A method for manufacturing a flame-retardant resin ornament

Abstract

This invention relates to the field of polyester resin technology, specifically to a method for preparing flame-retardant resin ornaments. The process includes: mold production, grouting, base grinding, repair and inspection, coloring, warehousing and inspection. This invention uses hollow microspheres and porous glass microspheres to fill unsaturated polyester resin, and uses a silane coupling agent to improve the interfacial bonding between the microspheres and the resin, resulting in better adhesion. This achieves lightweight and energy-saving resin ornaments. The flame-retardant resin ornaments prepared by this invention have good flexural strength and hardness. The corrosion resistance of the flame-retardant resin ornaments prepared by this invention is significantly improved compared to existing resin crafts; they are not prone to mold, corrosion, or deformation, and can be used for a long time.

Description

Technical Field

[0001] This invention relates to the field of polyester resin technology, and in particular to a method for preparing a flame-retardant resin ornament. Background Technology

[0002] Resin ornaments originated in Europe in the early 20th century. The main production area was Italy, but production gradually shifted to Guangdong, Fujian, and Zhejiang provinces in my country, with Fengze District in Quanzhou City, Fujian Province being the most famous. The development and production of resin ornaments follow a unique rhythm. Most products, similar to fashion, are highly seasonal, trendy, and time-sensitive, easily becoming outdated with short product cycles. During various traditional holidays, the market demand for resin crafts is very high. Every year, resin craft companies must continuously develop new products to meet market demands, especially with holidays such as Christmas, Easter, Valentine's Day, and Halloween.

[0003] Chinese Patent CN104249595A: Provides a method for manufacturing resin crafts, belonging to the field of craft manufacturing technology. The method for manufacturing resin crafts of this invention is achieved through the following technical solutions: (1) a mold is made of silicone rubber according to the shape of the resin craft; (2) an appropriate amount of filler is added to unsaturated resin and stirred evenly; (3) before pouring into the mold, a curing agent and an accelerator are added to the unsaturated resin, stirred evenly, and then poured into the mold; (4) after the resin cures, it is demolded to obtain the craft of the desired shape. The method for manufacturing resin crafts of this invention can cast various shapes of simulated crafts at room temperature, with rapid solidification, realistic details, and a simple process.

[0004] Chinese Patent CN108795006A relates to the field of organic materials technology, specifically a resin material for garden ornaments that is resistant to photo- and heat-induced corrosion and aging. This resin material comprises the following components: polycarbonate, ABS resin, modified mineral fibers, nano-titanium dioxide, talc, pigment, dodecyl thiodipropionate, butylated hydroxytoluene, light stabilizer, coupling agent, light diffusing agent, and plasticizer. The modified mineral fibers are obtained by acidification, softening, and surface modification of a mixture of brucite and wollastonite fibers. The light stabilizer is 2-hydroxy-4-methoxybenzophenone or 2-hydroxy-4-n-octyloxybenzophenone. Through the use of various additives, this resin material improves its anti-aging performance under the combined effects of various outdoor oxidizing factors, thereby extending the service life of garden ornaments made from this resin material.

[0005] Chinese Patent CN116063834A discloses a polyester resin composition, a processed product, and a preparation method. The polyester resin composition comprises, by weight, 100 parts of unsaturated polyester resin, 0.7-1.1 parts of accelerator, 1.0-1.3 parts of curing agent, more than 0.08 parts and less than or equal to 0.34 parts of a first colorant, and more than 0.08 parts and less than or equal to 0.34 parts of a second colorant, with a ratio of the first colorant to the second colorant of 1:(1-2). The first and second colorants are of different colors. This invention achieves a gradual transition between different colors in the polyester resin composition.

[0006] The resin ornaments mentioned above are complex to manufacture, costly, energy-intensive, and heavy, and have poor corrosion resistance and are prone to fading, which seriously affects their ornamental value. Summary of the Invention

[0007] To address the aforementioned problems, this invention provides a method for preparing flame-retardant resin ornaments, which mainly includes: mold production, slurry injection, base grinding, and coloring processes.

[0008] To further elaborate, the operating steps for the production mold are as follows:

[0009] A1: Mix the silicone and curing agent evenly at a ratio of 1:0.005-0.05;

[0010] A2: Mix plaster and water in a ratio of 1:1-5, then add the mixture from A1 and mix to obtain the mold.

