CN106046539B - A kind of double-layer coextrusion casting films - Google Patents

A kind of double-layer coextrusion casting films Download PDF

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CN106046539B
CN106046539B CN201610431446.9A CN201610431446A CN106046539B CN 106046539 B CN106046539 B CN 106046539B CN 201610431446 A CN201610431446 A CN 201610431446A CN 106046539 B CN106046539 B CN 106046539B
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terephthalic acid
tpa
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CN106046539A (en
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林福亮
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Jiangsu Qiushi Plastic Industry Co., Ltd.
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Jiangsu Qiushi Plastic Industry Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/10—Homopolymers or copolymers of propene
    • C08L23/12—Polypropene
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C41/00—Shaping by coating a mould, core or other substrate, i.e. by depositing material and stripping-off the shaped article; Apparatus therefor
    • B29C41/24—Shaping by coating a mould, core or other substrate, i.e. by depositing material and stripping-off the shaped article; Apparatus therefor for making articles of indefinite length
    • B29C41/32—Making multilayered or multicoloured articles
    • 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
    • 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
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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
    • B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
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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
    • B32B27/32—Layered products comprising a layer of synthetic resin comprising polyolefins
    • 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
    • B32B27/36—Layered products comprising a layer of synthetic resin comprising polyesters
    • 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
    • C08G63/68—Polyesters containing atoms other than carbon, hydrogen and oxygen
    • C08G63/682—Polyesters containing atoms other than carbon, hydrogen and oxygen containing halogens
    • C08G63/6824—Polyesters containing atoms other than carbon, hydrogen and oxygen containing halogens derived from polycarboxylic acids and polyhydroxy compounds
    • C08G63/6828—Polycarboxylic acids and polyhydroxy compounds in which at least one of the two components contains aliphatic unsaturation
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    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/68—Polyesters containing atoms other than carbon, hydrogen and oxygen
    • C08G63/685—Polyesters containing atoms other than carbon, hydrogen and oxygen containing nitrogen
    • C08G63/6854—Polyesters containing atoms other than carbon, hydrogen and oxygen containing nitrogen derived from polycarboxylic acids and polyhydroxy compounds
    • C08G63/6858—Polycarboxylic acids and polyhydroxy compounds in which at least one of the two components contains aliphatic unsaturation
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    • 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
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    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/91—Polymers modified by chemical after-treatment
    • C08G63/914—Polymers modified by chemical after-treatment derived from polycarboxylic acids and polyhydroxy compounds
    • C08G63/918—Polycarboxylic acids and polyhydroxy compounds in which at least one of the two components contains aliphatic unsaturation
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    • 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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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
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    • C08K9/04—Ingredients treated with organic substances
    • 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
    • B32B2250/00—Layers arrangement
    • B32B2250/24—All layers being polymeric
    • 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
    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
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    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/50—Properties of the layers or laminate having particular mechanical properties
    • B32B2307/54—Yield strength; Tensile strength
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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
    • 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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    • C08L2205/00—Polymer mixtures characterised by other features
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  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)
  • Polyesters Or Polycarbonates (AREA)

Abstract

The invention discloses a kind of double-layer coextrusion casting films, including pet layer and PP layers, the PP plastic pellets include following composition：PP, trihydroxy polypropylene oxide ether, N, N '-(4,4 '-methylenediphenyls) bismaleimide, trimethylolpropane tris methyl acrylate, 4,4 '-dihydroxy diphenyl sulfides, montmorillonite, paraffin, antioxidant 1010, nano TiO 2, polyether siloxane copolymer, methyl hydroxyethylcellulose, three tert-butyl peroxide silane of vinyl；The PET plastic particle includes following parts by weight composition：Terephthalic acid (TPA), ethylene glycol, maleic anhydride, 2- nitroterephthalic acid -4- methyl esters, 2,2- dimethyl -1,3-propanediol, 2, bis- bromo- 2- butene-1s of 3-, 4- glycol, 1,4- benzene dimethanols, 2- amino terephthalic acid (TPA), tetrabromo terephthalic acids, bis- (2- ethylhexyls) terephthalic acids, 4- bromos phthalic anhydride, 2,2-, bis- fluoro- 1,3- benzos two dislike cyclopentadienyl, magnesium fluosilicate, antiseptic.Pass through PP layers and the combination of pet layer so that entire composite membrane has high barrier, while the characteristics of be also provided with antibiotic property, anti-flammability.

Description

A kind of double-layer coextrusion casting films
Technical field
The present invention relates to a kind of packaging material, more particularly to a kind of double-layer coextrusion casting films.
Background technology
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 especially in some food packagings also Need some for the requirement of anti-microbial property, anti-flammability.Especially during long-time use, 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.
