High-temperature-resistant CHPO-cured putty with good polishing performance and preparation method thereof

Abstract

The application belongs to the technical field of putty, and particularly relates to a high-temperature-resistant CHPO curing putty with good polishing performance and a preparation method thereof. The high-temperature-resistant CHPO curing putty with good polishing performance comprises an A component and a B component. The A component comprises the following raw materials in parts by weight: linseed oil modified unsaturated polyester resin 140-160 parts, oleic acid modified air-drying unsaturated polyester resin 40-60 parts, dicyclopentadiene modified unsaturated polyester resin 90-110 parts, styrene 30-40 parts, drier 5-8 parts, accelerator 0.1-1.2 parts, dispersant 3-5 parts, thixotropic agent 8-12 parts, titanium white powder 12-16 parts, talc powder 400-500 parts, and pre-expanded polymer microspheres 5-10 parts. The application effectively solves the problems of poor polishing performance, poor adhesion to water-based epoxy primer and poor high-temperature resistance of traditional CHPO curing putty.

Description

Technical Field

[0001] This invention belongs to the field of putty technology, specifically relating to a high-temperature resistant CHPO-cured putty with good polishability and its preparation method. Background Technology

[0002] Atomic putty, also known as unsaturated polyester putty, is a filling material mainly made of unsaturated polyester resin. It has the advantages of thick application, rapid curing at room temperature, and good sanding properties, and is widely used in high-speed rail, automobile and other fields.

[0003] CHPO (cyclohexanone peroxide) is a commonly used curing agent for unsaturated polyester resins. It can cure at room temperature and has a wide applicable temperature range. However, in practical applications, traditional CHPO curing putty often faces many problems: poor sandability and long sanding time; poor adhesion to water-based epoxy primers; and poor high-temperature resistance, easily causing problems such as pinholes and cracking under high-temperature conditions. These problems not only affect construction efficiency but also the quality of repair.

[0004] The applicant's previous research results: Chinese patent publication number CN 118546558 A discloses a high-temperature resistant CHPO curable putty and its preparation method. The putty in this technical solution includes unsaturated polyester resin, talc powder, mica powder, calcium carbonate, titanium dioxide, fumed silica, modified 2-hydroxyethyl acrylate, cobalt isooctanoate, diphenylmethane diisocyanate, leveling agent, polymerization inhibitor, and CHPO. The prepared putty product has excellent flexibility, adhesion, and impact resistance, and also gives the product strong high-temperature resistance, with a temperature resistance of up to 200℃ on steel plates. However, the putty in this technical solution is applied directly to the substrate. The applicant subsequently found that its adhesion and high-temperature resistance when applied to water-based epoxy primers need to be improved. Summary of the Invention

[0005] To address the technical problems mentioned in the background section, the present invention aims to provide a high-temperature resistant CHPO curable putty with good sanding properties and its preparation method. The CHPO curable putty provided by the present invention is formulated by compounding linseed oil-modified unsaturated polyester resin, oleic acid-modified air-drying unsaturated polyester resin, and dicyclopentadiene-modified unsaturated polyester resin, and combined with specific pre-expanded polymer microspheres. This effectively solves the problems of poor sanding properties, poor adhesion to water-based epoxy primers, and poor high-temperature resistance of traditional CHPO curable putties.

[0006] To achieve the above objectives, the present invention provides the following technical solution:

[0007] The first aspect of this invention provides a high-temperature resistant CHPO curable putty with good polishing properties, comprising component A and component B. Component A comprises the following raw materials in parts by weight: 140-160 parts of linseed oil modified unsaturated polyester resin, 40-60 parts of oleic acid modified air-drying unsaturated polyester resin, 90-110 parts of dicyclopentadiene modified unsaturated polyester resin, 30-40 parts of styrene, 5-8 parts of drying agent, 0.1-1.2 parts of accelerator, 3-5 parts of dispersant, 8-12 parts of thixotropic agent, 12-16 parts of titanium dioxide, 400-500 parts of talc, and 5-10 parts of pre-expanded polymer microspheres.

[0008] Traditional putty has poor sanding properties due to its high surface hardness, toughness, or stickiness after resin curing. The inventors discovered that by compounding specific weight proportions of linseed oil-modified unsaturated polyester resin, oleic acid-modified air-drying unsaturated polyester resin, and dicyclopentadiene-modified unsaturated polyester resin, a putty with moderate surface hardness and non-stickiness to sandpaper can be obtained. At the same time, the dicyclopentadiene in the dicyclopentadiene-modified resin contains a bridged ring structure, which has high rigidity and thermal stability, while the long-chain structure of linseed oil and oleic acid gives the resin low shrinkage characteristics, which can reduce internal stress during curing and reduce curing shrinkage. The compound of the three not only improves the sanding properties of putty, but also improves adhesion and high-temperature resistance with water-based epoxy primers to a certain extent.

