CN106432898B - A kind of high barrier composite membrane - Google Patents
A kind of high barrier composite membrane Download PDFInfo
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- CN106432898B CN106432898B CN201610439111.1A CN201610439111A CN106432898B CN 106432898 B CN106432898 B CN 106432898B CN 201610439111 A CN201610439111 A CN 201610439111A CN 106432898 B CN106432898 B CN 106432898B
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- 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
- C08L23/10—Homopolymers or copolymers of propene
- C08L23/12—Polypropene
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C41/00—Shaping by coating a mould, core or other substrate, i.e. by depositing material and stripping-off the shaped article; Apparatus therefor
- B29C41/24—Shaping by coating a mould, core or other substrate, i.e. by depositing material and stripping-off the shaped article; Apparatus therefor for making articles of indefinite length
- B29C41/32—Making multilayered or multicoloured articles
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
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- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
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- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
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- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/32—Layered products comprising a layer of synthetic resin comprising polyolefins
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- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/36—Layered products comprising a layer of synthetic resin comprising polyesters
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/68—Polyesters containing atoms other than carbon, hydrogen and oxygen
- C08G63/682—Polyesters containing atoms other than carbon, hydrogen and oxygen containing halogens
- C08G63/6824—Polyesters containing atoms other than carbon, hydrogen and oxygen containing halogens derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/6828—Polycarboxylic acids and polyhydroxy compounds in which at least one of the two components contains aliphatic unsaturation
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- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/68—Polyesters containing atoms other than carbon, hydrogen and oxygen
- C08G63/685—Polyesters containing atoms other than carbon, hydrogen and oxygen containing nitrogen
- C08G63/6854—Polyesters containing atoms other than carbon, hydrogen and oxygen containing nitrogen derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/6858—Polycarboxylic acids and polyhydroxy compounds in which at least one of the two components contains aliphatic unsaturation
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- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/91—Polymers modified by chemical after-treatment
- C08G63/914—Polymers modified by chemical after-treatment derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/918—Polycarboxylic acids and polyhydroxy compounds in which at least one of the two components contains aliphatic unsaturation
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- B32—LAYERED PRODUCTS
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- B32B2250/00—Layers arrangement
- B32B2250/24—All layers being polymeric
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- B32B2307/00—Properties of the layers or laminate
- B32B2307/30—Properties of the layers or laminate having particular thermal properties
- B32B2307/306—Resistant to heat
- B32B2307/3065—Flame resistant or retardant, fire resistant or retardant
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- B32B2307/70—Other properties
- B32B2307/714—Inert, i.e. inert to chemical degradation, corrosion
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- C08L2205/00—Polymer mixtures characterised by other features
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Abstract
The invention discloses a kind of high barrier casting films, and PP plastic pellet and PET plastic particle are added to the PET/PP film being made in coextrusion casting film machine including pet layer and PP layers.PP plastic pellet carries out preparation by blending and modifying hair and N is added, and N '-(4,4 '-methylenediphenyl) bismaleimide, three methyl acrylate of hydroxymethyl-propane, 4,4 '-dihydroxy diphenyl sulfides improve its barrier property.PET plastic particle is modified by synthesis modification method, using terephthalic acid (TPA) and ethylene glycol as base-material, 2- nitroterephthalic acid -4- methyl esters, maleic anhydride, 2- methyl -2,4- pentanediol, 2,3- dibromo-2-butene-1,4-glycol, tetrabromo terephthalic acids, bis- (2- ethylhexyl) terephthalic acids, 4- bromo phthalic anhydride, 2- amino terephthalic acid (TPA), 2,2- dimethyl -1,3-propanediol: 10 parts, fluoro- 1, the 3- benzo two of 2,2- bis- dislike cyclopentadienyl, magnesium fluosilicate, antibacterial agent.It can be by the complementation between two kinds of materials, to achieve the effect that preferable high-barrier, a fire-retardant, antibacterial.
Description
Technical field
The present invention relates to a kind of packaging material, more particularly to a kind of high barrier composite membrane.
Background technique
High-isolation film is that the very strong material of barrier properties for gases and heat suture property, the very strong polyolefin of moisture barrier is same
Shi Jinhang is squeezed out, and is the film of multilayered structure.
Other new requirements are also had for high-resistant diaphragm in the prior art also especially in some food packagings
Need some requirements for anti-microbial property, anti-flammability.Especially in long-time use process, it can rise so that thin-film material produces
Raw certain aging, therefore be badly in need of one kind and appoint under long-time use condition that so there is high obstructing performance, and take into account anti-flammability and
The thin-film material of anti-microbial property.
Summary of the invention
In view of the deficiencies of the prior art, the present invention intends to provide one kind.
To achieve the above object, the present invention provides the following technical scheme that
PP plastic pellet and PET plastic particle are added in coextrusion casting film machine and are made by a kind of high barrier composite membrane
PET/PP film including pet layer and PP layers,
The PP plastic pellet includes following parts by weight composition:
PP:120 parts, trihydroxy polypropylene oxide ether: 25 parts, N, N '-(4,4 '-methylenediphenyl) bismaleimide
Amine: 5 parts, trimethylolpropane tris methyl acrylate: 15 parts, 4,4 '-dihydroxy diphenyl sulfides: 8 parts, montmorillonite: 8 parts, paraffin:
10 parts, antioxidant 1010: 0.2 part, nano TiO 2: 2 parts, polyether siloxane copolymer: 0.5 part, methyl hydroxyethylcellulose:
0.5 part, three tert-butyl peroxide silane of vinyl: 1 part；
The PET plastic particle includes following parts by weight composition:
Terephthalic acid (TPA): 1000 parts；Ethylene glycol: 600 parts；2- nitroterephthalic acid -4- methyl esters: 10 parts, maleic anhydride:
50 parts, 2- methyl -2,4- pentanediol: 5 parts, 2,3- dibromo-2-butene-1,4-glycol: 5 parts, tetrabromo terephthalic acids: 5 parts, double
(2- ethylhexyl) terephthalic acids: 8 parts, 4- bromo phthalic anhydride: 5 parts, 2- amino terephthalic acid (TPA): 15 parts, 2,2- dimethyl -1,3-
Propylene glycol: 10 parts, fluoro- 1, the 3- benzo two of 2,2- bis- dislike cyclopentadienyl: 3 parts, magnesium fluosilicate: 5 parts, antibacterial agent: 5 parts, adjacent bromine terephthaldehyde
Dimethyl phthalate: 10 parts.