Invention content
In view of the deficiencies of the prior art, the present invention intends to provide one kind.
To achieve the above object, the present invention provides following technical solutions：
PP plastic pellets and PET plastic particle are added in coextrusion casting film machine and are made by a kind of double-layer coextrusion casting films PET/PP films including pet layer and PP layers,
The PP plastic pellets include 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, maleic anhydride：50 parts, 2- nitroterephthalic acid -4- methyl esters： 10 parts, 2,2-dimethyl-1,3-propanediol：10 parts, 2,3- dibromo-2-butene-1,4-glycols：5 parts, Isosorbide-5-Nitrae-benzene dimethanol：8 Part, 2- amino terephthalic acid (TPA)s：15 parts, tetrabromo terephthalic acids：5 parts, bis- (2- ethylhexyls) terephthalic acids：8 parts, 4- bromobenzenes Acid anhydride：5 parts, 2,2-, bis- fluoro- 1,3- benzos two dislike cyclopentadienyl：3 parts, magnesium fluosilicate：5 parts, 5 parts of antiseptic.
As a further improvement on the present invention：The PP plastic pellets production method is：It is weighed according to weight proportion required Then under nitrogen protection each raw material weighed 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 comminutor and obtains PP plastic pellets.
As a further improvement on the present invention：The PET plastic particle production method is：
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, after reacting 30~50 minutes, Ti/Si systems are added 0.01~0.5 part of catalyst, the reaction was continued 10~30 minutes；
Step 3：200 parts of terephthalic acid (TPA) of addition, 50 parts of maleic anhydride, 10 parts of 2- nitroterephthalic acid -4- methyl esters, 180~200 DEG C are cooled to, is reacted 20~40 minutes；
Step 4：100 parts of terephthalic acid (TPA), 10 parts of 2,2-dimethyl-1,3-propanediol, 2,3-, bis- bromo- 2- butylene-is added 5 parts of Isosorbide-5-Nitrae-glycol, temperature are maintained at 180~200 DEG C, and 0.01~0.5 part of Ti/Si series catalysts are added, and react 20~30 minutes；
Step 5：200 parts of terephthalic acid (TPA), 100 parts of ethylene glycol, 8 parts of Isosorbide-5-Nitrae-benzene dimethanol, 2- amino terephthaldehydes is added 15 parts of acid is warming up to 200~250 DEG C, reacts 10~30 minutes, it is spare to obtain major ingredient；
Step 6：A reaction kettle is set up another in the preparation of auxiliary material, and 100 parts of phthalic acid, 100 parts of ethylene glycol, tetrabromo is added to benzene 5 parts of diacid, bis- 8 parts of (2- ethylhexyls) terephthalic acids, 5 parts of 4- bromos phthalic anhydride；Temperature is maintained at 180~200 DEG C, and Ti/ is added 0.01~0.5 part of Si series catalysts, it is spare that reaction obtains auxiliary material in 30~60 minutes；
Step 7：Auxiliary material is slowly added into the reaction kettle of major ingredient, addition while is stirred, and temperature is maintained at 40 ~50 degrees Celsius, 180~200 DEG C are to slowly warm up to after addition, insulated and stirred 20~40 minutes；
Step 8 is warming up to 250~280 DEG C, is reacted 30~60 minutes under 200~300Pa vacuum conditions；
Step 9：It completes adjacent 10 parts of the bromo terephthalic acid's dimethyl ester of addition, 2,2-, bis- fluoro- 1,3- benzos two after reacting and dislikes cyclopentadienyl 3 parts, 5 parts of magnesium fluosilicate, 5 parts of antiseptic, temperature controls at 100~120 DEG C, is stirred 30~after forty minutes, continues to stir, It is granulated to obtain PET plastic particle after being naturally cooling to 50~60 DEG C.
As a further improvement on the present invention：The antiseptic is prepared according to following methods：
Step A：In 10g nano silicon dioxides, the parachlorobenzoyl chloride of 2ml, the 4- bromobutanoylchlorides of 1ml, 1ml trichlorines is added Change phosphorus, is stirred to react 10~15 hours under the conditions of 20~30 DEG C, nano silicon dioxide is activated；
Step B：Mixture is centrifuged after the completion of reaction, uses chloroform, ethylene glycol, acetone to carry out successively clear It washes, is dried, obtain activation nano silicon dioxide；
Step C：It is sub- that 7g polyethyleneimines, 2g bis- (trimethyl silicon substrate) phosphinylidyne two are added in activating nano silicon dioxide Amine, 1g polycarbodiimides are added 0.1gKOH, are stirred 15~20 hours under conditions of 85 DEG C；
Step D：After reaction by centrifugation, it is used in combination methanol fully to be washed, is dried；
Step E：Nano grade silica particles after air-drying are encased in the isobutanol of 20ml, the 1 of 2ml is added later, The bromo- 3- methybutanes of 1- of 2- Bromofumes, the bromohexane of 6ml, 0.1g bromoacetyl bromides, 1ml, then stirred under the conditions of 70~80 DEG C 15~25 hours；
Step F：30~45 DEG C are cooled to after the completion of reaction, then 5ml potassium iodide is added thereto, are stirred 8~12 hours, warp Centrifugation is crossed, is fully washed with methanol, is then dried to obtain antiseptic.
