CN116178668A - Naphthalene diisocyanate composition and preparation method and application thereof - Google Patents

Abstract

本发明提供的萘二异氰酸酯组合物具备优异的热稳定性，制备得到的弹性体具有优异的机械性能。The present invention relates to a kind of naphthalene diisocyanate composition and its preparation method and application, described naphthalene diisocyanate composition comprises the compound shown in the formula (1) of naphthalene diisocyanate and 5-6000ppm,

The naphthalene diisocyanate composition provided by the invention has excellent thermal stability, and the prepared elastomer has excellent mechanical properties.

Description

A naphthalene diisocyanate composition and its preparation method and application

Technical Field

The invention relates to the technical field of isocyanates, and in particular to a naphthalene diisocyanate composition and a preparation method and application thereof.

Background Art

Naphthalene diisocyanate is an aromatic diisocyanate that has long been used as a raw material for polyurethane in various industrial products, especially in high-performance elastomer materials. Naphthalene diisocyanate can be obtained by reacting naphthalene diamine with phosgene (phosgene).

Naphthalene diisocyanate has a high melting point and is in solid form at room temperature. To facilitate its use and transportation, it is often heated to a molten state. Due to the characteristics of the isocyanate group, side reactions such as polymerization and hydrolysis often occur, and high temperature will accelerate the side reactions, thus affecting the quality of the product.

Therefore, the art is in urgent need of providing a naphthalene diisocyanate raw material with thermal stability and good mechanical properties.

Summary of the invention

In view of the shortcomings of the prior art, one of the purposes of the present invention is to provide a naphthalene diisocyanate composition having excellent thermal stability, and the prepared polyurethane elastomer has excellent mechanical properties.

To achieve this object, the present invention adopts the following technical solutions:

The present invention provides a naphthalene diisocyanate composition, which comprises naphthalene diisocyanate and 5-6000ppm (e.g., 6ppm, 10ppm, 12ppm, 15ppm, 20ppm, 40ppm, 50ppm, 60ppm, 100ppm, 150ppm, 200ppm, 210ppm, 250ppm, 300ppm, 320ppm, 350ppm, 400ppm, 450ppm, 500ppm, 1000ppm, 1500ppm, 2000ppm, 2500ppm, 3000ppm, 3500ppm, 4000ppm, 4500ppm, 5000ppm, 5500ppm, 5900ppm, etc.) of a compound represented by formula (1);

The researchers of the present invention have found that when the naphthalene diisocyanate composition contains 5-6000ppm of the compound of formula (1), it has excellent thermal stability and the prepared elastomer has excellent mechanical properties. When the content is less than 5ppm or greater than 6000ppm, the thermal stability will deteriorate.

The naphthalene diisocyanate composition of the present invention is a substantially single compound (i.e., naphthalene diisocyanate) containing 95 wt.% or more of naphthalene diisocyanate as a main component, but is defined as a naphthalene diisocyanate composition because it contains the compound represented by the chemical formula (1) as a minor component.

In the present invention, a naphthalene diisocyanate composition is referred to as an NDI composition, naphthalene diisocyanate is referred to as NDI, and the compound represented by the chemical formula (1) is referred to as NI.

Preferably, the naphthalene diisocyanate composition further comprises a bromine-containing compound;

Calculated by the mass of bromine element, the content of the bromine-containing compound is 0.2-60ppm, for example, 0.5ppm, 1ppm, 2ppm, 3ppm, 4ppm, 5ppm, 6ppm, 7ppm, 8ppm, 9ppm, 10ppm, 11ppm, 12ppm, 13ppm, 14ppm, 15ppm, 16ppm, 17ppm, 18ppm, 19ppm, 20ppm, 21ppm, 22ppm, 23ppm, 24ppm, 25ppm, 26ppm, 27ppm, 28ppm, 29ppm, 30ppm, 31ppm, 32ppm, 33ppm, 34ppm, 35ppm, 36ppm, 37ppm, 38ppm, 39ppm, 40ppm, 41ppm, 42ppm, 43ppm, 44ppm, 45ppm, 46ppm, 47ppm, 48ppm, 49ppm, 57ppm and the like. If the bromine content is too high, the NDI activity will be low, affecting the prepolymerization reaction. If the bromine content is too low, the activity will be too high, the prepared prepolymer will be uneven, and the reaction process will be highly exothermic, posing a safety risk.

In the present invention, the contents of the compound represented by formula (1) and the bromine-containing compound are based on the total mass of the composition.

Preferably, the naphthalene diisocyanate includes any one or a combination of at least two of 1,2-naphthalene diisocyanate, 1,3-naphthalene diisocyanate, 1,4-naphthalene diisocyanate, 1,5-naphthalene diisocyanate, and 1,8-naphthalene diisocyanate, preferably 1,5-naphthalene diisocyanate and/or 1,8-naphthalene diisocyanate, more preferably 1,5-naphthalene diisocyanate;

Preferably, the compound represented by formula (1) comprises any one or a combination of at least two of the following compounds:

In the present invention, NI is generated as a by-product in the production of NDI described below, and of course, it can be artificially added to obtain a desired content.

In the present invention, the content ratio of NI can be measured by gas chromatography analysis.

The second object of the present invention is to provide a method for preparing the naphthalene diisocyanate composition, the method comprising:

(1) isocyanate step: isocyanate-forming step: isolating naphthalenediamine or naphthalenediamine hydrochloride with phosgene in the presence of a reaction solvent to obtain a reaction product containing naphthalene diisocyanate and a compound represented by formula (1);

(2) Solvent separation and purification step: removing the solvent from the reaction product obtained in step (1), refining the solvent after removal to obtain a recycled solvent, and then returning it to the reaction system of step (1);

(3) Separation step: separating and purifying the desolventizing reaction product obtained in step (2) to obtain the naphthalene diisocyanate composition.

The isocyanate formation process in step (1) can be referred to as a phosgenation process, and the isocyanate formation reaction is a phosgenation reaction.

Specific examples of the phosgenation method include a method in which naphthalenediamine is directly reacted with phosgene (also referred to as a cold and hot two-stage phosgenation method), and a method in which a hydrochloride obtained by reacting naphthalenediamine with hydrochloric acid (hydrogen chloride) is reacted with phosgene in a reaction solvent (also referred to as an amine hydrochloride phosgenation method). Preferably, an amine phosgenation method is mentioned.

Preferably, the naphthalenediamine contains any one or a combination of the following mononaphthylamines:

Preferably, the content of mononaphthylamine in the naphthalene diamine is 10-10000ppm, for example 12ppm, 20ppm, 30ppm, 40ppm, 50ppm, 60ppm, 70ppm, 80ppm, 90ppm, 100ppm, 110ppm, 120ppm, 130ppm, 140ppm, 150ppm, 160ppm, 170ppm, 180ppm, 190ppm, 200ppm, 210ppm, 220ppm, 230ppm, 240ppm, 250ppm, 260ppm, 270ppm, 280ppm, 290ppm, 300ppm, 310ppm, 320ppm, 330ppm, 340ppm 0ppm, 350ppm, 360ppm, 370ppm, 380ppm, 390ppm, 400ppm, 410ppm, 420ppm, 430ppm, 440ppm, 450ppm, 460ppm, 470ppm, 480ppm, 490ppm, 500ppm, 1000ppm, 1500ppm, 2000ppm, 2500ppm, 3000ppm, 3500ppm, 4000ppm, 4500ppm, 5000ppm, 5500ppm, 6000ppm, 6700ppm, 7000ppm, 7500ppm, 7990ppm, 8590ppm, 9990ppm, etc.

