CN114452434A - Broad-spectrum antibacterial polyurethane foam dressing and preparation method and application thereof - Google Patents

Abstract

The invention discloses a broad-spectrum antibacterial polyurethane foam dressing and a preparation method and application thereof. The preparation method comprises the following steps: mixing polyether polyol, amine catalyst, zinc catalyst, organosilicon foam stabilizer, water, foaming Mixing agent, cymene and hexamidine bis(isethionate) salt uniformly to obtain a mixture; mixing diphenylmethane diisocyanate and the mixture uniformly, pouring into a mold for foaming, and demoulding after curing to obtain Broad spectrum antimicrobial polyurethane foam dressing. Through the specific selection and compounding of various polyether polyols, the prepared polyurethane dressing has good mechanical strength and softness, and has excellent antibacterial and bacteriostatic properties; at the same time, the catalysts used for preparing the dressing are safe Non-toxic, the prepared dressing is more suitable for application as a medical dressing.

Description

A kind of broad-spectrum antibacterial polyurethane foam dressing and preparation method and application thereof

technical field

The invention relates to the technical field of medical materials, in particular to a broad-spectrum antibacterial polyurethane foam and a preparation method and application thereof.

Background technique

At present, the development of science and technology has made people's requirements for medical dressings continue to increase. Traditional dressings such as gauze and cotton are easy to breed bacteria, and wound exudate is easy to form crusts with dry dermal tissue, which hinders epithelialization, and the wound is easy to adhere to the dressing. , when the dressing is opened, it will cause secondary trauma to the patient, so it is very important to invent a new type of wound dressing.

There are many types of dressings used clinically. Among them, the foam-type polyurethane medical dressing is suitable for the formation of granulation on the wound surface. The foam-type dressing can absorb excess wound exudate, and at the same time can block external foreign bodies and some bacteria, protect the exposed nerve endings. pain. At the same time, because the foam dressing is kept moist, it avoids the excessive evaporation of wound exudates to form dry scabs, so there will be no mechanical damage again when the dressing is changed, which is beneficial to the healing of the wound. There are many types of bacteria in wounds. Common pathogenic bacteria are Staphylococcus, Streptococcus, Escherichia coli, etc. Its characteristics are: the same pathogenic bacteria can cause several different purulent infections, such as Staphylococcus aureus can cause boils, Carbuncles, abscesses, wound infections, etc., and different pathogenic bacteria can cause the same disease, such as Staphylococcus aureus, Streptococcus and Escherichia coli can cause acute cellulitis, soft tissue abscess wound infection, etc. The common characteristics of purulent inflammation, namely redness, swelling, heat, pain and dysfunction, are also common in prevention and treatment. Existing antibacterial dressings are mainly produced by blending antibacterial agents and raw materials. Although they have antibacterial effects, most of them cannot achieve long-term bacteriostasis, and the antibacterial scope is narrow and the effect is poor. Therefore, it is necessary to propose a new antibacterial dressing for solving the above problems existing in the prior art.

SUMMARY OF THE INVENTION

The purpose of the present invention is to provide a broad-spectrum antibacterial polyurethane foam dressing and its preparation method and application, which are used to solve the problems of short antibacterial time, narrow antibacterial range and poor effect in existing antibacterial dressings.

In order to solve the above-mentioned technical problem, the first solution provided by the present invention is: a preparation method of a broad-spectrum antibacterial polyurethane foam dressing, comprising the following steps: uniformly mixing polyether polyol, amine catalyst, zinc catalyst and organosilicon Foaming agent, water, foaming agent, cymene, and hexamidine bis(isethionate) salt are mixed uniformly to obtain a mixture; diphenylmethane diisocyanate and the mixture are mixed uniformly, poured into a mold for foaming , and demoulding after curing to obtain a broad-spectrum antibacterial polyurethane foam dressing.

