Highly functionalised polyurethanes

The present invention relates to highly functional, highly branched polyurethanes, methods for producing the same, and monomers for producing this type of polyurethane. Highly functionalized molecules, namely dendrimers or arboroles, and hyperbranched polymers, also called hyperbranched polymers, have recently received attention in chemistry and pharmacy. Dendrimers are three-dimensional, highly regular, highly branched oligomers and polymeric compounds. It is formed by starting with small molecules and repeating the reaction sequentially and continuously. In this method, increasingly higher branches are formed at the ends, which are functional groups, in each case. Then, the functional group at the terminal becomes a starting point of further branching in order. A description of Dendrimer can be found in Tomalia et al. (DA Tomalia, AM Naylor, WA Goddard III, Angew. Chem., 1990, 102, 119-157). Highly branched polyurethanes include Spindler, JMJ Frechet, J. Chem Soc. Perkin Trans. I, 1993, 913). The monomer used here has the following structural formula.<img file="JP3781432B2_D0001.tif" />The isocyanate-terminated highly branched polyurethane can be produced by an addition polymerization reaction of this monomer. The problem in this case lies in the production of the monomer. The starting material used is a compound having the following structure.<img file="JP3781432B2_D0002.tif" />First, the hydroxyl group is blocked with tert-butyldiphenylsilyl chloride, and the nitro group is converted to an isocyanate group by hydrogenation followed by phosgenation. The isocyanate group is then blocked with phenol. To carry out the addition reaction, the blocking agent is removed. The production of highly branched polyurethanes is uneconomical by the methods described due to the need for phenol removal and the use of extremely expensive tert-butyldiphenylsilyl chloride. Kumar and S. Ramachrishnan, J. Chem. Soc., Chem. Commun. 1993, 1453 describe highly branched polyurethanes made from monomers with the following structures.<img file="JP3781432B2_D0003.tif" />Acid azides lose nitrogen on heating, and immediate dislocations occur to form isocyanates. This reacts further to give the hydroxyl-terminated polyurethane. Again, acid azides are easily decomposed and, in some cases, accompanied by vigorous reactions, making the production of starting monomers difficult. Furthermore, urethane groups formed from isocyanates and phenolic hydroxyl groups are heat unstable. An object of the present invention is to provide highly branched polyurethanes and dendrimeric polyurethanes that can be reproducibly produced from readily available monomers in a simple production process. The present inventors aim at a monomer containing one NCO group and n groups reactive with NCO groups, or one group and n NCO groups reactive with NCO groups. It has been found that this is achieved by the reaction of the containing monomers. The group reactive with the NCO group is particularly a mercapto group, preferably an amino group or a hydroxyl group, and n is in the range of 2 to 5, more preferably in the range of 2 to 4, especially in the range of 2 to 3. The range is preferred. The difference between highly branched polyurethanes and dendritic polyurethanes is that in dendritic polyurethanes starting from the reaction initiator nucleus, they are shell-like at a defined reaction stage (formation) and have a defined molar weight. Highly branched polyurethanes are irregularly constructed and have a molar weight distribution. These structural differences are shown in the schematic examples below. Monomer AB₂[Functional groups A and (B)_nHighly branched polyurethane formed from molecules containing:<img file="JP3781432B2_D0004.tif" />Reaction initiator nucleus I and monomer AB containing at least two functional groups B'₂Polyurethane dendrimer (dendritic polyurethane) formed from:<img file="JP3781432B2_D0005.tif" />In this regard, in the above case, A and B may be hydroxyl or isocyanate groups, BA is a urethane group and I is a reaction initiator nucleus containing at least two functional groups B'. Depending on the functional value, even more than the branches of the dendrimer as shown can be attached to the reaction initiator nucleus I. Monomer AB₂And in the reaction initiator nucleus I containing at least two functional groups B', A represents an NCO group or a group reactive with an NCO group, and B and B'are a group reactive with an NCO group or an NCO group. Represents, A is reactive to B and B', and n is a positive number, at least 2. It is preferable that the groups B and B'are NCO groups. Further, it is preferable that the NCO group of the group B is converted into a form in which the NCO group of the group B cannot react with the group reactive with the NCO group by blocking the group B. Blocking is generally done by the formation of uretadione or oxime. Further, the functional groups B and B'are generally groups that are reactive with the NCO group, and it is preferable that the functional groups B and B'are amino groups or hydroxyl groups. As the reaction initiator nucleus I, ammonia or at least a bifunctional amine; or an aliphatic, cyclic aliphatic or aromatic diol, triol, tetraol or sugar alcohol is generally used. The functional group B is preferably an H-functional group, particularly an amino group or a hydroxyl group. Blocking when the group B is a hydroxyl group is generally performed