CN111517994A - Sulfonate modified polyisocyanate and preparation method thereof - Google Patents

Sulfonate modified polyisocyanate and preparation method thereof Download PDF

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Publication number
CN111517994A
CN111517994A CN202010079185.5A CN202010079185A CN111517994A CN 111517994 A CN111517994 A CN 111517994A CN 202010079185 A CN202010079185 A CN 202010079185A CN 111517994 A CN111517994 A CN 111517994A
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sulfonate
cyclopentyl
polyisocyanate
modified polyisocyanate
modified
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王韬
朱伯承
谭星
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Guangdong Tuopu Synthesis Technology Co ltd
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Guangdong Tuopu Synthesis Technology Co ltd
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C303/00—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides
    • C07C303/32—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides of salts of sulfonic acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/77—Polyisocyanates or polyisothiocyanates having heteroatoms in addition to the isocyanate or isothiocyanate nitrogen and oxygen or sulfur
    • C08G18/775—Polyisocyanates or polyisothiocyanates having heteroatoms in addition to the isocyanate or isothiocyanate nitrogen and oxygen or sulfur sulfur
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
    • C09D175/04—Polyurethanes
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
    • C09J175/04—Polyurethanes

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  • Life Sciences & Earth Sciences (AREA)
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  • Wood Science & Technology (AREA)
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  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Polyurethanes Or Polyureas (AREA)

Abstract

The invention discloses sulfonate modified polyisocyanate and a preparation method thereof, wherein the sulfonate modified polyisocyanate is prepared by reacting polyisocyanate with a compound represented by the general formula R1‑HN‑R2‑SO3Preparing sulfonate of H (1); in the formula (1), R1Is a hydrocarbon group having 3 to 6 carbon atoms, R2Is a hydrocarbon group having 2 to 4 carbon atoms, and R1And R2Are not identical. The sulfonate-modified polyisocyanates according to the invention can be distributed homogeneously in aqueous coating materials or adhesives, the polyisocyanate mixtures according to the invention being produced as crosslinker components for aqueous polyurethane coatingsCoatings with outstanding optical properties, in particular high surface gloss, flow and high transparency, and also for the preparation of the known blocking agent-blocked polyisocyanates from polyurethane chemistry, are produced.

Description

Sulfonate modified polyisocyanate and preparation method thereof
Technical Field
The present invention relates to sulfonate-modified polyisocyanates and to a process for their preparation.
Background
Polyisocyanates are one of the main raw materials for polyurethane adhesives, and there are diisocyanates, triisocyanates and their modifications for the production of polyurethane adhesives, and polyisocyanates are the most important raw materials for the polyurethane industry.
In recent years, as the requirement for environmental protection is continuously increased, the water-dispersible polyisocyanate is widely applied in many fields, for example, the water-dispersible polyisocyanate can be used as a cross-linking agent component to form a water-based two-component polyurethane coating with a hydroxyl component, can be cured at room temperature, and the water resistance and the solvent resistance of the coating reach the performances of the traditional solvent type polyurethane coating and can be applied to the fields of automobiles, woodware, plastics and the like. As an additive in aqueous adhesives and sealing dispersions, adhesion of the adhesive to various materials, heat resistance, and the like are improved. Can be used as a cross-linking agent of textile forming materials in the textile industry and also can be used as an additive for improving the wet strength of paper.
The polyisocyanates can not be directly dispersed or emulsified in water due to strong lipophilicity, and can be used in an aqueous system to be crosslinked and cured with an aqueous dispersion containing hydroxyl functional groups only by being properly treated, namely, subjected to hydrophilic modification.
In order to solve these technical problems, the water-solubility of polyisocyanate was achieved by using external emulsifiers of cationic, anionic or nonionic type in the early days, but this method has the disadvantages of large amount of emulsifier, coarse particles after dispersion, poor storage stability, poor physical and mechanical properties of adhesive layer, poor water resistance, etc.
Later on, through a plurality of experiments, the hydrophilic modification of the polyisocyanate is realized by adding hydrophilic ionic groups into the polyisocyanate.
