CN109181056A - Antibacterial fresh-keeping film and preparation method thereof - Google Patents
Antibacterial fresh-keeping film and preparation method thereof Download PDFInfo
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- CN109181056A CN109181056A CN201810830811.2A CN201810830811A CN109181056A CN 109181056 A CN109181056 A CN 109181056A CN 201810830811 A CN201810830811 A CN 201810830811A CN 109181056 A CN109181056 A CN 109181056A
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- 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
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- 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
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- 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
- C08J2467/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
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Abstract
The present invention relates to a kind of antibacterial fresh-keeping films and preparation method thereof, the preparation liquid containing metal-modified dissaving polymer are stirred, antibacterial fresh-keeping film is made in vacuum outgas and drying.It is evenly dispersed in antibacterial fresh-keeping film obtained to have metal-modified dissaving polymer；Metal-modified dissaving polymer is the carboxylic dissaving polymer of end group and the network polymer that metal ion crosslinked is formed, and with insoluble insoluble characteristic, does not dissolve in most of organic solvents at 80 DEG C or less, does not melt in room temperature to T range, T >=370 DEG C；Crosslinking is to pass through ion key connection realization by acid ion Yu metal ion that coordination is keyed the carboxylic hyperbranched polymer molecule end of end group simultaneously with metal ion by the oxygen atom in the double bond inside the carboxylic hyperbranched polymer molecule of end group.Preparation method of the invention is simple, can add further amounts of metal-modified dissaving polymer compared to the prior art；Product anti-microbial property and good mechanical property is made.
Description
Technical field
The present invention relates to preservative film material field, it is related to a kind of antibacterial fresh-keeping film and preparation method thereof.
Background technique
Preservative film is a kind of plastic packing product, is usually made, is mainly used for micro- by polymerization reaction using ethylene as master batch
The occasions such as the heating of wave furnace food, refrigerator food save, fresh and prepared food packaging, family life, supermarket sales field, hotel and
Industrial food packaging applications are all widely used.Different according to material therefor and addition plasticiser, preservative film is divided into more
Seed type is applicable to different occasions.
When using fresh food such as preservative film packaging veterinary antibiotics, since package interior air circulation is poor, ambient humidity
Greatly, the microbial growth of package interior is easily caused, and packaged fruits and vegetables are still a biologic artifact, are carried out
The metabolic activities such as respiration are influenced easily to occur to rot by microorganism.
Type of preservative film at present on the market is various, and the preservative film of various materials is complete, but quality is irregular,
PVC fresh-preserving film is also still sold in the supermarket even having, PVC fresh-preserving film has carcinogenesis, can give the health band of user
It greatly endangers, has been command by and forbids.In addition, not only quality is bad for existing preservative film, easily torn in shreds by external force, Er Qiekang
Bacterium performance is general, and fresh-keeping timeliness is shorter, still has greater room for improvement.
Therefore, studying antimicrobial preservative film that a kind of anti-microbial property is excellent and mechanical property is good and preparation method thereof has very
Important meaning.
Summary of the invention
Present invention aim to address the bad problems of above-mentioned mechanical property existing in the prior art and anti-microbial property, mention
The antimicrobial preservative film and preparation method thereof excellent and good mechanical property for a kind of anti-microbial property.
In order to achieve the above object, the technical solution adopted by the present invention are as follows:
Antibacterial fresh-keeping film, it is evenly dispersed in antibacterial fresh-keeping film to have metal-modified dissaving polymer；
Metal-modified dissaving polymer is the carboxylic dissaving polymer of end group and the net that metal ion crosslinked is formed
Network polymer does not dissolve in organic solvent I at 80 DEG C or less, does not melt in room temperature to T range with insoluble insoluble characteristic
Melting, T >=370 DEG C, the fusing point of metal-modified dissaving polymer of the invention is higher than the melting temperature of most polymer,
It will not be melted when being blended with polymer melting, because blend machine-shaping is difficult without caused by；
The crosslinking is by the oxygen atom and metal in the double bond inside the carboxylic hyperbranched polymer molecule of end group
Ion is logical by the acid ion and metal ion of coordination key connection while the carboxylic hyperbranched polymer molecule end of end group
Cross what ion key connection was realized；
Metal ion may load on dissaving polymer in two forms:
A, dissaving polymer swelling after ,-the COOH of spherical surface and/orDissociation removes H+, with metal ion with
Ionic bond is linked, and is shown below:
Oxygen on b, carbonyl or phosphorus oxygen key is connected with metal ion with coordinate bond, is shown below:
Both the above mode exists, and usually, coordinate bond is bigger to insoluble contribution；
The organic solvent I is aromatic hydrocarbon solvent, fat hydrocarbon solvent, alicyclic hydrocarbon type solvent, halogenated hydrocarbon solvent, alcohol
Class solvent, esters solvent, ketones solvent, acetonitrile, pyridine, phenol, n,N-Dimethylformamide or n,N-dimethylacetamide, this
The metal-modified dissaving polymer of invention does not dissolve in most organic solvents, be only herein simply enumerate it is some commonly use it is molten
Agent.
As a preferred technical scheme:
It is thin according to standard GB1040.3-200 to measure anti-bacterial refreshing using tensilon for antibacterial fresh-keeping film as described above
The longitudinal tensile strength of film is 4.4~4.9N/25cm, and transverse tensile strength is 2.1~2.5N/25cm, lengthwise elongation at break
It is 328~340%, transverse breakage elongation percentage is 376~397%, thin with anti-bacterial refreshing using antibacterial fresh-keeping film as test specimen
It is contrast sample that unique difference of film, which is free from the sample of metal-modified dissaving polymer, in identical test condition
Lower carry out anti-microbial property test selects Escherichia coli and staphylococcus aureus to be coated in test specimen and contrast sample respectively
On, it is cultivated two days at a temperature of 37 DEG C, bacterial growth situation is observed daily, and carry out bacterium colony counting, as a result, it has been found that contrast sample
It is paved with sample in second day bacterium colony, test specimen did not observed bacterium colony at second day.The mechanics of antibacterial fresh-keeping film of the invention
Performance and excellent antibacterial performance.
