CN117820601A

CN117820601A - Naphthalene diisocyanate composition, preparation method and application thereof

Info

Publication number: CN117820601A
Application number: CN202410015450.1A
Authority: CN
Inventors: 王鹏飞; 杨颖�; 尚永华; 李明; 朱付林; 牛康宁; 朱岳栋; 石滨
Original assignee: Wanhua Chemical Group Co Ltd
Current assignee: Wanhua Chemical Group Co Ltd
Priority date: 2024-01-03
Filing date: 2024-01-03
Publication date: 2024-04-05

Abstract

The invention relates to a naphthalene diisocyanate composition, a preparation method and application thereof, wherein the naphthalene diisocyanate composition comprises naphthalene diisocyanate and 5-6000ppm of a compound shown as a formula (1),

Description

Naphthalene diisocyanate composition, preparation method and application thereof

Technical Field

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

Background

Naphthalene diisocyanate is an aromatic diisocyanate, and has been widely used as a raw material for polyurethane in various industrial products, particularly in high-performance elastomer materials. Naphthalene diisocyanate is obtainable by reacting naphthalene diamine with phosgene (phosgene).

NDI prepolymer has hot spot with short storage period, which makes the selling of prepolymer and elastomer processing difficult, and because NDI has melting point 127 deg.c, the prepolymerization reaction temperature is higher than 127 deg.c, and this results in lower NCO index, raised viscosity and final solidification. Accordingly, there is a need in the art to provide a naphthalene diisocyanate starting material capable of preparing high stability prepolymers.

Disclosure of Invention

In view of the deficiencies of the prior art, it is an object of the present invention to provide a naphthalene diisocyanate composition. The naphthalene diisocyanate composition has excellent thermal stability, the prepared prepolymer has excellent thermal stability, and the prepared polyurethane elastomer has excellent mechanical properties.

To achieve the purpose, the invention adopts the following technical scheme:

the present invention provides a naphthalene diisocyanate composition comprising naphthalene diisocyanate and 5 to 6000ppm, preferably 10 to 2000ppm of a compound represented by the formula (1);

the present inventors have found in the study that when the naphthalene diisocyanate composition contains 5 to 6000ppm of the compound of formula (1), the prepolymer prepared has excellent stability. A content of less than 5ppm or more than 6000ppm may deteriorate stability.

The naphthalene diisocyanate composition of the present invention includes 95wt.% or more of naphthalene diisocyanate, but is defined as a naphthalene diisocyanate composition since it contains a compound represented by the chemical formula (1) as a subcomponent.

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

Preferably, the naphthalene diisocyanate comprises any one or at least two of 1, 2-naphthalene diisocyanate, 1, 3-naphthalene diisocyanate, 1, 4-naphthalene diisocyanate, 1, 5-naphthalene diisocyanate, 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 the formula (1) includes, but is not limited to, any one or a combination of at least two of the following compounds:

in the present invention, NAI is produced as a by-product in the production of NDI described later, and naturally, it is also possible to artificially add the product to obtain a desired content.

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

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

(1) An isocyanate process:

a. mixing naphthalene diamine and phosgene in the presence of a solvent;

b. reacting naphthalene diamine with phosgene in a cold reaction unit to form an intermediate reactant comprising isocyanate, aminoacyl chloride, hydrochloride, naphthalene diamine and phosgene;

c. the intermediate reactant produced in the cold reaction unit is isocyanated in the hot reaction unit to obtain a reaction product containing naphthalene diisocyanate and the compound represented by formula (1).

Wherein the intermediate reactant obtained in carrying out reaction b comprises less than 80% of naphthalene diamine, preferably less than 70%, based on the molar amount of amine fed to the process. The lower limit of the content of the naphthalene diamine of the intermediate reactant obtained in the reaction b is not particularly required, but the content of the naphthalene diamine is controlled to be more than 1% in consideration of the cost of industrial production.

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

(3) And (3) a separation procedure: and (3) separating and purifying the desolvation reaction product obtained in the step (2) to obtain the naphthalene diisocyanate composition.

The isocyanation process of step (1) may be referred to as phosgenation, and the isocyanation reaction is phosgenation.

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

Preferably, the phosgenation of the amine is carried out by means of a two stage of cryo-and thermo-phos-genation. The luminescence process comprises the following steps: in the presence of a reaction solvent, naphthalene diamine and phosgene are mixed to carry out luminescence reaction, and naphthalene diamine cooling liquid is obtained. The actual obtained slurry in the cold light process is a slurry containing naphthalene diamine, naphthalene diamine hydrochloride, naphthalene diamine acyl chloride and a very small amount of naphthalene diisocyanate, and the slurry is directly applied to the isocyanate process.

Preferably, the naphthalene diamine comprises any one or at least two of 1, 2-naphthalene diamine, 1, 3-naphthalene diamine, 1, 4-naphthalene diamine, 1, 5-naphthalene diamine, and 1, 8-naphthalene diamine.

