Polyurethane imide high-temperature damping material and preparation method thereof

Abstract

The invention discloses a polyurethane imide high-temperature damping material and a preparation method thereof, and the preparation method comprises the following steps: (1) carrying out addition polymerization on 4, 4 '-diaminodiphenyl ether (ODA), pyromellitic dianhydride (PMDA) and N-methyl pyrrolidone (NMP) to obtain a first intermediate product (polyimide acid); (2) polymerizing hydrogenated diphenylmethane diisocyanate (HMDI) and polycaprolactone glycol (PCL) to obtain a second intermediate product (polyurethane damping modifier); (3) carrying out addition reaction on isocyanate groups in the second intermediate product and reactive hydrogen in the first intermediate product to obtain a third intermediate product; and (4) carrying out solvent volatilization curing and high-temperature imidization reaction on the third intermediate product to obtain the polyurethane-imide damping material. According to the invention, the polyurethane prepolymer is adopted as a damping modifier to be grafted to polyimide, so that the material not only retains the excellent damping performance of polyurethane, but also absorbs the characteristics of high flame retardance, high temperature resistance and the like of polyimide.

Description

Technical Field

[0001] The invention relates to the technical field of polymer materials, and in particular to a polyurethaneimide high-temperature damping material and a preparation method thereof. Background Art

[0002] Damping vibration reduction and noise reduction technology is one of the effective methods to control vibration and structural noise, and is becoming a hot research topic in industrially developed countries. Damping material is a functional material that can absorb vibration mechanical energy and convert it into heat energy, electrical energy, magnetic energy or other forms of energy and lose it. Polymer materials have good damping and vibration reduction effects due to their viscoelasticity, and their damping materials have been widely used in many fields, including satellites, aircraft, ships, and automobile industries. However, in the above fields, damping materials are required to have good high temperature resistance, mechanical properties, etc. while having shock absorption performance.

[0003] Polyimide refers to a type of polymer containing an imide ring on the main chain of the polymer, which is prepared by the step-by-step polymerization of compounds containing diamines and dianhydrides. Since polyimide molecules have a very stable aromatic heterocyclic structure, they exhibit excellent characteristics that other polymer materials cannot match, especially high and low temperature resistance. Polyimide is widely used in heat-resistant materials in aerospace equipment, insulation layers and packaging materials in the power and microelectronics information industries, fibers, engineering plastics, adhesives, etc. in high-tech industries due to its excellent thermal stability, mechanical properties, dielectric properties, radiation resistance, and acid-base stability.

[0004] The patent (CN118222092A) discloses a polyimide composition, a polyimide film and a preparation method thereof. The present application selects a PMR type polyimide or a precursor thereof with good high temperature resistance as a crosslinking agent, and utilizes a first polyimide or a precursor of the resin main body to undergo a crosslinking reaction with the crosslinking agent through the active end group sites on the main chain during the thermal curing process to achieve the purpose of chain extension, thereby improving its elongation at break while ensuring good thermal properties. However, the above invention improves the heat resistance, but due to the increased cohesive strength and the lack of damping performance, it cannot meet the shock absorption requirements of high-temperature vibration components.

[0005] Patent (CN118159599A) discloses a polyamic acid composition and a preparation method thereof, which can have excellent insulation breakdown voltage performance or corona discharge starting voltage while maintaining heat resistance or mechanical strength, and the polyimide covering prepared by using the polyamic acid composition according to the present invention has excellent voltage resistance characteristics. Although the above invention improves the electrical insulation performance, the material still has no damping performance and cannot meet the shock absorption of high-temperature vibration parts.

[0006] It can be seen that although polyimide has good heat resistance, mechanical properties, radiation resistance, etc., it does not have damping properties, which limits its application in the field of damping materials.

[0007] In view of this, this application is hereby filed. Summary of the invention

[0008] In order to solve the above technical problems, the present invention provides a polyurethaneimide high-temperature damping material and a preparation method thereof. By using a polyurethane prepolymer as a damping modifier to be grafted onto polyimide, the polyurethane and the polyimide can penetrate each other and cross-develop to form a new polymer structure. The molecular chain contains both the main structure of the soft and hard segment structure of the polyurethane and the polyimide segment in its hard segment and / or soft segment. Therefore, the material retains the excellent damping performance of the polyurethane and absorbs the high flame retardancy and high temperature resistance of the polyimide.

[0009] The present invention is achieved through the following technical solutions:

[0010] In a first aspect, the present invention provides a method for preparing a polyurethaneimide high temperature damping material, comprising the following steps:

[0011] (1) Using 4,4'-diaminodiphenyl ether (ODA), pyromellitic dianhydride (PMDA) and N-methylpyrrolidone (NMP), a first intermediate product (polyimide acid) is obtained by addition polymerization; the reaction route is as follows:

[0012]

[0013] (2) Hydrogenated diphenylmethane diisocyanate (HMDI) and polycaprolactone diol (PCL) are polymerized to obtain a second intermediate product (polyurethane damping modifier); the reaction route is as follows:

[0014]

[0015] (3) The isocyanate group in the second intermediate product is subjected to an addition reaction with the active hydrogen in the first intermediate product to obtain a third intermediate product; the reaction scheme is as follows:

[0016]

[0017] (4) The third intermediate product is subjected to solvent volatilization curing and high-temperature imidization reaction to obtain a polyurethane imide damping material. The reaction route is as follows:

[0018]

[0019] In a specific embodiment, in step (1), the mass percentages of the raw materials are as follows: 4,4'-diaminodiphenyl ether (ODA) is 24% to 32%, pyromellitic dianhydride (PMDA) is 18% to 26%, and the remaining raw material is N-methylpyrrolidone (NMP).

