CN116836366A - Super soft sponge - Google Patents
Super soft sponge Download PDFInfo
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- CN116836366A CN116836366A CN202311005267.5A CN202311005267A CN116836366A CN 116836366 A CN116836366 A CN 116836366A CN 202311005267 A CN202311005267 A CN 202311005267A CN 116836366 A CN116836366 A CN 116836366A
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- China
- Prior art keywords
- copper borate
- parts
- porous copper
- sponge
- stirring
- 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 103
- 229920005862 polyol Polymers 0.000 claims abstract description 52
- 150000003077 polyols Chemical class 0.000 claims abstract description 52
- 239000004952 Polyamide Substances 0.000 claims abstract description 51
- 229920002647 polyamide Polymers 0.000 claims abstract description 51
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 50
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims abstract description 39
- 239000008367 deionised water Substances 0.000 claims abstract description 36
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 36
- 239000004721 Polyphenylene oxide Substances 0.000 claims abstract description 27
- 229920000570 polyether Polymers 0.000 claims abstract description 27
- 229920000642 polymer Polymers 0.000 claims abstract description 27
- 239000003054 catalyst Substances 0.000 claims abstract description 26
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 22
- 229920002545 silicone oil Polymers 0.000 claims abstract description 22
- 239000011148 porous material Substances 0.000 claims abstract description 18
- 238000000034 method Methods 0.000 claims abstract description 10
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims abstract description 3
- 239000000843 powder Substances 0.000 claims description 57
- 238000003756 stirring Methods 0.000 claims description 46
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 37
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 36
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 34
- 238000006243 chemical reaction Methods 0.000 claims description 26
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 24
- FYSNRJHAOHDILO-UHFFFAOYSA-N thionyl chloride Chemical compound ClS(Cl)=O FYSNRJHAOHDILO-UHFFFAOYSA-N 0.000 claims description 24
- 150000001875 compounds Chemical class 0.000 claims description 21
- 239000000243 solution Substances 0.000 claims description 21
- 238000010438 heat treatment Methods 0.000 claims description 19
- 238000001035 drying Methods 0.000 claims description 18
- 238000001914 filtration Methods 0.000 claims description 18
- 238000005406 washing Methods 0.000 claims description 18
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical class C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 claims description 17
- 229910052757 nitrogen Inorganic materials 0.000 claims description 17
- 229920002635 polyurethane Polymers 0.000 claims description 16
- 239000004814 polyurethane Substances 0.000 claims description 16
- 238000002360 preparation method Methods 0.000 claims description 16
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 15
- ZDZVKPXKLLLOOA-UHFFFAOYSA-N Allylmalonic acid Chemical compound OC(=O)C(C(O)=O)CC=C ZDZVKPXKLLLOOA-UHFFFAOYSA-N 0.000 claims description 13
- MIROPXUFDXCYLG-UHFFFAOYSA-N pyridine-2,5-diamine Chemical compound NC1=CC=C(N)N=C1 MIROPXUFDXCYLG-UHFFFAOYSA-N 0.000 claims description 13
- 239000007789 gas Substances 0.000 claims description 12
- 230000001681 protective effect Effects 0.000 claims description 12
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 12
- 238000002390 rotary evaporation Methods 0.000 claims description 12
- 239000002904 solvent Substances 0.000 claims description 12
- PXQLVRUNWNTZOS-UHFFFAOYSA-N sulfanyl Chemical class [SH] PXQLVRUNWNTZOS-UHFFFAOYSA-N 0.000 claims description 12
- 238000010992 reflux Methods 0.000 claims description 11
- UUEWCQRISZBELL-UHFFFAOYSA-N 3-trimethoxysilylpropane-1-thiol Chemical compound CO[Si](OC)(OC)CCCS UUEWCQRISZBELL-UHFFFAOYSA-N 0.000 claims description 10
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 claims description 10
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 10
- ISAOCJYIOMOJEB-UHFFFAOYSA-N benzoin Chemical compound C=1C=CC=CC=1C(O)C(=O)C1=CC=CC=C1 ISAOCJYIOMOJEB-UHFFFAOYSA-N 0.000 claims description 10
- 239000000203 mixture Substances 0.000 claims description 10
- 150000001412 amines Chemical group 0.000 claims description 8
- IMNIMPAHZVJRPE-UHFFFAOYSA-N triethylenediamine Chemical compound C1CN2CCN1CC2 IMNIMPAHZVJRPE-UHFFFAOYSA-N 0.000 claims description 8
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 7
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 7
- 229910021538 borax Inorganic materials 0.000 claims description 7
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 claims description 7
- 239000004328 sodium tetraborate Substances 0.000 claims description 7
- 235000010339 sodium tetraborate Nutrition 0.000 claims description 7
- 239000005457 ice water Substances 0.000 claims description 6
- 239000004005 microsphere Substances 0.000 claims description 6
- 244000028419 Styrax benzoin Species 0.000 claims description 5
- 235000000126 Styrax benzoin Nutrition 0.000 claims description 5
- 235000008411 Sumatra benzointree Nutrition 0.000 claims description 5
