CS233472B1 - Production method of polyurethans - Google Patents

Abstract

The process of producing polyurethanes by reaction at least one aliphatic or aromatic up to the polyisocyanate being carried out such that the polyol used consists in part or a full polyesterpolyol prepared esterification, polyesterification, possibly by re-esterification of the acid component, partly or completely distilled the preparation of cyclohexanone and / or cyclohexanol oxidation of cyclohexanone and alcoholic aliphatic di-to teireolov.

Description

The invention relates to a process for the production of polyurethanes using polyester polyols prepared mainly from by-products from the production of cyclohexanone and / or cyclohexanol.

It is known that polyurethane materials are prepared by reacting active hydrogen containing compounds with long to polyisocyanates. Of the compounds having active hydrogen, polymers, mainly linear and branched polyether polyols and polyester polyols, are used for the production of polyurethanes. Suitable polyether polyols include, but are not limited to, ethylene oxide, propylene oxide, butylene oxide, and other alkylene oxide addition and polyaddition products with trimethylolpropene, glycerol, hexenetriol, pentaerythritol, sorbitol, dimethylolfenol hydroxy, triisopropylamine (triisopropylamine), triisopropylamine (triisopropylamine), triisopropylamine. The polyester polyols used in the production of polyurethanes are usually made by reacting a dicarboxylic acid, in particular adipic acid with glycols or in combination with polyhydric alcohols.

By a suitable choice of the polyol structure, isocyanate and reaction conditions, a variety of polyurethane materials can be prepared, such as rigid semi-rigid or macrofoam foams and their modifiers, as well as elastomers, adhesives, fibers, binders for paints and the like.

The starting materials used in the production of polyurethanes are commercial products of wetting purity, which is also reflected in the price of the final product. Moreover, their resources are technically and raw materials limited and for some selected applications it is necessary to modify them before use, e.g. by adding organic polyfunctional compounds.

According to the invention, the process for the production of polyurethanes by reacting at least one aliphatic or aromatic di- to polyisocyanate or mixtures thereof with a polyol in the presence of auxiliaries such as catalysts and stabilizers is such that the polyol used consists in part or in whole of polyesterpolyol obtainable by esterification, optionally by re-esterification of the acid component formed in whole or in part by a distillation residue from the production of cyclohexanone and / or cyclohexanol by oxidation of cyclohexane and an alcoholic component based on aliphatic di-tetraols.

An advantage of the process of making the polyurethanes of the present invention is that the polyester polyols prepared from by-products, generally isolated in the form of distillation residues from the cyclohexanone and / or cyclohexanol distillation by oxidation of cyclohexane, can be produced virtually all known species. polyurethane materials. Thus, it is the use of the polyol component to produce full-value products. Furthermore, the higher content of polar groups in the polyester polyol molecules increases the adhesion of the polyurethane films to the substrates, which is particularly suitable for application of polyurethanes in the function of adhesives of paints and components - additives to lubricating oils and the like. Last but not least, the ability to mix these polyurethanes with other polymers, as well as higher fillings with both mineral and organic fillers, is improved.

In the production of the polyurethanes according to the invention, on the one hand, the polyester polyol itself can be used on the basis of by-products, usually isolated as distillation residues from cyclohexanone production by oxidation of cyclohexane or mixed with other known polyester polyols or polyether polyols. Possible polyester polyols are products based on other polycarboxylic acids or their anhydrides with divalent or multifunctional alcohols. Adipic acid is suitable for their preparation, furthermore it can be: oxalic, malonic, succinic, glutaric, pimelic, cork or ezeleic, unsaturated dicarboxylic acids, e.g. maleic, fumaric, itaconic or phthalic anhydride and maleic anhydride. Suitable alcohols are ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, and optionally other polypropylene glycols, butylene glycols or polybutylene glycols. Among polyhydric alcohols, e.g. glycerol, hexanetriol, butanetriol, trimethylolpropane, trimethylolethane, pentaerythritol, mannitol or sorbitol and others.

Suitable polyether polyols which can be used to prepare mixtures with polyether terpolyol based on the by-products and / or by-products. The residues of cyclohexanone production by oxidation of cyclohexane are known. They are products of the reaction of polyhydric alcohols, polycarboxylic acids or phenolic compounds, with at least one low molecular weight 1,2-epoxy compound, such as e.g. propylene oxide. Low molecular weight, 1,2-epoxy compounds are: ethylene oxide, propylene oxide, butylene oxide, isobutylone oxide, 2,3-epoxyhexane, triethyl-2,3-epoxyoctane, epihydrohydrin, epibromohydrin, styrene oxide, glycidyl ether, butyl glycidyl ether, phenyl glycidyl ether, phenyl glycidyl ether, phenyl glycidyl ether, phenyl glycidyl ether, phenyl glycidyl ether , glycidyl benzodt, glycidylacetate, glycidyloctoate, glycidyl sorbate or glycidylalyl phthalate.