In addition, as required, the ratio of mononaphthylamine can be controlled to the above range by purifying the raw material naphthalenediamine, and the purification method is not particularly limited, and can be implemented by industrial separation technology such as distillation, crystallization, etc. It should be noted that the content ratio of mononaphthylamine substituents in the naphthalenediamine composition can also be adjusted by adding mononaphthylamine to naphthalenediamine.

Preferably, a crystallization process is used to purify naphthalenediamine, and the crystallization process includes: adding naphthalenediamine to a crystallizer, melting the naphthalenediamine by heating, lowering the temperature of the crystallizer to cool and crystallize to obtain a crude naphthalenediamine product, and raising the temperature of the crystallizer to sweat the crude naphthalenediamine product to obtain a naphthalenediamine product.

Preferably, the crystallizer comprises a kettle crystallizer or a tubular crystallizer.

Preferably, the cooling rate of the crystallizer is 2°C/min or less, for example, 0.01°C/min, 0.02°C/min, 0.03°C/min, 0.05°C/min, 0.09°C/min, 0.10°C/min, 0.20°C/min, 0.30°C/min, 0.50°C/min, 0.70°C/min, 0.90°C/min, 1.00°C/min, 1.30°C/min, 1.50°C/min, 1.70°C/min, 1.90°C/min, etc., preferably 1°C/min or less.

Preferably, the cooling rate of the crystallizer is above 0.0001°C/min, preferably above 0.01°C/min.

Preferably, the final crystallization temperature of the crystallizer is 90-180°C, such as 90°C, 92°C, 95°C, 97°C, 99°C, 100°C, 103°C, 107°C, 112°C, 117°C, 120°C, 121°C, 126°C, 127°C, 129°C, 130°C, 134°C, 140°C, 150°C, 160°C, 170°C, 175°C, etc., preferably 130-170°C.

Preferably, the heating rate of the crystallizer is 2°C/min or less, for example, 0.01°C/min, 0.02°C/min, 0.03°C/min, 0.05°C/min, 0.09°C/min, 0.10°C/min, 0.20°C/min, 0.30°C/min, 0.50°C/min, 0.70°C/min, 0.90°C/min, 1.00°C/min, 1.30°C/min, 1.50°C/min, 1.70°C/min, 1.90°C/min, etc., preferably 1°C/min or less.

Preferably, the heating rate of the crystallizer is above 0.0001°C/min, preferably above 0.01°C/min.

Preferably, the final sweating temperature of the crystallizer is 90-190°C, such as 90°C, 92°C, 95°C, 97°C, 99°C, 100°C, 103°C, 107°C, 112°C, 117°C, 120°C, 121°C, 126°C, 127°C, 129°C, 130°C, 134°C, 140°C, 144°C, 150°C, 160°C, 170°C, 180°C, 185°C, etc., preferably 165-185°C.

Preferably, the phosgenation of amines is carried out in two stages: cold photolysis and thermal photolysis. The cold photolysis step comprises: mixing naphthalenediamine with phosgene in the presence of a reaction solvent, and performing a cold photolysis reaction to obtain a naphthalenediamine cold photolysis liquid. The cold photolysis step actually obtains a slurry containing naphthalenediamine hydrochloride, naphthalenediamine acid chloride and a very small amount of naphthalene diisocyanate, and the slurry is directly used in the isocyanate step.

Preferably, the naphthalenediamine includes any one of 1,2-naphthalenediamine, 1,3-naphthalenediamine, 1,4-naphthalenediamine, 1,5-naphthalenediamine, and 1,8-naphthalenediamine, or a combination of at least two thereof.

Preferably, the cold light treatment step specifically comprises: introducing phosgene into a reaction solvent, then adding a reaction solvent amine solution containing naphthalenediamine, and then stirring and mixing the phosgene and the amine solution to perform a cold light treatment reaction to obtain the naphthalenediamine cold light treatment solution.

Preferably, the content of naphthalene diamine in the amine solution is 1.0 wt.% or more, for example, 4 wt.%, 5 wt.%, 6 wt.%, 7 wt.%, 8 wt.%, 9 wt.%, 10 wt.%, 11 wt.%, 12 wt.%, 13 wt.%, 14 wt.%, 15 wt.%, 16 wt.%, 17 wt.%, 18 wt.%, 19 wt.%, 20 wt.%, etc., preferably 3.0 wt.% or more.

Preferably, the content of naphthalenediamine in the amine solution is 50 wt.% or less, preferably 30 wt.% or less.

Preferably, the photochemical temperature in the cold photochemical process is above 0°C, for example, 1°C, 5°C, 10°C, 20°C, 30°C, 40°C, 50°C, 60°C, 70°C, 80°C, 90°C, 100°C, 110°C, 120°C, 130°C, etc., preferably above 10°C.

Preferably, the quenching temperature in the quenching step is 130° C. or less, preferably 80° C. or less, and more preferably 60° C. or less.

Preferably, the cold light treatment process is carried out under normal pressure or pressurized conditions.

Preferably, the pressure (gauge pressure) of the cold light treatment process is 0.01 MPaG or more, for example, 0.1 MPaG, 0.2 MPaG, 0.5 MPaG, 0.6 MPaG, 0.7 MPaG, 0.8 MPaG, 0.9 MPaG, etc., more preferably 0.02 MPaG or more.

Preferably, the pressure (gauge pressure) in the cold light treatment step is 1.0 MPaG or less, preferably 0.5 MPaG or less, and more preferably 0.4 MPaG or less.

Preferably, step (1) specifically comprises: introducing phosgene into naphthalene diamine to carry out a cold photochemical reaction; and continuing to introduce phosgene into the cold photochemical reaction solution to obtain a reaction product containing naphthalene diisocyanate and the compound represented by formula (1).

When the isocyanate reaction is carried out using a naphthalene diamine cold photochemical solution and phosgene, the target content of the compound of formula (1) can be obtained by optimizing the following parameters. It should be noted that the content ratio of NI in the naphthalene diisocyanate composition can also be adjusted by adding NI to the naphthalene diisocyanate composition.

Preferably, the molar amount of the phosgene is 4 times or more of the molar amount of the naphthalene diamine, for example, 5 times, 6 times, 7 times, 8 times, 9 times, 10 times, 12 times, 14 times, 16 times, 18 times, 20 times, 22 times, 24 times, 26 times, 28 times, 30 times, 32 times, 34 times, 36 times, 38 times, 40 times, 42 times, 44 times, 46 times, 48 times, etc., preferably 5 times or more, more preferably 6 times or more.

Preferably, the molar amount of the phosgene is 50 times or less, preferably 40 times or less, and more preferably 30 times or less of the molar amount of the naphthalene diamine.

Preferably, the reaction temperature in the isocyanate formation step is 80°C or higher, for example, 90°C, 100°C, 110°C, 120°C, 130°C, 140°C, 150°C, etc., preferably 100°C or higher.

