A benzene diisocyanate composition, a preparation method thereof, and an application thereof

Abstract

The present invention relates to a benzene diisocyanate composition, a preparation method and an application thereof. The benzene diisocyanate composition comprises benzene diisocyanate and 5 - 5000 ppm of a compound represented by formula (1). The elastomer prepared from the benzene diisocyanate composition provided by the present invention has excellent wear resistance.

Description

Technical Field

[0001] The invention relates to the technical field of isocyanates, and in particular to a phenylene diisocyanate composition and a preparation method and application thereof. Background Art

[0002] P-phenylene diisocyanate is a highly regular and symmetrical aromatic diisocyanate. It has been used as a raw material for polyurethane in various industrial products, especially in high-performance elastomer materials. Phenylene diisocyanate can be obtained by reacting phenylenediamine with phosgene (phosgene).

[0003] P-phenylene diisocyanate-based elastomers have excellent heat resistance and good dynamic properties. However, the wear resistance of p-phenylene diisocyanate-based elastomers is lower than that of naphthalene diisocyanate-based elastomers. Naphthalene diisocyanate is often not produced on a large scale due to restrictions on the raw material market, thus limiting its wide application in the downstream market. The market for p-phenylenediamine, the raw material of p-phenylene diisocyanate, is sufficient, and p-phenylene diisocyanate and its elastomers can be developed on a large scale.

[0004] Therefore, there is an urgent need in the art to provide a phenylene diisocyanate raw material that can stably produce a high wear-resistant elastomer. Summary of the invention

[0005] In view of the shortcomings of the prior art, one of the purposes of the present invention is to provide a phenylene diisocyanate composition. The polyurethane elastomer prepared from the phenylene diisocyanate composition has excellent wear resistance.

[0006] To achieve this object, the present invention adopts the following technical solutions:

[0007] In one aspect, the present invention provides a phenylene diisocyanate composition, comprising phenylene diisocyanate and 5-5000 ppm (e.g., 6 ppm, 10 ppm, 12 ppm, 15 ppm, 20 ppm, 40 ppm, 50 ppm, 60 ppm, 100 ppm, 150 ppm, 200 ppm, 210 ppm, 250 ppm, 300 ppm, 320 ppm, 350 ppm, 400 ppm, 450 ppm, 500 ppm, 1000 ppm, 1500 ppm, 2000 ppm, 2500 ppm, 3000 ppm, 3500 ppm, 4000 ppm, 4500 ppm, 5000 ppm, etc.) of a compound represented by formula (1);

[0008]

[0009] Among them, R is selected from hydrogen, C1-C12 alkyl, C3-C12 cycloalkyl, substituted C3-C12 cycloalkyl, phenyl, substituted phenyl, a five- or six-membered heteroaromatic group containing at least one atom selected from oxygen, sulfur, and nitrogen atoms, and a group containing at least one atom selected from oxygen, sulfur, and nitrogen atoms.

[0010] The researchers of the present invention found in the study that when the benzene diisocyanate composition contains 5-5000 ppm of the compound of formula (1), the prepared elastomer has excellent wear resistance. When the content is lower than 5 ppm or higher than 5000 ppm, the wear resistance will deteriorate.

[0011] The benzene diisocyanate composition of the present invention is a substantially single compound (i.e., benzene diisocyanate) containing more than 95 wt.% of benzene diisocyanate as the main component, but is defined as a benzene diisocyanate composition because it contains the compound shown by chemical formula (1) as a minor component.

[0012] In the present invention, the benzene diisocyanate composition is denoted as the PPDI composition, the benzene diisocyanate is denoted as PPDI, and the compound (hydroxybenzimidazole) shown by chemical formula (1) is denoted as PMZ.

[0013] Preferably, the benzene diisocyanate composition further includes a bromine-containing compound; the bromine-containing compound can be obtained by conventional methods in the art. In a specific embodiment, the content of the bromine-containing compound can be determined by ICP-OES analysis in terms of the mass of bromine element.

[0014] In terms of the mass of bromine element, the content of the bromine-containing compound is 0.5-50 ppm, such as 1 ppm, 2 ppm, 3 ppm, 4 ppm, 5 ppm, 6 ppm, 7 ppm, 8 ppm, 9 ppm, 10 ppm, 11 ppm, 12 ppm, 13 ppm, 14 ppm, 15 ppm, 16 ppm, 17 ppm, 18 ppm, 19 ppm, 20 ppm, 21 ppm, 22 ppm, 23 ppm, 24 ppm, 25 ppm, 26 ppm, 27 ppm, 28 ppm, 29 ppm, 30 ppm, 31 ppm, 32 ppm, 33 ppm, 34 ppm, 35 ppm, 36 ppm, 37 ppm, 38 ppm, 39 ppm, 40 ppm, 41 ppm, 42 ppm, 43 ppm, 44 ppm, 45 ppm, 46 ppm, 47 ppm, 48 ppm, 49 ppm, etc. If the bromine content is too high, it will cause low PPDI activity and affect the progress of the prepolymerization reaction. If the bromine content is too low, it will cause high activity, and the prepared prepolymer will be non-uniform and the reaction process will release heat violently, posing a safety risk.

[0015] In the present invention, the contents of the compound represented by formula (1) and the bromine-containing compound are both based on the total mass of the composition.

[0016] Preferably, the benzene diisocyanate includes any one or at least two combinations of 1,2-benzenediisocyanate (ortho-phenylene diisocyanate, OPDI), 1,3-benzenediisocyanate (meta-phenylene diisocyanate, MPDI), 1,4-benzenediisocyanate (para-phenylene diisocyanate, PPDI), and toluene diisocyanate, preferably 1,3-benzenediisocyanate and / or 1,4-benzenediisocyanate, more preferably 1,4-benzenediisocyanate.

[0017] Preferably, the compound represented by formula (1) includes any one or at least two combinations of the following compounds:

[0018]

[0019] In the present invention, PMZ is generated as a by-product in the production of PPDI described below. Of course, it can also be added artificially to obtain the required content.

[0020] In the present invention, the content ratio of PMZ can be determined by analysis using gas chromatography.

[0021] The second object of the present invention is to provide a method for preparing the benzene diisocyanate composition, and the preparation method includes:

[0022] (1) Isocyanate chemical process: subjecting phenylenediamine or phenylenediamine hydrochloride to an isocyanation reaction with phosgene in the presence of a reaction solvent to obtain a reaction product containing benzene diisocyanate and the compound represented by formula (1);

[0023] (2) Solvent separation and purification process: removing the solvent from the reaction product obtained in step (1), purifying the removed solvent to obtain a recycled solvent, and then returning it to the reaction system of step (1);

[0024] (3) Separation process: separating and purifying the solvent-removed reaction product obtained in step (2) to obtain the benzene diisocyanate composition.

