CN110938187A - Polyurethane slow-resilience sponge and preparation method thereof - Google Patents
Polyurethane slow-resilience sponge and preparation method thereof Download PDFInfo
- Publication number
- CN110938187A CN110938187A CN201911246824.6A CN201911246824A CN110938187A CN 110938187 A CN110938187 A CN 110938187A CN 201911246824 A CN201911246824 A CN 201911246824A CN 110938187 A CN110938187 A CN 110938187A
- Authority
- CN
- China
- Prior art keywords
- parts
- antibacterial agent
- silver
- sponge
- polyurethane
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
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
- C08G18/28—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
- C08G18/6677—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 having at least three hydroxy 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
- C08G18/4804—Two or more polyethers of different physical or chemical nature
-
- 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
- C08G18/50—Polyethers having heteroatoms other than oxygen
- C08G18/5096—Polyethers having heteroatoms other than oxygen containing silicon
-
- 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
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
- C08K3/08—Metals
-
- 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
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/32—Phosphorus-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
- 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
-
- 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
- C08K9/12—Adsorbed ingredients, e.g. ingredients on carriers
-
- 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
-
- 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
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
- C08K3/08—Metals
- C08K2003/0806—Silver
-
- 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
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/32—Phosphorus-containing compounds
- C08K2003/321—Phosphates
- C08K2003/328—Phosphates of heavy metals
-
- 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
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
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 polyurethane slow-rebound sponge and a preparation method thereof, relating to the technical field of sponge products, and the technical scheme is that the polyurethane slow-rebound sponge comprises the following components in parts by weight: 25-30 parts of epoxy polyether polyol, 8-10 parts of slow rebound polyether polyol, 1-3 parts of a cell opener, 0.2-0.4 part of a foam stabilizer, 0.2-0.4 part of a tin catalyst, 0.6-1.0 part of a chain extender, 0.2-0.4 part of a cross-linking agent, 1-2 parts of water, 0.2-0.4 part of an antibacterial agent and 10-15 parts of toluene diisocyanate; the antibacterial agent comprises the following components in parts by weight: 10 parts of nano zirconium phosphate silver-carrying antibacterial agent and 10-30 parts of alumina silver antibacterial agent. The antibacterial agent is obtained by compounding the nano zirconium phosphate silver-carrying antibacterial agent and the alumina silver antibacterial agent, so that the antibacterial performance of the polyurethane foam is improved while the mechanical performance of the polyurethane foam is not influenced.
Description
Technical Field
The invention relates to the technical field of sponge products, in particular to a polyurethane slow-rebound sponge and a preparation method thereof.
Background
The polyurethane slow-rebound sponge is also called memory sponge, has the characteristics of viscosity and elasticity, and can slowly recover the original shape after being deformed by external force; the polyurethane slow-rebound sponge has the characteristics of temperature sensing and viscous elasticity. In the prior art, the patent application publication No. CN102643404A discloses a slow-rebound polyether polyurethane sponge, which comprises 20-85 parts by weight of first polyol, 10-90 parts by weight of second polyol, 8-30 parts by weight of MDI isocyanate, a foaming agent, a catalyst, a surfactant, a flame retardant and 0.2-0.8 part by weight of a silicone rubber toughening agent; the first polyol is a polymer of ethylene glycol and propylene glycol, the functionality is 3, and the hydroxyl value is 45-99 mgKOH/g; the second polyol is a copolymer polyol of trimethylolpropane and butylene oxide, the EO content is more than 60 percent, and the hydroxyl value is 3-22 mgKOH/g.
The polyurethane slow-rebound sponge has good comfort and better soft touch, so the polyurethane slow-rebound sponge is widely applied to household products such as pillows, sleeping earplugs, mattresses, back cushions, sofas and the like; due to the characteristic of more foam holes of the polyurethane foam material, in the using process, the substances such as grease, scurf and the like generated by human skin are adhered to easily breed bacteria, so the polyurethane foam material needs to be subjected to antibacterial treatment; the antibacterial agent is generally divided into an organic antibacterial agent, an inorganic antibacterial agent and a natural antibacterial agent, wherein the inorganic antibacterial agent generally has good antibacterial property and antibacterial durability, but the antibacterial agent is poor in compatibility with a polymer matrix after being added, so that the stability and uniformity of foam cells in the polyurethane foaming process can be influenced; the compatibility of the organic antibacterial agent and a polymer matrix is improved, but the problems of poor heat resistance, easy hydrolysis and short effective period still exist; the natural antibacterial agent has the advantages of high safety and good biocompatibility, but the natural antibacterial agent also has the problems of poor heat resistance and short effective period. Therefore, how to improve the antibacterial performance of the polyurethane slow-rebound sponge without influencing the mechanical performance of the polyurethane slow-rebound sponge is a problem to be solved.