Preferably, the reaction temperature in the isocyanate formation step is 180° C. or lower, preferably 170° C. or lower, and more preferably 160° C. or lower.

Preferably, the isocyanate reaction time is 1 h or longer, for example 2 h, 3 h, 4 h, 6 h, 8 h, 10 h, 12 h, 14 h, 16 h, 18 h, 20 h, 22 h, 24 h, etc., preferably 3 h or longer.

Preferably, the isocyanate reaction time is 25 hours or less, preferably 20 hours or less.

Preferably, the isocyanate reaction is carried out under normal pressure or under pressure.

Preferably, the pressure (gauge pressure) of the isocyanate reaction is 0 MPaG or more, for example, 0.0004 MPaG, 0.0008 MPaG, 0.001 MPaG, 0.002 MPaG, 0.006 MPaG, 0.01 MPaG, 0.02 MPaG, 0.03 MPaG, 0.05 MPaG, 0.1 MPaG, 0.2 MPaG, 0.3 MPaG, 0.4 MPaG, 0.5 MPaG, 0.6 MPaG, etc., preferably 0.0005 MPaG or more, more preferably 0.001 MPaG or more, further preferably 0.003 MPaG or more, especially preferably 0.01 MPaG or more, particularly preferably 0.02 MPaG or more, and most preferably 0.03 MPaG or more.

Preferably, the pressure (gauge pressure) of the isocyanate reaction is 0.6 MPaG or less, preferably 0.4 MPaG or less, and more preferably 0.2 MPaG or less.

Preferably, the isocyanate reaction process is a batch process or a continuous process, preferably a continuous process.

Preferably, the isocyanate process can be an intermittent or continuous process. The continuous process is that the slurry (naphthalene diamine cold reaction liquid) generated in the cold reaction tank is continuously transported from the cold reaction tank to a hot reaction tank different from the cold reaction tank, and the naphthalene diamine cold reaction liquid is reacted with phosgene in the hot reaction tank, and the reaction liquid (reaction material) is continuously taken out from the hot reaction tank. The present invention does not specifically limit the number of reactors in the continuous process, and illustratively, it can be two, three, four, five or more.

If necessary, the reaction product of the isocyanate formation step may be subjected to a degassing step, a solvent separation and a refining step, and the remaining phosgene and the gases such as hydrogen chloride produced as a by-product may be removed from the reaction product using a known degassing tower. In the solvent separation and refining step, the reaction solvent is distilled from the reaction solution using a known distillation tower. Most of the solvent is returned to the isocyanate formation step after being refined.

In the present invention, examples of the reaction solvent include aromatic hydrocarbons such as benzene, toluene, and xylene, aliphatic hydrocarbons such as octane and decane, alicyclic hydrocarbons such as cyclohexane, methylcyclohexane, and ethylcyclohexane, halogenated aromatic hydrocarbons such as chlorotoluene, chlorobenzene, dichlorobenzene, dibromobenzene, and trichlorobenzene, nitrogen-containing compounds such as nitrobenzene, N,N-dimethylformamide, N,N-dimethylacetamide, and N,N'-dimethylimidazolidinone, ethers such as dibutyl ether, ethylene glycol dimethyl ether, and ethylene glycol diethyl ether, ketones such as heptanone, diisobutyl ketone, methylisobutyl ketone, and methylethyl ketone, fatty acid esters such as ethyl acetate, butyl acetate, amyl acetate, and ethoxyethyl acetate, and aromatic carboxylic acid esters such as methyl salicylate, dimethyl phthalate, dibutyl phthalate, and methyl benzoate. The reaction solvent may be used alone or in combination of two or more. Among the reaction solvents, halogenated aromatic hydrocarbons are preferred, and chlorobenzene and dichlorobenzene are more preferred.

If necessary, the desolventized reaction product may be subjected to a detarring step. The tar component may be removed from the reaction solution using known detarring equipment such as a short-path evaporator. It should be noted that the reaction product from which the tar component has been removed by the detarring step is recorded as an intermediate product.

Furthermore, the intermediate product may be purified as necessary. The purification method is not particularly limited and can be carried out using industrial separation techniques such as distillation and crystallization.

Preferably, the distillation is carried out in a distillation column.

Preferably, the distillation tower comprises a plate distillation tower or a packed distillation tower.

In a preferred embodiment of the present invention, the ratio of NI can be adjusted to the above range by controlling the reaction conditions and separation conditions. It should be noted that the ratio of NI in the NDI composition can also be adjusted by adding NI to the NDI composition.

Preferably, the number of theoretical plates of the distillation tower is 2 or more, for example 4, 6, 8, 10, 14, 18, 22, 24, 26, 28, 30, 32, 34, 36, 38, 40, 42, 44, 46, 48, 50, 52, 54, 56, 58, etc., preferably 5 or more.

Preferably, the number of theoretical plates of the distillation tower is 60 or less, preferably 40 or less.

Preferably, the top pressure of the distillation tower is above 0.1 kPa, for example, 0.2 kPa, 0.4 kPa, 0.6 kPa, 0.8 kPa, 1 kPa, 1.5 kPa, 2 kPa, 2.5 kPa, 3 kPa, 3.5 kPa, etc., preferably above 0.15 kPa.

Preferably, the top pressure of the distillation tower is below 4 kPa, preferably below 2.5 kPa.

Preferably, the top reflux ratio of the distillation tower is greater than 0.01, for example, 0.05, 0.1, 0.5, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 14, 18, 22, 24, 26, 28, 30, 32, 34, 36, 38, 40, 42, 44, 46, 48, 50, 52, 54, 56, 58, etc., preferably greater than 0.1.

Preferably, the top reflux ratio of the distillation tower is 60 or less, preferably 40 or less.

In a preferred technical solution of the present invention, the method for producing the above-mentioned naphthalene diisocyanate composition can be implemented, for example, using the flow chart shown in Figure 1. As shown in Figure 1, it mainly includes a cold photochemical unit. In the isocyanate unit described later, a continuous thermal photochemical unit (performed in a thermal photochemical reactor) is implemented to adjust the production amount of naphthalene diisocyanate and NI by appropriately adjusting the ratio of the mononaphthylamine substituent in the above-mentioned raw materials, the supply ratio of phosgene, the reaction temperature, the reaction pressure and the average residence time, etc. A phosgene removal unit and a solvent removal unit are set after the photochemical reactor to remove phosgene and solvent from the reaction solution, and a heavy component removal unit is set after the solvent removal unit to perform a tar removal process on the reaction product of the solvent removal, and then enter the refining unit for rectification to obtain the final product. Moreover, in the rectification separation described later, the content ratio of NI in the naphthalene diisocyanate composition is adjusted by appropriately adjusting the above-mentioned tower top reflux ratio, etc.

Specifically, first, a reaction solvent is loaded into a cold photochemical reactor. Then, phosgene is continuously supplied to the bottom of the cold photochemical reactor through a phosgene supply line at the above-mentioned supply ratio. In addition, the above-mentioned amine solution in which naphthalenediamine is dissolved in the reaction solvent is continuously supplied to the top of the cold photochemical reactor through an amine supply line. Then, while the interior of the cold photochemical reactor is maintained at the above-mentioned cold photochemical temperature and cold photochemical pressure, phosgene and the amine solution are stirred and mixed by a stirring blade (cold photochemical process). Thus, a slurry containing naphthalenediamine hydrochloride, naphthalenediamine chloride and a small amount of naphthalene diisocyanate is manufactured.

