High-resilience antibacterial foaming material as well as preparation method and application thereof

Abstract

The invention discloses a high-resilience antibacterial foaming material as well as a preparation method and application thereof. The high-resilience antibacterial foaming material comprises the following raw material components in parts by mass: 20-70 parts of polyether polyol; 12 to 64 parts of isocyanate; 20 to 70 parts of single-end hydroxyl polydimethylsiloxane quaternary ammonium salt; 0.3 to 3 parts of nano tourmaline powder; 0.5 to 5 parts of a cross-linking agent; 0.1 to 2 parts of a catalyst; 1-10 parts of a foaming agent; and 0.1 to 2.5 parts of a foam stabilizer. Quaternary ammonium salt is introduced into a polyurethane structure in a chemical bond mode, an antibacterial agent is prevented from falling off from a matrix, the antibacterial performance of the polyurethane foam material is guaranteed, and polydimethylsiloxane is introduced so that the high-temperature stability of polyurethane can be improved, and the high-temperature resilience performance of polyurethane can be kept; meanwhile, nano tourmaline powder is introduced, so that the foaming material can release negative oxygen ions in the using process, and sanitation is guaranteed and peculiar smell is reduced when the foaming material is applied to furniture articles such as pillows.

Description

Technical Field

[0001] The invention relates to the technical field of foaming materials, and in particular to a high-resilience antibacterial foaming material and a preparation method and application thereof. Background Art

[0002] The resilience of polyurethane foam refers to the ability of the material to quickly return to its original shape after being subjected to external force. High resilience can improve the comfort and durability of the material and is widely used in furniture, automobiles, sports equipment and other fields. However, traditional polyurethane foam materials have certain limitations in terms of resilience, especially in high temperature and high humidity environments, the material's resilience will be affected.

[0003] In addition, antibacterial properties are also an important performance indicator of polyurethane foam materials. Especially in the fields of medical care, hygiene, and home furnishing, the antibacterial properties of materials are directly related to the health and safety of users. Traditional polyurethane foam materials often do not have good antibacterial properties and are prone to breeding bacteria and mold, which shortens the service life of the materials and even causes health problems. Summary of the invention

[0004] The invention provides a high-resilience antibacterial foaming material and a preparation method and application thereof, so as to solve the technical problems of reduced high-temperature resilience and poor antibacterial performance of polyurethane.

[0005] In order to solve the above technical problems, the present invention provides a high-resilience antibacterial foaming material, comprising the following raw material components in parts by mass:

[0006] 20 to 70 parts of polyether polyol;

[0007] 12 to 64 parts of isocyanate;

[0008] 20 to 70 parts of mono-terminal hydroxyl polydimethylsiloxane quaternary ammonium salt;

[0009] 0.3 to 3 parts of nano tourmaline powder;

[0010] 0.5 to 5 parts of cross-linking agent;

[0011] Catalyst 0.1 to 2 parts;

[0012] 1 to 10 parts of foaming agent;

[0013] Foam stabilizer 0.1 to 2.5 parts.

[0014] In some embodiments, the single-terminal hydroxyl polydimethylsiloxane quaternary ammonium salt is prepared according to the following steps:

[0015] Dissolve polydimethylsiloxane and 3-glycidyloxypropyltrimethoxysilane in xylene, add Karstedt catalyst, stir at 60°C to 80°C for 4 to 6 hours under nitrogen protection, then dropwise add hydroxyl protective agent in a water bath at 0 to 5°C and stir for 1 to 2 hours, wash, filter and dry to obtain an intermediate; wherein the molar ratio of polydimethylsiloxane to 3-glycidyloxypropyltrimethoxysilane is 1:1.1;

[0016] The intermediate and n-butylamine are dissolved in anhydrous ethanol, and an alkaline catalyst is added. Under nitrogen protection, the mixture is stirred at 25°C to 60°C for 8h to 12h, wherein the molar ratio of polydimethylsiloxane to n-butylamine is 1:1.1; methyl iodide is added, and stirring is continued for 4h to 6h; a hydroxyl deprotecting agent is added, and stirring is continued for 1h to 2h at 25°C to 40°C, and then the mixture is cooled to room temperature, washed with deionized water, and dried with anhydrous sodium sulfate to obtain a single-ended hydroxyl polydimethylsiloxane quaternary ammonium salt.

