阅读说明：本技术 一种纳米银抗菌聚氨酯慢回弹海绵的制备方法 (Preparation method of nano-silver antibacterial polyurethane slow-resilience sponge ) 是由 汤振英 张聪丽 于 2021-08-06 设计创作，主要内容包括：本发明涉及一种纳米抗菌聚氨酯慢回弹海绵的制备方法；传统的聚氨酯慢回弹海绵材料对于抗菌要求不高,极少部分海绵需要有抗菌性,而传统的抗菌海绵的制造一般通过加入有机的抗菌剂来抗菌,有机的不反应的抗菌剂易迁移,对产品或者人也是一种伤害；并且有机抗菌材料随着迁移,效果会明显下降甚至消失；本发明通纳米银离子溶液,在聚氨酯泡沫生产过程中附于泡沫的经络上,不会迁移,并且纳米银离子会缓释释放,持续抗菌时间长,远超聚氨酯泡沫的使用寿命。(The invention relates to a preparation method of a nano antibacterial polyurethane slow-resilience sponge; the traditional polyurethane slow-recovery sponge material has low requirement on antibiosis, and a few sponges need to have antibiosis, while the traditional antibacterial sponge is generally made by adding organic antibacterial agents for antibiosis, and the organic nonreactive antibacterial agents are easy to migrate and are harmful to products or people; and the effect of the organic antibacterial material is obviously reduced or even disappears along with the migration; the nano silver ion solution is attached to the channels and collaterals of the foam in the production process of the polyurethane foam, cannot migrate, and can be released in a sustained manner, so that the continuous antibacterial time is long and the service life of the polyurethane foam is far prolonged.)

1. A preparation method of a nano-silver antibacterial polyurethane slow-recovery sponge is characterized by comprising the following steps: weighing 20 parts of polyether polyol A, 60 parts of polyether polyol B, 20 parts of polymer polyol C, 0.5 part of catalyst, 1 part of soft foam silicone oil, 1.4-1.6 parts of water, 0.05 part of stannous octoate, 1 part of cell opening agent and 0.2-0.4 part of nano-silver solution, placing the materials into a foaming cup, stirring and mixing uniformly, adding 38 parts of toluene diisocyanate, stirring at a high speed, pouring the mixture into a square mold for foaming after stirring uniformly, and curing for 48 hours after the foam is stabilized to obtain the nano-silver antibacterial polyurethane slow-resilience sponge.

2. The method for preparing the nano-silver antibacterial polyurethane slow-resilience sponge as claimed in claim 1, wherein the hydroxyl value of the polyether polyol A is 56, and the functionality of the polyether polyol A is 3; the hydroxyl value of the polyether polyol B is 240, and the functionality of the polyether polyol B is 3.

3. The preparation method of the nano-silver antibacterial polyurethane slow rebound sponge as claimed in claim 1, wherein the catalyst is Dabco 33 LV; the soft foam silicone oil is L-580; the cell opener is KY-1218; the toluene diisocyanate is TDI-80.

4. The preparation method of the nano-silver antibacterial polyurethane slow-recovery sponge as claimed in claim 1, wherein the preparation method of the polymer polyol C comprises the following steps: putting polyether polyol A, an initiator, a chain transfer agent, a dispersing agent, styrene and acrylonitrile into a mixing kettle, uniformly mixing to obtain a raw material mixture, adding the raw material mixture into a reactor filled with the chain transfer agent, carrying out free radical polymerization, and carrying out vacuum distillation after the reaction is finished to obtain polymer polyol C.

5. The method for preparing the nano-silver antibacterial polyurethane slow-recovery sponge as claimed in claim 1, wherein the high-speed stirring speed is 3000rpm, and the high-speed stirring time is 10 s.

6. The method for preparing the nano-silver antibacterial polyurethane slow-recovery sponge as claimed in claim 1, wherein the concentration of nano-silver in the nano-silver solution is 1000 mg/L.

7. The preparation method of the nano-silver antibacterial polyurethane slow-recovery sponge as claimed in claim 4, wherein the initiator is azobisisobutyronitrile; the chain transfer agent is one or the combination of two of ethylbenzene and xylene; the dispersing agent is transparent liquid which has viscosity of 3500mpa.s at 25 ℃ and is prepared by reacting polyether polyol C with maleic anhydride at 120 ℃ for 3 hours and adding ethylene oxide at 130 ℃ for end capping reaction for 6 hours, wherein the polyether polyol C has the ethylene oxide content of 14.5 percent, the hydroxyl value of 34 mgKOH/g and the molecular weight of 4800.

