Spraying-free composite material for automobile and preparation method of spraying-free composite material

Abstract

The invention belongs to the technical field of high polymer materials, and particularly belongs to a spraying-free composite material for an automobile and a preparation method of the spraying-free composite material. The spraying-free composite material for the automobile is prepared from the following components in parts by weight: 50 to 80 parts of PP (Polypropylene) resin, 10 to 15 parts of ABS (Acrylonitrile Butadiene Styrene) resin, 1 to 2 parts of a scratch-resistant agent, 1 to 2 parts of an adhesive, 0.1 to 0.3 part of a lubricant, 0.1 to 0.3 part of an oleophobic and hydrophobic material, 0.05 to 0.15 part of an antioxidant and 0.05 to 0.15 part of an ultraviolet absorbent. The spraying-free composite material for the automobile, provided by the invention, is relatively good in flowability and also has self-cleaning capability, ultraviolet resistance, wear resistance and self-repairing capability.

Description

Technical Field

[0001] The present disclosure relates to the technical field of polymer materials, and particularly relates to a spray-free composite material for automobiles and a preparation method thereof. Background Art

[0002] The spray-free plastic directly adds colored pigments (such as metal powder, mineral powder or other dyes) into the plastic raw materials, and then directly processes them into different plastic parts through injection molding or extrusion. These parts themselves have colors with different effects, and their surfaces do not need to be spray-treated anymore. The spray-free material is a material that can be directly injection-molded and can achieve a colorful appearance effect without spraying. Compared with the traditional spray material, the "spray painting" link is omitted. Therefore, the spray-free material has the advantages of low VOC and low odor, green environmental protection, recyclability; good gloss, beautiful appearance, no color fading, and rich hierarchical effects; one-time molding, short production cycle, and low comprehensive cost; 100% recyclable, no paint stripping, and sustainable utilization.

[0003] The spray-free plastics in the prior art have been widely used in the fields of household appliances and electronic products, but they have not been widely used in the automotive field. Therefore, there is an urgent need for a spray-free composite material that can be used in the automotive field. Summary of the Invention

[0004] The present disclosure provides a spray-free composite material for automobiles and a preparation method thereof to solve the deficiencies in the related art.

[0005] According to the first aspect of the embodiments of the present disclosure, a spray-free composite material for automobiles is provided. The spray-free composite material for automobiles comprises the following components in parts by weight: 50 - 80 parts of PP resin, 10 - 15 parts of ABS resin, 1 - 2 parts of scratch-resistant agent, 1 - 2 parts of adhesive, 0.1 - 0.3 parts of lubricant, 0.1 - 0.3 parts of oil-repellent and water-repellent material, 0.05 - 0.15 parts of antioxidant, and 0.05 - 0.15 parts of ultraviolet absorber.

[0006] In one aspect of the present disclosure, the scratch-resistant agent is selected from cerium dioxide nanoparticles.

[0007] In one aspect of the present disclosure, the cerium dioxide nanoparticles are prepared through the following steps: Step 1-a: Weigh cerium salt and add it to dilute nitric acid, and obtain the mixed solution of Step 1-a through stirring; Step 2-a: Age the mixed solution of Step 1-a, and then perform suction filtration, washing, and drying to obtain the solid of Step 2-a; Step 3-a: Calcinate the solid obtained in Step 2-a in an inert gas atmosphere. After calcination, wash and dry it to obtain the cerium dioxide nanoparticles.

[0008] In one aspect of the present disclosure, in Step 2-a, the aging time is selected from 12 - 20 h; preferably, the aging time is selected from 14 - 16 h; specifically, the aging time can be 12 h, 12.5 h, 13 h, 13.5 h, 14 h, 14.5 h, 15 h, 15.5 h, 16 h, 16.5 h, 17 h, 17.5 h, 18 h, 18.5 h, 19 h, 19.5 h or 20 h; but not limited thereto.

[0009] In one aspect of the present disclosure, in Step 3-a, the calcination temperature is selected from 650 °C - 800 °C; specifically, the calcination temperature is selected from 650 °C, 660 °C, 670 °C, 680 °C, 690 °C, 700 °C, 710 °C, 720 °C, 730 °C, 740 °C, 750 °C, 760 °C, 770 °C, 780 °C, 790 °C or 800 °C; but not limited thereto.

[0010] In one aspect of the present disclosure, in Step 3-a, the calcination time is selected from 3 - 8 h; specifically, the calcination time is selected from 3 h, 3.5 h, 4 h, 4.5 h, 5 h, 5.5 h, 6 h, 6.5 h, 7 h, 7.5 h or 8 h; but not limited thereto.

[0011] In one aspect of the present disclosure, specifically, the inert gas is nitrogen.

[0012] In one aspect of the present disclosure, specifically, the calcination process includes placing the solid obtained in Step 3 in a tubular furnace, introducing nitrogen, heating from room temperature to 700 °C - 750 °C at a heating rate of 5 °C / min, maintaining at this temperature for 5 - 7 h, and then naturally cooling to room temperature.

