CN115181230B - Preparation method of segmented polyurethane elastomer - Google Patents
Preparation method of segmented polyurethane elastomer Download PDFInfo
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- CN115181230B CN115181230B CN202211000886.0A CN202211000886A CN115181230B CN 115181230 B CN115181230 B CN 115181230B CN 202211000886 A CN202211000886 A CN 202211000886A CN 115181230 B CN115181230 B CN 115181230B
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- 229920003225 polyurethane elastomer Polymers 0.000 title claims abstract description 37
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- 239000000945 filler Substances 0.000 claims abstract description 51
- 239000002131 composite material Substances 0.000 claims abstract description 45
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims abstract description 32
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims abstract description 32
- 238000006243 chemical reaction Methods 0.000 claims abstract description 29
- 238000003756 stirring Methods 0.000 claims abstract description 29
- 238000002156 mixing Methods 0.000 claims abstract description 25
- 239000006185 dispersion Substances 0.000 claims abstract description 24
- 239000002994 raw material Substances 0.000 claims abstract description 22
- 239000007788 liquid Substances 0.000 claims abstract description 19
- 239000004970 Chain extender Substances 0.000 claims abstract description 18
- ZFIVKAOQEXOYFY-UHFFFAOYSA-N Diepoxybutane Chemical compound C1OC1C1OC1 ZFIVKAOQEXOYFY-UHFFFAOYSA-N 0.000 claims abstract description 16
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000012948 isocyanate Substances 0.000 claims abstract description 16
- 150000002513 isocyanates Chemical class 0.000 claims abstract description 16
- 229920000909 polytetrahydrofuran Polymers 0.000 claims abstract description 16
- PTBDIHRZYDMNKB-UHFFFAOYSA-N 2,2-Bis(hydroxymethyl)propionic acid Chemical compound OCC(C)(CO)C(O)=O PTBDIHRZYDMNKB-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000003963 antioxidant agent Substances 0.000 claims abstract description 13
- 230000003078 antioxidant effect Effects 0.000 claims abstract description 13
- 238000007731 hot pressing Methods 0.000 claims abstract description 13
- 239000002904 solvent Substances 0.000 claims abstract description 13
- 229920001730 Moisture cure polyurethane Polymers 0.000 claims abstract description 12
- 238000001816 cooling Methods 0.000 claims abstract description 11
- 238000001704 evaporation Methods 0.000 claims abstract description 11
- 238000000034 method Methods 0.000 claims abstract description 11
- 239000000203 mixture Substances 0.000 claims abstract description 11
- 239000012299 nitrogen atmosphere Substances 0.000 claims abstract description 11
- 239000003054 catalyst Substances 0.000 claims abstract description 8
- 238000012661 block copolymerization Methods 0.000 claims abstract description 5
- 238000001125 extrusion Methods 0.000 claims abstract description 5
- 229920002678 cellulose Polymers 0.000 claims description 37
- 239000001913 cellulose Substances 0.000 claims description 37
- VYFYYTLLBUKUHU-UHFFFAOYSA-N dopamine Chemical compound NCCC1=CC=C(O)C(O)=C1 VYFYYTLLBUKUHU-UHFFFAOYSA-N 0.000 claims description 32
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 27
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 claims description 26
- 229910052901 montmorillonite Inorganic materials 0.000 claims description 26
- 229920001046 Nanocellulose Polymers 0.000 claims description 22
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical group OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 claims description 22
- PUVAFTRIIUSGLK-UHFFFAOYSA-M trimethyl(oxiran-2-ylmethyl)azanium;chloride Chemical compound [Cl-].C[N+](C)(C)CC1CO1 PUVAFTRIIUSGLK-UHFFFAOYSA-M 0.000 claims description 22
- 239000012670 alkaline solution Substances 0.000 claims description 18
- 239000008367 deionised water Substances 0.000 claims description 16
- 229910021641 deionized water Inorganic materials 0.000 claims description 16
- 229960003638 dopamine Drugs 0.000 claims description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 16
- TUSDEZXZIZRFGC-UHFFFAOYSA-N 1-O-galloyl-3,6-(R)-HHDP-beta-D-glucose Natural products OC1C(O2)COC(=O)C3=CC(O)=C(O)C(O)=C3C3=C(O)C(O)=C(O)C=C3C(=O)OC1C(O)C2OC(=O)C1=CC(O)=C(O)C(O)=C1 TUSDEZXZIZRFGC-UHFFFAOYSA-N 0.000 claims description 14
- 239000001263 FEMA 3042 Substances 0.000 claims description 14
- LRBQNJMCXXYXIU-PPKXGCFTSA-N Penta-digallate-beta-D-glucose Natural products OC1=C(O)C(O)=CC(C(=O)OC=2C(=C(O)C=C(C=2)C(=O)OC[C@@H]2[C@H]([C@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)O2)OC(=O)C=2C=C(OC(=O)C=3C=C(O)C(O)=C(O)C=3)C(O)=C(O)C=2)O)=C1 LRBQNJMCXXYXIU-PPKXGCFTSA-N 0.000 claims description 14
- LRBQNJMCXXYXIU-NRMVVENXSA-N tannic acid Chemical compound OC1=C(O)C(O)=CC(C(=O)OC=2C(=C(O)C=C(C=2)C(=O)OC[C@@H]2[C@H]([C@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)O2)OC(=O)C=2C=C(OC(=O)C=3C=C(O)C(O)=C(O)C=3)C(O)=C(O)C=2)O)=C1 LRBQNJMCXXYXIU-NRMVVENXSA-N 0.000 claims description 14
- 229940033123 tannic acid Drugs 0.000 claims description 14
- 235000015523 tannic acid Nutrition 0.000 claims description 14
