The method of obtaining mdi and composition for polymeric materials

 

(57) Abstract:

The invention relates to methods for producing polyisocyanates used for various polymeric materials, as well as to compositions based on polyisocyanates. Describes how to obtain the MDI by blowing air containing between 0.01 and 0.1% by volume of ammonia, a mixture of polyvinylpolypyrrolidone, which is the product of vosganian mixture of polyvinylpolypyrrolidone followed by the separation of the main part of the phosgene, hydrogen chloride and solvent, at atmospheric pressure and temperatures up to 180C. Also describes a composition for polymeric materials, including 100 wt.h. MDI obtained above, and 40-230 wt.h. of toluene. Processing MDI in accordance with the specified method allows to obtain a product that does not contain volatile toxic substances, in particular of phenylisocyanate, and related, therefore, to the fourth class of epinasty according to GOST. Coatings on the basis of the proposed compounds have a good decorative and mechanical properties, resistant to water, acids, alkalis, petroleum products and have good frost resistance. The company is soda - more 1416 h, a diesel oil - more than 2 years. Water absorption is not more than 0.2% at an exposure of 30 days, and the compressive strength reaches to 13.2 MPa. 2 AD. and 2 C.p. f-crystals.

The invention relates to methods for producing polyisocyanates used for various polymeric materials, and to compositions based on polyisocyanates to produce polymeric materials.

Known methods for producing polyisocyanates, including vosganian mixture of polyvinylpolypyrrolidone in the solution and separation of the phosgene, hydrogen chloride and solvent from the resulting mixture of polyvinylpolypyrrolidone (Production and consumption of the isocyanate abroad. Obsorn. INF. Series: Attn. prom., M: Niitekhim, 1980). This mixture is often referred to as simply "polyisocyanate" (of PERSONS), "crude MDI", "polymeric MDI", then used to produce a variety of polyurethane materials directly or after the distillation of a mixture of parts contained 4,4’-diphenylmethanediisocyanate (DHS).

A method of obtaining MDI, including vosganian mixture of polyvinylpolypyrrolidone, Department of phosgene, hydrogen chloride and solvent from the resulting mixture polyphenylenevinylene is the atur 160-200C, mainly under vacuum at a residual pressure of 100-300 mm RT.article (GB 1362708, 2, 1974). Thanks to this processing with subsequent overheating up to 180-C and rapid cooling to a temperature below 100C, it is possible to reduce the content in PIZ unwanted contaminants - substances containing ionic and hydrolyzable chlorine that allows you to successfully use the CRPS for most of polyurethane materials. There are, however, ways of using isocyanates to obtain, for example, different coatings and building materials that require the use of products with different properties than PIZ obtained by known methods.

Known methods for producing such products, including vosganian mixture of polyvinylpolypyrrolidone, Department of phosgene, hydrogen chloride and solvent obtained from PIZ, the Stripping part of DHS from PIZ at 205-C under vacuum (residual pressure of 3-5 mm RT.cent.), add cold PIZ to kubulau residue and subsequent prolonged heating at the same temperature under vacuum (SU 287012, C 07 C 119/04, 1970) or at atmospheric pressure (SU 620481, C 07 C 118/02, C 07 C 119/042, 08 G 18/76, 1978). The resulting product, containing 24-26% of the isocyanate groups (content sotsialnogo destination. However, these methods are quite complex and energy-intensive.

Closest to the proposed to the technical essence is a method of obtaining MDI, including vosganian mixture of polyvinylpolypyrrolidone, Department of main parts of phosgene, hydrogen chloride and solvent from the resulting mixture of polyvinylpolypyrrolidone and blowing the mixture with air at a temperature of 150-180C and atmospheric pressure within 2-6 h (EN 2128674, 08 G 18/02, 08 L 79/00, 1999). The resulting product contains traces of volatile toxic substances (in particular, phenylisocyanate) and therefore requires compliance with certain caution in handling, as it belongs to the second class of danger according to GOST 12.1.007-76.

To obtain products that are safe when used in compositions for coatings, building materials, and other polymeric materials, method for obtaining MDI by blowing air mixture of polyvinylpolypyrrolidone, which is the product of vosganian mixture of polyvinylpolypyrrolidone followed by the separation of the main part of the phosgene, hydrogen chloride and conditioned air, containing between 0.01 and 0.1% by volume of ammonia.

