CN112679689A - Organosilicon quaternary ammonium salt modified polyurethane and preparation method and application thereof - Google Patents
Organosilicon quaternary ammonium salt modified polyurethane and preparation method and application thereof Download PDFInfo
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Abstract
The invention discloses organosilicon quaternary ammonium salt modified polyurethane and a preparation method and application thereof, wherein the organosilicon quaternary ammonium salt modified polyurethane is prepared from organosilicon quaternary ammonium salt, polyether polyol or polyester polyol, diisocyanate, organic metal catalyst, chain extender, defoaming agent and curing agent; wherein the structure of the organosilicon quaternary ammonium salt is shown as formula 1. The invention firstly prepares an organosilicon quaternary ammonium salt, and then grafts the organosilicon quaternary ammonium salt on a polyurethane branched chain. As the branched organosilicon is easy to migrate to the surface of the material, the quaternary ammonium salt connected with the branched organosilicon is enriched on the surface, the contact with bacteria is increased, the antibacterial effect is improved, the use amount of the antibacterial agent can be reduced, and the cost is saved. In addition, the branched chain organosilicon can effectively improve the hydrophobicity of the surface of the material compared with the organosilicon connected to the main chain, and is beneficial to keeping the surface of the material dry, thereby reducing the breeding of microorganisms such as bacteria, viruses and the like.
Description
Technical Field
The invention belongs to the field of high polymer materials, and particularly relates to organosilicon quaternary ammonium salt modified polyurethane and a preparation method and application thereof.
Background
The polyurethane has the advantages of wear resistance, tear resistance, good bending resistance and flexibility, convenient processing, low price and the like, and can be applied to various fields of medical materials, household appliances, toys, communication products, kitchen utensils and the like. However, since the polyether or polyester segment in the polyurethane macromolecule can be a carbon source for the growth of microorganisms, the polyurethane product can cause the growth of bacteria under proper temperature and humidity conditions during the use or storage process, which threatens the life health of human beings.
In order to overcome the above disadvantages, antibacterial agents are often used to modify polyurethanes to prepare antibacterial polyurethane materials.
The quaternary ammonium salt is a broad-spectrum and efficient bactericide, and can effectively enhance the antibacterial property of the polyurethane by modifying the polyurethane with the quaternary ammonium salt. The organic silicon has the characteristics of low surface energy and good hydrophobicity, can reduce the water absorption of the surface of the material, and is favorable for keeping the surface of the material dry, thereby reducing the growth and the propagation of microorganisms such as bacteria and the like. Therefore, the quaternary ammonium salt and the organosilicon are combined to prepare the organosilicon quaternary ammonium salt which is used for modifying polyurethane, so that the antibacterial capability of the polyurethane material can be enhanced.
For example: according to the method, chlorinated propyl-containing dihydroxy terminated polysiloxane is obtained through ring-opening copolymerization of self-made dihydroxy terminating agents MTS, 2,4, 6-tri (3-chloropropyl) -2,4, 6-trimethyl-cyclotrisiloxane and octamethylcyclotetrasiloxane (D4) by means of the billows and the like in Zhejiang university, quaternary ammonium salt groups with bactericidal performance are introduced into an organic silicon chain through quaternization, and polyurethane is synthesized through the reaction of hydroxyl and isocyanate. The results show that: when the content of the quaternary ammonium salt is 20%, the polyurethane has low surface energy characteristic, and the sterilization rate of the polyurethane to gram-positive bacteria and gram-negative bacteria can reach more than 90%.
The preparation process of the scheme is complex, the requirement on reaction conditions is high, a large number of reagents are used, the environment is not protected, and the organosilicon is embedded in the main chain of the polyurethane, so that the effect of reducing the surface energy is general.