- 229920002258 tannic acid Polymers 0.000 claims description 14
- 239000007853 buffer solution Substances 0.000 claims description 10
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 9
- 239000004202 carbamide Substances 0.000 claims description 9
- 238000001035 drying Methods 0.000 claims description 9
- 239000012535 impurity Substances 0.000 claims description 9
- 238000005406 washing Methods 0.000 claims description 9
- 239000000243 solution Substances 0.000 claims description 7
- 239000000155 melt Substances 0.000 claims description 2
- 239000007787 solid Substances 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 2
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 description 16
- 239000012975 dibutyltin dilaurate Substances 0.000 description 16
- 238000005303 weighing Methods 0.000 description 14
- 230000000052 comparative effect Effects 0.000 description 12
- 238000004132 cross linking Methods 0.000 description 8
- 230000008020 evaporation Effects 0.000 description 8
- 239000000463 material Substances 0.000 description 8
- 230000000844 anti-bacterial effect Effects 0.000 description 5
- 229920002635 polyurethane Polymers 0.000 description 5
- 239000004814 polyurethane Substances 0.000 description 5
- 238000005956 quaternization reaction Methods 0.000 description 4
- 239000004721 Polyphenylene oxide Substances 0.000 description 3
- 230000009471 action Effects 0.000 description 3
- 229920000728 polyester Polymers 0.000 description 3
- 229920000570 polyether Polymers 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- YCIMNLLNPGFGHC-UHFFFAOYSA-N catechol Chemical group OC1=CC=CC=C1O YCIMNLLNPGFGHC-UHFFFAOYSA-N 0.000 description 2
- 238000005341 cation exchange Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 229920005830 Polyurethane Foam Polymers 0.000 description 1
- 241000191967 Staphylococcus aureus Species 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000003242 anti bacterial agent Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 230000007123 defense Effects 0.000 description 1
- 230000004069 differentiation Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000012757 flame retardant agent Substances 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 239000011256 inorganic filler Substances 0.000 description 1
- 229910003475 inorganic filler Inorganic materials 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 238000009830 intercalation Methods 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 230000010355 oscillation Effects 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 239000011496 polyurethane foam Substances 0.000 description 1
- 238000004382 potting Methods 0.000 description 1
- 125000001453 quaternary ammonium group Chemical group 0.000 description 1
- 239000012744 reinforcing agent Substances 0.000 description 1
- 230000003014 reinforcing effect Effects 0.000 description 1
- 238000007142 ring opening reaction Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical group CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 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
- C08G18/08—Processes
- C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
- C08G18/12—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step using two or more compounds having active hydrogen in the first polymerisation step
-
- 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
- C08G18/34—Carboxylic acids; Esters thereof with monohydroxyl compounds
- C08G18/348—Hydroxycarboxylic acids
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
- C08G18/4854—Polyethers containing oxyalkylene groups having four carbon atoms in the alkylene group
-
- 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
- C08G18/6692—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/34
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
- C08L75/04—Polyurethanes
- C08L75/08—Polyurethanes from polyethers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/02—Flame or fire retardant/resistant
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Polyurethanes Or Polyureas (AREA)
Abstract
The invention discloses a preparation method of a block copolymerization polyurethane elastomer. The method comprises the following steps: step 1: under the nitrogen atmosphere, sequentially adding isocyanate, polytetrahydrofuran ether glycol, dimethylolpropionic acid and a catalyst into a reaction kettle, and reacting for 2-4 hours at the temperature of 75-85 ℃; when the-NCO content is 5% -8%, obtaining polyurethane prepolymer; adding a chain extender, adding a catalyst, and continuing the reaction for 4-5 hours; cooling to room temperature, sequentially adding the composite filler dispersion liquid and butadiene dioxide, and stirring at a high speed for 1-2 hours; evaporating to remove the solvent to obtain a prepolymerization raw material; step 2: mixing the prepolymerization raw material with an antioxidant, placing the mixture in a double-screw extruder, carrying out melt blending and extrusion; and hot-pressing by a vulcanizing machine to obtain the polyurethane elastomer.
Description
Technical Field
The invention relates to the technical field of polyurethane elastomers, in particular to a preparation method of a block copolymerization polyurethane elastomer.
