A hydrophilically modified HDPE composition and its use

Abstract

The application provides a hydrophilic modified HDPE composition and application thereof, and relates to the technical field of composite materials.The hydrophilic modified HDPE composition contains, in terms of weight parts, 100 parts of HDPE and 1-10 parts of a hydrophilic anthraquinone compound.The raw material components can further contain 0.1-2 carbon-based materials.The hydrophilic anthraquinone compound is obtained by reacting an anthraquinone compound and a diisocyanate compound and then reacting with a hydrophilic compound.The hydrophilic modified HDPE composition improves the hydrophilicity of HDPE, and introduces an anthraquinone structure, so that the denitrification effect on nitrogen-containing sewage can be improved.

Description

TECHNICAL FIELD

[0001] The present application belongs to the technical field of composite materials, and relates to a hydrophilic modified HDPE composition and application thereof. BACKGROUND

[0002] Nitrogen-containing sewage not only has important harm to water bodies, but also has adverse effects on ecosystems and humans. Promoting microbial degradation of nitrogen-containing compounds under anthraquinone compounds as redox mediators is an effective method for treating nitrogen-containing sewage. In order to improve the utilization rate of anthraquinone compounds and avoid the loss of water-soluble anthraquinone compounds and the "secondary pollution" to water bodies, loading anthraquinone compounds on a carrier is an effective method. Among them, the polymer carrier (such as high-density polyethylene HDPE) has the advantages of good corrosion resistance, good chemical stability, high mechanical strength, low density, easy processing and the like, but has the disadvantages of poor compatibility with anthraquinone compounds and hydrophobicity, which will affect the play of the effect of anthraquinone compounds as redox mediators.

[0003] Therefore, the technology of loading anthraquinone compounds on HDPE needs to be further improved and optimized to better play the effect of anthraquinone compounds as redox mediators and improve the denitrification effect on nitrogen-containing sewage. SUMMARY

[0004] In order to solve the above technical problems, the present application provides a hydrophilic modified HDPE composition and application thereof.

[0005] The technical scheme of the present application is as follows:

[0006] A hydrophilic modified HDPE composition, the raw material components comprise, by weight fraction: 100 parts of HDPE and 1-10 parts of hydrophilic anthraquinone compounds;

[0007] The preparation method of the hydrophilic anthraquinone compound is:

[0008] The anthraquinone compound and the diisocyanate compound are reacted to obtain an anthraquinone prepolymer;

[0009] The anthraquinone prepolymer and a hydrophilic compound are reacted to obtain the hydrophilic anthraquinone compound;

[0010] The hydrophilic compound contains active hydrogen that can react with NCO groups at 100℃.

[0011] Preferably, the anthraquinone compound contains one or a combination of two or more of primary amino groups, secondary amine groups and hydroxyl groups;

[0012] Preferably, the sum of the number of primary amino groups, secondary amine groups and hydroxyl groups on the structure of the anthraquinone compound is 1-2.

[0013] Preferably, the molar ratio of the anthraquinone compound and the diisocyanate compound is 1:1-2.

[0014] Preferably, the diisocyanate compound is selected from diisocyanate monomers and combinations thereof;

[0015] The combination is obtained by reacting the diisocyanate monomers with polyethylene glycol, polysiloxane diol or hydroxyl-terminated polyethylene glycol / polysiloxane block copolymer;

[0016] The NCO group content in the combination is not less than 5wt%.

[0017] Preferably, the active hydrogen in the hydrophilic compound is selected from one or a combination of two or more of hydroxyl, primary amino and secondary amino groups;

[0018] The hydrophilic compound further contains one or a combination of two or more of polyethylene glycol segment, sulfonic acid and its salt structure, carboxylic acid and its salt structure, sulfuric acid and its salt structure, phenol and its salt structure and phosphoric acid and its salt structure.

[0019] Preferably, the molar ratio of the NCO group in the anthraquinone prepolymer and the active hydrogen in the hydrophilic compound is 1:0.6-2.

