CN116854889A - Matcha sponge - Google Patents
Matcha sponge Download PDFInfo
- Publication number
- CN116854889A CN116854889A CN202311005257.1A CN202311005257A CN116854889A CN 116854889 A CN116854889 A CN 116854889A CN 202311005257 A CN202311005257 A CN 202311005257A CN 116854889 A CN116854889 A CN 116854889A
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- China
- Prior art keywords
- porous copper
- copper borate
- parts
- powder
- sponge
- Prior art date
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- DOVLHZIEMGDZIW-UHFFFAOYSA-N [Cu+3].[O-]B([O-])[O-] Chemical compound [Cu+3].[O-]B([O-])[O-] DOVLHZIEMGDZIW-UHFFFAOYSA-N 0.000 claims abstract description 138
- 239000000843 powder Substances 0.000 claims abstract description 87
- 239000004721 Polyphenylene oxide Substances 0.000 claims abstract description 61
- 229920000570 polyether Polymers 0.000 claims abstract description 61
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 52
- 239000008367 deionised water Substances 0.000 claims abstract description 40
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 40
- 229920005862 polyol Polymers 0.000 claims abstract description 25
- 150000003077 polyols Chemical class 0.000 claims abstract description 25
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 claims abstract description 23
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 22
- 239000003054 catalyst Substances 0.000 claims abstract description 20
- 229920002545 silicone oil Polymers 0.000 claims abstract description 20
- 239000011148 porous material Substances 0.000 claims abstract description 19
- 244000269722 Thea sinensis Species 0.000 claims abstract description 18
- 235000009569 green tea Nutrition 0.000 claims abstract description 18
- 238000012986 modification Methods 0.000 claims abstract description 17
- 230000004048 modification Effects 0.000 claims abstract description 17
- 238000004132 cross linking Methods 0.000 claims abstract description 8
- 230000004913 activation Effects 0.000 claims abstract description 3
- XXROGKLTLUQVRX-UHFFFAOYSA-N allyl alcohol Chemical compound OCC=C XXROGKLTLUQVRX-UHFFFAOYSA-N 0.000 claims description 74
- 238000003756 stirring Methods 0.000 claims description 46
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 36
- UBJVUCKUDDKUJF-UHFFFAOYSA-N Diallyl sulfide Chemical compound C=CCSCC=C UBJVUCKUDDKUJF-UHFFFAOYSA-N 0.000 claims description 32
- 238000001035 drying Methods 0.000 claims description 28
- 238000001914 filtration Methods 0.000 claims description 28
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 25
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 22
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 22
- 238000010438 heat treatment Methods 0.000 claims description 21
- 239000000243 solution Substances 0.000 claims description 21
- 238000005406 washing Methods 0.000 claims description 21
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical compound C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 claims description 19
- 238000002360 preparation method Methods 0.000 claims description 19
- 229920002635 polyurethane Polymers 0.000 claims description 16
- 239000004814 polyurethane Substances 0.000 claims description 16
- 238000002156 mixing Methods 0.000 claims description 15
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 claims description 14
- 235000019441 ethanol Nutrition 0.000 claims description 11
- 229910052757 nitrogen Inorganic materials 0.000 claims description 11
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 claims description 10
- 235000019400 benzoyl peroxide Nutrition 0.000 claims description 10
- 238000000034 method Methods 0.000 claims description 9
- 239000000203 mixture Substances 0.000 claims description 9
- 150000001412 amines Chemical group 0.000 claims description 8
- 230000000694 effects Effects 0.000 claims description 7
- 238000010992 reflux Methods 0.000 claims description 7
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 6
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 6
- 229910021538 borax Inorganic materials 0.000 claims description 6
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 claims description 6
- 239000004005 microsphere Substances 0.000 claims description 6
- 239000004328 sodium tetraborate Substances 0.000 claims description 6
- 235000010339 sodium tetraborate Nutrition 0.000 claims description 6
- 125000000101 thioether group Chemical group 0.000 claims description 6
- IMNIMPAHZVJRPE-UHFFFAOYSA-N triethylenediamine Chemical compound C1CN2CCN1CC2 IMNIMPAHZVJRPE-UHFFFAOYSA-N 0.000 claims description 6
- 239000011259 mixed solution Substances 0.000 claims description 5
- 230000008569 process Effects 0.000 claims description 4
- 238000006243 chemical reaction Methods 0.000 claims description 3
- 238000001816 cooling Methods 0.000 claims description 3
- 239000002245 particle Substances 0.000 claims description 3
- -1 polytetrafluoroethylene Polymers 0.000 claims description 3
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 3
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 3
- 238000005245 sintering Methods 0.000 claims description 3
- 239000007788 liquid Substances 0.000 claims description 2
- RUELTTOHQODFPA-UHFFFAOYSA-N toluene 2,6-diisocyanate Chemical compound CC1=C(N=C=O)C=CC=C1N=C=O RUELTTOHQODFPA-UHFFFAOYSA-N 0.000 claims description 2