Disclosure of Invention
The invention aims to provide a polyurethane slow-recovery sponge, which is an antibacterial agent obtained by compounding a nano zirconium phosphate silver-loaded antibacterial agent and an alumina silver antibacterial agent, and improves the antibacterial performance of polyurethane foam while not influencing the mechanical performance of the polyurethane foam.
The technical purpose of the invention is realized by the following technical scheme:
the polyurethane slow-rebound sponge comprises the following components in parts by weight: 25-30 parts of epoxy polyether polyol, 8-10 parts of slow rebound polyether polyol, 1-3 parts of a cell opener, 0.2-0.4 part of a foam stabilizer, 0.2-0.4 part of a tin catalyst, 0.6-1.0 part of a chain extender, 0.2-0.4 part of a cross-linking agent, 1-2 parts of water, 0.2-0.4 part of an antibacterial agent and 10-15 parts of toluene diisocyanate; the antibacterial agent comprises the following components in parts by weight: 10 parts of nano zirconium phosphate silver-carrying antibacterial agent and 10-30 parts of alumina silver antibacterial agent.
By adopting the technical scheme, the nano zirconium phosphate silver-loaded antibacterial agent is a silver inorganic antibacterial agent taking zirconium phosphate as a carrier, has a broad-spectrum bactericidal effect and has better compatibility with a polymer; the antibacterial agent obtained by compounding the nano zirconium phosphate silver-carrying antibacterial agent and the alumina silver antibacterial agent has good compatibility with a polyurethane material, can improve the thermal stability and the regularity of foam pores of the polyurethane foam, and improves the antibacterial performance of the polyurethane foam while not influencing the mechanical performance of the polyurethane foam.
Further, the foam stabilizer is a silicone surfactant.
By adopting the technical scheme, the silicone surfactant is a polysiloxane-polyalkylene oxide block copolymer, has wide processing latitude, can reduce the cracking tendency of foam, and can ensure that the prepared polyurethane slow-recovery sponge has high air permeability.
Further, the tin catalyst is stannous octoate.
By adopting the technical scheme, the stannous octoate is a catalyst for producing polyurethane foam, and the polyurethane foaming speed can be improved.
Further, the cross-linking agent is trimethylolpropane; the chain extender is diethylene glycol.
①, adding 10 parts of nano alumina into absolute ethyl alcohol, and then carrying out ultrasonic dispersion for 10-20min to obtain a suspension;
② adding 10-20 parts of 10-20wt% silver nitrate solution into the suspension, and filtering by vacuum impregnation to obtain precipitate;
③ the precipitate is calcined at the temperature of 350-450 ℃ for 30-60min to obtain the alumina silver antibacterial agent.
By adopting the technical scheme, the nano-alumina has good adsorption performance due to porosity, and can be prevented from agglomerating after ultrasonic dispersion, so that the silver-carrying efficiency is improved, and after decompression impregnation, the porous alumina can adsorb a large amount of silver ions, so that a good antibacterial effect is achieved.
Further, the nano alumina crystal is gamma phase, the average particle diameter is 20nm, and the specific surface area is 160m2/g。
By adopting the technical scheme, the particle size of the nano-alumina is 20nm, and the specific surface area is 160m2When per gram, the nano-alumina has good adsorption effect on silver ions, and can improve the silver-carrying capacity of the nano-alumina.
Further, the ultrasonic dispersion conditions in step ① are 50-80W power and 40-60kHz frequency.
By adopting the technical scheme, the nano-alumina can be fully dispersed in the absolute ethyl alcohol under the power of 50-80W and the frequency of 40-60kHz so as to avoid agglomeration, thereby improving the efficiency of adsorbing silver ions.
Further, in the step ②, the impregnation is performed under reduced pressure by evacuating the reaction pressure to 10mmHg and impregnating for 40-60 min.
By adopting the technical scheme, silver ions can be adsorbed on the nano alumina carrier through reduced pressure impregnation, and the antibacterial effect is achieved.
Further, the antibacterial agent is prepared by the following method: taking 10 parts by weight of nano zirconium phosphate silver-loaded antibacterial agent and 10-30 parts by weight of alumina silver antibacterial agent, adding 0.6-1 part by weight of monoglyceride laurate, 0.2-0.4 part by weight of fatty acid diethanolamide and 0.03-0.05 part by weight of titanate silane coupling agent, grinding at 80-100 ℃ for 20-30min, and drying at 120-160 ℃ for 6-8h to obtain the antibacterial agent.
