduction of zinc oxide in the composition helps to reduce the negative effects of various atmospheric factors both during storage of the composition and directly during operation of the coating. The use of diatomite, which contains a significant amount of bound water (from 3-15 wt.%), Which has a developed surface and an alkaline reaction of aqueous extract, contributes to a more efficient combination of the bulk components used in the manufacture of this material and leading to an increase in physical and mechanical properties coverings. The use of the specified modifier - 1,1-bis (4-hydroxyphenol) -2,2,3,3,4,4,5,5,6,6,7,7-dodecafluoroheptane improves the sedimentation stability of the composition by increasing the adsorption interaction on the border "oligomeric binder-solid phase".

As the oligobutadiene diol, the composition uses a copolymer of butadiene and isoprene PDI-1K (TU 38.103342-88) with a monomer ratio of 70:30, a molecular weight of 3000-3500; the content of hydroxyl groups, wt.% 0.75-0.89 and oligobutadiene diols with a molecular weight of 2000-5000; a polydispersity index of 1.20-1.35; Brookfield viscosity, (Pa · s) (25 ° C) 8.5-22; the content of terminal hydroxyl groups,%, 0.7-1.7; microstructure,%, 1,4-cis-10-15, 1,4-trans 20-25, 1,2- (vinyl) 60-70; distribution by OH groups (RTF),% non-functional 2, monofunctional 6, bifunctional 92; density, (kg / m ³ ) 900-910 (oligobutadiene diols Krasol LBH manufactured by Sartomer).

The mineral fillers of the composition are powders of medium fineness, for example, chalk, lime-screenings, kaolin, talc.

2,4,6-tri-tert-butylphenol is a crystalline powder with a greenish-yellow tint, is soluble in hydrocarbons, and has the following characteristics: melting point 129-131 ° C, mass fraction of ash - not more than 0.05%. Obtained by alkylation of phenol with isobutylene in the presence of a catalyst. The trade name is antioxidant P-23 (TU 6-14-26-77).

Ethyl silicate (TU 6-02-895-86) is a mixture of esters of orthosilicic acid. It is a reaction product of ethyl alcohol with silicon tetrachloride. It has the following characteristics: density, (kg / m ³ ) - 955-990; mass fraction of silicon dioxide,%, 31-34; mass fraction of tetraethoxysilane,%, 50-60; optical density at a wavelength of 600 nm 0.3-0.4.

As the isocyanate component in the composition, polymethylene polyphenyl polyisocyanate is obtained, obtained by phosgenation of the condensation product of aniline with formaldehyde (TU 2224-152-04691277-96). The content of isocyanate groups 29.5-31 wt.%.

As the organotin catalyst, tin octoate and tin dibutyl dilauurinate (TU 6-02-818-78) are used, and other organotin compounds used for the synthesis of polyurethanes can be used.

Zinc oxide (GOST 202-84) is used as a hardener and filler.

Diatomite (TU 5761-001-25310144-99) is a light porous rock from white to yellowish-gray. The average density of diatomite ranges from 0.15 to 0.6 (g / cm ³ ). Diatomite for 96% consists of aqueous silica (opal) of the general formula SiO ₂ · nH ₂ O.

As the specified modifier was used 1,1-bis (4-hydroxyphenol) -2,2,3,3,4,4,5,5,6,6,7,7-dodecafluoroheptane (melting point 122-123 ° C) . It is a product obtained by the interaction of phenol with 2,2,3,3,4,4,5,5,6,6,7,7-dodecanofluoroheptanal.

The reaction was carried out in a solvent (trifluoromethyl-2-chlorobenzene) with the ratio: two and a half equivalents of phenol per equivalent aldehyde. This reaction proceeds under fairly mild conditions and is catalyzed not only by hydrochloric acid, but also by a cation exchange resin (sulfonated polystyrene resin) [US 3388097, NPK 528/191, 1968], [T. Zinke., "Uber die Einwirkung von Brom und von Chlor auf Phenol: Substitutionsproducte, Pseudobromide und Pseudochloride." Justus Liebigs Annalen der Chemie V 343; p.75-99, 1905].

Additives may be added to the composition to give other advantages to the coating material. As a component that ensures a reduction in the consumption of the composition for the manufacture of a unit of coating area, rubber crumb is used. To improve the appearance of the composition can be introduced pigments.

For the manufacture of the composition, mixing equipment is used to ensure a homogeneous suspension of the filler in the volume of the composition with a milling degree of solid particles of not more than 100 microns. Polymethylene polyphenyl polyisocyanate, zinc oxide and an organotin catalyst are supplied complete with the composition and added to it at the place of laying the coating. The crumb rubber is mixed into the composition before the introduction of the hardener.

The composition and properties of the composition are shown in tables 1 and 2.

