TWM568263U - Oil absorbing water-permeable sponge - Google Patents

Abstract

An oil permeable sponge comprising a sponge body prepared by reacting a composition containing a compound A and a polyisocyanate compound. Agent A includes a polyol mixture, a blowing agent, a foam stabilizer, and a catalyst. The polyol mixture contains: a first polyol component having a hydroxyl value ranging from 33 to 60 mgKOH/g and an oxyethylene group content ranging from 50 to 80 mol%, a hydroxyl value ranging from 80 to 300 mgKOH/g, and an oxyethylene group content ranging from 50 to 80 mol% of the second polyol component, the graft polymer polyol component, the tetrafunctional polyol component, and glycerin, and the first polyol component and the second polyol component are used The sponge body is made super-lipophilic and super-hydrophilic, and the graft polymer polyol component, the tetrafunctional polyol component, and glycerin are used to increase the strength of the sponge body.

Description

Oil permeable sponge

The present invention relates to a polyurethane foaming sponge, and more particularly to a polyurethane foaming sponge for oil-water separation.

Taiwan Patent Publication No. I447217 discloses a composite having both superhydrophobic and superlipophilic functions, comprising a porous material having a sponge structure and a surface layer covering the surface of the backbone of the porous material. The material of the porous material is selected from the group consisting of wood cellulose, cellulose, foamed plastic polymer, polyether, polyvinyl alcohol, melamine, polyurethane or polyester. The skin layer includes a plurality of graphene sheets attached to the surface of the backbone of the porous material. The composite has a contact angle (superhydrophobicity) between 150° and 170° with water, and a contact angle (super-lipophilicity) between 0° and 10° between the composite and the oil. . The composite is capable of adsorbing only the oil in the oil-water mixture by its superhydrophobic and super-lipophilic properties, and the water in the oil-water mixture is not absorbed by the composite, thereby achieving the effect of oil-water separation.

However, the oil-water separation treatment is carried out using a composite having superhydrophobicity and super-lipophilicity. Since the specific gravity of the oil is lighter than water, it will be mixed in the upper layer of the oil-water mixture and mixed with oil and water. The water of the compound cannot pass through the composite, so the batch operation of oil-water separation is carried out by a mechanism in which the composite contacts the oil-water interface of the oil-water mixture to adsorb the oil. If the above composite is to be used for continuous oil-water separation treatment, especially when the oil-water mixture is continuously operated by pouring or injecting, the above-mentioned composite cannot pass water due to its superhydrophobic property, so the water will be compounded. The material is blocked and gradually accumulates. When the accumulated water is more and more concentrated and the oil is lighter than water and the fluidity is worse than water, the composite will become difficult to contact the oil-water interface of the oil-water mixture and cannot effectively absorb the oil. And a large amount of water may also destroy the composite or the processing line containing the composite.

Accordingly, it is an object of the present invention to provide an oil permeable sponge which can treat a mixture of oil and water continuously or in large quantities.

Thus, the novel oil permeable sponge comprises: a sponge body prepared by reacting a composition containing a compound A and a polyisocyanate compound, wherein the agent A comprises a polyol mixture, a foaming agent, a foam stabilizer and a catalyst, and the polyol mixture contains: a first polyol component for imparting super-lipophilicity and super-hydrophilicity to the sponge body, and the hydroxyl value range of the first polyol component is 33 to 60 mgKOH/g and an oxyethylene group content of 50 to 80 mol%, a second polyol component for imparting super-lipophilicity and superhydrophilicity to the sponge main body, and the second polyol component The hydroxyl value ranges from 80 to 300 mgKOH/g and the oxyethylene group content ranges from 50 to 80 mol%. A graft polymer polyol component for increasing the strength of the sponge body, a tetrafunctional polyol component for increasing the strength of the sponge body, and glycerin for increasing the strength of the sponge body.

The main function of the novel is that the oil permeable sponge penetrates the graft polymer polyol component, the tetrafunctional polyol component and glycerin to give the sponge body a fixed and dense shape and conforms to the mechanical strength of subsequent applications. And further, through the first polyol component and the second polyol component, the sponge body is provided with super-lipophilicity and super-hydrophilicity, so that the oil-permeable permeable sponge has high oil absorption and high water permeability, and the oil absorption When the water-permeable sponge is used for oil-water separation, water in the oil-water mixture can be passed through the sponge body, and at the same time, the oil is absorbed by the sponge body but does not pass through the sponge body, so that a better oil-water separation effect can be achieved.

