CN114316241A - Preparation method of polyether polyol for antibacterial polyurethane slow-resilience foam - Google Patents
Preparation method of polyether polyol for antibacterial polyurethane slow-resilience foam Download PDFInfo
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- CN114316241A CN114316241A CN202111473754.5A CN202111473754A CN114316241A CN 114316241 A CN114316241 A CN 114316241A CN 202111473754 A CN202111473754 A CN 202111473754A CN 114316241 A CN114316241 A CN 114316241A
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Abstract
The invention relates to a preparation method of polyether polyol for antibacterial polyurethane slow-resilience foam, belonging to the technical field of polyether polyol modification. The invention specifically comprises the following steps: adding an alcohol quinolone antibacterial agent, micromolecular diol and an alkali metal catalyst into a pressure-resistant reaction kettle, replacing nitrogen until the oxygen content in the kettle is less than 50ppm, adding an epoxy compound to carry out polymerization reaction, continuing internal pressure reaction for 3-5 hours after the reaction is finished, removing unreacted monomers to obtain crude polyether polyol, and neutralizing, hydrolyzing, adsorbing, dehydrating and filtering to obtain the antibacterial slow-rebound polyether polyol. The preparation method of the polyether polyol for the antibacterial polyurethane slow-resilience foam has scientific and reasonable design and simple operation, and enables the antibacterial groups to be permanently grafted on the polyurethane chain segments, thereby obtaining the polyurethane slow-resilience foam which is environment-friendly, safe and has lasting antibacterial property.
Description
Technical Field
The invention relates to a preparation method of polyether polyol for antibacterial polyurethane slow-resilience foam, belonging to the technical field of polyether polyol modification.
Background
Polyurethane slow-rebound foam is commonly used in daily life occasions of people, such as mattresses, pillows, sofas and the like. Due to the porosity and the moisture absorption of the polyurethane foam, after long-term use, skin chips, sweat stains and the like are remained in the pores of the polyurethane foam and are easy to breed bacteria, and the improvement of the antibacterial performance of the slow-rebound polyurethane foam material is very significant.
The prior art mostly achieves the antibacterial effect by additionally adding an antibacterial agent. The antibacterial agents are classified into inorganic antibacterial agents and organic antibacterial agents, wherein the organic antibacterial agents are classified into natural, low-molecular and high-molecular organic antibacterial agents. The inorganic antibacterial agent comprises nano silver, copper, titanium dioxide, zinc oxide and the like, the organic antibacterial agent comprises natural antibacterial materials such as polysaccharide, polypeptide, chitosan and the like, and synthetic organic antibacterial materials such as antibiotics, quaternary ammonium salt, guanidine compounds and the like.
The invention patent CN111440283A improves the antibacterial effect of the memory cotton through the synergistic effect of the nano silver and the far infrared additive, and the invention patent CN105400176A improves the antibacterial effect through the compounding of the organic antibacterial agent, the nano silver antibacterial agent and the chitosan, but is still an external blending mode in essence, and is easy to migrate to cause the reduction of the antibacterial performance and environmental pollution.
In patent CN113045726A, the polyguanidine modified isocyanate prepolymer is used to permanently graft an antibacterial group on a polyurethane chain segment, so that the prepared macromolecular antibacterial polyurethane memory cotton is obtained. In patent CN104892893B, polyether polyol composition and isocyanate are taken as basic raw materials, quinolone antibacterial agent is added to participate in polycondensation reaction, and the quinolone antibacterial agent is fixed on polyurethane material, so that the antibacterial polyurethane cushion material with lasting antibacterial, safe, harmless and efficient effects is obtained. However, none of the above patents relate to the use of antimicrobials in modified polyethers and excessive addition of monofunctional antimicrobials to the foam can affect the foam properties.
Disclosure of Invention
The invention aims to solve the technical problem of overcoming the defects in the prior art and provides a preparation method of polyether polyol for antibacterial polyurethane slow-resilience foam, which has scientific and reasonable design and simple operation, and enables an antibacterial group to be permanently grafted on a polyurethane chain segment, thereby obtaining the environment-friendly, safe and long-lasting antibacterial polyurethane slow-resilience foam.