Background
Polyurethane elastomer is a block linear polymer material which is between rubber and plastic and can be heated and plasticized, has the advantages of wider hardness range, pouring, potting, good shock absorption and the like, and is widely used in a plurality of industries such as electronic devices, medical treatment, national defense, food and the like.
Common polyurethane elastomers include polyether and polyester; compared with polyester type, polyether polyurethane elastomer has good rebound performance, but the mechanical property is weaker than that of polyester polyurethane elastomer; therefore, fillers are often introduced to increase the stiffness of the structure and to improve its mechanical properties. Typically a single inorganic filler, which has poor dispersibility in the polymer and interfacial compatibility with the polymer; due to the introduction, the toughness is reduced, and the impact resistance is reduced. Also, in order to increase the functionality of polyurethane elastomers, antibacterial and flame retardant agents are often incorporated, which also present dispersibility and compatibility issues. On the other hand, cast polyurethane has a lower degree of crosslinking than a kneaded polyurethane elastomer, resulting in poor mechanical properties. The differentiation of various properties reduces the universality of polyurethane elastomers.
In summary, solving the above problems, it is of great importance to prepare a block copolymerized polyurethane elastomer.
Disclosure of Invention
The invention aims to provide a preparation method of a block copolymerized polyurethane elastomer, which aims to solve the problems in the background technology.
In order to solve the technical problems, the invention provides the following technical scheme:
a method for preparing a block copolymerized polyurethane elastomer, comprising the following steps:
step 1: under the nitrogen atmosphere, sequentially adding isocyanate, polytetrahydrofuran ether glycol, dimethylolpropionic acid and a catalyst into a reaction kettle, and reacting for 2-4 hours at the temperature of 75-85 ℃; when the-NCO content is 5% -8%, obtaining polyurethane prepolymer; adding a chain extender, adding a catalyst, and continuing the reaction for 4-5 hours; cooling to room temperature, sequentially adding the composite filler dispersion liquid and butadiene dioxide, and stirring at a high speed for 1-2 hours; evaporating to remove the solvent to obtain a prepolymerization raw material;
step 2: mixing the prepolymerization raw material with an antioxidant, placing the mixture in a double-screw extruder, carrying out melt blending and extrusion; and hot-pressing by a vulcanizing machine to obtain the polyurethane elastomer.
Further, the raw materials of the prepolymerization raw material comprise the following components: 95-105 parts of isocyanate, 50-55 parts of polytetrahydrofuran ether glycol, 9-10 parts of dimethylolpropionic acid, 2-3 parts of catalyst, 15-25 parts of chain extender, 10-12 parts of composite filler and 3-5 parts of butadiene dioxide.
Further, the chain extender is 1, 4-butanediol and tannic acid with a mass ratio of 1:3.
Further, in the step 2, the antioxidant accounts for 1-2wt% of the mass of the prepolymerization raw material; the melt blending temperature is 175-185 ℃ and the extrusion temperature is 185-195 ℃; the hot pressing temperature is 135-145 ℃, the pressure is 8-12 mpa, and the time is 30-50 minutes.
Further, the concentration of the composite filler dispersion liquid is 5-6wt%, the solvent is a dopamine buffer solution, and the concentration of the dopamine is 2-5 mg/mL.
Further, the preparation method of the composite filler comprises the following steps: dispersing montmorillonite in deionized water by ultrasonic, adding quaternized cellulose, stirring for 5-8 hours, washing and drying to obtain composite filler; wherein the mass ratio of montmorillonite to quaternized cellulose is 2 (0.8-1.2).
Further, the preparation method of the quaternized cellulose comprises the following steps: precooling alkaline solution to-10 to-5 ℃, adding nanocellulose, and dissolving for 1 hour; adding 2, 3-epoxypropyl trimethyl ammonium chloride, stirring uniformly, and centrifuging to remove impurities; and carrying out homogeneous reaction for 1-2 days at room temperature to obtain the quaternized cellulose.
Further, the alkaline solution is a solution of sodium hydroxide and urea in a mass ratio of 7:13, and the solid content is 20wt%; the mass ratio of the nanocellulose to the 2, 3-epoxypropyl trimethyl ammonium chloride is 1 (0.2-0.3).
Further, the polyurethane elastomer is prepared by a preparation method of the block copolymerization polyurethane elastomer.
In the technical scheme, the composite filler is introduced, the dopamine solution and polyurethane are utilized for pre-crosslinking, and then the polyurethane is placed in a double-screw extruder for mixing and molding, so that the crosslinking property is enhanced. Due to the introduction of the composite filler, the mechanical property, flame retardance and antibacterial property of the polyurethane elasticity are effectively improved on the basis of ensuring toughness.
