A modified unsaturated polyester resin and a method for preparing the same

Abstract

The application discloses a modified unsaturated polyester resin, raw materials of which comprise 1,2-propylene glycol 20-30 parts by mass, diethylene glycol 2-10 parts, ethylene terephthalate 15-30 parts, ethylene glycol 5-10 parts, phthalic anhydride 25-30 parts, maleic anhydride 2-8 parts, artificial stone aggregate 20-40 parts, amino-terminated polyamide amine 5-15 parts, activated calcium carbonate 100-200 parts, styrene 20-30 parts, catalyst 0.1-1 part, polymerization inhibitor 1-2 parts and antioxidant 2-5 parts. The application discloses a preparation method of the modified unsaturated polyester resin. The modified unsaturated polyester resin obtained by the application has good fluidity, can accommodate more calcium carbonate powder for infiltration, effectively reduces the cost of artificial stone products, has high bending strength and compression strength, and can meet the performance requirement of artificial stone.

Description

Technical Field

[0001] This invention relates to the field of artificial stone technology, and in particular to a modified unsaturated polyester resin and its preparation method. Background Technology

[0002] Artificial stone is a man-made material made by mixing heavy calcium carbonate powder, natural marble powder and other powders as fillers with unsaturated polyester resin and then solidifying it. It is commonly used in many applications such as flooring, countertops, vertical columns, and monuments.

[0003] Unsaturated polyester resin has excellent mechanical properties, electrical properties and chemical corrosion resistance. Its cross-linked network structure gives artificial stone good mechanical properties and dimensional stability under heat and stress. In addition, it has excellent electrical properties and chemical corrosion resistance, and the processing technology is simple and the price is low.

[0004] Due to its superior performance, low cost, and easier availability compared to natural marble, artificial engineered stone is gaining wider acceptance in the market. Currently, because calcium carbonate powder is inexpensive, adding more calcium carbonate powder while reducing the amount of unsaturated polyester resin can significantly reduce costs. However, increasing the amount of calcium carbonate powder leads to a substantial decrease in the performance of the unsaturated resin, resulting in high viscosity and low flexural and compressive strength in the finished product, failing to meet the performance requirements of artificial engineered stone. This issue urgently needs to be addressed. Summary of the Invention

[0005] The purpose of this invention is to address the shortcomings of existing technologies by proposing a modified unsaturated polyester resin and its preparation method.

[0006] A modified unsaturated polyester resin, the raw materials of which, by weight, include: 20-30 parts of 1,2-propanediol, 2-10 parts of diethylene glycol, 15-30 parts of ethylene glycol, 5-10 parts of phthalic anhydride, 25-30 parts of maleic anhydride, 2-8 parts of artificial stone aggregate, 20-40 parts of amino-terminated polyamide amine, 5-15 parts of activated calcium carbonate, 100-200 parts of styrene, 0.1-1 parts of catalyst, 1-2 parts of polymerization inhibitor, and 2-5 parts of antioxidant.

[0007] Preferably, the antioxidant is at least one of antioxidant BHT, antioxidant TNP, antioxidant TPP, antioxidant 1010, antioxidant 1076, and antioxidant 1098.

[0008] Preferably, the polymerization inhibitor is p-phenol.

[0009] Preferably, the catalyst is zinc acetate.

[0010] Preferably, the generation of the terminal amino polyamide amine is 3-7.

[0011] Preferably, activated calcium carbonate is prepared by the following specific operation: polyacrylic acid is added to sodium hydroxide solution and stirred evenly, the temperature is adjusted to 30-40℃, calcium chloride is added and stirred for 1-2 hours, sodium carbonate is added and stirred for 10-20 hours, centrifuged, washed, and dried.

[0012] This invention uses polyacrylic acid and calcium chloride to react, and then adds sodium carbonate to make the resulting activated calcium carbonate not only effectively inhibits the problem of easy agglomeration of the original calcium carbonate, but also exists stably in the system with high dispersion uniformity. Moreover, the materials are cheap and the cost is low.

[0013] More preferably, the mass ratio of polyacrylic acid, calcium chloride, and sodium carbonate is 1-2:5-10:2-6.