[0025] The isocyanate chemical process in step (1) can be called the phosgenation method, and the isocyanation reaction is the phosgenation reaction.

[0026] As the phosgenation method, specifically, for example, a method of directly reacting phenylenediamine with phosgene (also the cold and hot two-stage phosgenation method), a method of reacting the hydrochloride obtained by reacting phenylenediamine with hydrochloric acid (hydrogen chloride) with phosgene in a reaction solvent (also called the phosgenation method of amine hydrochloride), etc. can be cited. Preferably, the phosgenation method of amine hydrochloride can be cited.

[0027] Preferably, the phenylenediamine contains any one or a combination of several of the diamino-substituted benzenes and / or toluenes shown in the following compounds:

[0028]

[0029] Preferably, the content of o-diamino-substituted benzene and / or toluene in the phenylenediamine is 10 - 8000 ppm, such as 10 ppm, 20 ppm, 30 ppm, 40 ppm, 50 ppm, 60 ppm, 70 ppm, 80 ppm, 90 ppm, 100 ppm, 110 ppm, 120 ppm, 130 ppm, 140 ppm, 150 ppm, 160 ppm, 170 ppm, 180 ppm, 190 ppm, 200 ppm, 210 ppm, 220 ppm, 230 ppm, 240 ppm, 250 ppm, 260 ppm, 270 ppm, 280 ppm, 290 ppm, 300 ppm, 310 ppm, 320 ppm, 330 ppm, 340 ppm, 350 ppm, 360 ppm, 370 ppm, 380 ppm, 390 ppm, 400 ppm, 410 ppm, 420 ppm, 430 ppm, 440 ppm, 450 ppm, 460 ppm, 470 ppm, 480 ppm, 490 ppm, 500 ppm, 1000 ppm, 1500 ppm, 2000 ppm, 2500 ppm, 3000 ppm, 3500 ppm, 4000 ppm, 4500 ppm, 5000 ppm, 5500 ppm, 6000 ppm, 6700 ppm, 7000 ppm, 7500 ppm, 7990 ppm, etc.

[0030] In addition, according to needs, the proportion of o-diamino-substituted benzene or toluene can be controlled within the above range by purifying the raw material phenylenediamine. There is no particular limitation on the purification method, and industrial separation techniques such as distillation and crystallization can be used for implementation. It should be noted that the proportion of o-diamino-substituted substances in the phenylenediamine composition can also be adjusted by adding o-diamino-substituted benzene or toluene to the phenylenediamine.

[0031] Preferably, the crystallization process is used for the purification of phenylenediamine. The crystallization process includes: adding phenylenediamine to a crystallizer, melting the phenylenediamine by heating, cooling and crystallizing by reducing the temperature of the crystallizer to obtain crude phenylenediamine, and sweating the crude phenylenediamine by raising the temperature of the crystallizer to obtain the phenylenediamine product.

[0032] Preferably, the crystallizer includes a kettle crystallizer or a tubular crystallizer.

[0033] Preferably, the cooling rate of the crystallizer is below 2 °C / min, such as 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 below 1 °C / min.

[0034] Preferably, the cooling rate of the crystallizer is above 0.0001 °C / min, preferably above 0.01 °C / min.

[0035] Preferably, the final crystallization temperature of the crystallizer is 90 - 135 °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, etc., preferably 110 - 130 °C.

[0036] Preferably, the heating rate of the crystallizer is below 2 °C / min, such as 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 below 1 °C / min.

[0037] Preferably, the heating rate of the crystallizer is above 0.0001 °C / min, preferably above 0.01 °C / min.

[0038] Preferably, the final sweating temperature of the crystallizer is 90 - 150 °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, etc., preferably 110 - 140 °C.

[0039] Preferably, the phosgenation of the amine is carried out in two stages: cold phosgenation and thermal phosgenation. The cold phosgenation process includes: mixing phenylenediamine with phosgene in the presence of a reaction solvent to carry out a cold phosgenation reaction, obtaining a cold phosgenation solution of phenylenediamine. What is actually obtained in the cold phosgenation process is a slurry containing phenylenediamine hydrochloride, phenylenediamine acyl chloride, and a very small amount of phenyl diisocyanate, and this slurry is directly applied to the isocyanate chemical process.

[0040] Preferably, the phenylenediamine includes any one or at least two combinations of 1,2-phenylenediamine (o-phenylenediamine (OPDA)), 1,3-phenylenediamine (m-phenylenediamine (MPDA)), 1,4-phenylenediamine (p-phenylenediamine (PPDA)), and toluene diamine (TDA).

[0041] Preferably, the cold phosgenation process specifically includes: introducing phosgene into the reaction solvent, then adding a reaction solvent amine solution containing phenylenediamine, and subsequently stirring and mixing the phosgene and the amine solution to carry out a cold phosgenation reaction, obtaining the cold phosgenation solution of phenylenediamine.

[0042] Preferably, the content of phenylenediamine in the amine solution is 1.0 wt.% or more, such as 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., and preferably 3.0 wt.% or more.

[0043] Preferably, the content of phenylenediamine in the amine solution is 50 wt.% or less, and preferably 30 wt.% or less.

[0044] Preferably, the reaction temperature in the cold phosgenation process is 0 °C or more, such as 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, 140 °C, 150 °C, etc., and preferably 10 °C or more.

[0045] Preferably, the reaction temperature in the cold phosgenation process is 160 °C or less, preferably 150 °C or less, and more preferably 140 °C or less.

[0046] Preferably, the cold phosgenation process is carried out under normal pressure or pressurized conditions.

[0047] Preferably, the pressure (gauge pressure) in the cold phosgenation process is 0.01 MPaG or more, such as 0.1 MPaG, 0.2 MPaG, 0.5 MPaG, 0.6 MPaG, 0.7 MPaG, 0.8 MPaG, 0.9 MPaG, etc., and more preferably 0.02 MPaG or more.

[0048] Preferably, the pressure (gauge pressure) in the phosgenation process is 1.0 MPaG or less, preferably 0.5 MPaG or less, and more preferably 0.4 MPaG or less.

[0049] Preferably, step (1) specifically includes: introducing phosgene into phenylenediamine to carry out phosgenation reaction; continuously introducing phosgene into the phosgenation reaction solution to obtain a reaction product containing phenyl diisocyanate and the compound shown in formula (1).