Antibacterial fresh-keeping film as described above, the aromatic hydrocarbon solvent are benzene,toluene,xylene, styrene, butyl first
Benzene or vinyltoluene；The fat hydrocarbon solvent is n-hexane, pentane, hexane or octane；The alicyclic hydrocarbon type solvent is ring
Hexane, cyclohexanone or toluene cyclohexanone；The halogenated hydrocarbon solvent be chlorobenzene, dichloro-benzenes, methylene chloride, chloroform, carbon tetrachloride,
Trichloro ethylene, tetrachloro-ethylene, trichloropropane or dichloroethanes；The alcohols solvent is methanol, ethyl alcohol, isopropanol, n-butanol, ring
Hexanol, benzyl alcohol, ethylene glycol or propylene glycol；The esters solvent is methyl acetate, ethyl acetate or propyl acetate；The ketone
Solvent is acetone, espeleton, methylisobutylketone, cyclohexanone or toluene cyclohexanone；
The aerial initial decomposition temperature of metal-modified dissaving polymer is 300~400 DEG C, and the metal changes
Property dissaving polymer partial size be 150~500nm.
Antibacterial fresh-keeping film as described above, the quantity of carboxyl accounts for end group in the carboxylic dissaving polymer of end group
The 25%~100% of total amount, the content of carboxyl depends on the degree of branching of the carboxylic dissaving polymer of end group, described hyperbranched
The end group of polymer is carboxyl, or also containing other groups such as hydroxyls；Carboxyl-content is too low to will lead to the network being cross-linked to form
The crosslinking points of polymer are very few, and spatial network is not sufficiently stable, and cannot form insoluble insoluble property；The end group is carboxylic super
Contain ester group in the molecule of branched polymer, the degree of branching of the carboxylic dissaving polymer of end group is 30~100%, institute
The weight average molecular weight for stating the carboxylic dissaving polymer of end group is 1100~50000g/mol.The carboxylic hyperbranched poly of end group
The degree of branching for closing object is higher, and the dissaving polymer of formation more levels off to dendritic, i.e., symmetry with higher,
In subsequent reaction, the space structure of formation is more stable, while the degree of branching of dissaving polymer is higher, and molecular weight is got over
Greatly, biggish molecular weight is meant to react with more metal ions.
Antibacterial fresh-keeping film as described above, the metal ion are Co2+、Ni2+、Cu2+Or Zn2+, the metal ion by
Its corresponding mol ratio of metal acetate provides, in the metal-modified dissaving polymer content of metal ion be 5.5~
12.5wt%.The too low functionality that will lead to metal-modified dissaving polymer obtained of metal ion content is poor, and can be right
Its insoluble insoluble characteristic impacts.
Antibacterial fresh-keeping film as described above, the preparation step of the metal-modified dissaving polymer are as follows:
(1) the carboxylic dissaving polymer of end group and mol ratio of metal acetate are dissolved in organic solvent II and deionization respectively
The carboxylic dissaving polymer solution of the end group that concentration is 0.7~1.25mol/L is obtained in water and concentration be 0.7~
The metal ion solution of 1.25mol/L, the organic solvent II are chloroform, acetone or n,N-Dimethylformamide；
(2) under the conditions of stirring and sonic oscillation, metal ion solution is added drop-wise to the carboxylic hyperbranched polymerization of end group
Reacted in object solution, after metal ion solution is added dropwise in the carboxylic dissaving polymer solution of end group, can rapidly with
The end group of dissaving structure is reacted, and metal ion is only capable of reacting with end group in the case where no sonic oscillation, i.e., most
End form at metal-modified dissaving polymer only surface layer have a circle metal be coordinated insoluble not crucible zone, inside be not coordinated；It is described
Stirring is mechanical stirring or magnetic agitation, and the rate of stirring is 200~500rpm, mixing speed determine to be formed it is metal-modified
The power of the size of dissaving polymer, sonic oscillation is 600~1200W, and the power of sonic oscillation is higher, and obtained metal changes
Property hyperbranched polymer structure it is more uniform, too low power will lead to resulting metal-modified dissaving polymer only surface layer be coordinated
Metal ion, inside are not coordinated；The speed of the dropwise addition is 0.5~2 drop/sec, and the volume of every drop is 0.05~0.1mL, is added dropwise
After in reaction system the molar ratio of the carboxylic dissaving polymer of end group and metal ion be 1:0.64~46.69；Gold
The additive amount for belonging to ion too low cannot form enough coordination structures to will lead to the metal-modified dissaving polymer to be formed insoluble
Insoluble property is impacted；
(3) mixed liquor after reaction is post-processed to obtain metal-modified dissaving polymer, the post-processing
Refer to and be filtered, washed and dried, the drying carries out under vacuum conditions, and vacuum degree is -0.1MPa, drying time 8
~12h, drying temperature are 25 DEG C.
Metal acetate salting liquid be added dropwise the carboxylic dissaving polymer solution of inlet side base in after, metal ion simultaneously by
Mol ratio of metal acetate ionizes the electrostatic attraction of the electrostatic attraction for the acetate ion to be formed and the carboxyl end group of dissaving polymer
Power, due to both electrostatic attractions approximation, metal ion will not rapidly by the carboxyl total overall reaction on dissaving polymer surface,
Metal ion is slow release in the whole process, can be deep into the inside of hyperbranched polymer molecule, with hyperbranched poly
The oxygen atom closed in the double bond inside object establishes more stable coordinate bond, the metal-modified dissaving polymer tool because prepared by
There is insoluble insoluble characteristic.
Antibacterial fresh-keeping film as described above, the carboxylic dissaving polymer of end group are to utilize A2+B3Synthesize legal system
?；
The A2Title and its corresponding structural formula it is as follows:
Pyrazine -2,3- dicarboxylic acids 2- carboxyethyl phenyl phosphinic acid 5- tert-butyl -1,3- benzene dicarboxylic acid 2- carboxyethyl phosphoric acid
The B3Title and its corresponding structural formula it is as follows:
1,1,1- tri- (methylol) propane three (2- ethoxy) chlorinated isocyanurates 2,4,5- trihydroxy benzene fourth
Ketone
The present invention also provides a kind of methods for preparing antibacterial fresh-keeping film as described above, will contain metal-modified hyperbranched poly
The preparation liquid of conjunction object is stirred, antibacterial fresh-keeping film is made in vacuum outgas and drying.
As a preferred technical scheme:
Method as described above, the preparation liquid are by by polyethylene, metal-modified dissaving polymer, anhydrous second
It is added made from hindered amine light stabilizer, acetic acid and antioxidant after alcohol, glycerol and deionized water mixing, stirring and standing.
