CN101619128B - Amido end-blocking non-ionic water-based isocyanate, preparation method and application thereof - Google Patents
Amido end-blocking non-ionic water-based isocyanate, preparation method and application thereof Download PDFInfo
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- CN101619128B CN101619128B CN2009100415850A CN200910041585A CN101619128B CN 101619128 B CN101619128 B CN 101619128B CN 2009100415850 A CN2009100415850 A CN 2009100415850A CN 200910041585 A CN200910041585 A CN 200910041585A CN 101619128 B CN101619128 B CN 101619128B
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Abstract
The invention discloses an amido end-blocking non-ionic water-based isocyanate, a preparation method and an application thereof. The preparation method comprises the following steps of: adding polyisocyanate, non-ionic hydrophilic monomer and multifunctional group substance containing active hydrogen into reaction equipment for reaction; then adding amido end-blocking agent to close free isocyanate groups, and obtaining the amido end-blocking non-ionic water-based isocyanate. The method has simple technique, mild reaction condition, convenient operation, and low production cost, simultaneously the prepared amido end-blocking non-ionic water-based isocyanate has stable dispersions, no agglomeration under higher and low temperature, long service life, excellent performance and moderate unblocking temperature, simultaneously overcomes the defects that in the prior art, an isocrosslinker and resin containing hydroxyl release isocyanato group with higher activity when in reaction so as to lead the reaction degree to be difficult to control, the preparation repeatability is poor, the stability is poor and the pollution is easy and the like, and solves the problems that in the free isocyanate group in the polyurethane crosslinker and coating has large reaction activity and is very sensitive to moisture and the like.
Description
Technical field
The invention belongs to the masked isocyanate field, particularly a kind of amido end-blocking non-ionic water-based isocyanate and preparation method thereof and application.
Background technology
Urethane is the synthetic materials of excellent property, for a long time, receives much concern.As the important source material-isocyanate-monomer of synthesis of polyurethane, because himself isocyanate groups and nucleophilic reagent have high reaction activity and high, make this system very active at normal temperatures, can't exist with the single component form.And during as coating or use, very responsive before polyurethane coating solidifies to moisture in the raw materials such as solvent, resin, pigment or the moisture in the damp atmosphere of working-yard, a lot of difficulties of application increase of giving polyurethane coating.People thirst for not only keeping urethane excellent chemical performance but also can improve the shortcoming that it uses.If can make isocyanate groups at room temperature to the reaction inactivation of reactive hydrogen, so just can coexist an individual system and needn't worry the influence of water with the aqueous polyurethane that contains reactive hydrogen, require also not strict to the water content in the resin of solvent, pigment and reactive hydrogen, improve stability, eliminated the murder by poisoning that causes because of the remaining isocyanate monomer.
Masked isocyanate is that isocyanate groups is by the prepared product of end-capping reagent end-blocking.By sealing, can make single-component product.Under certain temperature and other conditions, crosslinking reaction takes place in the isocyanate groups regeneration in the sealing urethane, generates heat-curable urethane.Just the end-blocking of free isocyanate groups has been turned into report as far back as Petersen in 1949.Wicks describes problems such as multiple end-capping reagent and using method thereof in detail in commentary paper in 1975.The Long Position of Japan is harvested the blocked isocyanate chemistry has also been done detailed commentary.Masked isocyanate has been widely used in preparing coating at present, especially water-borne coatings, because water-borne coatings is to be medium with water, have do not fire, nontoxic, free from environmental pollution, energy-conservation and easy advantage such as processing, and its viscosity and flowing property and polymericular weight are irrelevant, relative molecular weight can be transferred to desirable highest level, so be subject to people's attention day by day.The application of blocked isocyanate in coating mainly can be divided into: the performed polymer of (1) blocked isocyanate, and it is crosslinked to can be used as main film forming matter; (2) the masked isocyanate group is incorporated in other resins, directly as film forming matter, and crosslinkable; (3) masked isocyanate is as crosslinking and curing agent or other auxiliary agents of film-forming resin.
