Material putty for vehicle body and preparation method thereof
By using self-made air-drying and ultra-flexible unsaturated polyester resins and functional diluting crosslinking agents, a body filler with good mechanical properties and temperature change resistance was prepared, which solved the problem of the fragility of existing body fillers under vibration and hot and cold environments, and reduced the environmental pollution of styrene.
Patent Information
- Application Number
- CN202511343923.1
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2025-09-19
- Publication Date
- 2025-12-02
AI Technical Summary
Existing body filler is prone to bubbling, cracking, and peeling off in large pieces under prolonged vibration or alternating hot and cold external environments. Furthermore, the use of styrene-based substances in traditional putty products poses a threat to the environment and health.
Using self-made air-drying unsaturated polyester resin and ultra-flexible unsaturated polyester resin as raw materials, combined with functional diluent crosslinking agents, nano-alumina particles, etc., atomic putty is prepared through specific proportions and processes to reduce the use of styrene and improve the flexibility and heat resistance of the material.
It improves the mechanical properties and temperature resistance of putty, reduces the environmental pollution caused by styrene volatilization, enhances the toughness and impact resistance of the material, and reduces health hazards.
Smart Images
Figure SMS_1
Abstract
Description
Technical Field
[0001] This invention relates to the field of coating materials technology, specifically to an atomized putty for automotive bodies and its preparation method. Background Technology
[0002] Putty, typically a two-component product, uses unsaturated polyester resin as the base material, combined with crosslinking diluents, polymerization inhibitors, accelerators, fillers, and other additives to form the main putty, and curing agents and activators as auxiliary putties. Due to its advantages such as thick application, rapid curing, and easy sanding, it is currently a very active and rapidly developing filler material both domestically and internationally. It is also considered an ideal filler material. Nowadays, putty is used in many aspects such as interior and exterior wall decoration, home building materials production and installation, automobile manufacturing and repair, and caulking and filling of metal and non-metal materials. With the continuous development of my country's automobile industry, the application of putty in the vehicle manufacturing field is becoming increasingly widespread.
[0003] During vehicle operation, the paint on the car body is subjected to prolonged vibration and alternating temperature changes in the external environment. Therefore, the materials used for the car body must have good flexibility and resistance to temperature changes. Current putty products will blister, crack, and peel off in large pieces when subjected to prolonged vibration or alternating temperature changes. Furthermore, traditional putty products require the addition of diluents such as styrene, methylstyrene, or other vinyl derivatives of benzene during the preparation process. The amount of these products usually exceeds 30%. The vapor pressure of these styrene products is high at room temperature, making them highly volatile. They also have a pungent odor and are irritating to the eyes and upper respiratory tract mucosa. Their volatility and toxic side effects pose a great threat to the environment and the health of operators.
[0004] Therefore, improving the quality of existing putty products and developing a solution for putty materials for car bodies that have good mechanical properties, temperature resistance, and are environmentally friendly are urgent problems to be solved. Summary of the Invention
[0005] The technical problem to be solved by the present invention is to overcome the shortcomings of the prior art and provide an atomic putty material for vehicle bodies and its preparation method.
[0006] The technical solution provided by this invention can, to a certain extent, overcome the defects of the putty provided by the prior art.
[0007] To achieve the above objectives, the following technical solution is adopted:
[0008] A body filler material for automotive bodies, characterized in that it comprises component A and component B, wherein the weight ratio of each raw material in component A is:
[0009] Air-drying unsaturated polyester resin: 10-15 parts
[0010] Super-flexible unsaturated polyester resin: 20-25 parts
[0011] Functional diluted crosslinking agent: 5-10 parts
[0012] Defoamer: 0.1-0.3 parts
[0013] Talc powder: 20-40 parts
[0014] Titanium dioxide: 10-20 parts
[0015] Stabilizer: 0.5-1 part
[0016] Dispersant: 0.2-1.2 parts
[0017] Leveling agent: 0.6-1.6 parts
[0018] Cobalt isooctanoate: 0.1-0.5 parts
[0019] Polymerization inhibitor: 0.1-0.5 parts
[0020] The weight ratio of each raw material in component B is:
[0021] 15-30 parts of peroxide
[0022] 5-10 parts of fumed silica
[0023] The weight ratio of component A to component B is 100:1.5-3.
[0024] This invention also provides a method for preparing body filler for automotive materials, the preparation of which includes the following steps:
[0025] 1) Weigh each raw material component according to the above proportions;
[0026] 2) Weigh out the air-drying unsaturated polyester resin, the ultra-flexible unsaturated polyester resin and the polymerization inhibitor and add them to a high-speed disperser in sequence. Then add cobalt isooctanoate and mix at a speed of 300-400 r / min. Control the temperature at 70-80℃ and react for 2-3 hours. Then add the dispersant, leveling agent and defoamer respectively and mix at a speed of 500-600 r / min for 1-2 hours. Add part of the functional diluent crosslinking agent and stabilizer, then add talc and titanium dioxide and stir at a speed of 600-640 r / min for 2-3 hours. Finally, add the remaining part of the functional diluent crosslinking agent, increase the disperser speed to 1000-1400 r / min and stir for 1-2 hours. After standing for 0.5-1 hours, the atomic main ash component A is obtained.
[0027] 3) Add the weighed peroxide and fumed silica to the above-mentioned atomic putty component A, and stir for 2-5 hours to mix evenly to obtain the atomic putty for vehicle body materials.
