CN106117527B - A kind of high barrier PET/PP film - Google Patents
A kind of high barrier PET/PP film Download PDFInfo
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- CN106117527B CN106117527B CN201610443344.9A CN201610443344A CN106117527B CN 106117527 B CN106117527 B CN 106117527B CN 201610443344 A CN201610443344 A CN 201610443344A CN 106117527 B CN106117527 B CN 106117527B
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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
- 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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- 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
- B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
- B32B27/20—Layered products comprising a layer of synthetic resin characterised by the use of special additives using fillers, pigments, thixotroping agents
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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
- B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
- B32B27/22—Layered products comprising a layer of synthetic resin characterised by the use of special additives using plasticisers
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- B32—LAYERED PRODUCTS
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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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- 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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- 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
- B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- 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
- C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
- C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/16—Dicarboxylic acids and dihydroxy compounds
- C08G63/18—Dicarboxylic acids and dihydroxy compounds the acids or hydroxy compounds containing carbocyclic rings
- C08G63/181—Acids containing aromatic rings
- C08G63/183—Terephthalic acids
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- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
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- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2250/00—Layers arrangement
- B32B2250/24—All layers being polymeric
- B32B2250/246—All polymers belonging to those covered by groups B32B27/32 and B32B27/30
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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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- B32B2307/00—Properties of the layers or laminate
- B32B2307/70—Other properties
- B32B2307/714—Inert, i.e. inert to chemical degradation, corrosion
- B32B2307/7145—Rot proof, resistant to bacteria, mildew, mould, fungi
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- B32B2307/00—Properties of the layers or laminate
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- B32B2307/7242—Non-permeable
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- B32B2307/00—Properties of the layers or laminate
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Abstract
The invention discloses a kind of high barrier PET/PP 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- amino terephthalic acid (TPA), 2- nitroterephthalic acid -4- methyl esters, Isosorbide-5-Nitrae-diacetoxy benzene, Isosorbide-5-Nitrae-benzene dimethanol, 2 is added, 2- dimethyl -1,3-propanediol, 2,3- dibromo-2-butene-1,4-glycol, adjacent bromo terephthalic acid's dimethyl ester, 2, fluoro- 1, the 3- benzo two of 2- bis- dislikes cyclopentadienyl, magnesium fluosilicate carrys out tuning performance.It, can be by the complementation between two kinds of materials, to achieve the effect that preferable high-barrier, a fire-retardant, antibacterial by squeeze out and Multi-layer cast film being made PET plastic particle and PP plastic pellet progress coextrusion casting film machine.
Description
Technical field
The present invention relates to a kind of packaging material, more particularly to a kind of high barrier PET/PP film.
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 a kind of high barrier PET/PP film.For reality
Existing above-mentioned purpose, the present invention provides the following technical scheme that
PP plastic pellet and PET plastic particle are added in coextrusion casting film machine and make by a kind of high barrier PET/PP film
At include pet layer and PP layers of PET/PP film,
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, defoaming agent: 0.5 part, thickener: 0.5 part, coupling agent: 1 part；
The PET plastic particle includes following parts by weight composition:
Terephthalic acid (TPA): 1000 parts, ethylene glycol: 600 parts, 2- amino terephthalic acid (TPA): 15 parts, 2- nitroterephthalic acid-
4- methyl esters: 10 parts, Isosorbide-5-Nitrae-diacetoxy benzene: 7 parts, Isosorbide-5-Nitrae-benzene dimethanol: 8 parts, 2,2-dimethyl-1,3-propanediol: 10 parts,
2,3- dibromo-2-butene-1,4-glycols: 5 parts, adjacent bromo terephthalic acid's dimethyl ester: 10 parts, fluoro- 1, the 3- benzo two of 2,2- bis- evil
Cyclopentadienyl: 3 parts, magnesium fluosilicate: 5 parts, 5 parts of antibacterial agent.
