Use of polyurethane material in the preparation of latex product

Abstract

The present application discloses the use of a polyurethane material in the preparation of a latex product, wherein the polyurethane material comprises a waterborne polyurethane and nano-silver. The polyurethane material of the present application is made of a combination of a waterborne polyurethane and nano-silver, which gives rise to the said latex products not only having a broad spectrum of antimicrobial activity including inactivating HIV-1 and HSV, but also having the ability to inactivate the microorganism in a short time.

Claims

1. A method for the preparation of a latex product wherein the method comprises using a polyurethane material in the preparation of the latex product, the polyurethane material comprises a waterborne polyurethane and nano-silver at a weight ratio of 1000:1; wherein a method for preparing the polyurethane material comprising the waterborne polyurethane and nano-silver at the weight ratio of 1000:1 comprises: a first step (1): dissolving silver nitrate in water to obtain an aqueous silver nitrate solution with a concentration of 4 mg/ml; and a second step (2): mixing the silver nitrate solution prepared in the step (1) with a waterborne polyurethane emulsion, adding sodium borohydride, and then stirring the mixture for 2 hours until the silver ions are completely reduced to nano-silver to obtain the polyurethane material; wherein the molar ratio of silver nitrate to sodium borohydride is 1:2; wherein the waterborne polyurethane emulsion in the second step (2) is prepared by the following steps: a step (a): mixing a polyester polyol with an isocyanate and reacting at 80 C. for 1.5 hours, then adding a polyether polyol and further reacting at 80 C. for an additional 1.5 hours; a step (b): adding a hydrophilic cross-linking agent to the reactant obtained in the step (a) and reacting at 75 C. for 0.8 hours, decreasing the temperature to 55 C., adding a small molecular chain extender and reacting at 55 C. for 0.8 hour, further adding a catalyst and reacting so as to obtain a polyurethane prepolymer; a step (c): neutralizing the prepolymer obtained in the step (b) with a neutralizer, decreasing the temperature to lower than 30 C., then adding deionized water and stirring for 30 minutes to emulsify the mixture, so as to obtain a prepolymer dispersion; and a step (d): adding an epoxy silane coupling agent to the prepolymer dispersion obtained in the step (c) and reacting for 30 minutes, then adding an amino silane coupling agent and reacting for an additional 1 hour to obtain the waterborne polyurethane emulsion.

2. The method according to claim 1, wherein the latex product is a condom or a glove.

3. The method according to claim 1, wherein the amino silane coupling agent is 3-(2-aminoethyl) aminopropyl-trimethoxysilane and the epoxy silane coupling agent is 3-(2,3-epoxypropoxy) propyltrimethoxysilane; the weight ratio of the epoxy silane coupling agent to the amino silane coupling agent is 1:1.2-1.8; the amount of the epoxy silane coupling agent and the amino silane coupling agent are 20-50% of the total weight of the polyether polyol and the polyester polyol.

4. The method according to claim 1, wherein the isocyanate is a mixture of dicyclohexylmethane diisocyanate, isophorone diisocyanate and toluene diisocyanate, the weight ratio of dicyclohexylmethane diisocyanate, isophorone diisocyanate to toluene diisocyanate is 2-4:1-3:1; the polyester polyol comprises at least one of poly(ethylene glycol adipate) diol, poly(propylene glycol adipate) diol, poly(butylene glycol adipate) diol, poly(neopentyl glycol adipate) diol, poly(hexylene glycol adipate) diol, poly(ethylene 1,4-butylene glycol adipate) diol, poly(neopentyl 1,6-hexamethylene glycol adipate) diol, poly(castor oil adipate) polyol, polycaprolactone diol, and polycarbonate diol; the polyether polyol is polypropylene oxide glycol and/or polytetramethylene ether glycol; the weight ratio of the polyester polyol to the polyether polyol is 1:3-6.

5. The method according to claim 1, wherein the hydrophilic cross-linking agent is a mixture of dimethylolpropionic acid and 2-[(2-aminoethyl)amino]-ethanesulfonic acid monosodium salt, wherein the weight ratio of dimethylolpropionic acid to 2-[(2-aminoethyl)amino]-ethane sulfonic acid monosodium salt is 3-4:1; the small molecular chain extender is at least one of ethylene glycol, propylene glycol and butanediol; the catalyst is at least one of dibutyltin dilaurate, stannous octoate and dibutyltin dichloride.

