A 6-position linked naphthalene diisocyanate, a method for synthesizing the same and use thereof in preparing a naphthalene polyurethane material

Abstract

The present application provides a 6-position linked naphthalene diisocyanate, which is a halogenated acyl naphthylamine, prepared by Ullmann coupling reaction in the presence of a ligand and an inorganic base and under the protection of inert gas, with a metal or a salt thereof as a catalyst, followed by amide hydrolysis and then carbonylation reaction with a carbonylating agent. The present application also provides a synthesis method of the 6-position linked naphthalene diisocyanate. The present application also provides an application of the 6-position linked naphthalene diisocyanate in preparing urethane rubber and elastomer, urethane fiber, cast urethane rubber, urethane emulsion and paint, urethane adhesive, shock-absorbing foam material, energy-absorbing foam material and damping foam material. The 6-position linked naphthalene diisocyanate provided by the present application has four ring structures, high covalent bond stability, excellent chemical stability and thermal stability.

Description

TECHNICAL FIELD

[0001] The present application belongs to the technical field of urethane material preparation, and particularly relates to a 6-position binaphthyl diisocyanate, a synthesis method thereof, and application of the 6-position binaphthyl diisocyanate in preparation of binaphthyl polyurethane material. BACKGROUND

[0002] Polyurethane materials are divided into MDI type (polyurethane materials synthesized from diphenylmethane diisocyanate and polyols and their compounding auxiliaries, referred to as "MDI type"), TDI type (polyurethane materials synthesized from toluene diisocyanate, referred to as "TDI type"), NDI type (polyurethane materials synthesized from 1,5-naphthalene diisocyanate, referred to as "NDI type") and other types according to different isocyanates used. Polyurethane materials taking NDI as a synthetic intermediate have excellent performance advantages, and have outstanding dynamic compression performance, high mechanical properties and properties such as friction resistance and high temperature resistance. Such materials are widely used in automobile shock absorbers, forklift load wheels, bridge construction cushion blocks and military fields. NDI is one of the hard segment raw materials required for manufacturing high-elasticity and high-hardness polyurethane elastomers, and among isocyanate monomers on the market, very few can meet such harsh conditions. However, in some extreme environments, materials need to have stronger mechanical strength and toughness. SUMMARY

[0003] The present application aims to solve the problems in the prior art, and provides a 6-position binaphthyl diisocyanate, a synthesis method thereof, and application of the 6-position binaphthyl diisocyanate in preparation of binaphthyl polyurethane material. The binaphthyl diisocyanate involved in the present application is an important organic synthesis intermediate, which can react with macromolecular diols and polyols to be used for manufacturing polyurethane elastomers and polyurethane fibers with high elasticity and high toughness. The generated urethane has the characteristics of high strength, high toughness and easy processing. The binaphthyl diisocyanate has stable chemical bonds and dense molecular structure, and therefore has excellent thermal stability and tensile resistance. The generated binaphthyl polyurethane has high cohesive energy and impact modulus, and is widely used in high dynamic load and heat-resistant occasions. Therefore, the binaphthyl polyurethane as a high polymer material with excellent performance and wide application has important value in the synthesis method and technical application.

[0004] The technical scheme of the present application is as follows:

[0005] The 6-position binaphthyl diisocyanate is a halogenated acyl naphthylamine, which is prepared by undergoing an Ullmann coupling reaction in the presence of a ligand and under the protection of an inert gas, using a metal or a salt thereof as a catalyst, and then undergoing amide hydrolysis and carbonacylation reaction with a carbonacylation reagent.

[0006] A 6-position linked naphthalene diisocyanate as described above, wherein the halogenated acyl naphthylamine has the following structure (I), wherein X is chlorine, bromine, iodine, trifluoromethylsulfonyloxy or p-toluenesulfonyloxy; R1 is H, C1-C 10 alkyl, C1-C 10 alkoxy or C1-C 10 alkylthio,

[0007]

[0008] Preferably, X is chlorine and R1 is H.

