CN119060303A

CN119060303A - A polyisocyanate composition and its preparation method and application

Info

Publication number: CN119060303A
Application number: CN202411561654.1A
Authority: CN
Inventors: 谭星; 欧阳洁; 尹聪颖; 陈宏彬
Original assignee: Guangzhou Guanzhi New Material Technology Co ltd
Current assignee: Guangzhou Guanzhi New Material Technology Co ltd
Priority date: 2024-11-05
Filing date: 2024-11-05
Publication date: 2024-12-03
Anticipated expiration: 2044-11-05
Also published as: CN119060303B

Abstract

The invention relates to a polyisocyanate composition, a preparation method and application thereof, and belongs to the technical field of aqueous compositions. The polyisocyanate composition comprises (1) isocyanate groups, (2) at least one of groups shown in formulas (1 a), (1 b) and (1 c), and (3) sulfonate groups bonded in a urea bond OR urethane bond form and/OR polyethylene glycol monoalkyl ether groups bonded in a urethane bond form, wherein the content of the isocyanate groups is 12.0-26.0wt%, and the molar total amount of Si (OR) ₃ groups, sulfonate groups and/OR polyethylene glycol monoalkyl ether groups in formulas (1 a), (1 b) and (1 c) is 2-30% and 0.7-7% of the molar total amount of isocyanate groups, urethane groups and urea groups contained in the polyisocyanate composition. The water-based paint prepared from the polyisocyanate composition has excellent water resistance, salt spray resistance, adhesive force and drying speed, and simultaneously has good luster and hardness.

Description

Polyisocyanate composition and preparation method and application thereof

Technical Field

The invention relates to the technical field of aqueous compositions, in particular to a polyisocyanate composition, a preparation method and application thereof.

Background

Currently, there are increasing restrictions on Volatile Organic Compounds (VOCs) in coatings. In this context, waterborne coatings using water as the dispersion medium have replaced traditional solvent-borne coatings in a number of fields due to their lower VOC content. Hydrophilic modified isocyanate cross-linking agents are often adopted in the water-based paint, can be dispersed and emulsified in a water phase, and can be matched with water-based hydroxyl resin to obtain the high-performance water-based two-component polyurethane paint comparable to solvent-based paint.

Patent US4433095, US4663377 report the synthesis of nonionic hydrophilic isocyanate crosslinkers useful in waterborne two-component polyurethane coatings using mono-alkyl-terminated polyethers as hydrophilic modifiers. Patent US6767958 reports the synthesis of anionic hydrophilic isocyanate crosslinkers of the sulfonate type with 3- (cyclohexylamine) -1-propanesulfonic acid or 3- (cyclohexylamine) -1-ethanesulfonic acid as hydrophilic modifier, with excellent hardness and chemical resistance. However, these hydrophilic isocyanate crosslinking agents are still insufficient in water resistance, salt spray resistance, and adhesion to metal substrates.

In order to further improve the performance of the hydrophilic isocyanate crosslinking agent, the introduction of other crosslinking groups besides isocyanate becomes a research hot spot of the hydrophilic isocyanate crosslinking agent. Patent CN1637106a reports that modification of hydrophilic isocyanate crosslinkers with an addition product of an aminosilane and a maleic diester can improve the peel strength of canvas and cold rolled steel laminates. CN111116865B reports an aminosilane modified hydrophilic isocyanate crosslinking agent with sulfonic acid groups, which can prepare aqueous two-component polyurethane coating with high water resistance. However, in these hydrophilic isocyanate crosslinking agents, each NCO group modified with an aminosilane or a derivative thereof is introduced with only one silane group, which also means that more NCO groups are consumed for introducing more silane groups, and the increase in crosslinking density is limited, so there is room for further improvement.

Disclosure of Invention

Based on this, the object of the present invention is to overcome the defects or shortcomings of the prior art, and to provide a polyisocyanate composition which can be dispersed in water and can be widely used as a composition in an aqueous coating to improve the performance of the aqueous coating, and a preparation method and application thereof, wherein the aqueous coating prepared from the polyisocyanate composition has excellent water resistance, salt spray resistance, excellent adhesion and drying speed, and simultaneously has good gloss and hardness,

In order to achieve the above purpose, the invention adopts the following technical scheme:

a polyisocyanate composition comprising:

(1) An isocyanate group;

(2) At least one of the groups represented by the formulas (1 a), (1 b), (1 c);

wherein X is a divalent C1-C8 alkyl group, Y is a monovalent C1-C8 alkyl group, and R is methyl or ethyl;

(3) Sulfonate groups bonded in the form of urea linkages or urethane linkages, and/or polyethylene glycol monoalkyl ether groups bonded in the form of urethane linkages;

The polyisocyanate composition has an isocyanate group content of 12.0-26.0wt% (i.e., NCO value of 12.0-26.0%), a molar total of Si (OR) ₃ groups in the formulas (1 a), (1 b), (1 c) of 2-30% of the molar total of isocyanate groups, urethane groups and urea groups contained in the polyisocyanate composition, and a molar total of sulfonate groups and polyethylene glycol monoalkyl ether groups of 0.7-7% of the molar total of isocyanate groups, urethane groups and urea groups contained in the polyisocyanate composition.

In the polyisocyanate composition of the present invention, it is apparent to those skilled in the art that the group represented by the formula (1 a) contains a urethane group and two Si (OR) ₃ groups, the group represented by the formula (1 b) contains a urethane group and three Si (OR) ₃ groups, the group represented by the formula (1 c) contains a urea group and two Si (OR) ₃ groups, the sulfonate group bonded in the form of a urea bond OR a urethane bond contains a urea group OR a urethane group and a sulfonate group, and the polyethylene glycol monoalkyl ether group bonded in the form of a urethane bond contains a urethane group and a polyethylene glycol monoalkyl ether group.

The polyisocyanate composition provided by the invention has a relatively high NCO value (namely, NCO value is 12.0-26.0%) and a high-density silane group, the silane group can be hydrolyzed and crosslinked after contacting with an aqueous phase, the curing speed is accelerated, and the silane group can be bonded with a metal substrate to increase the adhesion and water resistance and salt spray resistance.

The inventors of the present invention have conducted repeated studies and found that the group structure of the formulae (1 a), (1 b) and (1 c) contains two OR three Si (OR) ₃ groups (silane groups), and that the Si (OR) ₃ group density in the polyisocyanate composition can be improved on the one hand, and that the group structure of the formulae (1 a), (1 b) and (1 c) has a closer distance between Si (OR) ₃ groups, and surprisingly, that the two OR three Si (OR) ₃ groups of the group structures of the formulae (1 a), (1 b) and (1 c) in the scheme of the present invention have a synergistic effect, and that the water-and salt spray-resistant properties, the adhesion and the drying rate of the aqueous coating composition of the present invention are more excellent, even if the polyisocyanate composition has the same Si (OR) ₃ group content, as the conventional scheme in which only one Si (OR) ₃ group is introduced. In the polyisocyanate composition of the present invention, the molar total amount of Si (OR) ₃ groups in the group structures represented by the formulas (1 a), (1 b) and (1 c) is 2 to 30% of the molar total amount of isocyanate groups, carbamate groups and urea groups contained in the polyisocyanate composition. If the ratio of the total mole amount of Si (OR) ₃ groups in the formulas (1 a), (1 b) and (1 c) is too low, the polyisocyanate composition is inferior in water resistance, salt spray resistance, adhesion and drying speed of a coating film formed after being used in an aqueous coating. If the ratio of the total mole amount of Si (OR) ₃ groups in the formulas (1 a), (1 b) and (1 c) is too high, the polyisocyanate composition is used in an aqueous coating material, and the compatibility with resins is poor, and the gloss and hardness of the formed coating film are poor.

In order to ensure good compatibility in an aqueous system, the polyisocyanate composition of the invention is increased in compatibility in the aqueous system by introducing hydrophilic groups, namely sulfonate groups bonded in the form of urea bonds or urethane bonds and/or polyethylene glycol monoalkyl ether groups bonded in the form of urethane bonds, and utilizing the sulfonate groups and/or the polyethylene glycol monoalkyl ether groups. In the polyisocyanate composition of the present invention, the molar total amount of sulfonate groups and/or polyethylene glycol monoalkyl ether groups is 0.7 to 7% of the molar total amount of isocyanate groups, urethane groups and urea groups contained in the polyisocyanate composition. If the ratio of sulfonate groups and/or polyethylene glycol monoalkyl ether groups is too low, the compatibility of the polyisocyanate composition in an aqueous system can be deteriorated, the gloss and surface effect of a coating film can be affected, and if the ratio of sulfonate groups and/or polyethylene glycol monoalkyl ether groups is too high, too many hydrophilic groups can be remained in the coating film, and the water resistance and salt spray resistance can be affected.

