CN114163781A - Application and preparation method of organic copper - Google Patents
Application and preparation method of organic copper Download PDFInfo
- Publication number
- CN114163781A CN114163781A CN202111426758.8A CN202111426758A CN114163781A CN 114163781 A CN114163781 A CN 114163781A CN 202111426758 A CN202111426758 A CN 202111426758A CN 114163781 A CN114163781 A CN 114163781A
- Authority
- CN
- China
- Prior art keywords
- antibacterial
- copper
- parts
- poly
- phenylene
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/04—Homopolymers or copolymers of ethene
- C08L23/06—Polyethene
-
- 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
-
- 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
- D01F6/92—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 polyesters
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2309/00—Characterised by the use of homopolymers or copolymers of conjugated diene hydrocarbons
- C08J2309/06—Copolymers with styrene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
- C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
- C08J2323/04—Homopolymers or copolymers of ethene
- C08J2323/06—Polyethene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2423/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
- C08J2423/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
- C08J2423/04—Homopolymers or copolymers of ethene
- C08J2423/06—Polyethene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2485/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing atoms other than silicon, sulfur, nitrogen, oxygen, and carbon; Derivatives of such polymers
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A50/00—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
- Y02A50/30—Against vector-borne diseases, e.g. mosquito-borne, fly-borne, tick-borne or waterborne diseases whose impact is exacerbated by climate change
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Manufacturing & Machinery (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Medicinal Chemistry (AREA)
- Health & Medical Sciences (AREA)
- General Chemical & Material Sciences (AREA)
- Textile Engineering (AREA)
- Materials Engineering (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
- Artificial Filaments (AREA)
Abstract
The invention discloses a method for preparing organic copper of a known compound and a preparation method thereof. The organic copper structure related by the invention is shown as a formula I or a formula II, and the application of the organic copper structure is application in preparing high polymer material polyolefin resin or synthetic rubber or synthetic fiber with an antibacterial function. The organic copper of the invention is dispersed in the polymer material in a molecular state, not only shows high antibacterial activity, but alsoThe organic copper compound can be uniformly dispersed in the polymer, thereby avoiding the agglomeration of copper and leading the polymer material to have higher antibacterial activity.
Description
Technical Field
The invention relates to a preparation method of a known compound organic copper and a related product thereof.
Background
Microbial infections have become the first killer of human health, and bring huge economic losses to people, particularly in the aspects of public medical health, food safety and the like. In daily life, a large amount of bacteria and fungi are hidden around people, and once people contact the bacteria and fungi, the bacteria and the fungi can be rapidly propagated and spread in the human body under proper conditions, so that various diseases are caused, and the health of the human body is damaged. In order to reduce the harm of bacteria and fungi to human health, the development of antibacterial products is very important for improving human health level. Products with antibacterial, deodorant and mildew-proof functions have great potential market demands. Synthetic polymer materials such as polyolefin, synthetic rubber and synthetic fiber, which are widely used in daily life, medical treatment and industry, have no antibacterial property, and development of related antibacterial polymer materials is urgently needed. At present, antibacterial agents are mainly added into the polymer materials to enable the polymer materials to have antibacterial performance.
Currently, the widely used antibacterial agent is prepared by adding the antibacterial agent into a high polymer material by processing methods such as in-situ polymerization, melt blending spinning, surface adsorption modification and the like of silver, copper, zinc and compounds thereof. However, inorganic antibacterial agents such as nano silver, nano copper oxide, nano zinc and nano zinc oxide, which are mainly used at present, have poor dispersibility in synthetic polymers, and thus the antibacterial performance is affected. CN202110675525.5 reports a method for preparing a nano-silver antibacterial masterbatch, in which a dispersing agent is used to disperse nano-silver into a carrier resin to obtain an antibacterial masterbatch, and the resin and the antibacterial masterbatch are melt-blended to obtain an antibacterial resin material, but the nano-silver nanoparticles have high surface energy and are easy to agglomerate, and the dispersing agent can achieve a certain dispersion effect, but the dispersing agent is easy to fall off from the surface of the nano-silver under high temperature conditions in the melt-blending processing engineering, so that silver ions are agglomerated, and the exertion of the antibacterial property of the nano-silver is limited. Chinese patent application 202011111333.3 discloses an antibacterial polyester and a method for preparing the same, in which copper is dispersedly added to the copolyester by mixing, and the method also has the aforementioned disadvantages.
