Polyurethane dispersant and the method for its preparation

Abstract

The present invention is related to a polyurethane dispersant and a preparation method thereof. The polyurethane dispersant is terminated by a nitrogen-containing heterocyclic compound during synthesis. The nitrogen-containing heterocyclic compound is prepared by subjecting anhydride and a compound containing a primary amine and a secondary amine or a hydroxyl or mercapto group to dehydration condensation. The condensed product is the nitrogen-containing heterocyclic compound, containing a reactive hydrogen. The structural formula of the compound containing the primary amine and the secondary amine or hydroxyl or mercapto group is shown as follows: ##STR00001##
wherein n=1 to 5, and preferably 2 to 4, R.sup.1 and R.sup.2 are respectively alkyls containing 1 to 8 carbons, R.sup.1 and R.sup.2 are independent of each other or connected by a chemical bond to form one or more saturated or unsaturated 4-member to 8-member rings, and X represents N, O, or S.

Claims

1. A polyurethane dispersant, which is terminated by a nitrogen-containing heterocyclic compound during synthesis, wherein the nitrogen-containing heterocyclic compound is prepared by subjecting anhydride and a compound containing a primary amine and a secondary amine or a hydroxyl or mercapto group to dehydration condensation, and the condensed product is the nitrogen-containing heterocyclic compound, containing a reactive hydrogen, and the compound containing the primary amine and the secondary amine or hydroxyl or mercapto group is selected from the group consisting of 3-(2-aminoethyl)indole, 4-(2-aminoethyl)phenylmethanol, 1H-imidazole-4-ethanamine, 2-(2-aminoethyl)phenol, 2-methylindole-3-ethylamine, N-ethyl-ethylenediamine, N-phenylethylenediamine, 3-amino-1-methylpyrazole, 2-(aminomethyl)morpholine, 5-(aminomethyl)indole, 4-(aminomethyl)benzalcohol, 5-aminomethylindazole, 2-(2-aminopropyl)pyrrole, 4-(2-aminopropyl)phenol, 1-(2-aminoethyl)piperazine, 4-methyl-5-aminoindole, 5-aminoisoindoline, 1-amino-4-hydroxylanthraquinone, 4-aminobenzimidazolinone, or 4-amino-3-mercaptopyridine.

2. A method to produce the polyurethane dispersant of claim 1, wherein the method comprises: reacting a Group A reactant comprising an isocyanate (NCO) group with a Group B reactant in a mixture of dimethyl benzene and butyl acetate with dibutyltin dilaurate (DBTDL) as catalyst at a temperature of about 70 to 80 C., wherein 1-90% of the isocyanate groups of the group A reactant are reacted with the group B reactant, adding a group C reactant and continuing the reaction at about 70 to 80 C., wherein 5-80% of the isocyanate groups of the group A reactant are reacted with the group C reactant, and wherein the total amount of the isocyanate groups reacted with group B and group C reactants is about 30-90%, and maintaining the reaction mixture at about 50 to 60 C., and adding a group D reactant to react with the rest of the isocyanate groups in the group A reactant, wherein the group A reactant comprises one or a plurality of isocyanate polymers with an average functionality of 2.0 to 6.0, group B reactant comprises monohydroxyl compounds of polyether or polyester or polyacrylic ester, group C reactant comprises a chain extender of two functionalities, and group D reactant comprises a nitrogen-containing heterocyclic compound.

3. A method according to claim 2, wherein the monohydroxyl compounds are obtained by a ring opening reaction of lactones with mono alcohols, or by polycondensation of mono alcohols, diols, dicarboxylic acids and anhydrides, or by polycondensation of mono alcohols and hydroxyl acids, or a combination thereof.

4. A method according to claim 2, wherein the extender of two functionalities is a diol, diamine, or dicarboxylic acid with an average molecular weight of 600 to 2000.

5. A method according to claim 3, wherein the monohydroxyl compounds of the polyester have a number-average molecular weight of 300 to 5000, and the monohydroxyl compounds of the polyether have a number-average molecular weight of 300 to 6000.

6. A method according to claim 5, wherein the monohydroxyl compounds of the polyester have a number-average molecular weight of 1000 to 3000, and the monohydroxyl compounds of the polyether have a number-average molecular weight of 1000 to 4000.