[0050] When carrying out the isocyanation reaction with the phenylenediamine phosgenation solution and phosgene, the target content of the compound of formula (1) can be obtained by preferably the following parameters. It should be noted that the content ratio of PMZ in the phenyl diisocyanate composition can also be adjusted by adding PMZ to the phenyl diisocyanate composition.

[0051] Preferably, the molar amount of the phosgene is 4 times or more of the molar amount of the phenylenediamine phosgenation solution, such as 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, and more preferably 6 times or more.

[0052] Preferably, the molar amount of the phosgene is 50 times or less of the phenylenediamine phosgenation molar amount, preferably 40 times or less, and more preferably 30 times or less.

[0053] Preferably, the reaction temperature in the isocyanation process is 80 °C or higher, such as 90 °C, 100 °C, 110 °C, 120 °C, 130 °C, 140 °C, 150 °C, etc., preferably 100 °C or higher.

[0054] Preferably, the reaction temperature in the isocyanation process is 180 °C or lower, preferably 170 °C or lower, and more preferably 160 °C or lower.

[0055] Preferably, the reaction time of the isocyanation reaction is 2 h or longer, such as 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.

[0056] Preferably, the reaction time of the isocyanation reaction is 25 h or shorter, preferably 20 h or shorter.

[0057] Preferably, the isocyanation reaction is carried out under normal pressure or pressurized conditions.

[0058] Preferably, the pressure (gauge pressure) of the isocyanation reaction is 0 MPaG or more, such as 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, particularly preferably 0.01 MPaG or more, especially preferably 0.02 MPaG or more, and most preferably 0.03 MPaG or more.

[0059] Preferably, the pressure (gauge pressure) of the isocyanation reaction is 0.6 MPaG or less, preferably 0.4 MPaG or less, and more preferably 0.2 MPaG or less.

[0060] Preferably, the isocyanation process is a batch process or a continuous process, preferably a continuous process.

[0061] The continuous process means that the slurry (phenylenediamine cold reaction solution) 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 phenylenediamine cold reaction solution reacts with phosgene in the hot reaction tank, and the reaction solution (reaction substance) is continuously taken out from the hot reaction tank. The present invention does not specifically limit the number of reaction kettles for the continuous process. Exemplarily, it can be two, three, four, five or more.

[0062] If necessary, a degassing process, a solvent separation and purification process can be carried out on the reaction product of the isocyanation process. The remaining carbonyl chloride phosgene, hydrogen chloride and other gases generated as by-products are removed from the reaction product by using a known degassing tower. In the solvent separation and purification process, the reaction solvent is distilled off from the reaction solution by using a known distillation tower. Most of the solvent returns to the isocyanation process after being refined.

[0063] 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'-dimethylimidazolinone; ethers such as dibutyl ether, ethylene glycol dimethyl ether, and ethylene glycol diethyl ether; ketones such as heptanone, diisobutyl ketone, methyl isobutyl ketone, and methyl ethyl 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 can 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.

[0064] If necessary, a defoaming process can be carried out on the reaction product after removing the solvent. The tar components are removed from the reaction solution using a known defoaming device such as a short-path evaporator. It should be noted that the reaction substance from which the tar components have been removed through the defoaming process is denoted as the intermediate substance.

[0065] In addition, if necessary, the intermediate substance can be purified, and the purification method is not particularly limited and can be carried out using industrial separation techniques such as rectification and crystallization.

[0066] Preferably, the rectification is carried out in a rectification column.

[0067] Preferably, the rectification column includes a plate rectification column or a packed rectification column.

[0068] In a preferred technical solution of the present invention, the proportion of PMZ can be adjusted to the above range by controlling the reaction conditions and separation conditions. It should be noted that the content ratio of PMZ in the PPDI composition can also be adjusted by adding PMZ to the PPDI composition.

[0069] Preferably, the number of theoretical plates of the rectification column is 2 or more, such as 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., and preferably 5 or more.

[0070] Preferably, the number of theoretical plates of the rectification column is 60 or less, and preferably 40 or less.

[0071] Preferably, the top pressure of the rectification column is 0.1 kPa or more, such as 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., and preferably 0.15 kPa or more.

[0072] Preferably, the top pressure of the rectification column is 4 kPa or less, and preferably 2.5 kPa or less.

[0073] Preferably, the top reflux ratio of the rectification column is 0.01 or more, such as 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., and preferably 0.1 or more.

[0074] Preferably, the top reflux ratio of the rectification column is 60 or less, and preferably 40 or less.

[0075] In a preferred technical solution of the present invention, the manufacturing method of the above-mentioned benzene diisocyanate composition can be implemented, for example, by using Figure 1 the flow chart shown. As Figure 1 shown, it mainly includes a cold photochemical unit. In the subsequent isocyanation unit, a continuous thermal photochemical unit (performed in a thermal photochemical kettle) is implemented. By appropriately adjusting the proportion of o-diamino substituents in the above raw materials, the supply proportion of phosgene, the reaction temperature, the reaction pressure, the average residence time, etc., the production amounts of benzene diisocyanate and PMZ are adjusted. A degassing unit and a desolventizing unit are arranged after the photochemical kettle to remove phosgene and solvent from the reaction liquid. And, a de-heavy component unit is arranged after the desolventizing unit to perform a de-tar process on the reaction product after desolventization, and then enter the refining unit for rectification to obtain the final product.

[0076] Moreover, in the subsequent rectification separation, by appropriately adjusting the above-mentioned top reflux ratio, etc., the content ratio of PMZ in the benzene diisocyanate composition is adjusted.

[0077] Specifically, first, a reaction solvent is charged into the cold photochemical kettle. Then, phosgene is continuously supplied to the bottom of the cold photochemical kettle through the phosgene supply line at the above-mentioned supply ratio. In addition, the above-mentioned amine solution in which phenylenediamine is dissolved in the reaction solvent is continuously supplied to the top of the cold photochemical kettle through the amine supply line. Then, while maintaining the inside of the cold photochemical kettle at the above-mentioned cold photochemical temperature and cold photochemical pressure, the phosgene and the amine solution are stirred and mixed by the stirring blades (cold photochemical process). Thus, a slurry containing phenylenediamine hydrochloride, phenylenediamine acyl chloride, and a small amount of benzene diisocyanate is produced.

[0078] Subsequently, a slurry containing hydrochloride of phenylenediamine, phenylenediamine acyl chloride, and a small amount of phenyl diisocyanate is continuously fed to the top of the thermal photochemical reactor through the cold photochemical liquid delivery line. That is, while continuously supplying phosgene and amine solution to the cold photochemical reactor, the slurry containing hydrochloride of phenylenediamine, phenylenediamine acyl chloride, and a small amount of phenyl diisocyanate is continuously withdrawn from the cold photochemical reactor and transported to the thermal photochemical reactor.