Preferably, polyether polyol, amine catalyst, zinc catalyst, silicone foam stabilizer, water, foaming agent, cymene, hexamidine bis(isethionate) salt, diphenylmethane diphenylmethane The mass ratio of isocyanate is 100: (0.1-0.5): (0.1-0.7): (1.2-3.5): (1-6): (1-15): (0.01-1): (0.01-1): ( 35 to 65).

Preferably, the polyether polyol is composed of any two or more of the A-type polyether polyols, B-type polyether polyols and C-type polyether polyols; the hydroxyl value of the A-type polyether polyols is 335 mgKOH/ g, the molecular weight is 1000; the hydroxyl value of the B type polyether polyol is 55 mgKOH/g, and the molecular weight is 4200; the hydroxyl value of the C type polyether polyol is 150 mgKOH/g, and the molecular weight is 2800.

Preferably, type A polyether polyol is polyether polyol 330N; type B polyether polyol is polyether polyol 3050D; type C polyether polyol is polyether polyol 505S.

Preferably, when the polyether polyol is composed of a mixture of type A polyether polyol and type B polyether polyol, the mass ratio of type A polyether polyol and type B polyether polyol is 1:1 to 1:10; When the polyol is composed of a mixture of A-type polyether polyol and C-type polyether polyol, the mass ratio of A-type polyether polyol and C-type polyether polyol is 1:1 to 1:8; When the polyether polyol and the C-type polyether polyol are mixed, the mass ratio of the B-type polyether polyol and the C-type polyether polyol is 1:1 to 1:8; the polyether polyol is composed of the A-type polyether polyol, When B-type polyether polyol and C-type polyether polyol are mixed, the mass ratio of A-type polyether polyol, B-type polyether polyol and C-type polyether polyol is 2:2:1～1:1:1 .

Preferably, the amine catalyst is triethylenediamine; the zinc catalyst is organic zinc ZCAT-H22.

Preferably, the blowing agent is dichloromethane.

Preferably, in the curing step, the curing temperature is 60-100° C., and the curing time is 18-24 h.

In order to solve the above-mentioned technical problems, the second solution provided by the present invention is: a broad-spectrum antibacterial polyurethane foam dressing, the broad-spectrum antibacterial polyurethane foam dressing is prepared by the preparation method of the broad-spectrum antibacterial polyurethane foam dressing in the aforementioned first solution. have to. Application of the broad-spectrum antibacterial polyurethane foam dressing as a medical dressing.

The beneficial effects of the present invention are: different from the situation in the prior art, the present invention provides a broad-spectrum antibacterial polyurethane foam dressing and its preparation method and application. Through the specific selection and compounding of various polyether polyols, the prepared The polyurethane dressing has good mechanical strength and softness, and has excellent antibacterial and bacteriostatic properties; at the same time, the catalysts used for preparing the dressing are safe and non-toxic, making the prepared dressing more suitable for application as a medical dressing.

Detailed ways

The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention. Obviously, the described embodiments are only a part of the embodiments of the present invention, rather than all the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those of ordinary skill in the art without creative efforts shall fall within the protection scope of the present invention.

For the first solution provided by the present invention, the preparation method of the broad-spectrum antibacterial polyurethane foam dressing comprises the following steps:

(1) uniformly mix polyether polyol, amine catalyst, zinc catalyst, silicone foam stabilizer, water, foaming agent, cymene, and hexamidine bis(isethionate) salt to obtain a mixture . In this step, polyether polyol, amine catalyst, zinc catalyst, silicone foam stabilizer, water, foaming agent, cymene, hexamidine bis(isethionate) salt, diphenylmethane The mass ratio of diisocyanates is 100: (0.1-0.5): (0.1-0.7): (1.2-3.5): (1-6): (1-15): (0.01-1): (0.01-1): (35-65).