The epoxides used for the preparation of the polyether polyols are, in particular, compounds which are formed by the substitution of hydrocarbons, ethers, sulfides, sulfones or esters by a monoepoxy group and which contain at most 18 C atoms per molecule. Low molecular weight alkylene oxides are usually used to prepare the polyether polyols. Furthermore, it may be polyesteramides or mixtures thereof with polyesters prepared in a known manner from polyhydric acids, alcohols, optionally amines, and the polythioethers described in German Pat. 1,105,156 or polyacetals (German Pat. 1,039,744 · 1,045,095).

Suitable isocyanate components include many organic polyisocyanates, in particular aryl polyisocyanates, of the benzol or naphthalene series, which are more reactive and less toxic than aliphatic compounds. Examples of these currently commercially available compounds are: 2,4-toluylene diisocyanate, 2,6-toluylene diisocyanate and mixtures thereof.

However, other isocyanates, e.g. phenylene diisocyanate, alpha-naphthylene diisocyanate, 4-toluylene diisocyanate, n-hexylene diisocyanate, methylene bis- (4-phenylene isocyanate), 3-ditoluylene-4,4'-diisocyanate, 3,3'-dimethoxyate, 3,3'-dimethoxyate , 5-naphthylene diisocyanate, 2,4-chlorophenylene diisocyanate, hexamethylene diisocyanate, 1,3-cyclopentylene diisocyanate,

1,2-cyclohexylenediisocyanate, 1,4-cyclohexylenediisocyanate, cyclopentylidene diisocyanate, cyclohexylidene diisocyanate, p-phenylene diisocyanate, m-phenylene diisocyanate, 4,4'-diphenylpropanidiisocyanate, phenylene diisocyanate, 4,4-diphenylene diisocyanate, 1,2-propylene diisocyanate, 1,2-butylene diisocyanate, ethylidene diisocyanate, propyliene · diisocyanate, butylidene diisocyanate, 1,3,5-triisocyanate, 2,4,5-triisocyanate, 2,4,5-trisocyanate triisocyanochlorobenzene, 4,4 ', 4-triphenylmethane triisocyanate, polymethylene polyphenylisocyanate or mixtures thereof.

High molecular weight polyisocyanates are generally the liquid reaction products of the diisocyanates and the polyhydroxy compounds or polyamines. In addition, polyisothiocyanates or mixtures of polyisocyanates may be used. Technical non-purified or crude polyisocyanates, e.g. Crude methylene bis (4-phenylisocyanate) mixture.

In the preparation of elastomers of thermoplastic powdered polyurethane urea or other compounds, it is suitable to use as the isocyanate component a prepolymer, a product after partially reacting the polyester polyol or mixtures thereof with diisocyanates. The choice of the type of diisocyanate used depends on the properties of the starting materials and the desired properties of the product.

The properties and properties of polyurethanes are greatly influenced by the type and amount of excipients which include activators, stabilizers, emulsifiers, blowing agents, fillers, flame retardants, dyes, pigments and the like. '

Many of the compounds described by J. H. Saunders and K. C.

Frish in the book Polyurethanes, Russian translation: Chimlya Polyurethane, IzdateTstvo Khimija, Moscow 1968. Of the compounds described, in particular tertiary amines, e.g. Ν, Ν'-dimethyloyclohexylamine, dimethylethanolamine, triethylenediamine, dimethylaniline, pyridine, ethylmorpholine, quinoline and the like, or organometallic compounds such as dibutyltin laurate, n-butyltin trichloride, trimethyltin hydroxide, trimethyltin disulfide, dimethyl tin disulfide, dimethyl tin disulfide, dimethyl tin disulfide, dimethyl tin disodium. When using uncleaned by-products, respectively. The catalytic effect of the metals present, in particular cobalt salts and other metals, should be taken into account in the residues of cyclohexanone production by oxidation of cyclohexane.

The effect of the catalysts is often increased by the correct choice of amounts, with a synergistic effect, in particular using tin salts and tertiary amines. By suitable choice of concentration, type and ratio of catalysts it is possible to influence not only the reaction of the hydroxyl group with the isocyanate, but also the formation and properties of the foam.