[0011] To further supplement, the grouting operation steps are as follows:

[0012] B1: Mix the modified resin, stone powder, accelerator, and 783 slow-drying water evenly in a ratio of 1:0.5-1.5:0.0005-0.001:0.0001-0.0008 to obtain a slurry;

[0013] B2: Mix the prepared slurry and curing agent in a ratio of 1:0.002-0.02;

[0014] B3: Pour the mixture of B2 into the mold and vacuum it. First, vacuum at -0.06 to -0.08 MPa for 10-30 seconds, then at -0.02 to -0.04 MPa for 10-30 seconds, and then at -0.1 to -0.2 MPa for 10-30 seconds. After completion, close the valve and slowly release the air after 10-30 seconds.

[0015] Furthermore, the curing agent is one or more of vinyltriamine, aminoethylpiperazine, methyl ethyl ketone peroxide, m-phenylenediamine, and diaminodiphenylmethane.

[0016] Furthermore, the accelerator is one or more of cobalt isooctanoate, zinc isooctanoate, cobalt naphthenate, N,N-dimethylaniline, and N,N-diethylaniline.

[0017] To further elaborate, the steps for grinding the bottom are as follows: use a grinding wheel and a 240 grit sandpaper for fine polishing.

[0018] To further elaborate, the coloring process is as follows: mix Xinhang paint and thinner in a ratio of 1:1-3, and then apply the color.

[0019] Furthermore, the method for preparing the modified resin is as follows:

[0020] C1: Weigh 5-10 parts of porous glass microspheres and 1-5 parts of hollow glass microspheres by weight, and dry them in an 80-100℃ drying oven for 1-4 hours.

[0021] C2: Weigh 0.05-0.3 parts by weight of silane coupling agent and 10-25 parts by weight of deionized water, stir and mix evenly to obtain an aqueous solution of silane coupling agent;

[0022] C3: Add the dried microbeads to the aqueous solution of silane coupling agent, stir for 30-90 min, and then dry in an oven at 80-100℃ for 1-4 h to obtain modified microbeads;

[0023] C4: Weigh 80-95 parts by weight of the unsaturated polyester resin modified with hollow glass microspheres, the modified microspheres, 0.5-1 parts by weight of the curing agent, and 0.1-0.5 parts by weight of the accelerator, mix and stir evenly to obtain the modified resin.

[0024] Furthermore, the silane coupling agent is one or more of γ-methacryloxypropyltrimethoxysilane, 3-(2,3-epoxypropoxy)propyltrimethoxysilane, vinyltrimethoxysilane, and vinyltriethoxysilane.

[0025] Furthermore, the preparation method of the hollow glass microsphere-modified unsaturated polyester resin is as follows:

[0026] D1: By weight: Add 4-8 parts (3-propyl isocyanate)methyldimethoxysilane, 100-120 parts hollow glass microspheres, and 500-1000 parts water to the reactor, stir vigorously at 30-40℃ for 20-60 minutes, filter, and dry.

[0027] D2: Add 10-20 parts of 4,6-dihydroxy-2-mercaptopyrimidine, 0.2-1.4 parts of butyltin oxide, 500-700 parts of DMF to the reaction vessel, and then add 30-50 parts of the product obtained in step D1. Stir and react at 50-75°C for 30-60 minutes.

[0028] D3: Add 0.02-0.2 parts of 1H,1H,11H-perfluoroundecyl acrylate and 2-5 parts of triethylamine to the D2 reactor, react at 70-85℃ for 30-50 minutes, then add 300-350 parts of unsaturated polyester resin, react at 70-85℃ for 50-100 minutes, remove DMF after the reaction is completed, and obtain the unsaturated polyester resin modified with hollow glass microspheres;

[0029] Furthermore, the unsaturated polyester resin mentioned is one or more of the following: unsaturated polyester resin No. 191, unsaturated polyester resin No. 193, unsaturated polyester resin No. 195 and No. 189, unsaturated polyester resin No. 196, unsaturated polyester resin No. 199, unsaturated polyester resin No. 128, and unsaturated polyester resin No. 168. Reaction mechanism:

[0030] (1) (3-propyl isocyanate)methyldimethoxysilane reacts with the hydroxyl groups on the surface of hollow glass microspheres to obtain glass microspheres containing propyl isocyanate.