Effectively, useful enclosure method and corresponding encapsulant are very big to the Blocking of Isocyanates influential effect.Existing various encapsulant respectively has relative merits to the sealing of isocyanate groups (NCO), is easy to make the NCO sealing as phenol compound, but sealing product dissociation temperature is higher, in use need consider the problem of free phenol environmental pollution; Oximes also is easy to make the NCO sealing, but when using the aldoxime class to make encapsulant, also can there be problems such as free aldehyde pollution in the price height.Phenols and oximes end-capping reagent all can not obtain watersoluble closed isocyanic ester sealing monomer, and the solvent-borne type closed isocyanic ester monomer has considerable influence because of using a large amount of solvents to environment, does not meet " greenization " growth requirement.At present, do not do the report that end-capping reagent prepares the non-ionic water-based isocyanate linking agent as yet relevant for amide substance.
Summary of the invention
The shortcoming that the primary purpose of the present invention is to overcome prior art provides a kind of preparation method of amido end-blocking non-ionic water-based isocyanate with not enough.
Another object of the present invention is to provide the amido end-blocking non-ionic water-based isocyanate of described preparation method's preparation.
A further object of the present invention is to provide the application of described amido end-blocking non-ionic water-based isocyanate.
Purpose of the present invention is achieved through the following technical solutions: a kind of preparation method of amido end-blocking non-ionic water-based isocyanate may further comprise the steps:
(1) the non-ionic hydrophilic monomer mixed with polyisocyanates in 1: 1.5 in molar ratio～1: 7, added organic solvent and catalyzer and reacted 1～5 hour down at 40～100 ℃, made non-ionic water-based isocyanate; The consumption of described organic solvent gets final product for non-ionic hydrophilic monomer and polyisocyanates are dissolved fully; Described catalyst consumption be the reaction system that constitutes of non-ionic hydrophilic monomer, polyisocyanates and organic solvent total mass 0.01～0.2%;
(2) then, under 30～80 ℃, in non-ionic water-based isocyanate, add the polyfunctional group substance reaction 3～7 hours that contains reactive hydrogen; Containing the polyfunctional group material of reactive hydrogen and the mol ratio of polyisocyanates is 1: 5～1: 10; Add acid amides then to unreacted isocyanate groups end-blocking, reacted 1～8 hour down at 50～100 ℃, cool to room temperature, adding water under the vigorous stirring disperses, and obtains amido end-blocking non-ionic water-based isocyanate; The active hydrogen group of acid amides and unreacted isocyanate group mol ratio are 1.1: 1～1.5: 1;
The described polyfunctional group material that contains reactive hydrogen is meant and contains at least three materials that contain active hydrogen functional groups in the structure;
At least a in the described preferred TriMethylolPropane(TMP) of polyfunctional group material, tetramethylolmethane, trimethylolpropane tris glycidyl ester, trimethylolpropane trimethacrylate, Viscoat 295 or the trihydroxymethyl propane that contains reactive hydrogen;
The preferred tolylene diisocyanate of described polyisocyanates, 1, the 6-hexamethylene diisocyanate, isophorone diisocyanate, ditan 4, the 4-vulcabond, 1, the 4-tetramethylene diisocyanate, 1,12-ten dimethylene diisocyanates, hexanaphthene-1,3 vulcabond, hexanaphthene-1, the 4-vulcabond, the double-hexyl methane vulcabond, 1, hexamethylene-diisocyanate, xylylene diisocyanate, naphthalene-1, the 5-vulcabond, Methylcyclohexyl diisocyanate, at least a in tetramethylxylylene diisocyanate or the poly methylene poly phenyl poly isocyanate;
At least a in the preferred polyoxyethylene glycol of described non-ionic hydrophilic monomer, poly glycol monomethyl ether, polyoxyethylene glycol monobutyl ether, polypropylene glycol, polyoxyethylene glycol propylene glycol copolymers, polypropylene glycol or the polypropylene glycol monobutyl ether;
Described organic solvent is non-proton type organic solvent;
At least a in the preferred acetone of described non-proton type organic solvent, methylethylketone, N-Methyl pyrrolidone, dioxane, N-ethyl acetate, dimethyl formamide or the tetrahydrofuran (THF);
Described catalyst pack contains organic tin catalyzer, tertiary amine catalyst and organo-metallic class catalyzer;
At least a in the preferred triethylenediamine of described catalyzer, dibutyl tin dilaurate, stannous octoate, lead octoate 36, cobalt octoate, iron octoate, zinc naphthenate or metatitanic acid four isobutyl esters.