[0020] More preferably, the hydrophilic compound is selected from hydrophilic aspartate resins;

[0021] The structure of the hydrophilic aspartate resin is shown in the following formula (1),

[0022] (1)

[0024] Wherein, X is C8-C24 alkylene, or a first polyethylene glycol divalent segment or a first polysiloxane divalent segment;

[0025] The structure of the first polyethylene glycol divalent segment is shown in the following formula (2),

[0026] -O(CH2CH2O) m (2)

[0027] Wherein, m=4-50;

[0028] The structure of the first polysiloxane divalent segment is shown in the following formula (3),

[0029] -Me2SiO(SiOMe2) p (SiOMeR3) q SiMe2- (3)

[0030] wherein Me represents methyl, R3 is selected from substituted C3-C20 hydrocarbon group, p = 10-200, q = 0-100;

[0031] R1 and R2 are both selected from the second polyethylene glycol monovalent segment;

[0032] The structure of the second polyethylene glycol monovalent segment is shown in the following formula (4),

[0033] -O(CH2CH2O) n CH3 (4)

[0034] wherein n = 4-50;

[0035] The average polymerization degree of the first polyethylene glycol divalent segment and the second polyethylene glycol monovalent segment is the same or different.

[0036] Preferably, the raw material component further comprises 0.1-2 parts of carbon-based material;

[0037] The carbon-based material is selected from carbon nanotubes, graphene or graphene oxide.

[0038] More preferably, the surface of the carbon-based material is treated with epoxy, primary amino, secondary amine or NCO groups.

[0039] Use of the hydrophilic modified HDPE composition described in any one of the above embodiments for treatment of nitrogen-containing wastewater.

[0040] The beneficial effects of the present application are:

[0041] (1) The present application obtains a hydrophilic anthraquinone compound by reaction of an anthraquinone prepolymer with a hydrophilic compound, improves the hydrophilicity of HDPE, is conducive to wetting of HDPE by nitrogen-containing wastewater, improves the promoting effect of anthraquinone as a redox mediator on denitrification, and thus the hydrophilic anthraquinone compound can further exert the denitrification effect of anthraquinone.

[0042] (2) When the hydrophilic anthraquinone compound further contains active hydrogen such as secondary amine group and hydroxyl group, it can further react with carbon-based material to combine anthraquinone, carbon-based material and hydrophilic structure together, and better exert the denitrification effect. DETAILED DESCRIPTION

[0043] The technical solutions of the present application are further described and explained in the following specific embodiments.

[0044] In one aspect, the present application proposes a hydrophilic modified HDPE composition, the raw material component comprises, by weight fraction: 100 parts of HDPE and 1-10 parts of hydrophilic anthraquinone compound;

[0045] The preparation method of the hydrophilic anthraquinone compound is:

[0046] The anthraquinone compound and the diisocyanate compound are reacted to obtain an anthraquinone prepolymer;

[0047] The anthraquinone prepolymer and the hydrophilic compound are reacted to obtain a hydrophilic anthraquinone compound;

[0048] The hydrophilic compound contains active hydrogen that can react with the NCO group at 100°C.

[0049] The present application improves the hydrophilicity of HDPE by adding the hydrophilic anthraquinone compound to HDPE, which is more conducive to the wettability of the hydrophilic modified HDPE composition (or the treatment filler made therefrom) to nitrogen-containing sewage, and the anthraquinone can be more fully contacted with the nitrogen-containing sewage and better play the role of redox mediator.

[0050] For the preparation of the hydrophilic anthraquinone compound, the anthraquinone compound and the diisocyanate compound are reacted to obtain an anthraquinone prepolymer containing NCO groups, which is then reacted with a hydrophilic compound. According to the performance of the hydrophilic compound, different properties can be introduced to the hydrophilic anthraquinone compound, and different properties can be given to the hydrophilic modified HDPE composition.

[0051] In the present application, the melt index (2.16 Kg, 190°C) of HDPE is not particularly limited and can be 0.5-20 g / min. The processing method of the hydrophilic modified HDPE composition is not particularly limited, for example, a double-screw extrusion molding method can be used to prepare a filler for sewage treatment. The filler can refer to CJ / T 461-2014 “High-density polyethylene suspended carrier filler for water treatment”, and be used in a moving bed biofilm reactor (MBBR) system to construct an electron transfer enhanced biofilm reactor system. For the above raw material components, other raw materials such as antioxidants, ultraviolet inhibitors, inorganic fillers (such as talc, kaolin, glass beads, zeolite) can also be added according to the performance requirements.