Disclosure of Invention
The invention aims to provide organosilicon quaternary ammonium salt modified polyurethane with improved antibacterial performance and surface performance. A novel organosilicon quaternary ammonium salt is synthesized and grafted on a polyurethane branched chain. As the organic silicon is easy to migrate to the surface of the material, the quaternary ammonium salt connected with the organic silicon is enriched on the surface, the contact with bacteria is increased, the antibacterial effect is improved, the using amount of the antibacterial agent can be reduced, and the cost is saved.
The purpose of the invention is realized by the following technical scheme:
the organic silicon quaternary ammonium salt modified polyurethane is prepared from the following raw materials in parts by weight:
5-30 parts of organic silicon quaternary ammonium salt, 100 parts of polyether polyol or polyester polyol, 11.2-50 parts of diisocyanate, 0.1-0.5 part of organic metal catalyst, 0-5 parts of chain extender, 0.1-2.0 parts of defoaming agent and 3-17 parts of curing agent.
The structure of the organosilicon quaternary ammonium salt is shown as formula 1:
wherein, R is1Is composed of
One of (1);
x is halogen, preferably F, Cl, Br or I;
the m is 4-65, n is 0-3, and p is 12, 14 or 16.
The molecular structure of the organosilicon quaternary ammonium salt only has one hydroxyl group, so that the part of the organosilicon quaternary ammonium salt which reacts with isocyanate only has one end, and the organosilicon quaternary ammonium salt is bound on a branched chain of polyurethane.
The preparation method of the organosilicon quaternary ammonium salt comprises the following steps:
mixing 15-17.5 parts of hydroxyl-containing quaternary ammonium salt, 9-12.5 parts of diisocyanate and 0.05-0.3 part of organic metal catalyst, stirring and reacting at 75-85 ℃ for 3-5 h, adding 25-250 parts of double-end hydroxyl polysiloxane, stirring and reacting at 80-95 ℃ for 3-8 h to obtain organic silicon quaternary ammonium salt; the parts are parts by weight;
the hydroxyl quaternary ammonium salt is one of dodecyl dimethyl (2-hydroxyl) ethyl ammonium halide, tetradecyl dimethyl (2-hydroxyl) ethyl ammonium halide or hexadecyl dimethyl (2-hydroxyl) ethyl ammonium halide.
The hydroxyl quaternary ammonium salt is preferably one of dodecyl dimethyl (2-hydroxyl) ethyl ammonium chloride, tetradecyl dimethyl (2-hydroxyl) ethyl ammonium chloride or hexadecyl dimethyl (2-hydroxyl) ethyl ammonium chloride.
The diisocyanate described herein is one of Toluene Diisocyanate (TDI), diphenylmethane-4, 4' -diisocyanate (MDI), isophorone diisocyanate (IPDI), Hexamethylene Diisocyanate (HDI), p-phenylene diisocyanate (PPDI), Xylylene Diisocyanate (XDI), 1, 4-cyclohexane diisocyanate (CHDI), naphthalene-1, 5-diisocyanate (NDI);
the diisocyanate described herein is preferably Toluene Diisocyanate (TDI) or diphenylmethane-4, 4' -diisocyanate (MDI).
The organic metal catalyst is at least one of stannous octoate, dibutyl tin dilaurate, lead octoate or di-n-butyltin diacetate, and dibutyl tin dilaurate with good catalytic effect is preferred.
The double-end hydroxyl polysiloxane is hydroxyl-terminated polysiloxane or silicon hydroxyl-terminated polysiloxane with the average molecular weight of 500-5000.
The above-mentioned production method is preferably carried out under an inert gas atmosphere.
In the raw material components of the organosilicon quaternary ammonium salt modified polyurethane, the polyether polyol has the molecular weight of 200-10000 and is at least one of polyoxypropylene ether polyol (PPG), polytetrahydrofuran ether Polyol (PTMEG) or tetrahydrofuran-propylene oxide copolyol; more preferably polyoxypropylene ether triol with average molecular weight of 300-6000.
