A high weather-resistant ABS composite decorative part for automobiles and its preparation method

Abstract

The present invention relates to the technical field of composite decorative parts, and specifically to a high weather-resistant ABS composite decorative part for automobiles and a preparation method thereof, including the following processes: extruding and pelletizing ABS, glass fiber, unsaturated hindered amine, initiator, antioxidant, and ultraviolet light absorber through a twin-screw extruder; the temperature of the extruder is 180-225 °C, the temperature of the head is 220 °C, and the rotation speed of the extruder is 250 r / min; injection molding to form a composite decorative part, and the temperature of the injection molding machine is 215-225 °C. Through the action of the initiator, the unsaturated hindered amine is grafted onto the molecular structure of the ABS resin in the present invention, improving the mechanical properties such as the impact strength and tensile strength of the composite decorative part, and being able to cooperate with the ultraviolet light absorber 5411 to further improve the light stability of the composite decorative part and reduce the migration and volatilization during use.

Description

Technical Field

[0001] The present invention relates to the technical field of composite decorative parts, and particularly to a highly weather-resistant ABS composite decorative part for automobiles and a preparation method thereof. Background Technique

[0002] As one of the general polymer materials with the largest output and the most extensive application at present, acrylonitrile-butadiene-styrene terpolymer (ABS) has excellent properties such as good impact resistance, high gloss, and processability, and has a wide range of applications in household appliances, electronic and electrical appliances, automotive parts, etc. ABS resin has good secondary processing performance and is suitable for decoration, spraying, etc. to improve aesthetics and comfort, and is widely used in automotive instrument panels, sun visors, rearview mirrors, door panels, grilles, etc. However, the ABS material contains an unsaturated butadiene double bond structure. In the natural environment, due to the influence of factors such as wind, rain, air oxidation, and sunlight ultraviolet damage, the butadiene double bond structure is easily oxidized and damaged, resulting in the degradation of the polymer molecular chain and the decline of material properties, thus reducing the comprehensive performance of ABS resin. This greatly hinders the application of ABS resin, and some added small molecule antioxidants, ultraviolet absorbers and other additives will migrate. Moreover, when used as the base resin in automotive parts, glass fiber is used for reinforcement. After aging, the interface between the glass fiber and the ABS resin will de-bond, causing surface cracking and serious deterioration of mechanical properties, which is not conducive to the long-term use of the composite material. Therefore, we propose a highly weather-resistant ABS composite decorative part for automobiles and a preparation method thereof. Summary of the Invention

[0003] The purpose of the present invention is to provide a highly weather-resistant ABS composite decorative part for automobiles and a preparation method thereof, so as to solve the problems raised in the above background technique.

[0004] To solve the above technical problems, the present invention provides the following technical solution: A preparation method of a highly weather-resistant ABS composite decorative part for automobiles, including the following processes:

[0005] Extrude and pelletize ABS, glass fiber, unsaturated hindered amine, initiator, antioxidant, and ultraviolet light absorber through a twin-screw extruder; the temperature of the extruder is 180-225 °C, the temperature of the die head is 220 °C, and the rotation speed of the extruder is 250 r / min;

[0006] Injection mold to form a composite decorative part, and the temperature of the injection molding machine is 215-225 °C.

[0007] Further, the decorative part comprises the following weight components: 85 to 100 parts of ABS, 15 to 18 parts of glass fiber, 0.3 to 0.5 part of unsaturated hindered amine, 0.2 to 0.3 part of initiator, 0.06 to 0.4 part of antioxidant, and 0.1 to 0.3 part of ultraviolet light absorber.

[0008] Further, the antioxidant comprises 0.05 to 0.25 part of antioxidant 1010 and 0.01 to 0.15 part of antioxidant 168.

[0009] Further, the ultraviolet light absorber is ultraviolet light absorber 5411.

[0010] Further, the unsaturated hindered amine is one of 4-acryloyloxy-1,2,2,6,6-pentamethylpiperidine, 4-methacryloyloxy-1,2,2,6,6-pentamethylpiperidine, 4-methacryloyloxy-2,2,6,6-tetramethylpiperidine, 4-acryloyloxy-2,2,6,6-tetramethylpiperidine, and 3-(2-dodecenyl)-1-(2,2,6,6-tetramethyl-4-piperidyl)pyrrolidine-2,5-dione;

[0011] Preferably, it is 3-(2-dodecenyl)-1-(2,2,6,6-tetramethyl-4-piperidyl)pyrrolidine-2,5-dione.