Then, the slurry containing naphthalenediamine hydrochloride, naphthalenediamine chloride and a small amount of naphthalene diisocyanate is continuously transported to the top of the hot photochemical reactor through the cold photochemical liquid transport line. That is, while phosgene and amine solution are continuously supplied to the cold photochemical reactor, the slurry containing naphthalenediamine hydrochloride, naphthalenediamine chloride and a small amount of naphthalene diisocyanate is continuously taken out from the cold photochemical reactor and transported to the hot photochemical reactor.

Next, phosgene is continuously supplied to the top of the thermal photochemical reactor by inserting a pipe at the above supply ratio. Then, while the interior of the thermal photochemical reactor is maintained at the above reaction temperature and reaction pressure, the slurry and phosgene are stirred and mixed (the first step of isocyanate formation process). Thus, the naphthalenediamine cold photochemical liquid reacts with phosgene to produce naphthalene diisocyanate as the main component, and NI and bromine-containing compounds or intermediates thereof are produced as by-products.

Thus, the luminescence step and the isocyanate step are continuously performed.

Then, a reaction liquid containing naphthalene diisocyanate, NI and a bromine-containing compound or an intermediate thereof, and a reaction solvent is produced. It should be noted that the total residence time in the isocyanate formation step is within the above range.

Next, the photochemical reaction liquid is continuously transported to the middle part of the dephosgenating tower through the reaction material transport line. The dephosgenating tower separates the photochemical liquid into gas containing phosgene and hydrogen chloride, etc., and liquid degassing materials containing naphthalene diisocyanate, NI and bromine-containing compounds or their intermediates, and reaction solvent, etc. (degassing step).

Next, the deaerated material is continuously transported to the desolventizing tower through the deaerated material transport line. Then, the desolventizing tower is used to distill the reaction solvent from the deaerated material (solvent separation and purification step) to obtain a desolventized material containing naphthalene diisocyanate, NI and a bromine-containing compound or an intermediate thereof.

Next, the desolvated material is continuously transported to the upper part of the detarrifier through the desolvated material transport line. Then, the detarrifier removes the tar component from the desolvated material to obtain an intermediate material containing naphthalene diisocyanate, NI and bromine-containing compounds (detarring step).

Next, the intermediate material is continuously fed to the distillation column through the intermediate material feeding line. Then, under the conditions of the distillation process described above (tower bottom temperature, tower top temperature, tower top pressure, tower bottom reflux ratio, tower top reflux ratio and residence time), low boiling points are distilled off from the intermediate material, and the naphthalene diisocyanate composition is taken out from the lower middle part of the tower.

Thereby, a naphthalene diisocyanate composition containing naphthalene diisocyanate, NI and a bromine-containing compound can be continuously produced.

The third object of the present invention is to provide a modified composition of a naphthalene diisocyanate composition, wherein the modified composition is a modified composition obtained by modifying the naphthalene diisocyanate composition described in the first object, wherein the modified naphthalene diisocyanate in the modified composition contains any one or a combination of at least two of the following (a)-(e) groups: (a) isocyanurate group, (b) uretdione group, (c) biuret group, (d) carbamate group, (e) urea group, (f) iminooxadiazinedione group, (g) allophanate group, (h) uretonimine group or (i) carbodiimide group.

A person skilled in the art can modify the naphthalene diisocyanate composition by a known method as needed to obtain a naphthalene diisocyanate-modified composition, and the naphthalene diisocyanate-modified composition can be suitably used as a raw material of a polyisocyanate component and a component containing an active hydrogen group as a polyurethane resin.

More specifically, the modified naphthalene diisocyanate containing the functional group (isocyanurate group) described above (a) is a trimer of naphthalene diisocyanate, and can be obtained, for example, by reacting a naphthalene diisocyanate composition in the presence of a known isocyanurate-forming catalyst to isocyanurate the naphthalene diisocyanate therein.

The modified naphthalene diisocyanate containing the functional group (b) (allophanate group) can be obtained by reacting a naphthalene diisocyanate composition with an alcohol and then further reacting the resulting mixture in the presence of a known allophanation catalyst.

The modified naphthalene diisocyanate containing the functional group (c) (biuret group) can be obtained by reacting a naphthalene diisocyanate composition with, for example, water, a tertiary alcohol (e.g., tert-butyl alcohol), a secondary amine (e.g., dimethylamine, diethylamine, etc.), and then further reacting the mixture in the presence of a known biuret catalyst.

The modified naphthalene diisocyanate containing the functional group (urethane group) of (d) can be obtained by reacting a naphthalene diisocyanate composition with a polyol component (for example, trimethylolpropane, etc.).

The modified naphthalene diisocyanate containing the functional group (urea group) described above (e) can be obtained by reacting a naphthalene diisocyanate composition with water, a polyamine component (described later), and the like.

The modified naphthalene diisocyanate (asymmetric trimer) containing the functional group (f) (iminooxadiazinedione group) can be obtained by reacting a naphthalene diisocyanate composition in the presence of a known iminooxadiazinedione catalyst to subject the naphthalene diisocyanate to iminooxadiazinedione (eg, trimerization).

The modified naphthalene diisocyanate containing the functional group (uretdione group) described above (g) can be obtained by heating a naphthalene diisocyanate composition at about 90°C to 200°C, or by reacting the naphthalene diisocyanate in the presence of a known uretdione catalyst to uretdione (e.g., dimerize) the naphthalene diisocyanate.

The modified naphthalene diisocyanate containing the functional group (h) (uretonimine group) can be obtained by reacting a naphthalene diisocyanate composition in the presence of a known carbodiimide catalyst to form a carbodiimide group and then adding naphthalene diisocyanate to the carbodiimide group.

The modified naphthalene diisocyanate containing the functional group (carbodiimide group) of (i) above can be obtained by reacting a naphthalene diisocyanate composition in the presence of a known carbodiimidization catalyst.

It should be noted that the naphthalene diisocyanate-modified composition may contain at least one of the functional groups (a) to (i) above, or may contain two or more. Such a naphthalene diisocyanate-modified composition may be produced by appropriately using the above-mentioned reactions in combination. In addition, the naphthalene diisocyanate-modified composition may be used alone or in combination of two or more.

A fourth object of the present invention is to provide a polyurethane resin, which is obtained by reacting the naphthalene diisocyanate composition described in the first object with a substance containing an active hydrogen group, or by reacting the modified composition described in the third object with a substance containing an active hydrogen group.

Examples of substances containing active hydrogen groups include polyol components (components mainly containing polyols having two or more hydroxyl groups), polythiol components (components mainly containing polythiol having two or more mercapto groups (thiol groups)), and polyamine components (compounds mainly containing polyamines having two or more amino groups).

Examples of the polyol component include low molecular weight polyols and high molecular weight polyols.

The low molecular weight polyol is a compound having two or more hydroxyl groups and having a number average molecular weight of 60 or more and less than 400.