As a preferred embodiment, the polyisocyanate composition of the present invention is a mixture of aliphatic polyisocyanates having the three types of groups (1), (2) and (3) described above. Namely, among the three types of groups (1), (2) and (3) mentioned above, the isocyanate groups are isocyanate groups on aliphatic polyisocyanates, the groups represented by the formulas (1 a), (1 b) and (1 c) are derived from isocyanate groups on aliphatic polyisocyanates, respectively, sulfonate groups bonded in the form of urea bonds or urethane bonds, and/or polyethylene glycol monoalkyl ether groups bonded in the form of urethane bonds are derived from isocyanate groups on aliphatic polyisocyanates, respectively.

As a preferable scheme, the group shown in the formula (1 a) is obtained by performing urethanization reaction between an isocyanate group on aliphatic polyisocyanate and a compound shown in the formula (2 a) and then performing addition reaction with trimethoxy-hydrosilicon and/or triethoxy-hydrosilicon;

In the formula (2 a), X is a divalent C1-C8 alkyl group, and Y is a monovalent C1-C8 alkyl group.

The isocyanate group on the aliphatic polyisocyanate and the hydroxyl group in the compound shown in the formula (2 a) are subjected to urethanization reaction to generate a reaction product containing a carbamate group, and two olefinic bonds on the reaction product are subjected to addition reaction with trimethoxy-hydrosilicon and/OR triethoxy-hydrosilicon to obtain a group shown in the formula (1 a), so that the carbamate group and two Si (OR) ₃ groups are arranged on the group shown in the formula (1 a).

As a preferable scheme, the group shown in the formula (1 b) is obtained by performing urethanization reaction between an isocyanate group on aliphatic polyisocyanate and a compound shown in the formula (2 b) and then performing addition reaction with trimethoxy-hydrosilicon and/or triethoxy-hydrosilicon;

In formula (2 b), X is a divalent C1-C8 alkyl group.

The isocyanate group on the aliphatic polyisocyanate and the hydroxyl group in the compound shown in the formula (2 b) are subjected to urethanization reaction to generate a reaction product containing carbamate groups, and three olefinic bonds on the reaction product are subjected to addition reaction with trimethoxy-hydrosilicon and/OR triethoxy-hydrosilicon to obtain a group shown in the formula (1 b), so that the carbamate groups and three Si (OR) ₃ groups are arranged on the group shown in the formula (1 b).

As a preferred embodiment, the group represented by formula (1 c) is obtained by reacting an isocyanate group on an aliphatic polyisocyanate with bis (3-trimethoxysilylpropyl) amine and/or bis (3-triethoxysilylpropyl) amine.

The isocyanate groups on the aliphatic polyisocyanate are reacted with bis (3-trimethoxysilylpropyl) amine and/OR bis (3-triethoxysilylpropyl) amine to obtain a group represented by formula (1 c), whereby the group represented by formula (1 c) has a urea group and two Si (OR) ₃ groups.

As a preferred embodiment, the sulfonate groups bonded in the form of urea bonds are obtained by reacting isocyanate groups on aliphatic polyisocyanates with sulfamic acid.

The isocyanate groups on the aliphatic polyisocyanate react with the amino groups on the sulfamic acid to give a reaction product having urea groups and sulfonate groups, i.e., sulfonate groups bonded in the form of urea bonds.

Preferably, the sulfamic acid is at least one of 2- (cyclohexylamino) ethanesulfonic acid, 3- (cyclohexylamino) propanesulfonic acid, and 4- (cyclohexylamino) butanesulfonic acid.

Further, the sulfonate group bonded in the form of urea bond is obtained by reacting an isocyanate group on aliphatic polyisocyanate with sulfamic acid, and then adding at least one of N, N-dimethylbutylamine, N-diethylmethylamine, N-diisopropylethylamine, N-dimethylcyclohexylamine, N-methylpiperidine, and N-ethylmorpholine in an amount of 20mol% or more based on the molar amount of sulfamic acid for neutralization. The compatibility of the polyisocyanate composition in an aqueous system can be improved by adding 20mol% or more of the above amine compound based on the molar amount of sulfamic acid for neutralization so that part (20 mol% or more) of the sulfonate groups bonded in the form of urea bonds exist in the form of neutralized sulfonate groups. Too low a degree of neutralization to form salts may result in insufficient hydrophilicity, affecting the compatibility of the polyisocyanate composition in aqueous systems. Preferably, at least one of N, N-dimethylbutylamine, N-diethylmethylamine, N-diisopropylethylamine, N-dimethylcyclohexylamine, N-methylpiperidine, N-ethylmorpholine is added in equal amounts based on the molar amount of sulfamic acid for neutralization. That is, among sulfonate groups bonded in the form of urea bonds, all sulfonate groups exist in the form of neutralized sulfonate groups, and the polyisocyanate composition is optimal in water solubility.

As a preferred embodiment, the sulfonate groups bonded in the form of urethane bonds are obtained by reacting isocyanate groups on aliphatic polyisocyanates with hydroxysulfonic acid.

The isocyanate groups on the aliphatic polyisocyanate react with the hydroxyl groups on the hydroxysulfonic acid to give a reaction product having urethane groups and sulfonate groups, i.e., sulfonate groups bonded in the form of urethane linkages.

Further, the sulfonate group bonded in the form of urethane bond is obtained by reacting an isocyanate group on aliphatic polyisocyanate with hydroxysulfonic acid, and then adding at least one of N, N-dimethylbutylamine, N-diethylmethylamine, N-diisopropylethylamine, N-dimethylcyclohexylamine, N-methylpiperidine, and N-ethylmorpholine in an amount of 20mol% or more based on the molar amount of the hydroxysulfonic acid for neutralization. Similarly, the compatibility of the polyisocyanate composition in an aqueous system can be improved by adding 20mol% or more of the above amine compound based on the molar amount of hydroxysulfonic acid for neutralization so that a part (20 mol% or more) of sulfonate groups bonded in the form of urethane bonds exist in the form of neutralized sulfonate groups. Too low a degree of neutralization to form salts may result in insufficient hydrophilicity, affecting the compatibility of the polyisocyanate composition in aqueous systems. Preferably, at least one of N, N-dimethylbutylamine, N-diethylmethylamine, N-diisopropylethylamine, N-dimethylcyclohexylamine, N-methylpiperidine, N-ethylmorpholine is added in equal amounts based on the molar amount of hydroxysulfonic acid for neutralization. That is, among sulfonate groups bonded in the form of urethane bonds, all sulfonate groups exist in the form of neutralized sulfonate groups, and the polyisocyanate composition is optimal in water solubility.

Preferably, the hydroxysulfonic acid is at least one of 2-hydroxyethanesulfonic acid, 3-hydroxypropylsulfonic acid, 4-hydroxybutanesulfonic acid, 5-hydroxypentanesulfonic acid, 6-hydroxyhexanesulfonic acid, hydroxybenzenesulfonic acid, and hydroxy (meth) benzenesulfonic acid.

As a preferred embodiment, the polyethylene glycol monoalkyl ether groups bonded in the form of urethane bonds are obtained by reacting an isocyanate group on an aliphatic polyisocyanate with a polyethylene glycol monoalkyl ether.

The isocyanate groups on the aliphatic polyisocyanate react with the hydroxyl groups on the polyethylene glycol monoalkyl ether to give a reaction product having a urethane group and a polyethylene glycol monoalkyl ether group, i.e., a polyethylene glycol monoalkyl ether group bonded in the form of a urethane bond.

Preferably, the polyethylene glycol monoalkyl ether is at least one of structures represented by formula (2);

In the formula (2), n has an average value of 6 to 17, and Z is a monovalent C1-C4 alkyl group. Too low a value of n may result in insufficient hydrophilicity, which affects the compatibility of the polyisocyanate composition in an aqueous system after introduction of the polyisocyanate composition, and too high a value of n may result in too high crystallinity of the polyisocyanate composition, which is difficult to rapidly disperse uniformly in an aqueous system after introduction of the polyisocyanate composition.