[0017] In some embodiments, the hydroxyl protecting agent includes one or more of trimethylsilyl chloride, triethylsilyl chloride, tert-butyldimethylsilyl chloride and isopropylsilyl chloride; the hydroxyl deprotecting agent includes any one of tetrabutylammonium fluoride, hydrogen fluoride and hydrochloric acid.

[0018] In some embodiments, the alkaline catalyst is one or more of potassium hydroxide, sodium hydroxide, sodium methoxide and tetramethylammonium hydroxide.

[0019] In some embodiments, the polyether polyol has a functionality of 2 or 3, a molecular weight of 4000 to 8000, and a hydroxyl value of 30 to 80 mg KOH / g.

[0020] In some embodiments, the nano-tourmaline powder is nano-tourmaline powder surface-treated with a silane coupling agent.

[0021] In some embodiments, the isocyanate is one or more of hexamethylene diisocyanate, diphenylmethane diisocyanate, toluene diisocyanate and isophorone diisocyanate.

[0022] In some of the embodiments, the crosslinking agent is a polyether polyol with toluene diamine as an initiator;

[0023] The catalyst is a tertiary amine catalyst (such as dimethylethanolamine) or a tin catalyst (such as stannous octoate);

[0024] The foaming agent is water;

[0025] The foam stabilizer is a siloxane stabilizer, such as polyether modified silicone oil.

[0026] The present invention provides a method for preparing a high-resilience antibacterial foam material, comprising the following steps:

[0027] Polyether polyol, single-end hydroxyl polydimethylsiloxane quaternary ammonium salt, nano tourmaline powder, crosslinking agent, catalyst, foam stabilizer and foaming agent are stirred at 15°C to 30°C at 1000 to 6000 rpm for 2h to 3h, and then isocyanate is added and stirred for 0.1min to 3min to obtain a high-resilience antibacterial foaming material.

[0028] The invention provides an application of a high-resilience antibacterial foaming material in furniture products, wherein the furniture products include pillows, cushions and mattresses.

[0029] Compared with the prior art, the present invention has at least the following beneficial effects:

[0030] The invention adopts the reaction between the hydroxyl group of the single-terminal hydroxyl polydimethylsiloxane quaternary ammonium salt and the NCO group of the isocyanate, so as to introduce the quaternary ammonium salt into the polyurethane structure through a chemical bond, thereby preventing the antibacterial agent from falling off from the matrix and ensuring the antibacterial property of the polyurethane foaming material. The introduction of the polydimethylsiloxane can improve the high-temperature stability of the polyurethane and maintain the high-temperature resilience of the polyurethane. Meanwhile, the nano-tourmaline powder is introduced so that the foaming material can release negative oxygen ions during use, and the hygiene is ensured and the odor is reduced when the foaming material is applied to furniture products such as pillows. DETAILED DESCRIPTION

[0031] In order to make the above-mentioned purpose, features and advantages of the present invention more obvious and easy to understand, the specific embodiments of the present invention are described in detail below. In the following description, many specific details are set forth to facilitate a full understanding of the present invention. However, the present invention can be implemented in many other ways different from those described herein, and those skilled in the art can make similar improvements without violating the connotation of the present invention, so the present invention is not limited by the specific embodiments disclosed below.

[0032] As used herein, the term "prepared from" is synonymous with "comprising." As used herein, the terms "comprising," "including," "having," "containing," or any other variation thereof, are intended to cover a non-exclusive inclusion. For example, a composition, process, method, article, or apparatus that comprises the listed elements is not necessarily limited to only those elements but may include other elements not expressly listed or inherent to such composition, process, method, article, or apparatus.