7. A method according to claim 2, wherein monohydroxyl compounds of polyacrylic ester are prepared using (methyl)acrylic ester CH.sub.2C(CH.sub.3)C(O)OR as a monomer under the telomerization of 2-mercaptoethanol with an initiator, wherein the number-average molecular weight is 300 to 20000, wherein R is an akyl group with 1 to 18 carbons.

8. The method according to claim 7, wherein the initiator is azobisisobutyronitrile (AIBN).

9. The method according to claim 7, wherein the number-average molecular weight is 500 to 10000.

10. The method according to claim 2, wherein the nitrogen-containing heterocyclic compound is prepared as follows: the anhydride and the compound which contains a primary amine and a secondary amine or a hydroxyl group or a mercapto group with a molar ratio of 1:1 react into the nitrogen-containing heterocyclic compound under 180 to 230 C. under dehydration condensation reaction, the reaction product is the nitrogen-containing heterocyclic compound with a reactive hydrogen, wherein the compound which contains a primary amine and a secondary amine or a hydroxyl group or a mercapto group is 3-(2-aminoethyl)indole, 4-(2-aminoethyl)phenylmethanol, 1H-imidazole-4-ethanamine, 2-(2-aminoethyl)phenol, 2-methylindole-3-ethylamine, N-ethyl-ethylenediamine, N-phenylethylenediamine, 3-amino-1-methylpyrazole, 2-(aminomethyl)morpholine, 5-(aminomethyl)indole, 4-(aminomethyl)benzalcohol, 5-aminomethylindazole, 2-(2-aminopropyl)pyrrole, 4-(2-aminopropyl)phenol, 1-(2-aminoethyl)piperazine, 4-methyl-5-aminoindole, 5-aminoisoindoline, 1-amino-4-hydroxylanthraquinone, 4-aminobenzimidazolinone, or 4-amino-3-mercaptopyridine.

11. The method according to claim 10, wherein the anhydride is phathalic anhydride, tetrahydrophthalic anhydride, methyl tetrahydrophthalic anhydride, chlorophthalic anhydride, bromophthalic anhydride, fluorophthalic anhydride, methylphthalic anhydride, naphthalene anhydride, or 2,3-naphthalenedicarboxylic anhydride.

Description

DESCRIPTION OF THE DRAWINGS

(1) FIG. 1 is the IR spectrum of the product in Example 2.

(2) FIG. 2 is the GPC spectrum of the product in Example 2.

DESCRIPTION OF THE PREFERRED EMBODIMENT

(3) The current invention is further illustrated by the following examples which do not limit the scope of protection of the current invention.

Example 1

(4) Preparation of Group B:

(5) The polyester mono alcohol B1 (the molar ratio of the reactants is: octanol:-caprolactone=1:14.65, Mn=1800).

(6) Under the protection of nitrogen, octanol (7.24 portion, 0.056 mol) and -caprolactone (92.76 portion, 0.814 mol) are added. With stirring, the temperature is increased to 110 C. Dibutyltin dilaurate (DBTDL, 0.03 portions, 10% of the butanol solution) is added and the temperature has increased to 170-180 C. and be maintained for 6 hours and white wax formed solid body under room temperature is formed with a hydroxyl value of 32. This is polyester mono alcohol B1 with a number average molecular weight of 1800.

(7) The polyester mono alcohol B2 (the molar ratio of the reactants is: octanol:-caprolactone=1:8.67, Mn=1600). Its preparation method is the same as that for B1, wherein a transparent liquid is obtained, with a hydroxyl value of 35 and a number average molecular weight of 1600.

(8) The polyester mono alcohol B3 (MMA:mercaptoethanol:AIBN=142:7.25:1, Mn=2000): Two dropwise addition kettle are prepared in advance, wherein they hold the following components respectively: Group A: methyl methacrylate (57 portions, 0.569 mol), group B: a mixture of 2-mercaptoethanol (2.33 portions, 0.029 mol), azodiisobutyronitrile (0.67 portions, 0.004 mol) and acetic ether (20 portions). Under the protection of nitrogen, acetic ether (20 portions) is added and the temperature is increased to the reflux temperature, and group A is started to be added dropwise. After half an hour, group B is started to be added and is finished after 200 minutes. After the addition, the temperature is kept at 80 C. until the solid body achieves its standard. Finally, the temperature is increased to 120 C., and the solvent is removed under vacuum. The solid body produced is light yellow, and transparent, with a hydroxyl value of 27.50, and a number average molecular weight of 2000.