Examples of the low molecular weight polyol include ethylene glycol, propylene glycol, 1,3-propanediol, 1,4-butanediol, 1,3-butanediol, 1,2-butanediol, 1,5-pentanediol, 1,6-hexanediol, neopentyl glycol, alkane (7-22) diol, diethylene glycol, triethylene glycol, dipropylene glycol, 3-methyl-1,5-pentanediol, alkane-1,2-diol (C (carbon number, hereinafter the same) 17-20), isosorbide, 1,3- or 1,4-cyclohexanedimethanol, and mixtures thereof. compounds, 1,4-cyclohexanediol, hydrogenated bisphenol A, 1,4-dihydroxy-2-butene, 2,6-dimethyl-1-octene-3,8-diol, diols such as bisphenol A, triols such as glycerol and trimethylolpropane, tetraols such as tetramethylolmethane (pentaerythritol) and diglycerol, pentahydric alcohols such as xylitol, hexahydric alcohols such as sorbitol, mannitol, allitol, iditol, dulcitol, altritol, inositol, dipentaerythritol, heptahydric alcohols such as avocado, octahydric alcohols such as sucrose, etc.

The low molecular weight polyols also include polyalkylene oxides having a number average molecular weight of 60 or more and less than 400 (including random and/or block copolymers of two or more alkylene oxides) obtained by adding alkylene oxides such as ethylene oxide and propylene oxide to the above alcohols as initiators.

The high molecular weight polyol is a compound having two or more hydroxyl groups and having a number average molecular weight of 400 or more, for example, 10000 or less, and preferably 5000 or less. Examples of the high molecular weight polyol include polyether polyols, polyester polyols, polycarbonate polyols, polyurethane polyols, epoxy polyols, vegetable oil polyols, polyolefin polyols, acrylic polyols, polysiloxane polyols, fluorine polyols, and vinyl monomer-modified polyols.

Examples of polyether polyols include polyoxy (C2-C3) alkylene polyols, polytetramethylene ether glycol, polytrimethylene ether glycol, etc. Examples of polyoxy (C2-C3) alkylene polyols include addition polymers of C2-3 alkylene oxides such as ethylene oxide and propylene oxide (including random and/or block copolymers of two or more alkylene oxides) using the above-mentioned low molecular weight polyols as initiators. In addition, specific examples of polyoxy (C2-3) alkylene include polyethylene glycol, polypropylene glycol, polyethylene polypropylene copolymers, etc.

Examples of the polytetramethylene ether glycol include a ring-opening polymer (polytetramethylene ether glycol) obtained by cationic polymerization of tetrahydrofuran and an amorphous polytetramethylene ether glycol obtained by copolymerizing a polymerization unit of tetrahydrofuran with the above-mentioned diol.

In addition, plant-derived polytetramethylene ether glycol produced using tetrahydrofuran produced from plant-derived raw materials such as furfural as a starting material may be mentioned.

Examples of polytrimethylene ether glycol include polyols produced by polycondensation of plant-derived 1,3-propylene glycol.

Examples of the polyester polyol include polycondensates obtained by reacting the above-mentioned low molecular weight polyol (preferably diol) and polybasic acid (preferably dibasic acid) under known conditions.

Examples of the polybasic acid include saturated aliphatic dicarboxylic acids (C11-C13) such as oxalic acid, malonic acid, succinic acid, methylsuccinic acid, glutaric acid, adipic acid, 1,1-dimethyl-1,3-dicarboxypropane, 3-methyl-3-ethylglutaric acid, azelaic acid, and sebacic acid; unsaturated aliphatic dicarboxylic acids such as maleic acid, fumaric acid, and itaconic acid; aromatic dicarboxylic acids such as phthalic acid, isophthalic acid, terephthalic acid, toluene dicarboxylic acid, and phthalic acid; Aromatic dicarboxylic acids, alicyclic dicarboxylic acids such as hexahydrophthalic acid, other carboxylic acids such as dimer acid, hydrogenated dimer acid, HET acid, and acid anhydrides derived from these carboxylic acids, such as oxalic anhydride, succinic anhydride, maleic anhydride, phthalic anhydride, 2-alkyl (C12-C18) succinic anhydride, tetrahydrophthalic anhydride, trimellitic anhydride, and acid halides derived from these carboxylic acids, such as oxalyl dichloride, adipoyl dichloride, sebacoyl dichloride, etc.

Examples of the polyester polyol include plant oil-based polyester polyols obtained by condensing the above-mentioned low molecular weight polyols with hydroxycarboxylic acids such as plant oil fatty acids containing hydroxy groups (e.g., castor oil fatty acids containing ricinoleic acid, hydrogenated castor oil fatty acids containing 12-hydroxystearic acid, etc.) under known conditions.

In addition, examples of polyester polyols include polycaprolactone polyols, polyvalerolactone polyols obtained by ring-opening polymerization of lactones such as ε-caprolactone and γ-valerolactone using the above-mentioned low molecular weight polyols (preferably diols) as initiators, and lactone polyester polyols obtained by copolymerizing these with the above-mentioned diols.

Examples of the polycarbonate polyol include a ring-opening polymer of ethylene carbonate using the above-mentioned low molecular weight polyol (preferably a diol) as an initiator, and an amorphous polycarbonate polyol obtained by copolymerizing the above-mentioned diol with a ring-opening polymer.

In addition, regarding the polyurethane polyol, there can be mentioned polyester polyurethane polyol, polyether polyol, polycarbonate polyurethane polyol, or polyester polyether polyurethane polyol obtained by reacting the polyester polyol, polyether polyol and/or polycarbonate polyol obtained by the above method with the above-mentioned polyisocyanate (including naphthalene diisocyanate. The same applies hereinafter) in a ratio where the equivalent ratio of hydroxyl group to isocyanate group (OH/NCO) is greater than 1, polyester polyurethane polyol, polyether polyurethane polyol, polycarbonate polyurethane polyol, or the like.

Examples of the epoxy polyol include epoxy polyols obtained by reaction of the above-mentioned low molecular weight polyols with polyfunctional halogenated alcohols such as epichlorohydrin and β-methylepichlorohydrin.

Examples of the vegetable oil polyol include hydroxyl group-containing vegetable oils such as castor oil and coconut oil, and examples thereof include castor oil polyol and ester-modified castor oil polyol obtained by reacting castor oil polyol with polypropylene polyol.

Examples of the polyolefin polyol include polybutadiene polyol and partially saponified ethylene-vinyl acetate copolymer.

Examples of the acrylic polyol include copolymers obtained by copolymerizing a hydroxyl group-containing acrylic acid ester and a copolymerizable vinyl monomer copolymerizable with the hydroxyl group-containing acrylic acid ester.

Examples of the hydroxyl group-containing acrylate include 2-hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, hydroxybutyl (meth)acrylate, 2,2-dihydroxymethylbutyl (meth)acrylate, polyhydroxyalkyl maleate, polyhydroxyalkyl fumarate, etc. Preferably, 2-hydroxyethyl (meth)acrylate is used.

