CN117586474A - Hydrophilic polyurethane filler and preparation method thereof - Google Patents
Hydrophilic polyurethane filler and preparation method thereof Download PDFInfo
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- CN117586474A CN117586474A CN202311562940.5A CN202311562940A CN117586474A CN 117586474 A CN117586474 A CN 117586474A CN 202311562940 A CN202311562940 A CN 202311562940A CN 117586474 A CN117586474 A CN 117586474A
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- hydrophilic polyurethane
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- 239000000945 filler Substances 0.000 title claims abstract description 56
- 229920002635 polyurethane Polymers 0.000 title claims abstract description 36
- 239000004814 polyurethane Substances 0.000 title claims abstract description 36
- 238000002360 preparation method Methods 0.000 title abstract description 10
- 229920002752 Konjac Polymers 0.000 claims abstract description 36
- 235000010485 konjac Nutrition 0.000 claims abstract description 36
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 31
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 25
- 229920000578 graft copolymer Polymers 0.000 claims abstract description 24
- 238000005187 foaming Methods 0.000 claims abstract description 20
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims abstract description 19
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000004721 Polyphenylene oxide Substances 0.000 claims abstract description 14
- 229920000570 polyether Polymers 0.000 claims abstract description 14
- 229920005862 polyol Polymers 0.000 claims abstract description 14
- 150000003077 polyols Chemical class 0.000 claims abstract description 14
- 239000006260 foam Substances 0.000 claims abstract description 13
- 238000003756 stirring Methods 0.000 claims abstract description 12
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 claims abstract description 9
- 239000012975 dibutyltin dilaurate Substances 0.000 claims abstract description 9
- 239000003381 stabilizer Substances 0.000 claims abstract description 9
- 150000001412 amines Chemical class 0.000 claims abstract description 8
- 239000003054 catalyst Substances 0.000 claims abstract description 8
- 239000011148 porous material Substances 0.000 claims abstract description 6
- 238000005303 weighing Methods 0.000 claims abstract description 6
- 238000000034 method Methods 0.000 claims description 12
- CRVGTESFCCXCTH-UHFFFAOYSA-N methyl diethanolamine Chemical group OCCN(C)CCO CRVGTESFCCXCTH-UHFFFAOYSA-N 0.000 claims description 11
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 9
- 238000006243 chemical reaction Methods 0.000 claims description 8
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 6
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 6
- 239000003431 cross linking reagent Substances 0.000 claims description 6
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 6
- 239000003999 initiator Substances 0.000 claims description 6
- LUEWUZLMQUOBSB-FSKGGBMCSA-N (2s,3s,4s,5s,6r)-2-[(2r,3s,4r,5r,6s)-6-[(2r,3s,4r,5s,6s)-4,5-dihydroxy-2-(hydroxymethyl)-6-[(2r,4r,5s,6r)-4,5,6-trihydroxy-2-(hydroxymethyl)oxan-3-yl]oxyoxan-3-yl]oxy-4,5-dihydroxy-2-(hydroxymethyl)oxan-3-yl]oxy-6-(hydroxymethyl)oxane-3,4,5-triol Chemical compound O[C@H]1[C@@H](O)[C@H](O)[C@@H](CO)O[C@H]1O[C@@H]1[C@@H](CO)O[C@@H](O[C@@H]2[C@H](O[C@@H](OC3[C@H](O[C@@H](O)[C@@H](O)[C@H]3O)CO)[C@@H](O)[C@H]2O)CO)[C@H](O)[C@H]1O LUEWUZLMQUOBSB-FSKGGBMCSA-N 0.000 claims description 5
- 229920002581 Glucomannan Polymers 0.000 claims description 5
- 229940046240 glucomannan Drugs 0.000 claims description 5
- ZIUHHBKFKCYYJD-UHFFFAOYSA-N n,n'-methylenebisacrylamide Chemical compound C=CC(=O)NCNC(=O)C=C ZIUHHBKFKCYYJD-UHFFFAOYSA-N 0.000 claims description 3
- 229910052757 nitrogen Inorganic materials 0.000 claims description 3
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 claims description 3
- 239000000843 powder Substances 0.000 claims description 3
- 241001312219 Amorphophallus konjac Species 0.000 description 11
- 235000001206 Amorphophallus rivieri Nutrition 0.000 description 11
- 238000010521 absorption reaction Methods 0.000 description 11
- 239000000252 konjac Substances 0.000 description 11
- 230000000694 effects Effects 0.000 description 10
- 244000005700 microbiome Species 0.000 description 10
- 229920005830 Polyurethane Foam Polymers 0.000 description 6
- 239000011496 polyurethane foam Substances 0.000 description 6
- 238000004062 sedimentation Methods 0.000 description 6
- 239000010865 sewage Substances 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 239000000203 mixture Substances 0.000 description 4
- 238000010170 biological method Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 238000009472 formulation Methods 0.000 description 3
- 230000002209 hydrophobic effect Effects 0.000 description 3