[0033] When amount, concentration or other value or parameter is expressed as range, preferred range or a series of upper preferred value and lower preferred value limit range, this should be understood as specifically disclosing all ranges formed by any pairing of any range upper limit or preferred value and any range lower limit or preferred value, regardless of whether the range is disclosed separately. For example, when disclosing range "1 to 5", described range should be interpreted as including range "1 to 4", "1 to 3", "1 to 2", "1 to 2 and 4 to 5", "1 to 3 and 5" etc. When numerical range is described in this article, unless otherwise stated, the range is intended to include its end value and all integers and fractions within the range.

[0034] In addition, the indefinite articles "a" and "an" before the elements or components of the present invention have no restrictions on the quantity requirements (i.e. the number of occurrences) of the elements or components. Therefore, "a" or "an" should be interpreted as including one or at least one, and the elements or components in the singular form also include the plural form, unless the number is obviously intended to be in the singular form.

[0035] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as those commonly understood by those skilled in the art of the present invention. The terms used herein in the specification of the present invention are only for the purpose of describing specific embodiments and are not intended to limit the present invention. The term "and / or" used herein includes any and all combinations of one or more related listed items.

[0036] 1. Preparation of single-terminal hydroxyl polydimethylsiloxane siloxane quaternary ammonium salt:

[0037] Dissolve polydimethylsiloxane and 3-glycidyloxypropyltrimethoxysilane in a molar ratio of 1:1.1 in xylene, add Karstedt catalyst, stir at 70°C for 5 hours under nitrogen protection, then dropwise add trimethylchlorosilane in a water bath at 0-5°C and stir for 2 hours, wash, filter and dry to obtain an intermediate;

[0038] The n-butylamine in a molar ratio of 1:1.1 to polydimethylsiloxane and the above intermediate are dissolved in anhydrous ethanol, potassium hydroxide is added, and the mixture is stirred at 50°C for 9 hours under nitrogen protection; methyl iodide is added and stirring is continued for 5 hours; hydrogen fluoride is added and stirring is continued at 40°C for 1.5 hours, and the mixture is cooled to room temperature, washed with deionized water and dried with anhydrous sodium sulfate to obtain a single-end hydroxyl polydimethylsiloxane quaternary ammonium salt.

[0039] 2. Surface treatment of nano tourmaline powder with silane coupling agent:

[0040] The nano-tourmaline powder was added to the ethanol solution of the silane coupling agent, stirred at 40°C for 4 hours to make the silane coupling agent evenly adsorbed on the surface of the nano-tourmaline powder, the solvent was removed by filtration, and vacuum dried at 100°C for 2 hours to obtain the surface-treated nano-tourmaline powder.

[0041] Example 1

[0042] A high-resilience antibacterial foaming material comprises the following raw material components in parts by mass:

[0043] 25 parts of polyether polyol (functionality 2, molecular weight 4000, hydroxyl value 30mg KOH / g); 15 parts of hexamethylene diisocyanate; 20 parts of single-end hydroxyl polydimethylsiloxane quaternary ammonium salt; 0.3 parts of nano tourmaline powder (surface treated with silane coupling agent); 0.5 parts of crosslinking agent; 0.3 parts of dimethylethanolamine; 1 part of water; 0.2 parts of polyether modified silicone oil.

[0044] The preparation method comprises: stirring polyether polyol, single-end hydroxyl polydimethylsiloxane quaternary ammonium salt, nano tourmaline powder, crosslinking agent, catalyst, foam stabilizer and foaming agent at 15°C and 6000 rpm for 2 hours, adding isocyanate and continuing stirring for 0.1 minute to obtain a high-resilience antibacterial foaming material.

[0045] Example 2

[0046] A high-resilience antibacterial foaming material comprises the following raw material components in parts by mass:

[0047] 70 parts of polyether polyol (functionality 2, molecular weight 6000, hydroxyl value 50mg KOH / g); 38 parts of hexamethylene diisocyanate; 25 parts of single-end hydroxyl polydimethylsiloxane quaternary ammonium salt; 1.5 parts of nano tourmaline powder (surface treated with silane coupling agent); 3 parts of crosslinking agent; 1 part of dimethylethanolamine; 5 parts of water; 1.5 parts of polyether modified silicone oil.

