CN111334879A - Preparation method and application of polyhexamethylene biguanide intercalated α -zirconium phosphate and antibacterial spandex - Google Patents
Preparation method and application of polyhexamethylene biguanide intercalated α -zirconium phosphate and antibacterial spandex Download PDFInfo
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- CN111334879A CN111334879A CN202010349782.5A CN202010349782A CN111334879A CN 111334879 A CN111334879 A CN 111334879A CN 202010349782 A CN202010349782 A CN 202010349782A CN 111334879 A CN111334879 A CN 111334879A
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F1/00—General methods for the manufacture of artificial filaments or the like
- D01F1/02—Addition of substances to the spinning solution or to the melt
- D01F1/10—Other agents for modifying properties
- D01F1/103—Agents inhibiting growth of microorganisms
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
- D01F6/88—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polycondensation products as major constituent with other polymers or low-molecular-weight compounds
- D01F6/94—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polycondensation products as major constituent with other polymers or low-molecular-weight compounds of other polycondensation products
Abstract
The invention discloses a preparation method of polyhexamethylene biguanide intercalation α -zirconium phosphate, which comprises the steps of firstly preparing polyhexamethylene biguanide, then reacting the obtained 1, 6-dicyandiamide hexane with hexamethylenediamine hydrochloride to obtain polyhexamethylene biguanide PHMB, and finally preparing polyhexamethylene biguanide intercalation α -zirconium phosphate PHMB/ZrP.
Description
Technical Field
The invention belongs to the technical field of textiles, and relates to a preparation method of polyhexamethylene biguanide intercalation α -zirconium phosphate, antibacterial spandex and a preparation method thereof, and antibacterial application of polyhexamethylene biguanide intercalation α -zirconium phosphate.
Background
Spandex, also known as polyurethane fiber, is an elastic fiber, which is the longest stretch of synthetic fibers. Because of excellent elasticity and recovery rate, the textile fabric can obtain good comfort only by adding a small amount of the monosodium glutamate. Because the spandex has the characteristics of excellent elasticity, high strength, good chemical resistance and the like, the spandex can be used for manufacturing elastic braided fabrics or textile fabrics, such as various underclothes, ski suits, sports suits, swimsuits, space suits and the like.
The antibacterial fiber is a fiber having a function of killing or inhibiting the growth of microorganisms. Spandex itself does not have a good antimicrobial function and requires addition of an antimicrobial agent to impart functionality by physical or chemical means. Antibacterial agents can be divided into two broad categories, inorganic antibacterial agents and organic antibacterial agents. The inorganic antibacterial agent mainly comprises silver, copper, zinc ions and metals thereof, and partial metal oxides. Among them, silver ions are most widely used. The inorganic antibacterial agent has the advantages of high safety, no drug resistance, good thermal stability and the like, but is not easy to disperse and run off, and the antibacterial process has slow effectiveness, so that the application of the inorganic antibacterial agent is limited. The organic antibacterial agent includes quaternary ammonium salt, quaternary phosphonium salt, alcohol, phenol, guanidine, organic metal, pyridine, imidazole, etc., wherein the quaternary ammonium salt is most widely used. The organic antibacterial agent has stronger initial bactericidal power, better bactericidal aging and broad spectrum, but is easy to run off, and has low thermal stability and chemical stability. Polyhexamethylene biguanide (PHMB) is a safe and efficient organic broad-spectrum antibacterial agent, is colorless and odorless, has broad-spectrum low toxicity, can continuously inhibit bacteria for a long time, has no bacterial drug resistance, and is applied to the production of medicines, dyes, explosives, agricultural chemicals and plastics, the biotechnology and other aspects. PHMB can be directionally adsorbed on microbial cell membranes of negatively charged bacteria, fungi and the like, and cell membranes are damaged by hydrophobic chains to be apoptotic, so that the PHMB is harmless to the electrically neutral animal and plant cell membranes. Relevant literature shows that the antibacterial effect of the polyhexamethylene biguanide (PHMB) can be further prolonged by loading the PHMB in a biological carbon residue material and an antibacterial gel.
