PU-doped MBBR filler composition, and preparation method and application thereof

Abstract

The application belongs to the technical field of MBBR fillers, and particularly relates to a PU doped MBBR filler composition, a preparation method and application thereof. The PU doped MBBR filler composition comprises polyolefin, anthraquinone modified polyurethane, antioxidant, additive, filler and optional compatilizer in a mass ratio of 100:(10-80):(0.3-1):(0.5-5):(10-20):(0-10). The preparation method of the anthraquinone modified polyurethane comprises polymerization of diaminianthraquinone, diisocyanate monomer and polyhydric alcohol in the presence of a catalyst. The polyolefin is modified by the polyurethane containing anthraquinone and long chain alkyl at the same time, so that the PU doped MBBR filler composition obtained has good mechanical strength, biocompatibility and wear resistance, and has high biofilm formation efficiency and strong sewage treatment capacity.

Description

Technical Field

[0001] The present invention belongs to the technical field of MBBR fillers, and in particular relates to a PU-doped MBBR filler composition, a preparation method thereof, and an application thereof. Background Art

[0002] The moving bed biofilm reactor (MBBR) is a newly emerging water treatment process. It draws on the advantages of both traditional activated sludge and biological contact oxidation processes to become a novel, highly efficient hybrid treatment method. This process purifies contaminated water through the metabolic activities of anaerobic and aerobic microorganisms. In MBBR treatment processes, the type, number, and activity of microorganisms determine the treatment load and effectiveness, and fillers, as microbial carriers, play a crucial role. Fillers provide a suitable growth environment for microorganisms, influencing their growth, reproduction, shedding, morphology, and spatial structure, ultimately affecting the efficiency of the MBBR process. Currently, commonly used fillers in biofilm processes include fixed, suspended, and dispersed fillers. From a raw material perspective, fillers primarily include inorganic and organic polymer fillers. Polyolefins are widely used in the preparation of elastic biofillers due to their low relative density, excellent mechanical strength, and corrosion resistance. However, in practical applications, they suffer from poor biocompatibility, poor wear resistance, and easy film release, which in turn compromise their wastewater treatment capacity.

[0003] In summary, it is of great significance to obtain MBBR fillers with good biocompatibility and wear resistance as well as biofilm efficiency and sewage treatment capacity without affecting the mechanical properties. Summary of the Invention

[0004] The purpose of the present invention is to address the defects of polyolefin-based MBBR fillers in the prior art, such as poor biocompatibility, poor wear resistance, low biofilm formation efficiency and weak sewage treatment capacity, and to propose a PU-doped MBBR filler composition that has good mechanical strength, biocompatibility and wear resistance, high biofilm formation efficiency and strong sewage treatment capacity.

[0005] Specifically, the PU-doped MBBR filler composition provided by the present invention includes a polyolefin, anthraquinone-modified polyurethane, an antioxidant, an auxiliary agent, a filler and an optional compatibilizer in a mass ratio of 100:(10-80):(0.3-1):(0.5-5):(10-20):(0-10); the preparation method of the anthraquinone-modified polyurethane includes polymerizing diaminoanthraquinone, a diisocyanate monomer and a polyol in the presence of a catalyst.

[0006] In a preferred embodiment, the polymerization reaction comprises the following steps:

[0007] S1, performing a polyaddition reaction on diaminoanthraquinone and diisocyanate monomer in the presence of a catalyst to obtain a polyurea prepolymer;

[0008] S2. Performing a chain extension reaction on the polyurea prepolymer obtained in step S1 and a polyol to obtain anthraquinone-modified polyurethane.

[0009] In a preferred embodiment, the compatibilizer is prepared by the following method:

[0010] S1. performing a polyaddition reaction on a polyether diol and / or a polyester diol and a diisocyanate monomer in the presence of a catalyst to obtain a polyurethane prepolymer;

[0011] S2. Performing a chain extension reaction on the polyurethane prepolymer obtained in step S1 and an alkyl diol to obtain a compatibilizer.

[0012] In a preferred embodiment, the molar ratio of the diaminoanthraquinone, diisocyanate monomer and catalyst is (0.5-0.85):1:(0.1-0.3).

[0013] In a preferred embodiment, the molar ratio of the NCO groups of the polyurea prepolymer to the OH groups of the polyol is 1:(0.95-1.05).