As a further improvement on 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, and 50 parts of terephthalic acid (TPA)s were added every 10 minutes, are eventually adding 2, 10 parts of 2- dimethyl-1,3-propylene glycols.
As a further improvement on 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 phenols, be added 200 parts of ethylene glycol, stir 5~15 minutes, add remaining 600 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 on the present invention：It is described Step 2: Step 4: in step 6 be added Ti/Si series catalysts when, First Ti/Si series catalysts 50ml ethylene glycol is diluted, in being added to reaction vessel.
It is PP plastic pellets first, PP plastic pellets are prepared by blending and modifying hair, wherein with PP major ingredients, add N, 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 improve entire barrier film strength.Montmorillonite and nanometer TiO2 is added thereto as modified material, and the performance for reducing cost, while being also will not decline.The addition of paraffin is as lubrication Agent enables to processing to be more prone to.Polyether siloxane copolymer is as antifoaming 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 play a diluting effect, so that terephthalic acid (TPA) slowly can occur to gather with ethylene glycol Ester reacts.
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 play a diluting effect, so as to benzene Slowly with ethylene glycol pet reaction can occur for dioctyl phthalate.
Since in above-mentioned steps, ethylene glycol is excessive, therefore part terephthalic acid (TPA) is filled into step 3, it is anti-to ensure Answer rate.And the maleic anhydride being added can increase the flexibility of whole segment, adjust the length of strand, can ensure segment While addition with preferable tensile strength, while 2- nitroterephthalic acid -4- methyl esters can consume part ethylene glycol, energy It is enough that amino and nitro are introduced in whole system, the weatherability of whole system can be enhanced, while also carrying phenyl group, Neng Gouhe Whole system similar compatibility improves whole compatibility, therefore can bring preferable uniformity, avoids carrying for Local Property It rises.
Continue to fill into addition terephthalic acid (TPA) in step 4, while 2,2-dimethyl-1,3-propanediol and 2 is added, 3- bis- Bromo- 2- butene-1s, 4- glycol adjust strand so that molecular weight product is more by the way that 2,2-dimethyl-1,3-propanediol is added Add uniformly, while the light transmittance of product can also be guaranteed.2,3- dibromo-2-butene-1,4-glycols can participate in reacting, will Bromine substituent is introduced into even section, can improve whole flame retardant property.
While step 5 fills into part terephthalic acid (TPA), ethylene glycol is also added, before react in, ethylene glycol by What is consumed is similar, and filling into ethylene glycol can ensure that reaction rate will not be lowered.Isosorbide-5-Nitrae-benzene dimethanol, the 2- being added later The addition of amino terephthalic acid (TPA), Isosorbide-5-Nitrae-benzene dimethanol enhances whole intensity, due to the branch of 2- amino terephthalic acid (TPA)s It is easy to be activated, therefore reduces temperature while can carry out normal pet reaction, additionally it is possible to avoid the hair of side reaction It is raw.
Step 6 is then the preparation process of auxiliary material, is still using terephthalic acid (TPA) and ethylene glycol as carrier, tetrabromo pair is added Phthalic acid, bis- (2- ethylhexyls) terephthalic acids, 4- bromo phthalic anhydrides；And the addition of tetrabromo terephthalic acids and 4- bromo phthalic anhydrides, it is main If bromine substituent is introduced into even section, its whole anti-flammability, the addition of bis- (2- ethylhexyls) terephthalic acids ensure that So that the polymerization site of tetrabromo terephthalic acids and 4- bromo phthalic anhydrides will not lean on too close, introduced under conditions of in intermolecular interaction Side-chain radical ensures the uniformity and stability of overall flame performance.
The auxiliary material in step 6 is slowly added into major ingredient later and is mixed, pressurization is carried out after closing very much, polymerisation occurs, Obtain the uniform polyester of physical property.