(1) In the scheme, polytetrahydrofuran ether glycol and isocyanate are used as main raw materials to prepare the polyether polyurethane elastomer, and dimethylolpropionic acid is generally used as a chain extender, and in the scheme, one of the polytetrahydrofuran ether glycol and the isocyanate is introduced with the main raw material, and the dihydroxyl is introduced into a long chain of the polyurethane prepolymer, so that carboxyl exists in a long chain structure, and the subsequent crosslinking degree is promoted. 1, 4-butanediol and tannic acid are used as chain extenders, wherein the introduction of tannic acid increases antibacterial property, and catechol structure is introduced; can be well pre-crosslinked with the composite filler in the dopamine buffer solution, and synergistically improves the antibacterial property and the mechanical property. On the other hand, the composite filler is introduced together with butadiene dioxide for the purpose of: the method utilizes the ring opening of butadiene dioxide to effectively improve the reaction crosslinking property of the composite filler, ensures the strength improvement, has a certain toughening effect, and effectively balances the rigidity and toughness of the polyurethane foam.
(2) The composite filler is prepared by quaternizing (cationizing) nanocellulose, then generating cation exchange reaction with montmorillonite, and intercalating in montmorillonite to improve dispersibility and compatibility of montmorillonite. At the same time, cellulose itself is also a reinforcing agent, so that a synergistic effect is generated after the cellulose is compounded with montmorillonite. The amount of nanocellulose and 2, 3-epoxypropyl trimethyl ammonium chloride introduced into the quaternized cellulose is limited. Because the 2, 3-epoxypropyl trimethyl ammonium chloride content represents the quaternization degree of the quaternized cellulose, and the relationship between the quaternization degree and the cation degree influences the ion exchange process with montmorillonite, if the quaternization degree is too high, the cation exchange process is saturated faster, so that the grafting amount of the quaternized cellulose is reduced, and the filler reinforcing property is reduced.
On the other hand, the composite filler is placed in a dopamine hydrochloric acid solution, and the dopamine adsorbed on the surface is self-polymerized with catechol structure of tannic acid serving as a chain extender in polyurethane, so that pre-crosslinking is formed, and the pre-crosslinking is polymerized in situ in a polyurethane elastomer, so that the toughness and interface interaction are improved, and the mechanical property is effectively improved.
Detailed Description
The following description of the technical solutions in the embodiments of the present invention will be clear and complete, and it is obvious that the described embodiments are only some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
In the examples below, the isocyanate is 2, 4-toluene diisocyanate; the molecular weight of polytetrahydrofuran ether glycol is 2000; the diameter of the nanocellulose is 4-10 nm, and the nanocellulose is purchased from Qihong technology.
Example 1:
step 1: (1) Weighing nanocellulose and 2, 3-epoxypropyl trimethyl ammonium chloride in a mass ratio of 1:0.25 for later use; dispersing sodium hydroxide and urea in a mass ratio of 7:13 in deionized water to obtain an alkaline solution with a concentration of 20%; precooling alkaline solution to-10 ℃, adding nano cellulose, and dissolving for 1 hour; adding 2, 3-epoxypropyl trimethyl ammonium chloride, stirring uniformly, and centrifuging to remove impurities; and carrying out homogeneous reaction for 1.5 days at room temperature to obtain the quaternized cellulose.
Weighing montmorillonite and quaternized cellulose with the mass ratio of 2:1 for standby; dispersing montmorillonite in deionized water by ultrasonic to obtain a dispersion liquid with the weight percent of 5, adding quaternized cellulose, stirring for 6 hours, washing and drying to obtain the composite filler.
(2) Dispersing 10 parts of composite filler in 4mg/mL dopamine buffer solution to obtain 5wt% composite filler dispersion for later use; under the nitrogen atmosphere, sequentially adding 100 parts of isocyanate, 53 parts of polytetrahydrofuran ether glycol, 10 parts of dimethylolpropionic acid and 2 parts of dibutyltin dilaurate into a reaction kettle, and reacting for 4 hours at the temperature of 80 ℃; when the-NCO content is 6%, obtaining polyurethane prepolymer; adding 20 parts of chain extender (1, 4-butanediol and tannic acid with the mass ratio of 1:3), adding 1 part of dibutyltin dilaurate, and continuously reacting for 4 hours; cooling to room temperature, sequentially adding the composite filler dispersion liquid and 4 parts of butadiene dioxide, and stirring at a high speed of 1200rpm for 1.5 hours; the solvent was removed by evaporation to give a prepolymerized material.
Step 2: mixing 100 parts of a prepolymerization raw material with 2 parts of an antioxidant in parts by weight, placing the mixture in a double-screw extruder, carrying out melt blending at the set temperature of 180 ℃ and extruding at the set temperature of 190 ℃; and (3) setting the hot pressing temperature to 140 ℃ and the pressure to 10MPa through a vulcanizing machine, and vulcanizing for 40 minutes to obtain the polyurethane elastomer.
Example 2:
step 1: (1) Weighing nanocellulose and 2, 3-epoxypropyl trimethyl ammonium chloride in a mass ratio of 1:0.2 for later use; dispersing sodium hydroxide and urea in a mass ratio of 7:13 in deionized water to obtain an alkaline solution with a concentration of 20%; precooling alkaline solution to-10 ℃, adding nano cellulose, and dissolving for 1 hour; adding 2, 3-epoxypropyl trimethyl ammonium chloride, stirring uniformly, and centrifuging to remove impurities; and carrying out homogeneous reaction for 1 day at room temperature to obtain the quaternized cellulose.