- 229960002130 benzoin Drugs 0.000 claims description 5
- -1 carbodiimide modified 4,4' -diphenylmethane diisocyanate Chemical class 0.000 claims description 5
- 235000019441 ethanol Nutrition 0.000 claims description 5
- 235000019382 gum benzoic Nutrition 0.000 claims description 5
- 239000003999 initiator Substances 0.000 claims description 5
- 239000011259 mixed solution Substances 0.000 claims description 5
- 230000001105 regulatory effect Effects 0.000 claims description 5
- 238000005303 weighing Methods 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 4
- 238000005245 sintering Methods 0.000 claims description 4
- 238000001816 cooling Methods 0.000 claims description 3
- 238000012986 modification Methods 0.000 claims description 3
- 230000004048 modification Effects 0.000 claims description 3
- 239000002245 particle Substances 0.000 claims description 3
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 3
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 3
- 239000007788 liquid Substances 0.000 claims description 2
- 238000004321 preservation Methods 0.000 claims description 2
- 230000008569 process Effects 0.000 claims description 2
- 238000006177 thiolation reaction Methods 0.000 claims description 2
- 239000000463 material Substances 0.000 abstract description 13
- 239000002994 raw material Substances 0.000 abstract description 5
- 239000000654 additive Substances 0.000 abstract description 3
- 230000000996 additive effect Effects 0.000 abstract description 3
- 239000003607 modifier Substances 0.000 abstract description 3
- 125000005442 diisocyanate group Chemical group 0.000 abstract description 2
- 231100000053 low toxicity Toxicity 0.000 abstract description 2
- 230000032683 aging Effects 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 5
- 230000006835 compression Effects 0.000 description 4
- 238000007906 compression Methods 0.000 description 4
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 2
- 230000035939 shock Effects 0.000 description 2
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 125000002252 acyl group Chemical group 0.000 description 1
- 125000003368 amide group Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 230000003139 buffering effect Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000005660 chlorination reaction Methods 0.000 description 1
- 238000012650 click reaction Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 239000007822 coupling agent Substances 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
- 229920001821 foam rubber Polymers 0.000 description 1
- 238000005187 foaming Methods 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 238000005461 lubrication Methods 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000008093 supporting effect Effects 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 125000000101 thioether group Chemical group 0.000 description 1
- 238000004383 yellowing 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
- C08G18/77—Polyisocyanates or polyisothiocyanates having heteroatoms in addition to the isocyanate or isothiocyanate nitrogen and oxygen or sulfur
- C08G18/78—Nitrogen
- C08G18/79—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates
- C08G18/797—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates containing carbodiimide and/or uretone-imine groups
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/30—Low-molecular-weight compounds
- C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
- C08G18/3203—Polyhydroxy compounds
- C08G18/3206—Polyhydroxy compounds aliphatic
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/63—Block or graft polymers obtained by polymerising compounds having carbon-to-carbon double bonds on to polymers
- C08G18/632—Block or graft polymers obtained by polymerising compounds having carbon-to-carbon double bonds on to polymers onto polyethers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
- C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
- C08G18/6666—Compounds of group C08G18/48 or C08G18/52
- C08G18/667—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38
- C08G18/6674—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3203
-
- 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
- C08K9/10—Encapsulated ingredients
-
- 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 an ultra-soft sponge, which comprises the following components in parts by weight: 30-50 parts of modified MDI, 44-68 parts of polyether polyol, 16-32 parts of polymer polyol, 12-24 parts of polyamide modified porous copper borate, 2-4 parts of pore opening agent, 1.5-3 parts of silicone oil, 0.5-1 part of catalyst, 0.6-1.2 parts of glycol and 2.1-4.2 parts of deionized water. The sponge material is prepared by the method, wherein the modified MDI is used as diisocyanate raw material, and has the advantages of higher stability, softness and fineness; the polyether polyol and the polymer polyol are used together as polyol raw materials, and have the advantages of low viscosity, low toxicity, good processability and high strength; the polyamide modified porous copper borate is used as an additive modifier, so that the pressure resistance and the elasticity of the sponge can be improved, and the durable usability of the sponge is also improved.