The polyester polyol is at least one of adipic acid polyester polyol, pimelic acid polyester polyol, suberic acid polyester polyol, glutaric acid polyester polyol, sebacic acid polyester polyol, ethylene glycol polyester polyol, succinic acid polyester polyol, polycaprolactone polyol, polycarbonate polyol, maleic anhydride polyester polyol, phthalic anhydride polyester polyol, terephthalic polyester polyol or random polyester polyol, wherein the average functionality is more than 3, and the average molecular weight is 400-6000; more preferably, the adipic acid polyester polyol or polycaprolactone polyol has an average functionality of 3 and an average molecular weight of 400 to 6000, which are easily controlled in the reaction.
The chain extender is at least one of 1, 4-butanediol, ethylene glycol, propylene glycol, hexanediol, cyclohexanediol, polyethylene terephthalate or trimethylolpropane monoallyl ether; 1, 4-butanediol is preferred.
The defoaming agent is an organic silicon defoaming agent and/or a mineral oil defoaming agent; silicone defoamers are preferred.
The curing agent is one of dimethylthiotoluenediamine (DMTDA, such as Ethacure300), 3 ' -dichloro-4, 4 ' -diaminodiphenylmethane (MOCA), diethyltoluenediamine (DETDA, such as Ethacure100), 3, 5-diamino-4-chlorophenylacetic acid isopropyl ester (such as CuA-60) or 4,4 ' -methylenebis (2, 6-diethyl-3-chloroaniline) (MCDEA); dimethylthiotoluenediamine (DMTDA, Ethacure300) is preferred.
The preparation method of the organosilicon quaternary ammonium salt modified polyurethane comprises the following steps:
mixing organic silicon quaternary ammonium salt, polyether polyol or polyester polyol, diisocyanate and an organic metal catalyst, stirring at 75-90 ℃ for reaction for 3-8 hours, adding a chain extender, a defoaming agent and a curing agent, and curing at 80-90 ℃ for 10-20 hours to obtain organic silicon quaternary ammonium salt modified polyurethane;
the above-mentioned production method is preferably carried out under an inert gas atmosphere.
The organosilicon quaternary ammonium salt modified polyurethane prepared by the invention has excellent antibacterial property and surface property on the basis of keeping the original advantages of polyurethane. Can be widely applied to the fields of communication products, kitchen utensils, office supplies, medical materials, food packaging, building materials, household appliances, toys, fabrics, shoes and the like.
Compared with the prior art, the invention has the following advantages and effects:
(1) the organosilicon quaternary ammonium salt modified polyurethane integrates the performances of quaternary ammonium salt, organosilicon and polyurethane, so that the polyurethane has excellent antibacterial performance and surface performance on the basis of keeping the original advantages.
(2) The invention firstly prepares an organosilicon quaternary ammonium salt, and then grafts the organosilicon quaternary ammonium salt on a polyurethane branched chain. As the branched organosilicon is easy to migrate to the surface of the material, the quaternary ammonium salt connected with the branched organosilicon is enriched on the surface, the contact with bacteria is increased, the antibacterial effect is improved, the use amount of the antibacterial agent can be reduced, and the cost is saved. In addition, the branched chain organosilicon can effectively improve the hydrophobicity of the surface of the material compared with the organosilicon connected to the main chain, and is beneficial to keeping the surface of the material dry, thereby reducing the breeding of microorganisms such as bacteria, viruses and the like.
(3) The preparation method of the polyurethane material has the advantages of simple synthesis steps, easily controlled conditions, safe operation, cheap and easily obtained raw materials, and suitability for industrial production; and no harmful solvent is used, so that the method has no pollution to the environment and accords with the development direction of green materials.
Detailed Description
The present invention will be described in further detail with reference to examples, but the embodiments of the present invention are not limited thereto.