- 238000010079 rubber tapping Methods 0.000 claims 4
- 239000000463 material Substances 0.000 abstract description 12
- 230000032683 aging Effects 0.000 abstract description 11
- 238000004383 yellowing Methods 0.000 abstract description 8
- 239000002994 raw material Substances 0.000 abstract description 4
- 230000008093 supporting effect Effects 0.000 abstract 1
- 239000000796 flavoring agent Substances 0.000 description 7
- 235000019634 flavors Nutrition 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 5
- 230000006835 compression Effects 0.000 description 3
- 238000007906 compression Methods 0.000 description 3
- 125000003700 epoxy group Chemical group 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
- 230000035699 permeability Effects 0.000 description 2
- 229910003849 O-Si Inorganic materials 0.000 description 1
- 229910003872 O—Si Inorganic materials 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000005576 amination reaction Methods 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 125000001033 ether group Chemical group 0.000 description 1
- 239000003205 fragrance Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000008104 plant cellulose Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 235000019633 pungent taste Nutrition 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 150000003568 thioethers Chemical class 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
Classifications
-
- 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
- C08G18/7614—Polyisocyanates or polyisothiocyanates cyclic aromatic containing only one aromatic ring
- C08G18/7621—Polyisocyanates or polyisothiocyanates cyclic aromatic containing only one aromatic ring being toluene diisocyanate including isomer mixtures
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K7/00—Use of ingredients characterised by shape
- C08K7/22—Expanded, porous or hollow particles
- C08K7/24—Expanded, porous or hollow particles inorganic
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K9/00—Use of pretreated ingredients
- C08K9/04—Ingredients treated with organic substances
- C08K9/06—Ingredients treated with organic substances with silicon-containing compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K9/00—Use of pretreated ingredients
- C08K9/08—Ingredients agglomerated by treatment with a binding agent
-
- 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
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2110/00—Foam properties
- C08G2110/0083—Foam properties prepared using water as the sole blowing agent
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
Abstract
The invention relates to a matcha sponge, which comprises the following components in parts by weight: 36-48 parts of toluene diisocyanate, 72-96 parts of polyether polyol, 15-20 parts of polyether modified porous copper borate, 3-5 parts of pore opening agent, 1.2-1.8 parts of silicone oil, 0.2-0.4 part of catalyst, 0.5-2.5 parts of green tea powder and 2-4 parts of deionized water; the polyether modified porous copper borate is prepared by sequentially carrying out surface activation treatment, surface modification treatment and surface crosslinking treatment on porous copper borate powder. The sponge material is prepared by using toluene diisocyanate, polyether polyol and polyether modified porous copper borate as main raw materials, and the prepared sponge material has good mechanical property and good elastic supporting property, and also has better performance in aspects of yellowing resistance and wet heat aging resistance.
Description
Technical Field
The invention relates to the field of sponge materials, in particular to a matcha sponge.
Background
The sponge, which is a porous material having excellent water absorption and can be used for cleaning articles, is made of polyester, polyurethane or plant cellulose with the development of industrial economy. Polyurethane sponge belongs to one kind of foamed plastic, and is widely used in clothing, packing, automobile, aviation, furniture and other fields due to its low density, high elasticity, high air permeability, high water resistance, etc.
However, in the process of using the sponge prepared by sponge factories in the current market, phenomena of yellowing and decline of physical and mechanical properties are easy to occur, particularly, the phenomenon is more obvious when the sponge is in a high-temperature and humid environment for a long time, and the service life of the sponge is generally shorter. In addition, most of the existing sponges are polyurethane sponges, and some smell residues exist in the preparation process, and some relatively pungent tastes exist in some cases, so that consumers can collide when using the sponges, and therefore, the aromatic sponges are required to be prepared to meet the market demands.
Disclosure of Invention
Aiming at the problems in the prior art, the invention aims to provide a matcha sponge.
The aim of the invention is realized by adopting the following technical scheme:
in a first aspect, the invention provides a matcha sponge, comprising, by weight:
36-48 parts of toluene diisocyanate, 72-96 parts of polyether polyol, 15-20 parts of polyether modified porous copper borate, 3-5 parts of pore opening agent, 1.2-1.8 parts of silicone oil, 0.2-0.4 part of catalyst, 0.5-2.5 parts of green tea powder and 2-4 parts of deionized water.