As a preferred embodiment, the aliphatic polyisocyanate is an aliphatic polyisocyanate having at least one of a uretdione structure, an isocyanurate structure, an allophanate structure, a biuret structure, an iminooxadiazinedione structure, and an oxadiazinetrione structure, which is formed based on at least one of 1, 6-hexamethylene diisocyanate, 1, 5-pentamethylene diisocyanate, and isophorone diisocyanate as a polymerization monomer.

The invention also provides a preparation method of the polyisocyanate composition, which comprises the following steps:

(S1) subjecting an aliphatic polyisocyanate to urethanization with a compound represented by the formula (2 a) and/or a compound represented by the formula (2 b) and then to hydrosilylation with trimethoxy monohydrogen silicon or triethoxy monohydrogen silicon in the presence of a heavy metal catalyst, and/or subjecting an aliphatic polyisocyanate to reaction with bis (3-trimethoxysilylpropyl) amine and/or bis (3-triethoxysilylpropyl) amine;

in the formula (2 a), X is divalent C1-C8 alkyl, and Y is monovalent C1-C8 alkyl;

In the formula (2 b), X is a divalent C1-C8 alkyl group;

(S2) reacting the reaction product of step (S1) with sulfamic acid and/or hydroxysulfonic acid and/or polyethylene glycol monoalkyl ether to obtain the polyisocyanate composition.

In the production method of the present invention, the isocyanate groups of the aliphatic polyisocyanate are mainly divided into three parts, a part of which is modified into at least one of the groups represented by the formulas (1 a), (1 b) and (1 c) in the step (S1), a part of which is modified into a sulfonate group bonded in the form of a urea bond or a urethane bond and/or a polyethylene glycol monoalkyl ether group bonded in the form of a urethane bond in the step (S2), and the remaining part of which does not participate in the reaction.

In the step (S1), a part of isocyanate groups on the aliphatic polyisocyanate can be subjected to urethanization reaction with the compound represented by the formula (2 a) and/OR the formula (2 b), and the product of urethanization reaction can be subjected to hydrosilylation reaction with trimethoxy-monohydrogen OR triethoxy-monohydrogen in the presence of a heavy metal catalyst to thereby produce a group represented by the formula (1 a) having a urethane group and two Si (OR) ₃ groups, and/OR a group represented by the formula (1 b) having a urethane group and three Si (OR) ₃ groups, and/OR a part of isocyanate groups on the aliphatic polyisocyanate can be subjected to reaction with bis (3-trimethoxysilylpropyl) amine and/OR bis (3-triethoxysilylpropyl) amine to thereby produce a group represented by the formula (1 c) having a urea group and two Si (OR) ₃ groups.

In the step (S2), part of isocyanate groups on the aliphatic polyisocyanate can react with sulfamic acid to obtain a reaction product with urea groups and sulfonate groups, namely sulfonate groups bonded in a urea bond form, part of isocyanate groups on the aliphatic polyisocyanate can react with hydroxysulfonic acid to obtain a reaction product with carbamate groups and sulfonate groups, namely sulfonate groups bonded in a carbamate bond form, and part of isocyanate groups on the aliphatic polyisocyanate can react with polyethylene glycol monoalkyl ether to obtain a reaction product with carbamate groups and polyethylene glycol monoalkyl ether groups, namely polyethylene glycol monoalkyl ether groups bonded in a carbamate bond form.

Accordingly, the molar total amount of isocyanate groups, urethane groups and urea groups contained in the polyisocyanate composition is the molar total amount of isocyanate groups of the aliphatic polyisocyanate before the reaction.

As a preferable embodiment, the compound represented by the formula (2 a) is trimethylolpropane diallyl ether, that is, X is methylene and Y is methyl in the compound represented by the formula (2 a).

As a preferable embodiment, the compound represented by the formula (2 b) is pentaerythritol triallyl ether, that is, X in the compound represented by the formula (2 b) is methylene.

In some embodiments, in the preparation method of the polyisocyanate composition, an organic solvent may also be added. The organic solvent selected is one that does not contain active hydrogen for reaction with isocyanate. The organic solvent is preferably aromatic hydrocarbon, ketone, ether, ester, etc.

In other embodiments, the organic solvent may not be added in the process for preparing the polyisocyanate composition. For environmental reasons, it is preferable not to add the organic solvent.

The present invention further provides the use of a polyisocyanate composition as described in any one of the preceding:

As one application, the present invention provides a crosslinkable composition comprising any of the above-described polyisocyanate compositions and a hydroxyl-containing aqueous resin.

As another application, the application of the polyisocyanate composition in preparing the water-based paint is specifically disclosed. The aqueous coating comprises the crosslinkable composition (i.e., comprising the polyisocyanate composition described in any of the above and a hydroxyl-containing aqueous resin). In the process of forming a coating film by construction and drying, isocyanate groups in the polyisocyanate composition undergo a crosslinking reaction with hydroxyl groups in the hydroxyl-containing aqueous resin to form a crosslinked network along with the volatilization of moisture, so that the coating film has better chemical resistance. The polyisocyanate composition is particularly suitable for water-based two-component polyurethane coating, and the water-based two-component polyurethane coating prepared from the polyisocyanate composition has excellent water resistance, salt spray resistance, adhesive force and drying speed, and simultaneously has good luster and hardness.

As a preferable scheme, the water-based paint comprises 10-20 parts by weight of the polyisocyanate composition and 60 parts by weight of the hydroxyl-containing water-based resin.

Further, the water-based paint also comprises other auxiliary agents, wherein the weight parts of the other auxiliary agents in the water-based paint are 2-60 parts. By adding other auxiliary agents, the performance and the decorative effect of the water-based paint can be improved. Preferably, the weight parts of the other auxiliary agents in the water-based paint are 5-40 parts.

As a preferable scheme, the other auxiliary agents comprise one or more of defoamer, flatting agent, cosolvent, color paste or thickener. The weight part of the defoaming agent in the water-based paint is 0.1-1 part, the weight part of the leveling agent in the water-based paint is 0.1-1 part, the weight part of the cosolvent in the water-based paint is 1-10 parts, the weight part of the color paste in the water-based paint is 1-40 parts, and the weight part of the thickener in the water-based paint is 0.1-2 parts. The paint has the advantages of eliminating bubbles generated in the stirring process and bubbles generated in the reaction process through the defoaming agent, improving the flatness of the surface of a paint film through the action of a leveling agent on the interface between water paint liquid and air, preventing the defects of benard vortex and the like, improving the film forming performance of the water paint through a cosolvent, establishing the volatilization gradient of the water paint, improving the surface effect of the paint film, providing the required covering power and color effect of the paint film through color paste, adjusting the rheological property of the water paint through a thickening agent, and improving the sagging resistance, splashing resistance and the like of the paint.

The defoaming agent is at least one of polysiloxane and mineral oil, the leveling agent is at least one of polysiloxane and acrylic leveling agent, the cosolvent is at least one of ethylene glycol butyl ether, propylene glycol butyl ether, diethylene glycol butyl ether, dipropylene glycol methyl ether and dipropylene glycol butyl ether, the color paste is at least one of inorganic color paste and organic color paste, and the thickener is at least one of polyurethane thickener, alkali swelling acrylic thickener and bentonite. The defoamer, the leveling agent, the cosolvent and the thickener are not limiting, and other types of defoamers, leveling agents, cosolvents, color pastes and thickeners can be selected by a person skilled in the art according to actual requirements.

The invention also provides a preparation method of the water-based paint, which comprises the following steps of uniformly mixing the components to obtain the water-based paint.

As yet another application, the present invention provides an article coated with the aqueous coating. Is formed by spraying the aqueous coating comprising the polyisocyanate composition onto a substrate surface.

Compared with the prior art, the invention has the following beneficial effects:

The polyisocyanate composition provided by the invention can be applied to water-based paint, and a coating film formed by the water-based paint has excellent water resistance, salt spray resistance, adhesive force and drying speed, and simultaneously has good luster and hardness.