Example 1
An organosilicon quaternary ammonium salt modified polyurethane is prepared by the following steps:
(1) preparation of organosilicon quaternary ammonium salt
15g of dodecyl dimethyl (2-hydroxy) ethyl ammonium chloride, 9g of toluene diisocyanate and 0.05g of dibutyl tin dilaurate are mixed, stirred and reacted for 5 hours at 75 ℃ under the protection of nitrogen, then 250g of double-end hydroxy polydimethylsiloxane (end capped by hydroxyl hydrocarbon group and with average molecular weight of 5000) is added, and stirred and reacted for 8 hours at 80 ℃ under the protection of nitrogen, so that the organosilicon quaternary ammonium salt is obtained.
(2) Preparation of organosilicon quaternary ammonium salt modified polyurethane
5g of organic silicon quaternary ammonium salt, 100g of polyether triol N330, 18g of toluene diisocyanate and 0.1g of dibutyl tin dilaurate are mixed, stirred and reacted for 8 hours at 75 ℃ under the protection of nitrogen, then 0.1g of organic silicon defoaming agent and 10g of dimethyl-sulfur-based toluene diamine are added, and the mixture is cured for 20 hours at 80 ℃ to obtain the organic silicon quaternary ammonium salt modified polyurethane.
Example 2
An organosilicon quaternary ammonium salt modified polyurethane is prepared by the following steps:
(1) preparation of organosilicon quaternary ammonium salt
Mixing 16g of tetradecyl dimethyl (2-hydroxy) ethyl ammonium chloride, 12.5g of diphenylmethane-4, 4' -diisocyanate and 0.1g of dibutyltin dilaurate, stirring and reacting at 80 ℃ for 4 hours under the protection of nitrogen, adding 100g of double-end hydroxy polydimethylsiloxane (silicon hydroxy end-capped, average molecular weight of 2000), and stirring and reacting at 85 ℃ for 5 hours under the protection of nitrogen to obtain the organosilicon quaternary ammonium salt.
(2) Preparation of organosilicon quaternary ammonium salt modified polyurethane
12g of organic silicon quaternary ammonium salt, 100g of polyoxypropylene ether triol JH-3030, 25.5g of diphenylmethane-4, 4 ' -diisocyanate and 0.1g of dibutyltin dilaurate are mixed, stirred and reacted for 6 hours at 80 ℃ under the protection of nitrogen, 4g of ethylene glycol and 0.9g of organic silicon defoamer and 10g of liquid 3,3 ' -dichloro-4, 4 ' -diaminodiphenylmethane are added, and the mixture is cured for 10 hours at 90 ℃ to prepare the organic silicon quaternary ammonium salt modified polyurethane.
Example 3
An organosilicon quaternary ammonium salt modified polyurethane is prepared by the following steps:
(1) preparation of organosilicon quaternary ammonium salt
17.5g of hexadecyl dimethyl (2-hydroxy) ethyl ammonium chloride, 11.2g of isophorone diisocyanate and 0.2g of lead octoate are mixed, stirred and reacted for 3 hours at 85 ℃ under the protection of nitrogen, 25g of double-end hydroxy polydimethylsiloxane (silicon hydroxy end-capped, average molecular weight is 500) is added, and stirred and reacted for 3 hours at 95 ℃ under the protection of nitrogen, so that the organosilicon quaternary ammonium salt is obtained.
(2) Preparation of organosilicon quaternary ammonium salt modified polyurethane
Mixing 15g of organic silicon quaternary ammonium salt, 100g of polyoxypropylene ether triol MN-3050, 23g of isophorone diisocyanate and 0.3g of lead caprylate, stirring and reacting for 3 hours at 90 ℃ under the protection of nitrogen, adding 3g of hexanediol, 1.6g of organic silicon defoamer, 12g of 3, 5-diamino-4-chlorobenzene isopropyl acetate, and curing for 15 hours at 85 ℃ to obtain the organic silicon quaternary ammonium salt modified polyurethane.