[0020] In a specific embodiment, in step (2), the mass percentages of the raw materials are as follows: the content of hydrogenated diphenylmethane diisocyanate (HMDI) is 25% to 45%, and the content of polycaprolactone diol (PCL) is 55% to 75%.

[0021] In a specific embodiment, in step (3), the mass percentages of the raw materials are as follows: the first intermediate product content is 85% to 95%, and the second intermediate product content is 5% to 15%.

[0022] In a specific embodiment, the synthesis process of step (1) is as follows:

[0023] (1.1) Add N-methylpyrrolidone (NMP) into the reaction kettle and stir. The feeding temperature is 10℃~30℃; the feeding environment is air atmosphere, relative humidity is 10RH~50RH; the stirring speed is 80~120RPM;

[0024] (1.2) 4,4'-diaminodiphenyl ether (ODA) is divided into 3 to 5 parts, preferably 4 to 5 parts, and added to the reaction kettle in batches, while heating to 35 to 60°C, preferably 45 to 55°C, and mixing for 0.5 to 3 hours, preferably 1 to 2 hours; after the previous ODA is completely dissolved, the next ODA is added;

[0025] (1.3) Pyromellitic dianhydride (PMDA) is divided into 3 to 10 parts, preferably 5 to 85 parts, and added to the reactor in batches. It is necessary to observe the temperature in the reactor each time the feed is added. After the feed is added, the temperature will gradually rise and then drop. After the temperature stabilizes, the next feed is started. The temperature of the reactor is controlled at 50 to 100°C, preferably 80 to 90°C, and the reaction time is 3 to 10 hours. When the temperature exceeds 100°C, cooling water is introduced to cool the temperature to 20 to 35°C, preferably 20 to 30°C, to obtain the first intermediate product.

[0026] In a specific embodiment, the synthesis process of step (2) is as follows:

[0027] (2.1) adding hydrogenated diphenylmethane diisocyanate (HMDI) into a reaction kettle and stirring at a stirring speed of 80 to 120 RPM, preferably 90 to 110 RPM, heating to 30 to 50° C., preferably 40 to 50° C., and filling with nitrogen (0.02 MPa to 0.10 MPa, preferably 0.03 MPa to 0.05 MPa) for protection;

[0028] (2.2) Divide polycaprolactone diol (PCL) into 3 to 7 parts, preferably 5 to 7 parts, and add them into the reactor in batches. The temperature of the reactor is 80 to 130° C., preferably 80 to 100° C., and the reaction time of a single feed is 2 to 5 hours, preferably 3 to 4 hours;

[0029] (2.3) After the isocyanate content in the reaction kettle reaches a preset value, the temperature of the reaction kettle is lowered to 20° C. to 35° C., preferably 20° C. to 30° C., to obtain a second intermediate product.

[0030] In a specific embodiment, the synthesis process of step (3) is as follows:

[0031] (3.1) adding the first intermediate product to a reaction kettle and stirring at a stirring speed of 80 to 120 RPM, preferably 90 to 100 RPM, heating to 30 to 50° C., preferably 30 to 40° C., and filling with nitrogen (0.02 MPa to 0.10 MPa, preferably 0.05 MPa to 0.07 MPa) for protection;

[0032] (3.2) The second intermediate product is divided into 3 to 5 portions, preferably 4 to 5 portions, and added to the reaction kettle in batches. The temperature of the reaction kettle is 50 to 80° C., preferably 60 to 70° C., and the single-feed reaction time is 1 to 3 hours, preferably 2.5 to 3 hours;

[0033] (3.3) After the acid ester content in the reaction kettle reaches a preset value, the temperature of the reaction kettle is lowered to 20° C. to 35° C., preferably 20° C. to 25° C., to obtain a third intermediate product.

[0034] In a specific embodiment, the synthesis process of step (4) is as follows:

[0035] (4.1) placing the third intermediate product into a vacuum degassing machine to remove air, and then adding the product into a mold, wherein the mold temperature is 50 to 130° C., preferably 80 to 100° C.; the temperature of the third intermediate product is 10 to 80° C., preferably 40 to 60° C.; the pouring speed is 0.2 to 5 L / min, preferably 0.5 to 1.0 L / min;

[0036] (4.2) The mold temperature is increased to 160 to 250°C, preferably 160 to 180°C, at a heating rate of 1°C / h to 30°C / h, preferably 10 to 15°C / h, to carry out an imidization reaction to obtain a polyurethane imide damping material.

[0037] In a second aspect, the present invention further provides a polyurethaneimide high temperature damping material, which is prepared by the above-mentioned preparation method of the polyurethaneimide high temperature damping material.

[0038] In a specific embodiment, the structural formula of the polyurethaneimide high temperature damping material is as follows:

[0039]

[0040] Compared with the prior art, the present invention has the following advantages and beneficial effects:

[0041] 1. A polyurethaneimide high-temperature damping material and a preparation method thereof provided in an embodiment of the present invention adopts a polyurethane prepolymer as a damping modifier to be grafted onto polyimide. The polyurethane and polyimide can mutually penetrate and cross-develop to form a new polymer structure. The molecular chain contains both the main structure of the soft and hard segment structure of the polyurethane and the polyimide segment in its hard segment and / or soft segment. Therefore, the material retains the excellent damping performance of the polyurethane and absorbs the high flame retardancy and high temperature resistance of the polyimide.

