A kind of high barrier casting films
Technical field
The present invention relates to a kind of packaging material, more particularly to a kind of high barrier composite membrane.
Background technology
High-isolation film is same for polyolefin very strong with heat suture property, moisture barrier for the very strong material of barrier properties for gases
Shi Jinhang extrusion forms, and is the thin film of multiple structure.
In prior art, other new requirements are also had for high-resistant diaphragm, particularly in some packagings for foodstuff, also can
Need some for the requirement of anti-microbial property, anti-flammability.Particularly during long-time use, can rise so that thin-film material produces
Life is certain aging, be therefore badly in need of a kind of appoint under long-time use condition so there is high obstructing performance, and take into account anti-flammability and
The thin-film material of anti-microbial property.
Content of the invention
In view of the shortcomings of the prior art, it is an object of the invention to provide a kind of.
For achieving the above object, the invention provides following technical scheme:
A kind of high barrier composite membrane, PP plastic pellet and PET particle is added in coextrusion casting film machine and makes
Including the PET/PP film of pet layer and PP layer,
Described PP plastic pellet includes following weight portion composition:
PP:120 parts, 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 following weight portion composition:
P-phthalic acid:1000 parts;Ethylene glycol:600 parts;2- nitroterephthalic acid -4- methyl ester:10 parts, maleic anhydride:
50 parts, 2- methyl -2,4- pentanediol:5 parts, 2,3- dibromo-2-butene-1,4-glycol:5 parts, tetrabromo terephthalic acids:5 parts, double
(2- ethylhexyl) terephthalic acids:8 parts, 4- bromo phthalic anhydride:5 parts, 2- amino p-phthalic acid:15 parts, 2,2- dimethyl -1,3-
Propylene glycol:10 parts, fluoro- 1, the 3- benzo two of 2,2- bis- dislike cyclopentadienyl:3 parts, magnesium fluosilicate:5 parts, 5 parts of antibacterial.
As a further improvement on the present invention:Described PP plastic pellet production method is:Weigh required according to weight proportion
Raw material, then under nitrogen protection, by each raw material stirring weighing uniformly, is stirred at room temperature 60-80min, is then heated to 60-80
DEG C, stir 2h, then temperature reduces 40-50 DEG C, stir 2h, be added to extruding pelletization in comminutor and obtain PP plastic pellet.
As a further improvement on the present invention:Described PET particle production method is:
The synthesis of step 1 first performed polymer:
Step 1-1:200 parts of p-phthalic acid, 140 parts of ethylene glycol are added in reactor, be warming up to 40 DEG C carry out pre-
Mixing;
Step 1-2:50 parts of maleic anhydride, 5 parts of 2,3- dibromo-2-butene-1,4-glycol is added to be warming up to 200~220
Degree Celsius carry out esterification, after reaction 30~50 minutes, add 0.01~0.5 part of Ti/Si series catalysts, continue reaction 10~
30 minutes;
Step 1-3:Add 200 parts of remaining phthalic acid, ethylene glycol 100,10 parts of 2- nitroterephthalic acid -4- methyl ester,
2- methyl -2,5 parts of 4- pentanediol continues reaction and is cooled to 180~200 DEG C, and it is standby that reaction obtains the first performed polymer in 20~40 minutes
With;
Step 2:The preparation of the second performed polymer
Step 2-1:200 parts of p-phthalic acids, 180 parts of ethylene glycol are added in reactor, be warming up to 40 DEG C carry out pre-
Mixing;
Step 2-2:It is warming up to 200~220 degrees Celsius and carries out esterification, after reacting 30~50 minutes, add
0.01~0.5 part of Ti/Si series catalysts, continue reaction 10~30 minutes;
Step 2-3:Add 100 parts of p-phthalic acid, 5 parts of tetrabromo terephthalic acids, double (2- ethylhexyl) terephthalic acids 8
Part, 4- bromo phthalic anhydride, 5 parts, maintain the temperature at 200~220 DEG C and carry out esterification to obtain the second performed polymer within 20~40 minutes standby