[0013] In one aspect of the present disclosure, the oleophobic and hydrophobic material is selected from compounds having the following structural formula I-A: Wherein, R1 and R2 are each independently selected from C3 - C12 alkyl groups, and the C3 - C12 alkyl groups are substituted by one or more fluorine atoms.

[0014] In one aspect of the present disclosure, R1 and R2 are the same group.

[0015] In one aspect of the present disclosure, preferably, R1 and R2 are the same group and are C5 - C8 alkyl groups each substituted by 6 - 10 fluorine atoms.

[0016] In one aspect of the present disclosure, the compound having the structural formula I-A is selected from the following compound I-1: In one aspect of the present disclosure, the ultraviolet absorber is selected from the compounds having the following structural formula I-B: Wherein, Ar1 is selected from C5-C15 aryl, and Ar1 contains at least one carbonyl group.

[0017] In one aspect of the present disclosure, preferably, Ar1 is an aryl containing a biphenyl structure, and Ar1 contains at least one carbonyl group.

[0018] In one aspect of the present disclosure, Ar1 adaptively contains at least one C1-C8 alkoxy group.

[0019] In one aspect of the present disclosure, the compound having the structural formula I-B is selected from the following compound II-1 or compound II-2: In one aspect of the present disclosure, the lubricant is selected from at least one of silicone grease, amide lubricants, stearic acid lubricants, polyolefin lubricants and ester lubricants.

[0020] In one aspect of the present disclosure, the antioxidant is selected from at least one of hindered phenol antioxidants, phosphite antioxidants, amine antioxidants and sulfur-containing antioxidants.

[0021] In one aspect of the present disclosure, the adhesive is selected from epoxy resin, polyvinyl chloride, polyacrylate, polyurethane or EVA hot melt adhesive.

[0022] According to the second aspect of the embodiments of the present disclosure, a method for preparing the aforementioned spray-free composite material for automobiles is provided. The preparation method includes the following steps: Step 1: Add PP resin, scratch-resistant agent, adhesive and lubricant into a first high-speed mixer and mix evenly to form a first premix; add ABS resin, oil-repellent and water-repellent material, antioxidant and ultraviolet absorber into a second high-speed mixer and mix evenly to form a second premix; Step 2: Synchronously feed the first premix and the second premix into an extruder according to a mass ratio, mix them through the extruder, plastify and extrude a strip, and pelletize the strip after cooling to obtain the spray-free composite material for automobiles.

[0023] The technical solutions provided by the embodiments of the present disclosure may include the following beneficial effects: (1) The cerium dioxide nanoparticles used in the present disclosure have high rigidity and creep resistance, and have better fluidity compared with other metal oxide particles, thus significantly improving the flow mark problem; moreover, the cerium dioxide nanoparticles used in the present disclosure also endow the composite material of the present disclosure with good wear resistance.

[0024] (2) The compound of Structural Formula I-A used in the present disclosure has good self-cleaning ability, and it has both hydrophobic and oleophobic effects. Moreover, the secondary amine group on the compound of Structural Formula I-A used in the present disclosure can form hydrogen bonds with polydopamine, and the amide group it carries also contributes to interfacial adhesion. Therefore, it also has good self-repair ability.

[0025] (3) The compound of Structural Formula I-A used in the present disclosure has good ultraviolet resistance, and it can combine with the groups on polydopamine, such as the combination of catechol group and mercapto group, improving its stability in the composite material; therefore, after being placed outdoors for a long time, its ultraviolet resistance will not decrease significantly.

[0026] It should be understood that the above general description and the following detailed description are only exemplary and explanatory, and cannot limit the present disclosure. Detailed Description of the Invention

[0027] Here, the exemplary embodiments will be described in detail. The embodiments described in the following exemplary embodiments do not represent all embodiments consistent with the present disclosure. On the contrary, they are only examples of devices and methods consistent with some aspects of the present disclosure as detailed in the appended claims.

[0028] To make the purpose, technical solutions and advantages of the present disclosure clearer, the technical solutions of the present disclosure will be clearly and completely described below in conjunction with the embodiments. Obviously, the described embodiments are part of the embodiments of the present disclosure, rather than all of the embodiments. The embodiments described herein are illustrative in nature and are used to provide a basic understanding of the present disclosure. The embodiments of the present disclosure should not be construed as limiting the present disclosure.

[0029] For the sake of brevity, the present disclosure only specifically discloses some numerical ranges. However, any lower limit can be combined with any upper limit to form a range not explicitly recited; and any lower limit can be combined with other lower limits to form a range not explicitly recited, and similarly any upper limit can be combined with any other upper limit to form a range not explicitly recited. In addition, each individually disclosed point or single numerical value itself can be used as a lower limit or an upper limit to be combined with any other point or single numerical value or with other lower limits or upper limits to form a range not explicitly recited.