Preferably, the toluene diisocyanate is TDI-80, and comprises 2, 4-toluene diisocyanate and 2, 6-toluene diisocyanate in a mass ratio of 8:2.
Preferably, the polyether polyol comprises at least one of polyether polyol ED56-200, polyether polyol EP-3600, polyether polyol EP-330N.
Preferably, the polyether modified porous copper borate is prepared by sequentially carrying out surface activation treatment, surface modification treatment and surface crosslinking treatment on porous copper borate powder.
Preferably, the pore opening agent is any one of polyurethane pore opening agent GS-28, polyurethane pore opening agent M-9955 and polyurethane pore opening agent Y-1900.
Preferably, the silicone oil is at least one of michaeli silicone oil L601C, michaeli silicone oil L580, and michaeli silicone oil L595.
Preferably, the catalyst is an amine catalyst a33, i.e. a liquid catalyst containing 33% by mass of Triethylenediamine (TEDA).
Preferably, the green tea powder is green tea flavor essence powder with the content of more than 99 percent and is purchased from Chengdu all-round macro-wetting biotechnology limited company.
The preparation process of the porous copper borate powder comprises the following steps:
1) Dissolving copper chloride in deionized water, adding ammonia water with the mass fraction of 25%, and fully stirring to obtain a first solution, wherein the mass ratio of the copper chloride to the deionized water to the ammonia water is 1.1:15:10; borax (Na) 2 B 4 O 7 ·10H 2 O) dissolving in deionized water, wherein the mass ratio of borax to deionized water is 0.9:10, so as to obtain a second solution;
2) Uniformly mixing the first solution and the second solution, pouring the mixture into a reaction kettle taking polytetrafluoroethylene as a lining, keeping the temperature of the first solution and the second solution at 140 ℃ for 10 hours, cooling to room temperature, filtering, washing with water, and drying to obtain pretreated copper borate microspheres;
3) And (3) placing the pretreated copper borate microspheres in a muffle furnace, heating to 550 ℃, and sintering for 8 hours to obtain the porous copper borate powder with the particle size of 4-8 mu m.
Preferably, the preparation method of the polyether modified porous copper borate comprises the following steps:
s1, surface activity treatment:
mixing porous copper borate powder and absolute ethyl alcohol in a flask, heating, refluxing and stirring for 2-5h, filtering and drying to obtain first porous copper borate powder; dripping gamma-aminopropyl triethoxysilane into deionized water, stirring uniformly, then adding first porous copper borate powder, stirring at 50-60 ℃ for 6-10h, filtering, washing with water, and drying to obtain second porous copper borate powder;
s2, surface modification treatment:
uniformly dispersing the second porous copper borate powder in N, N-dimethylacetamide, continuously stirring under the protection of nitrogen, gradually adding allyl alcohol glycidyl ether, heating to 70-80 ℃ after all the allyl alcohol glycidyl ether is added, stirring for 8-12h, filtering, washing with alcohol, and drying to obtain allyl alcohol ether modified porous copper borate;
s3, surface cross-linking treatment:
uniformly dispersing allyl alcohol ether modified porous copper borate and diallyl sulfide in N, N-dimethylacetamide, adding dibenzoyl peroxide under the protection of nitrogen, heating to 55-65 ℃, carrying out heat preservation and stirring for 10-15h, filtering, washing with alcohol, and drying to obtain polyether modified porous copper borate containing sulfide groups;
preferably, in the step S1, in the preparation process of the first porous copper borate powder, the mass ratio of the porous copper borate powder to the absolute ethyl alcohol is 1:10-20.
Preferably, in the step S1, in the process of preparing the second porous copper borate powder, the mass ratio of the first porous copper borate powder to the gamma-aminopropyl triethoxysilane to the deionized water is 1:0.02-0.04:10-20.
Preferably, in the S2, the mass ratio of the second porous copper borate powder to the allyl alcohol glycidyl ether to the N, N-dimethylacetamide is 1-1.6:0.22-0.44:10-20.
Preferably, in the S3, the mass ratio of the allyl alcohol ether modified porous copper borate, the diallyl sulfide and the N, N-dimethylacetamide is 1:0.23-0.46:10-20, and the mass ratio of the dibenzoyl peroxide to the diallyl sulfide is 0.03-0.07:1.
