CN106117527A - A kind of high barrier PET/PP film - Google Patents
A kind of high barrier PET/PP film Download PDFInfo
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- CN106117527A CN106117527A CN201610443344.9A CN201610443344A CN106117527A CN 106117527 A CN106117527 A CN 106117527A CN 201610443344 A CN201610443344 A CN 201610443344A CN 106117527 A CN106117527 A CN 106117527A
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/10—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
- 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
- B32B27/32—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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- 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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- C—CHEMISTRY; METALLURGY
- 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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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K13/00—Use of mixtures of ingredients not covered by one single of the preceding main groups, each of these compounds being essential
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- C08K3/34—Silicon-containing compounds
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/10—Esters; Ether-esters
- C08K5/12—Esters; Ether-esters of cyclic polycarboxylic acids
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- 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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- C08L2205/00—Polymer mixtures characterised by other features
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Abstract
The invention discloses a kind of high barrier PET/PP film, PP plastic pellet and PET particle are joined in coextrusion casting film machine and make the PET/PP film including pet layer and PP layer.PP plastic pellet is sent out by blending and modifying and is prepared addition N, N ' (4,4 ' methylenediphenyl) BMI, hydroxymethyl-propane three acrylic acid methyl ester., 4,4 ' dihydroxy diphenyl sulfides improve its barrier.PET particle is modified by synthesis modification method, with p-phthalic acid and ethylene glycol as base material, add 2 amino p-phthalic acids, 2 nitroterephthalic acid 4 methyl ester, Isosorbide-5-Nitrae diacetoxy benzene, Isosorbide-5-Nitrae benzene dimethanol, 2,2 dimethyl 1,3 propylene glycol, 2,3 dibromo 2 butylene Isosorbide-5-Nitrae glycol, adjacent bromo terephthalic acid's dimethyl ester, 2, cyclopentadienyl disliked by 2 difluoro 1,3 benzos two, magnesium fluosilicate carrys out tuning performance.Carry out extrusion make Multi-layer cast film by PET particle and PP plastic pellet being carried out coextrusion casting film machine, it is possible to by the complementation between bi-material, thus reach a preferable high-barrier, fire-retardant, antibacterial effect.
Description
Technical field
The present invention relates to a kind of packaging material, a kind of high barrier PET/PP film.
Background technology
High-isolation film be material the strongest for barrier properties for gases and heat sew up property, the strongest polyolefin of moisture barrier with
Shi Jinhang extrusion forms, and is the thin film of multiple structure.
Prior art also has for high-resistant diaphragm other new requirements, particularly in some packagings for foodstuff, also can
Need some for anti-microbial property, the requirement of anti-flammability.Particularly during long-time use, can rise so that thin-film material produces
Raw certain aging, being therefore badly in need of a kind of appointing under the conditions of long-time use so has high obstructing performance, and take into account anti-flammability and
The thin-film material of anti-microbial property.
Summary of the invention
The deficiency existed for prior art, it is an object of the invention to provide one.
For achieving the above object, the technical scheme is that
A kind of high barrier PET/PP film, joins PP plastic pellet and PET particle in coextrusion casting film machine and makes
Become to include the PET/PP film of pet layer and PP layer,
Described PP plastic pellet includes that following weight portion forms:
PP:120 part, trihydroxy polypropylene oxide ether: 25 parts, N, N '-(4,4 '-methylenediphenyl) bismaleimide
Amine: 5 parts, trimethylolpropane tris acrylic acid methyl ester.: 15 parts, 4,4 '-dihydroxy diphenyl sulfide: 8 parts, montmorillonite: 8 parts, paraffin:
10 parts, antioxidant 1010: 0.2 part, nano TiO 2: 2 parts, defoamer: 0.5 part, thickening agent: 0.5 part, coupling agent: 1 part；
Described PET particle includes that following weight portion forms:
P-phthalic acid: 1000 parts, ethylene glycol: 600 parts, 2-amino p-phthalic acid: 15 parts, 2-nitroterephthalic acid-
4-methyl ester: 10 parts, Isosorbide-5-Nitrae-diacetoxy benzene: 7 parts, Isosorbide-5-Nitrae-benzene dimethanol: 8 parts, 2，2-dimethyl-1，3-propanediol: 10
Part, 2,3-dibromo-2-butene-1,4-glycol: 5 parts, adjacent bromo terephthalic acid's dimethyl ester: 10 parts, 2,2-bis-fluoro-1,3-benzo two
Dislike luxuriant: 3 parts, magnesium fluosilicate: 5 parts, antibacterial 5 parts.
As a further improvement on the present invention: described PP plastic pellet production method is: weigh required according to weight proportion
Raw material, the most under nitrogen protection, by uniform for each raw material stirring weighed, be stirred at room temperature 60-80min, be then heated to 60-80
DEG C, stir 2h, then temperature reduces 40-50 DEG C, stirs 2h, joins extruding pelletization in comminutor and obtain PP plastic pellet.