[0052] In some embodiments, the anthraquinone compound contains one or a combination of two or more of primary amino groups, secondary amine groups and hydroxyl groups; the primary amino groups, the secondary amine groups and the hydroxyl groups contain active hydrogen, the NCO groups in the anthraquinone compound and the diisocyanate compound are reacted, and an anthraquinone prepolymer is obtained.

[0053] Further, the sum of the number of primary amino groups, secondary amino groups and hydroxyl groups in the anthraquinone compound is 1-2. By using the above technical solution, the cross-linking product of the anthraquinone compound and the diisocyanate compound can be avoided, so that the anthraquinone prepolymer that can continue to be used cannot be obtained. For example, the anthraquinone compound can be 1-aminoanthraquinone, 2-aminoanthraquinone, 1,5-diaminoanthraquinone, 2,5-diaminoanthraquinone, 2,6-diaminoanthraquinone, 2-hydroxyanthraquinone, 1,8-dihydroxyanthraquinone, N-hydroxypropyl-2-aminoanthraquinone, N-hydroxypropyl-5-aminoanthraquinone, and the like.

[0054] In some embodiments, the molar ratio of the anthraquinone compound and the diisocyanate compound is 1:1-2. For example, the molar ratio of the anthraquinone compound and the diisocyanate compound can be any value or any value between 1:1, 1:1.1, 1:1.2, 1:1.3, 1:1.4, 1:1.5, 1:1.6, 1:1.7, 1:1.8, 1:1.9, 1:2, and the like. For example, when there is only 1 of the hydroxyl group, the secondary amino group and the primary amino group in the anthraquinone compound, the molar ratio of the anthraquinone compound and the diisocyanate compound can be 1:1; when the sum of the number of the primary amino group, the secondary amino group and the hydroxyl group in the anthraquinone compound is 2, the molar ratio of the anthraquinone compound and the diisocyanate compound can be 1:1.2, 1:1.5, 1:1.8, 1:2, and the like.

[0055] In some embodiments, the diisocyanate compound is selected from diisocyanate monomers and combinations thereof;

[0056] The combination is obtained by reacting the diisocyanate monomer with polyethylene glycol, polysiloxane diol or hydroxyl-terminated polyethylene glycol / polysiloxane block copolymer;

[0057] The content of the NCO group in the combination is not less than 5wt%.

[0058] For example, the diisocyanate monomer can be dodecylbenzene-2,4-diisocyanate, 2-heptyl-3,4-bis(9-isocyanatononyl)-1-pentyl-cyclohexane (dimer diisocyanate), hexamethylene diisocyanate HDI, isophorone diisocyanate IPDI, etc. The combination obtained by reacting the diisocyanate monomer with polyethylene glycol introduces a polyethylene glycol segment with good hydrophilicity, further improving the hydrophilicity of the hydrophilic anthraquinone compound. The combination obtained by reacting the diisocyanate monomer with the hydroxyl-terminated polyethylene glycol / polydimethylsiloxane block copolymer introduces a polyethylene glycol segment with good hydrophilicity and a polydimethylsiloxane segment with strong hydrophobicity. The low surface energy of the polydimethylsiloxane segment can achieve phase separation and migration of the hydrophilic anthraquinone compound from HDPE and enrichment on the surface, which is conducive to the enrichment of the polyethylene glycol segment on the surface of HDPE and the improvement of the hydrophilic effect. When the diisocyanate monomer contains a long-chain alkyl group (such as an alkyl or alkylene group with 8-18 carbon atoms), the compatibility of the hydrophilic anthraquinone compound with HDPE is improved, changing from strong incompatibility to certain incompatibility, which is more conducive to the migration and enrichment of the hydrophilic anthraquinone compound on the surface, avoiding the shielding and hindering effects of the low-surface-energy polydimethylsiloxane segment on the hydrophilic segment on the surface. For example, the diisocyanate monomer is dodecylbenzene-2,4-diisocyanate or dimer diisocyanate, which contains a long-chain alkyl group. When the diisocyanate monomer reacts with the hydroxyl-terminated polyethylene glycol / polydimethylsiloxane block copolymer to obtain an anthraquinone prepolymer, the hydrophilic anthraquinone compound and HDPE are further incompatible to a certain extent, which can migrate to the surface, and the polyethylene glycol segment can also be enriched on the surface, which is more conducive to the effect of anthraquinone as a redox mediator.

