阅读说明：本技术 一种水性聚氨酯乳液、丁腈胶-聚氨酯复合乳液及其应用 (Waterborne polyurethane emulsion, nitrile rubber-polyurethane composite emulsion and application thereof ) 是由 王中武 丁超 陈平绪 付晓 戴剑 夏超 于 2020-12-30 设计创作，主要内容包括：本发明公开了一种抗菌水性聚氨酯乳液、丁腈胶-聚氨酯复合乳液及其应用。抗菌水性聚氨酯乳液通过如下方法制备得到：在真空脱水的聚合物多元醇中加入二异氰酸酯和催化剂,惰性气氛下预聚反应45～150分钟,加入羟基扩链剂在60～80℃下扩链反应60～180分钟,再加入双季铵盐封端剂封端反应30～60分钟,加入胺基中和剂中和,再搅拌加水进行乳化即得抗菌水性聚氨酯乳液。本发明的水性聚氨酯乳液将抗菌组分共价接枝到聚氨酯分子链上,与丁腈胶乳以特定比例复配使用制备得到丁腈胶-聚氨酯复合乳液,解决了现有小分子抗菌剂物理混合易扩散,不仅残留余毒,而且抗菌时效短的问题,手套的拉伸强度为18～26MPa,断裂伸长率为600～800％,耐药品性好,抑菌率≥90％,符合GB15979-2002要求。(The invention discloses an antibacterial aqueous polyurethane emulsion, a nitrile rubber-polyurethane composite emulsion and application thereof. The antibacterial waterborne polyurethane emulsion is prepared by the following method: adding diisocyanate and a catalyst into polymer polyol subjected to vacuum dehydration, carrying out prepolymerization reaction for 45-150 minutes in an inert atmosphere, adding a hydroxyl chain extender, carrying out chain extension reaction for 60-180 minutes at 60-80 ℃, adding a biquaternary ammonium salt end capping agent, carrying out end capping reaction for 30-60 minutes, adding an amino neutralizing agent for neutralization, stirring, adding water, and emulsifying to obtain the antibacterial waterborne polyurethane emulsion. According to the water-based polyurethane emulsion, an antibacterial component is covalently grafted onto a polyurethane molecular chain, and the polyurethane emulsion and butyronitrile latex are compounded in a specific proportion to prepare the butyronitrile rubber-polyurethane composite emulsion, so that the problems that the existing small-molecular antibacterial agent is easy to diffuse due to physical mixing, residual toxicity is caused, and antibacterial aging is short are solved, the tensile strength of gloves is 18-26 MPa, the elongation at break is 600-800%, the chemical resistance is good, the antibacterial rate is more than or equal to 90%, and the requirements of GB15979-2002 are met.)

1. An antibacterial aqueous polyurethane emulsion is characterized by being prepared by the following method:

adding diisocyanate and a catalyst into polymer polyol subjected to vacuum dehydration, carrying out prepolymerization reaction for 45-150 minutes in an inert atmosphere, adding a hydroxyl chain extender, carrying out chain extension reaction for 60-180 minutes at 60-80 ℃, adding a biquaternary ammonium salt end capping agent, carrying out end capping reaction for 30-60 minutes, adding an amino neutralizing agent for neutralization, stirring, adding water, emulsifying to obtain the antibacterial waterborne polyurethane emulsion,

wherein the biquaternary ammonium salt is a compound shown as a formula I:

formula I, wherein n is an integer from 4 to 16.

2. The antibacterial aqueous polyurethane emulsion according to claim 1, wherein the biquaternary ammonium salt is synthesized by the following steps: mixing N, N-dimethyl tertiary amine, hydrochloric acid and epoxy chloropropane in a molar ratio of 2.0-3.0: 1.0-1.5: 1.0, uniformly mixing in an ice bath, adding isopropanol, refluxing, stirring, reacting for 10-24 hours, decompressing, rotating, evaporating to dryness, and recrystallizing and purifying with propanol to obtain the product.

3. The antibacterial aqueous polyurethane emulsion according to claim 1, wherein the diisocyanate, the polymer polyol, the hydroxyl chain extender, the bis-quaternary ammonium salt capping agent and the amine-based neutralizing agent are used in amounts of: isocyanate group of diisocyanate: hydroxyl group of polymer polyol: hydroxyl group of the hydroxyl chain extender: hydroxyl group of bis-quaternary capping agent: the molar ratio of the amino groups of the amino group neutralizer is (2.0-3.5): (1.0-1.5): (0.5-1.5): (0.5-1.0): (0.45-1.8).

4. The antibacterial aqueous polyurethane emulsion according to claim 3, wherein the diisocyanate, the polymer polyol, the hydroxyl chain extender, the bis-quaternary ammonium salt capping agent and the amine-based neutralizing agent are used in amounts of: isocyanate group of diisocyanate: hydroxyl group of polymer polyol: hydroxyl group of the hydroxyl chain extender: hydroxyl group of bis-quaternary capping agent: the molar ratio of the amino groups of the amino group neutralizer is (3-3.5): (1-1.5): (1.0-1.2): (0.5-0.8): (1-1.2).

5. The nitrile rubber-polyurethane composite emulsion is characterized by being prepared by the following method:

s1, preparing a butyronitrile emulsion: taking the butyronitrile emulsion, and adjusting the pH value of the butyronitrile emulsion to 8.5-9.5;

s2, preparing a dispersed mixed solution: mixing and soaking 0.2-2 parts of sulfur, 0.3-1.5 parts of zinc oxide, 0.4-2 parts of titanium dioxide, 0.5-2 parts of accelerator, 0.5-2 parts of anti-aging agent, 0.04-0.1 part of dispersant, 0.5-2 parts of defoaming agent and 50-80 parts of pure water for 4 hours, and grinding to prepare a dispersed mixed solution with D90 of 5-10 mu m;

s3, preparing the nitrile butadiene rubber-polyurethane composite emulsion: mixing the butyronitrile emulsion, the dispersion mixed solution and the antibacterial aqueous polyurethane emulsion according to any one of claims 1 to 4 to obtain the butyronitrile rubber-polyurethane composite emulsion.