After polymerisation, whole system basic forming, the bromo terephthalic acid's dimethyl ester being added later, 2,2- Two fluoro- 1,3- benzos two dislike cyclopentadienyl, magnesium fluosilicate, antiseptic and belong to modifying agent, bromo terephthalic acid's dimethyl ester can with react The polymer of generation is reacted, and improves whole flame retardant property, 2,2- bis- fluoro- 1,3- benzos two dislike cyclopentadienyl itself can product it is whole The intensity of body, at the same it is close with polyethylene terephthalate in itself structure, therefore there is preferable compatibility, it can It is evenly distributed between strand, further strengthens whole anti-flammability.The addition of magnesium fluosilicate enables to improve poly- The intensity of ester, while can also play the role of a stabilizer so that polyester is no matter can during processing or use Embody certain stability.The addition of antiseptic can improve its whole anti-microbial property.
The phenomenon that in catalyst adition process, being diluted, local concentration can be prevented excessive and part is caused to be reunited.
2, the 6- di-tert-butyl-4-methy phenols being added before the reaction are a kind of general antioxidant, together with ethylene glycol Container is added, on the one hand to reaction vessel there are one cleaning action, on the other hand can also prevent polyester during the reaction by Oxidation.
On antiseptic, quaternary antiseptic, quaternary ammonium salt is selected to meet on nano silicon dioxide.
In the preparation process of antiseptic, nano silicon dioxide can be in chlorobenzoyl chloride, 4- bromobutanoylchlorides, phosphorus trichloride Under the conditions of be further activated, the especially addition of phosphorus trichloride can improve the activity function of nano silicon dioxide, make simultaneously Obtaining finally obtained antiseptic has preferably weatherability, i.e., preferable antibacterial effect can be also played during long-time use Fruit.
It is cleaned later, chloroform parachlorobenzoyl chloride, the dissolubility of phosphorus trichloride are preferable, can be taken Go out, and ethylene glycol can then take out remaining chloroform, finally be cleaned with acetone, can thoroughly take out residuals.
By active nano silica and polyethyleneimine, two (trimethyl silicon substrate) phosphinylidyne diimines, polycarbodiimide Reaction, nano-silica is fixed on by the group on polyethyleneimine, two (trimethyl silicon substrate) phosphinylidyne diimines, polycarbodiimide In SiClx.It is eventually adding the bromo- 3- methybutanes of 1,2- Bromofumes, 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 antiseptic is not susceptible to be lost in, so that antibacterial effect is more preferably steady on the carrier of nano silicon dioxide 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- methybutanes 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 antiseptic.
Therefore, the thermoplastic polyester material that prepared by the present invention, while there is preferable anti-flammability, antibiotic property, high intensity, In time after long-time use, still there is preferable anti-flammability, antibiotic property, high intensity.
Pass through PP layers and the combination of pet layer so that entire composite membrane has high barrier, while being also provided with antibacterial The characteristics of property, anti-flammability.
Specific implementation mode
Embodiment
PP plastic pellets and PET plastic particle are added in coextrusion casting film machine and are made by a kind of double-layer coextrusion casting films PET/PP films including pet layer and PP layers,
The PP plastic pellets include 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, maleic anhydride：50 parts, 2- nitroterephthalic acid -4- methyl esters： 10 parts, 2,2-dimethyl-1,3-propanediol：10 parts, 2,3- dibromo-2-butene-1,4-glycols：5 parts, Isosorbide-5-Nitrae-benzene dimethanol：8 Part, 2- amino terephthalic acid (TPA)s：15 parts, tetrabromo terephthalic acids：5 parts, bis- (2- ethylhexyls) terephthalic acids：8 parts, 4- bromobenzenes Acid anhydride：5 parts, 2,2-, bis- fluoro- 1,3- benzos two dislike cyclopentadienyl：3 parts, magnesium fluosilicate：5 parts, 5 parts of antiseptic.