Example 1. The introduction of the components of the composition is as follows. 100 g of Krasol oligobutadiene diol with a molecular weight of 2000% and a hydroxyl content of 1.7%, 2 g of the specified modifier, 50 g of chalk, 10 g of lime sifting, 0.1 g of tin octoate, 0, 5 g of 2,4,6-tri-tert-butylphenol, 0.8 g of ethyl silicate, 30 g of diatomite. The mixing of the components is carried out for 3 hours. To the resulting mixture was added 10 g of rubber crumb and stirred for 30 minutes, and then 20 g of polymethylene polyphenyl polyisocyanate, 20 g of zinc oxide were added and mixed again for 8 minutes. The resulting mass is poured into molds and incubated for 20-25 days at a temperature of 18-25 ° C.

Similarly, the compositions are prepared according to examples 2-10.

An example of a prototype. 100 g of Krasol oligobutadiene diol with a molecular weight of 2000% and a hydroxyl content of 1.7%, 5 g of glycerol, 15 g of a polysulfide oligomer - brand I thiol, 0.2 g of a modifying additive, 50 g of chalk, are loaded into a mixer with a 1 L volume of 1 liter, 10 g of lime screenings, 0.1 g of tin octoate, 0.5 g of 2,4,6-tri-tert-butylphenol, 0.8 g of ethyl silicate, 30 g of diatomite. The mixing of the components is carried out for 3 hours. To the resulting mixture was added 10 g of rubber crumb and stirred for 30 minutes, then 24 g of polyisocyanate, 20 g of zinc oxide were added and mixed again for 8 minutes. The resulting mixture is poured into molds and incubated for 20-25 days at a temperature of 18-25 ° C.

The coating samples are tested: physical and mechanical properties according to GOST 263-75, GOST 275-75, GOST 6950-73, GOST 2678-88, swelling in aggressive environments was determined according to GOST 2678-80, the dynamic modulus of elasticity and the tangent of the angle of mechanical loss are determined by the method single shock compression on a pendulum elastometer [Kuvshinsky EV, Sidorovich EA Pendulum elastometer KS. // Journal of Theoretical Physics, 1957. V.26 4, p.878-886. Sidorovich E.A., Kuvshinsky E.V. The study of shock compression of rubber. // Solid state physics. 1961 T.3. 11, p.3487-3494], ball rebound tests are performed according to DIN 18035, part 6 by determining the ratio of the ball rebound height from the coating compared to the concrete floor. The study of the behavior of materials at elevated temperatures was carried out by the differential thermal analysis method (using the Paulik-Paulik-Erdey instrument at a heating rate of 10 ° C / min in the temperature range 20-1000 ° C). Determination of sedimentation stability of the compositions was carried out according to GOST 10772-78.

As can be seen from tables 1 and 2, when the content of polymethylene polyphenyl polyisocyanate is less than 10 parts by weight strength properties of the coating are reduced. Exceeding the content of polymethylene polyphenyl polyisocyanate over 20 wt.h. leads to foaming of the composition.

Using less than 0.01 parts by weight Organotin catalyst leads to a decrease in the curing rate of the composition. When the content of the urethane catalyst is more than 1.10 parts by weight decreases the viability of the compositions.

When the concentration of the mineral filler is less than 60 parts by weight the strength properties of the coating material are reduced. The use of more than 100 parts by weight the amount of filler reduces the elongation of the cured material.

When the content of 2,4,6-tri-tert-butylphenol is less than 0.5 parts by weight the resistance of the coating to atmospheric aging is reduced. The use of 2,4,6-tri-tert-butylphenol in an amount of more than 1.5 parts by weight reduces the resistance to weathering.

The use of ethyl silicate in an amount of less than 0.8 wt.h. leads to a decrease in the dynamic performance of the coating. When using more than 1.6 parts by weight the amount of ethyl silicate decreases the strength properties of the coating.

When the concentration of zinc oxide is less than 10 parts by weight the strength properties of the coating material are reduced. Using more than 20 parts by weight the amount of zinc oxide leads to a decrease in the relative elongation of the cured material.

The use of diatomite in an amount of less than 20 wt.h. leads to a decrease in hardness of the coating. When the concentration of diatomite more than 30 parts by weight strength properties of the coating are reduced.