by ketalization or acetalization. In order to produce the compound of the present invention, first AB_nIt is necessary to produce a type of monomer. AB above_nIn, A and B are isocyanate groups and H-functional groups (functional groups having active hydrogen) reactive with them, respectively, and n is a positive number of 2 or more, particularly 2 or 3. As an example, AB based on 2,4-toluene diisocyanate (TDI) and trimethylolpropane_nThe monomer can be described first. First, one of the NCO groups in TDI is capped in a manner known per se. This is done, for example, by reacting with an oxime, phenol or other suitable blocking agent to form uretdione. Based on the different reactivity of the two NCO groups, in the case of 2,4-TDI, the NCO group at the 4-position is preferably blocked. The free NCO group can be reacted with a compound having at least 3 H-functional groups, such as trimethylolpropane, glycerol or alkanolamines (eg, diethanolamine). After removal of the capping agent, the molecule with two hydroxyl groups and one NCO group can be reacted by its reaction means, resulting in a highly branched or dendrimeric polyurethane. Similarly, that is, it is obtained by capping part of the isocyanate group and reacting the other part of the isocyanate group with at least 3 H-functional groups, especially all aliphatic and aromatic diisocyanates or polys. By reacting isocyanate, a monomer having one NCO group and at least two hydroxyl groups can be obtained. Particularly suitable isocyanates include 2,4-toluene diisocyanate (2,4-TDI), 2,6-toluene diisocyanate (2,6-TDI), and 2,4'-diphenylmethane diisocyanate (2,4'-. MDI), 4,4'-diphenylmethane diisocyanate (4,4'-MDI), 1,5-naphthylene diisocyanate (NDI), 1,4-phenylenediocyanide, 1,3-tetramethylxylylene diisocyanate (TMXDI), MDI hydride (HMDI), isophorone diisocyanate (IPDI), hexamethylene-1, 6-Diisocyanate (HDI), 2-Isocyanatepropylcyclohexylisocyanate (IPCI), 2-Butyl-2-ethylpentaethylene diisocyanate (BEPDI), Lysine diisocyanate (LDI), 1,12-dodecyldiisocyanate, Cyclohexyl-1,3- Alternatively, -1,4-diisocyanate and 2-methylpentamethylene diisocyanate (MPDI) can be mentioned. Conversely, by capping at least one H-functional group of a compound containing at least two H-functional groups and reacting it with a free (unreacted) H-functional group with an isocyanate group. AB_nIt is also possible to produce monomers. In the case of polyfunctional alcohols, the cap can be made, for example, by the formation of acetals or ketals. For example, the two hydroxyl groups of trimethylolpropane or glycerol are capped by reaction with acetone and the free hydroxyl groups react with the isocyanate group. This type of capped triol is reacted with 2,4-tolylene diisocyanate (TDI), where the NCO group at the 4-position is blocked, for example by the formation of uretdione or by reaction with an oxime such as acetone oxime. If so, a monomer containing 2 hydroxyl groups and 1 blocked NCO group can be obtained with high selectivity. The reaction can be schematically represented using trimethylolpropane (TMP), acetone, 2,4-TDI and acetone oxime:<img file="JP3781432B2_D0006.tif" /><img file="JP3781432B2_D0007.tif" />In the first step, a protected triol (1) is made from TMP and acetone; that is, two hydroxyl groups are capped. In the second step (where the first and second steps should not be interpreted in the order described), one NCO of 2,4-TDI is blocked with acetone oxime to give monoisocyanate (2). .. These two starting materials react to give compound (3) with two capped hydroxyl groups and capped isocyanate groups. Hydrolysis makes the hydroxyl groups reusable (4), and after liberation of the isocyanate groups gives a monomer that can react to give a highly branched or dendrimeric polyurethane. Instead of capped trimethylolpropane, capped glycerol, N-hydroxyalkyloxazolidine or dialkanolamine can also be used. When a dialkanolamine is used, it is preferable that the NH group reacts and the cap of the OH group can be eliminated. The reaction proceeds with a high selectivity. The isomerized monomer can be obtained by the reaction of acetone-capped TMP with 2,4-TDI. The reaction proceeds according to the following formula:<img file="JP3781432B2_D0008.tif" />Considering the high reactivity of the NCO group at the 4-position, this reaction also proceeds extremely selectively. Similarly, the free NCO group of compound (5) should be blocked with, for example, an oxime after the above reaction in order to facilitate the hydrolysis of dioxane without causing a reaction between the monomers. AB synthesized in a heterosexual relationship with (4) after hydrolysis of the dioxane ring_nThe monomer is obtained. Monomers capped in this way are stable even when stored at room temperature for several weeks. To produce the highly branched or dendrimeric polyurethane of the present invention, the functional groups of the monomers are activated to allow the reaction. In the simplest case, the highly branched polyurethane of the present invention can be produced by the one-pot method. To do this, the functional groups of the monomer molecules are activated so that they can react with each other to form urethane groups. Since the resulting oligomer or polymer is usually in a solid or highly viscous state, it is advantageous to carry out the reaction in solution. Suitable solvents are compounds commonly used in making polyurethane in solution, especially acetone, methyl ethyl