The inventor of the present invention has found through repeated researches that the group structure shown in the formulas (1 a), (1 b) and (1 c) contains two or three silane groups, so that after the isocyanate groups on the aliphatic polyisocyanate are modified into the groups shown in the formulas (1 a), (1 b) and (1 c), two or three silane groups can be introduced, so that the polyisocyanate composition has a higher NCO value and a high density of silane groups, the silane groups can hydrolyze and crosslink after contacting with an aqueous phase, the curing speed is increased, and the silane groups can bond with a metal substrate to increase the adhesion and the water resistance and salt fog resistance. Surprisingly, we have found that two or three closely spaced silane groups in the present solution produce a synergistic effect, and that the technical solution of the present invention is significantly more excellent even with the same silane content, compared to the conventional solution in which only one silane is introduced per isocyanate group modification. The polyisocyanate composition of the present invention increases the compatibility of the polyisocyanate composition in an aqueous system by introducing sulfonate groups and/or polyethylene glycol monoalkyl ether groups in order to ensure good compatibility in an aqueous system.

Detailed Description

The invention is further illustrated below with reference to examples. These examples are only for illustrating the present invention and are not intended to limit the scope of the present invention. The experimental methods in the examples below, in which specific conditions are not specified, are generally conducted under the conditions conventional in the art or according to the conditions recommended by the manufacturer, and the raw materials, reagents, etc. used, unless otherwise specified, are commercially available from conventional markets and the like. Any insubstantial changes and substitutions made by those skilled in the art in light of the above teachings are intended to be within the scope of the invention as claimed.

Example 1

The present embodiment provides a polyisocyanate composition A1 comprising:

(1) An isocyanate group;

(2) A group represented by the formula (1 a);

wherein X is methylene, Y is ethyl, and R is methyl;

(3) Sulfonate groups bonded in the form of urea bonds.

The polyisocyanate composition A1 of the present example was prepared by the following procedure:

The reaction flask was purged with nitrogen, 1020.0g of HDI-based polyisocyanate WANNATE HT-100 (Wanhua chemistry, NCO value: 22%), 51.4g of trimethylolpropane diallyl ether, warmed to 80℃for 6 hours, then 0.40g of Kadset catalyst (Pt content: 5000 ppm) was added, then 58.7g of trimethoxysilane was added dropwise at 80℃for 1 hour, and then the reaction was continued at 80℃for 2 hours. 24.0g of 4- (cyclohexylamino) -1-butanesulfonic acid, 13.0g of N, N-dimethylcyclohexylamine are added and the reaction is continued at a temperature of 90℃for 6h. Filtration gave a pale yellow transparent viscous liquid, namely polyisocyanate composition A1.

In the preparation of the polyisocyanate composition A1 of this example, the isocyanate groups on the polyisocyanates WANNATE HT-100 are divided into the following three parts:

① Part of isocyanate groups on polyisocyanate WANNATE HT-100 are subjected to urethanization reaction with trimethylolpropane diallyl ether, and the urethanization reaction product is subjected to addition reaction with trimethoxy hydrosilane in the presence of a heavy metal catalyst Pt to form a group shown in a formula (1 a), wherein X is methylene, Y is ethyl and R is methyl;

② Part of isocyanate groups on polyisocyanate WANNATE HT-100 reacts with 4- (cyclohexylamino) -1-butanesulfonic acid to form sulfonate groups bonded in the form of urea bonds, wherein the sulfonate groups bonded in the form of urea bonds contain urea groups and sulfonate groups;

③ A portion of the isocyanate groups on the polyisocyanates WANNATE HT-100 are not involved in the reaction.

The polyisocyanate composition A1 of this example had an NCO value of 17.9%, the molar amount of Si (OR) ₃ groups in the formula (1 a) was 9.0% of the molar total amount of isocyanate groups, urethane groups and urea groups (i.e., the molar total amount of NCO groups before the reaction) contained in the polyisocyanate composition A1, and the molar amount of sulfonate groups was 1.9% of the molar total amount of isocyanate groups, urethane groups and urea groups (i.e., the molar total amount of NCO groups before the reaction) contained in the polyisocyanate composition A1.

Example 2

The present embodiment provides a polyisocyanate composition A2 comprising:

(1) An isocyanate group;

(2) A group represented by the formula (1 b);

Wherein X is methylene, R is methyl;

(3) Sulfonate groups bonded in the form of urea bonds.

The polyisocyanate composition A2 of this example was prepared by the following procedure:

The reaction flask was purged with nitrogen, 1020.0g of HDI-based polyisocyanate WANNATE HT-100 (Wanhua chemistry, NCO value: 22%), 61.5g of pentaerythritol triallyl ether, warmed to 80℃for 6 hours, then 0.54g of Kadset catalyst (Pt content: 5000 ppm) was added, 88.0g of trimethoxysilane was added dropwise at 80℃for 1 hour, and then the reaction was continued at 80℃for 2 hours. 24.0g of 4- (cyclohexylamino) -1-butanesulfonic acid, 13.0g of N, N-dimethylcyclohexylamine are added and the reaction is continued at a temperature of 90℃for 6h. Filtration gave a pale yellow transparent viscous liquid, namely polyisocyanate composition A2.

In the preparation of the polyisocyanate composition A2 of this example, the isocyanate groups on the polyisocyanates WANNATE HT-100 are divided into the following three parts:

① Part of isocyanate groups on polyisocyanate WANNATE HT-100 is subjected to urethanization reaction with pentaerythritol triallyl ether, and the product of the urethanization reaction is subjected to addition reaction with trimethoxy hydrosilane in the presence of a heavy metal catalyst Pt to generate a group shown in a formula (1 b), wherein X is methylene and R is methyl;

The polyisocyanate composition A2 of this example had an NCO value of 17.3%, the molar amount of Si (OR) ₃ groups in the formula (1 b) was 13.5% of the molar total amount of isocyanate groups, urethane groups and urea groups (i.e., the molar total amount of NCO groups before the reaction) contained in the polyisocyanate composition A2, and the molar amount of sulfonate groups was 1.9% of the molar total amount of isocyanate groups, urethane groups and urea groups (i.e., the molar total amount of NCO groups before the reaction) contained in the polyisocyanate composition A2.

Example 3

The present embodiment provides a polyisocyanate composition A3 comprising:

(1) An isocyanate group;

(2) A group represented by the formula (1 c);

Wherein R is methyl;

(3) Sulfonate groups bonded in the form of urea bonds.

The polyisocyanate composition A3 of this example was prepared by the following procedure:

The reaction flask was purged with nitrogen, and 1020.0g of HDI-based polyisocyanate WANNATE HT-100 (Wanhua chemical, NCO value: 22%) 82.0g of bis (3-trimethoxysilylpropyl) amine was added and reacted at 80℃for 6 hours. 24.0g of 4- (cyclohexylamino) -1-butanesulfonic acid, 13.0g of N, N-dimethylcyclohexylamine are added and the reaction is continued at a temperature of 90℃for 6h. Filtration gave a pale yellow transparent viscous liquid, namely polyisocyanate composition A3.

In the preparation of the polyisocyanate composition A3 of this example, the isocyanate groups on the polyisocyanates WANNATE HT-100 are divided into the following three parts:

① Reacting a part of isocyanate groups on polyisocyanate WANNATE HT-100 with bis (3-trimethoxysilylpropyl) amine to form a group shown in formula (1 c), wherein R is methyl, and the group shown in formula (1 c) contains urea groups and two Si (OR) ₃ groups;

The polyisocyanate composition A3 of this example had an NCO value of 18.3%, the molar amount of Si (OR) ₃ groups in the formula (1 c) was 9.0% based on the total molar amount of isocyanate groups, urethane groups (content: 0) and urea groups (i.e., the total molar amount of NCO groups before the reaction) contained in the polyisocyanate composition A3, and the molar amount of sulfonate groups was 1.9% based on the total molar amount of isocyanate groups, urethane groups (content: 0) and urea groups (i.e., the total molar amount of NCO groups before the reaction) contained in the polyisocyanate composition.

Example 4

The present example provides a polyisocyanate composition A4 comprising:

(1) An isocyanate group;

(2) A group represented by the formula (1 a);

wherein X is methylene, Y is ethyl, and R is methyl;

(3) Polyethylene glycol monoalkyl ether groups bonded in the form of urethane linkages.

