CN1253484C - Hard polyurethane foam for liquid filtering medium and preparation method thereof - Google Patents
Hard polyurethane foam for liquid filtering medium and preparation method thereof Download PDFInfo
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- CN1253484C CN1253484C CN 03141535 CN03141535A CN1253484C CN 1253484 C CN1253484 C CN 1253484C CN 03141535 CN03141535 CN 03141535 CN 03141535 A CN03141535 A CN 03141535A CN 1253484 C CN1253484 C CN 1253484C
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Abstract
The present invention discloses hard polyurethane foam with an opening, which is used as a liquid filtering medium, and a preparation method thereof. The hard polyurethane foam with an opening is prepared by the reaction of polylol mixtures comprising modified castor oil, polyoxyethylene polylol and glycol with isocyanate by using water as a foaming agent under the condition of the existence of opening agents and catalysts (which can also be left out). The end-on load capacity (the intensity of compression) of the hard polyurethane foam with an opening is at least 0.5MPa, and the filtering precision of the hard polyurethane foam with an opening is 10 mum; the pressure difference limit received by the hard polyurethane foam with an opening is respectively 0.2MPa and 0.4MPa with respect to a water system and a non-water system, and the operating temperature limit of the opening hard polyurethane foam is respectively 60 DEG C and 80 DEG C with respect to the water system and the non-water system; the rated flow of the hard polyurethane foam with an opening is at least 5 L/min (HY-10). Compared with the existing liquid filtering medium, the present invention not only has the characteristics the existing liquid filtering medium, but also has the advantages of abundance and easy obtainment of raw materials, low cost, simple preparation technology, no pollution generated in the process of preparation, etc.
Description
Technical field
The present invention relates to a kind of urethane foam and preparation method thereof, specifically, relate to a kind of hard polyurethane foam that is used as liquid filtration media and preparation method thereof.
Background technology
General at present papery filter core, porous metal, the materials such as polyvinyl formal of using of liquid filtration material.Papery filter cartridge construction complexity, seal point is many, and its material is the short fiber material in on-fixed aperture, comes off easily, very easily produces the phenomenon that pulse, media migration, channel etc. cause secondary pollution; Though the filtering material long service life by porous metal are made costs an arm and a leg, clean difficulty; The polyvinyl formal material, though have that filtration efficiency height, pollutant holding capability are big, a long service life, advantage such as in light weight, but because its starting material use formaldehyde, there is severe contamination in production process, obtain today of paying attention to day by day in environmental issue, make the production of this product and use be subjected to great restriction.
Usually hard polyurethane foam is the closed pore system.Up to now, the hard polyurethane foams of perforate research is in order to prevent the size generation noticeable change of its foams under the environment of temperature noticeable change, and required percentage of open area reaches 90% and gets final product, and for example WO 98/28358, and patents such as WS 5856678 are described.And as the material of filtration medium, requiring must 100% perforate, otherwise does not just have flow.
Synthetic of the present invention is as the open-celled rigid polyurethane foam of liquid filtration material, and it not only possesses the characteristics of polyvinyl formal filtering material, and possesses simultaneously that manufacturing process is simple, making processes does not produce advantages such as pollution.
Summary of the invention
The object of the invention is, a kind of open-celled rigid polyurethane foam that is used as liquid filtration media and preparation method thereof is provided.
Technical scheme:
The said open-celled rigid polyurethane foam of the present invention comprises: make whipping agent with water, pore-creating agent, have or the catalyst-free existence condition under, the reaction of isocyanic ester and polyol blends is made, it is characterized in that said polyol blends comprises following component and content:
Functionality is 2～3, hydroxyl value is the modified castor oil of 240～360mgKOH/g, 40～80 (weight) %; Functionality is 5～6, hydroxyl value is the polyoxyethylene polyvalent alcohol of 170～200mgKOH/g, 20～60 (weight) %; Functionality is 2, hydroxyl value is 1750～～ethylene glycol of 1850mgKOH/g, 0～15 (weight) %.
Above-mentioned modified castor oil is that the molecular weight by Viscotrol C and three-functionality-degree carries out transesterification reaction and gets its content preferred 50～70 (weight) % less than 1000 polyvalent alcohols (as glycerine, trolamine and/or trihydroxy methyl propane); The content of polyoxyethylene polyvalent alcohol preferred 30～50 (weight) %.