α -zirconium phosphate (α -ZrP) is a typical cationic layered compound, belonging to monoclinic system, in α -ZrP structure, hydrogen proton on-OH can be directly or indirectly connected with alkali metal ions Li +, Na +, K +, Rb +, Cs + NH4The α -zirconium phosphate is also widely applied to the load of antibacterial agents such as silver ions and the like, but the mechanical strength of the material is influenced if the antibacterial slow-release effect is increased and the problem of agglomeration of α -ZrP in a matrix cannot be effectively solved.
With the increasing competition of spandex industry, the research of high value-added differentiated products has become the key development direction of each enterprise, and along with the rise of environmental protection and green development concepts, antibacterial fibers have gradually attracted the attention of the market, and some brand enterprises and application companies even put forward related products and begin to gain the market acceptance. The existing antibacterial deodorizing spandex mainly comprises silver ions, chitosan, metal oxides and the like.
Chinese published patent document CN201210078915.5 discloses "an antibacterial spandex fiber and a preparation method thereof", the antibacterial spandex fiber includes an antibacterial agent and a spandex fiber, the antibacterial agent includes nano silver and polyurethane as a dispersant, the antibacterial spandex fiber contains 0.01-1.0% by weight of nano silver based on the total dry weight of the fiber, that is, 100g of the antibacterial spandex fiber contains 0.01-1 g of nano silver based on the total dry weight of the fiber, and the nano silver is uniformly dispersed in the interior and on the surface of the spandex fiber. The defects are as follows: silver ions or inorganic substances such as silver oxide, zinc oxide and the like are directly added, so that the spandex polymer is easy to agglomerate, the mechanical strength of the spandex is reduced, the fiber is easy to discolor, and the corresponding effect durability is poor.
Disclosure of Invention
The invention aims to solve the technical problem of the prior art and provides a preparation method of polyhexamethylene biguanide intercalated α -zirconium phosphate, which has a good antibacterial effect and a small addition amount.
The invention also provides a preparation method of antibacterial spandex by using the polyhexamethylene biguanide intercalated α -zirconium phosphate as an antibacterial agent.
Still another object of the present invention is to provide the use of the aforementioned polyhexamethylene biguanide intercalated α -zirconium phosphate as an antimicrobial agent.
The technical problem to be solved by the invention is realized by the following technical scheme, and the invention discloses a preparation method of polyhexamethylene biguanide intercalation α -zirconium phosphate, which is characterized by comprising the following steps:
(1) preparation of polyhexamethylene biguanide: dissolving hexamethylene diamine hydrochloride and sodium dicyandiamide in a molar ratio of 1: 2.1-2.2 in n-butyl alcohol, performing reflux reaction for 6-10 h, evaporating solvent n-butyl alcohol, and repeatedly washing obtained white solid 1, 6-dicyandiamide-based hexane with water and absolute ethyl alcohol;
(2) mixing the obtained 1, 6-dicyandiamide-based hexane and hexamethylenediamine hydrochloride according to an equal molar ratio, adding a small amount of water, adjusting the pH value to 7-10, removing water at 55 ℃ in vacuum, and removing N for completely removing water2Protecting and heating to 155-160 ℃ for reaction for 20-100 min to obtain polyhexamethylene biguanide PHMB with certain molecular weight;
(3) the PHMB/ZrP is prepared by dispersing α -zirconium phosphate powder in ethanol, adding polyhexamethylene biguanide into the predispersion solution, reacting for 30-60 minutes in a microwave chemical reactor, separating and precipitating, washing for several times with ethanol, and drying to obtain an intercalation product PHMB/ZrP, namely polyhexamethylene biguanide intercalation α -zirconium phosphate.
The preparation method of polyhexamethylene biguanide intercalation α -zirconium phosphate further adopts the preferable technical scheme that the molecular weight of PHMB is 300-2000.
The preparation method of the polyhexamethylene biguanide intercalation α -zirconium phosphate further adopts the preferable technical scheme that the mass ratio of α -zirconium phosphate powder to polyhexamethylene biguanide is 1:1-1: 3.