[0014] More preferably, the concentration of the sodium hydroxide solution is 1-2 mol / L.

[0015] The preparation method of the above-mentioned modified unsaturated polyester resin includes the following steps: S1. Mix 1,2-propanediol, antioxidant, catalyst, diethylene glycol, and polyethylene terephthalate, stir at 180-200℃ for 1-2 hours, and keep warm for 2-4 hours to obtain the preform. a ; S2, Precast material a Cool to 150-160℃, add ethylene glycol, antioxidant, polymerization inhibitor, phthalic anhydride, and maleic anhydride, and maintain the temperature under steam reflux for 1-2 hours. Then raise the temperature to 180-200℃ and maintain it until the acid value of the system is 10-12.5 mg KOH / g to obtain the preform. b ; S3, Precast material b Cool to 150-160℃, add artificial stone aggregate and amino-terminated polyamide amine, stir for 10-30 minutes, then add activated calcium carbonate and styrene and stir until uniform.

[0016] Preferably, in S1, the preformed material a The acid value is less than 10 mg KOH / g. Beneficial effects

[0017] Preform of the present invention b The amino-terminated polyamide amine can react with activated calcium carbonate, which not only greatly enhances the bonding strength between calcium carbonate, artificial stone aggregate and unsaturated polyester, but also reduces the viscosity of the system of the present invention, thereby improving the wetting and dispersing performance of the present invention.

[0018] Because amino-terminated polyamide amines have large steric hindrance, and their molecules are spherical with cavities, this invention utilizes them in conjunction with preforms. bThis not only effectively promotes the dispersion of artificial stone aggregate in the system, but also facilitates the activation of calcium carbonate into the polyester resin, making it easier to process.

[0019] This invention continues to use artificial stone aggregate and amino-terminated polyamide amine compound, and reasonably controls the ratio to finally obtain unsaturated polyester resin. Within a certain fluidity requirement, an equal amount of unsaturated polyester resin can accommodate and impregnate more calcium carbonate powder. Since the surface of activated calcium carbonate has a polyacrylic acid structure, it can combine with amino-terminated polyamide amine during the curing process, which can reduce cracking and blistering, and also has higher strength, and can effectively reduce the cost of artificial stone products. Attached Figure Description

[0020] Figure 1 This is a comparison chart of the flowability of the modified unsaturated polyester resins obtained in Example 5 and Comparative Examples 1-2.

[0021] Figure 2 The diagram shows a comparison of the flexural strength and compressive strength of artificial granite slabs prepared using the methods of Example 5 and Comparative Examples 1-2. Detailed Implementation

[0022] The present invention will be further explained below with reference to specific embodiments.

[0023] Example 1 A modified unsaturated polyester resin, the raw materials of which include: 22 kg of 1,2-propanediol, 8 kg of diethylene glycol, 20 kg of ethylene glycol, 9 kg of ethylene glycol, 25 kg of phthalic anhydride, 6 kg of maleic anhydride, 25 kg of artificial stone aggregate, 8 kg of third-generation amino-terminated polyamide amine, 180 kg of activated calcium carbonate, 20 kg of styrene, 0.8 kg of zinc acetate, 1.1 kg of p-phenol, 1.8 kg of antioxidant 1076, and 1.5 kg of antioxidant BHT.

[0024] Activated calcium carbonate is prepared by the following specific operation: 2 kg of polyacrylic acid is added to 20 kg of 2 mol / L sodium hydroxide solution and stirred evenly. The temperature is adjusted to 30℃, 10 kg of calcium chloride is added and stirred for 1 h, 6 kg of sodium carbonate is added and stirred for 10 h, centrifuged, washed, and vacuum dried.

[0025] The preparation method of the above-mentioned modified unsaturated polyester resin includes the following steps: S1. 1,2-Propanediol, 1.8 kg of antioxidant 1076, zinc acetate, diethylene glycol, and ethylene terephthalate were added to a reaction vessel and stirred at 185℃ for 110 min, then kept at this temperature for 2.5 h to obtain a pre-prepared material with an acid value of 9.7 mg KOH / g. a ; S2, Precast material aThe temperature was lowered to 158℃, and ethylene glycol, 1.5 kg of antioxidant BHT, p-phenol, phthalic anhydride, and maleic anhydride were added. The mixture was kept at this temperature under reflux for 110 min, then heated to 185℃ and held until the system acid value reached 12.1 mg KOH / g, yielding the preform. b ; S3, Precast material b Cool to 152℃, add artificial stone aggregate and amino-terminated polyamide amine and stir for 25 minutes, then add activated calcium carbonate and styrene and stir evenly.