It was found that treatment of CRPS on the proposed method allows to obtain a product which, as well as the product obtained according to the method, can be used in the isocyanate compositions for various purposes, but it contains almost no volatile toxic substances (in particular, phenylisocyanate) and therefore refers to the fourth hazard class according to GOST 12.1.007-76. Apparently, this treatment allows along with transport these substances to make them selective transformation into non-volatile and non-toxic.

As a starting substance to obtain MDI under the proposed method can be used in any industrial modification PIZ received by postironium mixture of polyvinylpolypyrrolidone in the solution and separation of the main part of the phosgene, hydrogen chloride and solvent (and, if required, part of DHS) from the mixture of polyvinylpolypyrrolidone, for example, the polyisocyanate B grade on THE 113-03-38-106-98 or brand To THE 113-38-173-95 (Russia), the polyisocyanate mark D on THE 113-03-7822270-1-92 (Ukraine), Desmodw 44V (Bayer, Germany), etc.

Processing PIZ air containing ammonia, when is remesa; the use of air containing more than 0.1% of ammonia, does not lead to any additional benefits. The air handling saturated with ammonia to the desired concentration by known methods, for example by dosing the ammonia gas in the air flow.

Processing PIZ air containing ammonia at a temperature below 130C practically does not change its properties; the increase of treatment temperature above 180C leads to an excessive decrease in the content of NCO-groups and viscosity increase, worsening the compatibility of the obtained product with components of the compositions in which it is used. The required processing time PIZ air containing ammonia, depends on the temperature. To obtain the necessary quality of CRPS treatment at a temperature of 130C can be performed for 5 hours At finite temperature processing 180C is sufficient to bring the temperature of the processed PIZ to that value, and immediately cooled quickly.

Numerous isocyanate compositions for various polymer, in particular, urethane materials.

Among the known structures closest to the invention is a composition for polymeric materials, in particular covered the and the composition contains a mixture of polyvinylpolypyrrolidone, the treated air at a temperature of 150-180C and atmospheric pressure within 2-6 h or isocyanate composition, which is 100 wt.h. the thus treated mixture of polyvinylpolypyrrolidone contains 2.5-31 wt.h. solid waste generated during the processing and storage of mixtures of polyvinylpolypyrrolidone, the composition contains 30-70% by weight. isocyanate component and 70-30% by weight. toluene, or, equivalently, approximately 40-230 wt.h. toluene per 100 wt.h. isocyanate component.

In the composition of the isocyanate composition which is used as an isocyanate component, solid waste use waste generated on the surface of ICP, with the long-term storage in barrels or containers or in equipment production PIZ and DHS and removed during the cleaning of vessels or equipment. These wastes usually contain 2-12% of NCO-groups. To obtain the composition of the waste is mixed with a heated polyisocyanate, in which the waste is easily dissolved. Stirring is carried out directly in the process PIZ air or after a specified processing to the cooling PIZ.

To ensure the possibility of obtaining polymeric materials for various purposes with isolasi isocyanate component and toluene, characterized in that, as the isocyanate component contains a polyisocyanate obtained by blowing air containing between 0.01 and 0.1% by volume of ammonia, a mixture of polyvinylpolypyrrolidone, which is the product of vosganian mixture of polyvinylpolypyrrolidone followed by the separation of the main part of the phosgene, hydrogen chloride and solvent, at atmospheric pressure and temperatures up to 180C, in the following ratio, wt.h.:

The specified polyisocyanate 100

Toluene 40-230

The composition may include polyisocyanate obtained in the described manner, containing 100 wt.h. 2,5-31 wt.h. solid waste generated during processing and storage of the mixture of polyvinylpolypyrrolidone.

The composition as is known, can be used in polymer compositions for various purposes, but it contains almost no volatile toxic substances (in particular, phenylisocyanate) and therefore refers to the fourth hazard class according to GOST 12.1.007-76. The proposed composition may also optionally contain Tris(2-chloroethyl)-phosphate in an amount of from 65 to 130 wt.h. on 100 wt.h. isocyanate component that, due to the famous own.

The composition according to the invention is prepared by dissolving in toluene isocyanate component obtained as described above, and, if necessary, also adding Tris(2-chloroethyl)-phosphate.

The prepared composition can be used as cover. When used for this purpose part of the common methods applied to the surface of the protected objects, such as building structures or components (concrete, brick, wood, etc), and utverjdayut on the air for about one day. The composition can also be successfully used as an additional coating or binder used in the protection of building structures sheet of polymeric materials.

