An unsaturated polyester bulk molding compound and its production process

Abstract

This application relates to the technical field of the preparation of thermosetting molding compounds, and in particular to an unsaturated polyester bulk molding compound and its production process. An unsaturated polyester bulk molding compound includes 50 - 80 parts of unsaturated polyester resin, 10 - 20 parts of functionalized modified hydroxytyrosol, 20 - 60 parts of dipropylene glycol diacrylate, 1 - 2 parts of initiator, 0.7 - 1.3 parts of accelerator, 15 - 45 parts of glass fiber, 15 - 20 parts of eggshell powder, 80 - 120 parts of flame retardant, and 1 - 3 parts of mold release agent; its preparation method is: S1 preprocessing, S2 dispersion, S3 formulation, S4 drying, and S5 compression molding. An unsaturated polyester bulk molding compound of this application can reduce the harm to operators and the environment during the preparation or use process.

Description

Technical Field

[0001] This application relates to the technical field of thermosetting molding compound preparation, and particularly relates to an unsaturated polyester bulk molding compound and its production process. Background Art

[0002] BMC (Bulk Molding Compound), whose Chinese name is bulk molding compound. BMC is a semi-dry process for manufacturing a molding intermediate material for fiberglass-reinforced thermosetting products. It is pre-mixed into a paste from unsaturated polyester resin, low shrinkage agent, initiator, internal mold release agent, mineral filler, etc., and then thickener, colorant, etc. are added, and stirred with glass fibers of different lengths in a special material kettle for the thickening process, and finally a bulk intermediate material is formed, which can be used for molding and injection molding.

[0003] In the related art, Chinese Patent with publication number CN112322012A discloses a high-voltage-resistant polyester bulk molding compound composite material and its preparation method. This composite material is made from the following raw materials in parts by weight: 50 - 80 parts of unsaturated polyester resin, 10 - 30 parts of low shrinkage agent, 0.1 - 2 parts of initiator, 100 - 200 parts of aluminum hydroxide, 20 - 45 parts of glass fiber, 10 - 20 parts of calcium carbonate, 1 - 3 parts of mold release agent, 0.2 - 0.5 parts of color paste. Among them, the low shrinkage agent is composed of styrene with a mass percentage of 50 - 60% and polystyrene with 40 - 50%.

[0004] Regarding the above related art, the inventor believes that since the saturated vapor pressure of styrene in the low shrinkage agent is relatively high at room temperature and it is easy to volatilize, and styrene is a toxic gas with a pungent odor, its volatility and toxic side effects will cause great harm to the environment and the health of operators, so it needs to be improved. Summary of the Invention

[0005] In order to reduce the harm to operators and the environment when preparing or using an unsaturated polyester bulk molding compound, this application provides an unsaturated polyester bulk molding compound and its production process.

[0006] An unsaturated polyester bulk molding compound and its production process provided by this application adopt the following technical solutions:

[0007] In the first aspect, this application provides an unsaturated polyester bulk molding compound, adopting the following technical solutions:

[0008] An unsaturated polyester bulk molding compound, the plastic includes the following components in parts by weight:

[0009] 50 - 80 parts of unsaturated polyester resin;

[0010] 10 - 20 parts of functionalized modified hydroxytyrosol;

[0011] 20 - 60 parts of dipropylene glycol diacrylate;

[0012] 1 - 2 parts of initiator;

[0013] 0.7 - 1.3 parts of accelerator;

[0014] 15 - 45 parts of glass fiber;

[0015] 15 - 20 parts of eggshell powder;

[0016] 80 - 120 parts of flame retardant;

[0017] 1 - 3 parts of mold release agent.

[0018] By adopting the above technical solution, the functionalized modified hydroxytyrosol has low volatility and toxicity, and has high reactivity with unsaturated polyester resin, enabling the unsaturated polyester resin to undergo a cross-linking reaction to form a cross-linked network, so that the plastic exhibits good tensile strength, impact strength, flexural strength, and thermal stability. Therefore, the thermal properties and mechanical properties of the cured resin prepared from the functionalized modified hydroxytyrosol are comparable to those of the styrene-containing unsaturated polyester resin. Thus, the functionalized modified hydroxytyrosol can be used as a cross-linking component of the unsaturated polyester resin to replace styrene. When making or using unsaturated polyester bulk molding compounds, the harm to the health of operators and the environment can be reduced.

[0019] In traditional cured resins, styrene not only serves as a cross-linking component but also as a diluent. Its low viscosity and good compatibility with unsaturated polyester resin enable it to significantly reduce the viscosity of the unsaturated polyester resin. The functionalized modified hydroxytyrosol has a poor dilution effect on the unsaturated polyester resin, and the resulting plastic has a high viscosity. Therefore, the diluent dipropylene glycol diacrylate is added to the plastic. Dipropylene glycol diacrylate has good compatibility with the unsaturated polyester resin and can significantly reduce the viscosity of the resin system. Dipropylene glycol diacrylate and the functionalized modified hydroxytyrosol produce a synergistic effect, which helps to further improve the thermal stability and mechanical properties of the plastic.

