DE3240613A1 - Arylaliphatic polyisocyanurates and process for their preparation - Google Patents

Abstract

According to the invention, novel substances, arylaliphatic polyisocyanurates of the general formula <IMAGE> are proposed in which R represents C6H4=; CH2(C6H4)2=; C6H4(CH2)2= and R1 represents (CH2)6. A process for the preparation of aryl aliphatic polyisocyanurates by copolymerization of aromatic diisocyanates with aliphatic diisocyanates of the general formula OCN-R-NCO, in which R represents Ar(Alk), which are taken in a molar ratio of 3:1 to 0.25:1, at a temperature of 50-120 DEG C in a solvent medium which contains no active hydrogen - aromatic hydrocarbons, esters and ketones, in the presence of catalysts - naphthenates or octoates of the transition metals or their mixtures with acetate salts of alkaline or alkaline earth metals, is proposed, the catalyst being introduced in an amount of 0.1-1.5 %, relative to the total mass of the starting diisocyanates, and, to interrupt the copolymerization process, an acidic inhibitor being introduced into the reaction mass in a stoichiometric ratio, relative to the catalyst. The novel compounds according to the invention are extensively employed as curing agents for polyurethane lacquers and stains having improved properties.

Description

DESCRIPTION

The invention relates to new compounds, to arylaliphatic ones Polyisozyanurate and on a process for their preparation, which for use as an isocyanate component in paint and. Dye systems mainly in paint compositions for the post-processing of elastic underlays (leather, plastic, paper, fabric and other more) are provided.

Aromatic polyisocyanurates and processes for their are known Manufactured using naphthenates or octoates of the transition metals as catalysts (USPS 3252942, .K1. 260-775, 1966; GB-PS 809809, K1.

69 / lj, 1959; GB-PS 920080, Cl. 2 (3) C, 1963; GB-PS 954095, E1.C3R, 1964; SUIS 410061, K1. CO8G 33/02, 1974).

Less reactive aliphatic isocyanates are cyclotrimerized in the presence of naphthenates or octoates of the metals only with the addition of cocatalysts; carbamic acid esters are recommended as such. Mixed arylaliphatic polyisocyanates with isocyanurate rings are also known, for example cocyclotrimer of 2,4-toluene diisocyanate (TDI) and 1,6-hexamethylene isocyanate (HMDI), which is a product of the condensation of 3 TDI molecules and 2 HMDI molecules. (Advertising leaflet from the Bayer company dated December 1, 1967). A Cocyclotrimer - MoleRül has two isocyanurate rings and has the following structure: The technology of producing such a copolymer is not described. Catalysts for the mixed cyclopolymerization of aromatic and aliphatic diisocyanates are currently only highly active phosphine and amine derivatives, such as trialkylphosphines, mixtures of dimethylaminoethanol and glycidyl ester, tetramethylhexamethylenediamine (or butylamine), phenylglycidyl ester, epoxypyridines and others. C08G, 1968; Sorokin, MF, Schode LG, Siniza LA, Stachowskaaa MA

and Gavrilowa I.A. - two-component polyurethane compositions and coating materials on their basis. "Lacquers and dye stuffs and their use", 1974, No. 3, p. 4-6; US-PS 3517002, cl. 260-248, 19? L; U.S. Patent 336494 cl. 260-248, 1968; U.S. Patent 56,459-9, Kl. 260-77 / 5NC, 1972).

In the known process (US-PS 56459? 9, K1. 260-77.5NC, 1972), for example, mixed cyclotrimerization in the absence of a solvent at a ratio of HA4I: TDI = 0.2: 1 to 5: 1 by heating the mixture carried out at a temperature of 600C with tri-n-butylphosphine. Sank in 4.5 hours the isocyanate level from 48-50 to 36%. Then the unreacted monomers (63 XIassegO) distilled off in vacuo at a temperature of 180-190 ° C. The polymer yield was 37% by weight based on the initial charge of monomers. Molecular mass was 680-1010.

However, the existing methods have the following disadvantages: 1 .. Low degree of conversion of starting isocyanates; 2. Need for distillation of unreacted monomers in vacuum; 3. Difficulty performing the Control of the process due to the use of highly effective phosphine derivatives as Catalysts of Gocclotrimerization, in the presence of which the rate of the Polymerization increases more than 10 times; 4. possible formation of By-products, especially of uretidinediones, since the phosphine catalysts are the are the most important catalysts for the dimerization of isocyanates.

The aim of the present invention is to eliminate the mentioned disadvantages.