[0009] Furthermore, the preparation method of the linseed oil-modified unsaturated polyester resin includes the following steps:

[0010] S11. Add linseed oil, glycerol, lithium hydroxide, and sodium hydroxide to the reactor and heat to 240℃ for 3 hours;

[0011] S12. When cooled to 150℃, add tetrahydrophthalic anhydride, fumaric acid, and o-methylhydroquinone, then slowly heat to 220℃ and react for 5 hours, followed by vacuum dehydration for 2 hours.

[0012] S13. Determine the acid value. The reaction endpoint is when the acid value is less than 35 mg KOH / g.

[0013] S14. Add hydroquinone when the temperature is cooled to 150°C and continue cooling.

[0014] S15. Add styrene when the temperature cools to below 100°C.

[0015] Further, the mass ratio of the linseed oil, glycerol, lithium hydroxide, sodium hydroxide, tetrahydrophthalic anhydride, fumaric acid, o-methylhydroquinone, hydroquinone, and styrene is 40-60:15-30:0.001-0.1:0.001-0.1:10-20:10-15:0.01-0.1:0.01-0.1:20-50.

[0016] Furthermore, the preparation method of the oleic acid modified air-drying unsaturated polyester resin includes the following steps:

[0017] S21. Add o-methylhydroquinone, diethylene glycol, triethylene glycol, tetrahydrophthalic anhydride, dicyclopentadiene, maleic anhydride and oleic acid to the reactor, mix evenly, and slowly raise the temperature to 190-210℃ for 3-5 hours to maintain the esterification reaction.

[0018] S22. Measure the acid value. When the acid value is 80-90 mg KOH / g, cool down.

[0019] S23. When the temperature drops to 160℃, add trimethylolpropane diallyl ether dropwise over 0.5 hours.

[0020] S24. Slowly heat to 200℃ for 1 hour, then vacuum dehydrate for 0.5 hours to accelerate the esterification reaction;

[0021] S25. Determine the acid value. The reaction endpoint is defined as the acid value ≤ 40 mg KOH / g.

[0022] S26. Add hydroquinone when the temperature is cooled to 150°C and continue cooling.

[0023] S27. Add styrene when the temperature cools to below 100°C.

[0024] Further, the mass ratio of o-methylhydroquinone, diethylene glycol, triethylene glycol, tetrahydrophthalic anhydride, dicyclopentadiene, maleic anhydride, trimethylolpropane diallyl ether, oleic acid, hydroquinone, and styrene is 0.05-0.3:15-25:5-10:5-8:7-10:13-17:5-10:12-16:0.05-0.3:30-50.

[0025] Furthermore, the preparation method of the dicyclopentadiene-modified unsaturated polyester resin includes the following steps:

[0026] S31. Add o-methylhydroquinone, maleic anhydride and dicyclopentadiene to the reactor, heat to 80°C, and start stirring to react for 2 hours.

[0027] S32. Slowly add water to the reactor and react at 120-140℃ for 2 hours;

[0028] S33. Linoleic acid, trimethylolpropane, propylene glycol, ethylene glycol and diethylene glycol are added to the reactor and the temperature is slowly raised to 190°C. The reaction is carried out for 3 hours and then vacuum dehydrated for 1 hour. The acid value is measured. When the acid value is less than 30 mg KOH / g, it is taken as the reaction endpoint.

[0029] S34. When the temperature drops to 150°C, add hydroquinone and continue cooling. When the temperature drops below 100°C, add styrene.

[0030] Further, the mass ratio of o-methylhydroquinone, dicyclopentadiene, maleic anhydride, water, linolenic acid, trimethylolpropane, propylene glycol, ethylene glycol, diethylene glycol, hydroquinone, and styrene is 0.05-0.2:10-20:40-60:2-5:15-30:5-10:10-20:5-15:10-30:0.03-0.1:50-70.

[0031] Furthermore, the drying agent is cobalt isooctanoate.

[0032] Furthermore, the accelerator is dimethylaniline.

[0033] Furthermore, the thixotropic agent is selected from at least one of hydrogenated castor oil, bentonite, and fumed silica.

[0034] Furthermore, the titanium dioxide is rutile titanium dioxide.

[0035] Furthermore, the talc powder includes talc powder with a particle size of 400 mesh and talc powder with a particle size of 325 mesh.

[0036] Furthermore, the polymer microspheres have a core-shell structure, with the outer shell being thermoplastic acrylate and the core being nano-silica, nano-zirconia, and hydrocarbons.

[0037] Furthermore, the raw materials for the thermoplastic acrylate include acrylic acid, acrylonitrile, methyl methacrylate, isosorbide diacrylate, and diethylene glycol diacrylate.