[0009] A 6-position linked naphthalene diisocyanate as described above, wherein the product of the Ullmann coupling reaction has the following structure (II), wherein R1 is H, C1-C 10 alkyl, C1-C 10 alkoxy or C1-C 10 alkylthio,

[0010]

[0011] Preferably, R1 is H.

[0012] A 6-position linked naphthalene diisocyanate as described above, wherein the product of the amide hydrolysis reaction has the following structure (III),

[0013]

[0014] A 6-position linked naphthalene diisocyanate as described above, wherein the product of the carbonylation reaction has the following structure (IV),

[0015]

[0016] Based on the same inventive concept, the present application also provides a method for synthesizing a 6-position linked naphthalene diisocyanate, comprising the following steps:

[0017] Step one, the halogenated acyl naphthylamine is dissolved in an organic solvent, and a metal or a salt thereof is used as a catalyst in the presence of a ligand and under the protection of an inert gas to generate an alkyl acyl linked naphthalene amine through a Ullmann reaction; preferably, the halogenated acyl naphthylamine is dissolved in anhydrous DMF or anhydrous DMA solvent, and stirred and dissolved under the protection of nitrogen, and a Ullmann reaction occurs at 100-150°C under the action of a catalyst, a ligand and an inorganic base, and the reaction time is 24-48 h; after the reaction mixture is cooled, the solvent is evaporated and filtered, and column separation and purification are performed with ethyl acetate and n-heptane as eluents in a volume ratio of 1:4 to obtain a yellow solid product, i.e., an alkyl acyl linked naphthalene amine;

[0018] Optionally, the halogenated acyl naphthylamine is N-(6-chloronaphthalen-1-yl)acetamide.

[0019] Optionally, the catalyst is any one of cuprous iodide, cuprous oxide, or nickel chloride. Preferably, the catalyst is cuprous iodide.

[0020] Optionally, the ligand is N,N-dimethylethylenediamine or triphenylphosphine. Preferably, the ligand is N,N-dimethylethylenediamine.

[0021] Preferably, the step one is under basic conditions, and the basic conditions are adjusted by an inorganic base. Optionally, the inorganic base is any one of cesium carbonate or potassium carbonate. Preferably, the inorganic base is cesium carbonate.

[0022] Optionally, the molar ratio of the halogenated acyl naphthylamine to the catalyst is (8-12):1. Preferably, the molar ratio of the halogenated acyl naphthylamine to the catalyst is 10:1.

[0023] Optionally, the molar ratio of the halogenated acyl naphthylamine to the ligand is (8-12):9. Preferably, the molar ratio of the halogenated acyl naphthylamine to the ligand is 10:9.

[0024] Optionally, the molar ratio of the halogenated acyl naphthylamine to the inorganic base is 1:(1-3). Preferably, the molar ratio of the halogenated acyl naphthylamine to the inorganic base is 1:2.

[0025] Step two, the alkyl acyl binaphthylamine in step one is mixed with a small molecule alkyl alcohol solution under acidic conditions, heated to reflux, and hydrolyzed to generate binaphthyl diamine. Preferably, the alkyl acyl binaphthylamine in step one is added to a 36% concentrated hydrochloric acid and anhydrous ethanol mixed solution, heated to 85-95°C to reflux for 2-4h, cooled, filtered, and dried to obtain a yellow solid product, i.e., binaphthyl diamine.

[0026] Step three, the binaphthyl diamine in step two is subjected to a carbonylation reaction to generate 6-position binaphthyl diisocyanate. Preferably, the dried binaphthyl diamine in step two is dissolved in 1,2-dichlorobenzene solvent, stirred, and heated to 120°C, a 1,2-dichlorobenzene solution of triphosgene is slowly added dropwise to the binaphthyl diamine, the dropwise addition time is 48h, after the dropwise addition is completed, the heating is continued to reflux for 3-6h, until the reaction system is clear and transparent, the organic solvent is removed by liquid-liquid separation, to obtain a crude product of p-phenylene diisocyanate, which is further recrystallized in xylene to obtain a yellow solid product, i.e., 6-position binaphthyl diisocyanate.