[0031] (2) 3-Propyl isocyanate undergoes a condensation reaction with the dihydroxyl group of 4,6-dihydroxy-2-mercaptopyrimidine; the mercapto group then undergoes a mercapto-olefin addition reaction with 1H,1H,11H-perfluoroundecyl acrylate to obtain a hollow glass microsphere modified unsaturated polyester resin.

[0032] Technical effects:

[0033] The present invention provides a method for preparing a flame-retardant resin ornament, which, compared with the prior art, has the following significant advantages:

[0034] 1. The pyrimidines and perfluoroundecyl esters in the unsaturated polyester resin modified with hollow glass microspheres can reduce the flammability of the material. Pyrimidines can react with oxygen to produce non-flammable substances, thereby reducing the flammability of the material; perfluoroundecyl esters can also reduce the flammability of the material.

[0035] 2. The unsaturated polyester resin modified with hollow glass microspheres improves the surface finish of the resin ornaments. Perfluoroundecyl groups form a dense fluorocarbon film, reducing surface roughness and thus improving the surface finish of the material.

[0036] 3. It can prevent the ornaments from fading. The hollow glass microspheres have good heat insulation properties, which can reduce the temperature of the material surface and reduce the impact of high temperature on the material, thereby reducing color changes.

[0037] It should be understood that the above general description and the following detailed description are exemplary and explanatory only, and do not limit this application. Detailed Implementation

[0038] To facilitate understanding of the present invention, the invention will be described more fully and in detail below with reference to preferred embodiments, but the scope of protection of the present invention is not limited to the following specific embodiments.

[0039] Example 1

[0040] A method for preparing a flame-retardant resin ornament includes: producing a mold, injection molding, grinding the base, and coloring.

[0041] The operation steps of the production mold are as follows:

[0042] A1: Mix the silicone and curing agent evenly at a ratio of 1:0.005;

[0043] A2: Mix plaster and water in a 1:1 ratio, then add the mixture from A1 and mix to obtain the mold.

[0044] The grouting operation steps are as follows:

[0045] B1: Mix the modified resin, stone powder, accelerator, and 783 slow-drying water evenly in a ratio of 1:0.5:0.0005:0.0001 to obtain a slurry;

[0046] B2: Mix the prepared slurry and curing agent in a ratio of 1:0.002;

[0047] B3: Pour the mixture of B2 into the mold and vacuum it. First, vacuum at -0.06 MPa for 10 seconds, then at -0.02 MPa for 10 seconds, and then at -0.1 MPa for 10 seconds. After completion, close the valve and slowly release the air after 10 seconds.

[0048] The curing agent is vinyltriamine.

[0049] The accelerator is cobalt isooctanoate.

[0050] The grinding process involves using a grinding wheel and a 240 grit sandpaper belt for fine polishing.

[0051] The coloring process is as follows: mix Xinhang paint and thinner in a 1:1 ratio and then apply the color.

[0052] The method for preparing the modified resin is as follows:

[0053] C1: Weigh 5 kg of porous glass microspheres and 1 kg of hollow glass microspheres, and dry them in an 80℃ drying oven for 1 hour;

[0054] C2: Weigh 0.05 kg of silane coupling agent and 10 kg of deionized water, stir and mix evenly to obtain an aqueous solution of silane coupling agent;

[0055] C3: Add the dried microbeads to the aqueous solution of silane coupling agent, stir for 30 min, and then dry in an 80℃ drying oven for 1 h to obtain modified microbeads;

[0056] C4: Weigh 80 kg of unsaturated polyester resin modified with hollow glass microspheres, modified microspheres, 0.5 kg of curing agent, and 0.1 kg of accelerator, mix and stir evenly to obtain modified resin.

[0057] The silane coupling agent is γ-methacryloyloxypropyltrimethoxysilane.

[0058] The preparation method of the hollow glass microsphere modified unsaturated polyester resin is as follows:

[0059] D1: Add 4 kg of (3-propyl isocyanate)methyldimethoxysilane, 100 kg of hollow glass microspheres, and 500 kg of water to the reactor, stir vigorously at 30°C for 20 minutes, filter, and dry.