According to the teaching of WO 2001/88006, hydrophilized polyisocyanates can be obtained by reacting any polyisocyanate with 2- (cyclohexylamino) ethanesulfonic acid (CHES) or 3- (cyclohexylamino) propanesulfonic acid (CAPS), which as crosslinkers in aqueous coating systems result in coatings with high hardness and excellent solvent and chemical resistance. However, in this manner, the reaction time for preparing the sulfonate-modified polyisocyanate is long, the kinds of sulfonates which can be hydrophilically modified by the polyisocyanate by this reaction are small, only two of 3- (cyclohexylamino) -propanesulfonic acid and 2- (cyclohexylamino) -ethanesulfonic acid are disclosed, and it is clear that many other sulfonates having very similar structures cannot react with the polyisocyanate even under more severe conditions.
EP0443138A and EP0548669A propose the modification of polyisocyanates by introducing carboxyl groups. After the carboxyl groups are neutralized, the modified polyisocyanates can be easily dispersed in water without high shear forces. However, the disadvantage is that the carboxylic acid-modified polyisocyanates cannot be dispersed in systems having a pH of less than 5; furthermore, the ions formed after neutralization thereof with tertiary amines are good catalysts for the self-polymerization of isocyanates, which leads to a reduction in the storage stability of the modified polyisocyanates. Therefore, the carboxyl-modified polyisocyanates can generally be stored only in the unneutralized form and are neutralized before use, which is laborious and cumbersome to handle.
Disclosure of Invention
The present invention aims to provide a polyisocyanate excellent in water dispersibility, good in storage stability and having a good pot life (retention of isocyanate), and a process for producing the polyisocyanate.
In order to achieve the purpose, the invention adopts the following technical scheme:
scheme 1 of the present invention:
a sulfonate-modified polyisocyanate characterized by: which is prepared by reacting a polyisocyanate with a sulfonate represented by the following general formula (1);
R1——HN——R2——SO3H (1)
in the formula (1), R1Is a hydrocarbon group having 3 to 6 carbon atoms, R2Is a hydrocarbon group having 2 to 4 carbon atoms, and R1And R2Are not identical.
In the above formula (1), R1Comprising R11、R12、R13And R is1Including hydrocarbon groups containing a ring structure.
In the above scheme, R is11Is one of cyclopentyl, methyl cyclopentyl, dimethyl cyclopentyl and trimethyl cyclopentyl, R12Is cyclohexyl, cyclohexylmethyl, p-methylcyclohexyl, 2, 3-dimethylcyclohexyl, 3, 5-trisOne of methylcyclohexyl, 4-tert-butylcyclohexyl, cycloheptyl, cyclooctylmethyl, 2-norbornyl, 2-adamantyl and 3, 5-dimethyl-1-adamantyl; r13Is cyclopropyl.
In the above scheme, R is2Is one of propyl, ethyl, butyl and isobutyl.
In the above scheme, R is1Comprising R11，R11Is cyclopentyl; r2Is one of propyl, ethyl, butyl and isobutyl; or said R1Comprising R11And R12，R11Is cyclopentyl, R12Is cyclohexyl; r2Is one of propyl, ethyl, butyl and isobutyl; or said R1Comprising R11And R13，R11Is cyclopentyl, R13Is cyclopropyl; r2Is one of propyl, ethyl, butyl and isobutyl; or said R1Comprising R11、R12And R13，R11Is cyclopentyl, R12Is cyclohexyl; r13Is cyclopropyl; r2Is one of propyl, ethyl, butyl and isobutyl.
In the above scheme, R is1In R11、R12、R13The content of (A) is as follows: r11：1％-98％，R12：0％-98％，R13：0％-98％。
In the above scheme, the sulfonate modified polyisocyanate has the following characteristics:
a) an average isocyanate functionality of at least 1.8;
b) the NCO content is 4-38 wt%;
c)SO3-in an amount of 0.1 to 7 wt%,
and optionally
d) The content of ethoxy units bonded in the polyether chain is from 3 to 14% by weight, said polyether chain containing an average of from 10 to 20 ethoxy units.