[0028] Preferably, the preparation of the air-drying unsaturated polyester resin includes the following raw materials: 40-55 parts of phthalic anhydride, 5-10 parts of tetrahydrophthalic anhydride, 10-20 parts of maleic anhydride, 10-20 parts of neopentyl glycol, 10-20 parts of hexanediol, 20-30 parts of triethylene glycol, 10-20 parts of hydroquinone, 10-25 parts of phosphoric acid, 5-10 parts of sugar alcohol allyl ether, and 1-10 parts of hydroxyethyl methacrylate.
[0029] Preferably, the preparation process of the air-drying unsaturated polyester resin includes the following steps:
[0030] 1) Add tetrahydrophthalic anhydride, phthalic anhydride, hexanediol, neopentyl glycol, triethylene glycol and part of phosphoric acid to the reaction vessel in the required amounts. Raise the temperature to 150-200℃ and stir and heat for 2-5 hours. When the acid value of the reaction system reaches 45-50 mg KOH / g, cool down to 130℃.
[0031] 2) Add maleic anhydride and continue the reaction at 150-200 °C for 2-5 h. When the acid value of the system is less than 120 mg KOH / g, cool down to 130 °C, evacuate for 5 min, add sugar alcohol allyl ether and the remaining phosphoric acid, then purge with nitrogen for 5 min, and react at 150-200 °C for 2-5 h. The reaction ends when the acid value of the system is less than 40 mg KOH / g.
[0032] 3) Cool down to 130 ℃, evacuate for 5 min, then add hydroquinone and stir for 5 min; cool down to 60 ℃, add hydroxyethyl methacrylate and N,N-dimethyl-p-nitrosoaniline, stir for 20 min, and obtain an air-drying unsaturated polyester resin sample.
[0033] Preferably, the sugar alcohol allyl ether is sorbitol allyl ether and / or xylitol allyl ether.
[0034] Sugar alcohol allyl ethers contain allyl ether bonds, which are prone to hydrogen abstraction reactions by peroxide free radicals. This allows the resin to absorb oxygen from the air, and its double bonds can react with oxygen to produce peroxides. These peroxides can then decompose into free radicals under the action of an initiator, prompting the allyl ether to initiate a free radical polymerization reaction between the unsaturated double bonds in the polyester and the curing agent. This results in the resin having air-drying properties. Furthermore, sugar alcohol allyl ethers can provide multiple allyl ether bonds, resulting in high crosslinking density, faster drying, and higher film hardness.
[0035] Preferably, the preparation of the ultra-flexible unsaturated polyester resin includes the following raw materials:
[0036] 25-45 parts of long-chain aliphatic diols, 20-30 parts of long-chain linear dicarboxylic acids, 15-20 parts of maleic anhydride, 1-5 parts of polymerization inhibitor, 1-5 parts of catalyst, 10-20 parts of nano-alumina modified with silane coupling agent KH-560, and 10-30 parts of functional diluent crosslinking agent.
[0037] Preferably, the long-chain aliphatic diol is one or more of diethylene glycol, dipropylene glycol, and neopentyl glycol.
[0038] The ether bonds or side methyl groups of these alcohols provide rotational freedom for the chain segments, which can significantly enhance the flexibility and impact resistance of polymer materials when used as raw materials for polymer synthesis.
[0039] The general structural formula for long-chain linear dicarboxylic acids is: HOOC-(CH2) n -COOH, where n≥13, can be, for example, hexadecanoic acid and / or pentadecanoic acid.
[0040] The aforementioned long-chain linear dicarboxylic acids all possess relatively long methylene sequences, which can serve as flexible spacers, providing excellent flexibility and internal rotational freedom, thereby effectively improving the impact resistance and flexibility of polymer materials.
[0041] The functional diluting crosslinking agent is a compound of epoxidized vegetable oil acrylate and styrene in a mass ratio of 2:1. The epoxidized vegetable oil acrylate includes one or more of epoxidized soybean oil acrylate, epoxidized linseed oil acrylate, epoxidized castor oil acrylate, and epoxidized rapeseed oil acrylate.
[0042] Epoxidized vegetable oil acrylates have a large molecular weight and extremely low volatility. Using them to partially replace styrene can reduce the environmental pollution caused by styrene volatilization. Epoxidized vegetable oil acrylates are derived from vegetable oils, which can reduce dependence on petroleum resources and are environmentally friendly. Their long fatty acid chains are natural flexible segments. As a crosslinking agent, partially replacing styrene can reduce the impact of styrene on the brittleness of polymer materials. Their long fatty acid chain structure acts as a "built-in" toughening agent, which can significantly improve the toughness, impact resistance and elongation of the cured material and reduce brittle cracking. The polar ester bonds and possibly remaining hydroxyl groups in the molecule help to form good adhesion to a variety of substrates (especially metals).
[0043] Nano-alumina particles have a large specific surface area and form a strong interfacial interaction with the resin matrix. When the material is subjected to stress, nano-alumina particles can effectively transfer and disperse the stress without significantly reducing the modulus and heat resistance. Treatment with silane coupling agents ensures good dispersion and interfacial compatibility of the nanoparticles.
[0044] Preferably, the catalyst is benzyltrimethylammonium chloride, benzyltriethylammonium chloride, tetrabutylammonium chloride, or dodecyltrimethylammonium chloride; and the polymerization inhibitor is hydroquinone, methylhydroquinone, p-tert-butylcatechol, or p-benzoquinone.