[0059] For the hydroxyl-terminated polyethylene glycol / polydimethylsiloxane block copolymer, for example, the structure can be as shown in the following formula (5) or (6),

[0060] HO-EO-PDMS-EO-OH (5)

[0061] HO-PDMS-EO-PDMS-OH (6)

[0062] wherein EO represents a polyethylene glycol segment, PDMS represents a second polydimethylsiloxane divalent segment, the average polymerization degree DP of EO can be 4-50, and the DP of PDMS can be 10-200.

[0063] There is no particular limitation on the preparation method of the above-mentioned hydroxyl-terminated polyethylene glycol / polydimethylsiloxane block copolymer, such as the method of hydrosilylation reaction. Taking the hydroxyl-terminated polyethylene glycol / polydimethylsiloxane block copolymer shown in the above formula (5) as an example, one preparation method can be as follows: the terminal allyl polyethylene glycol HO(CH2CH2O) a reacts with the double-end silicon hydride polydimethylsiloxane HMe2Si(OSiMe2) bThe hydrosilylation reaction is carried out with OSiMe2H in a molar ratio of 2:1. Wherein, a and b represent the DP of EO and the DP of PDMS, respectively.

[0064] The content of NCO groups in the combination can be any value or any value between 5wt%, 5.5wt%, 6wt%, 6.5wt%, 7wt%, 7.5wt%, 8wt%, 8.5wt%, 9wt%, 9.5wt%, 10wt%, 10.5wt%, 11wt%, 11.5wt%, 12wt%, 12.5wt%, 13wt%, 13.5wt%, 14wt%, 14.5wt%, 15wt%, etc.

[0065] In some embodiments, the active hydrogen in the hydrophilic compound is selected from one or a combination of two or more of hydroxyl, primary amino and secondary amino groups; the hydrophilic compound contains active hydrogens such as hydroxyl, primary amino and secondary amino groups, which can react with the NCO groups of the anthraquinone prepolymer to obtain a hydrophilic anthraquinone compound.

[0066] The hydrophilic compound also contains one or a combination of two or more of polyethylene glycol segment, sulfonic acid and its salt structure, carboxylic acid and its salt structure, sulfuric acid and its salt structure, phenol and its salt structure, and phosphoric acid and its salt structure. These segments and / or structures have good hydrophilicity, and a hydrophilic anthraquinone compound can be obtained. For example, the hydrophilic compound can be polyethylene glycol, polyethylene glycol / polypropylene glycol copolymer, p-aminobenzenesulfonic acid, sodium p-aminobenzenesulfonate, 2-aminoacetic acid, sodium 2-aminoacetate, alanine, sodium alaninate, 6-aminohexanoic acid, sodium 6-aminohexanoate, etc.

[0067] In some embodiments, the hydrophilic compound is selected from a hydrophilic aspartate resin;

[0068] The structure of the hydrophilic aspartate resin is shown in the following formula (1),

[0069] (1)

[0071] Wherein, X is C8-C24 alkylene, or a first polyethylene glycol divalent segment or a first polysiloxane divalent segment;

[0072] The structure of the first polyethylene glycol divalent segment is shown in the following formula (2),

[0073] -O(CH2CH2O) m (2)

[0074] Wherein, m = 4-50;

[0075] The structure of the first polysiloxane divalent segment is shown in the following formula (3),

[0076] -Me2SiO(SiOMe2) p (SiOMeR3) q SiMe2-(3)

[0077] wherein Me represents methyl, R3 is selected from substituted C3-C20 hydrocarbon group, p = 10-200, q = 0-100;

[0078] R1 and R2 are both selected from the second polyethylene glycol monovalent segment;

[0079] The second polyethylene glycol monovalent segment has the following structure as shown in formula (4),

[0080] -O(CH2CH2O) n CH3(4)

[0081] wherein n = 4-50;

[0082] The average polymerization degree DP of the first polyethylene glycol divalent segment and the second polyethylene glycol monovalent segment is the same or different.