[0026] Example 2 A modified unsaturated polyester resin, the raw materials of which include: 28 kg of 1,2-propanediol, 4 kg of diethylene glycol, 25 kg of ethylene glycol, 6 kg of ethylene glycol, 30 kg of phthalic anhydride, 4 kg of maleic anhydride, 35 kg of artificial stone aggregate, 12 kg of 7th generation amino-terminated polyamide amine, 120 kg of activated calcium carbonate, 30 kg of styrene, 0.2 kg of zinc acetate, 1.7 kg of p-phenol, 1.2 kg of antioxidant 1076, and 2.5 kg of antioxidant TPP.

[0027] Activated calcium carbonate is prepared by the following specific operation: 1 kg of polyacrylic acid is added to 30 kg of 1 mol / L sodium hydroxide solution and stirred evenly. The temperature is adjusted to 40℃, 5 kg of calcium chloride is added and stirred for 2 h, 2 kg of sodium carbonate is added and stirred for 20 h, centrifuged, washed, and vacuum dried.

[0028] The preparation method of the above-mentioned modified unsaturated polyester resin includes the following steps: S1. Add 1,2-propanediol, 1.2 kg of antioxidant 1076, zinc acetate, diethylene glycol, and ethylene terephthalate to a reaction vessel, stir at 195℃ for 70 min, and maintain the temperature for 3.5 h to obtain a pre-formulated material with an acid value of 9.5 mg KOH / g. a ; S2, Precast material a The mixture was cooled to 152℃, and ethylene glycol, 2.5 kg of antioxidant TPP, p-phenol, phthalic anhydride, and maleic anhydride were added. The mixture was kept under reflux for 70 min, then heated to 195℃ and held until the system acid value reached 10.3 mg KOH / g, yielding the preform. b ; S3, Precast material b Cool to 158℃, add artificial stone aggregate and amino-terminated polyamide amine and stir for 15 minutes, then add activated calcium carbonate and styrene and stir evenly.

[0029] Example 3 A modified unsaturated polyester resin, the raw materials of which include: 24 kg of 1,2-propanediol, 7 kg of diethylene glycol, 21 kg of ethylene glycol, 8 kg of ethylene glycol, 27 kg of phthalic anhydride, 5.5 kg of maleic anhydride, 28 kg of artificial stone aggregate, 9 kg of fourth-generation amino-terminated polyamide amine, 160 kg of activated calcium carbonate, 22 kg of styrene, 0.7 kg of zinc acetate, 1.3 kg of p-phenol, and 3.4 kg of antioxidant BHT.

[0030] Activated calcium carbonate is prepared by the following specific operation: 1.7 kg of polyacrylic acid is added to 22 kg of 1.7 mol / L sodium hydroxide solution and stirred evenly. The temperature is adjusted to 33℃, 8 kg of calcium chloride is added and stirred for 80 min, 5 kg of sodium carbonate is added and stirred for 12 h, centrifuged, washed, and vacuum dried.

[0031] The preparation method of the above-mentioned modified unsaturated polyester resin includes the following steps: S1. 1,2-Propanediol, 1.6 kg of antioxidant BHT, zinc acetate, diethylene glycol, and ethylene terephthalate were added to a reaction vessel and stirred at 188℃ for 100 min, then kept at this temperature for 2.8 h to obtain a pre-formulated material with an acid value of 9.8 mg KOH / g. a ; S2, Precast material a The temperature was lowered to 156℃, and ethylene glycol, 1.8 kg of antioxidant BHT, p-phenol, phthalic anhydride, and maleic anhydride were added. The mixture was kept at this temperature under reflux for 100 min, then heated to 188℃ and held until the system acid value reached 11.4 mg KOH / g, yielding the preform. b ; S3, Precast material b Cool to 153℃, add artificial stone aggregate and amino-terminated polyamide amine, stir for 22 minutes, then add activated calcium carbonate and styrene and stir until uniform.

