Polyisocyanate modified with sulphamic acid, preparation method thereof and use thereof

Abstract

A polyisocyanate modified with sulphamic acid and a mixture thereof, the preparation method thereof, and the use thereof in the production of polyurethane, especially as a cross-linking ingredient in the field of aqueous coatings and adhesives containing groups that are capable of reacting with isocyanate groups.

Claims

1. A polyisocyanate modified with sulphamic acid, which is prepared by a reaction of a polyisocyanate and a sulphamic acid with the formula of ##STR00003## wherein in the reaction, the polyisocyanate is added through a two-step adding process, wherein a first portion of the polyisocyanate is mixed with the sulphamic acid, a tertiary amine and optionally a polyether, and the reaction lasts 3-5 h at 95-110 C., then the rest of the polyisocyanate is added, after cooling to room temperature, the polyisocyanate modified with sulphamic acid is obtained; wherein the first portion of the polyisocyanate represents 30-90 wt % of the total weight of the polyisocyanate, wherein R.sub.1 is one of cyclohexyl, methyl cyclohexyl, p-methyl cyclohexyl, 2-methyl cyclohexyl, 2,3-dimethyl cyclohexyl, 3,3,5-trimethyl cyclohexyl, 4-tertbutyl cyclohexyl, cycloheptyl, methyl cyclooctyl, 2-norcamphanyl, 2-adamantyl and 3,5-dimethyl-1-adamantyl, R.sub.2 is butyl; or R.sub.1 is one of methyl cyclohexyl, p-methyl cyclohexyl, 2-methyl cyclohexyl, 2,3-dimethyl cyclohexyl, 3,3,5-trimethyl cyclohexyl, 4-tertbutyl cyclohexyl, cycloheptyl, methyl cyclooctyl, 2-norcamphanyl, 2-adamantyl and 3,5-dimethyl-1-adamantyl, R.sub.2 is propyl; or R.sub.1 is one of cyclohexyl, methyl cyclohexyl, p-methyl cyclohexyl, 2-methyl cyclohexyl, 2,3-dimethyl cyclohexyl, 3,3,5-trimethyl cyclohexyl, 4-tertbutyl cyclohexyl, cycloheptyl, methyl cyclooctyl, 2-norcamphanyl, 2-adamantyl and 3,5-dimethyl-1-adamantyl, R.sub.2 is isobutyl; and wherein the amount of said sulphamic acid is 0.5-20 wt % of the total weight of the polyisocyanate and the sulphamic acid.

2. The polyisocyanate modified with sulphamic acid according to claim 1, characterized in that: a) the average functionality of isocyanate is at least 1.8, b) the content of isocyanate groups is 4.0-35.0 wt %, c) the content of SO.sub.3.sup. is 0.1-6.8 wt %, and d) the polyisocyanate modified with sulphamic acid optionally comprises a polyether with a molecular chain comprising average ethoxy units of 5-30, wherein the content of ethoxy units bonded to the molecular chain of the polyether is 0-15 wt % based on the total weight of the polyisocyanate, the sulphamic acid and the polyether.

3. The polyisocyanate modified with sulphamic acid according to claim 1, characterized in that said polyisocyanate applied in the reaction is one or more of aliphatic, alicyclic, aromatic, araliphatic polyisocyanates and modified polyisocyanates with average isocyanate functionality of 2.0-5.0 and isocyanate groups content of 7.0-32.0 wt %.