As a further improvement of the present invention: the PP plastic pellet production method are as follows: needed for weighing according to the weight ratio
Then under nitrogen protection weighed each raw material is stirred evenly, 60-80min is stirred at room temperature, is then heated to 60-80 by raw material
DEG C, 2h is stirred, then temperature reduces 40-50 DEG C, stirs 2h, is added to extruding pelletization in pelletizer and obtains PP plastic pellet.
As a further improvement of the present invention: the PET plastic particle production method are as follows:
The synthesis of first performed polymer of step 1:
Step 1-1: 200 parts of terephthalic acid (TPA), 140 parts of ethylene glycol are added in reaction kettle, are warming up to 40 DEG C and are carried out in advance
Mixing；
Step 1-2: be added 50 parts of maleic anhydride, 5 parts of 2,3- dibromo-2-butene-1,4-glycol be warming up to 200~220
Degree Celsius carrying out esterification is added 0.01~0.5 part of Ti/Si series catalysts after reaction 30~50 minutes, and the reaction was continued 10~
30 minutes；
Step 1-3: be added 200 parts of remaining phthalic acid, ethylene glycol 100,10 parts of 2- nitroterephthalic acid -4- methyl esters,
The reaction was continued is cooled to 180~200 DEG C for 5 parts of 2- methyl -2,4- pentanediol, and it is standby that reaction obtains the first performed polymer in 20~40 minutes
With；
Step 2: the preparation of the second performed polymer
Step 2-1: 200 parts of terephthalic acid (TPA)s, 180 parts of ethylene glycol are added in reaction kettle, are warming up to 40 DEG C and are carried out in advance
Mixing；
Step 2-2: 200~220 degrees Celsius of progress esterifications are warming up to and are added after reaction 30~50 minutes
0.01~0.5 part of Ti/Si series catalysts, the reaction was continued 10~30 minutes；
Step 2-3: 100 parts of terephthalic acid (TPA), 5 parts of tetrabromo terephthalic acids, bis- (2- ethylhexyl) terephthalic acids 8 is added
Part, 4- bromo phthalic anhydride, 5 parts, maintaining the temperature at 200~220 DEG C of progress, to obtain the second performed polymer within esterification 20~40 minutes standby
With；
Step 3: the preparation of third performed polymer
Step 3-1: by 15 parts of 2- amino terephthalic acid (TPA), 10 parts of 2,2-dimethyl-1,3-propanediol, terephthalic acid (TPA)
150 parts, 180 parts of ethylene glycol are added in reaction kettle, are warming up to 40 DEG C and are pre-mixed；
Step 3-2: 200~220 degrees Celsius of progress esterifications are warming up to, Ti/Si system is added after reaction 30~50 minutes
0.01~0.5 part of catalyst, the reaction was continued 10~30 minutes；
Step 3-3: 150 parts of terephthalic acid (TPA) are filled into, it is spare to obtain third performed polymer within sustained response 20~40 minutes；
Step 4: the first performed polymer, the second performed polymer, third performed polymer being mixed, temperature is controlled at 40 DEG C, is carried out
Stirring 1~2 hour, is warming up to 250~280 DEG C, 30~60 minutes progress polymerization reactions is reacted under 200~300Pa vacuum condition；
Step 5: completing adjacent 10 parts of the bromo terephthalic acid's dimethyl ester of addition, fluoro- 1, the 3- benzo two of 2,2- bis- after reacting and dislike cyclopentadienyl 3
Part, 5 parts of magnesium fluosilicate, 5 parts of antibacterial agent, temperature are controlled at 100~120 DEG C, it is stirred 30~after forty minutes, continue to stir,
It is granulated to obtain plastic pellet after being naturally cooling to 50~60 DEG C；
Step 6: plastic pellet is filmed.
As a further improvement of the present invention: the antibacterial agent is prepared according to following methods:
In step A:10g nano silica, the parachlorobenzoyl chloride of 2ml, the 4- bromobutanoylchloride of 1ml, 1ml trichlorine is added
Change phosphorus, is stirred to react 10~15 hours under the conditions of 20~30 DEG C, nano silica is activated；
Step B: being after the reaction was completed centrifuged mixture, is successively carried out using chloroform, ethylene glycol, acetone clear
It washes, is dried, obtain activation nano silica；
Step C: it is sub- that 7g polyethyleneimine, 2g bis- (trimethyl silicon substrate) phosphinylidyne two are added in activation nano silica
Amine, 1g polycarbodiimide are added 0.1gKOH, stir 15~20 hours under conditions of 85 DEG C；
Step D: it after reaction by centrifugation, and is sufficiently washed, is dried with methanol；
Step E: the nano grade silica particles after air-drying are encased in the isobutanol of 20ml, and the 1 of 2ml is added later,
2- Bromofume, the bromo-n-hexane of 6ml, 0.1g bromoacetyl bromide, 1ml the bromo- 3- methybutane of 1-, then stirred under the conditions of 70~80 DEG C
15~25 hours；
Step F: cooling to 30~45 DEG C after the reaction was completed, then 5ml potassium iodide is added thereto, stirs 8~12 hours, warp
Centrifugation is crossed, is sufficiently washed with methanol, is then dried to obtain antibacterial agent.
As a further improvement of the present invention: the step 1-3: 50 parts of terephthalic acid (TPA) is first added, second two is added later
100 parts of alcohol, remaining 150 parts of terephthalic acid (TPA)s are divided into three parts, and every the 50 parts of terephthalic acid (TPA)s of addition in 10 minutes, second is added later
The reaction was continued is cooled to 180~200 for glycol 100,10 parts of 2- nitroterephthalic acid -4- methyl esters, 5 parts of 2- methyl -2,4- pentanediol
DEG C, it is spare that reaction obtains the first performed polymer in 20~40 minutes.As a further improvement of the present invention: the step 1-1, step 2-
1, in step 3-1, before raw material is added, 2,6- di-tert-butyl-4-methy phenol is first added in the reaction vessel, 50 parts of second are added
Glycol stirs 5~15 minutes, adds surplus material.
As a further improvement of the present invention: the step 1, step 2, when Ti/Si series catalysts being added in step 3, first
Ti/Si series catalysts 50ml ethylene glycol is diluted, in being added to reaction vessel.
By squeeze out and Multi-layer cast film being made PET plastic particle and PP plastic pellet progress coextrusion casting film machine,
It can be by the complementation between two kinds of materials, to achieve the effect that preferable high-barrier, a fire-retardant, antibacterial.
