Nylon elastomer, preparation method thereof and nylon product

Abstract

The invention provides a nylon elastomer, a preparation method thereof and a nylon product. The nylon elastomer is prepared from the following raw materials in parts by mass: 35 to 65 parts of nylon material, 35 to 65 parts of polyether and 0.1 to 0.5 part of catalyst, wherein the number average molecular weight of the polyether is 250 to 1000; the nylon material is prepared from the following raw materials: first binary acid, second binary acid and diamine, the number of carbon atoms in the first binary acid is a, the number of carbon atoms in the second binary acid is b, and a-b is equal to 2. According to the invention, the nylon material with relatively low number-average molecular weight and polyether are reasonably proportioned, so that the melting temperature of the nylon elastomer obtained by polymerization is reduced; meanwhile, the nylon material is obtained by polymerizing the binary acid and the diamine with the difference of two carbon atoms, so that the crystallization uniformity and integrity of the nylon section can be improved, and the melting range of the nylon elastomer is shortened.

Description

Technical Field

[0001] The present application relates to the technical field of polymer materials, and in particular to a nylon elastomer, a preparation method thereof, and a nylon product. Background Art

[0002] Nylon elastomer is made of nylon and polyether connected by amide bonds or ester bonds, and its processing temperature is based on the melting temperature and melting range of the nylon segment. In nylon elastomer, due to the shortening of nylon molecular chains and the influence of polyether segments, the crystallization ability of nylon is suppressed, so that the melting temperature of nylon elastomer is lower than that of conventional nylon, making it have a wide range of application prospects at relatively low temperatures.

[0003] Since some chemical additives are sensitive to temperature, they cannot be effectively injected or extruded after exceeding a certain temperature. For example, the temperature of some chemical foaming agents and nylon elastomers cannot be greater than 160°C; therefore, the melting temperature of nylon elastomers should not be too high. Reducing the molecular weight of nylon and polyether can reduce the melting temperature of nylon elastomers, but it will also affect the crystallization integrity and uniformity of the nylon segment and increase the melting range, making nylon elastomers unable to meet the needs of low-temperature processing.

[0004] Therefore, traditional nylon elastomers still need further improvement. Summary of the invention

[0005] Based on this, one or more embodiments of the present application provide a nylon elastomer with low melting temperature and short melting range, a preparation method thereof, and a nylon product.

[0006] According to the first aspect of the present application, a nylon elastomer is provided, which comprises the following raw materials, calculated by weight: 35 to 65 parts of nylon material, 35 to 65 parts of polyether and 0.1 to 0.5 parts of catalyst;

[0007] The number average molecular weight of the polyether is 250-1000; the raw materials for preparing the nylon material include a first dibasic acid, a second dibasic acid and a diamine, the number of carbon atoms in the first dibasic acid is a, the number of carbon atoms in the second dibasic acid is b, and ab=2 is satisfied.

[0008] In some embodiments, the first dibasic acid comprises one or more of suberic acid, sebacic acid and dodecanedioic acid; and / or,

[0009] The second dibasic acid includes one or more of adipic acid, suberic acid and sebacic acid.

[0010] In some embodiments, the molar ratio of the first dibasic acid to the second dibasic acid is (55-75): (25-45).

[0011] In some embodiments, the diamine includes one or more of hexamethylenediamine, decanediamine and dodecanediamine.

[0012] In some embodiments, the nylon material is a random copolymer.

[0013] In some embodiments, the polyether includes one or more of polytetramethylene glycol and polytetramethylene diamine.

[0014] In some embodiments, the catalyst includes one or more of zirconium n-butoxide and phosphorous acid.

[0015] According to a second aspect of the present application, a method for preparing a nylon elastomer is provided, comprising the following steps:

[0016] The above-mentioned raw materials for preparing the nylon elastomer are provided, mixed, and reacted at 250° C. to 260° C. under vacuum conditions for 2 h to 4 h.

[0017] In some embodiments, the pressure of the vacuum condition is below 5 kPa.

[0018] According to a third aspect of the present application, a nylon product is provided, comprising the above-mentioned nylon elastomer.

[0019] Compared with the traditional technology, this application has the following beneficial effects:

[0020] The present invention reduces the melting temperature of the nylon elastomer obtained by polymerization by reasonably mixing nylon materials with low number average molecular weight and polyether; at the same time, the nylon material is obtained by polymerizing two dibasic acids with a carbon atom number difference of 2 with diamines, which can improve the crystallization uniformity and integrity of the nylon segment, thereby shortening the melting range of the nylon elastomer. The nylon elastomer of the present invention can be melt-blended with temperature-sensitive chemical additives at low temperatures, broadening the application range of the nylon elastomer.