Preferably, the luminescence process specifically includes: and (3) introducing phosgene into a reaction solvent, adding a reaction solvent amine solution containing naphthalene diamine, stirring and mixing the phosgene and the amine solution, and carrying out a luminescence reaction to obtain the naphthalene diamine cooling liquid.

The molar content of the naphthalene diamine in the cold reaction process can be regulated by controlling the concentration of the naphthalene diamine in the amine solution, the photochemical reaction temperature, the photochemical reaction pressure, the photochemical reaction time and the phosgene addition amount.

Preferably, the content of naphthalene diamine in the amine solution is 1.0wt.% or more, preferably 3.0wt.% or more.

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

Preferably, the photochemical temperature in the cold photochemical step is 0 ℃ or higher, preferably 10 ℃ or higher.

Preferably, the luminescence temperature in the luminescence process is 130 ℃ or lower, preferably 80 ℃ or lower, more preferably 60 ℃ or lower.

Preferably, the chill-photochemical process is performed under normal pressure or under pressure.

The pressure (gauge pressure) in the chill-stage is preferably 0.01MPaG or more, more preferably 0.02MPaG or more.

The pressure (gauge pressure) in the chill-stage is preferably 1.0MPaG or less, more preferably 0.5MPaG or less, and still more preferably 0.4MPaG or less.

Preferably, the molar amount of phosgene is 4 times or more, preferably 6 times or more, more preferably 8 times or more the molar amount of naphthalene diamine.

Preferably, the molar amount of phosgene is 50 times or less, preferably 30 times or less, more preferably 20 times or less the molar amount of naphthalene diamine.

Because naphthalene diamine has smaller solubility in solvents such as chlorobenzene, dichlorobenzene, toluene and the like, a layer of intermediate reactants (such as hydrochloride, carbamoyl chloride and the like) can be formed on the surfaces of amine particles in the reaction process of the amine and phosgene, so that further reaction of the phosgene and the amine is hindered, the conversion rate of the amine is low, the molar content of the amine in the reaction solution generated by the cold reaction unit is high, and finally the NAI content generated by the hot reaction unit is higher.

Preferably, the molar content of phenylenediamine in the cold reaction process can be adjusted by controlling the mixing intensity of the reactor, and a mixing device having a grinding function for solids in the reaction liquid, preferably a homogenizing pump, a grinding pump, a pulverizing pump, a colloid mill, a gear tooth type dispersing machine, and more preferably a mixing device having a fluted disc type dispersing structure, such as a homogenizing pump, a grinding pump, is preferably used.

Preferably, the toothed disc has a toothed disc gap of 500 μm or less, more preferably 200 μm or less.

Preferably, the residence time of the reaction solution by grinding using a mixing device is 1min or more, preferably 5min or more.

Preferably, the residence time of the reaction liquid by grinding using a mixing device is 180min or less, preferably 120min or less.

Preferably, the step (1) specifically includes: phosgene is introduced into naphthalene diamine to carry out luminescence reaction; and continuously introducing phosgene into the luminescence reaction liquid to perform thermal reaction, so as to obtain a reaction product containing naphthalene diisocyanate and the compound shown in the formula (1).

When the isocyanation reaction is carried out with phosgene using naphthalene diamine chill liquid, the target content of the compound of formula (1) can be obtained by preferably the following parameters. The content of NAI in the naphthalene diisocyanate composition may be adjusted by adding NAI to the naphthalene diisocyanate composition.

The thermal reaction temperature in the isocyanate process is preferably 80℃or higher, for example, 90℃100℃110℃120℃130℃140℃150℃and the like, and preferably 100℃or higher.

Preferably, the reaction temperature in the isocyanate-forming process is 180 ℃ or less, preferably 170 ℃ or less, more preferably 160 ℃ or less.

Preferably, the isocyanate reaction time is 1h or more, preferably 3h or more.

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

Preferably, the isocyanation reaction is carried out under normal pressure or under pressurized conditions.

The pressure (gauge pressure) of the isocyanation reaction is preferably 0MPaG or more, for example, 0.0005MPaG, 0.0008MPaG, 0.001MPaG, 0.003MPaG, 0.005MPaG, 0.01MPaG, preferably 0.0005MPaG or more, more preferably 0.001MPaG or more, further preferably 0.003MPaG or more, particularly preferably 0.01MPaG or more, particularly preferably 0.02MPaG or more, and most preferably 0.03MPaG or more.

The pressure (gauge pressure) of the isocyanation reaction is preferably 0.6MPaG or less, preferably 0.4MPaG or less, more preferably 0.2MPaG or less.

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

Preferably, the isocyanatoprocess may be a batch or continuous process. In the continuous step, the slurry (naphthalene diamine cold reaction liquid) produced in the cold reaction unit is continuously fed from the cold reaction unit to a different thermal reaction unit from the cold reaction unit, the naphthalene diamine cold reaction liquid is reacted with phosgene in the thermal reaction unit, and the reaction liquid (reaction substance) is continuously taken out from the thermal reaction unit. The number of reaction kettles in the continuous process is not particularly limited, and may be, for example, two, three, four, five or more.

