A kind of aminosulfonic acid modified polyisocyanate and its preparation method and application

Abstract

The invention discloses an aminosulfonic acid modified polyisocyanate and a preparation method and application thereof. The polyisocyanate is prepared by reacting raw materials including the following components a), b), c), and optionally d), e): a) at least one polyisocyanate, b) at least one aminosulfonic acid comprising at least one amino group and at least one sulfonic acid group, c) at least one hydroxycarboxylic acid comprising at least one hydroxyl group and at least one carboxylic acid group, d) at least one nonionic hydrophilic organic compound comprising at least one isocyanate reactive group, and e) at least one tertiary amine; wherein the weight ratio of component b) to component c) is 10-100:1. The invention can realize a modified polyisocyanate having significantly improved water dispersibility in a shorter reaction time.

Description

Technical Field

[0001] The invention relates to a modified polyisocyanate, in particular to an aminosulfonic acid modified polyisocyanate and a preparation method and application thereof. Background Art

[0002] At present, people's environmental awareness is becoming stronger and stronger, and environmental regulations are becoming more and more stringent. Consumers are eager to use environmentally friendly coatings and adhesives. Waterborne polyurethane dispersions can gradually match oily polyurethanes in terms of application performance, and have played an increasingly important role in various surface coating treatment fields such as coatings and adhesives. Most waterborne polyurethane dispersions need to be used in a two-component form in order to improve strength and wear resistance in practical applications, namely, a waterborne polyurethane dispersion component and a polyisocyanate curing agent component. Among them, the polyisocyanate used as a curing agent is mostly obtained by modifying polyisocyanates with hydrophilic groups. The hydrophilically modified water-dispersible polyisocyanates can be more easily dispersed into the waterborne polyurethane dispersion, and the resulting two-component water-based coating is safer, does not require the addition of volatile organic solvents, and is more in line with environmental protection development. In addition, water-dispersible polyisocyanates can also be used as starting components to prepare blocked isocyanate curing agents. Blocked isocyanate curing agents can be directly mixed with waterborne polyurethane dispersions for long-term storage and use, which will be a future development trend.

[0003] Pure polyisocyanates such as HDI trimer or IPDI trimer can also be used as crosslinkers in two-component waterborne coatings. However, due to the hydrophobicity of polyisocyanates themselves, it is difficult to disperse them in waterborne polyurethane dispersions. The state after mixing is very unstable, which greatly reduces the activation and use period of two-component waterborne coatings. Therefore, pure polyisocyanates are rarely used as crosslinkers. Polyisocyanates must be hydrophilically modified to achieve easy dispersion in waterborne coatings. After continuous development, there are two main technical means for hydrophilically modified polyisocyanates: non-ionic modification and (potential) ionic modification. Non-ionic modification mainly uses polyether substances containing hydroxyl groups, amino groups and other active hydrogen with isocyanate group NCO reaction activity. This type of modified water-dispersible polyisocyanates has been widely used, but a large amount of polyether is required to give polyisocyanates good water dispersibility, which results in permanent hydrophilicity of the final coating film, making the film weather resistance worse.

[0004] Ion-modified polyisocyanates can solve the problem of poor water resistance of the above-mentioned film. The main ionic groups used are carboxyl and sulfonic acid. For example, carboxyl groups are introduced to modify polyisocyanates in EP0443138A and EP0548669A. Neutralized carboxyl-modified polyisocyanates are easily dispersed in water-based coatings without requiring high shear forces. Polyhydroxycarboxylic acids such as dimethylolpropionic acid (DMPA) or dimethylolbutyric acid (DMBA) are often used, but the melting points of DMPA and DMBA are greater than 130°C, the required reaction temperature is very high, and it is easy to cause the appearance of the modified polyisocyanate to be muddy, and the user experience is poor. In addition, carboxyl-modified polyisocyanates are particularly sensitive to pH, and it is difficult to disperse successfully when the pH is less than 5; and the ions formed after neutralizing the carboxyl group with a neutralizing agent tertiary amine can catalyze the self-polymerization of the isocyanate group, which not only reduces the storage stability of the polyisocyanate, but also causes the viscosity of the modified polyisocyanate to increase.

[0005] Therefore, technicians use sulfonic acid groups to modify polyisocyanates to eliminate the defects of carboxyl modification. Sulfonic acid compounds that can be used include hydroxyethanesulfonic acid or hydroxypropanesulfonic acid described in DE4433929A, or polyether sulfonates. Sulfonic acid or sulfonate groups can bring hydrophilicity to polyisocyanates, but 2-hydroxypropanesulfonic acid therein is carcinogenic. Specific polyether sulfonates are mostly provided in the form of sodium salts, and the inability of sodium ions to escape from the coating film will also affect the water resistance of the coating film.