[0045] The preparation of the ultra-flexible unsaturated polyester resin includes the following steps:
[0046] 1) Under a nitrogen atmosphere, mix long-chain aliphatic diols, long-chain linear dicarboxylic acids, maleic anhydride, and a portion of polymerization inhibitor (30%-40% of the total amount), and reflux at 150-200℃ until the acid value reaches 20-30 mg KOH / g.
[0047] 2) Cool down to 140-160℃, add 1-5 parts of catalyst, nano-alumina modified with silane coupling agent KH-560 and the remaining polymerization inhibitor, react in a vacuum of 0.05-0.1MPa and 150-180℃ for 3-7 hours, then cool down to 100-130℃, add functional diluent crosslinking agent, and stir evenly to obtain ultra-flexible unsaturated polyester resin.
[0048] Preferably, the peroxide is benzoyl peroxide, ethyl peroxide, or diisopropylbenzene peroxide.
[0049] Preferably, the dispersant is a high molecular weight unsaturated polycarboxylic acid solution of organically modified polysiloxane.
[0050] Preferably, the stabilizer is one or more of polyvinylpyrrolidone, polyvinyl alcohol, and polyethylene glycol;
[0051] Preferably, the leveling agent is an acrylate leveling agent.
[0052] The beneficial effects of this invention are as follows:
[0053] 1. This invention uses self-made air-drying unsaturated polyester resin and ultra-flexible unsaturated polyester resin as raw materials for putty. The self-made air-drying unsaturated polyester resin increases the air-drying property of the resin and improves the crosslinking density of the polymer by using sugar alcohol allyl ether, which makes the paint film dry faster and has higher hardness. The ultra-flexible unsaturated polyester resin synthesized based on long-chain aliphatic diols and long-chain linear dicarboxylic acids can effectively improve the impact resistance and flexibility of polymer materials.
[0054] 2. This invention uses a functional diluent crosslinking agent to partially replace styrene, greatly reducing the environmental pollution caused by styrene volatilization, while retaining the excellent solubility and rigidity that styrene brings to the material. By using epoxidized vegetable oil acrylate as a functional diluent crosslinking agent, it can reduce dependence on petroleum resources, making it green and environmentally friendly. Its long oil and fat chains are natural flexible segments. Using it as a crosslinking agent to partially replace styrene can reduce the impact of styrene on the brittleness of polymer materials, and can also significantly improve the toughness, impact resistance and elongation of the cured material, reducing brittle cracking. The polar ester bonds and possibly remaining hydroxyl groups in the molecule help to form good adhesion to various substrates (especially metals). By adding nano alumina particles, the heat resistance and mechanical strength of the material can be improved to compensate for the reduced heat resistance and rigidity brought by styrene.
[0055] Additional aspects and advantages of the invention will be set forth in part in the description which follows, and will become apparent from the description or may be learned by means of the embodiments thereof. Detailed Implementation
[0056] To make the objectives, technical solutions, and advantages of the embodiments of the present invention clearer, the technical solutions of the embodiments of the present invention will be clearly and completely described below in conjunction with the embodiments of the present invention. Obviously, the described embodiments are only some embodiments of the present invention, and not all embodiments. Other embodiments obtained by those skilled in the art without inventive step are all within the scope of protection of the present invention.
[0057] In the embodiments and comparative examples of this invention, the peroxide is benzoyl peroxide.
[0058] In the embodiments and comparative examples of this invention, the dispersant is a high molecular weight unsaturated polycarboxylic acid solution of organically modified polysiloxane.
[0059] In the embodiments and comparative examples of this invention, the stabilizer is polyvinyl alcohol; the catalyst is benzyltrimethylammonium chloride; the polymerization inhibitor is methylhydroquinone; the leveling agent is acrylate leveling agent; the long-chain linear dicarboxylic acid is hexadecanoic acid; and the long-chain aliphatic acid is diethylene glycol and dipropylene glycol.
[0060] In the embodiments and comparative examples of the present invention, the functional diluting crosslinking agent is a compound of epoxidized vegetable oil acrylate and styrene in a mass ratio of 2:1, and the epoxidized vegetable oil acrylate is epoxidized soybean oil acrylate.
[0061] Unless otherwise specified, all raw materials used in the embodiments and comparative examples of this invention are commercially available conventional industrial products.
[0062] Example 1:
[0063] A body filler material for automotive bodies comprises component A and component B, wherein the weight ratio of the raw materials in component A is:
[0064] Air-drying unsaturated polyester resin: 10 parts
[0065] Super-flexible unsaturated polyester resin: 20 parts
[0066] Functional diluted crosslinking agent: 8 parts
[0067] Defoamer: 0.1 parts
[0068] Talc powder: 30 parts
[0069] Titanium dioxide: 10 parts
[0070] Stabilizer: 0.5 parts
[0071] Dispersant: 0.5 parts
[0072] Leveling agent: 0.6 parts
[0073] Cobalt isooctanoate: 0.5 parts
[0074] Polymerization inhibitor: 0.5 parts
[0075] The weight ratio of each raw material in component B is:
[0076] 20 parts of peroxide
[0077] 5 parts of fumed silica
[0078] The weight ratio of component A to component B is 100:2.
[0079] This invention also provides a method for preparing body filler for automotive materials, the preparation of which includes the following steps:
[0080] 1) Weigh each raw material component according to the above proportions;
[0081] 2) The weighed air-drying unsaturated polyester resin, ultra-flexible unsaturated polyester resin, and polymerization inhibitor were added sequentially to a high-speed disperser. Cobalt isooctanoate was then added, and the mixture was stirred at 400 rpm for 3 hours, with the temperature controlled at 80°C. Dispersant, leveling agent, and defoamer were then added, and the mixture was stirred at 600 rpm for 2 hours. A portion of the functional diluted crosslinking agent (30%-40% of the total amount) and stabilizer were added, followed by talc and titanium dioxide. The mixture was stirred at 600 rpm for 3 hours. Finally, the remaining functional diluted crosslinking agent was added, and the disperser speed was increased to 1400 rpm for 2 hours. After standing for 0.5 hours, the atomic-grade ash component A was obtained.