The invention also discloses a preparation method of the antibacterial spandex, which is characterized by comprising the following steps: the method comprises the following steps:
(1) preparation of prepolymer
Adding a solvent into a reactor, sequentially adding polytetramethylene ether glycol and polyisocyanate into the reactor under the stirring condition, reacting at the temperature of 69-89 ℃ for 90-120min to form a prepolymer, and adding the solvent for dissolving to prepare a prepolymer solution;
(2) chain extension reaction: when the prepolymer solution is cooled to 8 ℃, adding mixed amine into the prepolymer solution under the stirring condition to carry out chain extension reaction and chain termination reaction to prepare spandex polymer solution;
(3) preparing an antibacterial agent dispersion liquid: dissolving and dispersing the prepared PHMB/ZrP in a solvent to prepare an antibacterial agent dispersion liquid at the temperature of 30-60 ℃;
(4) preparing a spinning solution: adding an antibacterial agent dispersion liquid and a proper amount of auxiliary agent into the spandex polymer solution to obtain an antibacterial spandex spinning stock solution; the auxiliary agent is selected from anti-yellowing agent, delustering agent, antioxidant and magnesium stearate;
(5) spinning: after the spinning solution is cured at the temperature of 40-60 ℃, the dry spinning antibacterial spandex is prepared by a dry spinning system.
The preparation method of the antibacterial spandex has the particularly preferred technical scheme that: the weight ratio of each raw material is as follows: PHMB/ZrP accounts for 1 per mill to 1 percent of the total dry weight of the fiber
Diisocyanate 1500-; polytetramethylene ether glycol 5000-;
20-200 parts of mixed amine; solvent 2000-6000; 100-200 of auxiliary agent.
The preparation method of the antibacterial spandex has the particularly preferred technical scheme that: the diisocyanate compound is 4,4-MDI or 2, 4-MDI.
The preparation method of the antibacterial spandex has the particularly preferred technical scheme that: the mixed amine consists of a chain extender and a terminator; the chain extender is one or more selected from ethylenediamine, propylenediamine and pentylenediamine; the terminator is one or more selected from diethylamine, dipropylamine, cyclohexylamine, n-butanol and ethanolamine.
The preparation method of the antibacterial spandex has the particularly preferred technical scheme that: the solvent is N, N-dimethylacetamide or N, N-dimethylformamide.
The preparation method of the antibacterial spandex has the particularly preferred technical scheme that: the molecular weight of the polytetramethylene ether glycol is 1800-3000.
Use of polyhexamethylene biguanide intercalated α -zirconium phosphate obtained by the process according to any one of claims 1 to 3 as an antibacterial agent for the preparation of antibacterial spandex.
Compared with the prior art, the invention has the beneficial effects that:
(1) the preparation method of the polyhexamethylene biguanide intercalation α -zirconium phosphate can intercalate PHMB into ZrP, can further enhance the antibacterial slow-release effect, adopts a microwave heating mode, obviously increases the interval of ZrP layers, and can solve the agglomeration problem of ZrP, is different from a silver ion antibacterial agent, adopts the polyhexamethylene biguanide (PHMB) as an organic polymer antibacterial agent, and solves the problem that fibers discolor due to silver ions;
(2) the preparation method of the antibacterial spandex adopts polyhexamethylene biguanide intercalation α -zirconium phosphate as an antibacterial agent, and experiments show that the mechanical strength of the spandex after intercalation is increased, because the spacing between α -zirconium phosphate layers after intercalation is obviously increased, the problem of agglomeration is solved, and the spandex is distributed on a matrix more uniformly and presents a reinforcing phase.
Detailed Description
The following further describes particular embodiments of the present invention to facilitate further understanding of the present invention by those skilled in the art, and does not constitute a limitation to the right thereof.