[0012] Further, the initiator is one of azobisisobutyronitrile and azodiisovaleronitrile; preferably, it is azodiisovaleronitrile.

[0013] ABS: PA-777D, sourced from Chi Mei Industries Co., Ltd., Taiwan, China;

[0014] Glass fiber: alkali-free continuous glass fiber ER13-988A, sourced from China National Bluestar (Group) Co., Ltd.;

[0015] Antioxidant: 1010 and 168, sourced from Shandong Linyi Sanfeng Chemical Co., Ltd.;

[0016] Ultraviolet light absorber: 5411, sourced from Guangdong Keyou Materials Technology Co., Ltd.

[0017] In the above technical solution, using ABS as the base resin, glass fiber as the filler, and antioxidant and ultraviolet light absorber as the additives, a composite decorative part with excellent mechanical properties such as tensile strength, impact strength, and flexural strength and certain weather resistance is formed by co-extrusion and injection molding.

[0018] In the co - extrusion process, unsaturated hindered amines and initiators are added. Under the action of heat, the unsaturated carbon - carbon double bonds in the unsaturated hindered amines and the unsaturated butadiene double - bond structure in ABS undergo chemical bonding, grafting the unsaturated hindered amines onto ABS. This reduces the number of butadiene double - bond structures in ABS, alleviates the oxidation damage phenomenon, improves the weather resistance of the ABS resin, and enhances the ABS to a certain extent. At the same time, the introduction of hindered amines can cooperate with the ultraviolet absorber 5411 (hydroxyphenyl benzotriazole type), absorb ultraviolet light and capture free radicals, inhibit photo - oxidative degradation, and further improve the light stability of the prepared composite decorative parts. Moreover, the product formed by grafting hindered amines and ABS resin has the characteristics of high molecular weight, which can improve its thermal stability and acid - base resistance stability, reduce migration and volatilization during use, play a more long - term and effective light - stabilizing role, and is conducive to improving the light - stability protection ability of the prepared composite decorative parts.

[0019] Furthermore, graft - modifying ABS resin with unsaturated hindered amines increases the steric hindrance effect, hinders the movement of molecular chain segments. At the same time, due to the strong polarity of hindered amines, the interaction between molecular chains is enhanced, thereby improving the mechanical properties such as impact strength and tensile strength of the prepared composite decorative parts. And the glass fiber is confined in the molecular chain system of the unsaturated hindered - amine - graft - modified ABS resin, improving the interfacial bonding ability between the glass fiber and the ABS resin, and promoting the enhancement of the glass - fiber - reinforcement effect. By controlling the dosages of unsaturated hindered amines and initiators, while ensuring light stability, it is possible to avoid a significant reduction in the butadiene rubber phase that plays a toughening role in ABS, resulting in an increase in the rigidity of ABS.

[0020] Furthermore, the glass fiber is surface - modified, and the specific process includes the following:

[0021] (1) Place the glass fiber in a vacuum drying oven at 80 °C and dry for 2 - 3 h. Then place it in an ethanol solution of the coupling agent and soak for 10 - 15 h. Take it out, air - dry, and place it in an oven at 80 °C to dry and volatilize the ethanol to obtain coupling - modified glass fiber.

[0022] In the ethanol solution of the coupling agent, the volume ratio of γ - glycidoxypropyltrimethoxysilane to ethanol is (2.0 - 3.0):(97 - 98);

[0023] The ratio of glass fiber to the ethanol solution of the coupling agent is 10 g:100 mL;

[0024] In the above technical solution, the glass fiber is subjected to coupling modification, and the coupling agent is grafted onto the surface of the glass fiber by using a silicon-oxygen bond. Affected by the bond energy of the silicon-oxygen bond, when absorbing ultraviolet light, the silicon-oxygen bond is not easily broken, so that the interface between the glass fiber and the organic matter has more excellent weather resistance and anti-aging performance. The interfacial bonding ability between the coupled modified glass fiber and the poly-ABS resin is enhanced, the compatibility between the two is improved, and the interfacial bonding strength is increased, which can improve the reinforcing effect of the glass fiber in the ABS resin and is beneficial to the improvement of the mechanical properties of the composite decorative parts and the anti-pull-out performance of the glass fiber. The amount of the coupling agent is controlled to avoid excessive coupling agent causing dense cross-linking points in the follow-up, resulting in stress concentration, restricting the movement of molecular chains, and increasing the rigidity of the composite decorative parts.

