Environment-friendly unsaturated polyester cement mortar and preparation method thereof

Abstract

The environment-friendly unsaturated polyester cement mortar comprises a binding material and aggregate, the binding material is unsaturated polyester resin, and the aggregate comprises cement, standard sand, copper slag and iron slag. The raw materials are wide in source and easy to obtain. The copper slag and the iron slag are industrial solid wastes, have strong suitability with a resin material, can optimize the porosity and the fluidity of the mortar, also can significantly reduce the resin dosage of the mortar, and have excellent mechanical properties and corrosion resistance. In order to reduce the negative influence of volatilization of traditional styrene unsaturated polyester mortar on health and environment, 4-acryloylmorpholine is adopted to replace styrene to prepare environment-friendly unsaturated polyester resin, and a palm oil refining byproduct GC14 is further introduced to reduce the water absorption of the mortar and improve the water resistance and bio-based content of the mortar. And a new way is provided for preparation and application of the low-carbon mortar.

Description

Technical Field

[0001] The present invention relates to the technical field of novel building materials, in particular to an environmentally friendly unsaturated polyester cement mortar and a preparation method thereof. Background Art

[0002] Polymer mortar, a composite material composed of polymer resin and inorganic aggregates, effectively addresses the low bond strength, high shrinkage, and poor crack resistance of cement mortar. It is suitable for grouting joints, repairing concrete structures, and emergency repairs of roads and bridges, offering high wear resistance, high strength, and low permeability. Epoxy mortar, based on epoxy resin, despite its superior performance, is limited by its high cost. Furthermore, the preparation of epoxy mortar requires the addition of multiple chemical additives, posing a potential threat to the environment. Consequently, conventional styrene unsaturated polyester resins present the following challenges:

[0003] 1. Styrene, a commonly used crosslinking diluent in traditional styrene-based unsaturated polyester resins, is volatile and toxic, causing serious environmental pollution. It is classified as a Class 2B carcinogen by the International Agency for Research on Cancer and poses a serious health threat to workers in production plants. Therefore, finding environmentally friendly reactive solvents to replace styrene in the preparation of polymer cement mortar composites is key to achieving styrene-free unsaturated polyester resins.

[0004] 2. Furthermore, my country's metallurgical waste, which contains metals such as steel and copper, has high resource potential and market value, and effective reuse could generate significant economic benefits. However, due to its low reuse rate, it is currently primarily disposed of through backfilling and mixing with construction materials, which has adverse effects on the soil, atmosphere, and living environment. In particular, complex heavy metal pollution is difficult to control. Therefore, the application of metallurgical slag in unsaturated polyester cement mortar provides a new avenue for the resource utilization of metallurgical slag and promotes industry development. Summary of the Invention

[0005] The purpose of the present invention is to solve the above-mentioned problems and propose an environmentally friendly unsaturated polyester cement mortar and a preparation method thereof. 4-Acryloylmorpholine is used instead of styrene to prepare acryloylmorpholine unsaturated polyester resin, and GC14, a by-product of palm oil refining, is further introduced as a hydrophobic modifier to prepare unsaturated polyester resin cement mortar to reduce the water absorption of the mortar, improve its water resistance and bio-based content, and at the same time, copper slag and iron slag are used as aggregates, which not only effectively reduces environmental pollution, but also significantly improves the performance of the cement mortar, thereby realizing the resource utilization of solid waste.

[0006] In order to achieve the above purpose, the following technical solutions are adopted:

[0007] An environmentally friendly unsaturated polyester cement mortar comprises a cementitious material and aggregates. The cementitious material comprises an environmentally friendly unsaturated polyester resin, cobalt naphthenate and 2-butanone peroxide, and the aggregates comprise cement, standard sand, copper slag and iron slag.

[0008] Furthermore, the cementitious material accounts for 10% to 15% of the total mass of the mortar, and the aggregate accounts for 85% to 90% of the total mass of the mortar, wherein cement accounts for 5% to 10% of the mass of the aggregate, standard sand accounts for 50% to 60% of the mass of the aggregate, copper slag accounts for 5% to 15% of the mass of the aggregate, and iron slag accounts for 20% to 30% of the mass of the aggregate, and the sum of the total mass fractions of the cementitious material and the aggregate is 100%.

[0009] Furthermore, the environmentally friendly unsaturated polyester resin is a styrene-free unsaturated polyester resin, which is prepared from an unsaturated polyester prepolymer and a styrene-free reactive solvent. The unsaturated polyester prepolymer is synthesized with propylene glycol, isophthalic acid, butyl titanate, fumaric acid and 4-methoxyphenol as main raw materials, and the reactive solvent is composed of 4-acryloylmorpholine and GC14, a by-product of palm oil refining.

[0010] Furthermore, the propylene glycol accounts for 35% to 45% of the total mass of the unsaturated polyester prepolymer, the isophthalic acid accounts for 35% to 40% of the total mass of the unsaturated polyester prepolymer, the butyl titanate accounts for 0.1‰ to 0.6‰ of the total mass of the unsaturated polyester prepolymer, the fumaric acid accounts for 25% to 30% of the total mass of the unsaturated polyester prepolymer, and the 4-methoxyphenol accounts for 0 to 0.2‰ of the total mass of the unsaturated polyester prepolymer.

[0011] Furthermore, the synthesis method of the unsaturated polyester prepolymer is:

[0012] A1: Propylene glycol, isophthalic acid, and butyl titanate are mixed to obtain a mixture A. The mixture A is placed in an oil bath at 225°C to 235°C under nitrogen protection and mechanically stirred for 20 to 40 minutes. When the mixture A is cooled to 210°C, the reaction is continued for 360 to 380 minutes.

[0013] A2: Fumaric acid and 4-methoxyphenol are mixed to obtain a mixture B. After the temperature of the mixture A is reduced to 150° C., the mixture B is poured into the mixture A to obtain a mixture C. The mixture C is heated to 200° C. and reacted for 110 to 130 minutes, then heated to 230° C. and reacted for 130 to 150 minutes, then heated to 245° C. and reacted for 106 minutes. After the reaction is completed, the mixture is vacuumed for 40 to 60 minutes. After the mixture C is cooled to room temperature, an unsaturated polyester prepolymer, i.e., a styrene-free unsaturated polyester prepolymer, is obtained.