8. The preparation method of the nano-silver antibacterial polyurethane slow-recovery sponge as claimed in claim 4, wherein the mass ratio of the polyether polyol A to the initiator to the chain transfer agent to the dispersant to the styrene to the acrylonitrile is 6.75: 0.05:1.625:1:3.75:1.75.

9. The preparation method of the nano-silver antibacterial polyurethane slow-recovery sponge as claimed in claim 4, wherein the temperature of the free radical polymerization reaction is 120 ℃, and the pressure in the reactor is less than or equal to 0.5 MPa.

10. The method for preparing the nano-silver antibacterial polyurethane slow-recovery sponge as claimed in claim 4, wherein the total amount of styrene and acrylonitrile after vacuum distillation is less than or equal to 10 mg/L.

Technical Field

The invention belongs to the technical field of polyurethane foam, and particularly relates to a preparation method of a nano-silver antibacterial polyurethane slow-resilience sponge.

Background

As is well known, the sponge is more and more widely used, such as in the fields of automobile seats, children articles, household articles, shoe materials and the like, because many fields are in contact with human bodies and easily generate bacteria, higher requirements are provided for the antibacterial performance of the sponge, especially, the lasting antibacterial effect is particularly important, the antibacterial sponge in the current market mainly achieves the antibacterial effect by adding a macromolecular antibacterial agent, the antibacterial effect is linearly reduced along with the gradual disappearance of the antibacterial agent, and some antibacterial agents have toxic components and can damage the health of the human bodies after being diffused.

Disclosure of Invention

In order to solve the problems, the invention discloses a preparation method of nano-silver antibacterial polyurethane slow-resilience sponge with simple process and production conditions, and the invention selects a nano-silver solution to replace the method of adding an organic antibacterial agent in the prior art, thereby avoiding the harm of the organic antibacterial agent to the health of human bodies; the transparent nano silver solution is used for partially replacing water, the water in the nano silver solution reacts with isocyanate, silver ions are loaded on the channels and collaterals of foam, high-speed mixing and stirring are carried out in the foaming process, the nano silver ions can be uniformly loaded on the channels and collaterals of the foam, the silver ions have good antibacterial effect, the nano silver ions loaded on the channels and collaterals of the foam are released slowly and durably, the polyurethane slow-resilience sponge is protected durably, the bacterial breeding in the polyurethane slow-resilience sponge is avoided, and the physical performance of the polyurethane slow-resilience sponge is not influenced.

In order to achieve the purpose, the invention provides the following technical scheme:

a preparation method of a nano-silver antibacterial polyurethane slow-recovery sponge comprises the following steps: weighing 20 parts of polyether polyol A, 60 parts of polyether polyol B, 20 parts of polymer polyol C, 0.5 part of catalyst, 1 part of soft foam silicone oil, 1.4-1.6 parts of water, 0.05 part of stannous octoate, 1 part of cell opening agent and 0.2-0.4 part of nano-silver solution, placing the materials into a foaming cup, stirring and mixing uniformly, adding 38 parts of toluene diisocyanate, stirring at a high speed, pouring the mixture into a square mold for foaming after stirring uniformly, and curing for 48 hours after the foam is stabilized to obtain the nano-silver antibacterial polyurethane slow-resilience sponge.

Further, the polyether polyol a has a hydroxyl value of 56, the functionality of polyether polyol a is 3; the hydroxyl value of the polyether polyol B is 240, and the functionality of the polyether polyol A is 3.

Further, the catalyst is Dabco 33 LV; the soft foam silicone oil is L-580; the cell opener is KY-1218; the toluene diisocyanate is TDI-80.

Further, the preparation method of the polymer polyol C comprises the following steps: putting polyether polyol A, an initiator, a chain transfer agent, a dispersing agent, styrene and acrylonitrile into a mixing kettle, uniformly mixing to obtain a raw material mixture, putting the raw material mixture into a reactor filled with the chain transfer agent, carrying out free radical polymerization, and after the reaction is finished, carrying out vacuum distillation to obtain polymer polyol C.

Further, the rotation speed of the high-speed stirring is 3000rpm, and the time of the high-speed stirring is 10 s.