[0006] Patent CN1190450C proposed the use of 3-(cyclohexylamino)-propanesulfonic acid and 2-(cyclohexylamino)-ethanesulfonic acid to prepare modified polyisocyanates, and obtained modified polyisocyanates that are easy to disperse evenly in water and have excellent storage stability. After that, technicians explored a suitable method for modifying polycyanates with 4-(cyclohexylamino)-butanesulfonic acid, see CN104448232A for details.

[0007] Patents CN110396173A and CN110396165A found that in the presence of free radical scavengers and / or peroxide decomposers, antioxidants, the above aminosulfonic acid reacts with polyisocyanates to obtain modified polyisocyanates with lower viscosity and better water dispersibility. The free radical scavengers and / or peroxide decomposers, antioxidants such as 2,6-di-tert-butyl-4-methylphenol, 3-(3,5-di-tert-butyl-4-hydroxyphenyl) propionic acid and aliphatic branched C7- to C9-alcohol esters ( BASF SE, Ludwigshafen, DE), octadecyl 3-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate ( BASFSE, Ludwigshafen, DE) and / or bis(3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionic acid) dithioethyl ester ( BASF SE, Ludwigshafen, DE) and other materials are in powder or granular form, do not react with isocyanate, and most of them are difficult to dissolve in water. Therefore, they are difficult to evenly disperse in modified polyisocyanate and easily escape from water-based two-component coatings to destroy the surface flatness of the film. Moreover, most of these materials can only be purchased from overseas companies, and the price is expensive, which undoubtedly increases the cost of water-based two-component coatings.

[0008] The aminosulfonic acid mentioned in the above public applications has a high melting point, and it takes a long time to fully react with polyisocyanate even at high temperature. During the long reaction, the sulfonic acid groups are easily dehydrated and react with each other to produce sulfonic anhydride, which will weaken the hydrophilicity and emulsifiability. When more aminosulfonic acid compounds are used to improve the hydrophilicity, the NCO group content will inevitably be reduced, affecting the cross-linking performance of the modified polyisocyanate. Summary of the invention

[0009] In order to solve the above technical problems, the present invention provides an aminosulfonic acid modified polyisocyanate and a preparation method and application thereof. The present invention can achieve a modified polyisocyanate with significantly improved water dispersibility in a shorter reaction time, and the modified polyisocyanate is used to prepare a two-component water-based coating with a longer activation period, excellent film strength and high gloss.

[0010] To achieve the above purpose, the technical solution adopted by the present invention is as follows:

[0011] A sulfamic acid modified polyisocyanate is prepared by reacting raw materials comprising the following components a), b), c) and optionally d) and e):

[0012] a) at least one polyisocyanate,

[0013] b) at least one aminosulfonic acid comprising at least one amino group and at least one sulfonic acid group,

[0014] c) at least one hydroxycarboxylic acid comprising at least one hydroxyl group and at least one carboxylic acid group,

[0015] d) at least one nonionic hydrophilic organic compound comprising at least one isocyanate-reactive group,

[0016] e) at least one tertiary amine;

[0017] The weight ratio of component b) to component c) is 10-100:1, preferably 20-100:1.

[0018] As a preferred embodiment, component b) is used in an amount of 0.3-20.0%, preferably 0.5-10.0%, more preferably 1.0-6.0%, based on the total weight of components a) and b).

[0019] As a preferred embodiment, component d) is used in an amount of 0-5.0%, preferably 0-2.0%, based on the total weight of components a), b) and c).

[0020] Preferably, component d) is a monofunctional polycycloethoxy ether or a mixture of polycycloethoxy ether and polycyclopropoxy ether, preferably a polycycloethoxy ether with a number average molecular weight of 400-1200. The polymerized units of component d) are one or both of propylene oxide and ethylene oxide, wherein the amount of ethylene oxide is preferably at least 70 mol%, based on the total molar amount of the polymerized units. The aminosulfonic acid-modified polyisocyanate of the present invention may optionally contain the above-mentioned polyether.

[0021] The reaction of components a), b), c) and optionally component d) in the process according to the invention is carried out in the presence of at least one tertiary amine, component e), which serves to neutralize the sulfonic acid and carboxylic acid groups of components b) and c).