[0060] D2: Add 10 kg of 4,6-dihydroxy-2-mercaptopyrimidine, 0.2 kg of butyltin oxide, 500 kg of DMF to the reaction vessel, and then add 30 kg of the product obtained in step D1. Stir the reaction vessel at 50°C for 30 minutes.

[0061] D3: Add 0.02 kg of 1H,1H,11H-perfluoroundecyl acrylate and 2 kg of triethylamine to the D2 reactor, react at 70°C for 30 minutes, then add 300 kg of unsaturated polyester resin, react at 70°C for 50 minutes, remove DMF after the reaction is complete, and obtain the unsaturated polyester resin modified with hollow glass microspheres.

[0062] The unsaturated polyester resin is No. 191 unsaturated polyester resin.

[0063] Example 2

[0064] A method for preparing a flame-retardant resin ornament includes: producing a mold, injection molding, grinding the base, and coloring.

[0065] The operation steps of the production mold are as follows:

[0066] A1: Mix the silicone and curing agent evenly at a ratio of 1:0.02;

[0067] A2: Mix plaster and water in a 1:2 ratio, then add the mixture from A1 and mix to obtain the mold.

[0068] The grouting operation steps are as follows:

[0069] B1: Mix the modified resin, stone powder, accelerator, and 783 slow-drying water evenly in a ratio of 1:0.8:0.0006:0.0003 to obtain a slurry;

[0070] B2: Mix the prepared slurry and curing agent in a ratio of 1:0.01;

[0071] B3: Pour the mixture of B2 into the mold and vacuum it. First, vacuum at -0.07 MPa for 15 seconds, then at -0.03 MPa for 15 seconds, and then at -0.15 MPa for 15 seconds. After completion, close the valve and slowly release the air after 15 seconds.

[0072] The curing agent is aminoethylpiperazine.

[0073] The accelerator mentioned is zinc isooctanoate.

[0074] The grinding process involves using a grinding wheel and a 240 grit sandpaper belt for fine polishing.

[0075] The coloring process is as follows: mix Xinhang paint and thinner in a 1:2 ratio and then apply the color.

[0076] The method for preparing the modified resin is as follows:

[0077] C1: Weigh 6 kg of porous glass microspheres and 2 kg of hollow glass microspheres, and dry them in an 85℃ drying oven for 2 hours;

[0078] C2: Weigh 0.1 kg of silane coupling agent and 15 kg of deionized water, stir and mix evenly to obtain an aqueous solution of silane coupling agent;

[0079] C3: Add the dried microbeads to the aqueous solution of silane coupling agent, stir for 50 min, and then dry in an 85℃ drying oven for 2 h to obtain modified microbeads;

[0080] C4: Weigh 85 kg of unsaturated polyester resin modified with hollow glass microspheres, modified microspheres, 0.6 kg of curing agent, and 0.2 kg of accelerator, mix and stir evenly to obtain modified resin.

[0081] The silane coupling agent is 3-(2,3-epoxypropoxy)propyltrimethoxysilane.

[0082] The preparation method of the hollow glass microsphere modified unsaturated polyester resin is as follows:

[0083] D1: Add 5 kg of (3-propyl isocyanate)methyldimethoxysilane, 105 kg of hollow glass microspheres, and 600 kg of water to the reactor, stir vigorously at 35°C for 30 minutes, filter, and dry.

[0084] D2: Add 14 kg of 4,6-dihydroxy-2-mercaptopyrimidine, 0.6 kg of butyltin oxide, 550 kg of DMF to the reaction vessel, and then add 35 kg of the product obtained in step D1. Stir the reaction vessel at 60°C for 40 minutes.

[0085] D3: Add 0.1 kg of 1H,1H,11H-perfluoroundecyl acrylate and 3 kg of triethylamine to the reactor of D2, react at 75°C for 35 minutes, then add 315 kg of unsaturated polyester resin, react at 75°C for 70 minutes, remove DMF after the reaction is completed, and obtain the unsaturated polyester resin modified with hollow glass microspheres.

[0086] The unsaturated polyester resin is No. 193 unsaturated polyester resin.

[0087] Example 3

[0088] A method for preparing a flame-retardant resin ornament includes: producing a mold, injection molding, grinding the base, and coloring.