The polyisocyanate composition A4 of this example was prepared by the following procedure:

The reaction flask was purged with nitrogen, 1020.0g of HDI-based polyisocyanate WANNATE HT-100 (Wanhua chemistry, NCO value: 22%), 51.4g of trimethylolpropane diallyl ether, warmed to 80℃for 6 hours, then 0.40g of Kadset catalyst (Pt content: 5000 ppm) was added, then 58.7g of trimethoxysilane was added dropwise at 80℃for 1 hour, and then the reaction was continued at 80℃for 2 hours. 51.0g of polyethylene glycol monomethyl ether (molecular weight 500) was added, and then the reaction was continued for 8 hours at 90 ℃. Filtration gave a pale yellow transparent viscous liquid, namely polyisocyanate composition A4.

The structural formula of the polyethylene glycol monomethyl ether adopted in the embodiment is shown as the formula (2).

Wherein Z is methyl, and n has an average value of 10.6.

In the preparation of the polyisocyanate composition A4 of this example, the isocyanate groups on the polyisocyanates WANNATE HT-100 are divided into the following three parts:

① Part of isocyanate groups on polyisocyanate WANNATE HT-100 are subjected to urethanization reaction with trimethylolpropane diallyl ether, and the product of the urethanization reaction is subjected to addition reaction with trimethoxy hydrosilane in the presence of a heavy metal catalyst Pt to form a group shown in a formula (1 a), wherein X is methylene, Y is ethyl and R is methyl;

② Reacting a part of isocyanate groups on polyisocyanate WANNATE HT-100 with polyethylene glycol monomethyl ether to generate polyethylene glycol monoalkyl ether groups bonded in a form of a urethane bond, wherein the polyethylene glycol monoalkyl ether groups bonded in a form of a urethane bond contain the urethane group and the polyethylene glycol monoalkyl ether group;

In the polyisocyanate composition A4 of this example, the NCO value was 17.7%, the molar amount of Si (OR) ₃ groups in the formula (1 a) was 9.0% of the molar total amount of isocyanate groups, urethane groups and urea groups (i.e., the molar total amount of NCO groups before the reaction) contained in the polyisocyanate composition A4, and the molar amount of polyethylene glycol monoalkyl ether groups was 1.9% of the molar total amount of isocyanate groups, urethane groups and urea groups (i.e., the molar total amount of NCO groups before the reaction) contained in the polyisocyanate composition A4.

Example 5

The present example provides a polyisocyanate composition A5 comprising:

(1) An isocyanate group;

(2) A group represented by the formula (1 a);

wherein X is methylene, Y is ethyl, and R is methyl;

(3) Sulfonate groups bonded in the form of urea bonds.

The polyisocyanate composition A5 of this example was prepared by the following procedure:

the reaction flask was purged with nitrogen, 1020.0g of HDI-based polyisocyanate WANNATE HT-100 (Wanhua chemistry, NCO value: 22%), 12.9g of trimethylolpropane diallyl ether, warmed to 80℃for 6 hours, then 0.10g of Kadset catalyst (Pt content: 5000 ppm) was added, then 14.7g of trimethoxysilane was added dropwise at 80℃for 1 hour, and then the reaction was continued at 80℃for 2 hours. 24.0g of 4- (cyclohexylamino) -1-butanesulfonic acid, 13.0g of N, N-dimethylcyclohexylamine are added and the reaction is continued at a temperature of 90℃for 6h. Filtration gave a pale yellow transparent viscous liquid, namely polyisocyanate composition A5.

In the preparation of the polyisocyanate composition A5 of this example, the isocyanate groups on the polyisocyanates WANNATE HT-100 are divided into the following three parts:

The molar amount of Si (OR) ₃ groups in the formula (1 a) in the polyisocyanate composition A5 of this example was 20.0% and the molar amount of isocyanate groups, urethane groups and urea groups contained in the polyisocyanate composition A5 (i.e., the molar amount of NCO groups before the reaction) was 2.2%, and the molar amount of sulfonate groups was 1.9% of the molar amount of isocyanate groups, urethane groups and urea groups contained in the polyisocyanate composition A5 (i.e., the molar amount of NCO groups before the reaction).

Example 6

The present example provides a polyisocyanate composition A6 comprising:

(1) An isocyanate group;

(2) A group represented by the formula (1 a);

wherein X is methylene, Y is ethyl, and R is methyl;

(3) Sulfonate groups bonded in the form of urea bonds.

The polyisocyanate composition A6 of this example was prepared by the following procedure:

the reaction flask was purged with nitrogen, 1020.0g of HDI-based polyisocyanate WANNATE HT-100 (Wanhua chemistry, NCO value: 22%), 171.4g of trimethylolpropane diallyl ether was heated to 80℃for 6 hours, then 1.33g of Kadset catalyst (Pt content: 5000 ppm) was added, then 195.5g of trimethoxysilane was added dropwise at 80℃for 1 hour, and the reaction was continued at 80℃for 2 hours. 24.0g of 4- (cyclohexylamino) -1-butanesulfonic acid, 13.0g of N, N-dimethylcyclohexylamine are added and the reaction is continued at a temperature of 90℃for 6h. Filtration gave a pale yellow transparent viscous liquid, namely polyisocyanate composition A6.

In the preparation of the polyisocyanate composition A6 of this example, the isocyanate groups on the polyisocyanates WANNATE HT-100 are divided into the following three parts:

In the polyisocyanate composition A6 of this example, the NCO value was 13.0%, the molar amount of Si (OR) ₃ groups in the formula (1 a) was 29.9% of the molar total amount of isocyanate groups, urethane groups and urea groups (i.e., the molar total amount of NCO groups before the reaction) contained in the polyisocyanate composition A6, and the molar amount of sulfonate groups in A6 was 1.9% of the molar total amount of isocyanate groups, urethane groups and urea groups (i.e., the molar total amount of NCO groups before the reaction) contained in the polyisocyanate composition A6.

Example 7

The present example provides a polyisocyanate composition A7 comprising:

(1) An isocyanate group;

(2) A group represented by the formula (1 a);

wherein X is methylene, Y is ethyl, and R is methyl;

(3) Sulfonate groups bonded in the form of urea bonds.

The polyisocyanate composition A7 of this example was prepared by the following procedure:

The reaction flask was purged with nitrogen, 1020.0g of HDI-based polyisocyanate WANNATE HT-100 (Wanhua chemistry, NCO value: 22%), 51.4g of trimethylolpropane diallyl ether, warmed to 80℃for 6 hours, then 0.40g of Kadset catalyst (Pt content: 5000 ppm) was added, then 58.7g of trimethoxysilane was added dropwise at 80℃for 1 hour, and then the reaction was continued at 80℃for 2 hours. 9.0g of 4- (cyclohexylamino) -1-butanesulfonic acid, 4.9g of N, N-dimethylcyclohexylamine are added and the reaction is continued at a temperature of 90℃for 6h. Filtration gave a pale yellow transparent viscous liquid, namely polyisocyanate composition A7.

In the preparation of the polyisocyanate composition A7 of this example, the isocyanate groups on the polyisocyanates WANNATE HT-100 are divided into the following three parts:

The polyisocyanate composition A7 of this example had an NCO value of 18.5%, the molar amount of Si (OR) ₃ groups in the formula (1 a) was 9.0% of the molar total amount of isocyanate groups, urethane groups and urea groups (i.e., the molar total amount of NCO groups before the reaction) contained in the polyisocyanate composition A7, and the molar amount of sulfonate groups was 0.72% of the molar total amount of isocyanate groups, urethane groups and urea groups (i.e., the molar total amount of NCO groups before the reaction) contained in the polyisocyanate composition A7.

Example 8

The present example provides a polyisocyanate composition A8 comprising:

(1) An isocyanate group;

(2) A group represented by the formula (1 a);

wherein X is methylene, Y is ethyl, and R is methyl;

(3) Sulfonate groups bonded in the form of urea bonds.

The polyisocyanate composition A8 of this example was prepared by the following procedure:

the reaction flask was purged with nitrogen, 1020.0g of HDI-based polyisocyanate WANNATE HT-100 (Wanhua chemistry, NCO value: 22%), 51.4g of trimethylolpropane diallyl ether, warmed to 80℃for 6 hours, then 0.40g of Kadset catalyst (Pt content: 5000 ppm) was added, then 58.7g of trimethoxysilane was added dropwise at 80℃for 1 hour, and then the reaction was continued at 80℃for 2 hours. 87.0g of 4- (cyclohexylamino) -1-butanesulfonic acid, 47.0g of N, N-dimethylcyclohexylamine were added, and the reaction was continued at 90℃for 6 hours. Filtration gave a pale yellow transparent viscous liquid, namely polyisocyanate composition A8.