[0025] (2) Mix 4,4'-dihydroxybenzophenone and benzyltriethylammonium chloride, heat to 30-60 °C and stir to dissolve; add the coupled modified glass fiber, raise the temperature to 70-80 °C, and react for 4-5 h; cool to room temperature, wash with ethanol, and dry to constant weight to obtain phenol-modified glass fiber;

[0026] The mass ratio of the coupled modified glass fiber, 4,4'-dihydroxybenzophenone, and benzyltriethylammonium chloride is 100:(0.29-0.49):(0.009-0.015);

[0027] (3) Melt diphenyl sulfone by heating to 130-135 °C, add potassium carbonate anhydrous and decafluorobiphenyl, stir under the protection of an argon atmosphere, slowly add the phenol-modified glass fiber, and add it within 20-30 min. Raise the temperature to 140-145 °C, stir, and polymerize for 1.0-2.0 h; add 4,4'-dihydroxybenzophenone and react for 2.0-3.0 h; add 4-fluorostyrene and continue to react for 1.5-2.5 h; filter while it is hot, wash with acetone and deionized water, and dry in vacuo at 120 °C for 8-12 h to obtain modified glass fiber;

[0028] The mass ratio of the phenol-modified glass fiber, decafluorobiphenyl, 4,4'-dihydroxybenzophenone, and 4-fluorostyrene is 100:(0.45-0.76):(0.27-0.45):(0.17-0.28);

[0029] The mass ratio of the phenol-modified glass fiber to diphenyl sulfone is (10-15):100;

[0030] In the above technical solution, the reactants and reaction conditions are in an anhydrous state. Benzyltriethylammonium chloride is used as a catalyst to react the epoxy groups on the surface of the coupled and modified glass fiber with the phenolic hydroxyl groups in 4,4'-dihydroxybenzophenone. 4,4'-Dihydroxybenzophenone is grafted onto the surface of the glass fiber, introducing phenolic groups onto the glass fiber surface, which is beneficial for subsequent reactions. Using diphenyl sulfone as a solvent and potassium carbonate as a catalyst, the phenolic hydroxyl groups in the phenol-modified glass fiber react with the fluorine in decafluorobiphenyl, and 4,4'-dihydroxybenzophenone is added to continue the reaction. By setting the dosage and addition sequence of the materials, perfluorobiphenyl polyaryletherketone is introduced onto the surface of the glass fiber, improving the stability at the interface of the glass fiber, enhancing the processing performance of the glass fiber, and being able to toughen and strengthen the composite material of the glass fiber and ABS resin, improving the mechanical properties of the prepared composite decorative parts.

[0031] Graft 4-fluorostyrene at the end of the organic matter on the surface of the glass fiber to introduce an unsaturated double bond, enabling the modified glass fiber to be co-grafted with unsaturated hindered amine and ANS resin in the above-mentioned co-extrusion process, thereby forming an organic and inorganic three-dimensional network structure, which is beneficial for improving the mechanical properties of the prepared composite decorative parts. And the grafting reaction occurs at the interface of the glass fiber, which can promote the improvement of the interface bonding ability and interface weather resistance, avoid the deterioration of the two-phase interface bonding effect, resulting in the decline of the glass fiber reinforcement effect and the deterioration of the tensile strength, and ensure the continuous effectiveness of the weather resistance of the prepared composite decorative parts.

[0032] The unsaturated hindered amine is preferably 3-(2-dodecenyl)-1-(2,2,6,6-tetramethyl-4-piperidyl)pyrrolidine-2,5-dione with a hydrophobic long-chain alkyl group. Collaborating with perfluorobiphenyl polyaryletherketone can reduce the water absorption ability at the interface of the ABS resin and its interface with the glass fiber, avoiding the penetration of water molecules in the environment and causing the accelerated aging of the ABS resin.

[0033] Compared with the prior art, the beneficial effects of the present invention are as follows:

[0034] 1. The high-weather-resistant ABS composite decorative part for automobiles and its preparation method of the present invention graft unsaturated hindered amine into the molecular structure of the ABS resin through the action of an initiator, improving the mechanical properties such as the impact strength and tensile strength of the composite decorative part, and being able to cooperate with the ultraviolet absorber 5411 to further improve the light stability of the composite decorative part and reduce the migration and volatilization during use.