Example 1 preparation of antibacterial Spandex
The preparation method of the polyhexamethylene biguanide intercalation α -zirconium phosphate comprises the following steps:
(1) preparation of polyhexamethylene biguanide: dissolving hexamethylene diamine hydrochloride and sodium dicyandiamide in a molar ratio of 1: 2.1 in n-butyl alcohol, performing reflux reaction for 6 hours, evaporating solvent n-butyl alcohol, and repeatedly washing obtained white solid 1, 6-dicyandiamide-based hexane with water and absolute ethyl alcohol;
(2) mixing the obtained 1, 6-dicyandiamide-based hexane with hexamethylenediamine hydrochloride according to an equal molar ratio, adding a small amount of water, adjusting the pH value to 7, removing water at 55 ℃ in vacuum, and removing water completely by using N2Protecting and heating to 155 ℃ for reaction for 80min to obtain polyhexamethylene biguanide PHMB with certain molecular weight;
(3) the PHMB/ZrP is prepared by dispersing α -zirconium phosphate powder in ethanol, adding polyhexamethylene biguanide into the pre-dispersion solution, reacting for 30 minutes in a microwave chemical reactor, separating the precipitate, washing with ethanol for 3 times, and drying to obtain an intercalation product PHMB/ZrP, namely the polyhexamethylene biguanide intercalation α -zirconium phosphate.
PHMB has a molecular weight of 1000 and a mass ratio of α -zirconium phosphate powder to polyhexamethylene biguanide of 1: 1.
Secondly, the preparation method of the antibacterial spandex comprises the following steps:
(1) preparing a prepolymer: adding a solvent into a reactor, sequentially adding polytetramethylene ether glycol and polyisocyanate into the reactor under the stirring condition, reacting for 90min at the temperature of 69 ℃ to form a prepolymer, and adding the solvent for dissolving to prepare a prepolymer solution;
(2) chain extension reaction: when the prepolymer solution is cooled to 8 ℃, adding mixed amine into the prepolymer solution under the stirring condition to carry out chain extension reaction and chain termination reaction to prepare spandex polymer solution;
(3) preparing an antibacterial agent dispersion liquid:
dissolving and dispersing the prepared PHMB/ZrP in a solvent to prepare an antibacterial agent dispersion liquid at the temperature of 30 ℃;
(4) preparing a spinning solution: adding an antibacterial agent dispersion liquid and a proper amount of auxiliary agent into the spandex polymer solution to obtain an antibacterial spandex spinning stock solution; the auxiliary agent is selected from anti-yellowing agent, delustering agent, antioxidant and magnesium stearate;
(5) spinning: and (3) curing the spinning solution at the temperature of 40 ℃, and preparing the dry spinning antibacterial spandex by using a dry spinning system.
The weight ratio of each raw material is as follows:
PHMB/ZrP is 1 per mill of the total dry weight of the fiber; a diisocyanate 1500;
polytetramethylene ether glycol 5000; mixing amine 20; a solvent 2000; 100 of an auxiliary agent;
the diisocyanate compound is 4,4-MDI or 2, 4-MDI.
The mixed amine consists of a chain extender and a terminator; the chain extender is selected from one of ethylenediamine, propylenediamine and pentylenediamine; the terminator is one selected from diethylamine, dipropylamine, cyclohexylamine, n-butanol and ethanolamine. The solvent is N, N-dimethylacetamide or N, N-dimethylformamide. The molecular weight of the polytetramethylene ether glycol is 1800.
Example 2 preparation of antibacterial Spandex
The preparation method of the polyhexamethylene biguanide intercalation α -zirconium phosphate comprises the following steps:
(4) preparation of polyhexamethylene biguanide: dissolving hexamethylene diamine hydrochloride and sodium dicyandiamide in a molar ratio of 1: 2.2 in n-butyl alcohol, performing reflux reaction for 10 hours, evaporating solvent n-butyl alcohol, and repeatedly washing obtained white solid 1, 6-dicyandiamide-based hexane with water and absolute ethyl alcohol;
(5) mixing the obtained 1, 6-dicyandiamide-based hexane with hexamethylenediamine hydrochloride according to an equal molar ratio, adding a small amount of water, adjusting the pH value to 10, removing water at 55 ℃ in vacuum, and removing water completely by using N2Protecting and heating to 1Reacting at 60 ℃ for 100min to obtain polyhexamethylene biguanide PHMB with certain molecular weight;
(6) the PHMB/ZrP is prepared by dispersing α -zirconium phosphate powder in ethanol, adding polyhexamethylene biguanide into the pre-dispersion solution, reacting for 60 minutes in a microwave chemical reactor, separating and precipitating, washing with ethanol for a plurality of times, and drying to obtain an intercalation product PHMB/ZrP, namely a polyhexamethylene biguanide intercalation α -zirconium phosphate, PHMB has a molecular weight of 2000, and the mass ratio of α -zirconium phosphate powder to polyhexamethylene biguanide is 1: 3.