4. A preparation method of the polyisocyanate modified with sulphamic acid according to claim 1, characterized in that the polyisocyanate reacts with the sulphamic acid with the formula of ##STR00004## at the presence of a tertiary amine, wherein in the reaction, the polyisocyanate is added through a two-step adding process, wherein a first portion of the polyisocyanate is mixed with the sulphamic acid, the tertiary amine and optionally a polyether, and the reaction lasts 3-5 h at 95-110 C., then the rest of the polyisocyanate is added, after cooling to room temperature, the polyisocyanate modified with sulphamic acid is obtained; wherein the first portion of the polyisocyanate represents 30-90 wt % of the total weight of the polyisocyanate, wherein R.sub.1 is one of cyclohexyl, methyl cyclohexyl, p-methyl cyclohexyl, 2-methyl cyclohexyl, 2,3-dimethyl cyclohexyl, 3,3,5-trimethyl cyclohexyl, 4-tertbutyl cyclohexyl, cycloheptyl, methyl cyclooctyl, 2-norcamphanyl, 2-adamantyl and 3,5-dimethyl-1-adamantyl, R.sub.2 is butyl; or R.sub.1 is one of methyl cyclohexyl, p-methyl cyclohexyl, 2-methyl cyclohexyl, 2,3-dimethyl cyclohexyl, 3,3,5-trimethyl cyclohexyl, 4-tertbutyl cyclohexyl, cycloheptyl, methyl cyclooctyl, 2-norcamphanyl, 2-adamantyl and 3,5-dimethyl-1-adamantyl, R.sub.2 is propyl; or R.sub.1 is one of cyclohexyl, methyl cyclohexyl, p-methyl cyclohexyl, 2-methyl cyclohexyl, 2,3-dimethyl cyclohexyl, 3,3,5-trimethyl cyclohexyl, 4-tertbutyl cyclohexyl, cycloheptyl, methyl cyclooctyl, 2-norcamphanyl, 2-adamantyl and 3,5-dimethyl-1-adamantyl, R.sub.2 is isobutyl; and wherein the amount of the sulphamic acid is 0.5-20 wt % of the total weight of the polyisocyanate and the sulphamic acid.

5. The method according to claim 4, characterized in that said reaction is carried out under the presence of a polyether comprising ethoxy units, and/or the polyisocyanate used already comprises ethoxy polyether units.

6. The method according to claim 4, characterized in that said polyisocyanate is one or more of aliphatic, alicyclic, aromatic, araliphatic polyisocyanates and modified polyisocyanates with average isocyanate groups functionality of 2.0-5.0, and isocyanate groups content of 7.0-32.0 wt %.

7. The method according to claim 5, characterized in that the content of the ethoxy units bonded to the molecular chain of the polyether is 0-15 wt %.sub.7 based on the total weight of the polyisocyanate, the sulphamic acid and the polyether, the polyether is monohydric, the number-average molecular weight is 300-1000, and the average number of the ethoxy units in the molecular chain of the polyether is 5-30.

8. The method according to claim 4, characterized in that said tertiary amine is aliphatic and/or alicyclic substituted, non-cyclic and/or cyclic tertiary amine; and the molar ratio of said tertiary amine to the SO.sub.3.sup. group of the sulphamic acid is 0.2-2.0:1, and the molar ratio of isocyanate groups and groups which are reactive towards isocyanate groups is kept to 4-300:1.

9. The polyisocyanate modified with sulphamic acid according to claim 1, characterized in that, R.sub.1 is one of cyclohexyl, methyl cyclohexyl, p-methyl cyclohexyl and cycloheptyl, R.sub.2 is butyl; or R.sub.1 is methyl cyclohexyl, p-methyl cyclohexyl and 3,3,5-trimethyl cyclohexyl, R.sub.2 is propyl; or R.sub.1 is cyclohexyl and methyl cyclohexyl, R.sub.2 is isobutyl; and the amount of said sulphamic acid is 1-10 wt % of the total weight of the polyisocyanate and the sulphamic acid.

10. The polyisocyanate modified with sulphamic acid according to claim 2, characterized in that, a) the average functionality of isocyanate is 2.0-4.8, b) the content of isocyanate groups is 6.0-31.0 wt %, c) the content of SO.sub.3.sup. is 0.2-4.8 wt %, and d) the polyisocyanate modified sulphamic acid comprises the polyether with the molecular chain comprising average ethoxy units of 10-20, wherein the content of ethoxy units bonded to the molecular chain of the polyether is 4-12 wt % based on the total weight of the polyisocyanate, the sulphamic acid and the polyether.

11. The polyisocyanate modified with sulphamic acid according to claim 3, characterized in that, said polyisocyanate applied in the reaction is one or more of the aliphatic, alicyclic polyisocyanates and modified polyisocyanates with average isocyanate functionality of 2.0-4.0, and the isocyanate groups content of 12.0-25.0 wt %.

12. The polyisocyanate modified with sulphamic acid according to claim 3, characterized in that, said polyisocyanate applied in the reaction is isocyanurate modified groups-comprising polyisocyanates that are based on one or more of 1,6-hexamethylene diisocyanate, isophorone diisocyanate and 4,4-dicyclohexyl methane diisocyanate.