The PP plastic pellets production method is：Required raw material is weighed according to weight proportion, it then under nitrogen protection, will Each raw material weighed stirs evenly, and 60-80min is stirred at room temperature, and is then heated to 60-80 DEG C, stirs 2h, and then temperature reduces 40-50 DEG C, 2h is stirred, extruding pelletization in comminutor is added to and obtains PP plastic pellets.The PET plastic particle production method For：
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, after reacting 30~50 minutes, Ti/Si systems are added 0.01~0.5 part of catalyst, the reaction was continued 10~30 minutes；
Step 3：200 parts of terephthalic acid (TPA) of addition, 50 parts of maleic anhydride, 10 parts of 2- nitroterephthalic acid -4- methyl esters, 180~200 DEG C are cooled to, is reacted 20~40 minutes；
Step 4：100 parts of terephthalic acid (TPA), 10 parts of 2,2-dimethyl-1,3-propanediol, 2,3-, bis- bromo- 2- butylene-is added 5 parts of Isosorbide-5-Nitrae-glycol, temperature are maintained at 180~200 DEG C, and 0.01~0.5 part of Ti/Si series catalysts are added, and react 20~30 minutes；
Step 5：200 parts of terephthalic acid (TPA), 100 parts of ethylene glycol, 8 parts of Isosorbide-5-Nitrae-benzene dimethanol, 2- amino terephthaldehydes is added 15 parts of acid is warming up to 200~250 DEG C, reacts 10~30 minutes, it is spare to obtain major ingredient；
Step 6：A reaction kettle is set up another in the preparation of auxiliary material, and 100 parts of phthalic acid, 100 parts of ethylene glycol, tetrabromo is added to benzene 5 parts of diacid, bis- 8 parts of (2- ethylhexyls) terephthalic acids, 5 parts of 4- bromos phthalic anhydride；Temperature is maintained at 180~200 DEG C, and Ti/ is added 0.01~0.5 part of Si series catalysts, it is spare that reaction obtains auxiliary material in 30~60 minutes；Step 7：Auxiliary material is slowly added into major ingredient Reaction kettle in, addition while, is stirred, and temperature is maintained at 40~50 degrees Celsius, and 180 are to slowly warm up to after addition ~200 DEG C, insulated and stirred 20~40 minutes；
Step 8 is warming up to 250~280 DEG C, is reacted 30~60 minutes under 200~300Pa vacuum conditions；
Step 9：It completes adjacent 10 parts of the bromo terephthalic acid's dimethyl ester of addition, 2,2-, bis- fluoro- 1,3- benzos two after reacting and dislikes cyclopentadienyl 3 parts, 5 parts of magnesium fluosilicate, 5 parts of antiseptic, temperature controls at 100~120 DEG C, is stirred 30~after forty minutes, continues to stir, It is granulated to obtain PET plastic particle after being naturally cooling to 50~60 DEG C.
The antiseptic is prepared according to following methods：
Step A：In 10g nano silicon dioxides, the parachlorobenzoyl chloride of 2ml, the 4- bromobutanoylchlorides of 1ml, 1ml trichlorines is added Change phosphorus, is stirred to react 10~15 hours under the conditions of 20~30 DEG C, nano silicon dioxide is activated；
Step B：Mixture is centrifuged after the completion of reaction, uses chloroform, ethylene glycol, acetone to carry out successively clear It washes, is dried, obtain activation nano silicon dioxide；
Step C：It is sub- that 7g polyethyleneimines, 2g bis- (trimethyl silicon substrate) phosphinylidyne two are added in activating nano silicon dioxide Amine, 1g polycarbodiimides are added 0.1gKOH, are stirred 15~20 hours under conditions of 85 DEG C；
Step D：After reaction by centrifugation, it is used in combination methanol fully to be washed, is dried；
Step E：Nano grade silica particles after air-drying are encased in the isobutanol of 20ml, the 1 of 2ml is added later, The bromo- 3- methybutanes of 1- of 2- Bromofumes, the bromohexane of 6ml, 0.1g bromoacetyl bromides, 1ml, then stirred under the conditions of 70~80 DEG C 15~25 hours；
Step F：30~45 DEG C are cooled to after the completion of reaction, then 5ml potassium iodide is added thereto, are stirred 8~12 hours, warp Centrifugation is crossed, is fully washed with methanol, is then dried to obtain antiseptic.
In the step 5,50 parts of terephthalic acid (TPA) is first added, 100 parts of ethylene glycol is added later, remaining 150 parts to benzene Dioctyl phthalate is divided into three parts, and 50 parts of terephthalic acid (TPA)s were added every 10 minutes, are 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 phenols are first added in the reaction vessel, 200 parts of ethylene glycol are added, stirs 5~15 minutes, adds remaining 600 parts of ethylene glycol and 400 parts of terephthalic acid (TPA)s, be warming up to 40 DEG C of progress ready-mixeds.
It is described Step 2: Step 4: in step 6 be added Ti/Si series catalysts when, first by Ti/Si series catalysts 50ml Ethylene glycol dilutes, in being added to reaction vessel.
Comparative example：
Select PP particles and PET particles purchased in market, 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 particles select the 935 BK505 modelings of Dupont Expect particle.
Above-mentioned material is prepared into casting films by test, and thickness is 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 is tried hernia light irradiation 50,100,150,200 hours Above-mentioned test is carried out after testing.
