DE3106367A1 - Process for the preparation of alkene-unsaturated oligourethanes which are modified with N,N<1>-substituted aliphatic amines and contain 0.5-5% by weight of urea groups - Google Patents

Abstract

The present invention relates to the preparation technology of alkene-unsaturated oligourethanes and in particular a process for the preparation of alkene-unsaturated oligourethanes which are modified with N,N<1>-substituted aliphatic amines and contain 0.5-5% by weight of urea groups. According to the invention, the process for the preparation of alkene-unsaturated oligourethanes which are modified with N,N<1>-substituted aliphatic amines and contain 0.5-5% by weight of urea groups consists in reacting the di- or polyisocyanates with the polyols and the alkene-unsaturated hydroxyl-containing compounds at 20-70 DEG C in the presence of an antioxidant until a conversion, according to the isocyanate groups, of at least 80% by weight is achieved and the alkene-unsaturated oligourethane obtained is subsequently reacted with the N,N<1>-substituted aliphatic amines at 20-60 DEG C and in a ratio of the NCO groups to the NH2 groups equal to 0.05-5.

Description

description

The present invention relates to the production technology of alkene-unsaturated oligourethanes, and in particular processes for the preparation of alkene-unsaturated oligourethanes, those with N, N1-substituted aliphatic amines are modified and contain 0.5-5% by weight of urea groups, which are necessary for the polymerization reaction are capable according to the free radical mechanism.

The alkene-unsaturated oligourethanes substituted with N, N1- aliphatic amines are modified and contain 0.5-5 wt.% urea groups, are intended for the production of coverings, adhesives, compounds and hermetics.

A process is known for the preparation of oligourethanes unsaturated with alkene by reacting an excess of polyisocyanate with alkene-unsaturated hydroxyl-containing compounds Compounds at 20-60 ° C in the presence of an antioxidant in the medium of active monomer solvents. The product obtained with the free isocyanate groups is then bound with the polyhydroxyl bonds reacted with the formation of an alkene-unsaturated oligoure thanacrylate (II.A. Wytnowa i.a.

"Paints and Their Use" 1979, No. 1, pp. 34-38 I.A. Pronina inter alia "Paints and their Veruendung", 1977, No. 2, pp. 82-84).

The process that implements the excess is also known on polyisocyanate with a polyhydroxyl compound at 20-800C vDrs. The won Product with free isocyanate groups is set at 20-600C with alkene unsaturated hydroxyl-containing Compounds in the medium of active monomer solvents and in the presence of an antioxidant in µm (U.S. Patent 3509324).

The procedures mentioned characterize the long duration of the process and insufficient stability in the storage of the obtained alkene unsaturated Oli6ouretnane, which can be attributed to a poor degree of conversion of the isocyanate groups is.

The invention is based on the object in the method of production alkene-unsaturated oligouretanes, those with N, Nl-substituted aliphatic amines are modified and contain 0.5-5 wt.% urea groups, such components and to choose conditions of implementation of the procedure that ensure stability of the the creation of the final product would be granted and the duration of the synthesis would be shortened.

This object is achieved in that the method for production of alkene-unsaturated oligourethanes, those with N, N1-substituted aliphatic Amines are modified and contain 0.5-5 wt.% HarustD ££ groups, according to the invention is that you have the Di or. Polyisozyanate with the polyols and alkene unsaturated bydrofi; yl-containing compounds at 20-700C in the presence of an antioxidant until a degree of conversion of the isocyanate groups of at least 80% by weight is reached and then the alkene-unsaturated oligourethane with N, N1-substituted aliphatic amines at 20-600C and with a ratio of the NCO groups to the NH2 groups converts equal to 0.5-5.

Depending on which end product is sought can the implementation of the substances mentioned either at the same time or at their drive through successive use.

To reduce the effect of side reactions, the implementation the above-mentioned Eomponenten carried out in the medium of active monomer solvents.

