Polyether-modified polyisocyanate compositions

Abstract

The invention relates to a polyether-modified polyisocyanate composition obtainable by reaction of a system comprising: a) a polyisocyanate having an isocyanate group functionality of 2 to 4.5; b) a polyalkylene oxide monoether alcohol having a number average molecular weight of 900 g / mol to 2000 g / mol and a propylene oxide group content of 45 wt% to 100 wt%, relative to the total weight of the alkylene oxide groups of the polyalkylene oxide monoether alcohol; and c) optionally a catalyst; the system having an equivalent ratio of isocyanate groups to hydroxyl groups of 5:1 to 110:1; the polyisocyanate composition having the following characteristics: i) an average isocyanate functionality of 1.8 to 4.1; ii) an isocyanate group content of 8 to 20 wt%; and iii) an amount of polyalkylene oxide monoether structure of greater than 10 wt% and less than 50 wt%, both characteristics ii) and iii) relative to the total weight of the polyisocyanate composition.

Description

TECHNICAL FIELD

[0001] The present application relates to a polyether-modified polyisocyanate composition, a process for its preparation, its use as a starting component in the preparation of polyurethanes, its use as a crosslinking component for solvent-borne or solvent-free coatings, adhesives or sealants, its use as a starting component for the preparation of blocked polyisocyanates, its use in increasing the pot life of coatings, adhesives or sealants, a coating, adhesive or sealant comprising it, in particular a solvent-borne or solvent-free two-component coating comprising it. BACKGROUND

[0002] Solvent-borne or solvent-free two-component coatings comprising aspartate are widely used, especially in the field of floor coatings, due to their weather resistance, abrasion resistance, moisture and heat resistance, salt spray resistance, and their ability to meet the requirements of high solids, low viscosity and environmental protection. In addition to aspartate, the above-mentioned solvent-borne or solvent-free two-component coatings usually also contain a polyisocyanate component. In practical applications, the polyisocyanate and aspartate are mixed, and the two components usually react rapidly within a few seconds to a few minutes to form a highly crosslinked, solvent-free polyurea coating. Due to such a short pot life, the application of solvent-borne or solvent-free two-component coatings using application methods widely used in the floor field such as roller coating, brushing, etc. cannot be achieved, and special spraying equipment must be used for application, increasing the difficulty and cost of construction and greatly affecting the application of aspartate coatings in the field of floor coatings and the like.

[0003] Currently, the main methods for extending the pot life of solvent-borne or solvent-free two-component coatings containing aspartate are: 1) adding a large amount of active diluent or solvent to the coating to reduce the rate of increase in coating viscosity, thereby ensuring sufficient pot life, but many active diluents (such as vinylene carbonate) and solvents have certain toxicity, and the addition of a large amount of active diluent or solvent also causes additional environmental pollution, which does not meet the trend and requirements of environmental protection, as described in CN106147560A; 2) selecting a low-activity isocyanate-reactive compound, which can extend the pot life, but greatly prolongs the drying time of the coating, which cannot meet the drying requirements of the industry; 3) selecting a low-activity isocyanate, such as a large molecular weight isocyanate prepolymer, to reduce the reactivity and ensure sufficient pot life of the coating, but generally low-activity isocyanate prepolymers have high viscosity, which not only increases the difficulty of construction, but also reduces the drying efficiency of the coating, and the coating formed by such a coating has low hardness, and the surface of the coating cannot be completely dried for a very long time, as described in US20040067315A, CN102300894, US A 3428610 and WO2007 / 039133, therefore, low-activity isocyanates are only suitable for use in the fields of polyurethane elastomers or waterproof coatings.

[0004] DE102009012312A1 discloses a polyisocyanate obtained by reacting a diphenylmethane diisocyanate prepolymer and a monofunctional polypropylene polyether alcohol or a mixture of a monofunctional polypropylene polyether alcohol and a polyfunctional polyether alcohol, the monofunctional polypropylene polyether alcohol having a number average molecular weight of 500 g / mol to 25000 g / mol. The polyisocyanate has a high functionality and a low viscosity and contains a very small amount of free small molecule diisocyanate. The polyisocyanate is often used as a component of one-component or two-component adhesives or sealants, but due to its fast drying speed, it is often used in the soft foam and hard foam industry.

[0005] DE1914365C3 discloses a process for preparing a polyurethane sealant by reacting a monofunctional polyoxyethylene polyether alcohol having a number average molecular weight of 100 g / mol to 2000 g / mol with a polyisocyanate based on toluene diisocyanate.

[0006] DE50313746 D1, US5252696, US6426414, DE19863684181, DE19813112117, DE19958170 A1, DE59810651 D1, DE19822890 A1, DE502006010104 D1, DE102006008690A1, US2010105833A and US2012101210A, etc. patents also describe the technology of reacting monofunctional polyoxyethylene polyether alcohol and isocyanate to form polyisocyanate. This polyisocyanate can be dispersed in water and used as a crosslinking agent in two-component water-based coatings and adhesives.

[0007] The present application is devoted to finding a polyisocyanate that can have long pot life, high bubble free film thickness (BFFT) and fast drying performance, and the coating formed by the coating containing it has high hardness. SUMMARY

[0008] The present application relates to a polyether-modified polyisocyanate composition and a process for its preparation, its use as a starting component in the preparation of polyurethanes, its use as a crosslinking component for solvent-borne or solventless coatings, adhesives or sealants, its use as a starting component for the preparation of blocked polyisocyanates, its use in increasing the pot life of coatings, adhesives or sealants, a coating, adhesive or sealant containing it, in particular a solvent-borne or solventless two-component coating containing it. In the following, the solvent-borne or solventless two-component coating is also referred to as solvent-borne or solventless two-component coating composition.

[0009] The polyether-modified polyisocyanate composition according to the present application can be obtained by reacting a system comprising:

[0010] a) a polyisocyanate having an isocyanate group functionality of 2 to 4.5, comprising at least 35 wt.-% hexamethylene diisocyanate trimer, pentamethylene diisocyanate trimer, or a combination thereof;

[0011] b) a polyoxyalkylene monoether alcohol; and

[0012] c) optionally a catalyst;

[0013] said polyoxyalkylene monoether alcohol having a number average molecular weight of 900 g / mol to 2000 g / mol and a propylene oxide group content of 45 wt.-% to 100 wt.-%, relative to the total weight of the oxyalkylene groups of the polyoxyalkylene monoether alcohol;

[0014] said system having an equivalent ratio of isocyanate groups to hydroxyl groups of 5:1 to 110:1;

[0015] said polyisocyanate composition having the following characteristics:

[0016] i) an average isocyanate functionality of 1.8 to 4.1;

[0017] ii) an isocyanate group content of 8 wt.-% to 20 wt.-%, relative to the total weight of the polyisocyanate composition; and

[0018] iii) an amount of polyoxyalkylene monoether structures of more than 10 wt.-% and less than 50 wt.-%, relative to the total weight of the polyisocyanate composition.

[0019] According to one aspect of the present application, there is provided a process for preparing a polyether-modified polyisocyanate composition according to the present application, characterized in that a system comprising component a) a polyisocyanate having an isocyanate group functionality of 2 to 4.5, component b) a polyoxyalkylene monoether alcohol, and optionally component c) a catalyst, is mixed and reacted to form a polyether-modified polyisocyanate composition having the following characteristics: i) an average isocyanate functionality of 1.8 to 4.1; ii) an isocyanate group content of 8 to 20 wt.-%, relative to the total weight of the polyisocyanate composition; and iii) an amount of polyoxyalkylene monoether structures of more than 10 wt.-% and less than 50 wt.-%, relative to the total weight of the polyisocyanate composition; wherein the component a) polyisocyanate comprises at least 35 wt.-% hexamethylene diisocyanate trimer, pentamethylene diisocyanate trimer, or a combination thereof; the component b) polyoxyalkylene monoether alcohol has a number average molecular weight of 900 g / mol to 2000 g / mol and a propylene oxide group content of 45 wt.-% to 100 wt.-%, relative to the total weight of the oxyalkylene groups of the polyoxyalkylene monoether alcohol; and the system has an equivalent ratio of isocyanate groups to hydroxyl groups of 5:1 to 110:1.

[0020] According to still another aspect of the present application, there is provided a use of the polyether-modified polyisocyanate composition according to the present application as a starting component in the preparation of a polyurethane.

[0021] According to still another aspect of the present application, there is provided a use of the polyether-modified polyisocyanate composition according to the present application as a crosslinking component for a solvent- or solventless-type coating, adhesive or sealant.

[0022] According to still another aspect of the present application, there is provided a use of the polyether-modified polyisocyanate composition according to the present application as a starting component for the preparation of a blocked polyisocyanate blocked with a blocking agent.

[0023] According to still another aspect of the present application, there is provided a coating, adhesive or sealant comprising the polyether-modified polyisocyanate composition according to the present application.

[0024] According to still another aspect of the present application, there is provided a substrate coated with the coating, adhesive or sealant according to the present application.

[0025] According to still another aspect of the present application, there is provided a use of the polyether-modified polyisocyanate composition according to the present application in increasing the pot life of a coating, adhesive or sealant.

[0026] According to still another aspect of the present application, there is provided a solvent- or solventless-type two-component coating comprising an A component which is an isocyanate-reactive group-containing compound and a B component which is the polyether-modified polyisocyanate composition according to the present application.

[0027] The polyether-modified polyisocyanate composition of the present application can be applicable to a solvent- or solventless-type system.

[0028] The coating, adhesive or sealant comprising the polyether-modified polyisocyanate composition of the present application has the advantages of high bubble-free film thickness (BFFT), long workable time and high drying efficiency, and the coating layer formed therefrom has high hardness. DETAILED DESCRIPTION

[0029] The present application provides a polyether-modified polyisocyanate composition, which can be obtained by reacting a system comprising:

[0030] a) a polyisocyanate having an isocyanate group functionality of 2 to 4.5, comprising at least 35 wt% of hexamethylene diisocyanate trimer, pentamethylene diisocyanate trimer or a combination thereof;

[0031] b) a polyoxyalkylene monoether alcohol; and

[0032] c) optionally a catalyst;

[0033] the polyoxyalkylene monoether alcohol has a number average molecular weight of 900 g / mol to 2000 g / mol and an oxypropylene group content of 45 wt% to 100 wt% relative to the total weight of the oxyalkylene groups of the polyoxyalkylene monoether alcohol;

[0034] the equivalent ratio of isocyanate groups to hydroxyl groups of the system is 5:1 to 110:1;

[0035] the polyether-modified polyisocyanate composition has the following characteristics:

[0036] i) an average isocyanate functionality of 1.8 to 4.1;

[0037] ii) an isocyanate group content of 8 wt% to 20 wt% relative to the total weight of the polyisocyanate composition; and

[0038] iii) an amount of polyoxyalkylene monoether structure of more than 10 wt% and less than 50 wt% relative to the total weight of the polyisocyanate composition. The present application also provides a process for preparing the polyether-modified polyisocyanate composition, its use as a starting component in the preparation of polyurethanes, its use as a crosslinking component for solvent-borne or solventless coatings, adhesives or sealants, its use as a starting component for the preparation of blocked polyisocyanates blocked with blocking agents, its use in increasing the pot life of coatings, adhesives or sealants, a coating, adhesive or sealant comprising it and a substrate coated with a coating, adhesive or sealant, and a solvent-borne or solventless two-component coating composition comprising it.