ketone, dimethylformamide, ethyl acetate, benzene, xylene, chlorobenzene, dichlorobenzene, chloroform, methylene chloride, cyclic aliphatic hydrocarbons or It is toluene. Commonly known urethane forming catalysts, such as organic compounds, can be used to accelerate the reaction. Highly branched polyurethane is a material in a highly viscous or solid state. They are separated from the solvent used by precipitation and filtration, or by distillation removal of the solvent. Free caps that may be present in the solution are removed with the solvent. If desired, the hyperfunctional polyurethane may be purified, for example, by solvent washing, recrystallization or chromatography. In the production of the dendritic polyurethane of the present invention, a distinction should be made between the convergent method and the divergent method. The spreading method starts with the reaction initiator nucleus and adds a monomer around it from generation to generation. In this step, the protecting groups of the monomers must ensure that the monomers react only with the reaction initiator nuclei or the functional groups of the dendryer and not with each other. In the convergence method, individual branches are first synthesized and then linked to the reaction initiator nucleus. As an example, TMP as a reaction initiator nucleus containing at least two functional groups B', and TMP.<img file="JP3781432B2_D0009.tif" /><img file="JP3781432B2_D0010.tif" /><img file="JP3781432B2_D0011.tif" />By adding the monomer (5) to the free hydroxyl group of the dendryer, the generation of the dendryer can be further synthesized. Due to the regular structure of the dendryer molecule, the amount of monomer required for the synthesis of each generation can be calculated accurately and can be used for the synthesis. In order to synthesize a dendrimer having a defined structure, it is advantageous to isolate the reaction product after each generation synthesis, purify it, and use the product treated in this way for the next generation synthesis. is there. The dendritic polyurethane is advantageously produced in solution and the above solvents can be used. The urethanization catalyst can be used to accelerate the reaction. Convergent synthesis of dendritic polyurethane, i.e., synthesis of branches added to the reaction initiator nucleus, is possible in principle in the same way. When using the above monomers, in dendritic polyurethane convergent synthesis a monomer unit with two OH groups and one capped NCO group would be used as the starting molecule; eg molecule (4). And the monomer grafted for each generation (5). The addition of additional monomers is carried out as described above. The blocked hydroxyl group-containing branch synthesized in this way is added to the H-functional reaction initiator nucleus after activating the NCO group of the initiator monomer. After activation of the terminal hydroxyl group, its structure is perfectly compatible with the dendryer produced by the spreading method described above. A (B)_n(A, B and n are synonymous with the above) type monomers can also be produced using aliphatic isocyanates, as is clear from the examples of isocyanates that can be used in the present invention. As an example, the production of this type of monomer from trimethylolpropane capped with 1,6-hexamethylene diisocyanate (HDI) must be described herein. Since the reactivity of the two NCO groups in the HDI is identical, an excess capped alcohol should be used to make monourethane. The molar ratio of capped alcohol to diisocyanate is at least 3 diisocyanates to 1 alcohol, especially at least 5. Under these conditions, the reaction giving monourethane proceeds with high selectivity and high yield. Unreacted diisocyanates can be removed from the reaction product by a simple method, such as distillation. In general, the production of such monomers can be expressed as:<img file="JP3781432B2_D0012.tif" />As shown in the case of TDI-based monomers, this molecule can be linked directly to the reaction initiator nucleus with an H-functional group. After activation of the OH group, a 0th generation dendrimer is obtained, to which the molecule (9) can be added in sequence. In addition, the monomer can be made by blocking the free NCO group and then activating the hydroxyl group. It can be reacted in the same manner as described above to obtain a highly branched or dendritic polyurethane.<img file="JP3781432B2_D0013.tif" />Highly branched and dendritic polyurethanes can be used, for example, as polyurethane lacquers and paints or highly functional crosslinkers for polyurethane foams. The present invention will be described in more detail with reference to the following examples. &lt;Example&gt; [Example 1] Production of acetone-cap trimethylolpropane (isopropylidene-TMP, (1)) 250 g (1863 mmol) of trimethylolpropane, 750 ml of acetone, 750 ml of petroleum ether 30/75 and It was refluxed for 25 hours with 0.15 g of p-toluenesulfonic acid monohydrate. The water was then removed via a 50 cm filling tower for 21 hours. The solution was then cooled to room temperature, 0.5 g of sodium methoxide was added, and the mixture was stirred at room temperature for 1 hour. The solution was then filtered to remove excess solvent with a rotary evaporator and the residue distilled through a 15 cm Vigreux column under reduced pressure. The reaction product was a colorless liquid with a boiling point of 71-72 ° C (0.5 mbar) and its yield was 254 g, 78%.