[0014] In a preferred embodiment, the molar ratio of the polyether diol and / or polyester diol, the diisocyanate monomer and the catalyst is (0.5-0.8):1:(0.1-0.3).

[0015] In a preferred embodiment, the molar ratio of the NCO groups of the polyurethane prepolymer to the OH groups of the alkyl diol is 1:(0.95-1.05).

[0016] In a preferred embodiment, the polyolefin is selected as a homopolymer and / or a copolymer.

[0017] In a preferred embodiment, the antioxidant is selected from at least one of tea polyphenols, butylated hydroxyanisole, butylated hydroxytoluene, tert-butylhydroquinone, antioxidant 1010 and antioxidant 1076.

[0018] In a preferred embodiment, the diaminoanthraquinone is selected from at least one of 1,2-diaminoanthraquinone, 1,4-diaminoanthraquinone, 2,6-diaminoanthraquinone and 1,3-diaminoanthraquinone.

[0019] In a preferred embodiment, the diisocyanate monomers are each independently selected from at least one of isophorone diisocyanate, diphenylmethane diisocyanate, hexamethylene diisocyanate, toluene diisocyanate and dicyclohexylmethane diisocyanate.

[0020] In a preferred embodiment, the polyol includes at least an alkyl diol.

[0021] In a preferred embodiment, the polyol is a mixture of an alkyl diol and a polyether diol and / or a polyester diol.

[0022] In a preferred embodiment, the molar ratio of the alkyl diol, the polyether diol, and the polyester diol is 1:(1-3):(1-3).

[0023] In a preferred embodiment, the polyol is selected from at least one of polyether diol, polyester diol and alkyl diol.

[0024] In a preferred embodiment, the average molecular weight of the polyolefin is 500-2000.

[0025] In a preferred embodiment, the average molecular weight of the polyether diol is 200 to 5000.

[0026] In a preferred embodiment, the average molecular weight of the polyester diol is 1,000 to 20,000.

[0027] In a preferred embodiment, the general formula of the alkyl diol is HOR1OH, R1 is independently C 12 ~C 36 Alkylene.

[0028] The present invention provides a method for preparing the above-mentioned PU-doped MBBR filler composition, which comprises uniformly mixing polyolefin, anthraquinone-modified polyurethane, an antioxidant, an auxiliary agent, a filler and an optional compatibilizer, and then discharging the mixture to obtain the PU-doped MBBR filler composition.

[0029] The present invention also provides application of the PU-doped MBBR filler composition in sewage treatment.

[0030] The key to the present invention is to modify polyolefins by polyurethane containing both anthraquinone and long-chain alkyl groups. The obtained PU-doped MBBR filler composition has good biocompatibility, high mechanical strength and wear resistance, and improves the biofilm formation efficiency and sewage treatment capacity. DETAILED DESCRIPTION

[0031] The PU-doped MBBR filler composition provided by the present invention comprises a polyolefin, anthraquinone-modified polyurethane, an antioxidant, an additive, a filler and an optional compatibilizer in a mass ratio of 100:(10-80):(0.3-1):(0.5-5):(10-20):(0-10). Based on the content of polyolefin as 100 parts by weight, the content of the anthraquinone-modified polyurethane is 10-80 parts by weight, such as 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80 parts by weight or any value therebetween; the content of the antioxidant is 0.3-1 part by weight, such as 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, 1 part by weight or any value therebetween; the content of the additive is 0.5 19, 20, 30, 40, 50, 60, 70, 80, 90, 100, 150, 200, 300, 400, 500, 700, 800, 900, 1000, 2000, 3000, 4000, 7000, 8000, 900, 1000, 2000, 3000, 4000, 5 ...0, 10000, 20000, 30000, 40000, 5000, 7000, 8000, 9000, 10000, 20000, 30000, 30000

[0032] In the present invention, the anthraquinone-modified polyurethane is prepared by the following method:

[0033] S1, performing a polyaddition reaction on diaminoanthraquinone and diisocyanate monomer in the presence of a catalyst to obtain a polyurea prepolymer;

[0034] S2. Performing a chain extension reaction on the polyurea prepolymer obtained in step S1 and a polyol to obtain anthraquinone-modified polyurethane.

