Antibacterial mildewproof polyurethane composite material containing natural plant and a preparation method thereof

Abstract

The invention discloses an antibacterial mildewproof polyurethane composite material containing natural plant and a preparing method thereof. The composite material comprises component A and component B with a ratio of component A and component B being 100:(20-50) by weight. The component A by weight comprises: 30-60 parts plant oil polyether polyols; 20-50 parts polyether polyols I; 5-20 parts polyether polyols II; 5-20 parts composite plant extract; 0-0.5 parts catalyst; 0.5-2 parts surfactant; 0-2 parts cross-linking agent; 1.5-3 parts foaming agents. The component B by weight comprising 20-50 parts modified MDI. The composite material made according to the preparation method of the invention shows a good stability and the polyurethane products made according to the preparation method is degradable. The antibacterial mildewproof natural plant adopted by the composite material in the invention enables the composite material to prevent the bacteria breeding effectively and provides environmental protection.

Claims

1. An antibacterial mildewproof polyurethane composite material containing natural plant, characterized in that, said material is prepared from a component A and a component B in a weight ratio of 100:(20-50) by weight, wherein the component A comprises: 30-60 parts by weight of a plant oil-based polyether polyol; 20-50 parts by weight of polyether polyols I; 5-20 parts by weight of polyether polyols II; 5-20 parts by weight of a composite plant extract; 0-0.5 parts by weight of a catalyst; 0.5-2 parts by weight of a surfactant; 0-2 parts parts by weight of a cross-linking agent; and 1.5-3 parts by weight of foaming agents; and wherein the component B is modified methylene diphenyl diisocyanate; wherein the plant oil-based polyether polyol is a soybean polyol with a functionality of 2-14 and a hydroxyl value of 55-240 mg KOH/g; the polyether polyols I have a functionality of 3 and a hydroxyl value of 42 mg KOH/g; the polyether polyols II have a functionality of 2 and a hydroxyl value of 56-115 mg KOH/g; and the composite plant extract is an extract from a mixture of garlic, Chinese pulsatilla root, honeysuckle and sage.

2. The composite material according to claim 1, characterized in that, the catalyst is an amine catalyst.

3. The composite material according to claim 2, characterized in that, the amine catalyst is selected from the group consisting of bis(dimethylaminoethyl)ether, pentamethyldiethylenetriamine, N,N-dimethylcyclohexanamine, triethylenediamine and a delayed action catalyst.

4. The composite material according to claim 1, characterized in that, the cross-linking agent is a short chain polyhydroxyl compound with a functionality of 2-3.

5. The composite material according to claim 4, characterized in that, the cross-linking agent is glycol or diethanolamine.

6. The composite material according to claim 1, characterized in that, the foaming agents include water and/or dichlorofluoroethane.

7. The composite material according to claim 1, characterized in that, the surfactant is a hydrophilic silicone oil.

8. The composite material according to claim 1, characterized in that, the composite plant extract is, by mass percentage, extract has a particle size of greater or equal to 2000 mesh.

9. A method for preparing the composite material according to claim 1, characterized in that, said method comprises the following steps: (1) weighing a component A and a component B, wherein the component A contains 30-40 parts by weight of the plant oil-based polyether polyol, 20-50 parts by weight of the polyether polyols I, 5-20 parts by weight of the polyether polyols II, 5-20 parts by weight of the composite plant extract, 0-0.5 parts by weight of the catalyst, 0.5-2 parts by weight of the surfactant, 0-2 parts by weight of the cross-linking agent, and 1.5-3 parts by weight of the foaming agents and the component B is modified methylene diphenyl diisocyanate; (2) putting the plant oil based polyether polyol, polyether polyols I and polyether polyols II from step (1) into an agitator for mixing at 30-100 C.; (3) subjecting the mixture obtained from step (2) with the composite plant extract to a high-speed shearing, colliding, grinding and dispersion in a high speed dispersing agitator to achieve rapid mixing, dissolution, scattering and refinement; (4) stirring and mixing the mixture obtained from step (3) and the catalyst, the cross-linking agent, the surfactant and the foaming agent to obtain the component A, and then stirring and mixing the component A with the component B to conduct a reaction at 60 C.

10. The method according to claim 9, characterized in that, the composite plant extract is obtained by the following steps: immersing raw garlic, Chinese pulsatilla root, honeysuckle and sage in hot water at a temperature of 90-95 C. for 2 hours to form a mixture; filtering the mixture with an 80 meshes plastic filter; conducting concentration of the filtrate with a concentrator at a temperature of 90-95 C. a concentration of 1.15-1.18 degrees Baume; drying the concentrated product with a spray drying equipment with an inlet air temperature of 110-115 C. and an outlet air temperature of 90-95 C. for 2-3 hours to obtain a dried mixture comprising garlic, Chinese pulsatilla root, honeysuckle and sage in a weight ratio of 1:1:0.5:0.5; pulverizing the dried mixture through a pulverizer; and sieving the pulverized mixture through 2000 mesh sifter.