The preparation of the alkene-unsaturated oligourethane, which is substituted with N, Nl aliphatic amines and contains 0.5-5 wt.% urea groups can be realized in different ways. One of the variants of the procedure is described below.

A reaction vessel equipped with a stirrer, mercury seal, thermometer, The reflux condenser and metering device are filled with polyisocyanate and an antioxidant, an active monomer solvent, charged and warmed to 20-70 ° C. After that, will the same vessel with the help of the dosing device with an alkene-unsaturated hydroxyl-containing compound Connection loaded. The reaction mixture obtained is kept at 20-70 ° O until Achieving a conversion based on the isocyanate groups equal to 45-50% by weight. Thereafter, the vessel is charged with polyol and the reaction mass is up from held at least 80% by weight to achieve a conversion to the isocyanate groups #. At a temperature of 20-60 ° C., the reaction mass that is held is N, N1-substituted aliphatic amine in an amount equal to the ratio of the NCO groups to the E2 groups 0.5-5 added. Another variant for carrying out the invention consists in the following.

The reaction vessel, equipped with a stirrer, mercury seal, Thermometer, The reflux condenser and metering device are filled with polyisocyanate, an active monomer solvent, charged and heated to 20-700C in the presence of an antioxidant. After that, that will Vessel filled with polyol using the dosing device. The reaction leads one up to a degree of conversion according to the isocyanate groups equal to 45-50% by weight. The vessel is then charged with alkene-unsaturated hydroxyl-containing compounds and the reaction mass is kept until a degree of conversion has been reached on the isocyanate groups of at least 80% by weight, after which at a temperature of 20-OOC, N, N1-substituted aliphatic amine in an amount equal to the ratio of NCO groups are added to the NH2 groups 0.5-5.

Another variation on the method consists of all of the following Starting components are simultaneously at 20-70 ° C in the presence of an antioxidant introduced. The process takes place until a degree of conversion has been achieved on the isocyanate groups, up to 80% by weight. Thereafter, at a temperature of 20-60 ° C N, N1-substituted aliphatic amine in an amount equal to the ratio of NCO / NH2 groups 0.5-5 added.

The following starting components are used in all of the above-mentioned processes used.

The polyols used are polyalcohols (glycerine, trimethylolpropane and similar), oligoethers (oxypropylated resp.

oyäthylierte glycerine, trimethylolpropane and ethylenediamine with one MoleXular mass 500-3000) Oligoester (products of the esterification of fatty acids of the Vegetable oils by polyatomic Alcohols).

As vegetable oils or their fatty acids, castor oil, sunflower oil, Cottonseed oil and others can be used.

Of the di- and polyisocyanates, aromatic isocyanates are used (Isomers of 2,4 or 2,6-toluylene diisozanate in a ratio of 65/35, 80/20, 100/1, xylilene diisocyanate, 4, 41-diphenyl metaisozyanate, polyphenylene polyisocyanate, aliphatic isocyanates (1,6-hexamethylene diisocyanate, aliphatic 2,2,4- resp. 2,4,4 - trimethylhexamethylene diisocyanate) and cycloaliphatic isocyanates (3-isozyenatomethyl-3, 5,5 - trimethylcyclohexyl isocyanate) As an alkene-unsaturated hydroxyl-containing compound for example, monomethacrylic esters, ethylene glycols and allyl alcohol can be used. As an antioxidant, it is desirable to use hydroquinone, for example. As monomer solvents are the acrylic and methacrylic acid esters, styrene and vinyl toluene, i.e. compounds that undergo copolymerization reaction by the free radical mechanism are able to recommend. The alkene-unsaturated oligourethanes obtained according to the invention, which are modified with N, N1-substituted aliphatic amines and 0.5-5% by weight Containing urea groups have a high stability during storage (over three months) and high curing speed with a free radical mechanism under the influence of peroxide catalysts and radiation of high energies.