Among them, the polyether polyol is composed of any two or more of the A-type polyether polyol, B-type polyether polyol and C-type polyether polyol; the hydroxyl value of the A-type polyether polyol is 335 mgKOH/g , the molecular weight is 1000; the hydroxyl value of type B polyether polyol is 55mgKOH/g, and the molecular weight is 4200; the hydroxyl value of type C polyether polyol is 150mgKOH/g, and the molecular weight is 2800. Specifically, there are the following four ways: 1) When the polyether polyol is composed of a type A polyether polyol and a type B polyether polyol, the mass ratio of the type A polyether polyol and the type B polyether polyol is 1:1～ 1:10; 2) When the polyether polyol is composed of a mixture of type A polyether polyol and type C polyether polyol, the mass ratio of type A polyether polyol and type C polyether polyol is 1:1 to 1:8 3) When the polyether polyol is composed of a mixture of B-type polyether polyol and C-type polyether polyol, the mass ratio of B-type polyether polyol and C-type polyether polyol is 1:1 to 1:8; 4) When the polyether polyol is composed of A-type polyether polyol, B-type polyether polyol and C-type polyether polyol, the mass ratio of A-type polyether polyol, B-type polyether polyol and C-type polyether polyol It is 2:2:1～1:1:1. Combinations can be selected according to actual needs, which is not limited here.

In this embodiment, type A polyether polyol is polyether polyol 330N; type B polyether polyol is polyether polyol 3050D; type C polyether polyol is polyether polyol 505S; amine catalyst is triethylene Diamine, whose role is to catalyze the foaming reaction; the zinc catalyst is organozinc ZCAT-H22, whose role is to catalyze the gel reaction; the foaming agent is dichloromethane; by adjusting the amine catalyst and the zinc catalyst to the above ratio , so that the foaming reaction and the gelling reaction maintain a balanced development, so that the prepared foam dressing has a uniform and suitable foam cell structure and obtains a better foaming effect.

(2) Mixing the diphenylmethane diisocyanate with the mixture uniformly, pouring it into a mold for foaming, and demoulding after curing to obtain a broad-spectrum antibacterial polyurethane foam dressing. In this step, diphenylmethane diisocyanate is weighed according to the proportion, poured into the mixture prepared in step (1), mechanically stirred and mixed evenly, poured into a mold for foaming, and aged at 60 to 100 ° C for 18 to 24 hours, After demoulding, a broad-spectrum antibacterial polyurethane foam dressing was obtained.

For the second solution provided by the present invention, the broad-spectrum antibacterial polyurethane foam dressing is prepared by the preparation method of the broad-spectrum antibacterial polyurethane foam dressing in the aforementioned first solution, and the broad-spectrum antibacterial polyurethane foam dressing is used as a medical dressing.

The application effect of the broad-spectrum antibacterial polyurethane foam dressing in the present invention is tested and analyzed below through specific examples.

Example 1

In the present embodiment, the steps of preparing the broad-spectrum antibacterial polyurethane foam dressing are as follows:

In parts by mass, weigh 50 parts of type A polyether polyol, 50 parts of type B polyether polyol, 0.4 part of amine catalyst, 0.5 part of zinc catalyst, 2.5 parts of silicone foam stabilizer, 5 parts of water, 10 parts of methylene chloride, wherein the hydroxyl value of the A-type polyether polyol is 72 mgKOH/g, and its molecular weight is 5800; the hydroxyl value of the B-type polyether polyol is 80 mgKOH/g, and its molecular weight is 4200; stir the above raw materials evenly , add 55 parts of diphenylmethane diisocyanate, mix evenly, pour into a mold for foaming, age at 80° C. for 24 hours, and obtain a broad-spectrum antibacterial polyurethane foam dressing after demoulding.

Among them, the chemical structure and name of cymene are as follows:

INCI name: o-cymene-5-ol/o-Cymen-5-ol, CAS No: 3228-02-2, the following examples are all prepared by using the cymene.