[0082] 3) Add the weighed peroxide and fumed silica to the above-mentioned atomic putty component A, stir for 2 hours to mix evenly to obtain the atomic putty for the car body material.
[0083] The preparation of air-drying unsaturated polyester resin includes the following raw materials: 5 parts phthalic anhydride, 10 parts tetrahydrophthalic anhydride, 20 parts maleic anhydride, 20 parts neopentyl glycol, 10 parts hexanediol, 30 parts triethylene glycol, 20 parts hydroquinone, 25 parts phosphoric acid, 10 parts sugar alcohol allyl ether, and 5 parts hydroxyethyl methacrylate.
[0084] The preparation process of air-drying unsaturated polyester resin includes the following steps:
[0085] 1) Add tetrahydrophthalic anhydride, phthalic anhydride, hexanediol, neopentyl glycol, triethylene glycol and part of phosphoric acid (20%-30% of the total amount) to the reaction vessel in the required amount, raise the temperature to 200℃ and stir and heat for 5 h, and when the acid value of the reaction system reaches 50 mg KOH / g, lower the temperature to 130℃.
[0086] 2) Add maleic anhydride and continue the reaction at 200 °C for 5 h. When the acid value of the system is less than 120 mgKOH / g, cool down to 130 °C, evacuate for 5 min, add sugar alcohol allyl ether and the remaining phosphoric acid, then purge with nitrogen for 5 min, and react at 200 °C for 5 h. When the acid value of the system is less than 40 mgKOH / g, the reaction ends.
[0087] 3) Cool down to 130 ℃, evacuate for 5 min, then add hydroquinone and stir for 5 min; cool down to 60 ℃, add hydroxyethyl methacrylate and N,N-dimethyl-p-nitrosoaniline, stir for 20 min, and obtain an air-drying unsaturated polyester resin sample.
[0088] The preparation of ultra-flexible unsaturated polyester resin includes the following raw materials:
[0089] 45 parts of long-chain aliphatic diols, 30 parts of long-chain linear dicarboxylic acids, 20 parts of maleic anhydride, 4 parts of polymerization inhibitor, 3 parts of catalyst, 20 parts of nano-alumina modified with silane coupling agent KH-560, and 20 parts of functional diluent crosslinking agent.
[0090] The preparation of ultra-flexible unsaturated polyester resin includes the following steps:
[0091] 1) Under a nitrogen atmosphere, mix long-chain aliphatic diols, long-chain linear dicarboxylic acids, maleic anhydride, and a portion of polymerization inhibitor (30%-40% of the total amount), and reflux at 150°C until the acid value reaches 30 mg KOH / g.
[0092] 2) Cool down to 160℃, add catalyst, nano-alumina modified by silane coupling agent KH-560 and the remaining polymerization inhibitor, react in a vacuum of 0.1MPa and 180℃ for 5h, then cool down to 120℃, add functional diluent crosslinking agent, stir evenly to obtain ultra-flexible unsaturated polyester resin.
[0093] Example 2:
[0094] A body filler material for automotive bodies, characterized in that it comprises component A and component B, wherein the weight ratio of each raw material in component A is:
[0095] Air-drying unsaturated polyester resin: 12 parts
[0096] Super-flexible unsaturated polyester resin: 22 parts
[0097] Functional diluted crosslinking agent: 10 parts
[0098] Defoamer: 0.2 parts
[0099] Talc powder: 25 parts
[0100] Titanium dioxide: 15 parts
[0101] Stabilizer: 0.5 parts
[0102] Dispersant: 0.3 parts
[0103] Leveling agent: 0.6 parts
[0104] Cobalt isooctanoate: 0.5 parts
[0105] Polymerization inhibitor: 0.3 parts
[0106] The weight ratio of each raw material in component B is:
[0107] 25 parts of peroxide
[0108] 5 parts of fumed silica
[0109] The weight ratio of component A to component B is 100:1.9.
[0110] This invention also provides a method for preparing body filler for automotive materials, the preparation of which includes the following steps:
[0111] 1) Weigh each raw material component according to the above proportions;
[0112] 2) The weighed air-drying unsaturated polyester resin, ultra-flexible unsaturated polyester resin, and polymerization inhibitor were sequentially added to a high-speed disperser. Cobalt isooctanoate was then added, and the mixture was stirred at 350 rpm for 3 hours, with the temperature controlled at 80°C. Dispersant, leveling agent, and defoamer were then added, and the mixture was stirred at 600 rpm for 2 hours. A portion of the functional diluted crosslinking agent (30%-40% of the total amount) and stabilizer were added, followed by talc and titanium dioxide. The mixture was stirred at 640 rpm for 3 hours. Finally, the remaining functional diluted crosslinking agent was added, and the disperser speed was increased to 1000 rpm for 2 hours of stirring. After standing for 1 hour, the atomic-grade ash component A was obtained.
[0113] 3) Add the weighed peroxide and fumed silica to component A of the atomic putty, stir for 5 hours to mix evenly, and the atomic putty for the car body material is obtained.