[0020] Preferably, the preparation process of the functionalized modified hydroxytyrosol is as follows: Under a nitrogen atmosphere, 80 - 90 parts of methacrylic acid, 50 - 70 parts of hydroxytyrosol, and 13 - 15 parts of stannous octoate are mixed evenly by weight, and stirred and reacted at a rotation speed of 200 - 600 r / min. The reaction temperature is 50 - 70 °C, and the reaction time is 4 - 6 h to obtain the functionalized modified hydroxytyrosol.

[0021] By adopting the above technical solution, under the action of the catalyst stannous octoate, through the esterification reaction of methacrylic acid and the compound with hydroxyl group, a functionalized modified hydroxytyrosol containing C=C double bond can be synthesized, and the functionalized modified hydroxytyrosol can be used as a crosslinking component of unsaturated polyester resin. In addition, hydroxytyrosol contains functional groups with rigid structures, which helps to improve the impact strength and flexural strength of plastics.

[0022] Preferably, the initiator includes acetylacetone peroxide and tert-butyl peroxy-2-ethylhexanoate with a mass ratio of 1.5-4:1.

[0023] By adopting the above technical solution, during the preprocessing of plastics, acetylacetone peroxide with a lower initiation temperature decomposes to generate free radicals under the promotion of the promoter, thereby initiating the crosslinking reaction between the functionalized modified hydroxytyrosol and the unsaturated polyester resin. Since the crosslinking reaction is an exothermic reaction, the heat generated by the reaction will cause the decomposition of tert-butyl peroxy-2-ethylhexanoate with a higher initiation temperature, further initiating the crosslinking reaction of the unsaturated polyester resin. The combined use of acetylacetone peroxide and tert-butyl peroxy-2-ethylhexanoate can achieve the crosslinking reaction of the unsaturated polyester resin at room temperature or a lower temperature. It can not only reduce the residual amount of the functionalized modified hydroxytyrosol that does not participate in the crosslinking reaction, but also enable the unsaturated polyester resin to obtain a more complete crosslinking network, which helps to improve the tensile strength, impact strength, and flexural strength of plastics.

[0024] In addition, a synergistic effect can be generated between acetylacetone peroxide and tert-butyl peroxy-2-ethylhexanoate, further improving the initiation efficiency of the initiator. During the preprocessing of plastics, it can reduce the reaction temperature, shorten the time required for crosslinking, and improve production efficiency.

[0025] Preferably, the promoter includes onion extract and ferric chloride with a mass ratio of 6-12:1.

[0026] By adopting the above technical solution, since most traditional promoters are cobalt-containing compounds, but existing studies have shown that long-term exposure to an environment containing cobalt compounds will increase the risk of diseases such as lung limit positive and asthma, so the promoter is selected to use onion extract and ferric chloride to replace the cobalt-containing compounds, reducing the harm to operators. The onion extract can form a reaction system with the initiator, and in combination with ferric chloride, generate active free radicals through redox reaction, further initiating the curing reaction of the unsaturated polyester resin. In addition, the onion extract can weaken the secondary bonds between resin molecules, enhance the plasticity of resin molecules, and improve the flexural strength of plastics. The onion extract can also enhance the thermal stability of plastics.

[0027] Preferably, the glass fiber is 29-42 parts.

[0028] By adopting the above technical solutions, glass fiber can significantly improve the tensile strength, flexural strength and impact strength of plastics. With the increase of glass content, the tensile strength, flexural strength and impact strength of plastics show a trend of first increasing and then decreasing. When the glass fiber is 29 - 42 parts, the plastics have relatively high tensile strength, flexural strength and impact strength.

[0029] Preferably, the eggshell powder is modified, and the modification process is as follows: by weight, first dry 90 - 110 parts of eggshell powder at 70 - 80 °C for 4 - 7 h; then disperse 1 - 2 parts of titanate coupling agent in 50 - 60 parts of absolute ethanol to obtain a mixed solution; then mix the dried eggshell powder and the mixed solution evenly, stir at a rotation speed of 1500 - 2000 r / min, the stirring temperature is 85 - 95 °C, and the stirring time is 1 - 3 h to obtain a pre - prepared solution. Finally, filter and dehydrate the pre - prepared solution, and dry it at 100 - 115 °C for 2 - 4 h to obtain the modified eggshell powder.

[0030] By adopting the above technical solutions, the hydrophilic functional groups of the titanate coupling agent form chemical bonds with the eggshell powder, and the lipophilic functional groups form chemical bonds with the hydrophobic resin molecules, thereby improving the compatibility between the eggshell powder and the resin, and further enhancing the impact strength and tensile strength of the plastics. The modified eggshell powder can also reduce the decomposition of plastics due to external factors and enhance the stability of plastics.