[0030] In the present disclosure, the terms "comprise", "comprising" or any other variant thereof are intended to cover non-exclusive inclusion, such that a process, method, article or apparatus comprising a series of elements includes not only those elements but also other elements not expressly listed, or elements inherent to such process, method, article or apparatus. Without further limitation, an element qualified by the statement "comprising a..." does not preclude the presence of additional identical elements in the process, method, article or apparatus comprising the element.

[0031] In the description of the present disclosure, unless otherwise specified, "above" and "below" include the corresponding numbers.

[0032] Unless otherwise specified, the terms used in the present disclosure have the well-known meanings commonly understood by those skilled in the art. Unless otherwise specified, the numerical values of the various parameters mentioned in the present disclosure can be measured by various commonly used measurement methods in the art (for example, they can be tested according to the methods given in the embodiments of the present disclosure).

[0033] The term "about" is used to describe and account for small variations. When used in conjunction with an event or circumstance, the term can refer to instances in which the event or circumstance occurs precisely and instances in which the event or circumstance occurs very nearly. For example, when used in conjunction with a numerical value, the term can refer to a range of variation of ±10% less than or equal to the numerical value, such as less than or equal to ±5%, less than or equal to ±4%, less than or equal to ±3%, less than or equal to ±2%, less than or equal to ±1%, less than or equal to ±0.5%, less than or equal to ±0.1%, or less than or equal to ±0.05%. Additionally, sometimes quantities, ratios, and other numerical values are presented in a range format in the present disclosure. It should be understood that such range formats are for convenience and brevity and should be interpreted flexibly to include not only the numerical values expressly designated as range limits but also all individual numerical values or sub-ranges subsumed within the stated range as if each numerical value and sub-range were expressly designated.

[0034] A list of items connected by the terms "at least one of", "at least one", "at least one kind of" or other similar terms can mean any combination of the listed items. For example, if items A and B are listed, then the phrase "at least one of A and B" means only A; only B; or A and B. In another example, if items A, B, and C are listed, then the phrase "at least one of A, B, and C" means only A; or only B; only C; A and B (excluding C); A and C (excluding B); B and C (excluding A); or all of A, B, and C. Item A can include a single component or multiple components. Item B can include a single component or multiple components. Item C can include a single component or multiple components.

[0035] In the present disclosure, the term "alkyl" refers to an aliphatic hydrocarbon group, which can be straight-chain or branched-chain. A branched chain refers to one or more lower alkyl groups attached to a linear alkyl chain, such as methyl, ethyl, or propyl. For example, the term "C3-C12 alkyl" includes, but is not limited to: n-propyl, isopropyl, cyclopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, cyclobutyl, n-pentyl, isopentyl, neopentyl, cyclopentyl, methylcyclopentyl, n-hexyl, isohexyl, cyclohexyl, etc.

[0036] In the present disclosure, the term "aryl" refers to an aromatic monocyclic or polycyclic ring system. The aryl may optionally be substituted with one or more "ring system substituents", and the substituents may be the same or different, as defined in the present disclosure. Non-limiting examples of suitable aryls include phenyl and naphthyl.

[0037] In the present disclosure, the term "alkoxy" refers to -O-alkyl. The alkoxy can refer to a straight-chain, branched-chain or cyclic, saturated or unsaturated oxy-hydrocarbon chain, including, for example, methoxy, ethoxy, propoxy, isopropoxy, butoxy, tert-butoxy, and pentyloxy. The alkoxy can optionally be substituted with one or more alkoxy substituents. For example, the term "C1-C8 alkyl" includes, but is not limited to: methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, tert-butoxy, n-pentyloxy, isopentyloxy, or n-hexyloxy, etc.

[0038] In the present disclosure, the term "substituted or unsubstituted" means that the functional group described after this term may or may not have substituents. For example, "substituted or unsubstituted C3-C12 alkyl" means C3-C12 alkyl having substituents or unsubstituted C3-C12 alkyl. Among them, the number of substituents can be 1 or more than 2, and the substituents include at least one of halogen, alkyl, and aryl. It should be understood that when the number of substituents is greater than 1, each substituent may be the same or different.

[0039] In the present disclosure, cerium dioxide nanoparticles can be specifically prepared through the following steps: Step 1-a: Weigh cerium carbonate and add it to dilute nitric acid, and stir to obtain the mixed solution of Step 1-a; Step 2-a: Mix the mixed solution of Step 1-a and stir for 1-5 h, age for 12-20 h, and then filter, wash, and dry to obtain the solid of Step 2-a; Step 2-a: Place the solid of Step 2-a in a tubular furnace, introduce nitrogen, heat from room temperature to 700°C - 750°C at a heating rate of 5°C / min, hold at this temperature for 5-7 h, then naturally cool to room temperature, and then wash and dry to obtain cerium dioxide nanoparticles.

[0040] In the present disclosure, the compound having the structural formula I-A is selected from Compound I-1 (2,5-bis((3,3,4,4,5,5,6,6,6-nonafluorohexyl)oxy)terephthalohydrazide, CAS: 2569674-64-0), and its structural formula is as follows: In the present disclosure, Compound I-1 can be obtained commercially.

