CN-122011424-A - Modified polyester polyol, antibacterial polyurethane microporous elastomer and preparation method of elastomer

CN122011424ACN 122011424 ACN122011424 ACN 122011424ACN-122011424-A

Abstract

The invention belongs to the technical field of polyurethane elastomers, and particularly relates to a modified polyester polyol, an antibacterial polyurethane microporous elastomer and a preparation method of the elastomer. The modified polyester polyol is prepared by grafting modified Ag@SiO 2 , and the antibacterial polyurethane microporous elastomer is prepared by using the modified polyester polyol. The antibacterial polyurethane microporous elastomer is mainly prepared by mixing and curing an A component and a B component, wherein the A component mainly comprises conventional polyester polyol and modified polyester polyol, and the B component mainly comprises conventional polyester polyol, polyether polyol and isocyanate; according to the antibacterial polyurethane microporous elastomer and the preparation method thereof, the prepared polyurethane microporous elastomer has long-acting and stable antibacterial performance, is uniformly dispersed, and simultaneously maintains excellent physical and mechanical properties and a microporous structure.

Inventors

LIU GUANGCHEN
LI YINGQIAN
WAN ZHIQIANG
ZHOU SHUCHENG
XIN LANXIA
Qu Shaokang
MENG SUQING
LI WEI
LI YING
GAN JINGHU

Assignees

山东一诺威聚氨酯股份有限公司

Dates

Publication Date: 20260512
Application Date: 20260407

Claims (10)

1. The modified polyester polyol is characterized by comprising the following specific preparation methods: (1) Preparing Ag@SiO 2 , namely adding ethanol into silver sol for mixing, then adding ammonia water, adding tetraethoxysilane after mixing, and heating and drying to obtain Ag@SiO 2 ; (2) The Ag@SiO 2 is grafted and modified by dissolving a silane coupling agent and water in absolute ethyl alcohol, stirring the mixed solution, dispersing Ag@SiO 2 in the absolute ethyl alcohol, adding the mixed solution, heating for reaction, and cleaning and drying reactants to obtain grafted and modified Ag@SiO 2 ; (3) And (3) preparing polyester polyol, namely heating and dehydrating the conventional polyester polyol, cooling, mixing with grafted modified Ag@SiO 2 and isocyanate, heating for reaction, and obtaining the qualified isocyanate group to obtain the modified polyester polyol.
2. The modified polyester polyol according to claim 1, wherein the molar ratio of the conventional polyester polyol to the isocyanate in the step (3) is 1:0.6-1, and the amount of the grafted modified Ag@SiO 2 is 0.2-0.8wt% of the polyester polyol.
3. The modified polyester polyol according to claim 1, wherein the addition amount of the ethyl orthosilicate in the step (1) is 0.02-0.04 wt% of the total amount of silver sol, ethanol and ammonia water.
4. The modified polyester polyol according to claim 1, wherein the addition amount of Ag@SiO 2 in the step (2) is 40-60wt% of the total amount of the silane coupling agent, water and absolute ethyl alcohol.
5. An antibacterial polyurethane microporous elastomer prepared by the modified polyester polyol according to any one of claims 1 to 4, wherein the antibacterial polyurethane microporous elastomer comprises an A component and a B component, wherein the A component comprises conventional polyester polyol and modified polyester polyol, and the B component comprises conventional polyester polyol, polyether polyol and isocyanate; The number average molecular weight of the modified polyester polyol is 4000-6000g/mol, and the preparation process comprises the step of introducing an Ag@SiO 2 core-shell structure grafted and modified by a silane coupling agent into a conventional polyester polyol molecular chain in a chemical bonding mode.
6. The antimicrobial polyurethane microporous elastomer according to claim 5, wherein the component A comprises 60 to 80 parts of conventional polyester polyol, 25 to 40 parts of modified polyester polyol, 3 to 7 parts of chain extender, 0.2 to 0.5 part of cross-linking agent, 0.4 to 1 part of foam stabilizer, 1.0 to 2.0 parts of catalyst and 0.5 to 0.7 part of foaming agent, based on 100 parts of the total amount of the conventional polyester polyol and the modified polyester polyol, and the component B comprises 10 to 25 parts of conventional polyester polyol, 5 to 10 parts of polyether polyol and 65 to 85 parts of isocyanate.
7. The antimicrobial polyurethane microporous elastomer according to claim 5, wherein the conventional polyester polyol is prepared from a small-molecule polyol and a dibasic acid through an esterification condensation reaction, and has a number average molecular weight of 1500-2500 g/mol and a functionality of 2-2.06.
8. The method according to claim 5, wherein the isocyanate is one or a mixture of 4,4' -diphenylmethane diisocyanate and carbodiimide-modified MDI.
9. A process for producing an antimicrobial polyurethane microporous elastomer according to claim 5, comprising the steps of: 1) The preparation of the component A comprises the steps of mixing conventional polyester polyol, modified polyester polyol, chain extender, cross-linking agent, foam stabilizer, foaming agent and catalyst, and stirring at the normal pressure of 60-70 ℃ to obtain the component A; 2) Preparing a component B, namely mixing conventional polyester polyol and polyether polyol, controlling the temperature of the mixture to be 40-50 ℃, adding isocyanate, and reacting at 70-80 ℃ to obtain the component B, wherein the content of-NCO of the component B is 20.0-27.5wt%; 3) And (3) preparing the antibacterial polyurethane microporous elastomer, namely mixing the component A and the component B, injecting the mixture into a die with the temperature of 30-50 ℃, and curing the mixture for 10-20 min to obtain the antibacterial polyurethane microporous elastomer.
10. The method for preparing an antibacterial polyurethane microporous elastomer according to claim 9, wherein the mass ratio of the component A to the component B in the step 3) is 100:40-75.