Coatings on the basis of the proposed compounds have a good decorative and mechanical properties, particularly high abrasion resistance, resistant to destructive influences, in particular to the action of water, acids, alkalis, petroleum products, animal waste, etc. have a good frost resistance. The use of the composition for the coating of concrete and brick dramatically reduces the tendency of these materials to the formation of cracks, and when it is used for coatings on wood, he exhibits antiseptic properties of the complex polymer compositions, for example, by mixing with compounds containing active hydrogen atoms (simple and/or complex polyesters, polyamines etc) to obtain polyurethanes, politician etc.

The invention is illustrated by the following examples. Examples 1-5 illustrate the processing of the MDI according to the proposed method and the preparation of the isocyanate component of the proposed structure. Examples 6-13 illustrate the collection and use of the proposed structure.

EXAMPLE 1. The polyisocyanate B grade on THE 113-03-38-106-98 with a content of NCO-groups of 29.9% wt. and viscosity, determined at the time of expiry of the sample volume of 100 ml of a funnel with a diameter of 4 mm, which is equal to 50, obtained by continuous vosganian mixture of polyvinylpolypyrrolidone containing 16% of primary amino groups, in an environment of chlorobenzene (concentration of the mixture of amines in solution 10%), separating hydrogen chloride and excess phosgene and the chlorobenzene is distilled off under vacuum. The resulting product is heated for 1.5 h to 180C at a constant purge air containing 0,01% vol. ammonia, at a rate of 20 l/h per 1 kg of MDI and cooled rapidly. The content of NCO-groups after the treatment is to 29.3% wt., the viscosity of 50.2 the component to obtain the composition according to the invention.

EXAMPLE 2. The polyisocyanate brand To THE 113-38-173-95 with a content of NCO-groups 29,0% wt. and viscosity, determined at the time of expiry of the sample volume of 100 ml of a funnel with a diameter of 4 mm, which is equal to 12 min, get analogously to example 1, with the difference that after the distillation of chlorobenzene from it additionally is distilled off under vacuum part of DHS. The resulting product is heated for 1.5 h before 160S at a constant purge air containing 0.05% about. ammonia, with a rate of 18 l/h per 1 kg of MDI and maintained at this temperature and constant blowing for 2 hours the Content of NCO-groups after treatment (24% wt., viscosity - 16 min, volatile impurities are absent. The resulting product can be used as the isocyanate component for obtaining the composition according to the invention.

EXAMPLE 3. The polyisocyanate mark D on THE 113-03-7822270-1-92 with a content of NCO-groups of 30.5 wt.%, mass fractions hydrolyzable and chlorine ion, equal to 0.2% and a viscosity, determined at the time of expiry of the sample volume of 100 ml of a funnel with a diameter of 4 mm, which is 50 to receive analogously to example 1. The resulting product heated for 1 h to 150C at a constant purge air containing 0.1% vol. ammonia, with a speed of 15 l/h per 1 kg of politician is 23,0% wt., viscosity - 20 min, volatile impurities and hydrolyzable chlorine is absent. The resulting product can be used as the isocyanate component for obtaining the composition according to the invention.

EXAMPLE 4. The polyisocyanate B grade on THE 113-03-38-106-98 with a content of NCO-groups 31,0% wt. and viscosity, determined at the time of expiry of the sample volume of 100 ml of a funnel with a diameter of 4 mm, which is 50 to receive analogously to example 1. The resulting product heated for 1 h to 130C at a constant purge air containing 0.05% about. ammonia, at a rate of 20 l/h per 1 kg of MDI, and maintained at this temperature and constant purging for 0.5 hours then to the product add the solid waste produced during the processing and storage of mixtures of polyvinylpolypyrrolidone, 31 wt.h. on 100 wt.h. MDI, and mix the components for 1.5 h at the same temperature and purging air containing ammonia. In the mixing of waste are completely dissolved in the polyisocyanate, and the resulting mixture can be used as the isocyanate component for obtaining the composition according to the invention.

EXAMPLE 5. The polyisocyanate B grade on THE 113-03-38-106-98 recip is using mixtures of polyvinylpolypyrrolidone, enter in the amount of 2.5 wt.h. on 100 wt.h. MDI. The resulting mixture can be used as the isocyanate component for obtaining the composition according to the invention.

EXAMPLE 6. Protective coating for concrete surfaces prepared by diluting isocyanate component obtained in example 1, equal to the mass amount of toluene. After coating on the surface of the concrete and its complete curing, the compressive strength is 11.3 MPa, water absorption during exposure of the sample immersed in water for 30 days not more than 0.2%, the resistance (the time before the destruction) in 33% sulfuric acid 1416 h, 40% caustic soda solution more 1416 h, diesel oil for more than 2 years.