[0031] Preferably, the flame retardant includes aluminum hydroxide, zinc borate, polyborosiloxane, and ammonium polyphosphate with a mass ratio of 73 - 91:3 - 9:4 - 12:2 - 6.

[0032] By adopting the above technical solutions, aluminum hydroxide, zinc borate, polyborosiloxane, and ammonium polyphosphate are all excellent flame retardants, which can effectively improve the flame - retardant performance of plastics. Among them, zinc borate and ammonium polyphosphate have a synergistic effect, further improving the flame - retardancy of plastics. Polyborosiloxane can not only act as a flame retardant, but also have a synergistic effect with resin molecules to improve the thermal stability of plastics.

[0033] In the second aspect, the present application provides a production process for unsaturated polyester bulk molding compound, adopting the following technical solutions:

[0034] A production process for unsaturated polyester bulk molding compound includes the following steps:

[0035] S1 Pre - processing: According to the weight parts required by the formula, stir and knead unsaturated polyester resin, functionalized modified hydroxytyrosol, dipropylene glycol diacrylate, initiator, accelerator, and release agent. The stirring speed is 700 - 850 r / min, the stirring temperature is 20 - 45 °C, and the stirring time is 12 - 20 min to obtain a resin paste;

[0036] S2 Dispersion: According to the weight parts required by the formula, add eggshell powder and flame retardant to the resin paste obtained by S1 pre - processing, and stir and knead. The stirring speed is 700 - 850 r / min, the stirring temperature is 20 - 45 °C, and the stirring time is 25 - 45 min to obtain an intermediate product; S3 Preparation: According to the weight parts required by the formula, add glass fiber to the intermediate product obtained by S2 dispersion, and stir and knead. The stirring speed is 800 - 900 r / min, the stirring temperature is 20 - 45 °C, and the stirring time is 8 - 10 min to obtain a premix.

[0037] S4 Drying: Extrude the premix prepared in S3 into strips or pellets, and dry at 30 - 50 °C for 6 - 8 h to obtain an unsaturated polyester bulk molding compound.

[0038] S5 Compression Molding: Compress and mold the unsaturated polyester bulk molding compound prepared in S4 at 140 - 150 °C. The molding pressure is 3 - 5 MPa, the mold - closing speed is 20 - 30 mm / min. After pressure holding for 120 - 180 s, cool at room temperature for 18 - 24 h to obtain an unsaturated polyester bulk molding plastic.

[0039] In summary, the present application has the following beneficial effects:

[0040] 1. Functionalized modified hydroxytyrosol can be used as a cross - linking component of unsaturated polyester resin instead of styrene, and dipropylene glycol diacrylate can be used as a diluent component of unsaturated polyester resin instead of styrene. Both functionalized modified hydroxytyrosol and dipropylene glycol diacrylate are low - volatile and low - toxicity substances, which reduces the harm to operators and the environment when preparing or using unsaturated polyester bulk molding plastics.

[0041] 2. The initiator includes acetylacetone peroxide with a lower initiation temperature and tert - butyl peroxy - 2 - ethylhexanoate with a higher initiation temperature. The two form a composite initiation system, which makes the cross - linking reaction of unsaturated polyester resin more sufficient, helps to improve the tensile strength, impact strength, and flexural strength of the plastic; there is a synergistic effect between acetylacetone peroxide and tert - butyl peroxy - 2 - ethylhexanoate, which shortens the reaction time and improves production efficiency.

[0042] 3. The accelerator is selected as onion extract and ferric chloride to replace cobalt - containing compounds, avoiding the risk of increasing the incidence of diseases such as lung limit positive and asthma due to long - term exposure to cobalt - containing compounds, which helps to further reduce the harm to operators and the environment. The onion extract can also improve the flexural strength and thermal stability of the plastic. Specific Embodiments

[0043] The following further elaborates on this application in conjunction with embodiments. It should be specifically noted that: for those not specifying specific conditions in the following embodiments, they are carried out according to conventional conditions or conditions recommended by the manufacturer. Unless otherwise specified, the raw materials used in the following embodiments can all be obtained from ordinary commercial sources.

[0044] The embodiments of this application use the following raw materials:

[0045] The unsaturated polyester resin model is DC191, purchased from Wanqing Chemical Technology Co., Ltd.; the glass fiber is selected as 12mm chopped glass filaments; the eggshell powder has a particle size of 80 mesh, purchased from Xi'an Longmao Biotechnology Co., Ltd.; the mold release agent is selected as zinc stearate; the titanate coupling agent model is NXH-501, purchased from Nanjing Xuanhao New Materials Technology Co., Ltd.; the polyborosiloxane is selected as polydimethylsiloxane, model GB201-50, purchased from Shandong Jueneng Chemical Co., Ltd.; the ammonium polyphosphate model is FR-AP1002, purchased from Guangzhou Yinyuan New Materials Co., Ltd.; the alkylene glycidyl ether model is HK-66, purchased from Jiangsu Xinsu New Materials Co., Ltd.