Another effect of the novel is that the oil of the oil-water mixture is absorbed by the sponge and the water is not passed through the sponge, compared with the sponge having superhydrophobic and super-lipophilic properties, and the novel oil-absorbing sponge can quickly absorb the oil-water mixture. The water then allows water to flow out of the sponge body, and at the same time absorbs the oil in the oil-water mixture and leaves the oil in the sponge body, thereby achieving "filtering the water in the oil-water mixture" and "absorbing the oil in the oil-water mixture". The effect, therefore, the oil permeable sponge has a better oil-water separation effect.

Another effect of the novel is that the novel oil permeable sponge can quickly absorb water in the oil-water mixture and then let water flow out from the sponge body. The mixture is continuously or in a large amount in contact with the oil permeable sponge, and the water in the oil-water mixture continuously enters the sponge body and quickly penetrates from the sponge body without being blocked and accumulated by the oil permeable sponge, so the oil absorption Water permeable sponges are suitable for treating oil-water mixtures in a continuous or large amount.

1‧‧‧ Sponge body

Other features and effects of the present invention will be clearly shown in the embodiments with reference to the drawings, wherein: FIG. 1 is a schematic view of the oil permeable sponge of the present invention; FIG. 2 is an operation of the oil-water separation effect test of the novel oil permeable sponge Photograph of the method; Fig. 3 is a photograph of the result of the oil-water separation effect test of the novel oil-permeable and permeable sponge; Figure 4 is a photograph of the result of the oil-water separation effect test of the novel oil-permeable and permeable sponge; and Figure 5 is a photograph of the oil-absorbing and permeable sponge of the present invention. Photograph of the results of the oil-water separation effect test.

The following is a detailed description of this new content:

Referring to Figure 1, the oil permeable sponge comprises a sponge body 1.

Herein, "the sponge body 1 is super-lipophilic and super-hydrophilic" means that the contact angle of the oily substance with the sponge body 1 ranges from 0 to 10, and the contact angle of the aqueous substance with the sponge body 1 is 0° to 5°.

The composition for preparing the sponge main body 1 contains an A agent and a polyisocyanate compound, wherein the A agent includes a polyol mixture, a foaming agent, a foam stabilizer, and a catalyst, and each of the above components will be further described below.

<Polyol mixture>

The polyol mixture contains a first polyol component, a second polyol component, a graft polymer polyol component, a tetrafunctional polyol component, and glycerol. The main function of the first polyol component and the second polyol component is to provide the sponge body 1 with super-lipophilicity and super-hydrophilicity, so that the oil-permeable permeable sponge has high water permeability and high oil absorption. The main function of the graft polymer polyol component, the tetrafunctional polyol component and the glycerol is to increase the strength of the sponge body 1 so that the sponge body 1 has a fixed and dense shape and conforms to the subsequent The mechanical strength of the application.

The first polyol component has a hydroxyl value ranging from 33 to 60 mgKOH/g and an oxyethylene group content ranging from 50 to 80 mol%, when the hydroxyl value and the oxyethylene group content of the first polyol component are in the above range The first polyol component can provide the sponge body 1 to have super-lipophilicity and super-hydrophilicity; and when the hydroxyl value of the first polyol component is in the above range, the first polyol component can The sponge body 1 is provided with strength. Preferably, the first polyol component has an HLB value in the range of 5 to 12, which is more conducive to providing the sponge body 1 with super-lipophilicity and super-hydrophilicity. Preferably, the first polyol component has a weight average molecular weight ranging from 2,500 to 5,000. The kind of the first polyol component is not particularly limited and may be a polyester polyol, a polyether polyol or a polyether ester polyol. The alcohol may be a single polyol or a mixture of a plurality of polyols as long as the hydroxyl value and the oxyethylene group content of the first polyol component are in the above ranges. The source of the first polyol component may be self-synthesis or may be directly used as a commercially available product. For example, the first polyol component is an ethylene oxide containing a polyester, a polyether, and a modifier. And a reaction mixture of triethanolamine as a starter is reacted to obtain a commercially available polyol product having a hydroxyl value ranging from 33 to 60 mgKOH/g and an oxyethylene content ranging from 50 to 80 mol%. Preferably, the total amount of the agent A of the composition is 100% by weight, and the amount of the first polyol component is in the range of 30 to 70% by weight, which is more conducive to making the sponge body 1 super-lipophilic and Super hydrophilic, and more helpful to make the sponge body 1 have a fixed and dense shape and mechanical strength in accordance with subsequent applications; further, when the amount of the first polyol component is less than 30% by weight, the sponge body The super-lipophilic property and the super-hydrophilic property of 1 are less prominent. When the amount of the first polyol component is more than 70% by weight, the sponge body 1 has insufficient hardness and is less likely to be molded.