Preferably, the polyisocyanate is one or more of aliphatic, cycloaliphatic, aromatic, araliphatic polyisocyanates or modified polyisocyanates having an average isocyanate functionality of 2 to 4.5 and an NCO content of 5 to 35 weight percent.
Embodiment 2 of the present invention:
a process for producing a sulfonate-modified polyisocyanate, which comprises reacting a polyisocyanate with a sulfonate represented by the following general formula (1) in the presence of a tertiary amine;
R1——HN——R2——SO3H (1)
in the formula (1), R1Is a hydrocarbon group having 3 to 6 carbon atoms, R2Is a C2-4 hydrocarbon group, R1And R2Is not the same, and R1Comprising R11、R12、R13One or more of;
wherein,
R11is one of cyclopentyl, methyl cyclopentyl, dimethyl cyclopentyl and trimethyl cyclopentyl, R12Is one of cyclohexyl, cyclohexylmethyl, p-methylcyclohexyl, 2, 3-dimethylcyclohexyl, 3, 5-trimethylcyclohexyl, 4-tert-butylcyclohexyl, cycloheptyl, cyclooctylmethyl, 2-norbornyl, 2-adamantyl and 3, 5-dimethyl-1-adamantyl; r13Is cyclopropyl;
the dosage of the sulfonate is 0.3 to 21 weight percent of the total weight of the polyisocyanate and the sulfonate.
In the above-described preparation process, the reaction is carried out in the presence of polyethers which contain ethoxy units and/or the polyisocyanates used already contain ethoxy polyether units.
In the above preparation, the polyisocyanate having an average functionality, calculated as NCO, of greater than 1.8 and containing R11、R12、R13A sulfonate salt of one or more of (a); mixing with polyether and tertiary amine under rapid stirring.
In addition, the sulfonate-modified polyisocyanates of the present invention may also be applied to:
aspect 3 of the present invention: use of the sulfonate-modified polyisocyanates of the above scheme 1 as crosslinking components in aqueous two-component coatings or aqueous dispersion adhesives.
The 4 th aspect of the present invention: scheme 1 above the use of sulfonate-modified polyisocyanate starting components for the preparation of the known sealer-blocked polyisocyanates in polyurethane chemistry.
The product obtained by the above-described process for the preparation of sulfonate-modified polyisocyanates is a transparent, virtually colorless polyisocyanate which can be readily converted into a precipitate-resistant dispersion by merely stirring into water without the use of high shear forces.
The product prepared by the preparation method of the sulfonate modified polyisocyanate has higher average isocyanate functionality and high NCO content, SO that the sulfonate modified polyisocyanate still has good dispersibility under low SO 3-content, thereby having great advantages in the application of aqueous two-component coating. The two-component coatings prepared by using the sulfonate-modified polyisocyanates of the present invention have very good water resistance due to the low hydrophilic group content in addition to very good solvent and chemical resistance.
The aqueous coating compositions formulated from the products obtained by the above-described process for the preparation of sulfonate-modified polyisocyanates, into which, optionally, the auxiliaries and additives customary in the coating industry, such as flow control auxiliaries, dyes, color pigments, fillers, flatting agents or emulsifiers, can be incorporated, have good technical coating properties even on drying at room temperature;
the use of the above-described sulfonate-modified polyisocyanates as crosslinker components for aqueous polyurethane coatings leads to coatings having outstanding optical properties, in particular high surface gloss, flowability and high transparency.
In addition to the preferred use as crosslinker component for aqueous 2K PUR coatings, the polyisocyanate mixtures containing sulfonate groups according to the invention are very suitable as crosslinkers for aqueous dispersion adhesives, for leather and textile coatings or textile printing pastes, as AOX-free paper auxiliaries or even as additives for mineral building materials, such as concrete or mortar.
Detailed Description
Hereinafter, a mode for carrying out the present invention (hereinafter, referred to as "the present embodiment") will be described in detail. The present invention is not limited to the following embodiments. The present invention can be suitably modified within the scope of the gist of the present invention.