As a further improvement on the present invention: described PET particle production method is:
Step one: p-phthalic acid 400 parts, ethylene glycol 400 parts are joined in reactor, is warming up to 40 DEG C and prepares
Mixing；
Step 2: be warming up to 200～220 degrees Celsius and carry out esterification, after reacting 30～50 minutes, adds Ti/Si system
Catalyst 0.01～0.5 part, continue reaction 10～30 minutes；
Step 3: add p-phthalic acid 200 parts, 2-amino p-phthalic acid 5 parts, 2-nitroterephthalic acid-4-methyl ester
10 parts, it is cooled to 180～200 DEG C, reacts 20～40 minutes；
Step 4: add p-phthalic acid 100 parts, Isosorbide-5-Nitrae-diacetoxy benzene 7 parts, Isosorbide-5-Nitrae-benzene dimethanol 8 parts, 2,3-bis-
Bromo-2-butylene-Isosorbide-5-Nitrae-glycol 5 parts, temperature is maintained at 180～200 DEG C, enters Ti/Si series catalysts 0.01～0.5 part, reacts 20
～30 minutes；
Step 5: add p-phthalic acid 200 parts, ethylene glycol 100 parts, 2，2-dimethyl-1，3-propanediol: 10 parts, rise
Temperature, to 200～250 DEG C, is reacted 10～30 minutes；
Step 6: add phthalic acid 100 parts, ethylene glycol 100 parts is warming up to 250～280 DEG C, 200～300Pa vacuum bars
React 30～60 minutes under part；
Step 7: add after completing reaction adjacent bromo terephthalic acid's dimethyl ester 10 parts, 2,2-bis-fluoro-1, cyclopentadienyl disliked by 3-benzo two
3 parts, magnesium fluosilicate 5 parts, antibacterial 5 parts, temperature controls at 100～120 DEG C, after being stirred 30～40 minutes, continue stirring,
Carry out pelletize after being naturally cooling to 50～60 DEG C and obtain PET particle.
As a further improvement on the present invention: described antibacterial is prepared according to following method:
In step A:10g nano silicon, add the parachlorobenzoyl chloride of 2ml, the 4-bromobutanoylchloride of 1ml, 1ml trichlorine
Changing phosphorus, under the conditions of 20～30 DEG C, stirring reaction 10～15 hours, carry out activation to nano silicon；
Step B: after having reacted be centrifuged mixture, uses chloroform, ethylene glycol, acetone to carry out clearly successively
Wash, be dried, obtain activating nano silicon；
Step C: add 7g polymine, 2g bis-(trimethyl is silica-based) phosphinylidyne two Asia in activation nano silicon
Amine, 1g polycarbodiimide, add 0.1gKOH, stirs 15～20 hours under conditions of 85 DEG C；
Step D: react through centrifugal after terminating, and fully wash with methanol, be dried；
Step E: the nano grade silica particles after air-drying is encased in the isobutanol of 20ml, adds the 1 of 2ml afterwards,
2-Bromofume, the bromohexane of 6ml, 0.1g bromoacetyl bromide, the 1-bromo-3-methybutane of 1ml, then stir under the conditions of 70～80 DEG C
15～25 hours；
Step F: cool to 30～45 DEG C after having reacted, then it is added thereto to 5ml potassium iodide, stir 8～12 hours, warp
Cross centrifugal, fully wash with methanol, be then dried to obtain antibacterial.
As a further improvement on the present invention: in described step 5, p-phthalic acid 50 parts, afterwards addition second two it are initially charged
Alcohol 100 parts, remaining 150 parts of p-phthalic acids are divided into three parts, add 50 parts of p-phthalic acids every 10 minutes, are eventually adding 2,
2-dimethyl-1,3-propylene glycol 10 parts.
As a further improvement on the present invention: in described step one, before adding raw material, in reaction vessel, first add 2,
6-di-tert-butyl-4-methy phenol, adds 200 parts of ethylene glycol, stirs 5～15 minutes, add remaining 600 parts of ethylene glycol and
400 parts of p-phthalic acids, are warming up to 40 DEG C and carry out ready-mixed.
As a further improvement on the present invention: when described step 2 and step 4 add Ti/Si series catalysts, first will
Ti/Si series catalysts 50ml ethylene glycol dilutes, in joining reaction vessel.
Carry out extrusion make Multi-layer cast film by PET particle and PP plastic pellet being carried out coextrusion casting film machine,
By the complementation between bi-material, thus a preferable high-barrier, fire-retardant, antibacterial effect can be reached.
First being PP plastic pellet, PP plastic pellet is sent out by blending and modifying and is prepared, and wherein with PP major ingredient, adds N,
N '-(4,4 '-methylenediphenyl) BMI, reacts with PP, the molecule segment of regulation PP, strengthens entirety
Barrier property.The trimethylolpropane tris acrylic acid methyl ester. wherein added can have the most compatible with the molecule segment of PP
Agent, simultaneous with oh group, it is possible to obtain a preferable anti-fog performance in the final product.4,4 '-dihydroxy hexichol
The addition of thioether, provides hydroxyl on the one hand to whole system, simultaneously can also be with trimethylolpropane tris acrylic acid methyl ester.