[0046] Preparation Example 1:

[0047] The preparation process of onion extract is as follows: First, wash the fresh onions and cut them into filaments, then dry the onion filaments at 65°C for 3h, then crush them and filter with a 60-mesh sieve to obtain dry onion powder; then reflux extract the onion powder and 75% ethanol by volume at a ratio of 1:15 g / mL twice, with the extraction temperature being 80°C and the extraction time being 2h. During the extraction process, stir the raw materials once every 15 minutes for 3 minutes each time, collect the extracted filtrate to obtain the extract; vacuum rotary evaporate the extract at 50°C and then obtain the onion extract after freeze-drying.

[0048] Preparation Example 2:

[0049] The preparation process of functionalized modified hydroxytyrosol is as follows: Under a nitrogen atmosphere, mix 80 Kg of methacrylic acid, 50 Kg of hydroxytyrosol, and 13 Kg of stannous octoate evenly, stir and react at a speed of 200 r / min, with the reaction temperature being 50°C and the reaction time being 4h to obtain functionalized modified hydroxytyrosol.

[0050] Preparation Example 3:

[0051] The preparation process of functionalized modified hydroxytyrosol is as follows: Under a nitrogen atmosphere, mix 90 Kg of methacrylic acid, 70 Kg of hydroxytyrosol, and 15 Kg of stannous octoate evenly, stir and react at a speed of 600 r / min, with the reaction temperature being 70°C and the reaction time being 6h to obtain functionalized modified hydroxytyrosol.

[0052] Preparation Example 4:

[0053] The preparation process of functionalized modified hydroxytyrosol is as follows: Under a nitrogen atmosphere, 85 Kg of methacrylic acid, 60 Kg of hydroxytyrosol, and 14 Kg of stannous octoate are mixed evenly, stirred and reacted at a speed of 400 r / min, the reaction temperature is 60 °C, and the reaction time is 5 h to obtain functionalized modified hydroxytyrosol.

[0054] Preparation Example 5:

[0055] The preparation process of modified eggshell powder is as follows: First, 90 Kg of eggshell powder is dried at 70 °C for 4 h; then 1 Kg of titanate coupling agent is dispersed in 50 Kg of absolute ethanol to obtain a mixed solution; then the dried eggshell powder and the mixed solution are mixed evenly, stirred at a speed of 1500 r / min, the stirring temperature is 85 °C, and the stirring time is 1 h to obtain a pre-prepared solution. Finally, the pre-prepared solution is filtered and dehydrated, and dried at 100 °C for 2 h to obtain modified eggshell powder.

[0056] Preparation Example 6

[0057] The preparation process of modified eggshell powder is as follows: First, 110 Kg of eggshell powder is dried at 80 °C for 7 h; then 2 Kg of titanate coupling agent is dispersed in 60 Kg of absolute ethanol to obtain a mixed solution; then the dried eggshell powder and the mixed solution are mixed evenly, stirred at a speed of 2000 r / min, the stirring temperature is 95 °C, and the stirring time is 3 h to obtain a pre-prepared solution. Finally, the pre-prepared solution is filtered and dehydrated, and dried at 115 °C for 4 h to obtain modified eggshell powder.

[0058] Preparation Example 7

[0059] The preparation process of modified eggshell powder is as follows: First, 100 Kg of eggshell powder is dried at 75 °C for 5.5 h; then 1.5 Kg of titanate coupling agent is dispersed in 55 Kg of absolute ethanol to obtain a mixed solution; then the dried eggshell powder and the mixed solution are mixed evenly, stirred at a speed of 1750 r / min, the stirring temperature is 90 °C, and the stirring time is 2 h to obtain a pre-prepared solution. Finally, the pre-prepared solution is filtered and dehydrated, and dried at 107 °C for 3 h to obtain modified eggshell powder.

[0060] Example 1

[0061] The unsaturated polyester bulk molding compound comprises components with the following masses:

[0062] 50 Kg of unsaturated polyester resin;

[0063] 10 Kg of the functionalized modified hydroxytyrosol prepared in Preparation Example 2;

[0064] 20 Kg of dipropylene glycol diacrylate;

[0065] 1 Kg of MEKP;

[0066] Cobalt naphthenate 0.7 Kg;

[0067] 12 mm glass fiber short cut filaments 15 Kg;

[0068] Eggshell powder 15 Kg;

[0069] Aluminum hydroxide 80 Kg;

[0070] Zinc stearate 1 Kg.