- 229920001451 polypropylene glycol Polymers 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-N Propionic acid Substances CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 238000000053 physical method Methods 0.000 description 2
- 239000002861 polymer material Substances 0.000 description 2
- 239000010802 sludge Substances 0.000 description 2
- 241000894006 Bacteria Species 0.000 description 1
- WQZGKKKJIJFFOK-QTVWNMPRSA-N D-mannopyranose Chemical compound OC[C@H]1OC(O)[C@@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-QTVWNMPRSA-N 0.000 description 1
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000008103 glucose Substances 0.000 description 1
- 239000001963 growth medium Substances 0.000 description 1
- 238000009434 installation Methods 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 230000000813 microbial effect Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229920005615 natural polymer Polymers 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000011197 physicochemical method Methods 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 230000000750 progressive effect Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000036632 reaction speed Effects 0.000 description 1
- 238000005067 remediation Methods 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 230000003746 surface roughness Effects 0.000 description 1
- 239000012970 tertiary amine catalyst Substances 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F3/00—Biological treatment of water, waste water, or sewage
- C02F3/34—Biological treatment of water, waste water, or sewage characterised by the microorganisms used
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/4009—Two or more macromolecular compounds not provided for in one single group of groups C08G18/42 - C08G18/64
- C08G18/4072—Mixtures of compounds of group C08G18/63 with other macromolecular compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
- C08G18/4825—Polyethers containing two hydroxy groups
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/63—Block or graft polymers obtained by polymerising compounds having carbon-to-carbon double bonds on to polymers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
- C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
- C08G18/7657—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings
- C08G18/7664—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups
- C08G18/7671—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups containing only one alkylene bisphenyl group
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
- C08J9/12—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a physical blowing agent
- C08J9/14—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a physical blowing agent organic
- C08J9/143—Halogen containing compounds
- C08J9/144—Halogen containing compounds containing carbon, halogen and hydrogen only
- C08J9/145—Halogen containing compounds containing carbon, halogen and hydrogen only only chlorine as halogen atoms
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2101/00—Manufacture of cellular products
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2203/00—Foams characterized by the expanding agent
- C08J2203/14—Saturated hydrocarbons, e.g. butane; Unspecified hydrocarbons
- C08J2203/142—Halogenated saturated hydrocarbons, e.g. H3C-CF3
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2375/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
- C08J2375/04—Polyurethanes
- C08J2375/08—Polyurethanes from polyethers
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Polymers & Plastics (AREA)
- Medicinal Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Life Sciences & Earth Sciences (AREA)
- Microbiology (AREA)
- Engineering & Computer Science (AREA)
- Hydrology & Water Resources (AREA)
- Water Supply & Treatment (AREA)
- Environmental & Geological Engineering (AREA)
- Biodiversity & Conservation Biology (AREA)
- Materials Engineering (AREA)
- Polyurethanes Or Polyureas (AREA)
Abstract
The invention discloses a hydrophilic polyurethane filler and a preparation method thereof, wherein the preparation method comprises the following steps: sequentially weighing polyether polyol, an amine catalyst, dibutyl tin dilaurate, an organosilicon foam stabilizer, water, methylene dichloride, a hydrophilic agent, a pore opening agent and a konjak glucomannan-acrylic acid graft copolymer in a container, uniformly stirring, standing, adding the weighed diphenylmethane diisocyanate in the container, stirring for 5-15s, pouring into a foaming box for free foaming, placing in a baking oven for continuous foaming for 60min after foaming is stopped, and placing for 24h after finishing to obtain the hydrophilic polyurethane filler.
Description
Technical Field
The invention relates to the technical field of sewage treatment, in particular to a hydrophilic polyurethane filler and a preparation method thereof.