[0038] Traditional CHPO-cured putty often uses a large amount of talc powder as filler, resulting in high density, irregular particle shape, and difficulty in sanding. This also leads to shrinkage after drying and makes it difficult to prevent styrene from seeping into the water-based epoxy primer film, resulting in poor adhesion between the putty and the epoxy primer film. To solve this problem, this invention incorporates self-made pre-expanded polymer microspheres. The inventors discovered that, compared to traditional polymer microspheres, adding nano-silica and nano-zirconia during the polymer microsphere preparation process, followed by pre-expansion before adding to the putty system, not only effectively improves the sandability of the putty but also effectively... The improved adhesion to the epoxy primer film is likely due to the presence of rigid nano-silica and nano-zirconia particles, which can prevent styrene from penetrating into the water-based epoxy primer film to some extent. Simultaneously, the presence of a soft thermoplastic acrylate shell helps prevent shrinkage. The inventors discovered that introducing specific isosorbide diacrylate during the polymer microsphere preparation process can effectively improve the heat resistance of the putty. This is likely because the isosorbide diacrylate molecule contains a rigid bicyclic acetal backbone. Introducing it as a polymer monomer into the shell of the polymer microspheres further enhances their heat resistance.

[0039] Further, the preparation method of the pre-expanded polymer microspheres is as follows: polyvinyl alcohol, polyvinylpyrrolidone, nano-silica, nano-zirconia and deionized water are mixed and stirred evenly to obtain an aqueous phase; acrylic acid, acrylonitrile, methyl methacrylate, isosorbide diacrylate, diethylene glycol diacrylate, alkanes and benzoyl peroxide are mixed and stirred evenly to obtain an oil phase; the oil phase is added to the aqueous phase under stirring conditions, homogenized and stirred, heated and pressurized to react, and after the reaction is completed, washed, filtered and dried to obtain polymer microspheres; the polymer microspheres are dispersed in water and spray-dried to obtain pre-expanded polymer microspheres.

[0040] Furthermore, the particle size of the nano-silica is 100-500 nm.

[0041] Furthermore, the particle size of the nano-zirconia is 30-80 nm.

[0042] Furthermore, the mass ratio of polyvinyl alcohol, polyvinylpyrrolidone, nano-silica, nano-zirconia and deionized water is 0.2-0.5:0.3-0.6:20-30:20-30:300-500.

[0043] Further, the mass ratio of acrylic acid, acrylonitrile, methyl methacrylate, isosorbide diacrylate and diethylene glycol diacrylate is 20-30:20-30:20-30:10-40:0.5-1.

[0044] Further, the amount of benzoyl peroxide added is 0.5-2% of the total mass of acrylic acid, acrylonitrile, methyl methacrylate, isosorbide diacrylate and diethylene glycol diacrylate.

[0045] Furthermore, the amount of alkane added is 20-40% of the total mass of acrylic acid, acrylonitrile, methyl methacrylate, isosorbide diacrylate and diethylene glycol diacrylate.

[0046] Furthermore, the alkane is selected from at least one of n-butane, isobutane, n-pentane, and isopentane.

[0047] Furthermore, the mass ratio of the aqueous phase to the oil phase is 1:1.

[0048] Furthermore, the conditions for the heating and pressurizing reaction are: reacting at 50-60℃ and 0.5-0.6MPa for 20-24 hours.

[0049] Furthermore, the spray drying temperature is 130-150°C.

[0050] Furthermore, component B is cyclohexanone peroxide.

[0051] Furthermore, the mass ratio of component A to component B is 100:1.5-2.5.

[0052] The second aspect of this invention provides a method for preparing a high-temperature resistant CHPO hardened putty with good polishability, comprising the following steps:

[0053] The linseed oil-modified unsaturated polyester resin, oleic acid-modified air-drying unsaturated polyester resin, dicyclopentadiene-modified unsaturated polyester resin, dispersant, catalyst, accelerator, thixotropic agent, titanium dioxide, talc powder and pre-expanded polymer microspheres are stirred evenly, styrene is sprayed on, and stirring is continued to be evenly mixed to obtain component A.

[0054] When using it, mix components A and B evenly to obtain CHPO curing putty with good sanding properties and high temperature resistance.

[0055] Compared with the prior art, the advantages and beneficial effects of the present invention are as follows:

[0056] 1. This invention uses specific weight proportions of linseed oil-modified unsaturated polyester resin, oleic acid-modified air-drying unsaturated polyester resin, and dicyclopentadiene-modified unsaturated polyester resin to create a putty with moderate surface hardness that does not stick to sandpaper. Simultaneously, the dicyclopentadiene in the dicyclopentadiene-modified resin contains a bridged ring structure, exhibiting high rigidity and thermal stability. The long-chain structures of linseed oil and oleic acid impart low shrinkage characteristics to the resin, reducing internal stress during curing and decreasing curing shrinkage. This combination not only improves the sandability of the putty but also, to a certain extent, enhances its adhesion to water-based epoxy primers and its high-temperature resistance.