At least a in the preferred hexanolactam of described acid amides, Acetanilide, N-methylacetamide or the ring butyryl imines;
Described amido end-blocking non-ionic water-based isocyanate is as linking agent.
Described amido end-blocking non-ionic water-based isocyanate itself or as required through suitably being applied to a lot of fields after the modification comprises: (1) water-borne coatings: powder coating, coil coating, electrophoretic paint, automobile paint vehicle etc.; (2) the bonding processing of various base materials is used for the modification to plastics films such as PE, PET, PP, PVC, ABS or sheet material, fiber etc.; (3) be applied to the modification of biodegradable material, to the improvement of degradable macromolecule mechanical properties such as PLA, PCL, PHB; (4) coating-forming agent: fabric coating, leather coating, fibre finish, decoration coating etc.; (5) caking agent of natural plant fibre etc.
The present invention has following advantage and effect with respect to prior art:
(1) the present invention can adopt industrial raw material to be prepared, and cheap and easy to get as the technical grade polyisocyanates, toxicity is low, reaction conditions gentleness (reaction below 100 ℃), and technology is simple etc.
(2) the prepared amido end-blocking non-ionic water-based isocyanate of the present invention is stablized: being placed on 100 ℃ of 24h does not have the gel caking to occur, and proves that its heat-resistant stability is good; Be placed in-4～-8 ℃ the refrigerator-freezer freezingly, take out at room temperature and melt, repeats four times, do not have and precipitate, prove that its freeze-thaw stability is good.Long (can reach 6 months), excellent property of product usage period of the present invention, deblocking temperature moderate (being 105～170 ℃), overcome of the prior art for isocyanic ester with the active isocyano of differential responses, discharge the higher isocyano group of activity in the time of can not guaranteeing the resin reaction of linking agent and hydroxyl, level of response is difficult to control, the preparation poor repeatability, poor stability, defectives such as easy pollution.
(3) the present invention adopts acid amides as end-capping reagent, and environmental protection has adapted to the requirement of coatings chemistry to " greenization " development, thereby made it that more wide application prospect arranged.
Description of drawings
Fig. 1 is the DSC spectrogram of the amido end-blocking non-ionic water-based isocyanate of embodiment 1 preparation.
Fig. 2 is the infrared spectrum of the amido end-blocking non-ionic water-based isocyanate of embodiment 1 preparation.
Embodiment
The present invention is described in further detail below in conjunction with embodiment and accompanying drawing, but embodiments of the present invention are not limited thereto.
Embodiment 1
(1) with 0.1mol TDI (2, the 4-tolylene diisocyanate), 0.067mol PEG1000 (cetomacrogol 1000), agitator is equipped with in 15ml acetone and 3 stannous octoates addings, in the four-hole round-bottomed flask of the 250ml of airway, condenser, react 5h down at 40 ℃, make non-ionic water-based isocyanate;
(2) then, cool to 30 ℃, add 0.01mol TMP (TriMethylolPropane(TMP)), in 30 ℃ of reaction 7h; Add the 0.05mol hexanolactam then, reacted 8 hours down at 50 ℃, the Di-n-Butyl Amine method detects nothing-NCO group residue, cool to room temperature, add water under the vigorous stirring and disperse, obtain amido end-blocking non-ionic water-based isocyanate, be light yellow transparent thickness liquid state.