[0035] 2. The high weather-resistant ABS composite decorative part for automobiles and its preparation method according to the present invention graft the perfluorobiphenyl polyaryletherketone prepared from 4,4'-dihydroxybenzophenone and decafluorobiphenyl onto the surface of glass fiber through a coupling agent, and introduce 4-fluorostyrene, so that the modified glass fiber can be co-grafted with unsaturated hindered amine and ANS resin in the co-extrusion process, improving the mechanical properties of the composite decorative part, enhancing the interfacial bonding ability and interfacial weather resistance between the glass fiber and the ABS resin, avoiding the deterioration of the interfacial bonding effect between the two phases, resulting in the decline of the glass fiber reinforcement effect and the deterioration of the tensile strength, and ensuring the continuous effectiveness of the weather resistance of the prepared composite decorative part. Detailed implementation mode

[0036] The technical solutions in the embodiments of the present invention will be clearly and completely described below. Obviously, the described embodiments are only a part of the embodiments of the present invention, rather than all embodiments. All other embodiments obtained by those of ordinary skill in the art based on the embodiments of the present invention without creative efforts shall fall within the protection scope of the present invention.

[0037] Embodiment 1

[0038] (1) Preparation of modified glass fiber:

[0039] 1.1. Place 2 kg of glass fiber in a vacuum drying oven at 80 °C for 2 h, place it in a 20 L ethanol solution of coupling agent, and soak for 10 h; take it out, air dry, and place it in an oven at 80 °C to dry and volatilize the ethanol to obtain coupling-modified glass fiber.

[0040] In the ethanol solution of coupling agent, the volumes of γ-glycidoxypropyltrimethoxysilane and ethanol are 0.4 L:19.6 L in sequence.

[0041] 1.2. Take 5.8 g of 4,4'-dihydroxybenzophenone and 0.18 g of benzyltriethylammonium chloride, mix and heat to 30 °C with stirring to dissolve; add 2 kg of coupling-modified glass fiber, raise the temperature to 70 °C, and react for 4 h; cool to room temperature, wash with ethanol, and dry to constant weight to obtain phenol-modified glass fiber.

[0042] 1.3. Heat 20 kg of diphenyl sulfone to 130 °C to melt, add 87 g of anhydrous potassium carbonate and 90 g of decafluorobiphenyl, stir under argon atmosphere protection, slowly add 2 kg of phenol-modified glass fiber, add it all within 20 min, raise the temperature to 140 °C, stir, and polymerize for 1.0 h; add 54 g of 4,4'-dihydroxybenzophenone and react for 2.0 h; add 34 g of 4-fluorostyrene and continue to react for 1.5 h; filter while it is hot, wash with acetone and deionized water, and vacuum dry at 120 °C for 8 h to obtain modified glass fiber.

[0043] (2) Preparation of composite decorative part:

[0044] 10 kg of ABS, 1.5 kg of modified glass fiber, 30 g of unsaturated hindered amine 3-(2-dodecenyl)-1-(2,2,6,6-tetramethyl-4-piperidyl)pyrrolidine-2,5-dione, 20 g of initiator azodiisobutyronitrile, 5.0 g of antioxidant 1010 and 1.0 g of antioxidant 168, 10 g of ultraviolet absorber 5411 are extruded and pelletized through a twin-screw extruder; the temperature of the extruder is 180 - 225 °C, the temperature of the head is 220 °C, and the rotational speed of the extruder is 250 r / min;

[0045] Injection molding is carried out to form a composite decorative part, and the temperature of the injection molding machine is 215 °C.

[0046] Example 2

[0047] (1) Preparation of modified glass fiber:

[0048] 1.1. Place 2 kg of glass fiber in a vacuum drying oven at 80 °C and dry for 2.5 h, then place it in a 20 L ethanol solution of coupling agent and soak for 12 h; take it out, air dry, and place it in an oven at 80 °C to dry and volatilize the ethanol to obtain coupling-modified glass fiber;

[0049] In the ethanol solution of coupling agent, the volumes of γ-glycidoxypropyltrimethoxysilane and ethanol are (0.5) L: (19.5) L in sequence;

[0050] 1.2. Take 7.8 g of 4,4'-dihydroxybenzophenone and 0.24 g of benzyltriethylammonium chloride, mix them, heat to 45 °C and stir to dissolve; add 2 kg of coupling-modified glass fiber, raise the temperature to 75 °C, and react for 4.5 h; cool to room temperature, wash with ethanol, and dry to constant weight to obtain phenol-modified glass fiber;