The invention is based on the object of such new compounds, To develop aryl aliphatic polyisocyanurates, which made it possible to use them as hardeners to use for polyurethane corners and to produce paints with improved properties.

This object is achieved in that, according to the invention, new substances, arylaliphatic polyisocyanurates of the general formula: where R is 06114 = .; CH2 (C6H4) 2 =; C6E4 (CH2) 2 = and R1 for (CH2) 6 =, with molecular mass 1100-1500 are proposed.

According to the invention there is also an arylaliphatic polyisocyanurate of the general formula proposed with molecular mass 1100-1250.

According to the invention there is also a method for producing the above new substances through copolymerization of aromatic diisocyanates with aliphatic Diisozyanaten of the general formula OCN-R-NCO, where R is Ar or (Alk), the be taken in a molar ratio of 3: 1 to 0.25: 1, at a temperature from 50-120 ° C in the medium of a solvent that does not contain active hydrogens, aromatic hydrocarbons, esters and ketones in the presence of naphthenates or octoates of the transition metals or their mixtures with acetic acids Salts of alkaline or alkaline earth metals proposed, the Catalyst in an amount of 0.1-1.5%, based on the total mass of Auegangsdiisozyanate, is introduced; to interrupt the idischpolymerisation of the diisocyanates A certain degree of conversion becomes an acidic inhibitor in the reaction mass introduced in a stoichiometric ratio to the catalyst.

As aromatic diisocyanates, 2,4-tolylene diisocyanate or a mixture of isomers of 2,4- or 52,6-uoluylene diisocyanate in a mass ratio of isomers 80:20, 4,4-diphenylmethane diisocyanate or a mixture von isomers of 2,2-2,4- and 4,4-Dipheiiylmethandiisozyanats in a ratio 5:45:52 or xylylene diisocyanate can be used.

The aliphatic diisocyanate used is advantageously 1,6-hexamethylene diisocyanate.

The solvent used is preferably benzene, toluene, xylene, Ethyl acetate, butyl acetate, methyl ethyl ketone and cyclohexanone.

It is desirable to use octoates and naphthenates as a catalyst Mi, Fe, Co, Ni, Cu, .Zn, Zr, Ce, Pb or their mixtures with acetates of Li, Na, K, Ca, Ba and other more to be used, in addition, benzoyl chloride are used as acidic inhibitors or hypophosphorous acid is used.

Among the advantages of the method according to the invention for Manufacturing of arylaliphatic polyisocyanurates include: - Increase in yield of copolymer to 94-96% due to a higher degree of conversion of the starting diisocyanate en; - Elimination of the distillation stage of monomers; - easy control and management the process; - Possibility of producing a highly homogeneous product; - no Formation of by-products in the nature of uretidinediones, carbodiimides, linear Polymers and more. Arylaliphatic polyisocyanurates of the proposed Structure are used extensively as hardeners for polyurethane coatings. These paints differ advantageously in their properties from the polyurethane varnish-- and dye materials with similar purpose of elasticity and the Abrasion resistance almost doubles the drying time of coatings 1000C is reduced to 5-10 min and the pot life of paint and Dye systems (over 10 hours).

Polyurethane paints using the arylaliphatic according to the invention Polyisocyanurates can be used in the following areas: 1) As coatings For elastic materials: Bynthesis and natural leather, fabric, paper, plastic, rubber (to protect rubber with natural rubber. good adhesion to rubber is ensured and that allows to reduce the gas evolution of rubber in vacuum to 1.5 times); 2) for high quality finishing of wood in the furniture industry; 3) for protection of tennis strings; 4) as an adhesive for plastics, ceramics, glass, leather and others more.

The polyisocyanurates mentioned can also be used as modifiers for other resins: acrylic, epoxy, alkyd resins and as a polyisocyanate component high concentration of polyurethane varnishes.

According to the invention, new substances, arylaliphatic polyisocyanurates of the general formula: wherein R is C6H4 =; CH2 (C6H4) 2 =; C6H4 (CH2) 2 = and R stands for (CH2) 6.

The molecular mass of the polyisocyanurates, which is calculated according to the information from PMR spectroscopy and gel chromatographic analysis, is 1100-1500, the degree of monodispersity is 92-96%. The structure of the arylaliphatic polyisocyanurates was determined by the PMR - spectroscopy method with high resolution. The PMR spectra were recorded in an ESR spectrometer RG60 (USSR) with an operating frequency of 60 MHz. Tetrachloroethane or chloroform are used as solvents. For example, the arylaliphatic polyisocyanurate based on 2,4-toluene diisocyanate and 1,6-hexamethylene diisocyanate of the formula the following characteristics: molecular mass equal to 1100-1250; PIER spectroscopic analysis is as follows: chemical shifts of protons: a = 1.3 ppm (3H), b = 4.1 ppm (2H), C = 1.2-1.9 ppm (8H), d = 3.3 ppm (2H) and e = 6.8-7.5 ppm (3H).