< A sulfonate-modified polyisocyanate >
The sulfonate-modified polyisocyanate of the present embodiment is prepared by reacting a polyisocyanate with a sulfonate represented by the following general formula (1);
R1——HN——R2——SO3H (1)
in the formula (1), R1Is a hydrocarbon group having 3 to 6 carbon atoms, R2Is a hydrocarbon group having 2 to 4 carbon atoms, and R1And R2Are not identical.
In the above formula (1), R1Comprising R11、R12、R13And R is1Including hydrocarbon groups containing a ring structure.
In the above scheme, R is11Is cyclopentyl, R12Is one of cyclohexyl, cyclohexylmethyl, p-methylcyclohexyl, 2, 3-dimethylcyclohexyl, 3, 5-trimethylcyclohexyl, 4-tert-butylcyclohexyl, cycloheptyl, cyclooctylmethyl, 2-norbornyl, 2-adamantyl and 3, 5-dimethyl-1-adamantyl; r13Is cyclopropyl.
In the above scheme, R is2Is one of propyl, ethyl, butyl and isobutyl.
In the above scheme, R is1Comprising R11，R11Is cyclopentyl; r2Is one of propyl, ethyl, butyl and isobutyl; or said R1Comprising R11And R12，R11Is cyclopentyl, R12Is cyclohexyl; r2Is one of propyl, ethyl, butyl and isobutyl; or said R1Comprising R11、R12And R13，R11Is cyclopentyl, R12Is cyclohexyl; r13Is cyclopropyl; r2Is one of propyl, ethyl, butyl and isobutyl.
In the above scheme, R is1In R11、R12、R13The content of (A) is as follows: r11：1％-98％，R12：0％-98％，R13：0％-98％。
In the above scheme, the sulfonate modified polyisocyanate has the following characteristics:
a) an average isocyanate functionality of at least 1.8;
b) the NCO content is 4-38 wt%;
c)SO3-in an amount of 0.1 to 7 wt%,
and optionally
d) The content of ethoxy units bonded in the polyether chain is from 3 to 14% by weight, said polyether chain containing an average of from 10 to 20 ethoxy units.
Preferably, the polyisocyanate is one or more of aliphatic, cycloaliphatic, aromatic, araliphatic polyisocyanates or modified polyisocyanates having an average isocyanate functionality of 2 to 4.5 and an NCO content of 5 to 35 weight percent.
< polyisocyanates >
The polyisocyanate used in this embodiment may be one or more of aliphatic, cycloaliphatic, aromatic, araliphatic polyisocyanates or modified polyisocyanates, such as:
at least 1 diisocyanate compound selected from aliphatic diisocyanate, alicyclic diisocyanate, and aromatic diisocyanate, and/or polyisocyanate compound derived from these diisocyanate compounds. Preferably at least one selected from the group consisting of aliphatic polyisocyanates, alicyclic polyisocyanates, and araliphatic polyisocyanates.
The modified polyisocyanate is a modified polyisocyanate having a uretdione, isocyanurate, allophanate, biuret, iminooxadiazinedione and/or oxadiazinetrione structure, which is prepared by modifying a simple aliphatic, alicyclic, aromatic and/or araliphatic diisocyanate and synthesized from at least two diisocyanates.
Examples of the aliphatic diisocyanate include 1, 4-diisocyanatobutane, 1, 5-diisocyanatopentane, ethyl (2, 6-diisocyanato) hexanoate, 1, 6-diisocyanatohexane (HDI), 1, 9-diisocyanatononane, 1, 12-diisocyanatododecane, 2, 4-trimethyl-1, 6-diisocyanatohexane, and 2, 4, 4-trimethyl-1, 6-diisocyanatohexane. The alicyclic diisocyanate is not particularly limited, and examples thereof include 1, 3-bis (isocyanatomethyl) cyclohexane or 1, 4-bis (isocyanatomethyl) cyclohexane (hydrogenated XDI), 1, 3-diisocyanatocyclohexane or 1, 4-diisocyanatocyclohexane, 3, 5, 5-trimethyl-1-isocyanato-3- (isocyanatomethyl) cyclohexane (IPDI), 4' -diisocyanatodicyclohexylmethane (hydrogenated MDI), 2, 5-diisocyanatomethylnorbornane and 2, 6-diisocyanatomethylnorbornane.