Disclosure of Invention
The invention provides a new application of the existing compound, which overcomes the defects of the prior art, can effectively prevent metal particles from agglomerating and fully exert the antibacterial effect of the metal particles, and also provides a preparation method of related products of the metal particles.
The present compound is organic copper, and its use is in preparing antibiotic mother particle and high molecular material polyolefin resin, synthetic rubber or synthetic fiber1、R2And R3Are respectively C1～C30Is straight or branched alkyl or is C3～C30Is cycloalkyl or is C6～C30Any one of aryl groups of (1), and R1、R2And R3Can be the same or different, the polymerization degree n is 1-10000,
preferably, the substituent R of the organic copper is1、R2And R3Is C1～C20Straight or branched alkyl of (2), C3～C20Cycloalkyl or C6～C20Any of the aryl groups of (1).
More preferably, the organocopper of the invention is any one of the following compounds: copper polyterephthalate, copper poly-2-methyl terephthalate, copper polysuccinate, copper polypentanedioate, copper polyhexamate, copper polyheptate, copper suberate, copper polymaleate.
The preparation method of the organic copper comprises the following steps: the polymerization degree of the polymer can be adjusted by adopting the complex reaction of dicarboxylic acid compounds and copper ions under the alkaline condition, using monocarboxylic acid for end capping and adjusting the proportion of the monocarboxylic acid.
Specifically, the preparation method of the organic copper comprises the following steps: adding 5-15 parts by weight of p-dicarboxylic acid compound into 50 parts of water, slowly dropwise adding NaOH solution with a certain concentration under stirring until the pH of the reaction solution is 8, then adding 0.001-2 parts of sodium monocarboxylic acid, stirring until the sodium monocarboxylic acid is completely dissolved, and finally adding 1: 1 equivalent of Cu2+Reacting the ionic solution until the precipitate is completely generated, separating the precipitate, and washing to obtain the final product.
The organic copper structure of the invention which can be used for preparing high molecular material polyolefin resin or synthetic rubber or synthetic fiber with antibacterial function can also be shown as formula II, wherein R4、R5And R6Are respectively C6～C30Any one of aryl groups of (1), and R4、R5And R6The polymerization degree n is 1 to 10000,
preferably, the substituent R of the organocopper of the invention4、R5And R6Are respectively C6～C30Any of the aryl groups of (1).
More preferably, the organocopper of the invention is any one of the following compounds: poly (p-phenylene dioxycopper), poly (2-methyl-p-phenylene dioxycopper), poly (2-tert-butyl-p-phenylene dioxycopper), poly (2-amino-p-phenylene dioxycopper), poly (2-chloro-p-phenylene dioxycopper), poly (2-ethyl-p-phenylene dioxycopper), poly (2-tert-butyl-p-phenylene dioxycopper), poly (2-amino-p-phenylene dioxycopper), poly (2-chloro-p-phenylene dioxycopper), and poly (2-methyl-4-butyl-p-phenylene dioxycopper).
The preparation method of the organic copper comprises the following steps: the polymerization degree of the polymer is adjusted by adjusting the proportion of the monophenol.
Specifically, the preparation method of the organic copper antibacterial agent comprises the following steps: adding 5-15 parts by weight of p-diphenol compound into 50 parts of water, slowly dropwise adding NaOH solution with a certain concentration under stirring until the pH of the reaction solution is 8, adding 0.001-2 parts of monophenol, stirring until the monophenol is completely dissolved, and finally adding 1: 1 equivalent of Cu2+Reacting the ionic solution until the precipitate is completely generated, separating the precipitate, and washing to obtain the final product.