Of the available blowing agents, those compounds which generally liberate gaseous compounds when heated or converted with an isocyanate are usually used in the preparation of diapers. Low molecular weight liquids and water are preferably used in foaming. The reaction heat and the reaction of water with the diisocyanate causes foaming of the mixture to form a sufficient stable foam that maintains its form until the mass gels. Suitable low molecular weight liquids are fluorochlorohydrocarbons having a boiling point of between about 20 ° C and about 50 ° C or mixtures thereof, e.g. However, compounds having a boiling point of -50 to 10 ° C, and possibly higher, may be used.

As the blowing system used in foaming polyurethanes at elevated temperatures, U.S. Pat. 2,865,869 ·

The stabilizers absorb the formation, size and uniformity of the foam cells. polysloxane-polyoxyalkylan immers, described e.g. US Pat,

834,748 and 2,917,480.

The importance of emulsifiers is to improve the solubility of the reaction components and / or the auxiliaries. Many emulsifiers, such as dioctyl phthalate, dibutyl phthalate and the like, are suitable.

The process according to the invention can be carried out by known processes, in particular by pouring or spraying on conventional equipment used for the production of polyurethane compositions.

Depending on the type of foaming device, the method of dosing the individual components is selected.

The details of the production method as well as the other advantages are apparent from the examples.

EXAMPLE

For the production of rigid polyurethane foam, polyesterpolyol prepared by polyester-fractionation and transesterification of the distillation residues from the oxidation of cyclohexane, diethylene glycol and pentaerythritol in a weight ratio of 1: 1: 0.15 is used. To 100 g of the polyester polyol thus prepared (acid number 1 mg KOH / g, hydroxyl value 455 mg KOH / g, viscosity at 25 ° C 1.85 Pa.s) is mixed with 1 g silicone stabilizer (Tegostab B 1903),

1.5 g of dimethylcyclohexylamine, 0.1 g of stannous octoate, 2 g of emulsifier (Dispergiermittel EM) and 40 g of trichlorofluoromethane (Ledon-11) and after thorough homogenization, 125 g of crude 4,4'-methanediphenyldiisocyanate (Deamodur 44 V) are added. The foam start time is 19 s, the foam growth time 55 s, the foam sticking loss 55 s. A foam having a density of 30 kg.m-3 and a regular uniform structure and excellent dimensional stability over a temperature range of 90 ° C to -30 ° C is prepared.

Example 2

The powdered thermoplastic polyurethane urea is prepared from polyester polyol obtained by reacting the distillation residues from cyclohexanone production by oxidation of cyclohexane (from which they have removed metal compounds) by reaction with monoethylene glycol in a weight ratio of 1: 0.12 by the following procedure: 1000 g of polyester polyol 56 and an acid number of 1.2 mg KOH / g is reacted with 250 g of pure 4,4'-methanediphenyldilzoocyanate (Deamodur 44 V) with stirring at 90 ° C for 30 min. The resulting prepolymer containing 3.1 wt. of free NCO groups is added with vigorous stirring for 10 min to 70 ° C water containing 0.02 wt. a dispersant based on propoxylated higher fatty alcohols. The polyurethane urea obtained has a particle size of 50 to 250 runes, a bulk density of 580 kg.m ^-3 , mol. weight 155,000, content of NH ₂ groups 0.05% by weight, plasticization temperature 130-150 ° C and is suitable as modifier in the preparation of tough polyvinyl chloride.

Example 3

Water is removed from the polyester polyol (prepared by esterification of by-products isolated as dastlation residues from the production of cyclohexanone and cyclohexanol by oxidation of cyclohexane and ethylene glycol with a hydroxyl number of 56 mg KOH / g, an acid number of 2 mg KOH / g and a water content of 0.15 wt.). and stirring at 130 ° C for 2 h. Drying of 1,4-butylene glycol is carried out in a similar manner at 110 ° C for 1 h. The dewatered polyol is heated in a three-necked flask equipped with a stirrer, a separatory funnel and a nitrogen inlet to 90 ° C. The calculated amount of dllaocyanate heated to 60 ° C is then added with stirring. The reaction is carried out under a nitrogen atmosphere at 90 ° C and with vigorous stirring for 20 min.

To the thus prepared prepolymer heated to 80 ° 0, a calculated amount of 1,4> butylene glycol heated to 40 ° 0 is added. The mixture was flushed and stored well for 30 minutes and then poured into a tempered form, coated with an aepardtor. A slastomar is obtained which has these modulus values at a 100 8-stretch elongation of 8.31 µm. tensile strength «10,8 ΜΗ | ductility ^a 510 «; abrasion resistance = 442%.