[0021] In addition, the present invention can directly prepare nylon elastomer by heating, releasing pressure and evacuating, which has the advantages of simple preparation process, high polymerization efficiency and low preparation cost. BRIEF DESCRIPTION OF THE DRAWINGS

[0022] In order to more clearly illustrate the specific implementation methods of the present application or the technical solutions in the prior art, the drawings required for use in the specific implementation methods or the description of the prior art will be briefly introduced below. Obviously, the drawings described below are some implementation methods of the present application. For ordinary technicians in this field, other drawings can be obtained based on these drawings without paying any creative work.

[0023] Figure 1The DSC curves of the nylon elastomers prepared in Examples 1-2 and Comparative Examples 1-2 of the present application are shown in FIG. DETAILED DESCRIPTION

[0024] In order to make the above-mentioned purposes, features and advantages of the present application more obvious and easy to understand, the specific implementation methods of the present application are described in detail. In the following description, many specific details are set forth to facilitate a full understanding of the present application. However, the present application can be implemented in many other ways different from those described herein, and those skilled in the art can make similar improvements without violating the connotation of the present application, so the present application is not limited by the specific embodiments disclosed below.

[0025] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as those generally understood by those skilled in the art of the present application. The terms used herein in the specification of the present application are only for the purpose of describing specific embodiments and are not intended to limit the present application. Unless otherwise specifically stated, various raw materials, reagents, instruments and equipment used in the present application, etc. can be purchased from the market or can be prepared by existing methods.

[0026] In the present application, "further", "further", "particularly" and the like are used for descriptive purposes to indicate differences in content, but should not be construed as limiting the scope of protection of the present application.

[0027] In this application, "optionally", "optional", and "optional" mean optional or dispensable, that is, any one of the two parallel schemes of "yes" or "no". If multiple "options" appear in a technical solution, unless otherwise specified and there is no contradiction or mutual restriction, each "optional" is independent.

[0028] In the present application, the technical features described in an open manner include closed technical solutions composed of the listed features, and also include open technical solutions containing the listed features.

[0029] In the present application, when it comes to numerical intervals (i.e., numerical ranges), unless otherwise specified, the optional numerical distribution is considered continuous within the above numerical interval, and includes the two numerical endpoints (i.e., the minimum and maximum values) of the numerical range, and each numerical value between the two numerical endpoints. Unless otherwise specified, when the numerical interval only refers to the integers within the numerical interval, it includes the two endpoint integers of the numerical range, and each integer between the two endpoints. In this article, it is equivalent to directly listing each integer, such as t is an integer selected from 1 to 10, indicating that t is any integer selected from the integer group consisting of 1, 2, 3, 4, 5, 6, 7, 8, 9 and 10. In addition, when multiple ranges are provided to describe features or characteristics, these ranges can be combined. In other words, unless otherwise specified, the ranges disclosed herein should be understood to include any and all sub-ranges included therein.

[0030] The temperature parameters in this application, unless otherwise specified, are allowed to be either constant temperature treatment or to vary within a certain temperature range. It should be understood that the constant temperature treatment allows the temperature to fluctuate within the accuracy range controlled by the instrument. Fluctuations within the range of ±5°C, ±4°C, ±3°C, ±2°C, and ±1°C are allowed.

[0031] In a first aspect of the present application, a nylon elastomer is provided, which comprises the following raw materials, calculated by weight: 35 to 65 parts of nylon material, 35 to 65 parts of polyether and 0.001 to 0.005 parts of catalyst;

[0032] The number average molecular weight of the polyether is 250-1000; the raw materials for preparing the nylon material include a first dibasic acid, a second dibasic acid and a diamine, the number of carbon atoms in the first dibasic acid is a, the number of carbon atoms in the second dibasic acid is b, and ab=2 is satisfied.

[0033] The present invention reduces the melting temperature of the nylon elastomer obtained by polymerization by reasonably mixing nylon materials with low number average molecular weight and polyether; at the same time, the nylon material is obtained by polymerizing two dibasic acids with a carbon atom number difference of 2 with diamines, which can improve the crystallization uniformity and integrity of the nylon segment, thereby shortening the melting range of the nylon elastomer. The nylon elastomer of the present invention can be melt-blended with temperature-sensitive chemical additives at low temperatures, broadening the application range of the nylon elastomer.