[Example 2] Production of monourethane (2) from 2,4-TDI and acetone oxime 232 g of 2,4-toluene diisocyanate (1334 mmol) was first introduced into 1330 ml of dry acetone under a nitrogen atmosphere. .. 48.7 g of acetone oxime (667 mmol) was dissolved in 450 ml of dry acetone and it was added dropwise to the reaction solution for 8 hours at room temperature. The solution was left overnight and concentrated the next day on a rotary evaporator. The obtained crystalline product was recrystallized from acetone and washed with petroleum ether. The obtained product was a colorless solid having a melting point of 109 to 111 ° C, and the yield was 89.2 g, 54%.

[Example 3] Production of monourethane (5) from 2,4-TDI and isopropylidene-TMP 87.8 g of 2,4-toluene diisocyanate (504 mmol) was first introduced into 300 ml of petroleum ether 30/75. did. 44.0 g of the product obtained in Example 1 was dissolved in 80 ml of petroleum ether and added dropwise at room temperature over 8 hours in a nitrogen atmosphere. The solution was left overnight and the next day the solid was filtered under suction. The residue was washed twice and dried under reduced pressure. The obtained product was a colorless solid having a melting point of 135 to 137 ° C, and the yield was 81.2 g, 92%.

[Example 4] Production of diurethane (isomer of (3)) from 2,4-TDI, isopropylidene-TMP and acetone oxime 30.0 g of the reaction product obtained in Example 3 was added to 500 ml of dry acetone. Dissolved. A solution prepared by dissolving 6.29 g of acetone oxime in 100 ml of dry acetone was added dropwise to this solution under a nitrogen atmosphere for 2 hours, and then concentrated at 35 ° C. on a rotary evaporator. The residue was washed with petroleum ether 30/75 and dried under reduced pressure. The result was a colorless solid that melted after being left for a considerable period of time. The yield was 30.5 g, 83%.

[Example 5] Production of diurethane (3) from 2,4-TDI, acetone oxime and isopropylidene-TMP The reaction product obtained in 20 g of Example 2 and the reaction obtained in 14.1 g of Example 1. The products were added together in 160 ml of dry acetone, 8 μl of di-n-butyl dilaurate was added, and the solution was stirred at 45 ° C. for 16 hours. After this, the IR spectrum no longer showed the NCO band. The solution was concentrated on a rotary evaporator at 35 ° C. and the residue was kneaded with petroleum ether 30/75. The obtained paste was washed and dried under reduced pressure. The result was washed with petroleum ether 30/75 and then vacuum dried. The obtained product was a colorless, hygroscopic solid, and the yield was 26.9 g, 79%.