Description
Technical Field
The invention relates to the field of sponge materials, in particular to an ultra-soft sponge.
Background
With the increasing market demand, packaging liners of various materials are also in wide use, wherein sponge is one of them. The sponge is a foaming material, has the advantages of good buffering, shock resistance, heat insulation and the like, and has the characteristics of no toxicity, no odor, water absorption and the like. The sponge has the advantages of compact structure, lubrication surface, soft and elastic hand feeling, shock resistance, moisture resistance, skid resistance, wear resistance and the like, and can effectively prevent products from being damaged due to impact vibration in the transportation process. The sponge can buffer instant impact force and has super-strong plasticity, so that the sponge is applied to various fields, such as soles, inner liners of decorative boxes, inner liners of precision machines, buffer materials of electronic products and the like.
Most of the sponge materials in the market are polyurethane soft foam rubber, polyurethane is a polymer material which is common in life, and is widely applied to manufacturing various sponge products, and the polyurethane sponge material has good air permeability and perspiration property, moderate hardness and good supporting effect, so the polyurethane sponge material is often used for manufacturing mattresses. However, with the development of society, more and more people have higher demands on the sponge, and the sponge is required to be soft and comfortable, and also required to have good pressure resistance and elasticity, and further required to have longer service life.
Disclosure of Invention
Aiming at the problems in the prior art, the invention aims to provide an ultra-soft sponge.
The aim of the invention is realized by adopting the following technical scheme:
in a first aspect, the invention provides an ultra-soft sponge, comprising, by weight:
30-50 parts of modified MDI, 44-68 parts of polyether polyol, 16-32 parts of polymer polyol, 12-24 parts of polyamide modified porous copper borate, 2-4 parts of pore opening agent, 1.5-3 parts of silicone oil, 0.5-1 part of catalyst, 0.6-1.2 parts of glycol and 2.1-4.2 parts of deionized water.
Preferably, the modified MDI is carbodiimide modified 4,4' -diphenylmethane diisocyanate, and the specific model is Wanhua CDMDI-100L.
Preferably, the polyether polyol comprises at least one of polyether polyol ED56-200, polyether polyol EP-3600, polyether polyol EP-330N.
Preferably, the polymer polyol comprises at least one of polymer polyol HPOP-40, polymer polyol POP-3628 and polymer polyol POP-2045.
Preferably, the polyamide modified porous copper borate is prepared by sequentially carrying out sulfhydrylation treatment and polyether modification on the basis of 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 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%, wherein the mass ratio of the copper chloride to the deionized water to the ammonia water is 0.7-1.4:10-20:10, and fully stirring to obtain a first solution; borax (Na 2B) 4 O 7 ·10H 2 O) is dissolved in deionized water, and the mass ratio of borax to deionized water is 0.6-1.2:10, 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 mass ratio of the first solution to the second solution at 1:1.1-1.3, preserving the temperature at 130-150 ℃ for 10-12h, 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 500-600 ℃, and sintering for 5-10h to obtain the porous copper borate powder with the particle size of 4-8 mu m.
Preferably, the preparation process of the thiolation treatment of the porous copper borate powder comprises the following steps:
4) Dispersing porous copper borate powder in absolute ethyl alcohol, heating to reflux for 6-10h, filtering, washing with water and drying to obtain activated porous copper borate powder; wherein the mass ratio of the porous copper borate powder to the absolute ethyl alcohol is 1:8-12;
5) Placing activated porous copper borate powder into deionized water, fully dispersing, adding 3-mercaptopropyl trimethoxy silane, heating to 60-80 ℃, preserving heat, stirring for 5-8h, filtering, washing with water, and drying to obtain mercaptoporous copper borate powder; wherein the mass ratio of the activated porous copper borate powder to the 3-mercaptopropyl trimethoxy silane to the deionized water is 1:0.2-0.4:10-20.