Description

DETAILED DESCRIPTION OF ILLUSTRATED EMBODIMENTS

(1) For the purpose of promoting a better understanding of the technical solution of the present invention, the present invention will be explained in details with reference to the embodiments.

Example 1

(2) A preparation method of a polyurethane material according to the present invention comprised the steps of:

(3) the first step (1): dissolving silver nitrate in water to obtain an aqueous silver nitrate solution with a concentration of 4 mg/ml;

(4) the second step (2): mixing the silver nitrate solution prepared in the step (1) with a waterborne polyurethane emulsion, adding sodium borohydride, wherein the molar ratio of silver nitrate to sodium borohydride was 1:2, and then stirring the mixture for 2 h until the silver ions were completely reduced to nano-silver, the polyurethane material was obtained after the completion of the reaction, wherein in the polyurethane material the weight ratio of the waterborne polyurethane to the nano-silver is 1000:1.

(5) The waterborne polyurethane emulsion in the step (2) was prepared according to the steps of:

(6) the first step (a): mixing a polyester polyol with an isocyanate, reacting at 70 C. for 2 h, adding a polyether polyol and further reacting at 70 C. for an additional 2 h;

(7) the second step (b): adding a hydrophilic cross-linking agent, reacting at 70 C. for 1 h; decreasing the temperature to 50 C., adding a small molecular chain extender and reacting at 50 C. for 1 h; further adding a catalyst and reacting to obtain a polyurethane prepolymer;

(8) the third step (c): neutralizing the polyurethane prepolymer obtained in the step (b) with a neutralizer, decreasing the temperature to lower than 30 C., then adding deionized water and stirring for 30 min to emulsify the mixture to obtain a prepolymer dispersion;

(9) the fourth step (d): adding an epoxy silane coupling agent to the prepolymer dispersion obtained in the step (c) and reacting for 30 min, then adding an amino silane coupling agent to react for an additional 1 hour to obtain the waterborne polyurethane emulsion.

(10) The raw materials were added according to the following amount:

(11) the polyester polyol: poly(ethylene glycol adipate) diol (Mn=2015, homemade), 10 kg; poly(castor oil adipate) polyol (Mn=1000, Wei Commerce Co., Ltd, Tongliao, Inner Mongolia, China), 5 kg; and polycaprolactone diol (Mn=1000, Daicel Corporation, Japan), 5 kg;

(12) the polyether polyol: polypropylene oxide glycol (PPG1000, Mn=1000, Daicel Corporation, Japan), 60 kg; and polytetramethylene ether glycol (PTMG1000, Mn=1000, Daicel Corporation, Japan), 20 kg;

(13) the isocyanate: methylene-bis(4-cyclohexylisocyanate) H12MDI (Pastore Corporation), 60 kg; isophorone diisocyanate IPDI (Pastore Corporation), 40 kg; and toluene diisocynate TDI (Perstorp Chemical Corporation), 20 kg;

(14) the hydrophilic cross-linking agent: dimethylolpropionic acid DMPA (Pastore Corporation), 7.5 kg; and 2-[(2-aminoethyl)amino]-ethanesulfonic acid monosodium salt A95 (Degussa AG), 2.5 kg;

(15) the small molecular chain extender: 1,4-butanediol (Beijing Yili Fine Chemicals Co. Ltd), 6 kg;

(16) the catalyst: dibutyltin dilaurate (Beijing Yili Fine Chemicals Co. Ltd), 0.005 kg;

(17) the neutralizer: triethanolamine (Beijing Yili Fine Chemicals Co. Ltd), 15 kg;

(18) deionized water (homemade): 550 kg;

(19) the amino silane coupling agent: 3-(2-aminoethyl) aminopropyltrimethoxysilane KH-792 (Jiangshu Chenguang Coupling Reagent Co., Ltd), 11 kg;

(20) the epoxy-silane coupling agent: 3-(2,3-epoxypropoxy) propyltrimethoxysilane KH-560 (Jiangshu Chenguang Coupling Reagent Co., Ltd), 9 kg.

Example 2

(21) A preparation method of a polyurethane material according to the present invention comprised the steps of:

(22) the first step (1): dissolving silver nitrate in water to obtain an aqueous silver nitrate solution with a concentration of 4 mg/ml;

(23) the second step (2): mixing the silver nitrate solution prepared in the step (1) with a waterborne polyurethane emulsion, adding sodium borohydride, wherein the molar ratio of silver nitrate to sodium borohydride was 1:2, and then stirring the mixture for 2 h until the silver ions were completely reduced to nano-silver, the polyurethane material was obtained after the completion of the reaction, wherein in the polyurethane material the weight ratio of the waterborne polyurethane to the nano-silver is 1000:1.