[0022] As a preferred embodiment, component e) is used in an amount corresponding to the total molar equivalent ratio of tertiary amino groups to sulfonic acid groups and carboxylic acid groups in components b) and c);

[0023] Preferably, component e) is N,N-dimethylcyclohexylamine, triethylamine, trimethylamine, tripropylamine, tributylamine, N,N-dimethylethylamine, N,N-dimethylpropylamine, N,N-dimethylisopropylamine, N,N-dimethylbutylamine, N,N-dimethylisobutylamine, N,N-dimethyloctylamine, N,N-dimethyl-2-ethylhexylamine, N,N-diethylcyclohexylamine, N,N-dicyclohexylamine, Preferably, component e) is one or any mixture of triethylamine, N,N-dicyclohexylethylamine, tricyclohexylamine, N-methylpyrrolidine, N-ethylpyrrolidine, N-propylpyrrolidine, N-butylpyrrolidine, N-methylpiperidine, N-ethylpiperidine, N-propylpiperidine, N-butylpiperidine, N-methylmorpholine, N-ethylmorpholine, N-propylmorpholine, N-butylmorpholine, N-sec-butylmorpholine, N-tert-butylmorpholine, N-isobutylmorpholine. More preferably, component e) is one or more of triethylamine, N,N-dimethylcyclohexylamine, N-methylpiperidine, N-methylmorpholine, particularly preferably N,N-dimethylcyclohexylamine.

[0024] As a preferred embodiment, component a) is an aliphatic, alicyclic, aromatic, araliphatic polyisocyanate or a modified polyisocyanate thereof having an average isocyanate functionality of 2.0-5.0 and an NCO content of 7.0-32.0%; preferably based on hexamethylene diisocyanate (HDI), isophorone diisocyanate (IPDI) and 4,4'-dicyclohexylmethane diisocyanate (HDI). 12The present invention relates to a polyisocyanate having an isocyanurate group, wherein the polyisocyanate is a modified polyisocyanate having an isocyanurate group based on one or more of polyisocyanates in MDI, more preferably a polyisocyanate having an isocyanurate group based on HDI. The above polyisocyanate requirements include but are not limited to containing isocyanurate groups, and in addition thereto may also contain structures such as uretdione, allophanate, biuret, iminooxadiazinedione and / or oxadiazinedione.

[0025] Suitable sources of raw materials for the preparation of the polyisocyanates are those diisocyanates which can be prepared by phosgene or non-phosgene processes, for example any diisocyanate obtained by thermal decomposition of urethane. Preferably the diisocyanate is a diisocyanate with a molecular weight of 100-500 and with aliphatic, alicyclic, aramid or aromatic bonds. In the process of the present invention, preferably a polyisocyanate with less than 0.5%, more preferably less than 0.3% of free NCO monomers is used as component a).

[0026] As a preferred embodiment, component b) is selected from substances having the following structural formula:

[0027]

[0028] wherein R1 is one of cyclohexyl, cyclohexylmethyl, p-methylcyclohexyl, 2-methylcyclohexyl, 2,3-dimethylcyclohexyl, 3,3,5-trimethylcyclohexyl, 4-tert-butylcyclohexyl, cycloheptyl, and cyclooctylmethyl, and R2 is butylene, propylene, or isobutylene;

[0029] Preferably, component b) is one or more of 2-cyclohexylaminoethanesulfonic acid, 2-isopropylaminoethane-1-sulfonic acid, 3-isopropylaminopropane-1-sulfonic acid, 4-isopropylaminobutane-1-sulfonic acid, 2-cyclohexylaminoethane-1-sulfonic acid, 3-(cyclohexylamino)-1-propanesulfonic acid and 4-(cyclohexylamino)-1-butanesulfonic acid. Very particularly preferred component b) is 3-(cyclohexylamino)-1-propanesulfonic acid and 4-(cyclohexylamino)-1-butanesulfonic acid.

[0030] As a preferred embodiment, component c) is selected from substances having the following structural expressions:

[0031]

[0032] wherein R3 is selected from a linear alkyl group having 4 to 8 carbon atoms, and R4 is selected from a saturated linear group having 4 to 12 carbon atoms which may contain one or more ether bond oxygen atoms;

[0033] Preferably, component c) is selected from one or more of 12-hydroxyoctadecanoic acid, 6-hydroxydodecanoic acid, 11-hydroxyhexadecanoic acid, and 10-hydroxystearic acid. Particularly preferred are 12-hydroxyoctadecanoic acid and 10-hydroxystearic acid, with the structural formulas being and The component c) described in the present invention is mostly a solid substance with a melting point between 50-80°C.

[0034] A method for preparing the aminosulfonic acid modified polyisocyanate as described above, comprising: mixing components a), b), c) and optionally d) and e) and reacting them to obtain the aminosulfonic acid modified polyisocyanate;

[0035] Preferably, the reaction temperature is 80-120°C.

