A diamine containing a cyclohexane norbornane structure, a preparation method and application in preparing transparent nylon

Abstract

The application discloses a binary amine containing cyclohexane and norbornane structure, a preparation method and application in preparing transparent nylon. The application synthesizes a binary amine monomer containing cyclohexane and norbornane structure, and copolymerizes the binary amine monomer with aliphatic binary acid or norbornane-containing binary acid, aliphatic binary amine or norbornane-containing binary amine, to synthesize a transparent nylon containing norbornane structure. The cyclic structure with norbornane on the molecular chain can cause the regularity of the molecular chain to be destroyed, the crystallization ability to be reduced, the transparency of the nylon to be effectively improved, the processability of the nylon to be effectively improved due to the fact that a large number of cyclic structures are contained in the polymer chain and the polymer chain is a straight chain structure, the nylon has excellent thermal performance and mechanical performance, and the nylon has good solvent resistance and low dielectric constant.

Description

Technical Field

[0001] This invention provides a diamine containing cyclohexane and norbornene structures, a preparation method thereof, and its application in the preparation of transparent nylon, belonging to the field of transparent nylon technology. Background Technology

[0002] Polyamide, also known as nylon, is a class of polymers with amide groups on their main molecular chain. There are two main methods for its synthesis: condensation polymerization of diacids and diamines, such as nylon 66 and nylon 46; or using cyclic lactams as raw materials, such as nylon 6 and nylon 12. Nylon possesses excellent mechanical, processing, heat resistance, abrasion resistance, and solvent resistance properties, and is widely used in the automotive, railway, aerospace, electronics, and textile industries. By changing the types of diamines and diacids, nylon varieties with different properties can be obtained, such as general-purpose nylon, transparent nylon, and nylon elastomers. Among these, transparent nylon, due to its superior oil resistance, corrosion resistance, abrasion resistance, and scratch resistance compared to other transparent plastics, is widely used in the automotive, electronics, machinery, optics, and sports industries.

[0003] Chinese patent CN 114716667 A describes a transparent nylon 66, its synthesis method and application. It is prepared by using nylon 66 salt, hexamethylenediamine, bismaleimide and antioxidant. It uses multiple monomers to copolymerize and obtain transparent nylon. However, the preparation process of this method is complicated and the light transmittance is only 88% to 90%.

[0004] Chinese patent CN 114835894 A describes a transparent polyamide, a composition thereof, and a method for preparing the same. The transparent polyamide and its composition are prepared using adipic acid, hexamethylenediamine, a diamine containing cyclohexyl, and a diic acid monomer. The light transmittance is between 86% and 90%, the glass transition temperature is between 70°C and 82°C, and the temperature resistance is poor.

[0005] Chinese Patent CN 115975181 A describes a ternary copolymer transparent nylon and its preparation method. It employs a copolymerization process of three nylons: alicyclic transparent nylon, long-chain transparent nylon, and PA6T nylon. The light transmittance is between 89% and 90%, but the preparation process is relatively complex.

[0006] Therefore, it is necessary to develop a simple and efficient process for preparing transparent polyamides. Summary of the Invention

[0007] To address the aforementioned problems in the prior art, the present invention aims to provide a diamine containing cyclohexane and norbornene structures, the molecular formula of which simultaneously contains cyclohexane and norbornene structures, which can be used as a monomer raw material for preparing transparent nylon.

[0008] The present invention also aims to synthesize a transparent nylon containing a norbornene structure by copolymerizing the aforementioned diamine containing cyclohexane and norbornene with other raw materials. The process of this invention is simple. The cyclic structure of norbornene on the nylon molecular chain disrupts the molecular chain regularity, reduces crystallinity, and effectively improves the transparency of nylon, achieving a light transmittance of over 90%. Simultaneously, due to the large number of cyclic structures in the polymer chain, which are linear, the processability of nylon is also effectively improved, resulting in excellent thermal and mechanical properties, as well as good solvent resistance and a low dielectric constant.

[0009] In a first aspect, the present invention provides a diamine containing a cyclohexane and norbornene structure, having the structure shown in Formula 1 below:

[0010]

[0011] In Formula 1, each Ar is independently represented as a group having a cyclohexane structure, preferably at least one of the groups having the structures shown in Formulas 2-1 to 2-8:

[0012]

[0013] Secondly, the present invention provides a method for preparing a diamine containing a cyclohexane and norbornene structure as shown in Formula 1 above, the steps of which include:

[0014] Under nitrogen conditions, a diamine compound containing a benzonorbornene structure is mixed with anhydrous ethanol and a hydrogenation catalyst, hydrogen is introduced, and the mixture is heated to carry out a hydrogenation reaction to obtain the diamine containing a norbornene structure shown in Formula 1.

