Cannabidiol-containing bio-based polyurethane composite material and preparation method thereof

Abstract

Disclosed herein are a cannabidiol (CBD)-containing bio-based polyurethane composite material and a preparation thereof. The composite material is prepared from a component A and a component B in a weight ratio of 100:(20-50), where the component A includes 40-60 parts by weight of a vegetable oil-based polyol, 35-50 parts by weight of polyether polyol I, 0-10 parts by weight of polyether polyol II, 0.5-5 parts by weight of CBD, 0-5 parts by weight of a natural pigment, 0.5-3 parts by weight of silicon oil, 0-5 parts by weight of a cross-linking agent, 0.2-1 part by weight of a catalyst and 0.8-4 parts by weight of water, and the component B includes 20-50 parts by weight of modified methylene diphenyl diisocyanate (MDI).

Claims

1. A cannabidiol (CBD)-containing bio-based polyurethane composite material, wherein the cannabidiol (CBD)-containing bio-based polyurethane composite material is prepared from a component A and a component B in a weight ratio of 100:(20-50); wherein the component A comprises: 40-60 parts by weight of a vegetable oil-based polyol; 35-50 parts by weight of polyether polyol I; 0-10 parts by weight of polyether polyol II; 0.5-5 parts by weight of CBD; 0-5 parts by weight of a natural pigment; 0.5-3 parts by weight of silicon oil; 0-5 parts by weight of a cross-linking agent; 0.2-1 part by weight of a catalyst; and 0.8-4 parts by weight of water; the component B comprises: 20-50 parts by weight of modified methylene diphenyl diisocyanate (MDI); wherein the polyether polyol I is 15% ethylene oxide-capped propylene oxide polyether polyol having a number-average molecular weight of 1000-2000, a functionality of 3 and a hydroxyl value of 50-170 mg KOH/g; and the polyether polyol II is 15% propylene oxide-capped ethylene oxide polyether polyol having a functionality of 2 and a hydroxyl value of 100; and the modified MDI is prepared by modifying isocyanate with palm oil through steps of: 1) Weighing 100 parts by weight of the palm oil, 70-80 parts by weight of MDI-50 and 20-30 parts by weight of polymeric MDI; and 2) Dewatering the 100 parts by weight of the palm oil to a moisture content of less than 0.05% at 110-120° C.; adding 40-50 parts by weight of the MDI-50 into the dewatered palm oil at 75-80° C.; heating the reaction mixture under stirring to 100° C. followed by reaction for 2-4 h; cooling the reaction mixture to room temperature; and adding the 20-30 parts of the polymeric MDI and the remaining MDI-50 into the reaction mixture followed by stirring to produce the modified MDI.

2. The CBD-containing bio-based polyurethane composite material of claim 1, wherein the vegetable oil-based polyol is a cottonseed oil-based polyol having a functionality of 1-3 and a hydroxyl value of 60-140 mg KOH/g.

3. The CBD-containing bio-based polyurethane composite material of claim 1, wherein the CBD is an oily or powdery cannabidiol compound extracted from industrial hemp.

4. The CBD-containing bio-based polyurethane composite material of claim 1, wherein the natural pigment has a size of 100-500 mesh.

5. The CBD-containing bio-based polyurethane composite material of claim 1, wherein the silicon oil is a mixture of dimethyl silicone oil and polyether silicone oil in a weight ratio of 1:4.

6. A method for preparing the CBD-containing bio-based polyurethane composite material of claim 1, comprising: 1) Adding the vegetable oil-based polyol, the polyether polyol I and the polyether polyol II into a reactor followed by stirring at 50-70° C.; 2) Adding the silicon oil, the cross-linking agent, the catalyst and the water into the reactor in step (1) followed by centrifugation at 300-500 rpm; and 3) Adding the CBD, the natural pigment and the modified MDI into the reactor under stirring; and subjecting the reaction mixture to reactive molding at room temperature to produce the CBD-containing bio-based polyurethane composite material.

Description

DETAILED DESCRIPTION OF EMBODIMENTS

(1) This disclosure will be further described below with reference to the embodiments, but is not limited thereto. Unless otherwise specified, the experiments in the following embodiments are carried out according to conventional methods and conditions, or as instructed by the manufacture. Moreover, individual components are not limited to those used below, and any suitable combination of other materials mentioned above is also feasible.

(2) In the embodiments, a vegetable oil-based polyol was a cottonseed oil-based polyol having a functionality of 1-3 and a hydroxyl value of 60-140 mg KOH/g. Polyether polyol I was 15% ethylene oxide-capped propylene oxide polyether polyol having a molecular weight of 1000-2000, a functionality of 3 and a hydroxyl value of 50-170. Polyether polyol II was 15% propylene oxide-capped ethylene oxide polyether polyol having a functionality of 2 and a hydroxyl value of 100. CBD was an oily or powdery cannabidiol compound extracted from industrial hemp. A natural pigment had a size of 100-500 mesh. The natural pigment used herein was sodium copper chlorophyllin. Silicon oil was a mixture of dimethyl silicone oil and polyether silicone oil in a weight ratio of 1:4.