Description

DETAILED DESCRIPTION OF THE INVENTION

(1) The present invention is further described by way of examples in the following. It is not intended to limit the present invention to the scope of the examples described herein. The experimental methods in the following examples of which the specific condition is not specified shall be selected according to a conventional method and condition or according to a commodity specification. Moreover, in the following examples, the selection of each component is not limited to the described, but can be the combination of other types of raw materials mentioned in the previous paragraph of SUMMARY OF THE INVENTION. The L-580 in the following embodiments is a surfactant purchased from Momentive High-Tech Materials group of the United States.

Example 1

(2) The example provides an antibacterial mildewproof polyurethane composite material containing natural plant comprising component A and component B.

(3) The component A by weight comprises: 40 parts of plant oil polyether polyols; 40 parts of polyether polyols I; 10 parts of polyether polyols II; 5 parts of composite plant extract; 0.5 parts of triethylenediamine; 1 part of L-580; 2 parts of ethanediol; and 2 parts of water.

(4) The component B by weight comprises: 40 parts of modified MDI;

(5) The ratio of component A to component B is 100:40 by weight.

(6) The method of preparing the composite material is also provided in this example, which comprises following steps:

(7) (1) Weighing respective components mentioned above precisely;

(8) (2) Putting the plant oil-base polyether polyol, polyether polyol I, and polyether polyols II from step (1) into an agitator to mix them uniformly at 30-100 C.;

(9) (3) Subjecting the mixture of composite obtained from step (2) with plant extract to a high-speed shearing, colliding, grinding and dispersion in a high speed dispersing agitator to achieve rapid mixing, dissolution, scattering and refinement;

(10) (4) Stirring and mixing the mixture obtained from step (3) and catalyst, cross-linking agent, surfactant and foaming agent to obtain component A, and then stir and mix component A with component B to shape up by reacting under an environmental temperature of 60 C.

Example 2

(11) This example provides an antibacterial mildewproof polyurethane composite material containing natural plant comprising component A and component B.

(12) The component A by weight comprises: 40 parts of plant oil polyether polyols; 35 parts of polyether polyols I; 10 parts of polyether polyols II; 10 parts of composite plant extract; 0.5 parts of pentamethyldiethylenetriamine; 1 part of L-580; 2 parts of ethanediol; and 2 parts of dichlorofluoroethane

(13) The component B by weight comprises: 35 parts of modified MDI;

(14) The ratio of component A to component B is 100:30 by weight.

(15) The preparation method of the composite material is same as that of example 1.

Example 3

(16) This example provides an antibacterial mildewproof polyurethane composite material containing natural plant comprising component A and component B.

(17) The component A by weight comprises: 40 parts of plant oil polyether polyols; 35 parts of polyether polyols I; 12 parts of polyether polyols II; 10 parts of composite plant extract; 0.5 parts of bis(dimethylaminoethyl)ether; 1.2 parts of L-580; 2 parts of ethanediol; and 2.5 parts of water.

(18) The component B by weight comprises: 40 parts of modified MDI;

(19) The ratio of component A to component B is 100:40 by weight.

(20) The preparation method of the composite material is the same as that of example 1.

Example 4

(21) This example provides an antibacterial mildewproof polyurethane composite material containing natural plant comprising component A and component B.

(22) The component A by weight comprises: 30 parts by weight of plant oil polyether polyols; 35 parts of polyether polyols I; 15 parts of polyether polyols II; 8 parts of composite plant extract; 0.5 parts of triethylenediamine; 1 part of L-580; 2 parts of ethanediol; and 1 part of water.

(23) The component B by weight comprises: 35 parts of modified MDI;

(24) The ratio of component A to component B is 100:25 by weight.

(25) The preparation method of the composite material is the same as that of example 1.

(26) The above plant oil polyether polyol in examples 1 to 4 is soybean polyol with a functionality of 7-14, a hydroxyl value of 110-240 mg KOH/g, and a plant oil content of more than 95%; the polyether polyols I has a functionality of 3 and a hydroxyl value of 42 mg KOH/g; the polyether polyols II has a functionality of 1-2 and a hydroxyl value of 56-115 mg KOH/g; and the composite plant extract is an extract from a mixture of garlic, Chinese pulsatilla root, honeysuckle and sage.