[0079] Next, phosgene is continuously supplied to the top of the thermal photochemical reactor in the form of an inserted tube at the above-mentioned supply ratio. Subsequently, while maintaining the inside of the thermal photochemical reactor at the above-mentioned reaction temperature and reaction pressure, the slurry and phosgene are stirred and mixed. Thereby, the cold photochemical liquid of phenylenediamine reacts with carbonyl chloride to generate phenyl diisocyanate as the main component, and PMZ and bromine-containing compounds or their intermediates as by-products.

[0080] Thereby, the cold photochemical process and the isocyanate process are continuously carried out.

[0081] Subsequently, a reaction liquid containing phenyl diisocyanate, PMZ, bromine-containing compounds or their intermediates, and a reaction solvent is produced. It should be noted that the total residence time in the isocyanate process is within the above-mentioned range.

[0082] Next, the above-mentioned photochemical reaction liquid is continuously fed to the middle part of the degassing tower through the reaction substance delivery line. Through the degassing tower, the photochemical liquid is separated into a gas containing phosgene and hydrogen chloride, etc., and a degassed substance in liquid form containing phenyl diisocyanate, PMZ, bromine-containing compounds or their intermediates, and a reaction solvent (degassing process).

[0083] Next, the degassed substance is continuously fed to the middle of the solvent removal tower through the degassed substance delivery line. Subsequently, the reaction solvent is distilled off from the degassed substance by using the solvent removal tower (solvent separation and purification process) to obtain a degassed substance containing phenyl diisocyanate, PMZ, and bromine-containing compounds or their intermediates.

[0084] Next, the degassed substance is continuously fed to the upper part of the de-tarring device through the degassed substance delivery line. Subsequently, the tar component is removed from the degassed substance by using the de-tarring device to obtain an intermediate substance containing phenyl diisocyanate, PMZ, and bromine-containing compound intermediates (de-tarring process).

[0085] Next, the intermediate substance is continuously fed to the middle of the distillation column through the intermediate substance delivery line. Subsequently, under the conditions of the above-mentioned distillation process (bottom temperature, top temperature, top pressure, bottom reflux ratio, top reflux ratio, and residence time), the low-boiling substances are distilled off from the intermediate quality, and the phenyl diisocyanate composition is withdrawn from the lower part of the middle of the column.

[0086] Thus, a benzene diisocyanate composition containing benzene diisocyanate, PMZ and a bromine-containing compound can be continuously produced.

[0087] A third object of the present invention is to provide a modified composition of a benzene diisocyanate composition, which is a modified composition obtained by modifying the benzene diisocyanate composition described in one of the objects. The modified benzene diisocyanate in the modified composition contains any one or at least two combinations of the following groups (a)-(e): (a) isocyanurate group, (b) uretdione group, (c) biuret group, (d) carbamate group, (e) urea group, (f) iminooxadiazinedione group, (g) urethane group, (h) uretonimine group or (i) carbodiimide group.

[0088] Those skilled in the art can modify the benzene diisocyanate composition according to needs by using known methods to obtain a benzene diisocyanate modified composition, and the benzene diisocyanate modified composition is suitably used as a polyisocyanate component and a component containing an active hydrogen group as a raw material for polyurethane resin.

[0089] More specifically, the modified benzene diisocyanate containing the functional group (isocyanurate group) of the above (a) is a trimer of benzene diisocyanate, and can be obtained, for example, by reacting the benzene diisocyanate composition in the presence of a known isocyanuration catalyst to carry out isocyanuration of the benzene diisocyanate therein.

[0090] The modified benzene diisocyanate containing the functional group (urethane group) of the above (b) can be obtained by reacting the benzene diisocyanate composition with an alcohol and then further reacting it in the presence of a known urethanation catalyst.

[0091] The modified benzene diisocyanate containing the functional group (biuret group) of the above (c) can be obtained by reacting the benzene diisocyanate composition with, for example, water, a tertiary alcohol (e.g., tert-butanol, etc.), a secondary amine (e.g., dimethylamine, diethylamine, etc.), etc. and then further reacting it in the presence of a known biuretization catalyst.

[0092] The modified benzene diisocyanate containing the functional group (carbamate group) of the above (d) can be obtained by reacting the benzene diisocyanate composition with a polyol component (e.g., trimethylolpropane, etc.).

[0093] The modified benzene diisocyanate containing the functional group (urea group) of the above (e) can be obtained by reacting the benzene diisocyanate composition with water, a polyamine component (described later), etc.

[0094] A modified phenyl diisocyanate (asymmetric trimer) containing the functional group (iminooxadiazinedione group) of the above (f) can be obtained by reacting a phenyl diisocyanate composition in the presence of a known iminooxadiazinedionization catalyst to carry out iminooxadiazinedionization (such as trimerization) of the phenyl diisocyanate.

[0095] A modified phenyl diisocyanate containing the functional group (uretdione group) of the above (g) can be obtained by heating a phenyl diisocyanate composition at about 90°C - 200°C, or by reacting it in the presence of a known uretdionization catalyst to carry out uretdionization (such as dimerization) of the phenyl diisocyanate.

[0096] A modified phenyl diisocyanate containing the functional group (uretonimine group) of the above (h) can be obtained by reacting a phenyl diisocyanate composition in the presence of a known carbodiimidization catalyst to form a carbodiimide group, and then adding a phenyl diisocyanate to the carbodiimide group.

[0097] A modified phenyl diisocyanate containing the functional group (carbodiimide group) of the above (i) can be obtained by reacting a phenyl diisocyanate composition in the presence of a known carbodiimidization catalyst.

[0098] It should be noted that the phenyl diisocyanate modified composition only needs to contain at least one of the above functional groups (a)-(i), and may also contain two or more. Such a phenyl diisocyanate modified composition can be generated by appropriately combining the above reactions. In addition, the phenyl diisocyanate modified composition can be used alone or in combination of two or more.

[0099] A fourth object of the present invention is to provide a polyurethane resin, which is formed by reacting the phenyl 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.

[0100] Examples of the substance containing an active hydrogen group include a polyol component (a component mainly containing a polyol having two or more hydroxyl groups), a polythiol component (a component mainly containing a polythiol having two or more mercapto groups (thiol groups)), a polyamine component (a compound of a polyamine mainly containing two or more amino groups), etc.

[0101] Examples of the polyol component include low molecular weight polyols and high molecular weight polyols.

[0102] The low molecular weight polyol is a compound having two or more hydroxyl groups and a number average molecular weight of 60 or more and less than 400.