Based on the pi spectrum, a statistical avg cut molecule of the copolymer are represented in the form of three isocyanurate rings, which are linked to each other with both 2,4-TDI molecules and HMDI molecules will. The ratio d: b: c = 1: 2.9: 7.80 with a content of HMDI in the copolymer of 42.5% and d: b: c = = 1: 3.04: 8.1 with an HMDI content in the C.opolymer of 3622So.

The process for the preparation of arylaliphatic polyisocyanurates takes place according to the invention in the medium of solvents in a temperature range from 50-120 ° C in the presence of octoates or naphthenates of the transition metals or their mixtures with acetic acid salts of alkaline or alkaline earth metals as a catalyst.

As starting monomers for the production of arylaliphatic polyisocyanurates aromatic and aliphatic diisocyanates are used, as aromatic diisocyanates are 2,4-toluene diisocyanate or a mixture of isomers of 2,4-, 2,6-TDI, the are taken in a mass ratio of 80:20, 4,4-diphenylmethane diisocyanate or a mixture of isomers of 2,2-, 2,4- and 4,4-diphenylmethane diisocyanate, the be taken at the following ratio of 5:43:52, or xylylene diisocyanate used.

The aliphatic diisocyanate should expediently be hexamethylene diisocyanate be used.

The starting ratio of the aromatic and aliphatic isocyanates is 3: 1 to 0.25: 1.

Benzene, toluene, xylene, acetic acid ester, Ethyl acetate, butyl acetate, methyl ethyl ketone and cyclohexanone can be used.

Octoates are particularly preferred as catalysts and Transition metal naphthenates such as Mn, Fe, Co, Ni, Cu, Zn, Zr, Ce and Pb or their mixtures with acetic acidic salts of alkaline or alkaline earth Metals Li, Na, K, Ca, Ba and others. The total concentration of the respective catalyst is in a range from 0.1 to 1.5S based on the initial charge of Diisocyanates, varied.

To deactivate the catalytic centers, the system is in a certain polymerization stage an acidic inhibitor (benzoyl chloride, hypophosphorous Acid and others) added in a stoichiometric ratio to the catalyst. The arylaliphatic Polyisozyanurate- to be produced by the process according to the invention are characterized by increased elasticity and can mainly be used in lacquer compositions can be used for the post-processing of elastic underlays.

The increased elasticity is due to the new chemical structure of the arylaliphatic polyisocyanurate, which is expressed by the following general formula: wherein R is C6H4r; CH2 (C6H4) 2 =; C6H4 (CH2) 2 = and R1 stands for (CH2) 6, with molecular mass 1100-1500.

To better explain the present invention will the following examples are given for their implementation.

Example 1 In one with a thermometer, reflux condenser and one Flasks equipped with a stirrer are in mass proportions: Butyl acetate: HMDI and 2,4-TDI introduced in the following ratio of 50:20 and 30, respectively. There. Ratio 2,4-TDI: IIIYU) I. = = 1.5: 1. The mixture is mixed and the temperature increased to 1000C. then 0.25 parts by mass of cobalt nauthenate are added and the polymerizat ion is carried out up to a content of isocyanate groups of 8.5%. Then that will The mixture is cooled, diluted with butyl acetate to a dry residue of 50% and at room temperature a stoichiometric, based on the amount of catalyst of the benzoyl chloride (0.24 parts by mass) introduced.

A low-viscosity mass is obtained with the following characteristics:% NCO 8.0; Dry matter 50.0; Content of unreacted monomers equal to 3. IR spectrum gives absorption bands in the range 1420, 1715-1710 and 2280-2270 cm 1.

Molecular mass of the polyisocyanurate (gel chromatography, gel selfadex LH-20, eluent - dioxane) is 1250.

The TDI: RMDI ratio in the copolymer according to the PMR data is equal to 1.35: 1. In accordance with the PMR data, the statistical mean structure can be presented in the following form: The degree of polydispersity is 8%. The polymer yield is 94% based on the initial charge of isocyanates.