Weighing montmorillonite and quaternized cellulose with a mass ratio of 2:0.8 for standby; dispersing montmorillonite in deionized water by ultrasonic to obtain a dispersion liquid with the weight percent of 5, adding quaternized cellulose, stirring for 5 hours, washing and drying to obtain the composite filler.
(2) Dispersing 10 parts of composite filler in 5mg/mL dopamine buffer solution to obtain 5wt% composite filler dispersion for later use; under the nitrogen atmosphere, sequentially adding 95 parts of isocyanate, 50 parts of polytetrahydrofuran ether glycol, 10 parts of dimethylolpropionic acid and 1 part of dibutyltin dilaurate into a reaction kettle, and reacting for 4 hours at the temperature of 75 ℃; when the-NCO content is 8%, obtaining polyurethane prepolymer; 15 parts of chain extender (1, 4-butanediol and tannic acid with the mass ratio of 1:3) are added, 1 part of dibutyl tin dilaurate is added, and the reaction is continued for 4 hours; cooling to room temperature, sequentially adding the composite filler dispersion liquid and 3 parts of butadiene dioxide, and stirring at a high speed of 1200rpm for 2 hours; the solvent was removed by evaporation to give a prepolymerized material.
Step 2: mixing 100 parts of a prepolymerization raw material with 1 part of an antioxidant in parts by weight, placing the mixture in a double-screw extruder, carrying out melt blending at the set temperature of 175 ℃ and extruding at the set temperature of 185 ℃; and (3) setting the hot pressing temperature to be 135 ℃ and the pressure to be 12MPa through a vulcanizing machine, and vulcanizing for 30 minutes to obtain the polyurethane elastomer.
Example 3:
step 1: (1) Weighing nanocellulose and 2, 3-epoxypropyl trimethyl ammonium chloride in a mass ratio of 1:0.3 for later use; dispersing sodium hydroxide and urea in a mass ratio of 7:13 in deionized water to obtain an alkaline solution with a concentration of 20%; precooling alkaline solution to-5 ℃, adding nano cellulose, and dissolving for 1 hour; adding 2, 3-epoxypropyl trimethyl ammonium chloride, stirring uniformly, and centrifuging to remove impurities; and carrying out homogeneous reaction for 2 days at room temperature to obtain the quaternized cellulose.
Weighing montmorillonite and quaternized cellulose with the mass ratio of 2:1.2 for standby; dispersing montmorillonite in deionized water by ultrasonic to obtain a dispersion liquid with the weight percent of 5, adding the quaternary ammonium cellulose, stirring for 8 hours, washing and drying to obtain the composite filler.
(2) Dispersing 12 parts of composite filler in a dopamine buffer solution with the concentration of 2mg/mL according to parts by weight to obtain a composite filler dispersion liquid with the concentration of 6wt% for later use; under the nitrogen atmosphere, 105 parts of isocyanate, 55 parts of polytetrahydrofuran ether glycol, 9 parts of dimethylolpropionic acid and 2 parts of dibutyltin dilaurate are sequentially added into a reaction kettle, and the temperature is set to be 85 ℃ for reaction for 2 hours; when the-NCO content is 5%, obtaining polyurethane prepolymer; 25 parts of chain extender (1, 4-butanediol and tannic acid with the mass ratio of 1:3) are added, 1 part of dibutyl tin dilaurate is added, and the reaction is continued for 5 hours; cooling to room temperature, sequentially adding the composite filler dispersion liquid and 5 parts of butadiene dioxide, and stirring at a high speed of 1200rpm for 1 hour; the solvent was removed by evaporation to give a prepolymerized material.
Step 2: mixing 100 parts of a prepolymerization raw material with 2 parts of an antioxidant in parts by weight, placing the mixture in a double-screw extruder, carrying out melt blending at the setting temperature of 185 ℃, and extruding at the setting temperature of 195 ℃; and (3) setting the hot pressing temperature to 145 ℃ and the pressure to 8MPa through a vulcanizing machine, and vulcanizing for 30 minutes to obtain the polyurethane elastomer.
Comparative example 1: tannic acid was not introduced as a chain extender, and the rest was the same as example 1;
step 1: (1) Weighing nanocellulose and 2, 3-epoxypropyl trimethyl ammonium chloride in a mass ratio of 1:0.25 for later use; dispersing sodium hydroxide and urea in a mass ratio of 7:13 in deionized water to obtain an alkaline solution with a concentration of 20%; precooling alkaline solution to-10 ℃, adding nano cellulose, and dissolving for 1 hour; adding 2, 3-epoxypropyl trimethyl ammonium chloride, stirring uniformly, and centrifuging to remove impurities; and carrying out homogeneous reaction for 1.5 days at room temperature to obtain the quaternized cellulose.