[0103] Examples of the low molecular weight polyols 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 (C (carbon number, the same below) 7 - 22) diol, diethylene glycol, triethylene glycol, dipropylene glycol, 3 - methyl - 1,5 - pentanediol, alkane - 1,2 - diol (C17 - 20), isosorbide, 1,3 - or 1,4 - cyclohexanedimethanol and their mixtures, 1,4 - cyclohexanediol, hydrogenated bisphenol A, 1,4 - dihydroxy - 2 - butene, 2,6 - dimethyl - 1 - octene - 3,8 - diol, bisphenol A and other diols, glycerol, trimethylolpropane and other triols, pentaerythritol, diglycerol and other tetraols, xylitol and other pentaols, sorbitol, mannitol, allitol, iditol, dulcitol, adonitol, inositol, dipentaerythritol and other hexaols, avocitol and other heptaols, sucrose and other octaols, etc.

[0104] In addition, polyalkylene oxides having a number - average molecular weight of 60 or more and less than 400 (random and / or block copolymers containing two or more kinds of alkylene oxides) obtained by adding alkylene oxides such as ethylene oxide and propylene oxide using the above - mentioned alcohols as initiators are also included in the low molecular weight polyols.

[0105] The high molecular weight polyols are compounds having two 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 polyols include polyether polyols, polyester polyols, polycarbonate polyols, polyurethane polyols, epoxy polyols, vegetable oil polyols, polyolefin polyols, acrylic polyols, polysiloxane polyols, fluoropolyols, and vinyl monomer - modified polyols.

[0106] Examples of the polyether polyols include polyoxy (C2 - C3) alkylene polyols, polytetramethylene ether glycol, polytrimethylene ether glycol, etc. Examples of the polyoxy (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 two or more kinds of alkylene oxides) using the above - mentioned low molecular weight polyols as initiators. In addition, as the polyoxy (C2 - 3) alkylene, specifically, polyethylene glycol, polypropylene glycol, polyethylene - polypropylene copolymer, etc. can also be mentioned.

[0107] Examples of the polytetramethylene ether glycol include ring - opening polymers (polytetramethylene ether glycol) obtained by cationic polymerization of tetrahydrofuran, amorphous polytetramethylene ether glycol obtained by copolymerizing the polymerization units of tetrahydrofuran with the above - mentioned diols, etc.

[0108] In addition, plant-derived polytetramethylene ether glycol starting from tetrahydrofuran made from plant-derived raw materials such as furfural can also be cited.

[0109] As polytrimethylene ether glycol, for example, a polyol produced by polycondensation of plant-derived 1,3-propanediol can be cited.

[0110] As polyester polyol, for example, a condensate obtained by reacting the above-mentioned low molecular weight polyol (preferably a diol) with a polybasic acid (preferably a dibasic acid) under known conditions can be cited.

[0111] As polybasic acids, for example, saturated aliphatic dicarboxylic acids 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, sebacic acid (C11-C13), unsaturated aliphatic dicarboxylic acids such as maleic acid, fumaric acid, itaconic acid, aromatic dicarboxylic acids such as phthalic acid, isophthalic acid, terephthalic acid, toluene dicarboxylic acid, naphthalene dicarboxylic acid, 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 acyl halides derived from these carboxylic acids, such as oxalyl dichloride, adipoyl dichloride, sebacoyl dichloride, etc.

[0112] In addition, as polyester polyol, for example, a vegetable oil-based polyester polyol obtained by subjecting the above-mentioned low molecular weight polyol and a hydroxycarboxylic acid such as a vegetable oil fatty acid containing a hydroxyl group (for example, castor oil fatty acid containing ricinoleic acid, hydrogenated castor oil fatty acid containing 12-hydroxy stearic acid, etc.) to a condensation reaction can be cited.

[0113] In addition, as polyester polyol, for example, polycaprolactone polyol, polypentanolide polyol obtained by ring-opening polymerization of lactones such as ε-caprolactone, γ-valerolactone using the above-mentioned low molecular weight polyol (preferably a diol) as an initiator, and lactone-based polyester polyol obtained by copolymerizing them with the above-mentioned diol can be cited.

[0114] As polycarbonate polyol, for example, 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 the ring-opening polymer can be cited.

[0115] In addition, regarding polyurethane polyols, examples include polyester polyurethane polyols, polyether polyurethane polyols, polycarbonate polyurethane polyols, or polyester polyether polyurethane polyols obtained by reacting the polyester polyols, polyether polyols, and / or polycarbonate polyols obtained by the above method with the above polyisocyanates (including phenyl diisocyanate, the same below) in a ratio where the equivalent ratio of hydroxyl groups to isocyanate groups (OH / NCO) is greater than 1.

[0116] Examples of epoxy polyols include epoxy polyols obtained by reacting the above-mentioned low-molecular-weight polyols with polyfunctional haloalcohols such as epichlorohydrin and β-methyl epichlorohydrin.

[0117] Examples of vegetable oil polyols include hydroxyl group-containing vegetable oils such as castor oil and coconut oil. Examples include castor oil polyols or ester-modified castor oil polyols obtained by reacting castor oil polyols with polypropylene polyols.

[0118] Examples of polyolefin polyols include polybutadiene polyols and partially saponified ethylene-vinyl acetate copolymers.

[0119] Examples of acrylic polyols include copolymers obtained by copolymerizing an acrylic ester containing a hydroxyl group with a copolymerizable vinyl monomer copolymerizable with the acrylic ester containing a hydroxyl group.

[0120] Examples of acrylic esters containing a hydroxyl group include 2-hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, hydroxybutyl (meth)acrylate, 2,2-dihydroxymethylbutyl (meth)acrylate, polyhydroxyalkyl maleate, polyhydroxyalkyl fumarate, etc. Preferred examples include 2-hydroxyethyl (meth)acrylate.

[0121] Examples of copolymerizable vinyl monomers include (meth)acrylic acid alkyl esters (with 1-12 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, pentyl (meth)acrylate, isopentyl (meth)acrylate, hexyl (meth)acrylate, isononyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, cyclohexyl acrylate, isobornyl (meth)acrylate, and styrene, vinyltoluene, α-methylstyrene, etc.

[0122] Aromatic vinyl monomers, such as vinyl cyanides like (meth)acrylonitrile, vinyl monomers containing a carboxyl group like (meth)acrylic acid, fumaric acid, maleic acid, itaconic acid, or their alkyl esters, such as alkane polyol poly(meth)acrylates like ethylene glycol di(meth)acrylate, butanediol di(meth)acrylate, hexanediol di(meth)acrylate, oligoethylene glycol di(meth)acrylate, trimethylolpropane di(meth)acrylate, trimethylolpropane tri(meth)acrylate, vinyl monomers containing an isocyanate group like 3-(2-isocyanato-2-propyl)-α-methylstyrene, etc.