If necessary, the reaction product of the isocyanate-based process may be subjected to a degassing step, a solvent separation step and a purification step, and the residual phosgene and the gas such as hydrogen chloride produced as a by-product may be removed from the reaction product by a known degassing column. In the solvent separation and purification step, the reaction solvent is distilled off from the reaction solution by a known distillation column. Most of the solvent is returned to the isocyanate processing step after refining.

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, and halogenated aromatic hydrocarbons such as chlorotoluene, chlorobenzene, dichlorobenzene, dibromobenzene, and trichlorobenzene. The reaction solvent may be used alone or in combination of 2 or more. Among the reaction solvents, halogenated aromatic hydrocarbons are preferable, and chlorobenzene and dichlorobenzene are more preferable.

If necessary, the tar removal step may be performed on the solvent-removed reaction product. The tar component is removed from the reaction solution using a known tar removal device such as a short-path evaporator. The reaction substance from which tar components were removed in the tar removal step was referred to as an intermediate substance.

The intermediate may be purified, if necessary, by an industrial separation technique such as distillation and crystallization, without any particular limitation.

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

Preferably, the rectification column comprises a plate rectification column or a packed rectification column.

In a preferred embodiment of the present invention, the ratio of NAI can be adjusted to the above range by controlling the reaction conditions and the separation conditions. The content of NAI in the NDI composition may be adjusted by adding NAI to the NDI composition.

Preferably, the theoretical plate number of the rectifying column is 2 or more, preferably 5 or more.

Preferably, the theoretical plate number of the rectifying column is 60 or less, preferably 40 or less.

Preferably, the top pressure of the rectifying column is 0.1kPa or more, preferably 0.15kPa or more.

Preferably, the top pressure of the rectifying column is 4kPa or less, preferably 2.5kPa or less.

Preferably, the reflux ratio of the top of the rectifying column is 0.01 or more, preferably 0.1 or more.

Preferably, the reflux ratio at the top of the rectifying column is 60 or less, preferably 40 or less.

In a preferred embodiment of the present invention, the above-described method for producing a naphthalene diisocyanate composition can be carried out, for example, by using a flow chart shown in fig. 1. As shown in fig. 1, the reactor mainly comprises a luminescence unit, and in an isocyanate unit to be described later, a continuous thermal luminescence unit (carried out in a thermal luminescence reactor) is carried out, and the conversion rate of phenylenediamine is adjusted by appropriately adjusting the batch of a fluted disc, the residence time of a mixing device in the cold reaction unit, etc., so as to adjust the production amounts of naphthalene diisocyanate and NAI. And a phosgene removal unit and a solvent removal unit are arranged behind the photochemical kettle, the phosgene and the solvent are removed from the reaction solution, a heavy component removal unit is arranged behind the solvent removal unit, the tar removal procedure is carried out on the reaction product of the solvent removal, and the reaction product is distilled in a refining unit to obtain the final product. In addition, in the rectification separation described later, the content of NAI in the naphthalene diisocyanate composition is adjusted by appropriately adjusting the overhead reflux ratio or the like.

Specifically, first, a reaction solvent is charged into a luminescence reactor. Then, phosgene was continuously supplied to the bottom of the cryogenically chemical reactor through a phosgene supply line at the above-described supply ratio. The amine solution in which naphthalene diamine is dissolved in the reaction solvent is continuously supplied to the top of the luminescence reactor through an amine supply line. Then, while maintaining the inside of the luminescence reactor at the above luminescence temperature and luminescence pressure, the reaction substance in the luminescence reactor is introduced into a polishing pump by a pump to be polished and circulated back to the cold reaction reactor. Thus, a slurry comprising naphthalene diamine hydrochloride, naphthalene diamine acid chloride, naphthalene diamine, and a small amount of naphthalene diisocyanate was produced.

Then, a slurry containing naphthalene diamine hydrochloride, naphthalene diamine acyl chloride, naphthalene diamine and a small amount of naphthalene diisocyanate is continuously conveyed to the top of the thermal-polishing kettle through a luminescence liquid conveying line. That is, while continuously supplying phosgene and an amine solution to the luminescence reactor, a slurry containing naphthalene diamine hydrochloride, naphthalene diamine acid chloride, naphthalene diamine and a small amount of naphthalene diisocyanate is continuously taken out of the luminescence reactor and transferred to the thermal luminescence reactor.

Next, phosgene was continuously supplied to the top of the thermal-phosgenation reactor in the above-described supply ratio by way of an insertion tube. Then, the slurry and phosgene were stirred and mixed while maintaining the inside of the thermal reactor at the above-mentioned reaction temperature and reaction pressure (step 1 isocyanate-based step). Thus, the naphthalene diamine chill liquid reacts with phosgene to produce naphthalene diisocyanate as a main component and NAI as a by-product.