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:
Step 1: 400 parts of terephthalic acid (TPA), 400 parts of ethylene glycol are added in reaction kettle, 40 DEG C is warming up to and is prepared
Mixing；
Step 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: 200 parts of terephthalic acid (TPA) are added, 5 parts of 2- amino terephthalic acid (TPA), 2- nitroterephthalic acid -4- methyl esters
10 parts, 180~200 DEG C are cooled to, is reacted 20~40 minutes；
Step 4: 100 parts of terephthalic acid (TPA), Isosorbide-5-Nitrae -7 parts of diacetoxy benzene, 8 parts of Isosorbide-5-Nitrae-benzene dimethanol, 2,3- bis- is added
Bromo- 2- butene-1,5 parts of 4- glycol, temperature is maintained at 180~200 DEG C, enters 0.01~0.5 part of Ti/Si series catalysts, reaction 20
~30 minutes；
Step 5: 200 parts of terephthalic acid (TPA), 100 parts of ethylene glycol, 2,2-dimethyl-1,3-propanediol is added: 10 parts, rising
Temperature is reacted 10~30 minutes to 200~250 DEG C；
Step 6: be added 100 parts of terephthalic acid (TPA), 100 parts of ethylene glycol be warming up to 250~280 DEG C, 200~300Pa vacuum
Under the conditions of react 30~60 minutes；
Step 7: 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 are completed and dislikes cyclopentadienyl
3 parts, 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 PET plastic particle after being naturally cooling to 50~60 DEG C.
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 drying are encased in the isobutanol of 20ml, and the 1 of 2ml is added later,
2- Bromofume, the bromohexane of 6ml, 0.1g bromoacetyl bromide, 1ml the bromo- 3- methybutane of 1-, 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: in the step 5,50 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, every the 50 parts of terephthalic acid (TPA)s of addition in 10 minutes, are eventually adding 2,
10 parts of 2- dimethyl-1,3-propylene glycol.
As a further improvement of the present invention: in the step 1, before raw material is added, 2 are first added in the reaction vessel,
6- di-tert-butyl-4-methy phenol, is added 200 parts of ethylene glycol, stirs 5~15 minutes, add remaining 200 parts of ethylene glycol and
400 parts of terephthalic acid (TPA)s are warming up to 40 DEG C of progress ready-mixeds.
As a further improvement of the present invention: when Ti/Si series catalysts being added in the step 2 and step 4, first will
Ti/Si series catalysts are diluted with 50ml ethylene glycol, are then added in 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.
In step 1, most terephthalic acid (TPA), ethylene glycol are added in reaction vessel first, carry out one first
A pre-mixing process, while 40 DEG C are warming up to, it enables to its premixing more uniform, promotes intermolecular free movement.Energy
Enough it effectively prevent being added that an excess amount of reaction raw materials can there is a phenomenon where excessively polymerize suddenly.In later the step of two, start to rise
Temperature is to 200~220 degrees Celsius and Ti/Si series catalysts are added, and starts pet reaction, the ethylene glycol in entire reaction system
Amount is far longer than terephthalic acid (TPA), and one side ethylene glycol is solvent, can reduce and plays a diluting effect, so as to benzene
Slowly with ethylene glycol pet reaction can occur for dioctyl phthalate.
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.
Terephthalic acid (TPA) fully reacting in step 3 after the reaction by step 2, in system, it is therefore desirable to
Continue to supplement such as terephthalic acid (TPA), while the addition of 2- amino terephthalic acid (TPA), 2- nitroterephthalic acid -4- methyl esters can consume
While the ethylene glycol of part, amino and nitro can be introduced in whole system, can enhance the weatherability of whole system, simultaneously
Phenyl group is also had, whole compatibility can be improved with whole system similar compatibility, therefore can be brought preferable uniform
Property, avoid the promotion of Local Property.Reaction temperature is also reduced simultaneously, since 2- amino terephthalic acid (TPA), 2- nitro are to benzene
The branch of diacid -4- methyl esters is easy to be activated, therefore reduces temperature while being able to carry out normal pet reaction, moreover it is possible to
Enough avoid the generation of side reaction.
