RU2700684C1 - Polymer two-component composition - Google Patents

Abstract

FIELD: chemistry.

SUBSTANCE: invention relates to organometallic chemistry and chemical industry. Described is a polymer two-component composition for making heat-resistant materials and coatings. Two-component composition contains the first component – dicyclopentadiene in form of a colorless or yellowish hue of the liquid and the second component is a finely dispersed powder of Grubbs catalysts of pink color, dissolved in an organic solvent. Solvent is selected from phenylethyl and benzyl alcohol.

EFFECT: increased durability and reliability of surface coating of parts made from two-component composition during their operation, storage and transportation, as well as simplification of technology, ecological compatibility of its manufacturing and reduction of prime cost.

3 cl, 2 tbl, 7 ex

Description

FIELD OF THE INVENTION

The invention relates to organometallic chemistry and the chemical industry, in particular, to a method for combining the ingredients of a two-component polymer composition Rutepol ^® , intended for the production of polydicyclopentadiene for the subsequent manufacture of thermoacid-resistant materials and coatings with high physical and mechanical properties used for lining equipment, or to protect various containers premises from exposure to aggressive environments.

The level of development of the field of technology

Known polymer compositions WO 2011005136, RU No. 2404072, 2465286, 2527278, based on dicyclopentadiene and the polymerization of the reaction mass.

In particular, compositions are known containing up to 99.8 wt. % polydicyclopentadiene, from 0.05 to 0.99 wt. % of an antioxidant selected from the group: sterically hindered phenols, phenol derivatives, sterically hindered amine bases, from 0.05 to 0.99 wt. % saturated or unsaturated elastomer, from 0.000018 to 0.00010 wt. % of the catalyst, the remaining amount of material is made up of modifying additives, which can be contained either individually or together in the form of their various combinations, while the modifying additives are selected from group A) cyclopentene, cyclooctene, cyclooctadiene, norbornene, norbornadiene; B) trimers and / or tetramers of cyclopentadiene; C) dyes; D) compounds that change the activity of the catalytic system, selected from the group: amines, phosphines, phosphites, phosphoramides, organoaluminum compounds; E) fillers selected from the group: chopped glass or carbon filaments with a diameter of 6 to 17 μm and lengths of segments from 4 to 24 m, as well as structural glass, carbon and basalt fabrics with a thickness of 0.20 and 0.87 mm and specific mass from 250 to 900 g / m ² ; E) multi-walled carbon nanotubes with the number of walls from 2 to 20 and a diameter of from 7 to 30 nm. (RU No. 2465286).

Known polymer composition, which is a composite material based on polydicyclopentadiene, including a silicon-containing inorganic filler and a polymer matrix containing polydicyclopentadiene, characterized in that it includes a silicon-containing sizing agent, which is used as the following compounds or mixtures thereof: vinyltrimethoxysilane, vinyl-tris (2- ) silane, 3-methacryloxypropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-thiopropyltrialkoxysilane, 5-trialkoxysilyl-2-norbornene, N- [3- ( rimetoksisilil) propyl] -N '- (4-vinylbenzyl) ethylenediamine hydrochloride, wherein the composite material has the following composition:

silicon-containing inorganic filler - from 5.0 to 86.5% of the mass; polymer matrix - from 12.0 to 94.998% of the mass; organosilicon sizing - from 0.001 to 1.5% of the mass, and the organosilicon sizing is chemically bound to the filler and the polymer matrix, which is obtained from the following composition:

- dicyclopentadiene not less than 98% purity in an amount of from 33.0 to 99.3% of the mass;

- polymer modifier - from 0.499 to 60.0% of the mass;

- radical initiator - from 0.1 to 4.0% of the mass;

- polymer stabilizer - from 0.1 to 2.98% of the mass;

- catalyst (RU No. 2527278)

A known polymer composition for producing polydicyclopentadiene, comprising a solution of the catalyst in dicyclopentadiene and polymerizing the reaction mixture, where dicyclopentadiene is mixed with the catalyst at molar ratios of the catalyst and dicyclopentadiene from 1: 70,000 to 1: 1,000,000, and the polymerization is carried out by heating the reaction mixture from 30 to 200 ° C. . The introduction into the solution of modifying additives and polymerization of the reaction mass (RU No. 2402572, prototype).