In the preparation of the polyisocyanate composition A8 of this example, the isocyanate groups on the polyisocyanates WANNATE HT-100 are divided into the following three parts:

The polyisocyanate composition A8 of this example had an NCO value of 15.6%, the molar amount of Si (OR) ₃ groups in the formula (1 a) was 9.0% of the molar total amount of isocyanate groups, urethane groups and urea groups (i.e., the molar total amount of NCO groups before the reaction) contained in the polyisocyanate composition A8, and the molar amount of sulfonate groups was 6.9% of the molar total amount of isocyanate groups, urethane groups and urea groups (i.e., the molar total amount of NCO groups before the reaction) contained in the polyisocyanate composition A8.

Example 9

The present example provides a polyisocyanate composition A9 comprising:

(1) An isocyanate group;

(2) A group represented by the formula (1 a);

wherein X is methylene, Y is ethyl, and R is methyl;

The polyisocyanate composition A9 of this example was prepared by the following procedure:

The reaction flask was purged with nitrogen, 1020.0g of HDI-based polyisocyanate WANNATE HT-100 (Wanhua chemistry, NCO value: 22%), 51.4g of trimethylolpropane diallyl ether, warmed to 80℃for 6 hours, then 0.40g of Kadset catalyst (Pt content: 5000 ppm) was added, then 58.7g of trimethoxysilane was added dropwise at 80℃for 1 hour, and then the reaction was continued at 80℃for 2 hours. 29.9g of polyethylene glycol monobutyl ether (molecular weight 750) are added and then the reaction is continued for 8h at 90 ℃. Filtration gave a pale yellow transparent viscous liquid, namely polyisocyanate composition A9, having an NCO value of 18.2%.

Wherein Z is methyl, and n has an average value of 16.3.

In the preparation of the polyisocyanate composition A9 of this example, the isocyanate groups on the polyisocyanates WANNATE HT-100 are divided into the following three parts:

In the polyisocyanate composition A9 of this example, the NCO value was 18.2%, the molar amount of Si (OR) ₃ groups in the formula (1 a) was 9.0% of the molar total amount of isocyanate groups, urethane groups and urea groups (i.e., the molar total amount of NCO groups before the reaction) contained in the polyisocyanate composition A9, and the molar amount of polyethylene glycol monoalkyl ether groups was 0.74% of the molar total amount of isocyanate groups, urethane groups and urea groups (i.e., the molar total amount of NCO groups before the reaction) contained in the polyisocyanate composition A9.

Example 10

The present embodiment provides a polyisocyanate composition a10 comprising:

(1) An isocyanate group;

(2) A group represented by the formula (1 a);

wherein X is methylene, Y is ethyl, and R is methyl;

The polyisocyanate composition a10 of this example was prepared by the following procedure:

The reaction flask was purged with nitrogen, 1020.0g of HDI-based polyisocyanate WANNATE HT-100 (Wanhua chemistry, NCO value: 22%), 51.4g of trimethylolpropane diallyl ether, warmed to 80℃for 6 hours, then 0.40g of Kadset catalyst (Pt content: 5000 ppm) was added, then 58.7g of trimethoxysilane was added dropwise at 80℃for 1 hour, and then the reaction was continued at 80℃for 2 hours. 129.5g of polyethylene glycol monobutyl ether (molecular weight 350) are added and then the reaction is continued for 8h at 90 ℃. Filtration gave a pale yellow transparent viscous liquid, namely polyisocyanate composition a10.

Wherein Z is butyl, and n has an average value of 6.3.

In the preparation of the polyisocyanate composition A10 of this example, the isocyanate groups on the polyisocyanates WANNATE HT-100 are divided into the following three parts:

The polyisocyanate composition A10 of this example had an NCO value of 15.7%, the molar amount of Si (OR) ₃ groups in the formula (1 a) was 9.0% of the molar total amount of isocyanate groups, urethane groups and urea groups (i.e., the molar total amount of NCO groups before the reaction) contained in the polyisocyanate composition A10, and the molar amount of polyethylene glycol monoalkyl ether groups was 6.9% of the molar total amount of isocyanate groups, urethane groups and urea groups (i.e., the molar total amount of NCO groups before the reaction) contained in the polyisocyanate composition A10.

Example 11

This example provides a polyisocyanate composition a11,

(1) An isocyanate group;

(2) A group represented by the formula (1 a);

Wherein X is methylene, Y is ethyl, R is ethyl;

(3) Sulfonate groups bonded in the form of urea bonds.

The polyisocyanate composition a11 of this example was prepared by the following procedure:

The reaction flask was purged with nitrogen, 620.0g of HDI-based polyisocyanate WANNATE HT-100 (Wanhua chemistry, NCO value: 22%), 400.0g of IPDI-based polyisocyanate WANNATE IT-100 (Wanhua chemistry, NCO value: 17.4%), 501.1g of propylene glycol diacetate, 51.4g of trimethylolpropane diallyl ether, and the temperature was raised to 80℃for 6 hours, followed by the addition of 0.40g of Kadset catalyst (Pt content: 5000 ppm), followed by the dropwise addition of 78.8g of triethoxysilane at 80℃for 1 hour, followed by further reaction at 80℃for 2 hours. 24.0g of 2- (cyclohexylamino) -1-ethanesulfonic acid, 14.7g of N, N-dimethylcyclohexylamine were added, and the reaction was continued at 90℃for 6 hours. Filtration gave a pale yellow transparent viscous liquid, namely polyisocyanate composition a11.

In the preparation of the polyisocyanate composition A11 of this example, propylene glycol diacetate is used as a solvent to reduce the viscosity, and the total isocyanate groups on the polyisocyanate WANNATE HT-100 and the polyisocyanate WANNATE IT-100 are divided into three parts:

① Part of isocyanate groups on the polyisocyanate WANNATE HT-100 and/OR the polyisocyanate WANNATE IT-100 are subjected to urethanization reaction with trimethylolpropane diallyl ether, and the urethanization reaction product is subjected to addition reaction with triethoxysilane in the presence of a heavy metal catalyst Pt to generate a group shown in a formula (1 a), wherein X is methylene, Y is ethyl and R is ethyl;

② Reacting a portion of the isocyanate groups on the polyisocyanate WANNATE HT-100 and/or the polyisocyanate WANNATE IT-100 with 2- (cyclohexylamino) -1-ethanesulfonic acid to form sulfonate groups bonded in the form of urea bonds, wherein the sulfonate groups bonded in the form of urea bonds contain urea groups and sulfonate groups;

③ Some of the isocyanate groups on the polyisocyanates WANNATE HT-100 and/or the polyisocyanates WANNATE IT-100 do not participate in the reaction.

The polyisocyanate composition A11 of this example had an NCO value of 11.3%, the molar amount of Si (OR) ₃ groups in the formula (1 a) was 9.8% of the molar total amount of isocyanate groups, urethane groups and urea groups (i.e., the molar total amount of NCO groups before the reaction) contained in the polyisocyanate composition A11, and the molar amount of sulfonate groups was 2.4% of the molar total amount of isocyanate groups, urethane groups and urea groups (i.e., the molar total amount of NCO groups before the reaction) contained in the polyisocyanate composition A11.

Comparative example 1

The present comparative example provides a polyisocyanate composition B1 prepared by the following procedure:

The reaction flask was purged with nitrogen, 1020.0g of HDI-based polyisocyanate WANNATE HT-100 (Wanhua chemistry, NCO value: 22%), 49.0g of ethylene glycol monoallyl ether, heated to 80℃for 6 hours, then 0.40g of Kadset catalyst (Pt content: 5000 ppm) was added, then 58.7g of trimethoxysilane was added dropwise at 80℃for 1 hour, and then the reaction was continued at 80℃for 2 hours. 24.0g of 4- (cyclohexylamino) -1-butanesulfonic acid, 13.0g of N, N-dimethylcyclohexylamine are added and the reaction is continued at a temperature of 90℃for 6h. Filtration gave a pale yellow transparent viscous liquid, namely polyisocyanate composition B1.