Preferably, the preparation method of the polyamide modified porous copper borate comprises the following steps:
s1, adding 2-allyl malonic acid into thionyl chloride, introducing nitrogen as a protective gas, uniformly stirring in an ice water bath, adding a few drops of catalyst pyridine, gradually heating to 75-85 ℃, carrying out heat preservation reflux reaction for 5-6h, and removing a solvent by rotary evaporation after the reaction is finished to obtain 2-allyl malonyl chloride;
wherein the mass ratio of the 2-allylmalonic acid to the pyridine to the thionyl chloride is 1.4-2.1:0.02-0.06:8-16;
s2, dissolving 2, 5-diaminopyridine into chloroform, introducing nitrogen as a protective gas, adding 2-allylmalonyl chloride, stirring uniformly, adding triethylamine, stirring at room temperature for 12-16h, and removing the solvent by rotary evaporation after the reaction is finished to obtain a polyamide compound containing double bonds and pyridine groups;
wherein the mass ratio of the 2, 5-diaminopyridine to the 2-allylmalonyl chloride to the triethylamine to the chloroform is 0.7-1.1:1.2-1.8:0.03-0.07:10-16;
s3, dispersing the mercapto-based porous copper borate powder in N, N-dimethylacetamide, adding the polyamide compound obtained in the step S2, adding benzoin dimethyl ether as an initiator under the protection of nitrogen, using an ultraviolet lamp to irradiate and stir for 15-30min, and filtering, washing with alcohol and drying after the reaction is finished to obtain the polyamide modified porous copper borate containing thioether bonds and pyridine groups;
wherein the mass ratio of the mercapto-porous copper borate powder to the polyamide compound to the N, N-dimethylacetamide is 2.1-4.2:1:20-40.
In a second aspect, the present invention provides a method for preparing an ultra-soft sponge, comprising:
step 1, weighing polyether polyol, polymer polyol, polyamide modified porous copper borate, a pore opening agent, silicone oil, a catalyst, ethylene glycol and deionized water according to the amount, adding into a stirrer, and stirring at the speed of 600r/min at the temperature of 25-30 ℃ until the mixture is uniform;
and 2, adding the modified MDI into the mixed solution in the step 1, regulating the stirring speed to 1200r/min at 25-30 ℃, stirring for 10-20s, transferring into a preheated mold, preheating at 50-60 ℃, preserving heat for 5-10min, and demolding to obtain the ultra-soft sponge.
The beneficial effects of the invention are as follows:
1. the invention prepares a sponge material, and the main raw materials used by the sponge material comprise modified MDI, polyether polyol, polymer polyol and polyamide modified porous copper borate as an additive modifier. The modified MDI is used as a diisocyanate raw material, and has the advantages of higher stability, softness and fineness; the polyether polyol and the polymer polyol are used together as polyol raw materials, and have the advantages of low viscosity, low toxicity, good processability and high strength; the polyamide modified porous copper borate is used as an additive modifier, so that the pressure resistance and the elasticity of the sponge can be improved, and the durable usability of the sponge is also improved.
2. The polyamide modified porous copper borate is prepared on the basis of the prepared porous copper borate, and the porous copper borate powder is prepared by taking copper chloride as a copper source and borax as a boron source, performing hydrothermal reaction under the condition of ammonia water, and then sintering at high temperature.
3. The polyamide modified porous copper borate added in the invention is based on the prepared porous copper borate, firstly, the porous copper borate is treated by using a mercapto coupling agent to obtain mercapto porous copper borate powder; then 2-allylmalonic acid containing double carboxyl and double bond reacts with 2, 5-diaminopyridine containing double amino, and is combined with amino after acyl chlorination of carboxyl to obtain polyamide compound containing double bond and pyridine group; then mixing polyamide compound with mercapto porous copper borate, and finally preparing polymer coated porous copper borate through ultraviolet irradiation double bond-mercapto click reaction, wherein the coated polymer contains a large amount of amide groups, thioether groups and pyridine groups. The finally obtained polyamide modified porous copper borate is applied to the sponge, and the pressure resistance, the elasticity and the aging resistance of the sponge are improved.
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 view of the product of the ultra-soft sponge prepared in 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
An ultra-soft sponge comprises the following components in parts by weight:
40 parts of Wanhua CDMDI-100L (modified MDI), 56 parts of polyether polyol ED56-200, 24 parts of polymer polyol HPOP-40, 18 parts of polyamide modified porous copper borate, 3 parts of polyurethane pore opening agent GS-28, 2.5 parts of Michaelk silicone oil L601C, 0.8 part of amine catalyst A33, 0.9 part of ethylene glycol and 3.3 parts of deionized water.