The second polyol component has a hydroxyl value in the range of 80 to 300 mgKOH/g and an oxyethylene content in the range of 50 to 80 mol%, when the hydroxyl value and the oxyethylene content of the second polyol component are respectively Range, the second polyol component can provide the sponge body 1 to have super-lipophilicity and super-hydrophilicity; and when the hydroxyl value of the second polyol component is in the above range, the second polyol component The sponge body 1 can be provided with strength. Preferably, the second polyol component has an HLB in the range of 7 to 14, which is more conducive to providing the sponge body 1 with super-lipophilicity and super-hydrophilicity. Preferably, the second plurality The alcohol component has a weight average molecular weight ranging from 400 to 1900. The kind of the second polyol component is not particularly limited, and may be a polyester polyol, a polyether polyol or a polyether ester polyol, and may be a single polyol or a mixture of a plurality of polyols, as long as the The hydroxyl value and the oxyethylene group content of the second polyol component are each in the above range. The second polyol component may be self-synthesized or directly used as a commercially available product. For example, the second polyol component is an ethylene oxide containing a polyester, a polyether, and a modifier. And a reaction mixture of triethanolamine as a starter is reacted to obtain a commercially available polyol product having a hydroxyl value ranging from 80 to 300 mgKOH/g and an oxyethylene content ranging from 50 to 80 mol%. Preferably, the total amount of the agent A of the composition is 100% by weight, and the amount of the second polyol component is in the range of 15 to 50% by weight, which is more conducive to making the sponge body 1 super-lipophilic and Super hydrophilic, and more helpful to make the sponge body 1 have a fixed and dense shape and conform to the mechanical strength of the subsequent application; further, when the amount of the second polyol component is less than 15% by weight, the sponge body The super-lipophilic property and the super-hydrophilic property of 1 are less prominent, and when the amount of the second polyol component is more than 50% by weight, the sponge main body 1 is more likely to be brittle.

Preferably, the graft polymer polyols component has a hydroxyl value in the range of 20 to 40 mgKOH/g, and when the hydroxyl value of the graft polymer polyol component is in the above range, the composition can be lowered. The equivalent value of the object can also contribute slightly to the hardness of the sponge body 1. Preferably, the graft polymer polyol component has a weight average molecular weight ranging from 4,000 to 10,000, and when the weight average molecular weight of the graft polymer polyol component is in the above range, the viscosity and strength of the composition can be increased. . The kind of the graft polymer polyol component is not particularly limited, and is not limited to, for example, a polyester polyol grafted with a vinyl monomer, a polyether polyol grafted with a vinyl monomer, or any combination thereof. Commercially available products of the graft polymer polyol component are, for example but not limited to, POP 3428 and POP 3628 of Mitsui Chemicals Co., Ltd., Arcol ^® Polyol HS100 of Bayer AG, POP-H45 of Zibo Dexin Federal Chemical Industry Co., Ltd., etc. . Preferably, the total amount of the agent A of the composition is 100% by weight, and the amount of the graft polymer polyol component is in the range of 10 to 30% by weight, which is more conducive to making the sponge body 1 super-lipophilic. And superhydrophilic, and more helpful to make the sponge body 1 have a fixed and dense shape and to meet the mechanical strength of subsequent applications; further, when the amount of the graft polymer polyol component is less than 10% by weight, The hardness of the sponge main body 1 is insufficient, and when the amount of the graft polymer polyol component is more than 30% by weight, the super-lipophilic property and super-hydrophilic property of the sponge main body 1 are less prominent.