[0014] Furthermore, the preparation method of the styrene-free unsaturated polyester resin is:

[0015] B1: Grind a styrene-free unsaturated polyester prepolymer into a 70-120 mesh powder, mix 4-acryloylmorpholine and GC14, a by-product of palm oil refining, with the styrene-free unsaturated polyester prepolymer powder to obtain a mixture D, place the mixture D in a flask, and heat in an oil bath at 85°C to 95°C with slow stirring until the styrene-free unsaturated polyester prepolymer powder is completely dissolved, thereby obtaining an unsaturated polyester resin, i.e., a styrene-free unsaturated polyester resin.

[0016] Furthermore, in step B1, the unsaturated polyester prepolymer accounts for 0-50% of the mass of the unsaturated polyester resin, the 4-acryloylmorpholine accounts for 20-50% of the mass of the unsaturated polyester resin, and the palm oil refining by-product GC14 accounts for 0-30% of the mass of the unsaturated polyester resin.

[0017] Furthermore, a method for preparing an environmentally friendly unsaturated polyester cement mortar comprises the following steps:

[0018] S1: Cement, standard sand, copper slag, and iron slag are added to a mixing pot and stirred at a low speed for 20 to 40 seconds to obtain a mixture E, i.e., aggregate;

[0019] S2: Pour styrene-free unsaturated polyester resin into a beaker and stir at a low speed until uniform. Then, drop cobalt naphthenate and 2-methyl ethyl peroxide into the beaker and stir thoroughly for 20 to 40 seconds to obtain mixture F, i.e., gelling material. Pour mixture F into mixture E and continue stirring for 110 to 130 seconds.

[0020] S3: The stirred mortar is evenly loaded into a test mold brushed with a release paste and placed on a vibration table for 110 to 130 seconds before stopping to obtain a styrene-free unsaturated polyester cement mortar, i.e., an environmentally friendly unsaturated polyester cement mortar.

[0021] Furthermore, the copper slag is copper smelting waste slag, and its specific surface area is 912m 2 / kg, density is 3.91g / cm 3 The particle size distribution range is 0.283μm~563.677μm; the iron slag is iron smelting waste slag, and its specific surface area is 902m 2 / kg, density is 3.24g / cm 3 The particle size distribution range is 0.314μm to 859μm; cobalt naphthenate accounts for 0 to 2% of the mass of the unsaturated polyester resin, and 2-methyl ethyl peroxide accounts for 1 to 3% of the mass of the unsaturated polyester resin.

[0022] Compared with the prior art, the present invention has the following beneficial effects:

[0023] 1. The environmentally friendly unsaturated polyester cement mortar prepared by the present invention has the characteristics of one-time molding and can adapt to various curing conditions, including curing at room temperature and normal pressure, curing at low temperature, and rapid curing under heating and pressure.

[0024] 2. By using low-toxicity, low-volatility 4-acryloylmorpholine as a styrene alternative solvent, the double bond structure of 4-acryloylmorpholine can participate in the resin cross-linking reaction, significantly improving the resin's curing efficiency. Its low volatility effectively reduces organic compound emissions, demonstrating high environmental protection.

[0025] 3. The addition of GC14, a palm oil refining byproduct, as a modifier enhances the resin's performance and environmental friendliness. GC14's long alkyl chains are derived from plant-based natural fatty acids, making it renewable and low-carbon, and it exhibits excellent adaptability in hot and humid environments. With increasing GC14 addition, the resin's static mechanical properties remain satisfactory, while its water contact angle and swelling ratio decrease.

[0026] 4. Due to the steric hindrance effect of the long alkyl side chain of GC14, a by-product of palm oil refining, it reduces the exposure of the hydrophilic groups in 4-acryloylmorpholine and reduces the probability of contact with water molecules; the addition of GC14, a by-product of palm oil refining, also disperses the polar regions, weakens the overall hydrophilicity of the mortar, and forms a hydrophobic layer on the resin surface, which can effectively hinder the intrusion of water molecules in the short term, protect the internal cross-linked network, and enhance water resistance. BRIEF DESCRIPTION OF THE DRAWINGS

[0027] Figure 1 Schematic diagram of the copper slag particle size distribution of the environmentally friendly unsaturated polyester cement mortar of the present invention;

[0028] Figure 2 Schematic diagram of iron slag particle size distribution of the environmentally friendly unsaturated polyester cement mortar of the present invention;

[0029] Figure 3 Schematic diagram of the chemical formula of the styrene-free unsaturated polyester prepolymer of the environmentally friendly unsaturated polyester cement mortar of the present invention;

[0030] Figure 4 Schematic diagram of the static mechanical properties of the environmentally friendly unsaturated polyester resin in the environmentally friendly unsaturated polyester cement mortar according to an embodiment of the present invention;

[0031] Figure 5 Schematic diagram of the water contact angle of the environmentally friendly unsaturated polyester resin in the environmentally friendly unsaturated polyester cement mortar according to an embodiment of the present invention;

[0032] Figure 6Schematic diagram of the flexural strength of the environmentally friendly unsaturated polyester cement mortar at different ages according to an embodiment of the present invention;

[0033] Figure 7 Schematic diagram of the compressive strength of the environmentally friendly unsaturated polyester cement mortar at different ages according to an embodiment of the present invention;

[0034] Figure 8 Schematic diagram of the flexural strength of the environmentally friendly unsaturated polyester cement mortar at different ages according to an embodiment of the present invention;

[0035] Figure 9 Schematic diagram of the compressive strength of the environmentally friendly unsaturated polyester cement mortar at different ages according to an embodiment of the present invention;

[0036] Figure 10 Schematic diagram of the bonding strength of the environmentally friendly unsaturated polyester cement mortar according to an embodiment of the present invention;

