A 5-position binaphthyl diisocyanate, a synthetic method thereof and application thereof in preparing binaphthyl polyurethane materials

Abstract

The application discloses a 5-position linked naphthalene diisocyanate, a halogenated naphthylamine or a phenolic hydroxyl naphthylamine, which is subjected to an acylation reaction, then subjected to an Ullmann coupling reaction in the presence of a ligand and an inorganic base and under the protection of an inert gas by using a metal or a salt thereof as a catalyst, subjected to amide hydrolysis, and then subjected to a carbonacylation reaction with a carbonacylation reagent to obtain the 5-position linked naphthalene diisocyanate. The application further provides a synthesis method of the 5-position linked naphthalene diisocyanate. The application further provides an application of the 5-position linked naphthalene diisocyanate in preparation of 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 polylinked naphthalene urethane prepared by using the 5-position linked naphthalene diisocyanate has high cohesive energy and impact modulus, and can be widely applied to high dynamic load and heat-resistant occasions.

Description

TECHNICAL FIELD

[0001] The application belongs to the technical field of urethane material preparation, and particularly relates to a 5-position linked naphthalene diisocyanate, a synthesis method thereof and application of the 5-position linked naphthalene diisocyanate in preparation of linked naphthalene polyurethane material. BACKGROUND

[0002] Polyurethane, abbreviated as PU, is a kind of polymer material containing a large number of repeating urethane groups (-NHCOO-) in the molecular chain. Polyurethane elastomer is a special category of elastomers. From the molecular structure, polyurethane elastomer is a kind of block polymer, which is generally composed of a flexible long chain of an oligomer polyol as a soft segment, and a diisocyanate and a chain extender as a hard segment. The hard segment and the soft segment are alternately arranged to form a repeating structural unit. In addition to containing urethane groups, hydrogen bonds can be formed in and between polyurethane molecules, and microphase regions can be formed by the soft segment and the hard segment to produce microphase separation.

[0003] 1,5-naphthalene diisocyanate (abbreviated as "NDI") has unparalleled performance advantages, such as excellent dynamic compression performance, extremely high mechanical properties, and abrasion resistance and temperature resistance. At present, NDI polyurethane elastomer is widely used in automobile shock absorbers, forklift load wheels, bridge construction cushion blocks, military aspects, etc. NDI is a hard segment raw material of polyurethane, which can be used to manufacture high-elasticity and high-hardness polyurethane elastomers. However, in some extreme environments (high damping, high vibration scenes), the material needs to have stronger impact resistance, hardness, mechanical properties and shock absorption and energy absorption effects. There are very few isocyanate monomers on the market that can be used in such extreme harsh conditions. SUMMARY

[0004] The purpose of the present application is to solve the existing technical problems, and to provide a 5-position linked naphthalene diisocyanate, a synthesis method thereof and application of the 5-position linked naphthalene diisocyanate in preparation of linked naphthalene polyurethane material. The 5-position linked naphthalene diisocyanate provided by the present application is an important organic synthesis intermediate. By reacting with macromolecular diols and polyols, it is a new raw material in the manufacture of high-elasticity and high-hardness polyurethane elastomers. The generated urethane is suitable for new energy automobile battery shock absorption, bridge, military and other fields, and is also suitable for high-strength, high-hardness, wear-resistant and high-temperature-resistant extreme environments. At the same time, the 5-position linked naphthalene diisocyanate provided by the present application has stable chemical bonds and dense molecular structure, excellent thermal stability and tensile resistance, and the generated polylinked naphthalene urethane has high cohesive energy and impact modulus, especially suitable for high damping and high vibration scenes. Therefore, the polylinked naphthalene urethane provided by the present application is a high molecular material with excellent performance and wide application, and the synthesis method and technical application thereof have important value.

[0005] The technical scheme of the present application is implemented as follows:

[0006] A 5-position linked naphthalene diisocyanate, which is prepared by subjecting naphthylamine to acylation reaction, then subjecting the product to Ullmann coupling reaction in the presence of ligand and inorganic base and under the protection of inert gas with metal or its salt as catalyst, followed by amide hydrolysis, and then subjecting the product to carbonylation reaction with carbonylation reagent.

[0007] The 5-position linked naphthalene diisocyanate as described above, wherein the naphthylamine has the following structure of formula (I), wherein X is chlorine, bromine, iodine, trifluoromethylsulfonyloxy, p-toluenesulfonyloxy or phenolic hydroxyl.

[0008] Preferably, X is chlorine or phenolic hydroxyl.

[0009]

[0010] The 5-position linked naphthalene diisocyanate as described above, wherein the product of the acylation reaction of the naphthylamine has the following structure of formula (II), wherein R1 is linear or branched alkyl of C1-C6, alkoxy of C1-C6 or alkylthio of C1-C6; and X is chlorine, bromine, iodine, trifluoromethylsulfonyloxy, p-toluenesulfonyloxy or phenolic hydroxyl. 10 10 10

[0011]

[0012] The 5-position linked naphthalene diisocyanate as described above, wherein the product of the Ullmann coupling reaction has the following structure of formula (III), wherein R1 is linear or branched alkyl of C1-C6, alkoxy of C1-C6 or alkylthio of C1-C6, 10 10 10

[0013]

[0014] The 5-position linked naphthalene diisocyanate as described above, wherein the product of the amide hydrolysis reaction has the following structure of formula (IV),

[0015]

[0016] The 5-position linked naphthalene diisocyanate as described above, wherein the product of the carbonylation reaction has the following structure of formula (V),

[0017]

[0018] Based on the same inventive concept, the present application also provides a synthesis method of 5-position linked naphthalene diisocyanate, comprising the following steps:

[0019] ​​​​​​Step one, acylation reaction of naphthylamine and acylating agent, to generate halogen acyl naphthylamine or phenolic hydroxyl acyl naphthylamine.

[0020] Optionally, the naphthylamine is halogen naphthylamine or phenolic hydroxyl naphthylamine; preferably, the naphthylamine is 1-amino-5-chloronaphthalene or 1-amino-5-naphthol; more preferably, the naphthylamine is 1-amino-5-chloronaphthalene.

[0021] Optionally, the acylating agent in step one is any one of carboxylic acid, carboxylic acid ester, acid anhydride, acyl chloride; preferably, the acylating agent in step one is any one of acetic anhydride or acetic acid; more preferably, the acylating agent in step one is acetic anhydride.

[0022] Optionally, the molar ratio of naphthylamine to acylating agent is 4:(5-10); preferably, the molar ratio of naphthylamine to acylating agent is 4:5 or 4:10.

[0023] Optionally, halogen naphthylamine or phenolic hydroxyl naphthylamine is added with acylating agent, heated to 40-110℃, stirred for 60-120min, cooled, filtered, and dried to obtain halogen acyl naphthylamine or phenolic hydroxyl acyl naphthylamine. Preferably, heated to 80℃, stirred for 60min.

[0024] Step two, the halogen acyl naphthylamine or phenolic hydroxyl acyl naphthylamine in step one is dissolved in organic solvent, and subjected to Ullmann reaction in the presence of metal or its salt as catalyst, ligand, and inert gas protection, to generate alkyl acyl binaphthylamine.

[0025] Specifically, the halogen acyl naphthylamine or phenolic hydroxyl acyl naphthylamine in step one is dissolved in organic solvent, stirred and dissolved, subjected to Ullmann reaction in the presence of metal or its salt as catalyst, ligand, and inorganic base, and inert gas protection, the reaction time is 24-48h, the reaction mixture is filtered after cooling, and the solvent is evaporated, column separation and purification are carried out with ethyl acetate and n-heptane as eluent in a volume ratio of 1:4, and yellow solid product, i.e. alkyl acyl binaphthylamine, is obtained.

[0026] Optionally, the organic solvent is anhydrous N,N-dimethylformamide (hereinafter referred to as "anhydrous DMF") or dichloromethane. Preferably, the organic solvent is anhydrous DMF.

[0027] Optionally, the catalyst is any one of cuprous iodide, cuprous oxide, and nickel chloride. Preferably, the catalyst is cuprous iodide.

[0028] Optionally, the ligand is N,N-dimethylethylenediamine or triphenylphosphine. Preferably, the ligand is N,N-dimethylethylenediamine.

[0029] Preferably, the step two is under alkaline condition, and the alkaline condition is adjusted by inorganic base; optionally, the inorganic base is cesium carbonate.

[0030] Optionally, the molar ratio of the halogenated acyl naphthylamine or phenolic hydroxyl acyl naphthylamine to the catalyst is (8-12): 1. Preferably, the molar ratio of the halogenated acyl naphthylamine or phenolic hydroxyl acyl naphthylamine to the catalyst is 9: 1.

[0031] Optionally, the molar ratio of the halogenated acyl naphthylamine or phenolic hydroxyl acyl naphthylamine to the ligand is 2:(1-2). Preferably, the molar ratio of the halogenated acyl naphthylamine or phenolic hydroxyl acyl naphthylamine to the ligand is 2: 1.

[0032] Optionally, the molar ratio of the halogenated acyl naphthylamine or phenolic hydroxyl acyl naphthylamine to the inorganic base is 1:(1-3). Preferably, the molar ratio of the halogenated acyl naphthylamine or phenolic hydroxyl acyl naphthylamine to the inorganic base is 1: 2.

[0033] Step three, the alkyl acyl binaphthylamine in step two is heated to reflux with a small molecule alkyl alcohol solution under strong acid condition to generate binaphthyl diamine through hydrolysis reaction.

[0034] Optionally, the alkyl acyl binaphthylamine in step two is added to a mixed solution of 36% concentrated hydrochloric acid and anhydrous ethanol, heated to 75-95°C to reflux for 2-4h, cooled and filtered, and dried to obtain yellow solid product, i.e. binaphthyl diamine;

[0035] Step four, the binaphthyl diamine in step three is subjected to carbonylation reaction to generate 5-position binaphthyl diisocyanate.

[0036] Optionally, the mass ratio of the binaphthyl diamine to the carbonylation reagent is (3-5):(8-10). Most preferably, the mass ratio of the binaphthyl diamine to the carbonylation reagent is 4.27: 10.

[0037] Optionally, the binaphthyl diamine in step three is dissolved in 1,2-dichlorobenzene solvent, stirred and heated to 120°C, and 1,2-dichlorobenzene solution of triphosgene is slowly added to the binaphthyl diamine. The dropping time of the 1,2-dichlorobenzene solution is 48h. After the dropping is completed, the heating reflux is continued for 3-6h until the reaction system is clear and transparent. The organic solvent is removed by liquid separation to obtain crude p-phenylene diisocyanate. The crude product is recrystallized in xylene to obtain yellow solid product, i.e. 5-position binaphthyl diisocyanate.

[0038]

[0039] Based on the same inventive concept, the application further provides application of the 5-position linked naphthalene diisocyanate in preparation of 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.

[0040] Based on the same inventive concept, the application further provides a urethane material prepared from the 5-position linked naphthalene diisocyanate synthesized by the above method.

[0041] The application has the following advantages:

[0042] 1. The 5-position linked naphthalene diisocyanate provided by the application has four ring structures, high covalent bond stability, excellent chemical stability and high strength. The naphthalene rings are connected by C-C bonds, and the molecular structure has very strong rigidity. The rigid structure makes the urethane material have outstanding mechanical strength, high hardness, good resilience, excellent shock-absorbing and energy-absorbing performance, and the like.

[0043] 2. The 5-position linked naphthalene diisocyanate provided by the application has a large conjugated structure and stable chemical bonds, and the prepared linked naphthalene polyurethane material has a high loss factor, indicating that the greater the viscosity of the material. DETAILED DESCRIPTION

[0044] The technical solutions in the embodiments of the application will be described clearly and completely 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 scope of protection of the application.

[0045] 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.

[0046] Unless otherwise specified, the experimental methods used in the following examples are all conventional methods.

[0047] Unless otherwise specified, the materials, reagents and the like used in the following examples can be obtained from commercial channels.

[0048] In the following examples, the 1-amino-5-chloronaphthalene is purchased from Shanghai Yuan Ye Biotechnology Co., Ltd., with CAS No. 2750-80-3, density 1.289 g / cm 3 , molecular weight 177.63. The 1-amino-5-naphthol is purchased from

[0049] Example 1:

[0050] This example provides a 5-position linked naphthalene diisocyanate, and the synthesis method thereof comprises the following specific steps:

[0051] Step one, 1-amino-5-chloronaphthalene 7.1 g is weighed and added to acetic anhydride 4.7 mL, 0.02 g of zinc powder is added, heated to 80°C, and stirred for 60 min. The hot reaction liquid is poured into 200 mL of water, white crystals are precipitated, cooled, suction filtered, and dried to obtain N-(5-chloro-1-naphthyl)-acetamide 7.99 g, with a yield of 91%;

[0052] Step two, N-(5-chloro-1-naphthyl)-acetamide 7.99 g obtained in step one is dissolved in anhydrous DMF 50 mL and stirred to dissolve, cuprous iodide 0.8 g is added, N,N-dimethylethylenediamine 2 mL is added, cesium carbonate 23.5 g is added, and the temperature is slowly raised to 120°C under nitrogen protection. After 24 h of reaction, the reaction is completed, cooled, filtered, and the solvent is evaporated to dryness. Column separation and purification are carried out with ethyl acetate and n-heptane as eluents in a volume ratio of 1:4 to obtain yellow solid product 5.7 g, which is alkyl acyl linked naphthalene amine, with a yield of 86%.

[0053] Step three, the yellow solid product 5.7 g obtained in step two is added to a mixed solution of 50 mL of 36% concentrated hydrochloric acid and 50 mL of ethanol, heated to 85°C and refluxed for 3 h. After cooling, filtration and drying, yellow solid product 4.27 g is obtained, which is linked naphthalene diamine, with a yield of 97%.

[0054] Step four, the dried yellow solid linked naphthalene diamine 4.27 g in step three is dissolved in 1,2-dichlorobenzene solvent, stirred and heated to 120°C. A 1,2-dichlorobenzene solution of 50 g of triphosgene is slowly added to the biphenyl diamine solution, wherein the mass concentration of the 1,2-dichlorobenzene solution of triphosgene is 20%, and the dropping time is 48 h. After the addition is completed, continue to heat and reflux for 4 h until the reaction system is clear and transparent. The organic solvent is removed by liquid-liquid separation to obtain crude p-phenylene diisocyanate. The crude product is recrystallized in xylene to obtain yellow solid product 4.64 g, which is 5-position linked naphthalene diisocyanate, with a yield of 92%.

[0055] The product identification data are as follows:

[0056] GC-MS: 336.09;

[0057] NMR (400 MHz, DMSO-d6) δ: 8.77 (d, 2H, Ar-H), 8.55 (d, 2H, Ar-H), 8.41 (d, 2H, Ar-H), 7.78 (t, 2H, Ar-H), 7.74 (d, 2H, Ar-H), 7.37 (t, 2H, Ar-H);

[0058] 13C NMR (101 MHz, DMSO-d6) δ: 135.0, 134.2, 132.3, 131.4, 131.1, 128.4, 127.9, 127.7, 127.2, 125.5, 118.0

[0059] Example 2:

[0060] This embodiment provides a 5-position binaphthyl diisocyanate, and the synthesis method thereof comprises the following specific steps:

[0061] Step one, 1-amino-5-chloronaphthalene 7.1 g was weighed and added into acetic acid 5.7 mL, 0.05 g of zinc powder was added, and after stirring and heating to 105°C, the reaction was refluxed for 60 min. The hot reaction liquid was poured into 200 mL of cold water in a thin stream, white crystals were precipitated, and after cooling, suction filtration and drying, N-(5-chloro-1-naphthyl)-acetamide 7.82 g was obtained, with a yield of 89%.

[0062] Step two, N-(5-chloro-1-naphthyl)-acetamide 7.82 g obtained in step one was dissolved in 50 mL of anhydrous DMF and stirred to dissolve, 0.8 g of cuprous iodide was added, 4 mL of N,N-dimethylethylenediamine was added, 23.5 g of cesium carbonate was added, and the temperature was slowly increased to 120°C under nitrogen protection. After 24 h of reaction, the reaction was completed, and after cooling, the solvent was evaporated and filtered, and column separation and purification were carried out with ethyl acetate and n-heptane as eluent (volume ratio 1:4), to obtain yellow solid product 5.51 g, which was alkyl acyl binaphthyl amine, with a yield of 84%.

[0063] Step three, the yellow solid product obtained in step two was added to a mixture of 50 mL of 36% concentrated hydrochloric acid and 50 mL of ethanol, and heated to 75°C and refluxed for 2 h. After cooling, filtration and drying, yellow solid product 4.04 g was obtained, which was binaphthyl diamine, with a yield of 95%.

[0064] Step four, the dry yellow solid in step three is dissolved in 1,2-dichlorobenzene solvent, heated to 120°C under stirring, 50g of triphosgene in 1,2-dichlorobenzene solution is slowly added to the biphenyl diamine solution, wherein the mass concentration of triphosgene in 1,2-dichlorobenzene solution is 20%. After the dropwise addition is completed, continue to heat and reflux for 4h, until the reaction system is clear and transparent, remove the organic solvent by liquid-liquid separation, obtain the crude product of p-phenylene diisocyanate, recrystallize the crude product in xylene, obtain yellow solid product 4.44g, namely the 5-position binaphthyl diisocyanate, the yield is 93%.

[0065] The product identification data are as follows:

[0066] GC-MS: 336.09 NMR determination: 1H NMR (400 MHz, DMSO-d6) δ: 8.77 (d, 2H, Ar-H), 8.55 (d, 2H, Ar-H), 8.41 (d, 2H, Ar-H), 7.78 (t, 2H, Ar-H), 7.74 (d, 2H, Ar-H), 7.37 (t, 2H, Ar-H);

[0067] 13C NMR (101 MHz, DMSO-d6) δ: 135.0, 134.2, 132.3, 131.4, 131.1, 128.4, 127.9, 127.7, 127.2, 125.5, 118.0

[0068] Example 3:

[0069] The present embodiment provides a 5-position binaphthyl diisocyanate, and the synthesis method thereof comprises the following specific steps:

[0070] Step one, weigh 1-amino-5-naphthol 6.36g, add acetic anhydride 4.7mL, add 0.02g of zinc powder, stir and heat to 80°C, react for 60min, cool the reaction liquid to 200mL water, precipitate white crystals, cool, filter and dry to obtain N-(5-hydroxy-1-naphthyl)-acetamide 7.48g, the yield is 93%;

[0071] Step two, dissolve N-(5-hydroxy-1-naphthyl)-acetamide 7.48g and acid binding agent triethylamine 6.9mL in dichloromethane 50mL, cool to 0°C under ice water bath, stir and dissolve, add trifluoromethylsulfonyl chloride 4.7mL, slowly warm to room temperature, react for 2h, wash with water, separate the lower liquid, dry with anhydrous sodium sulfate, evaporate the solvent to obtain yellow solid product 10.85g, namely N-(5-trifluoromethanesulfonic acid oxygen-1-naphthyl)-acetamide, the yield is 88%.

[0072] Step three, the N-(5-trifluoromethanesulfonic acid oxo-1-naphthalene)-acetamide 10.85 g obtained in step two was dissolved in anhydrous DMF 50 mL and stirred to dissolve, and then nickel chloride 0.43 g and triphenylphosphine 8.66 g were added. The reaction was slowly heated to 120 °C under nitrogen protection, and the reaction was carried out for 24 h. After the reaction was completed, the solvent was evaporated after cooling and filtering, and column separation and purification were carried out with ethyl acetate and n-heptane (1:4 by volume) as eluent to obtain yellow solid product 5.17 g, which was the alkyl acyl dianaphthylamine, and the yield was 85%.

[0073] Step four, the yellow solid product 5.17 g obtained in step three was added to a mixed solution of 36% concentrated hydrochloric acid 50 mL and ethanol 50 mL, and heated to 75 °C and refluxed for 3 h. After cooling, filtering and drying, yellow solid product 3.79 g was obtained, which was the dianaphthylamine, and the yield was 95%.

[0074] Step five, the dried dianaphthylamine 3.79 g was dissolved in 1,2-dichlorobenzene 20 mL, and stirred and heated to 120 °C. A 45 g triphosgene 1,2-dichlorobenzene solution was slowly added dropwise to the dianaphthylamine solution, and the mass concentration of the triphosgene 1,2-dichlorobenzene solution was 20%. The dropwise time was 48 h. After the dropwise addition was completed, the heating and refluxing were continued for 4 h until the reaction system was clear and transparent. The organic solvent was removed by liquid separation to obtain the crude p-phenylene diisocyanate product. The crude product was recrystallized in xylene to obtain yellow solid product 4.08 g, which was the 5-position dianaphthyl diisocyanate, and the yield was 91%.

[0075] The product identification data are as follows:

[0076] GC-MS: 336.09;

[0077] NMR determination: 1H NMR (400 MHz, DMSO-d6) δ: 8.77 (d, 2H, Ar-H), 8.55 (d, 2H, Ar-H), 8.41 (d, 2H, Ar-H), 7.78 (t, 2H, Ar-H), 7.74 (d, 2H, Ar-H), 7.37 (t, 2H, Ar-H);

[0078] 13C NMR (101 MHz, DMSO-d6) δ: 135.0, 134.2, 132.3, 131.4, 131.1, 128.4, 127.9, 127.7, 127.2, 125.5, 118.0

[0079] Comparative example 1:

[0080] 1,5-naphthalene diisocyanate (hereinafter referred to as NDI), purchased from Qingdao Desheng Chemical Co., Ltd., CAS number: 3173-72-6.

[0081] The performance test was carried out on the urethane prepared by the prepolymer method using the naphthalene diisocyanate at position 5 described in Example 1 and the NDI described in Comparative Example 1, respectively.

[0082] In the following Application Example 1 and Application Example 2, the naphthalene diisocyanate at position 5 prepared in Example 1 has an NCO (isocyanate group) content of 21.88%; the NDI in Comparative Example 1 has an NCO (isocyanate group) content of 40.0%; the polyether triol EP-3600 is purchased from Shandong Lansheng Dongda Chemical Co., Ltd., has a molecular weight of 5000, a hydroxyl value of 26-30 mgKOH / g, and a moisture content of ≤0.05%; the pentafluorobutane HFC-365MFC is purchased from Shandong Aolun Chemical Co., Ltd., has a CAS number of 406-58-6; and the general-purpose silicon surfactant SH-493 is purchased from Hubei Longsheng Sihai New Material Co., Ltd.

[0083] Application Example 1:

[0084] A method for preparing naphthalene polyurethane by a prepolymer method, comprising the following steps:

[0085] (1) Excess naphthalene diisocyanate at position 5 of Example 1 is reacted with polyether triol EP-3600 at 85°C to form a prepolymer with an end-NCO group content of 8.5%;

[0086] (2) Pouring: the prepolymer is mixed with a chain extender component at a mass ratio of 100:11.5, the mixing speed is 2000 r / min, and the mixture is stirred for 30 s, then the reaction liquid is injected into a mold with a temperature of 90°C, and the product is demolded after pre-curing; wherein the chain extender component comprises the following components in parts by weight: chain extender 1, 4-butanediol 60 parts, catalyst triethylene diamine 30 parts, foaming agent pentafluorobutane HFC-365MFC 5 parts, and surfactant SH-493 5 parts;

[0087] (3) Post-curing: the demolded product is cured in an oven at 110°C for 12 hours, and then is placed at room temperature for 5 days to obtain the naphthalene polyurethane.

[0088] Application Example 2:

[0089] The difference between Application Example 1 and Application Example 2 is that the naphthalene diisocyanate at position 5 of Example 1 is replaced by the NDI in Comparative Example 1.

[0090] The polyurethanes prepared in Application Example 1 and Application Example 2 are tested for performance, and the results are shown in Table 1.

[0091] Table 1: Polyurethane prepared by a prepolymer process

[0092] Test item Unit Test method Example 1 Example 2 Density g / cm3 GB / T 1033.1-2008 1.07 1.05 Tensile strength MPa GB / T 1040-2006 4.9 3.4 Tensile elongation ％ GB / T 528-2009 306 261 Shore A HA GB T 2411-2008 82 73 Tear strength kN / m GB / T 10808-2006 4.8 3.4 Loss factor GB / T 18258-2000 0.43 0.35

[0093] According to the table 1, the polynaphthylene polyurethane prepared by the prepolymerization method using the 5-position linked naphthalene diisocyanate of the present application has better tensile strength, tensile elongation and tear strength, and has higher loss factor than the polynaphthylene polyurethane prepared by the prepolymerization method using the same process NDI. The above data show that the polynaphthylene polyurethane product prepared by the method of the present application has excellent performance and outstanding mechanical strength and shock absorption and energy absorption characteristics.

[0094] The above description of the embodiments is only for the convenience of those skilled in the art to understand the use, and those skilled in the art can select a suitable production process according to the needs of the product. Of course, the above only describes some embodiments of the present application, and is not used to limit the present application, any modification, equivalent replacement, improvement, etc. made within the spirit and principles of the present application shall be included in the protection scope of the present application.

Claims

1. A 5-position linked naphthalene diisocyanate, characterized in that, The structure of the 5-position linked naphthalene diisocyanate product is shown in the following formula (V), 。 2. The process for synthesis of 5-position linked naphthalene diisocyanate according to claim 1, wherein, The method comprises the following steps: Step one, the naphthalene amine is halogenated naphthalene amine or phenolic hydroxyl naphthalene amine, which is acylated with an acylating agent to generate halogenated acyl naphthalene amine or phenolic hydroxyl acyl naphthalene amine; Step two, the halogenated acyl naphthalene amine or phenolic hydroxyl acyl naphthalene amine in the step one is dissolved in an organic solvent, a metal or a salt thereof is used as a catalyst, an Ullmann reaction is generated in the presence of a ligand and under the protection of an inert gas to generate alkyl acyl linked naphthalene amine; Step three, the alkyl acyl linked naphthalene amine in the step two is hydrolyzed under the condition of a strong acid and a small molecule alkyl alcohol solution to generate linked naphthalene diamine by heating reflux; Step four, the linked naphthalene diamine in the step three is subjected to a carbonylation reaction to generate 5-position linked naphthalene diisocyanate.

3. A process for the synthesis of 5,5' bitriphenyl diisocyanate according to claim 2, characterized in that, The acylating agent in the step one is any one of carboxylic acid, carboxylic acid ester, acid anhydride and acyl chloride.

4. Application of the 5-position linked naphthalene diisocyanate in the preparation of polyurethane rubber and elastomer, polyurethane fiber, cast polyurethane rubber, polyurethane emulsion and paint, polyurethane adhesive, shock-absorbing foam material, energy-absorbing foam material and damping foam material.

5. A polyurethane material, characterized in that, The 5-position linked naphthalene diisocyanate is prepared by using the 5-position linked naphthalene diisocyanate in claim 1 or the synthesis method in any one of claims 2-3.

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