Background
At present, the conventional methods applied to sewage treatment in China comprise a physical method, a chemical method, a biological method and the like. The physical method has low equipment cost, simple and convenient operation and poor treatment effect. The chemical treatment has a higher cost although the treatment effect is better than that of the physical treatment. Compared with the traditional physicochemical method, the biological method mainly based on microbial remediation has the advantages of low cost, short time consumption, difficult secondary pollution, no ecological balance damage and the like, and is more and more paid attention to by students. Biological methods, which utilize microorganisms cultured by screening, convert toxic and harmful pollutants into non-toxic and harmless substances through degradation or bioconversion of microorganisms, have been widely used in sewage treatment.
The immobilized microorganism technology is a microorganism treatment technology which starts to develop in the last 60 th century. The free bacteria are fixed on the filler, so that the loss rate of microorganisms can be reduced, and the concentration of microorganisms (especially microorganisms with special functions) in the bioreactor can be increased. The filler can provide places for the adhesion and growth of microorganisms, and the properties such as the material, the surface roughness, the specific surface area and the like of the filler directly influence the speed of film formation and the amount of microorganisms, thereby influencing the biological sewage treatment effect. Polyurethane foam (PUF) carrier is an ideal growth medium, has high porosity and high specific surface area, can be used for fixing microorganisms, and has the characteristics of low price, convenient installation, long service life, difficult blockage and the like. In view of this, PUFs are widely used in the field of sewage treatment.
However, the structural units of polyurethane sponges which are common on the market at present are mostly hydrophobic chain segments and groups, so that the hydrophilicity is relatively poor. In order to increase the hydrophilicity of the polyurethane, water-absorbing substances may be added to the formulation or hydrophilic groups or segments may be incorporated into the polyurethane molecular chain. For example, zheng Kai is to strengthen the hydrophilicity of PUF, and hydrophilize and modify polyurethane foam (PUF) by chemical oxidation and acrylic acid grafting technology, so as to increase the real specific surface area, reduce the contact angle of the surface and effectively improve the hydrophilization performance.
Disclosure of Invention
In view of the above, the invention provides a hydrophilic polyurethane filler and a preparation method thereof, wherein polyether polyol and MDI are used as main raw materials, and konjak glucomannan-acrylic acid graft copolymer and various auxiliary agents are added, so that the polyurethane filler with good hydrophilicity and quick film forming effect is prepared by a simple one-step foaming method.
In order to achieve the above purpose, the present invention adopts the following technical scheme:
the hydrophilic polyurethane filler comprises the following components in parts by mass:
95-105 parts of polyether polyol, 55-65 parts of MDI (diphenylmethane diisocyanate), 25-35 parts of hydrophilic agent, 10-20 parts of pore-forming agent, 2-4 parts of konjak glucomannan-acrylic acid graft copolymer, 1-2 parts of dibutyltin dilaurate, 1-2 parts of organosilicon foam stabilizer, 1-2 parts of water, 0.5-1 part of methylene dichloride and 0.1-0.5 part of amine catalyst.
Preferably, the polyether polyol is PPG2000, and the hydroxyl value of the polyether polyol is 54-58mgKOH/g;
the hydrophilizing agent is ZL-480; the pore opening agent is ZL Y-1900; the amine catalyst is N-methyldiethanolamine.
Preferably, the konjac glucomannan-acrylic acid graft copolymer is prepared by the following method:
potassium persulfate is used as an initiator, and N, N' -methylene bisacrylamide is used as a cross-linking agent. 10.0g of konjak glucomannan and 100mL of acrylic acid neutralized by sodium hydroxide are added into a 500mL three-necked bottle together, stirred for 1h under the protection of nitrogen at 35 ℃ until the konjak powder swells, then 0.5g of initiator and 0.08g of cross-linking agent are added, stirred evenly, then placed into a water bath kettle at 60 ℃ for uniform reaction for 2h, and the product is taken out, dried, crushed and screened to obtain the konjak glucomannan-acrylic acid graft copolymer.
Konjak is a special resource in China, the main component of the konjak is Konjak Glucomannan (KGM), and heteropolysaccharide formed by connecting glucose and mannose by beta-glycosidic bond has good water absorption and moisture retention. In the present study, konjac glucomannan was modified and acrylic acid was grafted to synthesize a konjac glucomannan-propionic acid graft copolymer (KSAP) containing a large number of hydrophilic groups such as hydroxyl groups and carboxyl groups.