Performance to the amido end-blocking non-ionic water-based isocyanate for preparing is tested:
Package stability is analyzed: the package stability of having simulated closure water-based isocyanate linking agent by the centrifugation accelerates sedimentation experiment, acid amides is sealed water-based isocyanate to be placed in the whizzer behind the rotating speed centrifugal settling 15min with 3000r/min, precipitation does not produce, and proves that the acid amides sealing water-based isocyanate of preparation has 6 months shelf stable for periods;
Freeze-thaw stability: amido end-blocking non-ionic water-based isocyanate is placed on be refrigerated in-4～-8 ℃ the refrigerator-freezer and condenses, take out at room temperature again and melt, repeat four times, do not have precipitation and produce, proved that the amido end-blocking non-ionic water-based isocyanate freeze-thaw stability for preparing is good;
Heat-resistant stability: take out after amido end-blocking non-ionic water-based isocyanate placed 100 ℃ of vacuum drying oven 24h, outward appearance and former state are basic identical, do not have the gel precipitation phenomenon, prove that heat-resistant stability is good;
It is 120 ℃ that the DSC test obtains beginning the deblocking temperature, and the temperature when deblocking speed is maximum is 164.6 ℃, as shown in Figure 1.
Carry out infrared test, as can be seen from Figure 2 2260～2270cm
-1-disappearance of NCO group vibration bands of a spectrum, illustrate that end-blocking is complete.
Embodiment 2
(1) with embodiment 1 step (1), difference is to make non-ionic water-based isocyanate in 100 ℃ of reaction 1h;
(2) then, cool to 80 ℃, add 0.01mol TMP (TriMethylolPropane(TMP)), in 80 ℃ of reaction 3h; Add the 0.05mol hexanolactam then, reacted 1 hour down at 100 ℃, the Di-n-Butyl Amine method detects nothing-NCO group residue, cool to room temperature, add water under the vigorous stirring and disperse, obtain amido end-blocking non-ionic water-based isocyanate, be light yellow transparent thickness liquid state.
Performance to the amido end-blocking non-ionic water-based isocyanate for preparing is tested: testing method is with embodiment 1, the amido end-blocking non-ionic water-based isocyanate that obtains has 6 months shelf stable for periods, freeze-thaw stability is good, heat-resistant stability is good, and the temperature when deblocking speed is maximum is 164.6 ℃
Embodiment 3
(1) with embodiment 1 step (1), difference is to make non-ionic water-based isocyanate in 60 ℃ of reaction 3h;
(2) then, cool to 50 ℃, add 0.01mol TMP (TriMethylolPropane(TMP)), in 50 ℃ of reaction 5h; Be warming up to 70 ℃ then, add the 0.05mol hexanolactam, reacted 4 hours down at 70 ℃, the Di-n-Butyl Amine method detects nothing-NCO group residue, and cool to room temperature adds water under the vigorous stirring and disperses, obtain amido end-blocking non-ionic water-based isocyanate, be light yellow transparent thickness liquid state.
Performance to the amido end-blocking non-ionic water-based isocyanate for preparing is tested: testing method is with embodiment 1, the amido end-blocking non-ionic water-based isocyanate that obtains has 6 months shelf stable for periods, freeze-thaw stability is good, heat-resistant stability is good, and the temperature when deblocking speed is maximum is 164.6 ℃.
Embodiment 4
(1) with 0.1mol TDI (2, the 4-tolylene diisocyanate), 0.0143mol PPG1000 (polypropylene glycol 1000), agitator is equipped with in 10ml N-Methyl pyrrolidone and 3 dibutyl tin dilaurates addings, in the four-hole round-bottomed flask of the 250ml of airway, condenser, react 3h down at 60 ℃, make non-ionic water-based isocyanate;
(2) then, cool to 50 ℃, add 0.02mol TMP (TriMethylolPropane(TMP)), in 50 ℃ of reaction 5h; Be warming up to 70 ℃ then, add 0.12mol N-methylacetamide, reacted 4 hours down at 70 ℃, the Di-n-Butyl Amine method detects nothing-NCO group residue, and cool to room temperature adds water under the vigorous stirring and disperses, obtain amido end-blocking non-ionic water-based isocyanate, be faint yellow transparent thickness liquid state.