13. The polyisocyanate modified with sulphamic acid according to claim 4, characterized in that, R.sub.1 is one of cyclohexyl, methyl cyclohexyl, p-methyl cyclohexyl and cycloheptyl, R.sub.2 is butyl; or R1 is one of methyl cyclohexyl, p-methyl cyclohexyl and 3,3,5-trimethyl cyclohexyl, R.sub.2 is propyl; or R.sub.1 is one of cyclohexyl and cyclohexyl methyl, R.sub.2 is isobutyl; and the amount of the sulphamic acid is 1-10 wt % of the total weight of the polyisocyanate and the sulphamic acid.

14. The method according to claim 4, characterized in that, the first portion of the polyisocyanate represents 50-80 wt % of the total weight of the polyisocyanate.

15. The method according to claim 6, characterized in that, said polyisocyanate is one or more of the aliphatic, alicyclic polyisocyanates and modified polyisocyanates with average isocyanate groups functionality of 2.5-4.0, and the isocyanate groups content of 12.0-25.0 wt %.

16. The method according to claim 6, characterized in that, said polyisocyanate is isocyanurate modified groups-comprising polyisocyanates that are based on one or more of 1,6-hexamethylene diisocyanate, isophorone diisocyanate and 4,4-dicyclohexylmethane diisocyanate.

17. The method according to claim 7, characterized in that the content of the ethoxy units bonded to the polyether chain is 4-12 wt %, based on the total weight of the polyisocyanate, the sulphamic acid and the polyether, the polyether is monohydric, the number-average molecular weight is 400-800, and the number of the ethoxy units is 10-20.

18. The method according to claim 8, characterized in that, said tertiary amine is one or more of triethylamine, dimethyl cyclohexyl amine and N-methylmorpholine; and the molar ratio of said tertiary amine to the SO.sub.3.sup. group is 0.5-1.5:1, and the molar ratio of the isocyanate groups and groups which are reactive towards the isocyanate groups is kept to 6-200:1.

Description

DETAILED DESCRIPTION OF THE INVENTION

(1) The present invention will be further illustrated by the following examples, it should be noted that the examples are not the limitations for the extent of protection of the present invention.

(2) Raw Materials

(3) Component a)

(4) Polyisocyanate 1 (Wannate HT-100, Wanhua, Ningbo, polyisocyanates based on HDI, isocyanate groups content of 21.5-22.5 wt %, the average functionality of 3.3-3.8);

(5) Polyisocyanate 2 (Bayer NZ1, polyisocyanate based on HDI and IPDI, isocyanate groups content of 20 wt %, the average functionality of 3.3-3.5);

(6) Component b)

(7) 4-(cyclohexyl amino)-butane sulfonic acid: cyclohexylamine and 1,4-butyl sultone, corresponding to an equivalent molar ratio of 3:1, are admixed to dioxane solvent, and then react at 80 C. for 6 h, solids are obtained by washing with acetone until becoming white (for example, see US2007010573 A1);

(8) 4-(cyclohexylmethylamino)-butane sulfonic acid: it is prepared by cyclohexanemethylamine and 1,4-butyl sultone according to the above method;

(9) 4-(p-methyl cyclohexylamino)-butane sulfonic acid: it is prepared by p-methyl cyclohexaneamine and 1,4-butyl sultone according to the above method;

(10) 4-(cycloheptyl)-butane sulfonic acid: it is prepared by cycloheptane and 1,4-butyl sultone according to the above method;

(11) 3-(cyclohexylmethylamino)-propane sulfonic acid: it is prepared by cyclohexylmethylamine and 1,3-propane sultone according to the above method;

(12) 3-(p-methyl cyclohexyl amino)-propane sulfonic acid: it is prepared by p-methyl cyclohexylamine and 1,3-propane sultone according to the above method;

(13) 3-(3,3,5-trimethyl cyclohexyl amino)-propane sulfonic acid: it is prepared by 3,3,5-trimethyl cyclohexyl amine and 1,3-propane sultone according to the above method;

(14) 3-(cyclohexyl amino)-2-methyl-1-propane sulfonic acid: it is prepared by cyclohexyl amine and 1,3-butyl sulfone according to the above method;

(15) 3-(cyclohexyl methyl amino)-2-methyl-1-propane sulfonic acid: it is prepared by cyclohexyl methyl amine and 1,3-butyl sulfone according to the above method;

(16) Component c)

(17) Monohydric polyether that comprises ethoxy units (GEP-105, Wan hua rong wei, molecular weight of 500-600, an average hydroxyl value of 100-110 mg KOH/g, the number of ethoxyl units of 11-13);

(18) Please be noticed that the following examples are only used to testify the present invention but not to limit the invention. Unless otherwise defined, all the percentages relate to weight percentages.