The organic copper polymer obtained by the invention can be used as an antibacterial additive for synthesizing high molecular material polyolefin resin, synthetic rubber and synthetic fiber so as to prepare the materials with antibacterial performance.
The invention discloses a method for preparing antibacterial master batch by using organic copper shown in formula I, which comprises the following steps: uniformly mixing 5-30 parts of organic copper and 70-95 parts of polyethylene wax, heating for reaction for 30min, cooling, and grinding into powder to obtain the antibacterial agent master batch, wherein the parts are in parts by mass.
The invention discloses a method for preparing antibacterial master batch by using organic copper shown in formula II, which comprises the following steps: uniformly mixing 5-30 parts of organic copper and 70-95 parts of polyester resin, heating for reaction for 30min, cooling, and grinding into powder to obtain the antibacterial agent master batch, wherein the parts are by mass.
The method for preparing the antibacterial polyethylene by using the antibacterial master batch prepared from the organic copper shown in the formula I comprises the following steps: 1-5 parts of organic copper antibacterial agent master batch and 15-20 parts of polyethylene raw material are subjected to melting and banburying to obtain the organic copper antibacterial polyethylene, wherein the melting and banburying temperature is controlled at 190-210 ℃, and the parts are in parts by mass.
The method for preparing the antibacterial styrene butadiene rubber by using the antibacterial master batch prepared from the organic copper shown in the formula I comprises the following steps: taking 1-5 parts of organic copper antibacterial agent master batch and 15-20 parts of butadiene styrene rubber raw material, and carrying out banburying to obtain an organic copper antibacterial butadiene styrene rubber sheet, wherein the banburying temperature is controlled at 110-130 ℃, and the parts are in parts by mass.
The method for preparing the antibacterial polyester fiber by using the antibacterial master batch prepared from the organic copper shown in the formula II comprises the following steps: 1-5 parts of organic copper antibacterial agent master batch and 15-20 parts of polyester fiber raw material are taken, and the antibacterial polyester fiber is prepared by melt mixing of the organic copper polymer antibacterial agent master batch and a polyester fiber raw material melt, melt spinning, circular air blowing cooling, cluster oiling, drafting and winding, wherein the parts are in parts by mass.
The "parts" in the above-mentioned preparation methods are all parts by mass.
The organic copper polymer and the preparation method thereof have the advantages that: the organic copper is an organic copper polymer, has the characteristic that copper can be uniformly dispersed in a synthetic high molecular material, improves the melting temperature and the heat-resisting temperature of the antibacterial agent by introducing a dibasic acid and a dihydric phenol structure, avoids the decomposition and migration of the antibacterial agent in the high-temperature processing and using processes, has a similar structure in the antibacterial agent organic structure and the synthetic high molecular material matrix, greatly improves the compatibility with the dispersed matrix, realizes the dispersion, migration and other problems of antibacterial powder in the synthetic high molecular material, and has broad-spectrum antibacterial activity and good antibacterial performance, and has good application prospect for antibacterial modification of the synthetic high molecular material.
Drawings
FIG. 1 is a scanning electron microscope image of the distribution of copper element in the copper polyterephthalate antibacterial polyester fiber of the invention.
FIG. 2 is a scanning electron microscope image of the distribution of copper element in the poly-p-phenylene dioxygen copper antibacterial polyester fiber of the present invention.
FIG. 3 is a scanning electron microscope image of the distribution of copper element in the copper adipate antibacterial polyethylene of the present invention.
FIG. 4 is a scanning electron microscope image of the distribution of copper element in the copper suberate antibacterial styrene butadiene rubber of the present invention.
Detailed Description
The present invention will be further described with reference to the following examples.