The preparation method of the polyamide modified porous copper borate comprises the following steps:
s1, adding 2-allyl malonic acid into thionyl chloride, introducing nitrogen as a protective gas, uniformly stirring in an ice water bath, adding a few drops of catalyst pyridine, gradually heating to 80 ℃, preserving heat, carrying out reflux reaction for 5.5 hours, and removing a solvent by rotary evaporation after the reaction is finished to obtain 2-allyl malonyl chloride; wherein the mass ratio of the 2-allylmalonic acid to the pyridine to the thionyl chloride is 1.8:0.04:12;
s2, dissolving 2, 5-diaminopyridine into chloroform, introducing nitrogen as a protective gas, adding 2-allylmalonyl chloride, stirring uniformly, adding triethylamine, stirring at room temperature for 14h, and removing the solvent by rotary evaporation after the reaction is finished to obtain a polyamide compound containing double bonds and pyridine groups; wherein the mass ratio of the 2, 5-diaminopyridine to the 2-allylmalonyl chloride to the triethylamine to the chloroform is 0.8:1.5:0.05:12;
s3, dispersing the porous copper borate powder in absolute ethyl alcohol, heating to reflux for 8 hours, filtering, washing with water and drying to obtain activated porous copper borate powder; wherein the mass ratio of the porous copper borate powder to the absolute ethyl alcohol is 1:10; placing activated porous copper borate powder into deionized water, fully dispersing, adding 3-mercaptopropyl trimethoxy silane, heating to 70 ℃, preserving heat, stirring for 6 hours, filtering, washing with water, and drying to obtain mercapto porous copper borate powder; wherein the mass ratio of the activated porous copper borate powder to the 3-mercaptopropyl trimethoxysilane to the deionized water is 1:0.3:15.
S4, dispersing the mercapto-based porous copper borate powder in N, N-dimethylacetamide, adding the polyamide compound obtained in the step S2, adding benzoin dimethyl ether as an initiator under the protection of nitrogen, using an ultraviolet lamp to irradiate and stir for 25min, and after the reaction is finished, filtering, washing with alcohol and drying to obtain the polyamide modified porous copper borate containing thioether bonds and pyridine groups; wherein the mass ratio of the mercapto-porous copper borate powder to the polyamide compound to the N, N-dimethylacetamide is 3.2:1:30.
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 super soft sponge comprises the following steps:
step 1, weighing polyether polyol, polymer polyol, polyamide modified porous copper borate, a pore opening agent, silicone oil, a catalyst, ethylene glycol and deionized water according to the amount, adding into a stirrer, and stirring at the speed of 600r/min at the temperature of 25-30 ℃ until the mixture is uniform;
and 2, adding the modified MDI into the mixed solution in the step 1, regulating the stirring speed to 1200r/min at 25-30 ℃, stirring for 15s, transferring into a preheated mold, keeping the temperature at 50 ℃ for 10min, and demolding to obtain the ultra-soft sponge.
Example 2
An ultra-soft sponge comprises the following components in parts by weight:
30 parts of Wanhua CDMDI-100L (modified MDI), 44 parts of polyether polyol EP-3600, 16 parts of polymer polyol POP-3628, 12 parts of polyamide modified porous copper borate, 2 parts of polyurethane pore opening agent M-9955, 1.5 parts of Michaelis silicone oil L580, 0.5 part of amine catalyst A33, 0.6 part of ethylene glycol and 2.1 parts of deionized water.
The preparation method of the polyamide modified porous copper borate comprises the following steps:
s1, adding 2-allyl malonic acid into thionyl chloride, introducing nitrogen as a protective gas, uniformly stirring in an ice water bath, adding a few drops of catalyst pyridine, gradually heating to 75 ℃, preserving heat, carrying out reflux reaction for 5 hours, and removing a solvent by rotary evaporation after the reaction is finished to obtain 2-allyl malonyl chloride;
wherein the mass ratio of the 2-allylmalonic acid to the pyridine to the thionyl chloride is 1.4:0.02:8;
s2, dissolving 2, 5-diaminopyridine into chloroform, introducing nitrogen as a protective gas, adding 2-allylmalonyl chloride, stirring uniformly, adding triethylamine, stirring at room temperature for 12 hours, and removing a solvent by rotary evaporation after the reaction is finished to obtain a polyamide compound containing double bonds and pyridine groups;
wherein the mass ratio of the 2, 5-diaminopyridine to the 2-allylmalonyl chloride to the triethylamine to the chloroform is 0.7:1.2:0.03:10;
s3, dispersing the porous copper borate powder in absolute ethyl alcohol, heating to reflux for 6 hours, filtering, washing with water and drying to obtain activated porous copper borate powder; the preparation method of the porous copper borate powder is the same as that of the embodiment 1, and the mass ratio of the porous copper borate powder to the absolute ethyl alcohol is 1:8; placing activated porous copper borate powder into deionized water, fully dispersing, adding 3-mercaptopropyl trimethoxy silane, heating to 60 ℃, preserving heat and stirring for 5 hours, filtering, washing with water and drying to obtain mercapto porous copper borate powder; wherein the mass ratio of the activated porous copper borate powder to the 3-mercaptopropyl trimethoxysilane to the deionized water is 1:0.2:10.