Another object of the present invention is to provide a method for preparing the hydrophilic polyurethane filler, comprising:
sequentially weighing polyether polyol, an amine catalyst, dibutyl tin dilaurate, an organosilicon foam stabilizer, water, methylene dichloride, a hydrophilic agent, a pore opening agent and a konjak glucomannan-acrylic acid graft copolymer in a container, uniformly stirring, standing, adding the weighed diphenylmethane diisocyanate in the container, stirring for 5-15s, pouring into a foaming box for free foaming, placing in a baking oven for continuous foaming for 60min after foaming is stopped, and placing for 24h after finishing to obtain the hydrophilic polyurethane filler.
Preferably, the temperature of the oven is 55-65 ℃.
Preferably, the stirring time is 3min, and the stirring speed is 150rpm/min.
Preferably, the time of the standing is 1min.
Compared with the prior art, the invention has the following beneficial effects:
1. the preparation method of the polyurethane filler is simple to operate and low in cost;
2. the hydrophilic polyurethane sponge has good hydrophilic effect and good film forming effect;
3. the hydrophilic polyurethane sponge of the invention is added with the product konjak glucomannan-acrylic acid grafting copolymer (KSAP) modified by grafting of the unique natural polymer material konjak and acrylic acid, and has better improving effect on the hydrophilic performance of the polyurethane sponge.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings that are required to be used in the embodiments or the description of the prior art will be briefly described below, and it is obvious that the drawings in the following description are only embodiments of the present invention, and that other drawings can be obtained according to the provided drawings without inventive effort for a person skilled in the art.
FIG. 1 is a graph showing the comparison of the film formation amounts of different fillers.
Detailed Description
The following description of the embodiments of the present invention will be made clearly and completely with reference to the accompanying drawings, in which it is apparent that the embodiments described are only some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Example 1
The embodiment provides a hydrophilic polyurethane filler, which comprises the following components in parts by mass:
100 parts of polyether polyol (PPG 2000, hydroxyl value 58 mgKOH/g), 60 parts of MDI (diphenylmethane diisocyanate), 30 parts of hydrophilic agent (ZL-480), 15 parts of pore-forming agent (ZL Y-1900), 3 parts of konjak glucomannan-acrylic acid graft copolymer, 1 part of dibutyl tin dilaurate, 1 part of organosilicon foam stabilizer, 1.25 parts of water, 0.75 part of methylene dichloride and 0.3 part of N-methyldiethanolamine.
Example 2
The embodiment provides a hydrophilic polyurethane filler, which comprises the following components in parts by mass:
105 parts of polyether polyol (PPG 2000, hydroxyl value 54 mgKOH/g), 55 parts of MDI (diphenylmethane diisocyanate), 35 parts of hydrophilic agent (ZL-480), 10 parts of pore-forming agent (ZL Y-1900), 2 parts of konjak glucomannan-acrylic acid graft copolymer, 2 parts of dibutyl tin dilaurate, 1 part of organosilicon foam stabilizer, 1 part of water, 1 part of dichloromethane and 0.1 part of N-methyl diethanolamine.
Example 3
The embodiment provides a hydrophilic polyurethane filler, which comprises the following components in parts by mass:
95 parts of polyether polyol (PPG 2000, hydroxyl value 55 mgKOH/g), 65 parts of MDI (diphenylmethane diisocyanate), 25 parts of hydrophilic agent (ZL-480), 20 parts of pore-forming agent (ZL Y-1900), 4 parts of konjak glucomannan-acrylic acid graft copolymer, 1 part of dibutyl tin dilaurate, 1 part of organosilicon foam stabilizer, 0.5 part of water, 0.5 part of methylene dichloride and 0.5 part of N-methyldiethanolamine.
Example 4
The embodiment provides a preparation method of hydrophilic polyurethane filler, which comprises the following steps:
preparation of konjac glucomannan-propionic acid graft copolymer (KSAP): potassium persulfate is used as an initiator, and N, N' -methylene bisacrylamide is used as a cross-linking agent. 10.0g of konjak glucomannan and 100mL of acrylic acid neutralized by sodium hydroxide are added into a 500mL three-necked bottle together, stirred for 1h under the protection of nitrogen at 35 ℃ until the konjak powder swells, then 0.5g of initiator and 0.08g of cross-linking agent are added, stirred evenly, then placed into a water bath kettle at 60 ℃ for uniform reaction for 2h, and the product is taken out, dried, crushed and screened to obtain the konjak glucomannan-acrylic acid graft copolymer.