Method as described above, the content of each component is respectively as follows: 25~45wt% of polyethylene in the preparation liquid, metal changes
3~10wt% of property dissaving polymer, 1~6wt% of glycerol, 1~5wt% of hindered amine light stabilizer, 1~5wt% of dehydrated alcohol,
1~3wt% of acetic acid, 0.5~1wt% of antioxidant, deionized water surplus；
The time of the drying is 6~12 hours, and temperature is room temperature, and pressure is -0.1MPa, the hindered amine light stabilizer
For benzoic acid (2,2,6,6- tetramethyl -4- hydroxy piperidine) ester, bis- (2,2,6,6- tetramethyl -4- hydroxy piperidine) esters of decanedioic acid,
Nitrogen base three [acetic acid (2,2,6,6- tetramethyl -4- hydroxy piperidine) ester] or N, N '-bis- (2,2,6,6- tetramethyl-piperidyls) oneself two
Amine, the antioxidant are [β-(3,5 di-t-butyl 4- hydroxy-pheny) propionic acid] pentaerythritol ester or β-(3,5- di-t-butyls-
4- hydroxy phenyl) propionic acid octadecyl ester.
Invention mechanism:
After metal salt ionizes in aqueous solution, there is interactions for interionic, and cation is by anion around it
Electrostatic attraction, the anion also electrostatic attraction by surrounding cation.Ion by with xenogenesis charge from
It, will also be by the mutual expelling force of the ion with like charges while sub mutually attraction.Therefore, the behavior of ion in the solution is not
Be it is entirely free on his, metal ion solution concentration is bigger, and interionic interaction force is stronger.And end group is carboxylic hyperbranched
Polymer can be swollen in organic solvent II, when metal ion solution is slowly dropped to the carboxylic hyperbranched poly of end group
When in polymer solution, metal ion may be loaded in two forms on the carboxylic dissaving polymer of end group: (1) after being swollen
The carboxylic dissaving polymer surface of end group-COOH and/orH can be dissociated+,-COO-And/orWith
Metal ion is keyed by ion；(2) carbonyl and/or phosphorus oxygen double bond inside the carboxylic hyperbranched polymer structure of end group
On oxygen and metal ion by coordination key connection.
After metal acetate salting liquid is added drop-wise to the carboxylic dissaving polymer solution of end group by the present invention, due to acetate
The electrostatic attraction of ion pair metal ion is approximate with carboxyl, therefore metal ion will not be carboxylic by the end group of swelling rapidly
The carboxyl total overall reaction on dissaving polymer surface, forming one " outer close interior thin ", (i.e. surface engagement is intensive, and internal engagement is dilute
Dredge) structure, under the conditions of sonic oscillation, a part of metal ion can be from the end being keyed with metal ion by ion
The gap on the carboxylic dissaving polymer surface of base enters the internal junction of the carboxylic dissaving polymer of end group after swelling
In structure, and with inside the carboxylic hyperbranched polymer structure of end group phosphorus oxygen double bond or carbonyl it is sufficiently coordination cross-linked, formed equal
Even cross-linked structure avoids general so that metal-modified dissaving polymer obtained has insoluble insoluble property
Electrification complex ion complex is soluble in the defect of organic solvent, solves functional dissaving polymer additive amount when being blended
It is excessively high that difficult problem can be brought to Polymer moulding.
On this basis, metal-modified dissaving polymer obtained is mixed into preparation liquid by the present invention, and antibacterial is made and protects
Fresh film, the content of metal-modified dissaving polymer is adjustable in antibacterial fresh-keeping film, can be metal-modified hyperbranched by controlling
The content of polymer controls the anti-microbial property and mechanical performance of antibacterial fresh-keeping film.The utility model has the advantages that
(1) antibacterial fresh-keeping film of the invention, anti-microbial property and good mechanical performance, great application prospect；
(2) preparation method of antibacterial fresh-keeping film of the invention is mixed into metal-modified dissaving polymer in preparation liquid,
Metal-modified dissaving polymer has the characteristics that being insoluble in common organic solvents and heating does not melt, total with other polymers
Mix working hour can approximation be considered as inorganic particle, do not lose its it is functional under the premise of, influence to blend rheological property
Small, additive amount of the metal-modified dissaving polymer in preparation liquid is bigger compared with the prior art；
(3) preparation method of antibacterial fresh-keeping film of the invention, simple process and low cost have fabulous promotional value.
Specific embodiment
The invention will be further elucidated with reference to specific embodiments.It should be understood that these embodiments are merely to illustrate this hair
It is bright rather than limit the scope of the invention.In addition, it should also be understood that, after reading the content taught by the present invention, art technology
Personnel can make various changes or modifications the present invention, and such equivalent forms equally fall within the application the appended claims and limited
Fixed range.