0.1g samples accurately are weighed, are added in the triangular flask equipped with 99mL sterile waters, with ultrasonic wavelength-division 20min.It is added A concentration of 107CFU/mL bacteria suspensions of 1mL.It is another to take a triangular flask equipped with 99mL sterile waters 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 liquors are 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) 240 152
94 indexs of flame retardant rating UL V-0 V-1
Staphylococcus aureus antibiotic rate % 94 23
Escherichia coli antibiotic rate % 94 21
Folding oxygen transmission rate cm3/ (m224h0.1MPa) is not rubbed 0.3 1.5
Rub folding oxygen transmission rate cm3/ (m224h0.1MPa) 0.4 2.0
Transparency % 92% 85%
Table two：Through 50 hours test datas of hernia light irradiation
Embodiment Comparative example
Tensile strength (N/mm^2) 238 130
94 indexs of flame retardant rating UL V-0 V-1
Staphylococcus aureus antibiotic rate % 92 18
Escherichia coli antibiotic rate % 90 18
Folding oxygen transmission rate cm3/ (m224h0.1MPa) is not rubbed 0.4 1.0
Rub folding oxygen transmission rate cm3/ (m224h0.1MPa) 0.5 2.1
Transparency % 92% 85%
Table three：Through 100 hours test datas of hernia light irradiation
Embodiment Comparative example
Tensile strength (N/mm^2) 236 111
94 indexs of flame retardant rating UL V-0 V-2
Staphylococcus aureus antibiotic rate % 89 12
Escherichia coli antibiotic rate % 87 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 % 92% 80%
Table four：Through 150 hours test datas of hernia light irradiation
Embodiment Comparative example
Tensile strength (N/mm^2) 230 100
94 indexs of flame retardant rating UL V-0 V-2
Staphylococcus aureus antibiotic rate % 86 5
Escherichia coli antibiotic rate % 86 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) 219 80
94 indexs of flame retardant rating UL V-0 V-2
Staphylococcus aureus antibiotic rate % 83 5
Escherichia coli antibiotic rate % 81 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 % 92% 80%
By squeeze out and Multi-layer cast film being made PET plastic particle and PP plastic pellets 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 pellets first, PP plastic pellets are prepared by blending and modifying hair, wherein with PP major ingredients, add N, 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 improve entire barrier film strength.Montmorillonite and nanometer TiO2 is added thereto as modified material, and the performance for reducing cost, while being also will not decline.The addition of paraffin is as lubrication Agent enables to processing to be more prone to.Polyether siloxane copolymer is as antifoaming 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 play a diluting effect, so that terephthalic acid (TPA) slowly can occur to gather with ethylene glycol Ester reacts.
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 play a diluting effect, so as to benzene Slowly with ethylene glycol pet reaction can occur for dioctyl phthalate.
Since in above-mentioned steps, ethylene glycol is excessive, therefore part terephthalic acid (TPA) is filled into step 3, it is anti-to ensure Answer rate.And the maleic anhydride being added can increase the flexibility of whole segment, adjust the length of strand, can ensure segment While addition with preferable tensile strength, while 2- nitroterephthalic acid -4- methyl esters can consume part ethylene glycol, energy It is enough that amino and nitro are introduced in whole system, the weatherability of whole system can be enhanced, while also carrying phenyl group, Neng Gouhe Whole system similar compatibility improves whole compatibility, therefore can bring preferable uniformity, avoids carrying for Local Property It rises.
Continue to fill into addition terephthalic acid (TPA) in step 4, while 2,2-dimethyl-1,3-propanediol and 2 is added, 3- bis- Bromo- 2- butene-1s, 4- glycol adjust strand so that molecular weight product is more by the way that 2,2-dimethyl-1,3-propanediol is added Add uniformly, while the light transmittance of product can also be guaranteed.2,3- dibromo-2-butene-1,4-glycols can participate in reacting, will Bromine substituent is introduced into even section, can improve whole flame retardant property.
While step 5 fills into part terephthalic acid (TPA), ethylene glycol is also added, before react in, ethylene glycol by What is consumed is similar, and filling into ethylene glycol can ensure that reaction rate will not be lowered.Isosorbide-5-Nitrae-benzene dimethanol, the 2- being added later The addition of amino terephthalic acid (TPA), Isosorbide-5-Nitrae-benzene dimethanol enhances whole intensity, due to the branch of 2- amino terephthalic acid (TPA)s It is easy to be activated, therefore reduces temperature while can carry out normal pet reaction, additionally it is possible to avoid the hair of side reaction It is raw.
Step 6 is then the preparation process of auxiliary material, is still using terephthalic acid (TPA) and ethylene glycol as carrier, tetrabromo pair is added Phthalic acid, bis- (2- ethylhexyls) terephthalic acids, 4- bromo phthalic anhydrides；And the addition of tetrabromo terephthalic acids and 4- bromo phthalic anhydrides, it is main If bromine substituent is introduced into even section, its whole anti-flammability, the addition of bis- (2- ethylhexyls) terephthalic acids ensure that So that the polymerization site of tetrabromo terephthalic acids and 4- bromo phthalic anhydrides will not lean on too close, introduced under conditions of in intermolecular interaction Side-chain radical ensures the uniformity and stability of overall flame performance.