[0039] Solventless coatings, adhesives or sealants herein mean coatings, adhesives or sealants having a VOC content of less than 60 g / L.

[0040] The term "polyurethane" as used herein means polyurethane urea and / or polyurethane polyurea and / or polyurea and / or polythiourethane.

[0041] The term "trimer" as used herein means pure trimer, mixtures of trimer with higher homologues thereof containing more than one isocyanurate ring.

[0042] Polyether-modified polyisocyanate composition

[0043] The polyether-modified polyisocyanate composition of the present application can contain components which are not completely reacted within the system.

[0044] The polyether-modified polyisocyanate composition of the present application is transparent and almost colorless.

[0045] The polyether-modified polyisocyanate composition is preferably hydrophobic. Hydrophobic here means neither soluble nor dispersible in water.

[0046] The average isocyanate functionality of the polyether-modified polyisocyanate composition is preferably 2.0 to 4.0.

[0047] The isocyanate group content of the polyether-modified polyisocyanate composition is preferably 10% to 20% by weight, most preferably 12% to 18% by weight, relative to the total weight of the polyether-modified polyisocyanate composition.

[0048] The isocyanate group (NCO) content is preferably measured according to DIN-EN ISO 11909:2007-05.

[0049] The viscosity of the polyether-modified polyisocyanate composition in solvent-free form is preferably 1000 mPa-s to 2000 mPa-s.

[0050] The viscosity is preferably determined according to DIN EN ISO 3219:1994-10 at 23°C at a shear rate of 10 s -1 The MV-DIN spindle is selected.

[0051] The amount of polyoxyalkylene monoether structures of the polyether-modified polyisocyanate composition is preferably greater than 10% by weight and less than 50% by weight, further preferably 15% to 45% by weight, still preferably 20% to 40% by weight, again preferably 20% to 35% by weight, most preferably 24% to 35% by weight, relative to the total weight of the polyether-modified polyisocyanate composition.

[0052] The color value of the polyether-modified polyisocyanate composition is preferably below 120.

[0053] The polyisocyanate composition preferably comprises no more than 0.5% by weight of isophorone diisocyanate trimer, relative to the total weight of the polyether-modified polyisocyanate composition.

[0054] More preferably, the polyether-modified polyisocyanate composition is free of isophorone diisocyanate trimer.

[0055] The polyether-modified polyisocyanate composition is preferably an aliphatic-based polyisocyanate composition, a cycloaliphatic-based polyisocyanate composition, or a combination thereof.

[0056] The average isocyanate functionality of the polyether-modified polyisocyanate composition is calculated according to the following formula:

[0057]

[0058] wherein F: average isocyanate functionality of the polyether-modified polyisocyanate composition

[0059] ∑Equiv NCO: sum of isocyanate functionality equivalents of the polyisocyanate having an isocyanate group functionality of 2 to 4.5 of component a

[0060] ∑Equiv OH: sum of hydroxyl equivalents of the polyoxyalkylene monoether alcohol of component b

[0061] f NCO : isocyanate group functionality of the polyisocyanate having an isocyanate group functionality of 2 to 4.5 of component a) in the system, calculated from the isocyanate group content of the polyisocyanate and the molecular weight of the polyisocyanate, the molecular weight being determined according to DIN 55672-1 :2016-03 by gel permeation chromatography (GPC).

[0062] ∑mol OH: sum of the number of moles of the hydroxyl functionality of the polyoxyalkylene monoether alcohol of component b.

[0063] Component a) polyisocyanate having an isocyanate group functionality of 2 to 4.5

[0064] The isocyanate group functionality of the polyisocyanate having an isocyanate group functionality of 2 to 4.5 is preferably 2.5 to 4.4, most preferably 2.8 to 4.

[0065] The viscosity of the polyisocyanate having an isocyanate group functionality of 2 to 4.5 in a solvent-free form is preferably 500 mPa-s to 1500 mPa-s.

[0066] The isocyanate group content of the polyisocyanate having an isocyanate group functionality of 2 to 4.5 is preferably 15 wt% to 25 wt%, most preferably 16 wt% to 24 wt%, relative to the total weight of the polyisocyanate having an isocyanate group functionality of 2 to 4.5 of component a).

[0067] The polyisocyanate having an isocyanate group functionality of 2 to 4.5 comprises one or more of the following: hexamethylene diisocyanate trimer and pentamethylene diisocyanate trimer. The amount of the hexamethylene diisocyanate trimer, pentamethylene diisocyanate trimer, or a combination thereof is at least 35 wt%, preferably at least 40 wt%, further preferably at least 50 wt%, most preferably at least 65 wt%, relative to the total weight of the polyisocyanate having an isocyanate group functionality of 2 to 4.5.

[0068] It is preferred that the polyisocyanate having an isocyanate group functionality of 2 to 4.5 of component a) further comprises one other isocyanate.

[0069] The amount of the further isocyanate is preferably not more than 65 % by weight, further preferably not more than 60 % by weight, again preferably not more than 50 % by weight, most preferably not more than 35 % by weight, relative to the total weight of the polyisocyanate of component a) having an isocyanate group functionality of 2 to 4.5.

[0070] The further isocyanate is preferably one or more of the following: aliphatic polyisocyanates and cycloaliphatic polyisocyanates, further preferably aliphatic polyisocyanates, and also preferably one or more of the following: aliphatic isocyanate uretdione and aliphatic isocyanate biuret, and again preferably one or more of the following: hexamethylene diisocyanate uretdione and pentamethylene diisocyanate uretdione, most preferably hexamethylene diisocyanate uretdione.

[0071] The aliphatic polyisocyanates and cycloaliphatic polyisocyanates each independently preferably have one or more of the following structures: iminooxadiazinedione, isocyanurate, uretdione, allophanate and biuret. The aliphatic polyisocyanates and cycloaliphatic polyisocyanates are each independently prepared by simple diisocyanate modification and are synthesized from at least two diisocyanates, for example as described in DE-OS 1670666, 3700209, 3900053, EP A 336205 and EP A 339396. The diisocyanates are preferably diisocyanates having aliphatic and / or cycloaliphatic incorporated isocyanate groups with a number average molecular weight of 140 g / mol to 400 g / mol, preferably one or more of the following: 1,4-diisocyanatobutane, 1,6-diisocyanatohexane (HDI), 1,5-diisocyanatopentane (PDI), 1,5-diisocyanato-2,2-dimethylpentane, 2,2,4- and 2,4,4-trimethyl-1,6-diisocyanatohexane, 1,10-diisocyanatodecane, 1 -isocyanato-3,3,5-trimethyl-5-isocyanatomethylcyclohexane (isophorone diisocyanate, IPDI), 1,3- and 1,4-diisocyanatocyclohexane, 4,4'-diisocyanatodicyclohexylmethane and mixtures of these diisocyanates, and more preferably one or more of the following: 1,4-diisocyanatobutane, 1,6-diisocyanatohexane (HDI), 1,5-diisocyanatopentane (PDI), 1,5-diisocyanato-2,2-dimethylpentane, 2,2,4- and 2,4,4-trimethyl-1,6-diisocyanatohexane, 1,10-diisocyanatodecane, 1,3- and 1,4-diisocyanatocyclohexane, 4,4'-diisocyanatodicyclohexylmethane and mixtures of these diisocyanates.

[0072] The amount of said hexamethylene diisocyanate uretdione is preferably not more than 65 wt.-%, further preferably not more than 60 wt.-%, again preferably not more than 50 wt.-%, most preferably not more than 35 wt.-%, relative to the total weight of said component a) polyisocyanate having an isocyanate group functionality of 2 to 4.5.

[0073] When said system comprises two or more polyisocyanates, the isocyanate group functionality of said polyisocyanates refers to the average isocyanate group functionality of the two or more polyisocyanates.

[0074] The amount of said polyisocyanate having an isocyanate group functionality of 2 to 4.5 is preferably more than 30 wt.-%, most preferably more than 50 wt.-%, relative to the total weight of said system.

[0075] Component b) polyoxyalkylene monoether alcohol

[0076] The number average molecular weight of said component b) polyoxyalkylene monoether alcohol is preferably 920 g / mol to 1800 g / mol, further preferably 920 g / mol to 1500 g / mol, most preferably 920 g / mol to 1400 g / mol.

[0077] The propylene oxide group content of said component b) polyoxyalkylene monoether alcohol is preferably 50 wt.-% to 100 wt.-%, further preferably 60 wt.-% to 100 wt.-%, most preferably 80 wt.-% to 100 wt.-%, relative to the total weight of the oxyalkylene groups of said polyoxyalkylene monoether alcohol.

[0078] Said component b) polyoxyalkylene monoether alcohol is preferably polypropylene glycol monomethyl ether comprising on average 16 to 32 propylene oxide units, further preferably polypropylene glycol monomethyl ether comprising on average 16 to 27 propylene oxide units, most preferably polypropylene glycol monomethyl ether comprising on average 17 to 25 propylene oxide units.

[0079] Said polyoxyalkylene monoether alcohol can be obtained by known methods, the preferred starting components comprising at least one of a monohydric alcohol and a secondary monamine, either one or both.

[0080] Said monohydric alcohol is preferably a monohydric alcohol having a molecular weight of 32 g / mol to 150 g / mol, such as the monohydric alcohol used according to EPA-206059, most preferably one or more of the following: methanol and butanol.

[0081] Said secondary monamine is preferably one or more of the following: dimethylamine and diethylamine.

[0082] The oxyalkylene compound preferably comprises 45% by weight to 100% by weight, further preferably 50% by weight to 100% by weight, more preferably 60% by weight to 100% by weight, most preferably 80% by weight to 100% by weight of propylene oxide, relative to the total weight of the oxyalkylene compound.

[0083] The oxyalkylene compound can further comprise ethylene oxide, the amount of which is preferably not more than 55% by weight, further preferably not more than 40% by weight, most preferably not more than 20% by weight, relative to the total weight of the oxyalkylene compound.

[0084] The starting components are preferably reacted at 40°C to 150°C, most preferably at 60°C to 130°C.

[0085] The equivalent ratio of NCO / OH of the starting components is preferably 5:1 to 110:1, most preferably 8:1 to 90:1. The starting components are preferably continued to be reacted until the theoretically calculated isocyanate content is reached.

[0086] The hydroxyl value of the component b) polyoxyalkylene monoether alcohol is preferably 40 mg KOH / g to 61 mg KOH / g.