(24) The waterborne polyurethane emulsion in the step (2) was prepared according to the steps of:

(25) the first step (a): mixing a polyester polyol with an isocyanate, reacting at 80 C. for 1.5 h, then adding a polyether polyol and further reacting at 80 C. for an additional 1.5 h;

(26) the second step (b): adding a hydrophilic cross-linking agent, reacting at 75 C. for 0.8 h; decreasing the temperature to 55 C., adding a small molecular chain extender and reacting at 55 C. for 0.8 h; further adding a catalyst and reacting so as to obtain a polyurethane prepolymer;

(27) the third step (c): neutralizing the polyurethane prepolymer obtained in the step (b) with a neutralizer, decreasing the temperature to lower than 30 C., then adding deionized water and stirring for 30 min to emulsify the mixture, so as to obtain a prepolymer dispersion;

(28) the fourth step (d): adding an epoxy silane coupling agent to the prepolymer dispersion obtained in the step (c) and reacting for 30 min, then adding an amino silane coupling agent and reacting for an additional 1 hour to obtain the waterborne polyurethane emulsion.

(29) The raw materials were added according to the following amounts:

(30) the polyester polyol: poly(ethylene glycol adipate) diol (Mn=2015 homemade), 30 kg; poly(castor oil adipate) polyol (Mn=2000, Wei Commerce Co., Ltd, Tongliao, Inner Mongolia), 20 kg; and polycaprolactone diol (Mn=2000, Daicel Corporation, Japan), 10 kg;

(31) the polyether polyol: polypropylene oxide glycol (PPG1000, Mn=2000, Daicel Corporation, Japan), 144 kg; and polytetramethylene ether glycol (PTMG1000, Mn=1000, Daicel Corporation, Japan), 36 kg;

(32) the isocyanate: methylene-bis(4-cyclohexylisocyanate) H12MDI (Pastore Corporation), 89 kg; isophorone diisocyanate IPDI (Pastore Corporation), 59 kg; and toluene diisocynate TDI (Perstorp Chemical Corporation), 29.7 kg;

(33) the hydrophilic cross-linking agent: dimethylolpropionic acid DMPA (Pastore Corporation), 29 kg; and 2-[(2-aminoethyl)amino]-ethanesulfonic acid monosodium salt A95 (Degussa AG), 7 kg;

(34) the small molecular chain extender: 1,4-butanediol (Beijing Yili Fine Chemicals Co. Ltd), 19.2 kg;

(35) the catalyst: dibutyltin dilaurate (Beijing Yili Fine Chemicals Co. Ltd), 0.024 kg;

(36) the neutralizer: triethanolamine (Beijing Yili Fine Chemicals Co. Ltd), 20 kg;

(37) deionized water (homemade): 1000 kg;

(38) the amino silane coupling agent: 3-(2-aminoethyl) aminopropyltrimethoxysilane KH-792 (Jiangshu Chenguang Coupling Reagent Co., Ltd), 36 kg;

(39) the epoxy silane coupling agent: 3-(2,3-epoxypropoxy) propyltrimethoxysilane KH-560 (Jiangshu Chenguang Coupling Reagent Co., Ltd), 24 kg.

Example 3

(40) A preparation method of a polyurethane material according to the present invention comprised the steps of:

(41) the first step (1): dissolving silver nitrate in water to obtain an aqueous silver nitrate solution with a concentration of 4 mg/ml;

(42) the second step (2): mixing the silver nitrate solution prepared in the step (1) with a waterborne polyurethane emulsion, adding sodium borohydride, wherein the molar ratio of silver nitrate to sodium borohydride was 1:2, and then stirring the mixture for 1-10 h until the silver ions were completely reduced to nano-silver, the polyurethane material was obtained after the completion of the reaction, wherein in the polyurethane material the weight ratio of the waterborne polyurethane to the nano-silver is 4000:3.