The films made on the basis of the proposed compounds are characterized by bohe physical-mechanical and protective properties. the Stability of the alkene unsaturated Oligourethanes modified with X, Nl-substituted aliphatic amines, will be conditional upon a change in their Appreciated toughness during storage. The viscosity is measured according to Vi8kosimeter-4 measured at 200C. The product is considered stable when in the storage period no increase in conditional toughness by more than ten seconds over three months is observed.

To compare the stability of the alkene-unsaturated oligourethanes syntheses of polymerizable alkene-unsaturated oligourethanes were carried out, which are modified with N, N1-substituted aliphatic amines and 0.5-5 total% Contain urea groups and those with N, Nl-substituted aliphatic Amines are not modified. For this purpose, alkene-unsaturated oligourethanes are used used which are obtained on the basis of the same or similar starting components became. Data on comparative syntheses show that the alkene unsaturated Oligourethanes, which are N, Nl-substituted in the final stages of the process aliphatic amines obtained have a significantly greater stability than the alkene-unsaturated oligourethanes, the N, N1-substituted aliphatic Amines have not been modified.

The following will provide a better understanding of the present invention Examples of their implementation are given.

Example 1.

A heaping vessel provided with a Bühre.r, a Mercury seal, a thermometer, a reflux condenser and a dropping funnel is added with 76.1 g Methyl methacrylate, 174 g of -2,4-toluylene di-soyanate and 0.04 g of hydroquinone are charged. The mixture obtained is heated to 50-450C and slowly from the dropping funnel 130 g of ethylene glycol monomethacrylate were introduced. After the addition of ethylene glycol monomethacrylate has been completed the reaction mixture is 60 minutes at 5500 until a level is obtained Isocyanate groups held at 10.9-11.1 wt%; being the 4-carbakryloxyaminotolyl-2-isocyanate (Product A) is obtained.

In the reaction vessel equipped as above, 100 g of castor oil, interesterified with glycerine (with a hydroxyl group content of 9.1% by weight), and 25 g of styrene mixed. The mixture obtained is heated to 50-55 ° C and removed from the dropping funnel 203 g of product A are slowly introduced. After completing the introduction from product A into the reaction mass it is kept for 3-4 hours at 500G and up to 85oigen conversion of itocyanate groups, which is 0.7-1.1% by weight of the isocyanate groups is equivalent to. Then 6.28 g of diethylamine are added from the dropping funnel so that so that the temperature of the reaction mass does not exceed 500C and the temperature is maintained Reaction mass until the isocyanate groups are completely transformed.

The finished product is a goat solution of oligoester urethane in styrene which is modified with N, N1-substituted aliphatic amines, Contains 3.5-4.5% by weight of urea groups and has the following oil properties: Molecular mass - 1800-2200 Conditional toughness of a 50% solution in styrene according to the viscometer - 4 at 200C - 25-35 seconds, content of acrylic bonds - 68.9 g Br2 / 100 g oligourethane, stability - over 6 months.

Example 2.

A reaction flask, equipped as in Example 1, becomes mft 100 g of oxypropylated glycerine with a molecular mass of 500 and a content of hydroxyl groups 11.3% by weight and 25 g of methyl methacrylate charged. The mixture is heated to 50-55 ° C and slowly introduces 253 g of product A, obtained as in Example 1, in. To When the addition of product A is ended, the reaction mass is at 50 ° C. for 3-4 hours held up to a content of isocyanate groups-0,4-Os7 wt.%, which is 90-95 wt.% the degree of conversation of isocyanate groups. After that, from the cup funnel 4.6 g of dibutylamine are introduced and the reaction is complete at 60 ° C Disappearance of the isocyanate groups.

The finished product is a 70% solution of oligoester urethane in methyl methacrylate, which is modified with N, N1-substituted aliphatic amines is, contains 2.5% by weight of urea groups and has the following properties: Molecular mass - 1100-1350 Conditional viscosity of an own solution in styrene according to the viscometer - 4 at 2000 - 18-20 seconds, content of acrylic bindings - 80.5 g Br100 g oligourethane Stability over 6 months Example 3.