It is PP plastic pellet first, PP plastic pellet is prepared by blending and modifying hair, wherein N is added with PP major ingredient,
N '-(4,4 '-methylenediphenyl) bismaleimide, reacts with PP, adjusts the molecule segment of PP, whole to enhance
Barrier property.The trimethylolpropane tris methyl acrylate wherein added can have preferable compatible with the molecule segment of PP
Agent, simultaneous with hydroxyl group, a preferable anti-fog performance can be obtained in the final product.4,4 '-dihydroxy hexichol
On the one hand the addition of thioether provides hydroxyl to whole system, while can also be with trimethylolpropane tris methyl acrylate
Compatibility is more preferable, the phenyl ring of another aspect sulphur atom both ends connection, can be improved entire barrier film strength.Montmorillonite and nanometer
TiO2 is added thereto as modified material, and the performance for reducing costs, while being also will not decline.The addition of paraffin is as lubrication
Agent enables to processing to be more easier.Polyether siloxane copolymer is as defoaming agent, methyl hydroxyethylcellulose as thickener
The addition for adjusting viscosity, three tert-butyl peroxide silane of vinyl is added as coupling agent, in step 1, first by big portion
Terephthalic acid (TPA), the ethylene glycol divided is added in reaction vessel, carries out a pre-mixing process first, while being warming up to 40 DEG C,
It enables to its premixing more uniform, promotes intermolecular free movement.It can effectively prevent being added suddenly an excess amount of anti-
Answer that raw material can there is a phenomenon where excessively polymerize.In later the step of two, Ti/ is started to warm up to 200~220 degrees Celsius and is added
Si series catalysts start pet reaction, and the amount of ethylene glycol is far longer than terephthalic acid (TPA), one side second in entire reaction system
Glycol is solvent, can reduce and plays a diluting effect, so that terephthalic acid (TPA) slowly can occur to gather with ethylene glycol
Ester reaction.
Entire pet reaction is divided into and first prepares three kinds of different performed polymers, later again carries out three kinds of different performed polymers
Polycondensation reaction obtains polyester, has molecular weight uniform, physical property stability high, simultaneously because the group for introducing various functions is point
What step was polymerize, so, mutual interference is also considerably reduced, and obtains more stable effect.
In step 1, preparation for the first performed polymer, the first performed polymer using terephthalic acid (TPA) and ethylene glycol as matrix,
Most terephthalic acid (TPA), ethylene glycol are added in reaction vessel first, a pre-mixing process is carried out first, rises simultaneously
Temperature enables to its premixing more uniform, promotes intermolecular free movement to 40 DEG C.It can effectively prevent being added suddenly
The reaction raw materials of volume can there is a phenomenon where excessively polymerize.Maleic anhydride, the bromo- 2- butene-1 of 2,3- bis-, 4- bis- are added later
Alcohol adjusts the group on segment.Maleic anhydride can increase the flexibility of whole segment, adjust the length of strand, can guarantee
Segment has preferable tensile strength, and 2,3- dibromo-2-butene-1,4-glycols can participate in reacting, bromine substituent is introduced into
Even in section, whole flame retardant property can be improved.Maleic anhydride, 2,3- dibromo-2-butene-1,4-glycol have preferable simultaneously
Compatibility, so that the product obtained during the reaction is more uniform.Addition addition is remaining after reacting a period of time
Terephthalic acid (TPA), ethylene glycol, 2- nitroterephthalic acid -4- methyl esters, 2- methyl -2,4- pentanediol.Enable bromine substituent position
In the position compared with centered on of segment, prevent from being affected, terephthalic acid (TPA), ethylene glycol it is subsequent fill into can increase reaction speed
Degree ensure that production efficiency so that reaction will not slow down.The addition of 2- nitroterephthalic acid -4- methyl esters can consume portion simultaneously
While dividing ethylene glycol, amino and nitro can be introduced in whole system, can enhance the weatherability of whole system, simultaneously also
With phenyl group, whole compatibility can be improved, therefore preferable uniformity can be brought with whole system similar compatibility,
Avoid the promotion of Local Property.The addition of 2- methyl -2,4- pentanediol can adjust the cellular construction on strand, so that
After obtaining the first performed polymer, the first performed polymer can have better compatibility, while but also final polyester has more
Good weatherability.
It in step 2, equally uses using terephthalic acid (TPA) and ethylene glycol as matrix, so that in the first pre-polymerization of main chain Duan Shangyu
Body is similar, and filling into for subsequent terephthalic acid (TPA) mainly prevents reaction speed from reducing, and tetrabromo terephthalic acids and 4- bromobenzene
Bromine substituent is mainly introduced into even section by the addition of acid anhydride, ensure that its whole anti-flammability, bis- (2- ethylhexyls) are to benzene
The addition of diacid so that the polymerization site of tetrabromo terephthalic acids and 4- bromo phthalic anhydride will not lean on it is too close, in intermolecular interaction
Under the conditions of introduce side-chain radical, guarantee the uniformity and stability of overall flame performance.
In the preparation process of third performed polymer, directly by 15 parts of 2- amino terephthalic acid (TPA), 2,2- dimethyl -1,3- third
10 parts of glycol, 150 parts of terephthalic acid (TPA), 180 parts of ethylene glycol reacted, since the amount of reaction is less, need be not excessively load
The problem of heart implode, directly participates in reaction, and in third performed polymer is still based on terephthalic acid (TPA) and ethylene glycol
Matrix is wanted, by the way that 2,2-dimethyl-1,3-propanediol is added, strand is adjusted and is produced simultaneously so that molecular weight product is more uniform
The light transmittance of product can also be guaranteed.And the addition of 2- amino terephthalic acid (TPA), introduce amino so that third performed polymer and
Antibacterial agent tool is well bonded.Have polyester and antibacterial agent to be well bonded, ensure that antibacterial effect
Stablize.
The first performed polymer, the second performed polymer, third performed polymer are subjected to polymerization reaction later, obtain polyester.
After polymerization reaction, whole system basic forming, the bromo terephthalic acid's dimethyl ester being added later, 2,2-
Two fluoro- 1,3- benzos two dislike cyclopentadienyl, magnesium fluosilicate, antibacterial agent and belong to modifying agent, bromo terephthalic acid's dimethyl ester can with react
The polymer of generation is reacted, and improves whole flame retardant property, 2,2- bis- fluoro- 1,3- benzos two dislike cyclopentadienyl itself can product it is whole
The intensity of body, at the same it is close with polyethylene terephthalate in itself structure, therefore there is preferable compatibility, it can
It is evenly distributed between strand, further strengthens whole anti-flammability.The addition of magnesium fluosilicate enables to improve poly-
The intensity of ester, while can also play the role of a stabilizer, so that polyester is regardless of can in processing or use process
Embody certain stability.The addition of antibacterial agent can be improved its whole anti-microbial property.