(43) The waterborne polyurethane emulsion in the step (2) was prepared according to the steps of:

(44) the first step (a): mixing a polyester polyol with an isocyanate, reacting at 90 C. for 1 h, then adding polyether polyol and further reacting at 90 C. for an additional 1 hour;

(45) the second step (b): adding a hydrophilic cross-linking agent, reacting at 80 C. for 0.5 h; decreasing the temperature to 60 C., adding a small molecular chain extender and reacting at 60 C. for 0.5 h; further adding a catalyst and reacting so as to obtain a polyurethane prepolymer;

(46) the third step (c): neutralizing the polyurethane prepolymer obtained in the step (b) with a neutralizer, decreasing the temperature to lower than 30 C., then adding deionized water and stirring for 30 min to emulsify the mixture, so as to obtain a prepolymer dispersion;

(47) the fourth step (d): adding an epoxy silane coupling agent to the prepolymer dispersion obtained in the step (c) and reacting for 30 min, then adding an amino silane coupling agent and reacting for an additional 1 hour to obtain the waterborne polyurethane emulsion.

(48) The raw materials were added according to the following amounts:

(49) the polyester polyol: poly(ethylene glycol adipate) diol (Mn=2015, homemade), 12 kg; poly(castor oil adipate) polyol (Mn=1000, Wei Commerce Co., Ltd, Tongliao, Inner Mongolia), 4 kg; and polycaprolactone diol (Mn=1000, Daicel Corporation, Japan), 4 kg;

(50) the polyether polyol: polypropylene oxide glycol (PPG2000, Mn=2000, Daicel Corporation, Japan), 80 kg; and polytetramethylene ether glycol (PTMG2000, Mn=2000, Daicel Corporation, Japan), 20 kg;

(51) the isocyanate: methylene-bis(4-cyclohexylisocyanate) H12MDI (Pastore Corporation), 50 kg; isophorone diisocyanate IPDI (Pastore Corporation), 33.3 kg; and toluene diisocynate TDI (Perstorp Chemical Corporation), 16.7 kg;

(52) the hydrophilic cross-linking agent: dimethylolpropionic acid DMPA (Pastore Corporation), 18 kg; and 2-[(2-aminoethyl)amino]-ethanesulfonic acid monosodium salt A95 (Degussa AG), 6 kg;

(53) the small molecular chain extender: 1,4-butanediol (Beijing Yili Fine Chemicals Co. Ltd), 12 kg;

(54) the catalyst: dibutyltin dilaurate (Beijing Yili Fine Chemicals Co. Ltd), 0.018 kg;

(55) the neutralizer: triethanolamine (Beijing Yili Fine Chemicals Co. Ltd), 15 kg;

(56) deionized water (homemade): 455 kg;

(57) the amino silane coupling agent: 3-(2-aminoethyl) aminopropyltrimethoxysilane KH-792 (Jiangshu Chenguang Coupling Reagent Co., Ltd), 19 kg;

(58) the epoxy silane coupling agent: 3-(2,3-epoxypropoxy) propyltrimethoxysilane KH-560 (Jiangshu Chenguang Coupling Reagent Co., Ltd), 11 kg.

Example 4

(59) A preparation method of a polyurethane material according to the present invention comprised the steps of:

(60) the first step (1): dissolving silver nitrate in water to obtain an aqueous silver nitrate solution with a concentration of 4 mg/ml;

(61) the second step (2): mixing the silver nitrate solution prepared in the step (1) with a waterborne polyurethane emulsion, adding sodium borohydride, wherein the molar ratio of silver nitrate to sodium borohydride was 1:2, and then stirring the mixture for 1-10 h until the silver ions were completely reduced to nano-silver, the polyurethane material was obtained after the completion of the reaction, wherein in the polyurethane material the weight ratio of the waterborne polyurethane to the nano-silver is 2000:3.

(62) The waterborne polyurethane emulsion in the step (2) was prepared according to the steps of:

(63) the first step (a): mixing a polyester polyol with an isocyanate, reacting at 80 C. for 1.5 h, then adding a polyether polyol and further reacting at 80 C. for an additional 1.5 h;

(64) the second step (b): adding a hydrophilic cross-linking agent, reacting at 75 C. for 0.8 h; decreasing the temperature to 55 C., adding a small molecular chain extender to react at 55 C. for 0.8 h; further adding a catalyst and reacting so as to obtain a polyurethane prepolymer;

(65) the third step (c): neutralizing the polyurethane prepolymer obtained in the step (b) with a neutralizer, decreasing the temperature to lower than 30 C., then adding deionized water and stirring for 1 h to emulsify the mixture, so as to obtain a prepolymer dispersion;

(66) the fourth step (d): adding an epoxy silane coupling agent to the prepolymer dispersion obtained in the step (c) and reacting for 30 min, then adding an amino silane coupling agent and reacting for an additional 1 hour to obtain the waterborne polyurethane emulsion.