In a second aspect, the present invention provides a method for preparing a matcha sponge, comprising:
step 1, adding the weighed polyether polyol, polyether modified porous copper borate, a pore opening agent, silicone oil, a catalyst, green tea powder and deionized water into a stirrer, and uniformly mixing at a speed of 500r/min at room temperature;
and 2, adding toluene diisocyanate into the mixed solution in the step 1, stirring at the speed of 1000r/min for 10s at room temperature, transferring into a preheated mold, keeping the temperature at 50-60 ℃ for 5-10min, and demolding to obtain the matcha sponge.
The beneficial effects of the invention are as follows:
1. the invention prepares a novel sponge material, which is prepared by adopting toluene diisocyanate, polyether polyol and polyether modified porous copper borate as main raw materials, and the prepared sponge material has good mechanical property and good elastic support, and also has better performance in aspects of yellowing resistance and wet heat aging resistance. In addition, a small amount of green tea powder is added in the preparation process of the sponge, so that the sponge is richer in color, and can emit light green tea fragrance, and the experience of consumers is better.
2. Among the raw materials used in the invention, toluene diisocyanate and polyether polyol are used as main raw materials for producing polyurethane sponge, the sponge material produced by using the two materials has good flexibility and air permeability, but the elasticity is slightly insufficient, the aging resistance is relatively poor, and polyether modified porous copper borate is used as a modified material, and the addition of the polyether modified porous copper borate not only improves the elasticity and mechanical property of the sponge material, but also improves the aging resistance better.
3. The polyether modified porous copper borate is prepared by taking the prepared porous copper borate as a base, and sequentially carrying out amination treatment, allyl alcohol ether modification treatment and polyether modification treatment on the surface of the porous copper borate. The allyl alcohol ether modification treatment is to combine allyl alcohol glycidyl ether containing double bonds, epoxy groups and ether groups with aminated porous copper borate, and generate polyether compound containing double bonds to coat the surface of the porous copper borate through the combination of the epoxy groups and the amino groups; the polyether modification treatment is to combine thioether compounds of two double bonds, namely diallyl sulfide and allyl alcohol ether modified porous copper borate, and obtain polyether modified porous copper borate containing thioether groups through polymerization reaction of the double bonds. The prepared polyether modified porous copper borate is applied to the preparation of the sponge, and the mechanical property and the elasticity of the sponge are improved to a certain extent, and the yellowing resistance and the wet heat aging resistance of the sponge are also improved to a certain extent.
Drawings
The invention will be further described with reference to the accompanying drawings, in which embodiments do not constitute any limitation of the invention, and other drawings can be obtained by one of ordinary skill in the art without inventive effort from the following drawings.
FIG. 1 is a schematic diagram of the product of the Matcha sponge of example 1 of the present invention.
Detailed Description
The technical features, objects and advantages of the present invention will be more clearly understood from the following detailed description of the technical aspects of the present invention, but should not be construed as limiting the scope of the invention.
The starting materials, reagents or apparatus used in the following examples are all available from conventional commercial sources or may be obtained by methods known in the art unless otherwise specified.
The invention will be further described with reference to the following examples.
Example 1
The matcha sponge comprises the following components in parts by weight:
42 parts of TDI-80, 84 parts of polyether polyol ED56-200, 16 parts of polyether modified porous copper borate, 4 parts of polyurethane pore opening agent GS-28, 1.5 parts of Mickey silicon oil L601C, 0.3 part of amine catalyst A33, 1.5 parts of green tea flavor essence powder and 3 parts of deionized water.
The preparation method of the polyether modified porous copper borate comprises the following steps:
s1, surface activity treatment:
mixing porous copper borate powder and absolute ethyl alcohol in a flask, heating, refluxing and stirring for 3 hours, filtering and drying to obtain first porous copper borate powder; wherein the mass ratio of the porous copper borate powder to the absolute ethyl alcohol is 1:15.
Dripping gamma-aminopropyl triethoxysilane into deionized water, stirring uniformly, then adding first porous copper borate powder, stirring at 55 ℃ for 8 hours, filtering, washing with water, and drying to obtain second porous copper borate powder; wherein the mass ratio of the first porous copper borate powder to the gamma-aminopropyl triethoxysilane to the deionized water is 1:0.03:15.
S2, surface modification treatment:
uniformly dispersing the second porous copper borate powder in N, N-dimethylacetamide, continuously stirring under the protection of nitrogen, gradually adding allyl alcohol glycidyl ether, heating to 75 ℃ after all the allyl alcohol glycidyl ether is added, stirring for 10 hours, filtering, washing with alcohol, and drying to obtain allyl alcohol ether modified porous copper borate; wherein the mass ratio of the second porous copper borate powder to the allyl alcohol glycidyl ether to the N, N-dimethylacetamide is 1.3:0.33:15.