Pore-creating agent involved in the present invention comprises: polyoxyethylene polysiloxane (a), for example L-6164 and dioctyl ester fluid-like state compound (b), for example dioctyl phthalate (DOP) are 1: 1～1: 10 with (b) weight ratio (a), preferred 1: 3～1: 6.In the polyol blends of 100 weight parts, the consumption of pore-creating agent is 10～50 weight parts, preferred 20～40 weight parts.
The consumption of whipping agent water among the present invention (in the polyol blends of 100 weight parts) is 1～3 weight part, is preferably 1.5～2.5 weight parts.
Among the present invention isocyanic ester can select for use poly methylene poly phenyl poly isocyanate (as PAPI-44V20, Bayer AG; M-20S, BASF AG or ISO-5005, Huntsman, Benjamin company).Using isocyanate index is 90～110, is preferably 95～105.
When the said open-celled rigid polyurethane foam of preparation the present invention, can use amines catalyst, as pentamethyl-diethylenetriamine (PMDETA), triethylene diamine, dimethylamine sulfuric ether (A-1) or three [(dimethylamino) methyl] phenol (DMP-30).When adopting catalyzer, catalyst levels (in the polyol blends of 100 weight parts) is 0.1～2.0 weight part.In addition, according to different application scenarios, can also use other additive (as fire retardant, oxidation inhibitor etc.).
The method for preparing the said open-celled rigid polyurethane foam of the present invention comprises the steps:
(1) modification of Viscotrol C
With the molecular weight of Viscotrol C and three-functionality-degree less than 1000 polyvalent alcohols, in temperature of reaction is 200～240 ℃, preferred 210～230 ℃, carry out transesterification reaction under the secluding air condition, reaction times is 2～7h, preferred 3～5h, thus obtain that functionality is 2～3, hydroxyl value is the modified castor oil of 240～360mgKOH/g;
Last note low molecular weight polyols preferably glycerine and trolamine mixture, the mol ratio of Viscotrol C, glycerine and trolamine preferred 1: 0.8～1.6: 0.2～1.0, more preferably 1: 1.0～1.4: 0.3～0.8.
(2) polymerization
To comprise: by the modified castor oil of step (1) acquisition, the polyol blends that the ethylene glycol that polyoxyethylene polyvalent alcohol that functionality is 5～6, hydroxyl value is 170～200mgKOH/g and functionality are 2, hydroxyl value is 1750～1850mgKOH/g is formed by said ratio, with water be whipping agent, pore-creating agent in the presence of, with index be that 90～110 isocyanic ester make the said open-celled rigid polyurethane foam of the present invention by the prior art polymerization.
The said open-celled rigid polyurethane foam of the present invention is a kind of new liquid filtration medium, and its end is to loading capacity (compressive strength) 〉=0.5Mpa; Filtering accuracy 10 μ m; The pressure differential limit of bearing: water system 0.2MPa, non-water system 0.4Mpa; Operating temperature limit: 60 ℃ of water systems, 80 ℃ of non-water systems; Rated flow 〉=5L/min (HY-10).Compare with existing liquid filtration media, the characteristics that it not only has existing liquid filtration media and is had, and have that abundant raw material is easy to get, with low cost, preparation technology simply reaches preparation process and do not produce advantages such as pollution.
Specific implementation method:
Below routine by experiment the invention will be further described, but they do not constitute limiting the scope of the invention, and except as otherwise noted, all consumptions all refer to parts by weight.
Material therefor is as follows in an embodiment:
Polyvalent alcohol A: Viscotrol C is got by glycerin modification, and hydroxyl value is 280mgKOH/g.
Polyvalent alcohol B: Viscotrol C is by glycerine and trolamine modification and get, and hydroxyl value is 310mgKOH/g.
Polyvalent alcohol C: Viscotrol C is got by the trolamine modification, and hydroxyl value is 290mgKOH/g.
Polyvalent alcohol D: oxyethane and sorbyl alcohol adduct, hydroxyl value are 190mgKOH/g.
Polyol E: ethylene glycol, hydroxyl value are 1821mgKOH/g.
Pore-creating agent I L-6164 U.S. Compton Co.,Ltd.
Pore-creating agent II dioctyl phthalate (DOP).
Catalyzer DMP-30.
Isocyanic ester M-20S BASF AG.