[0041] In the present disclosure, the compound having the structural formula I-B is selected from Compound II-1 or Compound II-2, and its structural formula is as follows: In the present disclosure, Compound II-1 or Compound II-2 is a benzophenone compound, which can be prepared by reacting a benzophenone raw material with an acyl chloride; among them, Compound II-1 can be prepared by reacting 2,4-dihydroxybenzophenone with N-BOC p-aminobenzenesulfonyl chloride; Compound II-2 can be prepared by reacting 2,2'-dihydroxy-4-methoxybenzophenone with N-BOC p-aminobenzenesulfonyl chloride. The specific steps are shown in the examples.

[0042] The present disclosure will be further described below in conjunction with examples. It should be understood that these examples are only used to illustrate the present disclosure and not to limit the scope of the present disclosure.

[0043] Examples and comparative examples: Example 1: Example 1 includes the following steps: 1. Preparation of cerium dioxide nanoparticles: Weigh 7.8 g of cerium carbonate and add it to 150 mL of 2 mol / L nitric acid. After stirring, a cerium salt solution is obtained; the cerium salt solution and a fluorine-containing solution are mixed and stirred for 3 h, then aged for 16 h, then filtered, washed, and dried to obtain a solid; the aforementioned solid is placed in a tube furnace, nitrogen is introduced, and the temperature is raised from room temperature to 750 °C at a heating rate of 5 °C / min and maintained at this temperature for 6.5 h, then naturally cooled to room temperature, and then washed and dried to obtain the cerium dioxide nanoparticles of Example 1.

[0044] 2. Preparation of Compound II-1: The route for preparing Compound II-1 is as follows: In a 100 mL two-necked round-bottom flask, 1.0 mmol of 2,4-dihydroxybenzophenone was added, and 1.5 mL of anhydrous CH2Cl2 solvent was added to dissolve it completely. Then 1.2 mmol of triethylamine was added, and N2 was introduced. The mixture was stirred for 10 min under an ice-water bath. After that, 2.5 mmol of N-BOC p-aminobenzenesulfonyl chloride was added dropwise slowly (controlling the dropping speed at about one drop every 5 seconds). After the addition was completed, the mixture was restored to room temperature and reacted at a constant temperature for 2 h. The reaction progress was monitored by a TLC plate. After the reaction was complete, 2.5 mL of trifluoroacetic acid was added to remove the Boc group. After the reaction ended, the mixture was extracted and separated with an ethyl acetate solution, dried over anhydrous Na2SO4, filtered, and concentrated by rotary evaporation. Finally, compound II-1 was obtained by column chromatography separation method. 1 H NMR (600 MHz, CDCl3) δ 7.62(s, 1H), 7.61 (s, 2H), 7.59(d, J = 2.4 Hz, 1H), 7.57 (d, J = 7.5 Hz, 1H), 7.44-7.40 (m, 2H),7.38 (dd, J= 8.4, 2.0 Hz, 1H), 7.27 (d, J = 3.1 Hz, 1H), 7.09 (dd, J = 8.4, 2.3 Hz, 1H),7.04(d, J = 1.9 Hz, 1H), 6.68 (dd, J = 8.8, 2.3 Hz, 2H), 6.48 (dd, J = 8.8,2.4 Hz, 2H), 5.31 (d, J= 1.8 Hz, 1H), 4.13 (qd, J = 7.1, 1.6 Hz, 4H). 13 C NMR(151 MHz, CDCl 3 ) δ 192.96, 152.81,152.03, 147.65, 136.84, 133.76, 132.10,131.56, 131.12, 131.03, 130.39, 128.67, 121.99,121.23, 118.52, 114.33,114.12. HRMS (ESI) calcd for C 25 H 20 N2O7S2(M+Na) ＋ 547.0605,found 547.0612。

[0045] 3. Preparation of spray-free composite material: 70 parts of PP resin, 1.2 parts of cerium dioxide nanoparticles, 1.5 parts of binder and lubricant were added to the first high-speed mixer and mixed evenly to form the first premix; ABS resin, oil-repellent and water-repellent material, antioxidant and ultraviolet absorber were added to the second high-speed mixer and mixed evenly to form the second premix; the first premix and the second premix were synchronously fed into an extruder according to the mass ratio, mixed by the extruder, plasticized and extruded into a strip, and granulated after the strip was cooled to obtain the automotive spray-free composite material.

[0046] Example 2: Example 2 includes the following steps: 1. Preparation of fluorine-doped cerium dioxide nanoparticles: Weigh 7.8 g of cerium carbonate and add it to 150 mL of 2 mol / L nitric acid, and stir to obtain a cerium salt solution; weigh 0.3 g of ammonium fluoride and add it to 60 mL of 0.08 g / mL ammonium carbonate solution, and stir to obtain a fluorine-containing solution; Mix the cerium salt solution and the fluorine-containing solution, stir for 3 h, then age for 16 h, then filter, wash and dry to obtain a solid; place the aforementioned solid in a tubular furnace, introduce nitrogen, and heat from room temperature to 750 °C at a heating rate of 5 °C / min, hold at this temperature for 6.5 h, then cool naturally to room temperature, then wash and dry to obtain the fluorine-doped cerium dioxide nanoparticles of Example 2.