Embodiment 1
The preparation method of antibacterial fresh-keeping film, the specific steps are as follows:
(1) metal-modified dissaving polymer is prepared；
(1.1) A is utilized2+B3The carboxylic dissaving polymer of end group: wherein A is made in synthetic method2For pyrazine -2,3- dicarboxyl
Acid；B3For 1,1,1- tri- (methylol) propane；Contain ester group, carboxylic in the carboxylic hyperbranched polymer molecule of obtained end group
The quantity of base accounts for the 25% of end group total amount, the degree of branching 60%, weight average molecular weight 2000g/mol；
(1.2) the carboxylic dissaving polymer of end group is dissolved in obtained in chloroform concentration be 0.7mol/L end group contain
It is molten to be obtained the metal ion that concentration is 0.8mol/L by the dissaving polymer solution of carboxyl in deionized water for cobalt acetate dissolution
Liquid；
(1.3) under the conditions of the sonic oscillation that mechanical stirring and power that rate is 200rpm are 600W, by metal ion
Solution, which is added drop-wise in the carboxylic dissaving polymer solution of end group, to be reacted, wherein the speed being added dropwise is 0.5 drop/sec, often
The volume of drop is 0.05mL, after completion of dropwise addition in reaction system end group carboxylic dissaving polymer and metal ion mole
Than for 1:30.5；
(1.4) mixed liquor after reaction is filtered, washed and is dried to obtain and is insoluble insoluble metal-modified super
Branched polymer, wherein drying carries out under vacuum conditions, vacuum degree is -0.1MPa, drying time 8h, drying temperature
It is 25 DEG C；
Insoluble insoluble metal-modified dissaving polymer is made, is in the carboxylic hyperbranched polymer molecule of end group
Oxygen atom and Co in C=O double bond2+By coordination key connection simultaneously in the carboxylic hyperbranched polymer molecule of end group-
COO-Ion and Co2+It is keyed the network polymer to be formed by ion, there is insoluble insoluble characteristic, it is insoluble at 80 DEG C or less
In benzene,toluene,xylene, styrene, butyl toluene, vinyltoluene, n-hexane, pentane, hexane, octane, hexamethylene, hexamethylene
Ketone, toluene cyclohexanone, chlorobenzene, dichloro-benzenes, methylene chloride, chloroform, carbon tetrachloride, trichloro ethylene, tetrachloro-ethylene, trichloropropane,
Dichloroethanes, methanol, ethyl alcohol, isopropanol, n-butanol, cyclohexanol, benzyl alcohol, ethylene glycol, propylene glycol, methyl acetate, acetic acid second
Ester, propyl acetate, acetone, espeleton, methylisobutylketone, cyclohexanone, toluene cyclohexanone, acetonitrile, pyridine, phenol, N, N- bis-
Methylformamide and n,N-dimethylacetamide, in room temperature to not melting within the scope of 370 DEG C；Metal-modified dissaving polymer
Partial size is 220~280nm, and aerial initial decomposition temperature is 330 DEG C；Co in metal-modified dissaving polymer2+Contain
Amount is 8.3wt%；
(2) preparation liquid containing metal-modified dissaving polymer is prepared；
By weight, by 25 parts of polyethylene, 5 parts of metal-modified dissaving polymers, 1 part of dehydrated alcohol, 6 parts of glycerol and
1 part of benzoic acid (2,2,6,6- tetramethyl -4- hydroxy piperidine) ester, 1 part of second is added after 60 parts of deionized water mixing, stirring and standings
Preparation liquid is made in acid and 1 part of [β-(3,5 di-t-butyl 4- hydroxy-pheny) propionic acid] pentaerythritol ester；
(3) preparation liquid containing metal-modified dissaving polymer is stirred, vacuum outgas and dry obtained antibacterial are protected
Fresh film, wherein the dry time is 8 hours, temperature is room temperature, and pressure is -0.1MPa.
Tensilon is used to measure the longitudinal tensile strength of antibacterial fresh-keeping film according to standard GB1040.3-200 as 4.4N/
25cm, transverse tensile strength 2.1N/25cm, lengthwise elongation at break 330%, transverse breakage elongation percentage are 380%.This hair
Bright antibacterial fresh-keeping film difference with the prior art obtained is in preparation liquid of the present invention containing metal-modified dissaving polymer,
Using antibacterial fresh-keeping film produced by the present invention as test specimen, by the sample as a comparison of antibacterial fresh-keeping film made from the prior art
Product carry out anti-microbial property test under identical test condition, i.e., select Escherichia coli and staphylococcus aureus respectively
It is coated in test specimen and contrast sample, is cultivated two days at a temperature of 37 DEG C, observe bacterial growth situation daily, and carry out bacterium colony
It counts, the results showed that contrast sample is paved with sample in second day bacterium colony, and test specimen did not observed bacterium colony, therefore this at second day
The anti-microbial property of invention antibacterial fresh-keeping film is substantially better than the prior art, great application prospect.
Embodiment 2
The preparation method of antibacterial fresh-keeping film, the specific steps are as follows:
(1) metal-modified dissaving polymer is prepared；
(1.1) A is utilized2+B3The carboxylic dissaving polymer of end group: wherein A is made in synthetic method2Are as follows: 2- carboxyethyl phenyl
Phosphinic acids；B3Are as follows: three (2- carboxyethyl) chlorinated isocyanurates；Contain in the carboxylic hyperbranched polymer molecule of obtained end group
Ester group, the quantity of carboxyl account for the 27% of end group total amount, the degree of branching 53%, weight average molecular weight 43000g/mol；
(1.2) the carboxylic dissaving polymer dissolution of end group is obtained into the end group that concentration is 0.85mol/L in acetone
Carboxylic dissaving polymer solution, by nickel acetate dissolution obtain in deionized water concentration be 0.95mol/L metal from
Sub- solution；
(1.3) under the conditions of the sonic oscillation that magnetic agitation and power that rate is 300rpm are 900W, by metal ion
Solution, which is added drop-wise in the carboxylic dissaving polymer solution of end group, to be reacted, wherein the speed being added dropwise is 1 drop/sec, every drop
Volume be 0.08mL, after completion of dropwise addition in reaction system end group carboxylic dissaving polymer and metal ion molar ratio
For 1:28.2；
(1.4) mixed liquor after reaction is filtered, washed and is dried to obtain and is insoluble insoluble metal-modified super
Branched polymer, wherein drying carries out under vacuum conditions, vacuum degree is -0.1MPa, drying time 9h, drying temperature
It is 25 DEG C；
Insoluble insoluble metal-modified dissaving polymer is made, is in the carboxylic hyperbranched polymer molecule of end group
C=O double bond and oxygen atom and Ni in P=O double bond2+By coordination key connection, the carboxylic dissaving polymer of end group divides simultaneously
- COO in son-Ion andIon and Ni2+It is keyed the network polymer to be formed by ion, has insoluble insoluble
Characteristic does not dissolve in organic solvent I at 80 DEG C or less, and the specific type and embodiment 1 of organic solvent I are consistent, in room temperature to 375 DEG C
It is not melted in range；The partial size of metal-modified dissaving polymer is 150~300nm, and aerial initial decomposition temperature is
380℃；Ni in metal-modified dissaving polymer2+Content be 10.3wt%；
(2) preparation liquid containing metal-modified dissaving polymer is prepared；
By weight, by 30 parts of polyethylene, 3 parts of metal-modified dissaving polymers, 2 parts of dehydrated alcohols, 5 parts of glycerol and
3 parts of decanedioic acid bis- (2,2,6,6- tetramethyl -4- hydroxy piperidine) esters, 2 parts are added after 54 parts of deionized water mixing, stirring and standings
Preparation liquid is made in acetic acid and 1 part of β-(3,5- di-tert-butyl-hydroxy phenyl) propionic acid octadecyl ester；
(3) preparation liquid containing metal-modified dissaving polymer is stirred, vacuum outgas and dry obtained antibacterial are protected
Fresh film, wherein the dry time is 10 hours, temperature is room temperature, and pressure is -0.1MPa.