In the preparation of the polyisocyanate composition B1 of this comparative example, the isocyanate groups on the polyisocyanates WANNATE HT-100 are divided into the following three parts:

① Part of isocyanate groups on the polyisocyanate WANNATE HT-100 are subjected to urethanization reaction with ethylene glycol monoallyl ether, and the product of the urethanization reaction is subjected to addition reaction with trimethoxy hydrosilane in the presence of a heavy metal catalyst Pt, wherein the product of the addition reaction contains a carbamate group and a Si (OR) ₃ group;

The polyisocyanate composition B1 of the present comparative example had an NCO value of 17.1%, the polyisocyanate composition B1 did not contain the structures of the formulae (1 a), (1B) and (1 c), the molar amount of Si (OR) ₃ groups was 9.0% based on the molar total amount of isocyanate groups, urethane groups and urea groups (i.e., the molar total amount of NCO groups before the reaction) contained in the polyisocyanate composition B1, and the molar amount of sulfonate groups was 1.9% based on the molar total amount of isocyanate groups, urethane groups and urea groups (i.e., the molar total amount of NCO groups before the reaction) contained in the polyisocyanate composition B1.

Comparative example 2

The present comparative example provides a polyisocyanate composition B2 prepared by the following procedure:

The reaction flask was purged with nitrogen, and 1020.0g of HDI-based polyisocyanate WANNATE HT-100 (Wanhua chemistry, NCO value: 22%) and 168.7g of silane-functionalized aspartic acid (synthesized according to example 1 of patent CN1637106A, obtained by reacting diethyl maleate with gamma-aminopropyl trimethoxysilane) were added and reacted at 80℃for 6h. 24.0g of 4- (cyclohexylamino) -1-butanesulfonic acid, 13.0g of N, N-dimethylcyclohexylamine are added and the reaction is continued at a temperature of 90℃for 6h. Filtration gave a pale yellow transparent viscous liquid, namely polyisocyanate composition B2.

In the preparation of the polyisocyanate composition B2 of this comparative example, the isocyanate groups on the polyisocyanates WANNATE HT-100 are divided into the following three parts:

① A portion of the isocyanate groups on polyisocyanate WANNATE HT-100 are reacted with silane-functionalized aspartic acid, the reaction product containing urea groups and one Si (OR) ₃ group;

The polyisocyanate composition B2 of this comparative example had an NCO value of 16.2%, the polyisocyanate composition B2 did not contain the structures of the formulae (1 a), (1B) and (1 c), the molar amount of Si (OR) ₃ groups was 9.0% based on the molar total amount of isocyanate groups, urethane groups and urea groups (i.e., the molar total amount of NCO groups before the reaction) contained in the polyisocyanate composition B2, and the molar amount of sulfonate groups was 1.9% based on the molar total amount of isocyanate groups, urethane groups and urea groups (i.e., the molar total amount of NCO groups before the reaction) contained in the polyisocyanate composition B2.

Comparative example 3

The present comparative example provides a polyisocyanate composition B3 comprising:

(1) An isocyanate group;

(2) A group represented by the formula (1 a);

wherein X is methylene, Y is ethyl, and R is methyl;

(3) Sulfonate groups bonded in the form of urea bonds.

The polyisocyanate composition B3 of this comparative example was prepared by the following procedure:

The reaction flask was purged with nitrogen, 1020.0g of HDI-based polyisocyanate WANNATE HT-100 (Wanhua chemistry, NCO value: 22%), 6.4g of trimethylolpropane diallyl ether was heated to 80℃for 6 hours, then 0.05g of Kadset catalyst (Pt content: 5000 ppm) was added, then 7.3g of trimethoxysilane was added dropwise at 80℃for 1 hour, and then the reaction was continued at 80℃for 2 hours. 24.0g of 4- (cyclohexylamino) -1-butanesulfonic acid, 13.0g of N, N-dimethylcyclohexylamine are added and the reaction is continued at a temperature of 90℃for 6h. Filtration gave a pale yellow transparent viscous liquid, namely polyisocyanate composition B3.

In the preparation of the polyisocyanate composition B3 of this comparative example, the isocyanate groups on the polyisocyanates WANNATE HT-100 are divided into the following three parts:

The polyisocyanate composition B3 of the present comparative example had an NCO value of 20.4% and the molar amount of Si (OR) ₃ groups in the formula (1 a) was 1.1% of the molar total amount of isocyanate groups, urethane groups and urea groups (i.e., the molar total amount of NCO groups before the reaction) contained in the polyisocyanate composition B3. The molar amount of sulfonate groups was 1.9% of the molar total amount of isocyanate groups, urethane groups and urea groups (i.e., the molar total amount of NCO groups before reaction) contained in the polyisocyanate composition B3.

Comparative example 4

This comparative example provides a polyisocyanate composition B4 comprising:

(1) An isocyanate group;

(2) A group represented by the formula (1 a);

wherein X is methylene, Y is ethyl, and R is methyl;

(3) Sulfonate groups bonded in the form of urea bonds.

The polyisocyanate composition B4 of this comparative example was prepared by the following procedure:

The reaction flask was purged with nitrogen, 1020.0g of HDI-based polyisocyanate WANNATE HT-100 (Wanhua chemistry, NCO value: 22%), 214.3g of trimethylolpropane diallyl ether was heated to 80℃for 6 hours, then 1.67g of Kadset catalyst (Pt content: 5000 ppm) was added, then 244.4g of trimethoxysilane was added dropwise at 80℃for 1 hour, and then the reaction was continued at 80℃for 2 hours. 24.0g of 4- (cyclohexylamino) -1-butanesulfonic acid, 13.0g of N, N-dimethylcyclohexylamine are added and the reaction is continued at a temperature of 90℃for 6h. Filtration gave a pale yellow transparent viscous liquid, namely polyisocyanate composition B4.

In the preparation of the polyisocyanate composition B4 of this comparative example, the isocyanate groups on the polyisocyanates WANNATE HT-100 are divided into the following three parts:

The present comparative example provides a polyisocyanate composition B4 having an NCO value of 11.7%, the molar amount of Si (OR) ₃ groups in the formula (1 a) being 37.4% of the molar total amount of isocyanate groups, urethane groups and urea groups (i.e., the molar total amount of NCO groups before the reaction) contained in the polyisocyanate composition B4, and the molar amount of sulfonate groups being 1.9% of the molar total amount of isocyanate groups, urethane groups and urea groups (i.e., the molar total amount of NCO groups before the reaction) contained in the polyisocyanate composition B4.

Performance testing

The properties of the polyisocyanate compositions A1 to A11 of examples 1 to 11 and the polyisocyanate compositions B1 to B4 of comparative examples 1 to 4 were tested respectively as follows:

The polyisocyanate compositions A1 to A11 of examples 1 to 11, the polyisocyanate compositions B1 to B4 of comparative examples 1 to 4, and the commercially available water-dispersible polyisocyanate crosslinking agent OS-9018 (Guangzhou Guanzhu brand new material, solid content: 100%, NCO value: 20.1%) were formulated with commercially available aqueous hydroxyacrylic acid secondary fractions (trade name PA-3225, solid content: 45%, solid content of hydroxyl content: 2.2%) respectively, according to the formulation of Table 1, to prepare aqueous paints 1 to 16.

Table 1 aqueous coating formulation

The following performance tests were performed on the water-based paints 1 to 16, respectively:

and (3) water resistance test, namely diluting the just-prepared water-based paint with water to a proper viscosity, spraying the water-based paint on a polished carbon steel substrate, baking the carbon steel substrate for 2 hours at the film thickness of 23+/-3 mu m and the temperature of 70 ℃, soaking the carbon steel plate in water at the temperature of 40 ℃ for night, and observing whether foaming and light loss occur.

Salt spray resistance test on carbon steel substrate according to GB/T1771-2007.

Gloss test-test on carbon steel substrate, test was performed according to GB/T9754-2007.

Pencil hardness test-test was performed on glass substrates according to GB/T6739-1996.

Adhesion test, namely, testing according to GB 9286-98 on a carbon steel substrate, wherein the grade of 0-5 is the best grade of 0.

Drying speed-dry film thickness was sprayed on a carbon steel substrate at 23.+ -.3. Mu.m, and the dry-to-touch time was observed at 25 ℃.