A reaction flask, equipped as in Example 1, will with 40 g of oxypropylated glycerine (with a molecular mass of 3000 and a content of hydroxyl groups 1.6% by weight), 60 g of oxypropylated glycerine (with a molecular mass 500 and a content of hydroxyl groups of 11.3% by weight) and 25 g of methyl methacrylate loaded. The mixture obtained is heated to 50-55 ° C and removed from the dropping funnel 165.8 g of product A obtained as in Example 1 are introduced. After feeding of product A, the entire reaction mass is kept at 50 ° C. to a level Isocyanate groups 0.6-0.9 wt, which is an 87-92 wt% conversion of isocyanate groups is equivalent to.

Then 8.10 g of dibutylamine are removed from the dropping funnel over a period of three hours added in such a way that the temperature of the wax ion mass does not exceed 600C.

The finished product does not contain any free isocyanate groups and represents a goat solution of oligoester urethane in methyl methacrylate which is substituted with N, modified aliphatic amines, contains 28-3.1% by weight of urea groups and has the following properties.

Molecular mass - 3500 - 4000 Conditional viscosity of a 50% solution in styrene according to the viscometer - 4 at 200C - 51 seconds content of acrylic bonds - 38.6 g Br2 / 100 g oligouretane stability - over 8 months Example 4.

A reaction flask equipped as in Example 1 is loaded with 250 4.41 g diphenylmethane diisocyanate, 0.05 g hydroquinone and 95 g methyl methacrylate loaded. The mixture obtained heated to 200C and from the 150 g of ethylene glycol monomethacrylate are slowly added to the dropping funnel. To The reaction mass is kept at the end of the supply of monomethacrylic ester of ethylene glucol 90 minutes at 20-300C until the product has an isocyanate group content of 8.5-9.0 wt B.

The product obtained is a 4-carbocryloxyamine diphenylmethane - 4, - isocyanate (product 3).

In the reaction vessel, equipped as in Example 1, 100 g of the oxypropylated glycerin (with a molecular mass of 500 and a content of hydroxyl groups 11.3% by weight) mixed with 25 g of methyl methacrylate. The mixture obtained is heated to 40-50 ° C and give him 315 g of product B slowly from the dropping funnel to. After the addition of product B has ended, the reaction mass is kept at 45-550.degree up to an isocyanate content of 0.3 / 0.4% by weight in the course of 4-3 hours, which corresponds to a 92-95% by weight conversion of the isocyanate groups. From the dropping funnel one then leads 2.6 g of diethylamine so em, so that the temperature of the reaction mass Does not exceed 500C.

The finished product does not contain any free isocyanate groups and represents a 70% solution of oligoester urethane in methyl methacrylate which is N, N1-substituted aliphatic amines, contains 2-2.5% by weight of urea groups and the following Has properties: Molecular mass - 1300-1500 Conditional toughness of a 50% Solution in styrene according to the viscometer - 4 at 2000 - 65 seconds salary on acrylic bonds - 50 g Br2 / 100 g oligourethane stability - at least 6 months Example 5.

A reaction flask fitted with a stirrer, a mercury seal, a thermometer, a reflux condenser and a dropping funnel is filled with 174 g of 2.4 or 2.6 tolylene diisocyanate in a ratio of the isomers 65:35, 58 g styrene and 0.025 g of hydroquinone are charged and the mixture is heated to 55-60 ° G. Thereafter 58 g of allyl alcohol are slowly added from the dropping funnel. After the finished Addition of allyl alcohol keeps the reaction mass at 60-700C for 60 minutes Achievement of an isocyanate group content of 14-15% by weight.

The product obtained is a 4,6-earballyloxyaminotolyl-2-isocyanate the (product C).