Preparation method, this preparation method comprise with low molecular weight polyols castor oil modified preparation ricinolein polyvalent alcohol, under water is made condition that whipping agent and pore-creating agent exist, the mixture of polyisocyanates and polyvalent alcohol reacted, the formation filtering material in mould.
Embodiment 1
By the formulation open-cell rigid polyurethane foams filtering material that table 1 is given, listed every performance index are measured according to following method.Compressive strength is pressed DIN 53421 standard tests; Filtering accuracy, rated flow are pressed ISO 4572 standard tests; Pressure differential limit is pressed ISO 03968 standard test.
Table I
| Performance formula | Filtering material | |||||||||||
| 1 | 2 | 3 | 4 | 5 | 6 | 7 | 8 | 9 | 10 | 11 | 12 | |
| Polyvalent alcohol A | 100 | 70 | 60 | 50 | ||||||||
| B | 100 | 70 | 50 | 40 | ||||||||
| C | 100 | 70 | 50 | 30 | ||||||||
| D | 30 | 35 | 40 | 20 | 40 | 50 | 20 | 40 | 60 | |||
| E | 5 | 10 | 10 | 10 | 10 | 10 | 10 | 10 | ||||
| Pore-creating agent I | 5 | 5 | 5 | 5 | 5 | 5 | 5 | 5 | 5 | 5 | 5 | 5 |
| II | 20 | 20 | 20 | 20 | 20 | 20 | 20 | 20 | 20 | 20 | 20 | 20 |
| Water | 1.8 | 1.8 | 1.8 | 1.8 | 1.8 | 1.8 | 1.8 | 1.8 | 1.8 | 1.8 | 1.8 | 1.8 |
| DMP-30 | 1.5 | 1.5 | 1.5 | 1.5 | 1.5 | 1.5 | 1.5 | 1.5 | 1.5 | 1.5 | 1.5 | 1.5 |
| M-20S (index) | 100 | 100 | 100 | 100 | 100 | 100 | 98 | 100 | 100 | 100 | 100 | 100 |
| Molding density (kg/m 3) | 98.3 | 102 | 101 | 105 | 104 | 100 | 102 | 100 | 103 | 101 | 103 | 102 |
| Compressive strength (MPa) | 0.94 | 0.82 | 0.80 | 0.75 | 0.93 | 0.78 | 0.71 | 0.64 | 0.95 | 0.88 | 0.76 | 0.54 |
| Filtering accuracy (μ m) | 8 | 13 | 22 | 15 | 30 | 5 | 9 | 40 | ||||
| Rated flow (L/min) | 0 | 4.2 | 6.5 | 9.4 | 0 | 0 | 0.1 | 0.3 | 0 | 3.8 | 6.4 | 9.5 |
| Pressure differential limit water system (MPa) | ＞0.2 | ＞0.2 | ＞0.2 | ＞0.2 | ＞0.2 | ＞0.2 | ＞0.2 | ＞0.2 | ＞0.2 | ＞0.2 | ＞0.2 | ＞0.2 |
| The non-water system of pressure differential limit (MPa) | ＞0.4 | ＞0.4 | ＞0.4 | ＞0.4 | ＞0.4 | ＞0.4 | ＞0.4 | ＞0.4 | ＞0.4 | ＞0.4 | ＞0.4 | ＞0.4 |
Show clearly that by Table I different polyol blends, its synthetic hard polyurethane foam show bigger difference aspect filtering accuracy and rated flow.Can select the polyol blends of different proportionings according to different filtering material performance requriementss.