[0037] Figure 11 Schematic diagram of water absorption of environmentally friendly unsaturated polyester cement mortar according to an embodiment of the present invention;

[0038] Figure 12 Schematic diagram of water resistance of environmentally friendly unsaturated polyester cement mortar according to an embodiment of the present invention;

[0039] Figure 13 Schematic diagram of the porosity of the environmentally friendly unsaturated polyester cement mortar according to an embodiment of the present invention;

[0040] Figure 14 Schematic diagram of an environmentally friendly unsaturated polyester cement mortar according to an embodiment of the present invention;

[0041] The horizontal lines above and below the rectangular columns in each figure represent the standard deviation of the data mean. If there is no identical letter above the column, it means that the mean values of the two groups of data are significantly different, otherwise the difference is not significant (P>95%). DETAILED DESCRIPTION

[0042] The present invention is described in detail below with reference to the accompanying drawings and specific examples. All other embodiments obtained by those skilled in the art based on the embodiments of the present invention without creative work are within the scope of protection of the present invention. Where specific conditions are not specified in the examples, the experiments were carried out under conventional conditions or conditions recommended by the manufacturer. Reagents or instruments used, for which the manufacturer is not specified, are conventional products that can be purchased commercially.

[0043] An environmentally friendly unsaturated polyester cement mortar comprises a cementitious material and aggregates. The cementitious material comprises an unsaturated polyester resin, cobalt naphthenate and 2-butanone peroxide, wherein the unsaturated polyester resin is a styrene-free unsaturated polyester, and the aggregates comprise cement, standard sand, copper slag and iron slag.

[0044] Raw materials: Cement, P·O 42.5 ordinary Portland cement (chemical composition see Table 1), purchased from Fujian Jinniu Cement (Group) Co., Ltd.; standard sand, purchased from Xiamen ASO Standard Sand Co., Ltd.; copper slag provided by China Aluminum Southeast Copper Co., Ltd. (Ningde, Fujian) (chemical composition see Table 2), and iron slag provided by Shaanxi Longgang Group Xi'an Iron and Steel Co., Ltd. (chemical composition see Table 3); palm oil refining by-product GC14 was purchased from Weijit New Materials Technology (Taizhou) Co., Ltd.; other chemical reagents were purchased from Shanghai Aladdin Reagent Co., Ltd. (specific specifications see Table 4).

[0045] Table 1 Chemical composition of cement

[0046]

[0047] Table 2 Chemical composition of copper slag

[0048]

[0049] Table 3 Chemical composition of iron slag

[0050]

[0051] Table 4 Chemical reagents and manufacturers

[0052]

[0053] The environmentally friendly unsaturated polyester resin is a styrene-free unsaturated polyester resin, which is prepared from an unsaturated polyester prepolymer and a styrene-free reactive solvent. The unsaturated polyester prepolymer is synthesized with propylene glycol, isophthalic acid, butyl titanate, fumaric acid and 4-methoxyphenol as the main raw materials, and the reactive solvent is composed of 4-acryloylmorpholine and GC14, a by-product of palm oil refining.

[0054] like Figure 3 As shown, the synthesis method of unsaturated polyester prepolymer comprises the following steps:

[0055] A1: Propylene glycol, isophthalic acid, and butyl titanate were mixed to obtain a mixture A. The mixture A was placed in an oil bath at 230°C under nitrogen protection and mechanically stirred for 30 minutes. The mixture A was cooled to 210°C and the reaction was continued for 370 minutes.

[0056] A2: Fumaric acid and 4-methoxyphenol are mixed to obtain a mixture B. After the temperature of the mixture A is reduced to 150° C., the mixture B is poured into the mixture A to obtain a mixture C. The mixture C is heated to 200° C. and the reaction is continued for 120 min. The temperature is then increased to 230° C. and the reaction is continued for 140 min. The temperature is then increased to 245° C. and the reaction is continued for 106 min. After the reaction is completed, the mixture is vacuumed for 50 min. After the mixture C is cooled to room temperature, an unsaturated polyester prepolymer, i.e., a styrene-free unsaturated polyester prepolymer, is obtained.

[0057] The preparation method of styrene-free unsaturated polyester resin comprises the following steps:

[0058] B1: Grind a styrene-free unsaturated polyester prepolymer into a 70-120 mesh powder, mix 4-acryloylmorpholine and GC14, a by-product of palm oil refining, with the styrene-free unsaturated polyester prepolymer powder to obtain a mixture D, place the mixture D in a flask, and heat it in an oil bath at 90° C. with slow stirring until the styrene-free unsaturated polyester prepolymer powder is completely dissolved, thereby obtaining an unsaturated polyester resin, i.e., a styrene-free unsaturated polyester resin.

[0059] Furthermore, the palm oil refining by-product GC14 is a fatty acid derivative obtained by conventional modification process of palm oil refining by-product.

[0060] Furthermore, in step B1, the palm oil refining by-product GC14 is not added, and other conditions remain unchanged. When the styrene-free unsaturated polyester prepolymer powder is completely dissolved, the obtained resin is acryloylmorpholine unsaturated polyester resin.

[0061] The preparation method of environmentally friendly unsaturated polyester cement mortar comprises the following steps:

[0062] S1: Weigh cement, standard sand, copper slag, and iron slag, add them into a mortar mixing pot, and stir at low speed for 30 seconds to obtain mixture E;

[0063] S2: Weigh acryloylmorpholine unsaturated polyester resin, styrene-free unsaturated polyester resin, 2-methyl ethyl ketone peroxide, and cobalt naphthenate, prepare a gelling material mixture in proportion, add the mixture to mixture E, and continue stirring at low speed for 2 minutes;

[0064] S3: The mixed mortar is evenly loaded into a test mold brushed with release paste and placed on a vibration table for 2 minutes before stopping to obtain an unsaturated polyester resin mortar, i.e., an environmentally friendly unsaturated polyester cement mortar.

[0065] Furthermore, after the test mold is cured for 24 hours, it is demoulded and cured at room temperature for 3 days to obtain an environmentally friendly unsaturated polyester cement mortar specimen that is easy to test.