Sequentially weighing polyether polyol, N-methyl diethanolamine, dibutyl tin dilaurate, an organosilicon foam stabilizer, water, methylene dichloride, a hydrophilic agent, a pore opening agent and konjak glucomannan-acrylic acid graft copolymer according to any one of the formulas in examples 1-3, uniformly stirring by an electric stirrer, standing for a moment, controlling the whole process at normal temperature of 25 ℃, rapidly adding the weighed MDI into the beaker, stirring for 10 seconds, pouring into a foaming box for free foaming, placing into a 60-DEG oven for foaming for 60 minutes after the foaming is stopped, placing for 24 hours at room temperature after the foaming is finished, and cutting into a plurality of 200mm multiplied by 200mm cube blocks.
Performance testing
The properties of the hydrophilic polyurethane filler prepared by the formulation of example 1 were measured, and the water absorption, settling time, tensile strength, open cell content, etc. of the polyurethane filler were measured by the following methods, respectively.
The water absorption test comprises the steps of firstly, independently weighing 1 mass m1 of prepared filler by an electronic balance, throwing the 1 mass filler into water, taking out the filler after half an hour, sucking the water on the surface by filter paper, and weighing the mass m 2 . Water absorption= (m) 2 －m 1 )/m 1 ×100％。
Tensile strength was measured according to GB/T6344-2008 (test for tensile strength and elongation at break of flexible foam polymer material); the open cell content was measured according to GB/T10799-2008 (determination of the open and closed cell volume percentages of rigid foams).
The results are shown in Table 1:
TABLE 1
Effect of Konjac glucomannan-acrylic acid graft copolymer amount on the hydrophilic Properties of Filler
According to the formulation shown in example 1, the effect of the amount of the konjac glucomannan-acrylic acid graft copolymer on the hydrophilicity and physical properties of the sponge was examined by changing the composition of the konjac glucomannan-acrylic acid graft copolymer while controlling the other components except the konjac glucomannan-acrylic acid graft copolymer, and the results are shown in Table 2.
TABLE 2
As is clear from Table 2, the prepared hydrophilic filler has a relatively low water absorption and a relatively long sedimentation time in water without adding the konjac glucomannan-acrylic acid graft copolymer. With the increase of the consumption of the konjac glucomannan-acrylic acid graft copolymer, the water absorption rate of the prepared hydrophilic polyurethane filler is obviously improved, and the sedimentation time of the hydrophilic polyurethane filler in water is obviously shortened. This is probably because the konjac glucomannan-acrylic acid graft copolymer participates in the foaming reaction in the polyurethane preparation process, and the hydrophilic chain segment is introduced into the polyurethane molecular chain segment, so that the hydrophilic capacity of the sponge is improved, the water absorption rate of the sponge is increased, the self mass of the sponge is increased due to water absorption, and the sedimentation time in water is shortened.
Effect of the amount of the hydrophilizing agent ZL-480 on the hydrophilizing properties of the Filler
According to the formula shown in example 1, the influence of the amount of the hydrophilic agent ZL-480 on the hydrophilicity and physical properties of the filler was examined by changing the components of the hydrophilic agent ZL-480 by controlling the other components to be unchanged, and the results are shown in Table 3.
TABLE 3 Table 3
As can be seen from Table 3, if ZL-480 is not added, i.e., at a ZL-480 component content of 0, the water absorption of the prepared filler is relatively low, only 31%, and the sedimentation time in water is relatively long. And along with the increase of ZL-480 content, the water absorption rate of the prepared hydrophilic sponge is obviously improved, and the sedimentation time of the hydrophilic sponge in water is obviously shortened. This is also because ZL-480 participates in the foaming reaction, and introduces a hydrophilic segment into the polyurethane molecular segment, improving the hydrophilic ability of the sponge. When the amount of ZL-480 is 45 parts, the water absorption and sedimentation time of the filler are not greatly different from those of the filler when the amount of ZL-480 is 30. Therefore ZL-480 was selected to be used in an amount of 30 parts.
Influence of the amount of N-methyldiethanolamine of the amine catalyst on the Filler Properties
TABLE 4 Table 4
As can be seen from Table 4, when the amount of N-methyldiethanolamine is 0.1 to 0.3 parts, the tensile strength of the prepared filler increases with the increase of the amount of N-methyldiethanolamine, because the tertiary amine catalyst has a strong catalytic action, can promote the reaction of-NCO and-OH, promote the rapid growth of the molecular chain of the polymer, the rapid increase of the viscosity and the rapid increase of the skeleton strength of the foam network. With the increase of the dosage of the N-methyldiethanolamine, the polyurethane foam collapse reaction occurs, because the increase of the dosage of the N-methyldiethanolamine leads to the excessively high reaction speed of the-NCO and the water, thereby leading to the excessively high speed of generating the carbon dioxide gas and finally leading to the foam collapse reaction.