Preferably, the tetra-functional polyol component has a hydroxyl value in the range of 350 to 650 mgKOH/g, and when the hydroxyl value of the tetrafunctional polyol component is in the above range, the sponge body can be improved. The crosslinking density of 1 and the hardness of the sponge body 1 are increased. Preferably, the tetrafunctional polyol component has a weight average molecular weight ranging from 300 to 800, and when the weight average molecular weight of the tetrafunctional polyol component is in the above range, the sponge body 1 can have a preferred surface. Morphology. The kind of the tetrafunctional polyol component is not particularly limited, and is, for example, but not limited to, pentaerythritol-based polyether polyol or the like. Commercially available products of the tetrafunctional polyol component are, for example but not limited to, polyether polyol 4110, Dow Chemical's Voranol ^® 490, and the like. Preferably, the total amount of the agent A of the composition is 100% by weight, and the amount of the tetrafunctional polyol component is in the range of 1 to 5% by weight, so that the sponge body 1 has an appropriate hardness and a good resistance. a tearing force; further, when the amount of the tetrafunctional polyol component is less than 1% by weight, the hardness of the sponge body 1 is soft, and when the amount of the tetrafunctional polyol component is more than 5% by weight, the sponge The body 1 has a poor tear resistance.

The glycerol has a hydroxyl value in the range of 1827 mg KOH/g. Preferably, the total amount of the agent A of the composition is 100% by weight, and the amount of the glycerin is in the range of 1 to 5% by weight, so that the sponge body 1 has finer cells and better. Tear resistance; further, when the amount of the glycerin is less than 1% by weight, the pores of the sponge body 1 are coarse, and when the amount of the glycerin is more than 5% by weight, the tear resistance of the sponge body 1 Poor.

<foaming agent>

The kind of the foaming agent is not particularly limited, and a foaming agent generally used for preparing a polyurethane sponge can be used. Preferably, the foaming agent is water, and is foamed by using water as a foaming agent and reacting with a polyisocyanate compound to form carbon dioxide, which can be foamed in a non-toxic manner and can avoid non-aqueous use. The foaming agent remains in the problem caused by the sponge body 1. The amount of the foaming agent to be used is not particularly limited, and the amount of the foaming agent can be adjusted according to the density of the sponge main body 1. Preferably, the agent A of the composition The total amount is 100% by weight, and the blowing agent is used in an amount ranging from 0.7 to 4% by weight; further, when the amount of the foaming agent is less than 0.7% by weight, the density of the sponge body 1 is too high and the manufacturing cost is increased. When the amount of the foaming agent is more than 4% by weight, the density of the sponge main body 1 is too low, so that the super-lipophilic property and the super-hydrophilic property of the sponge main body 1 are less prominent.

<Foaming agent>

The foaming agent functions to increase the mutual solubility of the components in the composition, to control the pore size and distribution uniformity of the cells of the sponge main body 1, and in the process in which the composition is reacted and foamed to form the sponge main body 1. The cell wall of the sponge body 1 is made elastic to retain the gas and prevent the sponge body 1 from collapsing. The foam stabilizer is, for example but not limited to, an organic hydrazine surfactant or the like. The amount of the foam stabilizer is not particularly limited, and the amount of the foam stabilizer can be adjusted according to the density of the sponge body 1. Preferably, the total amount of the agent A of the composition is 100% by weight, and the amount of the foam stabilizer is in the range of 0.5 to 2% by weight; further, when the amount of the foaming agent is less than 0.5% by weight, the sponge The main body 1 cannot form cells and collapses. When the amount of the foaming agent is more than 2% by weight, the sponge main body 1 cannot have an open-cell structure (referring to a closed-cell structure) and shrink.

<catalyst>

The function of the catalyst is to control the cream time (CT) when the composition is reacted and foamed to form the sponge body 1, and the time during which the sponge body 1 is molded and matured. The catalyst is, for example but not limited to, triethylenediamine, dipropylene glycol or Any combination of the above, for example, the catalyst may consist of 33% by weight of triethylenediamine and 67% by weight of dipropylene glycol. Preferably, the total amount of the agent A of the composition is 100% by weight, and the amount of the catalyst is in the range of 0.2 to 1.0% by weight; further, when the amount of the catalyst is less than 0.2% by weight, the sponge is less likely to be made. The main body 1 is molded, and when the amount of the foaming agent is more than 1.0% by weight, the reaction time of the composition is too fast to allow the sponge main body 1 to have an open-cell structure.