The compatibility is more preferable, the phenyl ring that on the other hand sulphur atom two ends connect, it is possible to increase whole obstruct film strength.Montmorillonite and nanometer
TiO2 is added thereto as modified material, reduces cost, and the performance being also simultaneously will not decline.The addition of paraffin is as lubrication
Agent, it is possible to processing is more prone to.Polyether siloxane copolymer as defoamer, methyl hydroxyethylcellulose as thickening agent
Add regulation viscosity, vinyl three tert-butyl peroxide silane addition as coupling agent, in step one, first by big portion
The p-phthalic acid, the ethylene glycol that divide join in reaction vessel, first carry out a pre-mixing process, are warming up to 40 DEG C simultaneously,
Enable to its premixing more uniform, promote intermolecular free motion.Can effectively prevent from adding suddenly an excess amount of instead
Answer raw material that the phenomenon being excessively polymerized can occur.In step 2 afterwards, start to warm up to 200～220 degrees Celsius and add Ti/
Si series catalysts, starts pet reaction, and in whole reaction system, the amount of ethylene glycol is far longer than p-phthalic acid, on the one hand second
Glycol is solvent, it is possible to reduces and plays a diluting effect, so that p-phthalic acid can slowly gather with ethylene glycol generation
Ester reacts.
In step one, first most p-phthalic acid, ethylene glycol are joined in reaction vessel, first carry out one
Individual pre-mixing process, is warming up to 40 DEG C simultaneously, it is possible to makes its premixing more uniform, promotes intermolecular free motion.Energy
Enough effectively prevent from adding suddenly the phenomenon that an excess amount of reaction raw materials can occur excessively to be polymerized.In step 2 afterwards, start to rise
Temperature is to 200～220 degrees Celsius and adds Ti/Si series catalysts, starts pet reaction, ethylene glycol in whole reaction system
Amount be far longer than p-phthalic acid, on the one hand ethylene glycol is solvent, it is possible to reduces and plays a diluting effect, so that right
Phthalic acid can slowly and ethylene glycol generation pet reaction.
2 added before the reaction, 6-di-tert-butyl-4-methy phenol is a kind of general antioxidant, with ethylene glycol together
Add container, on the one hand reaction vessel is had a cleaning action, on the other hand also is able to prevent polyester quilt in course of reaction
Oxidation.
After the reaction of step 2 in step 3, the p-phthalic acid in system is the most reacted completely, it is therefore desirable to
Continuing to supplement such as p-phthalic acid, 2-amino p-phthalic acid, the addition of 2-nitroterephthalic acid-4-methyl ester simultaneously can consume
While part ethylene glycol, it is possible to introduce amino and nitro in whole system, it is possible to strengthen the weatherability of whole system, simultaneously
Also with phenyl group, it is possible to and whole system similar compatibility, improve the overall compatibility, therefore, it is possible to bring the most uniformly
Property, it is to avoid the lifting of Local Property.Also reduce reaction temperature, owing to 2-amino p-phthalic acid, 2-nitro are to benzene simultaneously
The side chain of diacid-4-methyl ester is easy to be activated, and therefore reduces temperature while can carrying out normal pet reaction, moreover it is possible to
Enough avoid the generation of side reaction.
In step 4, while continuing to fill into p-phthalic acid, it is additionally added Isosorbide-5-Nitrae-diacetoxy benzene, Isosorbide-5-Nitrae-benzene diformazan
Alcohol, 2,3-dibromo-2-butene-1,4-glycol changes the branched structure of molecule segment, the addition energy of Isosorbide-5-Nitrae-diacetoxy benzene
Enough the most preferably with the combination of later stage antibacterial, the addition of Isosorbide-5-Nitrae-benzene dimethanol enhances the intensity of entirety, and 2,3-bis-bromo-2-fourths
The addition of alkene-Isosorbide-5-Nitrae-glycol, it is possible to increase overall fire resistance.
Step 5 is while filling into p-phthalic acid, it is also desirable to fill into part ethylene glycol, prevents system viscosity excessive, sends out
Raw excessively polymerization, is simultaneously introduced 2，2-dimethyl-1，3-propanediol, Molecular regulator chain so that molecular weight product is more uniform, with
Time product light transmittance also be able to be guaranteed.
Addition in batches in step 5, owing to itself being provided with certain viscosity, is directly added into and is easy to make
Become the reunion of local.
In step 6, finally add remaining p-phthalic acid and ethylene glycol, carry out final polyreaction, obtain molecule
Measure bigger polymer.
In step 7, through the reaction of step 6, whole system basic forming, the bromo terephthalic acid added afterwards
Dimethyl ester, 2,2-bis-fluoro-1, cyclopentadienyl disliked by 3-benzo two, magnesium fluosilicate, antibacterial belong to modifying agent, bromo terephthalic acid's dimethyl ester
Can react with the polymer that reaction generates, the fire resistance that raising is overall, 2,2-bis-fluoro-1, cyclopentadienyl itself disliked by 3-benzo two
Can the overall intensity of goods, simultaneously close with polyethylene terephthalate in itself structure, therefore have preferably
The compatibility, it is possible to be evenly distributed between strand, with 2 be aggregated on strand, 3-dibromo-2-butene-1,4-glycol exists
In varying degrees, the anti-flammability of entirety is further strengthened.The addition of magnesium fluosilicate enables to improve the intensity of polyester, with
Time also be able to play the effect of a stabilizer so that polyester is no matter in processing or can embody during using certain
Stability.The addition of antibacterial can improve the anti-microbial property of its entirety.
In catalyst adition process, diluted, it is possible to prevent local concentration excessive and cause the phenomenon locally reunited.
On antibacterial, selecting quaternary antibacterial, its quaternary ammonium salt meets on nano silicon.