[0015] In this invention, the diamine compound containing the benzonorbornene structure is selected from 3,6-bis(4-aminophenoxy)benzonorbornene, 3,6-bis(3-aminophenoxy)benzonorbornene, 3,6-bis(2-aminophenoxy)benzonorbornene, 3,6-bis(4-amino-2-trifluoromethylphenoxy)benzonorbornene, 3,6-bis(5-amino-3-trifluoromethylphenoxy)benzonorbornene, and 3,6-bis(4-amino-3-trifluoromethylphenoxy)benzonorbornene. At least one of benzonorbornene, 3,6-bis(5-amino-2-pyridoxy)benzonorbornene, 3,6-bis(4-aminobiphenoxy)benzonorbornene, and 3,6-bis(4-aminophenoxyphenoxy)benzonorbornene, preferably at least one of 3,6-bis(4-aminophenoxy)benzonorbornene, 3,6-bis(4-amino-2-trifluoromethylphenoxy)benzonorbornene, and 3,6-bis(5-amino-2-pyridoxy)benzonorbornene;

[0016] The mass-to-volume ratio of the diamine compound containing the benzonorbornene structure to anhydrous ethanol is 50-150 g / L, for example, 50, 70, 90, 110, 130, or 150 g / L.

[0017] In this invention, the hydrogenation catalyst is a conventional choice in the field, such as at least one of homogeneous catalysts containing metals such as nickel and / or palladium, and at least one of supported catalysts containing metals such as palladium and / or nickel. Preferably, at least one of supported catalysts containing palladium and / or nickel is preferred, and more preferably, at least one of supported catalysts such as palladium on carbon, palladium silicate, and Raney nickel is preferred. Preferably, the active metal content in the hydrogenation catalyst is 5-10 wt%, for example, 5, 6, 7, 8, 9, or 10 wt%.

[0018] The amount of hydrogenation catalyst used is 6-15% of the mass of the diamine compound containing the benzonorbornene structure, for example, 6, 8, 10, 12, 14, or 15%.

[0019] In this invention, the pressure of hydrogen gas introduced is 4-10 MPa, for example 4, 5, 6, 7, 8, 9, 10 MPa, preferably 5-10 MPa.

[0020] In this invention, the hydrogenation reaction is carried out at a temperature of 150-220°C, such as 150, 170, 190, 210, or 220°C, preferably 180-220°C; and for a reaction time of 8-12 hours, such as 8, 9, 10, 11, or 12 hours.

[0021] In this invention, after the hydrogenation reaction is completed, post-processing processes such as cooling, filtration, crystallization, washing, and drying are also included. These are all conventional operations in the field, and there are no special requirements for them in this invention.

[0022] Thirdly, the present invention provides the application of the diamine containing cyclohexane and norbornene structure shown in Formula 1 above in the preparation of transparent nylon.

[0023] A method for preparing transparent nylon, wherein the raw material contains a diamine of formula 1 above containing a cyclohexane and norbornene structure, and the steps include:

[0024] (1) Preparation of di-nylon salt with norbornane structure: Dissolve aliphatic dicarboxylic acid and a diamine with norbornane structure or a dicarboxylic acid with norbornane structure and aliphatic diamine in water, heat and react under stirring, filter and dry to obtain di-nylon salt with norbornane structure.

[0025] (2) Preparation of a di-nylon salt with a cyclohexane-norbornane structure: a dicarboxylic acid with a norbornane structure and a diamine containing a cyclohexane-norbornane structure as shown in Formula 1 are dissolved in water, heated under stirring, filtered, and dried to obtain a di-nylon salt with a cyclohexane-norbornane structure.

[0026] (3) Preparation of transparent nylon: The binary nylon salt with norbornene structure in step (1), the binary nylon salt with cyclohexane and norbornene structure in step (2), and the catalyst are mixed and heated to the prepolymerization temperature in an inert protective gas environment. After vacuuming, the prepolymerization reaction is carried out, and then the temperature is raised to carry out the melt polycondensation reaction to obtain transparent nylon.

[0027] In this invention, the aliphatic dicarboxylic acid mentioned in step (1) is selected from at least one of 1,4-succinic acid, 1,5-glutaric acid, 1,6-adipic acid, 1,7-heptanenic acid, 1,8-octanoic acid, 1,9-azelaic acid, 1,10-sealic acid, 1,11-undecanoic acid, 1,12-dodecanoic acid, 1,13-tetratedic acid, and 1,14-tetradecanoic acid, preferably at least one of 1,6-adipic acid, 1,7-heptanenic acid, 1,8-octanoic acid, 1,9-azelaic acid, and 1,10-sealic acid.

[0028] In this invention, the diamine having a norbornene structure in step (1) is selected from norbornene dimethylamine, preferably at least one of norbornene-2,3-dimethylamine, norbornene-2,5-dimethylamine, and norbornene-2,6-dimethylamine, and more preferably at least one of norbornene-2,5-dimethylamine and norbornene-2,6-dimethylamine.

[0029] In this invention, the dicarboxylic acids having a norbornane structure described in steps (1) and (2) are each independently selected from norbornane dicarboxylic acids, preferably at least one of norbornane-2,3-dicarboxylic acid, norbornane-2,5-dicarboxylic acid, and norbornane-2,6-dicarboxylic acid, and more preferably at least one of norbornane-2,5-dicarboxylic acid and norbornane-2,6-dicarboxylic acid.