[0083] The hydrophilic compound adopts a hydrophilic aspartate resin, the side chain of the hydrophilic aspartate resin contains two second polyethylene glycol monovalent segments, which has high degree of freedom and can better play the role of the hydrophilic anthraquinone compound, which is helpful to the wetting effect of nitrogen-containing wastewater. When X in the above formula (1) is C8-C24 alkylene, the compatibility of the hydrophilic aspartate resin with HDPE can be improved, and the hydrophilic aspartate resin and HDPE are changed from high incompatibility to certain incompatibility; when X in the above formula (1) is the first polyethylene glycol divalent segment, the hydrophilicity of the hydrophilic anthraquinone compound can be enhanced; when X in the above formula (1) is the first polysiloxane divalent segment, it is conducive to the migration and enrichment of the hydrophilic anthraquinone compound on the surface of the hydrophilic modified HDPE composition (or the treatment filler made therefrom).

[0084] From the convenience of raw material acquisition and performance, etc., the above-mentioned first polysiloxane divalent segment and the second polysiloxane divalent segment can be polydimethylsiloxane segments, respectively. For example, for the first polysiloxane divalent segment shown in the above formula (3), q = 0. When the second polysiloxane divalent segment is a polydimethylsiloxane segment, the average polymerization degree DP can be 10-200.

[0085] The preparation method of the above-mentioned hydrophilic aspartate resin is not particularly limited, for example, the aspartate resin can be obtained by reacting diamin X(NH2)2 with maleic acid diethyl ester, and then ester exchange reaction with polyethylene glycol monomethyl ether, which is well known to those skilled in the art.

[0086] In some embodiments, the molar ratio of NCO groups in the anthraquinone prepolymer and active hydrogen in the hydrophilic compound is 1:0.6-2. For example, the molar ratio of NCO groups and active hydrogen can be any value or any value between 1:0.6, 1:0.7, 1:0.8, 1:0.9, 1:1, 1:1.1, 1:1.2, 1:1.3, 1:1.5, 1:1.6, 1:1.8, 1:2, etc. When the molar ratio of NCO groups and active hydrogen is higher than 1:1, such as 1:0.6, 1:0.8, etc., the NCO groups are in excess, and the obtained hydrophilic anthraquinone compound also contains NCO groups, which can continue to react with compounds containing active hydrogen, which can be derived from primary amino groups, secondary amino groups, hydroxyl groups, etc. When the molar ratio of NCO groups and active hydrogen is lower than 1:1, such as 1:1.2, 1:1.5, etc., the NCO groups are insufficient, and the obtained hydrophilic anthraquinone compound also contains active hydrogen, which can continue to react with some compounds, such as compounds containing NCO groups, epoxy groups, etc.

[0087] In some embodiments, the raw material component further comprises 0.1-2 parts of carbon-based material. The carbon-based material has good electrical conductivity, which can improve the performance of anthraquinone as a redox mediator, and further improve the denitrification performance of the nitrogen-containing wastewater. For example, the carbon-based material can be any value or any value between 0.1 parts, 0.2 parts, 0.3 parts, 0.5 parts, 0.6 parts, 0.8 parts, 1 part, 1.2 parts, 1.4 parts, 1.5 parts, 1.6 parts, 1.8 parts, 2 parts, etc. The carbon-based material can be carbon nanotubes, graphene, or graphene oxide.

[0088] Further, the surface of the carbon-based material is treated with epoxy groups, primary amino groups, secondary amine groups, or NCO groups. By using the above technical solution, the carbon-based material can further react with the hydrophilic anthraquinone compound and be bonded together through chemical bonds, better exerting the performance of the hydrophilic anthraquinone compound and the carbon-based material. For the surface treatment of the carbon-based material, an organic treatment agent can be used for treatment. The conventional organic treatment agent can be a silane coupling agent, such as KH-792, KH-560, KH-550, etc.

[0089] On the other hand, the present application also proposes an application of the hydrophilically modified HDPE composition described in any of the above embodiments for the treatment of nitrogen-containing wastewater. The nitrogen-containing compounds in the nitrogen-containing wastewater can be nitrate, ammonia nitrogen, nitrite, etc.

[0090] The technical solutions of the present application are further described and explained below according to various embodiments. Unless otherwise specified, the parts described in the following preparation examples and embodiments are parts by weight.

[0091] Preparation of hydrophilic anthraquinone compounds in Preparation Examples 1-3

[0092] Preparation Example 1

[0093] Under nitrogen protection, 1,5-diaminoanthraquinone and dodecylbenzene-2,4-diisocyanate were added into a reaction container in a molar ratio of 1:1.5, stirred at room temperature for 2 h, and then heated to 80°C for continuous reaction for 2 h to obtain an anthraquinone prepolymer.