Example 2

In the present embodiment, the steps of preparing the broad-spectrum antibacterial polyurethane foam dressing are as follows:

In parts by mass, weigh 30 parts of A-type polyether polyol, 70 parts of B-type polyether polyol, 0.2 part of amine catalyst, 0.4 part of zinc catalyst, 2 parts of silicone foam stabilizer, 5 parts of water, 8 parts of methylene chloride, wherein the hydroxyl value of the A-type polyether polyol is 72 mgKOH/g, and its molecular weight is 5800; the hydroxyl value of the B-type polyether polyol is 80 mgKOH/g, and its molecular weight is 4200; the above raw materials are stirred evenly , add 55 parts of diphenylmethane diisocyanate, mix evenly, pour into a mold for foaming, age at 80° C. for 24 hours, and obtain a broad-spectrum antibacterial polyurethane foam dressing after demoulding.

Example 3

In the present embodiment, the steps of preparing the broad-spectrum antibacterial polyurethane foam dressing are as follows:

In parts by mass, weigh 50 parts of A-type polyether polyol, 50 parts of B-type polyether polyol, 0.3 part of amine catalyst, 0.2 part of zinc catalyst, 1.5 part of silicone foam stabilizer, 5 parts of water, 10 parts of dichloromethane, 0.04 part of cymene, 0.06 part of hexamidine bis(isethionate) salt, wherein the hydroxyl value of the A-type polyether polyol is 72 mgKOH/g, and its molecular weight is 5800; The hydroxyl value of ether polyol is 112mgKOH/g, and its molecular weight is 2800; stir the above raw materials evenly, add 45 parts of diphenylmethane diisocyanate, mix well, pour into a mold for foaming, age at 80°C for 24h, and release the mold Then a broad-spectrum antibacterial polyurethane foam dressing was obtained.

Example 4

In the present embodiment, the steps of preparing the broad-spectrum antibacterial polyurethane foam dressing are as follows:

In parts by mass, weigh 30 parts of A-type polyether polyol, 70 parts of B-type polyether polyol, 0.3 part of amine catalyst, 0.4 part of zinc catalyst, 1.5 part of silicone foam stabilizer, 3.5 parts of water, 10 parts of methylene chloride, 0.05 part of cymene, 0.05 part of hexamidine bis(isethionate) salt, wherein the hydroxyl value of the A-type polyether polyol is 72 mgKOH/g, and its molecular weight is 5800; The hydroxyl value of ether polyol is 112mgKOH/g, and its molecular weight is 2800; stir the above raw materials evenly, add 45 parts of diphenylmethane diisocyanate, mix well, pour into a mold for foaming, age at 80°C for 24h, and release the mold Then a broad-spectrum antibacterial polyurethane foam dressing was obtained.

Example 5

In the present embodiment, the steps of preparing the broad-spectrum antibacterial polyurethane foam dressing are as follows:

In parts by mass, weigh 50 parts of type A polyether polyol, 50 parts of type B polyether polyol, 0.3 part of amine catalyst, 0.2 part of zinc catalyst, 2.5 parts of silicone foam stabilizer, 2.5 parts of water, 15 parts of methylene chloride, 0.05 part of cymene, 0.05 part of hexamidine bis(isethionate) salt, wherein the hydroxyl value of the A-type polyether polyol is 80 mgKOH/g, and its molecular weight is 4200; The hydroxyl value of ether polyol is 112mgKOH/g, and its molecular weight is 2800; stir the above raw materials evenly, add 40 parts of diphenylmethane diisocyanate, mix well, pour into a mold for foaming, age at 80°C for 24h, and release the mold Then a broad-spectrum antibacterial polyurethane foam dressing was obtained.

Example 6

In the present embodiment, the steps of preparing the broad-spectrum antibacterial polyurethane foam dressing are as follows:

In parts by mass, weigh 30 parts of type A polyether polyol, 30 parts of type B polyether polyol, 40 parts of type C polyether polyol, 0.2 part of amine catalyst, 0.3 part of zinc catalyst, 1.5 parts of organic Silicon foam stabilizer, 1.5 parts of water, 10 parts of dichloromethane, 0.05 parts of cymene, 0.05 parts of hexamidine bis(isethionate) salt, wherein the hydroxyl value of A-type polyether polyol is 80mgKOH/g , its molecular weight is 4200; the hydroxyl value of type B polyether polyol is 112mgKOH/g, and its molecular weight is 2800; the hydroxyl value of type C polyether polyol is 72gKOH/g, and its molecular weight is 4200; stir the above raw materials evenly, Add 40 parts of diphenylmethane diisocyanate, mix well, pour into a mold for foaming, age at 80° C. for 24 hours, and obtain a broad-spectrum antibacterial polyurethane foam dressing after demoulding.