[0035] In the preparation process of the above-mentioned anthraquinone-modified polyurethane, in step S1, the temperature of the addition polymerization reaction is preferably 50-70°C, such as 50°C, 52°C, 55°C, 58°C, 60°C, 62°C, 65°C, 68°C, 70°C or any value therebetween; the time of the addition polymerization reaction is preferably 3-5h, such as 3h, 3.5h, 4h, 4.5h, 5h or any value therebetween.

[0036] In the preparation process of the anthraquinone-modified polyurethane, in step S1, the molar ratio of the diaminoanthraquinone, diisocyanate monomer, and catalyst is preferably (0.5-0.85):1:(0.1-0.3). Based on 1 mol of the diisocyanate monomer, the molar amount of the diaminoanthraquinone is 0.5-0.85 mol, such as 0.5 mol, 0.6 mol, 0.7 mol, 0.8 mol, 0.85 mol, or any value therebetween; and the molar amount of the catalyst is 0.1-0.3 mol, such as 0.1 mol, 0.2 mol, 0.3 mol, or any value therebetween.

[0037] In the preparation process of the anthraquinone-modified polyurethane, in step S1, specific examples of the diaminoanthraquinone include, but are not limited to, at least one of 1,2-diaminoanthraquinone, 1,4-diaminoanthraquinone, 2,6-diaminoanthraquinone, and 1,3-diaminoanthraquinone. Specific examples of the diisocyanate monomer include, but are not limited to, at least one of isophorone diisocyanate, diphenylmethane diisocyanate, hexamethylene diisocyanate, toluene diisocyanate, and dicyclohexylmethane diisocyanate.

[0038] In the preparation process of the above-mentioned anthraquinone-modified polyurethane, in step S2, the temperature of the chain extension reaction is preferably 80-110°C, such as 80°C, 82°C, 85°C, 88°C, 90°C, 92°C, 95°C, 98°C, 100°C, 102°C, 105°C, 108°C, 110°C or any value therebetween; the time of the chain extension reaction is preferably 3-5h, such as 3h, 3.5h, 4h, 4.5h, 5h or any value therebetween.

[0039] In the preparation process of the above-mentioned anthraquinone-modified polyurethane, in step S2, the molar ratio of the NCO group of the polyurea prepolymer to the OH group of the polyol is preferably 1:(0.95-1.05), such as 1:0.95, 1:0.98, 1:1, 1:1.01, 1:1.02, 1:1.03, 1:1.04, 1:1.05 or any value therebetween.

[0040] In the preparation process of the anthraquinone-modified polyurethane, in step S2, the polyol is a mixture of an alkyl diol and a polyether diol and / or a polyester diol. Preferably, the molar ratio of the alkyl diol, the polyether diol, and the polyester diol is 1:(1-3):(1-3). Based on the molar weight of the alkyl diol as 1 mol, the molar weight of the polyether diol is 1-3 mol, such as 1 mol, 1.5 mol, 2 mol, 2.5 mol, 3 mol, or any value therebetween; and the molar weight of the polyester diol is 1-3 mol, such as 1 mol, 1.5 mol, 2 mol, 2.5 mol, 3 mol, or any value therebetween. The average molecular weight of the polyether diol is preferably 200 to 5000 g / mol, such as 200 g / mol, 500 g / mol, 800 g / mol, 1000 g / mol, 1500 g / mol, 2000 g / mol, 2500 g / mol, 3000 g / mol, 3500 g / mol, 4000 g / mol, 4500 g / mol, 5000 g / mol or any value therebetween. The average molecular weight of the polyester diol is preferably 1000 to 20000 g / mol, such as 1000 g / mol, 2000 g / mol, 5000 g / mol, 8000 g / mol, 10000 g / mol, 12000 g / mol, 15000 g / mol, 18000 g / mol, 20000 g / mol or any value therebetween. The general formula of the alkyl diol is HOR1OH, R1 is C 12 ~C 36 Alkylene. 12 ~C 36 Specific examples of the alkylene group include, but are not limited to, at least one of dodecylene, hexadecylene, heptadecylene, octadecylene, tetracosylene, and hexatriadecylene.

[0041] In the present invention, the compatibilizer is prepared by the following method:

[0042] S1. performing a polyaddition reaction on a polyether diol and / or a polyester diol and a diisocyanate monomer in the presence of a catalyst to obtain a polyurethane prepolymer;

[0043] S2. Performing a chain extension reaction on the polyurethane prepolymer obtained in step S1 and an alkyl diol to obtain a compatibilizer.