[0066] Among them, copper slag is copper smelting waste slag, and its specific surface area is 912m 2 / kg, density is 3.91g / cm 3 The particle size distribution range is 0.283μm~563.677μm; iron slag is iron smelting waste slag, and its specific surface area is 902m 2 / kg, density is 3.24g / cm 3 The particle size distribution range is 0.314μm~859μm.

[0067] Example 1:

[0068] The environmentally friendly unsaturated polyester resin is made of propylene glycol, isophthalic acid and fumaric acid. 175.3g of propylene glycol, 166.4g of isophthalic acid and 0.22g of butyl titanate are mixed and placed in an oil bath at 230°C under the protection of N2 for mechanical stirring and continuous reaction for 30min, then cooled to 210°C and continued to react for 370min; cooled to 150°C, poured with a mixture of 116.3g of fumaric acid and 0.048g of 4-methoxyphenol, heated to 200°C and continued to react for 120min, then heated to 230°C and reacted for 140min, and then heated to 245°C. The reaction was continued for 106 minutes. After the reaction was completed, vacuum suction was applied for 50 minutes, and the mixture was cooled to room temperature to obtain an unsaturated polyester prepolymer. The blending process was as follows: 162 g of the unsaturated polyester prepolymer was ground into 70-120 mesh powder in a mortar and then mixed with 162 g of 4-acryloylmorpholine, and the mixture was placed in a flask. Under the condition of a 90° C. oil bath, the mixture was heated and slowly stirred until the mixture was completely dissolved. After stirring evenly, an acryloylmorpholine unsaturated polyester resin was obtained, and then 1.62 g of a curing accelerator, cobalt naphthenate, and 6.48 g of an initiator, 2-methyl ethyl peroxide, were added to obtain a cured acryloylmorpholine unsaturated polyester resin.

[0069] Example 2:

[0070] The environmentally friendly unsaturated polyester resin is made of propylene glycol, isophthalic acid and fumaric acid. 175.3g of propylene glycol, 166.4g of isophthalic acid and 0.22g of butyl titanate are mixed and placed in an oil bath at 230°C under the protection of N2 for mechanical stirring and continuous reaction for 30min, then cooled to 210°C and continued to react for 370min; cooled to 150°C, poured with a mixture of 116.3g of fumaric acid and 0.048g of 4-methoxyphenol, heated to 200°C and continued to react for 120min, then heated to 230°C and continued to react for 140min, heated to 245°C and continued to react for 106min, vacuum pumped for 50min after the reaction, and cooled. The unsaturated polyester prepolymer is cooled to room temperature to obtain an unsaturated polyester prepolymer; the blending process comprises the following steps: grinding 162 g of the unsaturated polyester prepolymer into a 70-120 mesh powder in a mortar, mixing the powder with 97.2 g of 4-acryloylmorpholine and 64.8 g of palm oil refining by-product GC14, placing the mixture in a flask, heating and slowly stirring the mixture in an oil bath at 90° C. until the mixture is completely dissolved to obtain a styrene-free unsaturated polyester resin UA-20GC14 (the palm oil refining by-product GC14 accounts for 20% of the total mass of the resin), and then adding 1.62 g of a curing accelerator cobalt naphthenate and 6.48 g of an initiator 2-methyl ethyl peroxide to obtain the cured styrene-free unsaturated polyester resin UA-20GC14.

[0071] Example 3:

[0072] The environmentally friendly unsaturated polyester resin is made of propylene glycol, isophthalic acid and fumaric acid. 175.3g of propylene glycol, 166.4g of isophthalic acid and 0.22g of butyl titanate are mixed and placed in an oil bath at 230°C under the protection of N2 for mechanical stirring and continuous reaction for 30min, then cooled to 210°C and continued to react for 370min; cooled to 150°C, poured with a mixture of 116.3g of fumaric acid and 0.048g of 4-methoxyphenol, heated to 200°C and continued to react for 120min, then heated to 230°C and continued to react for 140min, heated to 245°C and continued to react for 106min, vacuum pumped for 50min after the reaction, and cooled. The unsaturated polyester prepolymer is cooled to room temperature to obtain an unsaturated polyester prepolymer; the blending process comprises the following steps: grinding 162 g of the unsaturated polyester prepolymer into a 70-120 mesh powder in a mortar, mixing the powder with 64.8 g of 4-acryloylmorpholine and 97.2 g of palm oil refining by-product GC14, placing the mixture in a flask, heating and slowly stirring the mixture in a 90°C oil bath until it is completely dissolved to obtain a styrene-free unsaturated polyester resin UA-30GC14 (the palm oil refining by-product GC14 accounts for 30% of the total mass of the resin), and then adding 1.62 g of a curing accelerator cobalt naphthenate and 6.48 g of an initiator 2-methyl ethyl peroxide to obtain the cured styrene-free unsaturated polyester resin UA-30GC14.

[0073] Example 4:

[0074] Preparation of environmentally friendly unsaturated polyester cement mortar, the specific steps are:

[0075] Test blocks were prepared according to DL / T 5126-2001 "Test Procedure for Polymer-Modified Cement Mortar". 135 g of cement, 405 g of iron slag, 1080 g of standard sand, and 270 g of copper slag were placed in a mixing pot and premixed at low speed for 30 seconds. Simultaneously, 270 g of acryloylmorpholine unsaturated polyester resin, 1.35 g of cobalt cyclohexane, and 5.40 g of 2-methyl ethyl peroxide were poured into a beaker and stirred for 30 seconds. After the cementitious materials were mixed evenly, they were poured into the mixing pot and stirred at low speed for about 2 minutes until they were fully mixed with the dry materials. The mortar mixture was then poured into a steel mold and vibrated on a vibration table for 2 minutes before stopping. The excess mortar mixture above the mold surface was scraped off and smoothed. The specimens were numbered and placed in a dry place for 1 day before demolding. They were then cured at room temperature for 3, 7, and 28 days before testing.