Examples of the aromatic diisocyanate include xylylene diisocyanate, tolylene diisocyanate, and diphenylmethane diisocyanate.
Among them, HDI, IPDI, hydrogenated XDI, and hydrogenated MDI are preferable.
< sulfonate salt >
As the sulfonic acid amine salt having a hydroxyl group used in the present embodiment, a sulfonic acid salt represented by the following general formula (1);
R1——HN——R2——SO3H (1)
in the formula (1), and R is as defined above1And R2Monovalent saturated hydrocarbon groups can be selected;
R1is a hydrocarbon group having 3 to 6 carbon atoms, R2Is a hydrocarbon group having 2 to 4 carbon atoms, and R1And R2Different;
R2is one of propyl, ethyl, butyl and isobutyl;
in the above formula (1), R1Comprising R11、R12、R13And R is1Including hydrocarbon groups containing a ring structure. Said R11Is cyclopentyl and 8 derivatives thereof; r12Cyclohexyl and its various derivatives, such as cyclohexylmethyl, p-methylcyclohexyl, 2, 3-dimethylcyclohexyl, 3, 5-trimethylcyclohexyl, 4-tert-butylcyclohexyl, cycloheptyl, cyclooctylmethyl, 2-norbornyl, 2-adamantyl and 3, 5-dimethyl-1-adamantyl; r13Is cyclopropyl.
According to the above, R1Can be in the following four forms:
1) said R1Comprising R11，R11Is cyclopentyl; r2Is one of propyl, ethyl, butyl and isobutyl;
2) said R1Comprising R11And R12，R11Is cyclopentyl, R12Is cyclohexyl; r2Is one of propyl, ethyl, butyl and isobutyl;
3) said R1Comprising R11And R13，R11Is cyclopentyl, R13Is cyclopropyl; r2Is one of propyl, ethyl, butyl and isobutyl;
4) said R1Comprising R11、R12And R13，R11Is cyclopentyl, R12Is cyclohexyl; r13Is cyclopropyl; r2Is one of propyl, ethyl, butyl and isobutyl.
And in the three forms, R1In R11、R12、R13The content proportion is as follows: r11：1％-98％，R12：0％-98％，R13：0％-98％。
As can be seen from the above, the reaction can be carried out by three kinds of hydrocarbon groups having different numbers of carbon atoms, and preferably, the 2 nd), 3 rd) and 4) modes can be selected.
In the above four modes, R1A hydrocarbon radical comprising at least one ring structure, if R1Comprising R11、R12、R13At least two of (1), then R11、R12、R13The combination of any two of them is also a ring structure; so that R1Is a ring structure.
< other Compounds >
The preparation of the sulfonate-modified polyisocyanates is carried out in the presence of tertiary amines and optionally in the presence of polyethers;
the tertiary amine is aliphatic and/or alicyclic substituted, acyclic and/or cyclic tertiary amine, and comprises tertiary monoamine such as trimethylamine, triethylamine, tripropylamine, dimethylcyclohexylamine, N-methylmorpholine, N-methylquinoline, N-ethylquinoline, etc.; or dibasic tertiary amines such as 1, 3-bis- (dimethylamino) -propane and N, N-dimethylpiperazine, and the like;
the starter used to prepare the polyether may be: saturated monoalcohols, for example methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, sec-butanol, the isomeric pentanols, hexanols, octanols, nonanols, n-decanols, n-dodecanols, n-tetradecanols, n-hexadecanols, cyclohexanol, hydroxymethylcyclohexane and 3-ethyl-3-hydroxymethyloxetane; unsaturated alcohols, aromatic alcohols, araliphatic alcohols, secondary monoamines, such as dimethylamine, diethylamine, dipropylamine, diisopropylamine, di-N-butylamine, diisobutylamine, bis (2-ethylhexyl) -amine, N-methyl-and N-ethyl-cyclohexylamine or dicyclohexylamine, heterocyclic secondary amines, etc.
