Polypropylene composite material as well as preparation method and application thereof

Abstract

The invention discloses a polypropylene composite material as well as a preparation method and application thereof. The polypropylene composite material comprises the following raw materials: polypropylene and an organic semiconductor master batch, the polypropylene composite material is prepared by adding the organic semiconductor master batch into the polypropylene, the polypropylene composite material is used for preparing the BOPP capacitor film, and then the BOPP capacitor film is used for preparing the thin-film capacitor, so that the high-temperature resistance of the thin-film capacitor can be remarkably improved.

Description

Technical Field

[0001] The present invention belongs to the technical field of polypropylene composite materials, and in particular relates to a polypropylene composite material and a preparation method and application thereof. Background Art

[0002] Film capacitors are an important basic electronic component, widely used in electronics, home appliances, communications, electricity and other industries.

[0003] Currently, the most commonly used film dielectric in film capacitors is BOPP. However, biaxially oriented polypropylene film has poor high-temperature resistance. The upper operating temperature limit for existing polypropylene film capacitors is approximately 105°C. When the operating temperature exceeds 85°C, most of the film's performance degrades, including a sharp drop in breakdown strength and a sharp increase in dielectric loss. This can easily lead to capacitor failures, compromising the safe and stable operation of the entire equipment system. In recent years, the development of new energy sectors such as photovoltaic and wind power generation, and especially new energy vehicles, has placed higher demands on film capacitors for miniaturization, high-temperature resistance, and high capacity.

[0004] In the prior art, additives such as cycloolefin copolymers or inorganic particles are often added to polypropylene to improve the heat resistance of polypropylene films, and thus the heat resistance of polypropylene film capacitors. However, after adding inorganic particles to polypropylene to form a film, the dielectric constant of the inorganic particles and the polypropylene differ significantly, which increases the local electric field, resulting in a decrease in the electrical strength of the film and a significant increase in dielectric loss, seriously affecting the dielectric properties of the capacitor film. In addition, the inorganic particles have poor dispersibility and uneven distribution in the polypropylene system, further reducing the dielectric properties of the polypropylene film and affecting its use.

[0005] After adding cycloolefin copolymer to polypropylene to form a film, although physical defects will not appear in the polymer capacitor film, the addition of a small amount of cycloolefin copolymer can only slightly improve the heat resistance of the capacitor film, and the improvement of the heat resistance of the polypropylene film is limited; if the heat resistance of the film capacitor needs to be greatly improved, the addition amount of cycloolefin copolymer needs to exceed 20%, and the addition of a large amount of cycloolefin copolymer will cause a significant decrease in the film-forming performance of the material. This is because cycloolefin copolymer has poor compatibility with polypropylene, and fiber stretching affects the subsequent biaxial stretching. At the same time, phase separation will gradually occur during long-term use, resulting in a decrease in the heat resistance of the material and affecting product quality. Therefore, effectively reducing the amount of cycloolefin copolymer added and effectively improving the heat resistance of film capacitors are problems that need to be solved urgently. Summary of the Invention

[0006] In view of the above deficiencies in the prior art, the polypropylene composite material is prepared by adding the organic semiconductor master batch into the polypropylene, the polypropylene composite material is used for preparing the BOPP capacitor film, and then the BOPP capacitor film is used for preparing the film capacitor, so that the high-temperature resistance of the film capacitor can be remarkably improved.

[0007] The polypropylene composite material comprises the following raw materials: polypropylene and an organic semiconductor master batch.

[0008] In some embodiments of the present application, the organic semiconductor master batch comprises a conjugated organic semiconductor polymer and a cyclic olefin polymer.

[0009] In some embodiments of the present application, the organic semiconductor master batch is used in an amount of 5-15% of the polypropylene composite material in terms of mass percentage.

[0010] In some embodiments of the present application, the conjugated organic semiconductor polymer is used in an amount of 0.1%-1% of the organic semiconductor master batch in terms of mass percentage.

[0011] In some embodiments of the present application, the conjugated organic semiconductor polymer is selected from poly(3-hexylthiophene) or a thiophene copolymer.

[0012] In some embodiments of the present application, the cyclic olefin polymer is selected from at least one of COC, COP and CBC.

[0013] In some embodiments of the present application, the thiophene copolymer is selected from any one of the following structures:

[0014] 、 、

[0015] The number average molecular weight is 4.7-17.3 KDa.

[0016] In some embodiments of the present application, the molar percentage of the hexylthiophene segment of the thiophene copolymer in the polythiophene segment is 80%-97.1%.

[0017] In some embodiments of the present application, the isotacticity of the thiophene copolymer is ≥80%.

[0018] In some embodiments of the present application, the crystallinity of the polypropylene composite material is ≥45%.

[0019] In some embodiments of the present application, the ash content of the polypropylene composite material is ≤20 ppm.

[0020] Another object of the present application is to provide a preparation method of the polypropylene composite material, comprising the following steps:

[0021] S1. crushing the cyclic olefin polymer into powder, mixing the cyclic olefin polymer powder and a solvent, heating and dissolving to obtain a cyclic olefin polymer solution;

[0022] S2. mixing the conjugated organic semiconductor polymer and a solvent, heating and dissolving to obtain a conjugated organic semiconductor polymer solution;

[0023] S3. mixing the cyclic olefin polymer solution and the conjugated organic semiconductor polymer solution into a homogeneous solution, adding a poor solvent to precipitate to obtain an organic semiconductor master batch;

[0024] S4. blending the organic semiconductor master batch with polypropylene powder, melt extruding to obtain a polypropylene composite material.

[0025] In some embodiments of the present application, in S1, the solvent is selected from toluene.