[0076] Example 5

[0077] Preparation of environmentally friendly unsaturated polyester cement mortar, the specific steps are:

[0078] Test blocks were prepared according to DL / T 5126-2001 "Test Procedure for Polymer-Modified Cement Mortar". 135 g of cement, 405 g of iron slag, 1080 g of standard sand, and 270 g of copper slag were placed in a mixing pot and premixed at low speed for 30 seconds. Simultaneously, 297 g of acryloylmorpholine unsaturated polyester resin, 1.49 g of cobalt cyclohexane, and 5.94 g of 2-methyl ethyl peroxide were poured into a beaker and stirred for 30 seconds. After the cementitious materials were mixed evenly, they were poured into the mixing pot and stirred at low speed for about 2 minutes until they were fully mixed with the dry materials. The mortar mixture was then poured into a steel mold and vibrated on a vibration table for 2 minutes before stopping. The excess mortar mixture above the mold surface was scraped off and smoothed. The specimens were numbered and placed in a dry place for 1 day before demolding. They were then cured at room temperature for 3, 7, and 28 days before testing.

[0079] Example 6

[0080] Preparation of environmentally friendly unsaturated polyester cement mortar, the specific steps are:

[0081] Test blocks were prepared according to DL / T 5126-2001 "Test Procedure for Polymer-Modified Cement Mortar". 135 g of cement, 405 g of iron slag, 1080 g of standard sand, and 270 g of copper slag were placed in a mixing pot and premixed at low speed for 30 seconds. Simultaneously, 324 g of acryloylmorpholine unsaturated polyester resin, 1.62 g of cobalt cyclohexane, and 6.48 g of 2-methyl ethyl peroxide were poured into a beaker and stirred for 30 seconds. After the cementitious materials were mixed evenly, they were poured into the mixing pot and stirred at low speed for about 2 minutes until they were fully mixed with the dry materials. The mortar mixture was then poured into a steel mold and vibrated on a vibration table for 2 minutes before stopping. The excess mortar mixture above the mold surface was scraped off and smoothed. The specimens were numbered and placed in a dry place for 1 day before demolding. They were then cured at room temperature for 3, 7, and 28 days before testing.

[0082] Example 7

[0083] Preparation of environmentally friendly unsaturated polyester cement mortar, the specific steps are:

[0084] Test blocks were prepared according to DL / T 5126-2001 "Test Procedure for Polymer-Modified Cement Mortar". 135 g of cement, 405 g of iron slag, 1080 g of standard sand, and 270 g of copper slag were placed in a mixing pot and premixed at low speed for 30 seconds. At the same time, 270 g of styrene-free unsaturated polyester resin UA-20GC14, 1.35 g of cobalt naphthenate, and 5.40 g of 2-methyl ethyl peroxide were poured into a beaker and stirred for 30 seconds. After the cementitious materials were mixed evenly, they were poured into the mixing pot and stirred at low speed for about 2 minutes until they were fully mixed with the dry materials. The mortar mixture was then poured into a steel mold and vibrated on a vibration table for 2 minutes before stopping. The excess mortar mixture above the mold surface was scraped off and smoothed. The specimens were numbered and placed in a dry place for 1 day before demolding. They were then cured at room temperature for 3, 7, and 28 days before testing.

[0085] Example 8

[0086] Preparation of environmentally friendly unsaturated polyester cement mortar, the specific steps are:

[0087] Test blocks were prepared according to DL / T 5126-2001 "Test Procedure for Polymer-Modified Cement Mortar". 135 g of cement, 405 g of iron slag, 1080 g of standard sand, and 270 g of copper slag were placed in a mixing pot and premixed at low speed for 30 seconds. At the same time, 270 g of styrene-free unsaturated polyester resin UA-30GC14, 1.35 g of cobalt naphthenate, and 5.40 g of 2-methyl ethyl peroxide were poured into a beaker and stirred for 30 seconds. After the cementitious materials were mixed evenly, they were poured into the mixing pot and stirred at low speed for about 2 minutes until they were fully mixed with the dry materials. The mortar mixture was then poured into a steel mold and vibrated on a vibration table for 2 minutes before stopping. The excess mortar mixture above the mold surface was scraped off and smoothed. The specimens were numbered and placed in a dry place for 1 day before demolding. They were then cured at room temperature for 3, 7, and 28 days before testing.

[0088] Performance testing and characterization of environmentally friendly unsaturated polyester cement mortar:

[0089] Static Resin Mechanical Properties Testing: The tensile and flexural properties of cured resin samples were measured using a microcomputer-controlled electronic universal testing machine (MTS, USA). Tensile testing was conducted in accordance with ASTM D638, while flexural testing was conducted in accordance with ASTM D790. Dumbbell-shaped specimens (100 mm long, 10 mm wide at both ends, 5 mm wide in the middle, 50 mm gauge length, and 3 mm thickness) were used for tensile testing; strip specimens (80 mm × 10 mm × 3 mm) were used for flexural testing. Each test set consisted of at least five specimens.

[0090] Resin swelling rate test: The swelling rate of thermosetting resin materials is determined by solvent extraction test according to ASTM D7567-09. After the dried sample (about 0.400g, recorded as w1) is wrapped with filter paper, Soxhlet extraction is performed with water at 120℃ for 12h. The swollen sample is collected and wiped and weighed (recorded as w g The expanded sample was dried in a vacuum oven at 120°C to a constant weight (denoted as w2).

[0091] Resin contact angle test: Use a contact angle meter (Chengde Dingsheng JY-82C), take a sample with a length and width of 2mm × 2mm or more, place it on the JY-82 contact angle test platform, use the equipment's automatic titration system to drop water drops, take a photo, and measure the contact angle using the goniometer method. The angle error range is ±0.5°.

[0092] Mortar mechanical properties testing: The flexural strength of the mortar was tested using rectangular specimens measuring 40 mm × 40 mm × 160 mm, in accordance with the "Test Method for Cement Mortar Strength" (GB / T17671-2021). After the flexural strength test, two halves of the specimens were removed and subjected to compressive strength testing at 3, 7, and 28 days using a microcomputer-controlled electronic pressure testing machine.