Examples of the copolymerizable vinyl monomer include alkyl (meth)acrylates (having 1 to 12 carbon atoms) such as methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, isopropyl (meth)acrylate, butyl (meth)acrylate, isobutyl (meth)acrylate, sec-butyl (meth)acrylate, tert-butyl (meth)acrylate, amyl (meth)acrylate, isopentyl (meth)acrylate, hexyl (meth)acrylate, isononyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, cyclohexyl acrylate, and isobornyl (meth)acrylate, and examples of alkyl (meth)acrylates (having 1 to 12 carbon atoms) such as styrene, vinyltoluene, and α-methylstyrene.

Aromatic vinyl monomers, for example, vinyl cyanides such as (meth)acrylonitrile, vinyl monomers containing carboxyl groups such as (meth)acrylic acid, fumaric acid, maleic acid, itaconic acid, or their alkyl esters, for example, ethylene glycol di(meth)acrylate, butanediol di(meth)acrylate, hexanediol di(meth)acrylate, oligoethylene glycol di(meth)acrylate, trimethylolpropane di(meth)acrylate, alkane polyol poly(meth)acrylates such as trimethylolpropane tri(meth)acrylate, vinyl monomers containing isocyanate groups such as 3-(2-isocyanate-2-propyl)-α-methylstyrene, etc.

The acrylic polyol can be obtained by copolymerizing these hydroxyl group-containing acrylic acid esters and copolymerizable vinyl monomers in the presence of a suitable solvent and a polymerization initiator.

In addition, acrylic polyols include, for example, silicone polyols and fluorine polyols.

Examples of the polysiloxane polyol include acrylic polyols obtained by blending a polysiloxane compound containing a vinyl group such as γ-methacryloxypropyltrimethoxysilane as a copolymerizable vinyl monomer during the copolymerization of the above-mentioned acrylic polyols.

Examples of the fluorine polyol include acrylic polyols obtained by blending, during copolymerization of the above-mentioned acrylic polyols, a fluorine compound containing a vinyl group such as tetrafluoroethylene or chlorotrifluoroethylene as a copolymerizable vinyl monomer.

The vinyl monomer-modified polyol can be obtained by reacting the above-mentioned high molecular weight polyol with a vinyl monomer such as the above-mentioned alkyl (meth)acrylate.

The above-mentioned polyol components can be used alone or in combination of two or more.

In addition, in the reaction of the polyisocyanate component and the component containing the active hydrogen group, when the equivalent ratio of the active hydrogen group to the isocyanate group is less than 1, an isocyanate group-terminated polymer having an isocyanate group at the molecular end is generated, and when the equivalent ratio of the active hydrogen group to the isocyanate group is greater than 1, an active hydrogen group-terminated polymer having an active hydrogen group at the molecular end is generated. Both the isocyanate group-terminated polymer and the active hydrogen group-terminated polymer are contained in the resin (polyurethane resin). The isocyanate group-terminated polymer is a one-component curing type resin.

As the use of polyurethane resin, specifically, it can be suitably applied to ink, transfer foil, adhesive, binder, gel, elastomer, foam, adhesive, liquid curing type sealing material, RIM molded product, micro foam polyurethane, various microcapsules, optical materials, water-based resin, thermosetting resin, active energy ray (for example, electron beam, ultraviolet light, etc.) curing resin, artificial and synthetic leather, coagulation powder, robot components, moving components, medical care materials, carbon fiber reinforced plastic (CFRP) base resin, transparent rubber, transparent hard resin, waterproof material, film , sheets, tubes, plates, speakers, sensors, organic electroluminescent components, solar power generation components, robot components, wearable components, sporting goods, leisure goods, medical supplies, nursing supplies, residential components, audio components, lighting components, chandeliers, outdoor lights, packaging, vibration-proof/anti-seismic/shock-absorbing components, sound-proof components, daily necessities, groceries, buffers, bedding, stress absorbing materials, stress relaxation materials, interior and exterior decorative parts of automobiles, conveyor components, components for office automation equipment, surface protection components for groceries, self-repairing materials, health appliances, etc.

The sixth object of the present invention is to provide an elastomeric material, which includes the polyurethane resin described in the fifth object.

Examples of the elastomer include cast polyurethane elastomer (CPU), thermoplastic polyurethane elastomer (TPU), thermosetting polyurethane elastomer (TSU), and rollable polyurethane elastomer.

The elastomer includes a soft segment formed by the reaction of naphthalene diisocyanate with a high molecular weight polyol, and a hard segment formed by the reaction of naphthalene diisocyanate with a low molecular weight polyol and/or a low molecular weight polyamine.

Such an elastomer can be produced, for example, by the reaction of a polyisocyanate component, a high molecular weight polyol (a component containing an active hydrogen group), and a low molecular weight polyol and/or a low molecular weight polyamine (a component containing an active hydrogen group). That is, the polyisocyanate component, the high molecular weight polyol, and the low molecular weight polyol and/or the low molecular weight polyamine are the raw materials of the elastomer.

As the high molecular weight polyol as the raw material of the elastomer, for example, there can be mentioned the above-mentioned polyester polyol (for example, polycaprolactone polyol, adipic acid-based polyester polyol (polyester polyol using adipic acid as the polybasic acid)), the above-mentioned polycarbonate polyol, and the above-mentioned polytetramethylene ether glycol (for example, polytetramethylene ether glycol), and preferably, there can be mentioned the adipic acid-based polyester polyol.

Examples of the low molecular weight polyol as the raw material of the elastomer include ethylene glycol and 1,4-butanediol, and preferably 1,4-butanediol is used.

As the low molecular weight polyamine as the raw material of the elastomer, for example, the low molecular weight polyamines mentioned above can be mentioned.

The elastomer can be produced by a known method such as a one-shot method or a prepolymer method.

In addition, as for the method for producing the elastomer, for example, bulk polymerization, solution polymerization, etc. can be utilized.

In addition, in the method for producing the elastomer, a known urethanization catalyst such as amines, organometallic compounds (e.g., organotin compounds, preferably dibutyltin dichloride, etc.) may be added to the elastomer raw material as required. Furthermore, as required, a plasticizer, an anti-caking agent, a heat stabilizer, a light stabilizer, an ultraviolet absorber, an anti-yellowing agent, an antioxidant, a mold release agent, a pigment, a dye, a lubricant, a nucleating agent, a filler, an anti-hydrolysis agent, etc. may be blended in an appropriate ratio in the elastomer.

Thus, an elastomer can be produced. Such an elastomer has excellent mechanical properties (elongation and strength), and in particular, excellent wear resistance.

In addition, the naphthalene diisocyanate-based elastomer material is usually manufactured by a prepolymer method. Specifically, a polyol compound and an isocyanate compound are mixed to obtain a prepolymer, and a suitable chain extender and a suitable auxiliary agent are optionally added. If necessary, the mixed solution (polymerizable composition) is degassed by an appropriate method and then injected into an injection mold for an elastomer material, which is usually slowly heated from a low temperature to a high temperature to polymerize. Then, the elastomer is demolded to obtain an elastomer.

Additionally, the elastomer can be vulcanized to optimize performance as needed.

If the NI content of the naphthalene diisocyanate composition for an elastomer material or the naphthalene diisocyanate-modified composition is 5 ppm or more and 6000 ppm or less, an elastomer material having high mechanical properties can be stably produced from the naphthalene diisocyanate composition for an elastomer material or the naphthalene diisocyanate-modified composition.