The auxiliary material in step 6 is slowly added into major ingredient later and is mixed, pressurization is carried out after closing very much, polymerisation occurs, Obtain the uniform polyester of physical property.
After polymerisation, whole system basic forming, the bromo terephthalic acid's dimethyl ester being added later, 2,2- Two fluoro- 1,3- benzos two dislike cyclopentadienyl, magnesium fluosilicate, antiseptic and belong to modifying agent, bromo terephthalic acid's dimethyl ester can with react The polymer of generation is reacted, and improves whole flame retardant property, 2,2- bis- fluoro- 1,3- benzos two dislike cyclopentadienyl itself can product it is whole The intensity of body, at the same it is close with polyethylene terephthalate in itself structure, therefore there is preferable compatibility, it can It is evenly distributed between strand, further strengthens whole anti-flammability.The addition of magnesium fluosilicate enables to improve poly- The intensity of ester, while can also play the role of a stabilizer so that polyester is no matter can during processing or use Embody certain stability.The addition of antiseptic can improve its whole anti-microbial property.
The phenomenon that in catalyst adition process, being diluted, local concentration can be prevented excessive and part is caused to be reunited.
2, the 6- di-tert-butyl-4-methy phenols being added before the reaction are a kind of general antioxidant, together with ethylene glycol Container is added, on the one hand to reaction vessel there are one cleaning action, on the other hand can also prevent polyester during the reaction by Oxidation.
On antiseptic, quaternary antiseptic, quaternary ammonium salt is selected to meet on nano silicon dioxide.
In the preparation process of antiseptic, nano silicon dioxide can be in chlorobenzoyl chloride, 4- bromobutanoylchlorides, phosphorus trichloride Under the conditions of be further activated, the especially addition of phosphorus trichloride can improve the activity function of nano silicon dioxide, make simultaneously Obtaining finally obtained antiseptic has preferably weatherability, i.e., preferable antibacterial effect can be also played during long-time use Fruit.
It is cleaned later, chloroform parachlorobenzoyl chloride, the dissolubility of phosphorus trichloride are preferable, can be taken Go out, and ethylene glycol can then take out remaining chloroform, finally be cleaned with acetone, can thoroughly take out residuals.
By active nano silica and polyethyleneimine, two (trimethyl silicon substrate) phosphinylidyne diimines, polycarbodiimide Reaction, nano-silica is fixed on by the group on polyethyleneimine, two (trimethyl silicon substrate) phosphinylidyne diimines, polycarbodiimide In SiClx.It is eventually adding the bromo- 3- methybutanes of 1,2- Bromofumes, 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 antiseptic is not susceptible to be lost in, so that antibacterial effect is more preferably steady on the carrier of nano silicon dioxide 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- methybutanes 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 antiseptic.
Therefore, the thermoplastic polyester material that prepared by the present invention, while there is preferable anti-flammability, antibiotic property, high intensity, In time after long-time use, still there is preferable anti-flammability, antibiotic property, high intensity.
Pass through PP layers and the combination of pet layer so that entire composite membrane has high barrier, while 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 (4)

1. a kind of double-layer coextrusion casting films, it is characterised in that：PP plastic pellets and PET plastic particle are added to coextrusion casting film The PET/PP films including pet layer and PP layers are made in machine,
The PP plastic pellets include following parts by weight composition：
PP：120 parts, trihydroxy polypropylene oxide ether：25 parts, N, N'- (4,4'- methylenediphenyls) bismaleimide：5 Part, trimethylolpropane tris methyl acrylate：15 parts, 4,4'- dihydroxy diphenyl sulfides：8 parts, montmorillonite：8 parts, paraffin：10 Part, antioxidant 1010：0.2 part, nano-TiO2：2 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, maleic anhydride:50 parts, 2- nitroterephthalic acid -4- methyl esters：10 Part, 2,2- dimethyl -1,3- propylene glycol：10 parts, bis- bromo- 2- butylene-1,4-diols of 2,3-：5 parts, 1,4- benzene dimethanols：8 parts, 2- amino terephthalic acid (TPA)s：15 parts, tetrabromo terephthalic acids：5 parts, bis- (2- ethylhexyls) terephthalic acids：8 parts, 4- bromo phthalic anhydrides： 5 parts, bis- fluoro- 1,3- benzos two of 2,2- dislike cyclopentadienyl：3 parts, magnesium fluosilicate：5 parts, 5 parts of antiseptic；Adjacent bromo terephthalic acid's dimethyl ester 10 Part；
The antiseptic is prepared according to following methods：
Step A：In 10g nano silicon dioxides, the parachlorobenzoyl chloride of 2ml, the 4- bromobutanoylchlorides of 1ml, 1ml tri-chlorinations is added Phosphorus is stirred to react 10 ~ 15 hours under the conditions of 20 ~ 30 DEG C, is activated to nano silicon dioxide；
Step B：Mixture is centrifuged after the completion of reaction, is cleaned successively using chloroform, ethylene glycol, acetone, into Row drying obtains activation nano silicon dioxide；
Step C：7g polyethyleneimines, 2g bis- (trimethyl silicon substrate) phosphinylidyne diimine, 1g are added in activating nano silicon dioxide Polycarbodiimide is added 0.1gKOH, is stirred 15 ~ 20 hours under conditions of 85 DEG C；
Step D：After reaction by centrifugation, it is used in combination methanol fully to be washed, is dried；
Step E：Nano grade silica particles after air-drying are encased in the isobutanol of 20ml, 1, the 2- bis- of 2ml is added later The bromo- 3- methybutanes of 1- of bromoethane, the bromohexane of 6ml, 0.1g bromoacetyl bromides, 1ml stir 15 ~ 25 under the conditions of 70 ~ 80 DEG C Hour；
Step F：Cool to 30 ~ 45 DEG C after the completion of reaction, then 5ml potassium iodide be added thereto, stir 8 ~ 12 hours, by from The heart is fully washed with methanol, is then dried to obtain antiseptic.