Performance to the amido end-blocking non-ionic water-based isocyanate for preparing is tested: testing method is with embodiment 1, the amido end-blocking non-ionic water-based isocyanate that obtains has 6 months shelf stable for periods, freeze-thaw stability is good, and heat-resistant stability is good, and the deblocking temperature is 135 ℃.
Embodiment 5
(1) with embodiment 4 steps (1), difference is to make non-ionic water-based isocyanate in 40 ℃ of reaction 5h;
(2) then, cool to 30 ℃, add 0.02mol TMP (TriMethylolPropane(TMP)), in 30 ℃ of reaction 7h; Be warming up to 50 ℃ then, add 0.16mol N-methylacetamide, reacted 8 hours down at 50 ℃, the Di-n-Butyl Amine method detects nothing-NCO group residue, and cool to room temperature adds water under the vigorous stirring and disperses, obtain amido end-blocking non-ionic water-based isocyanate, be faint yellow transparent thickness liquid state.
Performance to the amido end-blocking non-ionic water-based isocyanate for preparing is tested: testing method is with embodiment 1, the amido end-blocking non-ionic water-based isocyanate that obtains has 6 months shelf stable for periods, freeze-thaw stability is good, and heat-resistant stability is good, and the deblocking temperature is 135 ℃.
Embodiment 6
(1) with 0.1mol TDI (2, the 4-tolylene diisocyanate), 0.0143mol PEG1000 (cetomacrogol 1000), agitator is equipped with in 10ml N-Methyl pyrrolidone and 3 triethylenediamines addings, in the four-hole round-bottomed flask of the 250ml of airway, condenser, react 1h down at 100 ℃, make non-ionic water-based isocyanate;
(2) then, cool to 80 ℃, add 0.02mol TMP (TriMethylolPropane(TMP)), in 80 ℃ of reaction 3h; Be cooled to 50 ℃ then, reacted 1 hour down at 100 ℃ behind the adding 0.12mol Acetanilide, the Di-n-Butyl Amine method detects nothing-NCO group residue, cool to room temperature, add water under the vigorous stirring and disperse, obtain amido end-blocking non-ionic water-based isocyanate, be faint yellow transparent thickness liquid state.
Performance to the amido end-blocking non-ionic water-based isocyanate for preparing is tested: testing method is with embodiment 1, the amido end-blocking non-ionic water-based isocyanate that obtains has 6 months shelf stable for periods, freeze-thaw stability is good, and heat-resistant stability is good, and the deblocking temperature is 105 ℃.
Embodiment 7
(1) with 0.1mol IPDI (isophorone diisocyanate), 0.05mol PEG1000 (cetomacrogol 1000), agitator is equipped with in 15ml methylethylketone and 3 dibutyl tin dilaurates addings, in the four-hole round-bottomed flask of the 250ml of airway, condenser, react 3h down at 60 ℃, make non-ionic water-based isocyanate;
(2) then, cool to 50 ℃, add 0.0125mol TMP (TriMethylolPropane(TMP)), in 50 ℃ of reaction 5h; Be warming up to 70 ℃ then, add the 0.08mol hexanolactam, reacted 4 hours down at 70 ℃, the Di-n-Butyl Amine method detects nothing-NCO group residue, and cool to room temperature adds water under the vigorous stirring and disperses, obtain amido end-blocking non-ionic water-based isocyanate, be water white transparency thickness liquid state.
Performance to the amido end-blocking non-ionic water-based isocyanate for preparing is tested: testing method is with embodiment 1, the amido end-blocking non-ionic water-based isocyanate that obtains has 6 months shelf stable for periods, freeze-thaw stability is good, heat-resistant stability is good, and temperature was 170 ℃ when deblocking speed was maximum.