The phenomenon that in catalyst adition process, being diluted, local concentration can be prevented excessive and part is caused to be reunited.
2, the 6- di-tert-butyl-4-methy phenol being added before the reaction is a kind of general antioxidant, together with ethylene glycol
Container is added, on the one hand has a cleaning action to reaction vessel, on the other hand can also prevent polyester during the reaction by
Oxidation.
On antibacterial agent, quaternary antibacterial agent is selected, quaternary ammonium salt meets in nano silica.
In the preparation process of antibacterial agent, nano silica can be in chlorobenzoyl chloride, 4- bromobutanoylchloride, phosphorus trichloride
Under the conditions of be further activated, the especially addition of phosphorus trichloride can be improved the activity function of nano silica, make simultaneously
Obtaining finally obtained antibacterial agent has preferably weatherability, i.e., preferable antibacterial effect can be also played in long-time use process
Fruit.
It is cleaned later, chloroform parachlorobenzoyl chloride, the dissolubility of phosphorus trichloride are preferable, can be taken
Out, and ethylene glycol can then take out remaining chloroform, finally cleaned with acetone, can thoroughly take out residuals.
By active nano silica and polyethyleneimine, two (trimethyl silicon substrate) phosphinylidyne diimines, polycarbodiimide
Reaction, is fixed on nano-silica for the group on polyethyleneimine, two (trimethyl silicon substrate) phosphinylidyne diimines, polycarbodiimide
In SiClx.It is eventually adding the bromo- 3- methybutane of 1,2- Bromofume, bromo-n-hexane, bromoacetyl bromide, 1- and is fixed on active nano two
The group of silica reacts, and obtains quaternary ammonium salt antiseptic, and quaternary ammonium salt antiseptic has had been fastened to nanometer titanium dioxide
On the carrier of silicon.Such antibacterial agent is not susceptible to be lost, and makes antibacterial effect more preferably steady on the carrier of nano silica
It is fixed.It wherein reacts mainly in polyethyleneimine, two (trimethyl silicon substrate) phosphinylidyne diimines, polycarbodiimide and 1,2- dibromo second
It reacting between the bromo- 3- methybutane of alkane, bromo-n-hexane, bromoacetyl bromide, 1-, the quaternary ammonium salt for reacting generation has stiff stability,
The addition of especially two (trimethyl silicon substrate) phosphinylidyne diimines, enables to more preferable with the binding force of silica, is not easy from receiving
It falls off on rice silica, while the addition of bromoacetyl bromide also improves the activity of antibacterial agent.
Therefore, thermoplastic polyester material prepared by the present invention, while there is preferable anti-flammability, antibiotic property, high intensity,
In time after long-time use, still there is preferable anti-flammability, antibiotic property, high intensity.
By PP layers and the combination of pet layer, so that entire composite membrane has high barrier, while it being also provided with antibacterial
The characteristics of property, anti-flammability.
Specific embodiment
The present invention is described in further detail below in conjunction with embodiment given by attached drawing.
Embodiment
PP plastic pellet and PET plastic particle are added in coextrusion casting film machine and are made by a kind of high barrier composite membrane
PET/PP film including pet layer and PP layers,
The PP plastic pellet includes following parts by weight composition:
PP:120 parts, trihydroxy polypropylene oxide ether: 25 parts, N, N '-(4,4 '-methylenediphenyl) bismaleimide
Amine: 5 parts, trimethylolpropane tris methyl acrylate: 15 parts, 4,4 '-dihydroxy diphenyl sulfides: 8 parts, montmorillonite: 8 parts, paraffin:
10 parts, antioxidant 1010: 0.2 part, nano TiO 2: 2 parts, polyether siloxane copolymer: 0.5 part, methyl hydroxyethylcellulose:
0.5 part, three tert-butyl peroxide silane of vinyl: 1 part；
The PET plastic particle includes following parts by weight composition:
Terephthalic acid (TPA): 1000 parts；Ethylene glycol: 600 parts；2- nitroterephthalic acid -4- methyl esters: 10 parts, maleic anhydride:
50 parts, 2- methyl -2,4- pentanediol: 5 parts, 2,3- dibromo-2-butene-1,4-glycol: 5 parts, tetrabromo terephthalic acids: 5 parts, double
(2- ethylhexyl) terephthalic acids: 8 parts, 4- bromo phthalic anhydride: 5 parts, 2- amino terephthalic acid (TPA): 15 parts, 2,2- dimethyl -1,3-
Propylene glycol: 10 parts, fluoro- 1, the 3- benzo two of 2,2- bis- dislike cyclopentadienyl: 3 parts, magnesium fluosilicate: 5 parts, antibacterial agent: 5 parts, adjacent bromine terephthaldehyde
Dimethyl phthalate: 10 parts.