[0087] When the system comprises two or more polyoxyalkylene monoether alcohols, the number average molecular weight of the polyoxyalkylene monoether alcohol refers to the average number average molecular weight of the two or more polyoxyalkylene monoether alcohols; the propylene oxide group content of the polyoxyalkylene monoether alcohol refers to the average propylene oxide group content of the two or more polyoxyalkylene monoether alcohols, i.e. the average value of the propylene oxide group content of the two or more polyoxyalkylene monoether alcohols.

[0088] The number average molecular weight of the polyoxyalkylene monoether alcohol is preferably determined according to GBT 21863-2008 at 23°C by using gel permeation chromatography by using tetrahydrofuran as the mobile phase and polyethylene glycol as the standard sample.

[0089] The calculation method of the propylene oxide group content of the polyoxyalkylene monoether alcohol is as follows:

[0090]

[0091] Wherein:

[0092] is the average value of the propylene oxide group content of the polyoxyalkylene monoether alcohol

[0093] ∑b*PO%wt is the sum of the amount of propylene oxide groups in the polyoxyalkylene monoether alcohol

[0094] ∑b is the total amount of oxyalkylene groups of the polyoxyalkylene monoether alcohol.

[0095] When the system comprises two or more polyoxyalkylene monoether alcohols, the system preferably comprises at least one polyoxyalkylene monoether alcohol having a number average molecular weight of preferably 900 g / mol to 2000 g / mol, further preferably 920 g / mol to 1800 g / mol, still further preferably 920 g / mol to 1500 g / mol, most preferably 920 g / mol to 1400 g / mol; and a content of propylene oxide groups of preferably 45 wt.% to 100 wt.%, further preferably 60 wt.% to 100 wt.%, most preferably 80 wt.% to 100 wt.%, relative to the total weight of the propylene oxide groups of the polyoxyalkylene monoether alcohol.

[0096] The amount of the component b) polyoxyalkylene monoether alcohol is preferably greater than 10 wt.% and less than 50 wt.%, further preferably 15 wt.% to 45 wt.%, still further preferably 20 wt.% to 40 wt.%, again preferably 20 wt.% to 35 wt.%, most preferably 24 wt.% to 35 wt.%, relative to the total weight of the system.

[0097] Component c) catalyst

[0098] The component c) catalyst is preferably one or more of the following: sulfonic acid catalyst, phosphoric acid catalyst, tertiary amine catalyst, tertiary phosphine catalyst, tertiary hydroxyalkyl amine catalyst, and metal catalyst, most preferably one or more of the following: metal catalyst and phosphoric acid catalyst.

[0099] The sulfonic acid catalyst is preferably one or more of the following: methanesulfonic acid, p-toluenesulfonic acid, trifluoromethanesulfonic acid, perfluorobutanesulfonic acid, dodecylbenzenesulfonic acid, methyl- and ethyl-toluenesulfonate.

[0100] The phosphoric acid catalyst is preferably one or more of the following: silylated acid, monoalkyl phosphate, and dialkyl phosphate, further preferably one or more of the following: monobutyl phosphate, monotridecyl phosphate, dibutyl phosphate, dioctyl phosphate, trimethylsilylmethanesulfonate, trimethylsilyl trifluoromethanesulfonate, tris(trimethylsilyl) phosphate, and diethyltrimethylsilyl phosphate, most preferably one or more of the following: monobutyl phosphate and dibutyl phosphate.

[0101] The tertiary amine catalyst is preferably one or more of the following: triethylamine, tributylamine, N,N-dimethylaniline, N-ethylpiperidine, and N,N'-dimethylpiperazine.

[0102] The tertiary phosphine catalyst is preferably one or more of the following: triethylphosphine, tributylphosphine, and dimethylphenylphosphine.

[0103] The tertiary hydroxyalkylamine catalysts are preferably those described in GB 2 221 465 and / or GB 2 222 161, most preferably one or more of the following: triethanolamine, N-methyldiethanolamine, dimethylethanolamine, mixtures of tertiary bicyclic amines (e.g. DBU) with low molecular weight simple aliphatic alcohols, N-isopropyl diethanolamine and 1-(2-hydroxyethyl)pyrrolidine.

[0104] The metal catalysts can be those described in DEA 3240613, preferably one or more of the following: octanoates of manganese, octanoates of iron, octanoates of cobalt, octanoates of nickel, octanoates of copper, octanoates of zinc, octanoates of zirconium, octanoates of cerium, octanoates of lead, naphthenates of manganese, naphthenates of iron, naphthenates of cobalt, naphthenates of nickel, naphthenates of copper, naphthenates of zinc, naphthenates of zirconium, naphthenates of cerium, naphthenates of lead and mixtures of the above salts with lithium, sodium, potassium, calcium or barium acetates. The metal catalysts can also be those described in DEA 3219608, preferably one or more of the following: sodium salts of straight-chain or branched alkane carboxylic acids having up to 10 carbon atoms and potassium salts of straight-chain or branched alkane carboxylic acids having up to 10 carbon atoms, wherein the carboxylic acids are preferably one or more of the following: propionic acid, butyric acid, valeric acid, caproic acid, enanthic acid, caprylic acid, pelargonic acid, capric acid and undecanoic acid. The metal catalysts can also be the salts of alkali metals and / or the salts of alkaline earth metals described in EPA 0100129, preferably one or more of the following: aliphatic, cycloaliphatic or aromatic mono- and polycarboxylic acids having 2 to 20 carbon atoms, such as sodium benzoate or potassium benzoate. The metal catalysts can also be the alkali metal phenolates known from GB 1391066 A and GB 1386399 A, preferably one or more of the following: sodium phenolate and potassium phenolate. The metal catalysts can also be those known from GB 809809, preferably one or more of the following: alkali metal oxides, alkaline earth metal oxides, alkali metal hydroxides, alkaline earth metal hydroxides, alkali metal carbonates, alkaline earth metal carbonates, alkali metal alkoxides, alkaline earth metal alkoxides, alkali metal phenolates, alkaline earth metal phenolates, alkali metal salts of olefinatable compounds, metal salts of weak aliphatic carboxylic acids, metal salts of cycloaliphatic carboxylic acids, basic alkali metal compounds complexed with crown ethers and basic alkali metal compounds complexed with polyether alcohols. The metal catalysts can also be the potassium pyrrolidone salts known from EPA 0033581. The metal catalysts can also be the mono- or polycyclic complexes of titanium, zirconium and / or hafnium known from EPA 2883895, preferably one or more of the following: zirconium tetra-n-butyrate, zirconium tetra-2-ethylhexanoate and zirconium tetra-2-ethylhexanoate. The metal catalysts can also be tin compounds of the type described in European Polymer Journal, 16, 1979, 147-148, preferably one or more of the following: dibutyltin dichloride, diphenyltin dichloride, triphenyltin alcohol, tributyltin acetate, tributyltin oxide, tin octoate, dibutyl(dimethoxy)stannane and imidazole tributyltin.

[0105] The metal salts of weak aliphatic carboxylic acids and the metal salts of cycloaliphatic carboxylic acids are each independently preferably one or more of the following: sodium methoxide, sodium acetate, potassium acetate, sodium acetoacetate, lead 2-ethylhexanoate and lead naphthenate.

[0106] The basic alkali metal compound complexed with crown ether and the basic alkali metal compound complexed with polyether alcohol are each independently preferably one or more of the following: a complex of sodium or potassium carboxylate, which is known from EPA 0056158 and EPA 0056159.

[0107] When a metal catalyst is included in the system, a terminating agent is required after the reaction of the system is completed. In addition, the above-mentioned phosphoric acid catalyst, sulfonic acid catalyst, and their derivatives can be used here as the terminating agent. In addition to these two acid catalysts, other inorganic acids such as hydrochloric acid, phosphorous acid, acyl chlorides such as acetyl chloride, benzoyl chloride, or isophthaloyl dichloride can also be used as the terminating agent.

[0108] The amount of the catalyst is 0 to 0.02% by weight, relative to the total weight of the system.

[0109] Solvent

[0110] The system can further include a solvent which is inert to isocyanate groups.

[0111] The solvent can be known, and is preferably one or more of the following: ethyl acetate, butyl acetate, ethylene glycol monomethyl, ethyl ether acetate, 1-acetic acid 2-methoxypropyl-2-acetate, 2-butanone, 4-methyl-2-pentanone, cyclohexanone, toluene, propylene glycol diacetate, diethylene glycol dimethyl ether, diethylene glycol ethyl ether, butyl ether acetate, N-methyl pyrrolidone, and N-methyl caprolactam.

[0112] The amount of the solvent is 0 to 10% by weight, relative to the total weight of the system.

[0113] Process for the preparation of a polyether-modified polyisocyanate composition

[0114] It is preferred that the component b) polyoxyalkylene monoether alcohol is bonded to the component a) polyisocyanate via a urethane group.

[0115] The component a) polyisocyanate having an isocyanate group functionality of 2 to 4.5 which can be present in excess in the system is present in the polyether-modified polyisocyanate composition.

[0116] The polyether-modified polyisocyanate composition, when used, can be mixed with isocyanates other than the polyether-modified polyisocyanate composition of the present application, for example, can be mixed with unmodified isocyanates.

[0117] Use and two-component coating

[0118] The polyether-modified polyisocyanate composition can be used as a starting component for producing polyurethanes by an isocyanate polyaddition method.

[0119] The polyether-modified polyisocyanate composition can also be used as a crosslinking component in two-component coatings, either solvent-borne or solvent-free.

[0120] The molar ratio of isocyanate groups of the polyether-modified polyisocyanate composition to isocyanate-reactive groups of the compound containing isocyanate-reactive groups in the two-component coating composition is preferably 2:1.

[0121] The isocyanate-reactive groups are preferably one or more of the following: hydroxyl, thiol and amino, further preferably one or more of the following: secondary hydroxyl and amino, most preferably secondary amino.

[0122] The compound containing isocyanate-reactive groups preferably comprises at least one compound corresponding to formula I:

[0123]

[0124] wherein Z represents an organic group of valence n and inert to isocyanate groups at temperatures of 100°C or less, preferably a divalent hydrocarbon group obtained by removing amino groups from an aliphatic, araliphatic or cycloaliphatic polyamine, most preferably a diamine;

[0125] R1and R2, which can be the same or different, represent an organic group inert to isocyanate groups at temperatures of 100°C or less, preferably one or more of the following: methyl and ethyl;

[0126] R3and R4, which can be the same or different, represent hydrogen or an organic group inert to isocyanate groups at temperatures of 100°C or less, preferably hydrogen;

[0127] n represents an integer of at least 2, preferably an integer of 2 to 4, most preferably 2.

[0128] The compound containing isocyanate-reactive groups is prepared in known manner by reacting a corresponding primary polyamine corresponding to formula II:

[0129]

[0130] with a maleate and / or fumarate having optional substitution corresponding to formula III.