[0036] As a preferred embodiment, during the reaction, a catalyst and a solvent are optionally added.

[0037] In the method according to the present invention, the catalyst can be selected from common catalysts in polyurethane chemistry, such as one or more of triethylamine, pyridine, N-methylpyridine, zinc (II) octanoate, and bismuth neodecanoate. The amount of the catalyst can be 0.0001-1.0%, preferably 0.001-0.5%, based on the total weight of components a), b), c), and d). When the catalyst is the same raw material as the tert-butylamine in component e), it is preferably not added.

[0038] In the method according to the present invention, in order to reduce the viscosity of the product, the reaction can be carried out in a solvent inert to NCO groups, such as one or more solvents such as butanone, acetone, butyl acetate, N-ethylpyrrolidone, N-methylpyrrolidone, propylene glycol methyl ether acetate, and diethyl carbonate.

[0039] The invention relates to an application of the aminosulfonic acid modified polyisocyanate as described above or the aminosulfonic acid modified polyisocyanate prepared by the method described above as a starting component in the preparation of waterborne polyurethane materials and blocked polyisocyanates, and as a cross-linking component in the preparation of waterborne two-component coatings and waterborne adhesives.

[0040] The important role of component c) used in the present invention, i.e., hydroxycarboxylic acid, is not only to serve as a carboxylic acid hydrophilic group-modified polyisocyanate, but also to find a more surprising effect after experimental verification. As mentioned above, the traditional 3-cyclohexylaminopropane-1-sulfonic acid or 4-cyclohexylaminobutane-1-sulfonic acid-modified polyisocyanate, the melting point of such aminosulfonic acid is mostly above 200°C, and it always participates in the reaction in a solid state in the preparation of the modified polyisocyanate, while polyisocyanates such as HDI trimer are liquid, and the reaction between the two is an interfacial reaction, which easily results in residual aminosulfonic acid particles in the final product, turbid product, and incomplete reaction, which often occurs in synthetic experiments.

[0041] When the hydroxycarboxylic acid provided by the present invention, such as 12-hydroxystearic acid, is used to participate in the reaction with aminosulfonic acid, at the reaction temperature, the hydroxycarboxylic acid melts into a liquid, wets and wraps the aminosulfonic acid solid so that it can more easily enter the polyisocyanate for reaction. And because its hydrophobic alkyl chain and polar hydrophilic carboxyl group can just connect the hydrophobic polyisocyanate and the polar aminosulfonic acid, it plays a bridging role, making the reaction of aminosulfonic acid and polyisocyanate more rapid and thorough.

[0042] At the same time, the hydroxyl group of the hydroxycarboxylic acid of the present invention can also bond with the NCO group during the reaction and be grafted onto the polyisocyanate to play a hydrophilic modification role. Moreover, unlike traditional hydroxycarboxylic acids such as DMPA or DMBA, the reaction is slow or even incomplete.

[0043] The hydroxycarboxylic acid of the present invention can also be used as a surfactant or surfactant to connect the oil phase and the water phase because of its hydrophilic and hydrophobic effects. Therefore, when the hydroxycarboxylic acid participates in the modified polyisocyanate, the obtained hydrophilic modified polyisocyanate is more easily dispersed in the water-based two-component coating as a crosslinking agent, and will not destroy the stability of the waterborne polyurethane dispersion. Moreover, due to its long hydrophobic carbon chain, the water resistance and strength of the prepared water-based two-component coating film are improved. In addition, most of the hydroxycarboxylic acids mentioned in the present invention can be prepared from biomass raw materials, such as 12-hydroxystearic acid can be obtained by hydrogenation of ricinoleic acid, and the raw materials are widely available and low in cost, which is also one of the advantages of the present invention.

[0044] When the aminosulfonic acid modified polyisocyanate of the present invention is used as a crosslinking agent in a coating adhesive, the amount used is based on a molar ratio of NCO group to NCO reactive group of 0.5-2.5:1.0, preferably 0.8-1.5:1. When the modified polyisocyanate prepared according to the present invention is used to prepare a water-based two-component coating, it is surprisingly found that the hardness of the coating film is improved to a certain extent.

[0045] Finally, the aminosulfonic acid modified polyisocyanate of the present invention can also be blocked by a blocking agent known in polyurethane chemistry to prepare a blocked polyisocyanate emulsion for use in a one-component system. Suitable commonly used blocking agents include methyl ethyl ketone oxime, caprolactam, imidazole, 3,5-dimethylpyrazole, diethyl malonate, etc. or any mixture thereof. After the modified polyisocyanate of the present invention is used as a starting component and blocked with a blocking agent, a stable emulsion can be obtained by adding dispersed water under strong mechanical stirring. DETAILED DESCRIPTION

[0046] The present invention is further described below by means of specific examples. The examples described in the present invention are only used to illustrate the present invention and do not limit the scope of the present invention.