The disadvantages of the known compositions are due to the fact that they do not provide thermochemical resistance and durability in the manufacture of parts, which complicates their use, for example, for the manufacture of a plating bath. It is difficult or impossible to manufacture bathtubs without seams and / or folds.

The technical problem solved in accordance with the present useful invention is the creation of a technological composition for the manufacture of thermochemically resistant seamless bath parts, an expansion of the arsenal of compositions for the manufacture of parts for

galvanization of metal objects.

The technical result, which allows to solve the problem, is to increase the durability and reliability of the parts of the claimed composition during their operation, storage and transportation, mainly by ensuring high thermochemical resistance of the part: operating temperature up to 120 ° C, resistance up to 99.9% to various acid, 50% sulfuric acid, low moisture absorption of 0.05%, the allowable collision load during a free fall of 600 kg, the dielectric strength of 10.5 kW mm, surface resistivity of 3 × October ¹² th, and manufacturing details and reduced remission technology and environmental

cost price.

SUMMARY OF THE INVENTION

The essence of the invention lies in the fact that the polymer two-component composition contains the first component, which is a modified solution of dicyclopentadiene in the form of a colorless or yellowish tinge of liquid with a characteristic odor, and the second component, which is a fine powder of pink Grabbs catalysts, for dissolution in organic solvent, mainly in alcohol from the group: phenylethyl alcohol, benzyl alcohol, before mixing with the first component ..

Preferably, the first component, dicyclopentadiene, has a density of 0.99-1.01 g / cm ³ , a flash point of at least 45 ° C in a closed crucible, a boiling point of at least 17 0 ° C, and a self-ignition temperature of at least 468 ° C.

Preferably, the first component is dicyclopentadiene, contains antioxidant additives, functional additives.

Preferably, the first component, dicyclopentadiene, contains pigments or pigment pastes.

Preferably, the first and second component are selected with the possibility of reaction between them with a filler - silica flour, at room temperature 18-20 ° C, followed by curing.

Description of the invention

The two-component polymer composition consists of two main components: the first component is a modified solution of dicyclopentadiene in the form of a colorless or yellowish liquid with a characteristic odor, and the second component is a finely dispersed pink Grubbs catalyst powder, for dissolution in an organic solvent, mainly in alcohol from

groups: phenylethyl alcohol, benzyl alcohol, before mixing with the first component (A).

The first component - dicyclopentadiene has a density of 0.98-1.03 g / cm ³ , a flash point of at least 45 ° C in a closed crucible, a boiling point of at least 170 ° C, and a self-ignition temperature of at least 468 ° C.

The first component - dicyclopentadiene, contains antioxidant additives, functional additives.

The first component is dicyclopentadiene, which may contain pigments or pigment pastes, as well as fillers.

The first and second components are selected with the possibility of reaction between them with a filler - silica flour, at room temperature 18-20 ° C, followed by curing.

The second component (B) is a fine powder of pink Grabbs catalysts), which is dissolved in an organic solvent, mainly in alcohol from the group: phenylethyl alcohol, benzyl alcohol, before mixing with the first component (A).

It is possible to add filler in an amount of up to 50% of a mixture of components A and B, for example, in the form of quartz flour - marshalite. Marshalit (dusty quartz) - a finely divided mineral filler, produced on the basis of natural raw materials, contains at least 98% SiO ₂ .

The technology is greatly simplified due to the fact that, as a result of the dissolution of the Grubbs catalyst in an organic solvent, mainly in alcohol from the group: phenylethyl alcohol, benzyl alcohol, before mixing with component A, the components A and B react at room temperature 18-20 ° C, followed by curing.

Rutepol ^{® is} supplied as a two-component composition, one component of which is a modified solution based on dicyclopentadiene (Component A is a colorless or yellowish liquid with a characteristic odor, density 0.98-1.03 g / cm ^3. Flash point at least 45 ° C in a closed crucible, boiling point not lower than 170 ° С, autoignition temperature not lower than 468 ° С.