[0089] The operation steps of the production mold are as follows:

[0090] A1: Mix the silicone and curing agent evenly at a ratio of 1:0.04;

[0091] A2: Mix plaster and water in a 1:4 ratio, then add the mixture from A1 and mix to obtain the mold.

[0092] The grouting operation steps are as follows:

[0093] B1: Mix the modified resin, stone powder, accelerator, and 783 slow-drying water evenly in a ratio of 1:1.3:0.0008:0.0007 to obtain a slurry;

[0094] B2: Mix the prepared slurry and curing agent in a ratio of 1:0.015;

[0095] B3: Pour the mixture of B2 into the mold and vacuum it. First, vacuum at -0.07 MPa for 25 seconds, then at -0.03 MPa for 25 seconds, and then at -0.15 MPa for 25 seconds. After completion, close the valve and slowly release the air after 25 seconds.

[0096] The curing agent is methyl ethyl ketone peroxide.

[0097] The accelerator is cobalt naphthenate.

[0098] The grinding process involves using a grinding wheel and a 240 grit sandpaper belt for fine polishing.

[0099] The coloring process is as follows: mix Xinhang paint and thinner in a 1:2 ratio and then apply the color.

[0100] The method for preparing the modified resin is as follows:

[0101] C1: Weigh 9 kg of porous glass microspheres and 4 kg of hollow glass microspheres, and dry them in a 95℃ drying oven for 3 hours;

[0102] C2: Weigh 0.2 kg of silane coupling agent and 20 kg of deionized water, stir and mix evenly to obtain an aqueous solution of silane coupling agent;

[0103] C3: Add the dried microbeads to the aqueous solution of silane coupling agent, stir for 70 min, and then dry in a 95℃ drying oven for 3 h to obtain modified microbeads;

[0104] C4: Weigh 90 kg of unsaturated polyester resin modified with hollow glass microspheres, modified microspheres, 0.8 kg of curing agent, and 0.4 kg of accelerator, mix and stir evenly to obtain modified resin.

[0105] The silane coupling agent is vinyltrimethoxysilane.

[0106] The preparation method of the hollow glass microsphere modified unsaturated polyester resin is as follows:

[0107] D1: Add 7 kg of (3-propyl isocyanate)methyldimethoxysilane, 115 kg of hollow glass microspheres, and 800 kg of water to the reactor, stir vigorously at 35°C for 50 minutes, filter, and dry.

[0108] D2: Add 18 kg of 4,6-dihydroxy-2-mercaptopyrimidine, 1.2 kg of butyltin oxide, 650 kg of DMF to the reaction vessel, and then add 40 kg of the product obtained in step D1. Stir the reaction at 70°C for 50 minutes.

[0109] D3: Add 0.15 kg of 1H,1H,11H-perfluoroundecyl acrylate and 4 kg of triethylamine to the D2 reactor, react at 80°C for 45 minutes, then add 335 kg of unsaturated polyester resin, react at 80°C for 80 minutes, remove DMF after the reaction is complete, and obtain the unsaturated polyester resin modified with hollow glass microspheres.

[0110] The unsaturated polyester resin mentioned is unsaturated polyester resin No. 195 or No. 189.

[0111] Example 4

[0112] A method for preparing a flame-retardant resin ornament includes: producing a mold, injection molding, grinding the base, and coloring.

[0113] The operation steps of the production mold are as follows:

[0114] A1: Mix the silicone and curing agent evenly at a ratio of 1:0.05;

[0115] A2: Mix plaster and water in a 1:5 ratio, then add the mixture from A1 and mix to obtain the mold.

[0116] The grouting operation steps are as follows:

[0117] B1: Mix the modified resin, stone powder, accelerator, and 783 slow-drying water evenly in a ratio of 1:1.5:0.001:0.0008 to obtain a slurry;

[0118] B2: Mix the prepared slurry and curing agent in a ratio of 1:0.02.

[0119] B3: Pour the mixture of B2 into the mold and vacuum it. First, vacuum at -0.08 MPa for 30 seconds, then at -0.04 MPa for 30 seconds, and then at -0.2 MPa for 30 seconds. After completion, close the valve and slowly release the air after 30 seconds.

[0120] The curing agent is diaminodiphenylmethane.