[0131] R1COO-CR 3 =CR 4 -COOR2 III.

[0132] The primary polyamine corresponding to Formula II is preferably one or more of ethylenediamine, 1,2-diaminopropane, 1,4-diaminobutane, 1,3-diaminopentane, 1,6-diaminohexane, 2,5-diamino-2,5-dimethylhexane, 2,2,4-trimethyl-l,6-diaminohexane, 2,4,4-trimethyl-l,6-diaminohexane, 1,11-diaminoundecane, 1,12-diaminododecane, 1,3-cyclohexanediamine, 1,4-cyclohexanediamine, 1-amino-3,3,5-trimethyl-5-aminomethyl-cyclohexane, 2,4-hexahydrotoluenediamine, 2,6-hexahydrotoluenediamine, 2,4'-diaminodicyclohexylmethane, 4,4'-diaminodicyclohexylmethane, and 3,3'-dialkyl-4,4'-diamino-dicyclohexylmethane (e.g., 3,3'-dimethyl-4,4'-diamino-dicyclohexylmethane and 3,3'-diethyl-4,4'-diamino-dicyclohexylmethane), most preferably one or more of 1,4-diaminobutane, 1,6-diaminohexane, 2,2,4-trimethyl-l,6-diaminohexane, 2,4,4-trimethyl-l,6-diaminohexane, 1,3-cyclohexanediamine, 1,4-cyclohexanediamine, 1-amino-3,3,5-trimethyl-5-aminomethylcyclohexane, 2,4-hexahydrotoluenediamine, 2,6-hexahydrotoluenediamine, 4,4'-diamino-dicyclohexylmethane, 3,3'-dimethyl-4,4'-diamino-dicyclohexylmethane, and 3,3'-diethyl-4,4'-diamino-dicyclohexylmethane.

[0133] The primary polyamine can also be an aromatic polyamine, such as one or more of 2,4-diaminotoluene, 2,6-diaminotoluene, 2,4'-diaminodiphenylmethane, and 4,4'-diaminodiphenylmethane. Relatively high molecular weight polyether polyamines containing aliphatically bound primary amino groups are also suitable, such as the products sold under the Jeffamine trademark by Texaco.

[0134] The compounds suitable for preparing the optionally substituted maleate and / or fumarate corresponding to Formula III are each independently preferably one or more of dimethyl maleate, dimethyl fumarate, diethyl maleate, diethyl fumarate, di-n-butyl maleate, di-n-butyl fumarate, and the corresponding maleate or fumarate substituted with a methyl group.

[0135] The compound containing isocyanate-reactive groups is most preferably aspartate. The reaction is carried out, for example, at a temperature of from 0°C to 100°C using a corresponding primary polyamine corresponding to formula II and an optionally substituted maleate or fumarate corresponding to formula III in a ratio of at least 1 : 1. After the reaction, the excess starting material can be removed by distillation. The reaction can be carried out without a solvent or in the presence of a suitable solvent, for example, methanol, ethanol, propanol, dioxane, and mixtures of these solvents.

[0136] The components A and B of the two-component coating composition, solvent-borne or solvent-free, are preferably stored separately and mixed before use to obtain the two-component system.

[0137] The two-component coating composition preferably further comprises one or more of the following: auxiliaries and additives.

[0138] The coating can be carried out using mechanical tools known to the person skilled in the art or using a two-component spray gun.

[0139] The substrate is preferably one or more of the following: artificial stone, wood, artificial wood, marble, terrazzo, ceramic, linoleum, metal, mineral material, plastic, rubber, concrete, composite sheet, paper, leather, and glass. The substrate can be pretreated. The pretreatment is preferably polishing and / or coating.

[0140] The coating is preferably used to protect the surface of a floor, a wall, a reinforced concrete or a metal container or other surfaces that need protection.

[0141] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this application belongs. If a term is defined differently herein, the definition set forth herein is intended to control.

[0142] Unless otherwise indicated, all numbers expressing quantities of ingredients, reaction conditions, and so forth used in the specification and claims are to be understood as being modified in all instances by the term "about." Accordingly, unless otherwise indicated, the numerical parameters set forth in the specification and claims are approximations that can vary depending upon the desired properties sought to be obtained by the present application.

[0143] As used in the specification and claims, the terms "a", "an" and "the" are intended to include "at least one", or "one or more", unless otherwise indicated. For example, the term "a component" means one or more components.

[0144] As used herein, "and / or" means one or all of the listed items.

[0145] As used herein, "comprising" and "including" encompass the case where only the recited elements are present and the case where additional unrecited elements are also present.

[0146] The present application relates in particular to the following aspects:

[0147] 1. A polyether-modified polyisocyanate composition obtainable by reaction of a system comprising:

[0148] a) a polyisocyanate having an isocyanate group functionality of 2 to 4.5 comprising at least 35 wt.-% of hexamethylene diisocyanate trimer, pentamethylene diisocyanate trimer or a combination thereof;

[0149] b) a polyoxyalkylene monoether alcohol; and

[0150] c) optionally a catalyst;

[0151] said polyoxyalkylene monoether alcohol having a number average molecular weight of 900 g / mol to 2000 g / mol and a propylene oxide group content of 45 wt.-% to 100 wt.-% relative to the total weight of the oxyalkylene groups of the polyoxyalkylene monoether alcohol;

[0152] said system having an equivalent ratio of isocyanate groups to hydroxyl groups of 5:1 to 110:1;

[0153] said polyisocyanate composition having the following characteristics:

[0154] i) an average isocyanate functionality of 1.8 to 4.1;

[0155] ii) an isocyanate group content of 8 wt.-% to 20 wt.-% relative to the total weight of the polyisocyanate composition;

[0156] iii) an amount of polyoxyalkylene monoether structures of more than 10 wt.-% and less than 50 wt.-% relative to the total weight of the polyisocyanate composition.

[0157] 2. The polyether-modified polyisocyanate composition according to aspect 1 or 2, characterized in that the amount of polyoxyalkylene monoether structures is 15 wt.-% to 45 wt.-%, preferably 20 wt.-% to 40 wt.-%, further preferably 20 wt.-% to 35 wt.-%, most preferably 24 wt.-% to 35 wt.-% relative to the total weight of the polyisocyanate composition.

[0158] 3. The polyether-modified polyisocyanate composition according to any of the preceding aspects, characterized in that the component a) polyisocyanate having an isocyanate group functionality of 2 to 4.5 further comprises one additional isocyanate which is one or more of the following: aliphatic isocyanate uretdione and aliphatic isocyanate biuret.

[0159] 4. The polyether-modified polyisocyanate composition according to aspect 3, characterized in that the additional isocyanate is one or more of the following: hexamethylene diisocyanate uretdione and pentamethylene diisocyanate uretdione.

[0160] 5. The polyether-modified polyisocyanate composition according to any of the preceding aspects, characterized in that the polyalkylene oxide monoether alcohol has a propylene oxide group content of 50 wt.-% to 100 wt.-%, preferably 60 wt.-% to 100 wt.-%, most preferably 80 wt.-% to 100 wt.-%, relative to the total weight of the propylene oxide groups of the polyalkylene oxide monoether alcohol.

[0161] 6. The polyether-modified polyisocyanate composition according to any of the preceding aspects, characterized in that the polyalkylene oxide monoether alcohol is present in an amount of more than 10 wt.-% and less than 50 wt.-%, preferably 15 wt.-% to 45 wt.-%, further preferably 20 wt.-% to 40 wt.-%, again preferably 20 wt.-% to 35 wt.-%, most preferably 24 wt.-% to 35 wt.-%, relative to the total weight of the system.

[0162] 7. The polyether-modified polyisocyanate composition according to any of the preceding aspects, characterized in that the component b) polyalkylene oxide monoether alcohol has a number average molecular weight of 920 g / mol to 1800 g / mol, preferably 920 g / mol to 1500 g / mol, most preferably 920 g / mol to 1400 g / mol.

[0163] 8. The polyether-modified polyisocyanate composition according to any of the preceding aspects, characterized in that the polyisocyanate composition comprises not more than 0.5 wt.-% of isophorone diisocyanate trimer, relative to the total weight of the polyisocyanate composition; most preferably the polyisocyanate composition is free of isophorone diisocyanate trimer.

[0164] 9. The polyether-modified polyisocyanate composition according to any of the preceding aspects, characterized in that the component c) catalyst is one or more of the following: metal catalyst and phosphoric acid catalyst.

[0165] 10. A process for preparing the polyether-modified polyisocyanate composition of any of the above aspects, characterized by mixing and reacting a system comprising component a) a polyisocyanate having an isocyanate group functionality of 2 to 4.5, component b) a polyoxyalkylene monoether alcohol, and optionally component c) a catalyst to form a polyether-modified polyisocyanate composition having the following characteristics: i) an average isocyanate functionality of 1.8 to 4.1 ; ii) an isocyanate group content of 8 to 20 weight percent relative to the total weight of the polyisocyanate composition; and iii) an amount of polyoxyalkylene monoether structure of greater than 10 weight percent and less than 50 weight percent relative to the total weight of the polyisocyanate composition; wherein the component a) polyisocyanate comprises at least 35 weight percent of hexamethylene diisocyanate trimer, pentamethylene diisocyanate trimer, or a combination thereof; the component b) polyoxyalkylene monoether alcohol has a number average molecular weight of 900 g / mol to 2000 g / mol, an oxypropylene group content of 45 weight percent to 100 weight percent relative to the total weight of the oxyalkylene groups of the polyoxyalkylene monoether alcohol; and the system has an equivalent ratio of isocyanate groups to hydroxyl groups of 5:1 to 110:1.

[0166] 11. The process according to aspect 10, characterized in that the component b) polyoxyalkylene monoether alcohol is bonded to the component a) polyisocyanate via a urethane group.

[0167] 12. Use of the polyether-modified polyisocyanate composition according to any of aspects 1 to 9 as a starting component in the preparation of a polyurethane.

[0168] 13. Use of the polyether-modified polyisocyanate composition according to any of aspects 1 to 9 as a crosslinking component for solvent-borne or solventless coatings, adhesives, or sealants.

[0169] 14. Use of the polyether-modified polyisocyanate composition according to any of aspects 1 to 9 as a starting component for the preparation of blocked polyisocyanates blocked with blocking agents.

[0170] 15. A coating, adhesive, or sealant comprising the polyether-modified polyisocyanate composition according to any of aspects 1 to 9.

[0171] 16. The coating, adhesive, or sealant according to aspect 15, characterized in that the coating, adhesive, or sealant is solvent-borne or solventless.

[0172] 17. A substrate coated with the coating, adhesive, or sealant according to aspect 15 or 16.

[0173] 18. Use of the polyether-modified polyisocyanate composition according to any one of aspects 1 to 9 for increasing the pot life of a coating, adhesive or sealant.