In the preparation process of antibacterial, nano silicon can be at chlorobenzoyl chloride, 4-bromobutanoylchloride, Phosphorous chloride.
Under the conditions of be activated further, the particularly addition of Phosphorous chloride., it is possible to increase the activity function of nano silicon, make simultaneously
The antibacterial that must finally give has preferably weatherability, i.e. also is able to play preferable antibacterial effect during long-time use
Really.
Afterwards it is carried out, chloroform parachlorobenzoyl chloride, Phosphorous chloride. dissolubility preferable, it is possible to taken
Going out, ethylene glycol then can take out the chloroform of residual, finally cleans with acetone, it is possible to thoroughly takes out residuals.
By active nano silicon dioxide and polymine, two (trimethyl is silica-based) phosphinylidyne diimine, polycarbodiimide
Reaction, is fixed on nanometer two by the group on polymine, two (trimethyl is silica-based) phosphinylidyne diimine, polycarbodiimide
On silicon oxide.It is eventually adding glycol dibromide, bromohexane, bromoacetyl bromide, 1-bromo-3-methybutane and is fixed on active nano
The group of silicon dioxide reacts, and obtains quaternary ammonium salt antiseptic, and quaternary ammonium salt antiseptic has had been fastened to nano-silica
On the carrier of SiClx.Such antibacterial is not susceptible to run off, and makes antibacterial effect more preferably on the carrier of nano silicon
Stable.Wherein reaction is main at polymine, two (trimethyl is silica-based) phosphinylidyne diimine, polycarbodiimide and 1,2-dibromo
Reacting between ethane, bromohexane, bromoacetyl bromide, 1-bromo-3-methybutane, the quaternary ammonium salt that reaction generates has strong stability
Property, the addition of particularly two (trimethyl is silica-based) phosphinylidyne diimine, it is possible to make the adhesion with silicon dioxide more preferable, be difficult to from
Coming off on nano silicon, the addition of bromoacetyl bromide simultaneously also improves the activity of antibacterial.
By PP layer and the combination of pet layer so that whole composite membrane has possessed high barrier, the most also it is provided with antibacterial
Property, the feature of anti-flammability.
Detailed description of the invention
Embodiment
A kind of high barrier PET/PP film, joins PP plastic pellet and PET particle in coextrusion casting film machine and makes
Become to include the PET/PP film of pet layer and PP layer,
Described PP plastic pellet includes that following weight portion forms:
PP:120 part, trihydroxy polypropylene oxide ether: 25 parts, N, N '-(4,4 '-methylenediphenyl) bismaleimide
Amine: 5 parts, trimethylolpropane tris acrylic acid methyl ester.: 15 parts, 4,4 '-dihydroxy diphenyl sulfide: 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, vinyl three tert-butyl peroxide silane: 1 part；
Described PET particle includes that following weight portion forms:
P-phthalic acid: 1000 parts, ethylene glycol: 600 parts, 2-amino p-phthalic acid: 15 parts, 2-nitroterephthalic acid-
4-methyl ester: 10 parts, Isosorbide-5-Nitrae-diacetoxy benzene: 7 parts, Isosorbide-5-Nitrae-benzene dimethanol: 8 parts, 2，2-dimethyl-1，3-propanediol: 10
Part, 2,3-dibromo-2-butene-1,4-glycol: 5 parts, adjacent bromo terephthalic acid's dimethyl ester: 10 parts, 2,2-bis-fluoro-1,3-benzo two
Dislike luxuriant: 3 parts, magnesium fluosilicate: 5 parts, antibacterial 5 parts.
Needed raw material is weighed according to weight proportion, the most under nitrogen protection, by uniform for each raw material stirring weighed, room temperature
Stirring 60-80min, is then heated to 60-80 DEG C, stirs 2h, and then temperature reduces 40-50 DEG C, stirs 2h, joins comminutor
Middle extruding pelletization obtains PP plastic pellet.
Described PET particle production method is:
Step one: p-phthalic acid 400 parts, ethylene glycol 400 parts are joined in reactor, is warming up to 40 DEG C and prepares
Mixing；
Step 2: be warming up to 200～220 degrees Celsius and carry out esterification, after reacting 30～50 minutes, adds Ti/Si system
Catalyst 0.01～0.5 part, continue reaction 10～30 minutes；
Step 3: add p-phthalic acid 200 parts, 2-amino p-phthalic acid 5 parts, 2-nitroterephthalic acid-4-methyl ester
10 parts, it is cooled to 180～200 DEG C, reacts 20～40 minutes；
Step 4: add p-phthalic acid 100 parts, Isosorbide-5-Nitrae-diacetoxy benzene 7 parts, Isosorbide-5-Nitrae-benzene dimethanol 8 parts, 2,3-bis-
Bromo-2-butylene-Isosorbide-5-Nitrae-glycol 5 parts, temperature is maintained at 180～200 DEG C, enters Ti/Si series catalysts 0.01～0.5 part, reacts 20
～30 minutes；
Step 5: add p-phthalic acid 200 parts, ethylene glycol 100 parts, 2，2-dimethyl-1，3-propanediol: 10 parts, rise
Temperature, to 200～250 DEG C, is reacted 10～30 minutes；
Step 6: add phthalic acid 100 parts, ethylene glycol 100 parts is warming up to 250～280 DEG C, 200～300Pa vacuum bars
React 30～60 minutes under part；
Step 7: add after completing reaction adjacent bromo terephthalic acid's dimethyl ester 10 parts, 2,2-bis-fluoro-1, cyclopentadienyl disliked by 3-benzo two
3 parts, magnesium fluosilicate 5 parts, antibacterial 5 parts, temperature controls at 100～120 DEG C, after being stirred 30～40 minutes, continue stirring,
Carry out pelletize after being naturally cooling to 50～60 DEG C and obtain PET particle.