[0047] The raw materials and reagents used in the following examples and comparative examples of the present invention are all commercially available products, and the main raw material information is as follows:

[0048] Component a):

[0049] Polyisocyanate 1 (Ningbo Wanhua Wannate HT-100, HDI-based polyisocyanate, NCO=21.5-22.5wt%);

[0050] Polyisocyanate 2 (Ningbo Wanhua Wannate HT-600, HDI-based polyisocyanate, NCO=22.5-23.5wt%);

[0051] Polyisocyanate 3 (Bayer NZ1, polyisocyanate based on HDI and IPDI, NCO=20 wt %);

[0052] Component b):

[0053] 3-(Cyclohexylamino)-1-propanesulfonic acid (CAPS, purchased from Sigma-Aldrich Shanghai);

[0054] 4-(Cyclohexylamino)-1-butanesulfonic acid (CABS, purchased from Shanghai Aladdin Biochemical Technology Co., Ltd.);

[0055] Component c):

[0056] 12-Hydroxyoctadecanoic acid (purchased from Tongliao Weining Chemical Co., Ltd.);

[0057] 10-Hydroxystearic acid (purchased from Shanghai MacLean Biochemical Technology Co., Ltd.)

[0058] Component d)

[0059] Monofunctional polycycloethoxy ether 1 (Wanhua Rongwei GEP-105, molecular weight 500-600, hydroxyl value 100-110 mgKOH / g);

[0060] Monofunctional polycycloethoxy ether 2 (Lotte MPEG-1200, Korea, polyethylene glycol monomethyl ether with molecular weight 1200)

[0061] Monofunctional polycyclopropoxy ether 3 (MPPG-600 from Jiangsu Hai'an Petrochemical Plant, polypropylene glycol monomethyl ether with a molecular weight of 600)

[0062] Component e)

[0063] N,N-Dimethylcyclohexylamine (Wanhua Chemical)

[0064] N-Methylpiperidine (Shanghai MacLean Biochemical Technology Co., Ltd.)

[0065] N-Methylmorpholine (Shanghai MacLean Biochemical Technology Co., Ltd.)

[0066] The test methods used in the following examples and comparative examples of the present invention are as follows:

[0067] (1) Test of modified polyisocyanate mixture:

[0068] The NCO group content was tested by titration using Swiss Metrohm 905 potentiometric titrator;

[0069] The viscosity was tested using a Physical MCR 51 rheometer according to DIN EN ISO 3219:1994-10 at a shear rate of 250 s-1;

[0070] The color number was determined by spectrophotometry using a LICO 400 spectrophotometer.

[0071] Particle size of water dispersion: Take 25g of modified polyisocyanate, add 75g of deionized water, stir at high speed to make a 25% solid water dispersion. Then use Malvern particle size analyzer to test the particle size. The smaller the particle size, the better the dispersibility. Generally, the dispersed particle size in the range of 100-300nm represents the excellent water dispersibility of modified polyisocyanate.

[0072] (2) Performance test of two-component coatings:

[0073] Viscosity and activation period test: The two-component coating prepared with modified polyisocyanate was subjected to a four-cup viscosity test. The viscosity change within 4 hours at 35°C and the coating gelation and agglomeration time (i.e., the longest activation period) were recorded. The viscosity was determined by the four-cup flow time (s).

[0074] Paint film pendulum hardness test: within 2 hours, a thin layer of two-component paint is scraped on a special glass plate for testing, and placed in an environment of 25°C and 50% relative humidity for 24 hours, and then the paint film pendulum hardness is tested. Among them, the pendulum hardness is tested in accordance with the "Paint Film Hardness Determination Method Pendulum Damping Test" GB / T1730-1993, and the time value (s) from the decay of a certain value of the swing amplitude to the detection lower limit of the swing amplitude is tested. This time value reflects the hardness of the film; the greater the hardness of the film, the greater the corresponding time value.

[0075] Water resistance test: Apply two-component paint on the surface of furniture wood board, dry it for 30 minutes after construction, then dry it in a 35℃ oven overnight, and then test the water resistance. Specifically, soak the finished sample in deionized water for 24 hours, wipe off the water stains and observe the state of the paint film.

[0076] Gloss test: According to the "Determination of gloss of paint films" GB1743-79, the gloss of two-component coatings at a 60° angle is measured.