Example 1:
this example describes the preparation and application of copper polyterephthalate as an antimicrobial agent, with the specific structural formula (1):
the preparation process of the copper polyterephthalate comprises the following steps: in a 500mL beaker, 10g of terephthalic acid and 200mL of distilled water were added, a 10% NaOH solution was slowly added dropwise with stirring until the pH of the reaction solution became 8, 2g of sodium benzoate was added and stirred until completely dissolved, and finally 1: 1 equivalent of CuSO4And (3) reacting the solution until a precipitate is completely generated, pouring supernate, washing to obtain a final product, wherein the yield is 92%, and the decomposition temperature of the copper polyterephthalate is 315 ℃ measured by a thermogravimetric method.
The preparation process of the copper polyterephthalate master batch comprises the following steps: firstly, uniformly mixing 20 parts of copper polyterephthalate antibacterial agent and 80 parts of polyester resin, heating and reacting for 30min, cooling and grinding into powder to obtain the antibacterial agent master batch, wherein the content of copper element is measured to be 4.8%.
The preparation process of the copper polyterephthalate antibacterial polyester fiber comprises the following steps: 1 part of the copper terephthalate antibacterial agent master batch and 19 parts of the polyester fiber raw material are taken, and the antibacterial polyester fiber is prepared by melt mixing of the organic copper polymer antibacterial agent master batch and the polyester fiber raw material melt, melt spinning, circular air blowing cooling, bundling oiling, drafting and winding. The melt spinning process comprises the following steps: the spinning temperature is 275 ℃, the air speed of the circular blowing is 0.4m/min, the temperature of the circular blowing is 23 ℃, the humidity of the circular blowing is 35RH percent, the drafting multiple of the POY is 1.5 times, the spinning speed of the POY is 2800m/min, the drafting multiple of the FDY is 3.0 times, and the spinning speed is 4000 m/min.
The content of copper element in the poly-p-copper terephthalate antibacterial polyester fiber obtained in this example is 0.24% through detection, the distribution result of copper element in the fiber section measured by a scanning electron microscope is shown in fig. 1, the purple spots are copper element in the polyester fiber, and the test result shows that the copper element is uniformly dispersed in the polyester fiber. According to the GB15979-2002 standard, a film culture method is adopted for testing, escherichia coli, staphylococcus aureus and candida albicans are used as tested strains, and the antibacterial test result of the copper polyterephthalate antibacterial polyester fibers in the table 1 shows that the bacteriostasis rate is over 99.95 percent, and the copper polyterephthalate has good antibacterial activity on gram-positive bacteria, gram-negative bacteria and fungi.
TABLE 1 results of the antibacterial testing of the antibacterial polyester fibers of copper polyterephthalate
Example 2:
the preparation method and application method of the poly (p-phenylene dioxycopper) antibacterial agent described in this example have a specific structural formula (2):
the preparation process of the poly-p-phenylene dioxy copper comprises the following steps: in a 500mL beaker, 10g of hydroquinone and 200mL of distilled water were added, a 10% NaOH solution was slowly added dropwise with stirring until the pH of the reaction solution became 8, 1.8g of phenol was added thereto with stirring until complete dissolution, and finally 1: 1 equivalent of CuSO4And (3) reacting the solution until a precipitate is completely generated, pouring supernate and washing to obtain a final product, wherein the yield is 98%, and the decomposition temperature of the poly (p-phenylene dioxycopper) is 332 ℃ measured by a thermogravimetric analysis.
The preparation process of the poly-p-phenylene dioxy copper master batch comprises the following steps: firstly, uniformly mixing 20 parts of poly-p-phenylene dioxycopper antibacterial agent and 80 parts of polyester resin, heating and reacting for 30min, cooling and grinding into powder to obtain the antibacterial master batch, wherein the content of copper element is 5.9%.