[0047] 2. Preparation of Compound II-2: The route for preparing Compound II-2 is as follows: In a 100 mL two-necked round-bottom flask, add 1.0 mmol of 2,2'-dihydroxy-4-methoxybenzophenone, add 1.5 mL of anhydrous CH2Cl2 solvent to dissolve it completely, then add 1.2 mmol of triethylamine, introduce N2, stir in an ice-water bath for 10 min, and then slowly add 2.5 mmol of N-BOC p-aminobenzenesulfonyl chloride dropwise (control the speed at about one drop every 5 seconds). After the addition is complete, restore to room temperature and react at a constant temperature for 2 h. Monitor the reaction progress with a TLC plate. After the reaction is complete, add 2.5 mL of trifluoroacetic acid to remove the Boc group. After the reaction is over, extract and layer with ethyl acetate solution, dry over anhydrous Na2SO4, filter, spin dry, and finally obtain Compound II-2 by column chromatography separation. 11H NMR (600 MHz, DMSO) δ 7.53 (dt, J = 8.3, 4.3 Hz, 1H), 7.44 - 7.38 (m, 3H), 7.12 (dd, J = 8.7, 1.6 Hz, 2H), 7.09 (dd, J = 8.8, 1.6 Hz, 2H), 6.98 (dt, J = 8.8, 1.9 Hz, 1H), 6.94 (d, J = 8.2 Hz, 1H), 6.53 (dd, J = 8.8, 1.6 Hz, 2H), 6.51 - 6.45 (m, 2H), 6.30 (t, J = 2.1 Hz, 1H), 4.03 (q, J = 7.1 Hz, 1H), 3.74 (s, 3H), 3.33 (d, J = 1.9 Hz, 1H), 1.99 (s, 2H). 13 13C NMR (151 MHz, DMSO) δ 189.53, 170.60, 162.80, 155.05, 154.98, 148.70, 146.69, 134.39, 133.30, 132.87, 131.56, 130.73, 130.49, 127.02, 126.36, 123.06, 117.46, 117.29, 112.83, 112.59, 108.77, 60.02, 55.99. HRMS (ESI) calcd for C 26 H 22 N2O8S2 (M+Na) ＋ 577.0710, found 577.0720。

[0048] 3. Preparation of the thin film: Dissolve 0.25 g of the aforementioned compound II-2 and 0.4 g of 2,5-bis((3,3,4,4,5,5,6,6,6-nonafluorohexyl)oxy)terephthalohydrazide (compound I-1) in 30 mL of acetone, then add 10 g of dopamine hydrochloride; stir magnetically at 55 °C for 2.5 h. After the slurry becomes viscous, lower the temperature to room temperature, then add 0.75 g of the aforementioned fluorine-doped cerium dioxide nanoparticles, and stir mechanically for 0.3 h to obtain the slurry of Example 2; Provide a thermoplastic polyurethane elastomer base layer with a thickness of 150 μm (BASF 590A), coat the slurry of Example 2 on one surface of the base layer, and obtain a self-cleaning layer with a thickness of 70 μm after curing; Coat the solvent-based acrylic adhesive COPONYL on the other surface of the base layer, and obtain an adhesive layer with a thickness of 50 μm after curing; Obtain the automotive film of Example 2. Example 3: The steps of Example 3 are basically the same as those in Example 1, except that in the preparation of fluorine-doped cerium dioxide nanoparticles, the mass of ammonium fluoride used in Example 3 is 0.6 g.

[0049] Example 4: The steps of Example 4 are basically the same as those in Example 2, except that in the preparation of fluorine-doped cerium dioxide nanoparticles, the mass of ammonium fluoride used in Example 4 is 0.6 g.

[0050] Comparative Example 1: Comparative Example 1 includes the following steps: 1. Preparation of fluorine-doped cerium dioxide nanoparticles: The steps here in Comparative Example 1 are the same as those in Example 1.

[0051] 2. Preparation of compound II-1: The steps here in Comparative Example 1 are the same as those in Example 1.

[0052] 3. Preparation of the film: At room temperature, 30 parts by weight of polyaniline with an average degree of polymerization of 100 was dissolved in N-methylpyrrolidone to obtain a solution with a solid content of 30 wt%. After stirring evenly, 100 parts by weight of toluene diisocyanate (TDI) was added to the above mixed solution to obtain a polyurethane solution. Then, 0.25 g of the previously prepared Compound II-1 and 0.4 g of 2,5-bis((3,3,4,4,5,5,6,6,6-nonafluorohexyl)oxy)terephthalohydrazide (Compound I-1) were added, and mechanically stirred for 1.5 h to obtain the slurry of Comparative Example 1. A thermoplastic polyurethane elastomer base layer (BASF 590A) with a thickness of 150 μm was provided, and the slurry of Comparative Example 1 was coated on one surface of the base layer. After curing, a self-cleaning layer with a thickness of 70 μm was obtained. A solvent-based acrylic adhesive COPONYL was coated on the other surface of the base layer. After curing, an adhesive layer with a thickness of 50 μm was obtained. The automotive film of Comparative Example 1 was obtained.