[0027] Optionally, the mass ratio of the binaphthyl diamine to the carbonylation reagent is (4-5):(8-10). Most preferably, the mass ratio of the binaphthyl diamine to the carbonylation reagent is 4.53:8.

[0028] The reaction formula of the synthesis method of the 6-position linked naphthalene diisocyanate is shown in the following formula.

[0029]

[0030] Based on the same inventive concept, the application provides application of the 6-position linked naphthalene diisocyanate in preparation of urethane rubber and elastomer, urethane fiber, cast urethane rubber, urethane emulsion and paint, urethane adhesive and shock-absorbing, energy-absorbing and damping foam material.

[0031] The application has the following beneficial effects:

[0032] 1. The 6-position linked naphthalene diisocyanate provided by the application has four ring structures, has high covalent bond stability, has excellent chemical stability and thermal stability, and has the advantages of high hardness, high toughness, excellent dynamic performance and the like.

[0033] 2. The 6-position linked naphthalene diisocyanate provided by the application has a large conjugate structure and stable chemical bonds, and the prepared linked naphthalene polyurethane has a high melt index at 230 DEG C, and has good easy processing performance. DETAILED DESCRIPTION

[0034] The technical solutions in the embodiments of the application will be clearly and completely described below with reference to the contents in the embodiments of the application. Obviously, the described embodiments are only part of the embodiments of the application, rather than all the embodiments of the application. Based on the embodiments in the application, all other embodiments obtained by those skilled in the art without creative work fall within the protection scope of the application.

[0035] Unless otherwise defined, all technical and scientific terms used in the specification are the same as the meanings commonly understood by those skilled in the art to which the application belongs. The terms used in the specification of the application are only for the purpose of describing the specific embodiments and are not used to limit the application. The term "and / or" used in the specification includes any and all combinations of one or more related listed items.

[0036] Unless otherwise specified, the experimental methods used in the following examples are all conventional methods.

[0037] Unless otherwise specified, the materials, reagents and the like used in the following examples can be obtained from commercial channels.

[0038] In the following examples, the N-(6-chloronaphthalen-1-yl)acetamide is purchased from Javada Pharmaceutical Technology Development Co., Ltd., with a CAS number: 855883-83-9, a density of 1.303±0.06 g / cm 3 , and a molecular weight of 219.67.

[0039] Example 1

[0040] The 6-position linked naphthalene diisocyanate provided in this example has a synthesis method comprising the following specific steps:

[0041] Step one, weigh N-(6-chloronaphthalen-1-yl)acetamide 8.78 g and dissolve it in anhydrous DMF 50 mL, stir to dissolve, add cuprous iodide 0.8 g, add N, N-dimethyl ethylenediamine 4 mL (0.036 mol), add cesium carbonate 26 g, slowly warm to 120°C under nitrogen protection, react for 24 h, after the reaction is completed, cool, filter, and evaporate the solvent to dryness, use ethyl acetate and n-heptane with a volume ratio of 1:4 as eluent for column separation and purification, to obtain yellow solid product, i.e. alkyl acyl linked naphthalene amine 6.12 g, with a yield of 83%;

[0042] Step two, add the yellow solid product obtained in step two, i.e. alkyl acyl linked naphthalene amine 6.12 g, to a mixed solution of 50 mL of 36% concentrated hydrochloric acid and 50 mL of ethanol, heat to 75°C and reflux for 3 h, cool, filter, and dry to obtain yellow solid product, i.e. linked naphthalene diamine 4.53 g, with a yield of 96%.