[0123] Moreover, the acrylic polyol can be obtained by copolymerizing these hydroxyl group-containing acrylate esters and copolymerizable vinyl monomers in the presence of a suitable solvent and a polymerization initiator.

[0124] In addition, the acrylic polyol includes, for example, polysiloxane polyol and fluoropolyol.

[0125] As the polysiloxane polyol, for example, an acrylic polyol obtained by incorporating a vinyl group-containing polysiloxane compound such as γ-methacryloxypropyltrimethoxysilane as a copolymerizable vinyl monomer in the copolymerization of the above-mentioned acrylic polyol can be cited.

[0126] As the fluoropolyol, for example, an acrylic polyol obtained by incorporating a vinyl group-containing fluorine compound such as tetrafluoroethylene or chlorotrifluoroethylene as a copolymerizable vinyl monomer in the copolymerization of the above-mentioned acrylic polyol can be cited.

[0127] The vinyl monomer-modified polyol can be obtained by the reaction of the above-mentioned high molecular weight polyol and a vinyl monomer such as the above-mentioned (meth)acrylic acid alkyl ester.

[0128] The above polyol components can be used alone or in combination of two or more.

[0129] In addition, in the reaction of the polyisocyanate component and the component containing an 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 formed, 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 formed. Both the isocyanate group-terminated polymer and the active hydrogen group-terminated polymer are included in the resin (polyurethane resin). The isocyanate group-terminated polymer is a one-component curable resin.

[0130] As uses of the polyurethane resin, specifically, it can be suitably applied to inks, transfer foils, adhesives, binders, gels, elastomers, foams, adhesives, liquid-curing sealants, RIM molded articles, microcellular polyurethanes, various microcapsules, optical materials, aqueous resins, thermosetting resins, active energy ray (e.g., electron beam, ultraviolet ray, etc.) curable resins, artificial and synthetic leathers, solidifying powders, robot components, moving components, healthcare materials, base resins for carbon fiber reinforced plastics (CFRP), transparent rubbers, transparent rigid resins, waterproof materials, films, sheets, tubes, plates, speakers, sensors, organic electroluminescent components, solar power generation components, robot components, wearable components, sports goods, leisure goods, medical supplies, nursing supplies, residential components, audio components, lighting components, chandeliers, outdoor electric lights, packaging, anti-vibration / anti-seismic / damping components, soundproofing components, daily necessities, sundries, buffers, bedding, stress absorption materials, stress relaxation materials, interior and exterior decorative parts of automobiles, conveying mechanism components, components for office automation equipment, surface protection components for sundries, self-healing materials, health appliances, and other uses.

[0131] A sixth object of the present invention is to provide an elastomeric material, which includes the polyurethane resin described in the fifth object.

[0132] As elastomers, for example, cast polyurethane elastomers (CPU), thermoplastic polyurethane elastomers (TPU), thermosetting polyurethane elastomers (TSU), rollable polyurethane elastomers, etc. can be cited.

[0133] The elastomer contains soft segments formed by the reaction of phthalic diisocyanate and high molecular weight polyols, and hard segments formed by the reaction of phthalic diisocyanate and low molecular weight polyols and / or low molecular weight polyamines.

[0134] 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 raw materials for the elastomer.

[0135] Regarding the high molecular weight polyol as a raw material for the elastomer, for example, the above-mentioned polyester polyols (e.g., polycaprolactone polyols, adipic acid-based polyester polyols (polyester polyols using adipic acid as a polybasic acid)), the above-mentioned polycarbonate polyols, the above-mentioned polytetramethylene ether glycols (e.g., polytetramethylene ether glycol) can be cited, and adipic acid-based polyester polyols are preferably cited.

[0136] Examples of the low molecular weight polyols used as raw materials for the elastomer include, for example, ethylene glycol, 1,4-butanediol, etc., and 1,4-butanediol is preferably cited.

[0137] Examples of the low molecular weight polyamines used as raw materials for the elastomer include, for example, the above-mentioned low molecular weight polyamines.

[0138] The elastomer can be produced, for example, by known methods such as the one-shot method or the prepolymer method.

[0139] It should be noted that, regarding the production method of the elastomer, for example, bulk polymerization, solution polymerization, etc. can be used.

[0140] In addition, in the production method of the elastomer, if necessary, known urethanization catalysts such as amines, organometallic compounds (for example, organotin compounds, preferably dibutyltin dichloride, etc.) can be added to the elastomer raw materials. Further, if necessary, plasticizers, anti-caking agents, heat stabilizers, light stabilizers, ultraviolet absorbers, yellowing inhibitors, antioxidants, mold release agents, pigments, dyes, lubricants, nucleating agents, fillers, hydrolysis inhibitors, etc. can be compounded in the elastomer in appropriate proportions.

[0141] Thus, the elastomer can be produced. Such an elastomer has excellent mechanical properties (elongation and strength), especially outstanding wear resistance.

[0142] In addition, the elastomer material based on phenyl diisocyanate is usually produced by the prepolymer method. Specifically, a polyol compound and an isocyanate compound are mixed to obtain a prepolymer, and an appropriate chain extender is optionally added, and an appropriate auxiliary agent is optionally added. When necessary, the mixture (polymerizable composition) is defoamed by an appropriate method and then injected into an injection mold for the elastomer material, and it is usually slowly heated from a low temperature to a high temperature to polymerize it. Then, the elastomer is obtained by demolding.

[0143] In addition, if necessary, the elastomer can be vulcanized to optimize its performance.

[0144] If the content ratio of PMZ in the phenyl diisocyanate composition or phenyl diisocyanate-modified composition for the elastomer material is 5 ppm or more and 5000 ppm or less, a high wear-resistant elastomer material can be stably produced from the phenyl diisocyanate composition or phenyl diisocyanate-modified composition for the elastomer material.

[0145] The abrasion of the elastomer material provided by the present invention can be controlled within 25 mm 3 (abrasion test standard ISO4649).

[0146] The Taber abrasion (S42 / 4.9N) of the elastomer material provided by the present invention can be controlled within 7.5 mg (abrasion test standard ISO 9352).

[0147] Compared with the prior art, the present invention has the following beneficial effects:

[0148] The diphenyl diisocyanate composition provided by the present invention contains 5 - 5000 ppm of the compound of formula (1), and the elastomer prepared therefrom has excellent wear resistance. Brief Description of the Drawings

[0149] Figure 1 is a flowchart for preparing the diphenyl diisocyanate composition in the specific embodiment of the present invention; Specific Embodiments

[0150] (1) The determination methods for relevant tests in the present invention are as follows:

[0151] 1. Content ratio of compound PMZ

[0152] First, commercially available PMZ with a purity of 99 mol% is used as a reference substance, and analyzed by gas chromatography under the following conditions. A standard curve (external standard method) is made from the area values of the obtained gas chromatograms.