In described step 5, be initially charged p-phthalic acid 50 parts, afterwards add ethylene glycol 100 parts, remaining 150 parts right
Phthalic acid is divided into three parts, added 50 parts of p-phthalic acids every 10 minutes, is eventually adding 2，2-dimethyl-1，3-propanediol 10
Part.
In described step one, before adding raw material, first addition 2 in reaction vessel, 6-di-tert-butyl-4-methy phenol,
Add 200 parts of ethylene glycol, stir 5～15 minutes, add remaining 600 parts of ethylene glycol and 400 parts of p-phthalic acids, be warming up to
40 DEG C carry out ready-mixed.
When described step 2 and step 4 add Ti/Si series catalysts, first by Ti/Si series catalysts 50ml ethylene glycol
Dilution, in joining reaction vessel.,
Described antibacterial is prepared according to following method:
In step A:10g nano silicon, add the parachlorobenzoyl chloride of 2ml, the 4-bromobutanoylchloride of 1ml, 1ml trichlorine
Changing phosphorus, under the conditions of 20～30 DEG C, stirring reaction 10～15 hours, carry out activation to nano silicon；
Step B: after having reacted be centrifuged mixture, uses chloroform, ethylene glycol, acetone to carry out clearly successively
Wash, be dried, obtain activating nano silicon；
Step C: add 7g polymine, 2g bis-(trimethyl is silica-based) phosphinylidyne two Asia in activation nano silicon
Amine, 1g polycarbodiimide, add 0.1gKOH, stirs 15～20 hours under conditions of 85 DEG C；
Step D: react through centrifugal after terminating, and fully wash with methanol, be dried；
Step E: the nano grade silica particles after air-drying is encased in the isobutanol of 20ml, adds the 1 of 2ml afterwards,
2-Bromofume, the bromohexane of 6ml, 0.1g bromoacetyl bromide, the 1-bromo-3-methybutane of 1ml, then stir under the conditions of 70～80 DEG C
15～25 hours；
Step F: cool to 30～45 DEG C after having reacted, then it is added thereto to 5ml potassium iodide, stir 8～12 hours, warp
Cross centrifugal, fully wash with methanol, be then dried to obtain antibacterial.
Comparative example:
Select commercial PP particle and PET particle, join and coextrusion casting film machine carries out extrusion make coextrusion casting film.
PP particle selects the SFC-650BT casting films PP Pipe Compound of the carefree chemistry of Korea S, and PET particle selects the 935BK505 of Dupont to mould
Material particle.
Test, is all prepared as casting films by above-mentioned material, and thickness is 200 μm, tests its hot strength, transparency, antibacterial
Property, fire resistance, oxygen transmission rate when not rubbing folding, rub oxygen transmission rate after folding.And irradiate examination in 50,100,150,200 hours at hernia lamp
Above-mentioned test is carried out after testing.
Accurately weigh 0.1g sample, join in the triangular flask equipped with 99mL sterilized water, with ultrasonic wavelength-division 20min.Add
1mL concentration is 107CFU/mL bacteria suspension.Separately take a triangular flask equipped with 99mL sterilized water as blank, only add 1mL
Bacteria suspension.Above-mentioned triangular flask is placed in shaken cultivation case, in 37 DEG C, shaken cultivation 30min under the conditions of 200r/min.In triangular flask
Respectively take 0.2mL mixed liquor, suitably after dilution, be coated on culture dish, constant temperature culture 48～72h at 35 DEG C, carry 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 group；
B adds the average colony number of antimicrobial sample to be measured.
Staphylococcus aureus and escherichia coli are selected in the selection of strain.