S3, surface cross-linking treatment:
uniformly dispersing allyl alcohol ether modified porous copper borate and diallyl sulfide in N, N-dimethylacetamide, adding dibenzoyl peroxide under the protection of nitrogen, heating to 60 ℃, preserving heat and stirring for 12 hours, filtering, washing with alcohol, and drying to obtain polyether modified porous copper borate containing sulfide groups; wherein the mass ratio of the allyl alcohol ether modified porous copper borate to the diallyl sulfide to the N, N-dimethylacetamide is 1:0.35:15, and the mass ratio of the dibenzoyl peroxide to the diallyl sulfide is 0.05:1.
The preparation process of the porous copper borate powder comprises the following steps:
1) Dissolving copper chloride in deionized water, adding ammonia water with the mass fraction of 25%, and fully stirring to obtain a first solution, wherein the mass ratio of the copper chloride to the deionized water to the ammonia water is 1.1:15:10; borax (Na) 2 B 4 O 7 ·10H 2 O) dissolving in deionized water, wherein the mass ratio of borax to deionized water is 0.9:10, so as to obtain a second solution;
2) Uniformly mixing the first solution and the second solution, pouring the mixture into a reaction kettle taking polytetrafluoroethylene as a lining, keeping the temperature of the first solution and the second solution at 140 ℃ for 10 hours, cooling to room temperature, filtering, washing with water, and drying to obtain pretreated copper borate microspheres;
3) And (3) placing the pretreated copper borate microspheres in a muffle furnace, heating to 550 ℃, and sintering for 8 hours to obtain the porous copper borate powder with the particle size of 4-8 mu m.
The preparation method of the matcha sponge comprises the following steps:
step 1, adding the weighed polyether polyol, polyether modified porous copper borate, a pore opening agent, silicone oil, a catalyst, green tea powder and deionized water into a stirrer, and uniformly mixing at a speed of 500r/min at room temperature;
and 2, adding toluene diisocyanate into the mixed solution in the step 1, stirring at the speed of 1000r/min for 10s at room temperature, transferring into a preheated mold, preheating at the temperature of 55 ℃, preserving heat for 8min, and demolding to obtain the matcha sponge.
Example 2
The matcha sponge comprises the following components in parts by weight:
36 parts of TDI-80, 72 parts of polyether polyol EP-3600, 15 parts of polyether modified porous copper borate, 3 parts of polyurethane pore opening agent M-9955, 1.2 parts of Michaelis silicone oil L580, 0.2 part of amine catalyst A33, 0.5 part of green tea flavor essence powder and 2 parts of deionized water.
The preparation method of the polyether modified porous copper borate comprises the following steps:
s1, surface activity treatment:
mixing porous copper borate powder and absolute ethyl alcohol in a flask, heating, refluxing and stirring for 2 hours, filtering and drying to obtain first porous copper borate powder; the preparation method of the porous copper borate powder is the same as that of the example 1, and the mass ratio of the porous copper borate powder to the absolute ethyl alcohol is 1:10.
Dripping gamma-aminopropyl triethoxysilane into deionized water, stirring uniformly, then adding first porous copper borate powder, stirring for 6 hours at 50 ℃, filtering, washing with water, and drying to obtain second porous copper borate powder; wherein the mass ratio of the first porous copper borate powder to the gamma-aminopropyl triethoxysilane to the deionized water is 1:0.02:10.
S2, surface modification treatment:
uniformly dispersing the second porous copper borate powder in N, N-dimethylacetamide, continuously stirring under the protection of nitrogen, gradually adding allyl alcohol glycidyl ether, heating to 70 ℃ after all the allyl alcohol glycidyl ether is added, stirring for 8 hours, filtering, washing with alcohol, and drying to obtain allyl alcohol ether modified porous copper borate; wherein the mass ratio of the second porous copper borate powder to the allyl alcohol glycidyl ether to the N, N-dimethylacetamide is 1:0.22:10.
S3, surface cross-linking treatment:
uniformly dispersing allyl alcohol ether modified porous copper borate and diallyl sulfide in N, N-dimethylacetamide, adding dibenzoyl peroxide under the protection of nitrogen, heating to 55 ℃, preserving heat and stirring for 10 hours, filtering, washing with alcohol, and drying to obtain polyether modified porous copper borate containing sulfide groups; wherein the mass ratio of the allyl alcohol ether modified porous copper borate to the diallyl sulfide to the N, N-dimethylacetamide is 1:0.23:10, and the mass ratio of the dibenzoyl peroxide to the diallyl sulfide is 0.03:1.