S4, dispersing the mercapto-based porous copper borate powder in N, N-dimethylacetamide, adding the polyamide compound obtained in the step S2, adding benzoin dimethyl ether as an initiator under the protection of nitrogen, using an ultraviolet lamp to irradiate and stir for 15min, and after the reaction is finished, filtering, washing with alcohol and drying to obtain the polyamide modified porous copper borate containing thioether bonds and pyridine groups;
wherein the mass ratio of the mercapto-porous copper borate powder to the polyamide compound to the N, N-dimethylacetamide is 2.1:1:20.
The preparation method of the super soft sponge comprises the following steps:
step 1, weighing polyether polyol, polymer polyol, polyamide modified porous copper borate, a pore opening agent, silicone oil, a catalyst, ethylene glycol and deionized water according to the amount, adding into a stirrer, and stirring at the speed of 600r/min at the temperature of 25-30 ℃ until the mixture is uniform;
and 2, adding the modified MDI into the mixed solution in the step 1, regulating the stirring speed to 1200r/min at 25-30 ℃, stirring for 10-20s, transferring into a preheated mold, keeping the temperature at 50 ℃ for 10min, and demolding to obtain the ultra-soft sponge.
Example 3
An ultra-soft sponge comprises the following components in parts by weight:
50 parts of Wanhua CDMDI-100L (modified MDI), 68 parts of polyether polyol EP-330N, 32 parts of polymer polyol POP-2045, 24 parts of polyamide modified porous copper borate, 4 parts of polyurethane pore opening agent Y-1900, 3 parts of Michaelis silicone oil L595, 1 part of amine catalyst A33, 1.2 parts of ethylene glycol and 4.2 parts of deionized water.
The preparation method of the polyamide modified porous copper borate comprises the following steps:
s1, adding 2-allyl malonic acid into thionyl chloride, introducing nitrogen as a protective gas, uniformly stirring in an ice water bath, adding a few drops of catalyst pyridine, gradually heating to 85 ℃, preserving heat, carrying out reflux reaction for 6 hours, and removing a solvent by rotary evaporation after the reaction is finished to obtain 2-allyl malonyl chloride;
wherein the mass ratio of the 2-allylmalonic acid to the pyridine to the thionyl chloride is 2.1:0.06:16;
s2, dissolving 2, 5-diaminopyridine into chloroform, introducing nitrogen as a protective gas, adding 2-allylmalonyl chloride, stirring uniformly, adding triethylamine, stirring at room temperature for 16 hours, and removing a solvent by rotary evaporation after the reaction is finished to obtain a polyamide compound containing double bonds and pyridine groups;
wherein the mass ratio of the 2, 5-diaminopyridine to the 2-allylmalonyl chloride to the triethylamine to the chloroform is 1.1:1.8:0.07:16;
s3, dispersing the porous copper borate powder in absolute ethyl alcohol, heating to reflux for 10 hours, filtering, washing with water and drying to obtain activated porous copper borate powder; the preparation method of the porous copper borate powder is the same as that of the embodiment 1, and the mass ratio of the porous copper borate powder to the absolute ethyl alcohol is 1:12; placing activated porous copper borate powder into deionized water, fully dispersing, adding 3-mercaptopropyl trimethoxy silane, heating to 80 ℃, preserving heat and stirring for 8 hours, filtering, washing with water and drying to obtain mercapto porous copper borate powder; wherein the mass ratio of the activated porous copper borate powder to the 3-mercaptopropyl trimethoxysilane to the deionized water is 1:0.4:20.
S4, dispersing the mercapto-based porous copper borate powder in N, N-dimethylacetamide, adding the polyamide compound obtained in the step S2, adding benzoin dimethyl ether as an initiator under the protection of nitrogen, using an ultraviolet lamp to irradiate and stir for 30min, and after the reaction is finished, filtering, washing with alcohol and drying to obtain the polyamide modified porous copper borate containing thioether bonds and pyridine groups;
wherein the mass ratio of the mercapto-porous copper borate powder to the polyamide compound to the N, N-dimethylacetamide is 4.2:1:40.
The preparation method of the super soft sponge comprises the following steps:
step 1, weighing polyether polyol, polymer polyol, polyamide modified porous copper borate, a pore opening agent, silicone oil, a catalyst, ethylene glycol and deionized water according to the amount, adding into a stirrer, and stirring at the speed of 600r/min at the temperature of 25-30 ℃ until the mixture is uniform;
and 2, adding the modified MDI into the mixed solution in the step 1, regulating the stirring speed to 1200r/min at 25-30 ℃, stirring for 20s, transferring into a preheated mold, keeping the temperature at 60 ℃ for 5min, and demolding to obtain the ultra-soft sponge.