Embodiment 8
(1) makes non-ionic water-based isocyanate with embodiment 5 steps (1);
(2) then, cool to 30 ℃, add 0.02mol TMP (TriMethylolPropane(TMP)), in 30 ℃ of reaction 7h; Be warming up to 70 ℃ then, add 0.12mol N-methylacetamide, reacted 4 hours down at 70 ℃, the Di-n-Butyl Amine method detects nothing-NCO group residue, and cool to room temperature adds water under the vigorous stirring and disperses, obtain amido end-blocking non-ionic water-based isocyanate, be faint yellow transparent thickness liquid state.
Performance to the amido end-blocking non-ionic water-based isocyanate for preparing is tested: testing method is with embodiment 1, the amido end-blocking non-ionic water-based isocyanate that obtains has 6 months shelf stable for periods, freeze-thaw stability is good, and heat-resistant stability is good, and the deblocking temperature is 145 ℃.
Embodiment 9
(1) with 0.1mol IPDI (isophorone diisocyanate), 0.05mol PEG1000 (cetomacrogol 1000), agitator is equipped with in 15ml methylethylketone and 3 dibutyl tin dilaurates addings, in the four-hole round-bottomed flask of the 250ml of airway, condenser, react 3h down at 60 ℃, make non-ionic water-based isocyanate;
(2) then, cool to 50 ℃, add 0.0125mol TMP (TriMethylolPropane(TMP)), in 50 ℃ of reaction 5h; Be warming up to 70 ℃ then, add the 0.08mol Acetanilide, reacted 4 hours down at 70 ℃, the Di-n-Butyl Amine method detects nothing-NCO group residue, and cool to room temperature adds water under the vigorous stirring and disperses, obtain amido end-blocking non-ionic water-based isocyanate, be water white transparency thickness liquid state.
Performance to the amido end-blocking non-ionic water-based isocyanate for preparing is tested: testing method is with embodiment 1, the amido end-blocking non-ionic water-based isocyanate that obtains has 6 months shelf stable for periods, freeze-thaw stability is good, and heat-resistant stability is good, and the deblocking temperature is 115 ℃.
Embodiment 10
(1) with embodiment 4 steps (1), difference only is that polyisocyanates adopts 0.1mol HDI (hexamethylene diisocyanate), makes non-ionic water-based isocyanate;
(2) with embodiment 4 steps (2), obtain amides end-blocking non-ionic water-based isocyanate linking agent, be faint yellow transparent thickness liquid state.
Performance to the amido end-blocking non-ionic water-based isocyanate for preparing is tested: testing method is with embodiment 1, the amido end-blocking non-ionic water-based isocyanate that obtains has 6 months shelf stable for periods, freeze-thaw stability is good, and heat-resistant stability is good, and the deblocking temperature is 150 ℃.
Embodiment 11
(1) with 0.1mol XDI (xylylene diisocyanate), 0.0143mol PEG1000 (poly-hexylene glycol 1000), the 10ml N-Methyl pyrrolidone, agitator is equipped with in 3 dibutyl tin dilaurates addings, in the four-hole round-bottomed flask of the 250ml of airway, condenser, react 5h down at 40 ℃, make non-ionic water-based isocyanate;
(2) then, cool to 30 ℃, add 0.02mol TMP (TriMethylolPropane(TMP)), in 30 ℃ of reaction 7h; Be warming up to 50 ℃ then, add 0.16mol N-methylacetamide, reacted 8 hours down at 50 ℃, the Di-n-Butyl Amine method detects nothing-NCO group residue, and cool to room temperature adds water under the vigorous stirring and disperses, obtain amido end-blocking non-ionic water-based isocyanate, be faint yellow transparent thickness liquid state.
Performance to the amido end-blocking non-ionic water-based isocyanate for preparing is tested: testing method is with embodiment 1, the amido end-blocking non-ionic water-based isocyanate that obtains has 6 months shelf stable for periods, freeze-thaw stability is good, and heat-resistant stability is good, and the deblocking temperature is 165 ℃.