[0042] 2. A polyurethaneimide high-temperature damping material and a preparation method thereof provided in an embodiment of the present invention, wherein the prepared material has excellent damping performance, a damping factor ≥ 0.7, can withstand a working high temperature environment of 200°C to 270°C, and meets the working condition requirements of a primary circuit;

[0043] 3. A polyurethaneimide high-temperature damping material and a preparation method thereof provided in an embodiment of the present invention have good comprehensive performance, a tensile strength of 40MPa to 60MPa, and an elongation at break of 9% to 20%, and can provide good reliability in use. BRIEF DESCRIPTION OF THE DRAWINGS

[0044] In order to more clearly illustrate the technical solutions of the exemplary embodiments of the present invention, the drawings required for use in the embodiments will be briefly introduced below. It should be understood that the following drawings only show certain embodiments of the present invention and therefore should not be regarded as limiting the scope. For ordinary technicians in this field, other related drawings can be obtained based on these drawings without paying creative work.

[0045] Figure 1 A typical damping spectrum of the polyurethaneimide material provided in an embodiment of the present invention. DETAILED DESCRIPTION

[0046] In order to make the purpose, technical solutions and advantages of the present invention more clearly understood, the present invention is further described in detail below in conjunction with embodiments. The illustrative embodiments of the present invention and their description are only used to explain the present invention and are not intended to limit the present invention.

[0047] In the following description, a large number of specific details are set forth in order to provide a thorough understanding of the present invention. However, it is apparent to one of ordinary skill in the art that these specific details need not be employed to practice the present invention. In other embodiments, in order to avoid confusing the present invention, well-known materials or methods are not specifically described.

[0048] Throughout the specification, references to "one embodiment," "an embodiment," "an example," or "an example" mean that a particular feature, structure, or characteristic described in conjunction with the embodiment or example is included in at least one embodiment of the present invention. Therefore, the phrases "one embodiment," "an embodiment," "an example," or "an example" appearing in various places throughout the specification do not necessarily all refer to the same embodiment or example. In addition, particular features, structures, or characteristics may be combined in one or more embodiments or examples in any suitable combination and / or subcombination. The term "and / or" as used herein includes any and all combinations of one or more of the associated listed items.

[0049] The "range" disclosed in the present application is defined in the form of a lower limit and an upper limit, and a given range is defined by selecting a lower limit and an upper limit, and the selected lower limit and upper limit define the boundaries of the particular range. The range defined in this way can be inclusive or exclusive of the end values, and can be arbitrarily combined, that is, any lower limit can be combined with any upper limit to form a range. For example, if a range of 60 to 120 and 80 to 110 is listed for a particular parameter, it is understood that a range of 60 to 110 and 80 to 120 is also expected. In addition, if the minimum range values ​​1 and 2 are listed, and if the maximum range values ​​3, 4 and 5 are listed, the following ranges can all be expected: 1 to 3, 1 to 4, 1 to 5, 2 to 3, 2 to 4 and 2 to 5. In the present application, unless otherwise specified, the numerical range "a to b" represents an abbreviation of any real number combination between a and b, where a and b are both real numbers. For example, the numerical range "0-5" means that all real numbers between "0-5" are listed in this document, and "0-5" is just an abbreviation of these numerical combinations. In addition, when a parameter is expressed as an integer ≥ 2, it is equivalent to disclosing that the parameter is, for example, an integer of 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, etc.

[0050] If there is no special explanation, all steps of the present application can be performed sequentially or randomly, preferably sequentially. For example, the method includes steps (a) and (b), which means that the method may include steps (a) and (b) performed sequentially, or may include steps (b) and (a) performed sequentially. For example, the method may further include step (c), which means that step (c) may be added to the method in any order. For example, the method may include steps (a), (b) and (c), or may include steps (a), (c) and (b), or may include steps (c), (a) and (b), etc.

[0051] In a first aspect, the present invention provides a method for preparing a polyurethaneimide high temperature damping material, comprising the following steps:

[0052] (1) Preparation of polyimide precursor (first intermediate product polyimide acid):

[0053] (1.1) Add N-methylpyrrolidone (NMP) into the reaction kettle and stir. The feeding temperature is 10℃~30℃; the feeding environment is air atmosphere, relative humidity is 10RH~50RH; the stirring speed is 80~120RPM;

[0054] (1.2) 4,4'-diaminodiphenyl ether (ODA) is divided into 3 to 5 parts, preferably 4 to 5 parts, and added to the reaction kettle in batches, while heating to 35 to 60°C, preferably 45 to 55°C, and mixing for 0.5 to 3 hours, preferably 1 to 2 hours; after the previous ODA is completely dissolved, the next ODA is added;

[0055] (1.3) 3 to 10 parts, preferably 5 to 85 parts, of pyromellitic dianhydride (PMDA) are added to the reactor in batches. Each time the feed is added, the temperature in the reactor needs to be carefully observed. After the feed is added, the temperature will gradually rise and then drop. After the temperature stabilizes, the next feed is started. The reactor temperature is controlled at 50 to 100° C., preferably 80 to 90° C., and the reaction time is 3 to 10 hours. After the temperature exceeds 100° C., cooling water is introduced to cool the temperature to 20 to 35° C., preferably 20 to 30° C., to obtain the first intermediate product.

[0056] The mass percentages of the raw materials are as follows: 4,4'-diaminodiphenyl ether (ODA) is 24% to 32%, pyromellitic dianhydride (PMDA) is 18% to 26%, and the remaining raw material is N-methylpyrrolidone (NMP).