[0026] In some embodiments of the present application, in S1, the heating temperature is 120-160℃.

[0027] In some embodiments of the present application, in S2, the solvent is selected from toluene.

[0028] In some embodiments of the present application, in S2, the heating temperature is 120-160℃.

[0029] In some embodiments of the present application, in S3, the poor solvent is selected from at least one of methanol and ethanol.

[0030] In some embodiments of the present application, in S3, the volume ratio of the homogeneous solution to the poor solvent is 1:100-500.

[0031] In some embodiments of the present application, in S4, the melt extruding temperature is 180-230℃.

[0032] Another object of the present application is to provide the application of the polypropylene composite material or the polypropylene composite material prepared by the preparation method of the polypropylene composite material in preparing high-temperature-resistant BOPP capacitor films.

[0033] Compared with the prior art, the present application has the following beneficial effects:

[0034] (1) The polypropylene composite material is prepared by adding the organic semiconductor master batch into the polypropylene, the organic semiconductor master batch contains the conjugated organic semiconductor polymer and the cyclic olefin polymer, the conjugated organic semiconductor polymer is added to effectively improve the compatibility of the polypropylene and the cyclic olefin polymer, the polypropylene composite material is used for preparing the BOPP capacitor film, the high-temperature-resistant BOPP capacitor film can be prepared, and the high-temperature-resistant performance of the film capacitor can be significantly improved when the BOPP capacitor film is used for preparing the film capacitor.

[0035] (2) The adding amount of the cyclic olefin polymer in the high-temperature-resistant BOPP capacitor film is low, and the high-temperature-resistant performance of the film capacitor is significantly improved due to the addition of the conjugated organic semiconductor polymer. BRIEF DESCRIPTION OF DRAWINGS

[0036] Figure 1 The surface morphology diagram of the high-temperature-resistant BOPP capacitor film of Example 25. DETAILED DESCRIPTION

[0037] In order for those skilled in the art to better understand the technical solutions in the present application, the technical solutions of the present application will be described clearly and completely in combination with the embodiments of the present application. Obviously, the described embodiments are only some of the embodiments of the present application, not all the embodiments. Based on the embodiments in the present application, all other embodiments obtained by those skilled in the art without creative labor should belong to the scope of protection of the present application.

[0038] The raw materials used in the present application are all conventional commercial.

[0039] Example 1

[0040] The present embodiment provides a kind of polypropylene composite material, specific preparation steps are as follows:

[0041] S1.COC 4.95g is pulverized into powder, COC powder and toluene 50mL are mixed, heated and dissolved at 120~160 DEG C, and the cyclic olefin polymer solution is obtained;

[0042] S2.Congjugated organic semiconductor polymer 0.05g and toluene 0.5mL are mixed, heated and dissolved at 120~160 DEG C, and the conjugated organic semiconductor polymer solution is obtained;

[0043] S3.Cyclic olefin polymer solution and conjugated organic semiconductor polymer solution are mixed into homogeneous solution, add ethanol 25L, precipitate, take the precipitate, and the organic semiconductor master batch is obtained;

[0044] S4.Organic semiconductor master batch and polypropylene 95g powder are blended, and melt extrusion is carried out at 180-230 DEG C, and the polypropylene composite material is obtained;

[0045] The structure of the conjugated organic semiconductor polymer is shown as follows:

[0046] ;

[0047] The number average molecular weight Mn is 16397 Da, the PDI is 1.71, and the HT value is 91%.

[0048] Example 2

[0049] This embodiment provides a polypropylene composite material, and the specific preparation steps are as follows:

[0050] S1. Crush COC 14.985 g into powder, mix COC powder and toluene 750 mL, heat and dissolve at 120-160 DEG C to obtain a cyclic olefin polymer solution;

[0051] S2. Mix conjugated organic semiconductor polymer 0.015 g and toluene 0.2 mL, heat and dissolve at 120-160 DEG C to obtain a conjugated organic semiconductor polymer solution;

[0052] S3. Mix the cyclic olefin polymer solution and the conjugated organic semiconductor polymer solution into a homogeneous solution, add ethanol 75 L, precipitate, and take the precipitate to obtain an organic semiconductor master batch;

[0053] S4. Blend the organic semiconductor master batch with polypropylene 85 g powder, melt extrude at 180-230 DEG C to obtain a polypropylene composite material;

[0054] The structure of the conjugated organic semiconductor polymer is shown as follows:

[0055] ;

[0056] The number average molecular weight Mn is 7423 Da, the PDI is 1.45, and the HT value is 80%.

[0057] Example 3

[0058] This embodiment provides a polypropylene composite material, and the specific preparation steps are as follows:

[0059] S1. Crush COP 4.95 g into powder, mix COP powder and toluene 50 mL, heat and dissolve at 120-160 DEG C to obtain a cyclic olefin polymer solution;

[0060] S2. Mix conjugated organic semiconductor polymer 0.05 g and toluene 0.5 mL, heat and dissolve at 120-160 DEG C to obtain a conjugated organic semiconductor polymer solution;

[0061] S3. Mix the cyclic olefin polymer solution and the conjugated organic semiconductor polymer solution into a homogeneous solution, add 25 L of ethanol, precipitate, and take the precipitate to obtain an organic semiconductor master batch;

[0062] S4. Blend the organic semiconductor master batch with 95 g of polypropylene powder, melt extrude at 180-230°C to obtain a polypropylene composite material;

[0063] The structure of the conjugated organic semiconductor polymer is as shown below:

[0064] ;

[0065] The number average molecular weight Mn is 16397 Da, the PDI is 1.71, and the HT value is 91%.