The main substance is dicyclopentadiene, contains antioxidant additives, functional additives, may contain pigments or pigment pastes.),

Component B is a fine powder of pink Grabbs catalysts), which is dissolved in an organic solvent, mainly in alcohol from the group: phenylethyl alcohol, benzyl alcohol, before mixing with component A.

The reaction of components A and B occurs at room temperature 18-20 ° C, followed by curing.

Structure

Component A is a colorless or yellowish liquid with a characteristic odor. The main substance is dicyclopentadiene, contains antioxidant additives, functional additives, may contain pigments or pigment pastes, finely divided fillers.

Component B - catalyst, is a fine pink powder.

Brief manufacturing technology

Only a solution is made. Dicyclopentadiene is heated in a container at a temperature of 40-45 ° C to a fluid state, and then poured into hermetically sealed containers (cans) with already dosed solvents, antioxidants, functional additives, and pigments.

The catalyst is used ready to use. The necessary amount is weighed in proportion to the solution. Before direct mixing with component A, the catalyst must be dissolved in one of the solvents from the alcohol group.

The polymerization can be carried out with a finely divided filler, for example, quartz flour (marshalite).

The Grubbs process is a metathesis of olefins using Grubbs catalysts.

Grubbs catalysts - are a series of transition metal complexes used for the catalytic metathesis of olefins.

Olefins are hydrocarbon molecules containing a double bond in the carbon skeleton.

The olefin metathesis is a chemical reaction during which, with double bonds of alkenes participating in the reaction, the substituents are redistributed.

The metathesis polymerization of dicyclopentadiene - dicyclopentadiene with the help of Grubbs catalysts is polymerized to polydicyclopentadiene.

A promoter is a substance added to a catalyst in small amounts in order to improve its properties, such as activity, selectivity or stability.

Grubbs catalysts are dissolved in alcohols in a certain ratio and are used for the metathesis polymerization of dicyclopentadiene. ALCOHOL - a class of organic compounds containing one or more C — OH groups, while the hydroxyl group of OH is bonded to an aliphatic carbon atom.

The reaction occurs at room temperature 18-20 ° C. Some alcohols (phenylethyl, benzyl), when dissolved in them, the Grubbs catalyst act as promoters and accelerate the polymerization process. In addition, the Grubbs catalyst dissolved in some alcohols retains its properties longer than with other solvents.

Grubbs catalyst is called ruthenium organometallic catalysts exhibiting high reactivity in a variety of processes (ROMP, RCM, ADMET) and high tolerance to a variety of functional groups.

Ruthenium catalysts show low sensitivity to air, moisture and minor impurities in solvents. These catalysts can be stored for several weeks in air without decomposition. Often reactions with Grubbs type catalysts are slightly slower than with molybdenum ones, but their availability and ease of manufacture make them the most convenient for use in most cases, except for the most complex ones.

Application area

The composition is intended for the manufacture of heat and acid resistant products (based on heat and acid resistant

polymer), in particular, coatings, lining of equipment, hydrolysis baths, manufacturing of parts and products with high physical and mechanical properties.

The characteristics of the first component are shown in table 1

Examples of the manufacture of polymers Rutepol ^®

Example 1

Take 50 g of the composition Rutepol ^® and add 10 mg of dissolved Grubbs catalyst (200 mg / 100 g). Stirred for 30-60 seconds and placed in a mold. Polymerization starts at room temperature. After 30 minutes, the mixture smokes and polymerizes. After cooling, a solid transparent sample of polydicyclopentadiene (Rutepol ^® ) is light yellow in color.

Example 2

Take 50 g of the composition Rutepol ^® and add 10 mg of dissolved Grubbs catalyst (200 mg / 100 g). Stirred for 30 seconds. Add 20 g of silica flour (40%) and mix until smooth. Put in shape. Polymerization starts at room temperature. After 30 minutes, the mixture smokes and polymerizes. After cooling, a solid two-layer sample of polydicyclopentadiene (Rutepol ^® ) with an upper transparent layer of Rutepol ^® and a lower gray-brown layer of Rutepol ^® with a high content of silica flour is obtained.