Tensilon is used to measure the longitudinal tensile strength of antibacterial fresh-keeping film according to standard GB1040.3-200 as 4.4N/
25cm, transverse tensile strength 2.2N/25cm, lengthwise elongation at break 335%, transverse breakage elongation percentage are 379%.
Embodiment 3
The preparation method of antibacterial fresh-keeping film, the specific steps are as follows:
(1) metal-modified dissaving polymer is prepared；
(1.1) A is utilized2+B3The carboxylic dissaving polymer of end group: wherein A is made in synthetic method2Are as follows: tert-butyl -1 5-,
3- benzene dicarboxylic acid；B3Are as follows: 2,4,5- trihydroxybutyrophenone；Contain in the carboxylic hyperbranched polymer molecule of obtained end group
Ester group, the quantity of carboxyl account for the 25% of end group total amount, the degree of branching 30%, weight average molecular weight 15000g/mol；
(1.2) the carboxylic dissaving polymer of end group is dissolved in N,N-dimethylformamide and obtains concentration and is
The carboxylic dissaving polymer solution of the end group of 0.9mol/L, copper acetate dissolution is obtained concentration in deionized water is
The metal ion solution of 1.0mol/L；
(1.3) under the conditions of the sonic oscillation that magnetic agitation and power that rate is 400rpm are 700W, by metal ion
Solution, which is added drop-wise in the carboxylic dissaving polymer solution of end group, to be reacted, wherein the speed being added dropwise is 1 drop/sec, every drop
Volume be 0.06mL, after completion of dropwise addition in reaction system end group carboxylic dissaving polymer and metal ion molar ratio
For 1:46.69；
(1.4) mixed liquor after reaction is filtered, washed and is dried to obtain and is insoluble insoluble metal-modified super
Branched polymer, wherein drying carries out under vacuum conditions, vacuum degree is -0.1MPa, drying time 12h, dry temperature
Degree is 25 DEG C；
Insoluble insoluble metal-modified dissaving polymer is made, is in the carboxylic hyperbranched polymer molecule of end group
Oxygen atom and Cu in C=O double bond2+By coordination key connection simultaneously in the carboxylic hyperbranched polymer molecule of end group-
COO-Ion and Cu2+It is keyed the network polymer to be formed by ion, there is insoluble insoluble characteristic, it is insoluble at 80 DEG C or less
In organic solvent I, the specific type and embodiment 1 of organic solvent I are consistent, in room temperature to not melting within the scope of 380 DEG C；Metal changes
Property dissaving polymer partial size be 230~300nm, aerial initial decomposition temperature be 390 DEG C；It is metal-modified hyperbranched
Cu in polymer2+Content be 7.5wt%；
(2) preparation liquid containing metal-modified dissaving polymer is prepared；
By weight, by 30 parts of polyethylene, 6 parts of metal-modified dissaving polymers, 1 part of dehydrated alcohol, 1 part of glycerol and
1 part of [acetic acid (2,2,6,6- tetramethyl -4- hydroxy piperidine) of nitrogen base three is added after 58.5 parts of deionized water mixing, stirring and standings
Ester], 2 parts of acetic acid and 0.5 part of [β-(3,5 di-t-butyl 4- hydroxy-pheny) propionic acid] pentaerythritol ester preparation liquid is made；
(3) preparation liquid containing metal-modified dissaving polymer is stirred, vacuum outgas and dry obtained antibacterial are protected
Fresh film, wherein the dry time is 8 hours, temperature is room temperature, and pressure is -0.1MPa.
Tensilon is used to measure the longitudinal tensile strength of antibacterial fresh-keeping film according to standard GB1040.3-200 as 4.5N/
25cm, transverse tensile strength 2.1N/25cm, lengthwise elongation at break 328%, transverse breakage elongation percentage are 383%.
Embodiment 4
The preparation method of antibacterial fresh-keeping film, the specific steps are as follows:
(1) metal-modified dissaving polymer is prepared；
(1.1) A is utilized2+B3The carboxylic dissaving polymer of end group: wherein A is made in synthetic method2Are as follows: 2- carboxyethyl phosphorus
Acid；B3Are as follows: 2,4,5- trihydroxybutyrophenone；Contain ester group, carboxylic in the carboxylic hyperbranched polymer molecule of obtained end group
The quantity of base accounts for the 100% of end group total amount, the degree of branching 64%, weight average molecular weight 50000g/mol；
(1.2) the carboxylic dissaving polymer of end group is dissolved in the end group for obtaining that concentration is 1.05mol/L in chloroform
Zinc acetate dissolution is obtained the metal ion that concentration is 0.7mol/L by carboxylic dissaving polymer solution in deionized water
Solution；
(1.3) under the conditions of the sonic oscillation that mechanical stirring and power that rate is 500rpm are 1200W, by metal ion
Solution, which is added drop-wise in the carboxylic dissaving polymer solution of end group, to be reacted, wherein the speed being added dropwise is 0.5 drop/sec, often
The volume of drop is 0.09mL, after completion of dropwise addition in reaction system end group carboxylic dissaving polymer and metal ion mole
Than for 1:5.77；
(1.4) mixed liquor after reaction is filtered, washed and is dried to obtain and is insoluble insoluble metal-modified super
Branched polymer, wherein drying carries out under vacuum conditions, vacuum degree is -0.1MPa, drying time 8h, drying temperature
It is 25 DEG C；
Insoluble insoluble metal-modified dissaving polymer is made, is in the carboxylic hyperbranched polymer molecule of end group
C=O double bond and oxygen atom and Zn in P=O double bond2+By coordination key connection, the carboxylic dissaving polymer of end group divides simultaneously
- COO in son-Ion andIon and Zn2+It is keyed the network polymer to be formed by ion, has insoluble insoluble
Characteristic does not dissolve in organic solvent I at 80 DEG C or less, and the specific type and embodiment 1 of organic solvent I are consistent, in room temperature to 380 DEG C
It is not melted in range；The partial size of metal-modified dissaving polymer is 330~500nm, and aerial initial decomposition temperature is
300℃；Zn in metal-modified dissaving polymer2+Content be 9.3wt%；
(2) preparation liquid containing metal-modified dissaving polymer is prepared；
By weight, by 40 parts of polyethylene, 4 parts of metal-modified dissaving polymers, 4 parts of dehydrated alcohols, 2 parts of glycerol and
5 parts of N, bis- (2,2,6,6- tetramethyl-piperidyl) hexamethylene diamines of N '-, 1 part is added after 43.4 parts of deionized water mixing, stirring and standings
Preparation liquid is made in acetic acid and 0.6 part of β-(3,5- di-tert-butyl-hydroxy phenyl) propionic acid octadecyl ester；
(3) preparation liquid containing metal-modified dissaving polymer is stirred, vacuum outgas and dry obtained antibacterial are protected
Fresh film, wherein the dry time is 6 hours, temperature is room temperature, and pressure is -0.1MPa.