[0053] The difference between Comparative Example 1 and Example 1 is that the self-cleaning layer of Comparative Example 1 uses polyurethane instead of polydopamine.

[0054] Comparative Example 2: Comparative Example 2 includes the following steps: 1. Preparation of fluorine-doped cerium oxide nanoparticles: The steps here in Comparative Example 1 are the same as those in Example 1.

[0055] 2. Preparation of the film: 0.25 g of ultraviolet absorber UV-531 (2-hydroxy-4-n-octyloxybenzophenone, commercially available) and 0.4 g of 2,5-bis((3,3,4,4,5,5,6,6,6-nonafluorohexyl)oxy)terephthalohydrazide (Compound I-1) were added to 30 mL of acetone, and then 10 g of dopamine hydrochloride was added. Magnetically stirred at 55 °C for 2.5 h. After the slurry became viscous, the temperature was lowered to room temperature, and then 0.75 g of the previously prepared fluorine-doped cerium oxide nanoparticles was added, and mechanically stirred for 0.3 h to obtain the slurry of Example 1. A thermoplastic polyurethane elastomer base layer (BASF 590A) with a thickness of 150 μm was provided, and the slurry of Example 1 was coated on one surface of the base layer. After curing, a self-cleaning layer with a thickness of 70 μm was obtained. A solvent-based acrylic adhesive COPONYL was coated on the other surface of the base layer. After curing, an adhesive layer with a thickness of 50 μm was obtained. The automotive film of Comparative Example 2 was obtained.

[0056] The difference between Comparative Example 2 and Example 1 is that Comparative Example 2 uses 2-hydroxy-4-n-octyloxybenzophenone instead of Compound II-1 as the ultraviolet absorber.

[0057] Comparative Example 3: The steps of Comparative Example 3 are basically the same as those in Comparative Example 2. The difference is that Comparative Example 3 uses ultraviolet absorber UV-9 (2-hydroxy-4-methoxybenzophenone, commercially available) instead of ultraviolet absorber UV-531.

[0058] Comparative Example 4: Comparative Example 4 includes the following steps: 1. Preparation of fluorine-doped cerium dioxide nanoparticles: The steps here in Comparative Example 4 are the same as those in Example 1.

[0059] 2. Preparation of Compound II-1: The steps here in Comparative Example 4 are the same as those in Example 1.

[0060] 3. Preparation of the film: Add 0.25 g of the previously prepared Compound II-1 to 30 mL of acetone, and then add 10 g of dopamine hydrochloride; magnetically stir at 55 °C for 2.5 h. After the slurry becomes viscous, lower the temperature to room temperature, and then add 0.75 g of the previously prepared fluorine-doped cerium dioxide nanoparticles, and mechanically stir for 0.3 h to obtain the slurry of Example 1; provide a 150-μm-thick thermoplastic polyurethane elastomer substrate layer (BASF 590A), coat the slurry of Example 1 on one surface of the substrate layer, and obtain a self-cleaning layer with a thickness of 70 μm after curing; coat the solvent-based acrylic adhesive COPONYL on the other surface of the substrate layer, and obtain an adhesive layer with a thickness of 50 μm after curing; obtain the automotive film of Comparative Example 4.

[0061] The difference between Comparative Example 4 and Example 1 is that Comparative Example 4 does not add Compound I-1 (2,5-bis((3,3,4,4,5,5,6,6,6-nonafluorohexyl)oxy)terephthalohydrazide).

[0062] Comparative Example 5: Comparative Example 5 includes the following steps: 1. Preparation of cerium dioxide nanoparticles: Weigh 7.8 g of cerium carbonate, add it to 150 mL of 2 mol / L nitric acid, and stir to obtain a cerium salt solution; then add 0.5 g of ammonium carbonate solution, mix and stir for 3 h, then age for 16 h, then filter, wash, and dry to obtain a solid; place the aforementioned solid in a tubular furnace, introduce nitrogen, and heat from room temperature to 750 °C at a heating rate of 5 °C / min, maintain at this temperature for 6.5 h, then naturally cool to room temperature, and then wash and dry to obtain the cerium dioxide nanoparticles of Comparative Example 5.

[0063] 2. Preparation of Compound II-1: The steps here for Comparative Example 5 are the same as those in Example 1.