EXAMPLE 7. Protective coating for concrete surfaces prepared by diluting isocyanate component obtained in example 2, equal to the mass amount of toluene. After coating on the surface of the concrete and its complete curing, the compressive strength is 12.8 MPa, water absorption during exposure of the sample immersed in water for 30 days not more than 0.15%, the resistance (time before breaking down of 40% caustic soda solution over 1300 h, diesel oil more than 17500 h

EXAMPLE 8. Protective coating for concrete surface coating on the surface of the concrete and its complete curing, the compressive strength is 16.8 MPa, water absorption during exposure of the sample immersed in water for 30 days not more than 0.12%, the resistance (time before breaking down of 40% caustic soda solution 1400 h, diesel oil more than 17,000 hours

EXAMPLE 9. Protective coating for concrete surfaces prepared by mixing 100 wt.h. isocyanate component obtained in example 4, with 40 wt.h. of toluene. After coating on the surface of the concrete and its complete curing, the compressive strength is 12.2 MPa, water absorption during exposure of the sample immersed in water for 30 days not more than 0,28%, the resistance (the time before the destruction) in 33% sulfuric acid 1344 h, 40% caustic soda solution 1344 h, diesel oil more than 17,000 hours

EXAMPLE 10. Protective coating for concrete surfaces prepared by diluting isocyanate component obtained in example 5, equal to the mass amount of toluene. After coating on the surface of the concrete and its complete curing, the compressive strength is 13.2 MPa, water absorption during exposure of the sample immersed in water for 30 days not more than 0.14% of the resistance (the time before the destruction) in 33% sulfuric acid 1344 h, 40% caustic soda solution over 1300 h, diesel oil over 12,000 hours immersion of the samples in liquid ECA-0.2%, whereas the control samples had cracks, and weight increased by 14.1%.

EXAMPLE 11. Protective coating for silica brick is prepared by mixing 100 wt.h. isocyanate component obtained in example 5 to 70 wt.h. of toluene. After 2-3 times of coating on the surface of the brick (with a break each time for about 1 h for drying) and its complete curing, the compressive strength increases (compared to baseline) 4,0-4,8 MPa, water absorption during exposure of the sample immersed in water for 30 days, is not more than 1.5%. When tested for frost resistance according to GOST 10060.1-95 (alternate freezing and thawing) violating the integrity of the coated samples was not observed, whereas the control samples had cracks and chips.

EXAMPLE 12. Protective coating for wood surfaces prepared by mixing 100 wt.h. isocyanate component obtained in example 5 to 100 wt.h. toluene and 130 wt.h. Tris-(chloroethyl)-phosphate. After coating on the surface of wood samples and full curing, the samples were tested for fire resistance for fire 251-98 ("flame retardants and substances for wood and materials based on it. General requirements. Test methods"). The average th efficiency (weight loss of more than 9, but less than 25%; fire-retardant agent, providing inflammable wood).

EXAMPLE 13. Protective coating for wood surfaces prepared by mixing 100 wt.h. isocyanate component obtained in example 4, with 40 wt.h. toluene and 65 wt.h. Tris-(chloroethyl)-phosphate. After coating on the surface of wood samples and full curing, the samples were immersed in liquid waste pig breeding complex and kept for 6 months. The appearance of the samples did not change, and the increase in weight was 0.2%, whereas the control samples had cracks, and weight increased by 12.2%.

1. The method of obtaining MDI by blowing air mixture of polyvinylpolypyrrolidone, which is the product of vosganian mixture of polyvinylpolypyrrolidone followed by the separation of the main part of the phosgene, hydrogen chloride and solvent, at atmospheric pressure and temperatures up to 180C, characterized in that the purge mixture using air containing 0,01-0,1% vol. the ammonia.

2. The composition for polymeric materials, including isocyanate component and toluene, characterized in that as the isocyanate component, it contains the NAT 100

Toluene 40-230

3. The composition according to p. 2, characterized in that the polyisocyanate obtained by the method according to p. 1, contains 100 wt.h. 2,5-31 wt.h. solid waste generated during processing and storage of the mixture of polyvinylpolypyrrolidone.

4. The composition according to PP.2 and 3, characterized in that it further comprises Tris(2-chloroethyl)-phosphate in an amount of from 65 to 130 wt.h. on 100 wt.h. MDI.

 

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