Embodiment 12
(1) with 0.1mol HMDI (dicyclohexyl methane diisocyanate), 0.0143mol PEG1000 (cetomacrogol 1000), the 10ml N-Methyl pyrrolidone, agitator is equipped with in 3 triethylenediamines addings, in the four-hole round-bottomed flask of the 250ml of airway, condenser, react 1h down at 100 ℃, make non-ionic water-based isocyanate;
(2) then, cool to 80 ℃, add 0.02mol TMP (TriMethylolPropane(TMP)), in 80 ℃ of reaction 3h; Be cooled to 50 ℃ then, add the 0.12mol Acetanilide, be warming up to 100 ℃ of reactions 1 hour again, the Di-n-Butyl Amine method detects nothing-NCO group residue, and cool to room temperature adds water under the vigorous stirring and disperses, obtain amido end-blocking non-ionic water-based isocyanate, be water white transparency thickness liquid state.
Performance to the amido end-blocking non-ionic water-based isocyanate for preparing is tested: testing method is with embodiment 1, the amido end-blocking non-ionic water-based isocyanate that obtains has 6 months shelf stable for periods, freeze-thaw stability is good, and heat-resistant stability is good, and the deblocking temperature is 120 ℃.
Embodiment 13
(1) with 0.1mol NDI (naphthalene-1, the 5-vulcabond), 0.05mol PEG1000 (cetomacrogol 1000), the 15mL methylethylketone, agitator is equipped with in 3 dibutyl tin dilaurates addings, in the four-hole round-bottomed flask of the 250ml of airway, condenser, react 3h down, make non-ionic water-based isocyanate at 60 ℃;
(2) then, cool to 50 ℃, add 0.0125mol TMP (TriMethylolPropane(TMP)), in 50 ℃ of reaction 5h; Be warming up to 70 ℃ then, add the 0.08mol hexanolactam, in 70 ℃ of reactions 4 hours, the Di-n-Butyl Amine method detects nothing-NCO group residue, and cool to room temperature adds water under the vigorous stirring and disperses, obtain amido end-blocking non-ionic water-based isocyanate, be light yellow transparent thickness liquid state.
Performance to the amido end-blocking non-ionic water-based isocyanate for preparing is tested: testing method is with embodiment 1, the amido end-blocking non-ionic water-based isocyanate that obtains has 6 months shelf stable for periods, freeze-thaw stability is good, and heat-resistant stability is good, and the deblocking temperature is 160 ℃.
Embodiment 14
(1) with 0.1mol PAPI (poly methylene poly phenyl poly isocyanate), 0.067mol PEG1000 (cetomacrogol 1000), 15mL acetone, agitator is equipped with in 3 stannous octoates addings, in the four-hole round-bottomed flask of the 250ml of airway, condenser, react 3h down at 60 ℃, make non-ionic water-based isocyanate;
(2) then, cool to 50 ℃, add 0.01mol TMP (TriMethylolPropane(TMP)), in 50 ℃ of reaction 5h; Be warming up to 70 ℃ then, add the 0.12mol hexanolactam, in 70 ℃ of reactions 4 hours, the Di-n-Butyl Amine method detects nothing-NCO group residue, and cool to room temperature adds water under the vigorous stirring and disperses, obtain amido end-blocking non-ionic water-based isocyanate, be light yellow transparent thickness liquid state.
Performance to the amido end-blocking non-ionic water-based isocyanate for preparing is tested: testing method is with embodiment 1, the amido end-blocking non-ionic water-based isocyanate that obtains has 6 months shelf stable for periods, freeze-thaw stability is good, and heat-resistant stability is good, and the deblocking temperature is 166 ℃.
The foregoing description is a preferred implementation of the present invention; but embodiments of the present invention are not restricted to the described embodiments; other any do not deviate from change, the modification done under spirit of the present invention and the principle, substitutes, combination, simplify; all should be the substitute mode of equivalence, be included within protection scope of the present invention.