[0044] In the preparation process of the above-mentioned compatibilizer, in step S1, the temperature of the addition polymerization reaction is preferably 50-70°C, such as 50°C, 52°C, 55°C, 58°C, 60°C, 62°C, 65°C, 68°C, 70°C or any value therebetween; the time of the addition polymerization reaction is preferably 3-5h, such as 3h, 3.5h, 4h, 4.5h, 5h or any value therebetween.

[0045] In the preparation process of the compatibilizer, in step S1, the molar ratio of the polyether diol and / or polyester diol, the diisocyanate monomer, and the catalyst is preferably (0.5-0.8):1:(0.1-0.3). Based on 1 mol of the diisocyanate monomer, the molar amount of the diaminoanthraquinone is 0.5-0.8 mol, such as 0.5 mol, 0.6 mol, 0.7 mol, 0.8 mol, or any value therebetween; and the molar amount of the catalyst is 0.1-0.3 mol, such as 0.1 mol, 0.2 mol, 0.3 mol, or any value therebetween.

[0046] In the preparation process of the compatibilizer, in step S1, the average molecular weight of the polyether diol is preferably 200 to 5000 g / mol, such as 200 g / mol, 500 g / mol, 800 g / mol, 1000 g / mol, 1500 g / mol, 2000 g / mol, 2500 g / mol, 3000 g / mol, 3500 g / mol, 4000 g / mol, 4500 g / mol, 5000 g / mol, or any value therebetween. The average molecular weight of the polyester diol is preferably 1000 to 20000 g / mol, such as 1000 g / mol, 2000 g / mol, 5000 g / mol, 8000 g / mol, 10000 g / mol, 12000 g / mol, 15000 g / mol, 18000 g / mol, 20000 g / mol, or any value therebetween.

[0047] In the preparation process of the compatibilizer, in step S1, specific examples of the diisocyanate monomer include, but are not limited to, at least one of isophorone diisocyanate, diphenylmethane diisocyanate, hexamethylene diisocyanate, toluene diisocyanate and dicyclohexylmethane diisocyanate.

[0048] In the preparation process of the above-mentioned compatibilizer, in step S2, the temperature of the chain extension reaction is preferably 80-110°C, such as 80°C, 82°C, 85°C, 88°C, 90°C, 92°C, 95°C, 98°C, 100°C, 102°C, 105°C, 108°C, 110°C or any value therebetween; the time of the chain extension reaction is preferably 3-5h, such as 3h, 3.5h, 4h, 4.5h, 5h or any value therebetween.

[0049] In the preparation process of the above-mentioned compatibilizer, in step S2, the molar ratio of the NCO group of the polyurethane prepolymer to the OH group of the polyol is preferably 1:(0.95-1.05), such as 1:0.95, 1:0.98, 1:1, 1:1.01, 1:1.02, 1:1.03, 1:1.04, 1:1.05 or any value therebetween.

[0050] In the preparation process of the compatibilizer, in step S2, the general formula of the alkyl glycol is HOR1OH, R1 is C 12 ~C 36 Alkylene. 12 ~C 36 Specific examples of the alkylene group include, but are not limited to, at least one of dodecylene, hexadecylene, heptadecylene, octadecylene, tetracosylene, and hexatriadecylene.

[0051] In the present invention, the polyolefin is a homopolymer and / or a copolymer. Preferably, specific examples of the polyolefin include, but are not limited to, at least one of polyethylene, polypropylene, polybutene, polypentene, polyhexene, polyoctene, and poly(4-methyl-1-pentene).

[0052] In the present invention, the average molecular weight of the polyolefin is 500 to 2000 g / mol, such as 500 g / mol, 800 g / mol, 1000 g / mol, 1200 g / mol, 1500 g / mol, 1800 g / mol, 2000 g / mol or any value therebetween.

[0053] In the present invention, specific examples of the antioxidant include, but are not limited to, at least one of tea polyphenols, butylated hydroxyanisole, butylated hydroxytoluene, tert-butylhydroquinone, antioxidant 1010, and antioxidant 1076.

[0054] In the present invention, specific examples of the auxiliary agent include but are not limited to: at least one of a stabilizer, an inhibitor, a dispersant, a flame retardant, a diluent, an adhesion promoter, a dye, a pigment, a defoamer, a leveling agent, a leveling agent and an ion capture agent.