Example 1

(19) In a round bottom flask with four necks equipped with a mechanical stirrer, a condenser tube, a thermometer and a nitrogen inlet and outlet, 10 g (0.042 mol) 4-(cyclohexyl amino)-butanesulfonic acid, 5.4 g (0.042 mol) dimethyl cyclohexylamine were added to 133 g polyisocyanate 1 (0.70 mol). The reaction lasted for 5 h at 100 C. Then 57 g (0.29 mol) polyisocyanate 1 was added and mixed homogeneously. After cooling to room temperature, the polyisocyanates modified with sulphamic acid with the following characteristic data is obtained:

(20) solid content: 100%

(21) isocyanate groups content: 19.3 wt %

(22) average isocyanate groups functionality: 3.4

(23) viscosity (25 C.): 5000 mPa.Math.s

(24) SO3- content: 1.65 wt %

(25) ethoxyl unit content: 0

Example 2

(26) In a round bottom flask with four necks equipped with a mechanical stirrer, a condenser tube, a thermometer and a nitrogen inlet and outlet, 10 g (0.042 mol) 4-(cyclohexyl amino)-butanesulfonic acid, 5.4 g (0.042 mol) dimethyl cyclohexylamine were added to 95 g polyisocyanate 1 (0.50 mol). The reaction lasted for 3 h at 100 C. Then 95 g (0.50 mol) polyisocyanate 1 was added and mixed homogeneously. After cooling to room temperature, the polyisocyanate modified with sulphamic acid with the following characteristic data is obtained:

(27) solid content: 100%

(28) isocyanate groups content: 19.3 wt %

(29) average isocyanate groups functionality: 3.4

(30) viscosity (25 C.): 5000 mPa.Math.s

(31) SO3- content: 1.65 wt %

(32) ethoxyl unit content: 0

Example 3

(33) In a round bottom flask with four necks equipped with a mechanical stirrer, a condenser tube, a thermometer and a nitrogen inlet and outlet, 2 g (0.008 mol) 4-(cyclohexyl amino)-butanesulfonic acid, 1.08 g (0.008 mol) dimethyl cyclohexylamine were added to 138 g polyisocyanate 1 (0.73 mol). The reaction lasted for 5 h at 100 C. Then 60 g (0.32 mol) polyisocyanate 1 was added and mixed homogeneously. After cooling to room temperature, the polyisocyanate modified with sulphamic acid with the following characteristic data is obtained:

(34) solid content: 100%

(35) isocyanate groups content: 21.2 wt %

(36) average isocyanate groups functionality: 3.5

(37) viscosity (25 C.): 3500 mPa.Math.s

(38) SO3- content: 0.33 wt %

(39) ethoxyl unit content: 0

Example 4

(40) In a round bottom flask with four necks equipped with a mechanical stirrer, a condenser tube, a thermometer and a nitrogen inlet and outlet, 20 g (0.084 mol) 4-(cyclohexyl amino)-butanesulfonic acid, 10.8 g (0.084 mol) dimethyl cyclohexylamine were added to 126 g polyisocyanate 1 (0.69 mol). The reaction lasted for 5 h at 100 C. Then 54 g (0.30 mol) polyisocyanate 1 was added and mixed homogeneously. After cooling to room temperature, the polyisocyanate modified with sulphamic acid with the following characteristic data is obtained:

(41) solid content: 100%

(42) isocyanate groups content: 17.0 wt %

(43) average isocyanate groups functionality: 3.2

(44) viscosity (25 C.): 6300 mPa.Math.s

(45) SO3- content: 3.23 wt %

(46) ethoxyl unit content: 0

Example 5

(47) In a round bottom flask with four necks equipped with a mechanical stirrer, a condenser tube, a thermometer and a nitrogen inlet and outlet, 10 g (0.042 mol) 4-(cyclohexyl amino)-butanesulfonic acid, 5.4 g (0.042 mol) dimethyl cyclohexylamine, 22.8 g (0.041 mol) monohydric polyether GEP-105 were added to 133 g polyisocyanate 1 (0.70 mol). The reaction lasted for 5 h at 100 C. Then 57 g (0.29 mol) polyisocyanate 1 was added and mixed homogeneously. After cooling to room temperature, the polyisocyanate modified with sulphamic acid with the following characteristic data is obtained:

(48) solid content: 100%

(49) isocyanate groups content: 16.6 wt %

(50) average isocyanate groups functionality: 3.3

(51) viscosity (25 C.): 5700 mPa.Math.s

(52) SO3- content: 1.48 wt %

(53) ethoxyl unit content: 9.4 wt %

Example 6

(54) In a round bottom flask with four necks equipped with a mechanical stirrer, a condenser tube, a thermometer and a nitrogen inlet and outlet 10 g (0.042 mol) 4-(cyclohexyl amino)-butanesulfonic acid, 5.4 g (0.042 mol) dimethyl cyclohexylamine, 28 g (0.050 mol) monohydric polyether GEP-105 were added to 133 g polyisocyanate 1 (0.70 mol). The reaction lasted for 5 h at 100 C. Then 57 g (0.29 mol) polyisocyanate 1 was added and mixed homogeneously. After cooling to room temperature, the polyisocyanate modified with sulphamic acid with the following characteristic data is obtained:

(55) solid content: 100%

(56) isocyanate groups content: 16.0 wt %

(57) average isocyanate groups functionality: 3.1

(58) viscosity (25 C.): 3700 mPa.Math.s

(59) SO3- content: 1.43 wt %

(60) ethoxyl unit content: 11.3

Example 7

(61) In a round bottom flask with four necks equipped with a mechanical stirrer, a condenser tube, a thermometer and a nitrogen inlet and outlet, 10 g (0.084 mol) 4-(cyclohexyl amino)-butanesulfonic acid, 5.4 g (0.084 mol) dimethyl cyclohexylamine, 51.4 g propylene glycol methyl ether acetate were added to 133 g polyisocyanate 1 (0.90 mol). The reaction lasted for 3 h at 100 C. Then 57 g (0.29 mol) polyisocyanate 1 was added and mixed homogeneously. After cooling to room temperature, the polyisocyanate modified with sulphamic acid with the following characteristic data is obtained:

(62) solid content: 80%

(63) isocyanate groups content: 15.2 wt %

(64) average isocyanate groups functionality: 3.4

(65) viscosity (25 C.): 1200 mPa.Math.s

(66) SO3- content: 1.32 wt %

(67) ethoxyl unit content: 0

Example 8

(68) In a round bottom flask with four necks equipped with a mechanical stirrer, a condenser tube, a thermometer and a nitrogen inlet and outlet, 10 g (0.084 mol) 4-(cyclohexyl amino)-butanesulfonic acid, 5.4 g (0.084 mol) dimethyl cyclohexylamine were added to 133 g polyisocyanate 2 (0.63 mol). The reaction lasted for 3 h at 100 C. Then 57 g (0.27 mol) polyisocyanate 2 was added and mixed homogeneously. After cooling to room temperature, the polyisocyanate modified with sulphamic acid with the following characteristic data is obtained:

(69) solid content: 100%

(70) isocyanate groups content: 17.6 wt %

(71) average isocyanate groups functionality: 3.4

(72) viscosity (25 C.): 4800 mPa.Math.s

(73) SO3- content: 1.65 wt %

(74) ethoxyl unit content: 0

Example 9

(75) 10 g (0.042 mol) 3-(cyclohexyl methyl amino)-propanesulfonic acid was applied to replace the 10 g (0.042 mol) 4-(cyclohexyl amino)-butanesulfonic acid in example 1, the rest of items can be referred to example 1, the polyisocyanate modified with sulphamic acid with the following characteristic data is obtained:

(76) solid content: 100%

(77) isocyanate groups content: 19.2 wt %

(78) average isocyanate groups functionality: 3.4

(79) viscosity (25 C.): 4700 mPa.Math.s

(80) SO3- content: 1.65 wt %

(81) ethoxyl unit content: 0

Example 10

(82) 10 g (0.042 mol) 3-(p-methyl cyclohexyl amino)-propanesulfonic acid was used to replace the 10 g (0.042 mol) 4-(cyclohexyl amino)-butanesulfonic acid in example 1, the rest of items can be referred to example 1, the polyisocyanate modified with sulphamic acid with the following characteristic data is obtained:

(83) solid content: 100%

(84) isocyanate groups content: 19.3 wt %

(85) average isocyanate groups functionality: 3.3

(86) viscosity (25 C.): 5000 mPa.Math.s

(87) SO3- content: 1.65 wt %

(88) ethoxyl unit content: 0

Example 11

(89) 10 g (0.038 mol) 3-(3,3,5-trimethyl cyclohexyl amino)-propanesulfonic acid and 4.8 g (0.038 mol) dimethyl cyclohexylamine were used to replace the 10 g (0.042 mol) 4-(cyclohexyl amino)-butanesulfonic acid and 5.4 g (0.042 mol) dimethyl cyclohexylamine in example 1, the rest of items can be referred to example 1, the polyisocyanate modified with sulphamic acid with the following characteristic data is obtained:

(90) solid content: 100%

(91) isocyanate groups content: 19.4 wt %

(92) average isocyanate groups functionality: 3.4

(93) viscosity (25 C.): 4500 mPa.Math.s

(94) SO3- content: 1.44 wt %

(95) ethoxyl unit content: 0

Example 12

(96) 10 g (0.040 mol) 4-(p-methyl cyclohexyl amino)-butanesulfonic acid and 5.1 g (0.040 mol) dimethyl cyclohexylamine were used to replace the 10 g (0.042 mol) 4-(cyclohexyl amino)-butanesulfonic acid and 5.4 g (0.042 mol) dimethyl cyclohexylamine of example 1, the rest of items can be referred to example 1, the polyisocyanate modified with sulphamic acid with the following characteristic data is obtained:

(97) solid content: 100%

(98) isocyanate groups content: 19.2 wt %

(99) average isocyanate groups functionality: 3.4

(100) viscosity (25 C.): 4900 mPa.Math.s

(101) SO3- content: 1.57 wt %

(102) ethoxyl unit content: 0

Example 13

(103) 10 g (0.040 mol) 4-(cycloheptyl amino)-butanesulfonic acid and 5.1 g (0.040 mol) dimethyl cyclohexylamine were used to replace the 10 g (0.042 mol) 4-(cyclohexyl amino)-butanesulfonic acid and 5.4 g (0.042 mol) dimethyl cyclohexylamine in example 1, the rest of items can be referred to example 1, the polyisocyanate modified with sulphamic acid with the following characteristic data is obtained:

(104) solid content: 100%

(105) isocyanate groups content: 19.0 wt %

(106) average isocyanate groups functionality: 3.4

(107) viscosity (25 C.): 4800 mPa.Math.s

(108) SO3- content: 1.57 wt %

(109) ethoxyl unit content: 0

Example 14

(110) 10 g (0.040 mol) 4-(cyclohexyl methyl amino)-butanesulfonic acid and 5.1 g (0.040 mol) dimethyl cyclohexylamine were used to replace the 10 g (0.042 mol) 4-(cyclohexyl amino)-butanesulfonic acid and 5.4 g (0.042 mol) dimethyl cyclohexylamine in example 1, the rest of items can be referred to example 1, the polyisocyanate modified with sulphamic acid with the following characteristic data is obtained:

(111) solid content: 100%

(112) isocyanate groups content: 19.4 wt %

(113) average isocyanate groups functionality: 3.4

(114) viscosity (25 C.): 4700 mPa.Math.s

(115) SO3- content: 1.57 wt %

(116) ethoxyl unit content: 0

Example 15

(117) 10 g (0.042 mol) 3-(cyclohexyl amino)-2-methyl-1-propanesulfonic acid was used to replace the 10 g (0.042 mol) 4-(cyclohexyl amino)-butanesulfonic acid in example 1, the rest of items can be referred to example 1, the polyisocyanate modified with sulphamic acid with the following characteristic data is obtained:

(118) solid content: 100%

(119) isocyanate groups content: 19.2 wt %

(120) average isocyanate groups functionality: 3.4

(121) viscosity (25 C.): 5100 mPa.Math.s

(122) SO3- content: 1.65 wt %

(123) ethoxyl unit content: 0

Example 16

(124) 10 g (0.040 mol) 3-(cyclohexyl methyl amino)-2-methyl-1-propanesulfonic acid and 5.1 g (0.040 mol) dimethyl cyclohexylamine were used to replace the 10 g (0.042 mol) 4-(cyclohexyl amino)-butanesulfonic acid and 5.4 g (0.042 mol) dimethyl cyclohexylamine in example 1, the rest of items can be referred to example 1, the polyisocyanate modified with sulphamic acid with the following characteristic data is obtained:

(125) solid content: 100%

(126) isocyanate groups content: 19.3 wt %

(127) average isocyanate groups functionality: 3.4

(128) viscosity (25 C.): 5000 mPa.Math.s

(129) SO3- content: 1.64 wt %

(130) ethoxyl unit content: 0

Example 17

(131) 2.7 g (0.021 mol) dimethyl cyclohexylamine was used to replace the 5.4 g (0.042 mol) dimethyl cyclohexylamine in example 1, and the reaction time was prolonged to 6 h, the rest of items can be referred to example 1, the polyisocyanate modified with sulphamic acid with the following characteristic data is obtained:

(132) solid content: 100%

(133) isocyanate groups content: 19.3 wt %

(134) average isocyanate groups functionality: 3.4

(135) viscosity (25 C.): 4900 mPa.Math.s

(136) SO3- content: 1.65 wt %

(137) ethoxyl unit content: 0

Example 18

(138) 8.1 g (0.063 mol) dimethyl cyclohexylamine was used to replace the 5.4 g (0.042 mol) dimethyl cyclohexylamine in example 1, the rest of items can be referred to example 1, the polyisocyanate modified with sulphamic acid with the following characteristic data is obtained:

(139) solid content: 100%

(140) isocyanate groups content: 19.1 wt %

(141) average isocyanate groups functionality: 3.4

(142) viscosity (25 C.): 4700 mPa.Math.s

(143) SO3- content: 1.65 wt %

(144) ethoxyl unit content: 0

Comparative Example 1

(145) In a round bottom flask with four necks equipped with a mechanical stirrer, a condenser tube, a thermometer and a nitrogen inlet and outlet, 10 g (0.042 mol) 4-(cyclohexyl amino)-butanesulfonic acid, 5.4 g (0.042 mol) dimethyl cyclohexylamine were added to 190 g polyisocyanate 1 (0.99 mol). The reaction lasted for 20 h at 80 C. the reaction system was cloudy, which indicated that under said temperature, 4-(cyclohexylamino)-butanesulfonic acid did not react with polyisocyanates.

Comparative Example 2

(146) In a round bottom flask with four necks equipped with a mechanical stirrer, a condenser tube, a thermometer and a nitrogen inlet and outlet, 10 g (0.042 mol) 4-(cyclohexyl amino)-butanesulfonic acid, 5.4 g (0.042 mol) dimethyl cyclohexylamine were added to 190 g polyisocyanate 1 (0.99 mol). The reaction lasted for 10 h at. There's still a large amount of suspensions in the system, which means 4-(cyclohexylamino)-butanesulfonic acid could hardly react with polyisocyanates under such conditions.

Comparative Example 3

(147) In a round bottom flask with four necks equipped with a mechanical stirrer, a condenser tube, a thermometer and a nitrogen inlet and outlet, 10 g (0.042 mol) 4-(cyclohexyl amino)-butanesulfonic acid was added to 190 g polyisocyanate 1 (0.99 mol). The reaction lasted for 10 h at 110 C. The system was cloudy, which indicated that 4-(cyclohexylamino)-butanesulfonic acid did not react with polyisocyanates without the presence of tertiary amine.

Comparative Example 4

(148) In a round bottom flask with four necks equipped with a mechanical stirrer, a condenser tube, a thermometer and a nitrogen inlet and outlet, 10 g (0.084 mol) 3-(cyclohexyl amino)-propanesulfonic acid, 5.4 g (0.084 mol) dimethyl cyclohexylamine were added to 190 g polyisocyanate 1 (0.99 mol). The reaction lasted for 10 h at 80 C. After cooling to room temperature, the polyisocyanates modified with sulphamic acid with the following characteristic data is obtained:

(149) solid content: 100%

(150) isocyanate groups content: 19.2 wt %

(151) average isocyanate groups functionality: 3.4

(152) viscosity (25 C.): 4600 mPa.Math.s

(153) SO3- content: 1.76 wt %

(154) ethoxyl unit content: 0

Comparative Example 5

(155) 10 g 2-methylamino ethanesulfonic acid (0.08 mol) and 10.16 g dimethyl cyclohexylamine (0.08 mol) were used to replace the 10 g (0.042 mol) 4-(cyclohexyl amino)-butanesulfonic acid and the 5.4 g (0.042 mol) dimethyl cyclohexylamine in example 1, the rest of items can be referred to example 1. The reaction mixture was heated to 100 C. for 6 h. The system was turbid. Even the temperature was increased to 120 C., and a further reaction for 4 h, the system was still cloudy, which indicated that the 2-methylamino ethanesulfonic acid did not react with polyisocyanates and was present in the form of crystals in the system.