In step 4, Isosorbide-5-Nitrae-diacetoxy benzene, Isosorbide-5-Nitrae-benzene diformazan are additionally added while continuing to fill into terephthalic acid (TPA)
Alcohol, 2,3- dibromo-2-butene-1,4-glycol change the branched structure of molecule segment, Isosorbide-5-Nitrae-diacetoxy benzene addition energy
It is enough preferably and the combination of later period antibacterial agent, the addition of Isosorbide-5-Nitrae-benzene dimethanol enhances whole intensity, and 2,3- bis- bromo- 2- fourths
Alkene-Isosorbide-5-Nitrae-glycol addition, can be improved whole flame retardant property.
Step 5 is while filling into terephthalic acid (TPA), it is also desirable to fill into part ethylene glycol, prevent system viscosity excessive, send out
Raw excessively polymerization, while 2,2-dimethyl-1,3-propanediol is added, strand is adjusted, so that molecular weight product is more uniform, together
When product light transmittance can also be guaranteed.
Addition in batches in step 5 is directly added into due to itself already having certain viscosity and is easy to make
At the reunion of part.
Finally add remaining terephthalic acid (TPA) and ethylene glycol in step 6, carries out final polymerization reaction, obtain molecule
Measure biggish polymer.
In step 7, by the reaction of step 6, whole system basic forming, the bromo terephthalic acid being added later
Dimethyl ester, fluoro- 1, the 3- benzo two of 2,2- bis- dislike cyclopentadienyl, magnesium fluosilicate, antibacterial agent and belong to modifying agent, bromo terephthalic acid's dimethyl ester
It can be reacted with the polymer generated is reacted, improve whole flame retardant property, 2,2- bis- fluoro- 1,3- benzos two dislike cyclopentadienyl itself
It is capable of the intensity of product entirety, while close with polyethylene terephthalate in itself structure, therefore has preferable
Compatibility can be uniformly distributed between strand, exist with 2, the 3- dibromo-2-butene-1,4-glycol being aggregated on strand
In varying degrees, whole anti-flammability is further strengthened.The addition of magnesium fluosilicate enables to improve the intensity of polyester, together
When can also play the role of a stabilizer so that polyester regardless of can be embodied in processing or use process it is 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.
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, bromohexane, 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, bromohexane, 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.
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 make by a kind of high barrier PET/PP film
At include pet layer and PP layers of PET/PP film,
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- amino terephthalic acid (TPA): 15 parts, 2- nitroterephthalic acid-
4- methyl esters: 10 parts, Isosorbide-5-Nitrae-diacetoxy benzene: 7 parts, Isosorbide-5-Nitrae-benzene dimethanol: 8 parts, 2,2-dimethyl-1,3-propanediol: 10 parts,
2,3- dibromo-2-butene-1,4-glycols: 5 parts, adjacent bromo terephthalic acid's dimethyl ester: 10 parts, fluoro- 1, the 3- benzo two of 2,2- bis- evil
Cyclopentadienyl: 3 parts, magnesium fluosilicate: 5 parts, 5 parts of antibacterial agent.
Required raw material is weighed according to the weight ratio, then under nitrogen protection, weighed each raw material is stirred evenly, room temperature
60-80min is stirred, is then heated to 60-80 DEG C, stirs 2h, then temperature reduces 40-50 DEG C, stirs 2h, is added to pelletizer
Middle extruding pelletization obtains PP plastic pellet.
The PET particle production method are as follows:
Step 1: 400 parts of terephthalic acid (TPA), 400 parts of ethylene glycol are added in reaction kettle, 40 DEG C is warming up to and is prepared
Mixing；
Step 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: 200 parts of terephthalic acid (TPA) are added, 5 parts of 2- amino terephthalic acid (TPA), 2- nitroterephthalic acid -4- methyl esters
10 parts, 180~200 DEG C are cooled to, is reacted 20~40 minutes；
Step 4: 100 parts of terephthalic acid (TPA), Isosorbide-5-Nitrae -7 parts of diacetoxy benzene, 8 parts of Isosorbide-5-Nitrae-benzene dimethanol, 2,3- bis- is added
Bromo- 2- butene-1,5 parts of 4- glycol, temperature is maintained at 180~200 DEG C, enters 0.01~0.5 part of Ti/Si series catalysts, reaction 20
~30 minutes；
Step 5: 200 parts of terephthalic acid (TPA), 100 parts of ethylene glycol, 2,2-dimethyl-1,3-propanediol is added: 10 parts, rising
Temperature is reacted 10~30 minutes to 200~250 DEG C；
Step 6: be added 100 parts of terephthalic acid (TPA), 100 parts of ethylene glycol be warming up to 250~280 DEG C, 200~300Pa vacuum
Under the conditions of react 30~60 minutes；
Step 7: 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 are completed and dislikes cyclopentadienyl
3 parts, 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 PET plastic particle after being naturally cooling to 50~60 DEG C.
In the step 5,50 parts of terephthalic acid (TPA) is first added, 100 parts of ethylene glycol are added later, remaining 150 parts to benzene
Dioctyl phthalate is divided into three parts, every the 50 parts of terephthalic acid (TPA)s of addition in 10 minutes, is eventually adding 2,2-dimethyl-1,3-propanediol 10
Part.
In the step 1, before raw material is added, 2,6- di-tert-butyl-4-methy phenol is first added in the reaction vessel,
200 parts of ethylene glycol are added, stirs 5~15 minutes, adds remaining 200 parts of ethylene glycol and 400 parts of terephthalic acid (TPA)s, be warming up to
40 DEG C of progress ready-mixeds.
When Ti/Si series catalysts being added in the step 2 and step 4, first by Ti/Si series catalysts 50ml ethylene glycol
Dilution, is then added in reaction vessel.,
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 drying are encased in the isobutanol of 20ml, and the 1 of 2ml is added later,
2- Bromofume, the bromohexane of 6ml, 0.1g bromoacetyl bromide, 1ml the bromo- 3- methybutane of 1-, 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.
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 Dupont
935BK505 plastic pellet.
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 it was tried at hernia light irradiation 50,100,150,200 hours
Above-mentioned test is carried out after testing.
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) | 243 | 152 |
| 94 index of flame retardant rating UL | V-0 | V-1 |
| Staphylococcus aureus antibiotic rate % | 95 | 23 |
| Escherichia coli antibiotic rate % | 93 | 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) | 238 | 111 |
| 94 index of flame retardant rating UL | V-0 | V-2 |
| Staphylococcus aureus antibiotic rate % | 91 | 12 |
| Escherichia coli antibiotic rate % | 90 | 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) | 230 | 100 |
| 94 index of flame retardant rating UL | V-0 | V-2 |
| Staphylococcus aureus antibiotic rate % | 90 | 5 |
| Escherichia coli antibiotic rate % | 88 | 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) | 221 | 80 |
| 94 index of flame retardant rating UL | V-0 | V-2 |
| Staphylococcus aureus antibiotic rate % | 88 | 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.
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.
Terephthalic acid (TPA) fully reacting in step 3 after the reaction by step 2, in system, it is therefore desirable to
Continue to supplement such as terephthalic acid (TPA), while the addition of 2- amino terephthalic acid (TPA), 2- nitroterephthalic acid -4- methyl esters can consume
While the ethylene glycol of part, amino and nitro can be introduced in whole system, can enhance the weatherability of whole system, simultaneously
Phenyl group is also had, whole compatibility can be improved with whole system similar compatibility, therefore can be brought preferable uniform
Property, avoid the promotion of Local Property.Reaction temperature is also reduced simultaneously, since 2- amino terephthalic acid (TPA), 2- nitro are to benzene
The branch of diacid -4- methyl esters is easy to be activated, therefore reduces temperature while being able to carry out normal pet reaction, moreover it is possible to
Enough avoid the generation of side reaction.