Embodiment 2
Present embodiment illustrates different pore-creating agents and water consumption each performance impact to synthetic hard polyurethane foams filtering material.Table II has provided detailed prescription and every performance
Table II
| Performance formula | Filtering material | ||||||
| 1 | 2 | 3 | 4 | 5 | 6 | 7 | |
| Polyvalent alcohol C | 50 | 50 | 50 | 50 | 50 | 50 | 50 |
| Polyvalent alcohol D | 40 | 40 | 40 | 40 | 40 | 40 | 40 |
| Polyol E | 10 | 10 | 10 | 10 | 10 | 10 | 10 |
| Pore-creating agent I | 0 | 10 | 5 | 5 | 5 | 5 | 5 |
| Pore-creating agent II | 20 | 20 | 0 | 10 | 20 | 20 | 20 |
| Water | 1.8 | 1.8 | 1.8 | 1.8 | 2 | 3 | 1.8 |
| DMP-30 | 1.5 | 1.5 | 1.5 | 1.5 | 1.5 | 1.5 | 1.5 |
| M-20S (index) | 100 | 100 | 100 | 100 | 100 | 100 | 100 |
| Molding density (kg/m 3) | 103 | 102 | 102 | 101 | 150 | 88 | 100 |
| Compressive strength (MPa) | 0.76 | 0.75 | 0.78 | 0.77 | 1.30 | 0.57 | 0.77 |
| Filtering accuracy (μ m) | 50 | 5 | 8 | 8 | 2 | 7 | 15 |
| Rated flow (L/min) | 3 | 5.1 | 0.4 | 3 | 0.2 | 2.6 | 6.8 |
| Pressure differential limit water system (MPa) | ＞0.2 | ＞0.2 | ＞0.2 | ＞0.2 | ＞0.2 | ＞0.2 | ＞0.2 |
| The non-water system of pressure differential limit (MPa) | ＞0.4 | ＞0.4 | ＞0.4 | ＞0.4 | ＞0.4 | ＞0.4 | ＞0.4 |
Embodiment 3
Present embodiment explanation different catalysts and isocyanate index are to each performance impact of synthetic hard polyurethane foams filtering material.Table III has provided detailed prescription and every performance.
Table III
| Performance formula | Filtering material | |||||||||
| 1 | 2 | 3 | 4 | 5 | 6 | 7 | 8 | 9 | 10 | |
| Polyvalent alcohol C | 50 | 50 | 50 | 50 | 50 | 50 | 50 | 50 | 50 | 50 |
| Polyvalent alcohol D | 40 | 40 | 40 | 40 | 40 | 40 | 40 | 40 | 40 | 40 |
| Polyol E | 10 | 10 | 10 | 10 | 10 | 10 | 10 | 10 | 10 | 10 |
| Pore-creating agent I | 5 | 5 | 5 | 5 | 5 | 5 | 5 | 5 | 5 | 5 |
| Pore-creating agent II | 20 | 20 | 20 | 20 | 20 | 20 | 20 | 20 | 20 | 20 |
| Water | 1.8 | 1.8 | 1.8 | 1.8 | 1.8 | 1.8 | 1.8 | 1.8 | 1.8 | 1.8 |
| DMP-30 | 0.5 | 1.0 | 1.5 | 2.0 | 3.0 | 1.5 | 1.5 | 1.5 | 1.5 | 1.5 |
| M-20S (index) | 100 | 100 | 100 | 100 | 100 | 80 | 90 | 105 | 110 | 120 |
| Molding density (kg/m 3) | 101 | 102 | 105 | 101 | 100 | 105 | 100 | 102 | 102 | 101 |
| Compressive strength (MPa) | 0.74 | 0.74 | 0.75 | 0.73 | 0.70 | 0.51 | 0.62 | 0.77 | 0.83 | 0.98 |
| Filtering accuracy (μ m) | 45 | 28 | 22 | 20 | 15 | 27 | 25 | 21 | 13 | 9 |
| Rated flow (L/min) | 12.5 | 10.1 | 9.4 | 7.1 | 3.2 | 11.6 | 10.8 | 9.8 | 5.0 | 1.2 |
| Pressure differential limit water system (MPa) | ＞0.2 | ＞0.2 | ＞0.2 | ＞0.2 | ＞0.2 | ＜0.2 | ＞0.2 | ＞0.2 | ＞0.2 | ＞0.2 |
| The non-water system of pressure differential limit (MPa) | ＞0.4 | ＞0.4 | ＞0.4 | ＞0.4 | ＞0.4 | ＜0.4 | ＜0.4 | ＞0.4 | 0.32 | ＞0.4 |
Claims (11)
1, a kind of open-celled rigid polyurethane foam as liquid filtration media, it comprises: make whipping agent with water, pore-creating agent, have or the catalyst-free existence condition under, the reaction of isocyanic ester and polyol blends is made, it is characterized in that said polyol blends comprises following component and content:
Functionality is 2～3, hydroxyl value is the modified castor oil of 240～360mgKOH/g, 40～80 weight %; Functionality is 5～6, hydroxyl value is the polyoxyethylene polyvalent alcohol of 170～200mgKOH/g, 20～60 weight %; Functionality is 2, hydroxyl value is the ethylene glycol of 1750～1850mgKOH/g, 0～15 weight %;
Above-mentioned modified castor oil is that the molecular weight by Viscotrol C and three-functionality-degree gets less than 1000 polyvalent alcohols carry out transesterification reaction, and the isocyanate index that uses is 90～110, and in the polyol blends of 100 weight parts, the consumption of pore-creating agent is 10～50 weight parts; The consumption of whipping agent water is 1～3 weight part.