[0066] Example 4

[0067] This example provides a polypropylene composite material, and the specific preparation steps are as follows:

[0068] S1. Crush 14.985 g of COP into powder, mix the COP powder and 750 mL of toluene, heat and dissolve at 120-160°C to obtain a cyclic olefin polymer solution;

[0069] S2. Mix 0.015 g of conjugated organic semiconductor polymer and 0.2 mL of toluene, heat and dissolve at 120-160°C to obtain a conjugated organic semiconductor polymer solution;

[0070] S3. Mix the cyclic olefin polymer solution and the conjugated organic semiconductor polymer solution into a homogeneous solution, add 75 L of ethanol, precipitate, and take the precipitate to obtain an organic semiconductor master batch;

[0071] S4. Blend the organic semiconductor master batch with 85 g of polypropylene powder, melt extrude at 180-230°C to obtain a polypropylene composite material;

[0072] The structure of the conjugated organic semiconductor polymer is as shown below:

[0073] ;

[0074] The number average molecular weight Mn is 7423 Da, the PDI is 1.45, and the HT value is 80%.

[0075] Example 5

[0076] This example provides a polypropylene composite material, and the specific preparation steps are as follows:

[0077] S1. Crush 4.95 g of CBC into powder, mix the CBC powder and 50 mL of toluene, heat and dissolve at 120-160°C to obtain a cyclic olefin polymer solution;

[0078] S2. Mix conjugated organic semiconductor polymer 0.05 g and toluene 0.5 mL, heat to dissolve at 120-160℃, to obtain conjugated organic semiconductor polymer solution;

[0079] S3. Mix the cyclic olefin polymer solution and the conjugated organic semiconductor polymer solution into a homogeneous solution, add ethanol 25 L, precipitate, take the precipitate, to obtain organic semiconductor masterbatch;

[0080] S4. Blend the organic semiconductor masterbatch with polypropylene 95 g powder, melt extrude at 180-230℃, to obtain polypropylene composite material;

[0081] The structure of the conjugated organic semiconductor polymer is as follows:

[0082] ;

[0083] The number average molecular weight Mn is 16397 Da, the PDI is 1.71, and the HT value is 91%.

[0084] Example 6

[0085] This example provides a polypropylene composite material, and the specific preparation steps are as follows:

[0086] S1. Crush CBC 14.985 g into powder, mix the CBC powder and toluene 750 mL, heat to dissolve at 120-160℃, to obtain a cyclic olefin polymer solution;

[0087] S2. Mix conjugated organic semiconductor polymer 0.015 g and toluene 0.2 mL, heat to dissolve at 120-160℃, to obtain a conjugated organic semiconductor polymer solution;

[0088] S3. Mix the cyclic olefin polymer solution and the conjugated organic semiconductor polymer solution into a homogeneous solution, add ethanol 75 L, precipitate, take the precipitate, to obtain an organic semiconductor masterbatch;

[0089] S4. Blend the organic semiconductor masterbatch with polypropylene 85 g powder, melt extrude at 180-230℃, to obtain a polypropylene composite material;

[0090] The structure of the conjugated organic semiconductor polymer is as follows:

[0091] ;

[0092] The number average molecular weight Mn is 7423 Da, the PDI is 1.45, and the HT value is 80%.

[0093] Example 7

[0094] The embodiment provides a polypropylene composite material, and specific preparation steps are as follows:

[0095] S1. 4.95g of COC is crushed into powder, COC powder and 50ml of toluene are taken, heating and dissolving at 120-160 DEG C to obtain a cyclic olefin polymer solution;

[0096] S2. 0.05g of conjugated organic semiconductor polymer and 0.5ml of toluene are mixed, heating and dissolving at 120-160 DEG C to obtain a conjugated organic semiconductor polymer solution;

[0097] S3. The cyclic olefin polymer solution and the conjugated organic semiconductor polymer solution are mixed into a homogeneous solution, 25L of ethanol is added, precipitation is carried out, and the precipitate is taken to obtain an organic semiconductor master batch;

[0098] S4. The organic semiconductor master batch is blended with 95g of polypropylene powder, and melt extrusion is carried out at 180-230 DEG C to obtain a polypropylene composite material;

[0099] The structure of the conjugated organic semiconductor polymer is as follows:

[0100] ;

[0101] Wherein, the number average molecular weight Mn is 9.7KDa, the PDI is 3.51, the HT value is 80%, x=5mmol%, y=95mmol%.

[0102] Example 8

[0103] The embodiment provides a polypropylene composite material, and specific preparation steps are as follows:

[0104] S1. 14.985g of COC is crushed into powder, COC powder and 750ml of toluene are taken, heating and dissolving at 120-160 DEG C to obtain a cyclic olefin polymer solution;

[0105] S2. 0.015g of conjugated organic semiconductor polymer and 0.2ml of toluene are mixed, heating and dissolving at 120-160 DEG C to obtain a conjugated organic semiconductor polymer solution;

[0106] S3. The cyclic olefin polymer solution and the conjugated organic semiconductor polymer solution are mixed into a homogeneous solution, 75L of ethanol is added, precipitation is carried out, and the precipitate is taken to obtain an organic semiconductor master batch;

[0107] S4. The organic semiconductor master batch is blended with 85g of polypropylene powder, and melt extrusion is carried out at 180-230 DEG C to obtain a polypropylene composite material;

[0108] The structure of the conjugated organic semiconductor polymer is as follows:

[0109] ;

[0110] wherein the number average molecular weight Mn is 17.3 KDa, the PDI is 3.82, the HT value is 84.5%, x = 11.8 mmol%, and y = 88.2 mmol%.

[0111] Example 9

[0112] The present example provides a polypropylene composite material, and the specific preparation steps are as follows:

[0113] S1. COP 4.95 g is pulverized into powder, COP powder and toluene 50 mL are taken and mixed, heated to dissolve at 120-160°C to obtain a cyclic olefin polymer solution;

[0114] S2. Conjugated organic semiconductor polymer 0.05 g and toluene 0.5 mL are mixed, heated to dissolve at 120-160°C to obtain a conjugated organic semiconductor polymer solution;

[0115] S3. The cyclic olefin polymer solution and the conjugated organic semiconductor polymer solution are mixed into a homogeneous solution, 25 L of ethanol is added, precipitated, and the precipitate is taken to obtain an organic semiconductor master batch;

[0116] S4. The organic semiconductor master batch is blended with polypropylene 95 g powder, and melt extruded at 180-230°C to obtain a polypropylene composite material;

[0117] The structure of the conjugated organic semiconductor polymer is as shown below:

[0118] ;

[0119] wherein the number average molecular weight Mn is 9.7 KDa, the PDI is 3.51, the HT value is 80%, x = 5 mmol%, and y = 95 mmol%.

[0120] Example 10

[0121] The present example provides a polypropylene composite material, and the specific preparation steps are as follows:

[0122] S1. COP 14.985 g is pulverized into powder, COP powder and toluene 750 mL are taken and mixed, heated to dissolve at 120-160°C to obtain a cyclic olefin polymer solution;

[0123] S2. Conjugated organic semiconductor polymer 0.015 g and toluene 0.2 mL are mixed, heated to dissolve at 120-160°C to obtain a conjugated organic semiconductor polymer solution;

[0124] S3. The cyclic olefin polymer solution and the conjugated organic semiconductor polymer solution were mixed into a homogeneous solution, 75 L of ethanol was added, precipitated, and the precipitate was taken to obtain an organic semiconductor masterbatch;

[0125] S4. The organic semiconductor masterbatch was blended with 85g of polypropylene powder and melt-extruded at 180-230°C to obtain a polypropylene composite material;

[0126] The structure of the conjugated organic semiconductor polymer is shown below:

[0127] ;

[0128] Among them, the number average molecular weight Mn is 17.3 KDa, the PDI is 3.82, the HT value is 84.5%, x=11.8 mmol%, y=88.2 mmol%.

[0129] Example 11

[0130] This embodiment provides a polypropylene composite material, and the specific preparation steps are as follows:

[0131] S1. Grind 4.95 g of CBC into powder, mix the CBC powder with 50 mL of toluene, and heat at 120-160°C to dissolve the mixture to obtain a cyclic olefin polymer solution.

[0132] S2. 0.05 g of the conjugated organic semiconductor polymer and 0.5 mL of toluene were mixed and dissolved by heating at 120-160° C. to obtain a conjugated organic semiconductor polymer solution;

[0133] S3. The cyclic olefin polymer solution and the conjugated organic semiconductor polymer solution were mixed into a homogeneous solution, ethanol 25L was added, precipitated, and the precipitate was taken to obtain an organic semiconductor masterbatch;

[0134] S4. The organic semiconductor masterbatch was blended with 95g of polypropylene powder and melt-extruded at 180-230°C to obtain a polypropylene composite material;

[0135] The structure of the conjugated organic semiconductor polymer is shown below:

[0136] ;

[0137] Among them, the number average molecular weight Mn is 9.7 KDa, the PDI is 3.51, the HT value is 80%, x=5 mmol%, and y=95 mmol%.

[0138] Example 12

[0139] This embodiment provides a polypropylene composite material, and the specific preparation steps are as follows:

[0140] S1. Crush CBC 14.985 g into powder, mix CBC powder and toluene 750 mL, heat to dissolve at 120-160°C to obtain a cyclic olefin polymer solution;

[0141] S2. Mix conjugated organic semiconductor polymer 0.015 g and toluene 0.2 mL, heat to dissolve at 120-160°C to obtain a conjugated organic semiconductor polymer solution;

[0142] S3. Mix the cyclic olefin polymer solution and the conjugated organic semiconductor polymer solution into a homogeneous solution, add ethanol 75 L, precipitate, and take the precipitate to obtain an organic semiconductor master batch;

[0143] S4. Blend the organic semiconductor master batch with polypropylene 85 g powder, melt extrude at 180-230°C to obtain a polypropylene composite material;

[0144] The structure of the conjugated organic semiconductor polymer is as shown below:

[0145] ;

[0146] wherein the number average molecular weight Mn is 17.3 KDa, the PDI is 3.82, the HT value is 84.5%, x = 11.8 mmol%, and y = 88.2 mmol%.

[0147] Example 13

[0148] This example provides a polypropylene composite material, and the specific preparation steps are as follows:

[0149] S1. Crush COC 4.95 g into powder, mix COC powder and toluene 50 mL, heat to dissolve at 120-160°C to obtain a cyclic olefin polymer solution;

[0150] S2. Mix conjugated organic semiconductor polymer 0.05 g and toluene 0.5 mL, heat to dissolve at 120-160°C to obtain a conjugated organic semiconductor polymer solution;

[0151] S3. Mix the cyclic olefin polymer solution and the conjugated organic semiconductor polymer solution into a homogeneous solution, add ethanol 25 L, precipitate, and take the precipitate to obtain an organic semiconductor master batch;

[0152] S4. Blend the organic semiconductor master batch with polypropylene 95 g powder, melt extrude at 180-230°C to obtain a polypropylene composite material;

[0153] The structure of the conjugated organic semiconductor polymer is as shown below:

[0154] ;

[0155] The number average molecular weight Mn is 13.8 KDa, the PDI is 2.2, the HT value is 85%, x = 4.3 mmol%, and y = 95.7 mmol%.

[0156] Example 14

[0157] The present example provides a polypropylene composite material, and the specific preparation steps are as follows:

[0158] S1. Crush COC 14.985 g into powder, mix COC powder and toluene 750 mL, heat and dissolve at 120-160°C to obtain a cyclic olefin polymer solution;

[0159] S2. Mix conjugated organic semiconductor polymer 0.015 g and toluene 0.2 mL, heat and dissolve at 120-160°C to obtain a conjugated organic semiconductor polymer solution;

[0160] S3. Mix the cyclic olefin polymer solution and the conjugated organic semiconductor polymer solution into a homogeneous solution, add ethanol 75 L, precipitate, and take the precipitate to obtain an organic semiconductor master batch;

[0161] S4. Blend the organic semiconductor master batch with polypropylene 85 g powder, melt extrude at 180-230°C to obtain a polypropylene composite material;

[0162] The structure of the conjugated organic semiconductor polymer is as shown below:

[0163] ;

[0164] The number average molecular weight Mn is 4.7 KDa, the PDI is 1.3, the HT value is 83%, x = 20 mmol%, and y = 80 mmol%.

[0165] Example 15

[0166] The present example provides a polypropylene composite material, and the specific preparation steps are as follows:

[0167] S1. Crush COP 4.95 g into powder, mix COP powder and toluene 50 mL, heat and dissolve at 120-160°C to obtain a cyclic olefin polymer solution;

[0168] S2. Mix conjugated organic semiconductor polymer 0.05 g and toluene 0.5 mL, heat and dissolve at 120-160°C to obtain a conjugated organic semiconductor polymer solution;

[0169] S3. Mix the cyclic olefin polymer solution and the conjugated organic semiconductor polymer solution into a homogeneous solution, add ethanol 25 L, precipitate, and take the precipitate to obtain an organic semiconductor master batch;

[0170] S4. Blend the organic semiconductor masterbatch with 95 g of polypropylene powder, melt extrude at 180-230°C to obtain a polypropylene composite material;

[0171] The structure of the conjugated organic semiconductor polymer is as follows:

[0172] ;

[0173] The number average molecular weight Mn is 13.8 KDa, the PDI is 2.2, the HT value is 85%, x = 4.3 mmol%, and y = 95.7 mmol%.

[0174] Example 16

[0175] This example provides a polypropylene composite material, and the specific preparation steps are as follows:

[0176] S1. Crush COP 14.985 g into powder, mix COP powder and 750 mL of toluene, heat and dissolve at 120-160°C to obtain a cyclic olefin polymer solution;

[0177] S2. Mix conjugated organic semiconductor polymer 0.015 g and toluene 0.2 mL, heat and dissolve at 120-160°C to obtain a conjugated organic semiconductor polymer solution;

[0178] S3. Mix the cyclic olefin polymer solution and the conjugated organic semiconductor polymer solution into a homogeneous solution, add 75 L of ethanol, precipitate, and take the precipitate to obtain an organic semiconductor masterbatch;

[0179] S4. Blend the organic semiconductor masterbatch with 85 g of polypropylene powder, melt extrude at 180-230°C to obtain a polypropylene composite material;

[0180] The structure of the conjugated organic semiconductor polymer is as follows:

[0181] ;

[0182] The number average molecular weight Mn is 4.7 KDa, the PDI is 1.3, the HT value is 83%, x = 20 mmol%, and y = 80 mmol%.

[0183] Example 17

[0184] This example provides a polypropylene composite material, and the specific preparation steps are as follows:

[0185] S1. Crush CBC 4.95 g into powder, mix CBC powder and 50 mL of toluene, heat and dissolve at 120-160°C to obtain a cyclic olefin polymer solution;

[0186] S2. Mix the conjugated organic semiconductor polymer 0.05 g and toluene 0.5 mL, heat and dissolve at 120-160℃ to obtain a conjugated organic semiconductor polymer solution;

[0187] S3. Mix the cyclic olefin polymer solution and the conjugated organic semiconductor polymer solution to obtain a homogeneous solution, add ethanol 25 L, precipitate, and take the precipitate to obtain an organic semiconductor master batch;

[0188] S4. Blend the organic semiconductor master batch with polypropylene 95 g powder, melt extrude at 180-230℃ to obtain a polypropylene composite material;

[0189] The structure of the conjugated organic semiconductor polymer is shown below:

[0190] ;

[0191] The number average molecular weight Mn is 13.8 KDa, the PDI is 2.2, the HT value is 85%, x = 4.3 mmol%, and y = 95.7 mmol%.

[0192] Example 18

[0193] The present embodiment provides a polypropylene composite material, and the specific preparation steps are as follows:

[0194] S1. Crush CBC 14.985 g into powder, mix the CBC powder and toluene 750 mL, heat and dissolve at 120-160℃ to obtain a cyclic olefin polymer solution;

[0195] S2. Mix the conjugated organic semiconductor polymer 0.015 g and toluene 0.2 mL, heat and dissolve at 120-160℃ to obtain a conjugated organic semiconductor polymer solution;

[0196] S3. Mix the cyclic olefin polymer solution and the conjugated organic semiconductor polymer solution to obtain a homogeneous solution, add ethanol 75 L, precipitate, and take the precipitate to obtain an organic semiconductor master batch;

[0197] S4. Blend the organic semiconductor master batch with polypropylene 85 g powder, melt extrude at 180-230℃ to obtain a polypropylene composite material;

[0198] The structure of the conjugated organic semiconductor polymer is shown below:

[0199] ;

[0200] The number average molecular weight Mn is 4.7 KDa, the PDI is 1.3, the HT value is 83%, x = 20 mmol%, and y = 80 mmol%.

[0201] Example 19

[0202] The embodiment provides a polypropylene composite material, and specific preparation steps are as follows:

[0203] S1. 4.95g of COC is pulverized into powder, COC powder and 50ml of toluene are taken, heating and dissolving at 120-160 DEG C to obtain a cyclic olefin polymer solution;

[0204] S2. 0.05g of a conjugated organic semiconductor polymer and 0.5ml of toluene are mixed, heating and dissolving at 120-160 DEG C to obtain a conjugated organic semiconductor polymer solution;

[0205] S3. The cyclic olefin polymer solution and the conjugated organic semiconductor polymer solution are mixed into a homogeneous solution, 25L of ethanol is added, precipitation is carried out, and the precipitate is taken to obtain an organic semiconductor master batch;

[0206] S4. The organic semiconductor master batch is blended with 95g of polypropylene powder, and melt extrusion is carried out at 180-230 DEG C to obtain a polypropylene composite material;

[0207] The structure of the conjugated organic semiconductor polymer is as follows:

[0208] ;

[0209] Wherein, the number average molecular weight Mn is 13.5KKDa, the PDI is 2.5, the HT value is 87%, x=2.5mmol%, y=97.5mmol%.

[0210] Example 20

[0211] The embodiment provides a polypropylene composite material, and specific preparation steps are as follows:

[0212] S1. 14.985g of COC is pulverized into powder, COC powder and 750ml of toluene are taken, heating and dissolving at 120-160 DEG C to obtain a cyclic olefin polymer solution;

[0213] S2. 0.015g of a conjugated organic semiconductor polymer and 0.2ml of toluene are mixed, heating and dissolving at 120-160 DEG C to obtain a conjugated organic semiconductor polymer solution;

[0214] S3. The cyclic olefin polymer solution and the conjugated organic semiconductor polymer solution are mixed into a homogeneous solution, 75L of ethanol is added, precipitation is carried out, and the precipitate is taken to obtain an organic semiconductor master batch;

[0215] S4. The organic semiconductor master batch is blended with 85g of polypropylene powder, and melt extrusion is carried out at 180-230 DEG C to obtain a polypropylene composite material;

[0216] The structure of the conjugated organic semiconductor polymer is as follows:

[0217] ;

[0218] wherein the number average molecular weight Mn is 7.5 KKDa, the PDI is 2.1, the HT value is 89%, x = 13.9 mmol%, y = 86.1 mmol%.

[0219] Example 21

[0220] The present example provides a polypropylene composite material, and the specific preparation steps are as follows:

[0221] S1. COP 4.95g is pulverized into powder, COP powder and toluene 50mL are taken and mixed, heated to dissolve at 120~160℃, to obtain a cyclic olefin polymer solution;

[0222] S2. Conjugated organic semiconductor polymer 0.05g and toluene 0.5mL are mixed, heated to dissolve at 120~160℃, to obtain a conjugated organic semiconductor polymer solution;

[0223] S3. The cyclic olefin polymer solution and the conjugated organic semiconductor polymer solution are mixed into a homogeneous solution, 25L of ethanol is added, precipitated, and the precipitate is taken, to obtain an organic semiconductor masterbatch;

[0224] S4. The organic semiconductor masterbatch is blended with polypropylene 95g powder, and melt extruded at 180-230℃, to obtain a polypropylene composite material;

[0225] The structure of the conjugated organic semiconductor polymer is as shown below:

[0226] ;

[0227] wherein the number average molecular weight Mn is 13.5 KKDa, the PDI is 2.5, the HT value is 87%, x = 2.5 mmol%, y = 97.5 mmol%.

[0228] Example 22

[0229] The present example provides a polypropylene composite material, and the specific preparation steps are as follows:

[0230] S1. COP 14.985g is pulverized into powder, COP powder and toluene 750mL are taken and mixed, heated to dissolve at 120~160℃, to obtain a cyclic olefin polymer solution;

[0231] S2. Conjugated organic semiconductor polymer 0.015g and toluene 0.2mL are mixed, heated to dissolve at 120~160℃, to obtain a conjugated organic semiconductor polymer solution;

[0232] S3. Mix the cyclic olefin polymer solution and the conjugated organic semiconductor polymer solution into a homogeneous solution, add 75 L of ethanol, precipitate, and take the precipitate to obtain an organic semiconductor master batch;

[0233] S4. Blend the organic semiconductor master batch with 85 g of polypropylene powder, melt extrude at 180-230°C to obtain a polypropylene composite material;

[0234] The structure of the conjugated organic semiconductor polymer is as shown below:

[0235] ;

[0236] The number average molecular weight Mn is 7.5 KKDa, the PDI is 2.1, the HT value is 89%, x = 13.9 mmol%, and y = 86.1 mmol%.

[0237] Example 23

[0238] This example provides a polypropylene composite material, and the specific preparation steps are as follows:

[0239] S1. Crush CBC 4.95 g into powder, mix the CBC powder and 50 mL of toluene, heat and dissolve at 120-160°C to obtain a cyclic olefin polymer solution;

[0240] S2. Mix the conjugated organic semiconductor polymer 0.05 g and 0.5 mL of toluene, heat and dissolve at 120-160°C to obtain a conjugated organic semiconductor polymer solution;

[0241] S3. Mix the cyclic olefin polymer solution and the conjugated organic semiconductor polymer solution into a homogeneous solution, add 25 L of ethanol, precipitate, and take the precipitate to obtain an organic semiconductor master batch;

[0242] S4. Blend the organic semiconductor master batch with 95 g of polypropylene powder, melt extrude at 180-230°C to obtain a polypropylene composite material;

[0243] The structure of the conjugated organic semiconductor polymer is as shown below:

[0244] ;

[0245] The number average molecular weight Mn is 13.5 KKDa, the PDI is 2.5, the HT value is 87%, x = 2.5 mmol%, and y = 97.5 mmol%.

[0246] Example 24

[0247] This example provides a polypropylene composite material, and the specific preparation steps are as follows:

[0248] S1. Crush CBC 14.985 g into powder, mix CBC powder and toluene 750 mL, heat to dissolve at 120-160°C to obtain a cyclic olefin polymer solution;

[0249] S2. Mix conjugated organic semiconductor polymer 0.015 g and toluene 0.2 mL, heat to dissolve at 120-160°C to obtain a conjugated organic semiconductor polymer solution;

[0250] S3. Mix the cyclic olefin polymer solution and the conjugated organic semiconductor polymer solution into a homogeneous solution, add ethanol 75 L, precipitate, and take the precipitate to obtain an organic semiconductor masterbatch;

[0251] S4. Blend the organic semiconductor masterbatch with polypropylene 85 g powder, melt extrude at 180-230°C to obtain a polypropylene composite material;

[0252] The structure of the conjugated organic semiconductor polymer is as follows:

[0253] ;

[0254] wherein the number average molecular weight Mn is 7.5 KKDa, the PDI is 2.1, the HT value is 89%, x = 13.9 mmol%, and y = 86.1 mmol%.

[0255] Comparative Example 1

[0256] This comparative example provides a polypropylene composite material, which is different from Example 1 only in that no conjugated organic semiconductor polymer is added, and the specific preparation steps are as follows:

[0257] S1. Crush COC 5 g into powder, mix COC powder and toluene 50 mL, heat to dissolve at 120-160°C to obtain a cyclic olefin polymer solution, add ethanol 25 L, precipitate, and take the precipitate to obtain an organic semiconductor masterbatch;

[0258] S2. Blend the organic semiconductor masterbatch with polypropylene 95 g powder, melt extrude at 180-230°C to obtain a polypropylene composite material.

[0259] Comparative Example 2

[0260] This comparative example provides a polypropylene composite material, which is different from Example 1 only in that no conjugated organic semiconductor polymer is added, and the specific preparation steps are as follows:

[0261] S1. Crush COC 10 g into powder, mix COC powder and toluene 50 mL, heat to dissolve at 120-160°C to obtain a cyclic olefin polymer solution, add ethanol 25 L, precipitate, and take the precipitate to obtain an organic semiconductor masterbatch;

[0262] S2. Blend the organic semiconductor masterbatch with 90 g of polypropylene powder, melt extrude at 180-230°C to obtain a polypropylene composite material.

[0263] Comparative Example 3

[0264] This comparative example provides a polypropylene composite material, which is different from Example 1 only in that no conjugated organic semiconductor polymer is added. The specific preparation steps are as follows:

[0265] S1. Crush 20 g of COC into powder, mix the COC powder with 50 mL of toluene, heat and dissolve at 120-160°C to obtain a cyclic olefin polymer solution, add 25 L of ethanol, precipitate, and take the precipitate to obtain an organic semiconductor masterbatch;

[0266] S2. Blend the organic semiconductor masterbatch with 80 g of polypropylene powder, melt extrude at 180-230°C to obtain a polypropylene composite material.

[0267] Comparative Example 4

[0268] This comparative example provides a polypropylene composite material, which is different from Example 3 only in that no conjugated organic semiconductor polymer is added. The specific preparation steps are as follows:

[0269] S1. Crush 20 g of COP into powder, mix the COP powder with 50 mL of toluene, heat and dissolve at 120-160°C to obtain a cyclic olefin polymer solution, add 25 L of ethanol, precipitate, and take the precipitate to obtain an organic semiconductor masterbatch;

[0270] S2. Blend the organic semiconductor masterbatch with 80 g of polypropylene powder, melt extrude at 180-230°C to obtain a polypropylene composite material.

[0271] Comparative Example 5

[0272] This comparative example provides a polypropylene composite material, which is different from Example 5 only in that no conjugated organic semiconductor polymer is added. The specific preparation steps are as follows:

[0273] S1. Crush 20 g of CBC into powder, mix the CBC powder with 50 mL of toluene, heat and dissolve at 120-160°C to obtain a cyclic olefin polymer solution, add 25 L of ethanol, precipitate, and take the precipitate to obtain an organic semiconductor masterbatch;

[0274] S2. Blend the organic semiconductor masterbatch with 80 g of polypropylene powder, melt extrude at 180-230°C to obtain a polypropylene composite material.

[0275] Examples 25-48

[0276] This example provides a high-temperature-resistant BOPP capacitor film, and the specific preparation steps are as follows:

[0277] The polypropylene composite materials of Examples 1-24 were respectively added into a twin-screw extruder with a length-diameter ratio of 40:1, and processed into a plasticized uniform melt. The melt was extruded through a die to prepare a film casting, and the temperature of the die was 230°C. The film casting was biaxially stretched, and the longitudinal stretching was preheated at 143°C, stretched at 138°C, and set at 143°C. The transverse stretching was preheated at 165°C, stretched at 159°C, and set at 167°C. The film was subjected to corona surface treatment with a strength of 43 mN / m, and wound up, to obtain the high-temperature-resistant BOPP capacitor films of Examples 25-48 with a thickness of 5.5 μm.

[0278] Comparative Examples 6-10

[0279] The present comparative examples provide a high-temperature-resistant BOPP capacitor film, and the specific preparation steps are as follows:

[0280] The polypropylene composite materials of Comparative Examples 1-5 were respectively added into a twin-screw extruder with a length-diameter ratio of 40:1, and processed into a plasticized uniform melt. The melt was extruded through a die to prepare a film casting, and the temperature of the die was 230°C. The film casting was biaxially stretched, and the longitudinal stretching was preheated at 143°C, stretched at 138°C, and set at 143°C. The transverse stretching was preheated at 165°C, stretched at 159°C, and set at 167°C. The film was subjected to corona surface treatment with a strength of 43 mN / m, and wound up, to obtain the high-temperature-resistant BOPP capacitor films of Comparative Examples 6-10 with a thickness of 5.5 μm.

[0281] Examples 49-72

[0282] The present examples provide a film capacitor, and the specific preparation steps are as follows:

[0283] The high-temperature-resistant BOPP capacitor films of Examples 25-48 were respectively plated, wound, statically pressed, heat set, sprayed with gold, and packaged, to obtain the film capacitors of Examples 49-72.

[0284] Comparative Examples 11-15

[0285] The present comparative examples provide a film capacitor, and the specific preparation steps are as follows:

[0286] The high-temperature-resistant BOPP capacitor films of Comparative Examples 6-10 were respectively plated, wound, statically pressed, heat set, sprayed with gold, and packaged, to obtain the film capacitors of Comparative Examples 11-15.

[0287] Performance test:

[0288] The polypropylene composite materials of Examples 1-24 and Comparative Examples 1-5 were subjected to performance tests, and the results are shown in Table 1.

[0289] Table 1. Performance of polypropylene composite materials.

[0290]

[0291] From Table 1, it can be seen that the polypropylene composite prepared by the present application has a higher crystallinity.

[0292] The thin film capacitors of Examples 49-72 and Comparative Examples 11-15 were tested for performance, and the results are shown in Table 2.

[0293] Capacitance change rate test: The initial capacitance values of the thin film capacitors of Examples 49-72 and Comparative Examples 11-15 were tested by connecting the two electrodes of each to a power supply, respectively. Then the thin film capacitors of Examples 49-72 and Comparative Examples 11-15 were placed in a 125°C constant temperature oven, and a direct current voltage of 900V was applied. The capacitance values were measured after different hours of operation in the oven, and the last capacitance value was measured at 1000h. There were three groups of all experiments, and the capacitance change rate was calculated after averaging. If the capacitance change exceeded -5.0%, it meant that the capacitor had failed. The results are shown in Table 2.

[0294] Table 2. Capacitance change rate test results of thin film capacitor films.

[0295]

[0296] From Table 2, it can be seen that the thin film capacitors of the present application have a small capacitance change rate and high high-temperature durability.

[0297] Finally, it should be noted that the above examples are only used to illustrate the technical solutions of the present application and not to limit it. Although the present application has been described in detail with reference to the above examples, those of ordinary skill in the art should understand that the specific embodiments of the present application can be modified or replaced by equivalents after reading the present application. However, these modifications or changes do not deviate from the scope of the present application.

Claims

1. A polypropylene composite material, characterized in that The invention comprises the following raw materials: polypropylene and organic semiconductor masterbatch; the organic semiconductor masterbatch comprises a conjugated organic semiconductor polymer and a cyclic olefin polymer; Calculated by mass percentage, the amount of the organic semiconductor masterbatch is 5-15% of the polypropylene composite material.

2. The polypropylene composite material according to claim 1, wherein Calculated by mass percentage, the amount of the conjugated organic semiconductor polymer is 0.1% to 1% of the organic semiconductor masterbatch.

3. The polypropylene composite material according to claim 1, wherein The conjugated organic semiconductor polymer is selected from poly (3-hexylthiophene) or thiophene copolymer; The cyclic olefin polymer is selected from at least one of COC, COP, and CBC.

4. The polypropylene composite material according to claim 3, wherein The thiophene copolymer is selected from the following copolymers of any structure: 、 、 Among them, the number average molecular weight is 4.7~17.3KDa.

5. The polypropylene composite material according to claim 4, wherein The mole percentage of the hexylthiophene chain segment of the thiophene copolymer in the thiophene copolymer is 80% to 97.1%; The isotacticity of the thiophene copolymer is ≥80%.

6. The polypropylene composite material according to any one of claims 1 to 5, wherein The crystallinity of the polypropylene composite material is ≥45%; And / or, the ash content of the polypropylene composite material is ≤20 ppm.

7. The method for preparing the polypropylene composite material according to any one of claims 1 to 6, characterized in that: The steps include: S1. The cyclic olefin polymer is crushed into a powder, the cyclic olefin polymer powder is mixed with a solvent, and heated to dissolve to obtain a cyclic olefin polymer solution; S2. The conjugated organic semiconductor polymer and the solvent are mixed and heated to dissolve to obtain a conjugated organic semiconductor polymer solution; S3. The cyclic olefin polymer solution and the conjugated organic semiconductor polymer solution are mixed into a homogeneous solution, a poor solvent is added, and precipitated to obtain an organic semiconductor masterbatch; S4. Blending the organic semiconductor masterbatch with polypropylene powder, and melt-extruded to obtain a polypropylene composite material.

8. Use of the polypropylene composite material according to any one of claims 1 to 6 or the polypropylene composite material prepared by the preparation method of the polypropylene composite material according to claim 7 in the preparation of a high-temperature resistant BOPP capacitor film.

Images