A method for preparing unsaturated polyester resin from recycled materials containing saturated dibasic acid

Abstract

The invention discloses a method for preparing unsaturated polyester resin from a reclaimed material containing saturated binary acid. The unsaturated polyester resin is prepared from the saturated binary acid reclaimed material as a raw material, and cobalt and manganese catalysts remaining in the raw material are removed by virtue of oxalic acid and a thermal filtering method. A following three-kettle process is utilized: after the esterification reaction of the saturated binary acid and dihydric alcohol and the reaction of oxalic acid and cobalt and manganese ions are finished in a first kettle, thermally filtering the mixture, and introducing the mixture into a second kettle; finishing esterification condensation polymerization of the unsaturated binary acid and dihydric alcohol in the second kettle; and adding styrene into a third kettle, and carrying out dilution to obtain the product. By virtue of the method, the problem that the unsaturated polyester resin prepared from the saturated binary acid reclaimed material has a dark color is solved; the cobalt and manganese catalysts remaining in the raw material are removed by virtue of the oxalic acid and the thermal filtering method, the problem of dark color of resin which cannot be solved by virtue of a two-kettle process is solved by virtue of the three-kettle process, the cost can be remarkably lowered, and the PTA oxidation residue resource can be effectively utilized.

Description

technical field

[0001] The invention relates to a method for preparing unsaturated polyester resin from recycled materials containing saturated dibasic acid, which belongs to the technical field of chemical industry. Background technique

[0002] Unsaturated polyester resin (UPR) is a thermosetting resin, which is usually formed by esterification and polycondensation of saturated dibasic acid and dibasic alcohol and unsaturated dibasic acid and dibasic alcohol, and then diluted with a diluent. Under the action of accelerator and curing agent, the resin is cross-linked into a solid state with a bulky structure. If the resin is impregnated in glass fiber or glass cloth and solidified, it will become a glass fiber reinforced plastic product. Unsaturated polyester resins can produce different grades of resins with different properties according to different needs. The products are corrosion-resistant, high-strength, good electrical insulation, light in weight, and easy to form...

Examples

Embodiment 1

[0024] The primary esterification kettle is fed with 1932 kg of diethylene glycol and 1344 kg of ethylene glycol, 2934 kg of recycled saturated dibasic acid (containing 0.88% cobalt and manganese), and 5.9 kg of zinc acetate. The value is 7mgKOH / g, cooled to 185°C with cooling oil, added 43.6 kg of oxalic acid, kept for 1 hour, and filtered with nitrogen to remove cobalt manganese oxalate. After press filtration, throw 2618 kg of maleic anhydride, 120 kg of benzoic acid, 450 kg of propylene glycol, 0.19 kg of polymerization inhibitor, 8.7 kg of color reducer, and 10.2 kg of antioxidant, heat up to 210°C, keep warm and take samples to measure the acid value 50mgKOH / g, the viscosity is 350-400Pa·c, cool down to 190°C, start decompression and compression polymerization, gradually increase the vacuum degree to -0.08MPa, stabilize for 40 minutes, when the acid value drops to 30-35mgKOH / g, the viscosity is 500-550Pa· After the polycondensation is over, add 4.4 kg of paraffin and 0....

Embodiment 2

[0026] Feed 1974 kg of diethylene glycol and 1442 kg of ethylene glycol into the primary esterification tank, 2982 kg of recycled saturated dibasic acid (containing 0.88% cobalt and manganese), and 5.9 kg of zinc acetate. Value ≤ 7mgKOH / g, cooling oil to 185 ° C, add 44.3 kg oxalic acid, keep warm for 1 hour, nitrogen pressure filter to remove cobalt manganese oxalate. After press filtration, throw 2758 kg of maleic anhydride, 140 kg of benzoic acid, 436 kg of propylene glycol, 0.2 kg of polymerization inhibitor, 8.8 kg of color reducer, and 10.3 kg of antioxidant, heat up to 210°C, keep warm and take samples to measure the acid value 50mgKOH / g, the viscosity is 350-400Pa·c, cool down to 190°C, start decompression and compression polymerization, gradually increase the vacuum degree to -0.08MPa, stabilize for 40 minutes, when the acid value drops to 30-35mgKOH / g, the viscosity is 500-550Pa· After the polycondensation is over, add 4.47 kg of paraffin and 0.38 kg of hydroquinone...