[0057] (2) Preparation of polyurethane prepolymer (second intermediate product polyurethane damping modifier)

[0058] (2.1) adding hydrogenated diphenylmethane diisocyanate (HMDI) into a reaction kettle and stirring at a stirring speed of 80 to 120 RPM, preferably 90 to 110 RPM, heating to 30 to 50° C., preferably 40 to 50° C., and filling with nitrogen (0.02 MPa to 0.10 MPa, preferably 0.03 MPa to 0.05 MPa) for protection;

[0059] (2.2) Divide polycaprolactone diol (PCL) into 3 to 7 parts, preferably 5 to 7 parts, and add them into the reactor in batches. The temperature of the reactor is 80 to 130° C., preferably 80 to 100° C., and the reaction time of a single feed is 2 to 5 hours, preferably 3 to 4 hours;

[0060] (2.3) After the isocyanate content in the reaction kettle reaches a preset value, the temperature of the reaction kettle is lowered to 20° C. to 35° C., preferably 20° C. to 30° C., to obtain a second intermediate product;

[0061] The mass percentage of each raw material content is as follows: hydrogenated diphenylmethane diisocyanate (HMDI) content is 25% to 45%, polycaprolactone diol (PCL) content is 55% to 75%

[0062] (3) Polyurethane grafting modification (third intermediate product)

[0063] (3.1) adding the first intermediate product to a reaction kettle and stirring at a stirring speed of 80 to 120 RPM, preferably 90 to 100 RPM, heating to 30 to 50° C., preferably 30 to 40° C., and filling with nitrogen (0.02 MPa to 0.10 MPa, preferably 0.05 MPa to 0.07 MPa) for protection;

[0064] (3.2) The second intermediate product is divided into 3 to 5 portions, preferably 4 to 5 portions, and added to the reaction kettle in batches. The temperature of the reaction kettle is 50 to 80° C., preferably 60 to 70° C., and the single-feed reaction time is 1 to 3 hours, preferably 2.5 to 3 hours;

[0065] (3.3) After the acid ester content in the reaction kettle reaches a preset value, the temperature of the reaction kettle is lowered to 20° C. to 35° C., preferably 20° C. to 25° C., to obtain a third intermediate product;

[0066] The mass percentages of the raw materials are as follows: the first intermediate product content is 85% to 95%, and the second intermediate product content is 5% to 15%.

[0067] (4) Preparation by volatilization curing and high temperature imidization reaction,

[0068] (4.1) placing the third intermediate product into a vacuum degassing machine to remove air, and then adding the product into a mold, wherein the mold temperature is 50 to 130° C., preferably 80 to 100° C.; the temperature of the third intermediate product is 10 to 80° C., preferably 40 to 60° C.; the pouring speed is 0.2 to 5 L / min, preferably 0.5 to 1.0 L / min;

[0069] (4.2) The mold temperature is increased to 160 to 250°C, preferably 160 to 180°C, at a heating rate of 1°C / h to 30°C / h, preferably 10 to 15°C / h, to carry out an imidization reaction to obtain a polyurethane imide damping material.

[0070] In a second aspect, the present invention further provides a polyurethaneimide high temperature damping material, which is prepared by the above-mentioned preparation method of the polyurethaneimide high temperature damping material.

[0071] In a specific embodiment, the structural formula of the polyurethaneimide high temperature damping material is as follows:

[0072] Example 1

[0073] The embodiment of the present invention provides a method for preparing a polyurethaneimide high temperature damping material, comprising the following steps:

[0074] (1) Preparation of polyimide precursor (first intermediate product polyimide acid):

[0075] (1.1) Add N-methylpyrrolidone (NMP) into the reaction kettle and stir. The feeding temperature is 10℃~30℃; the feeding environment is air atmosphere, relative humidity is 10RH~50RH; the stirring speed is 80~120RPM;

[0076] (1.2) 4,4'-diaminodiphenyl ether (ODA) is divided into 3 to 5 parts, preferably 4 to 5 parts, and added to the reaction kettle in batches, while heating to 35 to 60°C, preferably 45 to 55°C, and mixing for 0.5 to 3 hours, preferably 1 to 2 hours; after the previous ODA is completely dissolved, the next ODA is added;

[0077] (1.3) 3 to 10 parts, preferably 5 to 85 parts, of pyromellitic dianhydride (PMDA) are added to the reactor in batches. Each time the feed is added, the temperature in the reactor needs to be carefully observed. After the feed is added, the temperature will gradually rise and then drop. After the temperature stabilizes, the next feed is started. The reactor temperature is controlled at 50 to 100° C., preferably 80 to 90° C., and the reaction time is 3 to 10 hours. After the temperature exceeds 100° C., cooling water is introduced to cool the temperature to 20 to 35° C., preferably 20 to 30° C., to obtain the first intermediate product.

[0078] The mass parts of the raw materials are as follows: 400 parts of 4,4'-diaminodiphenyl ether (ODA), 325 parts of pyromellitic dianhydride (PMDA), and 853 parts of N-methylpyrrolidone (NMP).

[0079] (2) Preparation of polyurethane prepolymer (second intermediate product polyurethane damping modifier)

[0080] (2.1) adding hydrogenated diphenylmethane diisocyanate (HMDI) into a reaction kettle and stirring at a stirring speed of 80 to 120 RPM, preferably 90 to 110 RPM, heating to 30 to 50° C., preferably 40 to 50° C., and filling with nitrogen (0.02 MPa to 0.10 MPa, preferably 0.03 MPa to 0.05 MPa) for protection;

[0081] (2.2) Divide polycaprolactone diol (PCL) into 3 to 7 parts, preferably 5 to 7 parts, and add them into the reactor in batches. The temperature of the reactor is 80 to 130° C., preferably 80 to 100° C., and the reaction time of a single feed is 2 to 5 hours, preferably 3 to 4 hours;

[0082] (2.3) After the isocyanate content in the reaction kettle reaches a preset value, the temperature of the reaction kettle is lowered to 20° C. to 35° C., preferably 20° C. to 30° C., to obtain a second intermediate product;

[0083] The mass parts of the raw materials are as follows: the content of hydrogenated diphenylmethane diisocyanate (HMDI) is 44 parts, and the content of polycaprolactone diol (PCL) is 84 parts.