[0064] 3. Preparation of the film: 0.25 g of the previously prepared Compound II-1 and 0.4 g of 2,5-bis((3,3,4,4,5,5,6,6,6-nonafluorohexyl)oxy)terephthalohydrazide (Compound I-1) were added to 30 mL of acetone, and then 10 g of dopamine hydrochloride was added; magnetically stirred at 55 °C for 2.5 h. After the slurry became viscous, the temperature was lowered to room temperature, and then 0.75 g of the previously prepared cerium oxide nanoparticles was added, and mechanically stirred for 0.3 h to obtain the slurry of Comparative Example 5; a thermoplastic polyurethane elastomer substrate layer with a thickness of 150 μm (BASF 590A) was provided, and the slurry of Comparative Example 5 was coated on one surface of the substrate layer. After curing, a self-cleaning layer with a thickness of 70 μm was obtained; a solvent-based acrylic adhesive COPONYL was coated on the other surface of the substrate layer. After curing, an adhesive layer with a thickness of 50 μm was obtained; the automotive film of Comparative Example 5 was obtained.

[0065] The difference between Comparative Example 5 and Example 1 is that Comparative Example 5 did not use fluorine-doped cerium oxide particles but ordinary cerium oxide particles.

[0066] Comparative Example 6: The steps of Comparative Example 6 are basically the same as those in Example 1, except that Comparative Example 6 used perfluoropolyether (meth)acrylate with an average molecular weight of 500 to replace Compound I-1 (2,5-bis((3,3,4,4,5,5,6,6,6-nonafluorohexyl)oxy)terephthalohydrazide).

[0067] Comparative Example 7: Comparative Example 7 includes the following steps: 1. Preparation of Compound II-1: The steps here for Comparative Example 4 are the same as those in Example 1.

[0068] 2. Preparation of the film: 0.25 g of the aforementioned compound II-1 prepared and 0.4 g of 2,5-bis((3,3,4,4,5,5,6,6,6-nonafluorohexyl)oxy)terephthalohydrazide (Compound I-1) were added to 30 mL of acetone, and then 10 g of dopamine hydrochloride was added; magnetically stirred at 55 °C for 2.5 h. After the slurry became viscous, the temperature was lowered to room temperature and mechanically stirred for 0.3 h to obtain the slurry of Comparative Example 7; a thermoplastic polyurethane elastomer base layer with a thickness of 150 μm (BASF 590A) was provided, and the slurry of Comparative Example 7 was coated on one side of the base layer. After curing, a self-cleaning layer with a thickness of 70 μm was obtained; a solvent-based acrylic adhesive COPONYL was coated on the other side of the base layer. After curing, an adhesive layer with a thickness of 50 μm was obtained; the automotive film of Comparative Example 7 was obtained.

[0069] The difference between Comparative Example 7 and Example 1 is that Comparative Example 7 does not contain cerium dioxide particles.

[0070] Anti-ultraviolet ability test: The ultraviolet absorption rate values of the samples of Examples 1-4 and Comparative Examples 1-5 after being placed outdoors for 1 day and 45 days were respectively tested, and the ultraviolet transmittance under light transmission conditions was tested using a spectrophotometer (Konica Corporation, Japan, model CM-5). The test results are shown in Table 1 below.

[0071] Table 1 It can be seen that the anti-ultraviolet abilities of Comparative Examples 1-3 and Comparative Example 5 are significantly inferior to those of Examples 1-4; because the prepared compounds II-1 and II-2 in the present disclosure introduce other aromatic rings and auxochrome group heteroatoms, compared with other common benzophenone ultraviolet absorbers, their absorption intensity will be improved. And, more importantly, the prepared compounds II-1 and II-2 in the present disclosure have two amino groups, which can bind to the groups on polydopamine, such as binding to catechol groups and mercapto groups, improving their stability in the self-cleaning layer. As can be seen from Examples 1-4, after being placed outdoors for 45 days, their anti-ultraviolet ability has not decreased significantly, while in Comparative Example 1, polyurethane is used instead of polydopamine, and the stability of the combination of compound II-1 and polyurethane is not as good as that of polydopamine; and the ultraviolet absorbers UV-531 and UV-9 used in Comparative Examples 2-3 do not contain amino groups, and their combination with polydopamine is not as stable as the combination of compound II-1 and polydopamine. Therefore, after being placed for 45 days, the anti-ultraviolet abilities of the samples in Comparative Examples 1-3 all decreased significantly.

[0072] Hydrophobic and oleophobic ability test: The water contact angle and oil contact angle (n - hexadecane) of the samples of Examples 1 - 2, Comparative Examples 1, 4, and 6 were tested after being placed outdoors for 1 day and 45 days respectively. The test results are shown in Table 2 below.

[0073] Table 2 It can be seen that compared with Comparative Example 6 using the commercially available hydrophobic and oleophobic agent perfluoropolyether (meth)acrylate, the initial hydrophobic ability of Compound I - 1 provided by the present disclosure is inferior. However, Compound I - 1 also has two amino groups, which can bind to the groups on polydopamine, such as catechol groups and mercapto groups, improving its stability in the material. Therefore, after being placed outdoors for 45 days, its hydrophobic and oleophobic abilities hardly decrease, while Comparative Example 6 using perfluoropolyether (meth)acrylate shows a more obvious decrease. Compared with Comparative Example 1, in Comparative Example 1, polyurethane is used instead of polydopamine, and the degree of stable binding of Compound I - 1 to polyurethane is not as good as that to polydopamine; moreover, polydopamine itself has oleophobic ability. Therefore, the oleophobic ability of Comparative Example 1 is significantly weaker than that of Examples 1 and 2.