Description

Modified polyester polyol, antibacterial polyurethane microporous elastomer and preparation method of elastomer Technical Field The invention belongs to the technical field of polyurethane elastomers, and particularly relates to a modified polyester polyol, an antibacterial polyurethane microporous elastomer and a preparation method of the elastomer. Background The polyurethane microporous elastomer is a high polymer material with excellent physical and mechanical properties, and the product is widely applied to a plurality of fields such as soles, sealing elements, buffer materials and the like by virtue of the outstanding characteristics of excellent elasticity, light weight, portability, wear resistance, oil resistance, chemical corrosion resistance and the like, is deeply favored by market consumers, and takes an important role in daily production and life. However, the elastomer has obvious performance defects in the actual use process, and particularly the problem is more remarkable in an application scene in a damp-heat environment for a long time. Taking the polyurethane microporous elastomer sole with the most wide application as an example, sweat generated in the walking process of people can lead the sole to be in a damp-heat state for a long time, harmful bacteria such as escherichia coli, staphylococcus aureus and the like are extremely easy to breed in the environment, so that the aging degradation of the sole material can be accelerated, the mechanical property and the service life of the sole material are reduced, bad odor can be generated due to bacterial metabolism, the use experience is directly influenced, and meanwhile, the propagation of bacteria can bring potential adverse effects to the health of a human body. In addition, in the fields of medical treatment, food contact and the like with higher requirements on sanitation, the problem of bacterial growth on the surface of the polyurethane microporous elastomer also limits the further application expansion of the polyurethane microporous elastomer, so that the polyurethane microporous elastomer is endowed with long-acting and stable antibacterial performance, and the polyurethane microporous elastomer becomes the research focus and urgent need in the field at present. At present, the mainstream technical means for solving the antibacterial problem of the polyurethane microporous elastomer in the industry is to directly add an antibacterial agent in the preparation process, inhibit bacterial growth and reproduction by the action of the antibacterial agent, and the method is simple and convenient to operate and low in cost, is the technical scheme closest to the subject of the invention in the prior art, and related technologies are disclosed in a plurality of prior patents. For example, patent CN106084176a discloses an environment-friendly antibacterial thermoplastic polyurethane elastomer and a preparation method thereof, the core is to realize the antibacterial function of the elastomer by adding an antibacterial agent into polyurethane raw materials, patent CN116003732a also adopts a mode of adding the antibacterial agent to prepare a yellowing-resistant antibacterial polyurethane sole raw material aiming at the antibacterial requirement of the polyurethane sole so as to try to solve the problems of bacterial growth and peculiar smell of the sole, and in addition, the polyurethane microporous foam elastomer disclosed in patent CN113801465A and the preparation method thereof also mention that the additional performances such as antibacterial performance can be realized by adding functional auxiliary agents, and the like, and basically still belong to the category of additive antibacterial technology. Although the antibacterial property of the polyurethane microporous elastomer can be improved to a certain extent by the additive antibacterial technology, the inherent defects which are difficult to overcome exist in the practical application and the processing process, and the stability and the durability of the antibacterial effect are seriously affected. Firstly, the compatibility between the antibacterial agent and polyurethane base materials (especially core raw materials such as polyester polyol and isocyanate) is poor, uneven dispersion easily occurs in the processing process, so that local defects are formed in the elastomer, the physical and mechanical properties of the product can be reduced, the antibacterial effect is obviously uneven, and the effective antibacterial effect cannot be achieved in partial areas. Secondly, most of the added antibacterial agents exist in a polyurethane system in a physical mixing mode, stable chemical combination is not formed between the antibacterial agents and polyurethane molecular chains, the antibacterial agents are extremely easy to separate out from the inside of an elastomer in long-term use, friction or damp-heat environments, on one hand, the antibacterial agents are lost, the antibac