(67) The raw materials were added according to the following amounts:

(68) the polyester polyol: poly(ethylene glycol adipate) diol (Mn=2015, homemade), 12 kg; poly(castor oil adipate) polyol (Mn=1000, Wei Commerce Co., Ltd, Tongliao, Inner Mongolia), 6 kg; and polycaprolactone diol (Mn=1000, Daicel Corporation, Japan), 3 kg;

(69) the polyether polyol: polypropylene oxide glycol (PPG1000, Mn=1000, Daicel Corporation, Japan), 105 kg; and polytetramethylene ether glycol (PTMG1000, Mn=1000, Daicel Corporation, Japan), 21 kg;

(70) the isocyanate: methylene-bis(4-cyclohexylisocyanate) H12MDI (Pastore Corporation), 67.5 kg; isophorone diisocyanate IPDI (Pastore Corporation), 45 kg; and toluene diisocynate TDI (Perstorp Chemical Corporation), 22.5 kg;

(71) the hydrophilic cross-linking agent: dimethylolpropionic acid DMPA (Pastore Corporation), 17 kg; and 2-[(2-aminoethyl)amino]-ethanesulfonic acid monosodium salt A95 (Degussa AG), 4 kg;

(72) the small molecular chain extender: 1,4-butanediol (Beijing Yili Fine Chemicals Co. Ltd), 20 kg;

(73) the catalyst: dibutyltin dilaurate (Beijing Yili Fine Chemicals Co. Ltd), 0.032 kg;

(74) the neutralizer: triethanolamine (Beijing Yili Fine Chemicals Co. Ltd), 18 kg;

(75) deionized water (homemade): 670 kg;

(76) the amino silane coupling agent: 3-(2-aminoethyl) aminopropyltrimethoxysilane KH-792 (Jiangshu Chenguang Coupling Reagent Co., Ltd), 31 kg;

(77) the epoxy silane coupling agent: 3-(2,3-epoxypropoxy) propyltrimethoxysilane KH-560 (Jiangshu Chenguang Coupling Reagent Co., Ltd), 19 kg.

Example 5

(78) A preparation method of a polyurethane material according to the present invention comprised the steps of:

(79) the first step (1): dissolving silver nitrate in water to obtain an aqueous silver nitrate solution with a concentration of 4 mg/ml;

(80) the second step (2): mixing the silver nitrate solution prepared in the step (1) with a waterborne polyurethane emulsion, adding sodium borohydride, wherein the molar ratio of silver nitrate to sodium borohydride was 1:2, and then stirring the mixture for 2 h until the silver ions were completely reduced to nano-silver, the polyurethane material was obtained after the completion of the reaction, wherein in the polyurethane material the weight ratio of the waterborne polyurethane to the nano-silver is 500:1.

(81) The waterborne polyurethane emulsion in the step (2) was prepared according to the steps of:

(82) the first step (a): mixing a polyester polyol with an isocyanate, reacting at 80 C. for 1.5 h, then adding a polyether polyol and further reacting at 80 C. for an additional 1.5 h;

(83) the second step (b): adding a hydrophilic cross-linking agent, reacting at 75 C. for 0.8 h; decreasing the temperature to 55 C., adding a small molecular chain extender and reacting at 55 C. for 0.8 h; further adding a catalyst and reacting so as to obtain a polyurethane prepolymer;

(84) the third step (c): neutralizing the polyurethane prepolymer obtained in the step (b), decreasing the temperature to lower than 30 C., then adding deionized water and stirring for 30 min to emulsify the mixture, so as to obtain a prepolymer dispersion;

(85) the fourth step (d): adding an epoxy silane coupling agent to the prepolymer dispersion obtained in the step (c) and reacting for 30 min, then adding an amino silane coupling agent and reacting for an additional 1 hour to obtain the waterborne polyurethane emulsion.