Table one: without hernia lamp exposure experiment data
| Embodiment | Comparative example | |
| Hot strength (N/mm^2) | 243 | 152 |
| Flame retardant rating UL 94 index | V-0 | V-1 |
| Staphylococcus aureus antibiotic rate % | 95 | 23 |
| Escherichia coli antibiotic rate % | 93 | 21 |
| Do not rub folding oxygen transmission rate cm3/ (m2 24h 0.1MPa) | 0.3 | 1.5 |
| Rub folding oxygen transmission rate cm3/ (m2 24h 0.1MPa) | 0.4 | 2.0 |
| Transparency % | 91% | 85% |
Table two: irradiate 50 hours test datas through hernia lamp
Table three: irradiate 100 hours test datas through hernia lamp
| Embodiment | Comparative example | |
| Hot strength (N/mm^2) | 238 | 111 |
| Flame retardant rating UL 94 index | V-0 | V-2 |
| Staphylococcus aureus antibiotic rate % | 91 | 12 |
| Escherichia coli antibiotic rate % | 90 | 11 |
| Do not rub folding oxygen transmission rate cm3/ (m2 24h 0.1MPa) | 0.6 | 1.5 |
| Rub folding oxygen transmission rate cm3/ (m2 24h 0.1MPa) | 0.7 | 2.0 |
| Transparency % | 91% | 80% |
Table four: irradiate 150 hours test datas through hernia lamp
| Embodiment | Comparative example | |
| Hot strength (N/mm^2) | 230 | 100 |
| Flame retardant rating UL 94 index | V-0 | V-2 |
| Staphylococcus aureus antibiotic rate % | 90 | 5 |
| Escherichia coli antibiotic rate % | 88 | 5 |
| Do not rub folding oxygen transmission rate cm3/ (m2 24h 0.1MPa) | 0.8 | 7 |
| Rub folding oxygen transmission rate cm3/ (m2 24h 0.1MPa) | 0.9 | 9 |
| Transparency % | 91% | 80% |
Table five: irradiate 200 hours test datas through hernia lamp
| Embodiment | Comparative example | |
| Hot strength (N/mm^2) | 221 | 80 |
| Flame retardant rating UL 94 index | V-0 | V-2 |
| Staphylococcus aureus antibiotic rate % | 88 | 5 |
| Escherichia coli antibiotic rate % | 85 | 5 |
| Do not rub folding oxygen transmission rate cm3/ (m2 24h 0.1MPa) | 1.0 | 10 |
| Rub folding oxygen transmission rate cm3/ (m2 24h 0.1MPa) | 1.0 | 11 |
| Transparency % | 91% | 80% |
Carry out extrusion make Multi-layer cast film by PET particle and PP plastic pellet being carried out coextrusion casting film machine,
By the complementation between bi-material, thus a preferable high-barrier, fire-retardant, antibacterial effect can be reached.
First being PP plastic pellet, PP plastic pellet is sent out by blending and modifying and is prepared, and wherein with PP major ingredient, adds N,
N '-(4,4 '-methylenediphenyl) BMI, reacts with PP, the molecule segment of regulation PP, strengthens entirety
Barrier property.The trimethylolpropane tris acrylic acid methyl ester. wherein added can have the most compatible with the molecule segment of PP
Agent, simultaneous with oh group, it is possible to obtain a preferable anti-fog performance in the final product.4,4 '-dihydroxy hexichol
The addition of thioether, provides hydroxyl on the one hand to whole system, simultaneously can also be with trimethylolpropane tris acrylic acid methyl ester.
The compatibility is more preferable, the phenyl ring that on the other hand sulphur atom two ends connect, it is possible to increase whole obstruct film strength.Montmorillonite and nanometer
Ti02 is added thereto as modified material, reduces cost, and the performance being also simultaneously will not decline.The addition of paraffin is as lubrication
Agent, it is possible to processing is more prone to.Polyether siloxane copolymer as defoamer, methyl hydroxyethylcellulose as thickening agent
Add regulation viscosity, vinyl three tert-butyl peroxide silane addition as coupling agent, in step one, first by big portion
The p-phthalic acid, the ethylene glycol that divide join in reaction vessel, first carry out a pre-mixing process, are warming up to 40 DEG C simultaneously,
Enable to its premixing more uniform, promote intermolecular free motion.Can effectively prevent from adding suddenly an excess amount of instead
Answer raw material that the phenomenon being excessively polymerized can occur.In step 2 afterwards, start to warm up to 200～220 degrees Celsius and add Ti/
Si series catalysts, starts pet reaction, and in whole reaction system, the amount of ethylene glycol is far longer than p-phthalic acid, on the one hand second
Glycol is solvent, it is possible to reduces and plays a diluting effect, so that p-phthalic acid can slowly gather with ethylene glycol generation
Ester reacts.
2 added before the reaction, 6-di-tert-butyl-4-methy phenol is a kind of general antioxidant, with ethylene glycol together
Add container, on the one hand reaction vessel is had a cleaning action, on the other hand also is able to prevent polyester quilt in course of reaction
Oxidation.
After the reaction of step 2 in step 3, the p-phthalic acid in system is the most reacted completely, it is therefore desirable to
Continuing to supplement such as p-phthalic acid, 2-amino p-phthalic acid, the addition of 2-nitroterephthalic acid-4-methyl ester simultaneously can consume
While part ethylene glycol, it is possible to introduce amino and nitro in whole system, it is possible to strengthen the weatherability of whole system, simultaneously
Also with phenyl group, it is possible to and whole system similar compatibility, improve the overall compatibility, therefore, it is possible to bring the most uniformly
Property, it is to avoid the lifting of Local Property.Also reduce reaction temperature, owing to 2-amino p-phthalic acid, 2-nitro are to benzene simultaneously
The side chain of diacid-4-methyl ester is easy to be activated, and therefore reduces temperature while can carrying out normal pet reaction, moreover it is possible to
Enough avoid the generation of side reaction.
In step 4, while continuing to fill into p-phthalic acid, it is additionally added Isosorbide-5-Nitrae-diacetoxy benzene, Isosorbide-5-Nitrae-benzene diformazan
Alcohol, 2,3-dibromo-2-butene-1,4-glycol changes the branched structure of molecule segment, the addition energy of Isosorbide-5-Nitrae-diacetoxy benzene
Enough the most preferably with the combination of later stage antibacterial, the addition of Isosorbide-5-Nitrae-benzene dimethanol enhances the intensity of entirety, and 2,3-bis-bromo-2-fourths
The addition of alkene-Isosorbide-5-Nitrae-glycol, it is possible to increase overall fire resistance.