[0055] In the present invention, specific examples of the filler include but are not limited to at least one of carbon black, silica, alumina, talc, calcium carbonate, glass microspheres, metal powder and polytetrafluoroethylene filler.

[0056] The preparation method of the PU-doped MBBR filler composition provided by the present invention comprises uniformly mixing a polyolefin, anthraquinone-modified polyurethane, an antioxidant, an additive, a filler, and an optional compatibilizer, and then discharging the mixture to obtain the PU-doped MBBR filler composition. The mixing method may be to simultaneously feed all the raw materials and then mix them together, or to feed and mix some of the raw materials in any order, followed by adding the remaining raw materials and continuing to mix, without particular limitation.

[0057] The present invention will be described in detail below through specific examples.

[0058] In the following examples and comparative examples, the parts of raw materials are all parts by weight.

[0059] Preparation Example 1 Preparation of anthraquinone-modified polyurethane

[0060] S1. Weigh 16.7 g (0.07 mol) of 2,6-diaminoanthraquinone and 22.2 g (0.1 mol) of isophorone diisocyanate into a reaction flask and stir thoroughly for 15 min. Then, add 3 g (0.02 mol) of triethanolamine dropwise under nitrogen protection. Continue the reaction at 65° C. for 4 h to obtain a polyurea prepolymer mixture.

[0061] S2, 40g (0.02mol) of polypropylene glycol (M n =2000 g / mol) and 1.8 g (0.009 mol) of 1,12-dodecanediol were added to the polyurea prepolymer mixture obtained in step S1, and the mixture was reacted at 90° C. for 4 h. The mixture was extracted with ethyl acetate, washed, and dried to obtain anthraquinone-modified polyurethane.

[0062] Preparation Example 2 Preparation of Anthraquinone Modified Polyurethane

[0063] S1. Weigh 11.9 g (0.05 mol) of 1,2-diaminoanthraquinone and 22.2 g (0.1 mol) of isophorone diisocyanate into a reaction flask and stir thoroughly for 15 min. Then, add 4.5 g (0.03 mol) of triethanolamine dropwise under nitrogen protection. Continue the reaction at 65° C. for 4 h to obtain a polyurea prepolymer mixture.

[0064] S2, 12.5g (0.025mol) of polypropylene glycol (M n=500 g / mol) and 5.05 g (0.025 mol) of 1,12-dodecanediol were added to the polyurea prepolymer mixture obtained in step S1, and the mixture was reacted at 90° C. for 4 h. The mixture was extracted with ethyl acetate, washed, and dried to obtain anthraquinone-modified polyurethane.

[0065] Preparation Example 3 Preparation of Anthraquinone Modified Polyurethane

[0066] S1. Weigh 19.1 g (0.08 mol) of 1,2-diaminoanthraquinone and 22.2 g (0.1 mol) of isophorone diisocyanate into a reaction flask and stir thoroughly for 15 min. Then, add 1.5 g (0.01 mol) of triethanolamine dropwise under nitrogen protection. Continue the reaction at 65° C. for 4 h to obtain a polyurea prepolymer mixture.

[0067] S2, 60g (0.012mol) of polypropylene glycol (M n =5000 g / mol) and 1.8 g (0.009 mol) of 1,12-dodecanediol were added to the polyurea prepolymer mixture obtained in step S1, and the mixture was reacted at 90° C. for 4 h. The mixture was extracted with ethyl acetate, washed, and dried to obtain anthraquinone-modified polyurethane.

[0068] Preparation Example 4 Preparation of Compatibilizer

[0069] S1, weigh 140g (0.07mol) of polypropylene glycol (M n =2000g / mol) and 22.2g (0.1mol) of isophorone diisocyanate were added to a reaction flask and stirred thoroughly for 15min. Then, 1.5g (0.01mol) of triethanolamine was added dropwise under nitrogen protection. The reaction was continued at 65°C for 4h to obtain a polyurethane prepolymer mixture.

[0070] S2. Add 6.1 g (0.03 mol) of 1,12-dodecanediol to the polyurethane prepolymer mixture obtained in step S1, continue the reaction at 90° C. for 4 hours, extract with ethyl acetate, wash, and dry to obtain a compatibilizer.