6. The nitrile-butadiene rubber-polyurethane composite emulsion as claimed in claim 5, wherein the mass ratio of the nitrile-butadiene emulsion, the dispersion mixture and the antibacterial aqueous polyurethane emulsion in S3 is 1-3: 1: 1-3.

7. The nitrile-butadiene rubber-polyurethane composite emulsion according to claim 6, wherein in S3, the mass ratio of the nitrile-butadiene emulsion to the dispersion mixture to the antibacterial aqueous polyurethane emulsion is 3:1: 1.

8. Use of the nitrile rubber-polyurethane composite emulsion according to claim 5 for the preparation of medical articles, food processing articles and/or electronic industry processing articles.

9. The nitrile rubber-polyurethane composite glove is characterized by being prepared by the following method: heating the hand mold to 80-110 ℃, then immersing the hand mold into calcium nitrate type solidification liquid, standing for 10-60s, then taking out, drying, then immersing into the butyronitrile rubber-polyurethane composite emulsion of claim 5, standing for 10-60s, then taking out, pre-vulcanizing, immersing into chlorine liquid, standing for 5-15 s, then taking out, cleaning, and demolding to obtain the butyronitrile rubber-polyurethane composite glove.

10. The nitrile rubber-polyurethane composite glove of claim 9, wherein the nitrile rubber-polyurethane composite glove has a tensile strength of 18 to 26MPa, an elongation at break of 600 to 800%, and a bacteriostatic rate of not less than 50%.

Technical Field

The invention relates to the technical field of synthesis and modification of high polymer materials, and more particularly relates to an aqueous polyurethane emulsion, a nitrile rubber-polyurethane composite emulsion and application thereof.

Background

Butadiene-acrylonitrile rubber is prepared by polymerizing butadiene and acrylonitrile through emulsion, and organic acid such as acrylic acid and methacrylic acid is introduced to further improve the oil resistance, wear resistance, tear resistance and other properties of the butadiene-acrylonitrile rubber, and the carboxyl butadiene-acrylonitrile rubber is obtained through modification. The butyronitrile gloves are made of butyronitrile latex, a vulcanizing agent, a vulcanization accelerator, an anti-aging agent, titanium dioxide, auxiliary materials and the like through processes of mixing, filtering, solidifying, drying and the like, have good mechanical properties, and rarely have allergy phenomena, but compared with natural latex, the synthetic butyronitrile rubber has obvious differences in flexibility and mechanical properties. Polyurethane is prepared by emulsion polymerization, has good flexibility, corrosion resistance, solvent resistance and biocompatibility, and various butyronitrile latex-polyurethane composite gloves appear in the prior art, for example, patent CN102977423A discloses a method for modifying natural latex by waterborne polyurethane, which comprises the steps of preparing a prepolymer by taking IPDI, PTMG, BDO and DMPA as raw materials, adding HEA to carry out end capping on end-NCO of the prepolymer, reacting for 50min, cooling to 40 ℃, adding triethylamine to carry out neutralization reaction to generate salt, reacting for 3-4min, adding water to carry out emulsification for 60min, and obtaining the waterborne polyurethane emulsion. The waterborne polyurethane and the natural latex are physically blended to obtain the waterborne polyurethane modified natural latex, so that the smoothness, compactness and mechanical strength of the natural latex film can be improved, and simultaneously, the escape of allergenic protein is reduced. CN101003165A discloses a method for manufacturing a disposable nitrile rubber-polyurethane composite glove, which comprises the steps of firstly forming a layer of nitrile rubber base film on a mould, then dip-coating aqueous polyurethane emulsion, and forming a polyurethane film outside the nitrile rubber base film. In the prior art, only the aqueous polyurethane emulsion is simply introduced to reduce the contact amount of protein, or a polyurethane coating is formed to improve the air permeability, and the polyurethane coating is not effectively modified by a polyurethane material. CN108752673A discloses a preparation method of disposable butyronitrile medical gloves, wherein polyurethane emulsion and graphene powder are added into butyronitrile emulsion according to a mass ratio, and the disposable butyronitrile medical gloves are prepared by dipping, molding and demolding. The polyurethane emulsion and the graphene powder are added into the butyronitrile latex after being subjected to ultrasonic pretreatment and mixed, so that the tensile strength and the protective chemical resistance of the butyronitrile gloves are ensured, the bacteriostatic action is well played, the hands of medical workers are protected to the greatest extent, and the medical workers are not damaged by germs which can easily corrode human skin.

The butyronitrile latex-polyurethane composite technology achieves the antibacterial purpose by introducing polyurethane into butyronitrile latex and blending the butyronitrile latex with a micromolecular antibacterial agent, and has the main defects that: 1. uneven mixing is easily caused, and the mechanical property of the butyronitrile gloves is influenced; 2. the micromolecule antibacterial agent is easy to diffuse, residual toxicity is remained, and the antibacterial effect is short. It can be seen that the existing modification methods for polyurethane materials cannot achieve good long-acting antibacterial performance, and the mechanical properties of butyronitrile gloves cannot be guaranteed to be stable during blending, so that the field expects to provide a novel butyronitrile rubber-polyurethane composite emulsion, which can achieve a long-acting antibacterial effect and guarantee the stable mechanical properties of butyronitrile materials.