By adopting the technical scheme, after the nano zirconium phosphate silver-carrying antibacterial agent and the aluminum oxide silver antibacterial agent are treated by the monoglyceride laurate, the fatty acid diethanolamide and the titanate silane coupling agent, the compatibility of the nano zirconium phosphate silver-carrying antibacterial agent and a matrix can be improved, and the antibacterial water resistance and the antibacterial durability of the polyurethane material can be improved, so that the antibacterial effect of the polyurethane material is improved while the mechanical property of the polyurethane material is not influenced.
The invention also aims to provide a preparation method of the polyurethane slow-rebound sponge.
The technical purpose of the invention is realized by the following technical scheme:
a preparation method of polyurethane slow-rebound sponge comprises the following steps:
25-30 parts of epoxy polyether polyol, 8-10 parts of slow rebound polyether polyol, 1-3 parts of a pore-forming agent, 0.2-0.4 part of a foam stabilizer, 0.2-0.4 part of a tin catalyst, 0.6-1.0 part of a chain extender, 0.2-0.4 part of a cross-linking agent, 1-2 parts of water and 0.2-0.4 part of an antibacterial agent by weight part, and stirring for 3-5min at the speed of 1500-3000r/min to obtain a mixture; adding 10-15 parts of toluene diisocyanate into the mixture, stirring for 6-10s at the temperature of 20-25 ℃, pouring into a mold preheated to 50-60 ℃, curing at normal temperature for 8-10min, and cooling for 1-3h to obtain the polyurethane slow-resilience sponge.
In summary, compared with the prior art, the invention has the following beneficial effects:
1. the nano zirconium phosphate silver-carrying antibacterial agent is a silver inorganic antibacterial agent taking zirconium phosphate as a carrier, has a broad-spectrum bactericidal effect and has better compatibility with a polymer; the antibacterial agent obtained by compounding the nano zirconium phosphate silver-carrying antibacterial agent and the alumina silver antibacterial agent has good compatibility with a polyurethane material, can improve the thermal stability and the regularity of foam pores of the polyurethane foam, and improves the antibacterial performance of the polyurethane foam while not influencing the mechanical performance of the polyurethane foam;
2. the nano alumina has good adsorption performance due to the porosity, and can be prevented from agglomerating after ultrasonic dispersion, so that the silver-carrying efficiency is improved, and after reduced-pressure impregnation, the porous alumina can adsorb a large amount of silver ions, so that a good antibacterial effect is achieved; the nanometer alumina has particle diameter of 20nm and specific surface area of 160m2When per gram, the nano-alumina has good adsorption effect on silver ions, and can improve the silver-carrying capacity of the nano-alumina;
3. after the nano zirconium phosphate silver-carrying antibacterial agent and the aluminum oxide silver antibacterial agent are treated by the monoglyceride laurate, the fatty acid diethanolamide and the titanate silane coupling agent, the compatibility of the nano zirconium phosphate silver-carrying antibacterial agent and a matrix can be improved, and the antibacterial water resistance and the antibacterial durability of a polyurethane material can be improved, so that the antibacterial effect of the polyurethane material is improved while the mechanical property of the polyurethane material is not influenced.
Detailed Description
The present invention will be described in further detail below.
Preparation of antibacterial agent the nano silver-loaded zirconium phosphate antibacterial agent in the following preparation is selected from the nano silver-loaded zirconium phosphate antibacterial agent provided by new material of Xuancheng crystal, Inc. and having a model number of VK-T08; the nano alumina is selected from 20nm of average particle diameter provided by Shanghai Tutcher and 160m of specific surface area2Gamma phase nano alumina per gram; the titanate silane coupling agent is selected from the titanate silane coupling agent with model number of JTW-311 provided by Nanjing warp weft chemical company Limited.
Preparation example 1: (1) preparing an alumina silver antibacterial agent: placing 10g of nano alumina in a reaction kettle, adding 20g of absolute ethyl alcohol into the reaction kettle, and performing ultrasonic dispersion for 10min under the conditions that the power is 50W and the frequency is 40kHz to obtain a suspension; adding 10g of 10 wt% silver nitrate solution into the suspension, vacuumizing the pressure of the reaction kettle to 10mmHg, carrying out reduced pressure impregnation for 40min, and filtering to obtain a precipitate; calcining the precipitate at 350 deg.C for 30min to obtain alumina silver antibacterial agent;
(2) preparing an antibacterial agent: taking 10g of nano zirconium phosphate silver-loaded antibacterial agent and 10g of alumina silver antibacterial agent, adding 0.6g of lauric acid monoglyceride, 0.2g of fatty acid diethanolamide and 0.03g of titanate silane coupling agent, grinding at the temperature of 80 ℃ for 20min, and drying at the temperature of 120 ℃ for 6h to obtain the antibacterial agent.