[0084] (3) Polyurethane grafting modification (third intermediate product)

[0085] (3.1) adding the first intermediate product to a reaction kettle and stirring at a stirring speed of 80 to 120 RPM, preferably 90 to 100 RPM, heating to 30 to 50° C., preferably 30 to 40° C., and filling with nitrogen (0.02 MPa to 0.10 MPa, preferably 0.05 MPa to 0.07 MPa) for protection;

[0086] (3.2) The second intermediate product is divided into 3 to 5 portions, preferably 4 to 5 portions, and added to the reaction kettle in batches. The temperature of the reaction kettle is 50 to 80° C., preferably 60 to 70° C., and the single-feed reaction time is 1 to 3 hours, preferably 2.5 to 3 hours;

[0087] (3.3) After the acid ester content in the reaction kettle reaches a preset value, the temperature of the reaction kettle is lowered to 20° C. to 35° C., preferably 20° C. to 25° C., to obtain a third intermediate product;

[0088] The mass parts of each raw material content are as follows: the first intermediate product content is 1578 parts respectively, the second intermediate product content is 128 parts;

[0089] (4) Preparation by volatilization curing and high temperature imidization reaction,

[0090] (4.1) placing the third intermediate product into a vacuum degassing machine to remove air, and then adding the product into a mold, wherein the mold temperature is 50 to 130° C., preferably 80 to 100° C.; the temperature of the third intermediate product is 10 to 80° C., preferably 40 to 60° C.; the pouring speed is 0.2 to 5 L / min, preferably 0.5 to 1.0 L / min;

[0091] (4.2) The mold temperature is increased to 160 to 250°C, preferably 160 to 180°C, at a heating rate of 1°C / h to 30°C / h, preferably 10 to 15°C / h, to carry out an imidization reaction to obtain a polyurethane imide damping material.

[0092] Example 2

[0093] The embodiment of the present invention provides a method for preparing a polyurethaneimide high temperature damping material. Based on the embodiment 1, the difference between the present embodiment and the embodiment 1 is that:

[0094] In step (1), the mass fractions of the raw materials are as follows: 400 parts of 4,4'-diaminodiphenyl ether (ODA), 325 parts of pyromellitic dianhydride (PMDA), and 907 parts of N-methylpyrrolidone (NMP).

[0095] In step (2), the mass fractions of the raw materials are as follows: the content of hydrogenated diphenylmethane diisocyanate (HMDI) is 62 parts, and the content of polycaprolactone diol (PCL) is 119 parts.

[0096] In step (3), the mass fractions of the contents of the various raw materials are as follows: the content of the first intermediate product is 1632 parts, and the content of the second intermediate product is 181 parts.

[0097] Example 3

[0098] The embodiment of the present invention provides a method for preparing a polyurethaneimide high temperature damping material. Based on the embodiment 1, the difference between the present embodiment and the embodiment 1 is that:

[0099] In step (1), the mass fractions of the raw materials are as follows: 400 parts of 4,4'-diaminodiphenyl ether (ODA), 325 parts of pyromellitic dianhydride (PMDA), and 968 parts of N-methylpyrrolidone (NMP).

[0100] In step (2), the mass fractions of the raw materials are as follows: the content of hydrogenated diphenylmethane diisocyanate (HMDI) is 83 parts, and the content of polycaprolactone diol (PCL) is 159 parts.

[0101] In step (3), the mass fractions of the contents of the various raw materials are as follows: the content of the first intermediate product is 1693 parts, and the content of the second intermediate product is 242 parts.

[0102] Example 4

[0103] The embodiment of the present invention provides a method for preparing a polyurethaneimide high temperature damping material. Based on the embodiment 1, the difference between the present embodiment and the embodiment 1 is that:

[0104] In step (1), the mass fractions of the raw materials are as follows: 400 parts of 4,4'-diaminodiphenyl ether (ODA), 325 parts of pyromellitic dianhydride (PMDA), and 1036 parts of N-methylpyrrolidone (NMP).

[0105] In step (2), the mass fractions of the raw materials are as follows: the content of hydrogenated diphenylmethane diisocyanate (HMDI) is 107 parts, and the content of polycaprolactone diol (PCL) is 204 parts.

[0106] In step (3), the mass fractions of the contents of the various raw materials are as follows: the content of the first intermediate product is 1761 parts, and the content of the second intermediate product is 311 parts.

[0107] Example 5

[0108] The embodiment of the present invention provides a method for preparing a polyurethaneimide high temperature damping material. Based on the embodiment 1, the difference between the present embodiment and the embodiment 1 is that:

[0109] In step (1), the mass fractions of the raw materials are as follows: 400 parts of 4,4'-diaminodiphenyl ether (ODA), 325 parts of pyromellitic dianhydride (PMDA), and 1117 parts of N-methylpyrrolidone (NMP).

[0110] In step (2), the mass fractions of the raw materials are as follows: the content of hydrogenated diphenylmethane diisocyanate (HMDI) is 135 parts, and the content of polycaprolactone diol (PCL) is 257 parts.

[0111] In step (3), the mass fractions of the contents of the various raw materials are as follows: the content of the first intermediate product is 1842 parts, and the content of the second intermediate product is 392 parts.

[0112] Example 6

[0113] The embodiment of the present invention provides a method for preparing a polyurethaneimide high temperature damping material. Based on the embodiment 1, the difference between the present embodiment and the embodiment 1 is that:

[0114] In step (1), the mass fractions of the raw materials are as follows: 400 parts of 4,4'-diaminodiphenyl ether (ODA), 325 parts of pyromellitic dianhydride (PMDA), and 1210 parts of N-methylpyrrolidone (NMP).