With;
Step 3:The preparation of the 3rd performed polymer
Step 3-1:By 15 parts of 2- amino p-phthalic acid, 10 parts of 2,2-dimethyl-1,3-propanediol, p-phthalic acid
150 parts, 180 parts of ethylene glycol be added in reactor, be warming up to 40 DEG C and carry out premixing;
Step 3-2:It is warming up to 200~220 degrees Celsius and carries out esterification, after reacting 30~50 minutes, add Ti/Si system
0.01~0.5 part of catalyst, continues reaction 10~30 minutes;
Step 3-3:Fill into 150 parts of p-phthalic acid, it is standby that sustained response obtains the 3rd performed polymer in 20~40 minutes;Step
4:First performed polymer, the second performed polymer, the 3rd performed polymer are mixed, temperature control, at 40 DEG C, is stirred 1~2 hour,
It is warming up to 250~280 DEG C, reaction under 200~300Pa vacuum condition carries out polyreaction in 30~60 minutes;
Step 5:Adjacent 10 parts of bromo terephthalic acid's dimethyl ester, fluoro- 1, the 3- benzo two of 2,2- bis- is added to dislike cyclopentadienyl 3 after completing reaction
Part, 5 parts of magnesium fluosilicate, 5 parts of antibacterial, temperature control, at 100~120 DEG C, after being stirred 30~40 minutes, continues stirring,
Carry out pelletize after being naturally cooling to 50~60 DEG C and obtain plastic pellet;
Step 6:Plastic pellet is filmed.
As a further improvement on the present invention:Described antibacterial is prepared according to following methods:
Step A:In 10g nano silicon, the parachlorobenzoyl chloride of addition 2ml, the 4- bromobutanoylchloride of 1ml, 1ml trichlorine
Change phosphorus, stirring reaction 10~15 hours under the conditions of 20~30 DEG C, activation is carried out to nano silicon;
Step B:After the completion of reaction, mixture is centrifuged, is carried out clearly using chloroform, ethylene glycol, acetone successively
Wash, be dried, obtain activating nano silicon;
Step C:Add 7g polyethyleneimine, 2g bis- (trimethyl silicon substrate) phosphinylidyne two sub- in activation nano silicon
Amine, 1g polycarbodiimide, add 0.1gKOH, stir 15~20 hours under conditions of 85 DEG C;
Step D:React through centrifugation after terminating, and fully washed with methanol, be dried;
Step E:Nano grade silica particles after air-drying are encased in the isobutanol of 20ml, add the 1 of 2ml afterwards,
2- Bromofume, the bromo-n-hexane 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 the completion of reaction, then be added thereto to 5ml potassium iodide, stir 8~12 hours, warp
Cross centrifugation, fully washed with methanol, be then dried to obtain antibacterial.
As a further improvement on the present invention:Described step 1-3:It is initially charged 50 parts of p-phthalic acid, add afterwards
100 parts of ethylene glycol, remaining 150 parts of p-phthalic acids are divided into three parts, every 10 minutes add 50 parts of p-phthalic acids, afterwards plus
Enter ethylene glycol 100,10 parts of 2- nitroterephthalic acid -4- methyl ester, 2- methyl -2,5 parts of 4- pentanediol continue reactions be cooled to 180~
200 DEG C, it is standby that reaction obtains the first performed polymer in 20~40 minutes.
As a further improvement on the present invention:In described step 1-1, step 2-1, step 3-1, before adding raw material, first
Add 2,6- di-tert-butyl-4-methy phenol in reaction vessel, add 50 parts of ethylene glycol, stir 5~15 minutes, add surplus
Excess material.
As a further improvement on the present invention:When adding Ti/Si series catalysts in described step 1, step 2, step 3, first
Ti/Si series catalysts are diluted with 50ml ethylene glycol, in being added to reaction vessel.
Make Multi-layer cast film by PET particle and PP plastic pellet being carried out coextrusion casting film machine carrying out extrusion,
Can be by the complementation between bi-material, thus reaching preferable high-barrier, fire-retardant, antibacterial a effect.