<polyisocyanate compound>

To help the sponge body 1 have a predetermined lower density (for example, a density of 25 to 100 kg/m ³ ), preferably, the polyisocyanate compound is selected from an aromatic diisocyanate compound. More preferably, the aromatic diisocyanate compound is selected from diphenylmethane diisocyanate, toluene diisocyanate or any combination of the foregoing. In order to allow the composition to have a suitable foaming activity and a suitable crosslinking density in the reaction, it is preferred that the total amount of the A agent of the composition is 100 parts by weight, and the amount of the polyisocyanate compound is in the range of 30 to 50 parts by weight.

The sponge body 1 is prepared by reacting the composition. The process conditions of the reaction are not particularly limited. The process conditions of the reaction can be adjusted by referring to the process conditions in the general preparation of the polyurethane sponge. For example, but not limited to, the temperature range of the reaction is The reaction time of the reaction ranges from 60 seconds to 120 seconds at 20 to 35 °C.

The density range of the sponge main body 1 of the oil permeable sponge is not particularly limited as long as the sponge main body 1 can have a fixed shape. Preferably, the sponge body 1 of the oil permeable sponge has a density of 25 to 100 kg/m ³ , and when the density of the sponge body 1 is in the above range, the structure of the sponge body 1 is denser and has better oil absorption efficiency. At the same time, the manufacturing cost of the oil permeable sponge is taken into consideration; further, when the density of the sponge body 1 is less than 25 kg/m ³ , the structure of the sponge body 1 is lower in density and has lower oil absorption efficiency when the sponge body is The density of 1 is greater than 100 kg/m ³ , and the production cost of the oil permeable sponge is high.

Preferably, the sponge body 1 of the oil permeable sponge has a pore density ranging from 25 to 50 PPI (Pores Per Inch); further, when the pore density of the sponge body 1 is less than 25 PPI, although the oil permeable sponge The oil absorption speed and the water permeable speed are relatively fast, but the oil absorption saturation of the oil permeable sponge is low. When the pore density of the sponge body 1 is greater than 50 PPI, although the oil permeable sponge has a higher oil absorption saturation, the water permeable speed is higher. slow.

In the embodiment of the preparation method of the novel oil permeable sponge, 30 to 70% by weight of the first polyol component (hydroxyl value 33 to 60 mgKOH/g, molecular weight 2500 to 5000, HLB value 5 to 12, oxygen) is contained. Vinyl content 50 to 80 mol%), 15 to 50 wt% of the second polyol component (hydroxyl value 80 to 300 mgKOH/g, molecular weight 400 to 1900, HLB value 7 to 14, oxyethylene content 50 to 80 mol%) 10 to 30 wt% of graft polymer polyol (hydroxyl value 20 to 40 mgKOH/g, molecular weight 4000 to 10,000), 1 to 5 wt% of tetrafunctional polyol (hydroxyl value 350 to 650 mgKOH/g, molecular weight 300 to 800 ), 1 to 5 wt% of glycerol (hydroxyl value 1827 mg KOH / g), 0.7 to 4 wt% of water, 0.2 to 1.0 wt% of catalyst (from 33 wt% of triethylenediamine and 67 wt% of dipropylene glycol) And 100 parts by weight of the A agent of 0.5 to 2 wt% of eucalyptus oil, and 30 to 50 parts by weight of diphenylmethane diisocyanate at 25. Stirring was carried out at ° C and atmospheric pressure to obtain a composition. The composition is placed in a mold for reaction (temperature of 20 to 35 ° C for 60 to 120 seconds), and then an oil permeable sponge (having a density of 25 to 100 kg/m ³ and a pore density of 25 to 50 PPI) is obtained. .

The oil-water separation effect of the novel oil permeable sponge is tested by the following experiment: after cutting the oil permeable sponge into three sponge pieces each having a diameter of 15.5 cm and a thickness of 5 cm, refer to FIG. 2, The sponge blocks are stacked vertically in a cylindrical transparent column with a diameter of 15 cm and a height of 400 cm. Then, an oil-water mixture (composed of 1 liter of water and 0.8 liter of waste engine oil) is poured into a cylindrical transparent column. . The degree of absorption of the waste oil in the oil-water mixture by the oil permeable sponge was observed, and the extent to which water in the oil-water mixture flowed through the oil permeable sponge. The test results of the oil-water separation effect of the novel oil-absorbing and permeable sponge are shown in Table 1 and Figures 3 to 5.