Example 2 The process is carried out as in Example 1, Jan. However, parts by mass of xylene become 25 parts by mass of the 4,4-diphenylmethane diisocyanate (MDI) and 17 parts by mass of HMDI added. The mixture is heated to 120 ° C and 0.6 parts by mass of manganese naphthenate are introduced.

The process is carried out until the content of NCO groups is equal to 7.5, then the mixture is cooled and inhibited as described in Example 1. The polymer produced has the following characteristics,%: NCO -?, 3; Dry matter 40; Free monomer content equal to 2.5. The IR spectrum has absorption strips in the range 1410, 1605, 1715-1710, 2280-2270 and 2960 cm -1. The ratio 4,4-MDT: HMDI in the copolymer is 1: 1.25 according to PMR data, molecular mass is 1300, the structure has the following form: The yield of copolymer is 95%, based on the starting charge of starting isocyanates, the degree of polydispersity is 7%.

Example 3 The process is carried out as in Example 1; but as an aromatic isocyanate a mixture of isomers 2,4-, 2,6-TDI (in mass ratio 80:20) and the catalyst used is 0.5 part by mass of a mixture the end Iron naphthenate and lithium acetate taken. After a hold time at one temperature from 80 ° C to a content of isocyanate groups of 7.8 is the reaction mass filtered through Schott filters and inhibited with hypophosphorous acid. The copolymer has the following characteristics,%: NCO -?, 5; Content of the unreacted monomers - 3, dry matter - 50.0. The yield of polymer is 93g0 based on the Initial charge of isocyanates, the degree of polydispersity is 6.5%, the IR and PMR spectra are similar to those in Example 1.

Example 4 The process is carried out as in Example 2; but the 56.4 parts by mass of ethyl acetate 12.5 parts by mass of 4,4-MDI and 34 parts by mass HMDI added.

The catalyst used is 0.12 part by weight of lead octoate.

The process is carried out at a temperature of 600 C up to a content of isocyanate groups of 8.7%, the mixture is further cooled and as in example 1 inhibited.

The polyisocyanurate has the following characteristics,%: NCO-8.1; Dry matter 42; ; Free monomer content 4.1.

The IR spectrum is as in Example 2. The ratio of 4,4-MDI: HMDI is, according to the PMR spectroscopy, 2.4: 1.0, the molecular mass is equal to 1350. The statistical average structure of the polyisocyanurate can be shown in the following form will: The yield sn copolymer is 90 and the degree of polydispersity is 8%.

Example 5 The process is carried out as in Example 1, as aromatic But diisocyanate becomes xylylene diisocyanate (KDI) and 0.75 parts by mass as a catalyst Zinc octoate used.

After holding the mixture at a temperature of 100 ° C The contents of the flask are cooled down to a content of NCO groups equal to 8.6 and inhibited with hypophosphorous acid.

The manufactured product has the following characteristics,%: NCO- 8.5, Dry matter is 49.5, content of free monomers is 2.5.

Molecular mass is 1150.

IR spectrum shows absorption bands in the range of 1410, 1600, 1710-1690, 2280-2270 and 2960-1 cm. The ratio of KDI: HMDI in the copolymer is after Information from PMR spectroscopy 1.4: 1.

The statistical average structure of the polyisocyanurate can be represented in the following form: The yield. of copolymer is 95 and the degree of polydispersity?%.

Example 6 The process is carried out as in Example 1, in the Flasks, however, are made in bulk proportions of toluene: HMDI and 2,4-TDI at a ratio given up by 60:10 and 30 respectively.

The ratio of 2,4-TDI: HMDI is 3: 1. The catalyst used is 0.04 Mass fractions of the mixture of nickel naphthenate and sodium acetate are used. To Mixing the reaction mass at a temperature of 1050C up to the content of NCO groups equal to 7.5%, the solution is cooled, filtered through a Schott filter and treated with Benzoylchlor.id inhibited.

The copolymer has the following characteristics,%: NCO-7.0; The dry matter is 40, the content of the unreacted monomers is 3 and the molecular mass is 1200. The IR spectrum is similar to that described in Example 1. According to PMR spectroscopy, the TDI: HMDI ratio in the copolymer is 2.8: 1, the statistical average molecule has the following formula: The yield of copolymer is 94 and the degree of polydispersity is 4.5%.

Example 7 The process is carried out as in Example 2, as aromatic Diisocyanate is a mixture of isomers MDI (2S2-, 2,4- and-4,4- in one Ratio 5:43:52) and as a catalyst copper octoate in an amount of 0.8 parts by weight taken. After holding the mixture at a temperature of 90 ° C up to a content of isocyanate groups the reaction mass becomes 8.9% cooled and inhibited with hypophosphorous acid.