Tensilon is used to measure the longitudinal tensile strength of antibacterial fresh-keeping film according to standard GB1040.3-200 as 4.7N/
25cm, transverse tensile strength 2.5N/25cm, lengthwise elongation at break 333%, transverse breakage elongation percentage are 385%.
Embodiment 5
The preparation method of antibacterial fresh-keeping film, the specific steps are as follows:
(1) metal-modified dissaving polymer is prepared；
(1.1) A is utilized2+B3The carboxylic dissaving polymer of end group: wherein A is made in synthetic method2Are as follows: pyrazine -2,3- two
Carboxylic acid；B3: three (2- carboxyethyl) chlorinated isocyanurates；Contain ester in the carboxylic hyperbranched polymer molecule of obtained end group
Base, the quantity of carboxyl account for the 44% of end group total amount, the degree of branching 84%, weight average molecular weight 6000g/mol；
(1.2) the carboxylic dissaving polymer dissolution of end group the end group that concentration is 1.0mol/L is obtained in acetone to contain
Cobalt acetate dissolution is obtained the metal ion that concentration is 1.25mol/L by the dissaving polymer solution of carboxyl in deionized water
Solution；
(1.3) under the conditions of the sonic oscillation that mechanical stirring and power that rate is 500rpm are 1100W, by metal ion
Solution, which is added drop-wise in the carboxylic dissaving polymer solution of end group, to be reacted, wherein the speed being added dropwise is 2 drops/sec, every drop
Volume be 0.1mL, after completion of dropwise addition in reaction system end group carboxylic dissaving polymer and metal ion molar ratio
For 1:0.64；
(1.4) mixed liquor after reaction is filtered, washed and is dried to obtain and is insoluble insoluble metal-modified super
Branched polymer, wherein drying carries out under vacuum conditions, vacuum degree is -0.1MPa, drying time 11h, dry temperature
Degree is 25 DEG C；
Insoluble insoluble metal-modified dissaving polymer is made, is in the carboxylic hyperbranched polymer molecule of end group
Oxygen atom and Co in C=O double bond2+By coordination key connection simultaneously in the carboxylic hyperbranched polymer molecule of end group-
COO-Ion and Co2+It is keyed the network polymer to be formed by ion, there is insoluble insoluble characteristic, it is insoluble at 80 DEG C or less
In organic solvent I, the specific type and embodiment 1 of organic solvent I are consistent, in room temperature to not melting within the scope of 370 DEG C；Metal changes
Property dissaving polymer partial size be 260~350nm, aerial initial decomposition temperature be 375 DEG C；It is metal-modified hyperbranched
Co in polymer2+Content be 6.3wt%；
(2) preparation liquid containing metal-modified dissaving polymer is prepared；
By weight, by 45 parts of polyethylene, 10 parts of metal-modified dissaving polymers, 4 parts of dehydrated alcohols, 5 parts of glycerol
Be added with the mixing of 30.7 parts of deionized waters, stirring and after standing 3 parts of benzoic acid (2,2,6,6- tetramethyl -4- hydroxy piperidine) esters,
Preparation liquid is made in 1.5 parts of acetic acid and 0.8 part of [β-(3,5 di-t-butyl 4- hydroxy-pheny) propionic acid] pentaerythritol ester；
(3) preparation liquid containing metal-modified dissaving polymer is stirred, vacuum outgas and dry obtained antibacterial are protected
Fresh film, wherein the dry time is 11 hours, temperature is room temperature, and pressure is -0.1MPa.
Tensilon is used to measure the longitudinal tensile strength of antibacterial fresh-keeping film according to standard GB1040.3-200 as 4.9N/
25cm, transverse tensile strength 2.4N/25cm, lengthwise elongation at break 328%, transverse breakage elongation percentage are 382%.
Embodiment 6
The preparation method of antibacterial fresh-keeping film, the specific steps are as follows:
(1) metal-modified dissaving polymer is prepared；
(1.1) A is utilized2+B3The carboxylic dissaving polymer of end group: wherein A is made in synthetic method2Are as follows: 2- carboxyethyl phenyl
Phosphinic acids；B3Are as follows: 2,4,5- trihydroxybutyrophenone；Contain ester in the carboxylic hyperbranched polymer molecule of obtained end group
Base, the quantity of carboxyl account for the 45% of end group total amount, the degree of branching 74%, weight average molecular weight 6000g/mol；
(1.2) the carboxylic dissaving polymer of end group is dissolved in obtained in chloroform concentration be 1.1mol/L end group contain
The dissaving polymer solution of carboxyl, it is molten by the metal ion that concentration is 1.15mol/L is obtained in cobalt acetate dissolution deionized water
Liquid；
(1.3) under the conditions of the sonic oscillation that magnetic agitation and power that rate is 300rpm are 1000W, by metal ion
Solution, which is added drop-wise in the carboxylic dissaving polymer solution of end group, to be reacted, wherein the speed being added dropwise is 2 drops/sec, every drop
Volume be 0.1mL, after completion of dropwise addition in reaction system end group carboxylic dissaving polymer and metal ion molar ratio
For 1:33.45；
(1.4) mixed liquor after reaction is filtered, washed and is dried to obtain and is insoluble insoluble metal-modified super
Branched polymer, wherein drying carries out under vacuum conditions, vacuum degree is -0.1MPa, drying time 10h, dry temperature
Degree is 25 DEG C；
Insoluble insoluble metal-modified dissaving polymer is made, is in the carboxylic hyperbranched polymer molecule of end group
C=O double bond and oxygen atom and Co in P=O double bond2+By coordination key connection, the carboxylic dissaving polymer of end group divides simultaneously
- COO in son-Ion andIon and Co2+It is keyed the network polymer to be formed by ion, has insoluble insoluble
Characteristic does not dissolve in organic solvent I at 80 DEG C or less, and the specific type and embodiment 1 of organic solvent I are consistent, in room temperature to 370 DEG C
It is not melted in range；The partial size of metal-modified dissaving polymer is 180~260nm, and aerial initial decomposition temperature is
375℃；Co in metal-modified dissaving polymer2+Content be 5.6wt%；
(2) preparation liquid containing metal-modified dissaving polymer is prepared；
By weight, by 30 parts of polyethylene, 10 parts of metal-modified dissaving polymers, 5 parts of dehydrated alcohols, 3 parts of glycerol
2 parts of [acetic acid (2,2,6,6- tetramethyl -4- hydroxyl piperazines of nitrogen base three are added with after 48.5 parts of deionized water mixing, stirring and standings
Pyridine) ester], 1 part of acetic acid and 0.5 part of β-(3,5- di-tert-butyl-hydroxy phenyl) propionic acid octadecyl ester preparation liquid is made；
(3) preparation liquid containing metal-modified dissaving polymer is stirred, vacuum outgas and dry obtained antibacterial are protected
Fresh film, wherein the dry time is 12 hours, temperature is room temperature, and pressure is -0.1MPa.