[0077] [Example 1]

[0078] 400 g of polyisocyanate 1 and 11.50 g of 3-(cyclohexylamino)-1-propanesulfonic acid, 0.16 g of 12-hydroxyoctadecanoic acid, and 6.65 g of N,N-dimethylcyclohexylamine were stirred together in a four-necked round-bottom flask at 80° C. under dry nitrogen. After 4.5 h of reaction, a substantially clear aminosulfonic acid-modified polyisocyanate mixture was obtained, which had the following characteristic data:

[0079]

[0080] [Comparative Example 1]

[0081] 400g of polyisocyanate 1, 11.50g of 3-(cyclohexylamino)-1-propanesulfonic acid and 6.65g of N,N-dimethylcyclohexylamine were stirred together in a four-necked round-bottom flask at 80°C under dry nitrogen. After 10.0h of reaction, some suspended particles still existed and the liquid in the flask was turbid. The liquid product was first filtered through a 325-mesh filter and then tested. The product had the following characteristic data:

[0082]

[0083]

[0084] [Example 2]

[0085] 400 g of polyisocyanate 2 and 2.0 g of 3-(cyclohexylamino)-1-propanesulfonic acid, 0.2 g of 10-hydroxystearic acid, and 1.10 g of N,N-dimethylcyclohexylamine were stirred together in a four-necked round-bottom flask at 100° C. under dry nitrogen. After 3.0 h of reaction, a substantially clear aminosulfonic acid-modified polyisocyanate mixture was obtained, which had the following characteristic data:

[0086]

[0087] [Example 3]

[0088] 400 g of polyisocyanate 3 and 10.0 g of 3-(cyclohexylamino)-1-propanesulfonic acid, 0.5 g of 12-hydroxyoctadecanoic acid, and 5.0 g of N,N-dimethylcyclohexylamine were stirred together in a four-necked round-bottom flask at 100° C. under dry nitrogen. After reacting for 2.5 h, a substantially clear aminosulfonic acid-modified polyisocyanate mixture was obtained, which had the following characteristic data:

[0089]

[0090] [Example 4]

[0091] 400 g of polyisocyanate 1 and 44.0 g of 4-(cyclohexylamino)-1-butanesulfonic acid, 0.45 g of 10-hydroxystearic acid, and 5.6 g of N,N-dimethylcyclohexylamine were stirred together in a four-necked round-bottom flask at 100° C. under dry nitrogen. After reacting for 2.5 h, a substantially clear aminosulfonic acid-modified polyisocyanate mixture was obtained, which had the following characteristic data:

[0092]

[0093] [Example 5]

[0094] 400 g of polyisocyanate 2 and 100 g of 4-(cyclohexylamino)-1-butanesulfonic acid, 1.0 g of 12-hydroxyoctadecanoic acid, and 12.0 g of N-methylpiperidine were stirred together in a four-necked round-bottom flask at 90° C. under dry nitrogen. After reacting for 3.0 h, a substantially clear aminosulfonic acid-modified polyisocyanate mixture was obtained, which had the following characteristic data:

[0095]

[0096] [Example 6]

[0097] 400 g of polyisocyanate 1 and 1.2 g of 3-(cyclohexylamino)-1-propanesulfonic acid, 0.12 g of 10-hydroxystearic acid, 20.10 g of GEP-105, and 1.40 g of N-methylmorpholine were stirred together in a four-necked round-bottom flask at 110° C. under dry nitrogen. After reacting for 3.0 h, a substantially clear aminosulfonic acid-modified polyisocyanate mixture was obtained, which had the following characteristic data:

[0098]

[0099] [Example 7]

[0100] 400 g of polyisocyanate 1, 8.5 g of 3-(cyclohexylamino)-1-propanesulfonic acid, 0.10 g of 12-hydroxyoctadecanoic acid, 4 g of GEP-105, 0.9 g of MPPG-600 and 5.12 g of N,N-dimethylcyclohexylamine were stirred together in a four-necked round-bottom flask at 100° C. under dry nitrogen. After reacting for 3.2 h, a substantially clear aminosulfonic acid-modified polyisocyanate mixture was obtained, which had the following characteristic data:

[0101]

[0102] [Example 8]

[0103] 400 g of polyisocyanate 3 and 8.5 g of 4-(cyclohexylamino)-1-butanesulfonic acid, 0.17 g of 10-hydroxystearic acid, 4.1 g of MPEG1200, and 4.56 g of N,N-dimethylcyclohexylamine were stirred together in a four-necked round-bottom flask at 110° C. under dry nitrogen. After reacting for 2.5 h, a substantially clear aminosulfonic acid-modified polyisocyanate mixture was obtained, which had the following characteristic data:

[0104]

[0105]

[0106] [Comparative Example 2]

[0107] 400 g of polyisocyanate 3 and 8.5 g of 4-(cyclohexylamino)-1-butanesulfonic acid, 2.52 g of 10-hydroxystearic acid, 4.1 g of MPEG1200, and 4.56 g of N,N-dimethylcyclohexylamine were stirred together in a four-necked round-bottom flask at 110° C. under dry nitrogen. After reacting for 2.5 h, a substantially clear aminosulfonic acid-modified polyisocyanate mixture was obtained, which had the following characteristic data:

[0108]

[0109]

Application examples

[0110] Using the modified polyisocyanate prepared in each embodiment and comparative example as a raw material, different water-based two-component coatings were formulated according to the following methods:

[0111] Prepare component A: 160 parts by weight of aqueous polyurethane dispersion (Wanhua Chemical), 1.2 parts by weight of wetting agent Tego270, 6 parts by weight of dipropylene glycol methyl ether and 10 parts by weight of dipropylene glycol butyl ether as film-forming aids, 1 part by weight of thickener U605, and 21.8 parts by weight of deionized water were mixed together and stirred evenly as coating component A;

[0112] Component B: 80 parts by weight of modified polyisocyanate and 20 parts by weight of propylene glycol methyl ether acetate are mixed and stirred evenly to obtain component B of the coating.

[0113] 100 parts by weight of component A and 10 parts by weight of component B were mixed and stirred evenly to obtain a two-component coating.

[0114] The particle size of the modified polyisocyanate aqueous dispersion and the performance test results of the water-based two-component coating are shown in Table 1:

[0115] Table 1. Paint film hardness test results

[0116]

[0117] The above is only a preferred embodiment of the present invention. It should be pointed out that ordinary technicians in this field can make several improvements and supplements without departing from the method of the present invention. These improvements and supplements should also be regarded as the scope of protection of the present invention.

Claims

1. A sulfamic acid modified polyisocyanate, characterized in that: Prepared by reacting the raw materials comprising the following a), b), c) and optionally d), e) components: a) at least one polyisocyanate, b) at least one aminosulfonic acid, c) at least one hydroxycarboxylic acid comprising at least one hydroxyl group and at least one carboxylic acid group, d) at least one nonionic hydrophilic organic compound comprising at least one isocyanate-reactive group, e) at least one tertiary amine; Wherein, the weight ratio of component b) to component c) is 10-100:1; The component b) is selected from substances having the following structural formula: Wherein R1 is one of cyclohexyl, cyclohexylmethyl, p-methylcyclohexyl, 2-methylcyclohexyl, 2,3-dimethylcyclohexyl, 3,3,5-trimethylcyclohexyl, 4-tert-butylcyclohexyl, cycloheptyl, and cyclooctylmethyl, and R2 is butylene, propylene, or isobutylene.

2. The aminosulfonic acid modified polyisocyanate according to claim 1, characterized in that: The weight ratio of component b) to component c) is 20-100:

1.

3. The aminosulfonic acid modified polyisocyanate according to claim 1, characterized in that Component b) is used in an amount of 0.3 to 20.0% based on the total weight of components a) and b).

4. The aminosulfonic acid modified polyisocyanate according to claim 3, characterized in that: Component b) is used in an amount of 0.5 to 10.0% based on the total weight of components a) and b).

5. The aminosulfonic acid modified polyisocyanate according to claim 3, characterized in that: Component b) is used in an amount of 1.0 to 6.0% based on the total weight of components a) and b).

6. The aminosulfonic acid modified polyisocyanate according to any one of claims 1 to 5, characterized in that: Component d) is used in an amount of 0 to 5.0% based on the total weight of components a), b) and c).

7. The aminosulfonic acid modified polyisocyanate according to claim 6, characterized in that: Component d) is used in an amount of 0 to 2.0% based on the total weight of components a), b) and c).

8. The aminosulfonic acid modified polyisocyanate according to claim 6, characterized in that: Component d) is a monofunctional polycycloethoxy ether or a mixture of polycycloethoxy ether and polycyclopropoxy ether.

9. The aminosulfonic acid modified polyisocyanate according to claim 8, characterized in that: Component d) is a polycycloethoxy ether having a number average molecular weight of 400-1200.

10. The aminosulfonic acid modified polyisocyanate according to any one of claims 1 to 5, characterized in that: Component e) is used in an amount corresponding to a total molar equivalent ratio of tertiary amino groups to sulfonic acid groups and carboxylic acid groups in components b) and c) of 0.2 to 2.