Thus, the cold light treatment step and the isocyanate treatment step are continuously performed.

Then, a reaction solution containing naphthalene diisocyanate, NAI, a reaction solvent, and the like is produced. The sum of residence times in the isocyanate process is within the above range.

Next, the above-mentioned photochemical reaction liquid is continuously fed to the middle of the column of the dephosgene column through a reaction material feed line. The photochemical liquid is separated into a gas containing phosgene, hydrogen chloride, and the like, and a liquid degassing substance containing naphthalene diisocyanate, NAI, a reaction solvent, and the like by a decarbonylation column (degassing step).

Next, the deaerated matter is continuously fed into the column of the desolventizing column through the deaerated matter feed line. Then, the reaction solvent was distilled off from the degassed material by using a desolventizing column (solvent separation and purification step) to obtain a desolventized material containing naphthalene diisocyanate and NAI.

Next, the desolventizing substance is continuously fed to the upper portion of the tar remover through the desolventizing substance feed line. Then, tar components are removed from the desolventized material by a tar remover to obtain an intermediate product containing naphthalene diisocyanate and NAI (tar removal step).

Next, the intermediate matters are continuously fed into the column of the rectifying column through the intermediate matters feeding line. Then, the low boiling substances are distilled from the intermediate quality under the conditions of the rectification step described above (bottom temperature, top pressure, bottom reflux ratio, top reflux ratio and residence time), and the naphthalene diisocyanate composition is withdrawn from the middle part of the column.

Thus, a naphthalene diisocyanate composition containing naphthalene diisocyanate and NAI can be continuously produced.

It is still another object of the present invention to provide a modified composition of a naphthalene diisocyanate composition, wherein the modified composition is a modified composition obtained by modifying a naphthalene diisocyanate composition according to one of the objects, and wherein the modified naphthalene diisocyanate in the modified composition contains any one or a combination of at least two of the following groups (a) to (e): (a) isocyanurate groups, (b) uretdione groups, (c) biuret groups, (d) urethane groups, (e) urea groups, (f) iminooxadiazinedione groups, (g) allophanate groups, (h) uretonimine groups, or (i) carbodiimide groups.

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

More specifically, the modified naphthalene diisocyanate having the functional group (isocyanurate group) of (a) is a naphthalene diisocyanate trimer, and is obtained, for example, by reacting a naphthalene diisocyanate composition in the presence of a known isocyanurate catalyst to isocyanurate the naphthalene diisocyanate.

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

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

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

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

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

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

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

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

The naphthalene diisocyanate-modified composition may contain at least 1 functional group of the above (a) to (i), or may contain 2 or more functional groups. Such naphthalene diisocyanate-modified compositions may be produced by suitably combining the reactions described above. In addition, the naphthalene diisocyanate-modified composition may be used alone or in combination of 2 or more.

The fourth object of the present invention is to provide a polyurethane prepolymer obtained by reacting the naphthalene diisocyanate composition of one of the objects with a polyol component or by reacting the modified composition of the third object with a substance having an active hydrogen group.

The polyol component comprises one or more of polyether polyols, polyester polyols, polymer polyols. Auxiliaries and/or additives may be added to the prepolymer, and examples thereof include castor oil and carbodiimides as additives to the polyol and the prepolymer.

The fifth object of the present invention is to provide a polyurethane resin obtained by reacting the naphthalene diisocyanate composition of one of the objects with an active hydrogen group-containing substance or by reacting the modified composition of the third object with an active hydrogen group-containing substance.

Examples of the active hydrogen group-containing substance include a polyol component (component mainly containing a polyol having 2 or more hydroxyl groups), a polythiol component (component mainly containing a polythiol having 2 or more mercapto groups (thiol groups)), and a polyamine component (compound mainly containing a polyamine having 2 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 2 or more hydroxyl groups and a number average molecular weight of 60 or more and less than 400.

Examples of the low molecular weight polyol include diols such as 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, the same applies hereinafter) 17-20), isosorbide, 1, 3-or 1, 4-cyclohexanedimethanol and mixtures thereof, 1, 4-cyclohexanediol, hydrogenated bisphenol A, 1, 4-dihydroxy-2-butene, 2, 6-dimethyl-1-octen-3, 8-diol, bisphenol A and the like, triols such as glycerin, trimethylol propane and the like, tetraols such as tetramethylol (pentaerythritol), tetraols such as xylitol and the like, pentaols such as sorbitol, mannitol, allitol, arabitol, dulcitol and the like.

In addition, a polyalkylene oxide having a number average molecular weight of 60 or more and less than 400 (a random and/or block copolymer containing 2 or more alkylene oxides) obtained by adding an alkylene oxide such as ethylene oxide or propylene oxide using the above-mentioned alcohol as an initiator is also contained in the low molecular weight polyol.