Example 4
An organosilicon quaternary ammonium salt modified polyurethane is prepared by the following steps:
(1) preparation of organosilicon quaternary ammonium salt
Mixing 15g of dodecyl dimethyl (2-hydroxy) ethyl ammonium chloride, 9g of hexamethylene diisocyanate and 0.1g of di-n-butyltin diacetate, stirring and reacting for 4 hours at 80 ℃ under the protection of nitrogen, adding 50g of double-end hydroxy polydimethylsiloxane (terminated by silicon hydroxyl and with the average molecular weight of 1000), and stirring and reacting for 7 hours at 85 ℃ under the protection of nitrogen to obtain the organosilicon quaternary ammonium salt.
(2) Preparation of organosilicon quaternary ammonium salt modified polyurethane
22.5g of organic silicon quaternary ammonium salt, 100g of polyoxypropylene ether triol 1618A, 12g of hexamethylene diisocyanate and 0.5g of di-n-butyltin diacetate are mixed and stirred to react for 5 hours at 75 ℃ under the protection of nitrogen, 3g of propylene glycol, 1g of organic silicon defoamer and 3g of 4, 4' -methylene bis (3-chloro-2, 6-diethylaniline) are added to be cured for 20 hours at 80 ℃, and the organic silicon quaternary ammonium salt modified polyurethane is prepared.
Example 5
An organosilicon quaternary ammonium salt modified polyurethane is prepared by the following steps:
(1) preparation of organosilicon quaternary ammonium salt
Mixing 16g of tetradecyl dimethyl (2-hydroxy) ethyl ammonium chloride, 9g of toluene diisocyanate and 0.3g of dibutyl tin dilaurate, stirring and reacting at 75 ℃ for 4h under the protection of nitrogen, adding 200g of double-end hydroxy polydimethylsiloxane (silicon hydroxyl end-capped, average molecular weight is 4000), and stirring and reacting at 85 ℃ for 6h under the protection of nitrogen to obtain the organosilicon quaternary ammonium salt.
(2) Preparation of organosilicon quaternary ammonium salt modified polyurethane
Mixing 30g of organic silicon quaternary ammonium salt, 100g of polyethylene glycol trimethylolpropane adipate with the average molecular weight of 3000 and the hydroxyl value of 56-60, 18g of toluene diisocyanate and 0.15g of dibutyl tin dilaurate, stirring and reacting for 8 hours at 75 ℃ under the protection of nitrogen, adding 3g of dihydroxy ethyl terephthalate, 1.2g of mineral oil defoaming agent and 17g of diethyl toluene diamine, and curing for 20 hours at 80 ℃ to obtain the organic silicon quaternary ammonium salt modified polyurethane.
Example 6
An organosilicon quaternary ammonium salt modified polyurethane is prepared by the following steps:
(1) preparation of organosilicon quaternary ammonium salt
17.5g of hexadecyl dimethyl (2-hydroxy) ethyl ammonium chloride, 12.5g of diphenylmethane-4, 4' -diisocyanate and 0.1g of dibutyl tin dilaurate are mixed, stirred and reacted for 4 hours at 85 ℃ under the protection of nitrogen, 75g of double-end hydroxy polydimethylsiloxane (with silicon hydroxy end-capped and average molecular weight of 1500) is added, and stirred and reacted for 5 hours at 90 ℃ under the protection of nitrogen, so that the organosilicon quaternary ammonium salt is obtained.
(2) Preparation of organosilicon quaternary ammonium salt modified polyurethane
Mixing 12g of organic silicon quaternary ammonium salt, 100g of polycaprolactone triol with the average molecular weight of 1500 and the hydroxyl value of 110-116, 50g of diphenylmethane-4, 4' -diisocyanate and 0.3g of dibutyltin dilaurate, stirring and reacting for 4 hours at 85 ℃ under the protection of nitrogen, adding 5g of 1, 4-butanediol, 2g of mineral oil defoaming agent and 12g of dimethylthiotoluenediamine, and curing for 15 hours at 85 ℃ to obtain the organic silicon quaternary ammonium salt modified polyurethane.