It can be seen from Table 1, Figure 3 to Figure 5 that within 3 seconds after the oil-water mixture is poured into the cylindrical transparent column, the sponge body of the oil-permeable permeable sponge quickly absorbs water and allows the absorbed water to be quickly And a large amount of effluent from the sponge, indicating that the oil permeable sponge can quickly absorb water and allow water to quickly flow out due to the super hydrophilicity and water permeability of the sponge body, so the oil permeable sponge has "filtering oil and water mixture The effect of water.

Furthermore, the oil permeable sponge is absorbed by the oil permeable sponge and is no longer discharged from the sponge within 5 seconds after the oil-water mixture is poured into the cylindrical transparent column, indicating that the oil permeable sponge Because the sponge body is super-lipophilic, it can quickly absorb oil and leave the oil in the sponge body, so the oil absorption The water sponge has the effect of "absorbing oil in the oil-water mixture".

It can be proved that the oil permeable sponge has the functions of "filtering the water in the oil-water mixture" and "absorbing the oil in the oil-water mixture", and the speed of filtering the water and absorbing the oil is very fast, and the oil permeable sponge can The absorbed water flows out quickly and in a large amount, so the oil permeable sponge not only has better oil-water separation effect, but is also suitable for continuous or large-scale treatment of oil-water mixture.

The new oil permeable sponge is suitable for oil leakage treatment, filtration and recovery of river and sea oil, soot filtration in the catering industry, kitchen cleaning grease and the like.

However, the above is only the embodiment of the present invention, and when it is not possible to limit the scope of the present invention, all the simple equivalent changes and modifications according to the scope of the patent application and the contents of the patent specification are still This new patent covers the scope.

Claims (10)

An oil permeable sponge comprising: a sponge body prepared by reacting a composition containing a agent A and a polyisocyanate compound, wherein the agent A comprises a polyol mixture, a foaming agent, a foam stabilizer And a catalyst, and the polyol mixture comprises: a first polyol component for imparting super-lipophilicity and superhydrophilicity to the sponge body, and the first polyol component has a hydroxyl value ranging from 33 to 60 The content of mgKOH/g and oxyethylene is in the range of 50 to 80 mol%, and the second polyol component is used to make the sponge body super-lipophilic and super-hydrophilic, and the second polyol component a hydroxyl value ranging from 80 to 300 mgKOH/g and an oxyethylene group content ranging from 50 to 80 mol%, a graft polymer polyol component for increasing the strength of the sponge body, a tetrafunctional polyol component, It is used to increase the strength of the sponge body and glycerin for increasing the strength of the sponge body. The oil permeable sponge according to claim 1, wherein the first polyol component has an HLB value ranging from 5 to 12. The oil permeable sponge according to claim 1, wherein the second polyol component has an HLB value ranging from 7 to 14. The oil permeable sponge according to claim 1, wherein the total amount of the agent A of the composition is 100% by weight, and the amount of the first polyol component ranges from 30 to 70% by weight. The oil permeable sponge according to claim 1, wherein the total amount of the agent A of the composition is 100% by weight, and the second polyol component is used in an amount ranging from 15 to 50% by weight. The oil permeable sponge according to claim 1, wherein the graft polymer polyol component has a hydroxyl value in the range of 20 to 40 mgKOH/g. The oil permeable sponge according to claim 1, wherein the tetrafunctional polyol component has a hydroxyl value ranging from 350 to 650 mgKOH/g. The oil permeable sponge according to claim 1, wherein the total amount of the agent A of the composition is 100% by weight, and the amount of the graft polymer polyol component is from 10 to 30% by weight, the tetrafunctionality The polyol component is used in an amount ranging from 1 to 5 wt%, and the glycerin is used in an amount ranging from 1 to 5 wt%. The oil permeable sponge according to claim 1, wherein the sponge body has a density ranging from 25 to 100 kg/m ³ . The oil permeable sponge according to claim 1, wherein the sponge body has a pore density ranging from 25 to 50 PPI.