[0034] Specifically, the number average molecular weight of the nylon material is reduced by adjusting the mass ratio of the dibasic acid and the diamine in the nylon material.

[0035] The number average molecular weight of nylon material can be calculated as follows:

[0036] Number average molecular weight of nylon material = (number of moles of acid or amine / number of moles of excess acid) × molecular weight of nylon repeating unit + molecular weight of excess acid

[0037] The present application uses two dibasic acids whose carbon number differs by 2, which can reduce the length of the molecular chain repeating unit to make the molecular chain more regular; and can ensure that the performance of the two dibasic acid monomers will not differ too much.

[0038] As an example, the mass fraction of nylon material can be 35 parts, 36 parts, 37 parts, 38 parts, 39 parts, 40 parts, 41 parts, 42 parts, 43 parts, 44 parts, 45 parts, 46 parts, 47 parts, 48 ​​parts, 49 parts, 50 parts, 51 parts, 52 parts, 53 parts, 54 parts, 55 parts, 56 parts, 57 parts, 58 parts, 59 parts, 60 parts, 61 parts, 62 parts, 63 parts, 64 parts, 65 parts, or any value within the range formed by any two of the above point values.

[0039] Furthermore, the mass fraction of the nylon material is 40 parts to 60 parts; furthermore, the mass fraction of the nylon material is 50 parts to 60 parts.

[0040] In some of these embodiments, the first dibasic acid includes one or more of suberic acid, sebacic acid, and dodecanedioic acid.

[0041] In some of these embodiments, the second dibasic acid includes one or more of adipic acid, suberic acid, and sebacic acid.

[0042] In some embodiments, the first dibasic acid is selected from suberic acid and the second dibasic acid is selected from adipic acid.

[0043] In some embodiments, the first dibasic acid is selected from sebacic acid and the second dibasic acid is selected from suberic acid.

[0044] In some embodiments, the first dibasic acid is selected from dodecanedioic acid and the second dibasic acid is selected from sebacic acid.

[0045] In some embodiments, the molar ratio of the first dibasic acid to the second dibasic acid is (55-75):(25-45).

[0046] It can be understood that controlling the molar ratio of the first dibasic acid to the second dibasic acid within the above range can further shorten the melting range of the nylon elastomer and has little effect on the melting temperature and other properties of the nylon material.

[0047] As an example, the molar ratio of the first dibasic acid to the second dibasic acid can be 55:45, 60:40, 65:35, 70:30, 75:25, or any value within the range formed by any two of the above ratios.

[0048] Furthermore, the molar ratio of the first dibasic acid to the second dibasic acid is (60-75):(25-40).

[0049] In some embodiments, based on the total moles of the first dibasic acid and the second dibasic acid, the molar proportion of the first dibasic acid is 55% to 75%, and the molar proportion of the second dibasic acid is 25% to 45%.

[0050] Furthermore, the molar ratio of the first dibasic acid is 60% to 75%, and the molar ratio of the second dibasic acid is 25% to 40%.

[0051] In some embodiments, the diamine includes one or more of hexamethylenediamine, decanediamine, and dodecanediamine.

[0052] In some of these embodiments, the nylon material is a random copolymer.

[0053] It can be understood that a random copolymer refers to two or more different monomers that undergo a polymerization reaction in a random manner under the action of an initiator or a catalyst, and the arrangement of the monomer units in the formed copolymer is irregular.

[0054] As an example, the mass fraction of the polyether can be 35, 36, 37, 38, 39, 40, 41, 42, 43, 44, 45, 46, 47, 48, 49, 50, 51, 52, 53, 54, 55, 56, 57, 58, 59, 60, 61, 62, 63, 64, 65 parts, or any value within the range formed by any two of the above point values.

[0055] Furthermore, the mass fraction of the polyether is 30 parts to 50 parts; furthermore, the mass fraction of the polyether is 40 parts to 50 parts.

[0056] In some of these embodiments, the polyether includes one or more of polytetrahydrofuran diol and polytetrahydrofuran diamine.

[0057] In some embodiments, the polyether is selected from polytetramethylene glycol.

