Composition for production of polymeric structural materials based on polyisocyanurates

FIELD: chemical industry; production of polymeric structural materials from hermosetting compositions based on polyisocyanurates.

SUBSTANCE: the invention is pertaining to the field of chemical industry, in particular, to production of polymeric structural materials from thermosetting compositions based on polyisocyanurates. The offered composition for production of the polymeric structural materials contains 100 mass % of a low-molecular quick-tenacious polymer with the terminal hydroxyl groups, 22.5-400 mass % of aromatic diisocyanate, 0.08-20 mass % of dimethylbenzylamine, 0.8-20 mass % of epoxydiane resins, 55-30 mass % of acetone, 2.0-22.5 mass % of a high-porous polymeric filler. At that in the capacity of the indicated polymeric filler they use a flexible polyurethane foam or a synthetic felt material (sintepone - synthetic winterizer). From the indicated composition by an industrial method for a short cycle of hot pressing produce polymeric items with a gradient modulus of elasticity (in any given direction) from 3 up to 2000 MPa. At that the material saves its elastic properties at any value of the modulus in the interval of temperatures from -50 up to 120°C, and may be used in shoe industry and tire industry, instrument-making industry and radio industry.

EFFECT: the invention allows to produce polymeric items with a gradient modulus of elasticity in any given direction within 3 up to 2000 Mpa, the material saves its elastic properties at any value of the modulus at temperatures of -50 °C up to 120°C.

3 cl, 5 ex, 1 tbl

 

The invention relates to the field of polymeric structural materials, and more specifically to receive these reinforced materials of thermosetting compositions based polyisocyanurate with arbitrarily adjustable elastic modulus in a continuous range from 3 to 2000 MPa.

The invention can most effectively be used in the production of various configuration items, in which no welding, gluing, and other known methods of joining parts is achieved by obtaining a monolithic seamless design with sharp or smooth, linear or non-linear gradient elasticity modulus and having elastic properties for any values of the modulus in the range of from 3 to 2000 MPa. This can be the production of rollers and gears, working silently in the Shoe industry to create a comfortable shoes, in which tensile forces perceives the rubbery part of the gradient material, and compression - plastic (hard) part. The materials can also function as shock absorbers, gaskets, membranes, easily mounted on the periphery. The invention can be used in the radio, in the instrument by replacing existing support different hardware.

Known composition [USSR Author's certificate No. 1558941 (1990), C 08 L 75/04. Publ. 23.04.1990. Bulletin no.15. “Composition of polii is ocianydata”, authors: Askadskii A., Pankratov, VA, Frenkel CM and others], including silicone carbofunctional diisocyanate and the catalyst is a tertiary amine in combination with alpha-oxide as socializaton when the following components in parts by weight:

silicone carbofunctional diisocyanate 100

the tertiary amine is 0.1-0.2

alpha-oxide 1.0 to 1.5

The materials obtained on the basis of this composition by the method of block-type thermal polymerization, have a modulus of elasticity of from 75 to 1700 MPa. Regulation of modulus of elasticity in these compositions is achieved by changing the molecular weight of the organic diisocyanate derived from Monomeric products with multistep synthesis, which includes the obligatory processing of intermediate and final products of different methods. The synthesis is carried out on a laboratory scale.

However, thermodynamic incompatibility of silicon carbofunctional diisocyanate, aromatic diisocyanates leads to phase separation of the composition in the polymerization process. This leads to the impossibility of obtaining low-modulus elastic polymers (with modulus less than 75 MPa) and with a continuous gradient of the modulus of one of the linear dimensions.

Known composition to obtain polyisocyanurate [Putin the Russian Federation No. 2061708 (1993), C 08 G 9/00 C 08 L 9/00. Epubl, bull.№16. “Composition of polyisocyanurates for polymer material with a given modulus of elasticity”, authors: Askadskii A. V. Pankratov, Svorak VA, Bychko K.A. and others], including low-molecular-weight flexible-chain polymer with terminal hydroxyl groups and a molecular weight (M) 1000-2500, an aromatic diisocyanate and an amine curing catalyst type in combination with alpha-oxide as socializaton in the following ratio of components, parts by weight:

aromatic diisocyanate 100

flexible-chain low-molecular polymer 17-517

the curing catalyst is 0.05 to 0.3

socialization 0,5-6

Additionally according to claim 2, the composition may contain fibrous and/or powdered mineral filler in the following ratio of components, parts by weight:

aromatic diisocyanate 100

low molecular weight rubber 17-517

the curing catalyst is 0.05 to 0.3

socialization 0,5-6

filler 1,3-10,0

Materials on the basis of this composition have a modulus of elasticity of from 3 to 2000 MPa, and they retain the elasticity in the temperature range from -50 to 100°C.