Preparation example 2: (1) preparing an alumina silver antibacterial agent: placing 10g of nano alumina in a reaction kettle, adding 20g of absolute ethyl alcohol into the reaction kettle, and performing ultrasonic dispersion for 15min under the conditions that the power is 65W and the frequency is 50kHz to obtain a suspension; adding 15g of 15 wt% silver nitrate solution into the suspension, vacuumizing the pressure of the reaction kettle to 10mmHg, carrying out reduced pressure impregnation for 50min, and filtering to obtain a precipitate; calcining the precipitate at 400 ℃ for 45min to obtain an alumina silver antibacterial agent;
(2) preparing an antibacterial agent: taking 10g of nano zirconium phosphate silver-loaded antibacterial agent and 20g of alumina silver antibacterial agent, adding 0.8g of lauric acid monoglyceride, 0.3g of fatty acid diethanolamide and 0.04g of titanate silane coupling agent, grinding at 90 ℃ for 25min, and drying at 140 ℃ for 7h to obtain the antibacterial agent.
Preparation example 3: (1) preparing an alumina silver antibacterial agent: placing 10g of nano alumina in a reaction kettle, adding 20g of absolute ethyl alcohol into the reaction kettle, and performing ultrasonic dispersion for 20min under the conditions of 80W of power and 60kHz of frequency to obtain a suspension; adding 20g of 20wt% silver nitrate solution into the suspension, vacuumizing the pressure of the reaction kettle to 10mmHg, carrying out reduced pressure impregnation for 60min, and filtering to obtain a precipitate; calcining the precipitate at 450 deg.C for 60min to obtain alumina silver antibacterial agent;
(2) preparing an antibacterial agent: taking 10g of nano zirconium phosphate silver-loaded antibacterial agent and 30g of alumina silver antibacterial agent, adding 1g of lauric acid monoglyceride, 0.4g of fatty acid diethanolamide and 0.05g of titanate silane coupling agent, grinding at 100 ℃ for 30min, and drying at 160 ℃ for 8h to obtain the antibacterial agent.
Preparation example 4: the difference between the preparation example and the preparation example 1 is that the alumina silver antibacterial agent is not added in the raw materials.
Preparation example 5: the difference between this preparation example and preparation example 1 is that the raw materials were not added with lauric acid monoglyceride, fatty acid diethanolamide, and titanate silane coupling agent.
Preparation example 6: this production example is different from production example 1 in that the lauric acid monoglyceride and fatty acid diethanolamide were not added to the raw materials.
Second, the polyether polyol in the following examples is selected from polyether polyol provided by Zhonghai shell brand and having a brand number of SC56-16S, the relative molecular mass of the polyether polyol is 3000, and the polyether polyol is prepared by ring-opening polymerization of propylene oxide/ethylene oxide by taking silicone oil as an initiator; the slow rebound polyether polyol is selected from slow rebound polyether polyol provided by Korea and having the model number of SR-308, and the hydroxyl value is 293-323; the toluene diisocyanate is selected from toluene diisocyanate T80 supplied by Cangzhou Daghiko Co; the pore former is selected from a pore former with the model number of KY-1206 provided by Ningbo Honghun polyurethane auxiliary agent company Limited; the foam stabilizer is selected from silicone surfactant with model number S-5822 provided by Pujia chemical Co., Ltd, of Foshan; the stannous octoate catalyst is selected from stannous octoate T9 provided by Shanghai Cao's chemical technology development Limited company; the chain extender is diethylene glycol; the cross-linking agent is trimethylolpropane.
Example 1: the polyurethane slow-rebound sponge is prepared by the following method: the method comprises the following steps:
25kg of epoxy polyether polyol, 8kg of slow rebound polyether polyol, 1kg of cell opener, 0.2kg of foam stabilizer, 0.2kg of tin catalyst, 0.6kg of chain extender, 0.2kg of cross-linking agent, 1kg of water and 0.2kg of antibacterial agent (selected from preparation example 1), and stirring the components at the speed of 1500r/min for 3min to obtain a mixture; and adding 10kg of toluene diisocyanate into the mixture, stirring for 6s at the temperature of 20 ℃, pouring into a mold preheated to 50 ℃, curing at normal temperature for 8min, and cooling for 1h to obtain the polyurethane slow-recovery sponge.
Example 2: the polyurethane slow-rebound sponge is prepared by the following method: the method comprises the following steps:
27.5kg of epoxy polyether polyol, 9kg of slow rebound polyether polyol, 2kg of a cell opener, 0.3kg of a foam stabilizer, 0.3kg of a tin catalyst, 0.8kg of a chain extender, 0.3kg of a cross-linking agent, 1.5kg of water and 0.3kg of an antibacterial agent (selected from preparation example 2), and stirring the components at the speed of 2000r/min for 4min to obtain a mixture; adding 12.5kg of toluene diisocyanate into the mixture, stirring for 8s at the temperature of 22 ℃, pouring into a mold preheated to 52 ℃, curing at normal temperature for 9min, and cooling for 2h to obtain the polyurethane slow-recovery sponge.