The preparation method of the matcha sponge comprises the following steps:
step 1, adding the weighed polyether polyol, polyether modified porous copper borate, a pore opening agent, silicone oil, a catalyst, green tea powder and deionized water into a stirrer, and uniformly mixing at a speed of 500r/min at room temperature;
and 2, adding toluene diisocyanate into the mixed solution in the step 1, stirring at the speed of 1000r/min for 10s at room temperature, transferring into a preheated mold, preheating at 50 ℃, preserving heat for 10min, and demolding to obtain the matcha sponge.
Example 3
The matcha sponge comprises the following components in parts by weight:
48 parts of TDI-80, 96 parts of polyether polyol EP-330N, 20 parts of polyether modified porous copper borate, 5 parts of polyurethane pore opening agent Y-1900, 1.8 parts of Michaelis silicone oil L595, 0.4 part of amine catalyst A33, 2.5 parts of green tea flavor essence powder and 4 parts of deionized water.
The preparation method of the polyether modified porous copper borate comprises the following steps:
s1, surface activity treatment:
mixing porous copper borate powder and absolute ethyl alcohol in a flask, heating, refluxing and stirring for 5 hours, filtering and drying to obtain first porous copper borate powder; the preparation method of the porous copper borate powder is the same as that of the example 1, and the mass ratio of the porous copper borate powder to the absolute ethyl alcohol is 1:20.
Dripping gamma-aminopropyl triethoxysilane into deionized water, stirring uniformly, then adding first porous copper borate powder, stirring at 60 ℃ for 10 hours, filtering, washing with water, and drying to obtain second porous copper borate powder; wherein the mass ratio of the first porous copper borate powder to the gamma-aminopropyl triethoxysilane to the deionized water is 1:0.04:20.
S2, surface modification treatment:
uniformly dispersing the second porous copper borate powder in N, N-dimethylacetamide, continuously stirring under the protection of nitrogen, gradually adding allyl alcohol glycidyl ether, heating to 80 ℃ after all the allyl alcohol glycidyl ether is added, stirring for 12 hours, filtering, washing with alcohol, and drying to obtain allyl alcohol ether modified porous copper borate; wherein the mass ratio of the second porous copper borate powder to the allyl alcohol glycidyl ether to the N, N-dimethylacetamide is 1.6:0.44:20.
S3, surface cross-linking treatment:
uniformly dispersing allyl alcohol ether modified porous copper borate and diallyl sulfide in N, N-dimethylacetamide, adding dibenzoyl peroxide under the protection of nitrogen, heating to 65 ℃, preserving heat and stirring for 15 hours, filtering, washing with alcohol, and drying to obtain polyether modified porous copper borate containing sulfide groups; wherein the mass ratio of the allyl alcohol ether modified porous copper borate to the diallyl sulfide to the N, N-dimethylacetamide is 1:0.46:20, and the mass ratio of the dibenzoyl peroxide to the diallyl sulfide is 0.07:1.
The preparation method of the matcha sponge comprises the following steps:
step 1, adding the weighed polyether polyol, polyether modified porous copper borate, a pore opening agent, silicone oil, a catalyst, green tea powder and deionized water into a stirrer, and uniformly mixing at a speed of 500r/min at room temperature;
and 2, adding toluene diisocyanate into the mixed solution in the step 1, stirring at the speed of 1000r/min for 10s at room temperature, transferring into a preheated mold, preheating at the temperature of 60 ℃, preserving heat for 5min, and demolding to obtain the matcha sponge.
Comparative example 1
A matcha sponge was prepared as in example 1, except that the polyether modified porous copper borate in the composition was replaced with porous copper borate.
Namely, the composition comprises the following components in parts by weight:
48 parts of TDI-80, 96 parts of polyether polyol EP-330N, 20 parts of porous copper borate, 5 parts of polyurethane pore opening agent Y-1900, 1.8 parts of Michaelis silicone oil L595, 0.4 part of amine catalyst A33, 2.5 parts of green tea flavor essence powder and 4 parts of deionized water.
Comparative example 2
A matcha sponge differs from example 1 only in that the polyether modified porous copper borate in the composition was replaced with surface-treated porous copper borate.
Namely, the composition comprises the following components in parts by weight:
48 parts of TDI-80, 96 parts of polyether polyol EP-330N, 20 parts of surface-activated porous copper borate, 5 parts of polyurethane pore opening agent Y-1900, 1.8 parts of Michaelis-O-Si oil L595, 0.4 part of amine catalyst A33, 2.5 parts of green tea flavor essence powder and 4 parts of deionized water.