[0057] 2. In the preparation of polymer microspheres, the present invention adds nano-silica and nano-zirconia, which are pre-expanded and then added to the putty system. This not only effectively improves the sandability of the putty, but also effectively improves the adhesion to the epoxy primer film. The inventors have found that introducing a specific isosorbide diacrylate during the preparation of polymer microspheres can effectively improve the heat resistance of the putty. Attached Figure Description

[0058] Figure 1 This is a physical image of the CHPO hardened putty with good sanding properties and high temperature resistance, as described in Example 2. Detailed Implementation

[0059] The technical solutions in the embodiments of the present invention will be clearly and completely described below. Obviously, the described embodiments are only some embodiments of the present invention, and not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of the present invention.

[0060] A method for preparing linseed oil-modified unsaturated polyester resin includes the following steps:

[0061] S11. Add linseed oil, glycerol, lithium hydroxide, and sodium hydroxide to the reactor and heat to 240℃ for 3 hours;

[0062] S12. When cooled to 150℃, add tetrahydrophthalic anhydride, fumaric acid, and o-methylhydroquinone, then slowly heat to 220℃ and react for 5 hours, followed by vacuum dehydration for 2 hours.

[0063] S13. Determine the acid value. The reaction endpoint is when the acid value is less than 35 mg KOH / g.

[0064] S14. Add hydroquinone when the temperature is cooled to 150°C and continue cooling.

[0065] S15. Add styrene when the temperature cools to below 100°C.

[0066] The mass ratio of linseed oil, glycerol, lithium hydroxide, sodium hydroxide, tetrahydrophthalic anhydride, fumaric acid, o-methylhydroquinone, hydroquinone, and styrene is 50:20:0.02:0.02:15:12:0.02:0.02:40.

[0067] A method for preparing oleic acid-modified air-drying unsaturated polyester resin includes the following steps:

[0068] S21. Add o-methylhydroquinone, diethylene glycol, triethylene glycol, tetrahydrophthalic anhydride, dicyclopentadiene, maleic anhydride and oleic acid to the reactor, mix evenly, and slowly heat to 200℃ for 4 hours to maintain the esterification reaction.

[0069] S22. Measure the acid value. When the acid value is 90 mg KOH / g, cool down.

[0070] S23. When the temperature drops to 160℃, add trimethylolpropane diallyl ether dropwise over 0.5 hours.

[0071] S24. Slowly heat to 200℃ for 1 hour, then vacuum dehydrate for 0.5 hours to accelerate the esterification reaction;

[0072] S25. Determine the acid value. The reaction endpoint is defined as the acid value ≤ 40 mg KOH / g.

[0073] S26. Add hydroquinone when the temperature is cooled to 150°C and continue cooling.

[0074] S27. Add styrene when the temperature cools to below 100°C.

[0075] The mass ratio of o-methylhydroquinone, diethylene glycol, triethylene glycol, tetrahydrophthalic anhydride, dicyclopentadiene, maleic anhydride, trimethylolpropane diallyl ether, oleic acid, hydroquinone, and styrene is 0.2:20:8:6:8:15:8:14:0.1:40.

[0076] A method for preparing dicyclopentadiene-modified unsaturated polyester resin includes the following steps:

[0077] S31. Add o-methylhydroquinone, maleic anhydride and dicyclopentadiene to the reactor, heat to 80°C, and start stirring to react for 2 hours.

[0078] S32. Slowly add water to the reactor and react at 130°C for 2 hours;

[0079] S33. Linoleic acid, trimethylolpropane, propylene glycol, ethylene glycol and diethylene glycol are added to the reactor and the temperature is slowly raised to 190°C. The reaction is carried out for 3 hours and then vacuum dehydrated for 1 hour. The acid value is measured. When the acid value is less than 30 mg KOH / g, it is taken as the reaction endpoint.

[0080] S34. When the temperature drops to 150°C, add hydroquinone and continue cooling. When the temperature drops below 100°C, add styrene.

[0081] The mass ratio of o-methylhydroquinone, dicyclopentadiene, maleic anhydride, water, linolenic acid, trimethylolpropane, propylene glycol, ethylene glycol, diethylene glycol, hydroquinone, and styrene is 0.1:15:55:3:20:8:15:8:20:0.06:60.

[0082] Example 1

[0083] A high-temperature resistant CHPO hardener with good abrasive properties comprises component A and component B. Component A comprises the following raw materials in parts by weight: 140 parts of linseed oil modified unsaturated polyester resin, 40 parts of oleic acid modified air-drying unsaturated polyester resin, 90 parts of dicyclopentadiene modified unsaturated polyester resin, 30 parts of styrene, 6 parts of drying agent, 0.8 parts of accelerator, 3 parts of dispersant, 8 parts of thixotropic agent, 12 parts of titanium dioxide, 400 parts of talc, and 5 parts of pre-expanded polymer microspheres.

[0084] The drying agent is cobalt isooctanoate.

[0085] The accelerator is dimethylaniline.

[0086] The dispersant is Tech-5044 from Shanghai Tiger Polymer Technology Co., Ltd. (Composition: copolymer solution containing pigment-loving groups, active part 50%, solvent: mixed diester).

[0087] The thixotropic agent is hydrogenated castor oil and fumed silica in a mass ratio of 3.5:2.