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

The naphthalene diisocyanate composition provided by the present invention contains 5-6000 ppm of the compound of formula (1), has excellent stability at high temperature, and the elastomer prepared therefrom has excellent mechanical properties.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is a flow chart of preparing a naphthalene diisocyanate composition in a specific embodiment of the present invention;

DETAILED DESCRIPTION

(I) The determination method of the relevant test in the present invention is as follows:

1. Content ratio of compound NI

First, commercially available NI with a purity of 99 mol% was used as a standard substance, and analysis was performed by gas chromatography under the following conditions, and a calibration curve was prepared from the area values of the obtained gas chromatogram (external standard method).

2. Content ratio of naphthalene diisocyanate

Analysis was performed by gas chromatography under the following conditions using NDI having a purity of 99 mol% as a standard substance by an internal standard method in the examples described later.

Instrument: Agilent 7890

(1) Chromatographic column: DB-5 (30m×0.25mm×0.25μm); (2) Injection volume: 0.5μL; (3) Split ratio: 1/30; (4) Inlet temperature: 260℃; (5) Column flow rate: 1.5mL/min; (6) Program temperature: 100℃ for 1min, then increase the temperature to 280℃ at 10℃/min and hold for 20min; (7) FID detector temperature: 280℃; (8) Hydrogen flow rate: 40mL/min, air flow rate: 400mL/min.

3. The bromine content in NDI was determined by ICP-OES analysis;

Instrument: Thermo Scientific ICAP 7200 ICP-OES.

4. The tensile strength of the elastomer is tested according to GB/T528-2009.

5. Tear strength is tested according to GB/T529-2008.

6. Shore A hardness is tested according to GB/T531-2008.

7. Rebound test shall be in accordance with GB/T7759-1996.

(II) Raw materials and sources

Table 1 Raw material information

Reagent name factory purity 1,5-Diaminonaphthalene Inokay ＞99.0％ Naphthylamine Inokay ＞99.0％ Naphthyl isocyanate Inokay ＞99.0％ chlorobenzene Maclean Analytical grade Polycaprolactone diol (molecular weight 2000) Daicel (grade 220N) Industrial Grade 1,4-Butanediol Sinopharm Analytical grade

For the convenience of understanding the present invention, the present invention lists the following embodiments. It should be understood by those skilled in the art that the embodiments are only to help understand the present invention and should not be regarded as specific limitations of the present invention.

It should be noted that, unless otherwise specified, "parts" and "%" are based on mass.

The method for controlling the content of mononaphthylamine in NDA is as follows:

Add NDA to the inner tube of the crystallizer and replace it with nitrogen three times; turn on the constant temperature oil bath and heat it to 195°C (in the experiment).

The temperature is the temperature of the heat carrier silicone oil in the oil bath pot). After the raw materials in the crystallizer are completely melted, the temperature of the oil bath tank is lowered to make the temperature in the crystallizer drop to slightly higher than the melting point temperature corresponding to the material.

After stabilizing for a period of time, the cooling crystallization operation is carried out. The oil bath temperature is controlled by the oil bath program so that the molten liquid in the crystallizer is linearly cooled and crystallized at a set rate; when the predetermined time is reached, the discharge valve is opened to discharge the mother liquor.

According to the temperature control program, gradually increase the oil bath temperature to perform the sweating operation.

The crystal layer is heated to melt all of it, and then discharged naturally. The product is collected in a collection tank and weighed for analysis. The specific composition is shown in Table 2.

Examples 1-7, Comparative Example 1

The above examples and comparative examples respectively provide a kind of NDI composition, and the specific composition thereof is shown in Table 2.

The preparation method of the NDI composition is as follows:

The NDI composition was manufactured using the process shown in FIG1 . Specifically, 800 parts by mass of chlorobenzene were charged into the cold photochemical reactor shown in FIG1 . Next, the cold photochemical temperature in the cold photochemical reactor was adjusted to 30° C., and the cold photochemical pressure (gauge pressure) in the cold photochemical reactor was adjusted to 0.06 MPaG. Then, 150 parts by mass of phosgene was introduced into the cold photochemical reactor from the phosgene supply line, and a mixed solution (amine solution) of 150 parts by mass of NDA and 1050 parts by mass of chlorobenzene was charged into the cold photochemical reactor from the amine supply line. Thus, NDA cold photochemical liquid slurry was prepared.

Next, phosgene was continuously blown into the cold photochemical reactor from the phosgene supply line at a supply rate of 100 parts by mass/hr, and an amine solution with an NDA concentration of 7.5 wt.% was continuously charged into the cold photochemical reactor from the amine supply line at a supply rate of 1000 parts by mass/hr, and at the same time, the NDA cold photochemical liquid was transported to the hot photochemical reactor through the cold photochemical liquid transport line.

Next, phosgene was continuously introduced into the thermal photochemical reactor at a supply rate shown in Table 2. Table 2 shows the reaction temperature and reaction pressure (gauge pressure) of the reactor, and the supply ratio of phosgene to 1 mol of NDA.

Thus, the NDA luminescence liquid reacts with phosgene to generate NDI, thereby preparing a reaction material containing NDI. In addition, a portion of the unreacted phosgene is condensed into the photochemical reactor by the condenser.

Next, the photochemical reaction liquid was continuously transported to the dephosgenating tower. Then, the reaction material was degassed in the dephosgenating tower. Next, the degassed material was discharged from the dephosgenating tower through the degassing material transport line and continuously transported to the desolvating tower. Thus, 120 parts by weight of desolvating material having an NDI concentration of 95 wt.% was prepared.

Next, the desolventized material is discharged from the desolventizing tower through the desolventizing material conveying line, and the removed solvent is refined in the solvent refining tower and then reused.

The solvent refining tower is filled with a filler equivalent to 15 theoretical plates, and its operating conditions are as follows:

Tower bottom temperature: 80-150℃

Tower top temperature: 60-140℃

Tower top pressure: as shown in Table 2

Top reflux ratio: as shown in Table 2

Residence time: 0.5-10h

The desolventized material is continuously conveyed to the detarrifier. Then, the desolventized material is detarred in the detarrifier to prepare an intermediate material. The content ratios of chlorobenzene (MCB), NDI, NI and bromine in the intermediate material are shown in Table 2.

Next, the intermediate material is continuously fed to the distillation tower at a supply rate of 100 parts by mass/hr. The distillation tower is filled with a filler equivalent to 5 theoretical plates. Then, in the distillation tower, the light component is removed from the top of the tower, and the NDI composition product is extracted from the tower.

The distillation conditions in the distillation tower are as follows:

Tower bottom temperature: 140-200℃

Tower top temperature: 130-190℃

Tower top pressure: 0-1.5KPa

Duration: 1-10h

The extraction rate and top reflux ratio of the distillation process are shown in Table 2.

Table 2 shows the content ratios of NDI, NI, and bromine element in the NDI composition.

Comparative Example 2

To the NDA obtained in Example 1, mononaphthylamine was added to a content of 2%, and the NDI composition of Comparative Example 2 was prepared under the same photochemical, concentration and separation conditions as in Example 1.