< preparation method >
The sulfonate-modified polyisocyanate of the present invention is prepared by reacting a polyisocyanate with a compound represented by the following general formula (1) R in the presence of a tertiary amine1——HN——R2——SO3Preparing sulfonate of H through reaction;
and R is1Comprising R11、R12、R13And R is1Including hydrocarbon groups containing a ring structure. Said R11Is cyclopentyl and 8 derivatives thereof; r12Cyclohexyl and its various derivatives, e.g. cyclohexylmethyl, p-methylcyclohexyl, 2, 3-dimethylcyclohexylOne of cyclohexyl, 3, 5-trimethylcyclohexyl, 4-tert-butylcyclohexyl, cycloheptyl, cyclooctylmethyl, 2-norbornyl, 2-adamantyl and 3, 5-dimethyl-1-adamantyl; r13Is cyclopropyl.
R2Is one of propyl, ethyl, butyl and isobutyl.
The sulfonate is used in an amount of 0.3 to 21 wt%, preferably 1 to 15 wt%, based on the total weight of polyisocyanate and sulfonate when prepared
Polyisocyanates having an average functionality, calculated as NCO, of more than 1.8, with a compound containing R11、R12、R13The sulfonate of one or more of (a) and (b) is mixed with the polyether and tertiary amine with rapid stirring.
The above-mentioned polyether has a functionality of 1, a number average molecular weight of 400-900, preferably 450-750, and a number of ethoxy units of 6-25, preferably 10-20.
The polyether described above has an ethoxy unit bonded in the polyether chain in the modified polyisocyanate in an amount of 0 to 20% by weight, preferably 3 to 15% by weight, based on the total weight of the polyisocyanate, the sulfonate and the polyether.
The molar ratio of the tertiary amine to the SO 3-groups of the sulfonate is 0.2-2.0: 1, preferably 0.5-1.5: 1.
In the above preparation method, the molar ratio of NCO groups to NCO-reactive groups is maintained at 4-300: 1; the molar ratio of NCO groups to NCO-reactive groups is kept at 6-200: 1.
< characteristics of polyisocyanate >
The polyisocyanate of the present embodiment is used as a starting component for the modified polyisocyanate prepared by the method of the present invention in an aqueous polyurethane synthetic material, particularly as a crosslinking agent in a water-dispersible two-component coating material or adhesive, from the viewpoints of hydrophilicity and stability.
The sulfonate-modified polyisocyanates according to the invention can be used, in addition to two-component coatings and adhesives as crosslinking components, as crosslinkers for textile finishing, printing coating adhesives and for crosslinking other aqueous dispersions or as auxiliaries for moistening paper.
< raw materials >
Component a)
Polyisocyanate 1: HDI isocyanurate group-containing polyisocyanates having an NCO content of 21.7% NCO functionality: 3.4;
polyisocyanate 2: HDI polyisocyanates containing isocyanurate and iminooxadiazinedione groups, NCO content: 23.4 percent; NCO functionality: 3.2;
component b)
Sulfonate 1 of the formula R1The method comprises the following steps: r11A cyclopentyl group;
sulfonate 2 of the formula R1The method comprises the following steps: r11And R12，R11Is cyclopentyl, R12Is cyclohexyl, wherein R1In parts by weight of (A), R112 wt% of R12Is 2 wt%;
sulfonate 3, of the formula R1The method comprises the following steps: r11And R13，R11Is cyclopentyl, R13Is cyclopropyl, wherein R1In parts by weight of (A), R112 wt% of R13Is 2 wt%;
sulfonate 4 of the formula R1The method comprises the following steps: r11，R12And R13，R11Is cyclopentyl, R12Is cyclohexyl, R13Is cyclopropyl, wherein R1In parts by weight of (A), R111 wt% of R12Is 95 wt%; r13Is 4 wt%
The dosage of the sulfonate is 0.3 to 21 weight percent of the total weight of the polyisocyanate and the sulfonate.
Component c)
The tertiary amine is used for neutralizing a sulfonic acid group in the sulfonate to form the sulfonate and is used as a phase transfer catalyst for catalyzing the reaction of the polyisocyanate and the sulfonate.