The high molecular weight polyol is a compound having 2 or more hydroxyl groups and a number average molecular weight of 400 or more, for example 10000 or less, preferably 5000 or less. Examples of the high molecular weight polyol include polyether polyol, polyester polyol, polycarbonate polyol, polyurethane polyol, epoxy polyol, vegetable oil polyol, polyolefin polyol, acrylic polyol, polysiloxane polyol, fluorine polyol, and vinyl monomer modified polyol.

Examples of the polyether polyol include a polyoxyalkylene (C2-C3) polyol, a polytetramethylene ether glycol, and a polytrimethylene ether glycol. Examples of the polyoxyalkylene (C2-C3) alkylene polyols include addition polymers of C2-3 alkylene oxides such as ethylene oxide and propylene oxide (random and/or block copolymers containing 2 or more alkylene oxides) using the above-mentioned low molecular weight polyols as an initiator. Further, as the polyoxyalkylene (C2-3) group, specifically, polyethylene glycol, polypropylene glycol, polyethylene polypropylene copolymer and the like can be mentioned.

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

In addition, plant-derived polytetramethylene ether glycol prepared from tetrahydrofuran produced from plant-derived materials such as furfural is also included.

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

Examples of the polyester polyol include polycondensates obtained by reacting the above low molecular weight polyol (preferably a diol) with a polybasic acid (preferably a 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-dimethyl-1, 3-dicarboxypropane, 3-methyl-3-ethylglutaric acid, azelaic acid, sebacic acid, and the like, unsaturated aliphatic dicarboxylic acids such as maleic acid, fumaric acid, itaconic acid, and the like, aromatic dicarboxylic acids such as phthalic acid, isophthalic acid, terephthalic acid, toluene dicarboxylic acid, phthalic acid, and the like, alicyclic dicarboxylic acids such as hexahydrophthalic acid, and the like, other carboxylic acids such as dimer acid, hydrogenated dimer acid, HET acid, and the like, and 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 the like, and acid halides derived from these carboxylic acids, such as oxalyl dichloride, adipoyl dichloride, and sebacoyl dichloride, and the like.

Examples of the polyester polyol include a vegetable oil-based polyester polyol obtained by condensation reaction of the low molecular weight polyol described above with a hydroxycarboxylic acid such as a vegetable oil fatty acid containing a hydroxyl group (for example, a castor oil fatty acid containing ricinoleic acid, a hydrogenated castor oil fatty acid containing 12-hydroxystearic acid, etc.) under known conditions.

Examples of the polyester polyol include a polycaprolactone polyol obtained by ring-opening polymerization of a lactone such as epsilon-caprolactone or gamma-valerolactone using the low molecular weight polyol (preferably a diol) as an initiator, a polycaprolactone polyol, and a lactone polyester polyol obtained by copolymerizing the above diol with the above polyol.

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

Further, examples of the polyurethane polyol include a polyester polyol, a polyether polyol and/or a polycarbonate polyol obtained by reacting the above-described polyester polyol, polyether polyol and/or polycarbonate polyol obtained by reacting the above-described polyisocyanate (including naphthalene diisocyanate; the same applies hereinafter) in a ratio of hydroxyl groups to isocyanate groups equivalent to (OH/NCO) of more than 1.

Examples of the epoxy polyol include those obtained by reacting the low molecular weight polyol described above with a polyfunctional halohydrin such as epichlorohydrin or β -methyl epichlorohydrin.

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

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

Examples of the acrylic polyol include a copolymer obtained by copolymerizing an acrylic ester having a hydroxyl group with a copolymerizable vinyl monomer copolymerizable with the acrylic ester having a hydroxyl group.

Examples of the hydroxyl group-containing acrylate include 2-hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate, 2-dihydroxymethylbutyl (meth) acrylate, polyhydroxyalkyl maleate, polyhydroxyalkyl fumarate, and the like. Preferable examples include 2-hydroxyethyl (meth) acrylate.

Examples of the copolymerizable vinyl monomer include (meth) acrylic acid alkyl esters (carbon number 1-12) 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, pentyl (meth) acrylate, isopentyl (meth) acrylate, hexyl (meth) acrylate, isononyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, cyclohexyl (meth) acrylate, isobornyl (meth) acrylate, and the like, for example, styrene, vinyl toluene, and α -methylstyrene.

Aromatic vinyl monomers, vinyl cyanide such as (meth) acrylonitrile, vinyl monomers containing a carboxyl group such as (meth) acrylic acid, fumaric acid, maleic acid, itaconic acid, or alkyl esters thereof, alkane polyol poly (meth) acrylates such as ethylene glycol di (meth) acrylate, butanediol di (meth) acrylate, hexanediol di (meth) acrylate, oligoethylene glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, and vinyl monomers containing an isocyanate group such as 3- (2-isocyanate-2-propyl) - α -methylstyrene.