Table 2 Conditions and results of Examples 1-7 and Comparative Examples 1-2

Thermal stability test

The NDI compositions of the above examples and comparative examples were subjected to thermal stability test and evaluation, as follows:

The initial NCO content (NCO%) of the NDI compositions of the above examples and comparative examples was measured by titration (HG/T2409-92). First, an excess of n-butylamine relative to the theoretical NCO content was added and reacted, and the residual excess n-butylamine was analyzed with 0.1N hydrochloric acid reagent. The results are shown in Table 3 below.

The NDI compositions of the above examples and comparative examples were placed in transparent glass bottles, filled with nitrogen and sealed, and then stored at 150°C for 5 hours to obtain stored compositions, and the NCO% of the stored compositions was measured in the same manner as above. The color of the compositions was observed with the naked eye. The results are shown in Table 3 below.

Table 3 Application effect data of NDI composition

As can be seen from Table 3, the present invention can effectively improve the thermal stability of the composition by controlling the content of NI in the NDI composition within 5-6000 ppm. The thermal stability performance of the compositions with a NI content lower than 5 ppm (Comparative Example 1) and higher than 6000 ppm (Comparative Example 2) is inferior to that of the present invention. The NDI composition provided by the present invention has better thermal stability.

Application performance testing

The NDI compositions of the above examples and comparative examples were used to prepare various elastomeric materials, and their performance was evaluated as follows:

Polycaprolactone diol (PCL-2000) was dehydrated in vacuum (0.7 Kpa) at 125°C for 2 h, stirred rapidly, and 2.5 molar equivalents of NDI composition were added under N2 protection. The mixture was kept at 125°C for 6-7 min, and the NCO% content was analyzed by sampling. When the analysis value reached 5%, the prepolymer was cooled to 100°C, 10 parts by weight of chain extender 1,4-butanediol (calculated based on 100 parts by weight of prepolymer) was added, and the mixture was mixed rapidly for 30 s. After vacuum degassing (0.7 Kpa), the mixture was poured into a mold preheated to 110°C, cured in an oven at 110°C for 10 min, demolded, and post-cured in an oven at 110°C for 24 h. The mixture was left at room temperature for one week, and post-cured again at 110°C for 24 h. This was repeated three times to achieve the best performance. The tensile strength of the elastomer was tested according to GB/T528-2009, the tear strength was tested according to GB/T529-2008, the Shore A hardness was tested according to GB/T531-2008, and the rebound was tested according to GB/T7759-1996. The test results are summarized in Table 4.

Table 4 Application effect data of NDI composition

As can be seen from Table 4, the present invention can effectively improve the mechanical properties (Shore A hardness, tensile strength, tear strength, and rebound) of the elastomer prepared from the composition by controlling the content of NI in the NDI composition within 5-6000 ppm. When the content of NI is lower than 5 ppm (Comparative Example 1) and higher than 6000 ppm (Comparative Example 2), the mechanical properties are inferior to those of the present invention. The NDI composition provided by the present invention has a better application prospect in various elastomeric materials.

The applicant declares that the present invention illustrates the detailed method of the present invention through the above-mentioned embodiments, but the present invention is not limited to the above-mentioned detailed method, that is, it does not mean that the present invention must rely on the above-mentioned detailed method to be implemented. Those skilled in the art should understand that any improvement of the present invention, equivalent replacement of various raw materials of the product of the present invention, addition of auxiliary components, selection of specific methods, etc., all fall within the protection scope and disclosure scope of the present invention.

Claims (10)

1. a naphthalene diisocyanate composition, is characterized in that, described naphthalene diisocyanate composition comprises the compound shown in the formula (1) of naphthalene diisocyanate and 5-6000ppm;

2. naphthalene diisocyanate composition according to claim 1, is characterized in that, also comprises bromine-containing compound in the described naphthalene diisocyanate composition; In terms of the quality of bromine element, the content of described bromine-containing compound is 0.2- 60ppm. 3. the naphthalene diisocyanate composition according to claim 1 or 2, is characterized in that, described naphthalene diisocyanate comprises 1,2-naphthalene diisocyanate, 1,3-naphthalene diisocyanate, 1,4-naphthalene diisocyanate , 1,5-naphthalene diisocyanate, 1,8-naphthalene diisocyanate, any one or a combination of at least two, preferably 1,5-naphthalene diisocyanate and/or 1,8-naphthalene diisocyanate, more preferably 1, 5-naphthalene diisocyanate; The compound represented by the formula (1) includes any one or a combination of at least two of the following compounds:

4. a preparation method of the naphthalene diisocyanate composition as described in any one of claim 1-3, is characterized in that, described preparation method comprises: (1) Isocyanate process: making naphthalene diamine or naphthalene diamine hydrochloride react with phosgene in the presence of a reaction solvent to perform isocyanate reaction to obtain a reaction product containing naphthalene diisocyanate and a compound shown in formula (1); (2) Solvent separation and refining process: solvent removal is carried out to the reaction product obtained in step (1), after removal, the solvent is refined to obtain a reused solvent, and then returned to the reaction system of step (1); (3) Separation process: separating and purifying the desolvated reaction product obtained in step (2) to obtain the naphthalene diisocyanate composition. 5. The preparation method according to claim 4, characterized in that the mononaphthylamine content in the naphthalene diamine is 10-10000ppm. 6. the preparation method as claimed in claim 4 or 5, is characterized in that, described naphthalene diamine comprises 1,2-naphthalene diamine, 1,3-naphthalene diamine, 1,4-naphthalene diamine, 1, Any one or at least two combinations of 5-naphthalene diamine and 1,8-naphthalene diamine; and/or, the reaction solvent is selected from aromatic hydrocarbons, aliphatic hydrocarbons, alicyclic hydrocarbons, Halogenated aromatic hydrocarbons, nitrogen-containing compounds, ethers, ketones, fatty acid esters, aromatic carboxylate solvents. 7. A modified composition of naphthalene diisocyanate composition, characterized in that, said modified composition is the naphthalene diisocyanate composition described in any one of claims 1-3 or as claimed in claim 4-6 The modified composition obtained by modifying the naphthalene diisocyanate composition prepared by any one of the preparation methods, the modified naphthalene diisocyanate in the modified composition contains the following (a)-(e) groups Any one or at least two combinations of groups: (a) isocyanurate group, (b) uretdione group, (c) biuret group, (d) urethane group, (e) Urea group, (f) iminooxadiazinedione group, (g) allophanate group, (h) uretonimine group or (i) carbodiimide group. 8. A two-component polyurethane, characterized in that, the two-component polyurethane raw material comprises A agent and B agent; The A agent comprises the naphthalene diisocyanate composition described in any one of claims 1-3 or the naphthalene diisocyanate composition prepared by the preparation method described in any one of claims 4-6 and/or claim 7 The modified composition; the B agent includes substances containing active hydrogen groups. 9. Two-component polyurethane as claimed in claim 8, characterized in that, the material containing active hydrogen groups is selected from polyol components (mainly containing polyol components with more than 2 hydroxyl groups), polysulfide Alcohol components (components mainly containing polythiols having two or more mercapto groups (thiol groups)), polyamine components (compounds mainly containing polyamines having two or more amino groups). 10. An elastomeric material, characterized in that the elastomeric material comprises the polyurethane resin according to claim 8 or 9.

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