Example 1 4

From polyester polyol, prepared by the polyesterification and transesterification of distillation residues from cyclohexanone production of oxycyclohexane (in which the bromine number is reduced by hydrogenation, colored impurities and metal compounds are removed by film distillation), ethylene glycol and butylene glycol having a hydroxyl number of 55 mg KOH / g, 2 mg KOH / g, a molecular weight of about 2,000 and a water content of 0.05 wt. was prepared as described in Example 3 with a prepolymer containing 15.5% free NCO groups.

The polyol component is prepared by mixing 60 wt. parts, i. 40 wt. polyether polyol having a hydroxyl value of 28 mg KOH / g, 70 wt. parts by weight of the polyester polyol described in the preceding section having a hydroxyl value of 55 mg KOH / g, 20 wt. parts of a polyester polyol having a hydroxyl value of 78 mg KOH / g and 55 wt. parts by weight of 1,4-butylene glycol, 1 wt. parts of a suds stabilizer, 0.2 wt. parts of stannous octoate, 0 5 wt. parts by weight of triethylenediamine, 11.5 wt. parts of dichloromethane and 11.5 wt. parts of trichlorofluoromethane.

The elastic integral polyurethane foam is prepared from 0.00 wt. parts of the prepolymer and 60 wt. of the polyol component, the isocyanate index is 103. The foam is flexible, resilient, with excellent break-through resistance.

Claims (1)

5 233472 alcohols. The polyurethane urea obtained has a particle size of 50 to 250 rpm, a bulk density of 580 kg / m @ 2, mole. weight 155,000, NH2 content of 0.05 wt%, plasticization temperature 130 to 150 ° C and is suitable as a modifier in the preparation of tough polyvinyl chloride. Example 3 Water is removed under vacuum to remove polyesterpolyol (prepared by esterification of byproducts, isolated from the dairy residues from the production of cyclohexanone and cyclohexanol by oxidation of cyclohexane and ethylene glycol with a hydroxyl number of 56 mg KOH / g, acid value 2 mg KOH / g and water content 0.15%). continuous stirring at 30 ° C for 2 h. Drying of 1,4-butylene glycol is carried out in a similar manner at 110 ° C for 1 h. The dehydrated polyol is heated in a three-necked flask equipped with a stirrer, a separating funnel through a nitrogen inlet to 90 ° C . Then, the calculated amount of hydrocarbyl heated to 60 ° C is added with stirring. The reaction was carried out under nitrogen at 90 ° C with vigorous stirring for 20 min. X of the prepolymer thus prepared, heated to 80 ° C, is added to the calculated 1.4% butylene glycol, heated to 40 ° C. The mixture is agitated and agitated for 30 minutes and then poured into a tempered mold coated with aeparener. It obtains an elastomer which has a modulus at 100 8 µm of overcoating of 8.31 µm. tensile strength < 19.8 MV < tb > abrasion resistance = 442%. Example 4 Polyesterpolyol prepared by polyesterification and transesterification of distillation residues from the production of cyclohexanone by oxidation of cyclohexane (in which the bromine number is hydrogenated before use, color impurities and metal compounds removed by film distillation), ethylene glycol and butylene glycol having a hydroxyl number of 55 mg KOH / g, number 1.2 mg KOH / g, a molecular weight of about 2,000 and a water content of 0.05% by weight are prepared according to the procedure described in Example 3 by prepolymer containing 15.5 56 free NCO groups. The polyol component is prepared by mixing 60 wt. Part, i.e. 40 wt. of a polyether polyol having a hydroxyl number of 28 mg KOH / g, 70 wt. parts of the polyester polyol described above with a hydroxyl number of 55 mg KOH / g, 20 wt. parts of a polyester polyol hydroxyl number of 78 mg KOH / g and 55 wt. of 1,4-butylene glycol, 1 wt. frequent foam stabilizer, 0.2 wt. parts of stannous octoate; parts of triethylenediamine, 11.5 wt. parts of dichloromethane and 11.5 wt. trichlorofluoromethane. A flexible integral polyurethane foam is prepared from 100 wt. parts of prepolymer and 60 wt. the polyol component, the isocyanate index is 103. The foam is flexible, resilient, with excellent breaking resistance. SUMMARY OF THE INVENTION A process for the production of polyurethanes by reacting at least one aliphatic or aromatic-to-polyisocyanate, or mixtures thereof with a polyol, in the presence of auxiliaries such as catalysts and stabilizers, characterized in that the polyol used consists of, or complete from, polyester polyol prepared by esterification, polyesterification, optionally re-esterification an acid component formed partly or completely by distillation from the production of cyclohexanone and / or cyclohexanol by oxidation of cyclohexane and an alcoholic component based on aliphatic di-tetraols.