The preparation method of the porous copper borate after the surface active treatment comprises the following steps:
mixing porous copper borate powder and absolute ethyl alcohol in a flask, heating, refluxing and stirring for 3 hours, filtering and drying to obtain first porous copper borate powder; the preparation method of the porous copper borate powder is the same as that of the example 1, and the mass ratio of the porous copper borate powder to the absolute ethyl alcohol is 1:15.
Dripping gamma-aminopropyl triethoxysilane into deionized water, stirring uniformly, then adding first porous copper borate powder, stirring for 8 hours at 55 ℃, filtering, washing with water, and drying to obtain porous copper borate subjected to surface activity treatment; wherein the mass ratio of the first porous copper borate powder to the gamma-aminopropyl triethoxysilane to the deionized water is 1:0.03:15.
Comparative example 3
A matcha sponge was different from example 1 only in that the polyether-modified porous copper borate in the composition was replaced with the surface-modified porous copper borate.
Namely, the composition comprises the following components in parts by weight:
48 parts of TDI-80, 96 parts of polyether polyol EP-330N, 20 parts of porous copper borate subjected to surface modification treatment, 5 parts of polyurethane pore opening agent Y-1900, 1.8 parts of Michaelis silicone oil L595, 0.4 part of amine catalyst A33, 2.5 parts of green tea flavor essence powder and 4 parts of deionized water.
The preparation method of the porous copper borate after the surface modification treatment comprises the following steps:
s1, surface activity treatment:
mixing porous copper borate powder and absolute ethyl alcohol in a flask, heating, refluxing and stirring for 3 hours, filtering and drying to obtain first porous copper borate powder; wherein the mass ratio of the porous copper borate powder to the absolute ethyl alcohol is 1:15.
Dripping gamma-aminopropyl triethoxysilane into deionized water, stirring uniformly, then adding first porous copper borate powder, stirring at 55 ℃ for 8 hours, filtering, washing with water, and drying to obtain second porous copper borate powder; wherein the mass ratio of the first porous copper borate powder to the gamma-aminopropyl triethoxysilane to the deionized water is 1:0.03:15.
S2, surface modification treatment:
uniformly dispersing the second porous copper borate powder in N, N-dimethylacetamide, continuously stirring under the protection of nitrogen, gradually adding allyl alcohol glycidyl ether, heating to 75 ℃ after all the allyl alcohol glycidyl ether is added, stirring for 10 hours, filtering, washing with alcohol, and drying to obtain porous copper borate subjected to surface modification treatment; wherein the mass ratio of the second porous copper borate powder to the allyl alcohol glycidyl ether to the N, N-dimethylacetamide is 1.3:0.33:15.
Experimental detection
The sponge materials prepared in example 1 and comparative examples 1 to 3 were subjected to performance test and comparison, and the results are shown in Table 1. The test items include tensile strength, elongation at break, yellowing resistance, compression set, tensile strength after humid heat aging, and elongation at break.
Tensile strength and elongation at break were measured by the method of reference standard ISO 1798-2008.
The yellowing resistance is calculated as a yellowing resistance rating, using a QUV ageing machine (300W, 72 h), in particular as measured by the gray card standard GB250-1995 comparison, with gray card class rating of 1-5 (rating 5 being highest).
Compression set was measured according to the method of standard ISO 1856-2007.
The conditions of the wet heat aging are as follows: the temperature is 80 ℃, the humidity is 95%, and the aging is 120 hours.
TABLE 1 comparison of Performance measurements of different sponge materials
As can be seen from Table 1, the sponge material prepared in example 1 of the present invention has higher mechanical strength, better compression resistance and stronger yellowing resistance than those of comparative examples 1 to 3; and the mechanical strength performance after the wet heat aging is better, which indicates that the aging resistance is stronger.
Finally, it should be noted that the above embodiments are only for illustrating the technical solution of the present invention, and not for limiting the scope of the present invention, and although the present invention has been described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that modifications or equivalent substitutions can be made to the technical solution of the present invention without departing from the spirit and scope of the technical solution of the present invention.
Claims (10)
1. The matcha sponge is characterized by comprising the following components in parts by weight:
36-48 parts of toluene diisocyanate, 72-96 parts of polyether polyol, 15-20 parts of polyether modified porous copper borate, 3-5 parts of pore opening agent, 1.2-1.8 parts of silicone oil, 0.2-0.4 part of catalyst, 0.5-2.5 parts of green tea powder and 2-4 parts of deionized water;
the toluene diisocyanate is TDI-80 and comprises 2, 4-toluene diisocyanate and 2, 6-toluene diisocyanate in a mass ratio of 8:2;
the polyether modified porous copper borate is prepared by sequentially carrying out surface activation treatment, surface modification treatment and surface crosslinking treatment on porous copper borate powder.