[0174] 19. A two-component coating, solvent borne or solventless, comprising a component A which is a compound containing isocyanate-reactive groups and a component B which is the polyether-modified polyisocyanate composition according to any one of aspects 1 to 9.

[0175] 20. The two-component coating according to aspect 19, characterized in that the compound containing isocyanate-reactive groups is aspartic ester.

[0176] Examples

[0177] All percentages in the present invention are percentages by weight, unless otherwise stated.

[0178] Analytical measurements of the present invention are performed at 23 ± 2 °C and 50 ± 5 % relative humidity, unless otherwise stated.

[0179] The isocyanate group (NCO) content is determined according to DIN-EN ISO 11909:2007-05.

[0180] The number average molecular weight of the isocyanate is determined according to DIN 55672-1 :2016-03 using gel permeation chromatography with tetrahydrofuran as mobile phase, polystyrene standards at 23 °C.

[0181] The number average molecular weight of the polyalkylene oxide monoether alcohol is determined according to GBT 21863-2008 using gel permeation chromatography with tetrahydrofuran as mobile phase, polyethylene glycol standards at 23 °C.

[0182] The non-volatile content is determined according to DIN EN ISO 3251 :2008-06 with measurement conditions including a drying temperature of 120 °C, a drying time of 2 hours, a test pan diameter of 75 mm and a test amount of 2 ± 0.02 g, the result being expressed in % by weight.

[0183] The viscosity is determined according to DIN EN ISO 3219:1994-10 at 23 °C, shear rate of 10 s -1 MV-DIN spindle is selected.

[0184] The amino group content is determined according to AFAM 2011-06054.

[0185] The hydroxyl value is determined according to ASTM D4274.

[0186] The color value is determined according to DIN-EN 1557:1997-03.

[0187] Bubble free film thickness (BFFT): The coating with different thicknesses was prepared on glass using a film applicator with adjustable film thickness (set film thickness of 100 μm, 200 μm and 400 μm) (test method of coating thickness: the cured coating was peeled off from the glass and measured using a film thickness gauge), the coating area was about 15 cm*10 cm, after the coating was cured for one day, no bubble was observed on the coating surface, then the bubble free film thickness was considered to be greater than or equal to the coating thickness. The ideal bubble free film thickness was greater than or equal to 100 μm.

[0188] Surface dry time: The coating was prepared on glass using a film applicator (set film thickness of 200 μm), according to GB / T 13477.5-2002, the surface of the coating was touched with a finger, if the coating was sticky but no paint was adhered to the finger, it was considered to be dry, the time taken from the coating was applied to the surface of the glass to the coating surface dry was the surface dry time. The ideal surface dry time was less than 120 minutes.

[0189] Pendulum hardness: The coating was prepared on glass using a film applicator (set film thickness of 200 μm), the hardness of the coating was measured using a BYK pendulum hardness meter. The pendulum hardness (1d) was the pendulum hardness of the coating after one day, the pendulum hardness (7d) was the pendulum hardness of the coating after seven days. The ideal pendulum hardness (7d) was greater than 60 seconds.

[0190] Pot life: The viscosity of the coating when the components were mixed and no additional components were added was the initial viscosity, the time taken for the viscosity of the coating to reach twice the initial viscosity was the pot life. The longer the pot life, the longer the operable time of the coating. The ideal pot life was greater than 20 minutes.

[0191] Raw materials and reagents

[0192] Hexamethylene diisocyanate trimer 1: A four-necked flask equipped with a stirrer, a thermometer, a reflux cooling tube, a nitrogen inlet tube and a dropping funnel was charged with hexamethylene diisocyanate (HDI) 850 g under a nitrogen atmosphere, heated to 65°C with stirring, then trimethyl-2-methyl-2-hydroxyethylammonium hydroxide (a solution diluted with isobutyl alcohol to 5% by weight) 5.5 g was added, when the NCO of the reaction solution was 45.6% by weight, 1.1 g of di-n-butyl phosphate was added to stop the reaction. After removing the unreacted monomers at 140°C and 0.05 mbar using a thin film evaporator, hexamethylene diisocyanate trimer 1 with a non-volatile content of 100% by weight, a viscosity of 1200 mPa·s (23.5°C), an NCO content of 23.0% by weight, an HDI monomer concentration of 0.25% by weight and an NCO functionality of 3.2 was obtained.

[0193] Hexamethylene diisocyanate trimer 2: The method for preparing hexamethylene diisocyanate trimer 1 was used with tetrabutylphosphonium fluoride solution (diluted to 50% with isopropanol / methanol in a weight ratio of 2:1) as catalyst. The reaction was terminated with dibutyl phosphate when the NCO content of the reaction solution reached 43%. Hexamethylene diisocyanate trimer 2 having a non-volatile content of 100% by weight, a viscosity of 700 mPa-s (23.5°C), an NCO content of 23.4% by weight, an HDI monomer concentration of 0.25% by weight and an NCO functionality of 3.2 was obtained.

[0194] Hexamethylene diisocyanate uretdione 3: To 1000 g (5.95 mol) of hexamethylene diisocyanate (HDI) were added successively at room temperature under dry nitrogen 2 g (0.2%) of N,N-diethylurea as stabilizer, 10 g (1.0%) of 1,3-butanediol as cocatalyst and 3 g (0.3% / 0.015 mol) of tri-n-butylphosphine as catalyst, and the mixture was then heated to 60°C. After a reaction time of 4 hours, the NCO content of the reaction mixture was 40.4%, corresponding to an oligomerization degree of 18.0%. The reaction was terminated with the addition of 2.8 g (0.015 mol) of methyl-p-toluenesulfonate and heating to 80°C for 1 hour. Thin layer distillation was performed at a temperature of 130°C. Then, at 105°C and a pressure of 0.15 mbar, a colorless polyisocyanate containing uretdione groups was obtained having an NCO content of 21.4%, a monomer HDI content of 0.07%, a viscosity of 185 mPa-s (23.5°C) and an NCO functionality of 2.5.

[0195] Desmophen NH 1420: aspartic ester with an amino equivalent weight of 279 and a viscosity of 1500 mPa.s (25°C), commercially available from Covestro AG, Germany.

[0196] Desmophen NH 2850: aspartic ester with an amino equivalent weight of 295 and a viscosity of 100 mPa.s (25°C), commercially available from Covestro AG, Germany.

[0197] T01-A: polyoxyalkylene monoether alcohol with 100% by weight of the oxypropylene groups of the polyoxyalkylene monoether alcohol being oxypropylene groups, a number average molecular weight of 800 g / mol, an OH value of 66.6 mg KOH / g and n-butanol as starting component.

[0198] TP-10: polyoxyalkylene monoether alcohol with 100% by weight of the oxypropylene groups of the polyoxyalkylene monoether alcohol being oxypropylene groups, a number average molecular weight of 1000 g / mol, an OH value of 55 mg KOH / g and n-butanol as starting component.

[0199] TD-10: polyoxyalkylene monoether alcohol, the oxypropylene groups represent 100 wt% of the oxyalkylene groups of the polyoxyalkylene monoether alcohol, number average molecular weight of 1200 g / mol, OH number of 44.65 mg KOH / g, starting components are oxypropylene and n-butanol.

[0200] LB25: polyoxyalkylene monoether alcohol, the oxyethylene groups represent 84.4 wt% of the oxyalkylene groups of the polyoxyalkylene monoether alcohol, number average molecular weight of 2250 g / mol, OH number of 25 mg KOH / g, starting components are oxyethylene, oxypropylene and diethylene glycol butyl ether, weight ratio of oxyethylene to oxypropylene is 84.4: 15.6.

[0201] MPEG 1000: polyoxyalkylene monoether alcohol, number average molecular weight of 1000 g / mol, OH number of 56 mg KOH / g, starting components are oxyethylene and methanol.

[0202] Tetrabutylphosphonium fluoride solution: purchased from Jinjinle Chemical.

[0203] DABCO NE310: tertiary amine catalyst, viscosity of 12 mPa-s (25 °C), commercially available from Air Chemical.

[0204] Dibutyl phosphate: commercially available from Sigma-Aldrich Shanghai Trading Co., Ltd.

[0205] DBTL12: commercially available from Sigma-Aldrich Shanghai Trading Co., Ltd.

[0206] Polyether-modified polyisocyanate composition 1

[0207] A solution was prepared by stirring 120 g (0.6571 eq) of hexamethylene diisocyanate trimer 1 and 0.04 g (0.00019 mol) of dibutyl phosphate in a 250 ml flask with a dropping funnel and nitrogen inlet, the resulting solution was heated to 120 °C, 30 g (0.0298 eq) of TP-10 was added dropwise to the flask over 45 minutes, the reaction was continued until the isocyanate group (NCO) content reached 17.46%, the heating was stopped, a polyether-modified polyisocyanate composition 1 was obtained, which was a colorless transparent solution and met the following property data:

[0208] Solid content: 100 wt%

[0209] NCO content: 17.5 wt% relative to the total weight of the polyether-modified polyisocyanate composition 1

[0210] Viscosity (23 °C): 1630 mPa-s

[0211] Color value (Hazen): 14

[0212] Isocyanate functionality: 3.05

[0213] The amount of polyoxyethylene monoether structure is 20% by weight relative to the total weight of the polyether-modified polyisocyanate composition 1.

[0214] The content of isophorone diisocyanate trimer is 0 by weight relative to the total weight of polyether-modified polyisocyanate composition 1.

[0215] Of which, TP-10 accounts for 20% by weight of the system.

[0216] Polyether-modified polyisocyanate composition 2

[0217] 100 g (0.5476 eq) of hexamethylene diisocyanate trimer 1 and 0.03 g (0.00014 mol) of butyl phosphate were added to a 250 ml flask equipped with a dropping funnel and a nitrogen inlet and stirred to obtain a solution. The resulting solution was heated to 120 °C, and 33.3 g (0.0331 eq) of TP-10 was added dropwise to the flask over 45 minutes until the isocyanate group (NCO) content reached 16.29%. Heating was then stopped to obtain polyether-modified polyisocyanate composition 2, which is a colorless and transparent solution and meets the following characteristics:

[0218] Solid content: 100% by weight

[0219] NCO content relative to the total weight of polyether-modified polyisocyanate composition 2: 16.29% by weight

[0220] Viscosity (23℃): 1560 mPa·s

[0221] Hazen value: 2

[0222] Isocyanate functionality: 3

[0223] The amount of polyoxyethylene monoether structure is 24.9% by weight relative to the total weight of the polyether-modified polyisocyanate composition 2.

[0224] The content of isophorone diisocyanate trimer is 0 by weight relative to the total weight of the polyether-modified polyisocyanate composition 2.

[0225] Of which, TP-10 accounted for 24.9% by weight of the system.