Secondly, the preparation method of the antibacterial spandex comprises the following steps:
(1) preparing a prepolymer: adding a solvent into a reactor, sequentially adding polytetramethylene ether glycol and polyisocyanate into the reactor under the stirring condition, reacting at the temperature of 89 ℃ for 120min to form a prepolymer, and adding the solvent for dissolving to prepare a prepolymer solution;
(2) chain extension reaction: when the prepolymer solution is cooled to 8 ℃, adding mixed amine into the prepolymer solution under the stirring condition to carry out chain extension reaction and chain termination reaction to prepare spandex polymer solution;
(3) preparing an antibacterial agent dispersion liquid: dissolving and dispersing the prepared PHMB/ZrP in a solvent to prepare an antibacterial agent dispersion liquid at the temperature of 60 ℃;
(4) preparing a spinning solution: adding an antibacterial agent dispersion liquid and a proper amount of auxiliary agent into the spandex polymer solution to obtain an antibacterial spandex spinning stock solution; the auxiliary agent is selected from anti-yellowing agent, delustering agent, antioxidant and magnesium stearate;
(5) spinning: and (3) curing the spinning solution at the temperature of 60 ℃, and preparing the dry spinning antibacterial spandex by using a dry spinning system.
The weight ratio of each raw material is as follows:
PHMB/ZrP represents 1% of the total dry weight of the fiber; diisocyanate 2500;
polytetramethylene ether glycol 10000; mixing amine 200; a solvent 6000; 200 of an auxiliary agent;
the diisocyanate compound is 4,4-MDI or 2, 4-MDI.
The mixed amine consists of a chain extender and a terminator; the chain extender is selected from one of ethylenediamine, propylenediamine and pentylenediamine; the terminator is one selected from diethylamine, dipropylamine, cyclohexylamine, n-butanol and ethanolamine. The solvent is N, N-dimethylacetamide or N, N-dimethylformamide. The molecular weight of the polytetramethylene ether glycol is 3000.
Example 3 preparation of antibacterial Spandex
The preparation method of the polyhexamethylene biguanide intercalation α -zirconium phosphate comprises the following steps:
(1) preparation of polyhexamethylene biguanide: dissolving hexamethylene diamine hydrochloride and sodium dicyandiamide in a molar ratio of 1: 2.1 in n-butyl alcohol, performing reflux reaction for 8 hours, evaporating solvent n-butyl alcohol, and repeatedly washing obtained white solid 1, 6-dicyandiamide-based hexane with water and absolute ethyl alcohol;
(2) mixing the obtained 1, 6-dicyandiamide-based hexane with hexamethylenediamine hydrochloride according to an equal molar ratio, adding a small amount of water, adjusting the pH value to 8, removing water at 55 ℃ in vacuum, and removing water completely by using N2Protecting and heating to 158 ℃ for reaction for 60min to obtain polyhexamethylene biguanide PHMB with certain molecular weight;
(3) the PHMB/ZrP is prepared by dispersing α -zirconium phosphate powder in ethanol, adding polyhexamethylene biguanide into the pre-dispersion solution, reacting for 45 minutes in a microwave chemical reactor, separating and precipitating, washing with ethanol for a plurality of times, and drying to obtain an intercalation product PHMB/ZrP, namely a polyhexamethylene biguanide intercalation α -zirconium phosphate PHMB, wherein the molecular weight of PHMB is 800, and the mass ratio of α -zirconium phosphate powder to polyhexamethylene biguanide is 1: 2.5.