[0030] In this invention, the aliphatic diamine mentioned in step (1) is selected from at least one of 1,4-butanediamine, 1,5-pentanediamine, 1,6-hexanediamine, 1,7-heptanediamine, 1,8-octanediamine, 1,9-nonanediamine, 1,10-decanediamine, 1,11-undecanediamine, 1,12-dodecanediamine, 1,13-tetanediamine, and 1,14-tetradecanediamine, preferably at least one of 1,6-hexanediamine, 1,7-heptanediamine, 1,8-octanediamine, 1,9-nonanediamine, and 1,10-decanediamine.

[0031] In this invention, when step (1) uses an aliphatic diacid and a diamine with a norbornene structure, or a diacid with a norbornene structure and an aliphatic diamine, the molar ratio of the diacid to the diamine is 1.05:1 to 1:1.05, for example 1.05:1, 1.03:1, 1.01:1, 1:1, 1:1.01, 1:1.03, 1:1.05, preferably 1.01:1 to 1:1.04;

[0032] The aliphatic dicarboxylic acid and the diamine having a norbornene structure, or the dicarboxylic acid and the aliphatic diamine having a norbornene structure, have a concentration in water of 50-150 g / L based on the total mass of the mixture, for example, 50, 70, 90, 110, 130, 150 g / L.

[0033] In this invention, the reaction in step (1) is carried out at a temperature of 60-80℃, for example 60, 65, 70, 75, 80℃, and for a time of 0.5-2h, for example 0.5, 0.8, 1.1, 1.4, 1.7, 2h.

[0034] In this invention, the molar ratio of the dicarboxylic acid with a norbornene structure in step (2) to the diamine containing cyclohexane and a norbornene structure shown in Formula 1 is 1.05:1 to 1:1.05, for example 1.05:1, 1.03:1, 1.01:1, 1:1, 1:1.01, 1:1.03, 1:1.05, preferably 1.01:1 to 1:1.04;

[0035] The dicarboxylic acid having a norbornene structure and the diamine containing cyclohexane and a norbornene structure as shown in Formula 1, based on their total mass, have a concentration in water of 50-150 g / L, for example 50, 70, 90, 110, 130, or 150 g / L.

[0036] In this invention, the reaction in step (2) is carried out at a temperature of 60-80℃, for example 60, 65, 70, 75, 80℃, and for a time of 0.5-2h, for example 0.5, 0.8, 1.1, 1.4, 1.7, 2h.

[0037] In this invention, the mass ratio of the binary nylon salt with norbornene structure in step (1) to the binary nylon salt with cyclohexane and norbornene structure in step (2) is 0.4:1 to 1:1, for example 0.4:1, 0.5:1, 0.6:1, 0.7:1, 0.8:1, 0.9:1, 1:1;

[0038] In this invention, the catalyst in step (3) is selected from at least one of phosphorus-containing metal catalysts and phosphorus-containing organic catalysts, preferably sodium hypophosphite and at least one of phosphoric acid, preferably phosphoric acid;

[0039] Preferably, the amount of catalyst used is 0.005-0.01% of the total mass of the binary nylon salt with norbornene structure in step (1) and the binary nylon salt with cyclohexane and norbornene structure in step (2), for example 0.005, 0.006, 0.007, 0.008, 0.009, 0.01%.

[0040] In this invention, the inert protective gas in step (3) is selected from at least one of nitrogen, carbon dioxide, and helium, with nitrogen being preferred.

[0041] In this invention, the prepolymerization reaction in step (3) has a reaction temperature of 220-250℃, for example 220, 230, 240, 250℃, preferably 235-250℃; a reaction time of 1-3h, for example 1, 1.5, 2, 2.5, 3h, preferably 1.5-2h; and a reaction pressure of -(0.01-0.05)MPaG, for example -0.01, -0.02, -0.03, -0.04, -0.05MPaG.

[0042] In this invention, the melt polycondensation reaction in step (3) has a reaction temperature of 260-280℃, a reaction time of 30-60min, and a reaction pressure of -(0.05-0.10)MPaG, for example -0.05, -0.06, -0.07, -0.08, -0.09, or -0.1MPaG.

[0043] Fourthly, the present invention provides a transparent nylon material prepared by the above method.

[0044] The transparent nylon described in this invention has a light transmittance of up to 92%, a glass transition temperature (Tg) of over 130°C, a tensile strength greater than 100 MPa, a water absorption rate of less than 1.5%, good dielectric properties, and is resistant to a variety of solvents.

[0045] The transparent nylon material described in this invention is suitable for use in the automotive, electronics, machinery, optics, and sporting goods industries, and is particularly suitable for manufacturing optical lenses, automotive lenses, mobile phone lenses, underwater lenses, etc.

[0046] Compared with the prior art, the beneficial effects of the technical solution of the present invention are as follows:

[0047] This process uses four readily available monomers to copolymerize and prepare transparent nylon materials. The process is simple, the light transmittance is greater than 90%, and due to the large number of cyclic structures and linear structure in the polymer chain, it exhibits excellent thermal and mechanical properties, as well as good solvent resistance and a low dielectric constant. Specific implementation method.

[0048] To better understand the technical solution of the present invention, the content of the present invention will be further described below with reference to the following specific embodiments, but the content of the present invention is not limited to the following embodiments.

[0049] The main raw material sources in the embodiments and comparative examples of this invention are as follows; unless otherwise specified, all other raw materials were obtained through ordinary commercial channels:

[0050] Palladium on carbon (5%), anhydrous ethanol: Beijing Innocare Technology Co., Ltd.;

[0051] Adipic acid, heptapic acid, octanoic acid, azelaic acid, hexamethylenediamine, heptapic acid, octanoic acid, nonadiamine: Shanghai Aladdin Biochemical Technology Co., Ltd.;

[0052] 3,6-Bis(4-aminophenoxy)benzonorbornene: synthesized according to patent CN113511980B;

[0053] 3,6-Bis(4-amino-2-trifluoromethylphenoxy)benzonorbornene: synthesized according to patent CN113511980B;

[0054] 3,6-Bis(5-amino-2-pyridoxy)benzonorbornene: synthesized according to patent CN113511980B;

[0055] Norbornene-2,5-dicarboxylic acid: synthesized according to patent CN103459365A;

[0056] Norbornene-2,6-dicarboxylic acid: synthesized according to patent CN103459365A;

[0057] Norbornene-2,6-dimethylamine: synthesized according to patent CN101443308B;

[0058] Norbornene-2,5-dimethylamine: synthesized according to patent CN101443308B.

[0059] Examples 1-3: Preparation of diamines containing cyclohexane and norbornene structures as shown in Formula 1

[0060] Example 1

[0061] Preparation of diamines containing cyclohexane and norbornene structures:

[0062] 4.5 g of palladium on carbon (5%) was added to a reaction vessel. Under nitrogen conditions, 72 g (0.202 mol) of 3,6-bis(4-aminophenoxy)benzonorbornene and 1 L of anhydrous ethanol were added to a 2 L reaction vessel. The mixture was purged with nitrogen three times and hydrogen three times to maintain a hydrogen environment. The system was then heated to 180 °C and the hydrogen pressure was set to 5 MPa. The reaction was carried out for 12 h. After the reaction was completed, the palladium on carbon was removed by filtration. The filtrate was then poured into a large amount of water for low-temperature crystallization. The precipitate was collected, filtered, washed, and vacuum dried to obtain 70.7 g (0.188 mol) of white powder, namely 3,6-bis(4-aminocyclohexyloxy)cyclohexanenorbornene.

[0063] The structure is as follows:

[0064] Characterization: H 1 NMR(CDCl3)δ1.00-2.00(30H,m),2.00-4.00(6H,m),5.00-6.00(4H,s).

[0065] Example 2

[0066] Preparation of diamines containing cyclohexane and norbornene structures:

[0067] 16.5 g of palladium on carbon (5%) was added to a reactor. Under nitrogen conditions, 110 g (0.224 mol) of 3,6-bis(4-amino-2-trifluoromethylphenoxy)benzonorbornene and 1 L of anhydrous ethanol were added to a 2 L reactor. The reactor was purged with nitrogen three times and hydrogen three times to maintain a hydrogen environment. The system was then heated to 200 °C and the hydrogen pressure was set to 4 MPa. The reaction was carried out for 8 h. After the reaction was completed, the palladium on carbon was removed by filtration. The filtrate was then poured into a large amount of water and crystallized at low temperature. The precipitate was collected, filtered, washed, and vacuum dried to obtain 105 g (0.205 mol) of white powder, namely 3,6-bis(4-amino-2-trifluoromethylcyclohexyloxy)cyclohexanenorbornene.

[0068] The structure is as follows:

[0069] Characterization: H 1 NMR(CDCl3)δ1.00-2.00(26H,m),2.00-4.00(8H,m),5.00-6.00(4H,s).

[0070] Example 3

[0071] Preparation of diamines containing cyclohexane and norbornene structures:

[0072] 13.2 g of palladium on carbon (5%) was added to a reaction vessel. Under nitrogen conditions, 150 g (0.278 mol) of 3,6-bis(5-amino-2-pyridoxy)benzonorbornene and 1 L of anhydrous ethanol were added to a 2 L reaction vessel. The mixture was purged with nitrogen three times and hydrogen three times to maintain a hydrogen environment. The system was then heated to 220 °C and the hydrogen pressure was set to 10 MPa. The reaction was carried out for 10 h. After the reaction was completed, the palladium on carbon was removed by filtration. The filtrate was then poured into a large amount of water and crystallized at low temperature. The precipitate was collected, filtered, washed, and vacuum dried to obtain 146 g (0.255 mol) of white powder, namely 3,6-bis(5-amino-bis(2-cyclohexyloxy))cyclohexanenorbornene.

[0073] The structure is as follows:

[0074] Characterization: H 1 NMR(CDCl3)δ1.00-2.00(46,m),2.00-4.00(10H,m),5.00-6.00(4H,s).

[0075] Example 4-11 Preparation of transparent nylon

[0076] Example 4

[0077] (1) Preparation of binary nylon salts containing norbornene:

[0078] 27.45 g (0.188 mol) of adipic acid and 28.95 g (0.188 mol) of norbornane 2,5-dimethylamine were dissolved in 1 L of water at 60 °C. After reacting for 2 h, the mixture was filtered and dried to obtain 52.4 g of binary nylon salt.

[0079] (2) Preparation of a binary nylon salt containing cyclohexane and norbornene:

[0080] 34.59 g (0.188 mol) of norbornane 2,5-dicarboxylic acid and 70.7 g (0.188 mol) of 3,6-bis(4-aminocyclohexyloxy)cyclohexane and norbornane prepared in Example 1 were dissolved in 1 L of water at 60 °C. After reacting for 2 h, the mixture was filtered and dried to obtain 105.2 g of binary nylon salt.

[0081] (3) Preparation of transparent nylon:

[0082] 157.6g of the two binary nylon salts from steps (1) and (2) above, along with 8mg of phosphoric acid, were sequentially added to a 1L reactor. The reactor was purged with nitrogen three times, heated to 235℃, and then evacuated. The prepolymerization reaction was carried out at -0.01MPaG for 3 hours. The temperature was then increased to 280℃, and the melt polycondensation reaction was carried out at -0.1MPaG for 30 minutes. After the reaction was completed, the nylon was drawn into fibers and granulated to obtain 140g of transparent nylon.

[0083] Example 5

[0084] (1) Preparation of binary nylon salts containing norbornene:

[0085] 53.24 g (0.458 mol) hexamethylenediamine and 94.86 g (0.515 mol) norbornane-2,5-dicarboxylic acid were dissolved in 1 L of water at 70 °C and reacted for 0.5 h. After filtration and drying, 135 g of a binary nylon salt containing norbornane was obtained.

[0086] (2) Preparation of binary nylon salts containing cyclohexane and norbornene:

[0087] 39.8 g of norbornane-2,6-dicarboxylic acid and 99 g (0.193 mol) of 3,6-bis(4-aminocyclohexyloxy)cyclohexane and norbornane prepared in Example 2 were dissolved in 1 L of water at 80 °C. After reacting for 2 h, the mixture was filtered and dried to obtain 135 g of binary nylon salt.

[0088] (3) Preparation of transparent nylon:

[0089] 270g of the two binary nylon salts and 13.5mg of phosphoric acid from steps (1) and (2) above were sequentially added to a 1L reactor. Nitrogen was used to purge the reactor three times. After heating to 250℃, a vacuum was drawn and a prepolymerization reaction was carried out at -0.05MPaG for 2 hours. Then, the temperature was raised to 260℃ and a vacuum was drawn. A melt polycondensation reaction was carried out at -0.09MPaG for 60 minutes. After the reaction time was reached, the nylon was drawn into fibers and granulated to obtain 250g of transparent nylon.

[0090] Example 6

[0091] (1) Preparation of binary nylon salts containing norbornene:

[0092] 32.75 g (0.188 mol) of octanoic acid and 29.53 g (0.192 mol) of norbornane-2,5-dimethylamine were dissolved in 0.7 L of water at 80 °C and reacted for 1.5 h. After filtration and drying, 57.4 g of a binary nylon salt containing norbornane was obtained.

[0093] (2) Preparation of binary nylon salts containing cyclohexane and norbornene:

[0094] In Example 4, 3,6-bis(4-aminocyclohexyloxy)cyclohexanenorbornene was replaced with 3,6-bis(5-amino-bis(2-cyclohexyloxy))cyclohexanenorbornene. 112 g (0.196 mol) of 3,6-bis(5-amino-bis(2-cyclohexyloxy))cyclohexanenorbornene prepared in Example 3 and 34.6 g (0.188 mol) of norbornene 2,5-dicarboxylic acid were used, and the rest was the same as in Example 4, to prepare 142.6 g of the binary nylon salt.

[0095] (3) Preparation of transparent nylon:

[0096] 204g of the two binary nylon salts and 20.4mg of phosphoric acid from steps (1) and (2) above were sequentially added to a 1L reactor. Nitrogen was purged three times, and the mixture was heated to 220℃ and then vented. The prepolymerization reaction was carried out at -0.04MPaG for 2 hours. Then the temperature was raised to 275℃, and a vacuum was drawn. The melt polycondensation reaction was carried out at -0.05MPaG for 50 minutes. After the reaction time was reached, the mixture was drawn into fibers and granulated to obtain 180g of transparent nylon.

[0097] Example 7

[0098] (1) Preparation of binary nylon salts containing norbornene:

[0099] In Example 6, octanoic acid was replaced with octanoic acid diamine, and norbornane-2,5-dicarboxylic acid was replaced with norbornane-2,5-dicarboxylic acid. 27.66 g (0.192 mol) of octanoic acid diamine and 36.06 g (0.196 mol) of norbornane-2,5-dicarboxylic acid were dissolved in 0.6 L of water at 70 °C and reacted for 2 h. After filtration and drying, 58.1 g of a binary nylon salt containing norbornane was obtained.

[0100] (2) Preparation of binary nylon salts containing cyclohexane and norbornene:

[0101] Same as Example 4.

[0102] (3) Preparation of transparent nylon:

[0103] 163.3g of the two binary nylon salts and 8.4mg of phosphoric acid were sequentially added to a 1L reactor, and other conditions were the same as in Example 6, to obtain 150g of transparent nylon.

[0104] Example 8

[0105] (1) Preparation of binary nylon salts containing norbornene structure:

[0106] In Example 7, octyldiamine was replaced with nonadiamine. 30.94 g (0.196 mol) of nonadiamine and 34.96 g (0.19 mol) of norbornane-2,5-dicarboxylic acid were dissolved in 1 L of water at 70 °C and reacted for 2 h. After filtration and drying, 63 g of a binary nylon salt containing norbornane was obtained.

[0107] (2) Preparation of binary nylon salts containing cyclohexane and norbornene:

[0108] Same as Example 4.

[0109] (3) Preparation of transparent nylon:

[0110] 168.2g of the two binary nylon salts and 8.65mg of phosphoric acid were sequentially added to a 1L reactor. The inert gas was replaced three times. After heating to 270℃, the gas was vented and prepolymerized at -0.06MPaG for 2 hours. Then, the temperature was raised to 280℃, and a vacuum was drawn. The melt polycondensation reaction was carried out at -0.03MPaG for 50 minutes. After the reaction time was reached, the mixture was drawn into fibers and granulated to obtain 160g of transparent nylon.

[0111] Example 9

[0112] (1) Preparation of binary nylon salts containing norbornene structure:

[0113] In Example 7, octanoic acid was replaced with azelaic acid. 35.76 g (0.190 mol) of azelaic acid and 29.41 g (0.191 mol) of norbornane-2,5-dicarboxyamine were dissolved in 0.7 L of water at 80 °C and reacted for 1.5 h. After filtration and drying, 60.2 g of a binary nylon salt containing norbornane was obtained.

[0114] (2) Preparation of binary nylon salts containing cyclohexane and norbornene:

[0115] Same as Example 4.

[0116] (3) Preparation of transparent nylon:

[0117] 165.4g of the two binary nylon salts and 16.5mg of phosphoric acid were sequentially added to a 1L reactor. The inert gas was replaced three times. After heating to 230℃, the gas was vented and prepolymerized at -0.02MPaG for 2 hours. Then, the temperature was raised to 275℃, and a vacuum was drawn. The melt polycondensation reaction was carried out at -0.08MPaG for 50 minutes. After the reaction time was reached, the nylon was drawn into fibers and granulated to obtain 115g of transparent nylon.

[0118] Example 10

[0119] (1) Preparation of binary nylon salts containing norbornene structure:

[0120] In Example 4, norbornane-2,5-dicarboxylic acid was replaced with norbornane-2,6-dicarboxylic acid, while other conditions remained the same as in Example 4.

[0121] Steps (2) and (3): Same as in Example 4.

[0122] Example 11

[0123] (1) Preparation of binary nylon salts containing norbornene structure:

[0124] In Example 4, norbornene-2,5-dimethylamine was replaced with norbornene-2,6-dimethylamine, while other conditions remained the same as in Example 4.

[0125] Steps (2) and (3): Same as in Example 4.

[0126] Comparative Example 1

[0127] Transparent nylon was prepared according to the method of Example 4, except that the 3,6-bis(4-aminocyclohexyloxy)cyclohexane and norbornene prepared in Example 1 was replaced with hexamethylenediamine, while other operations and conditions remained unchanged.

[0128] Comparative Example 2

[0129] Transparent nylon was prepared according to the method in Example 4, except that norbornene-2,5-dimethylamine was replaced with hexamethylenediamine, while other operations and conditions remained unchanged.

[0130] The performance test parameters and corresponding test methods in the various embodiments and comparative examples of this invention are as follows:

[0131] Light transmittance: GB / T 2410-2008;

[0132] Glass transition temperature: GB / T 19466.2-2004;

[0133] Tensile strength: GB / T 1040.1-2018;

[0134] Elongation at break: GB / T 1040.1-2018;

[0135] Water absorption rate: GB / T 8810-2005;

[0136] Dielectric properties: GB / T1409-2006;

[0137] Solubility: GB / T 11547-2008.

[0138] The test results of light transmittance, glass transition temperature, tensile strength, elongation at break, and water absorption in the various embodiments and comparative examples of this invention are shown in Table 1:

[0139] Table 1. Performance test results of the examples and comparative examples.

[0140] Example 4 92 140 103.9 0.78 Example 5 92 141 112.2 0.96 Example 3 91 135 118.5 1.21 Example 4 91 135 125.6 1.13 Example 5 91 132 132.8 0.89 Example 6 90 132 138.8 0.96 Example 7 90 130 140.2 1.02 Example 8 92 138 139.5 0.86 Comparative Example 1 84 80 101.2 2.71 Comparative Example 2 86 105 105.5 2.61

[0141] The dielectric performance test results of the various embodiments and comparative examples of this invention are shown in Table 2:

[0142] Table 2. Dielectric property test results of the examples and comparative examples.

[0143]

[0144]

[0145] In the various embodiments and comparative examples of this invention, the solubility of transparent nylon in N-methylpyrrolidone, N,N-dimethylformamide, dimethyl sulfoxide, and m-cresol was tested, and the results are shown in Table 3.

[0146] Table 3. Solubility test results of the examples and comparative examples

[0147] Example 1 Slightly soluble upon heating Slightly soluble upon heating Slightly soluble at room temperature Slightly soluble upon heating Example 2 Slightly soluble upon heating Slightly soluble upon heating Slightly soluble at room temperature Slightly soluble upon heating Example 3 Slightly soluble upon heating Slightly soluble upon heating Slightly soluble at room temperature Slightly soluble upon heating Example 4 Slightly soluble upon heating Slightly soluble upon heating Slightly soluble at room temperature Slightly soluble upon heating Example 5 Slightly soluble upon heating Slightly soluble upon heating Slightly soluble at room temperature Slightly soluble upon heating Example 6 Slightly soluble upon heating Slightly soluble upon heating Slightly soluble at room temperature Slightly soluble upon heating Example 7 Slightly soluble upon heating Slightly soluble at room temperature Slightly soluble at room temperature Slightly soluble upon heating Example 8 Slightly soluble upon heating Slightly soluble upon heating Slightly soluble at room temperature Slightly soluble upon heating Comparative Example 1 Slightly soluble at room temperature Slightly soluble at room temperature Slightly soluble at room temperature Slightly soluble at room temperature Comparative Example 2 Slightly soluble at room temperature Slightly soluble upon heating Slightly soluble at room temperature Slightly soluble at room temperature

Claims

1. A diamine containing a cyclohexane and norbornene structure, characterized in that, It has the structure shown in Equation 1: (Equation 1) In Formula 1, Ar is independently represented by at least one of the groups with the structures shown in Formulas 2-1 to 2-8 below: (Equation 2-1) (Equation 2-2) (Equation 2-3) (Equation 2-4) (Equation 2-5) (Equation 2-6) (Equation 2-7) (Equation 2-8).

2. A method for preparing a diamine containing a cyclohexane and norbornene structure as described in claim 1, characterized in that the step... include: Under nitrogen conditions, a diamine compound containing a benzonorbornene structure is mixed with anhydrous ethanol and a hydrogenation catalyst, hydrogen is introduced, and the mixture is heated to carry out a hydrogenation reaction to obtain the diamine containing a norbornene structure shown in Formula 1.

3. The preparation method according to claim 2, characterized in that, The diamine compound containing the benzonorbornene structure is selected from at least one of 3,6-bis(4-aminophenoxy)benzonorbornene, 3,6-bis(3-aminophenoxy)benzonorbornene, 3,6-bis(2-aminophenoxy)benzonorbornene, 3,6-bis(4-amino-2-trifluoromethylphenoxy)benzonorbornene, 3,6-bis(5-amino-3-trifluoromethylphenoxy)benzonorbornene, 3,6-bis(4-amino-3-trifluoromethylphenoxy)benzonorbornene, 3,6-bis(5-aminopyridyl-2-oxy)benzonorbornene, 3,6-bis(4-aminobiphenoxy)benzonorbornene, and 3,6-bis(4-aminophenoxyphenoxy)benzonorbornene; and / or The mass-to-volume ratio of the diamine compound containing the benzonorbornene structure to anhydrous ethanol is 50-150 g / L.

4. The preparation method according to claim 3, characterized in that, The diamine compound containing the benzonorbornene structure is selected from at least one of 3,6-bis(4-aminophenoxy)benzonorbornene, 3,6-bis(4-amino-2-trifluoromethylphenoxy)benzonorbornene, and 3,6-bis(5-amino-2-pyridoxy)benzonorbornene.

5. The preparation method according to claim 2, characterized in that, The hydrogenation catalyst is at least one of the following: a homogeneous catalyst containing nickel and / or palladium metal, and a supported catalyst containing palladium and / or nickel metal; and / or The amount of hydrogenation catalyst used is 6-15% of the mass of the diamine compound containing the benzonorbornene structure; and / or The pressure of hydrogen gas introduced is 4-10 MPa; and / or The hydrogenation reaction is carried out at a temperature of 150-220℃ for 8-12 hours.

6. The preparation method according to claim 5, characterized in that, The hydrogenation catalyst is at least one of palladium on carbon, palladium silicon dioxide, and Raney nickel.

7. The preparation method according to claim 5, characterized in that, The active metal content in the hydrogenation catalyst is 5-10 wt%.

8. The preparation method according to claim 5, characterized in that, The pressure of hydrogen gas introduced is 5-10 MPa.

9. The preparation method according to claim 5, characterized in that, The hydrogenation reaction is carried out at a temperature of 180-220℃.

10. A method for preparing transparent nylon, characterized in that, The raw material contains the diamine containing a cyclohexane-norbornene structure as described in claim 1, or the diamine containing a cyclohexane-norbornene structure prepared by the method described in any one of claims 2-9, and the steps include: (1) Preparation of di-nylon salt with norbornane structure: Dissolve aliphatic dicarboxylic acid and a diamine with norbornane structure or a dicarboxylic acid with norbornane structure and aliphatic diamine in water, heat and react under stirring, filter and dry to obtain di-nylon salt with norbornane structure. (2) Preparation of a di-nylon salt with a cyclohexane-norbornane structure: a dicarboxylic acid with a norbornane structure and a diamine containing a cyclohexane-norbornane structure as shown in Formula 1 are dissolved in water, heated under stirring, filtered, and dried to obtain a di-nylon salt with a cyclohexane-norbornane structure. (3) Preparation of transparent nylon: The binary nylon salt with norbornene structure in step (1), the binary nylon salt with cyclohexane and norbornene structure in step (2), and the catalyst are mixed and heated to the prepolymerization temperature in an inert protective gas environment. After vacuuming, the prepolymerization reaction is carried out, and then the temperature is raised to carry out the melt polycondensation reaction to obtain transparent nylon.

11. The preparation method according to claim 10, characterized in that, The aliphatic dicarboxylic acid in step (1) is selected from at least one of 1,4-succinic acid, 1,5-glutaric acid, 1,6-adipic acid, 1,7-heptanedic acid, 1,8-octanoic acid, 1,9-azelaic acid, 1,10-sealic acid, 1,11-undecanoic acid, 1,12-dodecanoic acid, 1,13-tetratedic acid, and 1,14-tetradecanoic acid; and / or The diamine having a norbornene structure in step (1) is selected from norbornene dimethylamine; and / or The dicarboxylic acids having a norbornene structure mentioned in steps (1) and (2) are each independently selected from norbornene dicarboxylic acids; and / or The aliphatic diamine in step (1) is selected from at least one of 1,4-butanediamine, 1,5-pentanediamine, 1,6-hexanediamine, 1,7-heptanediamine, 1,8-octanediamine, 1,9-nonanediamine, 1,10-decanediamine, 1,11-undecanediamine, 1,12-dodecanediamine, 1,13-tridecanediamine, and 1,14-tetradecanediamine; and / or In step (1), when using an aliphatic diacid with a diamine having a norbornene structure, or a diacid with a norbornene structure and an aliphatic diamine, the molar ratio of the diacid to the diamine is 1.05:1 to 1:1.05; and / or The aliphatic dicarboxylic acid and the diamine having a norbornene structure, or the dicarboxylic acid having a norbornene structure and the aliphatic diamine, have a concentration in water of 50-150 g / L based on the total mass of the mixture; and / or The reaction described in step (1) is carried out at a temperature of 60-80℃ for a time of 0.5-2h.

12. The preparation method according to claim 11, characterized in that, The diamine having a norbornene structure is selected from at least one of norbornene-2,3-dimethylamine, norbornene-2,5-dimethylamine, and norbornene-2,6-dimethylamine.

13. The preparation method according to claim 11, characterized in that, The dicarboxylic acids having a norbornane structure are each independently selected from at least one of norbornane-2,3-dicarboxylic acid, norbornane-2,5-dicarboxylic acid, and norbornane-2,6-dicarboxylic acid.

14. The preparation method according to claim 11, characterized in that, The molar ratio of the diacid to the diamine is 1.01:1 to 1:1.

04.

15. The preparation method according to claim 10, characterized in that, In step (2), the molar ratio of the dicarboxylic acid having a norbornene structure to the diamine containing cyclohexane and a norbornene structure shown in Formula 1 is 1.05:1 to 1:1.05; and / or The dicarboxylic acid having a norbornene structure and the diamine of Formula 1 containing cyclohexane and a norbornene structure, dissolved in water at a concentration of 50-150 g / L based on their total mass; and / or The reaction described in step (2) is carried out at a temperature of 60-80℃ for a time of 0.5-2h.

16. The preparation method according to claim 15, characterized in that, The molar ratio of the dicarboxylic acid having a norbornene structure to the diamine containing cyclohexane and a norbornene structure shown in Formula 1 is 1.01:1 to 1:1.

04.

17. The preparation method according to claim 10, characterized in that, In step (3), the mass ratio of the di-nylon salt with a norbornene structure in step (1) to the di-nylon salt with a cyclohexane and norbornene structure in step (2) is 0.4:1 to 1:1; and / or The catalyst in step (3) is selected from at least one of phosphorus-containing metal catalysts and phosphorus-containing organic catalysts; and / or The amount of catalyst used is 0.005-0.01% of the total mass of the binary nylon salt with norbornene structure in step (1) and the binary nylon salt with cyclohexane and norbornene structure in step (2).

18. The preparation method according to claim 17, characterized in that, The catalyst is selected from at least one of sodium hypophosphite and phosphoric acid.

19. The preparation method according to claim 10, characterized in that, The inert protective gas in step (3) is selected from at least one of nitrogen, carbon dioxide, and helium; and / or The prepolymerization reaction in step (3) is carried out at a temperature of 220-250℃, a reaction time of 1-3h, and a reaction pressure of -(0.01-0.05) MPaG; and / or The melt polycondensation reaction in step (3) has a reaction temperature of 260-280℃, a reaction time of 30-60min, and a reaction pressure of -(0.05-0.10)MPaG.

20. The preparation method according to claim 19, characterized in that, The prepolymerization reaction is carried out at a temperature of 235-250℃ for 1.5-2 hours.

21. A transparent nylon material prepared by the method according to any one of claims 10-20.

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