[0114] The preparation of air-drying unsaturated polyester resin includes the following raw materials: 55 parts phthalic anhydride, 10 parts tetrahydrophthalic anhydride, 15 parts maleic anhydride, 10 parts neopentyl glycol, 20 parts hexanediol, 20 parts triethylene glycol, 20 parts hydroquinone, 25 parts phosphoric acid, 10 parts sugar alcohol allyl ether, and 10 parts hydroxyethyl methacrylate.
[0115] Preferably, the preparation process of the air-drying unsaturated polyester resin includes the following steps:
[0116] 1) Add tetrahydrophthalic anhydride, phthalic anhydride, hexanediol, neopentyl glycol, triethylene glycol and part of phosphoric acid (30%-40% of the total amount) to the reaction vessel in the required amount, raise the temperature to 180℃ and stir and heat for 5 h. When the acid value of the reaction system reaches 50 mg KOH / g, lower the temperature to 130℃.
[0117] 2) Add maleic anhydride and continue the reaction at 200 °C for 5 h. When the acid value of the system is less than 120 mgKOH / g, cool down to 130 °C, evacuate for 5 min, add sugar alcohol allyl ether and the remaining phosphoric acid, then purge with nitrogen for 5 min, and react at 180 °C for 5 h. When the acid value of the system is less than 40 mgKOH / g, the reaction ends.
[0118] 3) Cool down to 130 ℃, evacuate for 5 min, then add hydroquinone and stir for 5 min; cool down to 60 ℃, add hydroxyethyl methacrylate and N,N-dimethyl-p-nitrosoaniline, stir for 20 min, and obtain an air-drying unsaturated polyester resin sample.
[0119] The preparation of ultra-flexible unsaturated polyester resin includes the following raw materials:
[0120] 45 parts of long-chain aliphatic diols, 30 parts of long-chain linear dicarboxylic acids, 20 parts of maleic anhydride, 3 parts of polymerization inhibitor, 2 parts of catalyst, 20 parts of nano-alumina modified with silane coupling agent KH-560, and 15 parts of functional diluent crosslinking agent.
[0121] The preparation of ultra-flexible unsaturated polyester resin includes the following steps:
[0122] 2) Under a nitrogen atmosphere, mix long-chain aliphatic diols, long-chain linear dicarboxylic acids, maleic anhydride, and a portion of the polymerization inhibitor (30%-40% of the total amount), and reflux at 200°C until the acid value reaches 30 mg KOH / g.
[0123] The temperature was lowered to 140℃, and 4 parts of catalyst, nano-alumina modified with silane coupling agent KH-560 and the remaining polymerization inhibitor were added. The mixture was reacted at 180℃ under vacuum of 0.1MPa for 7 hours. The temperature was then lowered to 130℃, and a functional diluent crosslinking agent was added. The mixture was stirred until homogeneous to obtain an ultra-flexible unsaturated polyester resin.
[0124] Example 3
[0125] A body filler material for automotive bodies comprises component A and component B, wherein the weight ratio of the raw materials in component A is:
[0126] Air-drying unsaturated polyester resin: 14 parts
[0127] Super-flexible unsaturated polyester resin: 22 parts
[0128] Functional diluted crosslinking agent: 9 parts
[0129] Defoamer: 0.1 parts
[0130] Talc powder: 20 parts
[0131] Titanium dioxide: 20 parts
[0132] Stabilizer: 0.5 parts
[0133] Dispersant: 0.2 parts
[0134] Leveling agent: 0.6 parts
[0135] Cobalt isooctanoate: 0.3 parts
[0136] Polymerization inhibitor: 0.4 parts
[0137] The weight ratio of each raw material in component B is:
[0138] 30 parts peroxide
[0139] 10 parts of fumed silica
[0140] The weight ratio of component A to component B is 100:2.2.
[0141] This invention also provides a method for preparing body filler for automotive materials, the preparation of which includes the following steps:
[0142] 1) Weigh each raw material component according to the above proportions;
[0143] 2) The weighed air-drying unsaturated polyester resin, ultra-flexible unsaturated polyester resin and polymerization inhibitor were added to a high-speed disperser in sequence, and then cobalt isooctanoate was added. The mixture was stirred at 380 rpm and the temperature was controlled at 80 ℃ for 3 hours. Then, dispersant, leveling agent and defoamer were added and stirred at 600 rpm for 2 hours. A portion of functional diluent crosslinking agent (30%-40% of the total amount) and stabilizer were added. Talc powder and titanium dioxide were added and stirred at 640 rpm for 3 hours. Finally, the remaining portion of functional diluent crosslinking agent was added, and the disperser speed was increased to 1200 rpm and stirred for 2 hours. After standing for 1 hour, the atomic main ash component A was obtained.
[0144] 3) Add the weighed peroxide and fumed silica to the above-mentioned atomic putty component A, stir for 5 hours to mix evenly to obtain the atomic putty for the car body material.
[0145] The preparation of air-drying unsaturated polyester resin includes the following raw materials: 45 parts phthalic anhydride, 8 parts tetrahydrophthalic anhydride, 13 parts maleic anhydride, 14 parts neopentyl glycol, 15 parts hexanediol, 26 parts triethylene glycol, 14 parts hydroquinone, 20 parts phosphoric acid, 8 parts sugar alcohol allyl ether, and 6 parts hydroxyethyl methacrylate.
[0146] The preparation process of air-drying unsaturated polyester resin includes the following steps:
[0147] 1) Add tetrahydrophthalic anhydride, phthalic anhydride, hexanediol, neopentyl glycol, triethylene glycol and part of phosphoric acid (30%-40% of the total amount) to the reaction vessel in the required amounts. Raise the temperature to 180℃ and stir and heat for 3 h. When the acid value of the reaction system reaches 50 mg KOH / g, cool down to 130℃.