[0071] A production process of unsaturated polyester bulk molding compound, comprising the following steps:

[0072] S1 Preprocessing: According to the required weights in the formula, stir and knead unsaturated polyester resin, functionalized modified hydroxytyrosol, dipropylene glycol diacrylate, MEKP, cobalt naphthenate, and zinc stearate. The stirring speed is 700 r / min, the stirring temperature is 20 °C, and the stirring time is 12 min to obtain a resin paste;

[0073] S2 Dispersion: According to the required weights in the formula, add eggshell powder and aluminum hydroxide to the resin paste obtained in S1 preprocessing and stir and knead. The stirring speed is 700 r / min, the stirring temperature is 20 °C, and the stirring time is 25 min to obtain an intermediate product;

[0074] S3 Preparation: According to the required weights in the formula, add glass fiber to the intermediate product obtained in S2 dispersion and stir and knead. The stirring speed is 800 r / min, the stirring temperature is 20 °C, and the stirring time is 8 min to obtain a premix;

[0075] S4 Drying: Extrude the premix prepared in S3 into strips or pellets and dry at 30 °C for 6 h to obtain unsaturated polyester bulk molding compound;

[0076] S5 Compression molding: Clamp and pressurize the unsaturated polyester bulk molding compound prepared in S4 at 140 °C. The molding pressure is 3 MPa, the clamping speed is 20 mm / min. After 120 s of pressure holding, cool at room temperature for 18 h to obtain unsaturated polyester bulk molding compound.

[0077] Example 2

[0078] The unsaturated polyester bulk molding compound comprises the following components by mass:

[0079] Unsaturated polyester resin 80 Kg;

[0080] Functionalized modified hydroxytyrosol prepared in Preparation Example 2 20 Kg;

[0081] Dipropylene glycol diacrylate 60 Kg;

[0082] MEKP 2 Kg;

[0083] 1.3 Kg of cobalt naphthenate;

[0084] 45 Kg of 12 mm chopped glass fiber;

[0085] 20 Kg of eggshell powder;

[0086] 120 Kg of aluminum hydroxide;

[0087] 3 Kg of zinc stearate.

[0088] A production process of unsaturated polyester bulk molding compound includes the following steps:

[0089] S1 Preprocessing: According to the required weights in the formula, stir and knead unsaturated polyester resin, functionalized modified hydroxytyrosol, dipropylene glycol diacrylate, MEKP, cobalt naphthenate, and zinc stearate. The stirring speed is 850 r / min, the stirring temperature is 45 °C, and the stirring time is 20 min to obtain a resin paste;

[0090] S2 Dispersion: According to the required weights in the formula, add eggshell powder and aluminum hydroxide to the resin paste obtained in S1 and stir and knead. The stirring speed is 850 r / min, the stirring temperature is 45 °C, and the stirring time is 45 min to obtain an intermediate product;

[0091] S3 Preparation: According to the required weights in the formula, add glass fiber to the intermediate product obtained in S2 and stir and knead. The stirring speed is 900 r / min, the stirring temperature is 45 °C, and the stirring time is 10 min to obtain a premix;

[0092] S4 Drying: Extrude the premix prepared in S3 into strips or pellets and dry at 50 °C for 8 h to obtain unsaturated polyester bulk molding compound;

[0093] S5 Compression molding: Close the mold and apply pressure to the unsaturated polyester bulk molding compound prepared in S4 at 150 °C. The molding pressure is 5 MPa, the mold closing speed is 30 mm / min. After 180 s of pressure holding, cool at room temperature for 24 h to obtain unsaturated polyester bulk molding compound.

[0094] Example 3

[0095] The unsaturated polyester bulk molding compound includes the following components by mass:

[0096] 65 Kg of unsaturated polyester resin;

[0097] 15 Kg of functionalized modified hydroxytyrosol prepared in Preparation Example 2;

[0098] 40 Kg of dipropylene glycol diacrylate;

[0099] 1.5 Kg of MEKP;

[0100] 1 Kg of cobalt naphthenate;

[0101] 30 Kg of 12 mm glass fiber short cut filaments;

[0102] 17.5 Kg of eggshell powder;

[0103] 100 Kg of aluminum hydroxide;

[0104] 2 Kg of zinc stearate.

[0105] A production process of an unsaturated polyester bulk molding compound, comprising the following steps:

[0106] S1 Pretreatment: According to the required weights in the formula, stir and knead unsaturated polyester resin, functionalized modified hydroxytyrosol, dipropylene glycol diacrylate, MEKP, cobalt naphthenate, and zinc stearate. The stirring speed is 775 r / min, the stirring temperature is 32 °C, and the stirring time is 16 min to obtain a resin paste;

[0107] S3 Preparation: According to the required weights in the formula, add glass fiber to the intermediate product obtained by dispersion in S2 and stir and knead. The stirring speed is 850 r / min, the stirring temperature is 32 °C, and the stirring time is 9 min to obtain a premix;

[0108] S4 Drying: Extrude the premix prepared in S3 into strips or pellets and dry at 40 °C for 7 h to obtain an unsaturated polyester bulk molding compound;

[0109] S5 Compression molding: Clamp and pressurize the unsaturated polyester bulk molding compound prepared in S4 at 145 °C. The molding pressure is 4 MPa, the mold closing speed is 25 mm / min. After 150 s of pressure holding, cool at room temperature for 21 h to obtain an unsaturated polyester bulk molding compound.