[0226] Polyether-modified polyisocyanate composition 3

[0227] Into a 250 ml flask with a dropping funnel and nitrogen inlet, 240 g (1.3143 eq) of hexamethylene diisocyanate trimer 1 and 0.05 g (0.00024 mol) of butyl phosphate were stirred to obtain a solution, the resulting solution was heated to 120 °C, 102 g (0.1012 eq) of TP-10 was added dropwise into the flask over 45 minutes, the reaction was continued until the isocyanate group (NCO) content reached 14.95% and heating was stopped, to obtain a polyether-modified polyisocyanate composition 3 which was a colorless transparent solution and met the following property data:

[0228] Solid content: 100% by weight

[0229] NCO content: 14.95% by weight relative to the total weight of the polyether-modified polyisocyanate composition 3

[0230] Viscosity (23 °C): 1807 mPa-s

[0231] Color value (Hazen): 35

[0232] Isocyanate functionality: 2.95

[0233] Amount of polyalkylene oxide monoether structures: 29.8% by weight relative to the total weight of the polyether-modified polyisocyanate composition 3

[0234] Content of isophorone diisocyanate trimer: 0% by weight relative to the total weight of the polyether-modified polyisocyanate composition 3.

[0235] wherein TP-10 represents an amount of 29.8% by weight of the system.

[0236] Polyether-modified polyisocyanate composition 4

[0237] Into a 250 ml flask with a dropping funnel and nitrogen inlet, 240 g (1.3143 eq) of hexamethylene diisocyanate trimer 1 were stirred to obtain a solution. The resulting solution was heated to 120 °C, 129.3 g (0.1283 eq) of TP-10 was added dropwise into the flask over 45 minutes, the reaction was continued until the isocyanate group (NCO) content reached 13.7% and heating was stopped, to obtain a polyether-modified polyisocyanate composition 4 which was a colorless transparent solution and met the following property data:

[0238] Solid content: 100% by weight

[0239] NCO content: 13.7% by weight relative to the total weight of the polyether-modified polyisocyanate composition 4

[0240] Viscosity (23 °C): 1594 mPa-s

[0241] Color value (Hazen): 51

[0242] Isocyanate functionality: 2.89

[0243] Amount of polyalkylene oxide monoether structure: 35.0 wt% relative to the total weight of polyether-modified polyisocyanate composition 4

[0244] Content of isophorone diisocyanate trimer: 0 wt% relative to the total weight of polyether-modified polyisocyanate composition 4.

[0245] wherein TP-10 amounts to 35.0 wt% of the system.

[0246] Polyether-modified polyisocyanate composition 5

[0247] hexamethylene diisocyanate trimer 1 was added to a 500 ml flask with a dropping funnel and nitrogen inlet and stirred to obtain a solution. The resulting solution was heated to 120°C and 160.3 g (0.1588 eq) of TP-10 was added dropwise to the flask over 45 minutes until the isocyanate group (NCO) content reached 12.18%. The heating was stopped and polyether-modified polyisocyanate composition 5 was obtained, which was a colorless transparent solution and met the following property data:

[0248] Solid content: 100 wt%

[0249] NCO content: 12.18 wt% relative to the total weight of polyether-modified polyisocyanate composition 5

[0250] Viscosity (23°C): 1948 mPa-s

[0251] Color value (Hazen): 36

[0252] Isocyanate functionality: 2.80

[0253] Amount of polyalkylene oxide monoether structure: 40 wt% relative to the total weight of polyether-modified polyisocyanate composition 5

[0254] Content of isophorone diisocyanate trimer: 0 wt% relative to the total weight of polyether-modified polyisocyanate composition 5.

[0255] wherein TP-10 amounts to 40.0 wt% of the system.

[0256] Polyether-modified polyisocyanate composition 6

[0257] A solution was prepared by stirring 120 g (0.6766 eq) of hexamethylene diisocyanate trimer 2 and 0.0362 g (0.00017 mol) of butyl phosphate in a 250 ml flask with a dropping funnel and nitrogen inlet. The resulting solution was heated to 120 °C. A mixture of 30.60 g (0.0364 eq) of T01-A and 20.4 g (0.0165 eq) of TP-10 was added dropwise to the flask over 45 minutes until the isocyanate group (NCO) content reached 15.44%. The heating was stopped and a polyether-modified polyisocyanate composition 6 was obtained which was a colorless transparent solution and which met the following property data:

[0258] Solids content: 100 wt.%

[0259] NCO content: 15.44 wt.% based on the total weight of the polyether-modified polyisocyanate composition 6

[0260] Viscosity (23 °C): 1012 mPa-s

[0261] Color value (Hazen): 39

[0262] Isocyanate functionality: 3.04

[0263] Amount of polyalkylene oxide monoether structures: 29.82 wt.% based on the total weight of the polyether-modified polyisocyanate composition 6

[0264] Content of isophorone diisocyanate trimer: 0 wt.% based on the total weight of the polyether-modified polyisocyanate composition 6.

[0265] wherein the average number average molecular weight of T01-A and TP-10 is 923 g / mol, the weight and amount of T01-A and TP-10 in the system: 29.82 wt.%.

[0266] Polyether-modified polyisocyanate composition 7

[0267] A solution was prepared by stirring 160 g (0.8857 eq) of hexamethylene diisocyanate trimer 1 and 0.0068 g (0.000032 mol) of butyl phosphate in a 250 ml flask with a dropping funnel and nitrogen inlet. The solution was heated to 120 °C. A mixture of 52.33 g (0.0523 eq) of TP-10 and 16.24 g (0.0072 eq) of LB25 was added dropwise to the flask over 45 minutes until the isocyanate group (NCO) content reached 15.02%. The heating was stopped and a polyether-modified polyisocyanate composition 7 was obtained which was a colorless transparent solution and which met the following property data:

[0268] Solids content: 100 wt.%

[0269] NCO content: 15.02 wt.-% based on the total weight of the polyether-modified polyisocyanate composition 7

[0270] Viscosity (23°C): 1654 mPa-s

[0271] Color value (Hazen): 6

[0272] Isocyanate functionality: 2.98

[0273] Amount of polyalkylene oxide monoether structures: 29.82 wt.-% based on the total weight of the polyether-modified polyisocyanate composition 7

[0274] Content of isophorone diisocyanate trimer: 0 wt.-% based on the total weight of the polyether-modified polyisocyanate composition 7.

[0275] wherein the average number average molecular weight of TP-10 and LB 25 is 1151 g / mol, the amount of TP-10 and LB 25 in the system is 29.82 wt.-%; the average of the content of propylene oxide groups of TP-10 and the content of propylene oxide groups of LB 25 is 80 wt.-%.

[0276] Polyether-modified polyisocyanate composition 8

[0277] hexamethylene diisocyanate trimer 1 and 0.007 g (0.000033 mol) of butyl phosphonate were stirred in a 250 ml flask with a dropping funnel and nitrogen inlet to obtain a solution. The solution was heated to 120°C. A mixture of 27.43 g (0.0274 eq) of TP-10 and 41.14 g (0.0183 eq) of LB 25 was added dropwise to the flask over 45 minutes until the isocyanate group (NCO) content reached 15.31 %. The heating was stopped and a polyether-modified polyisocyanate composition 8 was obtained which was a colorless transparent solution and which complied with the following property data:

[0278] Solid content: 100 wt.-%

[0279] NCO content: 15.31 wt.-% based on the total weight of the polyether-modified polyisocyanate composition 8

[0280] Viscosity (23°C): 1574 mPa-s

[0281] Color value (Hazen): 9

[0282] Isocyanate functionality: 3.03

[0283] Amount of polyalkylene oxide monoether structures: 29.82 wt.-% based on the total weight of the polyether-modified polyisocyanate composition 8

[0284] Content of isophorone diisocyanate trimer 0 wt.-% based on the total weight of the polyether-modified polyisocyanate composition 8.

[0285] wherein the average number average molecular weight of TP-10 and LB 25 is 1500 g / mol, the weight sum of TP-10 and LB 25 amounts to 29.82 wt.-% of the system, and the average of the oxypropylene group content of TP-10 and the oxypropylene group content of LB 25 is 49.4 wt.-%.

[0286] Polyether-modified polyisocyanate composition 9

[0287] hexamethylene diisocyanate trimer 1 and 0.0068 g (0.000032 mol) of butyldiglycol phosphate into a 500 ml flask with dropping funnel and nitrogen inlet and stirred to a solution. The solution was heated to 120 °C. A mixture of 35.4 g (0.0427 eq) of T01-A and 33.1 g (0.0147 eq) of LB 25 was added dropwise to the flask over 45 minutes until the isocyanate group (NCO) content reached 15.01 %. The heating was stopped and a polyether-modified polyisocyanate composition 9 was obtained which was a colorless transparent solution and which complied with the following property data:

[0288] solid content: 100 wt.-%

[0289] NCO content: 15.01 wt.-% based on the total weight of the polyether-modified polyisocyanate composition 9.

[0290] viscosity (23 °C): 1537 mPa-s

[0291] color value (Hazen): 116

[0292] isocyanate functionality: 2.99

[0293] amount of polyalkylene oxide monoether structures: 29.82 wt.-% based on the total weight of the polyether-modified polyisocyanate composition 9.

[0294] Content of isophorone diisocyanate trimer 0 wt.-% based on the total weight of the polyether-modified polyisocyanate composition 9.

[0295] wherein the average number average molecular weight of T01-A and LB 25 is 1159 g / mol, the weight sum of T01-A and LB 25 amounts to 29.82 wt.-% of the system, and the average of the oxypropylene group content of T01-A and the oxypropylene group content of LB 25 is 60 wt.-%.

[0296] Polyether-modified polyisocyanate composition 10

[0297] Into a 500 ml flask with a dropping funnel and nitrogen inlet, 160 g (0.8857 eq) of hexamethylene diisocyanate trimer 1 and 0.0068 g (0.000032 mol) of butylene phosphate were stirred to obtain a solution. The solution was heated to 120 °C. A mixture of 45.48 g (0.0455 eq) of TP-10 and 23.10 g (0.0103 eq) of LB 25 was added dropwise into the flask over 45 minutes. The reaction was continued until the isocyanate group (NCO) content reached 14.96%. The heating was stopped and a polyether-modified polyisocyanate composition 10 was obtained, which was a colorless transparent solution and met the following property data:

[0298] Solid content: 100 wt.%

[0299] NCO content: 14.96 wt.% relative to the total weight of the polyether-modified polyisocyanate composition 10

[0300] Viscosity (23 °C): 1762 mPa-s

[0301] Color value (Hazen): 12

[0302] Isocyanate functionality: 3.0

[0303] Amount of polyalkylene oxide monoether structures: 29.82 wt.% relative to the total weight of the polyether-modified polyisocyanate composition 10

[0304] Content of isophorone diisocyanate trimer: 0 wt.% relative to the total weight of the polyether-modified polyisocyanate composition 10.