Step 5 is while filling into p-phthalic acid, it is also desirable to fill into part ethylene glycol, prevents system viscosity excessive, sends out
Raw excessively polymerization, is simultaneously introduced 2，2-dimethyl-1，3-propanediol, Molecular regulator chain so that molecular weight product is more uniform, with
Time product light transmittance also be able to be guaranteed.
Addition in batches in step 5, owing to itself being provided with certain viscosity, is directly added into and is easy to make
Become the reunion of local.
In step 6, finally add remaining p-phthalic acid and ethylene glycol, carry out final polyreaction, obtain molecule
Measure bigger polymer.
In step 7, through the reaction of step 6, whole system basic forming, the bromo terephthalic acid added afterwards
Dimethyl ester, 2,2-bis-fluoro-1, cyclopentadienyl disliked by 3-benzo two, magnesium fluosilicate, antibacterial belong to modifying agent, bromo terephthalic acid's dimethyl ester
Can react with the polymer that reaction generates, the fire resistance that raising is overall, 2,2-bis-fluoro-1, cyclopentadienyl itself disliked by 3-benzo two
Can the overall intensity of goods, simultaneously close with polyethylene terephthalate in itself structure, therefore have preferably
The compatibility, it is possible to be evenly distributed between strand, with 2 be aggregated on strand, 3-dibromo-2-butene-1,4-glycol exists
In varying degrees, the anti-flammability of entirety is further strengthened.The addition of magnesium fluosilicate enables to improve the intensity of polyester, with
Time also be able to play the effect of a stabilizer so that polyester is no matter in processing or can embody during using certain
Stability.The addition of antibacterial can improve the anti-microbial property of its entirety.
In catalyst adition process, diluted, it is possible to prevent local concentration excessive and cause the phenomenon locally reunited.
On antibacterial, selecting quaternary antibacterial, its quaternary ammonium salt meets on nano silicon.
In the preparation process of antibacterial, nano silicon can be at chlorobenzoyl chloride, 4-bromobutanoylchloride, Phosphorous chloride.
Under the conditions of be activated further, the particularly addition of Phosphorous chloride., it is possible to increase the activity function of nano silicon, make simultaneously
The antibacterial that must finally give has preferably weatherability, i.e. also is able to play preferable antibacterial effect during long-time use
Really.
Afterwards it is carried out, chloroform parachlorobenzoyl chloride, Phosphorous chloride. dissolubility preferable, it is possible to taken
Going out, ethylene glycol then can take out the chloroform of residual, finally cleans with acetone, it is possible to thoroughly takes out residuals.
By active nano silicon dioxide and polymine, two (trimethyl is silica-based) phosphinylidyne diimine, polycarbodiimide
Reaction, is fixed on nano-silica by the group on polymine, two (trimethyl is silica-based) phosphinylidyne diimine, polycarbodiimide
In SiClx.It is eventually adding glycol dibromide, bromohexane, bromoacetyl bromide, 1-bromo-3-methybutane and is fixed on active nano two
The group of silicon oxide 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 is not susceptible to run off, and makes antibacterial effect the most steady on the carrier of nano silicon
Fixed.Wherein reaction is main in polymine, two (trimethyl is silica-based) phosphinylidyne diimine, polycarbodiimide and 1,2-dibromo second
Reacting between alkane, bromohexane, bromoacetyl bromide, 1-bromo-3-methybutane, the quaternary ammonium salt that reaction generates has stiff stability,
The addition of particularly two (trimethyl is silica-based) phosphinylidyne diimine, it is possible to make the adhesion with silicon dioxide more preferable, be difficult to from receiving
Coming off on rice silicon dioxide, the addition of bromoacetyl bromide simultaneously also improves the activity of antibacterial.
By PP layer and the combination of pet layer so that whole composite membrane has possessed high barrier, the most also it is provided with antibacterial
Property, the feature of anti-flammability.
The above is only the preferred embodiment of the present invention, and protection scope of the present invention is not limited merely to above-mentioned enforcement
Example, all technical schemes belonged under thinking of the present invention belong to protection scope of the present invention.It should be pointed out that, for the art
Those of ordinary skill for, some improvements and modifications without departing from the principles of the present invention, these improvements and modifications are also
Should be regarded as protection scope of the present invention.
Claims (7)
1. a high barrier PET/PP film, it is characterised in that: PP plastic pellet and PET particle are joined coextrusion casting
Film machine is made the PET/PP film including pet layer and PP layer,
Described PP plastic pellet includes that following weight portion forms:
PP:120 part, trihydroxy polypropylene oxide ether: 25 parts, N, N '-(4,4 '-methylenediphenyl) BMI: 5
Part, trimethylolpropane tris acrylic acid methyl ester.: 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, vinyl three tert-butyl peroxide silane: 1 part；
Described PET particle includes that following weight portion forms:
P-phthalic acid: 1000 parts, ethylene glycol: 600 parts, 2-amino p-phthalic acid: 15 parts, 2-nitroterephthalic acid-4-first
Ester: 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-glycol: 5 parts, adjacent bromo terephthalic acid's dimethyl ester: 10 parts, 2,2-bis-fluoro-1, cyclopentadienyl disliked by 3-benzo two: 3
Part, magnesium fluosilicate: 5 parts, antibacterial 5 parts.