Comparative Example 1

Commercially available Baederser antibacterial dressings were selected as comparative examples.

Test 1 Antimicrobial Test

The antibacterial test was carried out on the polyurethane foam dressings prepared in the above examples 1 to 6, and the antibacterial test used Gram-negative bacteria (Escherichia coli) and Gram-positive bacteria (Staphylococcus aureus) to evaluate the model biofouling of the film's antibacterial properties. , the test steps are as follows: first, put the membrane sample (1cm×1cm) into a petri dish, and disinfect it with ultraviolet light for 30 minutes; Incubate for 24 hours at 37°C. After incubation, the bacteria were removed from the membrane surface and transferred to 50 mL of PBS solution (pH=7.4); then, the bacterial solution was plated on agar plates and incubated at 37°C for an additional 24 hours; finally, bacterial colonies were counted , and calculate the antibacterial rate. The test results are shown in Table 1. It can be seen that the sterilization rate of the dressing prepared by the present invention to Escherichia coli and Staphylococcus aureus is maintained at more than 80%, which is much higher than the sterilization level of the commercially available antibacterial dressing in Comparative Example 1. Better antibacterial effect.

Table 1 Antibacterial test

Test 2 Cytotoxicity test

The cytotoxicity test was carried out on the polyurethane foam dressings prepared in the above examples 1 to 6, and compared with the comparative example 1. The specific test steps are as follows: First, extract the sample leachate, and immerse the sterilized sample in 1 mL of DMEM medium , kept at 37 °C for 24 h; then the medium was sterilized by filtration using a sterile filter (pore size: 0.22 μm); subsequently, fibroblasts were seeded into each well of a 96-well plate and incubated at 37 °C Incubate for 24 hours; then replace the medium with 500 μL of leaching solution or original medium containing 10% fetal bovine serum; after 24 hours, replace the medium with 100 μL of original medium containing 10 μL of CCK8 solution, then incubate at 37°C for 2 hours ; Finally, use a microplate reader to measure the OD value at a wavelength of 450 nm, and calculate the cell viability. The test results are shown in Table 1. It can be seen that the cell survival rate of the dressing prepared by the present invention remains above 90%, which is greater than that of the commercially available antibacterial dressing in Comparative Example 1. Commercial dressings are more suitable for application as medical dressings.

Table 2 Cytotoxicity test

Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Comparative Example 1 cell viability 90% 93% 89% 92% 91% 95% 83%

Test 3 Mechanical Strength Test

The mechanical strength test of the polyurethane foam dressings prepared in the above examples 1 to 6 was carried out, and compared with the comparative example 1. The test results are shown in Table 1. It can be seen that the tensile strength of the dressings prepared by the present invention is much greater than that of the comparative example. The tensile strength of the commercially available antibacterial dressing in 1 proves that the dressing prepared by the present invention has more excellent mechanical strength than the commercially available dressing.

Table 3 Mechanical Strength Test

Different from the situation in the prior art, the present invention provides a broad-spectrum antibacterial polyurethane foam dressing and its preparation method and application. Mechanical strength and softness, and excellent antibacterial and bacteriostatic properties; at the same time, the catalysts used for preparing the dressing are safe and non-toxic, making the prepared dressing more suitable for application as a medical dressing.

It should be noted that the above embodiments all belong to the same inventive concept, and the description of each embodiment has its own emphasis. For details not described in individual embodiments, reference may be made to descriptions in other embodiments.