The acrylic polyol can be obtained by copolymerizing an acrylic ester containing a hydroxyl group and a copolymerizable vinyl monomer in the presence of an appropriate solvent and a polymerization initiator.

The acrylic polyol includes, for example, a polysiloxane polyol and a fluorine polyol.

As the polysiloxane polyol, for example, an acrylic polyol obtained by blending a vinyl-containing polysiloxane compound such as γ -methacryloxypropyl trimethoxysilane as a copolymerizable vinyl monomer in the copolymerization of the above acrylic polyol can be mentioned.

Examples of the fluorine polyol include an acrylic polyol obtained by blending a vinyl group-containing fluorine compound such as tetrafluoroethylene and chlorotrifluoroethylene as a copolymerizable vinyl monomer in the copolymerization of the above acrylic polyol.

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

The above-mentioned polyol component may be used alone or in combination of 2 or more.

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

Specifically, the polyurethane resin can be suitably used for applications such as inks, transfer foils, adhesives, gels, elastomers, foams, adhesives, liquid-curable sealing materials, RIM molded articles, micro-foam polyurethanes, various microcapsules, optical materials, aqueous resins, thermosetting resins, active energy ray (e.g., electron beam, ultraviolet ray, etc.) curable resins, artificial and synthetic leather, setting powders, robot members, moving members, medical care materials, base resins of Carbon Fiber Reinforced Plastics (CFRP), transparent rubbers, transparent hard resins, waterproof materials, films, sheets, pipes, plates, speakers, sensors, organic electroluminescent members, solar power generation members, robot members, wearable members, sporting goods, leisure goods, medical goods, nursing goods, house components, acoustic members, lighting members, chandeliers, outdoor lamps, packages, vibration/shock/vibration absorbing members, soundproof members, daily necessities, sundry goods, bumpers, sleeping wares, stress absorbing materials, stress relieving materials, automobile interior and exterior parts, conveyor members, automatic members, vibration-proof members, sundry equipment, office equipment, and health care equipment.

It is a sixth object of the present invention to provide an elastomer material comprising the polyurethane resin of the fifth object.

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

The elastomer is prepared by reacting naphthalene diisocyanate with a polyol component and a chain extender.

In the method for producing an elastomer, a known urethane catalyst such as an amine or an organometallic compound (for example, an organotin compound, preferably dibutyltin dichloride or the like) may be added to the elastomer raw material, if necessary. Further, if necessary, a plasticizer, an antiblocking agent, a heat stabilizer, a light stabilizer, an ultraviolet absorber, a yellowing inhibitor, an antioxidant, a mold release agent, a pigment, a dye, a lubricant, a nucleating agent, a filler, a hydrolysis inhibitor, and the like may be blended in an appropriate ratio to the elastomer.

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

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

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

the naphthalene diisocyanate composition provided by the invention contains 5-6000ppm of the compound of the formula (1), and the prepared prepolymer has excellent stability.

Drawings

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

Detailed Description

The method for measuring the relevant test in the invention is as follows:

1. molar content of naphthalene diamine

And (3) taking the reaction liquid (mass A), carrying out suction filtration, washing a filter cake for 2-3 times by using dichloromethane, drying the filter cake (mass B), placing the filter cake in tetrahydrofuran, stirring to fully dissolve the naphthalene diamine, filtering and drying to obtain the filter cake (mass C), wherein the mass C minus the mass B is the mass of the naphthalene diamine, and the mass C is the molar content of the naphthalene diamine compared with the total amount of the naphthalene diamine put in.

2. Structure determination and content ratio of compound NAI

The determination of the NAI structure is made by GCMS.

Derivatizing a reaction solution containing NAI: one drop of the reaction solution was mixed with 600uL of acetonitrile, 300uL of bis (trimethylsilyl) trifluoroacetamide, 100uL of pyridine, and heated at 70℃for 30min, to be tested.

Instrument: agilent 8890

The testing method comprises the following steps: (1) chromatography column: DB-5 (30 m.times.0.25 mm.times.0.25 μm); (2) sample injection amount: 1 μl; (3) split ratio: 1/50; (4) sample inlet temperature: 280 ℃; (5) temperature programming: keeping the temperature at 50 ℃ for 2min, heating to 80 ℃ at 5 ℃/min, heating to 280 ℃ at 15 ℃/min, and keeping the temperature for 15min; transmission line temperature: 300 ℃.

Analysis results: the peak with the molecular weight of 256 in the mass spectrum is the derivative of NAI, and the structure is as follows:

analysis was performed by gas chromatography under the following conditions, and the content of the compound NAI was obtained by normalizing the area values of the obtained gas chromatogram.

Instrument: agilent 7890

(1) Chromatographic column: DB-5 (30 m.times.0.25 mm.times.0.25 μm); (2) sample injection amount: 0.5. Mu.L; (3) split ratio: 1/30; (4) sample inlet temperature: 260 ℃; (5) column flow rate: 1.5mL/min; (6) temperature programming: maintaining 1min at 100deg.C, heating to 280 deg.C at 10deg.C/min, and maintaining for 20min; (7) FID detector temperature: 280 ℃; (8) hydrogen flow rate: 40mL/min, air flow rate: 400mL/min.