[0093] Mortar bond strength test: Referencing "Repair Mortar" (JC / T 2381-2016), interfacial flexural strength was used as the evaluation metric. The concrete specimens were 7 days old. The experimental base specimens were ordinary cement mortar (flexural strength 6.50 MPa) and ultra-high-strength cement mortar (flexural strength 21.50 MPa).

[0094] Mortar water absorption test: Test in accordance with the "Test Procedure for Polymer Modified Cement Mortar" (DL / T5126-2001).

[0095] Mortar water resistance test: After the mortar specimens were immersed in water for a certain period of time, the flexural strength was tested using rectangular specimens measuring 40mm × 40mm × 160mm, in accordance with the "Test Method for Cement Mortar Strength" (GB / T 17671-2021). After the flexural strength test, two halves of the specimens were removed and subjected to compressive strength tests at 3, 7, and 28 days using a microcomputer-controlled electronic pressure testing machine.

[0096] Porosity test of specimens: The pore analysis of mortar specimens was performed using the AutoPore IV 9500 high-performance fully automatic mercury intrusion instrument produced by Micromeritics, USA.

[0097] Scanning electron microscopy analysis (micromorphology / energy spectrum scanning): The images were taken using a German ZEISS Gemini 300 field emission scanning electron microscope with an accelerating voltage of 3 kV. The gold treatment was performed using an Oxford Quorum SC7620 sputtering coater, and the gold-sputtering target was a gold-palladium alloy.

[0098] Test results and analysis

[0099] Resin static mechanical properties test

[0100] Example 1, Example 2, Example 3 are the static mechanical properties of environmentally friendly unsaturated polyester cured resin ( Figure 4). With the increase in the amount of palm oil refining by-product GC14, the tensile strength, flexural strength and flexural modulus of acryloylmorpholine unsaturated polyester resin decreased significantly. Specifically, the tensile strength of acryloylmorpholine unsaturated polyester resin is 64.34MPa. After adding 20% and 30% of palm oil refining by-product GC14, its tensile strength dropped to 38.09MPa and 27.71MPa, respectively, with a decrease of 40.8% and 56.9%, respectively. The flexural strength and flexural modulus of acryloylmorpholine unsaturated polyester resin are 123.19MPa and 4081.76MPa, respectively. After adding 20% and 30% of palm oil refining by-product GC14, the flexural strength dropped to 79.29MPa and 60.12MPa, respectively, with a decrease of 35.6% and 51.2%, respectively; the flexural modulus dropped to 1112.65MPa and 610.73MPa, respectively, with a decrease of 72.7% and 85.1%, respectively. This indicates that the addition of palm oil refining by-product GC14 significantly reduces the mechanical properties of acryloylmorpholine unsaturated polyester resin.

[0101] Resin swelling rate test

[0102] Comparing Example 1 with Example 2, the swelling ratio of the environmentally friendly unsaturated polyester resin after Soxhlet extraction in water (Table 5) is shown. A high swelling ratio indicates a strong water absorption capacity, low crosslinking density, and high molecular chain freedom, leading to decreased mechanical properties. Conversely, a low swelling ratio indicates a high crosslinking density and improved water resistance. The swelling ratio calculation formula is as follows.

[0103] Swelling ratio (%) = 1 + [ρ1 (w g -w2)ρ2·w2]×100%

[0104] Where ρ1 is the density of the resin, g / cm 3 ; ρ2 is the density of the solvent, g / cm 3 .

[0105] Table 5 Swelling rate of environmentally friendly unsaturated polyester resin

[0106]

[0107] Resin water contact angle test

[0108] Comparing Example 1 with Example 2, the water contact angle of the environmentally friendly unsaturated polyester resin ( Figure 5 The contact angle is an important parameter for measuring the wettability of liquids on solid surfaces. The water contact angle of acryloylmorpholine unsaturated polyester resin is 67°, indicating hydrophilicity. The water contact angle of UA-GC14, a styrene-free unsaturated polyester resin modified with GC14, a palm oil refining byproduct, increases to 83.19°, significantly improving its surface hydrophobicity.

[0109] Mortar mechanical properties test

[0110] Depend on Figure 6 The 3-day flexural strengths of the environmentally friendly unsaturated polyester cement mortars in Example 4 (resin accounting for 12.5% of the total mortar mass), Example 5 (resin accounting for 13.6% of the total mortar mass), and Example 6 (resin accounting for 14.6% of the total mortar mass) were 32.71 MPa, 32.24 MPa, and 31.03 MPa, respectively; the 7-day flexural strengths were 33.20 MPa, 33.53 MPa, and 33.25 MPa, respectively; and the 28-day flexural strengths were 34.92 MPa, 34.58 MPa, and 34.03 MPa, respectively. The flexural strengths of the three examples showed no significant differences at different ages, indicating that the resin dosage had a relatively small effect on the mortar's flexural strength.

[0111] Depend on Figure 7 As can be seen, the 3-day compressive strengths of the environmentally friendly unsaturated polyester cement mortars of Examples 4, 5, and 6 were 92.04 MPa, 92.03 MPa, and 93.15 MPa, respectively; the 7-day compressive strengths were 94.49 MPa, 97.15 MPa, and 102.42 MPa, respectively; and the 28-day compressive strengths were 97.83 MPa, 98.25 MPa, and 103.25 MPa, respectively. At 3 and 28 days, the compressive strengths of the three examples showed no significant difference. At 7 days, the compressive strength of Example 6 was only 8% higher than that of Example 5. This indicates that appropriately reducing the dosage of acryloylmorpholine unsaturated polyester resin has limited impact on the mechanical properties of the mortar.