Tensilon is used to measure the longitudinal tensile strength of antibacterial fresh-keeping film according to standard GB1040.3-200 as 4.8N/
25cm, transverse tensile strength 2.4N/25cm, lengthwise elongation at break 331%, transverse breakage elongation percentage are 395%.
Embodiment 7
The preparation method of antibacterial fresh-keeping film, the specific steps are as follows:
(1) metal-modified dissaving polymer is prepared；
(1.1) A is utilized2+B3The carboxylic dissaving polymer of end group: wherein A is made in synthetic method2Are as follows: tert-butyl -1 5-,
3- benzene dicarboxylic acid；B3Are as follows: 2,3,4- trihydroxy-acetophenone；Contain in the carboxylic hyperbranched polymer molecule of obtained end group
Ester group, the quantity of carboxyl account for the 37% of end group total amount, the degree of branching 85%, weight average molecular weight 37000g/mol；
(1.2) the carboxylic dissaving polymer of end group is dissolved in N,N-dimethylformamide and obtains concentration and is
The carboxylic dissaving polymer solution of the end group of 1.25mol/L, copper acetate dissolution is obtained concentration in deionized water is
The metal ion solution of 1.2mol/L；
(1.3) under the conditions of the sonic oscillation that mechanical stirring and power that rate is 200rpm are 600W, by metal ion
Solution, which is added drop-wise in the carboxylic dissaving polymer solution of end group, to be reacted, wherein the speed being added dropwise is 2 drops/sec, every drop
Volume be 0.05mL, after completion of dropwise addition in reaction system end group carboxylic dissaving polymer and metal ion molar ratio
For 1:9.1；
(1.4) mixed liquor after reaction is filtered, washed and is dried to obtain and is insoluble insoluble metal-modified super
Branched polymer, wherein drying carries out under vacuum conditions, vacuum degree is -0.1MPa, drying time 12h, dry temperature
Degree is 25 DEG C；
Insoluble insoluble metal-modified dissaving polymer is made, is in the carboxylic hyperbranched polymer molecule of end group
Oxygen atom and Cu in C=O double bond2+By coordination key connection simultaneously in the carboxylic hyperbranched polymer molecule of end group-
COO-Ion and Cu2+It is keyed the network polymer to be formed by ion, there is insoluble insoluble characteristic, it is insoluble at 80 DEG C or less
In organic solvent I, the specific type and embodiment 1 of organic solvent I are consistent, in room temperature to not melting within the scope of 370 DEG C；Metal changes
Property dissaving polymer partial size be 310~480nm, aerial initial decomposition temperature be 360 DEG C；It is metal-modified hyperbranched
Cu in polymer2+Content be 12.3wt%；
(2) preparation liquid containing metal-modified dissaving polymer is prepared；
By weight, by 25 parts of polyethylene, 5 parts of metal-modified dissaving polymers, 3 parts of dehydrated alcohols, 3 parts of glycerol and
4 parts of decanedioic acid bis- (2,2,6,6- tetramethyl -4- hydroxy piperidine) esters, 3 are added after 56.3 parts of deionized water mixing, stirring and standings
Preparation liquid is made in part acetic acid and 0.7 part of β-(3,5- di-tert-butyl-hydroxy phenyl) propionic acid octadecyl ester；
(3) preparation liquid containing metal-modified dissaving polymer is stirred, vacuum outgas and dry obtained antibacterial are protected
Fresh film, wherein the dry time is 10 hours, temperature is room temperature, and pressure is -0.1MPa.
Tensilon is used to measure the longitudinal tensile strength of antibacterial fresh-keeping film according to standard GB1040.3-200 as 4.4N/
25cm, transverse tensile strength 2.5N/25cm, lengthwise elongation at break 339%, transverse breakage elongation percentage are 391%.
Embodiment 8~20
The preparation method of antibacterial fresh-keeping film, preparation step and embodiment 1 are almost the same, the difference is that in step (1.1)
Middle A2And B3Type, insoluble insoluble metal-modified dissaving polymer obtained not melt temperature scope, starting thermal decomposition temperature
The content of degree, partial size and metal ion, is specifically shown in Table 1, obtained insoluble insoluble metal-modified hyperbranched polymerization
The carboxylic hyperbranched polymer molecule of end group is specifically shown in Table 2 with metal ion crosslinked situation in object, final obtained anti-
Longitudinal tensile strength, transverse tensile strength, lengthwise elongation at break and the transverse breakage elongation percentage of bacterium antistaling film are specifically shown in Table 3
It is shown:
Table 1
Table 2
Table 3
Claims (10)
1. antibacterial fresh-keeping film, it is characterized in that: evenly dispersed in antibacterial fresh-keeping film have metal-modified dissaving polymer；
Metal-modified dissaving polymer is that the carboxylic dissaving polymer of end group gathers with the network that metal ion crosslinked is formed
Object is closed, with insoluble insoluble characteristic, organic solvent I is not dissolved at 80 DEG C or less, is not melted in room temperature to T range, T >=
370℃；
The crosslinking is by the oxygen atom and metal ion in the double bond inside the carboxylic hyperbranched polymer molecule of end group
By coordination key connection simultaneously the carboxylic hyperbranched polymer molecule end of end group acid ion and metal ion by from
Sub-key connection is realized；
The organic solvent I is that aromatic hydrocarbon solvent, fat hydrocarbon solvent, alicyclic hydrocarbon type solvent, halogenated hydrocarbon solvent, alcohols are molten
Agent, esters solvent, ketones solvent, acetonitrile, pyridine, phenol, N,N-dimethylformamide or DMAC N,N' dimethyl acetamide.