Example 3: the polyurethane slow-rebound sponge is prepared by the following method: the method comprises the following steps:
30kg of epoxy polyether polyol, 10kg of slow rebound polyether polyol, 3kg of cell opener, 0.4kg of foam stabilizer, 0.4kg of tin catalyst, 1.0kg of chain extender, 0.4kg of cross-linking agent, 2kg of water and 0.4kg of antibacterial agent (selected from preparation example 3), and stirring at the speed of 3000r/min for 5min to obtain a mixture; adding 15kg of toluene diisocyanate into the mixture, stirring for 10s at the temperature of 25 ℃, pouring into a mold preheated to 60 ℃, curing for 10min at normal temperature, and cooling for 3h to obtain the polyurethane slow-recovery sponge.
Third, comparative example
Comparative example 1: this comparative example is different from example 1 in that an antibacterial agent was prepared from the preparation example 4.
Comparative example 2: this comparative example is different from example 1 in that an antibacterial agent was prepared from the preparation example 5.
Comparative example 3: this comparative example differs from example 1 in that the antibacterial agent was prepared from preparation example 6.
Fourthly, performance test
The polyurethane slow rebound sponges prepared in examples 1-3 and comparative examples 1-3 were tested for their performance according to the following procedure, and the test results are shown in Table 1.
Tensile strength and elongation at break were tested according to GB/T6344-2008 "tensile strength and elongation at break of Flexible foam Polymer".
The rebound resilience is tested according to GB/T6670-2008 'determination of rebound resilience by falling ball method for flexible foam polymer material'.
Antibacterial ratio the antibacterial ratio of escherichia coli, staphylococcus aureus and candida albicans was tested according to AATCC Test Method 100 (bacteria count assay) Test samples.
The water-resistant antibacterial rate is tested by adopting the following method: and soaking the sample in deionized water for 96h, and then testing the antibacterial rates of escherichia coli, staphylococcus aureus and candida albicans of the sample.
The antibacterial durability is tested by the following method: after the sample is placed in an environment with the temperature of 25 ℃ and the humidity of 60% RH for 3 months, the long-acting antibacterial rate of escherichia coli, staphylococcus aureus and candida albicans of the sample is tested again.
TABLE 1
The data in table 1 show that the polyurethane slow-rebound sponge prepared by the invention has good mechanical properties such as tensile strength, elongation at break and the like, and has good rebound rate, and in addition, the short-term antibacterial, waterproof antibacterial and long-acting antibacterial rates of the polyurethane slow-rebound sponge prepared by the invention are all more than 99%, which shows that the polyurethane slow-rebound sponge prepared by the invention has good antibacterial effect and antibacterial durability.
The antibacterial agent of comparative example 1 was prepared from preparation example 4; compared with example 1, the short-term antibacterial rate of comparative example 1 has no obvious change, but the water-resistant antibacterial rate and the long-term antibacterial rate of the polyurethane slow-rebound sponge are obviously reduced, which shows that the addition of the alumina silver antibacterial agent is helpful for improving the water-resistant antibacterial rate and the antibacterial durability of the polyurethane slow-rebound sponge.
The antibacterial agent of comparative example 2 was prepared from preparation example 5, and the antibacterial agent of comparative example 3 was prepared from preparation example 6; compared with example 1, the short-term antibacterial rate of comparative example 2 and comparative example 3 is not obviously changed, but the water-resistant antibacterial rate of comparative example 2 and comparative example 3 is reduced, which shows that the water-resistant antibacterial rate of the polyurethane slow-rebound sponge can be improved by adding the lauric acid monoglyceride and the fatty acid diethanolamide; the tensile strength and elongation at break of comparative example 2 were reduced compared to example 1, indicating that the titanate silane coupling agent helps to improve the compatibility of the antimicrobial agent with the polymer, thereby reducing the problem of the reduction of mechanical properties caused by the addition of the antimicrobial agent.
The present embodiment is only for explaining the present invention, and it is not limited to the present invention, and those skilled in the art can make modifications of the present embodiment without inventive contribution as needed after reading the present specification, but all of them are protected by patent law within the scope of the claims of the present invention.
Claims (10)
1. A polyurethane slow-rebound sponge is characterized in that: the paint comprises the following components in parts by weight: 25-30 parts of epoxy polyether polyol, 8-10 parts of slow rebound polyether polyol, 1-3 parts of a cell opener, 0.2-0.4 part of a foam stabilizer, 0.2-0.4 part of a tin catalyst, 0.6-1.0 part of a chain extender, 0.2-0.4 part of a cross-linking agent, 1-2 parts of water, 0.2-0.4 part of an antibacterial agent and 10-15 parts of toluene diisocyanate;
the antibacterial agent comprises the following components in parts by weight: 10 parts of nano zirconium phosphate silver-carrying antibacterial agent and 10-30 parts of alumina silver antibacterial agent.