Weighing montmorillonite and quaternized cellulose with the mass ratio of 2:1 for standby; dispersing montmorillonite in deionized water by ultrasonic to obtain a dispersion liquid with the weight percent of 5, adding quaternized cellulose, stirring for 6 hours, washing and drying to obtain the composite filler.
(2) Dispersing 10 parts of composite filler in 4mg/mL dopamine buffer solution to obtain 5wt% composite filler dispersion for later use; under the nitrogen atmosphere, sequentially adding 100 parts of isocyanate, 53 parts of polytetrahydrofuran ether glycol, 10 parts of dimethylolpropionic acid and 2 parts of dibutyltin dilaurate into a reaction kettle, and reacting for 4 hours at the temperature of 80 ℃; when the-NCO content is 6%, obtaining polyurethane prepolymer; adding 20 parts of 1, 4-butanediol, adding 1 part of dibutyltin dilaurate, and continuing to react for 4 hours; cooling to room temperature, sequentially adding the composite filler dispersion liquid and 4 parts of butadiene dioxide, and stirring at a high speed of 1200rpm for 1.5 hours; the solvent was removed by evaporation to give a prepolymerized material.
Step 2: mixing 100 parts of a prepolymerization raw material with 2 parts of an antioxidant in parts by weight, placing the mixture in a double-screw extruder, carrying out melt blending at the set temperature of 180 ℃ and extruding at the set temperature of 190 ℃; and (3) setting the hot pressing temperature to 140 ℃ and the pressure to 10MPa through a vulcanizing machine, and vulcanizing for 40 minutes to obtain the polyurethane elastomer.
Comparative example 2: the composite filler was directly added, and the rest was the same as in example 1;
step 1: (1) Weighing nanocellulose and 2, 3-epoxypropyl trimethyl ammonium chloride in a mass ratio of 1:0.25 for later use; dispersing sodium hydroxide and urea in a mass ratio of 7:13 in deionized water to obtain an alkaline solution with a concentration of 20%; precooling alkaline solution to-10 ℃, adding nano cellulose, and dissolving for 1 hour; adding 2, 3-epoxypropyl trimethyl ammonium chloride, stirring uniformly, and centrifuging to remove impurities; and carrying out homogeneous reaction for 1.5 days at room temperature to obtain the quaternized cellulose.
Weighing montmorillonite and quaternized cellulose with the mass ratio of 2:1 for standby; dispersing montmorillonite in deionized water by ultrasonic to obtain a dispersion liquid with the weight percent of 5, adding quaternized cellulose, stirring for 6 hours, washing and drying to obtain the composite filler.
(2) According to parts by weight, 100 parts of isocyanate, 53 parts of polytetrahydrofuran ether glycol, 10 parts of dimethylolpropionic acid and 2 parts of dibutyltin dilaurate are sequentially added into a reaction kettle in a nitrogen atmosphere, and the temperature is set to be 80 ℃ for reaction for 4 hours; when the-NCO content is 6%, obtaining polyurethane prepolymer; adding 20 parts of chain extender (1, 4-butanediol and tannic acid with the mass ratio of 1:3), adding 1 part of dibutyltin dilaurate, and continuously reacting for 4 hours; cooling to room temperature, sequentially adding 10 parts of composite filler and 4 parts of butadiene dioxide, and stirring at a high speed of 1200rpm for 1.5 hours; the solvent was removed by evaporation to give a prepolymerized material.
Step 2: mixing 100 parts of a prepolymerization raw material with 2 parts of an antioxidant in parts by weight, placing the mixture in a double-screw extruder, carrying out melt blending at the set temperature of 180 ℃ and extruding at the set temperature of 190 ℃; and (3) setting the hot pressing temperature to 140 ℃ and the pressure to 10MPa through a vulcanizing machine, and vulcanizing for 40 minutes to obtain the polyurethane elastomer.
Comparative example 3: butadiene dioxide was not added, and the rest was the same as in example 1;
step 1: (1) Weighing nanocellulose and 2, 3-epoxypropyl trimethyl ammonium chloride in a mass ratio of 1:0.25 for later use; dispersing sodium hydroxide and urea in a mass ratio of 7:13 in deionized water to obtain an alkaline solution with a concentration of 20%; precooling alkaline solution to-10 ℃, adding nano cellulose, and dissolving for 1 hour; adding 2, 3-epoxypropyl trimethyl ammonium chloride, stirring uniformly, and centrifuging to remove impurities; and carrying out homogeneous reaction for 1.5 days at room temperature to obtain the quaternized cellulose.
Weighing montmorillonite and quaternized cellulose with the mass ratio of 2:1 for standby; dispersing montmorillonite in deionized water by ultrasonic to obtain a dispersion liquid with the weight percent of 5, adding quaternized cellulose, stirring for 6 hours, washing and drying to obtain the composite filler.