As the said open-celled rigid polyurethane foam of claim 1, it is characterized in that 2, wherein said polyol blends comprises following component and content:
Modified castor oil 50～70 weight %
Polyoxyethylene polyvalent alcohol 30～50 weight %
Ethylene glycol 0～15 weight %.
3, preparation is characterized in that as the method for claim 1 or 2 said open-celled rigid polyurethane foams said preparation method comprises the steps:
(1) modification of Viscotrol C
With the molecular weight of Viscotrol C and three-functionality-degree less than 1000 polyvalent alcohols, in temperature of reaction is 200～240 ℃, carry out transesterification reaction under the secluding air condition, the reaction times is 2～7h, thereby obtains that functionality is 2～3, hydroxyl value is the modified castor oil of 240～360mgKOH/g;
(2) polymerization
To comprise: by the modified castor oil of step (1) acquisition, the polyol blends that the ethylene glycol that polyoxyethylene polyvalent alcohol that functionality is 5～6, hydroxyl value is 170～200mgKOH/g and functionality are 2, hydroxyl value is 1750～1850mgKOH/g is formed by claim 1 or 2 described proportionings, comprising: in the polyol blends of 100 weight parts, the consumption of pore-creating agent is 10～50 weight parts; The consumption of whipping agent water is under 1～3 weight part condition, with index be that 90～110 polyisocyanic acid polyisocyanate polyadditions make target compound.
As the said preparation method of claim 3, it is characterized in that 4, wherein the isocyanate index that uses is 95～105, in the polyol blends of 100 weight parts, the consumption of pore-creating agent is 20～40 weight parts; The consumption of whipping agent water is 1.5～2.5 weight parts.
As the said preparation method of claim 4, it is characterized in that 5, wherein said molecular weight is glycerine and trolamine mixture less than 1000 polyvalent alcohols, the mol ratio of Viscotrol C, glycerine and trolamine is 1: 0.8～1.6: 0.2～1.0.
As the said preparation method of claim 5, it is characterized in that 6, wherein the temperature of reaction of modified castor oil is 210～230 ℃, the reaction times is 3～5h.
7, as the said preparation method of claim 6, it is characterized in that wherein isocyanic ester is selected poly methylene poly phenyl poly isocyanate for use, pore-creating agent is selected the mixture of polyoxyethylene polysiloxane and dioctyl ester fluid-like state compound for use.
As the said preparation method of claim 7, it is characterized in that 8, wherein the weight ratio of polyoxyethylene polysiloxane and dioctyl ester fluid-like state compound is 1: 1～1: 10 in the mixture of polyoxyethylene polysiloxane and dioctyl ester fluid-like state compound.
As the said preparation method of claim 8, it is characterized in that 9, wherein said dioctyl ester fluid-like state compound is a dioctyl phthalate (DOP).
10, as the said preparation method of claim 9, it is characterized in that, is catalyzer with the aminated compounds in the polyreaction, and in the polyol blends of 100 weight parts, its consumption is 0.1～2.0 weight part.
As the said preparation method of claim 10, it is characterized in that 11, wherein said aminated compounds is pentamethyl-diethylenetriamine, triethylene diamine, dimethylamine sulfuric ether or three [(dimethylamino) methyl] phenol.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101238161B (en) * | 2005-08-12 | 2011-07-06 | 三井化学株式会社 | Composition for polyurethane foam, polyurethane foam obtained from the composition, and use thereof |
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| CN110478981A (en) * | 2019-08-28 | 2019-11-22 | 安徽伟创聚合材料科技有限公司 | A kind of novel biomass foamed material and preparation method thereof for sewage treatment |
| CN110982041A (en) * | 2019-12-11 | 2020-04-10 | 江西科技师范大学 | Castor oil-based polyurethane foam and preparation method thereof |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101238161B (en) * | 2005-08-12 | 2011-07-06 | 三井化学株式会社 | Composition for polyurethane foam, polyurethane foam obtained from the composition, and use thereof |
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