Modified fluororesin with good toughness and adhesive property as well as preparation method and application of modified fluororesin

Abstract

The invention provides 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: 20-150 parts of fluororesin, 2-20 parts of ionic liquid and 0.1-5 parts of zinc oxide. Fluororesin is toughened through the ionic liquid, the processing aid is screened on the basis, and the adhesive property 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 fluororubber, nitrile rubber and the like, and can be compounded to be used as an oil filling pipe material. In addition, the preparation method is simple, only simple melt blending is needed, and the preparation method can be well suitable for industrial production.

Description

Technical Field

[0001] The invention belongs to the field of polymer materials, and in particular relates to a modified fluororesin with good toughness and bonding properties, a preparation method and application thereof. Background Art

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

[0003] Automobile fuel pipes are usually composed of a variety of composite materials, and one of the multi-layer structures that make up the fuel pipe is THV. Tetrafluoroethylene-hexafluoropropylene-vinylidene fluoride copolymer (THV) was developed by Dyneon Corporation in the United States in the 1980s and is the softest fluoroplastic on the market. When compounded with other materials into a multi-layer structure, its flexibility is very outstanding. Another important feature of THV is that it is easy to bond and can be bonded to other materials without surface treatment. Therefore, it is often used in combination with fluororubber as a fuel pipe material. THV materials are currently mainly imported from abroad, and there are no good alternative products in China.

[0004] The synthesis of THV substitutes requires more and more complex industrial equipment, and it is difficult to carry out industrial production in a short time. Existing fluororesins are blended and modified, or THV substitutes can be prepared by using ethylene tetrafluoroethylene copolymer resin (ETFE), perfluoroethylene propylene copolymer (FEP), polyvinylidene fluoride (PVDF), polyvinylidene fluoride-hexafluoropropylene copolymer (PVDF-HFP), conductive fillers, nanocomposites and other methods. However, due to the application environment of the material, it needs to be co-extruded with fluororubber, so its melting point cannot be too low or too high, and it must match the vulcanization temperature of fluororubber (160-180°C). The melting point of PVDF-HFP with better toughness is only 130-145°C, while the melting points of ETFE, FEP and the like are generally above 240°C. Therefore, only PVDF is the most suitable material, with a melting point of 165-180°C, but its toughness is very poor, and it cannot be directly and tightly bonded with fluororubber, etc., so it is necessary to improve its toughness and improve its bonding performance. Summary of the invention

[0005] The object of the present invention is to provide a modified fluororesin with good toughness and bonding properties, and a preparation method and use thereof.

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

[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] Alternatively, it is prepared from the following raw materials in parts by weight: 50 to 90 parts of polyvinylidene fluoride, 5 to 50 parts of polyvinylidene fluoride-hexafluoropropylene copolymer, 5 to 10 parts of ionic liquid, and 1 to 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] Alternatively, it 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, it 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] Furthermore, the ionic liquid is an imidazole ionic liquid.

[0013] Furthermore, the ionic liquid is 1-butyl-3-methylimidazolium tetrafluoroborate or 1-hexyl-3-methylimidazolium bis(fluorosulfonyl)imide.

[0014] The present invention also provides a method for preparing the modified fluororesin, the method comprising the following steps: melting the fluororesin, adding ionic liquid and zinc oxide for mixed reaction, and obtaining the modified fluororesin. Furthermore, the melting temperature is 180-200°C, and the reaction time is 5-15 minutes.

[0015] Furthermore, the melting temperature is 190° C. and the reaction time is 10 min.

[0016] The present invention also provides the use of the modified fluororesin in preparing materials for the aerospace and automobile industries.

[0017] Furthermore, the automotive industry material is a refueling pipe and a fuel pipe of a fuel vehicle.

[0018] In the present invention, ionic liquid refers to a molten salt that is liquid at room temperature and is composed of organic cations and inorganic anions (or organic anions).

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

[0020] Obviously, according to the above contents of the present invention, in accordance with common technical knowledge and customary means in the art, without departing from the above basic technical ideas of the present invention, other various forms of modification, replacement or change may be made.

[0021] The above contents of the present invention are further described in detail below through specific implementation methods in the form of examples. However, this should not be understood as the scope of the above subject matter of the present invention being limited to the following examples. All technologies realized based on the above contents of the present invention belong to the scope of the present invention. DETAILED DESCRIPTION

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

[0023] The polyvinylidene fluoride (PVDF) of the present invention was purchased from Zhejiang Funolin New Chemical Materials Co., Ltd., with a model number of FL2006; the polyvinylidene fluoride-hexafluoropropylene copolymer (PVDF-HFP) was purchased from Zhejiang Funolin New Chemical Materials Co., Ltd., with a model number of FL2606.

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

[0025] Example 1

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

[0027] Preparation method:

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

[0029] (2) Add zinc oxide and continue mixing for 5 minutes to obtain a modified fluororesin material.