The PP plastic pellet production method are as follows: required raw material is weighed according to the weight ratio, it then under nitrogen protection, will
Weighed each raw material stirs evenly, and 60-80min is stirred at room temperature, and is then heated to 60-80 DEG C, stirs 2h, and then temperature reduces
40-50 DEG C, 2h is stirred, extruding pelletization in pelletizer is added to and obtains PP plastic pellet.As a further improvement of the present invention: institute
State PET plastic particle production method are as follows:
The synthesis of first performed polymer of step 1:
Step 1-1: 200 parts of terephthalic acid (TPA), 140 parts of ethylene glycol are added in reaction kettle, are warming up to 40 DEG C and are carried out in advance
Mixing；
Step 1-2: be added 50 parts of maleic anhydride, 5 parts of 2,3- dibromo-2-butene-1,4-glycol be warming up to 200~220
Degree Celsius carrying out esterification is added 0.01~0.5 part of Ti/Si series catalysts after reaction 30~50 minutes, and the reaction was continued 10~
30 minutes；
Step 1-3: be added 200 parts of remaining phthalic acid, ethylene glycol 100,10 parts of 2- nitroterephthalic acid -4- methyl esters,
The reaction was continued is cooled to 180~200 DEG C for 5 parts of 2- methyl -2,4- pentanediol, and it is standby that reaction obtains the first performed polymer in 20~40 minutes
With；
Step 2: the preparation of the second performed polymer
Step 2-1: 200 parts of terephthalic acid (TPA)s, 180 parts of ethylene glycol are added in reaction kettle, are warming up to 40 DEG C and are carried out in advance
Mixing；
Step 2-2: 200~220 degrees Celsius of progress esterifications are warming up to and are added after reaction 30~50 minutes
0.01~0.5 part of Ti/Si series catalysts, the reaction was continued 10~30 minutes；
Step 2-3: 100 parts of terephthalic acid (TPA), 5 parts of tetrabromo terephthalic acids, bis- (2- ethylhexyl) terephthalic acids 8 is added
Part, 4- bromo phthalic anhydride, 5 parts, maintaining the temperature at 200~220 DEG C of progress, to obtain the second performed polymer within esterification 20~40 minutes standby
With；
Step 3: the preparation of third performed polymer
Step 3-1: by 15 parts of 2- amino terephthalic acid (TPA), 10 parts of 2,2-dimethyl-1,3-propanediol, terephthalic acid (TPA)
150 parts, 180 parts of ethylene glycol are added in reaction kettle, are warming up to 40 DEG C and are pre-mixed；
Step 3-2: 200~220 degrees Celsius of progress esterifications are warming up to, Ti/Si system is added after reaction 30~50 minutes
0.01~0.5 part of catalyst, the reaction was continued 10~30 minutes；
Step 3-3: 150 parts of terephthalic acid (TPA) are filled into, it is spare to obtain third performed polymer within sustained response 20~40 minutes；
Step 4: the first performed polymer, the second performed polymer, third performed polymer being mixed, temperature is controlled at 40 DEG C, is carried out
Stirring 1~2 hour, is warming up to 250~280 DEG C, 30~60 minutes progress polymerization reactions is reacted under 200~300Pa vacuum condition；
Step 5: completing adjacent 10 parts of the bromo terephthalic acid's dimethyl ester of addition, fluoro- 1, the 3- benzo two of 2,2- bis- after reacting and dislike cyclopentadienyl 3
Part, 5 parts of magnesium fluosilicate, 5 parts of antibacterial agent, temperature are controlled at 100~120 DEG C, it is stirred 30~after forty minutes, continue to stir,
It is granulated to obtain plastic pellet after being naturally cooling to 50~60 DEG C；
Step 6: plastic pellet is filmed.
The antibacterial agent is prepared according to following methods:
In step A:10g nano silica, the parachlorobenzoyl chloride of 2ml, the 4- bromobutanoylchloride of 1ml, 1ml trichlorine is added
Change phosphorus, is stirred to react 10~15 hours under the conditions of 20~30 DEG C, nano silica is activated；
Step B: being after the reaction was completed centrifuged mixture, is successively carried out using chloroform, ethylene glycol, acetone clear
It washes, is dried, obtain activation nano silica；
Step C: it is sub- that 7g polyethyleneimine, 2g bis- (trimethyl silicon substrate) phosphinylidyne two are added in activation nano silica
Amine, 1g polycarbodiimide are added 0.1gKOH, stir 15~20 hours under conditions of 85 DEG C；
Step D: it after reaction by centrifugation, and is sufficiently washed, is dried with methanol；
Step E: the nano grade silica particles after air-drying are encased in the isobutanol of 20ml, and the 1 of 2ml is added later,
2- Bromofume, the bromo-n-hexane of 6ml, 0.1g bromoacetyl bromide, 1ml the bromo- 3- methybutane of 1-, then stirred under the conditions of 70~80 DEG C
15~25 hours；
Step F: cooling to 30~45 DEG C after the reaction was completed, then 5ml potassium iodide is added thereto, stirs 8~12 hours, warp
Centrifugation is crossed, is sufficiently washed with methanol, is then dried to obtain antibacterial agent.
As a further improvement of the present invention: the step 1-3: 50 parts of terephthalic acid (TPA) is first added, second two is added later
100 parts of alcohol, remaining 150 parts of terephthalic acid (TPA)s are divided into three parts, and every the 50 parts of terephthalic acid (TPA)s of addition in 10 minutes, second is added later
The reaction was continued is cooled to 180~200 for glycol 100,10 parts of 2- nitroterephthalic acid -4- methyl esters, 5 parts of 2- methyl -2,4- pentanediol
DEG C, it is spare that reaction obtains the first performed polymer in 20~40 minutes.The step 1-1, step 2-1, in step 3-1, raw material is being added
Before, 2,6- di-tert-butyl-4-methy phenol is first added in the reaction vessel, 50 parts of ethylene glycol are added, stirs 5~15 minutes, then
Surplus material is added.The step 1, step 2 when Ti/Si series catalysts being added in step 3, are first used Ti/Si series catalysts
50ml ethylene glycol dilution, in being added to reaction vessel.
Comparative example:
Select commercially available PP particle and PET particle, be added in coextrusion casting film machine carry out squeeze out coextrusion casting film is made.PP
Particle selects the SFC-650BT of the carefree chemistry of South Korea to be cast film special material, and PET particle selects the 935BK505 plastics of Dupont
Particle.
Test, is prepared into casting films for above-mentioned material, with a thickness of 200 μm, tests its tensile strength, transparency, antibacterial
Property, flame retardant property, oxygen transmission rate when not rubbing folding, rub oxygen transmission rate after folding.And at hernia light irradiation 50,100,150,200 hours
Above-mentioned test is carried out after test.
0.1g sample is accurately weighed, is added in the triangular flask equipped with 99mL sterile water, with ultrasonic wavelength-division 20min.It is added
1mL concentration is 107CFU/mL bacteria suspension.It separately takes the triangular flask equipped with 99mL sterile water as blank control, 1mL is only added
Bacteria suspension.Above-mentioned triangular flask is placed in shaken cultivation case, the shaken cultivation 30min under the conditions of 37 DEG C, 200r/min.In triangular flask
0.2mL mixed liquor is respectively taken, after appropriate dilution, is coated on culture dish, 48~72h of constant temperature incubation at 35 DEG C, carries out bacterium colony meter
Number.Above-mentioned two groups of samples respectively do 3 parallel laboratory tests, and antibiotic rate calculates as follows: R=[(A-B)/A] * 100%
R --- antibiotic rate,
The average colony number of A --- blank control group；
B --- the average colony number of antimicrobial sample to be measured is added.
Staphylococcus aureus and Escherichia coli are selected in the selection of strain.