[0043] Step three, dissolve the dried linked naphthalene diamine 4.53 g in 1,2-dichlorobenzene 20 mL, stir and heat to 120°C, slowly add 40 g of triphosgene in 1,2-dichlorobenzene solution to the biphenyl diamine solution, wherein the mass concentration of triphosgene in 1,2-dichlorobenzene solution is 20%, the dropwise addition time is 48 h, after the dropwise addition is completed, continue to heat and reflux for 4 h, until the reaction system is clear and transparent, remove the organic solvent by liquid-liquid separation, to obtain crude p-phenylene diisocyanate, recrystallize the crude product in xylene to obtain yellow solid product, i.e. 6-position linked naphthalene diisocyanate 4.98 g, with a yield of 93%.

[0044] The product identification data are as follows:

[0045] GC-MS: 336.09 NMR: 1H NMR (300 MHz, CDC13): 8.34 (s, 2H), 7.93 (d, 2H, J = 8.6 Hz), 7.88 (d, 2H, J = 8.6 Hz), 7.69 (d, 2H, J = 8.2 Hz), 7.37 (dd, 2H, J1= 8.2, J2= 7.3 Hz), 7.28 (d, 2H, J = 7.3 Hz). 13C NMR (125 MHz, CDC13): 139.6, 133.6, 130.3, 129.1, 128.8, 126.6, 126.0, 125.8, 125.7, 122.7, 121.3.

[0046] Example 2:

[0047] The synthesis method of the 6-position binaphthyl diisocyanate provided by the embodiment comprises the following specific steps:

[0048] Step one, weigh N-(6-chloronaphthalen-1-yl)acetamide 8.78 g and dissolve it in anhydrous N,N-dimethylacetamide (DMA) 50 mL, stir and dissolve, add cuprous oxide 0.57 g, add N,N-dimethyl ethylenediamine 4 mL, add potassium carbonate 26 g, slowly warm to 120°C under nitrogen protection, react for 24 h, after the reaction is completed, cool and filter, evaporate the solvent, use ethyl acetate and n-heptane with a volume ratio of 1:4 as eluent for column separation and purification, to obtain yellow solid product, i.e. alkyl acyl binaphthyl amine 5.82 g, with a yield of 79%.

[0049] Step two, add the yellow solid product alkyl acyl binaphthyl amine 5.82 g obtained in step two to a mixed solution of 36% concentrated hydrochloric acid 50 mL and ethanol 50 mL, warm to 75°C, heat to reflux for 2 h, cool, filter and dry to obtain yellow solid product, i.e. binaphthyl diamine 4.31 g, with a yield of 96%.

[0050] Step three, dissolve the binaphthyl diamine 4.31 g dried in step three in 1,2-dichlorobenzene 20 mL, stir and heat to 120°C, slowly drop 45 g of triphosgene in 1,2-dichlorobenzene solution into the binaphthyl diamine solution, wherein the mass concentration of the triphosgene in 1,2-dichlorobenzene solution is 20%. The dropping time is 48 h, after the dropping is completed, continue to heat to reflux for 4 h, until the reaction system is clear and transparent, remove the organic solvent by liquid separation, to obtain crude p-phenylene diisocyanate, recrystallize the crude product in xylene, to obtain yellow solid product, i.e. 6-position binaphthyl diisocyanate 4.69 g, with a yield of 92%.

[0051] The product identification data are as follows:

[0052] GC-MS: 336.09 NMR: 1H NMR (300 MHz, CDC13): 8.34 (s, 2H), 7.93 (d, 2H, J = 8.6 Hz), 7.88 (d, 2H, J = 8.6 Hz), 7.69 (d, 2H, J = 8.2 Hz), 7.37 (dd, 2H, J1= 8.2, J2= 7.3 Hz), 7.28 (d, 2H, J = 7.3 Hz). 13C NMR (125 MHz, CDC13): 139.6, 133.6, 130.3, 129.1, 128.8, 126.6, 126.0, 125.8, 125.7, 122.7, 121.3.