[0115] In step (2), the mass fractions of the raw materials are as follows: the content of hydrogenated diphenylmethane diisocyanate (HMDI) is 135 parts, and the content of polycaprolactone diol (PCL) is 257 parts.

[0116] In step (3), the mass fractions of the contents of the various raw materials are as follows: the content of the first intermediate product is 1842 parts, and the content of the second intermediate product is 392 parts.

[0117] Comparative Example 1

[0118] The difference between this comparative example and Example 1 is that: the second intermediate product is not used to perform damping modification on the first intermediate product;

[0119] In step (1), the mass fractions of the raw materials are as follows: 400 parts of 4,4'-diaminodiphenyl ether (ODA), 218 parts of pyromellitic dianhydride (PMDA), and 618 parts of N-methylpyrrolidone (NMP).

[0120] Comparative Example 2

[0121] The difference between this comparative example and Example 1 is that: the second intermediate product is not used to perform damping modification on the first intermediate product;

[0122] In step (1), the mass fractions of the raw materials are as follows: 400 parts of 4,4'-diaminodiphenyl ether (ODA), 242 parts of pyromellitic dianhydride (PMDA), and 642 parts of N-methylpyrrolidone (NMP).

[0123] Comparative Example 3

[0124] The difference between this comparative example and Example 1 is that: the second intermediate product is not used to perform damping modification on the first intermediate product;

[0125] In step (1), the mass fractions of the raw materials are as follows: 400 parts of 4,4'-diaminodiphenyl ether (ODA), 267 parts of pyromellitic dianhydride (PMDA), and 668 parts of N-methylpyrrolidone (NMP).

[0126] Comparative Example 4

[0127] The difference between this comparative example and Example 1 is that: the second intermediate product is not used to perform damping modification on the first intermediate product;

[0128] In step (1), the mass fractions of the raw materials are as follows: 400 parts of 4,4'-diaminodiphenyl ether (ODA), 295 parts of pyromellitic dianhydride (PMDA), and 696 parts of N-methylpyrrolidone (NMP).

[0129] Comparative Example 5

[0130] The difference between this comparative example and Example 1 is that: the second intermediate product is not used to perform damping modification on the first intermediate product;

[0131] In step (1), the mass fractions of the raw materials are as follows: 400 parts of 4,4'-diaminodiphenyl ether (ODA), 325 parts of pyromellitic dianhydride (PMDA), and 725 parts of N-methylpyrrolidone (NMP).

[0132] Comparative Example 6

[0133] The difference between this comparative example and Example 1 is that: the second intermediate product is not used to perform damping modification on the first intermediate product;

[0134] In step (1), the mass fractions of the raw materials are as follows: 400 parts of 4,4'-diaminodiphenyl ether (ODA), 359 parts of pyromellitic dianhydride (PMDA), and 759 parts of N-methylpyrrolidone (NMP).

[0135] Comparative Example 7

[0136] The difference between this comparative example and Example 1 is that: the second intermediate product is not used to perform damping modification on the first intermediate product;

[0137] In step (1), the mass fractions of the raw materials are as follows: 400 parts of 4,4'-diaminodiphenyl ether (ODA), 394 parts of pyromellitic dianhydride (PMDA), and 794 parts of N-methylpyrrolidone (NMP).

[0138] Comparative Example 8

[0139] The difference between this comparative example and Example 1 is that: the second intermediate product is not used to perform damping modification on the first intermediate product;

[0140] In step (1), the mass fractions of the raw materials are as follows: 400 parts of 4,4'-diaminodiphenyl ether (ODA), 436 parts of pyromellitic dianhydride (PMDA), and 836 parts of N-methylpyrrolidone (NMP).

[0141] Table 1

[0142]

[0143] Table 2

[0144]

[0145] From the data in Table 2, it can be seen that after the polyurethane-modified polyimide resin is used in Examples 1 to 6 of the present invention, the addition of the second intermediate product increases the molecular distance of the polyimide, improves the molecular motion space of the polyimide, and significantly increases the damping factor, indicating that the polyurethane modification increases the damping performance of the polyimide, while its mechanical properties and high temperature resistance are also maintained well. Comparative Examples 1 to 8 do not add polyurethane-modified polyimide, so their damping factors are small and do not exceed 0.2.

[0146] Comparative Example 9

[0147] The difference between this comparative example and Example 1 is:

[0148] In step (1), the mass fractions of the raw materials are as follows: 400 parts of 4,4'-diaminodiphenyl ether (ODA), 325 parts of pyromellitic dianhydride (PMDA), and 764 parts of N-methylpyrrolidone (NMP).

[0149] In step (2), the mass fractions of the raw materials are as follows: 13 parts of hydrogenated diphenylmethane diisocyanate (HMDI) and 26 parts of polycaprolactone diol (PCL).

[0150] In step (3), the mass fractions of the contents of the various raw materials are as follows: the content of the first intermediate product is 1489 parts, and the content of the second intermediate product is 39 parts.

[0151] Comparative Example 10

[0152] The difference between this comparative example and Example 1 is:

[0153] In step (1), the mass fractions of the raw materials are as follows: 400 parts of 4,4'-diaminodiphenyl ether (ODA), 325 parts of pyromellitic dianhydride (PMDA), and 806 parts of N-methylpyrrolidone (NMP).

[0154] In step (2), the mass fractions of the raw materials are as follows: 28 parts of hydrogenated diphenylmethane diisocyanate (HMDI) and 53 parts of polycaprolactone diol (PCL).