2. antibacterial fresh-keeping film according to claim 1, which is characterized in that measure antibacterial according to standard GB1040.3-200 and protect
The longitudinal tensile strength of fresh film is 4.4~4.9N/25cm, and transverse tensile strength is 2.1~2.5N/25cm, and longitudinal fracture is prolonged
Stretching rate is 328~340%, and transverse breakage elongation percentage is 376~397%.
3. antibacterial fresh-keeping film according to claim 1, which is characterized in that the aromatic hydrocarbon solvent is benzene, toluene, two
Toluene, styrene, butyl toluene or vinyltoluene；The fat hydrocarbon solvent is n-hexane, pentane, hexane or octane；Institute
Stating alicyclic hydrocarbon type solvent is hexamethylene, cyclohexanone or toluene cyclohexanone；The halogenated hydrocarbon solvent is chlorobenzene, dichloro-benzenes, dichloro
Methane, chloroform, carbon tetrachloride, trichloro ethylene, tetrachloro-ethylene, trichloropropane or dichloroethanes；The alcohols solvent is methanol, second
Alcohol, isopropanol, n-butanol, cyclohexanol, benzyl alcohol, ethylene glycol or propylene glycol；The esters solvent is methyl acetate, ethyl acetate
Or propyl acetate；The ketones solvent is acetone, espeleton, methylisobutylketone, cyclohexanone or toluene cyclohexanone；
The aerial initial decomposition temperature of metal-modified dissaving polymer is 300~400 DEG C, described metal-modified super
The partial size of branched polymer is 150~500nm.
4. antibacterial fresh-keeping film according to claim 3, which is characterized in that the carboxylic dissaving polymer of end group
The quantity of middle carboxyl accounts for the 25%~100% of end group total amount, contains in the molecule of the carboxylic dissaving polymer of end group
Ester group, the degree of branching of the carboxylic dissaving polymer of end group are 30~100%, the carboxylic hyperbranched poly of end group
The weight average molecular weight for closing object is 1100~50000g/mol.
5. antibacterial fresh-keeping film according to claim 4, which is characterized in that the metal ion is Co2+、Ni2+、Cu2+Or
Zn2+, the metal ion provides by its corresponding mol ratio of metal acetate, metal ion in the metal-modified dissaving polymer
Content is 5.5~12.5wt%.
6. antibacterial fresh-keeping film according to claim 5, which is characterized in that the system of the metal-modified dissaving polymer
Standby step are as follows:
(1) the carboxylic dissaving polymer of end group and mol ratio of metal acetate are dissolved in organic solvent II and deionized water respectively
It obtains the carboxylic dissaving polymer solution of the end group that concentration is 0.7~1.25mol/L and concentration is 0.7~1.25mol/L
Metal ion solution, the organic solvent II be chloroform, acetone or n,N-Dimethylformamide；
(2) under the conditions of stirring and sonic oscillation, it is molten that metal ion solution is added drop-wise to the carboxylic dissaving polymer of end group
It is reacted in liquid, the stirring is mechanical stirring or magnetic agitation, and the rate of stirring is 200~500rpm, the ultrasound vibration
The power swung is 600~1200W, and the speed of the dropwise addition is 0.5~2 drop/sec, and the volume of every drop is 0.05~0.1mL, is added dropwise
After in reaction system the molar ratio of the carboxylic dissaving polymer of end group and metal ion be 1:0.64~46.69；
(3) mixed liquor after reaction is post-processed to obtain metal-modified dissaving polymer, the post-processing refers to
Be filtered, washed and dried, the drying carries out under vacuum conditions, vacuum degree be -0.1MPa, drying time be 8~
12h, drying temperature are 25 DEG C.
7. antibacterial fresh-keeping film according to claim 6, which is characterized in that the carboxylic dissaving polymer of end group
It is to utilize A2+B3Made from synthetic method, the A2For pyrazine -2,3- dicarboxylic acids, 2- carboxyethyl phenyl phosphinic acid, tert-butyl -1 5-,
3- benzene dicarboxylic acid or 2- carboxyethyl phosphoric acid, the B3For 1,1,1- tri- (methylol) propane, three (2- ethoxy) chlorinated isocyanurates,
2,4,5- trihydroxybutyrophenone, 2,3,4- trihydroxy-acetophenone or 1,2,4- trihydroxy benzene.
8. the method for preparing antibacterial fresh-keeping film as described in any one of claims 1 to 7, it is characterized in that: will contain metal-modified
The preparation liquid of dissaving polymer is stirred, antibacterial fresh-keeping film is made in vacuum outgas and drying.
9. according to the method described in claim 8, it is characterized in that, the preparation liquid is by by polyethylene, metal-modified super
Branched polymer, dehydrated alcohol, glycerol and deionized water mixing, stirring and stand after be added hindered amine light stabilizer, acetic acid and
Made from antioxidant.
10. according to the method described in claim 9, it is characterized in that, the content of each component is respectively as follows: poly- second in the preparation liquid
25~45wt% of alkene, metal-modified 3~10wt% of dissaving polymer, 1~6wt% of glycerol, hindered amine light stabilizer 1~
5wt%, 1~5wt% of dehydrated alcohol, 1~3wt% of acetic acid, 0.5~1wt% of antioxidant, deionized water surplus；
The time of the drying is 6~12 hours, and temperature is room temperature, and pressure is -0.1MPa, and the hindered amine light stabilizer is benzene
Formic acid (2,2,6,6- tetramethyl -4- hydroxy piperidine) ester, decanedioic acid bis- (2,2,6,6- tetramethyl -4- hydroxy piperidine) esters, nitrogen base
Three [acetic acid (2,2,6,6- tetramethyl -4- hydroxy piperidine) esters] or bis- (2,2,6, the 6- tetramethyl-piperidyl) hexamethylene diamines of N, N ' -, institute
Stating antioxidant is [β-(3,5 di-t-butyl 4- hydroxy-pheny) propionic acid] pentaerythritol ester or β-(3,5- di-t-butyl -4- hydroxyl
Base phenyl) propionic acid octadecyl ester.
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| US6025462A (en) * | 1997-03-06 | 2000-02-15 | Eic Laboratories, Inc. | Reflective and conductive star polymers |
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