2. a kind of double-layer coextrusion casting films according to claim 1, it is characterised in that：The PP plastic pellets production method For：Required raw material is weighed according to weight proportion, then under nitrogen protection, each raw material weighed is stirred evenly, is stirred at room temperature 60-80min is then heated to 60-80 DEG C, stirs 2h, and then temperature reduces 40-50 DEG C, stirs 2h, is added in comminutor and squeezes Go out granulation and obtains PP plastic pellets.
3. a kind of double-layer coextrusion casting films according to claim 1 or 2, it is characterised in that：The PET plastic particle production Method is：
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 carries out prepared mix It closes；
Step 2：200 ~ 220 degrees Celsius of progress esterifications are warming up to, after reacting 30 ~ 50 minutes, Ti/Si series catalysts are added 0.01 ~ 0.5 part, the reaction was continued 10 ~ 30 minutes；
Step 3：200 parts of terephthalic acid (TPA), 50 parts of maleic anhydride, 10 parts of 2- nitroterephthalic acid -4- methyl esters, cooling is added To 180 ~ 200 DEG C, react 20 ~ 40 minutes；
Step 4：100 parts of terephthalic acid (TPA), 10 parts of 2,2- dimethyl -1,3- propylene glycol, bis- bromo- 2- butene-1s of 2,3-, 4- is added 5 parts of glycol, temperature are maintained at 180 ~ 200 DEG C, and 0.01 ~ 0.5 part of Ti/Si series catalysts are added, and react 20 ~ 30 minutes；
Step 5：200 parts of terephthalic acid (TPA), 100 parts of ethylene glycol, 8 parts of 1,4- benzene dimethanols, 2- amino terephthalic acid (TPA) 15 is added Part, 200 ~ 250 DEG C are warming up to, reacts 10 ~ 30 minutes, it is spare to obtain major ingredient；
Step 6：A reaction kettle is set up another in the preparation of auxiliary material, and 100 parts of terephthalic acid (TPA), 100 parts of ethylene glycol, tetrabromo is added to benzene two 5 parts of acid, bis- 8 parts of (2- ethylhexyls) terephthalic acids, 5 parts of 4- bromos phthalic anhydride；Temperature is maintained at 180 ~ 200 DEG C, and Ti/Si systems are added 0.01 ~ 0.5 part of catalyst, it is spare that reaction obtains auxiliary material in 30 ~ 60 minutes；
Step 7：Auxiliary material is slowly added into the reaction kettle of major ingredient, addition while is stirred, and temperature is maintained at 40 ~ 50 Degree Celsius, 180 ~ 200 DEG C are to slowly warm up to after addition, insulated and stirred 20 ~ 40 minutes；
Step 8 is warming up to 250 ~ 280 DEG C, is reacted 30 ~ 60 minutes under 200 ~ 300Pa vacuum conditions；
Step 9：Adjacent 10 parts of bromo terephthalic acid's dimethyl ester is added in completion after reacting, bis- fluoro- 1,3- benzos two of 2,2- dislike 3 parts of cyclopentadienyl, 5 parts of magnesium fluosilicate, 5 parts of antiseptic, 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 double-layer coextrusion casting films according to claim 3, it is characterised in that：It is described Step 2: Step 4: step When Ti/Si series catalysts being added in six, first Ti/Si series catalysts 50ml ethylene glycol is diluted, is then added in reaction vessel.
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