Disclosure of Invention

The invention aims to solve the technical problem that the antibacterial modification of the existing polyurethane material is mainly carried out by blending with a small-molecular antibacterial agent, so that the mechanical property of the butyronitrile material is influenced, and the defect that the excellent long-acting antibacterial property cannot be achieved are overcome, and the antibacterial aqueous polyurethane emulsion is provided.

The invention also aims to provide the butyronitrile rubber-polyurethane composite emulsion, and the specific modified antibacterial aqueous polyurethane emulsion is adopted to replace the existing polyurethane material modified by physical blending to prepare the butyronitrile rubber-polyurethane composite emulsion, so that the long-acting antibacterial property of the butyronitrile rubber-polyurethane composite emulsion is improved, and the stability of the mechanical property is ensured.

The invention also aims to provide application of the nitrile rubber-polyurethane composite emulsion in preparation of medical supplies, food processing supplies and/or electronic industry processing supplies.

The invention further aims to provide the nitrile rubber-polyurethane composite gloves.

The above purpose of the invention is realized by the following technical scheme:

an antibacterial aqueous polyurethane emulsion is prepared by the following method:

adding diisocyanate and a catalyst into polymer polyol subjected to vacuum dehydration, carrying out prepolymerization reaction for 45-150 minutes in an inert atmosphere, adding a hydroxyl chain extender, carrying out chain extension reaction for 60-180 minutes at 60-80 ℃, adding a biquaternary ammonium salt end capping agent, carrying out end capping reaction for 30-60 minutes, adding an amino neutralizing agent for neutralization, stirring, adding water, emulsifying to obtain the antibacterial waterborne polyurethane emulsion,

wherein the biquaternary ammonium salt is a compound shown as a formula I:

formula I, wherein n is an integer from 4 to 16.

Wherein, it is required to be noted that:

the bis-quaternary capping agent may be

Or (b).

The diisocyanate is one or the combination of more of isophorone diisocyanate, toluene diisocyanate, diphenylmethane diisocyanate, 1, 6-hexamethylene diisocyanate or L-lysine diisocyanate;

the polyol is one or a combination of more of polyester polyol, polyether polyol, polycarbonate polyol or vegetable oil-based polyol;

the hydroxyl chain extender is one or a combination of more of dimethylolpropionic acid or dimethylolbutyric acid;

the amino neutralizer is one or a combination of more of triethylamine, sodium hydroxide, sodium bicarbonate or ammonia water;

the catalyst is one or more of dibutyltin laurate, stannous octoate, zinc octoate or triethylene diamine, and the dosage of the catalyst is 0.1-1% of the total mass of the whole prepolymerization reaction.

The solid content of the antibacterial waterborne polyurethane emulsion is 5-50%.

The antibacterial property is that the end capping agent contains biquaternary ammonium salt which is a high-efficiency broad-spectrum antibacterial agent, so that the water-based polyurethane emulsion has excellent antibacterial property after being added. According to the invention, the antibacterial component is covalently grafted to the polyurethane molecular chain through chemical bonding, so that the micromolecular antibacterial agent is not easy to leak out, the problems that the existing micromolecular antibacterial agent is easy to diffuse, residual toxicity is caused, and the antibacterial aging is short are solved, and the long-acting antibacterial performance is endowed to the material while the mechanical performance of the polyurethane is not changed.

Meanwhile, the polyurethane is composed of macromolecular polyol, and the micromolecular chain extender and isocyanate form a hard segment to form a microphase separation structure similar to a sea-island structure, wherein the hard segment can play a role in crosslinking, and the flexible soft segment with a continuous phase can effectively improve the elongation at break of the material, so that the softness of the glove is improved; secondly, under the state of high microphase separation degree, the molecular structure of the soft polyurethane segment has better mobility, thereby being beneficial to the air permeability of the material and having certain improvement effect on the softness and the air permeability of the glove.

Preferably, the bis-quaternary ammonium salt is synthesized by: mixing N, N-dimethyl tertiary amine, hydrochloric acid and epoxy chloropropane in a molar ratio of 2.0-3.0: 1.0-1.5: 1.0, uniformly mixing in an ice bath, adding isopropanol, refluxing, stirring, reacting for 10-24 hours, decompressing, rotating, evaporating to dryness, and recrystallizing and purifying with propanol to obtain the product.

Preferably, the diisocyanate, the polymer polyol, the hydroxyl chain extender, the bis-quaternary ammonium salt capping agent and the amine-based neutralizing agent are used in the following amounts: isocyanate group of diisocyanate: hydroxyl group of polymer polyol: hydroxyl group of the hydroxyl chain extender: hydroxyl group of bis-quaternary capping agent: the molar ratio of the amino groups of the amino group neutralizer is (2.0-3.5): (1.0-1.5): (0.5-1.5): (0.5-1.0): (0.45-1.8).

The mechanical property and the antibacterial activity of the polyurethane can be effectively regulated and controlled by controlling the using amounts of the diisocyanate, the polymer polyol, the hydroxyl chain extender, the biquaternary ammonium salt end-capping reagent and the amino neutralizer.