The preparation process of the poly-p-phenylene dioxy copper antibacterial polyester fiber comprises the following steps: 1 part of poly-p-phenylene copper dioxide antibacterial agent master batch and 19 parts of polyester fiber raw material are taken, and the antibacterial polyester fiber is prepared by melt mixing of the organic copper polymer antibacterial agent master batch and the polyester fiber raw material melt, melt spinning, circular air blowing cooling, bundling oiling, drafting and winding. The melt spinning process comprises the steps of spinning at 285 ℃, circulating air blowing at a speed of 0.5m/min, circulating air blowing at a temperature of 25 ℃, circulating air blowing at a humidity of 45 RH%, drafting multiple of POY (polyester pre-oriented yarn) of 2.0 times, spinning at a speed of 3500m/min of POY, drafting multiple of FDY of 4.5 times and spinning at a speed of 4800 m/min.
The content of copper element in the poly-p-phenylene dioxygen copper antibacterial polyester fiber obtained in the embodiment is 0.28% through detection, the distribution result of the copper element in the fiber section measured by a scanning electron microscope is shown in fig. 2, the purple spots are the copper element in the polyester fiber, and the test result shows that the copper element is uniformly dispersed in the polyester fiber. According to the GB15979-2002 standard, a film culture method is adopted for testing, escherichia coli, staphylococcus aureus and candida albicans are used as tested strains, and the antibacterial test results of the poly-p-phenylene dioxygen antibacterial polyester fibers in the table 2 show that the antibacterial rate is over 99.95 percent, and the poly-p-phenylene dioxygen has good antibacterial activity on gram-positive bacteria, gram-negative bacteria and fungi.
TABLE 2 antibacterial test results for poly (p-phenylene dioxy copper) antibacterial polyester fiber
Example 3:
the preparation method and application method of the copper adipate antibacterial agent described in this example have a specific structural formula (3):
the preparation process of the copper polyhexamate comprises the following steps: 10g of adipic acid and 200mL of distilled water were added to a 500mL beaker, a 10% NaOH solution was slowly added dropwise with stirring until the pH of the reaction solution became 8, 1.5g of sodium butyrate was added thereto and stirred until the solution was completely dissolved, and finally 1: 1 equivalent of CuSO was added4And (3) reacting the solution until a precipitate is completely generated, pouring supernate, washing to obtain a final product, wherein the yield is 98%, and the decomposition temperature of the copper adipate is 226 ℃ measured by a thermal weight loss method.
The preparation process of the poly copper adipate master batch comprises the following steps: firstly, uniformly mixing 20 parts of copper adipate antibacterial agent and 80 parts of polyethylene wax, heating for reaction for 30min, cooling, grinding into powder to obtain the antibacterial agent master batch, and measuring the content of copper element to be 5.7%.
The preparation process of the copper adipate antibacterial polyethylene comprises the following steps: 1 part of the poly copper adipate antibacterial agent master batch and 19 parts of polyethylene raw materials are taken, and the organic copper antibacterial polyethylene sheet is obtained through double-screw melt injection molding, wherein the injection molding temperature is controlled at 190-210 ℃.
The copper adipate antibacterial polyethylene obtained in the example is detected to have a copper content of 0.28%, and the distribution result of copper elements in the polyethylene section measured by a scanning electron microscope is shown in fig. 3, and the purple spots are copper elements in the polyethylene, and the test result shows that the copper elements are uniformly dispersed in the polyethylene. According to the GB15979-2002 standard, a film culture method is adopted for testing, escherichia coli, staphylococcus aureus and candida albicans are used as tested strains, and the test results of the copper adipate antibacterial polyethylene in the table 3 show that the antibacterial rate is over 99.95 percent, and the copper adipate has good antibacterial activity on gram-positive bacteria, gram-negative bacteria and fungi.
TABLE 3 antibacterial test results for copper polyhexamate antibacterial polyethylene
Example 4:
the preparation and application of the copper suberate antibacterial agent described in this example are shown in the following formula (4)
The preparation process of the copper suberate is as follows: adding 10g suberic acid and 200mL distilled water into 500mL beaker, slowly adding 10% NaOH solution dropwise under stirring until pH of reaction solution is 8, adding 1.2g sodium propionate, stirring until completely dissolving, and adding 1: 1 equivalent of CuSO4Reacting the solution until a precipitate is completely generated, pouring supernate, and washing to obtain a final product with the yield of 95 percent, and the decomposition temperature of the copper octanedioate is 232 ℃ measured by a thermal weight loss method.