The tertiary amine may be used in combination with a catalyst generally used in the polyurethane science, and triethylamine, pyridine, picoline, etc.;
the content of tertiary amine is 0.001-0.6 of the total amount of the reaction components.
Component d)
Polyether: monofunctional polyethers containing ethoxy units;
the polyether content is 13 to 23 wt% of the total amount of component a), component b) and component d).
< example >
Example 1:
stirring 95g of polyisocyanate 1 together with 5g of (cyclopentyl) sulfonate 1 and 2.7g of tertiary amine at 80 ℃ to 100 ℃ for 4 to 6h under dry nitrogen, and after cooling to room temperature, obtaining a cyclic acid salt modified polyisocyanate mixture solution of the present invention having the following characteristic data:
NCO content: 19.2 wt%;
average NCO functionality: 3.3
Viscosity (25 ℃): 5000 mPa.s;
SO3-content: 1.64 wt%;
ethoxy unit content: 0;
example 2:
stirring 95g of polyisocyanate 1 together with 5g of (cyclopentyl) sulfonate 1, 2.7g of tertiary amine and 14.9g of polyether under dry nitrogen at 80 ℃ to 100 ℃ for 4 to 6h, after cooling to room temperature, a solution of a cyclic acid salt-modified polyisocyanate mixture according to the invention is obtained with the following characteristic data:
NCO content: 16.7 wt%;
average NCO functionality: 3.2
Viscosity (25 ℃): 5500 mPas;
SO3-content: 1.46 wt%;
ethoxy unit content: 10.1 wt%;
various proportions of polyisocyanates were reacted with various sulfonates, tertiary amines and polyethers according to examples 1 and 2, and tables 1 and 2 below show the composition of the reaction mixture in parts by weight and the characteristic data of the product.
TABLE 1
Figure BDA0002379674620000111
Figure BDA0002379674620000121
The previous description of the disclosed embodiments is provided to enable any person skilled in the art to make or use the present invention. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the invention. Thus, the present invention is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.

Claims (11)

1. A sulfonate-modified polyisocyanate characterized by: which is prepared by reacting a polyisocyanate with a sulfonate represented by the following general formula (1);
R1-HN-R2-SO3H (1)
in the formula (1), R1Is a hydrocarbon group having 3 to 6 carbon atoms, R2Is a hydrocarbon group having 2 to 4 carbon atoms, and R1And R2Are not identical.
2. A sulfonate modified polyisocyanate according to claim 1, characterized in that: in the above formula (1), R1Comprising R11、R12、R13And R is1Including hydrocarbon groups containing a ring structure.
3. A sulfonate modified polyisocyanate according to claim 2, characterized in that: said R11Is one of cyclopentyl, methyl cyclopentyl, dimethyl cyclopentyl and trimethyl cyclopentyl, and R12 is cyclohexyl, cyclohexylmethyl, p-methylcyclohexyl, 2, 3-dimethyl cyclopentylOne of hexyl, 3, 5-trimethylcyclohexyl, 4-tert-butylcyclohexyl, cycloheptyl, cyclooctylmethyl, 2-norbornyl, 2-adamantyl and 3, 5-dimethyl-1-adamantyl; r13Is cyclopropyl.
4. A sulfonate modified polyisocyanate according to claim 1, characterized in that: said R2Is one of propyl, ethyl, butyl and isobutyl.
5. A sulfonate modified polyisocyanate according to claim 3, characterized in that: said R1Comprising R11，R11Is cyclopentyl; r2Is one of propyl, ethyl, butyl and isobutyl;
or said R1Comprising R11And R12，R11Is cyclopentyl, R12Is cyclohexyl; r2Is one of propyl, ethyl, butyl and isobutyl;
or said R1Comprising R11And R13，R11Is cyclopentyl, R13Is cyclopropyl; r2Is one of propyl, ethyl, butyl and isobutyl;
or said R1Comprising R11、R12And R13，R11Is cyclopentyl, R12Is cyclohexyl; r13Is cyclopropyl; r2Is one of propyl, ethyl, butyl and isobutyl.