Further preferably, the diisocyanate, the polymer polyol, the hydroxyl chain extender, the bis-quaternary ammonium salt capping agent and the amine-based neutralizing agent are used in the following amounts: isocyanate group of diisocyanate: hydroxyl group of polymer polyol: hydroxyl group of the hydroxyl chain extender: hydroxyl group of bis-quaternary capping agent: the molar ratio of the amino groups of the amino group neutralizer is (3-3.5): (1-1.5): (1.0-1.2): (0.5-0.8): (1-1.2). The invention also specifically protects the nitrile rubber-polyurethane composite emulsion, which is prepared by the following method:

s1, preparing a butyronitrile emulsion: taking 100 parts of butyronitrile emulsion, and adjusting the pH value of the butyronitrile emulsion to 8.5-9.5;

s2, preparing a dispersed mixed solution: mixing and soaking 0.2-2 parts of sulfur, 0.3-1.5 parts of zinc oxide, 0.4-2 parts of titanium dioxide, 0.5-2 parts of accelerator, 0.5-2 parts of anti-aging agent, 0.04-0.1 part of dispersant, 0.5-2 parts of defoaming agent and 50-80 parts of pure water for 4 hours, and grinding to prepare a dispersed mixed solution with the particle size D90 of 5-10 microns;

s3, preparing the nitrile butadiene rubber-polyurethane composite emulsion: and uniformly mixing the butyronitrile emulsion, the dispersion mixed solution and the antibacterial waterborne polyurethane emulsion, and standing for 12-30 h to obtain the butyronitrile rubber-polyurethane composite emulsion.

Wherein the solid content of the butyronitrile emulsion in the S1 ranges from 20% to 40%.

The pH of S1 can be adjusted by adding KOH or aqueous ammonia.

In S2:

the dispersant is sodium dodecyl benzene sulfonate or sodium dodecyl sulfate;

the accelerator is ZDBC (zinc dibutyl dithiocarbamate) or ZDEC (zinc diethyl dithiocarbamate) singly or in a compound way, and the compound proportion is 1: 1.

the anti-aging agent is N- (4-anilinophenyl) maleimide with solid content of 50%.

The defoaming agent is polyether modified emulsion.

In S2, D90 of the dispersion liquid mixture is controlled to be 5-10 μm, and the dispersion liquid can exist stably under the condition, and the effect is good.

The S3 is kept stand for 12-30 hours mainly to ensure that the sulfur and the accelerator are fully and uniformly mixed and carry out the pre-crosslinking reaction in the early stage, and simultaneously, the zinc oxide and the carboxyl in the nitrile rubber can form a chemical bond to improve the strength of the product

According to the butyronitrile rubber-polyurethane composite emulsion, the polyurethane emulsion grafted with the antibacterial group through chemical bond bonding is introduced into the traditional butyronitrile rubber, so that the butyronitrile rubber-polyurethane composite emulsion has antibacterial performance and can further improve the flexibility and air permeability of the traditional butyronitrile gloves.

The mixing proportion of the butyronitrile emulsion, the dispersion mixed liquid and the antibacterial aqueous polyurethane emulsion in the butyronitrile rubber-polyurethane composite emulsion is also a key influencing factor of the invention.

Preferably, in S3, the mass ratio of the butyronitrile emulsion to the dispersion mixture to the antibacterial aqueous polyurethane emulsion is 1-3: 1: 1-3.

Further preferably, in S3, the mass ratio of the butyronitrile emulsion to the dispersion liquid to the antibacterial aqueous polyurethane emulsion is 3:1: 1.

The application of the nitrile rubber-polyurethane composite emulsion in the preparation of medical supplies, food processing supplies and/or electronic industry processing supplies is also within the protection scope of the application.

The invention also provides a nitrile rubber-polyurethane composite glove which is prepared by the following method: heating the hand mold to 30-70 ℃, then immersing the hand mold into calcium nitrate type solidification liquid, standing for 10-40 s, then taking out, drying, then immersing into butyronitrile rubber-polyurethane composite emulsion, standing for 10-30 s, then taking out, pre-vulcanizing, immersing into chlorine liquid, standing for 30-60 s, then taking out, cleaning, and demolding to obtain the butyronitrile rubber-polyurethane composite glove.

The calcium nitrate type solidification liquid contains 5-15% of calcium nitrate, 0-5% of calcium carbonate, 0.1-0.5% of wetting agent and 1-3% of separant.

The calcium nitrate type solidification liquid mainly plays a role in assisting in processing, forming and demolding.

The prevulcanization temperature of the invention is 80-150 ℃, and the preferable vulcanization temperature is as follows: the temperature is 90-130 ℃, scorching is easy to occur when the temperature is too high, and the mechanical property of the product is influenced when the temperature is too low and vulcanization is incomplete.

Preferably, the tensile strength of the butyronitrile rubber-polyurethane composite glove is 18-26 MPa, the elongation at break is 600-800%, and the antibacterial rate is more than or equal to 50%.

Compared with the prior art, the invention has the beneficial effects that:

the invention provides an antibacterial aqueous polyurethane emulsion, wherein an antibacterial component is covalently grafted onto a polyurethane molecular chain, so that a small-molecular antibacterial agent is not easy to seep out, and the small-molecular antibacterial agent and butyronitrile latex are compounded and used according to a specific proportion to prepare the butyronitrile rubber-polyurethane composite emulsion, so that the problems of easiness in diffusion of the conventional small-molecular antibacterial agent due to physical mixing, residual toxicity and short antibacterial time are solved, the material has long-acting antibacterial performance while the mechanical property of the polyurethane is not changed, and the prepared butyronitrile gloves have more excellent flexibility and air permeability, and can be widely applied to preparation of medical supplies, food processing supplies and/or electronic industry processing supplies.

The butyronitrile rubber-polyurethane composite glove has the advantages of 18-26 MPa of tensile strength, 600-800% of elongation at break, good drug resistance, and more than or equal to 50% of antibacterial rate to escherichia coli and staphylococcus aureus, and meets the requirement of GB 15979-2002.