[0051] 1.3. Heat 20 kg of diphenyl sulfone to melt at 132 °C, add 117 g of anhydrous potassium carbonate and 121 g of decafluorobiphenyl, stir under argon atmosphere protection, slowly add 2.3 kg of phenol-modified glass fiber, add it all within 25 min, raise the temperature to 142 °C, stir, and polymerize for 1.5 h; add 72 g of 4,4'-dihydroxybenzophenone and react for 2.5 h; add 45 g of 4-fluorostyrene and continue to react for 2.0 h; filter while it is hot, wash with acetone and deionized water, and vacuum dry at 120 °C for 10 h to obtain modified glass fiber;

[0052] (2) Preparation of composite decorative part:

[0053] 9.2 kg of ABS, 1.6 kg of modified glass fiber, 40 g of unsaturated hindered amine 3-(2-dodecenyl)-1-(2,2,6,6-tetramethyl-4-piperidyl)pyrrolidine-2,5-dione, 25 g of initiator azodiisooctanenitrile, 15 g of antioxidant 1010, 8 g of antioxidant 168, and 20 g of ultraviolet absorber 5411 were extruded and pelletized by a twin-screw extruder; the temperature of the extruder was 180 - 225 °C, the head temperature was 220 °C, and the rotational speed of the extruder was 250 r / min;

[0054] Injection molding was carried out to form a composite decorative part, and the temperature of the injection molding machine was 220 °C.

[0055] Example 3

[0056] (1) Preparation of modified glass fiber:

[0057] 1.1. 2 kg of glass fiber was placed in a vacuum drying oven at 80 °C and dried for 3 h, then placed in a 20 L ethanol solution of coupling agent and soaked for 15 h; taken out, air-dried, and placed in an oven at 80 °C to dry and volatilize the ethanol to obtain coupling-modified glass fiber;

[0058] In the ethanol solution of coupling agent, the volumes of γ-glycidoxypropyltrimethoxysilane and ethanol were 0.6 L:19.4 L in sequence;

[0059] 1.2. 9.8 g of 4,4'-dihydroxybenzophenone and 0.30 g of benzyltriethylammonium chloride were mixed and heated to 60 °C with stirring for dissolution; 2 kg of coupling-modified glass fiber was added, and the temperature was raised to 80 °C and reacted for 5 h; cooled to room temperature, washed with ethanol, and dried to constant weight to obtain phenol-modified glass fiber;

[0060] 1.3. 20 kg of diphenyl sulfone was heated to melt at 135 °C, 147 g of anhydrous potassium carbonate and 152 g of decafluorobiphenyl were added, stirred under argon atmosphere protection, 3 kg of phenol-modified glass fiber was slowly added within 30 min, the temperature was raised to 145 °C, stirred, and polymerized for 2.0 h; 90 g of 4,4'-dihydroxybenzophenone was added and reacted for 3.0 h; 56 g of 4-fluorostyrene was added and reacted for another 2.5 h; filtered while it was hot, washed with acetone and deionized water, and vacuum-dried at 120 °C for 12 h to obtain modified glass fiber;

[0061] (2) Preparation of composite decorative part:

[0062] 8.5 kg of ABS, 1.8 kg of modified glass fiber, 50 g of unsaturated hindered amine 3-(2-dodecenyl)-1-(2,2,6,6-tetramethyl-4-piperidyl)pyrrolidine-2,5-dione, 30 g of initiator azodiisobutyronitrile, 25 g of antioxidant 1010, 15 g of antioxidant 168, and 30 g of ultraviolet light absorber 5411 are extruded and pelletized through a twin-screw extruder; the temperature of the extruder is 180 - 225 °C, the temperature of the head is 220 °C, and the rotation speed of the extruder is 250 r / min;

[0063] Injection molding is carried out to form a composite decorative part, and the temperature of the injection molding machine is 225 °C.

[0064] Example 4

[0065] Compared with Example 1, for the unsaturated hindered, 4-methacryloyloxy-2,2,6,6-tetramethylpiperidine of equal mass is selected, and for the initiator, azodiisobutyronitrile of equal mass is selected; that is, the preparation of the composite decorative part in step (2):

[0066] 10 kg of ABS, 1.5 kg of modified glass fiber, 30 g of unsaturated hindered amine 4-methacryloyloxy-2,2,6,6-tetramethylpiperidine, 20 g of initiator azodiisobutyronitrile, 5.0 g of antioxidant 1010, 1.0 g of antioxidant 168, and 10 g of ultraviolet light absorber 5411 are extruded and pelletized through a twin-screw extruder; the temperature of the extruder is 180 - 225 °C, the temperature of the head is 220 °C, and the rotation speed of the extruder is 250 r / min; Injection molding is carried out to form a composite decorative part, and the temperature of the injection molding machine is 215 °C.