[0121] The accelerator is N,N-diethylaniline.

[0122] The grinding process involves using a grinding wheel and a 240 grit sandpaper belt for fine polishing.

[0123] The coloring process is as follows: mix Xinhang paint and thinner in a 1:3 ratio and then apply the color.

[0124] The method for preparing the modified resin is as follows:

[0125] C1: Weigh 10kg of porous glass microspheres and 5kg of hollow glass microspheres, and dry them in a 100℃ drying oven for 4 hours;

[0126] C2: Weigh 0.3 kg of silane coupling agent and 25 kg of deionized water, stir and mix evenly to obtain an aqueous solution of silane coupling agent;

[0127] C3: Add the dried microbeads to the aqueous solution of silane coupling agent, stir for 90 min, and then dry in a 100℃ drying oven for 4 h to obtain modified microbeads;

[0128] C4: Weigh 95 kg of unsaturated polyester resin modified with hollow glass microspheres, modified microspheres, 1 kg of curing agent, and 0.5 kg of accelerator, mix and stir evenly to obtain modified resin.

[0129] The silane coupling agent is vinyltriethoxysilane.

[0130] The preparation method of the hollow glass microsphere modified unsaturated polyester resin is as follows:

[0131] D1: Add 8 kg of (3-propyl isocyanate)methyldimethoxysilane, 120 kg of hollow glass microspheres, and 1000 kg of water to the reactor, stir vigorously at 40°C for 60 minutes, filter, and dry.

[0132] D2: Add 20 kg of 4,6-dihydroxy-2-mercaptopyrimidine, 1.4 kg of butyltin oxide, 700 kg of DMF to the reactor, and then add 50 kg of the product obtained in step D1. Stir the reaction at 75°C for 60 minutes.

[0133] D3: Add 0.2 kg of 1H,1H,11H-perfluoroundecyl acrylate and 5 kg of triethylamine to the D2 reactor, react at 85°C for 50 minutes, then add 350 kg of unsaturated polyester resin, react at 85°C for 100 minutes, remove DMF after the reaction is complete, and obtain the unsaturated polyester resin modified with hollow glass microspheres.

[0134] The unsaturated polyester resin is No. 168 unsaturated polyester resin.

[0135] Comparative Example 1

[0136] In this example, (3-propyl isocyanate)methyldimethoxysilane is not added during the preparation of the unsaturated polyester resin modified with hollow glass microspheres, and the rest is the same as in Example 1.

[0137] Comparative Example 2

[0138] In this example, 4,6-dihydroxy-2-mercaptopyrimidine is not added during the preparation of the unsaturated polyester resin modified with hollow glass microspheres, and the rest is the same as in Example 1.

[0139] Comparative Example 3

[0140] In this example, 1H,1H,11H-perfluoroundecyl acrylate is not added during the preparation of the unsaturated polyester resin modified with hollow glass microspheres, and the rest is the same as in Example 1.

[0141] Example Test Method:

[0142] 1. Flame retardancy is tested according to GB / T2460-93 standard;

[0143] 2. The thermal conductivity was tested using the transient hot wire method.

[0144] Table of test results

[0145] Example 1 38 0.038 Smooth surface Example 2 40 0.029 Smooth surface Example 3 43 0.021 Smooth surface Example 4 45 0.012 Smooth surface Comparative Example 1 24.5 0.085 Surface rough Comparative Example 2 28 0.069 Slightly rough surface Comparative Example 3 30 0.061 Slightly rough surface

[0146] Based on the data analysis of the above embodiments and comparative examples, the flame-retardant resin ornaments prepared by the present invention have a high oxygen index, indicating that pyrimidine and perfluoroundecyl ester in the unsaturated polyester resin modified with hollow glass microspheres can reduce the flammability of the material; the flame-retardant resin ornaments prepared by the present invention have good surface smoothness; the flame-retardant resin ornaments prepared by the present invention have low thermal conductivity and good heat insulation performance.