(9) Polyether mono alcohol B4 (MPEG 2000, Mn=2000), B4 is a commercial product with a hydroxyl value of 28 and is a white wax solid body under room temperature.

(10) Polyether mono alcohol B5 (beta-butoxy EO:PO=1:1 mono alcohol, Mn=1000), B5 is a commercial product with a hydroxyl value of 56, and is a transparent liquid under room temperature.

(11) Preparation of group C: diol C1 (molar ratio of the reactants is butanediol:-caprolactone: -valerolactone=1:5.46:0.94, Mn=00). Under the protection of nitrogen, 1,4-butanedil (11.20 portions, 0.124 mol), -caprolactone (77.22 portions, 0.677 mol), -valerolactone (11.58 portions, 0.116 mol) are added. The mixture is stirred until the temperature increases to 130 C. Zirconium tetra-n-butoxy is then added (0.3 portions, 30% butanol solution). The temperature is then increased to 175-180 C. and be maintained for more than 6 hours until the solid body obtained achieves its standard. A wax like solid body is obtained with a hydroxyl value of 141 and a number average molecular weight of 800.

(12) Diol C2 (molar ratio of the reactants is PEG 200:-caprolactone=1:10.53, Mn=1400): The procedure is the same as that for C1. White wax-like solid body is achieved, with a hydroxyl value of 40 and a number average molecular weight of 1400.

(13) Diol C3 (PEG 800, Mn=800): C3 is a commercial product, with a hydroxyl value of 140, and is a white, wax-like solid body.

(14) Preparation of Group D:

(15) The anchoring terminal group D1 (the molar ratio of the reactants is: phathalic anhydride:4-aminobenzimidazole=1:1). Under the protection of nitrogen, phathalic anhydride (52.66 portions, 0.356 mol), 4-aminobenzimidazole (47.34 portions, 0.356 mol) are added and the temperature is gradually increased to 180 C. and is maintained until the acetic value is stable. The temperature is then increased to 220-230 C., and maintained until the acetic value is less than 1. The temperature is then decreased to 80 C. NMP is used to dilute the solution to 50% until a light brown color is obtained. This is the anchoring terminal group D1.

(16) The anchoring terminal group D2 (the molar ratio of the reactants is: phathalic anhydride:3-(2-aminoethyl)indole=1:1). The method is the same as the method for the preparation of D1, wherein 3-(2-aminoethyl)indole is used to replace 4-aminobenzimidazole, and a 50% light brown liquid is obtained. This is the anchoring terminal group D2. EIMS shows that D1 has a molecular weight of 259.9.

(17) The anchoring terminal group D3 (the molar ratio of the reactants is: phathalic anhydride:1-(2-aminoethyl) piperazin=1:1). The method is the same as the method for the preparation of D1, wherein 1-(2-aminoethyl) piperazin is used to replace 4-aminobenzimidazole, and a 50% light brown liquid is obtained. This is the anchoring terminal group D3.

(18) The anchoring terminal group D4 (the molar ratio of the reactants is: 2,3-naphthalenedicarboxylic anhydride:2-(aminomethyl)morpholine=1:1). The method is the same as the method for the preparation of D1, wherein 2-(aminomethyl)morpholine is used to replace 4-aminobenzimidazole, and a 50% light brown liquid is obtained. This is the anchoring terminal group D4.

(19) Preparation of Polyurethane Dispersant

(20) Control example 1: Under the protection of nitrogen, 21.63 portions of Desmodur IL (51% butyl acetate solution, product from Bayer), 24.52 portions of mixed solution (dimethyl benzene:butyl acetate=4:1), 24.33 portions of mono alcohol B1 and 0.1 portion of DBTDL (10% butyl acetate solution), have the temperature increased to 70 C., and be maintained to the extent when NCO is stable. 1.7 portion of diol C1 is added, the temperature is maintained until NCO is stable. A mixture of 3.09 portions of 4-(2-aminoethyl) pyridine and 24.72 portions of propylene glycol mono-methyl ether acetate (MPA) is added and kept warm under the temperature of 60 C. The solid body obtained contains 40% light yellow liquid with certain viscosity, and has an amine value of 10.2.