[0088] The titanium dioxide is rutile titanium dioxide.

[0089] The talc powder is in a mass ratio of 1.7:1, with a particle size of 400 mesh and 325 mesh.

[0090] The pre-expanded polymer microspheres are prepared as follows: polyvinyl alcohol, polyvinylpyrrolidone, nano-silica, nano-zirconia and deionized water are mixed and stirred evenly to obtain an aqueous phase; acrylic acid, acrylonitrile, methyl methacrylate, isosorbide diacrylate, diethylene glycol diacrylate, alkanes and benzoyl peroxide are mixed and stirred evenly to obtain an oil phase; the oil phase is added to the aqueous phase under stirring conditions, homogenized and stirred, heated and pressurized to react, and after the reaction is completed, washed, filtered and dried to obtain polymer microspheres; the polymer microspheres are dispersed in water and spray-dried to obtain pre-expanded polymer microspheres.

[0091] The particle size of the nano-silica is 200 nm.

[0092] The particle size of the nano-zirconia is 30 nm.

[0093] The mass ratio of polyvinyl alcohol, polyvinylpyrrolidone, nano silica, nano zirconium oxide and deionized water is 0.3:0.5:25:25:500.

[0094] The mass ratio of acrylic acid, acrylonitrile, methyl methacrylate, isosorbide diacrylate and diethylene glycol diacrylate is 25:25:25:30:0.6.

[0095] The amount of benzoyl peroxide added is 1% of the total mass of acrylic acid, acrylonitrile, methyl methacrylate, isosorbide diacrylate and diethylene glycol diacrylate.

[0096] The amount of alkane added is 30% of the total mass of acrylic acid, acrylonitrile, methyl methacrylate, isosorbide diacrylate and diethylene glycol diacrylate.

[0097] The alkane is isopentane.

[0098] The mass ratio of the aqueous phase to the oil phase is 1:1.

[0099] The conditions for the heating and pressurizing reaction were: reaction at 60℃ and 0.6MPa pressure for 24h.

[0100] The spray drying temperature is 140℃.

[0101] Component B is cyclohexanone peroxide.

[0102] The mass ratio of component A to component B is 100:2.

[0103] The preparation method of the above-mentioned high-temperature resistant CHPO hardened putty with good polishability includes the following steps:

[0104] The linseed oil-modified unsaturated polyester resin, oleic acid-modified air-drying unsaturated polyester resin, dicyclopentadiene-modified unsaturated polyester resin, dispersant, catalyst, accelerator, thixotropic agent, titanium dioxide, talc powder and pre-expanded polymer microspheres are stirred evenly, styrene is sprayed on, and stirring is continued to be evenly mixed to obtain component A.

[0105] When using it, mix components A and B evenly to obtain CHPO curing putty with good sanding properties and high temperature resistance.

[0106] Example 2

[0107] A high-temperature resistant CHPO hardener with good abrasive properties comprises component A and component B. Component A comprises the following raw materials in parts by weight: 150 parts of linseed oil modified unsaturated polyester resin, 50 parts of oleic acid modified air-drying unsaturated polyester resin, 100 parts of dicyclopentadiene modified unsaturated polyester resin, 35 parts of styrene, 7 parts of drying agent, 1 part of accelerator, 4 parts of dispersant, 10 parts of thixotropic agent, 14 parts of titanium dioxide, 450 parts of talc, and 7 parts of pre-expanded polymer microspheres.

[0108] The drying agent is cobalt isooctanoate.

[0109] The accelerator is dimethylaniline.

[0110] The dispersant is Tech-5044 from Shanghai Tiger Polymer Technology Co., Ltd. (Composition: copolymer solution containing pigment-loving groups, active part 50%, solvent: mixed diester).

[0111] The thixotropic agent is hydrogenated castor oil and fumed silica in a mass ratio of 3.5:2.

[0112] The titanium dioxide is rutile titanium dioxide.

[0113] The talc powder is in a mass ratio of 1.7:1, with a particle size of 400 mesh and 325 mesh.

[0114] The pre-expanded polymer microspheres are prepared as follows: polyvinyl alcohol, polyvinylpyrrolidone, nano-silica, nano-zirconia and deionized water are mixed and stirred evenly to obtain an aqueous phase; acrylic acid, acrylonitrile, methyl methacrylate, isosorbide diacrylate, diethylene glycol diacrylate, alkanes and benzoyl peroxide are mixed and stirred evenly to obtain an oil phase; the oil phase is added to the aqueous phase under stirring conditions, homogenized and stirred, heated and pressurized to react, and after the reaction is completed, washed, filtered and dried to obtain polymer microspheres; the polymer microspheres are dispersed in water and spray-dried to obtain pre-expanded polymer microspheres.

[0115] The particle size of the nano-silica is 200 nm.

[0116] The particle size of the nano-zirconia is 30 nm.

[0117] The mass ratio of polyvinyl alcohol, polyvinylpyrrolidone, nano silica, nano zirconium oxide and deionized water is 0.3:0.5:25:25:500.