0.

11. The aminosulfonic acid modified polyisocyanate according to claim 10, characterized in that: Component e) is used in an amount corresponding to a total molar equivalent ratio of tertiary amino groups to sulfonic acid groups and carboxylic acid groups in components b) and c) of 0.5 to 1.

5.

12. The aminosulfonic acid modified polyisocyanate according to claim 10, characterized in that: Component e) is used in an amount corresponding to a total molar equivalent ratio of tertiary amino groups to sulfonic acid groups and carboxylic acid groups in components b) and c) of 0.95 to 1.

05.

13. The aminosulfonic acid modified polyisocyanate according to claim 10, characterized in that: Component e) is N,N-dimethylcyclohexylamine, triethylamine, trimethylamine, tripropylamine, tributylamine, N,N-dimethylethylamine, N,N-dimethylpropylamine, N,N-dimethylisopropylamine, N,N-dimethylbutylamine, N,N-dimethylisobutylamine, N,N-dimethyloctylamine, N,N-dimethyl-2-ethylhexylamine, N,N-diethylcyclohexylamine, N,N-dicyclohexylmethylamine The invention can be any one or any mixture of the following: 1,2-dicyclohexylamine, 2,3-dicyclohexylethylamine, 2,4-dicyclohexylamine, 3,4-dicyclohexylamine, 4,5-dicyclohexylamine, 5,6-dicyclohexylamine, 6,7-dicyclohexylamine, 7,8-dicyclohexylamine, 8,9-dicyclohexylamine, 9,10-dicyclohexylamine, 11,12-dicyclohexylamine, 13,14-dicyclohexylamine, 15,16-dicyclohexylamine, 17,18-dicyclohexylamine, 18,19-dicyclohexylamine, 1 ...9,10-dicyclohexylamine, 19,10-dicyclohexylamine, 19,10-dicyclohexylamine, 14. The aminosulfonic acid modified polyisocyanate according to claim 1, characterized in that: Component a) is an aliphatic, alicyclic, aromatic, or araliphatic polyisocyanate or a modified polyisocyanate thereof having an average isocyanate functionality of 2.0-5.0 and an NCO content of 7.0-32.0%.

15. The aminosulfonic acid modified polyisocyanate according to claim 14, characterized in that: Component a) is a modified polyisocyanate having isocyanurate groups based on one or more of hexamethylene diisocyanate, isophorone diisocyanate and 4,4′-dicyclohexylmethane diisocyanate.

16. The aminosulfonic acid modified polyisocyanate according to any one of claims 1 to 5, characterized in that: Component b) is one or more of 2-cyclohexylaminoethanesulfonic acid, 2-isopropylaminoethane-1-sulfonic acid, 3-isopropylaminopropane-1-sulfonic acid, 4-isopropylaminobutane-1-sulfonic acid, 2-cyclohexylaminoethane-1-sulfonic acid, 3-(cyclohexylamino)-1-propanesulfonic acid and 4-(cyclohexylamino)-1-butanesulfonic acid.

17. The aminosulfonic acid modified polyisocyanate according to claim 16, characterized in that: Component c) is selected from substances having the following structural expressions: Wherein R3 is selected from a straight chain alkyl group having 4 to 8 carbon atoms, and R4 is selected from a saturated straight chain group having 4 to 12 carbon atoms.

18. The aminosulfonic acid modified polyisocyanate according to claim 17, characterized in that: Component c) is selected from one or more of 12-hydroxyoctadecanoic acid, 6-hydroxydodecanoic acid, 11-hydroxyhexadecanoic acid and 10-hydroxystearic acid.

19. A method for preparing the aminosulfonic acid modified polyisocyanate according to any one of claims 1 to 5, characterized in that: include: Components a), b), c) and optionally d) and e) are mixed and reacted to obtain aminosulfonic acid-modified polyisocyanate.

20. The method for preparing aminosulfonic acid modified polyisocyanate according to claim 19, characterized in that: The reaction temperature is 80-120°C.

21. The method for preparing aminosulfonic acid modified polyisocyanate according to claim 19, characterized in that: During the reaction, a catalyst and a solvent are optionally added.

22. An application of the aminosulfonic acid modified polyisocyanate as described in any one of claims 1 to 18 or the aminosulfonic acid modified polyisocyanate prepared by the method described in any one of claims 19 to 21 as a starting component in the preparation of waterborne polyurethane materials and blocked polyisocyanates, and as a cross-linking component in the preparation of waterborne two-component coatings and waterborne adhesives.

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