Secondly, the preparation method of the antibacterial spandex comprises the following steps:
(1) preparing a prepolymer: adding a solvent into a reactor, sequentially adding polytetramethylene ether glycol and polyisocyanate into the reactor under the stirring condition, reacting at the temperature of 79 ℃ for 95min to form a prepolymer, and adding the solvent for dissolving to prepare a prepolymer solution;
(2) chain extension reaction: when the prepolymer solution is cooled to 8 ℃, adding mixed amine into the prepolymer solution under the stirring condition to carry out chain extension reaction and chain termination reaction to prepare spandex polymer solution;
(3) preparing an antibacterial agent dispersion liquid: dissolving and dispersing the prepared PHMB/ZrP in a solvent to prepare an antibacterial agent dispersion liquid at the temperature of 45 ℃;
(4) preparing a spinning solution: adding an antibacterial agent dispersion liquid and a proper amount of auxiliary agent into the spandex polymer solution to obtain an antibacterial spandex spinning stock solution; the auxiliary agent is selected from 1 or 2 of anti-yellowing agent, delustering agent, antioxidant and magnesium stearate;
(5) spinning: and (3) curing the spinning solution at the temperature of 50 ℃, and preparing the dry spinning antibacterial spandex by using a dry spinning system.
The weight ratio of each raw material is as follows:
PHMB/ZrP is 5 per mill of the total dry weight of the fiber; diisocyanate 2000;
polytetramethylene ether glycol 8000; mixing amine 50; a solvent 4000; an auxiliary agent 150;
the diisocyanate compound is 4,4-MDI or 2, 4-MDI.
The mixed amine consists of a chain extender and a terminator; the chain extender is one or more selected from ethylenediamine, propylenediamine and pentylenediamine; the terminator is one or more selected from diethylamine, dipropylamine, cyclohexylamine, n-butanol and ethanolamine. The solvent is N, N-dimethylacetamide or N, N-dimethylformamide. The molecular weight of the polytetramethylene ether glycol is 2500.
Example 4 comparative experiment of antimicrobial spandex preparation:
first, experiment purpose
The effect of the antibacterial agent PHMB/ZrP in antibacterial spandex is verified through a comparison experiment.
Second, grouping experiments
The experiment is divided into 2 groups of comparative examples and 4 groups of experimental examples, which are as follows:
comparative example 1
1575g of polytetramethylene ether glycol with molecular weight of 2000 and 365g of 4,4-MDI react at 80 ℃ for 120min to obtain isocyanate groups at two ends, 3301g of N, N-dimethylacetamide is added to dissolve the prepolymer, and the temperature is reduced to 10 ℃. Adding 33.9g of ethylenediamine and 5.59g of diethylamine into 750g of N, N-dimethylacetylether, mixing to obtain an ammonia mixed solution, adding the ammonia mixed solution into the prepolymer cooled to 10 ℃ while stirring, and finally obtaining the high-viscosity stable polymer. To the polymer solution were added 3.2g of an anti-yellowing agent, 6.54g of delustering agent titanium dioxide, 1.7g of an antioxidant, and 7.9g of magnesium stearate to obtain a spinning dope. Finally, the spinning solution is cured at the temperature of 40 ℃, and then the spandex is prepared by the processes of liquid discharge, spitting, stretching, false twisting, oiling and the like by means of a dry spinning system.
(II) comparative example 2
As in comparative example 1, except that an antibacterial liquid was added, the antibacterial liquid was obtained by mixing 10g of Ag/ZrP with 50g of N, N-dimethylacethyl, and was added to the polymer solution together with an auxiliary.
(III) Experimental example 1
(1) Preparation of polyhexamethylene biguanide: dissolving hexamethylene diamine hydrochloride and sodium dicyandiamide in a molar ratio of 1: 2.1 in n-butyl alcohol, performing reflux reaction for 8 hours, evaporating solvent n-butyl alcohol, and repeatedly washing obtained white solid 1, 6-dicyandiamide-based hexane with water and absolute ethyl alcohol; mixing the obtained 1, 6-dicyandiamide-based hexane and hexamethylenediamine hydrochloride according to an equal molar ratio, adding a small amount of water, adjusting the pH value to be about 8, removing water at 55 ℃ in vacuum, protecting the water by using N2 gas when the water is completely removed, heating to 155 ℃, and reacting for 30min to obtain polyhexamethylene biguanide PHMB with the relative molecular mass of about 600;
(2) the preparation of PHMB/ZrP comprises the steps of dispersing 10g of α -zirconium phosphate powder in 200ml of ethanol, then adding 30g of polyhexamethylene biguanide into the pre-dispersion solution, reacting for 40 minutes in a microwave chemical reactor under 300W, separating precipitates, washing for 3 times by using ethanol, and drying to obtain an intercalation product PHMB/ZrP.