[0305] wherein the average number average molecular weight of TP-10 and LB 25 is 1230 g / mol, the amount of TP-10 and LB 25 in the system is 29.82 wt.%, and the average of the content of propylene oxide groups of TP-10 and the content of propylene oxide groups of LB 25 is 72 wt.%.

[0306] Polyether-modified polyisocyanate composition 11

[0307] Into a 250 ml flask with a dropping funnel and nitrogen inlet, 70 g (0.3887 eq) of hexamethylene diisocyanate trimer 1, 35 g (0.1815 eq) of hexamethylene diisocyanate uretdione 3 and 0.0021 g of DBTL 12 were stirred to obtain a solution. The solution was heated to 50 °C. 45 g (0.0455 eq) of TP-10 was added dropwise into the flask over 45 minutes until the isocyanate group (NCO) content reached 14.48%. The heating was stopped and a polyether-modified polyisocyanate composition 11 was obtained which was a colorless transparent solution and met the following property data:

[0308] Solid content: 100 wt.%

[0309] NCO content: 14.48 wt.% relative to the total weight of the polyether-modified polyisocyanate composition 11

[0310] Viscosity (23 °C): 1144 mPa-s

[0311] Color value (Hazen): 14

[0312] Isocyanate functionality: 2.70

[0313] Amount of polyalkylene oxide monoether structures: 29.82 wt.% relative to the total weight of the polyether-modified polyisocyanate composition 11

[0314] Content of isophorone diisocyanate trimer: 0 wt.% relative to the total weight of the polyether-modified polyisocyanate composition 11.

[0315] Wherein, the amount of TP-10 by weight of the system: 29.82 wt.%.

[0316] Polyether-modified polyisocyanate composition 12

[0317] Into a 500 ml flask with a dropping funnel and nitrogen inlet, 315 g (1.7490 eq) of hexamethylene diisocyanate trimer 1, 105 g (0.5445 eq) of hexamethylene diisocyanate uretdione 3 and 0.008 g of DBTL 12 were stirred to obtain a solution. The solution was heated to 50 °C. 180 g (0.1822 eq) of TP-10 was added dropwise into the flask over 45 minutes until the isocyanate group (NCO) content reached 14.67%. The heating was stopped and a polyether-modified polyisocyanate composition 12 was obtained which was a colorless transparent solution and met the following property data:

[0318] Solid content: 100 wt.%

[0319] NCO content: 14.67 wt.% relative to the total weight of the polyether-modified polyisocyanate composition 12

[0320] Viscosity (23°C): 1252 mPa-s

[0321] Color (Hazen): 13

[0322] Isocyanate functionality: 2.76

[0323] Amount of polyalkylene oxide monoether structure: 29.82 wt% relative to the total weight of the polyether-modified polyisocyanate composition 12

[0324] Content of isophorone diisocyanate trimer: 0 wt% relative to the total weight of the polyether-modified polyisocyanate composition 12.

[0325] wherein TP-10 is present in the system in an amount of: 29.82 wt%.

[0326] Comparative polyether-modified polyisocyanate composition 1

[0327] hexamethylene diisocyanate trimer 1 and 0.0059 g (0.000026 mol) of butyl phosphonate were stirred in a 250 ml flask with a dropping funnel and nitrogen inlet to obtain a solution. The solution was heated to 120°C. 17.8 g (0.0178 eq) of TP-10 was added dropwise to the flask over 45 minutes and the reaction was continued until the isocyanate group (NCO) content reached 20.46%. The heating was stopped and a comparative polyether-modified polyisocyanate composition 1 was obtained which was a colorless transparent solution and which met the following property data:

[0328] Solid content: 100 wt%

[0329] NCO content: 20.46 wt% relative to the total weight of the comparative polyether-modified polyisocyanate composition 1.

[0330] Viscosity (23°C): 1485 mPa-s

[0331] Color (Hazen): 17

[0332] Isocyanate functionality: 3.13

[0333] Amount of polyalkylene oxide monoether structure: 10 wt% relative to the total weight of the comparative polyether-modified polyisocyanate composition 1

[0334] Content of isophorone diisocyanate trimer: 0 wt% relative to the total weight of the comparative polyether-modified polyisocyanate composition 1.

[0335] wherein TP-10 is present in the system in an amount of: 10 wt%.

[0336] Comparative polyether-modified polyisocyanate composition 2

[0337] Into a 250 ml flask with a dropping funnel and nitrogen inlet, 100 g (0.5190 eq) of hexamethylene diisocyanate trimer 1 and 0.0063 g (0.00003 mol) of butylene phosphate were stirred to obtain a solution. The solution was heated to 120 °C. 100 g (0.1012 eq) of TP-10 was added dropwise into the flask over 45 minutes until the isocyanate group (NCO) content reached 9.55%. The heating was stopped to obtain a comparative polyether-modified polyisocyanate composition 2, which was a colorless transparent solution and met the following property data:

[0338] Solid content: 100 wt.%

[0339] NCO content: 9.55 wt.% relative to the total weight of the comparative polyether-modified polyisocyanate composition 2

[0340] Viscosity (23 °C): 2065 mPa-s

[0341] Color value (Hazen): 32

[0342] Isocyanate functionality: 2.58

[0343] Amount of polyalkylene oxide monoether structures: 50 wt.% relative to the total weight of the comparative polyether-modified polyisocyanate composition 2

[0344] Content of isophorone diisocyanate trimer: 0 wt.% relative to the total weight of the comparative polyether-modified polyisocyanate composition 2.

[0345] wherein TP-10 is present in the system in an amount of: 50 wt.%.

[0346] Comparative polyether-modified polyisocyanate composition 3

[0347] Into a 500 ml flask with a dropping funnel and nitrogen inlet, 240 g (1.3531 eq) of hexamethylene diisocyanate trimer 2 and 0.06 g (0.00028 mol) of butylene phosphate were stirred to obtain a solution. The resulting solution was heated to 120 °C. 102 g (0.1213 eq) of TOl-A was added dropwise into the flask over 45 minutes until the isocyanate group (NCO) content reached 15.24%. The heating was stopped to obtain a comparative polyether-modified polyisocyanate composition 3, which was a colorless transparent solution and met the following property data:

[0348] Solid content: 100 wt.%

[0349] NCO content: 15.24 wt.% relative to the total weight of the comparative polyether-modified polyisocyanate composition 3

[0350] Viscosity (23°C): 948 mPa-s

[0351] Color (Hazen): 17

[0352] Isocyanate functionality: 2.92

[0353] Amount of polyalkylene oxide monoether structure: 29.82 wt% relative to the total weight of the comparative polyether-modified polyisocyanate composition 3

[0354] Content of isophorone diisocyanate trimer: 0 wt% relative to the total weight of the comparative polyether-modified polyisocyanate composition 3.

[0355] wherein T01-A is present in an amount of: 29.82 wt%.

[0356] Comparative polyether-modified polyisocyanate composition 4

[0357] A solution was prepared by stirring 160 g (0.8857 eq) of hexamethylene diisocyanate trimer 1 and 0.043 g (0.0003 mol) of butyl diglycolate in a 500 ml flask with a dropping funnel and nitrogen inlet. The resulting solution was heated to 120°C. A mixture of 24 g (0.0243 eq) of TP-10 and 44.57 g (0.0446 eq) of MPEG 1000 was added dropwise to the flask over 45 minutes until the isocyanate group (NCO) content reached 14.81%. The heating was stopped and a comparative polyether-modified polyisocyanate composition 4 was obtained which was a colorless transparent solution and met the following property data:

[0358] Solid content: 100 wt%

[0359] NCO content: 14.81 wt% relative to the total weight of the comparative polyether-modified polyisocyanate composition 4

[0360] Viscosity (23°C): 1201 mPa-s

[0361] Color (Hazen): 11

[0362] Isocyanate functionality: 2.95

[0363] Amount of polyalkylene oxide monoether structure: 29.82 wt% relative to the total weight of the comparative polyether-modified polyisocyanate composition 4

[0364] Content of isophorone diisocyanate trimer: 0 wt% relative to the total weight of the comparative polyether-modified polyisocyanate composition 4.

[0365] wherein the average number average molecular weight of TP-10 and MPEG 1000 is 1000 g / mol, the weight amount of TP-10 and MPEG 1000 in the system is 29.82 wt.%, and the average of the oxypropylene group content of TP-10 and the oxypropylene group content of MPEG 1000 is 35 wt.%.

[0366] Comparative polyether-modified polyisocyanate composition 5

[0367] To a 500 ml flask with a dropping funnel and nitrogen inlet, 160 g (0.8305 eq) of hexamethylene diisocyanate uretdione 3 was stirred to obtain a solution. The resulting solution was heated to 120 °C. 68.57 g (0.0649 eq) of TP-10 was added dropwise to the flask over 45 minutes and the reaction was continued until the isocyanate group (NCO) content reached 13.86%. The heating was stopped and a comparative polyether-modified polyisocyanate composition 5 was obtained, which was a colorless transparent solution and met the following property data:

[0368] Solid content: 100 wt.%

[0369] NCO content: 13.86 wt.% relative to the total weight of the comparative polyether-modified polyisocyanate composition 5

[0370] Viscosity (23 °C): 509.6 mPa-s

[0371] Color value (Hazen): 37

[0372] Isocyanate functionality: 2.3

[0373] Amount of polyalkylene oxide monoether structures: 29.82 wt.% relative to the total weight of the comparative polyether-modified polyisocyanate composition 5

[0374] Content of isophorone diisocyanate trimer: 0 wt.% relative to the total weight of the comparative polyether-modified polyisocyanate composition 5.

[0375] wherein the weight amount of TP-10 in the system is 29.82 wt.%.

[0376] Comparative polyether-modified polyisocyanate composition 6

[0377] Into a 250 ml flask with a dropping funnel and nitrogen inlet, 35 g (0.1943 eq) of hexamethylene diisocyanate trimer 1, 70 g (0.3630 eq) of hexamethylene diisocyanate uretdione 3 and 0.0021 g of DBTL 12 were stirred to obtain a solution. The resulting solution was heated to 50 °C. 45 g (0.0455 eq) of TP-10 was added dropwise into the flask over 45 minutes and the reaction was continued until the isocyanate group (NCO) content reached 14.25%. The heating was stopped and a comparative polyether-modified polyisocyanate composition 6 was obtained, which was a colorless transparent solution and met the following property data:

[0378] Solid content: 100 wt.%

[0379] NCO content: 14.25 wt.% relative to the total weight of the comparative polyether-modified polyisocyanate composition 6

[0380] Viscosity (23 °C): 639.8 mPa-s

[0381] Color value (Hazen): 9

[0382] Isocyanate functionality: 2.49

[0383] Amount of polyalkylene oxide monoether structures: 29.82 wt.% relative to the total weight of the comparative polyether-modified polyisocyanate composition 6

[0384] Content of isophorone diisocyanate trimer: 0 wt.% relative to the total weight of the comparative polyether-modified polyisocyanate composition 6.