[0048] The preparation method comprises: stirring polyether polyol, single-end hydroxyl polydimethylsiloxane quaternary ammonium salt, nano tourmaline powder, crosslinking agent, catalyst, foam stabilizer and foaming agent at 25°C and 2000 rpm for 3 hours, adding isocyanate and continuing stirring for 2 minutes to obtain a high-resilience antibacterial foaming material.

[0049] Example 3

[0050] A high-resilience antibacterial foaming material comprises the following raw material components in parts by mass:

[0051] 70 parts of polyether polyol (functionality 3, molecular weight 8000, hydroxyl value 80mg KOH / g); 64 parts of hexamethylene diisocyanate; 65 parts of single-end hydroxyl polydimethylsiloxane quaternary ammonium salt; 3 parts of nano tourmaline powder (surface treated with silane coupling agent); 5 parts of crosslinking agent; 2 parts of dimethylethanolamine; 10 parts of water; 2.5 parts of polyether modified silicone oil.

[0052] The preparation method comprises: stirring polyether polyol, single-end hydroxyl polydimethylsiloxane quaternary ammonium salt, nano tourmaline powder, crosslinking agent, catalyst, foam stabilizer and foaming agent at 30°C and 1000 rpm for 3 hours, adding isocyanate and continuing stirring for 3 minutes to obtain a high-resilience antibacterial foaming material.

[0053] Comparative Example 1

[0054] The difference from Example 1 is that, in Comparative Example 1, no single-terminal hydroxyl polydimethylsiloxane quaternary ammonium salt is added.

[0055] Comparative Example 2

[0056] The difference from Example 1 is that Comparative Example 2 uses equimolar amounts of hydroxy-terminated polydimethylsiloxane and carboxymethyl chitosan quaternary ammonium salt instead of mono-hydroxy-terminated dimethylsiloxane quaternary ammonium salt.

[0057] Comparative Example 3

[0058] The difference from Example 1 is that in Comparative Example 3, no nano tourmaline powder is added.

[0059] Comparative Example 4

[0060] The difference from Example 1 is that the nano-tourmaline powder of Comparative Example 4 is not treated in any way.

[0061] Comparative Example 5

[0062] The difference from Example 1 is that in Comparative Example 5, single-terminal hydroxyl polydimethylsiloxane quaternary ammonium salt and nano tourmaline powder are not added.

[0063] The polyurethane foam materials obtained in Examples 1 to 3 and Comparative Examples 1 to 5 were prepared into pillows, and the pillows were tested for performance. The resilience performance test (including material testing after heat treatment at room temperature and 85°C for 30 minutes) was in accordance with GB / T 6670-2008, the antibacterial performance test was in accordance with GB / T 20944.3-2008, and the purification performance was in accordance with GB / T30128-2013. The test results are shown in Table 1:

[0064] Table 1 Performance test results of Examples 1 to 3 and Comparative Examples 1 to 5

[0065]

[0066]

[0067] It can be seen from Table 1 that the room temperature rebound rates of Examples 1 to 3 are all maintained above 55, and the rebound rate after heat treatment does not decrease significantly, indicating that Examples 1 to 3 can maintain good high temperature rebound performance; the antibacterial rate and negative oxygen ion content of Examples 1 to 3 are significantly better than those of Comparative Examples 1 to 5, and have excellent antibacterial and purification performance. Compared with Comparative Examples 1 to 5, it can be seen that the addition of single-terminal hydroxyl polydimethylsiloxane quaternary ammonium salt and nano tourmaline powder in Example 1 has a synergistic effect on high temperature rebound performance, antibacterial performance and purification performance.

[0068] The technical features of the above-described embodiments may be arbitrarily combined. To make the description concise, not all possible combinations of the technical features in the above-described embodiments are described. However, as long as there is no contradiction in the combination of these technical features, they should be considered to be within the scope of this specification.

[0069] The specific embodiments described above further illustrate the purpose, technical solutions and beneficial effects of the present invention. It should be understood that the above description is only a specific embodiment of the present invention and is not intended to limit the scope of protection of the present invention. It is particularly pointed out that for those skilled in the art, any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention should be included in the scope of protection of the present invention.