The XRD pattern of α -ZrP has a strong diffraction peak (002) at 11.89 deg., while the 002 peak of PHMB/ZrP after intercalation shifts to a lower 2.26 deg., which means that PHMB has successfully entered the α -ZrP interlayer and the interlayer spacing increases from 0.117nm to 3.27nm (the thickness of the lamina of α -ZrP is 0.63mm, which has been deducted), the increase is significant.
(3) Preparing antibacterial spandex: 1575g of polytetramethylene ether glycol with molecular weight of 2000 and 4,4-MDI365g react at 80 ℃ for 120min to obtain isocyanate groups at two ends, 3301g of N, N-dimethylacetamide is added to dissolve the prepolymer, and the temperature is reduced to 10 ℃. Adding 33.9g of ethylenediamine and 5.59g of diethylamine into 750g of N, N-dimethylacetylchloride, mixing to obtain an ammonia mixed solution, adding the ammonia mixed solution into the prepolymer cooled to 10 ℃ while stirring, and finally obtaining a high-viscosity stable polymer; 2g of PHMB/ZrP was added to 10g of N, N-dimethylacethyl and mixed to obtain an antibacterial solution, and the antibacterial solution, 3.2g of an anti-yellowing agent, 6.54g of delustering agent titanium dioxide, 1.7g of an antioxidant and 7.9g of magnesium stearate were added to the polymer solution to obtain a spinning dope. Finally, the spinning solution is cured at the temperature of 40 ℃, and then the antibacterial spandex with the addition of 1 per mill is prepared by the aid of a dry spinning system through processes of liquid discharge, spitting, stretching, false twisting, oiling and the like.
(IV) Experimental example 2
The PHMB preparation method is the same as the experimental example 1, except that the temperature is finally raised to 155 ℃ for reaction for 20min to obtain polyhexamethylene biguanide PHMB with the relative molecular mass of about 300; the PHMB/ZrP mass ratio is 2:1, 5g of PHMB/ZrP is added into 25g of N, N-dimethyl acetyl for mixing, and finally the antibacterial spandex with the addition of 2.5 per mill is obtained.
(fifth) Experimental example 3
PHMB is prepared as in experiment example 1, except that the temperature is raised to 155 ℃ for 80min to obtain polyhexamethylene biguanide PHMB with relative molecular mass of about 1000; the mass ratio of PHMB/ZrP is 2:1, 10g of PHMB/ZrP is added into 50g of N, N-dimethyl acetyl for mixing, and finally the antibacterial spandex with the addition of 5 per mill is obtained.
(sixth) Experimental example 4
The PHMB preparation method is as in experimental example 1, except that the temperature is finally raised to 160 ℃ for reaction for 100min, and polyhexamethylene biguanide PHMB with the relative molecular mass of about 2000 is obtained; the mass ratio of PHMB/ZrP is 1:1, 20g of PHMB/ZrP is added into 100g of N, N-dimethyl acetyl for mixing, and finally the antibacterial spandex with the addition of 1% is obtained.
Third, experimental results
The results of the comparative experiment and the technical indexes obtained by detection are shown in the following table,
as can be seen from the table above, the experimental example shows excellent performance on the antibacterial spandex, and mainly shows that the antibacterial spandex has good antibacterial effect, small addition amount of the antibacterial agent, good elongation at break, high strength and the like.