[0067] Step (1) is the same as that in Example 1 to obtain a composite decorative part.

[0068] Comparative Example 1

[0069] (1) Preparation of modified glass fiber:

[0070] 1.1. Place 2 kg of glass fiber in a vacuum drying oven at 80 °C and dry for 2 h, then place it in a 20 L ethanol solution of coupling agent and soak for 10 h; take it out, air dry, and place it in an oven at 80 °C to dry and volatilize the ethanol to obtain coupling-modified glass fiber;

[0071] In the ethanol solution of coupling agent, the volumes of γ-glycidoxypropyltrimethoxysilane and ethanol are 0.4 L:19.6 L in sequence;

[0072] 1.2. Take 3.0 g of 4-hydroxystyrene and 0.18 g of benzyltriethylammonium chloride, mix them, heat to 30 °C and stir to dissolve; add 2 kg of coupling-modified glass fiber, raise the temperature to 70 °C, and react for 4 h; cool to room temperature, wash with ethanol, and dry to constant weight to obtain modified glass fiber;

[0073] Step (2) is the same as that in Example 1 to obtain a composite decorative part.

[0074] Comparative Example 2

[0075] (1) Preparation of modified glass fiber:

[0076] 1.1. Place 2 kg of glass fiber in a vacuum drying oven at 80 °C for 2 h, then place it in a 20 L ethanol solution of coupling agent and soak for 10 h; take it out, air dry, and place it in an oven at 80 °C to dry and volatilize the ethanol to obtain coupling-modified glass fiber.

[0077] The volumes of γ-glycidoxypropyltrimethoxysilane and ethanol in the ethanol solution of coupling agent are 0.4 L:19.6 L in sequence.

[0078] 1.2. Take 5.8 g of 4,4'-dihydroxybenzophenone and 0.18 g of benzyltriethylammonium chloride, mix them, heat to 30 °C and stir to dissolve; add 2 kg of coupling-modified glass fiber, raise the temperature to 70 °C, and react for 4 h; cool to room temperature, wash with ethanol, and dry to constant weight to obtain phenol-modified glass fiber.

[0079] 1.3. Heat 20 kg of diphenyl sulfone to 130 °C to melt it, add 87 g of anhydrous potassium carbonate and 90 g of decafluorobiphenyl, stir under the protection of an argon atmosphere, slowly add 2 kg of phenol-modified glass fiber, add it within 20 min, raise the temperature to 140 °C, stir, and polymerize for 1.0 h; add 54 g of 4,4'-dihydroxybenzophenone and react for 2.0 h; filter while it is hot, wash with acetone and deionized water, and dry in a vacuum at 120 °C for 8 h to obtain modified glass fiber.

[0080] Step (2) is the same as that in Example 1 to obtain a composite decorative part.

[0081] Comparative Example 3

[0082] (1) Preparation of modified glass fiber:

[0083] Place 2 kg of glass fiber in a vacuum drying oven at 80 °C for 2 h, then place it in a 20 L ethanol solution of coupling agent and soak for 10 h; take it out, air dry, and place it in an oven at 80 °C to dry and volatilize the ethanol to obtain modified glass fiber.

[0084] The volumes of γ-glycidoxypropyltrimethoxysilane and ethanol in the ethanol solution of coupling agent are 0.4 L:19.6 L in sequence.

[0085] Step (2) is the same as that in Example 1 to obtain a composite decorative part.

[0086] Comparative Example 4

[0087] (2) Preparation of composite decorative part:

[0088] 10 kg of ABS, 1.5 kg of modified glass fiber, 20 g of initiator azobisisobutyronitrile, 5.0 g of antioxidant 1010, 1.0 g of antioxidant 168, and 10 g of ultraviolet absorber 5411 were extruded and pelletized through a twin-screw extruder; the temperature of the extruder was 180 - 225 °C, the temperature of the die head was 220 °C, and the rotational speed of the extruder was 250 r / min; injection molding was carried out to form a composite decorative part, and the temperature of the injection molding machine was 215 °C.