[0155] In step (3), the mass fractions of the contents of the various raw materials are as follows: the content of the first intermediate product is 1531 parts, and the content of the second intermediate product is 81 parts.

[0156] Comparative Example 11

[0157] The difference between this comparative example and Example 1 is:

[0158] In step (1), the mass fractions of the raw materials are as follows: 400 parts of 4,4'-diaminodiphenyl ether (ODA), 325 parts of pyromellitic dianhydride (PMDA), and 1320 parts of N-methylpyrrolidone (NMP).

[0159] In step (2), the mass fractions of the raw materials are as follows: 204 parts of hydrogenated diphenylmethane diisocyanate (HMDI) and 390 parts of polycaprolactone diol (PCL).

[0160] In step (3), the mass fractions of the contents of the various raw materials are as follows: the content of the first intermediate product is 2045 parts, and the content of the second intermediate product is 594 parts.

[0161] Comparative Example 12

[0162] The difference between this comparative example and Example 1 is:

[0163] In step (1), the mass fractions of the raw materials are as follows: 400 parts of 4,4'-diaminodiphenyl ether (ODA), 325 parts of pyromellitic dianhydride (PMDA), and 1452 parts of N-methylpyrrolidone (NMP).

[0164] In step (2), the mass fractions of the raw materials are as follows: 250 parts of hydrogenated diphenylmethane diisocyanate (HMDI) and 477 parts of polycaprolactone diol (PCL).

[0165] In step (3), the mass fractions of the contents of the various raw materials are as follows: the content of the first intermediate product is 2177 parts, and the content of the second intermediate product is 727 parts.

[0166] Comparative Example 13

[0167] The difference between this comparative example and Example 1 is:

[0168] In step (1), the mass fractions of the raw materials are as follows: 400 parts of 4,4'-diaminodiphenyl ether (ODA), 325 parts of pyromellitic dianhydride (PMDA), and 1614 parts of N-methylpyrrolidone (NMP).

[0169] In step (2), the mass fractions of the raw materials are as follows: 305 parts of hydrogenated diphenylmethane diisocyanate (HMDI) and 583 parts of polycaprolactone diol (PCL).

[0170] In step (3), the mass fractions of the contents of each raw material are as follows: the content of the first intermediate product is 2339 parts, and the content of the second intermediate product is 888 parts.

[0171] Table 3

[0172]

[0173] Table 4

[0174]

[0175]

[0176] It can be seen from Table 4 above that as the amount of polyurethane modifier (second intermediate product) increases, the cohesive strength of polyimide decreases, the molecular motion caused by external stress increases, the molecular friction increases, the damping performance is optimized, and the damping factor increases. However, with the excessive addition of polyurethane modifier (second intermediate product), the mechanical properties and high temperature resistance of the material decrease.

[0177] Example 7

[0178] The embodiment of the present invention provides a method for preparing a polyurethaneimide high temperature damping material. In step (1) of this embodiment, the mass fractions of the contents of each raw material are as follows, which are the same as those in embodiment 3:

[0179] The difference from Example 3 is that:

[0180] In step (2), the mass fractions of the raw materials are as follows: the content of hydrogenated diphenylmethane diisocyanate (HMDI) is 124 parts, and the content of polycaprolactone diol (PCL-500) is 119 parts.

[0181] In step (3), the mass fractions of the contents of the various raw materials are as follows: the content of the first intermediate product is 1693 parts, and the content of the second intermediate product is 119 parts.

[0182] Example 8

[0183] The embodiment of the present invention provides a method for preparing a polyurethaneimide high temperature damping material. In step (1) of this embodiment, the mass fractions of the contents of each raw material are as follows, which are the same as those in embodiment 3:

[0184] The difference from Example 3 is:

[0185] In step (2), the mass fractions of the raw materials are as follows: the content of hydrogenated diphenylmethane diisocyanate (HMDI) is 83 parts, and the content of polycaprolactone diol (PCL-1000) is 159 parts.

[0186] In step (3), the mass fractions of the contents of the various raw materials are as follows: the content of the first intermediate product is 1693 parts, and the content of the second intermediate product is 159 parts.

[0187] Example 9

[0188] The embodiment of the present invention provides a method for preparing a polyurethaneimide high temperature damping material. In step (1) of this embodiment, the mass fractions of the contents of each raw material are as follows, which are the same as those in embodiment 3:

[0189] The difference from Example 3 is that:

[0190] In step (2), the mass fractions of the raw materials are as follows: 50 parts of hydrogenated diphenylmethane diisocyanate (HMDI) and 192 parts of polycaprolactone diol (PCL-2000).

[0191] In step (3), the mass fractions of the contents of the various raw materials are as follows: the content of the first intermediate product is 1693 parts, and the content of the second intermediate product is 192 parts.

[0192] Comparative Example 14

[0193] In step (1) of this comparative example, the mass fractions of the raw materials are the same as those in Example 3. The difference between this comparative example and Example 3 is that:

[0194] In step (2), the mass fractions of the raw materials are as follows: 36 parts of hydrogenated diphenylmethane diisocyanate (HMDI) and 206 parts of polycaprolactone diol (PCL-3000).

[0195] In step (3), the mass fractions of the contents of the various raw materials are as follows: the content of the first intermediate product is 1693 parts, and the content of the second intermediate product is 206 parts.

[0196] Comparative Example 15

[0197] In step (1) of this comparative example, the mass fractions of the raw materials are as follows, which are the same as those in Example 3. The difference between this comparative example and Example 3 is that:

[0198] In step (2), the mass fractions of the raw materials are as follows: 28 parts of hydrogenated diphenylmethane diisocyanate (HMDI) and 214 parts of polycaprolactone diol (PCL-4000).