[0148] 2) Add maleic anhydride and continue the reaction at 180 °C for 4 h. When the acid value of the system is less than 120 mgKOH / g, cool down to 130 °C, evacuate for 5 min, add sugar alcohol allyl ether and the remaining phosphoric acid, then purge with nitrogen for 5 min, and react at 180 °C for 4 h. When the acid value of the system is less than 40 mgKOH / g, the reaction ends.
[0149] 3) Cool down to 130 ℃, evacuate for 5 min, then add hydroquinone and stir for 5 min; cool down to 60 ℃, add hydroxyethyl methacrylate and N,N-dimethyl-p-nitrosoaniline, stir for 20 min, and obtain an air-drying unsaturated polyester resin sample.
[0150] The preparation of ultra-flexible unsaturated polyester resin includes the following raw materials:
[0151] 30 parts of long-chain aliphatic diol, 25 parts of long-chain linear dicarboxylic acid, 18 parts of maleic anhydride, 1 part of polymerization inhibitor, 1 part of catalyst, 15 parts of nano-alumina modified with silane coupling agent KH-560, and 18 parts of functional diluent crosslinking agent.
[0152] The preparation of ultra-flexible unsaturated polyester resin includes the following steps:
[0153] 3) Under a nitrogen atmosphere, mix long-chain aliphatic diols, long-chain linear dicarboxylic acids, maleic anhydride, and a portion of the polymerization inhibitor (30%-40% of the total amount), and reflux at 180°C until the acid value reaches 25 mg KOH / g.
[0154] The temperature was lowered to 150℃, and a catalyst, nano-alumina modified with silane coupling agent KH-560, and the remaining polymerization inhibitor were added. The mixture was reacted at 180℃ under vacuum of 0.1MPa for 3 hours, then the temperature was lowered to 100℃, and a functional diluent crosslinking agent was added. The mixture was stirred until homogeneous to obtain an ultra-flexible unsaturated polyester resin.
[0155] Comparative Example 1
[0156] As a comparative example of the present invention, the only difference between Comparative Example 1 and Example 1 is that no ultra-flexible unsaturated polyester resin is added in Comparative Example 1, and 30 parts of air-drying unsaturated polyester resin are added. All other steps are the same.
[0157] Comparative Example 2:
[0158] As a comparative example of the present invention, Comparative Example 2 differs from Example 1 only in that air-drying unsaturated polyester resin is not added in Comparative Example 1, and 30 parts of ultra-flexible unsaturated polyester resin are added; the other steps are the same.
[0159] Comparative Example 3:
[0160] A body filler material for automotive bodies, characterized in that it comprises component A and component B, wherein the weight ratio of each raw material in component A is:
[0161] Air-drying unsaturated polyester resin: 12 parts
[0162] Super-flexible unsaturated polyester resin: 22 parts
[0163] Styrene: 10 parts
[0164] Defoamer: 0.2 parts
[0165] Talc powder: 25 parts
[0166] Titanium dioxide: 15 parts
[0167] Stabilizer: 0.5 parts
[0168] Dispersant: 0.3 parts
[0169] Leveling agent: 0.6 parts
[0170] Cobalt isooctanoate: 0.5 parts
[0171] Polymerization inhibitor: 0.3 parts
[0172] The weight ratio of each raw material in component B is:
[0173] 25 parts of peroxide
[0174] 5 parts of fumed silica
[0175] The weight ratio of component A to component B is 100:1.9.
[0176] A method for preparing body filler for automotive bodies, comprising the following steps:
[0177] 1) Weigh each raw material component according to the above proportions.
[0178] 2) The weighed air-drying unsaturated polyester resin, ultra-flexible unsaturated polyester resin and polymerization inhibitor were added to a high-speed disperser in sequence, and then cobalt isooctanoate was added. The mixture was stirred at 350 r / min and the temperature was controlled at 80℃ for 3 h. Then the dispersant, leveling agent and defoamer were added respectively, and the mixture was stirred at 600 r / min for 2 h. Then some styrene and stabilizer were added, and then talc powder and titanium dioxide were added. The mixture was stirred at 640 r / min for 3 h. Finally, the remaining styrene was added, and the disperser speed was increased to 1000 r / min and stirred for 2 h. After standing for 1 h, the atomic gray component A was obtained.
[0179] 3) Add the weighed peroxide and fumed silica to the above-mentioned atomic putty component A, and stir for 5 hours to mix evenly to obtain the atomic putty for vehicle body materials.
[0180] The preparation of air-drying unsaturated polyester resin includes the following raw materials: 55 parts phthalic anhydride, 10 parts tetrahydrophthalic anhydride, 15 parts maleic anhydride, 10 parts neopentyl glycol, 20 parts hexanediol, 20 parts triethylene glycol, 20 parts hydroquinone, 25 parts phosphoric acid, 10 parts sugar alcohol allyl ether, and 10 parts hydroxyethyl methacrylate.
[0181] The preparation process of air-drying unsaturated polyester resin includes the following steps:
[0182] 1) Add tetrahydrophthalic anhydride, phthalic anhydride, hexanediol, neopentyl glycol, triethylene glycol and part of phosphoric acid to the reaction vessel in the required amounts. Raise the temperature to 180°C and stir and heat for 5 h. When the acid value of the reaction system reaches 50 mg KOH / g, cool down to 130°C.