[0030] Example 2

[0031] Formula: 90 parts of PVDF, 10 parts of PVDF-HFP, 10 parts of 1-hexyl-3-methylimidazolium bis(fluorosulfonyl)imide salt, and 1 part of zinc oxide.

[0032] Preparation method:

[0033] (1) According to the formula, PVDF and PVDF-HFP were put into an internal mixer at 190°C, and after they were melted, 1-hexyl-3-methylimidazolium bis(fluorosulfonyl)imide salt was added and mixed for 5 minutes;

[0034] (2) Add zinc oxide and continue mixing for 5 minutes to obtain a modified fluororesin material.

[0035] Example 3

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

[0037] Preparation method:

[0038] (1) PVDF and PVDF-HFP were put into an internal mixer at 190°C according to the formula, and after they were melted, 1-butyl-3-methylimidazolium tetrafluoroborate was added and mixed for 5 minutes;

[0039] (2) Add zinc oxide and continue mixing for 5 minutes to obtain a modified fluororesin material.

[0040] The following comparative samples are prepared by comparative examples.

[0041] Comparative Example 1

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

[0043] Preparation method:

[0044] According to the formula, PVDF was put into an internal mixer at 190° C., and after it was melted, zinc oxide was added and mixed for 5 minutes to obtain a modified fluororesin material.

[0045] Comparative Example 2

[0046] Formula: 100 parts of PVDF and 10 parts of 1-butyl-3-methylimidazolium tetrafluoroborate.

[0047] Preparation method:

[0048] According to the formula, PVDF was put into an internal mixer at 190° C., and after it was melted, 1-butyl-3-methylimidazolium tetrafluoroborate was added and mixed for 5 minutes to obtain a modified fluororesin material.

[0049] Comparative Example 3

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

[0051] Preparation method:

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

[0053] (2) Add magnesium oxide and continue mixing for 5 minutes to obtain a modified fluororesin material.

[0054] The tensile strength, elongation at break, melting point and peel strength of the modified fluororesin materials obtained by comparing Examples 1-3 and Comparative Examples 1-3 were used to screen the effect of the processing aid on the bonding performance of the modified fluororesin (see Table 1). The tensile strength and elongation at break were tested according to the standard ASTM D638 (film), the melting point test method was based on the standard ASTM D4591, and the peel strength test method was based on the standard GB / T2791-1995.

[0055] Table 1

[0056]

[0057] By comparing Example 1 with Comparative Example 1, it can be seen that the addition of ionic liquid can effectively improve the toughness of PVDF. By comparing Example 1 with Comparative Example 3, it can be seen that zinc oxide cannot be replaced by magnesium oxide. By comparing Example 1 with Comparative Examples 1-2, it can be seen that only by adding ionic liquid and zinc oxide at the same time, the bonding performance can be improved through the interaction between the two.

[0058] By comparing Examples 1-3, it can be seen 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 drops too much and cannot match the vulcanization temperature of fluororubber. Among them, the modified fluororesin material obtained under the specific formula of Example 2 has excellent toughness and bonding properties, as well as a suitable melting point, and the best comprehensive performance.

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

[0060] In summary, the present invention provides a modified fluororesin with good toughness and bonding properties, and a preparation method and use thereof. The present invention effectively toughens the fluororesin by using ionic liquid, and further screens a processing aid on this basis, and improves the bonding properties of the modified fluororesin by the synergistic effect of zinc oxide and ionic liquid, so that it can be bonded with fluororubber, nitrile rubber, etc., and used in combination as a fuel filler pipe material. In addition, the preparation method of the present invention is simple, and can be simply melt blended, and can be well applied to industrial production.

Claims

1. A modified fluororesin, 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 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 modified fluororesin 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 ionic liquid, and 1-1.5 parts of zinc oxide; Alternatively, it is prepared from the following raw materials in parts by weight: 50 to 90 parts of polyvinylidene fluoride, 5 to 50 parts of polyvinylidene fluoride-hexafluoropropylene copolymer, 5 to 10 parts of ionic liquid, and 1 to 1.5 parts of zinc oxide.

3. The modified fluororesin according to claim 1, characterized in that 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; Alternatively, it 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, it 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.

4. The modified fluororesin according to claim 1, characterized in that The ionic liquid is an imidazole ionic liquid.

5. The modified fluororesin according to claim 4, characterized in that The ionic liquid is 1-butyl-3-methylimidazolium tetrafluoroborate or 1-hexyl-3-methylimidazolium bis(fluorosulfonyl)imide.

6. A method for preparing the modified fluororesin according to any one of claims 1 to 5, characterized in that: The method comprises the following steps: kneading and melting the fluororesin, and then adding ionic liquid and zinc oxide for mixed reaction to obtain the modified fluororesin.

7. The method according to claim 6, characterized in that The melting temperature is 180-200° C., and the reaction time is 5-15 minutes.

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

9. Use of the modified fluororesin according to any one of claims 1 to 5 in the preparation of materials for the aerospace and automotive industries.

10. The use according to claim, characterized in that: The automobile industry materials are fuel pipes and fuel pipes of fuel vehicles.

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