(2) Dispersing 10 parts of composite filler in 4mg/mL dopamine buffer solution to obtain 5wt% composite filler dispersion for later use; under the nitrogen atmosphere, sequentially adding 100 parts of isocyanate, 53 parts of polytetrahydrofuran ether glycol, 10 parts of dimethylolpropionic acid and 2 parts of dibutyltin dilaurate into a reaction kettle, and reacting for 4 hours at the temperature of 80 ℃; when the-NCO content is 6%, obtaining polyurethane prepolymer; adding 20 parts of chain extender (1, 4-butanediol and tannic acid with the mass ratio of 1:3), adding 1 part of dibutyltin dilaurate, and continuously reacting for 4 hours; cooling to room temperature, sequentially adding the composite filler dispersion liquid, and stirring at a high speed of 1200rpm for 1.5 hours; the solvent was removed by evaporation to give a prepolymerized material.
Step 2: mixing 100 parts of a prepolymerization raw material with 2 parts of an antioxidant in parts by weight, placing the mixture in a double-screw extruder, carrying out melt blending at the set temperature of 180 ℃ and extruding at the set temperature of 190 ℃; and (3) setting the hot pressing temperature to 140 ℃ and the pressure to 10MPa through a vulcanizing machine, and vulcanizing for 40 minutes to obtain the polyurethane elastomer.
Comparative example 4: montmorillonite was used as a filler, and the rest was the same as in example 1;
step 1: according to parts by weight, dispersing 10 parts of montmorillonite in 4mg/mL dopamine buffer solution to obtain 5wt% filler solution for later use; under the nitrogen atmosphere, sequentially adding 100 parts of isocyanate, 53 parts of polytetrahydrofuran ether glycol, 10 parts of dimethylolpropionic acid and 2 parts of dibutyltin dilaurate into a reaction kettle, and reacting for 4 hours at the temperature of 80 ℃; when the-NCO content is 6%, obtaining polyurethane prepolymer; adding 20 parts of chain extender (1, 4-butanediol and tannic acid with the mass ratio of 1:3), adding 1 part of dibutyltin dilaurate, and continuously reacting for 4 hours; cooling to room temperature, sequentially adding the filler solution and 4 parts of butadiene dioxide, and stirring at a high speed of 1200rpm for 1.5 hours; the solvent was removed by evaporation to give a prepolymerized material.
Step 2: mixing 100 parts of a prepolymerization raw material with 2 parts of an antioxidant in parts by weight, placing the mixture in a double-screw extruder, carrying out melt blending at the set temperature of 180 ℃ and extruding at the set temperature of 190 ℃; and (3) setting the hot pressing temperature to 140 ℃ and the pressure to 10MPa through a vulcanizing machine, and vulcanizing for 40 minutes to obtain the polyurethane elastomer.
Comparative example 5: in the preparation process of the quaternized cellulose, the mass ratio of the 2, 3-epoxypropyl trimethyl ammonium chloride is increased, and the rest is the same as that of the example 1;
step 1: (1) Weighing nanocellulose and 2, 3-epoxypropyl trimethyl ammonium chloride in a mass ratio of 1:0.5 for later use; dispersing sodium hydroxide and urea in a mass ratio of 7:13 in deionized water to obtain an alkaline solution with a concentration of 20%; precooling alkaline solution to-10 ℃, adding nano cellulose, and dissolving for 1 hour; adding 2, 3-epoxypropyl trimethyl ammonium chloride, stirring uniformly, and centrifuging to remove impurities; and carrying out homogeneous reaction for 1.5 days at room temperature to obtain the quaternized cellulose.
Weighing montmorillonite and quaternized cellulose with the mass ratio of 2:1 for standby; dispersing montmorillonite in deionized water by ultrasonic to obtain a dispersion liquid with the weight percent of 5, adding quaternized cellulose, stirring for 6 hours, washing and drying to obtain the composite filler.
(2) Dispersing 10 parts of composite filler in 4mg/mL dopamine buffer solution to obtain 5wt% composite filler dispersion for later use; under the nitrogen atmosphere, sequentially adding 100 parts of isocyanate, 53 parts of polytetrahydrofuran ether glycol, 10 parts of dimethylolpropionic acid and 2 parts of dibutyltin dilaurate into a reaction kettle, and reacting for 4 hours at the temperature of 80 ℃; when the-NCO content is 6%, obtaining polyurethane prepolymer; adding 20 parts of chain extender (1, 4-butanediol and tannic acid with the mass ratio of 1:3), adding 1 part of dibutyltin dilaurate, and continuously reacting for 4 hours; cooling to room temperature, sequentially adding the composite filler dispersion liquid and 4 parts of butadiene dioxide, and stirring at a high speed of 1200rpm for 1.5 hours; the solvent was removed by evaporation to give a prepolymerized material.
Step 2: mixing 100 parts of a prepolymerization raw material with 2 parts of an antioxidant in parts by weight, placing the mixture in a double-screw extruder, carrying out melt blending at the set temperature of 180 ℃ and extruding at the set temperature of 190 ℃; and (3) setting the hot pressing temperature to 140 ℃ and the pressure to 10MPa through a vulcanizing machine, and vulcanizing for 40 minutes to obtain the polyurethane elastomer.