A kind of high barrier PET/PP film the most according to claim 1, it is characterised in that: described PP plastic pellet producer
Method is: weigh needed raw material according to weight proportion, and the most under nitrogen protection, by uniform for each raw material stirring weighed, room temperature is stirred
Mixing 60-80min, be then heated to 60-80 DEG C, stir 2h, then temperature reduces 40-50 DEG C, stirs 2h, joins in comminutor
Extruding pelletization obtains PP plastic pellet.
A kind of high barrier PET/PP film the most according to claim 1 and 2, it is characterised in that: described PET particle is raw
Product method is:
Step one: join in reactor by p-phthalic acid 400 parts, ethylene glycol 400 parts, being warming up to 40 DEG C, to carry out preparation mixed
Close；
Step 2: be warming up to 200～220 degrees Celsius and carry out esterification, after reacting 30～50 minutes, adds the catalysis of Ti/Si system
Agent 0.01～0.5 part, continue reaction 10～30 minutes；
Step 3: addition p-phthalic acid 200 parts, 2-amino p-phthalic acid 5 parts, 2-nitroterephthalic acid-4-methyl ester 10 parts,
It is cooled to 180～200 DEG C, reacts 20～40 minutes；
Step 4: add p-phthalic acid 100 parts, Isosorbide-5-Nitrae-diacetoxy benzene 7 parts, Isosorbide-5-Nitrae-benzene dimethanol 8 parts, 2,3-bis-is bromo-
2-butylene-Isosorbide-5-Nitrae-glycol 5 parts, temperature is maintained at 180～200 DEG C, enters Ti/Si series catalysts 0.01～0.5 part, reacts 20～30
Minute；
Step 5: add p-phthalic acid 200 parts, ethylene glycol 100 parts, 2，2-dimethyl-1，3-propanediol: 10 parts, be warming up to
200～250 DEG C, react 10～30 minutes；
Step 6: add phthalic acid 100 parts, ethylene glycol 100 parts is warming up to 250～280 DEG C, under 200～300Pa vacuum conditions
React 30～60 minutes；
Step 7: add after completing reaction adjacent bromo terephthalic acid's dimethyl ester 10 parts, 2,2-bis-fluoro-1,3-benzo two dislike cyclopentadienyl 3 parts,
Magnesium fluosilicate 5 parts, antibacterial 5 parts, temperature controls at 100～120 DEG C, after being stirred 30～40 minutes, continues stirring, natural
Carry out pelletize after being cooled to 50～60 DEG C and obtain PET particle.
A kind of high barrier PET/PP film the most according to claim 3, it is characterised in that: described antibacterial is according to following side
Prepared by method:
In step A:10g nano silicon, add the parachlorobenzoyl chloride of 2ml, the 4-bromobutanoylchloride of 1ml, 1ml tri-chlorination
Phosphorus, under the conditions of 20～30 DEG C, stirring reaction 10～15 hours, carry out activation to nano silicon；
Step B: after having reacted be centrifuged mixture, uses chloroform, ethylene glycol, acetone to be carried out successively, enters
Row is dried, and obtains activating nano silicon；
Step C: add 7g polymine, 2g bis-(trimethyl is silica-based) phosphinylidyne diimine, 1g in activation nano silicon
Polycarbodiimide, adds 0.1gKOH, stirs 15～20 hours under conditions of 85 DEG C；
Step D: react through centrifugal after terminating, and fully wash with methanol, be dried；
Step E: the nano grade silica particles after air-drying is encased in the isobutanol of 20ml, adds the 1 of 2ml afterwards, 2-bis-
Bromoethane, the bromo-n-hexane of 6ml, 0.1g bromoacetyl bromide, the 1-bromo-3-methybutane of 1ml, then under the conditions of 70～80 DEG C stir 15～
25 hours；
Step F: cool to 30～45 DEG C after having reacted, then it is added thereto to 5ml potassium iodide, stir 8～12 hours, Jing Guoli
The heart, fully washs with methanol, is then dried to obtain antibacterial.
A kind of high barrier PET/PP film the most according to claim 4, it is characterised in that: in described step 5, it is initially charged
P-phthalic acid 50 parts, afterwards addition ethylene glycol 100 parts, remaining 150 parts of p-phthalic acids are divided into three parts, added every 10 minutes
Enter 50 parts of p-phthalic acids, be eventually adding 2，2-dimethyl-1，3-propanediol 10 parts.
A kind of high barrier PET/PP film the most according to claim 5, it is characterised in that: in described step one, adding
Before raw material, first addition 2,6-di-tert-butyl-4-methy phenol in reaction vessel, add 200 parts of ethylene glycol, stir 5～15 points
Clock, adds remaining 600 parts of ethylene glycol and 400 parts of p-phthalic acids, is warming up to 40 DEG C and carries out ready-mixed.
A kind of high barrier PET/PP film the most according to claim 3, it is characterised in that: in described step 2 and step 4
When adding Ti/Si series catalysts, first Ti/Si series catalysts 50ml ethylene glycol is diluted, in joining reaction vessel.
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| CN107312248A (en) * | 2017-08-22 | 2017-11-03 | 安徽松泰包装材料有限公司 | A kind of high-barrier antibacterial polypropylene film |
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