[0110] Example 4

[0111] The difference from Example 3 is that the functionalized modified hydroxytyrosol prepared in Preparation Example 2 is replaced with the functionalized modified hydroxytyrosol prepared in Preparation Example 3 in equal mass.

[0112] Example 5

[0113] The difference from Example 3 is that the functionalized modified hydroxytyrosol prepared in Preparation Example 2 is replaced with the functionalized modified hydroxytyrosol prepared in Preparation Example 4 in equal mass.

[0114] Example 6

[0115] The difference from Example 5 is that MEKP is replaced with 0.9 Kg of acetylacetone peroxide and 0.6 Kg of tert-butyl peroxy-2-ethylhexanoate in equal mass.

[0116] Example 7

[0117] The difference from Example 5 is that the same mass of MEKP is replaced with 1.2 Kg of acetylacetone peroxide and 0.3 Kg of tert-butyl peroxy-2-ethylhexanoate.

[0118] Example 8

[0119] The difference from Example 5 is that the same mass of MEKP is replaced with 1 Kg of acetylacetone peroxide and 0.5 Kg of tert-butyl peroxy-2-ethylhexanoate.

[0120] Example 9

[0121] The difference from Example 8 is that the same mass of cobalt naphthenate is replaced with 0.86 Kg of onion extract and 0.14 Kg of iron chloride.

[0122] Example 10

[0123] The difference from Example 8 is that the same mass of cobalt naphthenate is replaced with 0.92 Kg of onion extract and 0.08 Kg of iron chloride.

[0124] Example 11

[0125] The difference from Example 8 is that the same mass of cobalt naphthenate is replaced with 0.9 Kg of onion extract and 0.1 Kg of iron chloride.

[0126] Example 12

[0127] The difference from Example 11 is that the addition amount of 12 mm short glass fiber filaments is 29 Kg.

[0128] Example 13

[0129] The difference from Example 11 is that the addition amount of 12 mm short glass fiber filaments is 42 Kg.

[0130] Example 14

[0131] The difference from Example 11 is that the addition amount of 12 mm short glass fiber filaments is 39 Kg.

[0132] Example 15

[0133] The difference from Example 14 is that the same mass of eggshell powder is replaced with the modified eggshell powder prepared in Preparation Example 5.

[0134] Example 16

[0135] The difference from Example 14 is that the same mass of eggshell powder is replaced with the modified eggshell powder prepared in Preparation Example 6.

[0136] Example 17

[0137] The difference from Example 14 is that the eggshell powder is replaced with the modified eggshell powder prepared in Preparation Example 7 in equal mass.

[0138] Example 18

[0139] The difference from Example 17 is that 3 Kg of aluminum hydroxide is replaced with zinc borate in equal mass, 4 Kg of aluminum hydroxide is replaced with polydimethylsiloxane in equal mass, and 2 Kg of aluminum hydroxide is replaced with ammonium polyphosphate in equal mass.

[0140] Example 19

[0141] The difference from Example 17 is that 9 Kg of aluminum hydroxide is replaced with zinc borate in equal mass, 12 Kg of aluminum hydroxide is replaced with polydimethylsiloxane in equal mass, and 6 Kg of aluminum hydroxide is replaced with ammonium polyphosphate in equal mass.

[0142] Example 20

[0143] The difference from Example 17 is that 6 Kg of aluminum hydroxide is replaced with zinc borate in equal mass, 8 Kg of aluminum hydroxide is replaced with polydimethylsiloxane in equal mass, and 4 Kg of aluminum hydroxide is replaced with ammonium polyphosphate in equal mass.

[0144] Comparative Example 1

[0145] The difference from Example 3 is that the functionalized modified hydroxytyrosol and dipropylene glycol diacrylate are both replaced with styrene in equal mass.

[0146] Comparative Example 2

[0147] The difference from Example 3 is that the dipropylene glycol diacrylate is replaced with alkylene glycidyl ether in equal mass.

[0148] Comparative Example 3

[0149] The difference from Example 3 is that the functionalized modified hydroxytyrosol is replaced with styrene in equal mass.