The preparation process of the copper suberate antibacterial master batch comprises the following steps: firstly, uniformly mixing 20 parts of copper octanedioate antibacterial agent and 80 parts of polyethylene wax, heating and reacting for 30min, cooling, and grinding into powder to obtain the antibacterial agent master batch, wherein the content of copper element is 5.2%.
The preparation process of the copper suberate antibacterial styrene butadiene rubber comprises the following steps: 1 part of the copper octanedioate antibacterial master batch and 19 parts of styrene butadiene rubber raw material are taken, and an organic copper antibacterial styrene butadiene rubber sheet is obtained through mixing, wherein the mixing temperature is controlled at 110-130 ℃.
The copper suberate antibacterial styrene butadiene rubber obtained in the example is detected to have a copper element content of 0.25% in the styrene butadiene rubber, the distribution result of the copper element in the cross section of the styrene butadiene rubber measured by a scanning electron microscope is shown in fig. 4, the purple spots are the copper element in the styrene butadiene rubber, and the test result shows that the copper element is uniformly dispersed in the styrene butadiene rubber. According to GB15979-2002 standard, a film culture method is adopted for testing, escherichia coli, staphylococcus aureus and candida albicans are used as tested strains, and the antibacterial test result of the copper suberate antibacterial styrene butadiene rubber in the table 4 shows that the bacteriostasis rate is over 99.95 percent, and the copper suberate has good antibacterial activity on gram-positive bacteria, gram-negative bacteria and fungi.
TABLE 4 results of antibacterial testing of copper octanedioate antibacterial styrene butadiene rubber
Claims (11)
1. Use of an organocopper of formula I, wherein R1、R2And R3Are respectively C1～C30Is straight or branched alkyl or is C3～C30Is cycloalkyl or is C6～C30Any one of aryl groups of (1), and R1、R2And R3The polymerization degrees are the same or different, and n is 1-10000, and the method is characterized in that the compound is used for preparing high-molecular compound with antibacterial functionUse of polyolefin resin or synthetic rubber or synthetic fibre as sub-material
2. Use of an organocopper according to claim 1, characterized in that said R is1、R2And R3 isC1～C20Straight or branched alkyl of (2), C3～C20Cycloalkyl or C6～C20Any of the aryl groups of (1).
3. The use of an organocopper according to claim 2, characterized in that said organocopper is any one of the following compounds: copper polyterephthalate, copper poly-2-methyl terephthalate, copper polysuccinate, copper polypentanedioate, copper polyhexamate, copper polyheptate, copper suberate, copper polymaleate.
4. Use of an organocopper of formula II, wherein R4、R5And R6Are respectively C6～C30Any one of aryl groups of (1), and R4、R5And R6The same or different, the degree of polymerization n is 1-10000, and the application of the compound in preparing high molecular material polyolefin resin or synthetic rubber or synthetic fiber with antibacterial function
5. Use of an organocopper according to claim 4, characterized in that R4、R5And R6Are respectively C6～C20Any of the aryl groups of (1).
6. Use of organocopper according to claim 5, characterized in that the organocopper is any one of the following compounds: poly (p-phenylene dioxycopper), poly (2-methyl-p-phenylene dioxycopper), poly (2-tert-butyl-p-phenylene dioxycopper), poly (2-amino-p-phenylene dioxycopper), poly (2-chloro-p-phenylene dioxycopper), poly (2-ethyl-p-phenylene dioxycopper), poly (2-tert-butyl-p-phenylene dioxycopper), poly (2-amino-p-phenylene dioxycopper), poly (2-chloro-p-phenylene dioxycopper), and poly (2-methyl-4-butyl-p-phenylene dioxycopper).