[0058] As an example, the number average molecular weight of the polyether can be 250, 300, 350, 400, 450, 500, 550, 600, 650, 700, 750, 800, 850, 900, 950, 1000, or any value within the range formed by any two of the foregoing values.

[0059] Furthermore, the number average molecular weight of the polyether is 300-700; furthermore, the number average molecular weight of the polyether is 650.

[0060] In some embodiments, the polyether is selected from polytetrahydrofuran diol having a number average molecular weight of 650.

[0061] The melting temperature of nylon elastomer can be effectively lowered by lowering the number average molecular weight of nylon and polyether, but the crystallinity of the nylon segment will decrease, thereby increasing the melting range. In this regard, two dibasic acids with a carbon atom number difference of 2 are further polymerized with diamines to obtain nylon materials, thereby improving the crystallization uniformity and integrity of the nylon segment, thereby shortening the melting range of the nylon elastomer. As a result, the final nylon elastomer has both a lower melting temperature and a shorter melting range.

[0062] In the present application, "number average molecular weight" refers to a value obtained by dividing the sum of the molecular weights of all molecules in a polymer by the total number of molecules.

[0063] As an example, the mass fraction of the catalyst can be 0.1 part, 0.15 part, 0.2 part, 0.25 part, 0.3 part, 0.35 part, 0.4 part, 0.45 part, 0.5 part, or any value within the range formed by any two of the above point values.

[0064] In some embodiments, the catalyst includes one or more of zirconium n-butoxide (Zr(OB)4) and phosphorous acid.

[0065] In some embodiments, the catalyst is selected from zirconium n-butoxide or phosphorous acid.

[0066] It can be understood that the catalyst can form specific binding points, namely active centers, with the monomer molecules; the monomer molecules interact with each other such as adsorption and coordination on these active centers, thereby initiating polymerization reactions.

[0067] The nylon elastomer of the present application has good hardness performance and tear strength, reduces the melting temperature of the nylon elastomer, shortens the melting range, and improves the crystallization uniformity and integrity of the nylon segment.

[0068] In a second aspect of the present application, a method for preparing a nylon elastomer is provided, comprising the following steps:

[0069] The raw materials for preparing the nylon elastomer of the first aspect are provided, mixed, and reacted at 250° C. to 260° C. under vacuum conditions for 2 h to 4 h.

[0070] In some embodiments, the method for preparing the above-mentioned nylon elastomer comprises the following steps:

[0071] According to the first aspect, a first dibasic acid, a second dibasic acid, a diamine, a polyether, and a catalyst are provided, mixed with a solvent, and reacted at 250° C. to 260° C. under vacuum conditions for 2 h to 4 h.

[0072] In some embodiments, the solvent includes deionized water.

[0073] In some embodiments, the preparation method of the above-mentioned nylon elastomer comprises the following steps: providing the preparation raw materials of the nylon elastomer of the first aspect, mixing, heating to 250°C~260°C, releasing the pressure, evacuating, and reacting for 2h~4h.

[0074] As an example, the reaction temperature can be 250°C, 251°C, 252°C, 253°C, 254°C, 255°C, 256°C, 257°C, 258°C, 259°C, 260°C, or any value within the range formed by any two of the above point values.

[0075] As an example, the reaction time can be 2h, 2.1h, 2.2h, 2.3h, 2.4h, 2.5h, 2.6h, 2.7h, 2.8h, 2.9h, 3h, 3.1h, 3.2h, 3.3h, 3.4h, 3.5h, 3.6h, 3.7h, 3.8h, 3.9h, 4h, or any value within the range formed by any two of the above point values.

[0076] In some embodiments, the pressure of the vacuum condition is 5 kPa or less.

[0077] As an example, the pressure of the vacuum condition can be 0.1 kPa, 0.2 kPa, 0.3 kPa, 0.4 kPa, 0.5 kPa, 0.6 kPa, 0.7 kPa, 0.8 kPa, 0.9 kPa, 1 kPa, 2 kPa, 3 kPa, 4 kPa, 5 kPa, or any value within the range formed by any two of the above point values.

[0078] The above-mentioned preparation method of the present application only requires one step, that is, directly heating to 250° C., releasing the pressure and evacuating the mixture to carry out the reaction, and has the advantages of simple preparation process, high polymerization efficiency and low cost.

[0079] In a third aspect of the present application, a nylon product is provided, comprising the above-mentioned nylon elastomer.

[0080] As an example, the above-mentioned nylon products can be used as soles, sports protective gear, auto parts, medical equipment, wires and cables, electronic equipment casings, etc.

[0081] The present application will be further described below in conjunction with specific examples and comparative examples, but they should not be construed as limiting the scope of protection of the present application. The raw materials involved in the following specific examples, unless otherwise specified, can all be sourced from commercial sources, the instruments used, unless otherwise specified, can all be sourced from commercial sources, and the processes involved, unless otherwise specified, are all conventionally selected by those skilled in the art.

[0082] The sources of some of the raw materials used in the examples and comparative examples of this application are as follows:

[0083] Sebacic acid was purchased from Hengshui Jinghua Chemical Co., Ltd.;

[0084] Dodecanedioic acid was purchased from Shandong Guiyuan Biotechnology Co., Ltd.;

[0085] Decanediamine was purchased from Wuxi Yinda Nylon Co., Ltd.;

[0086] Polytetrahydrofurandiol was purchased from Hyosung (Jiaxing) Co., Ltd., South Korea;

[0087] Zirconium n-butoxide was purchased from Guangdong Wengjiang Chemical Reagent Co., Ltd.;

[0088] Phosphorous acid was purchased from Shandong West Asia Chemical Co., Ltd.

[0089] Example 1

[0090] (1) Weigh 250 g of sebacic acid, 520 g of dodecane dicarboxylic acid, 350 g of decanediamine, 100 g of deionized water, 43 g of Zr(OB), and 950 g of polytetrahydrofuran diol with a number average molecular weight of 650, mix them, and put them into a 5 L high-pressure reactor equipped with a stirrer. The molar ratio of sebacic acid to dodecane dicarboxylic acid is about 64.6:35.4.

[0091] (2) The reactor was heated to 250°C, and then vacuumed to below 5000 Pa. The reaction was continued for 4 hours to obtain a nylon elastomer.

[0092] Example 2

[0093] (1) Weigh 175 g of sebacic acid, 600 g of dodecane dicarboxylic acid, 350 g of decanediamine, 100 g of deionized water, 43 g of Zr(OB), and 950 g of polytetrahydrofuran diol with a number average molecular weight of 650, mix them, and put them into a 5 L autoclave equipped with a stirrer. The molar ratio of sebacic acid to dodecane dicarboxylic acid is about 75:25.

[0094] (2) The reactor was heated to 250°C, and then vacuumed to below 5000 Pa. The reaction was continued for 4 hours to obtain a nylon elastomer.

[0095] Example 3

[0096] (1) Weigh 250 g of sebacic acid, 520 g of dodecane dicarboxylic acid, 350 g of decanediamine, 100 g of deionized water, 43 g of Zr(OB), and 950 g of polytetrahydrofuran diol with a number average molecular weight of 650, mix them, and put them into a 5 L high-pressure reactor equipped with a stirrer. The molar ratio of sebacic acid to dodecane dicarboxylic acid is about 64.6:35.4.

[0097] (2) The mixture obtained in step (1) is placed in nitrogen and heated to 210°C, at which point the autogenous pressure reaches 1.9 MPa. The pressure is maintained for reaction for 1 hour, then the temperature is raised to 250°C, and the pressure in the autoclave is evacuated to below 5000 Pa to produce a nylon elastomer.

[0098] Example 4

[0099] (1) Weigh 195 g of sebacic acid, 415 g of dodecane dicarboxylic acid, 280 g of decanediamine, 100 g of deionized water, 43 g of Zr(OB), and 1140 g of polytetrahydrofuran diol with a number average molecular weight of 1000, mix them, and put them into a 5 L autoclave equipped with a stirrer. The molar ratio of sebacic acid to dodecane dicarboxylic acid is about 64.6:35.4.

[0100] (2) The reactor was heated to 250°C, and then vacuumed to below 5000 Pa. The reaction was continued for 4 hours to obtain a nylon elastomer.

[0101] Example 5

[0102] (1) Weigh 250 g of sebacic acid, 520 g of dodecane dicarboxylic acid, 350 g of decanediamine, 100 g of deionized water, 3 g of phosphorous acid, and 950 g of polytetrahydrofuran diol with a number average molecular weight of 650, mix them, and put them into a 5 L high-pressure reactor equipped with a stirrer. The molar ratio of sebacic acid to dodecane dicarboxylic acid is about 64.6:35.4.

[0103] (2) The reactor was heated to 250°C, and then vacuumed to below 5000 Pa. The reaction was continued for 2.5 hours to obtain a nylon elastomer.

[0104] Example 6

[0105] Weigh 105g of sebacic acid, 675g of dodecane dicarboxylic acid, 350g of decanediamine, 100g of deionized water, 3g of Zr(OB)4, and 950g of polytetrahydrofuran diol with a number average molecular weight of 650, mix, and put into a 5L autoclave with a stirrer. Wherein, the molar ratio of sebacic acid to dodecane dicarboxylic acid is about 85:15.

[0106] (2) The reactor was heated to 250°C, and then vacuumed to below 5000 Pa. The reaction was continued for 4 hours to obtain a nylon elastomer.

[0107] Comparative Example 1

[0108] (1) 800 g of dodecanedioic acid, 350 g of decanediamine, 100 g of deionized water, 3 g of Zr(OB)4, and 990 g of polytetrahydrofuran diol with a number average molecular weight of 650 were mixed and placed in a 5 L high-pressure reactor equipped with a stirrer.

[0109] (2) The reactor was heated to 250°C, and then vacuumed to below 5000 Pa. The reaction was continued for 4 hours to obtain a nylon elastomer.

[0110] Comparative Example 2

[0111] (1) 730 g of dodecanedioic acid, 375 g of decanediamine, 100 g of deionized water, 3 g of phosphorous acid, and 950 g of polytetrahydrofuran diol with a number average molecular weight of 1000 were mixed and placed in a 5 L autoclave equipped with a stirrer.

[0112] (2) The reactor was heated to 250°C, and then vacuumed to below 5000 Pa. The reaction was continued for 4 hours to obtain a nylon elastomer.

[0113] Comparative Example 3

[0114] (1) Weigh 210 g of suberic acid, 520 g of dodecanedioic acid, 350 g of decanediamine, 100 g of deionized water, 43 g of Zr(OB), and 950 g of polytetrahydrofuran diol with a number average molecular weight of 650, mix them, and place them in a 5 L autoclave equipped with a stirrer.

[0115] (2) The reactor was heated to 250°C, and then vacuumed to below 5000 Pa. The reaction was continued for 4 hours to obtain a nylon elastomer.

[0116] The types and proportions of the raw materials prepared in the above examples and comparative examples are shown in Table 1.

[0117] Table 1

[0118]

[0119] The performance of the nylon elastomers prepared in the above examples and comparative examples was tested; the performance results are shown in Table 2.

[0120] Viscosity test: The relative viscosity of the polymer solution with 25℃ and 99% mass concentration of meta-cresol as solvent is carried out according to the national standard 12006.1-2009 Plastic Polyamide Part I: Viscosity Number Determination. The instrument is an Ubbelohde viscometer with a capillary inner diameter of 1.03mm±2%. The determination method is as follows: weigh 0.125g of the nylon elastomer prepared above, dissolve it in 25mL of 99% meta-cresol, wait for it to be completely dissolved, and obtain a copolymer solution. Take the Ubbelohde viscometer with a capillary inner diameter of 1.03mm±2% and place it in a constant temperature water bath at 25℃. Quickly take an appropriate amount of meta-cresol and inject it into the Ubbelohde viscometer. After the constant temperature is maintained for 0.5h, measure the time required for meta-cresol to stay from the upper scale line to the lower scale line. Repeat three times, the error is not less than 0.2s, and the average value is set as t0. The falling time of the copolymer solution is measured in the same way, and the average value t is taken; the relative viscosity ηr=t / t0 is calculated.

[0121] Tear strength test: Prepare and test the specimens according to GB / T529-2008; test the right-angle specimens, and test at least 5 specimens, the thickness of the specimens is 2mm, the length is greater than 100mm, the width is 19±0.05mm, and the radius of the right-angle cut of 90° in the middle is 127±0.05mm; take the average value of the results.

[0122] Shore hardness test: Test according to GB / T2411-80; test at least 5 points, the sample size is 100mm×100mm, the top of the indenter is greater than 9mm from the edge of the sample, and the interval between the two test points is greater than 6mm; the result is the average value.

[0123] Melting temperature and melting range test: Use differential scanning calorimetry (DSC) to test at a heating and cooling rate of 10°C / min, and the second heating process shall prevail.

[0124] The "polymerization time" in Table 2 refers to the time from the addition of materials to the termination of the reaction.