[0071] Preparation Example 5 Preparation of Compatibilizer

[0072] S1, weigh 70g (0.035mol) of polypropylene glycol (M n =2000g / mol), 105g (0.035mol) polycaprolactone diol (M n =3000g / mol) and 22.2g (0.1mol) of isophorone diisocyanate were added to a reaction flask and stirred thoroughly for 15 minutes. Then, 1.5g (0.01mol) of triethanolamine was added dropwise under nitrogen protection. The reaction was continued at 65°C for 4 hours to obtain a polyurethane prepolymer mixture.

[0073] S2. Add 6.1 g (0.03 mol) of 1,12-dodecanediol to the polyurethane prepolymer mixture obtained in step S1, and continue the reaction at 90° C. for 4 hours to obtain a compatibilizer.

[0074] Preparation Example 6 Preparation of Compatibilizer

[0075] S1, weigh 210g (0.07mol) of polycaprolactone diol (M n =3000g / mol) and 22.2g (0.1mol) of isophorone diisocyanate were added to a reaction flask and stirred thoroughly for 15 minutes. Then, 1.5g (0.01mol) of triethanolamine was added dropwise under nitrogen protection. The reaction was continued at 65°C for 4 hours to obtain a polyurethane prepolymer mixture.

[0076] S2. Add 6.1 g (0.03 mol) of 1,12-dodecanediol to the polyurethane prepolymer mixture obtained in step S1, and continue the reaction at 90° C. for 4 hours to obtain a compatibilizer.

[0077] Comparative Preparation Example 1 Preparation of Reference Polyurethane

[0078] Weigh 22.2g (0.1mol) of isophorone diisocyanate, 36g (0.018mol) of polypropylene glycol (M n =2000g / mol) and 1.2g (0.006mol) of 1,12-dodecanediol were added into a reaction flask and stirred thoroughly for 15min. 3g (0.02mol) of triethanolamine was added dropwise under nitrogen protection. The reaction was continued at 90°C for 4h, and the mixture was extracted with ethyl acetate, washed, and dried to obtain a reference polyurethane.

[0079] Comparative Preparation Example 2 Preparation of Reference Polyurethane

[0080] S1. Weigh 16.7 g (0.07 mol) of 2,6-diaminoanthraquinone and 22.2 g (0.1 mol) of isophorone diisocyanate into a reaction flask and stir thoroughly for 15 min. Then, add 3 g (0.02 mol) of triethanolamine dropwise under nitrogen protection. Continue the reaction at 65° C. for 4 h to obtain a polyurea prepolymer mixture.

[0081] S2, 48g (0.024mol) of polypropylene glycol (M n =2000 g / mol) was added to the polyurea prepolymer mixture obtained in step S1, and the mixture was reacted at 90° C. for 4 h. The mixture was extracted with ethyl acetate, washed, and dried to obtain anthraquinone-modified polyurethane.

[0082] Example 1 Preparation of PU-doped MBBR filler composition

[0083] Weigh 100 parts of polyethylene (M n =2000 g / mol), 40 parts of the anthraquinone-modified polyurethane of Preparation Example 1, 0.3 parts of an antioxidant (tea polyphenols), 3 parts of an auxiliary agent (dispersant), 20 parts of a filler (silicon dioxide), and 5 parts of a compatibilizer of Preparation Example 4 were added to a dispersing mixing device and mixed evenly. The resulting mixture was then heated to a molten state and cooled and formed into a mold to obtain a PU-doped MBBR filler composition.

[0084] Example 2 Preparation of PU-doped MBBR filler composition

[0085] Weigh 100 parts of polyethylene (M n =500g / mol), 80 parts of anthraquinone-modified polyurethane of Preparation Example 1, 1 part of antioxidant (tea polyphenols), 0.5 parts of auxiliary agent (dispersant), 10 parts of filler (silicon dioxide), and 10 parts of compatibilizer of Preparation Example 4 were added into a dispersing mixing equipment and mixed evenly. The resulting mixture was then heated to a molten state and cooled and formed into a mold to obtain a PU-doped MBBR filler composition.

[0086] Example 3 Preparation of PU-doped MBBR filler composition

[0087] Weigh 100 parts of polyethylene (M n =1000 g / mol), 10 parts of the anthraquinone-modified polyurethane of Preparation Example 1, 0.6 parts of an antioxidant (tea polyphenols), 5 parts of an auxiliary agent (dispersant), 15 parts of a filler (silicon dioxide), and 0 parts of a compatibilizer were added to a dispersing mixing device and mixed evenly. The resulting mixture was then heated to a molten state and cooled and formed into a mold to obtain a PU-doped MBBR filler composition.