[0385] wherein the amount of TP-10 by weight in the system: 29.82 wt.%.

[0386] Process for the preparation of two-component coatings of the examples and comparative examples Polyether-modified polyisocyanate composition

[0387] Formulation of A component: Isocyanate group reactive components Desmophen NH 1420 and Desmophen NH 2850 were mixed at a weight ratio of 4:1 at room temperature and stirred for 10-30 minutes to obtain the A component.

[0388] Table 1 is the B component and coating performance test results of the two-component coatings of Examples 1-12. Table 2 is the B component and coating performance test results of the two-component coatings of Comparative Examples 1-8. According to the B components listed in Table 1, Table 2, the B component was mixed with the prepared A component and NE310 (the amount of NE310 was 0.2 wt.% of the weight of the B component) was added, and the mixture was stirred at room temperature for 3-5 minutes to obtain a two-component coating. The molar ratio of the NCO groups of the B component to the isocyanate reactive groups of the A component was 2:1.

[0389]

[0390]

[0391] The two-component coating of Example 1-12 has a long pot life, a short tack-free time, a large pendulum hardness and a large bubble film thickness (BFFT), the two-component coating has a long workable time, a high drying efficiency and a high coating hardness of the coating formed by the coating.

[0392] The B component of Comparative Example 1 is a comparative polyether-modified polyisocyanate composition 1, the amount of polyalkylene oxide monoether structure of the comparative polyether-modified polyisocyanate composition 1 is 10 wt%, the polyalkylene oxide monoether alcohol TP-10 used in the preparation process of the comparative polyether-modified polyisocyanate composition 1 accounts for 10 wt% of the system for preparing the comparative polyether-modified polyisocyanate composition 1, the pot life of the two-component coating of Comparative Example 1 is short, and the workable time of the two-component coating is short.

[0393] The B component of Comparative Example 2 is a comparative polyether-modified polyisocyanate composition 2, the amount of polyalkylene oxide monoether structure of the comparative polyether-modified polyisocyanate composition 2 is 50 wt%, the polyalkylene oxide monoether alcohol TP-10 used in the preparation process of the comparative polyether-modified polyisocyanate composition 2 accounts for 50 wt% of the system for preparing the comparative polyether-modified polyisocyanate composition 2, the tack-free time of the two-component coating of Comparative Example 2 is long, the pendulum hardness is low, the drying efficiency of the two-component coating is low, and the coating hardness of the coating formed by the coating is low.

[0394] The B component of Comparative Examples 3 and 5 is hexamethylene diisocyanate trimer 1 or 2, which is a polyisocyanate that is not polyether-modified, the pot life of the two-component coating comprising hexamethylene diisocyanate trimer 1 or 2 is short and the BFFT is low, and the workable time of the two-component coating is short.

[0395] The B component of Comparative Example 4 is a comparative polyether-modified polyisocyanate composition 3, the number average molecular weight of the polyalkylene oxide monoether alcohol T01-A used in the preparation process of the comparative polyether-modified polyisocyanate composition 3 is 800 g / mol, the pot life of the two-component coating of Comparative Example 4 is short, and the workable time of the two-component coating is short.

[0396] The B component of Comparative Example 6 is a comparative polyether-modified polyisocyanate composition 4, the content of propylene oxide groups of the polyalkylene oxide monoether alcohol used in the preparation process of the comparative polyether-modified polyisocyanate composition 4 accounts for less than 45 wt% of the content of polyalkylene oxide groups of the polyalkylene oxide monoether alcohol, the pendulum hardness of the two-component coating of Comparative Example 6 is low, and the coating hardness of the coating formed by the two-component coating is low.

[0397] The B component of Comparative Example 7 is Comparative Polyether-modified Polyisocyanate Composition 5, which is prepared using a polyisocyanate that is hexamethylene diisocyanate uretdione 3 and does not include hexamethylene diisocyanate trimer. The two-component coating of Comparative Example 7 has a long tack-free time, low pendulum hardness, and the two-component coating has a low drying efficiency and the coating formed from the coating has a low hardness.

[0398] The polyether-modified polyisocyanate compositions of the B component of Examples 11-12 and Comparative Example 8 are prepared using a polyisocyanate that is a mixture of hexamethylene diisocyanate trimer 1 and hexamethylene diisocyanate uretdione 3, with the difference being that the hexamethylene diisocyanate trimer comprises at least 35 wt% of the polyisocyanate content of the system for Examples 11 and 12. The pot life, tack-free time, and pendulum hardness of the two-component coatings of Examples 11 and 12 are significantly better than that of Comparative Example 8, i.e., the workability, drying efficiency, and hardness of the coating formed from the coating of Examples 11 and 12 are significantly better than that of Comparative Example 8.

[0399] It is readily apparent to those skilled in the art that the present application is not limited to the specific details of the foregoing, and that the present application can be implemented in other specific forms without departing from the spirit or essential characteristics thereof. Accordingly, the embodiments described are to be considered in all respects as illustrative and not restrictive, the scope of the application being indicated by the appended claims rather than by the foregoing description, and all changes which come within the meaning and range of equivalency of the claims are therefore intended to be embraced therein.

Claims

1. A polyether-modified polyisocyanate composition, obtained from the reaction of a system comprising: a) a polyisocyanate having an isocyanate group functionality of 2 to 4.5, selected from the group consisting of hexamethylene diisocyanate trimer, pentamethylene diisocyanate trimer, or combinations thereof; b) a polyoxyalkylene monoether alcohol; and c) optionally, a catalyst; said polyoxyalkylene monoether alcohol having a number average molecular weight of 900 g / mol to 2000 g / mol, and a propylene oxide group content of 80 wt% to 100 wt%, relative to the total weight of the oxyalkylene groups of the polyoxyalkylene monoether alcohol; said system having an equivalent ratio of isocyanate groups to hydroxyl groups of 5:1 to 110:1; said polyisocyanate composition having the following characteristics: i) an average isocyanate functionality of 1.8 to 4.1; ii) an isocyanate group content of 8 wt% to 20 wt%, relative to the total weight of the polyisocyanate composition; and iii) an amount of polyoxyalkylene monoether structure of greater than 10 wt% and less than or equal to 35 wt%, relative to the total weight of the polyisocyanate composition.

2. The polyether-modified polyisocyanate composition according to claim 1, characterized in that, said amount of polyoxyalkylene monoether structure is 15 wt% to 35 wt%, relative to the total weight of the polyisocyanate composition.

3. The polyether-modified polyisocyanate composition according to claim 1 or 2, characterized in that, said amount of polyoxyalkylene monoether structure is 20 wt% to 35 wt%, relative to the total weight of the polyisocyanate composition.

4. The polyether-modified polyisocyanate composition according to claim 1 or 2, characterized in that, said amount of polyoxyalkylene monoether structure is 24 wt% to 35 wt%, relative to the total weight of the polyisocyanate composition.

5. The polyether-modified polyisocyanate composition according to claim 1 or 2, characterized in that, said amount of polyoxyalkylene monoether alcohol is greater than 10 wt% and less than or equal to 35 wt%, relative to the total weight of the system.

6. The polyether-modified polyisocyanate composition according to claim 1 or 2, characterized in that, said amount of polyoxyalkylene monoether alcohol is 15 wt% to 35 wt%, relative to the total weight of the system.

7. The polyether-modified polyisocyanate composition according to claim 1 or 2, characterized in that, said amount of polyoxyalkylene monoether alcohol is 20 wt% to 35 wt%, relative to the total weight of the system.

8. The polyether-modified polyisocyanate composition according to claim 1 or 2, characterized in that, said amount of polyoxyalkylene monoether alcohol is 24 wt% to 35 wt%, relative to the total weight of the system.

9. The polyether-modified polyisocyanate composition according to claim 1 or 2, characterized in that, said polyoxyalkylene monoether alcohol has a number average molecular weight of 920 g / mol to 1800 g / mol.

10. The polyether-modified polyisocyanate composition according to claim 1 or 2, characterized in that, said polyoxyalkylene monoether alcohol has a number average molecular weight of 920 g / mol to 1500 g / mol.

11. The polyether-modified polyisocyanate composition according to claim 1 or 2, characterized in that, said polyoxyalkylene monoether alcohol has a number average molecular weight of 920 g / mol to 1400 g / mol.

12. The polyether-modified polyisocyanate composition according to claim 1 or 2, characterized in that, said polyisocyanate composition contains no more than 0.5 wt% of isophorone diisocyanate trimer, relative to the total weight of the polyisocyanate composition.

13. The polyether-modified polyisocyanate composition according to claim 1 or 2, characterized in that, said polyisocyanate composition contains no isophorone diisocyanate trimer.

14. The polyether-modified polyisocyanate composition according to claim 1 or 2, characterized in that, said component c) catalyst is one or more of the following: a metal catalyst and a phosphoric acid catalyst.

15. Process for the preparation of the polyether-modified polyisocyanate composition according to any of claims 1 to 14, characterized in that, Mixing and reacting a system comprising component a) a polyisocyanate having an isocyanate group functionality of 2 to 4.5, component b) a polyoxyalkylene monoether alcohol, and optionally component c) a catalyst to form a polyether-modified polyisocyanate composition having the following characteristics: i) an average isocyanate functionality of 1.8 to 4.1; ii) an isocyanate group content of 8 to 20 weight percent relative to the total weight of the polyisocyanate composition; and iii) an amount of polyoxyalkylene monoether structure of greater than 10 weight percent and less than or equal to 35 weight percent relative to the total weight of the polyisocyanate composition; wherein the component a) polyisocyanate is selected from hexamethylene diisocyanate trimer, pentamethylene diisocyanate trimer, or a combination thereof; the component b) polyoxyalkylene monoether alcohol has a number average molecular weight of 900 g / mol to 2000 g / mol, an oxypropylene group content of 80 weight percent to 100 weight percent relative to the total weight of the oxyalkylene groups of the polyoxyalkylene monoether alcohol; and the equivalent ratio of isocyanate groups to hydroxyl groups of the system is 5:1 to 110:

1.

16. Use of the polyether-modified polyisocyanate composition according to any one of claims 1 to 14 as a starting component in the preparation of a polyurethane or as a starting component for the preparation of a blocked polyisocyanate blocked with a blocking agent or as a crosslinking component for solvent-borne or solventless coatings, adhesives, or sealants.

17. Use of the polyether-modified polyisocyanate composition according to any one of claims 1 to 14 for increasing the pot life of a coating, adhesive, or sealant.

18. A solvent-borne or solventless two-component coating composition comprising an A component which is a compound containing isocyanate-reactive groups and a B component which is the polyether-modified polyisocyanate composition according to any one of claims 1 to 14.

19. The two-component coating composition according to claim 18, characterized in that The compound containing isocyanate-reactive groups is aspartate.

20. A substrate coated with the solvent-borne or solventless two-component coating composition according to claim 18 or 19.

Images