Comparative example 1
The preparation of the quaternary ammonium salt modified polyurethane comprises the following steps:
mixing 1.5g of tetradecyl dimethyl (2-hydroxy) ethyl ammonium chloride, 100g of polyoxypropylene ether triol JH-3030, 25.5g of diphenylmethane-4, 4 ' -diisocyanate and 0.1g of dibutyltin dilaurate, stirring and reacting at 80 ℃ for 6 hours under the protection of nitrogen, adding 4g of ethylene glycol and 0.9g of organic silicon defoamer and 10g of liquid 3,3 ' -dichloro-4, 4 ' -diaminodiphenylmethane, and curing at 90 ℃ for 10 hours to obtain the quaternary ammonium salt modified polyurethane.
Comparative example 2
The preparation of the quaternary ammonium salt modified polyurethane comprises the following steps:
5g of hexadecyl dimethyl (2-hydroxy) ethyl ammonium chloride, 100g of polyoxypropylene ether triol MN-3050, 23g of isophorone diisocyanate and 0.3g of lead octoate are mixed, stirred and reacted for 3 hours at 90 ℃ under the protection of nitrogen, 3g of hexanediol, 1.6g of organic silicon defoamer and 12g of 3, 5-diamino-4-chlorobenzene isopropyl acetate are added, and the mixture is cured for 15 hours at 85 ℃ to prepare the quaternary ammonium salt modified polyurethane.
Comparative example 3
The preparation of the quaternary ammonium salt modified polyurethane comprises the following steps:
4.5g of dodecyl dimethyl (2-hydroxy) ethyl ammonium chloride, 100g of polyoxypropylene ether triol 1618A, 12g of hexamethylene diisocyanate and 0.5g of di-n-butyltin diacetate are mixed, stirred and reacted at 75 ℃ for 5 hours under the protection of nitrogen, then 3g of propylene glycol, 1g of organic silicon defoamer and 3g of 4, 4' -methylene bis (3-chloro-2, 6-diethylaniline) are added, and the mixture is cured at 80 ℃ for 20 hours to prepare the quaternary ammonium salt modified polyurethane.
Comparative example 4
The preparation of the quaternary ammonium salt modified polyurethane comprises the following steps:
mixing 2.1g of tetradecyl dimethyl (2-hydroxy) ethyl ammonium chloride, 100g of polyethylene glycol trimethylolpropane adipate with the average molecular weight of 3000 and the hydroxyl value of 56-60, 18g of toluene diisocyanate and 0.15g of dibutyl tin dilaurate, stirring and reacting at 75 ℃ for 8 hours under the protection of nitrogen, adding 3g of dihydroxy ethyl terephthalate, 1.2g of mineral oil defoaming agent and 17g of diethyl toluene diamine, and curing at 80 ℃ for 20 hours to obtain the quaternary ammonium salt modified polyurethane.
The polyurethanes prepared in the above examples and comparative examples were subjected to antibacterial property tests and surface property tests, and the results are shown in table 1.
TABLE 1 bacteriostasis rate and Water contact Angle of the polyurethanes
| Sample (I) | Escherichia coli inhibitory rate (%) | Inhibitory rate (% | Water contact Angle (°) |
| Example 1 | 32.2 | 35.8 | 86.5 |
| Example 2 | 68.3 | 69.2 | 89 |
| Example 3 | 84.4 | 85.5 | 77 |
| Example 4 | 90.7 | 91.5 | 79 |
| Example 5 | 73.4 | 75.2 | 90 |
| Example 6 | 78.6 | 80.8 | 80.5 |
| Comparative example 1 | 56.2 | 57.2 | 76 |
| Comparative example 2 | 79.1 | 80.7 | 63 |
| Comparative example 3 | 82.4 | 83.3 | 65 |
| Comparative example 4 | 61.2 | 63.0 | 73 |
As can be seen from table 1: examples 1 to 6 are silicone quaternary ammonium salt-modified polyurethanes, and the antibacterial properties thereof are enhanced with the increase in the content of quaternary ammonium salt and the increase in the molecular weight of silicone.