6. A sulfonate-modified polyisocyanate according to claim 2 or 5, characterized in that: said R1In R11、R12、R13The content of (A) is as follows:
R11：1％-98％，R12：0％-98％，R13：0％-98％。
7. a sulfonate-modified polyisocyanate according to any one of claims 1 to 5, wherein:
a) an average isocyanate functionality of at least 1.8;
b) the NCO content is 4-38 wt%;
c)SO3-in an amount of 0.1 to 7 wt%,
and optionally
d) The content of ethoxy units bonded in the polyether chain is from 3 to 14% by weight, said polyether chain containing an average of from 10 to 20 ethoxy units.
8. A sulfonate-modified polyisocyanate according to any one of claims 1 to 5, wherein: the polyisocyanate is one or more of aliphatic, alicyclic, aromatic and araliphatic polyisocyanates or modified polyisocyanates with the average isocyanate functionality of 2-4.5 and the NCO content of 5-35 wt%.
9. A method for preparing sulfonate modified polyisocyanate is characterized in that: reacting a polyisocyanate with a sulfonate represented by the following general formula (1) in the presence of a tertiary amine;
R1-HN-R2-SO3H (1)
in the formula (1), R1Is a hydrocarbon group having 3 to 6 carbon atoms, R2Is a C2-4 hydrocarbon group, R1And R2Is not the same, and R1Comprising R11、R12、R13One or more of;
wherein,
R11is one of cyclopentyl, methyl cyclopentyl, dimethyl cyclopentyl and trimethyl cyclopentyl; r12Is one of cyclohexyl, cyclohexylmethyl, p-methylcyclohexyl, 2, 3-dimethylcyclohexyl, 3, 5-trimethylcyclohexyl, 4-tert-butylcyclohexyl, cycloheptyl, cyclooctylmethyl, 2-norbornyl, 2-adamantyl and 3, 5-dimethyl-1-adamantyl; r13Is cyclopropyl;
the dosage of the sulfonate is 0.3 to 21 weight percent of the total weight of the polyisocyanate and the sulfonate.
10. The process for preparing a sulfonate-modified polyisocyanate according to claim 9, wherein: the reaction is carried out in the presence of polyethers which contain ethoxy units and/or the polyisocyanates used already contain ethoxy polyether units.
11. The process for preparing a sulfonate-modified polyisocyanate according to claim 8, wherein: polyisocyanates having an average functionality, calculated as NCO, of more than 1.8, with a compound containing R11、R12、R13A sulfonate salt of one or more of (a); mixing with polyether and tertiary amine under rapid stirring.
CN202010079185.5A 2020-02-03 2020-02-03 Sulfonate modified polyisocyanate and preparation method thereof Pending CN111517994A (en)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115466201A (en) * 2021-06-11 2022-12-13 万华化学集团股份有限公司 Sulfonic acid modified polyisocyanate and preparation method thereof
WO2024000342A1 (en) * 2022-06-30 2024-01-04 万华化学集团股份有限公司 Hydrophilically modified polyisocyanate, and preparation method therefor and use thereof

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Publication number Priority date Publication date Assignee Title
CN104448232A (en) * 2013-09-13 2015-03-25 万华化学集团股份有限公司 Sulfamic acid modified polyisocyanate and preparation method and application thereof

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104448232A (en) * 2013-09-13 2015-03-25 万华化学集团股份有限公司 Sulfamic acid modified polyisocyanate and preparation method and application thereof

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115466201A (en) * 2021-06-11 2022-12-13 万华化学集团股份有限公司 Sulfonic acid modified polyisocyanate and preparation method thereof
WO2022257585A1 (en) * 2021-06-11 2022-12-15 万华化学集团股份有限公司 Sulfonic acid-modified polyisocyanate and preparation method therefor
CN115466201B (en) * 2021-06-11 2024-05-03 万华化学集团股份有限公司 Sulfonic acid modified polyisocyanate and preparation method thereof
WO2024000342A1 (en) * 2022-06-30 2024-01-04 万华化学集团股份有限公司 Hydrophilically modified polyisocyanate, and preparation method therefor and use thereof

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