Comparative example 1
The sponge differs from example 1 only in that the polyamide-modified porous copper borate in the composition is replaced by porous copper borate (porous copper borate is prepared in the same way as example 1), i.e. the sponge comprises, in parts by weight:
40 parts of Vanhua CDMDI-100L (modified MDI), 56 parts of polyether polyol ED56-200, 24 parts of polymer polyol HPOP-40, 18 parts of porous copper borate, 3 parts of polyurethane pore opening agent GS-28, 2.5 parts of Michaelis silicone oil L601C, 0.8 part of amine catalyst A33, 0.9 part of ethylene glycol and 3.3 parts of deionized water.
Comparative example 2
The only difference compared with example 1 is that the polyamide modified porous copper borate in the components is replaced by mercapto porous copper borate powder, i.e. the sponge comprises, in parts by weight:
40 parts of Wanhua CDMDI-100L (modified MDI), 56 parts of polyether polyol ED56-200, 24 parts of polymer polyol HPOP-40, 18 parts of mercapto-porous copper borate powder, 3 parts of polyurethane pore opening agent GS-28, 2.5 parts of Mickey silicone oil L601C, 0.8 part of amine catalyst A33, 0.9 part of ethylene glycol and 3.3 parts of deionized water.
The preparation process of the mercapto-porous copper borate powder was the same as in example 1.
Comparative example 3
The only difference compared to example 1 is that the polyamide-modified porous copper borate in the composition is replaced with a polyamide compound, i.e., the sponge comprises, in parts by weight:
40 parts of Vanhua CDMDI-100L (modified MDI), 56 parts of polyether polyol ED56-200, 24 parts of polymer polyol HPOP-40, 18 parts of polyamide compound, 3 parts of polyurethane pore opening agent GS-28, 2.5 parts of Michaelis silicone oil L601C, 0.8 part of amine catalyst A33, 0.9 part of ethylene glycol and 3.3 parts of deionized water.
The preparation process of the polyamide compound comprises the following steps:
s1, adding 2-allyl malonic acid into thionyl chloride, introducing nitrogen as a protective gas, uniformly stirring in an ice water bath, adding a few drops of catalyst pyridine, gradually heating to 80 ℃, preserving heat, carrying out reflux reaction for 5.5 hours, and removing a solvent by rotary evaporation after the reaction is finished to obtain 2-allyl malonyl chloride; wherein the mass ratio of the 2-allylmalonic acid to the pyridine to the thionyl chloride is 1.8:0.04:12;
s2, dissolving 2, 5-diaminopyridine into chloroform, introducing nitrogen as a protective gas, adding 2-allylmalonyl chloride, stirring uniformly, adding triethylamine, stirring at room temperature for 14h, and removing the solvent by rotary evaporation after the reaction is finished to obtain a polyamide compound containing double bonds and pyridine groups; wherein the mass ratio of the 2, 5-diaminopyridine to the 2-allylmalonyl chloride to the triethylamine to the chloroform is 0.8:1.5:0.05:12.
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.
Tear strength was measured according to the method of standard GB/T10808-2006.
Rebound resilience is expressed as rebound rate and is measured by the method of reference standard GB/T6670-2008.
Compression set was measured according to the method of standard ISO 1856-2007.
The conditions of high temperature aging are: aging at 150deg.C for 24 hr.
The conditions of the wet heat aging are as follows: the temperature is 90 ℃, 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 tensile strength, elongation at break and tear strength of the sponge material prepared in example 1 of the present invention are all significantly improved as compared with comparative examples 1 to 3; and the rebound resilience and compression set perform better, indicating that the compression resistance and elasticity perform better. In addition, the retention rate of the tensile strength and the elongation at break after high-temperature aging and wet heat aging is higher, the high temperature resistance and the humidity and heat aging resistance are stronger, can be applied for a long time in a relatively severe environment.
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 ultra-soft sponge is characterized by comprising the following components in parts by weight:
30-50 parts of modified MDI, 44-68 parts of polyether polyol, 16-32 parts of polymer polyol, 12-24 parts of polyamide modified porous copper borate, 2-4 parts of pore opening agent, 1.5-3 parts of silicone oil, 0.5-1 part of catalyst, 0.6-1.2 parts of glycol and 2.1-4.2 parts of deionized water;
the modified MDI is carbodiimide modified 4,4' -diphenylmethane diisocyanate, and the specific model is Wanhua CDMDI-100L;
the polyamide modified porous copper borate is prepared by sequentially carrying out sulfhydrylation treatment and polyether modification on the basis of porous copper borate powder.