[0150] Performance Test:

[0151] The tensile properties of the unsaturated polyester bulk molding compounds of Examples 1 - 20 and Comparative Examples 1 - 3 were tested by referring to the method described in GB / T 1447 - 2005 "Test Method for Tensile Properties of Fiber Reinforced Plastics". The plastics were prepared with Type III specimen dimensions and a thickness of 6 mm. The results are shown in Table 1.

[0152] The impact toughness of the unsaturated polyester bulk molding compounds of Examples 1 - 20 and Comparative Examples 1 - 3 was tested by referring to the method described in GB / T 1451 - 2005 "Test Method for Notched Izod Impact Strength of Fiber Reinforced Plastics". The width of the plastic specimens was 10 mm, and the notch direction was the same as the pressing direction. The results are shown in Table 1.

[0153] The flexural properties of the unsaturated polyester bulk molding compounds of Examples 1-20 and Comparative Examples 1-3 were tested according to the method described in GB / T 1449-2005 "Test Method for Flexural Properties of Fiber Reinforced Plastics". The thickness of the plastic specimens was 4 mm, the width was 15 mm, and the length was 25 mm. The results are shown in Table 1.

[0154] The reactivity of the unsaturated polyester bulk molding compounds of Examples 1-20 and Comparative Examples 1-3 was tested according to the method described in GB / T 36532-2018 "Determination of Curing Characteristics of Thermosetting Molding Compounds and Prepregs for Fiber Reinforced Plastics" to reflect the curing characteristics of the plastics. The results are shown in Table 1.

[0155] Table 1 Record Table of Tensile Properties, Impact Toughness, Flexural Properties, and Reactivity Results of Unsaturated Polyester Bulk Molding Compounds

[0156]

[0157]

[0158] It can be seen from Table 1 that:

[0159] 1. By comparing the test results of Examples 1-3 and Comparative Example 1, functionalized modified hydroxytyrosol and dipropylene glycol diacrylate can be used to replace styrene as the crosslinking and diluting components of unsaturated polyester resin, and have a high reactivity with unsaturated polyester resin, making the plastics exhibit good tensile strength, impact strength, and flexural strength.

[0160] 2. By comparing the test results of Examples 1-3 and Comparative Example 2, dipropylene glycol diacrylate and functionalized modified hydroxytyrosol improve the mechanical properties of the plastics.

[0161] 3. By comparing the test results of Examples 1-3 and Comparative Example 3, adding functionalized modified hydroxytyrosol can improve the tensile strength, impact strength, and flexural strength of the plastics.

[0162] 4. By comparing the test results of Example 3 and Examples 4-5, as the content of functionalized modified hydroxytyrosol increases, the reactivity of functionalized modified hydroxytyrosol with unsaturated polyester resin increases, and the impact strength and flexural strength of the plastics are significantly improved.

[0163] 5. By comparing the test results of Example 5 and Examples 6-8, acetylacetone peroxide and tert-butyl peroxy-2-ethylhexanoate can significantly enhance the crosslinking reactivity of unsaturated polyester resin and improve the tensile strength, impact strength, and flexural strength of the plastics.

[0164] 6. By comparing the test results of Example 8 and Examples 9 - 11, it can be obtained that onion extract and ferric chloride can significantly improve the crosslinking reaction activity of unsaturated polyester resin, and onion extract can increase the flexural strength of plastics.

[0165] 7. By comparing the test results of Example 11 and Examples 12 - 14, when the addition amount of 12mm short glass fiber filaments is 29 - 42 Kg, it can significantly improve the tensile strength, impact strength and flexural strength of plastics.

[0166] 8. By comparing the test results of Example 12 and Examples 15 - 17, it can be obtained that the modified eggshell powder can improve the compatibility between the eggshell and resin molecules, which helps to improve the impact strength and tensile strength of plastics.

[0167] Refer to the method described in GB / T 2408 - 2021 "Plastics - Determination of burning behavior - Horizontal and vertical methods" to conduct the burning performance test of plastics on the unsaturated polyester bulk molding compounds of Examples 1 - 20. The flame retardant grade is determined according to the standard of decreasing level by level of V - 0, V - 1, V - 2, and the V - 2 flame retardant performance is the worst. The obtained results are shown in Table 2.

[0168] Refer to the method described in GB / T 1634.2 - 2019 "Plastics - Determination of heat distortion temperature - Part 2: Plastics and hard rubbers" to conduct the heat distortion temperature test of plastics on the unsaturated polyester bulk molding compounds of Examples 1 - 20, which reflects the thermal stability of plastics. The obtained results are shown in Table 2.

[0169] Table 2 Record table of flame retardancy and thermal stability results of unsaturated polyester bulk molding compounds

[0170]

[0171]

[0172] As can be seen from Table 2:

[0173] 1. By comparing the test results of Example 8 and Examples 9 - 11, it can be obtained that onion extract can improve the thermal stability of plastics.