The preparation method of the polyether polyol for the antibacterial polyurethane slow-resilience foam comprises the following steps:
adding an alcohol quinolone antibacterial agent, micromolecular diol and an alkali metal catalyst into a pressure-resistant reaction kettle, replacing nitrogen until the oxygen content in the kettle is less than 50ppm, adding an epoxy compound to carry out polymerization reaction, continuing internal pressure reaction for 3-5 hours after the reaction is finished, removing unreacted monomers to obtain crude polyether polyol, and neutralizing, hydrolyzing, adsorbing, dehydrating and filtering to obtain the antibacterial slow-rebound polyether polyol.
Preferably, the alcoholic quinolone antibacterial agent is one or both of 2, 6-biquinolinediol or 2, 7-dihydroxyquinolinediol.
Preferably, the small molecular glycol initiator is one or more of propylene glycol, diethylene glycol or dipropylene glycol, and the use amount of the small molecular glycol initiator is 5-15 times of the molar amount of the antibacterial agent.
Preferably, the alkali metal catalyst is one or two of potassium hydroxide or sodium hydroxide, and the dosage of the alkali metal catalyst accounts for 0.2-0.4% of the crude polyether polyol.
Preferably, the epoxy compound is obtained by random copolymerization of one or two of propylene oxide and ethylene oxide, the initial feeding temperature is 80 +/-2 ℃, and the temperature is gradually increased to 105-120 ℃ along with the reaction.
And the neutralization is to add phosphoric acid with the mass concentration of 70% or 85% into the crude polyether polyol, neutralize until the pH is 6.5-7.5, and stir for 0.5-1.5 hours.
And in the hydrolysis, pure water accounting for 3-5% of the weight of the crude polyether polyol is added to convert the end alkoxide group into the end hydroxyl group under the stirring state.
And in the adsorption step, one or two of magnesium silicate or aluminum silicate accounting for 0.1-0.4% of the total mass are added into the hydrolyzed polyether polyol, and the mixture is stirred for 0.5-1.5 hours.
And the dehydration is to remove water to a mass content of less than 0.05% by vacuumizing at a temperature of 100-130 ℃ and a pressure of-0.1-0.093 MPa.
Compared with the prior art, the invention has the following beneficial effects:
(1) the quinolone antibacterial agent is used as an initiator to synthesize polyether polyol, and conventional low molecular weight polyether polyol is replaced in a polyurethane slow-resilience foam formula, so that an antibacterial group can be permanently grafted on a polyurethane chain segment, and thus the polyurethane slow-resilience foam which is environment-friendly, safe and has a lasting antibacterial property is obtained;
(2) the invention has scientific and reasonable design, simple operation and low reaction activity of the solid antibacterial agent, the early reaction activity is improved by adding the low molecular weight polyether polyol initiator, the requirement on a production device is greatly reduced, and the conventional polyether polyol production device can produce the antibacterial agent.
Detailed Description
The present invention will be further described with reference to comparative examples and examples.
The method is a conventional method unless otherwise specified. The starting materials are commercially available from the open literature unless otherwise specified.
Example 1
Adding 16.1g of 2, 6-biquinoline diol, 68.4g of propylene glycol and 6g of potassium hydroxide into a pressure-resistant reaction kettle, replacing the nitrogen until the oxygen content in the kettle is less than 50ppm, adding 2100g of propylene oxide, carrying out polymerization reaction at 110 +/-5 ℃, continuing internal pressure reaction for 4 hours after the reaction is finished, and removing unreacted monomers to obtain the crude polyether polyol.
Adding 70% phosphoric acid by mass into the crude polyether polyol, neutralizing to pH 6.0, stirring for 1 hour, adding 8g of pure water, stirring for 0.5 hour, adding 2g of magnesium silicate and 2g of aluminum silicate by mass, and stirring for 0.5 hour. And (3) vacuumizing at the temperature of 120 +/-10 ℃ and under the pressure of-0.1 MPa to remove water, and filtering to obtain the antibacterial slow-rebound polyether polyol A with the hydroxyl value of 56.5 mgKOH/g.