[0032] Example 4 A modified unsaturated polyester resin, the raw materials of which include: 26 kg of 1,2-propanediol, 5 kg of diethylene glycol, 23 kg of ethylene glycol, 7 kg of ethylene glycol, 29 kg of phthalic anhydride, 4.5 kg of maleic anhydride, 32 kg of artificial stone aggregate, 11 kg of 6th generation amino-terminated polyamide amine, 140 kg of activated calcium carbonate, 28 kg of styrene, 0.3 kg of zinc acetate, 1.5 kg of p-phenol, and 3.6 kg of antioxidant TPP.

[0033] Activated calcium carbonate is prepared by the following specific operation: 1.3 kg of polyacrylic acid is added to 28 kg of 1.3 mol / L sodium hydroxide solution and stirred evenly. The temperature is adjusted to 37°C, 6 kg of calcium chloride is added and stirred for 100 min, 3 kg of sodium carbonate is added and stirred for 18 h, centrifuged, washed, and vacuum dried.

[0034] The preparation method of the above-mentioned modified unsaturated polyester resin includes the following steps: S1. 1,2-Propanediol, 1.4 kg of antioxidant TPP, zinc acetate, diethylene glycol, and ethylene terephthalate were added to a reaction vessel and stirred at 192℃ for 80 min, then kept at this temperature for 3.2 h to obtain a pre-formulated material with an acid value of 9.7 mg KOH / g. a ; S2, Precast material a The mixture was cooled to 154℃, and ethylene glycol, 2.2 kg of antioxidant TPP, p-phenol, phthalic anhydride, and maleic anhydride were added. The mixture was kept under reflux for 80 min, then heated to 192℃ and held until the system acid value reached 10.7 mg KOH / g, yielding the pre-formulated material. b ; S3, Precast material b Cool to 157℃, add artificial stone aggregate and amino-terminated polyamide amine and stir for 18 minutes, then add activated calcium carbonate and styrene and stir evenly.

[0035] Example 5 A modified unsaturated polyester resin, the raw materials of which include: 25 kg of 1,2-propanediol, 6 kg of diethylene glycol, 22 kg of ethylene glycol, 7.5 kg of ethylene glycol, 28 kg of phthalic anhydride, 5 kg of maleic anhydride, 30 kg of artificial stone aggregate, 10 kg of fifth-generation amino-terminated polyamide amine, 150 kg of activated calcium carbonate, 25 kg of styrene, 0.5 kg of zinc acetate, 1.4 kg of p-phenol, and 3.5 kg of antioxidant 1010.

[0036] Activated calcium carbonate is prepared by the following specific operation: 1.5 kg of polyacrylic acid is added to 25 kg of 1.5 mol / L sodium hydroxide solution and stirred evenly. The temperature is adjusted to 35℃, 7 kg of calcium chloride is added and stirred for 90 min, 4 kg of sodium carbonate is added and stirred for 15 h, centrifuged, washed, and vacuum dried.

[0037] The preparation method of the above-mentioned modified unsaturated polyester resin includes the following steps: S1. Add 1,2-propanediol, 1.5 kg of antioxidant 1010, zinc acetate, diethylene glycol, and ethylene terephthalate to a reaction vessel, stir at 190℃ for 90 min, and maintain the temperature for 3 h to obtain a pre-prepared material with an acid value of 9.9 mg KOH / g. a ; S2, Precast material a The mixture was cooled to 155℃, and ethylene glycol, 2 kg of antioxidant 1010, p-phenol, phthalic anhydride, and maleic anhydride were added. The mixture was kept at this temperature under reflux for 90 min, then heated to 190℃ and held until the system acid value reached 11.1 mg KOH / g, yielding the pre-formulated material. b ; S3, Precast material b Cool to 155℃, add artificial stone aggregate and amino-terminated polyamide amine and stir for 20 minutes, then add activated calcium carbonate and styrene and stir evenly.