[0053] Example 3:

[0054] The synthesis method of the 6-position binaphthyl diisocyanate provided by the embodiment comprises the following specific steps:

[0055] Step one, weigh N-(6-chloronaphthalen-1-yl)acetamide 8.78 g and dissolve it in anhydrous N,N-dimethylacetamide (DMA) 50 mL, stir and dissolve, add nickel chloride 0.52 g and triphenylphosphine 10.49 g, slowly warm to 120°C under nitrogen protection, react for 24 h, after the reaction is completed, cool and filter, evaporate the solvent, use ethyl acetate and n-heptane with a volume ratio of 1:4 as eluent for column separation and purification, to obtain yellow solid product, namely alkyl acyl binaphthyl amine 6.04 g, with a yield of 82%.

[0056] Step two, add the yellow solid product alkyl acyl binaphthyl amine 6.04 g obtained in step one to a mixed solution of 36% concentrated hydrochloric acid 50 mL and ethanol 50 mL, warm to 75°C, heat to reflux for 3 h, cool, filter and dry to obtain yellow solid product, namely binaphthyl diamine 4.47 g, with a yield of 96%.

[0057] Step three, dissolve the dried binaphthyl diamine 4.47 g obtained in step two in 1,2-dichlorobenzene 20 mL, stir and heat to 120°C, slowly drop 40 g of triphosgene in 1,2-dichlorobenzene solution into the binaphthyl diamine solution, wherein the mass concentration of the triphosgene in 1,2-dichlorobenzene solution is 20%. The dropping time is 48 h, after the dropping is completed, continue to heat to reflux for 4 h, until the reaction system is clear and transparent, remove the organic solvent by liquid separation, to obtain crude p-phenylene diisocyanate, recrystallize the crude product in xylene, to obtain yellow solid product, namely 6-position binaphthyl diisocyanate 4.82 g, with a yield of 91%.

[0058] The product identification data are as follows:

[0059] GC-MS: 336.09 NMR: 1H NMR (300 MHz, CDC13): 8.34 (s, 2H), 7.93 (d, 2H, J = 8.6 Hz), 7.88 (d, 2H, J = 8.6 Hz), 7.69 (d, 2H, J = 8.2 Hz), 7.37 (dd, 2H, J1= 8.2, J2= 7.3 Hz), 7.28 (d, 2H, J = 7.3 Hz). 13C NMR (125 MHz, CDC13): 139.6, 133.6, 130.3, 129.1, 128.8, 126.6, 126.0, 125.8, 125.7, 122.7, 121.3.

[0060] Comparative Example 1

[0061] 1,5-naphthalene diisocyanate (hereinafter referred to as NDI) was purchased from Qingdao Desheng Chemical Co., Ltd., CAS No.: 3173-72-6.

[0062] The properties of the urethane prepared by the prepolymer method using the 6-position linked naphthalene diisocyanate described in Example 1 and the NDI of Comparative Example 1 were tested.

[0063] In the following Application Examples 1 and 2, the 6-position linked naphthalene diisocyanate prepared in Example 1 had a NCO (isocyanate group) content of 21.8%; the NDI had a NCO (isocyanate group) content of 40.0%; the polyether triol EP-3600 was purchased from Shandong Lansheng Dongda Chemical Co., Ltd., had a molecular weight of 5000, a hydroxyl value of 32.5-35.5 mgKOH / g, and a moisture content of ≤0.05%; the VORASURF TM The DC 193 silicone surfactant was purchased from Dow Chemical.