Table one: without hernia lamp exposure experiment data
| Embodiment | Comparative example | |
| Tensile strength (N/mm^2) | 253 | 152 |
| 94 index of flame retardant rating UL | V-0 | V-1 |
| Staphylococcus aureus antibiotic rate % | 96 | 23 |
| Escherichia coli antibiotic rate % | 94 | 21 |
| Folding oxygen transmission rate cm3/ (m224h0.1MPa) is not rubbed | 0.3 | 1.5 |
| Rub folding oxygen transmission rate cm3/ (m224h0.1MPa) | 0.4 | 2.0 |
| Transparency % | 91% | 85% |
Table two: through 50 hours test datas of hernia light irradiation
Table three: through 100 hours test datas of hernia light irradiation
| Embodiment | Comparative example | |
| Tensile strength (N/mm^2) | 248 | 111 |
| 94 index of flame retardant rating UL | V-0 | V-2 |
| Staphylococcus aureus antibiotic rate % | 93 | 12 |
| Escherichia coli antibiotic rate % | 92 | 11 |
| Folding oxygen transmission rate cm3/ (m224h0.1MPa) is not rubbed | 0.6 | 1.5 |
| Rub folding oxygen transmission rate cm3/ (m224h0.1MPa) | 0.7 | 2.0 |
| Transparency % | 91% | 80% |
Table four: through 150 hours test datas of hernia light irradiation
| Embodiment | Comparative example | |
| Tensile strength (N/mm^2) | 243 | 100 |
| 94 index of flame retardant rating UL | V-0 | V-2 |
| Staphylococcus aureus antibiotic rate % | 91 | 5 |
| Escherichia coli antibiotic rate % | 89 | 5 |
| Folding oxygen transmission rate cm3/ (m224h0.1MPa) is not rubbed | 0.8 | 7 |
| Rub folding oxygen transmission rate cm3/ (m224h0.1MPa) | 0.9 | 9 |
| Transparency % | 91% | 80% |
Table five: through 200 hours test datas of hernia light irradiation
| Embodiment | Comparative example | |
| Tensile strength (N/mm^2) | 235 | 80 |
| 94 index of flame retardant rating UL | V-0 | V-2 |
| Staphylococcus aureus antibiotic rate % | 90 | 5 |
| Escherichia coli antibiotic rate % | 85 | 5 |
| Folding oxygen transmission rate cm3/ (m224h0.1MPa) is not rubbed | 1.0 | 10 |
| Rub folding oxygen transmission rate cm3/ (m224h0.1MPa) | 1.0 | 11 |
| Transparency % | 91% | 80% |
By squeeze out and Multi-layer cast film being made PET plastic particle and PP plastic pellet progress coextrusion casting film machine,
It can be by the complementation between two kinds of materials, to achieve the effect that preferable high-barrier, a fire-retardant, antibacterial.
It is PP plastic pellet first, PP plastic pellet is prepared by blending and modifying hair, wherein N is added with PP major ingredient,
N '-(4,4 '-methylenediphenyl) bismaleimide, reacts with PP, adjusts the molecule segment of PP, whole to enhance
Barrier property.The trimethylolpropane tris methyl acrylate wherein added can have preferable compatible with the molecule segment of PP
Agent, simultaneous with hydroxyl group, a preferable anti-fog performance can be obtained in the final product.4,4 '-dihydroxy hexichol
On the one hand the addition of thioether provides hydroxyl to whole system, while can also be with trimethylolpropane tris methyl acrylate
Compatibility is more preferable, the phenyl ring of another aspect sulphur atom both ends connection, can be improved entire barrier film strength.Montmorillonite and nanometer
TiO2 is added thereto as modified material, and the performance for reducing costs, while being also will not decline.The addition of paraffin is as lubrication
Agent enables to processing to be more easier.Polyether siloxane copolymer is as defoaming agent, methyl hydroxyethylcellulose as thickener
The addition for adjusting viscosity, three tert-butyl peroxide silane of vinyl is added as coupling agent, in step 1, first by big portion
Terephthalic acid (TPA), the ethylene glycol divided is added in reaction vessel, carries out a pre-mixing process first, while being warming up to 40 DEG C,
It enables to its premixing more uniform, promotes intermolecular free movement.It can effectively prevent being added suddenly an excess amount of anti-
Answer that raw material can there is a phenomenon where excessively polymerize.In later the step of two, Ti/ is started to warm up to 200~220 degrees Celsius and is added
Si series catalysts start pet reaction, and the amount of ethylene glycol is far longer than terephthalic acid (TPA), one side second in entire reaction system
Glycol is solvent, can reduce and plays a diluting effect, so that terephthalic acid (TPA) slowly can occur to gather with ethylene glycol
Ester reaction.
Entire pet reaction is divided into and first prepares three kinds of different performed polymers, later again carries out three kinds of different performed polymers
Polycondensation reaction obtains polyester, has molecular weight uniform, physical property stability high, simultaneously because the group for introducing various functions is point
What step was polymerize, so, mutual interference is also considerably reduced, and obtains more stable effect.
In step 1, preparation for the first performed polymer, the first performed polymer using terephthalic acid (TPA) and ethylene glycol as matrix,
Most terephthalic acid (TPA), ethylene glycol are added in reaction vessel first, a pre-mixing process is carried out first, rises simultaneously
Temperature enables to its premixing more uniform, promotes intermolecular free movement to 40 DEG C.It can effectively prevent being added suddenly
The reaction raw materials of volume can there is a phenomenon where excessively polymerize.Maleic anhydride, the bromo- 2- butene-1 of 2,3- bis-, 4- bis- are added later
Alcohol adjusts the group on segment.Maleic anhydride can increase the flexibility of whole segment, adjust the length of strand, can guarantee
Segment has preferable tensile strength, and 2,3- dibromo-2-butene-1,4-glycols can participate in reacting, bromine substituent is introduced into
Even in section, whole flame retardant property can be improved.Maleic anhydride, 2,3- dibromo-2-butene-1,4-glycol have preferable simultaneously
Compatibility, so that the product obtained during the reaction is more uniform.Addition addition is remaining after reacting a period of time
Terephthalic acid (TPA), ethylene glycol, 2- nitroterephthalic acid -4- methyl esters, 2- methyl -2,4- pentanediol.Enable bromine substituent position
In the position compared with centered on of segment, prevent from being affected, terephthalic acid (TPA), ethylene glycol it is subsequent fill into can increase reaction speed
Degree ensure that production efficiency so that reaction will not slow down.The addition of 2- nitroterephthalic acid -4- methyl esters can consume portion simultaneously
While dividing ethylene glycol, amino and nitro can be introduced in whole system, can enhance the weatherability of whole system, simultaneously also
With phenyl group, whole compatibility can be improved, therefore preferable uniformity can be brought with whole system similar compatibility,
Avoid the promotion of Local Property.The addition of 2- methyl -2,4- pentanediol can adjust the cellular construction on strand, so that
After obtaining the first performed polymer, the first performed polymer can have better compatibility, while but also final polyester has more
Good weatherability.