Comparative examples 1 to 4 are quaternary ammonium salt modified polyurethanes, containing no silicone. The types and contents of the hydroxyl quaternary ammonium salts in the examples 2, 3, 4 and 5 are the same as those in the comparative examples 1, 2, 3 and 4 in sequence. By comparison, it can be seen that: examples 2, 3, 4, 5 are more antibacterial than corresponding comparative examples 1, 2, 3, 4, which shows that the organosilicon can help quaternary ammonium salt groups to migrate to the surface of the material, and improve the sterilization efficiency.
The water contact angles of the examples 2, 3, 4 and 5 are larger than those of the corresponding comparative examples 1, 2, 3 and 4, which shows that the addition of the organic silicon overcomes the defect of hydrophilicity of quaternary ammonium salt groups, and the polyurethane has stronger hydrophobicity, so that the drying of the surface of the material is kept, and the growth of bacteria is reduced.
The above examples illustrate that the silicone quaternary ammonium salt modified polyurethane of the present invention has superior antibacterial properties and hydrophobicity compared to the quaternary ammonium salt modified polyurethane without silicone, and in particular, the silicone of the present invention grafted on the branched chain can enhance this advantage.
The performance test methods in the above examples are as follows:
the water contact angle was measured using a JC2000D contact angle measuring instrument (Shanghai Med digital technology Equipment Co., Ltd.) using ultrapure water as the water used for the test, and 5 points were measured for each sample and averaged.
And (3) antibacterial experiment:the test strains are Escherichia coli and Staphylococcus aureus, and the mother liquor is obtained by culturing in nutrient broth at 37 deg.C for 24 hr. 0.2mL of mother liquor is sucked by a pipette, added into a test tube containing 1.8mL of sterilized water, and the bacterial liquid is diluted for 10 times, wherein the content of selected bacteria is 1 multiplied by 105～5×105CFU/mL bacterial liquid is used as inoculated sample bacterial liquid. According to the national standard GB/T4789.2-2010, 0.4mL of inoculated bacterial liquid is uniformly dripped into the control group and the antibacterial material group, and the polyethylene film is covered on the sample. Placing into a blank culture dish, placing into a super clean bench irradiated by natural light, and culturing at 37 deg.C for 6 h. The samples cultured for 6 hours and the polyethylene film were washed several times with 10mL of sterilized water, and the washed liquid was collected. 0.2mL of the solution was taken out, spread on a solid agar medium, and cultured in a 37 ℃ incubator for 24 hours. The plaques on the samples were counted and the antibacterial rate was calculated. Groups were made in parallel and the mean was taken.
The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and all such changes, modifications, substitutions, combinations, and simplifications are intended to be included in the scope of the present invention.
Claims (10)
1. The organosilicon quaternary ammonium salt modified polyurethane is characterized by being prepared from the following raw materials in parts by weight:
5-30 parts of organic silicon quaternary ammonium salt, 100 parts of polyether polyol or polyester polyol, 11.2-50 parts of diisocyanate, 0.1-0.5 part of organic metal catalyst, 0-5 parts of chain extender, 0.1-2.0 parts of defoaming agent and 3-17 parts of curing agent;
the structure of the organosilicon quaternary ammonium salt is shown as formula 1:
wherein, R is1Is composed of
One of (1);
x is halogen, m is 4-65, n is 0-3, and p is 12, 14 or 16.
2. The silicone quaternary ammonium salt-modified polyurethane according to claim 1, characterized in that: and X is F, Cl, Br or I.