Detailed Description

The present invention will be further described with reference to specific embodiments, but the present invention is not limited to the examples in any way. The starting reagents employed in the examples of the present invention are, unless otherwise specified, those that are conventionally purchased.

Wherein, the raw material sources of the components of the invention are explained as follows:

the polytetrahydrofuran ether glycol PTMG with the molecular weight of 2000 is derived from: (ii) the chemistry of the dow;

castor oil CO is derived from: tianjin Fuyu fine chemical industry;

the polytetrahydrofuran ether glycol PTMG with the molecular weight of 1500 is derived from: (ii) the chemistry of the dow;

the polypropylene glycol PPG with a molecular weight of 1000 is derived from: (ii) the chemistry of the dow;

isophorone diisocyanate is derived from: basf, inc;

the L-lysine diisocyanate LDI is derived from: hadamard, Inc.;

the stannous octoate is derived from: shanghai Aladdin Biotechnology Ltd;

dibutyltin dilaurate was derived from: shanghai Aladdin Biotechnology Ltd;

dimethylol butanoic acid DMBA was derived from: shanghai Aladdin Biotechnology Ltd;

the sulfonate chain extender CA95 was derived from: york, yari chemical ltd, york;

the butyronitrile emulsion is prepared from the following components: korea brocade lake petrochemicals;

the triethylamine is from chemical Limited of Jinan brilliant Hao;

sulfur is from Hunan Xin chemical industry;

the zinc oxide is from the Wanrun chemical industry;

titanium dioxide is from the company Benke latex Ltd;

the accelerator is zinc dibutyl dithiocarbamate, is sourced from Benke latex Co., Ltd, and has a solid content of 50%;

the anti-aging agent is N- (4-anilinophenyl) maleimide which is sourced from Benziaceae latex Co., Ltd, and the solid content is 50%;

the dispersant is dispersant NNO, which is sourced from Rongyida Limited;

the defoaming agent is polyether modified emulsion and is from Shanghai Mulberry well chemical industry Co.

The detection indexes of the performance of the invention are as follows:

the detection method of the tensile strength and the elongation at break comprises the following steps: ASTM D412-2015 vulcanizate and thermoplastic elastomer tensile test method.

The method for detecting the drug resistance comprises the following steps:

the detection method of the antibacterial performance comprises the following steps: the disinfection and bacteriostasis performance test adopts an immersion culture method to test the microbiological indexes, and the reference is GB 15979-2002.

Example 1

An antibacterial aqueous polyurethane emulsion is prepared by the following method:

1) dehydrating the polymer polyol at a temperature of 100 ℃ for 120 minutes under vacuum;

2) cooling to 60 ℃, adding a catalyst and diisocyanate, and carrying out prepolymerization reaction for 120 minutes under stirring and nitrogen protection;

3) adding a chain extender, and carrying out chain extension reaction for 120 minutes at 78 ℃;

4) adding a biquaternary ammonium salt end capping agent for end capping reaction for 60 minutes;

5) reducing the reaction temperature to room temperature, and adding a neutralizing agent for neutralization;

6) adding water under strong stirring for emulsification for 120 minutes to obtain the antibacterial aqueous polyurethane emulsion with the solid content of 30 percent.

The chemical structure of the biquaternary ammonium salt end-capping agent is shown as follows:

the preparation method comprises the following steps:

n, N-dimethyl N-octylamine, hydrochloric acid and epoxy chloropropane are mixed according to a molar ratio of 2.3: 1.1: 1, uniformly mixing in an ice bath, adding isopropanol, refluxing, stirring, reacting for 20 hours, decompressing, rotating, evaporating to dryness, and recrystallizing and purifying with propanol to obtain the product.

The polymer polyol is polytetrahydrofuran ether glycol PTMG with molecular weight of 2000;

the diisocyanate is isophorone diisocyanate;

the catalyst is stannous octoate;

the chain extender is dimethylolbutanoic acid DMBA;

the neutralizer is: triethylamine.

The dosage of diisocyanate, polyol, chain extender, end-capping agent and neutralizing agent in the reaction is as follows: isocyanate group of isophorone: hydroxyl group of PTMG: hydroxyl group of DMBA: hydroxyl group of bis-quaternary capping agent: the molar ratio of the amine groups of the neutralizing agent is 3:1.5:1.0:0.5: 1.0.

The nitrile butadiene rubber-polyurethane composite emulsion is prepared by the following method:

s1, preparing a butyronitrile emulsion: adding KOH with the mass fraction of 3% into 100 parts of butyronitrile emulsion, and adjusting the pH value of the latex solution to 9.5-10.5;

s2, preparing a dispersed mixed solution: 1.5 parts of sulfur, 1 part of zinc oxide, 1.5 parts of titanium dioxide, 0.5 part of accelerator, 1 part of anti-aging agent, 0.05 part of dispersant, 1 part of defoamer and 50 parts of pure water, mixing and soaking for 4 hours, and grinding for 6 hours at room temperature by a ball mill to form a dispersed mixed solution with the particle size of D90 being less than or equal to 8 microns;

s3, preparing the nitrile butadiene rubber-polyurethane composite emulsion: mixing the butyronitrile emulsion, the dispersion mixed solution and the antibacterial aqueous polyurethane emulsion according to the mass ratio of 3:1:1, and soaking for 20s to obtain the butyronitrile rubber-polyurethane composite emulsion.