The above-mentioned embodiments only represent the embodiments of the present invention, and the descriptions thereof are relatively specific and detailed, but should not be construed as limiting the scope of the invention patent. It should be pointed out that for those of ordinary skill in the art, without departing from the concept of the present invention, several modifications and improvements can also be made, which all belong to the protection scope of the present invention. Therefore, the protection scope of the patent of the present invention should be subject to the appended claims.

Claims (10)

1. a preparation method of broad-spectrum antibacterial polyurethane foam dressing, is characterized in that, comprises the steps: Mixing the polyether polyol, amine catalyst, zinc catalyst, silicone foam stabilizer, water, foaming agent, cymene and hexamidine bis(isethionate) salt uniformly to obtain a mixture; The diphenylmethane diisocyanate and the mixture are mixed evenly, poured into a mold for foaming, and demoulded after curing to obtain a broad-spectrum antibacterial polyurethane foam dressing. 2. according to the preparation method of the broad-spectrum antibacterial polyurethane foam dressing described in claim 1, it is characterized in that, described polyether polyol, amine catalyst, zinc catalyst, silicone foam stabilizer, water, foaming agent , cymene, hexamidine bis(isethionate) salt, and the mass ratio of diphenylmethane diisocyanate is 100: (0.1 to 0.5): (0.1 to 0.7): (1.2 to 3.5): (1 to 6): (1 to 15): (0.01 to 1): (0.01 to 1): (35 to 65). 3. according to the preparation method of the broad-spectrum antibacterial polyurethane foam dressing described in claim 1, it is characterized in that, described polyether polyol is composed of A type polyether polyol, B type polyether polyol and C type polyether polyol Any two or more of them are mixed; The hydroxyl value of the A-type polyether polyol is 335 mgKOH/g, and the molecular weight is 1000; The hydroxyl value of the B-type polyether polyol is 55 mgKOH/g, and the molecular weight is 4200; The C-type polyether polyol has a hydroxyl value of 150 mgKOH/g and a molecular weight of 2800. 4. according to the preparation method of the broad-spectrum antibacterial polyurethane foam dressing described in claim 2, it is characterized in that, described A type polyether polyol is polyether polyol 330N; The B-type polyether polyol is polyether polyol 3050D; The C-type polyether polyol is polyether polyol 505S. 5. according to the preparation method of the broad-spectrum antibacterial polyurethane foam dressing described in claim 2, it is characterized in that, when described polyether polyol is mixed by A type polyether polyol and B type polyether polyol, described A The mass ratio of class polyether polyol and class B polyether polyol is 1:1 to 1:10; When the polyether polyol is composed of the A-type polyether polyol and the C-type polyether polyol, the mass ratio of the A-type polyether polyol and the C-type polyether polyol is 1:1 to 1:8; When the polyether polyol is composed of a mixture of a B-type polyether polyol and a C-type polyether polyol, the mass ratio of the B-type polyether polyol and the C-type polyether polyol is 1:1 to 1:8; When the polyether polyol is composed of A-type polyether polyol, B-type polyether polyol and C-type polyether polyol, the A-type polyether polyol, B-type polyether polyol and C-type polyether polyol The mass ratio of alcohol is 2:2:1～1:1:1. 6 . The method for preparing a broad-spectrum antibacterial polyurethane foam dressing according to claim 1 , wherein the amine catalyst is triethylenediamine; and the zinc catalyst is organic zinc ZCAT-H22. 7 . 7. The preparation method of the broad-spectrum antibacterial polyurethane foam dressing according to claim 1, wherein the foaming agent is dichloromethane. 8 . The method for preparing a broad-spectrum antibacterial polyurethane foam dressing according to claim 1 , wherein, in the curing step, the curing temperature is 60-100° C., and the curing time is 18-24 h. 9 . 9 . A broad-spectrum antibacterial polyurethane foam dressing, characterized in that, the broad-spectrum antibacterial polyurethane foam dressing is prepared by the method for preparing a broad-spectrum antibacterial polyurethane foam dressing according to any one of claims 1 to 8 . 10. The application of the broad-spectrum antibacterial polyurethane foam dressing as claimed in claim 9 as a medical dressing.