[0183] 2) Add maleic anhydride and continue the reaction at 200 °C for 5 h. When the acid value of the system is less than 120 mgKOH / g, cool down to 130 °C, evacuate for 5 min, add sugar alcohol allyl ether and the remaining phosphoric acid, then purge with nitrogen for 5 min, and react at 180 °C for 5 h. When the acid value of the system is less than 40 mgKOH / g, the reaction ends.
[0184] 3) Cool down to 130 ℃, evacuate for 5 min, then add hydroquinone and stir for 5 min; cool down to 60 ℃, add hydroxyethyl methacrylate and N,N-dimethyl-p-nitrosoaniline, stir for 20 min, and obtain an air-drying unsaturated polyester resin sample.
[0185] The preparation of ultra-flexible unsaturated polyester resin includes the following raw materials:
[0186] 45 parts of long-chain aliphatic diols, 30 parts of long-chain linear dicarboxylic acids, 20 parts of maleic anhydride, 3 parts of polymerization inhibitor, 2 parts of catalyst, 20 parts of nano-alumina modified with silane coupling agent KH-560, and 15 parts of styrene.
[0187] The preparation of ultra-flexible unsaturated polyester resin includes the following steps:
[0188] 2) Under a nitrogen atmosphere, a mixture of long-chain aliphatic diol, long-chain linear dicarboxylic acid, maleic anhydride, and a portion of the polymerization inhibitor is refluxed at 200°C until the acid value reaches 30 mg KOH / g.
[0189] The temperature was lowered to 140℃, and 4 parts of catalyst, nano-alumina modified with silane coupling agent KH-560 and the remaining polymerization inhibitor were added. The mixture was reacted at 180℃ under vacuum of 0.1MPa for 7 hours, then the temperature was lowered to 130℃, styrene was added, and the mixture was stirred evenly to obtain an ultra-flexible unsaturated polyester resin.
[0190] The putty materials prepared in the above embodiments and comparative examples were subjected to performance testing. Five samples from each of Examples 1-3 and Comparative Examples 1-3 were taken for performance testing:
[0191] 1) Conduct a putty film appearance test according to HG / T4561-2013 standard;
[0192] 2) Perform the surface drying time test according to GB / T 1728-79 standard;
[0193] 3) Conduct impact resistance testing according to GB / T1749 standard;
[0194] 4) Conduct flexibility tests according to GB / T1748 standard; conduct bending tests according to GB / T16406 standard;
[0195] 5) Conduct adhesion testing according to GB / T5210 standard;
[0196] The temperature resistance test specifically includes: applying putty to the automotive substrate, placing it at room temperature for 8 hours, placing the substrate in a 60°C forced-air constant temperature oven for 8 hours, removing it and placing it at room temperature for 8 hours, then placing it in a -60°C freezer for 8 hours, removing it and placing it at room temperature for 8 hours, and so on. No cracking or peeling occurs as one cycle. The VOCs volatility test specifically includes: according to the standard TB / T3139 "Limits of Hazardous Substances in Interior Materials and Indoor Air of Locomotives and Rolling Stock", testing the VOCs content of the putty provided in Examples 1-3 and Comparative Examples 1-3, testing each group of samples three times, and taking the average value.
[0197] The test results are shown in Table 1 below:
[0198] Table 1. Performance test results of the products:
[0199]
[0200] As shown in Table 1 above, the paint films formed by the body filler products prepared in Examples 1-3 of this application far exceed the technical specifications in all the above test items. They exhibit excellent flexibility, adhesion, impact strength, and temperature resistance; short surface drying time; low VOC content (not exceeding 70 g / L); and low toxicity, meeting environmental protection requirements and protecting the health of operators and users. The body filler products prepared in this application can significantly improve the vehicle's service life, making the vehicle surface less prone to peeling and breakage, thus improving vehicle safety. Based on the test results, Comparative Example 2, without the addition of air-drying unsaturated polyester resin, has a longer surface drying time. Adding the self-made air-drying unsaturated polyester resin results in faster paint film drying. The addition of sugar alcohol allyl ether increases the resin's air-drying properties and improves the polymer's crosslinking density, thereby increasing the paint film's drying rate and hardness. Comparative Example 1 shows that the mechanical properties of the product obtained without the addition of ultra-flexible unsaturated polyester resin are significantly reduced. Adding the self-made allyl ether... The super-flexible unsaturated polyester resin synthesized from long-chain aliphatic diols and long-chain linear dicarboxylic acids can effectively improve the impact resistance and flexibility of the product. Further, comparing with Comparative Examples 1-3, it can be seen that this invention partially replaces styrene with a functional diluent crosslinking agent, effectively reducing the environmental pollution caused by styrene volatilization, while retaining the excellent solubility and rigidity of styrene. By using epoxidized vegetable oil acrylate as a functional diluent crosslinking agent, dependence on petroleum resources can be reduced, making it environmentally friendly. Its long fatty acid chains are natural flexible segments; using it as a crosslinking agent to partially replace styrene can reduce the impact of styrene on the brittleness of the polymer material, and can also significantly improve the toughness, impact resistance, and elongation of the cured material, reducing brittle cracking. The polar ester bonds and possibly remaining hydroxyl groups in the molecule help to form good adhesion to various substrates (especially metals). By adding nano-alumina particles, the heat resistance and mechanical strength of the material can be improved to compensate for the reduced heat resistance and rigidity caused by styrene.