Example 2
Adding 8g of 2, 6-biquinoline diol, 8g of 2, 7-dihydroxyquinoline diol, 68.4g of propylene glycol and 6g of potassium hydroxide into a pressure-resistant reaction kettle, replacing nitrogen until the oxygen content in the kettle is less than 50ppm, adding 1750g of propylene oxide and 300g of ethylene oxide, carrying out polymerization reaction at the temperature of 115 +/-5 ℃, continuing internal pressure reaction for 4 hours after the reaction is finished, and removing unreacted monomers to obtain the crude polyether polyol.
Adding 70% phosphoric acid into crude polyether polyol, neutralizing to pH 6.0, stirring for 1 hr, adding 8g pure water, stirring for 0.5 hr, adding 2g magnesium silicate and 1g aluminum silicate, and stirring for 0.5 hr. And (3) vacuumizing at the temperature of 110 +/-10 ℃ and under the pressure of-0.093 MPa to remove water, and filtering to obtain the antibacterial slow-rebound polyether polyol B with the hydroxyl value of 57.2 mgKOH/g.
Example 3
Adding 16.1g of 2, 7-dihydroxyquinoline glycol, 53g of diethylene glycol, 53g of dipropylene glycol and 5g of potassium hydroxide into a pressure-resistant reaction kettle, replacing nitrogen until the oxygen content in the kettle is less than 50ppm, adding 1300g of propylene oxide and 100g of ethylene oxide, carrying out polymerization reaction at the temperature of 115 +/-5 ℃, continuing internal pressure reaction for 5 hours after the reaction is finished, and removing unreacted monomers to obtain the crude polyether polyol.
Adding 70% phosphoric acid by mass into the crude polyether polyol, neutralizing to pH 6.5, stirring for 1 hour, adding 10g of pure water, stirring for 0.5 hour, adding 3g of magnesium silicate by mass, and stirring for 0.5 hour. And (3) vacuumizing at the temperature of 120 +/-5 ℃ and under the pressure of-0.095 MPa to remove water, and filtering to obtain the antibacterial slow-rebound polyether polyol C with the hydroxyl value of 79.2 mgKOH/g.
The application example is as follows:
foaming according to the following slow rebound polyurethane foam formulation,
the manufacturer F8001B is Shandong-Nowei New Material Co., Ltd, the silicone oil BL-7118 is Shanghai Maihao chemical science and technology Co., Ltd, the modified isocyanate DG5412 is Shandong-Nowei polyurethane Co., Ltd, the polyether polyol A, B, C is the polyether prepared in examples 1-3, and the rest is a general product sold in the conventional market. The bacteriostasis rate is detected according to the national standard GB/T20944, and the bacteriostasis rate is detected after 50 times of water washing, and the result is as follows:
TABLE 1
Claims (10)
1. A preparation method of polyether polyol for antibacterial polyurethane slow-resilience foam is characterized by comprising the following steps: taking an alcohol quinolone antibacterial agent and micromolecular diol as a composite initiator, taking alkali metal as a catalyst, carrying out ring-opening polymerization with an epoxy compound to obtain crude polyether polyol, and then carrying out post-treatment to obtain the polyether polyol for the antibacterial polyurethane slow-resilience foam.
2. The method for preparing polyether polyol for antibacterial polyurethane slow rebound foam according to claim 1, wherein: the alcohol quinolone antibacterial agent is one or two of 2, 6-biquinolyl diol or 2, 7-dihydroxyquinolyl diol.
3. The method for preparing polyether polyol for antibacterial polyurethane slow rebound foam according to claim 1, wherein: the small molecular glycol is one or more of propylene glycol, diethylene glycol or dipropylene glycol.
4. The method for preparing polyether polyol for antibacterial polyurethane slow rebound foam according to claim 1 or 3, wherein: the dosage of the micromolecular diol is 5-15 times of the molar weight of the antibacterial agent.
5. The method for preparing polyether polyol for antibacterial polyurethane slow rebound foam according to claim 1, wherein: the alkali metal is one or two of potassium hydroxide or sodium hydroxide.