A butyronitrile rubber-polyurethane composite glove is prepared by the following steps:

(1) heating the hand mold to 55 ℃, immersing the hand mold into calcium nitrate type solidification liquid, standing for 10s, taking out the hand mold, and drying the hand mold for 3 minutes at the temperature of 110 ℃;

(2) cooling the dried hand mold to 65 ℃, immersing the hand mold into the mixed dipping latex, taking out the hand mold after staying for 20s, and pre-vulcanizing the hand mold for 30 minutes at 130 ℃;

(3) and cooling the hand mold to 50 ℃, immersing the hand mold into chlorine liquid with the concentration of 0.5%, standing for 50s, taking out the hand mold, cleaning, and demolding to obtain the long-acting antibacterial nitrile rubber-polyurethane latex glove.

Example 2

The nitrile butadiene rubber-polyurethane composite emulsion is prepared by the following method:

s1, preparing a butyronitrile emulsion: adding KOH with the mass fraction of 3% into 100 parts of butyronitrile emulsion, and adjusting the pH value of the latex solution to 9.5-10.5;

s2, preparing a dispersed mixed solution: 1.5 parts of sulfur, 1 part of zinc oxide, 1.5 parts of titanium dioxide, 0.5 part of accelerator, 1 part of anti-aging agent, 0.05 part of dispersant, 1 part of defoamer and 50 parts of pure water, mixing and soaking for 4 hours, and grinding for 6 hours at room temperature by a ball mill to form a dispersed mixed solution with the particle size of D90 being less than or equal to 8 microns;

s3, preparing the nitrile butadiene rubber-polyurethane composite emulsion: and (3) mixing the butyronitrile emulsion, the dispersion mixed solution and the antibacterial aqueous polyurethane emulsion in the embodiment 1 according to the mass ratio of 2:1:2, and soaking for 20s to obtain the butyronitrile rubber-polyurethane composite emulsion.

A nitrile rubber-polyurethane composite glove, the preparation method is the same as example 1.

Example 3

The nitrile butadiene rubber-polyurethane composite emulsion is prepared by the following method:

s1, preparing a butyronitrile emulsion: adding KOH with the mass fraction of 3% into 100 parts of butyronitrile emulsion, and adjusting the pH value of the latex solution to 9.5-10.5;

s2, preparing a dispersed mixed solution: 1.5 parts of sulfur, 1 part of zinc oxide, 1.5 parts of titanium dioxide, 0.5 part of accelerator, 1 part of anti-aging agent, 0.05 part of dispersant, 1 part of defoamer and 50 parts of pure water, mixing and soaking for 4 hours, and grinding for 6 hours at room temperature by a ball mill to form a dispersed mixed solution with the particle size of D90 being less than or equal to 8;

s3, preparing the nitrile butadiene rubber-polyurethane composite emulsion: and (3) mixing the butyronitrile emulsion, the dispersion mixed solution and the antibacterial aqueous polyurethane emulsion in the embodiment 1 according to the mass ratio of 1:1:3, and soaking for 20s to obtain the butyronitrile rubber-polyurethane composite emulsion.

A nitrile rubber-polyurethane composite glove, the preparation method is the same as example 1.

Example 4

An antibacterial aqueous polyurethane emulsion is prepared by the following method:

1) dehydrating the polymer polyol at a temperature of 100 ℃ for 120 minutes under vacuum;

2) cooling to 60 ℃, adding diisocyanate and a catalyst, and carrying out prepolymerization reaction for 120 minutes under stirring and nitrogen protection;

3) adding a chain extender, and carrying out chain extension reaction for 120 minutes at 78 ℃;

4) adding a biquaternary ammonium salt end capping agent for end capping reaction for 60 minutes;

5) reducing the reaction temperature to room temperature, and adding a neutralizing agent for neutralization;

6) adding water under strong stirring for emulsification for 120 minutes to obtain the antibacterial aqueous polyurethane emulsion with the solid content of 30 percent.

Wherein, the chemical structure of the biquaternary ammonium salt end capping agent is as follows:

composition of polytetrahydrofuran ether glycol PTMG with molecular weight of 2000 and castor oil CO as polymer polyol

The diisocyanate is: l-lysine diisocyanate LDI

The catalyst is as follows: dibutyl tin dilaurate

The chain extender comprises: dimethylolpropionic acid DMPA

The neutralizer is: sodium hydroxide

The dosage of diisocyanate, polyol, chain extender, end-capping agent and neutralizing agent in the reaction is as follows: isocyanate group of LDI: hydroxyl group of PTMG: hydroxyl group of CO: hydroxyl group of DMPA: hydroxyl group of the blocking agent: the molar ratio of the amine groups of the neutralizing agent is 3:0.8:0.2:1.0:0.8: 1.0.

A nitrile rubber-polyurethane composite emulsion prepared by the method of example 1.

A nitrile rubber-polyurethane composite glove, the preparation method is the same as example 1.

Example 5

An antibacterial aqueous polyurethane emulsion is prepared by the following method:

1) dehydrating the polymer polyol at a temperature of 100 ℃ for 120 minutes under vacuum; :

2) cooling to 60 ℃, adding diisocyanate and a catalyst, and carrying out prepolymerization reaction for 120 minutes under stirring and nitrogen protection;

3) adding a chain extender, and carrying out chain extension reaction for 120 minutes at 78 ℃;

4) adding a biquaternary ammonium salt end capping agent for end capping reaction for 60 minutes;

5) reducing the reaction temperature to room temperature, and adding a neutralizing agent for neutralization;

6) adding water under strong stirring for emulsification for 120 minutes to obtain the antibacterial aqueous polyurethane emulsion with the solid content of 30 percent.

Wherein, the chemical structure of the biquaternary ammonium salt end capping agent is as follows:

the polymer polyol is polytetrahydrofuran ether glycol PTMG with molecular weight of 1500 and polypropylene glycol PPG with molecular weight of 1000

The diisocyanate is: isophorone diisocyanate (IPDI);

the catalyst is as follows: dibutyltin laurate octoate;

the chain extender comprises: DMBA and sulfonate chain extender CA 95;

the neutralizer is: triethylamine.

The dosage of diisocyanate, polyol, chain extender, end-capping agent and neutralizing agent in the reaction is as follows: isocyanate group of IPDI: hydroxyl group of PTMG: hydroxyl group of PPG: hydroxyl group of DMBA: hydroxyl group of CA 95: hydroxyl group of the blocking agent: the mole ratio of the amine groups of the neutralizer is 3.5: 0.75: 0.25: 1.2: 0.5: 0.4: 1.2.

a nitrile rubber-polyurethane composite emulsion prepared by the method of example 1.

A nitrile rubber-polyurethane composite glove, the preparation method is the same as example 1.

Example 6

An antibacterial aqueous polyurethane emulsion is prepared by the following method:

1) dehydrating the polymer polyol at a temperature of 100 ℃ for 120 minutes under vacuum;

2) cooling to 60 ℃, adding diisocyanate and a catalyst, and carrying out prepolymerization reaction for 120 minutes under stirring and nitrogen protection;

3) adding a chain extender, and carrying out chain extension reaction for 120 minutes at 78 ℃;

4) adding a biquaternary ammonium salt end capping agent for end capping reaction for 60 minutes;

5) reducing the reaction temperature to room temperature, and adding a neutralizing agent for neutralization;

6) adding water under strong stirring for emulsification for 120 minutes to obtain the antibacterial aqueous polyurethane emulsion with the solid content of 30 percent.

Wherein, the chemical structure of the biquaternary ammonium salt is as follows:

the preparation method comprises the following steps:

mixing N, N-dimethylhexadecylamine, hydrochloric acid and epoxy chloropropane according to a molar ratio of 2.4: 1.1: 1, uniformly mixing in an ice bath, adding isopropanol, refluxing, stirring, reacting for 20 hours, decompressing, rotating, evaporating to dryness, and recrystallizing and purifying with propanol to obtain the product.

The polymer polyol is polytetrahydrofuran ether glycol PTMG with molecular weight of 2000;

the diisocyanate is isophorone diisocyanate;

the catalyst is stannous octoate;

the chain extender is a mixture of dimethylolbutanoic acid DMBA and CA 95;

the neutralizer is: triethylamine.

The dosage of diisocyanate, polyol, chain extender, end-capping agent and neutralizing agent in the reaction is as follows: isocyanate group of isophorone: hydroxyl group of PTMG: hydroxyl group of DMBA: hydroxyl group of bis-quaternary capping agent: the molar ratio of the amine groups of the neutralizing agent is 3:1.5:1.0:0.5: 1.0.

A nitrile rubber-polyurethane composite emulsion, and the preparation method is the same as example 1.

A nitrile rubber-polyurethane composite glove, the preparation method is the same as example 1.

Comparative example 1

A butyronitrile glove is prepared by the following steps:

preparing modified nitrile latex:

1) and (3) adding 1mol/L KOH into 100 parts of butyronitrile emulsion, and adjusting the pH value of the latex solution to 8.5-9.5.

2) 1.5 parts of sulfur, 1 part of zinc oxide, 1.5 parts of titanium dioxide, 0.5 part of accelerator, 1 part of anti-aging agent, 0.05 part of dispersant, 1 part of defoamer and 50 parts of pure water are mixed and soaked for 4 hours, and the mixture is ground for 6 hours at room temperature by a ball mill to form a dispersed mixed solution with the particle size of D90 being less than or equal to 8 microns;

3) and mixing the butyronitrile emulsion and the dispersion mixed solution according to the mass ratio of 8:2, and standing for 4 hours to obtain the butyronitrile rubber-polyurethane composite emulsion.

Preparing a butyronitrile glove:

(1) heating the hand mold to 80-110 ℃, immersing the hand mold into calcium nitrate type solidification liquid, standing for 10s, taking out, and drying the hand mold for 3 minutes at 110 ℃;

(2) cooling the dried hand mold to 65 ℃, immersing the hand mold into the mixed dipping latex, taking out the hand mold after staying for 20s, and pre-vulcanizing the hand mold for 30 minutes at 130 ℃;

(3) and cooling the hand mold to 50 ℃, immersing the hand mold into chlorine liquid with the concentration of 0.5%, standing for 50s, taking out the hand mold, cleaning, and demolding to obtain the long-acting antibacterial nitrile rubber gloves.

Comparative example 2

An aqueous polyurethane emulsion was prepared in the same manner as in example 1.

The nitrile butadiene rubber-polyurethane composite emulsion is prepared by the following method:

s1, preparing a butyronitrile emulsion: adding 1mol/L KOH into 100 parts of butyronitrile emulsion, and adjusting the pH value of the latex solution to 8.5-9.5;

s2, preparing a dispersed mixed solution: 1.5 parts of sulfur, 1 part of zinc oxide, 1.5 parts of titanium dioxide, 0.5 part of accelerator, 1 part of anti-aging agent, 0.05 part of dispersant, 1 part of defoamer and 50 parts of pure water, mixing and soaking for 4 hours, and grinding for 6 hours at room temperature by a ball mill to form a dispersed mixed solution with the particle size of 100-200 mu m;

s3, preparing the nitrile butadiene rubber-polyurethane composite emulsion: mixing the butyronitrile emulsion, the dispersion mixed solution and the antibacterial aqueous polyurethane emulsion according to the mass ratio of 4:1:3, and soaking for 4 hours to obtain the butyronitrile rubber-polyurethane composite emulsion.