2. A matcha sponge as claimed in claim 1, wherein the polyether polyol comprises at least one of polyether polyol ED56-200, polyether polyol EP-3600, polyether polyol EP-330N.
3. The matcha sponge of claim 1 wherein the tapping agent is any one of polyurethane tapping agent GS-28, polyurethane tapping agent M-9955, polyurethane tapping agent Y-1900.
4. The matcha sponge of claim 1 wherein the silicone oil is at least one of michaelvan silicone oil L601C, michaelvan silicone oil L580, michaelvan silicone oil L595.
5. A matcha sponge as claimed in claim 1, characterized in that the catalyst is an amine catalyst a33, a liquid catalyst containing 33% by mass of triethylenediamine.
6. A matcha sponge as claimed in claim 1, wherein the matcha powder is a matcha-flavored essence powder having a content of > 99% purchased from dujingwang macrobiosciences ltd.
7. A matcha sponge as in claim 1 wherein the porous copper borate powder is prepared by a process comprising:
1) Dissolving copper chloride in deionized water, adding ammonia water with the mass fraction of 25%, and fully stirring to obtain a first solution, wherein the mass ratio of the copper chloride to the deionized water to the ammonia water is 1.1:15:10; dissolving borax (Na 2B4O7 & 10H 2O) in deionized water, wherein the mass ratio of the borax to the deionized water is 0.9:10, so as to obtain a second solution;
2) Uniformly mixing the first solution and the second solution, pouring the mixture into a reaction kettle taking polytetrafluoroethylene as a lining, keeping the temperature of the first solution and the second solution at 140 ℃ for 10 hours, cooling to room temperature, filtering, washing with water, and drying to obtain pretreated copper borate microspheres;
3) And (3) placing the pretreated copper borate microspheres in a muffle furnace, heating to 550 ℃, and sintering for 8 hours to obtain the porous copper borate powder with the particle size of 4-8 mu m.
8. The matcha sponge of claim 1 wherein the polyether modified porous copper borate is prepared by a process comprising:
s1, surface activity treatment:
mixing porous copper borate powder and absolute ethyl alcohol in a flask, heating, refluxing and stirring for 2-5h, filtering and drying to obtain first porous copper borate powder; dripping gamma-aminopropyl triethoxysilane into deionized water, stirring uniformly, then adding first porous copper borate powder, stirring at 50-60 ℃ for 6-10h, filtering, washing with water, and drying to obtain second porous copper borate powder;
s2, surface modification treatment:
uniformly dispersing the second porous copper borate powder in N, N-dimethylacetamide, continuously stirring under the protection of nitrogen, gradually adding allyl alcohol glycidyl ether, heating to 70-80 ℃ after all the allyl alcohol glycidyl ether is added, stirring for 8-12h, filtering, washing with alcohol, and drying to obtain allyl alcohol ether modified porous copper borate;
s3, surface cross-linking treatment:
uniformly dispersing allyl alcohol ether modified porous copper borate and diallyl sulfide in N, N-dimethylacetamide, adding dibenzoyl peroxide under the protection of nitrogen, heating to 55-65 ℃, preserving heat and stirring for 10-15h, filtering, washing with alcohol, and drying to obtain polyether modified porous copper borate containing sulfide groups.
9. The matcha sponge of claim 8, wherein in S1, the mass ratio of the porous copper borate powder to the absolute ethanol is 1:10-20; in the S1, in the preparation process of the second porous copper borate powder, the mass ratio of the first porous copper borate powder to the gamma-aminopropyl triethoxysilane to the deionized water is 1:0.02-0.04:10-20; in the S2, the mass ratio of the second porous copper borate powder to the allyl alcohol glycidyl ether to the N, N-dimethylacetamide is 1-1.6:0.22-0.44:10-20; in the S3, the mass ratio of the allyl alcohol ether modified porous copper borate, the diallyl sulfide and the N, N-dimethylacetamide is 1:0.23-0.46:10-20, and the mass ratio of the dibenzoyl peroxide to the diallyl sulfide is 0.03-0.07:1.
10. A method of preparing a matcha sponge as in claim 1, comprising:
step 1, adding the weighed polyether polyol, polyether modified porous copper borate, a pore opening agent, silicone oil, a catalyst, green tea powder and deionized water into a stirrer, and uniformly mixing at a speed of 500r/min at room temperature;
and 2, adding toluene diisocyanate into the mixed solution in the step 1, stirring at the speed of 1000r/min for 10s at room temperature, transferring into a preheated mold, keeping the temperature at 50-60 ℃ for 5-10min, and demolding to obtain the matcha sponge.
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