3. Naphthalene diisocyanate content

The NDI of 99mol% purity in the examples described below was used as a standard substance, and was analyzed by gas chromatography under the following conditions by an internal standard method.

Instrument: agilent 7890

(II) raw materials and sources

TABLE 1 raw material information

To facilitate understanding of the present invention, examples are set forth below. It will be apparent to those skilled in the art that the examples are merely to aid in understanding the invention and are not to be construed as a specific limitation thereof.

Unless otherwise specified, "parts" and "%" are based on mass.

Examples 1 to 7 and comparative examples 1 and 3

The above examples and comparative examples each provide an NDI composition with specific compositions shown in table 2.

The preparation method of the NDI composition comprises the following steps:

NDI compositions were made using the procedure shown in fig. 1. Specifically, 800 parts by mass of chlorobenzene was charged into a luminescence reactor shown in FIG. 1. Next, the luminescence temperature in the luminescence reactor was adjusted to 50℃and the luminescence pressure (gauge pressure) in the luminescence reactor was adjusted to 0.06MPaG. Then, 150 parts by mass of phosgene was introduced into the autoclave through a 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 autoclave through an amine supply line. Thus, an NDA luminescence liquid slurry was prepared.

Next, phosgene was continuously blown into the autoclave through the phosgene supply line at a supply rate of 100 parts by mass/hr, and an amine solution having an NDA concentration of 7.5wt.% was continuously charged into the autoclave through the amine supply line at a supply rate of 1000 parts by mass/hr, while the reactants were fed to the grinding pump through the actinic liquid feed line and circulated back to the autoclave through the actinic liquid feed line in accordance with the gap and residence time of the fluted disc shown in table 2, while the NDA luminescence liquid was fed to the one-pot for thermal irradiation through the actinic liquid feed line.

Next, phosgene was continuously introduced into the thermal-phosgenation reactor. Table 2 shows the reaction temperature and reaction pressure (gauge pressure) of the reactor and the ratio of phosgene supply to NDA 1 mol.

Thus, NDA luminescence liquid is reacted with phosgene to produce NDI, thereby preparing a reaction substance containing NDI. In addition, a part of the unreacted phosgene is condensed by a condenser into an photochemical kettle.

Next, the photochemical reaction liquid was continuously fed into the dephosgene column. The reaction mass is then degassed in a dephosgene column. Next, the deaerated matter is discharged from the deaeration tower through a deaerated matter transporting line, and is continuously transported into the deaeration tower. Thus, 120 parts by mass of desolventized material having a concentration of NDI of 95wt.% was prepared.

Next, the desolventizing substance is discharged from the desolventizing column through a desolventizing substance delivery line, and the desolventized solvent is purified by a solvent purifying column and then reused.

The solvent refining column was packed with a packing material corresponding to 15 theoretical plates, and the operating conditions thereof were as follows:

bottom temperature: 80-150deg.C

Overhead temperature: 60-140 DEG C

Overhead pressure: 2-30kpa

Overhead reflux ratio: 2-10

Residence time: 0.5-10h

Continuously conveying the solvent-removed material into a tar remover. Then, the desolventizing substance is subjected to tar removal in a tar remover to prepare an intermediate substance. The content ratios of chlorobenzene (MCB), NDI, and NAI in the intermediate materials are shown in Table 2.

Next, the intermediate matters were continuously fed into the rectifying column by a feed rate of 100 parts by mass/hr. The rectifying column was packed with a packing material having a theoretical plate number of 5. Then, in the rectifying column, light components are removed from the top of the column, and NDI composition products are withdrawn from the column.

The rectification conditions in the rectification column are as follows:

bottom temperature: 140-200deg.C

Overhead temperature: 130-190 DEG C

Overhead pressure: 0-1.5KPa

Residence time: 1-10h

The recovery rate and the overhead reflux ratio in the rectification step are shown in Table 2.

Thus, NDI compositions were produced. The NDI and NAI content ratios in the NDI compositions are shown in table 2.

Comparative example 2

To the intermediate material obtained in example 1 was added NAI to a content of 1.5%, 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 for examples 1-7 and comparative examples 1-3

/>

Application Performance test

The NDI compositions of the above examples and comparative examples were used to prepare prepolymers and performance evaluation was performed as follows:

prepolymer Synthesis and evaluation

Vacuum (0.7 Kpa) dehydrating polycaprolactone diol (PCL-2000) at 125 ℃ for 2 hours, rapidly stirring, adding 2.5 molar equivalent of NDI composition under the protection of N2, reacting at 125 ℃ for 6-7min while preserving heat, sampling and analyzing the NCO% content, stopping the reaction when the analysis value reaches 4-5%, and filling nitrogen for protection.