[0088] Example 4 Preparation of PU-doped MBBR filler composition

[0089] A PU-doped MBBR filler composition was prepared according to the method of Example 1, except that the anthraquinone-modified polyurethane of Preparation Example 1 was replaced by the anthraquinone-modified polyurethane of Preparation Example 2 with the same mass fraction. The other conditions were the same as in Example 1 to obtain a PU-doped MBBR filler composition.

[0090] Example 5 Preparation of PU-doped MBBR filler composition

[0091] A PU-doped MBBR filler composition was prepared according to the method of Example 1, except that the anthraquinone-modified polyurethane of Preparation Example 1 was replaced by the anthraquinone-modified polyurethane of Preparation Example 3 with the same mass fraction. The other conditions were the same as in Example 1 to obtain a PU-doped MBBR filler composition.

[0092] Example 6 Preparation of PU-doped MBBR filler composition

[0093] A PU-doped MBBR filler composition was prepared according to the method of Example 1, except that the compatibilizer of Preparation Example 4 was replaced by the compatibilizer of Preparation Example 6 with the same mass fraction. The other conditions were the same as in Example 1 to obtain a PU-doped MBBR filler composition.

[0094] Comparative Example 1 Preparation of Reference MBBR Filler Composition

[0095] A reference MBBR filler composition was prepared according to the method of Example 1, except that the anthraquinone-modified polyurethane of Preparation Example 1 was replaced by the reference polyurethane of Comparative Preparation Example 1 with the same mass fraction. The other conditions were the same as in Example 1 to obtain a reference MBBR filler composition.

[0096] Comparative Example 2 Preparation of Reference MBBR Filler Composition

[0097] A reference MBBR filler composition was prepared according to the method of Example 1, except that the anthraquinone-modified polyurethane of Preparation Example 1 was replaced by the reference polyurethane of Comparative Preparation Example 1 with the same mass fraction. The other conditions were the same as in Example 1 to obtain a reference MBBR filler composition.

[0098] Test Case

[0099] (1) Mechanical strength test

[0100] A. Tensile Strength Test: The sample to be tested was made into a dumbbell-shaped specimen according to ASTM D638-08. The specimen was broken using a universal testing machine at a tensile rate of 5 mm / min. The tensile strength was tested. The results are shown in Table 1.

[0101] B. Compressive Strength Test: The samples to be tested were made into dumbbell-shaped specimens according to ASTM D638-08. The specimens were extruded using a universal testing machine at an extrusion rate of 5 mm / min to test their compressive strength. The results are shown in Table 1.

[0102] (2) Wear resistance test: The wear resistance test was performed by sanding the surface of the sample back and forth 100 times with 3M662XW diamond sandpaper to test the mass change and calculate the wear rate. The results are shown in Table 1.

[0103] (3) Test of biofilm efficiency and purification efficiency:

[0104] A. The sludge was put into a biochemical pool and water was added to make the sludge concentration 1000 mg / L. A carbon source was then added to the biochemical pool to control the COD value at 250 mg / L. The biological fillers in the embodiment and the comparative example were then added and allowed to stand for 2 h, aerated for 2 h, aerated for 2 h, and allowed to stand for 2 h. This operation was repeated until the thickness of the biofilm on the filler surface grew to 0.5 mm. This time was recorded as the number of days for biofilm formation. The results are shown in Table 1.

[0105] B. Use artificial preparation to simulate domestic sewage, control the water temperature at 25℃, the influent COD concentration is about 330mg / L, the TN concentration is about 55mg / L, and the NH4 + -N concentration is about 40 mg / L, dissolved oxygen concentration is 7-8 mg / L, and the removal rates of COD, TN, NH3-N, and TP are calculated after the completion of biofilm formation and 24 hours of normal operation. The results are shown in Table 2.