[0118] The mass ratio of acrylic acid, acrylonitrile, methyl methacrylate, isosorbide diacrylate and diethylene glycol diacrylate is 25:25:25:30:0.6.

[0119] The amount of benzoyl peroxide added is 1% of the total mass of acrylic acid, acrylonitrile, methyl methacrylate, isosorbide diacrylate and diethylene glycol diacrylate.

[0120] The amount of alkane added is 30% of the total mass of acrylic acid, acrylonitrile, methyl methacrylate, isosorbide diacrylate and diethylene glycol diacrylate.

[0121] The alkane is isopentane.

[0122] The mass ratio of the aqueous phase to the oil phase is 1:1.

[0123] The conditions for the heating and pressurizing reaction were: reaction at 60℃ and 0.6MPa pressure for 24h.

[0124] The spray drying temperature is 140℃.

[0125] Component B is cyclohexanone peroxide.

[0126] The mass ratio of component A to component B is 100:2.

[0127] The preparation method of the above-mentioned high-temperature resistant CHPO hardened putty with good polishability includes the following steps:

[0128] The linseed oil-modified unsaturated polyester resin, oleic acid-modified air-drying unsaturated polyester resin, dicyclopentadiene-modified unsaturated polyester resin, dispersant, catalyst, accelerator, thixotropic agent, titanium dioxide, talc powder and pre-expanded polymer microspheres are stirred evenly, styrene is sprayed on, and stirring is continued to be evenly mixed to obtain component A.

[0129] When using, mix components A and B thoroughly to obtain a high-temperature resistant, sanding-friendly CHPO hardened putty. See the image below. Figure 1 As shown.

[0130] Example 3

[0131] A high-temperature resistant CHPO hardener with good abrasive properties comprises component A and component B. Component A comprises the following raw materials in parts by weight: 160 parts of linseed oil modified unsaturated polyester resin, 60 parts of oleic acid modified air-drying unsaturated polyester resin, 110 parts of dicyclopentadiene modified unsaturated polyester resin, 40 parts of styrene, 8 parts of drying agent, 1.2 parts of accelerator, 5 parts of dispersant, 12 parts of thixotropic agent, 16 parts of titanium dioxide, 500 parts of talc, and 10 parts of pre-expanded polymer microspheres.

[0132] The drying agent is cobalt isooctanoate.

[0133] The accelerator is dimethylaniline.

[0134] The dispersant is Tech-5044 from Shanghai Tiger Polymer Technology Co., Ltd. (Composition: copolymer solution containing pigment-loving groups, active part 50%, solvent: mixed diester).

[0135] The thixotropic agent is hydrogenated castor oil and fumed silica in a mass ratio of 3.5:2.

[0136] The titanium dioxide is rutile titanium dioxide.

[0137] The talc powder is in a mass ratio of 1.7:1, with a particle size of 400 mesh and 325 mesh.

[0138] The pre-expanded polymer microspheres are prepared as follows: polyvinyl alcohol, polyvinylpyrrolidone, nano-silica, nano-zirconia and deionized water are mixed and stirred evenly to obtain an aqueous phase; acrylic acid, acrylonitrile, methyl methacrylate, isosorbide diacrylate, diethylene glycol diacrylate, alkanes and benzoyl peroxide are mixed and stirred evenly to obtain an oil phase; the oil phase is added to the aqueous phase under stirring conditions, homogenized and stirred, heated and pressurized to react, and after the reaction is completed, washed, filtered and dried to obtain polymer microspheres; the polymer microspheres are dispersed in water and spray-dried to obtain pre-expanded polymer microspheres.

[0139] The particle size of the nano-silica is 200 nm.

[0140] The particle size of the nano-zirconia is 30 nm.

[0141] The mass ratio of polyvinyl alcohol, polyvinylpyrrolidone, nano silica, nano zirconium oxide and deionized water is 0.3:0.5:25:25:500.

[0142] The mass ratio of acrylic acid, acrylonitrile, methyl methacrylate, isosorbide diacrylate and diethylene glycol diacrylate is 25:25:25:30:0.6.

[0143] The amount of benzoyl peroxide added is 1% of the total mass of acrylic acid, acrylonitrile, methyl methacrylate, isosorbide diacrylate and diethylene glycol diacrylate.

[0144] The amount of alkane added is 30% of the total mass of acrylic acid, acrylonitrile, methyl methacrylate, isosorbide diacrylate and diethylene glycol diacrylate.

[0145] The alkane is isopentane.

[0146] The mass ratio of the aqueous phase to the oil phase is 1:1.

[0147] The conditions for the heating and pressurizing reaction were: reaction at 60℃ and 0.6MPa pressure for 24h.

[0148] The spray drying temperature is 140℃.

[0149] Component B is cyclohexanone peroxide.

[0150] The mass ratio of component A to component B is 100:2.