[0112] Depend on Figure 8It can be seen that Example 4 (cementitious material is acryloylmorpholine unsaturated polyester resin and palm oil refining by-product GC14 is not introduced), Example 7 (cementitious material is styrene-free unsaturated polyester resin UA-20GC14 and palm oil refining by-product GC14 accounts for 20% of the total resin mass), and Example 8 (cementitious material is styrene-free unsaturated polyester resin UA-30GC14 and palm oil refining by-product GC14 accounts for 30% of the total resin mass) show the effect of the dosage of palm oil refining by-product GC14 on the flexural strength of environmentally friendly unsaturated polyester cement mortar. At the same resin dosage, the flexural strength of Example 4 at 3d, 7d, and 28d are respectively The 3d, 7d and 28d flexural strengths of Example 7 are 30.32 MPa, 30.72 MPa and 35.35 MPa respectively. Compared with Example 4, the early strength of the mortar of Example 7 is affected, but the 28d flexural strength is increased by about 1.2%; the 3d, 7d and 28d flexural strengths of Example 8 are 27.52 MPa, 29.63 MPa and 32.82 MPa respectively. The early strengths of 3d and 7d are reduced by 15.9% and 10.8% respectively compared with that of Example 4. Although the flexural strength of the mortar at 28d age has recovered, it is still lower than that of the control group.

[0113] Depend on Figure 9 It can be seen that Example 4, Example 7, and Example 8 show the effect of the dosage of palm oil refining by-product GC14 on the compressive strength of environmentally friendly unsaturated polyester cement mortar. Under the same resin dosage, the compressive strength of Example 4 at 3d, 7d, and 28d are 92.04MPa, 94.49MPa, and 97.83MPa respectively; the compressive strength of Example 7 at 3d, 7d, and 28d are 69.07MPa, 72.72MPa, and 89.54MPa respectively. The compressive strength of Example 8 at 3d, 7d and 28d decreased by 8.5% compared with Example 4. The compressive strength of Example 8 at 3d, 7d and 28d were 57.84MPa, 63.54MPa and 70.19MPa respectively, and the compressive strength of Example 8 at 28d decreased by 28.3% compared with Example 4. This shows that the introduction of palm oil refining by-product GC14 has a significant effect on the compressive strength of the mortar. Excessive addition of palm oil refining by-product GC14 may lead to uneven cross-linking structure, reduce material rigidity, and further weaken the compressive strength of the mortar.

[0114] Mortar bond strength test

[0115] Depend on Figure 10It can be seen that, comparing the interfacial flexural tensile strengths of Example 4, Example 7, and Example 8, on the ordinary cement mortar base test block, the mortar flexural tensile strength of Example 4 is 6.76 MPa. The interfacial flexural tensile strength of the mortar of Example 7 is increased to 6.80 MPa; the strength of Example 8 is reduced to 6.65 MPa. The fracture surfaces of all test blocks are on the base test blocks, indicating that the addition of palm oil refining by-product GC14 does not significantly affect the interfacial bonding properties of the mortar. When ultra-high-strength cement mortar is used as the base test block, the interfacial flexural tensile strength of the mortar of Example 4 is 9.32 MPa; the interfacial flexural tensile strength of the mortar of Example 7 is increased to 10.10 MPa; the interfacial flexural tensile strength of the mortar of Example 8 is increased to 9.41 MPa, and the fracture surface is mainly concentrated on the contact surface between the repair material and the base, and the repair material remains intact, showing high interfacial bonding strength.

[0116] Mortar water absorption test

[0117] The water absorption test was conducted on the mortars of Example 4 and Example 7. Water absorption is an important indicator for evaluating the water resistance of mortar materials. Figure 11 It can be seen that the water absorption rate of the mortar of Example 4 increases with the extension of the immersion time, from less than 5% at 2 days to about 40% at 28 days, and after immersion for 28 days, it has obviously lost its original rigidity macroscopically. The mortar of Example 7 shows better water resistance under the same conditions, and the water absorption rate at 28 days is only 7.7%, which is much lower than the mortar of Example 4.

[0118] Mortar water resistance test

[0119] The mortars of Example 4 and Example 7 were subjected to water immersion tests. Figure 12 As can be seen, the compressive strength of the mortar in Example 4 reached 97.83 MPa after 28 days of drying and curing. However, after 7 days of immersion in water, the strength dropped rapidly to 38.58 MPa, and the flexural strength dropped from 34.92 MPa to 13.42 MPa. After 28 days of immersion in water, the mortar in Example 7 maintained a compressive strength of 34.42 MPa, while the flexural strength gradually decreased from 35.35 MPa to 7.73 MPa. The mortar in Example 7 exhibited better durability in water than the mortar in Example 4. The introduction of an appropriate amount of GC14, a palm oil refining byproduct, helped improve the mortar's water resistance.

[0120] Mortar porosity test

[0121] Mercury intrusion test is the most commonly used analytical method for testing the pore structure of mortar specimens. Figure 13As can be seen from Table 6, the porosity of the specimen in Example 4 is 3.22% and the average pore diameter is 34.32 nm. The porosity of the specimen in Example 7 is 0.24% higher than that in Example 4, and its average pore diameter is 27.45 nm, which is 20.0% lower than that in Example 2. This indicates that the pore size distribution in Example 7 is more within the harmless pore range. Therefore, the introduction of GC14, a palm oil refining by-product, optimizes the pore distribution structure of the mortar, improving both the porosity and pore distribution characteristics.

[0122] Table 6 Pore parameters of environmentally friendly unsaturated polyester resin cement mortar

[0123]

[0124] Scanning electron microscopy analysis

[0125] like Figure 14 The results show that the interface of the mortar in Example 4 deteriorates after long-term water immersion, with gaps forming between the aggregate and the mortar, localized slurry spalling, and low interfacial bond strength and water resistance. This trend is consistent with the decline in mechanical strength of the acryloylmorpholine unsaturated polyester resin mortar after water immersion, confirming its insufficient structural stability in a water environment. Figure 14 The results show that the mortar of Example 7 exhibits better interface stability after being immersed in water. There is no obvious gap between the aggregate and the slurry. Only slight peeling occurs in the local area close to the outside, and the internal structure remains dense, indicating that the palm oil refining by-product GC14 effectively enhances the mortar's resistance to water intrusion and mechanical property stability.