[0153] 2. Content ratio of diphenyl diisocyanate

[0154] PPDI with a purity of 99 mol% in the following examples is used as a reference substance, and analyzed by gas chromatography under the following conditions using the internal standard method.

[0155] Instrument: Agilent 7890

[0156] (1) Chromatographic column: DB - 5 (30 m × 0.25 mm × 0.25 μm); (2) Injection volume: 0.5 μL; (3) Split ratio: 1 / 30; (4) Injection port temperature: 260 °C; (5) Column flow rate: 1.5 mL / min; (6) Programmed temperature rise: Hold at 100 °C for 1 min, rise to 280 °C at 10 °C / min, and hold for 20 min; (7) FID detector temperature: 280 °C; (8) Hydrogen flow rate: 40 mL / min, air flow rate: 400 mL / min.

[0157] 3. The bromine element content in PPDI is determined by ICP - OES analysis;

[0158] Instrument: Thermo Scientific ICAP 7200 ICP - OES

[0159] 4. Wear test method for elastomer: ISO 4649

[0160] 5. Taber wear (S42 / 4.9N) test method for elastomer: ISO 9352

[0161] (II) Raw materials and sources

[0162] Table 1 Raw Materials and Sources Reagent Name Manufacturer Purity p-Phenylenediamine Annuo Chemistry ＞99.0％ o-Phenylenediamine Annuo Chemistry ＞99.0％ Hydroxybenzimidazole Energy Chemical ＞99.0％ Polycaprolactone Diol (Molecular Weight 2000) Daicel (Grade 220N) Industrial Grade 1,4-Butanediol Sinopharm Analytical Reagent

[0163] For the convenience of understanding the present invention, the following examples are listed. Those skilled in the art should understand that the said examples are only for helping to understand the present invention and should not be regarded as specific limitations on the present invention.

[0164] It should be noted that unless otherwise specified, "parts" and "%" are based on mass.

[0165] The control method for the content of o-phenylenediamine in PPDA is as follows:

[0166] Add PPDA into the inner tube of the crystallizer, and displace it with nitrogen for 3 times; turn on the constant temperature oil bath and heat it to 145 °C (the temperature in the experiment

[0167] is the temperature of the heat carrier silicone oil in the oil bath), after the raw materials in the crystallizer are completely melted, lower the temperature of the oil bath tank to make the temperature in the crystallizer drop to slightly higher than the melting point temperature corresponding to the material.

[0168] Stabilize for a period of time, perform cooling crystallization operation, and control the oil bath temperature through the program of the oil bath to make the molten liquid in the crystallizer linearly cool and crystallize at a set rate; when the predetermined time is reached, open the discharge valve to discharge the mother liquor.

[0169] According to the temperature control program, gradually increase the oil bath temperature to perform sweating operation.

[0170] Heat the crystal layer to make it all melt, discharge it naturally, collect the product with a collection tank, and weigh and analyze it. The specific composition is shown in Table 2 for details.

[0171] Examples 1-7, Comparative Example 1

[0172] The above examples and comparative examples respectively provide a PPDI composition, and the specific composition is shown in Table 2 for details.

[0173] The preparation method of the PPDI composition is as follows:

[0174] Using Figure 1 the process shown to manufacture the PPDI composition. Specifically, load 800 parts by mass of chlorobenzene into Figure 1In the shown cold photochemical reactor. Next, adjust the cold photochemical temperature in the cold photochemical reactor to 30 °C, and adjust the cold photochemical pressure (gauge pressure) in the cold photochemical reactor to 0.05 MPaG. Then, introduce 150 parts by mass of phosgene into the cold photochemical reactor through the phosgene supply line, and charge a mixed solution (amine solution) of 150 parts by mass of PPDA and 1050 parts by mass of chlorobenzene into the cold photochemical reactor through the amine supply line. Thus, a PPDA cold photochemical liquid slurry is prepared.

[0175] Next, continuously blow phosgene into the cold photochemical reactor through the phosgene supply line at a supply rate of 100 parts by mass / hr, and continuously charge an amine solution with a PPDA concentration of 7.5 wt.% into the cold photochemical reactor through the amine supply line at a supply rate of 1000 parts by mass / hr. At the same time, transport the PPDA cold photochemical liquid to the first hot photochemical reactor through the cold photochemical liquid transport line.

[0176] Next, continuously introduce phosgene into the hot photochemical reactor at the supply rates shown in Table 2. The reaction temperature and reaction pressure (gauge pressure) of the reaction kettle, and the supply ratio of phosgene relative to 1 mol of PPDA are shown in Table 2.

[0177] Thus, react the PPDA cold photochemical liquid with phosgene to generate PPDI, and prepare a reaction substance containing PPDI. In addition, a part of the unreacted phosgene is condensed by the condenser into the photochemical reactor.

[0178] Next, continuously transport the photochemical reaction liquid to the degassing tower. Then, degas the reaction substance in the degassing tower. Next, discharge the degassed substance from the degassing tower through the degassed substance transport line and continuously transport it to the solvent removal tower. Thus, 120 parts by mass of a solvent-removed substance with a PPDI concentration of 95 wt.% is prepared.

[0179] Next, discharge the solvent-removed substance from the solvent removal tower through the solvent-removed substance transport line, and the removed solvent is refined by the solvent refining tower and then recycled.

[0180] The solvent refining tower is filled with a packing equivalent to 15 theoretical plates, and its operating conditions are as follows:

[0181] Bottom temperature: 80 - 130 °C

[0182] Top temperature: 60 - 120 °C

[0183] Top pressure: As shown in Table 2

[0184] Top reflux ratio: As shown in Table 2

[0185] Residence time: 0.5 - 10 h

[0186] The material after solvent removal is continuously fed into a de-tarring device. Then, the solvent-removed material is de-tarred in the de-tarring device to prepare an intermediate material. The content ratios of chlorobenzene (MCB), PPDI, PMZ, and bromine element in the intermediate material are shown in Table 2.

[0187] Next, the intermediate material is continuously fed into a rectification column at a supply rate of 100 mass parts / hr. For the rectification column, packing equivalent to 5 theoretical plates is filled. Then, in the rectification column, light components are removed from the top of the column, and a PPDI composition product is withdrawn from the middle of the column.