[0094] Under nitrogen protection, the anthraquinone prepolymer and polyethylene glycol (DP = 12.6) were added into a reaction container in a molar ratio of 1:1.2, stirred at room temperature for 3 h, and then heated to 100°C for continuous reaction for 2 h to obtain a hydrophilic anthraquinone compound.

[0095] Preparation Example 2

[0096] Under nitrogen protection, 1,5-diaminoanthraquinone and dodecylbenzene-2,4-diisocyanate were added into a reaction container in a molar ratio of 1:1.8, stirred at room temperature for 2 h, and then heated to 80°C for continuous reaction for 2 h to obtain an anthraquinone prepolymer.

[0097] Under nitrogen protection, the anthraquinone prepolymer and the hydroxyl-terminated polyethylene glycol / polysiloxane block copolymer were added into a reaction container in a molar ratio of 1:1.3, stirred at room temperature for 3 h, and then heated to 100°C for continuous reaction for 2 h to obtain a hydrophilic anthraquinone compound.

[0098] The hydroxyl-terminated polyethylene glycol / polysiloxane block copolymer was obtained by hydrosilylation reaction of allyl-terminated polyethylene glycol HO(CH2CH2O) 10.7 CH2CH=CH2 and bis-silicon hydride polysiloxane HMe2Si(OSiMe2) 30.5 OSiMe2H in a molar ratio of 2:1.

[0099] Preparation Example 3

[0100] Under nitrogen protection, HDI and bis-hydroxypropyl polydimethylsiloxane (DP = 45.2) were added into a reaction container in a molar ratio of 1.6:1, stirred at room temperature for 2 h, and then heated to 60°C for continuous reaction for 2 h to obtain an HDI binder.

[0101] Under nitrogen protection, 2,6-diaminoanthraquinone and the HDI binder were added into a reaction container in a molar ratio of 1:1.4, stirred at room temperature for 2 h, and then heated to 80°C for continuous reaction for 3 h to obtain an anthraquinone prepolymer.

[0102] Under nitrogen protection, the anthraquinone prepolymer and the hydrophilic aspartic acid ester resin were added into a reaction container in a molar ratio of 1.3:1, stirred at room temperature for 3 h, and then heated to 100°C for continuous reaction for 3 h to obtain a hydrophilic anthraquinone compound.

[0103] A hydrophilic aspartate resin is shown by the above formula (1), wherein X is dodecylene, and R1 and R2 are both polyethylene glycol monomethyl ether segments (DP 15.4).

[0104] Example 1

[0105] The raw material components of the HDPE composition of this example include 100 parts of HDPE (melt index 5 g / min) and 5 parts of the hydrophilic anthraquinone compound of Preparation Example 1.

[0106] After the HDPE and the hydrophilic anthraquinone compound are dried to remove water, respectively, they are uniformly mixed and then transferred to a twin-screw extruder to be melt-extruded into a filler. The temperature for melt-extrusion is 170-190°C, and the die temperature is 180°C.

[0107] Comparative Example 1

[0108] The difference between this comparative example and Example 1 is that in Example 1, 5 parts of the hydrophilic anthraquinone compound are replaced by 1.1 parts of 1,5-diaminoanthraquinone. The remaining steps remain unchanged.

[0109] Comparative Example 2

[0110] The difference between this comparative example and Example 1 is that in Example 1, 5 parts of the hydrophilic anthraquinone compound are replaced by a combination of 1.1 parts of 1,5-diaminoanthraquinone and 4 parts of polyethylene glycol (DP 12.6). The remaining steps remain unchanged.

[0111] Example 2

[0112] The difference between this example and Example 1 is that in Example 1, the hydrophilic anthraquinone compound of Preparation Example 1 is replaced by an equal weight of the hydrophilic anthraquinone compound of Preparation Example 2. The remaining steps remain unchanged.

[0113] Example 3

[0114] The difference between this example and Example 2 is that in Example 2, the hydrophilic anthraquinone compound of Preparation Example 2 is adjusted from 5 parts to 1 part. The remaining steps remain unchanged.

[0115] Example 4

[0116] The difference between this example and Example 2 is that in Example 2, the hydrophilic anthraquinone compound of Preparation Example 2 is adjusted from 5 parts to 10 parts. The remaining steps remain unchanged.