Further, the concentration of the nano silver in the nano silver solution is 1000 mg/L.

Further, the initiator is dimethyl azodiisobutyrate; the chain transfer agent is one or the combination of two of ethylbenzene and xylene; further, the dispersant is a transparent liquid which is prepared by reacting polyether polyol C with maleic anhydride at 120 ℃ for 3 hours, and adding ethylene oxide at 130 ℃ for end capping reaction for 6 hours to obtain a product with the viscosity of 3500mpa.s at 25 ℃; the polyether polyol C has the ethylene oxide content of 14.5 percent, the hydroxyl value of 34 mgKOH/g and the molecular weight of 4800.

Further, the mass ratio of the polyether polyol A to the initiator to the chain transfer agent to the dispersant to the styrene to the acrylonitrile is 6.75: 0.05:1.625:1:3.75:1.75.

Further, the temperature of the free radical polymerization reaction is 120 ℃, and the pressure in the reactor is less than or equal to 0.5 MPa.

Further, the total amount of the styrene and the acrylonitrile after the vacuum distillation is less than or equal to 10 mg/L.

Compared with the prior art, the invention has the following advantages and beneficial effects:

according to the invention, by adding the silver ion solution, after water in the solution reacts with isocyanate, silver ions are loaded on the channels and collaterals of the foam and cannot migrate, and nano silver ions are released slowly, so that the continuous antibacterial time is long, the service life of the polyurethane foam is prolonged, the slow-resilience foam is protected for a long time, and the breeding of bacteria in the slow-resilience foam is avoided.

The antibacterial effect of the polyurethane slow-rebound sponge prepared by using the nano-silver solution antibacterial agent is better than that of the traditional antibacterial agent, and the physical performance of the polyurethane slow-rebound sponge is not influenced by using the nano-silver solution.

Detailed Description

The technical solutions provided by the present invention will be described in detail below with reference to specific examples, and it should be understood that the following specific embodiments are only illustrative of the present invention and are not intended to limit the scope of the present invention.

The raw materials used in the examples are all commercially available unless otherwise specified.

Dabco 33 LV: purchased from mai chart high and new materials, inc;

l-580: purchased from mai chart high and new materials, inc;

dabco T-9: purchased from the air chemical industry, usa;

KY-1218: purchased from Shenzhen, Wei Hongxin science and technology Limited;

colorless transparent nano silver solution (1000 ppm): purchased from jin nano technologies ltd;

FRESCHE 4850 antimicrobials: from Jiangsu chemical (Shanghai) Co Ltd

TDI-80: from basf, ltd;

polyether polyol C: JQN-330N, available from Nanjing Jinxiu chemical group, Inc.

Example 1

Polyether polyol A: 92g of glycerol and 0.15g of a bimetallic catalyst were added to the reactor and a mixture of 2668gPO/240g of EO was passed in continuously at 135 ℃ to give a polyether polyol A having a hydroxyl number of 56 and a functionality of 3.

Polyether polyol B: adding 92g of glycerol and 1.4g of KOH into a reaction kettle, and continuously introducing 608g of propylene oxide to obtain crude ether; 21g of water, 2.8g of phosphoric acid (85% concentration) and 1.4g of magnesium silicate as an adsorbent were added thereto, and the mixture was dehydrated to 0.05% in vacuo and then filtered to obtain polyether polyol B.

Polyether polyol C: JQN-330N, the ethylene oxide content is: 14.5% (by weight), hydroxyl value: 34 mgKOH/g, molecular weight 4800, Nanjing Jinxiu chemical group Co., Ltd.

Dispersing agent: polyether polyol C and maleic anhydride are reacted at 120 ℃ for 3 hours, and ethylene oxide is added at 130 ℃ for a capping reaction for 6 hours to prepare a transparent liquid having a viscosity of 3500mpa.s at 25 ℃.

Polymer polyol C: mixing 540g of base polyether polyol D-560S, 4g of dimethyl azodiisobutyrate, 100g of ethylbenzene, 30g of xylene, 80g of dispersant, 300g of styrene and 140g of acrylonitrile in a mixing kettle to form a raw material mixture; the full-kettle ethylbenzene is respectively added into a first reactor and a second reactor which are connected in series in a double-kettle way, and the temperature is raised to 120 ℃. Maintaining the temperature at 120 ℃ and the pressure at 0.5Mpa, continuously feeding the raw material mixture from the mixing kettle to the inlet of the first reactor and simultaneously discharging from the outlet of the second reactor; after the discharge from the second reactor, the residual ethylenic monomers (styrene and acrylonitrile) were removed by vacuum distillation to a total content of less than 10ppm, giving polymer polyol C.