As the closest to the technical essence, this composition is chosen as a prototype.

The disadvantages of the composition of the prototype are related to the fact that when using net polyisocyanurate polymers in the form of a monolith with h is discontinuous gradient of the modulus of elasticity of from 3 to 2000 MPa obtained after pouring the composition in a sealed form in process block thermal polymerization, through progressive multiple heating from room temperature to the final 160-200°C. due to the high viscosity of the low molecular weight flexible-chain polymer composition in the preparation it is necessary to heat and stir in vacuum or fill composition in the form to combine with simultaneous vacuum to eliminate foaming. The duration of the heat treatment increases the volume of the polymerizing mass. This is because the process of polycyclotrimerisation due ekzotermicheskie reaction is accompanied by a noticeable dissipation, proportional to the volume of the polymerizing mass. This can lead to uncontrolled rise in temperature and acceleration of adverse reactions affecting the solidity obtained in the form of a block polymer, its structure and properties [Ski, Lmigateway, Caicco. Polymer sciense ser. Conn. A. V.37. No. 5. S]. Shrinkage due to leaking chemical process, and a thermal shrinkage accompanying the process, causing the formation of shrink holes on the surface of the polymer. From such a composition of the prototype can not be obtained structural polymeric materials with modulus greater than 1000-1200 MPa, because of cross-linked structure, it will become brittle and break easily under load. is therefore to reduce the brittleness of the solid polyisocyanurate in the patent prototype in claim 2 in composition to impose a fine powder or fibrous fillers in very small quantities (1.3 to 10 parts by weight). Thus deteriorate the technological parameters of the composition due to the sharp increase in its viscosity, and the conditions of transformation into a finished polymeric material essentially does not change. As a result, the process becomes even more cumbersome. These factors combined with high adhesion of the composition of the prototype to the traditional materials of which these forms are usually made, was the cause that produced from materials not found still practical application.

The purpose of this invention is to provide compositions for the preparation of polymer composite materials on the basis of polyisocyanurate with arbitrarily adjustable elastic modulus in compression in the range from 3 to 2000 MPa, which you can get more technological way and to process into finished products of any given shape by the industrial way of hot pressing. However, they retain polyisocyanurate polymers specified range of elastic moduli and have better physical and mechanical properties.

This object is achieved in that the composition for polymeric structural materials with arbitrarily adjustable elastic modulus in compression in the range from 3 to 2000 MPa on the basis of polyisocyanurate consisting of nizkomolekulyarnogo flexible-chain polymer with integral Hydra is cellname groups and a molecular weight of from 1700 to 2200, aromatic diisocyanate, catalyst - dimethylbenzylamine in combination with epoxygenase resin as socializaton contains additionally a highly porous polymeric media and acetone in the following ratio of components in parts:

flexible-chain low-molecular polymer with terminal hydroxyl groups 100

aromatic diisocyanate 22,5-400

dimethylbenzylamine of 0.08 to 2.0

epoxygenase resin 0,8-20

acetone 55-30

highly porous polymeric media 2,0-22,5

As a highly porous media using flexible polyurethane foam in the following ratio of components, wt. including:

flexible-chain low-molecular polymer with terminal hydroxyl groups 100

aromatic diisocyanate 22,5-400

dimethylbenzylamine of 0.08 to 2.0

epoxygenase resin 0,8-20

acetone 55-40

flexible polyurethane foam 3,5-10

In another case, as a highly porous polymer carrier used synthetic felt material in the following ratio of components, wt. including:

flexible-chain low-molecular polymer c terminal hydroxyl groups 100

aromatic diisocyanate 22,5-400

dimethylbenzylamine of 0.08 to 2.0

epoxygenase resin 0,8-10

acetone 55-30

synthetic felt material 2,0-22,5

As low-molecular-weight flexible-chain polymers is sportsouth:

the copolymer of propylene oxide and tetrahydrofuran with M 1700, butadiene rubber with terminal hydroxyl groups, and M 2000-2500 or polypropyleneglycol with 2000-2200 M.

As the aromatic diisocyanate use of 2,4-toluenediisocyanate, 4,4' - diphenylmethanediisocyanate.

As epoxygenase resin using a low molecular weight oligomer-based epichlorohydrin and 4,4'-diphenylolpropane with the content of epoxy groups of 20-22%.

Used in the inventive compositions elastic polyurethane foam stamps-e has an open-cellular structure, the apparent density of 25-30 kg/m3and porosity of 97.8%vol.

As a highly porous felted media use synthetic felt on the basis of polyethylene terephthalate fibers (polyester)having an apparent density 50-6 kg/m3and porosity 95-99,6%vol.