It in step 2, equally uses using terephthalic acid (TPA) and ethylene glycol as matrix, so that in the first pre-polymerization of main chain Duan Shangyu
Body is similar, and filling into for subsequent terephthalic acid (TPA) mainly prevents reaction speed from reducing, and tetrabromo terephthalic acids and 4- bromobenzene
Bromine substituent is mainly introduced into even section by the addition of acid anhydride, ensure that its whole anti-flammability, bis- (2- ethylhexyls) are to benzene
The addition of diacid so that the polymerization site of tetrabromo terephthalic acids and 4- bromo phthalic anhydride will not lean on it is too close, in intermolecular interaction
Under the conditions of introduce side-chain radical, guarantee the uniformity and stability of overall flame performance.
In the preparation process of third performed polymer, directly by 15 parts of 2- amino terephthalic acid (TPA), 2,2- dimethyl -1,3- third
10 parts of glycol, 150 parts of terephthalic acid (TPA), 180 parts of ethylene glycol reacted, since the amount of reaction is less, need be not excessively load
The problem of heart implode, directly participates in reaction, and in third performed polymer is still based on terephthalic acid (TPA) and ethylene glycol
Matrix is wanted, by the way that 2,2-dimethyl-1,3-propanediol is added, strand is adjusted and is produced simultaneously so that molecular weight product is more uniform
The light transmittance of product can also be guaranteed.And the addition of 2- amino terephthalic acid (TPA), introduce amino so that third performed polymer and
Antibacterial agent tool is well bonded.Have polyester and antibacterial agent to be well bonded, ensure that antibacterial effect
Stablize.
The first performed polymer, the second performed polymer, third performed polymer are subjected to polymerization reaction later, obtain polyester.
After polymerization reaction, whole system basic forming, the bromo terephthalic acid's dimethyl ester being added later, 2,2-
Two fluoro- 1,3- benzos two dislike cyclopentadienyl, magnesium fluosilicate, antibacterial agent and belong to modifying agent, bromo terephthalic acid's dimethyl ester can with react
The polymer of generation is reacted, and improves whole flame retardant property, 2,2- bis- fluoro- 1,3- benzos two dislike cyclopentadienyl itself can product it is whole
The intensity of body, at the same it is close with polyethylene terephthalate in itself structure, therefore there is preferable compatibility, it can
It is evenly distributed between strand, further strengthens whole anti-flammability.The addition of magnesium fluosilicate enables to improve poly-
The intensity of ester, while can also play the role of a stabilizer, so that polyester is regardless of can in processing or use process
Embody certain stability.The addition of antibacterial agent can be improved its whole anti-microbial property.
The phenomenon that in catalyst adition process, being diluted, local concentration can be prevented excessive and part is caused to be reunited.
2, the 6- di-tert-butyl-4-methy phenol being added before the reaction is a kind of general antioxidant, together with ethylene glycol
Container is added, on the one hand has a cleaning action to reaction vessel, on the other hand can also prevent polyester during the reaction by
Oxidation.
On antibacterial agent, quaternary antibacterial agent is selected, quaternary ammonium salt meets in nano silica.
In the preparation process of antibacterial agent, nano silica can be in chlorobenzoyl chloride, 4- bromobutanoylchloride, phosphorus trichloride
Under the conditions of be further activated, the especially addition of phosphorus trichloride can be improved the activity function of nano silica, make simultaneously
Obtaining finally obtained antibacterial agent has preferably weatherability, i.e., preferable antibacterial effect can be also played in long-time use process
Fruit.
It is cleaned later, chloroform parachlorobenzoyl chloride, the dissolubility of phosphorus trichloride are preferable, can be taken
Out, and ethylene glycol can then take out remaining chloroform, finally cleaned with acetone, can thoroughly take out residuals.
By active nano silica and polyethyleneimine, two (trimethyl silicon substrate) phosphinylidyne diimines, polycarbodiimide
Reaction, is fixed on nano-silica for the group on polyethyleneimine, two (trimethyl silicon substrate) phosphinylidyne diimines, polycarbodiimide
In SiClx.It is eventually adding the bromo- 3- methybutane of 1,2- Bromofume, bromo-n-hexane, bromoacetyl bromide, 1- and is fixed on active nano two
The group of silica reacts, and obtains quaternary ammonium salt antiseptic, and quaternary ammonium salt antiseptic has had been fastened to nanometer titanium dioxide
On the carrier of silicon.Such antibacterial agent is not susceptible to be lost, and makes antibacterial effect more preferably steady on the carrier of nano silica
It is fixed.It wherein reacts mainly in polyethyleneimine, two (trimethyl silicon substrate) phosphinylidyne diimines, polycarbodiimide and 1,2- dibromo second
It reacting between the bromo- 3- methybutane of alkane, bromo-n-hexane, bromoacetyl bromide, 1-, the quaternary ammonium salt for reacting generation has stiff stability,
The addition of especially two (trimethyl silicon substrate) phosphinylidyne diimines, enables to more preferable with the binding force of silica, is not easy from receiving
It falls off on rice silica, while the addition of bromoacetyl bromide also improves the activity of antibacterial agent.
Therefore, thermoplastic polyester material prepared by the present invention, while there is preferable anti-flammability, antibiotic property, high intensity,
In time after long-time use, still there is preferable anti-flammability, antibiotic property, high intensity.
By PP layers and the combination of pet layer, so that entire composite membrane has high barrier, while it being also provided with antibacterial
The characteristics of property, anti-flammability.
The above is only a preferred embodiment of the present invention, protection scope of the present invention is not limited merely to above-mentioned implementation
Example, all technical solutions belonged under thinking of the present invention all belong to the scope of protection of the present invention.It should be pointed out that for the art
Those of ordinary skill for, several improvements and modifications without departing from the principles of the present invention, these improvements and modifications
It should be regarded as protection scope of the present invention.