2. The polyurethane slow rebound sponge as set forth in claim 1, wherein: the foam stabilizer is a silicone surfactant.
3. The polyurethane slow rebound sponge as set forth in claim 1, wherein: the tin catalyst is stannous octoate.
4. The polyurethane slow rebound sponge as set forth in claim 1, wherein: the cross-linking agent is trimethylolpropane; the chain extender is diethylene glycol.
5. The polyurethane slow-resilience sponge as claimed in claim 1, wherein the alumina-supported silver antibacterial agent is prepared by adding anhydrous ethanol into ① parts of nano alumina, and ultrasonically dispersing for 10-20min to obtain a suspension;
② adding 10-20 parts of 10-20wt% silver nitrate solution into the suspension, and filtering by vacuum impregnation to obtain precipitate;
③ the precipitate is calcined at the temperature of 350-450 ℃ for 30-60min to obtain the alumina silver antibacterial agent.
6. The polyurethane slow rebound sponge as set forth in claim 5, wherein: the nanometer alumina crystal is gamma phase, the average grain diameter is 20nm, the specific surface area is 160m2/g。
7. The polyurethane slow rebound sponge as set forth in claim 5, wherein the ultrasonic dispersion in step ① is carried out under the conditions of 50-80W power and 40-60kHz frequency.
8. The polyurethane slow recovery sponge as claimed in claim 5, wherein the impregnation under reduced pressure in step ② is carried out by evacuating the reaction pressure to 10mmHg and impregnating for 40-60 min.
9. The polyurethane slow rebound sponge as set forth in claim 5, wherein: the antibacterial agent is prepared by the following method: taking 10 parts by weight of nano zirconium phosphate silver-loaded antibacterial agent and 10-30 parts by weight of alumina silver antibacterial agent, adding 0.6-1 part by weight of monoglyceride laurate, 0.2-0.4 part by weight of fatty acid diethanolamide and 0.03-0.05 part by weight of titanate silane coupling agent, grinding at 80-100 ℃ for 20-30min, and drying at 120-160 ℃ for 6-8h to obtain the antibacterial agent.
10. A preparation method of polyurethane slow-rebound sponge is characterized by comprising the following steps: the method comprises the following steps:
25-30 parts of epoxy polyether polyol, 8-10 parts of slow rebound polyether polyol, 1-3 parts of a pore-forming agent, 0.2-0.4 part of a foam stabilizer, 0.2-0.4 part of a tin catalyst, 0.6-1.0 part of a chain extender, 0.2-0.4 part of a cross-linking agent, 1-2 parts of water and 0.2-0.4 part of an antibacterial agent by weight part, and stirring for 3-5min at the speed of 1500-3000r/min to obtain a mixture; adding 10-15 parts of toluene diisocyanate into the mixture, stirring for 6-10s at the temperature of 20-25 ℃, pouring into a mold preheated to 50-60 ℃, curing at normal temperature for 8-10min, and cooling for 1-3h to obtain the polyurethane slow-resilience sponge.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201911246824.6A CN110938187A (en) | 2019-12-07 | 2019-12-07 | Polyurethane slow-resilience sponge and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201911246824.6A CN110938187A (en) | 2019-12-07 | 2019-12-07 | Polyurethane slow-resilience sponge and preparation method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN110938187A true CN110938187A (en) | 2020-03-31 |
Family
ID=69909386
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201911246824.6A Pending CN110938187A (en) | 2019-12-07 | 2019-12-07 | Polyurethane slow-resilience sponge and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN110938187A (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111454429A (en) * | 2020-06-10 | 2020-07-28 | 泉州玺堡家居科技有限公司 | MDI (diphenylmethane diisocyanate) tapping technology-based high-breathability slow-resilience cotton and preparation method thereof |
| CN113045729A (en) * | 2021-02-01 | 2021-06-29 | 腾飞科技股份有限公司 | Antibacterial cup and production process thereof |
| CN113372709A (en) * | 2021-07-26 | 2021-09-10 | 华侨大学 | Preparation method of antibacterial slow-resilience polyurethane sponge |
| CN113563558A (en) * | 2021-08-06 | 2021-10-29 | 南京金栖化工集团有限公司 | Preparation method of nano-silver antibacterial polyurethane slow-resilience sponge |