(3) The modified MDI was prepared by modifying isocyanate with palm oil. Specifically, 100 parts by weight of the palm oil, 70-80 parts by weight of MDI-50 and 20-30 parts by weight of polymeric MDI were weighed. 100 parts by weight of the palm oil was dewatered to a moisture content of less than 0.05% at 110-120° C., and then 40-50 parts by weight of the MDI-50 was added into the dewatered palm oil at 75-80° C. The reaction mixture was heated under stirring to 100° C. followed by reaction for 2-4 h. The reaction mixture was cooled to room temperature. The polymeric MDI and the remaining MDI-50 were added into the reaction mixture followed by stirring to produce the CBD-containing bio-based polyurethane composite material.

(4) Five examples and a comparative example were provided herein, and the composition thereof was shown in Table 1.

(5) TABLE-US-00001 TABLE 1 Composition of Examples 1-5 and Comparative example Comparative Example 1 Example 2 Example 3 Example 4 Example 5 example Vegetable 45 40 60 42 43 50 oil-based polyol Polyether 45 50 35 37 35 40 polyol I Polyether 3 0 1 10 5 0 polyol II CBD 0.5 2 0.7 3 5 0 Natural 1.5 5 0.5 0 2 0 pigment Silicon oil 0.5 1 1.5 2 3 2 Cross-linking 2.5 1 0 1 5 6 agent Catalyst 0.5 0.2 0.3 1 0.6 2 Water 1 0.8 2 4 1.4 1.5 Modified 25 20 40 50 30 30 MDI

(6) The preparation of the CBD-containing bio-based polyurethane composite materials in Examples 1-5 was described as follows. 1) The vegetable oil-based polyol, the polyether polyol I and the polyether polyol II were added into a reactor and stirred at 50-70° C. 2) The silicon oil, the cross-linking agent, the catalyst and the water were added into the reactor in step (1) and centrifuged at 300-500 rpm. 3) The CBD, the natural pigment and the modified MDI were added into the reactor in step (2) under stirring, and subjected to reactive molding at room temperature.

(7) 1. Antibacterial Activity Test

(8) The composite materials obtained in Examples 1-5 and Comparative example were quantitatively evaluated for the antibacterial activity according to ISO 20743:2013, and the results were presented in Table 2, where Ma: logarithm of bacterial concentration at initial stage; Mb: logarithm of the number of bacteria after 24 h of the incubation without the composite material; Mc: logarithm of the number of bacteria after 24 h of the incubation with the composite material; S: logarithm of the number of bacteria after 24 h of the antibacterial treatment; and the inoculated bacterial strain was Staphylococcus aureus.

(9) TABLE-US-00002 TABLE 2 Antibacterial activity of polyurethane composite materials in Examples 1-5 and Comparative example (Ma) Log 2.04 × 10.sup.4 = 4.3 (Mb) Log 9.65 × 10.sup.6 = 7.0 Growth Value (F1 = Mb − Ma) 2.7 Logarithm of Logarithm of the number the number Percentage of The number of recovered of decreased the reduced Sample of bacteria bacteria (Mc) bacteria (S) bacteria Example 1 3.20 × 10{circumflex over ( )}1 1.8 4.8 >96.0% Example 2 4.20 × 10{circumflex over ( )}1 1.3 5.3 >93.6% Example 3 5.50 × 10{circumflex over ( )}1 1.5 4.3 >95.2% Example 3 4.50 × 10{circumflex over ( )}1 1.4 4.5 >95.6% Example 5 <1.50 × 10{circumflex over ( )}1  <1.0 >5.6 >97.8% Comparative 3.10 × 10{circumflex over ( )}4 6.2 1.3 .sup. >56% example

(10) Table 2 showed that compared to the composite material in Comparative Example, the composite materials prepared by the method provided herein had superior antibacterial activity. Furthermore, among the five samples provided herein, the composite material obtained in Example 5 exhibited the highest decline percentage in the number of bacteria and the smallest number of recovered bacteria, which indicated that the composite material of Example 5 had the optimal antibacterial activity.

(11) 2. Mildew Resistance Test

(12) The composite materials obtained in Examples 1-5 and Comparative example were tested for the mildew resistance according to the standards of AATCC 30, and the results were shown in Tables 3 and 4.

(13) TABLE-US-00003 TABLE 3 Resistance of polyurethane composite materials in Examples 1-5 and Comparative example to Aspergillus niger Aspergillus niger Bacterial inhibition (ATCC #6275) Sample zone (mm) Surface inhibition (%) Example 1 0 97.7 Example 2 0 98.3 Example 3 0 97.5 Example 3 0 96.1 Example 5 0 99.2 Comparative example 0 55

(14) Referring to Table 3, it was demonstrated that the composite materials prepared by the method provided herein had excellent antibacterial activity, and the composite material obtained in Example 5 had the optimal surface inhibition effect on Aspergillus niger.

(15) TABLE-US-00004 TABLE 4 Resistance of polyurethane composite materials in Examples 1-5 and Comparative example to Trichoderma virens Trichoderma virens Bacterial inhibition (ATCC #9645) Sample zone (mm) Surface inhibition (%) Example 1 0 96 Example 2 0 95 Example 3 0 96 Example 3 0 95 Example 5 0 98 Comparative example 0 30

(16) Table 4 showed that the composite materials prepared by the method provided herein had desirable antibacterial activity, and the composite material obtained in Example 5 had the best surface inhibition effect on Trichoderma vixens.

(17) The above-mentioned embodiments are merely illustrative of the technical solutions and features of the present disclosure to enable those skilled in the art to understand and implement this disclosure, and are not intended to limit the scope of the present disclosure. Any changes and modifications made without departing from the spirit of this disclosure should fall within the scope of the present disclosure.