The initial NCO content (NCO%) of the prepolymer prepared from the NDI compositions of the above examples and comparative examples was measured by titration (HG/T2409-92). First, N-butylamine in excess of the theoretical NCO content was added and allowed to react, and the residual excess N-butylamine was analyzed with a 0.1N hydrochloric acid reagent.

The prepolymers prepared from the NDI compositions of the above examples and comparative examples were placed in transparent glass bottles, the glass bottles were filled with nitrogen gas and sealed, and then each was stored at 80 ℃ for 30 days to obtain a stored prepolymer, and the nco% of the stored prepolymer was measured in the same manner as described above, and the test results are summarized in table 4.

TABLE 4NDI composition application Effect data

As is clear from Table 4, the present invention can effectively improve the stability of the prepolymer prepared from the composition by controlling the NAI content in the NDI composition to be within 5-6000ppm, wherein the NAI content is lower than 5ppm (comparative example 3) and higher than 6000ppm (comparative examples 1 and 2), the stability is inferior to that of the present invention, the NCO content is severely reduced after the composition is stored for 30 days at 80 ℃, the prepolymer is solidified, and the prepolymer is difficult to be melted again for use after heating.

The applicant states that the detailed method of the present invention is illustrated by the above examples, but the present invention is not limited to the detailed method described above, i.e. it does not mean that the present invention must be practiced in dependence upon the detailed method described above. It should be apparent to those skilled in the art that any modification of the present invention, equivalent substitution of raw materials for the product of the present invention, addition of auxiliary components, selection of specific modes, etc., falls within the scope of the present invention and the scope of disclosure.

Claims

1. A naphthalene diisocyanate composition, characterized in that the naphthalene diisocyanate composition comprises naphthalene diisocyanate and 5 to 6000ppm, preferably 10 to 2000ppm of a compound represented by formula (1):

2. naphthalene diisocyanate composition according to claim 1, characterized in that the naphthalene diisocyanate comprises any one or at least two combinations of 1, 2-naphthalene diisocyanate, 1, 3-naphthalene diisocyanate, 1, 4-naphthalene diisocyanate, 1, 5-naphthalene diisocyanate, 1, 8-naphthalene diisocyanate, preferably 1, 5-naphthalene diisocyanate and/or 1, 8-naphthalene diisocyanate, more preferably 1, 5-naphthalene diisocyanate;

preferably, the naphthalene diisocyanate composition includes 95wt.% or more naphthalene diisocyanate.

3. The naphthalene diisocyanate composition according to claim 1, wherein the compound represented by formula (1) comprises, but is not limited to, any one or a combination of at least two of the following compounds:

4. a process for preparing a naphthalene diisocyanate composition according to any of claims 1 to 3, which comprises:

(1) An isocyanate process:

a. mixing naphthalene diamine and phosgene in the presence of a solvent;

Wherein the intermediate reactant obtained in carrying out reaction b comprises less than 80%, preferably less than 70%, of amine, based on the molar amount of amine fed to the process.

5. The method of claim 3 or 4, wherein the naphthalene diamine comprises any one or a combination of at least two of 1, 2-naphthalene diamine, 1, 3-naphthalene diamine, 1, 4-naphthalene diamine, 1, 5-naphthalene diamine, and 1, 8-naphthalene diamine; and/or the number of the groups of groups,

the reaction solvent is selected from aromatic hydrocarbon, aliphatic hydrocarbon, alicyclic hydrocarbon, halogenated aromatic hydrocarbon, nitrogen-containing compound, ether, ketone, fatty acid ester and aromatic carboxylic ester solvent.

6. A modified composition of a naphthalene diisocyanate composition, characterized in that the modified composition is a naphthalene diisocyanate composition according to any one of claims 1 to 3 or a modified composition obtained by modifying a naphthalene diisocyanate composition prepared by the preparation method according to any one of claims 4 to 6, wherein the modified naphthalene diisocyanate in the modified composition contains any one or a combination of at least two of the following groups (a) to (e): (a) isocyanurate groups, (b) uretdione groups, (c) biuret groups, (d) urethane groups, (e) urea groups, (f) iminooxadiazinedione groups, (g) allophanate groups, (h) uretonimine groups, or (i) carbodiimide groups.

7. A polyurethane prepolymer obtainable by reacting the naphthalene diisocyanate composition of any one of claims 1 to 3 with a polyol component or by reacting the modified composition of claim 6 with a substance containing active hydrogen groups;

preferably, the polyol component comprises one or more of polyether polyols, polyester polyols, polymer polyols;

preferably, auxiliaries and/or additives can also be added to the prepolymer.

8. A polyurethane resin obtained by reacting the naphthalene diisocyanate composition according to any one of claims 1 to 3 or the modified composition according to claim 6 with a substance having an active hydrogen group.

9. An elastomeric material comprising the polyurethane resin of claim 8.