| CN114350078A (en) * | 2021-11-25 | 2022-04-15 | 宏至翎包装制品(昆山)有限公司 | Antibacterial EPS plastic foam and preparation method thereof |
Citations (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1998050446A1 (en) * | 1997-05-06 | 1998-11-12 | Magla World-Wide L.L.C. | Flexible, substantially open celled polyurethane foam and method of making same |
| CN101134112A (en) * | 2006-08-28 | 2008-03-05 | 厦门量子星科技有限公司 | Silver-carrying active aluminum oxide antimicrobials and method for preparing the same |
| JP2011046038A (en) * | 2009-08-26 | 2011-03-10 | Ｂａｓｆ Ｉｎｏａｃポリウレタン株式会社 | Method for manufacturing polyurethane foam |
| CN102153722A (en) * | 2011-02-25 | 2011-08-17 | 北京万博汇佳科贸有限公司 | Slow-resilience polyether polyol and method for manufacturing slow-resilience soft foam therewith |
| CN102875758A (en) * | 2012-10-11 | 2013-01-16 | 晋大纳米科技（厦门）有限公司 | Washing endurance, long-acting, antimicrobial and mildewproof sponge, and preparation method thereof |
| CN104530380A (en) * | 2014-12-28 | 2015-04-22 | 甘肃银光聚银化工有限公司 | Slowly-recoverable foam |
| CN104804361A (en) * | 2014-01-28 | 2015-07-29 | 深圳齐心集团股份有限公司 | Antibacterial resin composite material and preparation method thereof |
| CN105251437A (en) * | 2014-07-16 | 2016-01-20 | 中国石油化工股份有限公司 | Stationary phase for solid phase extraction and separation of heavy oil hydrocarbons |
| CN106147206A (en) * | 2016-07-26 | 2016-11-23 | 福建师范大学泉港石化研究院 | A kind of yellowing-resistant antibacterial mobile phone shell sheath and preparation method thereof |
| CN106220806A (en) * | 2016-07-26 | 2016-12-14 | 福建师范大学泉港石化研究院 | A kind of antibacterial thermoplastic polyurethane and preparation method thereof |
| CN106750176A (en) * | 2017-01-20 | 2017-05-31 | 青岛科技大学 | A kind of preparation method of slow-recovery sponge material |
| CN107568210A (en) * | 2017-09-05 | 2018-01-12 | 绵竹耀隆化工有限公司 | A kind of basic zirconium phosphate complex antimicrobials and preparation method thereof |
| CN109251302A (en) * | 2017-07-12 | 2019-01-22 | 董伟 | polyurethane memory sponge and preparation method thereof |
-
2019
- 2019-12-07 CN CN201911246824.6A patent/CN110938187A/en active Pending
Patent Citations (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1998050446A1 (en) * | 1997-05-06 | 1998-11-12 | Magla World-Wide L.L.C. | Flexible, substantially open celled polyurethane foam and method of making same |
| CN101134112A (en) * | 2006-08-28 | 2008-03-05 | 厦门量子星科技有限公司 | Silver-carrying active aluminum oxide antimicrobials and method for preparing the same |
| JP2011046038A (en) * | 2009-08-26 | 2011-03-10 | Ｂａｓｆ Ｉｎｏａｃポリウレタン株式会社 | Method for manufacturing polyurethane foam |
| CN102153722A (en) * | 2011-02-25 | 2011-08-17 | 北京万博汇佳科贸有限公司 | Slow-resilience polyether polyol and method for manufacturing slow-resilience soft foam therewith |
| CN102875758A (en) * | 2012-10-11 | 2013-01-16 | 晋大纳米科技（厦门）有限公司 | Washing endurance, long-acting, antimicrobial and mildewproof sponge, and preparation method thereof |
| CN104804361A (en) * | 2014-01-28 | 2015-07-29 | 深圳齐心集团股份有限公司 | Antibacterial resin composite material and preparation method thereof |
| CN105251437A (en) * | 2014-07-16 | 2016-01-20 | 中国石油化工股份有限公司 | Stationary phase for solid phase extraction and separation of heavy oil hydrocarbons |
| CN104530380A (en) * | 2014-12-28 | 2015-04-22 | 甘肃银光聚银化工有限公司 | Slowly-recoverable foam |
| CN106147206A (en) * | 2016-07-26 | 2016-11-23 | 福建师范大学泉港石化研究院 | A kind of yellowing-resistant antibacterial mobile phone shell sheath and preparation method thereof |
| CN106220806A (en) * | 2016-07-26 | 2016-12-14 | 福建师范大学泉港石化研究院 | A kind of antibacterial thermoplastic polyurethane and preparation method thereof |
| CN106750176A (en) * | 2017-01-20 | 2017-05-31 | 青岛科技大学 | A kind of preparation method of slow-recovery sponge material |
| CN109251302A (en) * | 2017-07-12 | 2019-01-22 | 董伟 | polyurethane memory sponge and preparation method thereof |
| CN107568210A (en) * | 2017-09-05 | 2018-01-12 | 绵竹耀隆化工有限公司 | A kind of basic zirconium phosphate complex antimicrobials and preparation method thereof |
Non-Patent Citations (5)
| Title |
|---|