A nitrile rubber-polyurethane composite glove, the preparation method is the same as example 1.

Comparative example 3

An antibacterial aqueous polyurethane emulsion was prepared as in example 1.

The nitrile butadiene rubber-polyurethane composite emulsion is prepared by the following method:

s1, preparing a butyronitrile emulsion: adding 1mol/L KOH or ammonia water into 100 parts of butyronitrile emulsion, and adjusting the pH value of the latex solution to 8.5-9.5;

s2, preparing a dispersed mixed solution: 1.5 parts of sulfur, 1 part of zinc oxide, 1.5 parts of titanium dioxide, 0.5 part of accelerator, 1 part of anti-aging agent, 0.05 part of dispersant, 1 part of defoamer and 50 parts of pure water, mixing and soaking for 4 hours, and grinding for 6 hours at room temperature by a ball mill to form a dispersion mixed solution with the particle size of 100-200 mu m;

s3, preparing the nitrile butadiene rubber-polyurethane composite emulsion: mixing the butyronitrile emulsion, the dispersion mixed solution and the antibacterial aqueous polyurethane emulsion according to the mass ratio of 3:3:4, and soaking for 4 hours to obtain the butyronitrile rubber-polyurethane composite emulsion.

A preparation method of the nitrile rubber-polyurethane composite glove is the same as that of the example 1.

Comparative example 4

An aqueous polyurethane emulsion is prepared by the following method:

1) dehydrating the polymer polyol at a temperature of 100 ℃ for 120 minutes under vacuum;

2) cooling to 60 ℃, adding diisocyanate and a catalyst, and carrying out prepolymerization reaction for 120 minutes under stirring and nitrogen protection;

3) adding a chain extender, and carrying out chain extension reaction for 120 minutes at 78 ℃;

4) reducing the reaction temperature to room temperature, and adding a neutralizing agent for neutralization;

5) adding water under strong stirring for emulsification for 120 minutes to obtain the aqueous polyurethane emulsion with the solid content of 30 percent.

The polymer polyol is polytetrahydrofuran ether glycol PTMG with molecular weight of 2000

The diisocyanate is isophorone diisocyanate

The catalyst is stannous octoate

The chain extender is dimethylolbutanoic acid DMBA

The neutralizer is: triethylamine

The dosage of diisocyanate, polyalcohol, chain extender and neutralizer in the reaction is as follows: isocyanate group of isophorone: hydroxyl group of PTMG: hydroxyl group of DMBA: the molar ratio of the amine groups of the neutralizing agent was 3:1.5:1.0: 1.0.

The nitrile butadiene rubber-polyurethane composite emulsion is prepared by the following method:

s1, preparing a butyronitrile emulsion: adding KOH with the mass fraction of 3 percent into 100 parts of butyronitrile emulsion, and adjusting the pH value of the latex solution to 9.5-10.5;

s2, preparing a dispersed mixed solution: 1.5 parts of sulfur, 1 part of zinc oxide, 1.5 parts of titanium dioxide, 0.5 part of accelerator, 1 part of anti-aging agent, 0.05 part of dispersant, 1 part of defoamer and 50 parts of pure water, mixing and soaking for 4 hours, and grinding for 6 hours at room temperature by a ball mill to form a dispersed mixed solution with the particle size of D90 being less than or equal to 8-mum;

s3, preparing the nitrile butadiene rubber-polyurethane composite emulsion: mixing the butyronitrile emulsion, the dispersion mixed solution and the waterborne polyurethane emulsion according to the mass ratio of 60:20:20, and soaking for 4 hours to obtain the butyronitrile rubber-polyurethane composite emulsion.

A nitrile rubber-polyurethane composite glove, the preparation method of which is the same as example 1.

Result detection

The nitrile rubber-polyurethane composite gloves prepared in the above examples and comparative examples are respectively subjected to tensile strength and elongation tests of mechanical properties and tests of chemical resistance, disinfection and antibacterial performance,

the results of the above tests for tensile strength and elongation are shown in table 1 below:

TABLE 1 tensile Strength and elongation testing of the nitrile glove end product

	Tensile Strength (MPa)	Elongation at Break (%)
			Example 1	21	620
Example 2	20	680
			Example 3	18	750
Example 4	17	730
			Example 5	17	730
Example 6	17	740
			Comparative example 1	16	550
Comparative example 2	16	550
			Comparative example 3	16	550
Comparative example 4	20	780

Table 2. chemical resistance test and disinfection, bacteriostatic performance test of the final product of nitrile gloves:

the detection of the antibacterial rates of escherichia coli and staphylococcus aureus of the nitrile rubber-polyurethane glove products obtained in the embodiments is more than or equal to 50%, and the glove conforms to GB 15979-2002.

From the above table, it can be seen that, with the addition of the antibacterial waterborne polyurethane emulsion, the tensile strength and elongation of the butyronitrile gloves are improved, and the sterilization and bacteriostasis performance of the product is greatly improved.

In comparative example 4, the waterborne polyurethane without the biquaternary ammonium salt end capping agent is adopted, the end capping is not added, the cross-linking reaction can be generated during the emulsification, the mechanical property of the material can be improved, and the antibacterial effect is not generated.

It should be understood that the above-described embodiments of the present invention are merely examples for clearly illustrating the present invention, and are not intended to limit the embodiments of the present invention. Other variations and modifications will be apparent to persons skilled in the art in light of the above description. And are neither required nor exhaustive of all embodiments. Any modification, equivalent replacement, and improvement made within the spirit and principle of the present invention should be included in the protection scope of the claims of the present invention.