[0038] Comparative Example 1 A modified unsaturated polyester resin, the raw materials of which include: 25 kg of 1,2-propanediol, 6 kg of diethylene glycol, 22 kg of ethylene glycol, 7.5 kg of ethylene glycol, 28 kg of phthalic anhydride, 5 kg of maleic anhydride, 30 kg of artificial stone aggregate, 10 kg of fifth-generation amino-terminated polyamide amine, 150 kg of nano-calcium carbonate, 25 kg of styrene, 0.5 kg of zinc acetate, 1.4 kg of p-phenol, and 3.5 kg of antioxidant 1010.

[0039] The preparation method of the above-mentioned modified unsaturated polyester resin includes the following steps: S1. Add 1,2-propanediol, 1.5 kg of antioxidant 1010, zinc acetate, diethylene glycol, and ethylene terephthalate to a reaction vessel, stir at 190℃ for 90 min, and maintain the temperature for 3 h to obtain a pre-prepared material with an acid value of 9.9 mg KOH / g. a ; S2, Precast material a The mixture was cooled to 155℃, and ethylene glycol, 2 kg of antioxidant 1010, p-phenol, phthalic anhydride, and maleic anhydride were added. The mixture was kept at this temperature under reflux for 90 min, then heated to 190℃ and held until the system acid value reached 11.1 mg KOH / g, yielding the pre-formulated material. b ; S3, Precast material b Cool to 155℃, add artificial stone aggregate and amino-terminated polyamide amine and stir for 20 minutes, then add nano calcium carbonate and styrene and stir evenly.

[0040] Comparative Example 2 A modified unsaturated polyester resin, the raw materials of which include: 25 kg of 1,2-propanediol, 6 kg of diethylene glycol, 22 kg of ethylene glycol, 7.5 kg of ethylene glycol, 28 kg of phthalic anhydride, 5 kg of maleic anhydride, 30 kg of artificial stone aggregate, 150 kg of activated calcium carbonate, 25 kg of styrene, 0.5 kg of zinc acetate, 1.4 kg of p-phenol, and 3.5 kg of antioxidant 1010.

[0041] Activated calcium carbonate is prepared by the following specific operation: 1.5 kg of polyacrylic acid is added to 25 kg of 1.5 mol / L sodium hydroxide solution and stirred evenly. The temperature is adjusted to 35℃, 7 kg of calcium chloride is added and stirred for 90 min, 4 kg of sodium carbonate is added and stirred for 15 h, centrifuged, washed, and vacuum dried.

[0042] The preparation method of the above-mentioned modified unsaturated polyester resin includes the following steps: S1. Add 1,2-propanediol, 1.5 kg of antioxidant 1010, zinc acetate, diethylene glycol, and ethylene terephthalate to a reaction vessel, stir at 190℃ for 90 min, and maintain the temperature for 3 h to obtain a pre-prepared material with an acid value of 9.9 mg KOH / g. a ; S2, Precast material a The mixture was cooled to 155℃, and ethylene glycol, 2 kg of antioxidant 1010, p-phenol, phthalic anhydride, and maleic anhydride were added. The mixture was kept at this temperature under reflux for 90 min, then heated to 190℃ and held until the system acid value reached 11.1 mg KOH / g, yielding the pre-formulated material. b ; S3, Precast material b Cool to 155℃, add artificial stone aggregate and stir for 20 minutes, then add activated calcium carbonate and styrene and stir evenly.

[0043] The modified unsaturated polyester resins obtained in Example 5 and Comparative Examples 1-2 were kneaded into spherical shapes, placed on a polyester film, and allowed to stand. A timer was started, and the spheres naturally spread out to form discs. After 15 minutes, the maximum diameter of the disc was precisely measured using calipers. Within the same time frame, a larger disc diameter indicates better flowability.

[0044] like Figure 1 As shown, the modified unsaturated polyester resin obtained in Example 5 has the largest diameter, indicating that the modified unsaturated polyester resin obtained in Example 5 has the best flowability.

[0045] The applicant believes that this is due to the preform material of the present invention. b The amino-terminated polyamide amine can react with activated calcium carbonate, reducing the viscosity of the system and thus improving the wetting and dispersing properties of the invention. This effectively promotes the dispersion of artificial stone aggregate in the system and facilitates the entry of activated calcium carbonate into the polyester resin, making it easier to process.