[0151] The preparation method of the above-mentioned high-temperature resistant CHPO hardened putty with good polishability includes the following steps:

[0152] The linseed oil-modified unsaturated polyester resin, oleic acid-modified air-drying unsaturated polyester resin, dicyclopentadiene-modified unsaturated polyester resin, dispersant, catalyst, accelerator, thixotropic agent, titanium dioxide, talc powder and pre-expanded polymer microspheres are stirred evenly, styrene is sprayed on, and stirring is continued to be evenly mixed to obtain component A.

[0153] When using it, mix components A and B evenly to obtain CHPO curing putty with good sanding properties and high temperature resistance.

[0154] Comparative Example 1

[0155] The difference between this comparative example and Example 2 is as follows:

[0156] A high-temperature resistant CHPO hardener with good abrasive properties comprises component A and component B. Component A comprises the following raw materials in parts by weight: 120 parts of linseed oil modified unsaturated polyester resin, 65 parts of oleic acid modified air-drying unsaturated polyester resin, 115 parts of dicyclopentadiene modified unsaturated polyester resin, 35 parts of styrene, 7 parts of drying agent, 1 part of accelerator, 4 parts of dispersant, 10 parts of thixotropic agent, 14 parts of titanium dioxide, 450 parts of talc, and 7 parts of pre-expanded polymer microspheres; the rest are the same.

[0157] Comparative Example 2

[0158] The difference between this comparative example and Example 2 is as follows:

[0159] A high-temperature resistant CHPO hardener with good abrasive properties comprises component A and component B. Component A comprises the following raw materials in parts by weight: 180 parts of linseed oil modified unsaturated polyester resin, 35 parts of oleic acid modified air-drying unsaturated polyester resin, 85 parts of dicyclopentadiene modified unsaturated polyester resin, 35 parts of styrene, 7 parts of drying agent, 1 part of accelerator, 4 parts of dispersant, 10 parts of thixotropic agent, 14 parts of titanium dioxide, 450 parts of talc, and 7 parts of pre-expanded polymer microspheres; the rest are the same.

[0160] Comparative Example 3

[0161] The difference between this comparative example and Example 2 is as follows:

[0162] Replace the linseed oil-modified unsaturated polyester resin with an equal mass of oleic acid-modified air-drying unsaturated polyester resin; all other aspects remain the same.

[0163] Comparative Example 4

[0164] The difference between this comparative example and Example 2 is as follows:

[0165] Replace the oleic acid-modified air-drying unsaturated polyester resin with an equal mass of dicyclopentadiene-modified unsaturated polyester resin; all other aspects remain the same.

[0166] Comparative Example 5

[0167] The difference between this comparative example and Example 2 is as follows:

[0168] Replace the dicyclopentadiene-modified unsaturated polyester resin with an equal mass of linseed oil-modified unsaturated polyester resin; all other aspects remain the same.

[0169] Comparative Example 6

[0170] The difference between this comparative example and Example 2 is as follows:

[0171] Replace the pre-expanded polymer microspheres with an equivalent mass of commercially available hollow ceramic microspheres; everything else remains the same.

[0172] Comparative Example 7

[0173] The difference between this comparative example and Example 2 is as follows:

[0174] The pre-expanded polymer microspheres were obtained by pre-expanding commercially available thermally expanded foamed microspheres (the outer shell is a thermoplastic acrylate polymer, and the core is a spherical plastic particle composed of hydrocarbons, Shanghai Wai Dian International Trade Co., Ltd., model: 120DU15) at 130°C; all other aspects were the same.

[0175] Comparative Example 8

[0176] The difference between this comparative example and Example 2 is as follows:

[0177] In the preparation of pre-expanded polymer microspheres, isosorbide diacrylate was replaced with an equal mass of methyl methacrylate; all other steps remained the same.

[0178] Performance testing:

[0179] The putty from the above examples and comparative examples was applied to a substrate with a thickness of 400µm (the substrate surface was coated with a 50µm thick water-based epoxy primer), and the following performance tests were performed:

[0180] 1. Polishability: Tested according to GB / T1770;

[0181] 2. Adhesion (after 24 hours): Tested according to GB / T5210;

[0182] 3. High temperature resistance: Tested according to GB / T1735: Bake at 200℃ for 2 hours and observe whether blistering, cracking or peeling occurs. Any phenomenon is considered unqualified.

[0183] The test results are shown in Table 1 below.

[0184] Table 1 Performance Test Results

[0185]

[0186] As can be seen from Table 1 above, the putty provided by the present invention has the advantages of good sandability, high temperature resistance, and good adhesion to water-based epoxy primer.

[0187] Compared with Example 2, the weight proportions of linseed oil modified unsaturated polyester resin, oleic acid modified air-drying unsaturated polyester resin and dicyclopentadiene modified unsaturated polyester resin in Comparative Examples 1 and 2 are not within the scope of protection claimed in this invention. As a result, the adhesion between the resulting putty and the water-based epoxy primer decreased, and the heat resistance also decreased.