Claims (10)
1. A preparation method of polyhexamethylene biguanide intercalation α -zirconium phosphate is characterized by comprising the following steps:
(1) preparation of polyhexamethylene biguanide: dissolving hexamethylene diamine hydrochloride and sodium dicyandiamide in a molar ratio of 1: 2.1-2.2 in n-butyl alcohol, performing reflux reaction for 6-10 h, evaporating solvent n-butyl alcohol, and repeatedly washing obtained white solid 1, 6-dicyandiamide-based hexane with water and absolute ethyl alcohol;
(2) mixing the obtained 1, 6-dicyandiamide-based hexane and hexamethylenediamine hydrochloride according to an equal molar ratio, adding a small amount of water, adjusting the pH value to 7-10, removing water at 55 ℃ in vacuum, and removing N for completely removing water2Protecting and heating to 155-160 ℃ for reaction for 20-100 min to obtain polyhexamethylene biguanide PHMB with certain molecular weight;
(3) the PHMB/ZrP is prepared by dispersing α -zirconium phosphate powder in ethanol, adding polyhexamethylene biguanide into the predispersion solution, reacting for 30-60 minutes in a microwave chemical reactor, separating and precipitating, washing for several times with ethanol, and drying to obtain an intercalation product PHMB/ZrP, namely polyhexamethylene biguanide intercalation α -zirconium phosphate.
2. The method of claim 1, wherein the molecular weight of PHMB is 300-2000.
3. The method for preparing polyhexamethylene biguanide intercalation α -zirconium phosphate according to claim 1, wherein the mass ratio of α -zirconium phosphate powder to polyhexamethylene biguanide is 1:1-1: 3.
4. A preparation method of antibacterial spandex is characterized by comprising the following steps: the method comprises the following steps:
(1) preparation of prepolymer
Adding a solvent into a reactor, sequentially adding polytetramethylene ether glycol and polyisocyanate into the reactor under the stirring condition, reacting at the temperature of 69-89 ℃ for 90-120min to form a prepolymer, and adding the solvent for dissolving to prepare a prepolymer solution;
(2) chain extension reaction
When the prepolymer solution is cooled to 8 ℃, adding mixed amine into the prepolymer solution under the stirring condition to carry out chain extension reaction and chain termination reaction to prepare spandex polymer solution;
(3) preparation of antibacterial agent dispersion
Dissolving and dispersing PHMB/ZrP prepared according to the claim 1, 2 or 3 in a solvent to prepare an antibacterial agent dispersion liquid under the condition of 30-60 ℃;
(4) preparation of the spinning dope
Adding an antibacterial agent dispersion liquid and a proper amount of auxiliary agent into the spandex polymer solution to obtain an antibacterial spandex spinning stock solution; the auxiliary agent is selected from anti-yellowing agent, delustering agent, antioxidant and magnesium stearate;
(5) spinning
After the spinning solution is cured at the temperature of 40-60 ℃, the dry spinning antibacterial spandex is prepared by a dry spinning system.
5. The method for preparing antibacterial spandex according to claim 4, characterized in that: the weight ratio of each raw material is as follows:
PHMB/ZrP accounts for 1 per mill to 1 percent of the total dry weight of the fiber
Diisocyanate 1500-; polytetramethylene ether glycol 5000-;
20-200 parts of mixed amine; solvent 2000-6000; 100-200 of auxiliary agent.
6. The method for preparing antibacterial spandex according to claim 4, characterized in that: the diisocyanate compound is 4,4-MDI or 2, 4-MDI.
7. The method for preparing antibacterial spandex according to claim 4, characterized in that: the mixed amine consists of a chain extender and a terminator; the chain extender is one or more selected from ethylenediamine, propylenediamine and pentylenediamine; the terminator is one or more selected from diethylamine, dipropylamine, cyclohexylamine, n-butanol and ethanolamine.
8. The method for preparing antibacterial spandex according to claim 4, characterized in that: the solvent is N, N-dimethylacetamide or N, N-dimethylformamide.
9. The method for preparing antibacterial spandex according to claim 4, characterized in that: the molecular weight of the polytetramethylene ether glycol is 1800-3000.
10. Use of polyhexamethylene biguanide intercalated α -zirconium phosphate obtained by the process according to any one of claims 1 to 3 as an antibacterial agent for the preparation of antibacterial spandex.
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