[0046] Artificial slabs were prepared using the methods of Example 5 and Comparative Examples 1-2. Since the size of the artificial stone aggregate and activated calcium carbonate in Example 5 and Comparative Examples 1-2 was less than 6 mm, the physical properties of the obtained artificial slabs were measured with reference to the fine aggregate slabs in GB / T 35157-2017 "Resin-type Synthetic Stone Slabs".

[0047] like Figure 2 As shown, the artificial granite slabs prepared using the method in Example 5 exhibit the highest flexural strength and compressive strength.

[0048] The applicant believes that this is due to the preform material of the present invention. b With the addition of terminal amino-terminated polyamide amine, it can react with activated calcium carbonate, greatly enhancing the bonding strength between calcium carbonate, artificial stone aggregate and unsaturated polyester. Since the surface of activated calcium carbonate has a polyacrylic acid structure, it can combine with terminal amino-terminated polyamide amine during the curing process, which can reduce cracking and blistering, and also increase the strength.

[0049] The above description is only a preferred embodiment of the present invention, but the scope of protection of the present invention is not limited thereto. Any equivalent substitutions or modifications made by those skilled in the art within the scope of the technology disclosed in the present invention, based on the technical solution and inventive concept of the present invention, should be covered within the scope of protection of the present invention.

Claims

1. A modified unsaturated polyester resin, characterized in that, The raw materials, by weight, include: 20-30 parts of 1,2-propanediol, 2-10 parts of diethylene glycol, 15-30 parts of ethylene glycol, 5-10 parts of phthalic anhydride, 25-30 parts of maleic anhydride, 2-8 parts of artificial stone aggregate, 20-40 parts of amino-terminated polyamide amine, 100-200 parts of activated calcium carbonate, 20-30 parts of styrene, 0.1-1 parts of catalyst, 1-2 parts of polymerization inhibitor, and 2-5 parts of antioxidant. Activated calcium carbonate is prepared by the following specific operation: polyacrylic acid is added to sodium hydroxide solution and stirred evenly, the temperature is adjusted to 30-40℃, calcium chloride is added and stirred for 1-2 hours, sodium carbonate is added and stirred for 10-20 hours, centrifuged, washed and dried.

2. The modified unsaturated polyester resin according to claim 1, characterized in that, The antioxidant is at least one of the following: antioxidant BHT, antioxidant TNP, antioxidant TPP, antioxidant 1010, antioxidant 1076, and antioxidant 1098.

3. The modified unsaturated polyester resin according to claim 1, characterized in that, The polymerization inhibitor is p-phenol.

4. The modified unsaturated polyester resin according to claim 1, characterized in that, The catalyst is zinc acetate.

5. The modified unsaturated polyester resin according to claim 1, characterized in that, The generation number of terminal amino-terminated polyamide amines is 3-7.

6. The modified unsaturated polyester resin according to claim 1, characterized in that, The mass ratio of polyacrylic acid, calcium chloride, and sodium carbonate is 1-2:5-10:2-6.

7. The modified unsaturated polyester resin according to claim 1, characterized in that, The concentration of the sodium hydroxide solution is 1-2 mol / L.

8. A method for preparing the modified unsaturated polyester resin according to any one of claims 1-7, characterized in that, The steps include the following: S1. Mix 1,2-propanediol, antioxidant, catalyst, diethylene glycol, and polyethylene terephthalate, stir at 180-200℃ for 1-2 hours, and keep warm for 2-4 hours to obtain the preform. a ; S2, Precast material a Cool to 150-160℃, add ethylene glycol, antioxidant, polymerization inhibitor, phthalic anhydride, and maleic anhydride, and maintain the temperature under steam reflux for 1-2 hours. Then raise the temperature to 180-200℃ and maintain it until the acid value of the system is 10-12.5 mg KOH / g to obtain the preform. b ; S3, Precast material b Cool to 150-160℃, add artificial stone aggregate and amino-terminated polyamide amine, stir for 10-30 minutes, then add activated calcium carbonate and styrene and stir until uniform.

9. The method for preparing the modified unsaturated polyester resin according to claim 8, characterized in that, In S1, precast material a The acid value is less than 10 mg KOH / g.

Images