[Example 6] Production of Urethane Diol (4) 15.2 g of the reaction product obtained in Example 5 was dissolved in 190 ml of methanol and 45 ml of water, and 0.04 g of oxalic acid was added to this solution. The solution was stirred at room temperature for 72 hours. Methanol was removed from this solution using a rotary evaporator at 30 ° C. The aqueous residue was extracted with ethyl acetate and the ethyl acetate layer was dried over sodium sulfate overnight and then concentrated on a rotary evaporator. The result was a yellowish solid with a melting point of 53-55 ° C and a yield of 8.8 g, 64%.

[Example 7] Production of urethane diol isomer of (4) 30.0 g of the product obtained in Example 4 was dissolved in 80 ml of methanol and 20 ml of water, and 0.09 g of oxalic acid was added to this solution. It was. The solution was stirred at room temperature for 24 hours. The solution was then stripped of most of the methanol on a rotary evaporator at 30 ° C. The aqueous residue was extracted with ethyl acetate and the ethyl acetate layer was dried over sodium sulfate overnight and then concentrated on a rotary evaporator. The result was a yellowish solid with a melting point of 54-56 ° C and a yield of 14.6 g, 54%.

[Example 8] Production of Urethane Diol from 2,4-TDI, Acetone Oxime and Diethanolamine 6.37 g (60.6 mmol) of diethanolamine was dissolved in 100 ml of dry acetone. To this, a solution prepared by dissolving 15.0 g (60.6 mmol) of the reaction product obtained in Example 2 in 120 ml of dry acetone was added dropwise to the solution in a nitrogen atmosphere for 2 hours at room temperature. The solution was stirred at room temperature for 1 hour and left overnight. The solution was then concentrated on a rotary evaporator at 35 ° C. and the residue was removed in a small amount of dry acetone. The resulting solution was covered with a small amount of petroleum ether 30/75 and left overnight at 3 ° C. The crystallization product was suction filtered and dried under reduced pressure. The result was a colorless solid, the yield of which was 9.6 g, 45%.

[Example 9] Production of highly branched polyurethane from 2,4-TDI and TMP 9.5 g of the product obtained in Example 6 was dissolved in 500 ml of methyl ethyl ketone, and 25 μl of di-n-butyl dilaurate was added. It was. The solution was heated to 80 ° C and stirred at this temperature for 24 hours. The resulting solid was suction filtered, washed with methyl ethyl ketone and dried under reduced pressure. By GPC analysis using standard polystyrene, the following characteristic values: M_n= 431, M_w= 1066, M_w/ M_n= 2.48, was obtained.

[Example 10] Production of highly branched polyurethane from 2,4-TDI and TMP 19.0 g of the product obtained in Example 7 was dissolved in 500 ml of monochlorobenzene. The solution was heated to 100 ° C. with stirring and maintained at this temperature for 3 hours. The resulting solid was suction filtered, washed with monochlorobenzene and dried under reduced pressure. By GPC analysis, characteristic value: M_n= 568, M_w= 1292, M_w/ M_n= 2.28, was obtained.

[Example 11] Production of highly branched polyurethane from 2,4-TDI and diethanolamine 8.8 g of the product obtained in Example 8 was dissolved in 500 ml of methyl ethyl ketone. The solution was then heated to 80 ° C. and stirred at this temperature for 24 hours. The resulting solid was suction filtered, washed with methyl ethyl ketone and dried under reduced pressure. By GPC analysis, characteristic value: M_n= 1012, M_w= 1983, M_w/ M_n= 1.96, was obtained.

[Example 12] Production of 0th generation dendryer (6) from 2,4-TDI and isopropylidene-TMP Monourethane (5) obtained in Example 3 of 20.0 g was added to 100 ml of dry acetone at 40 ° C. Dissolved in, 2.57 g of trimethylolpropane and 5 μl of di-n-butyl dilaurate were added. The solution was then refluxed under a nitrogen atmosphere for 6 hours. The NCO band was no longer present in the IR spectrum of this solution. The solution was filtered, then cooled and concentrated on a rotary evaporator at 45 ° C. The obtained yellowish oil was left overnight at room temperature. It was then viscous and kneaded and crystallized in petroleum ether 30/75. The solids were washed with petroleum ether 30/75 and then vacuum dried. The result was 15.6 g of a colorless solid.