In step 4, Isosorbide-5-Nitrae-diacetoxy benzene, Isosorbide-5-Nitrae-benzene diformazan are additionally added while continuing to fill into terephthalic acid (TPA)
Alcohol, 2,3- dibromo-2-butene-1,4-glycol change the branched structure of molecule segment, Isosorbide-5-Nitrae-diacetoxy benzene addition energy
It is enough preferably and the combination of later period antibacterial agent, the addition of Isosorbide-5-Nitrae-benzene dimethanol enhances whole intensity, and 2,3- bis- bromo- 2- fourths
Alkene-Isosorbide-5-Nitrae-glycol addition, can be improved whole flame retardant property.
Step 5 is while filling into terephthalic acid (TPA), it is also desirable to fill into part ethylene glycol, prevent system viscosity excessive, send out
Raw excessively polymerization, while 2,2-dimethyl-1,3-propanediol is added, strand is adjusted, so that molecular weight product is more uniform, together
When product light transmittance can also be guaranteed.
Addition in batches in step 5 is directly added into due to itself already having certain viscosity and is easy to make
At the reunion of part.
Finally add remaining terephthalic acid (TPA) and ethylene glycol in step 6, carries out final polymerization reaction, obtain molecule
Measure biggish polymer.
In step 7, by the reaction of step 6, whole system basic forming, the bromo terephthalic acid being added later
Dimethyl ester, fluoro- 1, the 3- benzo two of 2,2- bis- dislike cyclopentadienyl, magnesium fluosilicate, antibacterial agent and belong to modifying agent, bromo terephthalic acid's dimethyl ester
It can be reacted with the polymer generated is reacted, improve whole flame retardant property, 2,2- bis- fluoro- 1,3- benzos two dislike cyclopentadienyl itself
It is capable of the intensity of product entirety, while close with polyethylene terephthalate in itself structure, therefore has preferable
Compatibility can be uniformly distributed between strand, exist with 2, the 3- dibromo-2-butene-1,4-glycol being aggregated on strand
In varying degrees, whole anti-flammability is further strengthened.The addition of magnesium fluosilicate enables to improve the intensity of polyester, together
When can also play the role of a stabilizer so that polyester regardless of can be embodied in processing or use process it is 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.
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, bromohexane, 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, bromohexane, 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.
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 (6)
1. a kind of high barrier PET/PP film, it is characterised in that: PP plastic pellet and PET plastic particle are added to coextrusion casting
The PET/PP film including pet layer and PP layers is made in film 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- amino terephthalic acid (TPA): 15 parts, 2- nitroterephthalic acid -4- first
Ester: 10 parts, 1,4- diacetoxy benzene: 7 parts, 1,4- benzene dimethanol: 8 parts, 2,2- dimethyl -1,3- propylene glycol: 10 parts, 2,3-
Two bromo- 2- butylene-1,4-diols: 5 parts, adjacent bromo terephthalic acid's dimethyl ester: 10 parts, the fluoro- 1,3- benzo two of 2,2- bis- dislike cyclopentadienyl: 3
Part, magnesium fluosilicate: 5 parts, 5 parts of antibacterial agent；
Antibacterial agent is stated to be prepared according to following methods:
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 carried out air-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 bromohexane of 6ml, 0.1g bromoacetyl bromide, 1ml the bromo- 3- methybutane of 1-, 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.
2. a kind of high barrier PET/PP film according to claim 1, it is characterised in that: the PP plastic pellet producer
Method are as follows: weigh required raw material according to the weight ratio, then under nitrogen protection, weighed each raw material is stirred evenly, room temperature is stirred
60-80min is mixed, is then heated to 60-80 DEG C, stirs 2h, then temperature reduces 40-50 DEG C, stirs 2h, is added in pelletizer
Extruding pelletization obtains PP plastic pellet.