Experiment: the polyurethane elastomers prepared in examples and comparative examples were subjected to performance testing, and tensile strength and elongation at break were measured using a mechanical property tester; the inhibition of staphylococcus aureus was measured using the oscillation method and the limiting oxygen index method was used to characterize flame retardancy. The results obtained are shown in the following table:
conclusion: as can be seen from the data of examples 1-3, the polyurethane elastomer prepared in the scheme has excellent tensile strength and elongation at break, and simultaneously has good antibacterial rate and flame retardance. In comparative examples 1 to 2, in comparative example 1, since tannic acid was introduced, and in comparative example 2, dopamine was not introduced, the pre-crosslinking property was lowered, and the mechanical properties were lowered. In comparative example 3, since butadiene dioxide was not introduced, elongation at break was lowered. In comparative example 4, the mechanical properties were reduced by using montmorillonite alone as a filler; in comparative example 5, the degree of quaternization of cellulose was increased due to the addition of 2, 3-epoxypropyl trimethyl ammonium chloride, and the grafting ratio of the quaternized cellulose was reduced, resulting in a decrease in performance.
It is noted that relational terms such as first and second, and the like are used solely to distinguish one entity or action from another entity or action without necessarily requiring or implying any actual such relationship or order between such entities or actions. Moreover, the terms "comprises," "comprising," or any other variation thereof, are intended to cover a non-exclusive inclusion, such that a process, method, article, or apparatus that comprises a list of elements does not include only those elements but may include other elements not expressly listed or inherent to such process, method, article, or apparatus.
Finally, it should be noted that: the foregoing description is only a preferred embodiment of the present invention, and the present invention is not limited thereto, but it is to be understood that modifications and equivalents of some of the technical features described in the foregoing embodiments may be made by those skilled in the art, although the present invention has been described in detail with reference to the foregoing embodiments. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (4)
1. A preparation method of a block copolymerization polyurethane elastomer is characterized in that: the method comprises the following steps:
step 1: under the nitrogen atmosphere, sequentially adding isocyanate, polytetrahydrofuran ether glycol, dimethylolpropionic acid and a catalyst into a reaction kettle, and reacting for 2-4 hours at the temperature of 75-85 ℃; when the-NCO content is 5% -8%, obtaining polyurethane prepolymer; adding a chain extender, adding a catalyst, and continuing the reaction for 4-5 hours; cooling to room temperature, sequentially adding the composite filler dispersion liquid and butadiene dioxide, and stirring at a high speed for 1-2 hours; evaporating to remove the solvent to obtain a prepolymerization raw material;
step 2: mixing the prepolymerization raw material with an antioxidant, placing the mixture in a double-screw extruder, carrying out melt blending and extrusion; hot-pressing by a vulcanizing machine to obtain a polyurethane elastomer;
the raw materials of the prepolymerization raw material comprise the following components: 95-105 parts of isocyanate, 50-55 parts of polytetrahydrofuran ether glycol, 9-10 parts of dimethylolpropionic acid, 2-3 parts of catalyst, 15-25 parts of chain extender, 10-12 parts of composite filler and 3-5 parts of butadiene dioxide;
the chain extender is 1, 4-butanediol and tannic acid with the mass ratio of 1:3;
the concentration of the composite filler dispersion liquid is 5-6wt%, the solvent is a dopamine buffer solution, and the concentration of dopamine is 2-5 mg/mL;
the preparation method of the composite filler comprises the following steps: dispersing montmorillonite in deionized water by ultrasonic, adding quaternized cellulose, stirring for 5-8 hours, washing and drying to obtain composite filler; wherein the mass ratio of montmorillonite to quaternized cellulose is 2 (0.8-1.2);
the preparation method of the quaternized cellulose comprises the following steps: precooling alkaline solution to-10 to-5 ℃, adding nanocellulose, and dissolving for 1 hour; adding 2, 3-epoxypropyl trimethyl ammonium chloride, stirring uniformly, and centrifuging to remove impurities; carrying out homogeneous reaction for 1-2 days at room temperature to obtain quaternized cellulose; the mass ratio of the nanocellulose to the 2, 3-epoxypropyl trimethyl ammonium chloride is 1 (0.2-0.3).
2. The method for producing a block copolymerized polyurethane elastomer according to claim 1, characterized in that: in the step 2, the antioxidant accounts for 1-2wt% of the mass of the prepolymerization raw material; the melt blending temperature is 175-185 ℃ and the extrusion temperature is 185-195 ℃; the hot pressing temperature is 135-145 ℃, the pressure is 8-12 MPa, and the time is 30-50 minutes.
3. The method for producing a block copolymerized polyurethane elastomer according to claim 1, characterized in that: the alkaline solution is a solution of sodium hydroxide and urea with a mass ratio of 7:13, and the solid content is 20wt%.
4. The polyurethane elastomer prepared by the preparation method of the block copolymerization polyurethane elastomer according to any one of claims 1-3.
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