(86) The raw materials were added according to the following amounts:

(87) the polyester polyol: poly(ethylene glycol adipate) diol (Mn=2015, homemade), 8 kg; poly(castor oil adipate) polyol (Mn=1000, Wei Commerce Co., Ltd, Tongliao, Inner Mongolia), 2 kg; and polycaprolactone diol (Mn=1000, Daicel Corporation, Japan), 2 kg;

(88) the polyether polyol: polypropylene oxide glycol (PPG1000, Mn=1000, Daicel Corporation, Japan), 450 kg; and polytetramethylene ether glycol (PTMG1000, Mn=1000, Daicel Corporation, Japan), 15 kg;

(89) the isocyanate: methylene-bis(4-cyclohexylisocyanate) H12MDI (Pastore Corporation), 35 kg; isophorone diisocyanate IPDI (Pastore Corporation), 23.3 kg; and toluene diisocynate TDI (Perstorp Chemical Corporation), 11.7 kg;

(90) the hydrophilic cross-linking agent: dimethylolpropionic acid DMPA (Pastore Corporation), 10 kg; and 2-[(2-aminoethyl)amino]-ethanesulfonic acid monosodium salt A95 (Degussa AG). 3 kg;

(91) the small molecular chain extender: 1,4-butanediol (Beijing Yili Fine Chemicals Co. Ltd) 10.8 kg;

(92) the catalyst: dibutyltin dilaurate (Beijing Yili Fine Chemicals Co. Ltd), 0.014 kg;

(93) the neutralizer: triethanolamine (Beijing Yili Fine Chemicals Co. Ltd), 10 kg;

(94) deionized water (homemade): 400 kg;

(95) the amino silane coupling agent: 3-(2-aminoethyl) aminopropyltrimethoxysilane KH-792 (Jiangshu Chenguang Coupling Reagent Co., Ltd), 22 kg;

(96) the epoxy silane coupling agent: 3-(2,3-epoxypropoxy) propyltrimethoxysilane KH-560 (Jiangshu Chenguang Coupling Reagent Co., Ltd), 14 kg.

Comparative Example 1

(97) In the comparative Example 1, a preparation method of a polyurethane material was substantially the same as described in Example 2 except that the step (d) was performed as follows: adding 60 kg 3-(2-aminoethyl) aminopropyltrimethoxysilane KH-792 (available from Jiangshu Chenguang Coupling Reagent Co., Ltd) to the prepolymer dispersion obtained in the step (c) and reacting for 1 h to obtain the waterborne polyurethane emulsion.

Comparative Example 2

(98) In comparative Example 2, a preparation method of a polyurethane material was substantially the same as described in Example 2 except that the step (d) was performed as follows: adding 60 kg 3-(2,3-epoxypropoxy)propyltrimethoxysilane KH-560 (available from Jiangshu Chenguang Coupling Reagent Co., Ltd) to the prepolymer dispersion obtained in the step (c) and reacting for 1 h to obtain the waterborne polyurethane emulsion.

Comparative Example 3

(99) In comparative Example 3, a preparation method of a polyurethane material was substantially the same as described in Example 2 except that the polyester polyol in the step (a) was replaced with 60 kg poly(ethylene glycol adipate) diol (Mn=2015, homemade).

Comparative Example 4

(100) In comparative Example 4, a preparation method of a polyurethane material was substantially the same as described in Example 2 except that the polyester polyol in the step (a) was replaced with 60 kg poly(castor oil adipate) polyol (Mn=2000, available from Wei Commerce Co., Ltd, Tongliao, Inner Mongolia).

Comparative Example 5

(101) In comparative Example 5, a preparation method of a polyurethane material was substantially the same as described in Example 2 except that the polyester polyol in the step (a) was replaced with 60 kg polycaprolactone diol (Mn=2000, available from Daicel Corporation, Japan).

Comparative Example 6

(102) In comparative Example 6, a preparation method of a polyurethane material was substantially the same as described in Example 2 except that the polyester polyol in the step (a) was replaced with 30 kg poly(ethylene glycol adipate) diol (Mn=2015, homemade) and 30 kg poly(castor oil adipate) polyol (Mn=2000, available from Wei Commerce Co., Ltd, Tongliao, Inner Mongolia).

Comparative Example 7

(103) In comparative Example 7, a preparation method of a polyurethane material was substantially the same as described in Example 2 except that the polyester polyol in the step (a) was replaced with 30 kg poly(ethylene glycol adipate) diol (Mn=2015, homemade) and 30 kg polycaprolactone diol (Mn=2000, Daicel Corporation, Japan).

Comparative Example 8

(104) In comparative Example 8, a preparation method of a polyurethane material was substantially the same as described in Example 2 except that the polyester polyol in step (a) was replaced with 30 kg poly(castor oil adipate) polyol (Mn=2000, available from Wei Commerce Co., Ltd, Tongliao, Inner Mongolia) and 30 kg polycaprolactone diol (Mn=2000, Daicel Corporation, Japan).