(21) Control example 2: Under the protection of nitrogen, 12.2 portions of Desmodur N (75% butyl acetate:dimethyl benzene=1:1 solution, product from Bayer), 22.65 portions of mixed solution (dimethyl benzene:butyl acetate=1:1), 28.75 portions of mono alcohol B2 and 0.1 portion of DBTDL (10% butyl acetate solution), have the temperature increased to 70 C., and be maintained to the extent when NCO is stable. 1.57 portion of polyethyleneglycol 800 (PEG 800) is added, the temperature is maintained until NCO is stable. A mixture of 12.2 portions of 3-benzimidazol-1-propionic acid-2-hydroxyethyl acrylate (50% NMP solution, it is the Michael addition product of benzimidazole and hydroxyethyl acrylate. Its production method is according to the mature method in state of the art.) and 22.65 portions of MPA has its temperature increased to 60 C. and maintained for 1 hour. The solid body obtained contains 45% light yellow liquid with certain viscosity, and has an amine value of 13.2.

Example 2

(22) The preparation method of polyurethane dispersant is the same as control example 1. The difference lies in that Desmodur IL (19.02 portion), polyester mono alcohol B1 (23.38 portion), diol C1 (1.55 portion), anchoring terminal group D2 (11.10 portion) are used to replace the corresponding components, and the solid body contains 40% light yellow transparent liquid with certain viscosity. The amine value is 3.2. FIG. 1 is the IR spectrum of the products. FIG. 1 is the GPC spectrum of the products. The analytic result is listed in Table 1:

(23) TABLE-US-00001 Mn Mw Mp Mz Mz + 1 Degree of Sample (Daltons) (Daltons) (Daltons) (Daltons) (Daltons) Dispersion Mz/Mw Mz + 1/Mw 1 2811 5454 6155 8266 11200 1.9407 1.5155 2.0534

Example 3

(24) The preparation method of polyurethane dispersant is the same as control example 1. The difference lies in that Desmodur IL (17.81 portion), polyester mono alcohol B1 (23.75 portion), PEG 2000 (2.23 portion), anchoring terminal group D1 (10.39 portion) are used to replace the corresponding components, and the solid body contains 40% light yellow transparent liquid with certain viscosity. The amine value is 5.8.

Example 4

(25) The preparation method of polyurethane dispersant is the same as control example 1. The difference lies in that Desmodur IL (19.66 portion), polyester mono alcohol B2 (22.33 portion), PEG 2000 (2.21 portion), anchoring terminal group D3 (11.14 portion) are used to replace the corresponding components, and the solid body contains 40% light yellow transparent liquid with certain viscosity. The amine value is 12.5.

Example 5

(26) The preparation method of polyurethane dispersant is the same as control example 1. The difference lies in that Desmodur IL (20.78 portion), polyester mono alcohol B3 (21.76 portion), PEG 2000 (1.39 portion), anchoring terminal group D2 (12.12 portion) are used to replace the corresponding components, and the solid body contains 40% light yellow transparent liquid with certain viscosity. The amine value is 3.5.

Example 6

(27) The preparation method of polyurethane dispersant is the same as example 2. The difference lies in that Desmodur N (11.92 portion), polyester mono alcohol B2 (27.74 portion), PEG 1000 (1.53 portion), anchoring terminal group D3 (13.62 portion) are used to replace the corresponding components, and the solid body contains 45% light yellow transparent liquid with certain viscosity. The amine value is 4.8.

Example 7

(28) The preparation method of polyurethane dispersant is the same as control example 2. The difference lies in that Desmodur N (13.32 portion), polyester mono alcohol B5 (25.21 portion), PEG 2000 (3.53 portion), anchoring terminal group D1 (12.0 portion) are used to replace the corresponding components, and the solid body contains 45% light yellow transparent liquid with certain viscosity. The amine value is 13.3.

Example 8

(29) The preparation method of polyurethane dispersant is the same as control example 2. The difference lies in that Desmodur HL (15.35 portion, 60% butyl acetate solution, product from bayer), polyester mono alcohol B1 (23.37 portion), PEG 800 (1.34 portion), anchoring terminal group D2 (12.02 portion) are used to replace the corresponding components, and the solid body contains 40% light yellow transparent liquid with certain viscosity. The amine value is 3.8.