[0089] Step (1) was the same as Comparative Example 3 to obtain a composite decorative part.

[0090] Comparative Example 5

[0091] 10 kg of ABS, 1.5 kg of glass fiber, 5.0 g of antioxidant 1010, 1.0 g of antioxidant 168, and 10 g of ultraviolet absorber 5411 were extruded and pelletized through a twin-screw extruder; the temperature of the extruder was 180 - 225 °C, the temperature of the die head was 220 °C, and the rotational speed of the extruder was 250 r / min; injection molding was carried out to form a composite decorative part, and the temperature of the injection molding machine was 215 °C.

[0092] Experiment

[0093] The composite decorative parts obtained in Examples 1 - 4 and Comparative Examples 1 - 5 were taken to prepare specimens, and their properties were detected and the test results were recorded respectively:

[0094] The specimens were placed under the conditions of a temperature of 27 °C and a relative humidity of 60 RH% and kept at a constant temperature and humidity for 48 h;

[0095] Tensile strength: Referring to GB / T 1040, the tensile rate was 50 mm / min;

[0096] Flexural strength: Referring to GB / T 9341, the flexural rate was 2 mm / min;

[0097] Izod notched impact strength: Referring to GB / T 1843;

[0098] Weather resistance: Referring to GB / T 16422.2, the xenon lamp test conditions were: exposure cycle of 18 min with water spraying, irradiance of 0.51 W / m 2 (340 nm), and the test time was 1000 h;

[0099] Referring to GB / T 16422.3, the ultraviolet aging test time was 1000 h.

[0100] Table 1: Before aging

[0101]

[0102]

[0103] Table 2: After xenon lamp aging

[0104] Tensile strength (MPa) Flexural strength (MPa) <![CDATA[Impact strength (kJ / m 2 )]]> Example 1 80.4 116.09 10.6 Example 2 85.3 123.1 13.1 Example 3 88.0 127.0 14.6 Example 4 80.1 115.4 10.3 Comparative Example 1 76.6 110.1 8.7 Comparative Example 2 77.3 112.0 8.6 Comparative Example 3 72.5 108.5 7.4 Comparative Example 4 67.0 106.7 6.7 Comparative Example 5 63.6 103.5 6.1

[0105] Table 3: After ultraviolet aging

[0106]

[0107]

[0108] According to the data in the above table, the following conclusions can be clearly obtained:

[0109] The composite decorative parts obtained in Examples 1-4 are compared with the composite decorative parts obtained in Comparative Examples 1-5. From the test results,

[0110] Compared with the comparative examples, the composite decorative parts obtained in Examples 1-4 have higher tensile strength, flexural strength and impact strength data, and after xenon lamp aging and ultraviolet aging, the retention rates of tensile strength, flexural strength and impact strength are higher, which fully demonstrates that the present invention has achieved the improvement of the mechanical properties and weather resistance of the prepared composite decorative parts;

[0111] Compared with Example 1, the modified glass fiber in Comparative Example 1 does not have the components decafluorobiphenyl and 4,4'-dihydroxybenzophenone; the modified glass fiber in Comparative Example 2 does not have the component 4-fluorostyrene; the modified glass fiber in Comparative Example 3 is coupling-modified glass fiber; compared with Comparative Example 3, Comparative Example 4 does not have the component unsaturated hindered amine on the basis of Comparative Example 3; the composite decorative parts in Comparative Example 5 are made of ABS and glass fiber and do not have the components unsaturated hindered amine and initiator; for the composite decorative parts obtained in Comparative Examples 1-5, their tensile strength, flexural strength and impact strength data are deteriorated compared with Example 1, and after xenon lamp aging and ultraviolet aging, the retention rates of tensile strength, flexural strength and impact strength are reduced; it can be seen that the setting of the components and their processes of the prepared composite decorative parts in this application can promote the improvement of their mechanical properties and weather resistance.

[0112] It should be noted that in this article, relational terms such as first and second are only used to distinguish one entity or operation from another entity or operation, and do not necessarily require or imply any actual relationship or order between these entities or operations. Moreover, the term "comprises", "comprising" or any other variation thereof is intended to cover a non-exclusive inclusion, such that a process, method, article or device 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 device.

[0113] Finally, it should be noted that the above are only preferred embodiments of the present invention and are not intended to limit the present invention. Although the present invention has been described in detail with reference to the foregoing embodiments, those skilled in the art can still modify the technical solutions described in the foregoing embodiments, or perform equivalent replacements for some of the technical features. Any modifications, equivalent replacements, improvements, etc. made within the spirit and principle of the present invention shall be included within the protection scope of the present invention.