[0174] 2. By comparing the test results of Example 14 and Examples 15 - 17, it can be obtained that the modified eggshell powder can also reduce the self - decomposition of plastics due to external factors and enhance the thermal stability of plastics.

[0175] 3. By comparing the test results of Example 17 and Examples 18 - 20, it can be obtained that the flame retardant system composed of aluminum hydroxide, zinc borate, polyborosiloxane and ammonium polyphosphate can improve the flame retardant performance of plastics and also improve the thermal stability of plastics.

[0176] The above are all preferred embodiments of the present application, and the protection scope of the present application is not limited thereby. Therefore, all equivalent changes made according to the structure, shape, and principle of the present application shall be covered within the protection scope of the present application.

Claims

1. An unsaturated polyester bulk molding compound, characterized in that, The plastic includes the following components in parts by weight: Unsaturated polyester resin: 50 - 80 parts; Functionalized modified hydroxytyrosol: 10 - 20 parts; Tripropylene glycol diacrylate: 20 - 60 parts; Initiator: 1 - 2 parts; Accelerator: 0.7 - 1.3 parts; Glass fiber: 15 - 45 parts; Eggshell powder: 15 - 20 parts; Flame retardant: 80 - 120 parts; Release agent: 1 - 3 parts; The preparation process of the functionalized modified hydroxytyrosol is as follows: Under the environment of passing nitrogen, 80 - 90 parts of methacrylic acid, 50 - 70 parts of hydroxytyrosol, and 13 - 15 parts of stannous octoate are mixed evenly by weight, stirred and reacted at a rotation speed of 200 - 600 r / min, the reaction temperature is 50 - 70 °C, and the reaction time is 4 - 6 h to obtain the functionalized modified hydroxytyrosol.

2. The unsaturated polyester bulk molding compound according to claim 1, wherein: The initiator includes acetylacetone peroxide and tert-butyl peroxy-2-ethylhexanoate with a mass ratio of 1.5 - 4:

1.

3. The unsaturated polyester bulk molding compound according to claim 1, characterized in that: The accelerator includes onion extract and ferric chloride with a mass ratio of 6 - 12:

1.

4. The unsaturated polyester bulk molding compound according to claim 1, wherein: The glass fiber is 29 - 42 parts.

5. The unsaturated polyester bulk molding compound according to claim 1, characterized in that: The eggshell powder is modified, and the modification process is as follows: By weight, first dry 90 - 110 parts of eggshell powder at 70 - 80 °C for 4 - 7 h; then disperse 1 - 2 parts of titanate coupling agent in 50 - 60 parts of absolute ethanol to obtain a mixed solution; then mix the dried eggshell powder and the mixed solution evenly, stir at a rotation speed of 1500 - 2000 r / min, the stirring temperature is 85 - 95 °C, and the stirring time is 1 - 3 h to obtain a pre-prepared solution. Finally, filter and dehydrate the pre-prepared solution and dry it at 100 - 115 °C for 2 - 4 h to obtain the modified eggshell powder.

6. The unsaturated polyester bulk molding compound according to claim 1, characterized in that: The flame retardant includes aluminum hydroxide, zinc borate, polyborosiloxane, and ammonium polyphosphate with a mass ratio of 73 - 91:3 - 9:4 - 12:2 - 6.

7. The production process of the unsaturated polyester bulk molding compound according to any one of claims 1-6, characterized in that, It includes the following steps: S1 Preprocessing: According to the parts by weight required by the formula, stir and knead unsaturated polyester resin, functionalized modified hydroxytyrosol, tripropylene glycol diacrylate, initiator, accelerator, and release agent, the stirring speed is 700 - 850 r / min, the stirring temperature is 20 - 45 °C, and the stirring time is 1 - 2 h to obtain a resin paste; S2 Dispersion: According to the parts by weight required by the formula, add eggshell powder and flame retardant to the resin paste obtained in S1 preprocessing and stir and knead, the stirring speed is 1000 - 1100 r / min, the stirring temperature is 20 - 45 °C, and the stirring time is 25 - 45 min to obtain an intermediate product; S3 Preparation: According to the parts by weight required by the formula, add glass fiber to the intermediate product obtained in S2 dispersion and stir and knead, the stirring speed is 800 - 900 r / min, the stirring temperature is 20 - 45 °C, and the stirring time is 8 - 10 min to obtain a premix; S4 Drying: Extrude the premix prepared in S3 into strips or pellets and dry it at 30 - 50 °C for 6 - 8 h to obtain an unsaturated polyester bulk molding compound; S5 Compression Molding: The unsaturated polyester bulk molding compound prepared in S4 is subjected to mold clamping and pressurization at 140 - 150 °C, with a molding pressure of 3 - 5 MPa, a mold clamping speed of 20 - 30 mm / min. After pressure holding for 120 - 180 s, it is cooled at room temperature for 18 - 24 h to obtain the unsaturated polyester bulk molding compound.

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