The test results are shown in the following table:

TABLE 2 test results of Water-based paint

The water-based paint formulation of Table 1 and the performance test results of Table 2 show that the water-based paint 1-11 to which the polyisocyanate compositions A1-A11 of examples 1-11 of the present invention were added has more excellent water resistance, salt spray resistance, adhesion and drying speed, and comparable gloss and hardness, because two or three silane groups having a relatively short distance, i.e., two or three silane groups having a relatively high NCO value and a high density having a relatively high water phase hydrolysis resistance, a relatively high metal adhesion and a relatively high water spray resistance, a relatively high water-crosslinking speed and a relatively high water-crosslinking effect, and a relatively high water-mist resistance, are introduced into the group structure of the groups represented by the formulas (1 a), (1B) and (1 c) in the polyisocyanate compositions A1-A11, i.e., the isocyanate groups on the aliphatic polyisocyanates are modified into the groups represented by the formulas (1 a), (1B) and (1 c), and the silane groups having a relatively high NCO value and a relatively high density having a relatively high water phase hydrolysis resistance, the silane groups having a relatively high water spray resistance and a relatively high water spray resistance, and a relatively good water-resistant adhesion, and a relatively good water-crosslinking effect, and a relatively good water-mist resistance are produced by the silane groups, respectively, which are formed by the silane groups and the silane groups on the aliphatic polyisocyanates are modified into the groups represented by formulas (1 a) and (1B) and (1) and.

The aqueous coating compositions 12 and 13 prepared from the polyisocyanate compositions B1 and B2 of comparative examples 1 to 2 were inferior in water resistance, salt spray resistance, adhesion and drying rate to the polyisocyanate compositions of the present invention having the same molar amount of Si (OR) ₃ groups, because the polyisocyanate compositions B1 and B2 of comparative examples 1 to 2 had a lower NCO value due to the high amount of NCO groups consumed for the modification, because the polyisocyanate compositions B1 and B2 did not contain the group structures represented by the formulas (1 a), (1B) and (1 c) and only one silane group was introduced after the isocyanate groups on the aliphatic polyisocyanate were modified with ethylene glycol monoallyl ether and trimethoxyhydrosilane in this order. The aqueous coating 14 of the polyisocyanate composition B3 of comparative example 3 is inferior in water resistance, salt spray resistance, adhesion and drying speed because the proportion of Si (OR) ₃ groups in the structure of formula (1 a) in the polyisocyanate composition B3 is too low. The aqueous coating 15 of the polyisocyanate composition B4 of comparative example 4 has poor gloss and hardness due to the excessively high proportion of Si (OR) ₃ groups in the structure of formula (1 a) in the polyisocyanate composition B4, which may be a possibility that the excessively high proportion of silane groups leads to deterioration in compatibility of the polyisocyanate composition B4 with resins.

The above examples illustrate only a few embodiments of the invention, which are described in detail and are not to be construed as limiting the scope of the invention. It should be noted that modifications and improvements can be made by those skilled in the art without departing from the spirit of the invention, and the invention is intended to encompass such modifications and improvements.

Claims

1. A polyisocyanate composition characterized by comprising:

(1) An isocyanate group;

(2) At least one of the groups represented by the formulas (1 a), (1 b), (1 c);

(3) Sulfonate groups bonded in the form of urea linkages or urethane linkages and/or polyethylene glycol monoalkyl ether groups bonded in the form of urethane linkages;

The polyisocyanate composition contains 12.0-26.0wt% of isocyanate groups, the molar total amount of Si (OR) ₃ groups in the formulas (1 a), (1 b) and (1 c) is 2-30% of the molar total amount of isocyanate groups, carbamate groups and urea groups in the polyisocyanate composition, and the molar total amount of sulfonate groups and/OR polyethylene glycol monoalkyl ether groups is 0.7-7% of the molar total amount of isocyanate groups, carbamate groups and urea groups in the polyisocyanate composition.

2. The polyisocyanate composition according to claim 1, wherein the isocyanate groups are isocyanate groups on aliphatic polyisocyanates, the groups represented by the formulae (1 a), (1 b), (1 c) are derived from isocyanate groups on aliphatic polyisocyanates, respectively, sulfonate groups bonded in the form of urea bonds or urethane bonds, and/or polyethylene glycol monoalkyl ether groups bonded in the form of urethane bonds are derived from isocyanate groups on aliphatic polyisocyanates, respectively.

3. The polyisocyanate composition according to claim 2, wherein:

the group shown in the formula (1 a) is obtained by performing urethanization reaction on isocyanate groups on aliphatic polyisocyanates and a compound shown in the formula (2 a) and then performing addition reaction on the isocyanate groups and trimethoxy-hydrosilicon and/or triethoxy-hydrosilicon;

The group shown in the formula (1 b) is obtained by performing urethanization reaction on isocyanate groups on aliphatic polyisocyanates and a compound shown in the formula (2 b) and then performing addition reaction on the isocyanate groups and trimethoxy-hydrosilicon and/or triethoxy-hydrosilicon;

In the formula (2 b), X is a divalent C1-C8 alkyl group;

the group represented by the formula (1 c) is obtained by reacting an isocyanate group on an aliphatic polyisocyanate with bis (3-trimethoxysilylpropyl) amine and/or bis (3-triethoxysilylpropyl) amine.

4. The polyisocyanate composition according to claim 2, wherein:

The sulfonate group bonded in the form of urea bond is obtained by reacting isocyanate group on aliphatic polyisocyanate with sulfamic acid;

The sulfonate group bonded in the form of urethane bond is obtained by reacting isocyanate group on aliphatic polyisocyanate with hydroxysulfonic acid;

The polyethylene glycol monoalkyl ether group bonded in the form of a urethane bond is obtained by reacting an isocyanate group on aliphatic polyisocyanate with a polyethylene glycol monoalkyl ether, wherein the polyethylene glycol monoalkyl ether is at least one of structures shown in formula (2);

In the formula (2), n has an average value of 6 to 17, and Z is a monovalent C1-C4 alkyl group.

5. The composition of claim 2 to 4, wherein the aliphatic polyisocyanate is an aliphatic polyisocyanate having at least one of a uretdione structure, an isocyanurate structure, an allophanate structure, a biuret structure, an iminooxadiazinedione structure and an oxadiazinetrione structure, which is formed as a polymerized monomer based on at least one of 1, 6-hexamethylene diisocyanate, 1, 5-pentamethylene diisocyanate and isophorone diisocyanate.

6. The polyisocyanate composition according to claim 4, wherein the sulfamic acid is at least one of 2- (cyclohexylamino) ethanesulfonic acid, 3- (cyclohexylamino) propanesulfonic acid and 4- (cyclohexylamino) butanesulfonic acid, and the hydroxysulfonic acid is at least one of 2-hydroxyethanesulfonic acid, 3-hydroxypropanesulfonic acid, 4-hydroxybutanesulfonic acid, 5-hydroxypentanesulfonic acid, 6-hydroxyhexanesulfonic acid, hydroxybenzenesulfonic acid and hydroxy (meth) benzenesulfonic acid.

7. The polyisocyanate composition of claim 4 wherein:

the sulfonate group bonded in the form of urea bond is obtained by reacting isocyanate group on aliphatic polyisocyanate with sulfamic acid, and then adding at least one of N, N-dimethylbutylamine, N-diethylmethylamine, N-diisopropylethylamine, N-dimethylcyclohexylamine, N-methylpiperidine and N-ethylmorpholine which are more than 20mol percent based on the molar quantity of the sulfamic acid for neutralization;

the sulfonate group bonded in the form of urethane bond is obtained by reacting isocyanate group on aliphatic polyisocyanate with hydroxysulfonic acid, and then adding at least one of N, N-dimethylbutylamine, N-diethylmethylamine, N-diisopropylethylamine, N-dimethylcyclohexylamine, N-methylpiperidine and N-ethylmorpholine in an amount of 20mol% or more based on the molar amount of the hydroxysulfonic acid for neutralization.

8. A process for preparing the polyisocyanate composition according to claim 1 to 7, comprising the steps of:

In the formula (2 b), X is a divalent C1-C8 alkyl group;

9. An aqueous coating composition comprising the polyisocyanate composition according to any one of claims 1 to 7 and a hydroxyl group-containing aqueous resin.

10. An article coated with the aqueous coating of claim 9.