[0117] Example 5

[0118] The difference between this example and Example 2 is that in Example 2, the raw material components further include 0.2 parts of untreated single-walled carbon nanotubes SWMT. The remaining steps remain unchanged.

[0119] Example 6

[0120] The difference between this example and Example 5 is that in Example 5, SWMT is equal in weight and the surface is treated with silane coupling agent KH-560. The remaining steps remain unchanged.

[0121] Example 7

[0122] The raw material components of the HDPE composition of this example include 100 parts of HDPE (melt index 5 g / min) and 6 parts of the hydrophilic anthraquinone compound of Preparation Example 3.

[0123] After the HDPE and the hydrophilic anthraquinone compound are dried to remove water, they are uniformly mixed and then transferred to a twin-screw extruder for melt extrusion to form a filler. The temperature for melt extrusion is 170-190°C, and the die temperature is 180°C.

[0124] Comparative Example 3

[0125] The difference between this comparative example and Example 7 is that in Example 7, 6 parts of the hydrophilic anthraquinone compound are replaced by a combination of 1 part of 2-aminoanthraquinone and 5 parts of the hydrophilic aspartic acid ester resin of Preparation Example 3. The remaining steps remain unchanged.

[0126] Example 8

[0127] The difference between this example and Example 7 is that in Example 7, the raw material components further include 0.5 parts of amino-modified SWMT. The remaining steps remain unchanged.

[0128] The amino-modified SWMT is SWMT treated with a KH-550 silane coupling agent for surface modification.

[0129] Performance Test

[0130] 1. Hydrophilicity: tested using a water contact angle tester. The olefin polymer compositions of Examples 1-8 and Comparative Examples 1-3 were each prepared into a thin plate with dimensions of 20 cm x 20 cm x 2 mm, and the water contact angle was tested at five positions, including four corners and the middle of the same surface of the thin plate, and the average of the five results was taken as the water contact angle, as shown in Table 1 below.

[0131] Table 1 Water Contact Angle Test Results

[0132]

[0133] Therefore, based on the data in Table 1 above, the addition of the hydrophilic anthraquinone compound to the HDPE can significantly reduce the hydrophobicity of the HDPE, and the hydrophilicity of the obtained HDPE composition is good.

[0134] 2. Denitrification performance test: 500 ml of denitrification medium with an initial concentration of 50 mg / L (initial concentration of nitrate is 50 mg / L) was prepared, 3% of the microorganisms activated and cultured in LB medium were inoculated, the inoculated denitrification medium was placed in a constant temperature shaker, the temperature was set to 36°C, the rotation speed was 120 r / min, so that 10 g of the filler to be tested in the medium was in good fluidization state, sampling was taken every 5 h, the obtained sample was centrifuged at 3000 rpm for 10 min, then the supernatant was taken for quantitative dilution, the absorbance was measured by ultraviolet spectrophotometer to calculate the corresponding concentration, and the denitrification rate was calculated. The denitrification rate at time t is (C0-Ct) / C0x100%, wherein C0is the initial concentration of nitrate, Ctis the concentration of nitrate at time t. Each sample to be tested was measured three times, and the average value of the three results was taken. t t

[0135] The results are shown in Table 2 below, wherein the blank group uses HDPE alone as the filler.

[0136] Table 2 Denitrification rate / %

[0137]

[0138] Comparing Example 1 and Comparative Example 1, the denitrification efficiency in Comparative Example 1 is slower due to the lack of hydrophilic components. Comparing Example 1 and Example 2, Example 1 and Example 7, and Example 2 and Example 7, the anthraquinone content in Examples 2 and 7 is significantly lower than that in Example 1, and the anthraquinone content is lower, but the filler in Examples 2 and 7 still has good denitrification effect because the hydrophilic anthraquinone compounds can migrate and enrich on the surface of the filler. Comparing Example 1, Example 5 and Example 6, and Example 7 and Example 8, the addition of carbon-based materials can significantly improve the denitrification effect.

[0139] 3. Filler stability: the filler to be tested was soaked in water for 72 h, then taken out and air-dried at room temperature for 24 h, then tested according to the above denitrification performance test, and the denitrification rate retention rate at 15 h was tested. Denitrification rate retention rate = post-soaking denitrification rate / pre-soaking denitrification rate x 100%. The higher the denitrification rate retention rate, the better the stability of the denitrification performance of the filler.