Example 3

Take 50 g of the composition Rutepol and add 0.15 g (0.3%) of the thickener BYK 410. Stir for 20-30 seconds. Then add 10 mg of dissolved Grubbs catalyst (200 mg / 100 g) and mix for another 30 seconds. Add 20 g of silica flour (40%) and mix until smooth. Put in shape. Polymerization starts at room temperature. After 30-40 minutes, the process of smoke and polymerization begins. After cooling, a homogeneous gray-brown sample of polydicyclopentadiene (Rutepol ^® ) with quartz flour is obtained.

Example 4

Take 50 g of the composition Rutepol ^® , add 0.15 g (0.3%) of carbon black and mix until the mixture is homogeneous. Then add 10 mg of dissolved Grubbs catalyst (200 mg / 100 g) and mix for 30-60 seconds. Put in shape. Polymerization starts at room temperature. After 30 minutes, the process of smoke and polymerization begins. After cooling, a solid sample of black polydicyclopentadiene (Rutepol ^® ) is obtained.

Example 5

Take 50 g of the composition Rutepol ^® and add 10 mg of dissolved Grubbs catalyst (200 mg / 100 g). Stirred for 30 seconds.

Add 15 g of micromarble (30%) and mix until smooth. Put in shape. Polymerization starts at room temperature. After 30-40 minutes, the process of smoke and polymerization begins. After cooling, a uniform white sample of polydicyclopentadiene (Rutepol ^® ) with micromarble is obtained. Such a sample is slightly inferior in hardness to other samples.

Example 6

Take 50 g of the composition Rutepol ^® and add 0.15 g (0.3%) of the additive-thickener BYK 410. Stirred for 20-30 seconds. Then add 10 mg of dissolved Grubbs catalyst (200 mg / 100 g) and mix for another 30 seconds. Add 10 g of microspheres (20%) and mix until a homogeneous mass. Put in shape. Polymerization starts at room temperature. After 30-40 minutes, the process of smoke and polymerization begins. After cooling, a gray homogeneous sample of polydicyclopentadiene (Rutepol ^® ) with microspheres and a density of less than 1 is obtained.

Example 7

Take 50 g of the composition Rutepol ^® and add 1.5 g (3%) of bitumen-rubber mastic and mix until a homogeneous mass is obtained. Then add 10 mg of dissolved Grubbs catalyst (200 mg / 100 g) and mix for 30-60 seconds. Put in shape. Polymerization starts at room temperature. After 30 minutes, the process of smoke and polymerization begins. After cooling, a solid homogeneous sample of dark brown polydicyclopentadiene (Rutepol ^® ) is obtained.

The results of determining the mechanical properties under compression (protocol No. IL “IK CTO” / 625-2018) of the Rutepol ^® material manufactured according to Example 1 are shown in Table 2: tensile strength (and temporary or ab), elastic limit, yield strength, elastic modulus .

The surface of parts made of polydicyclopentadiene obtained from a two-component polymer composition is obtained without foreign inclusions, delaminations and cracks.

The two-component polymer composition provides the product made of Rutepol ^® material with the proper performance indicators (strength, low thermal and electrical conductivity, resistance to aggressive environments, durability, low combustibility).

In addition, the product can be made in a wide range of colors.

Using the present invention allows to increase the durability and reliability of the surface coating of parts made from the inventive composition during their operation, storage and transportation, as well as simplifying the technology, environmental friendliness of its manufacture and cost reduction.

Claims (3)

1. A two-component polymer composition for the manufacture of thermally acid-resistant materials and coatings, containing two components, where the first component is dicyclopentadiene in the form of a colorless or yellowish tint of the liquid, and the second component is a finely dispersed pink Grabbs catalyst powder dissolved in an organic solvent, which is an alcohol from the group: phenylethyl alcohol, benzyl alcohol. 2. The composition according to claim 1, characterized in that the first component further comprises a pigment. 3. The composition according to claim 1, characterized in that it further comprises a silica flour filler.