Claims

1. A preparation method of a highly weather-resistant ABS composite decorative part for automobiles, characterized in that: It includes the following processes: Extrude and pelletize ABS, glass fiber, unsaturated hindered amine, initiator, antioxidant, and ultraviolet light absorber through a twin-screw extruder; the temperature of the extruder is 180 - 225°C, the temperature of the head is 220°C, and the rotational speed of the extruder is 250 r / min; Injection mold to form a composite decorative part, and the temperature of the injection molding machine is 215 - 225°C; The glass fiber is surface-modified, specifically It includes the following processes: (1) Place the glass fiber in a vacuum drying oven at 80°C and dry for 2 - 3 h, then place it in a coupling agent ethanol solution and soak for 10 - 15 h to obtain coupling-modified glass fiber; (2) Take 4,4'-dihydroxybenzophenone and benzyltriethylammonium chloride, mix them, heat to 30 - 60°C and stir to dissolve; add the coupling-modified glass fiber, raise the temperature to 70 - 80°C, and react for 4 - 5 h to obtain phenol-modified glass fiber; (3) Heat diphenyl sulfone to 130 - 135°C to melt it, add potassium carbonate anhydrous and decafluorobiphenyl, stir under argon atmosphere protection, slowly add the phenol-modified glass fiber, add it within 20 - 30 min, raise the temperature to 140 - 145°C, stir, and polymerize for 1.0 - 2.0 h; add 4,4'-dihydroxybenzophenone and react for 2.0 - 3.0 h; add 4-fluorostyrene and continue to react for 1.5 - 2.5 h to obtain modified glass fiber.

2. The preparation method of a highly weather-resistant ABS composite decorative part for automobiles according to claim 1, characterized in that: The decorative part includes the following weight components: 85 - 100 parts of ABS, 15 - 18 parts of glass fiber, 0.3 - 0.5 parts of unsaturated hindered amine, 0.2 - 0.3 parts of initiator, 0.06 - 0.4 parts of antioxidant, and 0.1 - 0.3 parts of ultraviolet light absorber.

3. The preparation method of a highly weather-resistant ABS composite decorative part for automobiles according to claim 2, characterized in that: The antioxidant includes 0.05 - 0.25 parts of antioxidant 1010 and 0.01 - 0.15 parts of antioxidant 168; the ultraviolet light absorber is ultraviolet light absorber 5411.

4. The preparation method of a highly weather-resistant ABS composite decorative part for an automobile according to claim 2, characterized in that: The unsaturated hindered amine is one of 4-acryloyloxy-1,2,2,6,6-pentamethylpiperidine, 4-methacryloyloxy-1,2,2,6,6-pentamethylpiperidine, 4-methacryloyloxy-2,2,6,6-tetramethylpiperidine, 4-acryloyloxy-2,2,6,6-tetramethylpiperidine, 3-(2-dodecenyl)-1-(2,2,6,6-tetramethyl-4-piperidyl)pyrrolidine-2,5-dione.

5. The preparation method of a highly weather-resistant ABS composite decorative part for automobiles according to claim 2, characterized in that: The initiator is one of azobisisobutyronitrile and azodiisovaleronitrile.

6. The preparation method of a highly weather-resistant ABS composite decorative part for an automobile according to claim 1, characterized in that: In the coupling agent ethanol solution, the volume ratio of γ-glycidoxypropyltrimethoxysilane to ethanol is (2.0 - 3.0):(97 - 98).

7. According to the preparation method of a high weather-resistant ABS composite decorative part for automobiles described in claim 1, it is characterized in that: The mass ratio of the coupling-modified glass fiber, 4,4'-dihydroxybenzophenone, and benzyltriethylammonium chloride is 100:(0.29 - 0.49):(0.009 - 0.015).

8. The preparation method of a highly weather-resistant ABS composite decorative part for automobiles according to claim 1, characterized in that: The mass ratio of the phenol-modified glass fiber, decafluorobiphenyl, 4,4'-dihydroxybenzophenone, and 4-fluorostyrene is 100:(0.45 - 0.76):(0.27 - 0.45):(0.17 - 0.28).

9. An automotive high-weather-resistant ABS composite decorative part prepared by the preparation method according to any one of claims 1-8.

Images