A reaction flask equipped as described above is filled with 100 g of oxypropylated glycerine (with a molecular weight of 500 and a content of hydroxyl groups 11.3% by weight) and 25 g of styrene are charged. The mass obtained is heated to 50-55 ° C and slowly add 192.3 g of product C from a dropping funnel. After the termination the addition of product C, the reaction mass is for 3-4 hours at 60 ° C Maintained up to a content of isozynate groups of 1.5-0.8% by weight, which is 80-90% by weight Conversion of the isocyanate groups corresponds. Furthermore, from the dropping funnel 4.2 g of diethylamine were added and the reaction mixture at 200 ° C. until it disappeared of the isocyanate groups held.

The finished product is a 70-violet solution of oligoester urethane in Styrene modified with N, Nl-substituted aliphatic amines, 2,5 Contains up to 3.5% by weight of urea groups and has the following properties: Molecular mass - 1200-1300 Conditional viscosity of an own solution in styrene according to the Yiskosimeter-4 at 200C - 46 seconds content of allyl bonds - 78-82 g Br2 / 100 g oligourethane Stability - over 9 months Example 6.

A four-necked flask, equipped as in Example 1, is 55.7 g of toluylene diisocyanate charged in a ratio of isomers 2.4 and 2.6 such as 65:35 and heated to 40-50 ° C. In the same flask are slowly poured out of the dropping funnel 74.5 g of castor oil, transesterified with 10% triethanolamine (manufactured according to patent specification of the GDR No. 120656, 1976) and dissolved in 53.85 g of methyl methacrylate and 0.1 g Hydroquinone, added. After the completion of the feed of the interesterified castor oil the mass is 1-0.5 hours at 60-70 ° C until it contains isocyanate groups 7-7.3 wt.% Held. Thereafter, the reaction mass 31.3 from the dropping funnel g of ethylene glycol monomethacrylate added. At the above-mentioned temperature, the reaction takes 5-5.5 hours to a content of isocyanate groups of 1.5-56% by weight carried out, which corresponds to an 80-85% by weight conversion of the isocyanate groups. After the isocyanate group content has been reached, in the reaction mass 6.9 g of diethylamine from the dropping funnel 40-500C introduced. After a holding time of 15 minutes, the mixture obtained is obtained the finished product that has no isocyanate groups.

The product obtained is a 70% solution of oligoester urethane acrylate in methyl methacrylate, which is modified with N, N1-substituted aliphatic amines contains 3.75-4.2% by weight of urea groups and has the following properties: Molecular mass - 2100-2200 Conditional toughness of a 5O% solution in styrene the viscometer-4 at 20bC - 50 seconds content of acrylic bonds - 83.2 g Br2 / 100 g oligourethane stability - over six months Example 7.

A reaction vessel equipped as in Example 1 is filled with 74.5 g of methyl methacrylate, 168 g of 1,6-hexamethylene diisocyanate and 0.04 g of hydroquinone were charged. The mixture obtained is heated to 40-5QOC and given from the dropping funnel slowly adding 130 g of ethylene glycol monomethacrylate. After the feeding of Ethyleneglykolmonomethakrylester the reaction mass is kept for 55 minutes until it is achieved a content of isocyanate groups of 11.1-11.5% by weight. The product obtained represents a 6-carbacrylolcyaminohexyl-1-isocyanate (product D).

A reaction flask equipped as in Example 1 is filled with 100 g of oxypropylated glycerine (with a molecular mass 500 and one Content of hydroxyl groups 11.3%) and 25 g of methyl methacrylate charged. The whole The mixture is warmed to 50-55 ° C. and slowly 247 g are added to it from the dropping funnel Product D at. After the end of the addition of product D, the reaction mass at 50-55 ° C 3 hours until a content of isocyanate groups 0.7-0.9 is achieved % By weight, which corresponds to an 85-87% by weight conversion of the isocyanate groups. Then 5.2 g of diethylamine are slowly added from the dropping funnel and the entire reaction mass is 15 minutes until the isocyanate groups have completely disappeared held.