3. a kind of high barrier PET/PP film according to claim 2, it is characterised in that: the PET plastic particle production
Method are as follows:
Step 1: 400 parts of terephthalic acid (TPA), 400 parts of ethylene glycol are added in reaction kettle, are warming up to 40 DEG C and are carried out prepared mix
It closes；
Step 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: 200 parts of terephthalic acid (TPA) are added, 15 parts of 2- amino terephthalic acid (TPA), 2- nitroterephthalic acid -4- methyl esters 10
Part, 180 ~ 200 DEG C are cooled to, is reacted 20 ~ 40 minutes；
Step 4: it is bromo- that 100 parts of terephthalic acid (TPA), 7 parts of 1,4- diacetoxy benzene, 8 parts of 1,4- benzene dimethanol, 2,3- bis- is added
2- butene-1,5 parts of 4- glycol, temperature is maintained at 180 ~ 200 DEG C, enters 0.01 ~ 0.5 part of Ti/Si series catalysts, reacts 20 ~ 30 points
Clock；
Step 5: 200 parts of terephthalic acid (TPA), 100 parts of ethylene glycol, 2,2-dimethyl-1,3-propanediol is added: 10 parts, being warming up to
It 200 ~ 250 DEG C, reacts 10 ~ 30 minutes；
Step 6: be added 100 parts of terephthalic acid (TPA), 100 parts of ethylene glycol be warming up to 250 ~ 280 DEG C, under 200 ~ 300Pa vacuum condition
Reaction 30 ~ 60 minutes；
Step 7: 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 PET plastic particle after 50 ~ 60 DEG C.
4. a kind of high barrier PET/PP film according to claim 3, it is characterised in that: in the step 5, be first added
50 parts of terephthalic acid (TPA) is added 100 parts of ethylene glycol later, and remaining 150 parts of terephthalic acid (TPA)s are divided into three parts, adds every 10 minutes
Enter 50 parts of terephthalic acid (TPA)s, is eventually adding 10 parts of 2,2-dimethyl-1,3-propanediol.
5. a kind of high barrier PET/PP film according to claim 4, it is characterised in that: in the step 1, add
Before raw material, 2,6- di-tert-butyl-4-methy phenol is first added in the reaction vessel, 200 parts of ethylene glycol are added, stirs 5 ~ 15 points
Clock adds remaining 200 parts of ethylene glycol and 400 parts of terephthalic acid (TPA)s, is warming up to 40 DEG C of progress ready-mixeds.
6. a kind of high barrier PET/PP film according to claim 5, it is characterised in that: in the step 2 and step 4
When Ti/Si series catalysts are added, first Ti/Si series catalysts 50ml ethylene glycol is diluted, is then added in reaction vessel.
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Effective date of registration: 20200511 Address after: No. 247-299, Dongcheng Road, Longgang City, Wenzhou City, Zhejiang Province 325000 Patentee after: Wenzhou Baofeng Packaging Technology Co.,Ltd. Address before: Longgang Dongcheng road Wenzhou City, Zhejiang province 325802 No. 351 Patentee before: CANGNAN BAOFENG PRINTING Co.,Ltd. |
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Address after: No. 247-299, Dongcheng Road, Longgang City, Wenzhou City, Zhejiang Province 325000 Patentee after: Wenzhou Baofeng Packaging Technology Co.,Ltd. Address before: Longgang Dongcheng road Wenzhou City, Zhejiang province 325802 No. 351 Patentee before: CANGNAN BAOFENG PRINTING Co.,Ltd. |
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Denomination of invention: A high barrier PET/PP film Effective date of registration: 20221128 Granted publication date: 20190215 Pledgee: Zhejiang Tailong Commercial Bank Co.,Ltd. Wenzhou Cangnan Qianku small and micro enterprise franchise sub branch Pledgor: Wenzhou Baofeng Packaging Technology Co.,Ltd. Registration number: Y2022330003241 |
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