Claims (2)
1. a kind of high barrier composite membrane, it is characterised in that: PP plastic pellet and PET plastic particle are added to coextrusion casting film
The PET/PP film including pet layer and PP layers is made in machine,
The PP plastic pellet includes following parts by weight composition:
PP:120 parts, trihydroxy polypropylene oxide ether: 25 parts, N, N'- (4,4'- methylenediphenyl) bismaleimide: 5
Part, trimethylolpropane tris methyl acrylate: 15 parts, 4,4'- dihydroxy diphenyl sulfide: 8 parts, montmorillonite: 8 parts, paraffin: 10
Part, antioxidant 1010: 0.2 part, nano TiO 2: 2 parts, polyether siloxane copolymer: 0.5 part, methyl hydroxyethylcellulose:
0.5 part, three tert-butyl peroxide silane of vinyl: 1 part；
The PET plastic particle includes following parts by weight composition:
Terephthalic acid (TPA): 1000 parts；Ethylene glycol: 600 parts；2- nitroterephthalic acid -4- methyl esters: 10 parts, maleic anhydride: 50
Part, 2- methyl -2,4-PD: 5 parts, the bromo- 2- butylene-1,4-diol of 2,3- bis-: 5 parts, tetrabromo terephthalic acids: 5 parts, bis- (2-
Ethylhexyl) terephthalic acids: 8 parts, 4- bromo phthalic anhydride: 5 parts, 2- amino terephthalic acid (TPA): 15 parts, 2,2- dimethyl -1,3- third
Glycol: 10 parts, the fluoro- 1,3- benzo two of 2,2- bis- dislike cyclopentadienyl: 3 parts, magnesium fluosilicate: 5 parts, antibacterial agent: 5 parts, adjacent bromo terephthalic acid
Dimethyl ester: 10 parts；The PP plastic pellet production method are as follows: required raw material is weighed according to the weight ratio, then in nitrogen protection
Under, weighed each raw material is stirred evenly, 60-80min is stirred at room temperature, is then heated to 60-80 DEG C, stirs 2h, then temperature
40-50 DEG C is reduced, 2h is stirred, is added to extruding pelletization in pelletizer and obtains PP plastic pellet；
The PET plastic particle production method are as follows:
The synthesis of first performed polymer of step 1:
Step 1-1: 200 parts of terephthalic acid (TPA), 140 parts of ethylene glycol are added in reaction kettle, 40 DEG C is warming up to and is pre-mixed；
Step 1-2: 50 parts of maleic anhydride is added, bis- 5 parts of bromo- 2- butylene-1,4-diol of 2,3- is warming up to 200 ~ 220 degrees Celsius
It carries out esterification and is added 0.01 ~ 0.5 part of Ti/Si series catalysts, the reaction was continued 10 ~ 30 minutes after reaction 30 ~ 50 minutes；
Step 1-3: be added 200 parts of remaining terephthalic acid (TPA), 100 parts of ethylene glycol, 10 parts of 2- nitroterephthalic acid -4- methyl esters,
The reaction was continued is cooled to 180 ~ 200 DEG C for 5 parts of 2- methyl -2,4- pentanediol, and it is spare that reaction obtains the first performed polymer in 20 ~ 40 minutes；
Step 2: the preparation of the second performed polymer
Step 2-1: 200 parts of terephthalic acid (TPA)s, 180 parts of ethylene glycol are added in reaction kettle, 40 DEG C is warming up to and is pre-mixed；
Step 2-2: 200 ~ 220 degrees Celsius of progress esterifications are warming up to, Ti/Si series catalysts is added after reaction 30 ~ 50 minutes
0.01 ~ 0.5 part, the reaction was continued 10 ~ 30 minutes；
Step 2-3: 100 parts of terephthalic acid (TPA), 5 parts of tetrabromo terephthalic acids, bis- 8 parts of (2- ethylhexyl) terephthalic acids, 4- is added
5 parts of bromo phthalic anhydride, maintaining the temperature at 200 ~ 220 DEG C of progress, to obtain the second performed polymer within esterification 20 ~ 40 minutes spare；
Step 3: the preparation of third performed polymer
Step 3-1: by 15 parts of 2- amino terephthalic acid (TPA), 10 parts of 2,2- dimethyl -1,3- propylene glycol, 150 parts of terephthalic acid (TPA),
180 parts of ethylene glycol are added in reaction kettle, are warming up to 40 DEG C and are pre-mixed；
Step 3-2: 200 ~ 220 degrees Celsius of progress esterifications are warming up to, Ti/Si series catalysts is added after reaction 30 ~ 50 minutes
0.01 ~ 0.5 part, the reaction was continued 10 ~ 30 minutes；
Step 3-3: 150 parts of terephthalic acid (TPA) are filled into, it is spare to obtain third performed polymer within sustained response 20 ~ 40 minutes；
Step 4: the first performed polymer, the second performed polymer, third performed polymer being mixed, temperature is controlled at 40 DEG C, is stirred 1
~ 2 hours, 250 ~ 280 DEG C are warming up to, 30 ~ 60 minutes progress polymerization reactions are reacted under 200 ~ 300Pa vacuum condition；
Step 5: adjacent 10 parts of bromo terephthalic acid's dimethyl ester is added in completion after reacting, the fluoro- 1,3- benzo two of 2,2- bis- dislikes 3 parts of cyclopentadienyl,
5 parts of magnesium fluosilicate, 5 parts of antibacterial agent, temperature are controlled at 100 ~ 120 DEG C, it is stirred 30 ~ after forty minutes, continue to stir, naturally drop
Temperature is to being granulated to obtain plastic pellet after 50 ~ 60 DEG C；
Step 6: plastic pellet is filmed.
2. a kind of high barrier composite membrane according to claim 1, it is characterised in that: the antibacterial agent is according to following methods
Preparation:
In step A:10g nano silica, the parachlorobenzoyl chloride of 2ml, the 4- bromobutanoylchloride of 1ml, 1ml tri-chlorination is added
Phosphorus is stirred to react 10 ~ 15 hours under the conditions of 20 ~ 30 DEG C, activates to nano silica；
Step B: being after the reaction was completed centrifuged mixture, is successively cleaned using chloroform, ethylene glycol, acetone, into
Row drying obtains activation nano silica；
Step C: 7g polyethyleneimine, 2g bis- (trimethyl silicon substrate) phosphinylidyne diimine, 1g is added in activation nano silica
Polycarbodiimide is added 0.1gKOH, stirs 15 ~ 20 hours under conditions of 85 DEG C；
Step D: it after reaction by centrifugation, and is sufficiently washed, is dried with methanol；
Step E: the nano grade silica particles after air-drying are encased in the isobutanol of 20ml, and 1, the 2- bis- of 2ml is added later
Bromoethane, the bromo-n-hexane of 6ml, 0.1g bromoacetyl bromide, 1ml the bromo- 3- methybutane of 1-, then under the conditions of 70 ~ 80 DEG C stir 15 ~ 25
Hour；
Step F: cooling to 30 ~ 45 DEG C after the reaction was completed, then thereto be added 5ml potassium iodide, stir 8 ~ 12 hours, by from
The heart is sufficiently washed with methanol, is then dried to obtain antibacterial agent.
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