(27) The content of composite plant extract is 10-30:1(%) and the particle size is 2000 meshes or above. The composite plant extract is obtained by the following steps: putting raw materials of garlic, Chinese pulsatilla root, honeysuckle and sage into hot water of 90-95 C. to soak these materials in an amount of water of 14 times for 2 hours, filtering the soaked materials with 80 meshes plastic filter, conducting concentration of the filtrate by a concentrator under a temperature of 90-95 C. to a baume degree of 1.15-1.18, the concentrated products are dried with a spray drying equipment under an inlet air temperature of 110-115 C. and an outlet air temperature of 90-95 C. for 2-3 hours, weighing the dried up garlic, Chinese pulsatilla root, honeysuckle and sage respectively by a weight ratio of 1:1:0.5:0.5 to be shattered and intensively mixed through a pulverizer, sieving the mixture through a sifter of 2000 meshes with residue on the sifter being further crushed and then sieved repeatedly in this way.

Example 5

Comparative Experiment of Antibacterial

(28) An experiment on antibacterial performance is carried out for the antibacterial mildewproof polyurethane composite materials containing natural plant obtained from examples 1 to 4.

(29) Testing method:

(30) The antimicrobial property of the samples was quantitatively evaluated referring to ISO 20743:2013.

(31) Testing results:

(32) M.sub.a=logarithm of the concentration of bacterial inoculation amount at the beginning

(33) M.sub.b=logarithm of the bacteria quantity after 24 hours of inoculation (in samples without antibacterial treatment)

(34) M.sub.c=logarithm of the bacteria quantity after 24 hours of inoculation (in samples with antibacterial treatment)

(35) S=logarithm of bacteria quantity reduced after 24 hours (in samples with antibacterial treatment)

(36) The bacterium inoculated is Staphylococcus aureu.

(37) TABLE-US-00001 TABLE 1 Contrast Experimental Results of Antibacterial Performance (M.sub.a) log2.04 10.sup.4 = 4.3 (M.sub.b) log9.65 10.sup.6 = 7.0 (F.sub.1 = M.sub.b M.sub.a) growth value 2.7 Logarithm of bacteria Logarithm of Ratio of recovery bacteria bacteria Sample Bacteria quantity quantity quantity description quantity (M.sub.c) decrease (S) decrease % Example 1 1.90 10 {circumflex over ()}5 5.3 1.7 >93.0% Example 2 7.00 10 {circumflex over ()}1 1.8 5.0 >98% Example 3 <2.00 10 {circumflex over ()}1 <1.3 >5.5 >97.2% Example 4 1.70 10 {circumflex over ()}2 2.2 4.6 >95% Control 3.10 10 {circumflex over ()}6 6.2 1.1 >55% Example

(38) Table 1 shows that the composite material made according to the preparation method of the invention has a good antibacterial performance. The composite material made from components according to the preparation method of examples 2 and 3 shows a better antibacterial performance with a higher ratio of bacteria decrease and a smaller recovery quantity logarithm of recovery amount.

Example 6

Contrast Experiment of Mildewproof

(39) An experiment of mildewproof performance is carried out on the antibacterial mildewproof polyurethane composite material containing natural plant obtained from examples 1 to 4.

(40) TABLE-US-00002 TABLE 2 Result of Experiments against Aspergillus niger According to the AATCC 30 test standard Aspergillus niger Bacteria inhibition (ATCC #6275) Name zone (MM) Surface inhibition (%) Example 1 0 93.1 Example 2 0 96.2 Example 3 0 98.5 Example 4 0 94.1 Control Example 0 50

(41) As can be seen from Table 2, the polyurethane composite material made according to the preparation method of the invention has a good mildewproof performance. Moreover, the polyurethane composite material made according to the formula of example 3 has a better mildewproof performance.

(42) TABLE-US-00003 TABLE 3 Result of Experimental against Trichoderma virens According to the AATCC 30 test standard Trichoderma virens Bacteria inhibition zone (ATCC #9645) Name (MM) Surface inhibition (%) Example 1 0 91 Example 2 0 95 Example 3 10 96 Example 4 3 92 Control Example 0 25

(43) As can be seen from Table 3, the polyurethane composite materials made according to the preparation method of the invention has a good mildewproof performance, among which the polyurethane composite material made from the formula of example 3 has a better superficial inhibition performance against Trichoderma vixens.

(44) The examples are merely illustrative of the technical ideas and features of the present invention for the purpose of enabling those skilled in the art to understand the contents of the present invention and to implement the present invention but not limiting the protection scope of the invention. Equivalent changes or modifications made according to the spirit of the present invention should be covered by the protection scope of the present invention.