[0140] The results are shown in Table 3 below.

[0141] Table 3 Denitrification rate retention rate / %

[0142]

[0143] ​​From the results of Tables 2 and 3, it can be seen that when polyethylene glycol or hydrophilic aspartate resins are directly added to HDPE, the molecular weight is not large enough and the compatibility with HDPE is very poor, and thus the denitrogenation effect of the filler cannot be provided for a long time.

[0144] The basic principles, main features and advantages of the present application have been shown and described above. It should be understood by those skilled in the art that the present application is not limited by the above-described embodiments, which are merely preferred embodiments of the present application, and the scope of the present application is not limited by the above-described embodiments. Equivalent changes and modifications made in accordance with the scope of the present application and the content of the specification should still be within the scope of the present application. The scope of the present application is defined by the appended claims and their equivalents.

Claims

1. A hydrophilically modified HDPE composition, characterized in that, The raw material components, by weight, include: 100 parts HDPE and 1-10 parts hydrophilic anthraquinone compounds; The preparation method of the hydrophilic anthraquinone compound is as follows: Anthraquinone compounds and diisocyanate compounds are reacted to obtain anthraquinone prepolymers; The anthraquinone compound contains one or more of primary amino, secondary amino, and hydroxyl groups; The anthraquinone compound has a total of 1-2 primary amino groups, secondary amino groups, and hydroxyl groups in its structure; The diisocyanate compound is selected from diisocyanate monomers and their conjugates; The conjugate is obtained by reacting the diisocyanate monomer with polyethylene glycol, polysiloxane glycol or hydroxyl-terminated polyethylene glycol / polysiloxane block copolymer; The NCO group content in the complex is not less than 5 wt%; The anthraquinone prepolymer is reacted with a hydrophilic compound to obtain the hydrophilic anthraquinone compound; The hydrophilic compound contains active hydrogen that can react with NCO groups at 100°C; The active hydrogen in the hydrophilic compound is selected from one or a combination of two or more of hydroxyl, primary amino, and secondary amino groups; The hydrophilic compound also contains one or more of the following: polyethylene glycol segments, sulfonic acid and its salts, carboxylic acid and its salts, sulfuric acid and its salts, phenol and its salts, and phosphoric acid and its salts.

2. The hydrophilically modified HDPE composition according to claim 1, characterized in that The molar ratio of the anthraquinone compound to the diisocyanate compound is 1:1-2.

3. The hydrophilically modified HDPE composition according to claim 1, characterized in that The molar ratio of the NCO group in the anthraquinone prepolymer to the active hydrogen in the hydrophilic compound is 1:0.6-2.

4. The hydrophilically modified HDPE composition of claim 1, wherein, The hydrophilic compound is selected from hydrophilic aspartic acid ester resin; The structure of the hydrophilic aspartic acid ester resin is shown in formula (1). （1） Wherein, X is a C8-C24 alkylene group, or a first polyethylene glycol divalent segment or a first polysiloxane divalent segment; The structure of the first polyethylene glycol divalent segment is shown in equation (2) below. -0(CH2CH2O) m - (2) Where m = 4 - 50; The structure of the first polysiloxane divalent segment is shown in equation (3) below. - Me2SiO(SiOMe2) p (SiOMeR3) q SiMe2- (3) Where Me represents methyl, R3 is selected from substituted C3-C20 hydrocarbon groups, p=10-200, q=0-100; R1 and R2 are both selected from the second polyethylene glycol monovalent segment; The structure of the second polyethylene glycol monovalent segment is shown in equation (4) below. -O(CH2CH2O) n CH3(4) Where n = 4 - 50; The average degree of polymerization of the first polyethylene glycol divalent segment and the second polyethylene glycol monovalent segment may be the same or different.

5. The hydrophilically modified HDPE composition of claim 1, wherein, The raw material components also include 0.1-2 parts of carbon-based materials; The carbon-based material is selected from carbon nanotubes or graphene.

6. The hydrophilically modified HDPE composition according to claim 5, characterized in that The surface of the carbon-based material is treated with epoxy, primary amino, secondary amino, or NCO groups.

7. Use of the hydrophilically modified HDPE composition according to any one of claims 1 to 6, characterized in that Used for the treatment of nitrogen-containing wastewater.

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