Claims

1. A method for preparing a flame-retardant resin ornament, characterized by: Production of molds, injection molding, base grinding, and coloring; The grouting operation steps are as follows: B1: Mix the modified resin, stone powder, accelerator, and 783 slow-drying water evenly in a ratio of 1:0.5-1.5:0.0005-0.001:0.0001-0.0008 to obtain a slurry; B2: Mix the prepared slurry and curing agent in a ratio of 1:0.002-0.02; B3: Pour the mixture of B2 into the mold and vacuum it. First, vacuum at -0.06~-0.08 MPa for 10-30 seconds, then at -0.02~-0.04 MPa for 10-30 seconds, and then at -0.1~-0.2 MPa for 10-30 seconds. After completion, close the valve and slowly release the air after 10-30 seconds. The method for preparing the modified resin is as follows: C1: Weigh 5-10 parts of porous glass microspheres and 1-5 parts of hollow glass microspheres by weight, and dry them in an 80-100℃ drying oven for 1-4 hours. C2: Weigh 0.05-0.3 parts by weight of silane coupling agent and 10-25 parts by weight of deionized water, stir and mix evenly to obtain an aqueous solution of silane coupling agent; C3: Add the dried microbeads to the aqueous solution of silane coupling agent, stir for 30-90 min, and then dry in an oven at 80-100℃ for 1-4 h to obtain modified microbeads; C4: Weigh 80-95 parts by weight of the unsaturated polyester resin modified with hollow glass microspheres, the modified microspheres, 0.5-1 parts by weight of the curing agent, and 0.1-0.5 parts by weight of the accelerator, mix and stir evenly to obtain the modified resin; The preparation method of the hollow glass microsphere modified unsaturated polyester resin is as follows: D1: By weight: Add 4-8 parts (3-propyl isocyanate)methyldimethoxysilane, 100-120 parts hollow glass microspheres, and 500-1000 parts water to the reactor, stir vigorously at 30-40℃ for 20-60 minutes, filter, and dry. D2: Add 10-20 parts of 4,6-dihydroxy-2-mercaptopyrimidine, 0.2-1.4 parts of butyltin oxide, 500-700 parts of DMF to the reaction vessel, and then add 30-50 parts of the product obtained in step D1. Stir and react at 50-75°C for 30-60 minutes. D3: Add 0.02-0.2 parts of 1H,1H,11H-perfluoroundecyl acrylate and 2-5 parts of triethylamine to the D2 reactor, react at 70-85℃ for 30-50 minutes, then add 300-350 parts of unsaturated polyester resin, react at 70-85℃ for 50-100 minutes, remove DMF after the reaction is completed, and obtain the unsaturated polyester resin modified with hollow glass microspheres; The unsaturated polyester resin is one or more of the following: No. 191 unsaturated polyester resin, No. 193 unsaturated polyester resin, No. 195 and No. 189 unsaturated polyester resin, No. 196 unsaturated polyester resin, No. 199 unsaturated polyester resin, No. 128 unsaturated polyester resin, and No. 168 unsaturated polyester resin.

2. The method for preparing a flame-retardant resin ornament according to claim 1, characterized in that: The operation steps of the production mold are as follows: A1: Mix the silicone and curing agent evenly at a ratio of 1:0.005-0.05; A2: Mix plaster and water in a ratio of 1:1-5, then add the mixture from A1 and mix to obtain the mold.

3. The method for preparing a flame-retardant resin ornament according to claim 1, characterized in that: The curing agent is one or more of vinyltriamine, aminoethylpiperazine, methyl ethyl ketone peroxide, m-phenylenediamine, and diaminodiphenylmethane.

4. The method for preparing a flame-retardant resin ornament according to claim 1, characterized in that: The accelerator is one or more of cobalt isooctanoate, zinc isooctanoate, cobalt naphthenate, N,N-dimethylaniline, and N,N-diethylaniline.

5. The method for preparing a flame-retardant resin ornament according to claim 1, characterized in that: The grinding process involves using a grinding wheel and a 240 grit sandpaper belt for fine polishing.

6. The method for preparing a flame-retardant resin ornament according to claim 1, characterized in that: The coloring process is as follows: mix Xinhang paint and thinner in a ratio of 1:1-3 and then apply the color.

7. The method for preparing a flame-retardant resin ornament according to claim 1, characterized in that: The silane coupling agent is one or more of γ-methacryloxypropyltrimethoxysilane, 3-(2,3-epoxypropoxy)propyltrimethoxysilane, vinyltrimethoxysilane, and vinyltriethoxysilane.