The copolymer produced has the following characteristics,%: NCO-8.5; Dry matter 39; Free monomer content 3.5. Molecular mass is 1350.

IR and PMR spectra are as in Example 2.

The yield of copolymer is 94 and the degree of polydispersity.

Example 8 The process is carried out as in Example 1, in But flasks are made in proportions by weight of butyl acetate: HMDI and 2,4-TDI in a ratio introduced by 50:40:10.

A mixture is used as the catalyst. of cobalt naphthenate and Barium acetate in one. Amount of 0.45 parts by mass.

After mixing at a temperature of 80 ° C to a level at NCO groups of 7.5, the mixture is cooled, filtered off and treated with benzoyl chloride inhibited.

The copolymer produced has the following characteristics,%: NCO 7,); Dry matter 51.5; Free monomer content 2.1. Molecular mass is 1150.

IR and PMR spectra are as in Example 1.

According to the PMR spectroscopy, the 2,4-TDI content is: HMDI in the copolymer equal to 1: 2.5.

The statistical average structure has the following form: The yield of copolymer is 96 and the degree of polydispersity is 5%.

Example 9 The process is carried out as in Example 5, as a solvent but cyclohexanone and zirconium octoate as a catalyst in an amount of 0.75 Mass fractions used. After holding the mixture at a temperature of 1100C until the isocyanate number equals 8.5, the contents of the flask are cooled and treated with 3enzoyl chloride inhibited.

The copolymer has the following characteristics,%: NCO 8.2; Dry matter 50; Free monomer content 2.5. Molecular mass is 1200.

IR and PMR spectra are as in Example 5.

The yield of copolymer is 95 and the degree of polydispersity 6.0%.

Claims (8)

ARYLALIPHATIC POLYISOZYANURATE AND METHOD FOR THEIR PRODUCTION PATENT CLAIMS: 1. Arylaliphatic polyisocyanurates of the general formula: wherein R is C6H4 =; CH2 (C6H4) 2 =; C6H4 (CH2) 2 = and R1 stands for (CH2) 6 = with a molecular mass of 1100-1500. 2. Arylaliphatic polyisocyanurate of the general formula with molecular mass 1100-1250. 3. Process for the preparation of arylaliphatic polyisocyanurates according to claims 1-2, d u r c h ek e n n z e i c h n e t that the copolymerization aromatic isocyanates with aliphatic diisocyanates of the general formula OCH - R - NCO, where R is Ar (Alk), which is in a molar ratio of 3: 1 to 0.25: 1 can be taken at a temperature of 50-120 ° C in the medium of a solvent, that does not contain atoms of active hydrogen, aromatic hydrocarbons, esters and ketones in the presence of catalysts, naphthenates and octoates, respectively of the transition metals or their mixtures with acetic acidic salts of alkaline or alkaline earth metals is carried out using a catalyst in an amount of 0.1-1.5%, based on the total mass of starting diisocyanates, is introduced, and an acidic inhibitor to interrupt the copolymerization of the diisocyanates in a stoichiometric ratio, based on the catalyst, of the reaction mass is admitted. 4. The method according to claim 3, d a d u r c h g ek e n n z e i c h n e t that as aromatic diisocyanates 2,4-toluylene diisocyanate, respectively a mixture of isomers of 2,4- and 2,6-tolylene diisocyanate in a ratio from 80:20; 4,4-Diphenylmethanediisozyanat or a mixture of isomers of the 2,2-, 2,4- and 4,4-1) iphenylmethanediisozyanats in a ratio of 5:43:52 or xylylene diisocyanate can be used. 5. The method according to claim 3, d a d u r c h g k e n.n z e i c h n e t that 1,6-Ilexamethylend iisozyanat is used as the aliphatic diisocyanate. 6. The method according to claim 3, d a d u r c h. g ek e n n z e i c n e t that benzene, toluene, xylene, ethyl acetate, butyl acetate, Methyl ethyl ketone and cyclohexanone are used. ?. Method according to Claim 3, d u r c h g ek e n n n z e i c h n e t that octoates or naphthenates of Mri, Fe, Co, Ni, Cu, Zn, Zr, Ce, Pb or their mixtures with acetic acid salts more alkaline respectively alkaline earth metals Li, Na, E, Ca and Ba can be used. 8. The method according to claim 5, d a d u r c h g ek e n n z e i c h n e t that benzoyl chloride or hypophosphorous acid are used as inhibitors will.