7. The method for preparing the antibacterial master batch by using the organic copper shown in the formula I is characterized by uniformly mixing 5-30 parts of organic copper and 70-95 parts of polyethylene wax, heating for reaction for 30min, cooling, and grinding into powder to obtain the antibacterial master batch, wherein the parts are parts by mass.
8. The method for preparing the antibacterial master batch by using the organic copper shown in the formula II is characterized by uniformly mixing 5-30 parts of organic copper and 70-95 parts of polyester resin, heating and reacting for 30min, cooling, and grinding into powder to obtain the antibacterial master batch, wherein the parts are parts by mass.
9. The method for preparing the antibacterial polyethylene from the organic copper antibacterial masterbatch of claim 7 is characterized in that 1-5 parts of the organic copper antibacterial masterbatch and 15-20 parts of polyethylene raw materials are subjected to melting and banburying to obtain the organic copper antibacterial polyethylene, wherein the melting and banburying temperature is controlled to be 190-210 ℃, and the parts are in parts by mass.
10. The method for preparing the antibacterial styrene-butadiene rubber by using the organic copper antibacterial master batch as claimed in claim 7 is characterized in that 1-5 parts of the organic copper antibacterial master batch and 15-20 parts of styrene-butadiene rubber raw material are subjected to banburying to obtain an organic copper antibacterial styrene-butadiene rubber sheet, wherein the banburying temperature is controlled at 110-130 ℃, and the parts are parts by mass.
11. The method for preparing the antibacterial polyester fiber from the master batch according to claim 8 is characterized in that 1-5 parts by mass of the organic copper antibacterial agent master batch and 15-20 parts by mass of the polyester fiber raw material are subjected to melt mixing of the organic copper polymer antibacterial agent master batch and the polyester fiber raw material, and then the antibacterial polyester fiber is prepared by melt spinning, circular blowing cooling, cluster oiling and drafting winding.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111426758.8A CN114163781B (en) | 2021-11-27 | 2021-11-27 | Application and preparation method of organic copper |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111426758.8A CN114163781B (en) | 2021-11-27 | 2021-11-27 | Application and preparation method of organic copper |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN114163781A true CN114163781A (en) | 2022-03-11 |
| CN114163781B CN114163781B (en) | 2023-07-14 |
Family
ID=80481270
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202111426758.8A Active CN114163781B (en) | 2021-11-27 | 2021-11-27 | Application and preparation method of organic copper |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN114163781B (en) |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH09176495A (en) * | 1995-12-28 | 1997-07-08 | Furukawa Electric Co Ltd:The | Outdoor insulating polymer material composition and outdoor high voltage instrument |
| JP2004161632A (en) * | 2002-11-11 | 2004-06-10 | Daiwa Fine Chemicals Co Ltd (Laboratory) | Antibacterial, bactericidal or antifungal silver colloid composition and product utilizing the composition |
| US20090269379A1 (en) * | 2005-10-12 | 2009-10-29 | Heinz Herbst | Material Having Antibacterial and Antifungal Properties |
| CN109836622A (en) * | 2017-11-28 | 2019-06-04 | 中国科学院化学研究所 | A kind of organic-inorganic hybrid nanometer anti-biotic material and its preparation method and application |
| CN111393713A (en) * | 2019-11-25 | 2020-07-10 | 浙江工业大学 | Preparation method and application of inorganic-organic composite antibacterial agent |
| CN111793155A (en) * | 2019-04-08 | 2020-10-20 | 中国石油化工股份有限公司 | Antibacterial high polymer material and preparation method and application thereof |
-
2021
- 2021-11-27 CN CN202111426758.8A patent/CN114163781B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH09176495A (en) * | 1995-12-28 | 1997-07-08 | Furukawa Electric Co Ltd:The | Outdoor insulating polymer material composition and outdoor high voltage instrument |