Example 2

Weighing 200g of polyether polyol A, 600g of polyether polyol B, 200g of polymer polyol C, 5g of Dabco 33LV, 10g of L-580, 16g of water, 0.5g of Dabco T-9, 10g of KY-1218 and 2g of nano silver solution, placing the materials into a reaction kettle, stirring and mixing the materials uniformly, adding 380g of TDI-80, stirring the materials at a high speed of 3000rpm for 10s, stirring the materials uniformly, pouring the materials into a square mold for foaming, and curing the foams for 48 hours after the foams are stabilized to obtain the nano antibacterial polyurethane slow-resilience sponge.

Example 3

Weighing 200g of polyether polyol A, 600g of polyether polyol B, 200g of polymer polyol C, 5g of Dabco 33LV, 10g L-580, 14g of water, 0.5g of Dabco T-9, 10g of KY-1218 and 4g of nano silver solution, placing the materials into a reaction kettle, stirring and mixing the materials uniformly, adding 380g of TDI-80, stirring the materials at a high speed of 3000rpm for 10s, stirring the materials uniformly, pouring the materials into a square mold for foaming, and curing the foams for 48 hours after the foams are stabilized to obtain the nano antibacterial polyurethane slow-resilience sponge.

Comparative example 1

200g of polyether polyol A, 600g of polyether polyol B, 200g of polymer polyol C, 5g of Dabco 33LV, 10g L-580, 18g of water, 0.5g of Dabco T-9, 10g of KY-1218 and 0g of FRESCHE 4850 antibacterial agent are weighed and placed in a reaction kettle, 380g of TDI-80 is added after stirring and mixing uniformly, 3000rpm is high-speed stirring is carried out for 10s, the mixture is poured into a square mold after stirring uniformly for foaming, and after foam is stabilized, curing is carried out for 48 hours to obtain the polyurethane slow-resilience sponge.

Comparative example 2

200g of polyether polyol A, 600g of polyether polyol B, 200g of polymer polyol C, 5g of Dabco 33LV, 10g L-580, 18g of water, 0.5g of Dabco T-9, 10g of KY-1218 and 2g of FRESCHE 4850 antibacterial agent are weighed and placed in a reaction kettle, 380g of TDI-80 is added after stirring and mixing uniformly, 3000rpm is high-speed stirring is carried out for 10s, the mixture is poured into a square mold after stirring uniformly for foaming, and after foam is stabilized, curing is carried out for 48 hours to obtain the polyurethane slow-resilience sponge.

Comparative example 3

200g of polyether polyol A, 600g of polyether polyol B, 200g of polymer polyol C, 5g of Dabco 33LV, 10g L-580, 18g of water, 0.5g of Dabco T-9, 10g of KY-1218 and 4g of FRESCHE 4850 antibacterial agent are weighed and placed in a reaction kettle, 380g of TDI-80 is added after stirring and mixing uniformly, 3000rpm is high-speed stirring is carried out for 10s, the mixture is poured into a square mold after stirring uniformly for foaming, and after foam is stabilized, curing is carried out for 48 hours to obtain the polyurethane slow-resilience sponge.

Performance testing

With reference to methods for testing antibacterial performance of materials in GB2591-2003 and ISO22196:2007, antibacterial performance of the polyurethane slow-resilience sponges prepared in examples 2 and 3, comparative examples 1 and 2 and comparative examples 3 is evaluated, physical performance of the sponges is also detected, and antibacterial rates of staphylococcus aureus and escherichia coli at different times are shown in Table 1; the physical property test results of the polyurethane slow rebound sponge are shown in table 2.

TABLE 1 antimicrobial ratio against Staphylococcus aureus and Escherichia coli at different times

TABLE 2 Slow rebound polyurethane sponge physical Properties

The technical means disclosed in the invention scheme are not limited to the technical means disclosed in the above embodiments, but also include the technical scheme formed by any combination of the above technical features. It should be noted that those skilled in the art can make various improvements and modifications without departing from the principle of the present invention, and such improvements and modifications are also considered to be within the scope of the present invention.