Comparative Example 9

(105) In comparative Example 9, a preparation method of a polyurethane material was substantially the same as described in Example 2 except that the polyether polyol in the step (a) was replaced with 180 kg polypropylene oxide glycol (PPG2000, Mn=2000, Daicel Corporation, Japan).

Comparative Example 10

(106) In comparative Example 10, a preparation method of a polyurethane material was substantially the same as described in Example 2 except that the polyether polyol in step (a) was replaced with 180 kg polytetramethylene ether glycol (PTMG1000, Mn=1000, Daicel Corporation, Japan).

Example 6

(107) The physical properties of the polyurethane materials prepared in Examples 1-5 as well as in Comparative Examples 1-10 were tested as follows with the results listed in Table 1. The mechanical properties (tensile strength, and elongation at break) were tested according to GB/T1040.2 of the National Standard; the samples were soaked at a room temperature of 25-28 C. to analyze color variation, viscosity with the corresponding time recorded; the antimicrobial (anti-staphylococcus aureus) activities were tested according to QB/T2591 (Test for Antimicrobial Activity of Antimicrobial Plastics) of the National Standard.

(108) TABLE-US-00001 TABLE 1 Tensile Elongation Water Killing Rate in Strength at Break Tolerance Staphylococcus Example (MPa) (%) (d) Aureus (%) Example 1 34 580 20 96.8 Example 2 36 600 25 99.99 Example 3 35 560 21 98.7 Example 4 34 530 21 96.59 Example 5 33 570 19 95.89 Comparative 31 550 20 98.5 Example 1 Comparative 30 540 21 98.9 Example 2 Comparative 28 480 19 97.8 Example 3 Comparative 25 470 18 98.6 Example 4 Comparative 27 490 19 98.7 Example 5 Comparative 30 510 20 98.9 Example 6 Comparative 28 500 21 99.1 Example 7 Comparative 31 490 20 98.7 Example 8 Comparative 29 490 22 97.9 Example 9 Comparative 37 590 24 99.5 Example 10

Example 7

(109) Condoms were prepared by the polyurethane materials made according to the Examples 1-5 and the Comparative Examples 1-10, respectively. The performances of the condoms were tested.

(110) 1. Cytotoxicity

(111) Before performing the antimicrobial test, any potential harms caused by polyurethane condoms (PUCs) coated with nano-silver were required to be assessed. Firstly, 5 groups of same amount of human cervical carcinoma cells (HeLa cells) were added to contact with the condoms made from the polyurethane materials prepared according to Examples 1-5 mentioned in Example 7 both for 10, 60 and 240 min. After the contacts, the HeLa cells were cultured under normal conditions and analyzed by cell proliferation assay (WST-1) 4 days later.

(112) It was found that that contact with the condoms for 4 h had no adverse effect on the growth of HeLa cells, which therefore demonstrated that the condoms made from the polyurethane materials prepared according to Examples 1-5 had no significant impact on the survival and the growth of HeLa cells.

(113) 2. Inhibitory Effect of the Condoms Prepared in Example 7 on HIV-1

(114) It was tested whether the condoms prepared in Example 7 could directly inactivate HIV-1. Firstly, HIV-1 (pNL4.3) were incubated in the mediums containing the condoms (1 square centimeter) prepared in Example 7 for 5, 10, 30, 60 or 120 min, respectively. During these periods the mediums were continuously shaken to make the viruses and the condoms fully contact. Meanwhile, pNL4.3-GFP+ viruses without contacting the condoms were used as positive control. After incubation, the supernatant containing viruses were collected to test their virulence to CD4+C8166T cells.

(115) It was found that HIV exposed to the condoms made from the polyurethane materials prepared by Comparative Examples 1-10 has an inhibited virulence. A more significant inhibitive effect was seen on the virulence of the HIV-1 that were exposed to the condoms made from the polyurethane materials prepared by examples 1-5. More particularly, most of the HIV-1 lost their virulence to CD4+ cells in the first 5 minutes after their exposure to the condoms made from the polyurethane materials prepared in accordance with Example 2. Significantly, after 10-minute exposure to the condoms prepared by the polyurethane materials of Example 2, all HIV-1 (pNL4.3 viruses) lost their virulence. Comparatively speaking, most of the HIV-1 exposed to the condoms made from the polyurethane materials prepared according to Examples 1, 3, 4 did not lose their virulence to CD4+ cells until their exposure exceeded 30 minutes. Where the exposure time were increased to 60 minutes all HIV-1 were deprived of their virulence.