2. An ultrasoft 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 ultra-soft sponge of claim 1, wherein the polymer polyol comprises at least one of polymer polyol HPOP-40, polymer polyol POP-3628, polymer polyol POP-2045.
4. The ultra-soft sponge according to claim 1, wherein the pore-forming agent is any one of polyurethane pore-forming agent GS-28, polyurethane pore-forming agent M-9955 and polyurethane pore-forming agent Y-1900.
5. The ultra-soft 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.
6. An ultrasoft sponge as claimed in claim 1, wherein the catalyst is an amine catalyst a33, a liquid catalyst containing Triethylenediamine (TEDA) in an amount of 33% by mass.
7. The ultra-soft sponge of 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%, wherein the mass ratio of the copper chloride to the deionized water to the ammonia water is 0.7-1.4:10-20:10, and fully stirring to obtain a first solution; dissolving borax (Na 2B4O7 & 10H 2O) in deionized water, wherein the mass ratio of the borax to the deionized water is 0.6-1.2:10, 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 mass ratio of the first solution to the second solution at 1:1.1-1.3, preserving the temperature at 130-150 ℃ for 10-12h, 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 500-600 ℃, and sintering for 5-10h to obtain the porous copper borate powder with the particle size of 4-8 mu m.
8. An ultrasoft sponge as claimed in claim 1, wherein the preparation process of the thiolation treatment of the porous copper borate powder comprises:
4) Dispersing porous copper borate powder in absolute ethyl alcohol, heating to reflux for 6-10h, filtering, washing with water and drying to obtain activated porous copper borate powder; wherein the mass ratio of the porous copper borate powder to the absolute ethyl alcohol is 1:8-12;
5) Placing activated porous copper borate powder into deionized water, fully dispersing, adding 3-mercaptopropyl trimethoxy silane, heating to 60-80 ℃, preserving heat, stirring for 5-8h, filtering, washing with water, and drying to obtain mercaptoporous copper borate powder; wherein the mass ratio of the activated porous copper borate powder to the 3-mercaptopropyl trimethoxy silane to the deionized water is 1:0.2-0.4:10-20.
9. The ultra-soft sponge of claim 1, wherein the preparation method of the polyamide modified porous copper borate comprises the following steps:
s1, adding 2-allyl malonic acid into thionyl chloride, introducing nitrogen as a protective gas, uniformly stirring in an ice water bath, adding a few drops of catalyst pyridine, gradually heating to 75-85 ℃, carrying out heat preservation reflux reaction for 5-6h, and removing a solvent by rotary evaporation after the reaction is finished to obtain 2-allyl malonyl chloride;
wherein the mass ratio of the 2-allylmalonic acid to the pyridine to the thionyl chloride is 1.4-2.1:0.02-0.06:8-16;
s2, dissolving 2, 5-diaminopyridine into chloroform, introducing nitrogen as a protective gas, adding 2-allylmalonyl chloride, stirring uniformly, adding triethylamine, stirring at room temperature for 12-16h, and removing the solvent by rotary evaporation after the reaction is finished to obtain a polyamide compound containing double bonds and pyridine groups;
wherein the mass ratio of the 2, 5-diaminopyridine to the 2-allylmalonyl chloride to the triethylamine to the chloroform is 0.7-1.1:1.2-1.8:0.03-0.07:10-16;
s3, dispersing the mercapto-based porous copper borate powder in N, N-dimethylacetamide, adding the polyamide compound obtained in the step S2, adding benzoin dimethyl ether as an initiator under the protection of nitrogen, using an ultraviolet lamp to irradiate and stir for 15-30min, and filtering, washing with alcohol and drying after the reaction is finished to obtain the polyamide modified porous copper borate containing thioether bonds and pyridine groups;
wherein the mass ratio of the mercapto-porous copper borate powder to the polyamide compound to the N, N-dimethylacetamide is 2.1-4.2:1:20-40.
10. The method for preparing the ultra-soft sponge according to claim 1, comprising the steps of:
step 1, weighing polyether polyol, polymer polyol, polyamide modified porous copper borate, a pore opening agent, silicone oil, a catalyst, ethylene glycol and deionized water according to the amount, adding into a stirrer, and stirring at the speed of 600r/min at the temperature of 25-30 ℃ until the mixture is uniform;
and 2, adding the modified MDI into the mixed solution in the step 1, regulating the stirring speed to 1200r/min at 25-30 ℃, stirring for 10-20s, transferring into a preheated mold, preheating at 50-60 ℃, preserving heat for 5-10min, and demolding to obtain the ultra-soft sponge.
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