[Example 13] Production of 0th generation dendrimer (7) from 2,4-TDI and TMP by activation of OH group 12 g of product (6) obtained in Example 12 was dissolved in 80 ml of methanol. , 20 ml of water and 2 ml of 0.1 mol hydrochloric acid were added to this solution. It was allowed to stand at room temperature for 72 hours, neutralized with sodium carbonate, then filtered, and then methanol was removed on a rotary evaporator at 30 ° C. The aqueous residue was extracted with ethyl acetate, and the ethyl acetate layer was dried over sodium sulfate and concentrated at 30 ° C. on a rotary evaporator to obtain a dried product. A 5.4 g yellowish solid was obtained.

[Example 14] Production of first-generation dendryer (8) from 2,4-TDI and TMP Reaction product (7) obtained in Example 12 of 4.00 g and reaction production of Example 3 of 7.90 g. Together, they were dissolved in 50 ml of dry acetone, 2.5 μl of di-n-butyl dilaurate was added, and the solution was stirred under a nitrogen atmosphere at 50 ° C. for 4 hours. The NCO band was no longer present in the IR spectrum of this solution. The solution was concentrated on a rotary evaporator at 35 ° C., the residue was removed in 80 ml of methanol, 5 ml of water and 1 ml of 0.1 M hydrochloric acid were added, and the solution was allowed to stand overnight at room temperature. Excess sodium carbonate was added, then the solution was filtered, and then methanol was removed on a rotary evaporator at 30 ° C. The aqueous residue was extracted with ethyl acetate, and the ethyl acetate layer was dried over sodium sulfate and concentrated at 30 ° C. on a rotary evaporator to obtain a dried product. The reaction product was a yellowish solid. The yield was 5.8 g.

[Example 15] Production of 2nd Generation Dendylmer from 2,4-TDI and TMP The reaction product obtained in Example 14 of 4.00 g and the reaction product of Example 3 of 5.75 g were added to 70 ml of acetone. Dissolved in, 3.5 μl of di-n-butyl dilaurate was added, and the mixture was stirred under a nitrogen atmosphere at 50 ° C. for 3 hours. The NCO band was no longer present in the IR spectrum of this solution. The solution was concentrated on a rotary evaporator at 35 ° C to dryness. 2.0 g of residue was dissolved in 80 ml of methanol and 5 ml of water and 1 ml of 1 M hydrochloric acid were added. The solution was stirred at room temperature for 24 hours. Excess sodium carbonate was added, then the solution was filtered, and then methanol was removed on a rotary evaporator at 30 ° C. The aqueous residue was extracted with ethyl acetate, and the ethyl acetate layer was dried over sodium sulfate and concentrated at 30 ° C. on a rotary evaporator to obtain a dried product. The reaction product was a yellowish solid. The yield was 0.6 g.

[Example 16] Production of monourethane (9) from HDI and isopropylidene-TMP 1680 g (10 mol) of HDI and 0.84 g of di-n-butyl dilaurate were stirred in a nitrogen atmosphere at 50 ° C. Heated up to. 348 g of the reaction product obtained in Example 1 was added dropwise over 30 minutes with stirring at this temperature. After completion of the dropping, the reaction mixture was left at this temperature for an additional 30 minutes. The monomeric HDI was removed from the reaction product by distillation with a thin layer evaporator at 165 ° C. and 2.5 mbar. The resulting reaction product had the following properties; Purity: 88.6% (Area% by GPC) NCO Content: 12.3 wt% Viscosity (25 ° C): 1200 mPa · s Residual Monomer Content: &lt; 0.2 wt% [Example 17] Production of Monourethane from HDI and Isopropyridene Glycerol Instead of the reaction product obtained from Example 1, 264 g (2 mol) of isopropylidene glycerol (Fluka) The procedure was the same as in Example 16 except that AG) was added. The resulting reaction product had the following properties; Purity: 89% (Area% by GPC) NCO Content: 13.7 wt% Viscosity (25 ° C): 174 mPa · s Residual Monomer Content: &lt; 0.2 wt% [Example 18] Production of diurethane from HDI, isopropylidene-TMP and acetone oxime 100 g of the reaction product obtained in Example 16 and 50 mg of di-n-butyl dilaurate were first introduced. Then, an equimolar amount of acetone oxime dissolved in dry acetone was added dropwise at room temperature for 15 minutes with stirring in a nitrogen atmosphere. After completion of the dropwise addition, the reaction mixture was stirred at room temperature for an additional hour. Acetone was then removed with a rotary evaporator and the reaction product was purified by column chromatography on silica gel using ethyl acetate as an eluent. The viscosity of the obtained reaction product was 2140 mPa · s (23 ° C).