3. The silicone quaternary ammonium salt-modified polyurethane according to claim 1, characterized in that: the preparation method of the organosilicon quaternary ammonium salt comprises the following steps:
mixing 15-17.5 parts of hydroxyl-containing quaternary ammonium salt, 9-12.5 parts of diisocyanate and 0.05-0.3 part of organic metal catalyst, stirring and reacting at 75-85 ℃ for 3-5 h, adding 25-250 parts of double-end hydroxyl polysiloxane, stirring and reacting at 80-95 ℃ for 3-8 h to obtain organic silicon quaternary ammonium salt; the parts are parts by weight.
4. The silicone quaternary ammonium salt-modified polyurethane according to claim 1 or 3, characterized in that: the diisocyanate is one of toluene diisocyanate, diphenylmethane-4, 4' -diisocyanate, isophorone diisocyanate, hexamethylene diisocyanate, p-phenylene diisocyanate, xylylene diisocyanate, 1, 4-cyclohexane diisocyanate or naphthalene-1, 5-diisocyanate.
5. The silicone quaternary ammonium salt-modified polyurethane according to claim 3, characterized in that:
the hydroxyl quaternary ammonium salt is one of dodecyl dimethyl (2-hydroxyl) ethyl ammonium halide, tetradecyl dimethyl (2-hydroxyl) ethyl ammonium halide or hexadecyl dimethyl (2-hydroxyl) ethyl ammonium halide;
the double-end hydroxyl polysiloxane is hydroxyl-terminated polysiloxane or silicon hydroxyl-terminated polysiloxane with the average molecular weight of 500-5000.
6. The silicone quaternary ammonium salt-modified polyurethane according to claim 1, characterized in that: the polyether polyol has a molecular weight of 200-10000 and is at least one of polyoxypropylene ether polyol, polytetrahydrofuran ether polyol or tetrahydrofuran-oxypropylene copolyol.
7. The silicone quaternary ammonium salt-modified polyurethane according to claim 1, characterized in that: the polyester polyol is at least one of adipic acid polyester polyol, pimelic acid polyester polyol, suberic acid polyester polyol, glutaric acid polyester polyol, sebacic acid polyester polyol, ethylene glycol polyester polyol, succinic acid polyester polyol, polycaprolactone polyol, polycarbonate polyol, maleic anhydride polyester polyol, phthalic anhydride polyester polyol, terephthalic polyester polyol or random polyester polyol with the average functionality of more than 3 and the average molecular weight of 400-6000.
8. The silicone quaternary ammonium salt-modified polyurethane according to claim 1, characterized in that:
the organic metal catalyst is at least one of stannous octoate, dibutyl tin dilaurate, lead octoate or di-n-butyltin diacetate;
the chain extender is at least one of 1, 4-butanediol, ethylene glycol, propylene glycol, hexanediol, cyclohexanediol, polyethylene terephthalate or trimethylolpropane monoallyl ether;
the defoaming agent is an organic silicon defoaming agent and/or a mineral oil defoaming agent;
the curing agent is one of dimethylthiotoluenediamine, 3 ' -dichloro-4, 4 ' -diaminodiphenylmethane, diethyltoluenediamine, 3, 5-diamino-4-chlorophenylacetic acid isopropyl ester or 4,4 ' -methylenebis (2, 6-diethyl-3-chloroaniline).
9. The method for preparing the organosilicon quaternary ammonium salt modified polyurethane according to any one of claims 1 to 8, characterized by comprising the steps of:
mixing the organic silicon quaternary ammonium salt, polyether polyol or polyester polyol, diisocyanate and an organic metal catalyst, stirring at 75-90 ℃ for reaction for 3-8 h, adding a chain extender, a defoaming agent and a curing agent, and curing at 80-90 ℃ for 10-20 h to obtain the organic silicon quaternary ammonium salt modified polyurethane.
10. Use of the silicone quaternary ammonium salt-modified polyurethane according to any one of claims 1 to 8 in communication products, kitchen utensils, office supplies, medical materials, food packaging, building materials, home appliances, toys, fabrics, and footwear.
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