[0188] The rectification conditions in the rectification column are as follows:

[0189] Bottom temperature: 110 - 130 °C

[0190] Top temperature: 100 - 110 °C

[0191] Top pressure: 0 - 1.5 KPa

[0192] Residence time: 1 - 10 h

[0193] The withdrawal amount and top reflux ratio in the rectification process are shown in Table 2.

[0194] Thus, a PPDI composition is manufactured. The content ratios of PPDI, PMZ, and bromine element in the PPDI composition are shown in Table 2.

[0195] Comparative Example 2

[0196] O-Phenylenediamine is added to the PPDA obtained in Example 1 to a content of 2%, and a PPDI composition of Comparative Example 2 is prepared under the same photochemical, concentration, and separation conditions as in Example 1.

[0197] Table 2 Conditions and Results of Examples 1 - 7 and Comparative Examples 1 - 2

[0198]

[0199] Application Performance Test

[0200] The PPDI compositions of the above examples and comparative examples are used to prepare various elastomeric materials, and performance evaluations are carried out as follows:

[0201] The polycaprolactone diol (PCL-2000) was dehydrated under vacuum (0.7 Kpa) at 125 °C for 2 h, then cooled to 80 °C and stirred rapidly. Under N2 protection, 2.5 molar equivalents of the PPDI composition were added, and the reaction was carried out at 85 °C for 120 min while maintaining the temperature. The content of NCO% was analyzed by sampling. When the analyzed value reached 5%, the prepolymer was cooled to 90 °C, and 10 parts by weight of the chain extender 1,4-butanediol (calculated based on 100 parts by weight of the prepolymer) was added. After rapid mixing for 30 s, degassing was carried out under vacuum (0.7 Kpa), and then it was poured into a mold that had been preheated to 120 °C and coated with a mold release agent. It was cured in an oven at 120 °C for 10 min, demolded, post-vulcanized in an oven at 120 °C for 24 h, parked at room temperature for one week, and then post-vulcanized at 120 °C for 24 h again. This was repeated three times to achieve the best performance. The abrasion of the elastomer was tested according to standard ISO 4649, and the Taber abrasion (S42 / 4.9N) of the elastomer was tested according to standard ISO 9352. The test results are summarized in Table 3.

[0202] Table 3 Application effect data of PPDI composition

[0203]

[0204] As can be seen from Table 1, by controlling the content of PMZ in the PPDI composition within 5 - 5000 ppm, the wear resistance of the elastomer prepared from the composition can be effectively improved. When the content of PMZ is less than 5 ppm (Comparative Example 1) or higher than 5000 ppm (Comparative Example 2), the wear resistance is inferior to that of the present invention. The PPDI composition provided by the present invention has a better application prospect in various elastomer materials.

[0205] The applicant declares that the present invention uses the above embodiments to illustrate the detailed method of the present invention, but the present invention is not limited to the above detailed method, that is, it does not mean that the present invention must rely on the above detailed method to be implemented. Those skilled in the art should understand that any improvement to the present invention, the equivalent substitution of each raw material of the product of the present invention, the addition of auxiliary components, and the selection of specific methods, etc., all fall within the protection scope and the disclosure scope of the present invention.

Claims

1. A benzene diisocyanate composition, the benzene diisocyanate composition comprising benzene diisocyanate and 5 - 5000 ppm of a compound represented by formula (1); the benzene diisocyanate composition contains 99.7 wt.% or more of benzene diisocyanate; Among them, R is selected from hydrogen, C1 - C12 alkyl, C3 - C12 cycloalkyl, substituted C3 - C12 cycloalkyl, phenyl, substituted phenyl, a five - or six - membered heteroaromatic group containing at least one atom selected from oxygen, sulfur, and nitrogen atoms, a group containing at least one atom selected from oxygen, sulfur, and nitrogen atoms; the compound represented by formula (1) includes any one or at least two combinations of the following compounds:

2. The phenyl diisocyanate composition according to claim 1, characterized in that, The benzene diisocyanate composition further includes a bromine - containing compound; based on the mass of bromine element, the content of the bromine - containing compound is 0.5 - 50 ppm.

3. The preparation method of the benzene diisocyanate composition according to any one of claims 1-2, characterized in that, The preparation method includes: (1) Isocyanate chemical process: Reacting phenylenediamine or phenylenediamine hydrochloride with phosgene in the presence of a reaction solvent to carry out an isocyanation reaction to obtain a reaction product containing benzene diisocyanate and the compound represented by formula (1); (2) Solvent separation and refining process: Removing the solvent from the reaction product obtained in step (1), and after solvent removal, refining the solvent to obtain a recycled solvent, and then returning it to the reaction system of step (1); (3) Separation process: Separating and purifying the solvent - removed reaction product obtained in step (2) to obtain the benzene diisocyanate composition.

4. The preparation method according to claim 3, wherein The phenylenediamine contains any one or several combinations of diamino - substituted benzene and / or toluene represented by the following compounds: The content of o-diamino-substituted benzene and / or toluene in the phenylenediamine is 10 - 8000 ppm.

5. The preparation method according to claim 3 or 4, characterized in that, In step (1), the phenylenediamine includes any one or at least two combinations of 1,2 - phenylenediamine, 1,3 - phenylenediamine, 1,4 - phenylenediamine, and toluenediamine; and / or, the reaction solvent is selected from aromatic hydrocarbons, aliphatic hydrocarbons, cycloaliphatic hydrocarbons, halogenated aromatic hydrocarbons, nitrogen - containing compounds, ethers, ketones, fatty acid esters, and aromatic carboxylic acid esters.

6. A modified composition of a benzene diisocyanate composition, characterized in that, The modified composition is a modified composition obtained by modifying the benzene diisocyanate composition according to any one of claims 1 - 2 or the benzene diisocyanate composition prepared by the preparation method according to any one of claims 3 - 5. The modified benzene diisocyanate in the modified composition contains any one or at least two combinations of the following groups (a) - (e): (a) isocyanurate group, (b) uretdione group, (c) biuret group, (d) carbamate group, (e) urea group, (f) iminooxadiazinedione group, (g) urethane group, (h) uretonimine group, or (i) carbodiimide group.

7. A polyurethane resin, characterized in that, The polyurethane resin is formed by reacting the benzene diisocyanate composition according to any one of claims 1 - 2 or the benzene diisocyanate composition prepared by the preparation method according to any one of claims 3 - 5 or the modified composition of the benzene diisocyanate composition according to claim 6 with a substance containing an active hydrogen group.

8. The polyurethane resin according to claim 7, wherein, The substance containing an active hydrogen group is selected from polyol components, polythiol components, and polyamine components.

9. An elastomeric material, which comprises the polyurethane resin according to claim 7 or 8.

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