[0106] Table 1

[0107]

[0108]

[0109] Table 2

[0110] serial number COD (%) <![CDATA[NH4 + -N(%)]]> TN (%) Example 1 89.1 93.6 87.5 Example 2 92.7 95.0 90.3 Example 3 90.7 93.9 86.9 Example 4 88.5 94.2 88.2 Example 5 87.6 90.5 85.5 Example 6 85.1 89.3 82.4 Comparative Example 1 74.8 80.5 73.3 Comparative Example 2 77.2 82.9 75.1

[0111] Although the embodiments of the present invention have been shown and described above, it will be understood that the above embodiments are illustrative and are not to be construed as limitations on the present invention. A person skilled in the art may change, modify, replace and modify the above embodiments within the scope of the present invention without departing from the principles and purpose of the present invention.

Claims

1. A PU-doped MBBR filler composition, characterized in that: The PU-doped MBBR filler composition comprises a polyolefin, anthraquinone-modified polyurethane, an antioxidant, an additive, a filler, and an optional compatibilizer in a mass ratio of 100:(10-80):(0.3-1):(0.5-5):(10-20):(0-10); the preparation method of the anthraquinone-modified polyurethane comprises polymerizing diaminoanthraquinone, a diisocyanate monomer, and a polyol in the presence of a catalyst; The polymerization reaction comprises the following steps: S1, performing a polyaddition reaction on diaminoanthraquinone and diisocyanate monomer in the presence of a catalyst to obtain a polyurea prepolymer; S2, performing a chain extension reaction on the polyurea prepolymer obtained in step S1 and a polyol to obtain anthraquinone-modified polyurethane; The polyol comprises at least an alkyl diol; The general formula of the alkyl diol is HOR1OH, R1 is independently C 12 ~C 36 Alkylene.

2. The PU-doped MBBR filler composition according to claim 1, characterized in that The compatibilizer is prepared by the following method: S1. performing a polyaddition reaction on a polyether diol and / or a polyester diol and a diisocyanate monomer in the presence of a catalyst to obtain a polyurethane prepolymer; S2. Performing a chain extension reaction on the polyurethane prepolymer obtained in step S1 and an alkyl diol to obtain a compatibilizer.

3. The PU-doped MBBR filler composition according to claim 1, characterized in that The molar ratio of the diaminoanthraquinone, diisocyanate monomer and catalyst is (0.5-0.85):1:(0.1-0.3); the molar ratio of the NCO group of the polyurea prepolymer to the OH group of the polyol is 1:(0.95-1.05).

4. The PU-doped MBBR filler composition according to claim 2, characterized in that The molar ratio of the polyether diol and / or polyester diol, diisocyanate monomer and catalyst is (0.5-0.8):1:(0.1-0.3); the molar ratio of the NCO group of the polyurethane prepolymer to the OH group of the alkyl diol is 1:(0.95-1.05).

5. The PU-doped MBBR filler composition according to claim 1, characterized in that The polyolefin is a homopolymer and / or a copolymer; the antioxidant is selected from at least one of tea polyphenols, butylated hydroxyanisole, butylated hydroxytoluene, tert-butylhydroquinone, antioxidant 1010 and antioxidant 1076.

6. The PU-doped MBBR filler composition according to any one of claims 1 to 5, characterized in that: The diaminoanthraquinone is selected from at least one of 1,2-diaminoanthraquinone, 1,4-diaminoanthraquinone, 2,6-diaminoanthraquinone and 1,3-diaminoanthraquinone; and the diisocyanate monomers are each independently selected from at least one of isophorone diisocyanate, diphenylmethane diisocyanate, hexamethylene diisocyanate, toluene diisocyanate and dicyclohexylmethane diisocyanate.

7. The PU-doped MBBR filler composition according to claim 1, characterized in that The polyol is a mixture of an alkyl diol and a polyether diol and / or a polyester diol.

8. The PU-doped MBBR filler composition according to claim 7, characterized in that: The molar ratio of the alkyl diol, polyether diol and polyester diol is 1:(1-3):(1-3); the average molecular weight of the polyolefin is 500-2000 g / mol; the average molecular weight of the polyether diol is 200-5000 g / mol; and the average molecular weight of the polyester diol is 1000-20000 g / mol.

9. The method for preparing the PU-doped MBBR filler composition according to any one of claims 1 to 8, characterized in that: The method comprises the steps of uniformly mixing polyolefin, anthraquinone-modified polyurethane, an antioxidant, an auxiliary agent, a filler and an optional compatibilizer, and then discharging the mixture to obtain a PU-doped MBBR filler composition.

10. Use of the PU-doped MBBR filler composition according to any one of claims 1 to 8 in sewage treatment.

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