[0201] The above embodiments are merely illustrative of the principles and effects of the present invention and are not intended to limit the invention. Any person skilled in the art can modify or alter the above embodiments without departing from the spirit and scope of the invention. Therefore, all equivalent modifications or alterations made by those skilled in the art without departing from the spirit and technical concept disclosed in the present invention should still be covered by the claims of the present invention.
Claims
1. A type of body filler for automotive bodies, characterized in that, It includes component A and component B, wherein the weight ratio of each raw material in component A is: Air-drying unsaturated polyester resin: 10-15 parts Super-flexible unsaturated polyester resin: 20-25 parts Functional diluted crosslinking agent: 5-10 parts Defoamer: 0.1-0.3 parts Talc powder: 20-40 parts Titanium dioxide: 10-20 parts Stabilizer: 0.5-1 part Dispersant: 0.2-1.2 parts Leveling agent: 0.6-1.6 parts Cobalt isooctanoate: 0.1-0.5 parts Polymerization inhibitor: 0.1-0.5 parts The weight ratio of each raw material in component B is: 15-30 parts of peroxide 5-10 parts of fumed silica The weight ratio of component A to component B is 100:1.5-3.
2. The body filler for vehicle bodies according to claim 1, characterized in that, The preparation process of the air-drying unsaturated polyester resin includes the following steps: 1) Add tetrahydrophthalic anhydride, phthalic anhydride, hexanediol, neopentyl glycol, triethylene glycol and part of phosphoric acid to the reaction vessel in the required amounts. Raise the temperature to 150-200℃ and stir and heat for 2-5 hours. When the acid value of the reaction system reaches 45-50 mg KOH / g, cool down to 130℃. 2) Add maleic anhydride and continue the reaction at 150-200 °C for 2-5 h. When the acid value of the system is less than 120 mg KOH / g, cool down to 130 °C, evacuate for 5 min, add sugar alcohol allyl ether and the remaining phosphoric acid, then purge with nitrogen for 5 min, and react at 150-200 °C for 2-5 h. When the acid value of the system is less than 40 mg KOH / g, the reaction ends. 3) Cool down to 130 ℃, evacuate for 5 min, then add hydroquinone and stir for 5 min; cool down to 60 ℃, add hydroxyethyl methacrylate and N,N-dimethyl-p-nitrosoaniline, stir for 20 min, and obtain an air-drying unsaturated polyester resin sample.
3. The body filler for vehicle bodies according to claim 2, characterized in that, The sugar alcohol allyl ether is sorbitol allyl ether and / or xylitol allyl ether.
4. The body filler for vehicle bodies according to claim 1, characterized in that, The preparation of the ultra-flexible unsaturated polyester resin includes the following steps: 1) Under a nitrogen atmosphere, mix long-chain aliphatic diols, long-chain linear dicarboxylic acids, maleic anhydride, and some polymerization inhibitors, and reflux at 150-200℃ until the acid value reaches 20-30 mgKOH / g. 2) Cool down to 140-160℃, add 1-5 parts of catalyst, nano-alumina modified with silane coupling agent KH-560 and the remaining polymerization inhibitor, react in a vacuum of 0.05-0.1MPa and 150-180℃ for 3-7 hours, then cool down to 100-130℃, add functional diluent crosslinking agent, and stir evenly to obtain ultra-flexible unsaturated polyester resin.
5. The body filler for vehicle bodies according to claim 4, characterized in that, The long-chain aliphatic diol is one or more of diethylene glycol, dipropylene glycol, and neopentyl glycol; the long-chain linear dicarboxylic acid has the general structural formula: HOOC-(CH2). n -COOH, where n≥13.
6. The body filler for vehicle bodies according to claim 1, characterized in that, The functional diluting crosslinking agent is a compound of epoxidized vegetable oil acrylate and styrene in a mass ratio of 2:
1. The epoxidized vegetable oil acrylate includes one or more of epoxidized soybean oil acrylate, epoxidized linseed oil acrylate, epoxidized castor oil acrylate, and epoxidized rapeseed oil acrylate.
7. The body filler for vehicle bodies according to claim 4, characterized in that, The catalyst is benzyltrimethylammonium chloride, benzyltriethylammonium chloride, tetrabutylammonium chloride, or dodecyltrimethylammonium chloride.
8. The body filler for vehicle bodies according to claim 1, characterized in that, The polymerization inhibitor is hydroquinone, methyl hydroquinone, p-tert-butylcatechol, or p-benzoquinone; the leveling agent is an acrylate leveling agent.
9. A method for preparing body filler material for automobiles as described in any one of claims 1-8, comprising the following steps: 1) Weigh each raw material component according to the above proportions; 2) Weigh out the air-drying unsaturated polyester resin, the ultra-flexible unsaturated polyester resin and the polymerization inhibitor and add them to a high-speed disperser in sequence. Then add cobalt isooctanoate and mix at a speed of 300-400 r / min. Control the temperature at 70-80℃ and react for 2-3 hours. Then add the dispersant, leveling agent and defoamer respectively and mix at a speed of 500-600 r / min for 1-2 hours. Add part of the functional diluent crosslinking agent and stabilizer, then add talc and titanium dioxide and stir at a speed of 600-640 r / min for 2-3 hours. Finally, add the remaining part of the functional diluent crosslinking agent, increase the disperser speed to 1000-1400 r / min and stir for 1-2 hours. After standing for 0.5-1 hours, the atomic main ash component A is obtained. 3) Add the weighed peroxide and fumed silica to the above-mentioned atomic putty component A, and stir for 2-5 hours to mix evenly to obtain the atomic putty for vehicle body materials.