Claims (9)
1. the preparation method of an amido end-blocking non-ionic water-based isocyanate may further comprise the steps:
(1) the non-ionic hydrophilic monomer mixed with polyisocyanates in 1: 1.5 in molar ratio～1: 7, added organic solvent and catalyzer and reacted 1～5 hour down at 40～100 ℃, made non-ionic water-based isocyanate; Described catalyst consumption be the reaction system that constitutes of non-ionic hydrophilic monomer, polyisocyanates and organic solvent total mass 0.01～0.2%;
(2) then, under 30～80 ℃, in non-ionic water-based isocyanate, add the polyfunctional group substance reaction 3～7 hours that contains reactive hydrogen; Containing the polyfunctional group material of reactive hydrogen and the mol ratio of polyisocyanates is 1: 5～1: 10; Add acid amides then to unreacted isocyanate groups end-blocking, reacted 1～8 hour down at 50～100 ℃, cool to room temperature, adding water under the vigorous stirring disperses, and obtains amido end-blocking non-ionic water-based isocyanate; The active hydrogen group of acid amides and unreacted isocyanate group mol ratio are 1.1: 1～1.5: 1;
The described polyfunctional group material that contains reactive hydrogen is meant and contains at least three materials that contain active hydrogen functional groups in the structure;
Described non-ionic hydrophilic monomer is polyoxyethylene glycol or polypropylene glycol.
2. according to the preparation method of the described amido end-blocking non-ionic water-based isocyanate of claim 1, it is characterized in that: described polyisocyanates is a tolylene diisocyanate, 1, the 6-hexamethylene diisocyanate, isophorone diisocyanate, 1, the 4-tetramethylene diisocyanate, 1,12-ten dimethylene diisocyanates, hexanaphthene-1,3 vulcabond, hexanaphthene-1, the 4-vulcabond, the double-hexyl methane vulcabond, 1, hexamethylene-diisocyanate, xylylene diisocyanate, naphthalene-1, the 5-vulcabond, Methylcyclohexyl diisocyanate, at least a in tetramethylxylylene diisocyanate or the poly methylene poly phenyl poly isocyanate.
3. according to the preparation method of the described amido end-blocking non-ionic water-based isocyanate of claim 1, it is characterized in that: described organic solvent is non-proton type organic solvent; Described catalyzer is at least a in tertiary amine catalyst or the organo-metallic class catalyzer.
4. according to the preparation method of the described amido end-blocking non-ionic water-based isocyanate of claim 3, it is characterized in that: described non-proton type organic solvent is at least a in acetone, methylethylketone, N-Methyl pyrrolidone, dioxane, dimethyl formamide or the tetrahydrofuran (THF); Described catalyzer is at least a in triethylenediamine, dibutyl tin dilaurate, stannous octoate, lead octoate 36, cobalt octoate, iron octoate, zinc naphthenate or metatitanic acid four isobutyl esters.
5. according to the preparation method of the described amido end-blocking non-ionic water-based isocyanate of claim 1, it is characterized in that: the described polyfunctional group material that contains reactive hydrogen is at least a in TriMethylolPropane(TMP) or the tetramethylolmethane.
6. according to the preparation method of the described amido end-blocking non-ionic water-based isocyanate of claim 1, it is characterized in that: described acid amides is at least a in hexanolactam, Acetanilide, N-methylacetamide or the ring butyryl imines.
7. the amido end-blocking non-ionic water-based isocyanate of each described preparation method preparation of claim 1～6.
8. the described amido end-blocking non-ionic water-based isocyanate of claim 7 is applied to do linking agent.
9. the application of described amido end-blocking non-ionic water-based isocyanate according to Claim 8 is characterized in that, described amido end-blocking non-ionic water-based isocyanate is used for following field as linking agent: (1) water-borne coatings; (2) the bonding processing of various base materials; (3) be applied to the modification of biodegradable material; (4) coating-forming agent; (5) caking agent of natural plant fibre.
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