[0074] Friction resistance and self - healing ability test: The self - healing abilities of Examples 1 - 2, Comparative Examples 2, 4, and Comparative Examples 6 - 7 were tested respectively. The coated surface of Q235 steel was placed face - down on 600 - mesh sandpaper with a size of 25 cm × 20 cm, a 20 - g weight was loaded on the sample, and the sample was pulled to move 25 cm at a speed of 5 cm / s and then pulled back in the opposite direction at the same speed. At this time, it was recorded as 1 wear cycle (50 cm). The samples of Examples 1 - 2, Comparative Examples 2 - 4, and Comparative Examples 6 - 7 were respectively subjected to 5 wear cycles, and then their water contact angles and oil contact angles were tested; the results are shown in Table 3.

[0075] Table 3 Comparing Examples 1 - 2 and Comparative Example 7, it can be seen that the presence of cerium dioxide particles can greatly enhance the wear resistance; comparing Examples 1 - 2 and Comparative Examples 4 and 6, it can be seen that Examples 1 - 2 have better self - healing ability because the secondary amine groups on Compound I - 1 can form hydrogen bonds with polydopamine, and the amide groups contained in Compound I - 1 also contribute to interfacial adhesion; and the sulfonate groups between Compound II - 1 and Compound II - 1 molecules can also adhere to the polydopamine substrate, thus having better self - healing ability.

[0076] Other embodiments of the present disclosure will be readily apparent to those skilled in the art upon consideration of the specification and practice of the disclosure herein. The present disclosure is intended to cover any variations, uses, or adaptations of the present disclosure that follow the general principles of the present disclosure and include known common general knowledge or conventional technical means in the technical field not disclosed by the present disclosure.

Claims

1. A spray-free composite material for automobiles, characterized in that: The spray-free composite material for automobiles comprises the following components in parts by weight: 50-80 parts of PP resin, 10-15 parts of ABS resin, 1-2 parts of scratch resistant agent, 1-2 parts of adhesive, 0.1-0.3 parts of lubricant, 0.1-0.3 parts of oleophobic and hydrophobic material, 0.05-0.15 parts of antioxidant and 0.05-0.15 parts of UV absorber.

2. The spray-free composite material for automobiles according to claim 1, characterized in that: The anti-scratch agent is selected from cerium dioxide nanoparticles.

3. The spray-free composite material for automobiles according to claim 2, characterized in that: The cerium dioxide nanoparticles are prepared by the following steps: Step 1-a: Weigh a cerium salt, add it to dilute nitric acid, and stir to obtain a mixed solution of step 1-a; Step 2-a: aging the mixed solution of step 1-a, and then filtering, washing and drying to obtain the solid of step 2-a; Step 3-a: calcining the solid obtained in step 2-a under an inert gas atmosphere, washing and drying the solid after calcination to obtain the cerium dioxide nanoparticles.

4. The spray-free composite material for automobiles according to claim 1, characterized in that: The oleophobic and hydrophobic material is selected from compounds having the following structural formula IA: Wherein, R1 and R2 are each independently selected from a C3-C12 alkyl group, and the C3-C12 alkyl group is substituted by one or more fluorine atoms.

5. The spray-free composite material for automobiles according to claim 4, characterized in that: The compound having structural formula IA is selected from the following compound I-1: 。 6. The spray-free composite material for automobiles according to claim 1, characterized in that: The ultraviolet absorber is selected from compounds having the following structural formula IB: Wherein, Ar1 is selected from C5-C15 aromatic groups, and Ar1 contains at least one carbonyl group.

7. The spray-free composite material for automobiles according to claim 6, characterized in that: The compound having structural formula IB is selected from the following compound II-1 or compound II-2: 。 8. The spray-free composite material for automobiles according to claim 1, characterized in that: The lubricant is selected from at least one of silicone grease, amide lubricant, stearic acid lubricant, polyolefin lubricant and ester lubricant; The antioxidant is selected from at least one of hindered phenol antioxidants, phosphite antioxidants, amine antioxidants and sulfur-containing antioxidants; The adhesive is selected from epoxy resin, polyvinyl chloride, polyacrylate, polyurethane or EVA hot melt adhesive.

9. A method for preparing the spray-free composite material for automobiles according to any one of claims 1 to 8, characterized in that: The preparation method comprises the following steps: Step 1: Add PP resin, scratch resistant agent, adhesive and lubricant into the first high-mixer and mix them evenly to form a first premix; add ABS resin, oleophobic and hydrophobic material, antioxidant and ultraviolet absorber into the second high-mixer and mix them evenly to form a second premix; Step 2: Feed the first premix and the second premix into the extruder simultaneously according to the mass ratio, mix them in the extruder, extrude the material strips after plasticization, and pelletize the material strips after cooling to obtain the spray-free composite material for automobiles.

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