Table 1 Name of components Composition, parts by weight Prototype Pat. 2445755 one 2 3 four 5 6 7 8 9 10 Oligobutadiene Diol: OPDI-1K - - one hundred one hundred - - - - - - - Krasol LBH one hundred one hundred - - one hundred one hundred one hundred one hundred one hundred one hundred one hundred ineral filler: - a piece of chalk fifty - - 80 90 one hundred - - - 80 fifty - lime screenings 10 - - twenty - - - - - twenty 10 - kaolin - one hundred - - - - one hundred - one hundred - - - talc - - one hundred - - - - 60 - - - Glycerol - - - - - - - - - - 5 Polysulfide oligomer - - - - - - - - - - fifteen The specified modifier 2 2 2 3 3 3 1,0 1,5 3,5 3,5 0.2 Tin Octoate 0.1 0.01 - - 0.05 - 0.10 - - - 0.1 Tin Dibutyl Dilaurate - - 0,03 1.10 - 0.05 - 0.15 0.01 1,5 - 2,4,6-tri-tert-butylphenol 0.5 1,0 1,5 1,0 0.5 1,0 0.25 2.0 1,0 1,0 0.5 Ethyl silicate 0.8 1.3 1,6 0.9 1.4 0.8 0.4 2,5 1,5 1,6 0.8 Rubber crumb 10 - 10 - 10 - - - - - 10 Pigment green M - 5 - 7 - - - - 5 5 - Polymethylene Polyphenyl Polyisocyanate twenty eighteen 16 fourteen 10 twenty 6 8 twenty 25 24 Zinc oxide twenty fifteen fifteen 10 10 twenty 5 25 fifteen twenty twenty Diatomite thirty twenty thirty 25 twenty 25 fifteen 5 fifty 40 thirty Note: 1. The molecular weight / content of hydroxyl groups (%) of oligobutadiene diol Krasol LBH in the examples is: in example 1, 2 and the prototype 2000 / 1.70; in example 5, 6, 10 - 4000 / 0.85; in example 7, 5000 / 0.70; in example 8, 9 - 1500 / 2.30; in example 3, 4 - PDI-1K - 3000 / 0.8. 2. As the specified modifier in examples 1-10, 1,1-bis (4-hydroxyphenol) -2,2,3,3,4,4,5,5,6,6,7,7-dodecafluoroheptane is used, in the prototype modifying additive is 1H, 1H, 11H-trihydroperfluoroundecanoxy- (2H-hydroxyethyl) -oligo-2-methyl-1-oxylidene. 3. As a plasticizer in the prototype used glycerin.

table 2 Coverage Ratios Indicator values Prototype Pat. 2445755 one 2 3 four 5 6 7 8 9 10 The amount of solid phase in the sample,% 93 91 90 89 78 71 66 69 80 73 90 Shore A hardness, arb. 79 76 72 69 59 64 52 47 58 55 79 Conditional Strength, MPa 3.3 3,1 3.0 2.6 1.9 2,4 1,6 1.8 2.0 1,6 3.4 Relative extension, % 220 225 230 235 235 245 255 220 230 245 225 Bounce Elasticity,% 56 54 51 49 39 43 37 34 43 46 59 Dynamic modulus of elasticity, MPa 6.7 6.1 5.7 5.8 4.1 4.6 2,5 3,7 3.9 4.0 6.8 Mechanical loss tangent 0,092 0,098 0.107 0.114 0.150 0.134 0.158 0.172 0.134 0.124 0,094 Basketball Rebound,% 122 117 113 107 93 101 79 101 109 106 125 Bounce the tennis ball,% 121 114 110 104 90 98 76 93 103 one hundred 123 Water absorption,% 1,0 1.3 1,6 1.9 2.9 2,3 3,5 3.9 4,5 4.0 - Swelling in an acidic environment,% 0.9 1,2 1,6 2,3 2.9 2,5 3,1 4.0 4.3 4.1 - Alkaline swelling,% 0.6 0.8 1,0 1,2 2.0 1,6 2.2 2.7 3.0 2.6 - Temperature before loss, mass, ° C 320 315 285 270 235 255 240 250 275 250 -

When the concentration of the specified modifier is less than 2 wt.h. reduced thermal and aggressive resistance, physico-mechanical and dynamic properties of the material, as well as sedimentation stability of the composition. Using more than 3 parts by weight the amount of modifier leads to an increase in the consumption of the isocyanate component.

Thus, the proposed composition is characterized by increased sedimentation stability and allows to obtain thermo- and aggressive-resistant elastic coatings while maintaining the level of dynamic and physico-mechanical characteristics in comparison with the prototype.

Claims (1)

Coating composition comprising oligobutadiene diol, mineral filler, polymethylene polyphenyl polyisocyanate with an isocyanate content of 29.5-31.0 wt.%, An organotin catalyst and 2,4,6-tri-tert-butylphenol, ethyl silicate, zinc oxide, diatomite, modifier, characterized in that 1,1-bis (4-hydroxyphenol) -2,2,3,3,4,4,5,5,6,6,7,7-dodecafluoroheptane of the following formula is used as a modifier:

in the following ratio of components, parts by weight:
Oligobutadiene diol one hundred Mineral filler 60-100 Polymethylene Polyphenyl Polyisocyanate 10-20 Organotin catalyst 0.01-1.10 2,4,6-tri-tert-butylphenol 0.5-1.5 Ethyl silicate 0.8-1.6 Zinc oxide 10-20 Diatomite 20-30 The specified modifier 2-3