Example 19

The Application in Aqueous Two-Component Coatings

(156) 47.12 g hydroxyl-acrylic resin (Antkote 2033) with hydroxyl value of 3.3, solid content of 46%, pH of 7.5-8.0, 0.6 g wetting agent (Surfynol 104BC), 2.22 g dispersing agent (Borchi Gen SN 95), 0.16 g levelling agent (Baysilone Paint Additive 3468) diluted to 10% by ethyleneglycol butyl ether, 27.65 g titanium white and 7.06 g deionized water were mixed and then grinded to fineness of less than 20 m. Then 14.2 g polyisocyanates modified with sulphamic acids according to the invention from said examples or the comparative examples were added. The obtained two-component mixture was applied on different substrates and dried for 30 min at 80 C. after being dried on the surface. The coating films with properties shown in the table 1 below were obtained.

(157) TABLE-US-00001 TABLE 1 Properties of the coating films Sulphamic acid Example Example Example Example Example Comparative modified polyisocyanate Example 1 Example 6 Example 9 10 11 12 13 14 Example 16 example 4 Processing time 4 h 4 h 4 h 4 h 4 h 4 h 4 h 4 h 4 h 3.5 h Pendulum-rocker 137 132 145 136 137 132 132 132 134 130 hardness* (k), s Pencil hardness* H H H H H H H H H H (Mitsubish, scratch) Gloss* 74/89 78/85 76/82 78/81 75/89 72/83 72/83 72/83 70/89 73/88 (20/60), % Impact* (1 kg), cm 50 50 62 52 56 52 52 52 54 54 flexibility**, mm 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 adhesion** 0-1 0-1 0-1 0-1 0-1 0-1 0-1 0-1 0-1 0-1 degree (cross-hatching) degree degree degree degree degree degree degree degree degree Deionized water 96 h 90 h 96 h 84 h 84 h 88 h 86 h 90 h 90 h 72 h resistance, no change Acid No No No No No No No No No No change resistance/5% change change change change change change change change change sulfuric acid, 24 h Base 8 h 8 h 7 h 8 h 8 h 7 h 8 h 8 h 7 h 6 h resistance/5% sodium hydroxide, no change Salt water No No No No No No No No No No change resistance/5% change change change change change change change change change sodium chloride, 72 h Fog-corrosion /5% pass pass pass pass pass pass pass pass pass retardancy*** Sodium chloride, 5 d PS: standard of adhesion: 0 (very good)-5 (poor) *substrates of glass panels, tested condition of 25 C. and 50% RH, the wet film thickness of 100 m **substrates of tinplates, the dry film thickness of 40 m ***substrates of carbon steel, the dry film thickness of 40 m

(158) The data showed that, compared with the sulphamic acid modified polyisocyanate according to comparative example 4, the sulphamic acid modified polyisocyanates according to other examples through two-step adding process possess longer processing time in the two-component coating system, and the two-component coating films possess better water-resistance and base resistance.

Example 20

Preparation of Blocked Modified Polyisocyanates

(159) In a round bottom flask with four necks equipped with a mechanical stirrer, a condenser tube, a thermometer and a nitrogen inlet and outlet, 12.5 g (0.053 mol) 4-(cyclohexyl amino)-butanesulfonic acid, 6.8 g (0.053 mol) dimethyl cyclohexylamine were added to 166 g (0.87 mol) polyisocyanate 1. The reaction lasted for 3 h at 100 C. Then 71 g (0.37 mol) polyisocyanate 1 was added and mixed homogeneously. Because the viscosity of the reaction system was relative high, 64.7 g N-ethyl-pyrrolidone was added to dilute the mixture at 60-70 C. 114 g (1.19 mol) the blocking agent 3,5-dimethylpyrazole was added in the course of 0.5 h, until the NCO content of the system was lower than 0.1 wt %, the blocked polyisocyanates modified with suphamic acid was obtained.

(160) Under vigorous mechanical stirring conditions, 200 g deionized water was added slowly to the above 200 g blocked sulphamic acid modified polyisocyanate, stable white emulsions with blue light was prepared.

(161) solid content: 40 wt %

(162) particle size (nm): 89

(163) blocked isocyanate groups content (based on the emulsion): 5.7 wt %

(164) viscosity (25 C.): 210 mPa.Math.s

(165) solvent content: 6.9 wt %