[0064] Application Example 1

[0065] A method for preparing a poly-linked naphthalene urethane by a prepolymer method, comprising the following steps:

[0066] (1) Excess 6-position linked naphthalene diisocyanate of Example 1 was reacted with polyether triol EP300N at 95°C to form a prepolymer with a terminal-NCO group content of 8%;

[0067] (2) Casting: The prepolymer was mixed with a chain extender component at a mass ratio of 100:12, the mixing speed was 1500 r / min, and the mixture was stirred for 30 s. The reaction liquid was injected into a mold with a temperature of 95°C, and the mold was removed after pre-curing. The chain extender component included the following components in parts by weight: chain extender 1, 6-hexanediol 52 parts, catalyst dimethylcyclohexylamine 35 parts, foaming agent deionized water 5 parts, and VORASURF TMDC 193 silicone surfactant 8 parts

[0068] (3) Post-curing: the demolded product was cured in an oven at 105℃ for 12h, and then placed at room temperature for 3d to obtain the binaphthyl polyurethane.

[0069] Application Example 2:

[0070] The difference between the application example 1 and the application example 2 is that the binaphthyl diisocyanate No. 5 of the example 1 is replaced by NDI.

[0071] The polyurethanes prepared in the application example 1 and the application example 2 were tested for their performance, and the results are shown in Table 1.

[0072] Table 1: Polyurethane prepared by prepolymerization process

[0073] Test item Unit Test method Example 1 Example 2 Density g / cm 3 ]] GB / T 1033.1-2008 1.03 1.05 Tensile strength MPa GB / T 1040-2006 4.9 3.3 Tensile elongation ％ GB / T 528-2009 308 246 Shore A HA GB T 2411-2008 78 71 Tear strength kN / m GB / T 10808-2006 4.5 3.2 Melt index g / 10min.230℃ GB / T 3682 17.1 9.2

[0074] As shown in Table 1, the binaphthyl polyurethane prepared by prepolymerization process using the binaphthyl diisocyanate of the present application has better tensile strength, tensile elongation and tear strength than the polyurethane prepared by prepolymerization process using NDI. The above data show that the polyurethane product prepared by the method of the present application has excellent performance and outstanding mechanical strength, and has a high melt index at 230℃, indicating that it has good easy processing performance.

[0075] The above description of the examples is only for the convenience of understanding the use by the person skilled in the art, and the person skilled in the art can select a suitable production process according to the product needs. Of course, the above only describes some of the embodiments of the present application, and is not intended to limit the present application. Any modification, equivalent replacement, improvement, etc. of the description within the spirit and principles of the present application shall be included in the protection scope of the present application.

Claims

1. A 6-position naphthalene diisocyanate, characterized in that, The structure of the 6-position naphthalene diisocyanate is shown in formula (Ⅳ). 。 2. The method for synthesizing naphthalene diisocyanate at position 6 according to claim 1, characterized in that, Includes the following steps: Step 1: Halogenated acyl naphthylamine is dissolved in an organic solvent and, with a metal or its salt as a catalyst, undergoes a Ullmann reaction in the presence of a ligand and under inert gas protection to generate alkyl acyl naphthylamine. Step 2: The alkyl acyl-binaphthylamine from Step 1 undergoes a hydrolysis reaction under acidic conditions by heating and refluxing with a small molecule alkyl alcohol mixture to generate binaphthyldiamine. Step 3: The naphthyl diamine from Step 2 undergoes a carbonylation reaction to generate naphthyl diisocyanate at position 6.

3. The method for synthesizing a 6-position naphthalene diisocyanate according to claim 2, characterized in that, The catalyst in step one is any one of cuprous iodide, cuprous oxide, and nickel chloride.

4. The method for synthesizing naphthalene diisocyanate at position 6 according to claim 2, characterized in that, The ligand in step one is N,N-dimethylethylenediamine.

5. The method for synthesizing naphthalene diisocyanate at position 6 according to claim 2, characterized in that, The carbonylating agent in step three is phosgene or triphosgene.

6. The application of the 6-position naphthalene diisocyanate according to claim 1 or the 6-position naphthalene diisocyanate according to any one of claims 2 to 5 in the preparation of polyurethane rubber and elastomers, polyurethane fibers, cast polyurethane rubber, polyurethane emulsions and coatings, polyurethane adhesives, shock-absorbing foam materials, energy-absorbing foam materials, and damping foam materials.

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