The product obtained is a goat solution of Olig oe steruret hanakrylat in Met hylmet hakrylat, the N, Nl - substituted aliphatic Amines is modified, contains 1.75-2% by weight of urea groups and the following properties has: molecular mass - 1100-1300, content of acrylic bonds - 58.3 g Br2 / 100 g oligourethane Conditional toughness according to the viscometer -4 - at 200C -120 seconds Stability - over six months.

EXAMPLE 8.

A reaction flask equipped as in Example: 1 is labeled 222 g of 3-isocyanate methyl 3, 55-trimethylcyclohexyl isocyanate, 130 g of ethylene glycol monomethacrylate 100 g castor oil, interesterified with glycerine with a content of Hydroxyl groups 9.1% by weight, 113 g of methyl methacrylate and 0.05 g of hydroquinone charged. The won Reaction mass is heated to 45-53 ° C for 4-5 hours and holds it up to one 85-90Gea OigerL conversion of the isocyanate groups, resulting in a content of 0.7-0.9% by weight Corresponds to isocyanate groups.

The vessel is then charged with 5.1 g of diethylamine and kept at 40-45 ° C within 2-3 hours until the isocyanate groups are completely converted held.

The finished product is a 70% solution of oligoester urethane acrylate in methyl methacrylate which is substituted with N, N1-substituted aliphatic amines is, contains 2-2.5% by weight of urea groups and has the following properties: Molecular mass - 1100-1300 content of acrylic bonds - 58.3 g Br2 / 100 g oligourethane. Conditional toughness one show solution in styrene after the viscometer-4 - at 200C - 140 seconds Stability - over 6 months Example 9 (for comparison) In a reaction vessel equipped As in Example 1, 100 g of castor oil, transesterified with glycerine (with a content of hydroxyl groups 9.1% by weight), and 25 g of methyl methacrylate mixed. One warms up the mass aif 50-55 ° C and slowly leads from the dropping funnel g of product A, obtained as in Example 1. After the product has been fed A. the heating mass at 55 0 up to a content of isocyanate groups of 0.41 wt. held for 9 hours.

The finished product turned into organic after 4 days Solvent-insoluble gummy mass.

Example 10. (for comparison) A reaction flask equipped as in Example 1, 100 g of oxypropylated glycerine (with a molecular mass 500 and a hydroxyl group content of 11.3% by weight) and 25 g of methyl methacrylate. The mixture is warmed to 50-55 ° C. and 253 g of product A are slowly added as in example 1, too. After the feed has ended, the reaction mass is at 55 ° C to such a content of isocyanate groups of 0.35 wt, $ held for 7 hours. The finished oligourethane acrylate turned into organic after 3 days Solvent-insoluble jelly-like mass.

Claims (3)

PROCESS FOR THE PRODUCTION OF ALKENE-UNSATURATED OLIGOURETHANES, THAT ARE MODIFIED WITH N, N1-SUBSTITUTED ALIPHATIC AMINES AND ARE 0.5 - 5% BY WEIGHT URESE GROUPS INCLUDE PTENT CLAIMS experienced for the creation of alkene unsaturated Oligourethanes modified with N, N1-substituted aliphatic amines and contain 0.5-5% by weight of urea groups, d u r c h e k e n n z e i c n e t that one a) the Di or. Polyisozyanate with polyols and alkene unsaturated hydroxyl-containing compounds at 20-700C in the presence of an antioxidant Reacts until a conversion to the isocyanate groups at least 80 wt.% Achieved and b) the alkene-unsaturated oligourethane obtained with N, N1-substituted ones aliphatic amines at 20-600C and a ratio of the NCO groups to the Ng2 groups converts equal to 0.5-5. 2. The method according to claim 1, d a d u r c h g e -k u n ri z e i c n e t that one c) the implementation with the simultaneous introduction of starting components or also during their subsequent addition. 3. The method of claim 1, d a d u r c h g e -k e n n z e i c n e t that one d) to reduce side reactions steps a) and b) Performs in the medium of active monomers as a solvent.