6. The method for preparing polyether polyol for antibacterial polyurethane slow rebound foam according to claim 1 or 5, wherein: the dosage of the alkali metal is 0.2-0.4% of the mass of the crude polyether polyol.
7. The method for preparing polyether polyol for antibacterial polyurethane slow rebound foam according to claim 1, wherein: the epoxy compound is obtained by random copolymerization of one or two of propylene oxide and ethylene oxide, the initial feeding temperature is 80 +/-2 ℃, and the temperature is increased to 105-120 ℃ along with the reaction.
8. The method for preparing polyether polyol for antibacterial polyurethane slow rebound foam according to claim 1, wherein: the post-treatment comprises neutralization, hydrolysis, adsorption, dehydration and filtration.
9. The method for preparing polyether polyol for antibacterial polyurethane slow rebound foam according to claim 8, wherein: and during neutralization, adding 70% or 85% phosphoric acid into the crude polyether polyol, neutralizing until the pH value is 6.5-7.5, and stirring for 0.5-1.5 hours.
10. The method for preparing polyether polyol for antibacterial polyurethane slow rebound foam according to claim 8, wherein: the adsorbent used for adsorption is one or two of magnesium silicate or aluminum silicate, and the dosage of the adsorbent is 0.1-0.3% of the total mass of the hydrolyzed polyether polyol.
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| CN101792524A (en) * | 2010-02-05 | 2010-08-04 | 中国科学院上海有机化学研究所 | Glycosyl polyethers, preparation method thereof and use thereof |
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| CN104892893A (en) * | 2015-06-29 | 2015-09-09 | 鹤山市鹤威科技发展有限公司 | Polyurethane cushion material with anti-bacterial function and preparation method and application thereof |
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| CN105315451A (en) * | 2015-11-25 | 2016-02-10 | 山东一诺威新材料有限公司 | Slow-recovery polyether polyol and preparation method thereof and slow-recovery foam and preparation method thereof |
| CN108359089A (en) * | 2018-01-11 | 2018-08-03 | 大连九信精细化工有限公司 | A kind of antibiotic property poly(aryl ether ketone) material and preparation method thereof |
| JP2019048781A (en) * | 2017-09-11 | 2019-03-28 | 日本ゼオン株式会社 | Antibacterial agent, composition for molded body and crosslinking composition using the same |
| CN111019115A (en) * | 2019-12-20 | 2020-04-17 | 上海东大化学有限公司 | Antibacterial polyether and preparation method thereof |
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2021
- 2021-11-30 CN CN202111473754.5A patent/CN114316241A/en active Pending
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101883810A (en) * | 2007-09-11 | 2010-11-10 | 巴斯夫欧洲公司 | Polyglycerol anti-microbial agents and compositions |
| CN101792524A (en) * | 2010-02-05 | 2010-08-04 | 中国科学院上海有机化学研究所 | Glycosyl polyethers, preparation method thereof and use thereof |
| CN104892893A (en) * | 2015-06-29 | 2015-09-09 | 鹤山市鹤威科技发展有限公司 | Polyurethane cushion material with anti-bacterial function and preparation method and application thereof |
| CN105315449A (en) * | 2015-11-25 | 2016-02-10 | 山东一诺威新材料有限公司 | Polyether polyol used for low-density gaseousness and slow-resilience foam, preparation method of polyether polyol and slow-resilience foam and preparation method thereof |
| CN105315451A (en) * | 2015-11-25 | 2016-02-10 | 山东一诺威新材料有限公司 | Slow-recovery polyether polyol and preparation method thereof and slow-recovery foam and preparation method thereof |
| JP2019048781A (en) * | 2017-09-11 | 2019-03-28 | 日本ゼオン株式会社 | Antibacterial agent, composition for molded body and crosslinking composition using the same |
| CN108359089A (en) * | 2018-01-11 | 2018-08-03 | 大连九信精细化工有限公司 | A kind of antibiotic property poly(aryl ether ketone) material and preparation method thereof |
| CN111019115A (en) * | 2019-12-20 | 2020-04-17 | 上海东大化学有限公司 | Antibacterial polyether and preparation method thereof |
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