Embodiment 3

[0028] The primary esterification kettle is fed with 2044 kg of diethylene glycol and 1428 kg of ethylene glycol, 3024 kg of recycled saturated dibasic acid (containing 0.88% cobalt and manganese), and 6.0 kg of zinc acetate. Value ≤ 7mgKOH / g, cooling oil to 185 ° C, add 44.9 kg oxalic acid, keep warm for 1 hour, nitrogen pressure filter to remove cobalt manganese oxalate. After press filtration, throw 2752 kg of maleic anhydride, 145 kg of benzoic acid, 430 kg of propylene glycol, 0.2 kg of polymerization inhibitor, 9.0 kg of color reducer, and 10.5 kg of antioxidant, heat up to 210°C, keep warm and take samples to measure the acid value 50mgKOH / g, the viscosity is 350-400Pa·s, cool down to 190°C, start decompression and compression polymerization, gradually increase the vacuum degree to -0.08MPa, stabilize for 40 minutes, when the acid value drops to 30-35mgKOH / g, the viscosity is 500-550Pa· After the polycondensation is over, add 4.5 kg of paraffin and 0.38 kg of hydroquin...

technical field

[0001] The invention relates to a method for preparing unsaturated polyester resin from recycled materials containing saturated dibasic acid, which belongs to the technical field of chemical industry. Background technique

[0002] Unsaturated polyester resin (UPR) is a thermosetting resin, which is usually formed by esterification and polycondensation of saturated dibasic acid and dibasic alcohol and unsaturated dibasic acid and dibasic alcohol, and then diluted with a diluent. Under the action of accelerator and curing agent, the resin is cross-linked into a solid state with a bulky structure. If the resin is impregnated in glass fiber or glass cloth and solidified, it will become a glass fiber reinforced plastic product. Unsaturated polyester resins can produce different grades of resins with different properties according to different needs. The products are corrosion-resistant, high-strength, good electrical insulation, light in weight, and easy to form...

Examples

Embodiment 1

[0024] The primary esterification kettle is fed with 1932 kg of diethylene glycol and 1344 kg of ethylene glycol, 2934 kg of recycled saturated dibasic acid (containing 0.88% cobalt and manganese), and 5.9 kg of zinc acetate. The value is 7mgKOH / g, cooled to 185°C with cooling oil, added 43.6 kg of oxalic acid, kept for 1 hour, and filtered with nitrogen to remove cobalt manganese oxalate. After press filtration, throw 2618 kg of maleic anhydride, 120 kg of benzoic acid, 450 kg of propylene glycol, 0.19 kg of polymerization inhibitor, 8.7 kg of color reducer, and 10.2 kg of antioxidant, heat up to 210°C, keep warm and take samples to measure the acid value 50mgKOH / g, the viscosity is 350-400Pa·c, cool down to 190°C, start decompression and compression polymerization, gradually increase the vacuum degree to -0.08MPa, stabilize for 40 minutes, when the acid value drops to 30-35mgKOH / g, the viscosity is 500-550Pa· After the polycondensation is over, add 4.4 kg of paraffin and 0....

Embodiment 2

[0026] Feed 1974 kg of diethylene glycol and 1442 kg of ethylene glycol into the primary esterification tank, 2982 kg of recycled saturated dibasic acid (containing 0.88% cobalt and manganese), and 5.9 kg of zinc acetate. Value ≤ 7mgKOH / g, cooling oil to 185 ° C, add 44.3 kg oxalic acid, keep warm for 1 hour, nitrogen pressure filter to remove cobalt manganese oxalate. After press filtration, throw 2758 kg of maleic anhydride, 140 kg of benzoic acid, 436 kg of propylene glycol, 0.2 kg of polymerization inhibitor, 8.8 kg of color reducer, and 10.3 kg of antioxidant, heat up to 210°C, keep warm and take samples to measure the acid value 50mgKOH / g, the viscosity is 350-400Pa·c, cool down to 190°C, start decompression and compression polymerization, gradually increase the vacuum degree to -0.08MPa, stabilize for 40 minutes, when the acid value drops to 30-35mgKOH / g, the viscosity is 500-550Pa· After the polycondensation is over, add 4.47 kg of paraffin and 0.38 kg of hydroquinone...

Embodiment 3

[0028] The primary esterification kettle is fed with 2044 kg of diethylene glycol and 1428 kg of ethylene glycol, 3024 kg of recycled saturated dibasic acid (containing 0.88% cobalt and manganese), and 6.0 kg of zinc acetate. Value ≤ 7mgKOH / g, cooling oil to 185 ° C, add 44.9 kg oxalic acid, keep warm for 1 hour, nitrogen pressure filter to remove cobalt manganese oxalate. After press filtration, throw 2752 kg of maleic anhydride, 145 kg of benzoic acid, 430 kg of propylene glycol, 0.2 kg of polymerization inhibitor, 9.0 kg of color reducer, and 10.5 kg of antioxidant, heat up to 210°C, keep warm and take samples to measure the acid value 50mgKOH / g, the viscosity is 350-400Pa·s, cool down to 190°C, start decompression and compression polymerization, gradually increase the vacuum degree to -0.08MPa, stabilize for 40 minutes, when the acid value drops to 30-35mgKOH / g, the viscosity is 500-550Pa· After the polycondensation is over, add 4.5 kg of paraffin and 0.38 kg of hydroquin...