Film forming amount comparison experiment with different fillers in the market
Prepare 3 1L beakers labeled samples 1, 2, 3. 500ML of activated sludge was added to each of the three beakers, and 2 different fillers were added to each beaker. Sample 1 was a Qingdao group of bright fillers, sample 2 was a Kong Lingcai hydrophobic filler, and sample 3 was a filler of example 1. Before the three groups of samples are tested, the weight and the volume are required to be weighed, the filler is added to adsorb sludge through physical adsorption, after the filler is waited for 4 hours, all the filler is taken out, and the filler is baked in an oven at 100 ℃ for 10 hours, and then the weight is weighed, so that the film hanging quantity of each group of filler is obtained. The results are shown in FIG. 1.
As shown in fig. 1, the film-forming amount of the filler is the best, the next is the celadon and bright filler, and the worst film-forming amount is the Kong Lingcai hydrophobic filler.
In the present specification, each embodiment is described in a progressive manner, and each embodiment is mainly described in a different point from other embodiments, and identical and similar parts between the embodiments are all enough to refer to each other. For the device disclosed in the embodiment, since it corresponds to the method disclosed in the embodiment, the description is relatively simple, and the relevant points refer to the description of the method section.
The previous description of the disclosed embodiments is provided to enable any person skilled in the art to make or use the present invention. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the invention. Thus, the present invention is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.
Claims (7)
1. The hydrophilic polyurethane filler is characterized by comprising the following components in parts by mass:
95-105 parts of polyether polyol, 55-65 parts of diphenylmethane diisocyanate, 25-35 parts of hydrophilic agent, 10-20 parts of pore-forming agent, 2-4 parts of konjak glucomannan-acrylic acid graft copolymer, 1-2 parts of dibutyltin dilaurate, 1-2 parts of organosilicon foam stabilizer, 1-2 parts of water, 0.5-1 part of methylene dichloride and 0.1-0.5 part of amine catalyst.
2. A hydrophilic polyurethane filler according to claim 1, wherein,
the polyether polyol is PPG2000, and the hydroxyl value of the polyether polyol is 54-58mgKOH/g;
the hydrophilizing agent is ZL-480; the pore opening agent is ZL Y-1900; the amine catalyst is N-methyldiethanolamine.
3. A hydrophilic polyurethane filler as defined in claim 2, wherein,
the konjak glucomannan-acrylic acid graft copolymer is prepared by the following steps:
potassium persulfate is used as an initiator, and N, N' -methylene bisacrylamide is used as a cross-linking agent. 10.0g of konjak glucomannan and 100mL of acrylic acid neutralized by sodium hydroxide are added into a 500mL three-necked bottle together, stirred for 1h under the protection of nitrogen at 35 ℃ until the konjak powder swells, then 0.5g of initiator and 0.08g of cross-linking agent are added, stirred evenly, then placed into a water bath kettle at 60 ℃ for uniform reaction for 2h, and the product is taken out, dried, crushed and screened to obtain the konjak glucomannan-acrylic acid graft copolymer.
4. A method of preparing a hydrophilic polyurethane filler as claimed in claim 3, comprising:
sequentially weighing polyether polyol, an amine catalyst, dibutyl tin dilaurate, an organosilicon foam stabilizer, water, methylene dichloride, a hydrophilic agent, a pore opening agent and a konjak glucomannan-acrylic acid graft copolymer in a container, uniformly stirring, standing, adding the weighed diphenylmethane diisocyanate in the container, stirring for 5-15s, pouring into a foaming box for free foaming, placing in a baking oven for continuous foaming for 60min after foaming is stopped, and placing for 24h after finishing to obtain the hydrophilic polyurethane filler.
5. The method for preparing a hydrophilic polyurethane filler according to claim 4, wherein the temperature of the oven is 55-65 ℃.
6. The method for preparing a hydrophilic polyurethane filler according to claim 4, wherein the stirring time is 3min and the stirring speed is 150rpm/min.
7. The method for preparing a hydrophilic polyurethane filler according to claim 4, wherein the standing time is 1min.
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