[Example 19] Production of Diurethane from HDI, Isopropyridene Glycerol and Acetone Oxime Except for using 100 g of the reaction product obtained from Example 17 instead of the reaction product obtained from Example 16. The same procedure as in Example 18 was performed.

[Example 20] Production of Urethane Diol (10) 20 g of the reaction product obtained from Example 18 was first introduced and then mixed with 100 ml of methanol, 20 ml of water and 15 ml of 0.1 mol hydrochloric acid. added. The mixture was stirred at 30 ° C. for 8 hours and then left overnight. It was extracted 3 times by shaking with 50 ml of ethyl acetate each. All ethyl acetate extracts were combined and washed with 20 ml of 0.1 molar sodium carbonate solution and then twice with 20 ml of water. After removing the aqueous layer, the organic layer was dried over sodium sulfate. After removing ethyl acetate, NCO-cap diol was obtained. Hydrolysis was performed quantitatively. Viscosity: 1070 mPa · s (23 ° C) [Example 21] Production of Urethane Diols from HDI, Acetone Oxime and Isopropylidene Glycerol Obtained from 20 g of Example 19 instead of the reaction product obtained from Example 18. The same procedure as in Example 20 was carried out except that the reaction product obtained was used. Viscosity: 4740 mPa · s (23 ° C) [Example 22] 100 g of highly branched polyurethane from HDI and TMP The product obtained in Example 20 was treated with 100 mg of di-n-butyl dilaurate and round bottom. In the flask, it was heated at 110 ° C. under a nitrogen atmosphere. Samples were taken every 2 hours for gel permeation chromatography analysis. It was found that the molar mass of the product increased continuously. After heating for 10 hours, the product with molar mass distribution was obtained with the following characteristic values; melting point width: 45-50 ° CM_n: 872g / mol M_w: 1532g / mol M_w/ M_n: 1.76 In addition, the product contained 12.6 area% of starting material.

[Example 23] Highly branched polyurethane from HDI and glycerol Similar to Example 22 except that the reaction product obtained from Example 20 was used instead of the reaction product obtained from Example 20. The procedure was performed. Melting point width: 48-52 ° CM_n: 830g / mol M_w: 1161g / mol M_w/ M_n: 1.40 [Example 24] Preparation of 0th generation dendryer from HDI and TMP using TMP as the reaction initiator nucleus 1 mol of the reaction product obtained in Example 16 and 50 ml of dried methyl ethyl ketone were first introduced. It was then heated to 70 ° C. A solution of 0.3 mol of trimethylolpropane dissolved in 150 ml of methyl ethyl ketone was added with stirring, stirred at 110 ° C for 15 minutes under a stream of nitrogen, and the mixture was further stirred at 70 ° C for 90 minutes. The solvent was removed on a rotary evaporator and the residue was separated by chromatography on silica gel using ethyl acetate as an eluent. Obtained 0th generation dendrimer with capped hydroxyl group and its characteristic values: Viscosity (10 wt% butyl acetate solution, 50 ° C): 2140 mPa · s Elemental analysis: C₅₇H₁₀₄O₁₈Calculated values: C: 58.97, H: 8.97, N: 7.24 Measured values: C: 58.70, H: 9.18, N: 6.98 [Example 25] Production of 0th generation dendrimer from HDI and TMP by activation of OH group The reaction product obtained in 10 g of Example 24 was treated with 30 ml of methanol, 60 ml of water and 13 ml of 1 mol hydrochloric acid, and the mixture was stirred under reflux for 8 hours. Methanol was then removed on a rotary evaporator and the residue was collected in 100 ml of methyl ethyl ketone, which was washed first with 15 ml aqueous 1 molar sodium carbonate solution and then with 20 ml of water. After removing the aqueous layer, the organic layer was dried with sodium carbonate. After removal of the solvent, a 0th generation terminal hydroxyl group dendryer was obtained. Viscosity: 7110 mPa · s (10 wt% butyl acetate solution, 50 ° C) Elemental analysis: C₄₈H₉₂N₆O₁₈Calculated: C: 55.37, H: 8.91, N: 8.07 Measured: C: 55.30, H: 9.01, N: 7.80