Claims

1. A high resilience antibacterial foam material, characterized in that: The invention comprises the following raw material components in parts by mass: 20 to 70 parts of polyether polyol; 12 to 64 parts of isocyanate; 20 to 70 parts of mono-terminal hydroxyl polydimethylsiloxane quaternary ammonium salt; 0.3 to 3 parts of nano tourmaline powder; 0.5 to 5 parts of cross-linking agent; Catalyst 0.1 to 2 parts; 1 to 10 parts of foaming agent; Foam stabilizer 0.1 to 2.5 parts.

2. The high resilience antibacterial foam material according to claim 1, characterized in that: The mono-terminal hydroxyl polydimethylsiloxane quaternary ammonium salt is prepared according to the following steps: Dissolve polydimethylsiloxane and 3-glycidyloxypropyltrimethoxysilane in xylene, add Karstedt catalyst, stir at 60°C to 80°C for 4 to 6 hours under nitrogen protection, then dropwise add hydroxyl protective agent in a water bath at 0 to 5°C and stir for 1 to 2 hours, wash, filter and dry to obtain an intermediate; wherein the molar ratio of polydimethylsiloxane to 3-glycidyloxypropyltrimethoxysilane is 1:1.1; The intermediate and n-butylamine are dissolved in anhydrous ethanol, and an alkaline catalyst is added. Under nitrogen protection, the mixture is stirred at 25°C to 60°C for 8h to 12h, wherein the molar ratio of polydimethylsiloxane to n-butylamine is 1:1.1; methyl iodide is added, and stirring is continued for 4h to 6h; a hydroxyl deprotecting agent is added, and stirring is continued for 1h to 2h at 25°C to 40°C, and then the mixture is cooled to room temperature, washed with deionized water, and dried with anhydrous sodium sulfate to obtain a single-ended hydroxyl polydimethylsiloxane quaternary ammonium salt.

3. The high resilience antibacterial foam material according to claim 2, characterized in that: The hydroxyl protecting agent includes one or more of trimethylsilyl chloride, triethylsilyl chloride, tert-butyldimethylsilyl chloride and isopropylsilyl chloride; the hydroxyl deprotecting agent includes any one of tetrabutylammonium fluoride, hydrogen fluoride and hydrochloric acid.

4. The high resilience antibacterial foam material according to claim 2, characterized in that: The alkaline catalyst is one or more of potassium hydroxide, sodium hydroxide, sodium methoxide and tetramethylammonium hydroxide.

5. The high resilience antibacterial foam material according to claim 1, characterized in that: The functionality of the polyether polyol is 2 or 3, the molecular weight is 4000-8000, and the hydroxyl value is 30-80 mg KOH / g.

6. The high resilience antibacterial foam material according to claim 1, characterized in that: The nano-tourmaline powder is nano-tourmaline powder surface-treated with a silane coupling agent.

7. The high resilience antibacterial foam material according to claim 1, characterized in that: The isocyanate is one or more of hexamethylene diisocyanate, diphenylmethane diisocyanate, toluene diisocyanate and isophorone diisocyanate.

8. The high resilience antibacterial foam material according to claim 1, characterized in that: The cross-linking agent is a polyether polyol with toluenediamine as an initiator; The catalyst is a tertiary amine catalyst or a tin catalyst; The foaming agent is water; The foam stabilizer is a silicone stabilizer.

9. A method for preparing a high-resilience antibacterial foam material according to any one of claims 1 to 8, characterized in that: The following steps are involved: Polyether polyol, single-end hydroxyl polydimethylsiloxane quaternary ammonium salt, nano tourmaline powder, crosslinking agent, catalyst, foam stabilizer and foaming agent are stirred at 15°C to 30°C at 1000 to 6000 rpm for 2h to 3h, and then isocyanate is added and stirred for 0.1min to 3min to obtain a high-resilience antibacterial foaming material.

10. An application of the high resilience antibacterial foam material according to any one of claims 1 to 8 in furniture products, characterized in that: The furniture items include pillows, cushions and mattresses.

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