The essential difference between the claimed composition from the known is in the presence of it in a small amount of elastic polymer carrier. Its special feature is the high open porosity greater than 95 vol.%. It determines the ability of the media to absorb and retain in such a large quantity of the reaction composition, its presence has no effect on the elastic-deformation properties from the polymer material. The media is used for is to keep the composition with the to transfer it to the mold. The reaction of formation of reticulate polymer polyisocyanurate structure ends quantified directly in a closed mold in a short cycle hot pressing.

The claimed composition allows industrial way in a short cycle hot pressing to produce polymer products necessary structures in which on any given direction modulus of elasticity varies smoothly or abruptly in any range from 3 to 2000 MPa. This material retains elasticity and not viscoelasticity at any value of the modulus in the temperature range from -50 to 120°C.

Use of the claimed compositions containing highly porous polymeric media, significantly reduces the process of obtaining construction materials on the basis of polyisocyanurate with freely adjustable in the range from 3 to 2000 MPa modulus of elasticity, eliminates the fragility inherent in the high modulus polyisocyanurates, and allows us to give a qualitatively new characteristics of polymeric structural materials. Achieved when using the proposed composition of the simplicity of the process design production of making real their practical use in various industries, such as footwear, tire, radio industry, instrument-making./p>

Composition to obtain a polymer-based materials polyisocyanurate continuous and smoothly varying elastic modulus in the range of from 3 to 2000 MPa and processed into products by hot pressing is prepared as follows:

1) low Molecular weight polymer with terminal hydroxyl groups is dissolved in acetone, mixed with 2.2-fold molar excess of an aromatic diisocyanate for 4 hours at 56°; add a curing catalyst, obtained a preliminary mixing of dimethylbenzylamine and epoxygenase resin, and

stirred for further 1 hour at 56°C. Receive a so-called "elastic" composition.

2) a low Molecular weight polymer with terminal hydroxyl groups is dissolved in acetone, mixed with excessive in relation to equimolecular amount of aromatic diisocyanate for 4 hours at 56°; add a curing catalyst, obtained a preliminary mixing of dimethylbenzylamine and epoxygenase resin, and stirred for further 1 hour at 56°C. Receive a so-called "hard" song.

3) highly porous media in the procurement of the necessary forms are placed in vertical form. The composition is placed in dispensers mixer specially designed installation, allowing you to mix and simultaneously adjusted continuously against the sustained fashion the ratio of "flexible" and "rigid" in the total composition, fill in the form. As a result, the composition changes gradually in height from "hard" with excessive content of the diisocyanate to the "elastic" with excessive content of low molecular weight polymer. After soaking in the solution for 5-10 min raw prepreg is dried at 60-70°C for 1-4 hours, placed in a mold and pressed at 150°S, specific pressure of 200-250 kg/cm2aged for 1-3 min per 1 mm thickness of the product.

The specific formulations of the inventive compositions and properties of the obtained materials is given in the table. In example 3, the characteristic of the material obtained outside of the claimed method, which shows that: when using media with porosity 87,7% vol. the order increases the elastic modulus in compression.

The curves of stress relaxation for materials obtained shows that for any values of modulus of elasticity in the whole range of mechanical behavior in all directions is elastic characteristic of polymer glasses.

1. The composition for polymeric structural materials based polyisocyanurate consisting of low-molecular-weight flexible-chain polymer with integral hydro is strong groups and a molecular weight of from 1700 to 2200, aromatic diisocyanate, catalyst - dimethylbenzylamine in combination with epoxygenase resin as socializaton, characterized in that it further comprises a highly porous polymeric media and acetone in the following ratio of components, parts by weight:

flexible-chain low-molecular polymer with terminal hydroxyl groups 100

aromatic diisocyanate 22,5-400

dimethylbenzylamine of 0.08 to 2.0

epoxygenase resin 0,8-20

acetone 55-30

highly porous polymeric media 2,0-22,5

2. The composition according to claim 1, characterized in that as a highly porous media using flexible polyurethane foam in the following ratio, wt. including:

flexible-chain low-molecular polymer with terminal hydroxyl groups 100

aromatic diisocyanate 22,5-400

dimethylbenzylamine of 0.08 to 2.0

epoxygenase resin 0,8-20

acetone 55-40

flexible polyurethane foam 3,5-10

3. The composition according to claim 1, characterized in that as a highly porous media using synthetic felt material in the following ratio, wt. including:

flexible-chain low-molecular polymer c end

hydroxyl groups 100

aromatic diisocyanate 22,5-400

dimetilan the ylamine 0,08-2,0

epoxygenase resin 0,8-10

acetone 55-30

synthetic felt material 2,0-22,5



 

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2 cl, 1 tbl, 3 ex

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6 ex, 1 dwg

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6 ex, 1 dwg

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6 dwg, 2 tbl, 6 ex

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