[0199] In step (3), the mass fractions of the contents of the various raw materials are as follows: the content of the first intermediate product is 1693 parts, and the content of the second intermediate product is 214 parts.

[0200] Table 5

[0201]

[0202]

[0203] Table 6

[0204]

[0205] It can also be seen from Table 6 that the more the second intermediate products, the better the damping performance; however, the more the second intermediate products, the lower the tensile strength, the lower the deformation temperature, and the worse the heat resistance. In addition, it can be seen that as the molecular chain length of the second intermediate product gradually increases, the intermolecular distance of the polyimide is increased, the molecular motion space of the polyimide is increased, and the damping factor is significantly increased, indicating that increasing the molecular chain length of the second intermediate product can increase the damping performance of the polyimide. However, if the molecular chain length of the second intermediate product is too long, the tensile strength is lower, the deformation temperature is lower, and the heat resistance is worse.

[0206] The specific implementation methods described above further illustrate the objectives, technical solutions and beneficial effects of the present invention in detail. It should be understood that the above description is only a specific implementation method of the present invention and is not intended to limit the scope of protection of the present invention. Any modifications, equivalent substitutions, improvements, etc. made within the spirit and principles of the present invention should be included in the scope of protection of the present invention.

Claims

1. A method for preparing a polyurethaneimide high temperature damping material, characterized in that: The steps include: (1) using 4,4'-diaminodiphenyl ether (ODA), pyromellitic dianhydride (PMDA) and N-methylpyrrolidone (NMP) to obtain a first intermediate product through addition polymerization; (2) using hydrogenated diphenylmethane diisocyanate (HMDI) and polycaprolactone diol (PCL) to polymerize to obtain a second intermediate product; (3) subjecting the isocyanate group in the second intermediate product to an addition reaction with the active hydrogen in the first intermediate product to obtain a third intermediate product; (4) subjecting the third intermediate product to solvent volatilization curing and high-temperature imidization reaction to obtain a polyurethane imide damping material.

2. The method for preparing a polyurethaneimide high temperature damping material according to claim 1, characterized in that: In the step (1), the mass percentages of the raw materials are as follows: 4,4'-diaminodiphenyl ether (ODA) is 24% to 32%, pyromellitic dianhydride (PMDA) is 18% to 26%, and the remaining raw material is N-methylpyrrolidone (NMP).

3. The method for preparing a polyurethaneimide high temperature damping material according to claim 1, characterized in that: In step (2), the mass percentages of the raw materials are as follows: the content of hydrogenated diphenylmethane diisocyanate (HMDI) is 25% to 45%, and the content of polycaprolactone diol (PCL) is 55% to 75%.

4. The method for preparing a polyurethaneimide high temperature damping material according to claim 1, characterized in that: In step (3), the mass percentage of the content of each raw material is as follows: the content of the first intermediate product is 85% to 95%, and the content of the second intermediate product is 5% to 15%.

5. The method for preparing a polyurethaneimide high temperature damping material according to claim 1, characterized in that: The synthesis process of step (1) is as follows: (1.1) Add N-methylpyrrolidone (NMP) into a reaction kettle and stir; (1.2) Divide 4,4'-diaminodiphenyl ether (ODA) into 3 to 5 portions and add them into the reaction kettle in batches. Raise the temperature to 35°C to 60°C and mix for 0.5h to 3h. (1.3) Pyromellitic dianhydride (PMDA) is divided into 3 to 10 portions and added into a reaction kettle in portions. The temperature of the reaction kettle is controlled at 50 to 100° C. and the reaction time is 3 to 10 hours to obtain a first intermediate product.

6. The method for preparing a polyurethaneimide high temperature damping material according to claim 1, characterized in that: The synthesis process of step (2) is as follows: (2.1) Add hydrogenated diphenylmethane diisocyanate (HMDI) into a reaction kettle and stir, raise the temperature to 30-50°C, and fill with nitrogen (0.02MPa-0.10MPa) for protection; (2.2) Divide polycaprolactone diol (PCL) into 3 to 7 portions and add them into a reactor in batches. The temperature of the reactor is 80 to 130° C. and the reaction time of a single feed is 2 to 5 hours. (2.3) After the isocyanate content in the detection reactor reaches a preset value, the temperature is lowered to stop the reaction and a second intermediate product is obtained.

7. The method for preparing a polyurethaneimide high temperature damping material according to claim 1, characterized in that: The synthesis process of step (3) is as follows: (3.1) Add the first intermediate product into the reaction kettle, stir, heat to 30-50°C, and fill with nitrogen (0.02MPa-0.10MPa) for protection; (3.2) The second intermediate product is divided into 3 to 5 portions and added into the reactor in batches. The temperature of the reactor is 50 to 80°C and the reaction time of a single feed is 1 to 3 hours; (3.3) After the acid ester content in the detection reactor reaches a preset value, the temperature is lowered to stop the reaction and the third intermediate product is obtained.

8. The method for preparing a polyurethaneimide high temperature damping material according to claim 1, characterized in that: The synthesis process of step (4) is as follows: (4.1) placing the third intermediate product into a vacuum degassing machine to remove air, and adding it into a mold at a mold temperature of 50 to 130° C.; (4.2) The mold temperature is increased to 160 to 250° C. at a heating rate of 1° C. / h to 30° C. / h to perform an imidization reaction to obtain a polyurethane imide damping material.

9. A polyurethaneimide high temperature damping material, characterized in that: The invention is prepared by the preparation method according to any one of claims 1 to 8.

10. The polyurethaneimide high temperature damping material according to claim 9, characterized in that: The structural formula of polyurethaneimide high temperature damping material is as follows:

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