Example 9

(30) The preparation method of polyurethane dispersant is the same as control example 2. The difference lies in that Desmodur HL (13.72 portion), polyester mono alcohol B4 (25.03 portion), diol C2 (1.34 portion), anchoring terminal group D3 (10.37 portion) are used to replace the corresponding components, and the solid body contains 40% light yellow transparent liquid with certain viscosity. The amine value is 4.5.

The Test Results of the Present Invention

(31) In order to assess the dispersion property of the polyurethane dispersant according to the present invention, a corresponding graining paste is prepared. The stability of the graining paste is assessed and it is added into a resin and its coloring capability is determined. The result is shown as follows:

(32) TABLE-US-00002 TABLE 2 the formulation of the graining paste (weight ratio) Graining Graining Graining Graining Graining Graining Component PasteI PasteII PasteIII PasteIV PasteV PasteVI hydroxy acrylic resin 31 31 31 30 30 30 (NV = 60%) Dispersant Control 1 15 / / / / / Example 2 / 15 / / / / Example 4 / / 15 / / / Example 2 / / / 8.9 / / Example 6 / / / / 8.9 / Example 7 / / / / / 8.9 Pigment Yellow 110 15 15 15 / / / FW200 / / / 10 10 10 Mixed solvent 39 39 39 51.1 51.1 51.1 Total 100 100 100 100 100 100

(33) Table 2 shows the graining pastes containing polyurethane dispersant of the current invention and a control dispersant respectively. The method for production is as follows: In the shaking bottle, dispersant, a mixture of dimethylbenzene and propylene glycol monomethyl ether acetate with a ratio of 1:1, pigment and resin are added sequentially and mixed by stirring. Finally glass balls are added (diameter 2-3 mm). The dispersion is carried out in a shaking machine for 2 hours and the graining paste is thus obtained.

(34) Table 3 shows the viscosity of the graining paste and its stability under 50

(35) TABLE-US-00003 TABLE 3 Viscosity of graining paste and its thermostability Graining Graining Graining Graining Graining Graining Paste I Paste II Paste III Paste IV Paste V Paste VI viscosity*(5turn) 994.2 196.8 238.2 921.7 211.2 180.5 viscosity(50turn) 164.7 125.3 124.3 182.3 115.0 100.1 50 C. After one stable stable stable stable stable stable thermostabiltiy week After two Little clear stable stable Little clear stable stable weeks liquid in the liquid in the upper layer upper layer After three Clear Little clear stable Clear stable stable weeks liquid in the liquid in the liquid in the upper layer upper layer upper layer increases increases After four Small Small Small Small Small Small weeks number of number of number of of number amount amount particle particles particles of particles of clear of clear precipitate precipitates precipitates precipitates liquid in the liquid in the upper layer upper layer *BROOKFIELD RVDV-I viscosity meter

(36) The above graining paste is made to paint using the ratio of hydroxy acrylic resin:graining paste:solidifier:mixed solvent 5:3:2.5:1.5. The method for production is as follows: hydroxy acrylic resin is mixed with the graining paste and the dispersion is carried out in a high speed stirring machine (5000 rpm*3 min). Solvent and solidifier is added and stirred with hand. After filtration, it is painted onto polyester chips and dried under room temperature. The luster of the chips is shown as follows:

(37) TABLE-US-00004 TABLE 4 paint luster data paint I paint II paintIII paintIV paint V paintVI 20 degree 88 91 92 85 90 91 luster

(38) According to table 3 and 4, in comparison with traditional polyurethane dispersant, the polyurethane dispersant of the current invention uses a new anchoring terminal group and therefore has an enhanced adsorption ability to pigment. As a result, the viscosity of the graining paste (II, III, V, VI) decreases significantly and its stability under 50 C. is improved. Furthermore, due to the increased adsorption ability of the anchoring terminal group, the dispersant can better stabilize the released pigment particles and thus overcome the reconglomeration phenomenum among the pigment particles due to vann der Waals force. The pigment can be dispersed into even smaller particle diameter. Therefore, the luster data have been improved and the coloring effect is enhanced.