| JP2004161632A (en) * | 2002-11-11 | 2004-06-10 | Daiwa Fine Chemicals Co Ltd (Laboratory) | Antibacterial, bactericidal or antifungal silver colloid composition and product utilizing the composition |
| US20090269379A1 (en) * | 2005-10-12 | 2009-10-29 | Heinz Herbst | Material Having Antibacterial and Antifungal Properties |
| CN109836622A (en) * | 2017-11-28 | 2019-06-04 | 中国科学院化学研究所 | A kind of organic-inorganic hybrid nanometer anti-biotic material and its preparation method and application |
| CN111793155A (en) * | 2019-04-08 | 2020-10-20 | 中国石油化工股份有限公司 | Antibacterial high polymer material and preparation method and application thereof |
| CN111393713A (en) * | 2019-11-25 | 2020-07-10 | 浙江工业大学 | Preparation method and application of inorganic-organic composite antibacterial agent |
Non-Patent Citations (1)
| Title |
|---|
| SEEMA CHITLANGIA1等: "ANTIBACTERIAL AND ANTIFUNGAL STUDY ON NOVEL Ag(I) -15C5 COMPLEXES", 《EUROPEAN JOURNAL OF BIOMEDICAL AND PHARMACEUTICAL SCIENCES》 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN114163781B (en) | 2023-07-14 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN104963028B (en) | Antibacterial polyester fibers and preparation method for same | |
| CN112323173B (en) | Organic copper antibacterial polyester fiber and preparation method thereof | |
| CN111548607B (en) | Preparation method of antibacterial color master batch and stock solution colored PET antibacterial functional fiber | |
| Teli et al. | Polyester nanocomposite fibers with antibacterial properties | |
| CN112574510A (en) | Antibacterial ultraviolet aging resistant modified PP composite material and preparation method thereof | |
| CN102719929A (en) | Method for preparing functional polyamide fiber | |
| CN114672894A (en) | Antibacterial polyamide yarn and preparation process thereof | |
| CN113321868A (en) | White copper-based antibacterial master batch for fibers and preparation method thereof | |
| Magesh et al. | Effect of biopolymer blend matrix on structural, optical and biological properties of chitosan–agar blend ZnO nanocomposites | |
| CN109183181A (en) | A kind of graphene conductive polyester fiber with antibiotic effect | |
| CN104073911A (en) | Preparation method for nano silver antibacterial polyester | |
| CN113577027A (en) | Reinforced preparation method of polymer-stabilized inorganic antibacterial nanoparticles | |
| CN114163781A (en) | Application and preparation method of organic copper | |
| CN114149660B (en) | Application and preparation method of organic zinc | |
| CN101519516A (en) | Nano modified polyvinyl chloride composite material | |
| CN116809022A (en) | Preparation method and application of copper-particle-loaded magnetic porous carbon sphere with catalysis and bacteriostasis functions | |
| CN113929997B (en) | Environment-friendly inorganic composite nano antibacterial and mildew-proof polymer master batch and preparation method and application thereof | |
| CN1235231C (en) | Process for preparing light-colour electrically conductive Sb-dopped SnO2 powder | |
| CN114853054B (en) | Preparation method, product and application of silver-doped zinc oxide antibacterial and antiviral nano powder | |
| CN114395221B (en) | Quaternary blending degradable intercalation antibacterial high-permeability preservative film and preparation method thereof | |
| CN114044959A (en) | Application and preparation method of organic silver | |
| CN109097856B (en) | Copper-based antibacterial master batch and preparation method thereof | |
| TW202146553A (en) | Masterbatch, resin composition, molded article, and manufacturing methods thereof | |
| CN111549392B (en) | Preparation method of antibacterial polyphenylene sulfide fiber | |
| KR101824189B1 (en) | Manufacturing method of hydrate of zinc carboxylate, hydrate of zinc carboxylate manufactured therefrom and material for antimicrobial plastic comprising the hydrate of zinc carboxylate |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |