A modified fluororesin having good toughness and adhesive properties, and a method for preparing and use thereof

Abstract

The application provides a modified fluororesin with good toughness and bonding performance, and a preparation method and application thereof, and belongs to the field of high polymer materials. The modified fluororesin is prepared from the following raw materials in parts by weight: fluororesin 20-150 parts, ionic liquid 2-20 parts, and zinc oxide 0.1-5 parts. The fluororesin is toughened by the ionic liquid, and on this basis, a processing aid is screened, and the bonding performance of the modified fluororesin is improved through the synergistic effect of the zinc oxide and the ionic liquid, so that the modified fluororesin can be bonded with fluorine rubber, nitrile rubber and the like, and is used as a fuel filling pipe material. In addition, the preparation method is simple, and can be simply melt-blended, and can be well applied to industrial production.

Description

TECHNICAL FIELD

[0001] The present application belongs to the field of high polymer materials, and particularly relates to a modified fluororesin with good toughness and bonding performance, and a preparation method and use thereof. BACKGROUND

[0002] In fuel oil vehicles, fuel pipelines connecting the oil tank and the engine are usually required to have low fuel permeability for safety. In addition, the working temperature around the engine is high, and therefore fluororubber and fluororesin products with excellent heat resistance are widely used in this field.

[0003] Automobile fuel pipelines are usually composed of multiple materials, and one of the multiple layers of the fuel pipeline is THV. Tetrafluoroethylene-hexafluoropropylene-vinylidene fluoride copolymer (THV) is the softest fluoroplastic in the market developed by Dyneon Company in the 1980s, and is very flexible when compounded with other materials into a multilayer structure. Another important feature of THV is that it is easy to bond without surface treatment. Therefore, it is often used in combination with fluororubber as a fuel pipeline material. THV materials are currently mainly imported from abroad, and there is no good substitute product in China.

[0004] It is difficult to carry out industrial production in a short time to synthesize and prepare a substitute for THV, which requires more and more complex industrial equipment. The existing fluororesin is modified by blending or using ethylene tetrafluoroethylene copolymer resin (ETFE), perfluoroethylene propylene copolymer (FEP), polyvinylidene fluoride (PVDF), polyvinylidene fluoride-hexafluoropropylene copolymer (PVDF-HFP), conductive filler, nanocomposite material, etc. to prepare a substitute for THV. However, due to the application environment of the material, it needs to be co-extruded with fluororubber, so the melting point cannot be too low or too high, and needs to match the vulcanization temperature (160-180℃) of fluororubber. The melting point of PVDF-HFP with good toughness is only 130-145℃, and the melting point of ETFE, FEP, etc. is generally above 240℃, so only PVDF is the most suitable material, with a melting point of 165-180℃. However, its toughness is poor, and it cannot be directly tightly bonded with fluororubber, etc. Therefore, it is necessary to improve the toughness and increase the bonding performance. SUMMARY

[0005] The present application aims to provide a modified fluororesin with good toughness and bonding performance, and a preparation method and use thereof.

[0006] The application provides a modified fluororesin, which is prepared from the following raw materials in parts by weight: 20-150 parts of fluororesin, 2-20 parts of ionic liquid and 0.1-5 parts of zinc oxide; the fluororesin is polyvinylidene fluoride or a mixture of polyvinylidene fluoride and polyvinylidene fluoride-hexafluoropropylene copolymer.

[0007] The modified fluororesin is prepared from the following raw materials in parts by weight: 90-110 parts of polyvinylidene fluoride, 5-10 parts of ionic liquid and 1-1.5 parts of zinc oxide.

[0008] Or, the modified fluororesin is prepared from the following raw materials in parts by weight: 50-90 parts of polyvinylidene fluoride, 5-50 parts of polyvinylidene fluoride-hexafluoropropylene copolymer, 5-10 parts of ionic liquid and 1-1.5 parts of zinc oxide.

[0009] Further,

[0010] The modified fluororesin is prepared from the following raw materials in parts by weight: 100 parts of polyvinylidene fluoride, 10 parts of ionic liquid and 1 part of zinc oxide.

[0011] Or, the modified fluororesin is prepared from the following raw materials in parts by weight: 90 parts of polyvinylidene fluoride, 5-15 parts of polyvinylidene fluoride-hexafluoropropylene copolymer, 10 parts of ionic liquid and 1 part of zinc oxide; preferably, the modified fluororesin is prepared from the following raw materials in parts by weight: 90 parts of polyvinylidene fluoride, 5-15 parts of polyvinylidene fluoride-hexafluoropropylene copolymer, 10 parts of ionic liquid and 1 part of zinc oxide.

[0012] Further, the ionic liquid is imidazole ionic liquid.

[0013] Further, the ionic liquid is 1-butyl-3-methylimidazolium tetrafluoroborate or 1-hexyl-3-methylimidazolium bisfluorosulfonimide.

[0014] The application further provides a method for preparing the modified fluororesin, which comprises the following steps: melt compounding the fluororesin, then adding the ionic liquid and zinc oxide to mix and react, so as to obtain the modified fluororesin.

[0015] Further, the melt temperature is 190 DEG C and the reaction time is 10 min.

[0016] The application further provides the use of the modified fluororesin in preparing aerospace and automobile industry materials.

[0017] Further, the automobile industry material is a fuel filling pipe and fuel pipe of a fuel automobile.

[0018] In the present application, the ionic liquid refers to a fused salt in a liquid state at room temperature, which is composed of an organic cation and an inorganic anion (or an organic anion).

[0019] The present application effectively toughens the fluororesin by the ionic liquid, and further screens the processing aid on this basis, improves the bonding performance of the modified fluororesin through the synergistic effect of zinc oxide and the ionic liquid, so that it can be bonded with fluoro rubber, nitrile rubber and the like, and is used as a fuel pipe material in combination. In addition, the preparation method of the present application is simple, which can be simply melt blended and can be well applied to industrial production.

[0020] Obviously, according to the above content of the present application, according to the ordinary technical knowledge and common means in the art, other various forms of modification, replacement or change can be made without departing from the above basic technical idea of the present application.

[0021] The above content of the present application will be further described in detail through the specific embodiments below. However, it should not be understood that the scope of the above subject matter of the present application is limited to the following examples. Any technology realized based on the above content of the present application belongs to the scope of the present application. DETAILED DESCRIPTION

[0022] The raw materials and equipment used in the present application are known products, which are obtained by purchasing commercially available products.

[0023] The polyvinylidene fluoride (PVDF) used in the present application is purchased from Zhejiang Funolin New Material Co., Ltd., and the model number is FL2006; the polyvinylidene fluoride-hexafluoropropylene copolymer (PVDF-HFP) is purchased from Zhejiang Funolin New Material Co., Ltd., and the model number is FL2606.

[0024] In the formula of the specific embodiment of the present application, "parts" means weight parts, and 1 part is 1 g.

[0025] Example 1

[0026] Formula: PVDF 100 parts, 1-butyl-3-methylimidazolium tetrafluoroborate 10 parts, zinc oxide 1 part.

[0027] Preparation method:

[0028] (1) According to the formula, the PVDF is put into the internal mixer at 190℃, and after it is melted, the 1-butyl-3-methylimidazolium tetrafluoroborate is added and mixed for 5 min;

[0029] (2) After adding zinc oxide and continuing to mix for 5 min, the modified fluororesin material is obtained.

[0030] Example 2

[0031] Formulation: PVDF 90 parts, PVDF-HFP 10 parts, 1-hexyl-3-methylimidazolium bisfluorosulfonylimide salt 10 parts, zinc oxide 1 part.

[0032] Preparation method:

[0033] (1) According to the formulation, PVDF and PVDF-HFP were put into the internal mixer at 190°C, and after melting, 1-hexyl-3-methylimidazolium bisfluorosulfonylimide salt was added and mixed for 5 min;

[0034] (2) After adding zinc oxide and continuing to mix for 5 min, a modified fluororesin material was obtained.

[0035] Example 3

[0036] Formulation: PVDF 50 parts, PVDF-HFP 50 parts, 1-butyl-3-methylimidazolium tetrafluoroborate salt 5 parts, zinc oxide 1.5 parts.

[0037] Preparation method:

[0038] (1) According to the formulation, PVDF and PVDF-HFP were put into the internal mixer at 190°C, and after melting, 1-butyl-3-methylimidazolium tetrafluoroborate salt was added and mixed for 5 min;

[0039] (2) After adding zinc oxide and continuing to mix for 5 min, a modified fluororesin material was obtained.

[0040] The following comparative examples were prepared for comparison with the samples.

[0041] Comparative Example 1

[0042] Formulation: PVDF 100 parts, zinc oxide 1 part.

[0043] Preparation method:

[0044] According to the formulation, PVDF was put into the internal mixer at 190°C, and after melting, zinc oxide was added and mixed for 5 min to obtain a modified fluororesin material.

[0045] Comparative Example 2

[0046] Formulation: PVDF 100 parts, 1-butyl-3-methylimidazolium tetrafluoroborate salt 10 parts.

[0047] Preparation method:

[0048] According to the formulation, PVDF was put into the internal mixer at 190°C, and after melting, 1-butyl-3-methylimidazolium tetrafluoroborate salt was added and mixed for 5 min to obtain a modified fluororesin material.

[0049] Comparative Example 3

[0050] Formulation: PVDF 100 parts, 1-butyl-3-methylimidazolium tetrafluoroborate 10 parts, magnesium oxide 1 part.

[0051] Preparation method:

[0052] (1) According to the formulation, PVDF was put into the internal mixer at 190°C, and after it was melted, 1-butyl-3-methylimidazolium tetrafluoroborate was added and mixed for 5 min;

[0053] (2) After adding magnesium oxide and continuing to mix for 5 min, the modified fluororesin material was obtained.

[0054] The tensile strength, elongation at break, melting point and peel strength of the modified fluororesin materials obtained in Comparative Examples 1-3 and Comparative Examples 1-3 were compared to screen the influence of processing aids on the adhesion properties of the modified fluororesin (see Table 1). The tensile strength and elongation at break were tested according to standard ASTM D638 (film), the melting point was tested according to standard ASTM D4591, and the peel strength was tested according to standard GB / T2791-1995.

[0055] Table 1

[0056]

[0057] It can be seen from the comparison of Example 1 and Comparative Example 1 that the addition of ionic liquid can effectively improve the toughness of PVDF. It can be seen from Example 1 and Comparative Example 3 that zinc oxide cannot be replaced by magnesium oxide. It can be seen from Example 1 and Comparative Examples 1-2 that only by simultaneously adding ionic liquid and zinc oxide, through the interaction of the two, can the adhesion properties be improved.

[0058] It can be seen from the comparison of Examples 1-3 that on the basis of Example 1, replacing PVDF with a mixture of PVDF and PVDF-HFP can further improve the toughness of the modified fluororesin material; however, when the amount of PVDF-HFP added is too much, the melting point of the modified fluororesin material obtained in Example 3 decreases too much, which cannot match the vulcanization temperature of fluororubber. Among them, the modified fluororesin material obtained under the specific formulation of Example 2 has excellent toughness and adhesion properties, as well as a suitable melting point, and the comprehensive performance is the best.

[0059] It can be seen from the comparison of Examples 1-3 and Comparative Examples 1-3 that the simultaneous addition of ionic liquid and zinc oxide can improve the adhesion properties of the modified fluororesin, and further, the addition of suitable PVDF-HFP can further improve the toughness of the modified fluororesin.

[0060] In conclusion, the application provides a modified fluororesin with good toughness and bonding performance, and a preparation method and application thereof. The fluororesin is effectively toughened by an ionic liquid, and on this basis, a processing aid is further screened, the bonding performance of the modified fluororesin is improved through the synergistic effect of zinc oxide and the ionic liquid, so that the modified fluororesin can be bonded with fluoro rubber, nitrile rubber and the like, and is used as a fuel pipe material. In addition, the preparation method is simple, and can be simply melt blended, and can be well applied to industrial production.

Claims

1. The use of a modified fluoropolymer in the preparation of materials for the aerospace and automotive industries, characterized in that, The modified fluororesin is prepared from the following raw materials in parts by weight: 20-150 parts of fluororesin, 2-20 parts of imidazole ionic liquid, and 0.1-5 parts of zinc oxide; the fluororesin is polyvinylidene fluoride or a mixture of polyvinylidene fluoride and polyvinylidene fluoride-hexafluoropropylene copolymer.

2. The use according to claim 1, characterized in that, The modified fluororesin is prepared from the following raw materials in parts by weight: 90-110 parts of polyvinylidene fluoride, 5-10 parts of imidazole ionic liquid, and 1-1.5 parts of zinc oxide. Alternatively, it can be prepared from the following raw materials in parts by weight: 50-90 parts of polyvinylidene fluoride, 5-50 parts of polyvinylidene fluoride-hexafluoropropylene copolymer, 5-10 parts of imidazole ionic liquid, and 1-1.5 parts of zinc oxide.

3. The use according to claim 1, characterized in that, The modified fluororesin is prepared from the following raw materials in parts by weight: 100 parts polyvinylidene fluoride, 10 parts imidazole ionic liquid, and 1 part zinc oxide. Alternatively, it can be prepared from the following raw materials in parts by weight: 90 parts polyvinylidene fluoride, 5-15 parts polyvinylidene fluoride-hexafluoropropylene copolymer, 10 parts imidazole ionic liquid, and 1 part zinc oxide.

4. The use according to any one of claims 1 to 3, characterized in that, The imidazole ionic liquid is 1-butyl-3-methylimidazolium tetrafluoroborate or 1-hexyl-3-methylimidazolium difluorosulfonylimide salt.

5. The use according to claim 1, characterized in that, The preparation method of the modified fluororesin includes the following steps: melting and mixing the fluororesin, then adding imidazole ionic liquid and zinc oxide to react, thereby obtaining the modified fluororesin.

6. The use according to claim 5, characterized in that, The melting temperature is 180~200℃, and the reaction time is 5~15min.

7. The use according to claim 5, characterized in that, The melting temperature is 190°C, and the reaction time is 10 min.

8. The use according to claim 1, characterized in that, The automotive industry materials mentioned are the refueling pipes and fuel lines for gasoline-powered vehicles.

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