[0126] The above description is merely a preferred embodiment of the present application and is not intended to limit the present application. Those skilled in the art will appreciate that the present application may have other optimization schemes and additional functions. Any modifications, equivalent substitutions, improvements, etc. made within the spirit and principles of the present application shall be included within the scope of protection of the present application.

Claims

1. An environmentally friendly unsaturated polyester cement mortar, characterized by: The invention comprises a cementitious material and an aggregate. The cementitious material comprises an unsaturated polyester resin, cobalt naphthenate and 2-butyl ketone peroxide. The unsaturated polyester resin is a styrene-free unsaturated polyester. The aggregate comprises cement, standard sand, copper slag and iron slag.

2. The environmentally friendly unsaturated polyester cement mortar according to claim 1, characterized in that: The cementitious material accounts for 10% to 15% of the total mass of the mortar, and the aggregate accounts for 85% to 90% of the total mass of the mortar, wherein cement accounts for 5% to 10% of the mass of the aggregate, standard sand accounts for 50% to 60% of the mass of the aggregate, copper slag accounts for 5% to 15% of the mass of the aggregate, and iron slag accounts for 20% to 30% of the mass of the aggregate. The sum of the total mass fractions of the cementitious material and the aggregate is 100%.

3. The environmentally friendly unsaturated polyester cement mortar according to claim 1, characterized in that: The unsaturated polyester resin is a styrene-free unsaturated polyester, which is prepared from an unsaturated polyester prepolymer and a styrene-free reactive solvent. The unsaturated polyester prepolymer is synthesized using propylene glycol, isophthalic acid, butyl titanate, fumaric acid and 4-methoxyphenol as main raw materials, and the reactive solvent is composed of 4-acryloylmorpholine and GC14, a by-product of palm oil refining.

4. The environmentally friendly unsaturated polyester cement mortar according to claim 3, characterized in that: The propylene glycol accounts for 35% to 45% of the total mass of the unsaturated polyester prepolymer, the isophthalic acid accounts for 35% to 40% of the total mass of the unsaturated polyester prepolymer, the butyl titanate accounts for 0.1‰ to 0.6‰ of the total mass of the unsaturated polyester prepolymer, the fumaric acid accounts for 25% to 30% of the total mass of the unsaturated polyester prepolymer, and the 4-methoxyphenol accounts for 0 to 0.2‰ of the total mass of the unsaturated polyester prepolymer.

5. The environmentally friendly unsaturated polyester cement mortar according to claim 3, characterized in that: The synthetic method of described unsaturated polyester prepolymer is: A1: Propylene glycol, isophthalic acid, and butyl titanate are mixed to obtain a mixture A. The mixture A is placed in an oil bath at 225°C to 235°C under nitrogen protection and mechanically stirred for 20 to 40 minutes. When the mixture A is cooled to 210°C, the reaction is continued for 360 to 380 minutes. A2: Fumaric acid and 4-methoxyphenol are mixed to obtain a mixture B. After the temperature of the mixture A is reduced to 150° C., the mixture B is poured into the mixture A to obtain a mixture C. The mixture C is heated to 200° C. and reacted for 110 to 130 minutes, then heated to 230° C. and reacted for 130 to 150 minutes, then heated to 245° C. and reacted for 106 minutes. After the reaction is completed, the mixture is vacuumed for 40 to 60 minutes. After the mixture C is cooled to room temperature, an unsaturated polyester prepolymer, i.e., a styrene-free unsaturated polyester prepolymer, is obtained.

6. The environmentally friendly unsaturated polyester cement mortar according to claim 1, characterized in that: The preparation method of the styrene-free unsaturated polyester resin is: B1: Grind a styrene-free unsaturated polyester prepolymer into a 70-120 mesh powder, mix 4-acryloylmorpholine and GC14, a by-product of palm oil refining, with the styrene-free unsaturated polyester prepolymer powder to obtain a mixture D, place the mixture D in a flask, and heat in an oil bath at 85°C to 95°C with slow stirring until the styrene-free unsaturated polyester prepolymer powder is completely dissolved, thereby obtaining an unsaturated polyester resin, i.e., a styrene-free unsaturated polyester resin.

7. The environmentally friendly unsaturated polyester cement mortar according to claim 6, characterized in that: In step B1, the unsaturated polyester prepolymer accounts for 0-50% of the mass of the unsaturated polyester resin, the 4-acryloylmorpholine accounts for 20-50% of the mass of the unsaturated polyester resin, and the palm oil refining by-product GC14 accounts for 0-30% of the mass of the unsaturated polyester resin.

8. A method for preparing the environmentally friendly unsaturated polyester cement mortar according to any one of claims 1 to 7, characterized in that: The steps include: S1: Cement, standard sand, copper slag, and iron slag are added to a mixing pot and stirred at a low speed for 20 to 40 seconds to obtain a mixture E, i.e., aggregate; S2: Pour the styrene-free unsaturated polyester resin into a beaker and stir evenly at a low speed. Then, drop the cobalt cyclohexaneate and 2-butanone peroxide into the beaker and stir thoroughly for 20 to 40 seconds to obtain a mixture F, i.e., a cementitious material. Pour the mixture F into the mixture E and continue stirring for 110 to 130 seconds to obtain a styrene-free unsaturated polyester cement mortar, i.e., an environmentally friendly unsaturated polyester cement mortar.

9. The method for preparing the environmentally friendly unsaturated polyester cement mortar according to claim 8, wherein: In steps S1 and S2, the copper slag is copper smelting waste slag with a specific surface area of 912m 2 / kg, density is 3.91g / cm 3 The particle size distribution range is 0.283μm~563.677μm; the iron slag is iron smelting waste slag, and its specific surface area is 902m 2 / kg, density is 3.24g / cm 3 The particle size distribution range is 0.314μm to 859μm; cobalt naphthenate accounts for 0 to 2% of the mass of the unsaturated polyester resin, and 2-methyl ethyl peroxide accounts for 1 to 3% of the mass of the unsaturated polyester resin.

Images