| DAGOSTIN V S，等: "Bactericidal polyurethane foam mattresses: Microbiological characterization and effectiveness", 《MATERIALS SCIENCE & ENGINEERING C-MATERIALS FOR BIOLOGICAL APPLICATIONS》 * |
| 于新，等: "《天然食品添加剂》", 31 March 2014, 中国轻工业出版社 * |
| 吴继贤，等: "磷酸锆载银抗菌粉在鞋材中的应用及相应的抗菌性能测试", 《2014年（首届）抗菌科学与技术论坛论文摘要集》 * |
| 汪多仁: "《现代日用化工产品》", 31 March 2000, 冶金工业出版社 * |
| 马振瀛，等: "《防霉学》", 28 February 1990, 云南科技出版社 * |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111454429A (en) * | 2020-06-10 | 2020-07-28 | 泉州玺堡家居科技有限公司 | MDI (diphenylmethane diisocyanate) tapping technology-based high-breathability slow-resilience cotton and preparation method thereof |
| CN113045729A (en) * | 2021-02-01 | 2021-06-29 | 腾飞科技股份有限公司 | Antibacterial cup and production process thereof |
| WO2022160407A1 (en) * | 2021-02-01 | 2022-08-04 | 腾飞科技股份有限公司 | Antibacterial cups and production process therefor |
| CN113372709A (en) * | 2021-07-26 | 2021-09-10 | 华侨大学 | Preparation method of antibacterial slow-resilience polyurethane sponge |
| CN113563558A (en) * | 2021-08-06 | 2021-10-29 | 南京金栖化工集团有限公司 | Preparation method of nano-silver antibacterial polyurethane slow-resilience sponge |
| CN114350078A (en) * | 2021-11-25 | 2022-04-15 | 宏至翎包装制品(昆山)有限公司 | Antibacterial EPS plastic foam and preparation method thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN110938187A (en) | Polyurethane slow-resilience sponge and preparation method thereof | |
| CN112063177A (en) | Antibacterial and mildew-proof high-temperature vulcanized silicone rubber and preparation method thereof | |
| CN110577625B (en) | Breathable slow-rebound polyurethane foam plastic and preparation method and application thereof | |
| CN110283293B (en) | Latex-like polyurethane soft foam prepared from isocyanate-terminated prepolymer | |
| JP2015511972A (en) | Low density foam and foam-based articles | |
| CN113603861B (en) | Antistatic low-temperature-resistant slow-rebound polyurethane sponge material and preparation method thereof | |
| CN113025030B (en) | Antibacterial graphene polyurethane composite sponge material and preparation method and application thereof | |
| CN111560107A (en) | Antibacterial anti-mite sponge and preparation method thereof | |
| CN110885417A (en) | Compression-resistant low-density TDI (toluene diisocynate) type high-resilience foam sponge and preparation method thereof | |
| CN111171278A (en) | Antibacterial polyurethane slow-resilience foam and preparation method thereof | |
| CN110240686A (en) | A kind of high-performance high-hard, transparent polyurethane elastomer and preparation method thereof | |
| CN103254402B (en) | Preparation method of water-swellable elastomer material | |
| CN110922558A (en) | Slow-resilience polyurethane expanded foam and preparation method thereof | |
| WO2017194033A1 (en) | Polyurethane molded plastic mattress composition and preparation method therefor | |
| CN112708126B (en) | Polyether polyol for imitation latex polyurethane foam and preparation method thereof, and low-temperature-resistant imitation latex foam and preparation method thereof | |
| CN111574683B (en) | High-bearing memory cotton and preparation method and application thereof | |
| CN112457554A (en) | Environment-friendly composite mattress containing bamboo fibers and preparation method thereof | |
| CN113121777A (en) | Flame-retardant graphene polyurethane composite sponge material and application thereof | |
| CN104725831B (en) | The preparation method of ventilative antistatic polyurethane low resilience urethane foam resilient foam material | |
| CN115678097A (en) | Medical high-absorption polyurethane foam dressing and preparation method thereof | |
| CN112266454B (en) | Application of hydroxyl-terminated polymer in preparation of multifunctional polyurethane soft foam dressing | |
| CN113372709A (en) | Preparation method of antibacterial slow-resilience polyurethane sponge | |
| CN104140519B (en) | Low-bounce ice-cold breathable sponge and preparing process thereof | |
| CN112111146A (en) | Rigid polyurethane foam plastic and preparation method thereof | |
| CN110964309A (en) | High-hardness sponge and processing technology thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20200331 |
|
| RJ01 | Rejection of invention patent application after publication |