(116) 3. Inhibitory Effect of the Condoms Prepared in Example 7 on Macrophage-Tropic (M-Tropic) HIV-1

(117) Inhibitory effect of the condoms prepared in Example 7 on M-tropic HIV-1 was further tested. M-tropic HIV-1 (pNL4.3-BAL virus strain) were incubated in the mediums containing the condoms prepared in Example 7 for 5, 10, 30 or 60 minutes, respectively. After incubation, the supernatant containing viruses were collected to test their virulence to HeLa-gal-CD4.sup.+-CCR5.sup.+ cells. And a same amount of pNL4.3-BAL viruses without contacting the condoms were used as positive control. After 48-hour infection, the infected cells were detected using MAGI.

(118) It was found that macrophage-tropic HIV-1 exposed to the condoms made from the polyurethane materials prepared by Comparative Examples 1-10 were inhibited, while HIV exposed to the condoms made from the polyurethane materials prepared by Examples 1-5 are more significantly inhibited, compared to the positive control. More particularly, all viruses lost their virulence in the first 10 minutes after their exposure to the condoms made from the polyurethane material prepared according to Example 1.

(119) The results demonstrated that the condoms made from the polyurethane materials prepared according to Examples 1-5 are not only effective against T-tropic viruses, but also against M-tropic viruses. It is well known that different HIV strains are distinctly different in pathogenicity, virulence and susceptibility to the antiviral agents. Therefore, it is important to further assess the broad-spectrum antiviral activity of the condoms made from the polyurethane materials prepared according to Examples 1-5 against different HIV-1 strains and antibiotic resistant strains.

(120) 4. Inhibitory Effect of the Condoms Prepared in Example 7 on Herpes Simplex Virus

(121) Herpes simplex virus (HSV) is a common infectious pathogen that can infect people at different ages worldwide. The clinical manifestations of HSV-1 infection range from asymptomatic infection, herpes labialis to severe encephalitis, etc., whereas HSV-2 causes genital herpes. It is reported that, over the past decade, HSV infection has been increasing sharply due to the increase of the number of immunocompromised patients and the spread of HIV infection. Furthermore, a large number of observational data shows that genital HSV-2 infection can facilitate HIV passing through the vaginal mucosa. Therefore, it is necessary to test whether the condoms prepared in the above examples can prevent herpes simplex virus infection.

(122) Firstly, liquid cultures containing HSV-1 or HSV-2 viruses (50-500 PFU) were mixed with the condoms prepared in Example 7 for 30 minutes. Then, the supernatant containing the viruses was collected to infect Vero-E6 cells. The cytopathic effect caused by the viruses was recorded after 48 hours of infection. It was found that the HSV-1 and HSV-2 exposed to the condoms made from the polyurethane materials prepared according to comparative Examples 1-10 still retained a certain degree of virulence. While the HSV-1 and HSV-2 exposed to the condoms made from the polyurethane materials prepared according to Examples 1-5 completely lost their virulence. The results clearly indicate that the condoms made from the polyurethane materials prepared according to Examples 1-5 have a strong ability to inactivate HSV-1 and HSV-2.

(123) 5. Inhibitory Effect of the Condoms Prepared in Example 7 on Bacteria and Fungi

(124) Besides HIV-1 and HSV, the inhibitory effects of the condoms prepared in Example 7 on bacteria and fungi were also tested. The condoms prepared in Example 7 were found to have significant antibacterial activity where the condoms made from common polyurethane (PUC) do not display such property.

(125) It is thus concluded that the condoms made from the polyurethane materials prepared according to Examples 1-5 not only have a broad-spectrum antibacterial and antiviral activity but also have the ability to inactivate the microorganism in a short time. Particularly, the condom made from the polyurethane materials prepared according to Examples 2 shows the best effect.

(126) Although the description of the embodiments of the present disclosure has been detailed described, the described embodiments are merely considered, in all respects, as illustrative and not restrictive on the scope of the invention. It would be appreciated by those skilled in the art. However modifications and alternatives can be made with those details, changes are only allowed within the scope of the present disclosure. The whole scope of the present disclosure is provided by attached claims and any equivalents thereof.