[0125] Table 2

[0126]

[0127] From the above table and Figure 1 It can be seen that compared with Comparative Example 2, in Comparative Example 1, the molecular weight of the nylon material is reduced by adjusting the ratio of the nylon material, and the molecular weight of the polyether is reduced at the same time. The hardness performance of the prepared nylon elastomer remains basically unchanged, the melting temperature is reduced, but the melting range is significantly increased.

[0128] Compared with Comparative Examples 1-2, two dibasic acids with a carbon atom number difference of 2 are added in Examples 1-6, and the nylon elastomer finally obtained has a lower melting temperature and a shorter melting range while having substantially the same hardness. Figure 1 It is the DSC curve diagram of Example 1-2 and Comparative Example 1-2.

[0129] In Comparative Example 3, the carbon number of the first dibasic acid and the carbon number of the second dibasic acid differ by 4, and the melting temperature of the obtained nylon elastomer increases and the melting range becomes longer.

[0130] Compared with Comparative Examples 1 to 3, Examples 1 to 6 contain two dibasic acids and the difference in the number of carbon atoms of the two dibasic acids is 2. Not only does the melting temperature decrease again, but the peak area becomes larger, the melting range becomes shorter, and the peak shape becomes relatively sharp, that is, it has better crystal uniformity and integrity.

[0131] Compared with Example 3, the nylon elastomers of Examples 1-2 are prepared by a one-step temperature increase reaction, and the polymerization time is significantly shortened and the polymerization efficiency is higher.

[0132] Compared with Example 1, the use of phosphorous acid as a catalyst in Example 5 further shortens the polymerization time.

[0133] Compared with Example 1, the molar ratio of the first dibasic acid to the second dibasic acid in Example 6 is 85:15, which is a larger ratio. The melting temperature of the nylon elastomer finally obtained is significantly higher than that of Example 1, and the melting range is longer.

[0134] The technical features of the above-described embodiments may be arbitrarily combined. To make the description concise, not all possible combinations of the technical features in the above-described embodiments are described. However, as long as there is no contradiction in the combination of these technical features, they should be considered to be within the scope of this specification.

[0135] The above-mentioned embodiments only express several implementation methods of the present application, and the descriptions thereof are relatively specific and detailed, but they cannot be understood as limiting the scope of the invention patent. It should be pointed out that, for a person of ordinary skill in the art, several variations and improvements can be made without departing from the concept of the present application, and these all belong to the protection scope of the present application. Therefore, the protection scope of the present application shall be subject to the attached claims.

Claims

1. A nylon elastomer, characterized in that: The preparation raw materials include the following by weight: 35 to 65 parts of nylon material, 35 to 65 parts of polyether and 0.1 to 0.5 parts of catalyst; The number average molecular weight of the polyether is 250-1000; the raw materials for preparing the nylon material include a first dibasic acid, a second dibasic acid and a diamine, the number of carbon atoms in the first dibasic acid is a, the number of carbon atoms in the second dibasic acid is b, and ab=2 is satisfied.

2. The nylon elastomer according to claim 1, characterized in that: The first dibasic acid comprises one or more of suberic acid, sebacic acid and dodecanedioic acid; and / or, The second dibasic acid includes one or more of adipic acid, suberic acid and sebacic acid.

3. The nylon elastomer according to claim 1, characterized in that: The molar ratio of the first dibasic acid to the second dibasic acid is (55-75):(25-45).

4. The nylon elastomer according to any one of claims 1 to 3, characterized in that: The diamine includes one or more of hexamethylenediamine, decanediamine and dodecanediamine.

5. The nylon elastomer according to any one of claims 1 to 3, characterized in that: The nylon material is a random copolymer.

6. The nylon elastomer according to any one of claims 1 to 3, characterized in that: The polyether comprises one or more of polytetrahydrofuran diol and polytetrahydrofuran diamine.

7. The nylon elastomer according to any one of claims 1 to 3, characterized in that The catalyst includes one or more of zirconium n-butoxide and phosphorous acid.

8. A method for preparing a nylon elastomer, characterized in that: The steps include: Provide the raw materials for preparing the nylon elastomer according to any one of claims 1 to 7, mix them, and react them at 250° C. to 260° C. under vacuum conditions for 2 h to 4 h.

9. The method for preparing a nylon elastomer according to claim 8, characterized in that: The pressure of the vacuum condition is 5 kPa or less.

10. A nylon product, characterized in that: The nylon elastomer comprising any one of claims 1 to 7.

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