[0188] Compared with Example 2, Comparative Examples 3-5 lacked any of the components of linseed oil modified unsaturated polyester resin, oleic acid modified air-drying unsaturated polyester resin, and dicyclopentadiene modified unsaturated polyester resin. As a result, the sanding properties of the resulting putty were worse, the adhesion to the water-based epoxy primer was significantly reduced, and the heat resistance was decreased.

[0189] Compared with Example 2, Comparative Example 6 replaced the pre-expanded polymer microspheres with ceramic hollow microspheres, resulting in poorer sandability of the resulting putty and a significant decrease in adhesion to the water-based epoxy primer.

[0190] Compared with Example 2, Comparative Example 7 replaced the pre-expanded polymer microspheres with commercially available pre-expanded polymer microspheres, resulting in decreased adhesion of the atomized putty to the water-based epoxy primer and decreased heat resistance.

[0191] Compared with Example 2, Comparative Example 8 did not contain isosorbide diacrylate during the preparation process of the pre-expanded polymer microspheres, resulting in decreased adhesion between the resulting putty and the water-based epoxy primer, and decreased heat resistance.

[0192] The above description represents the preferred embodiments of the present invention. It should be noted that those skilled in the art can make various improvements and modifications without departing from the principles of the present invention, and these improvements and modifications should also be considered within the scope of protection of the present invention.

Claims

1. A high-temperature resistant CHPO hardened putty with good polishing properties, characterized in that, The product comprises component A and component B. Component A comprises the following raw materials in parts by weight: 140-160 parts of linseed oil modified unsaturated polyester resin, 40-60 parts of oleic acid modified air-drying unsaturated polyester resin, 90-110 parts of dicyclopentadiene modified unsaturated polyester resin, 30-40 parts of styrene, 5-8 parts of drying agent, 0.1-1.2 parts of accelerator, 3-5 parts of dispersant, 8-12 parts of thixotropic agent, 12-16 parts of titanium dioxide, 400-500 parts of talc, and 5-10 parts of pre-expanded polymer microspheres.

2. The good polishing and high temperature resistant CHPO cured putty according to claim 1, characterized in that, The drying agent is cobalt isooctanoate; the accelerator is dimethylaniline.

3. The good polishing and high temperature resistant CHPO cured putty according to claim 2, characterized in that, The thixotropic agent is selected from at least one of hydrogenated castor oil, bentonite, and fumed silica.

4. The good polishing and high temperature resistant CHPO cured putty according to any one of claims 1-3, characterized in that, The polymer microspheres have a core-shell structure, with the outer shell being thermoplastic acrylate and the core being nano-silica, nano-zirconia, and hydrocarbons.

5. The good polishing and high temperature resistant CHPO cured putty according to claim 4, characterized in that, The raw materials for the thermoplastic acrylate include acrylic acid, acrylonitrile, methyl methacrylate, isosorbide diacrylate, and diethylene glycol diacrylate.

6. The good polishing and high temperature resistant CHPO cured putty according to claim 5, characterized in that, The pre-expanded polymer microspheres are prepared as follows: polyvinyl alcohol, polyvinylpyrrolidone, nano-silica, nano-zirconia and deionized water are mixed and stirred evenly to obtain an aqueous phase; acrylic acid, acrylonitrile, methyl methacrylate, isosorbide diacrylate, diethylene glycol diacrylate, alkanes and benzoyl peroxide are mixed and stirred evenly to obtain an oil phase; the oil phase is added to the aqueous phase under stirring conditions, homogenized and stirred, heated and pressurized to react, and after the reaction is completed, washed, filtered and dried to obtain polymer microspheres; the polymer microspheres are dispersed in water and spray-dried to obtain pre-expanded polymer microspheres.

7. The good polishing and high temperature resistant CHPO cured putty according to claim 6, characterized in that, The nano-silica has a particle size of 100-500 nm; the nano-zirconia has a particle size of 30-80 nm.

8. The good polishing and high temperature resistant CHPO cured putty according to claim 7, characterized in that, The mass ratio of acrylic acid, acrylonitrile, methyl methacrylate, isosorbide diacrylate and diethylene glycol diacrylate is 20-30:20-30:20-30:10-40:0.5-1.

9. The good polishing and high temperature resistant CHPO cured putty according to any one of claims 5-8, characterized in that, Component B is cyclohexanone peroxide; the mass ratio of component A to component B is 100:1.5-2.

5.

10. The method for preparing the high-temperature-resistant CHPO-based putty with good polishing property according to any one of claims 1-9, characterized in that, Includes the following steps: The linseed oil-modified unsaturated polyester resin, oleic acid-modified air-drying unsaturated polyester resin, dicyclopentadiene-modified unsaturated polyester resin, dispersant, catalyst, accelerator, thixotropic agent, titanium dioxide, talc powder and pre-expanded polymer microspheres are stirred evenly, styrene is sprayed on, and stirring is continued to be evenly mixed to obtain component A. When using it, mix components A and B evenly to obtain CHPO curing putty with good sanding properties and high temperature resistance.

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