It is PP plastic pellet first, PP plastic pellet is sent out by blending and modifying and is prepared, wherein with PP major ingredient, add N,
N '-(4,4 '-methylenediphenyl) BMI, is reacted with PP, adjusts the molecule segment of PP, to strengthen overall
Barrier property.Wherein interpolation trimethylolpropane tris acrylic acid methyl ester. can with the molecule segment of PP have preferably compatible
Agent, simultaneous with oh group, a preferable anti-fog performance can be obtained in the final product.4,4 '-dihydroxy hexichol
The addition of thioether, on the one hand provides hydroxyl to whole system, simultaneously can also be with trimethylolpropane tris acrylic acid methyl ester.
The compatibility is more preferable, the phenyl ring that another aspect sulphur atom two ends connect, it is possible to increase entirely intercept 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, enables to processing and is more prone to.Polyether siloxane copolymer is as defoamer, methyl hydroxyethylcellulose as thickening agent
Add and adjust viscosity, the addition of vinyl three tert-butyl peroxide silane as coupling agent, in step one, first by big portion
The p-phthalic acid dividing, ethylene glycol are added in reaction vessel, carry out a pre-mixing process first, 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 anti-
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, start pet reaction, the amount of ethylene glycol is far longer than p-phthalic acid, one side second in whole reaction system
Glycol is solvent, can reduce and play a diluting effect, so that p-phthalic acid can slowly be gathered with ethylene glycol generation
Ester reacts.
Whole pet reaction is divided into and first prepares three kinds of different performed polymers, again three kinds of different performed polymers are carried out afterwards
Polycondensation reaction, obtains polyester, and it is high to have molecular weight uniform, physical property stability, simultaneously because the group introducing various functions is point
Step is polymerized, and so, interference each other is also considerably reduced, and obtains more stable effect.
In step 1, for the preparation of the first performed polymer, the first performed polymer using p-phthalic acid and ethylene glycol as matrix,
First most p-phthalic acid, ethylene glycol are added in reaction vessel, carry out a pre-mixing process first, rise simultaneously
, to 40 DEG C, it is more uniform to enable to its premixing for temperature, promotes intermolecular free motion.Can effectively prevent from adding suddenly
The reaction raw materials of volume can occur the phenomenon being excessively polymerized.Add maleic anhydride, the bromo- 2-butylene-Isosorbide-5-Nitrae-two of 2,3- bis- afterwards
Alcohol adjusts the group on segment.Maleic anhydride can increase the flexibility of overall segment, the length of Molecular regulator chain, ensure that
Segment has preferable tensile strength, and 2,3- dibromo-2-butene-1,4-glycols can participate in reacting, and bromine substituent is incorporated into
Even in section, it is possible to increase overall fire resistance.Maleic anhydride, 2,3- dibromo-2-butene-1,4-glycol have preferably simultaneously
The compatibility so that the product obtaining during the course of the reaction is more uniform.Add remaining after reaction a period of time
P-phthalic acid, ethylene glycol, 2- nitroterephthalic acid -4- methyl ester, 2- methyl -2,4- pentanediol.Enable bromine substituent position
In segment relatively centered on position, prevent from being affected, p-phthalic acid, subsequently filling into of ethylene glycol can increase reaction speed
Degree is so that reaction will not slow down it is ensured that production efficiency.The addition of 2- nitroterephthalic acid -4- methyl ester can consume portion simultaneously
While dividing ethylene glycol, amino and nitro can be introduced in whole system, the weatherability of whole system can be strengthened, also simultaneously
With phenyl group, the overall compatibility can be improved with whole system similar compatibility, therefore, it is possible to bring preferable uniformity,
Avoid the lifting of Local Property.2- methyl -2, the addition of 4- pentanediol can cellular construction on Molecular regulator chain so that
After obtaining the first performed polymer, the first performed polymer can have the more preferable compatibility, so that final polyester is had more simultaneously
Good weatherability.
In step 2, equally adopt using p-phthalic acid and ethylene glycol as matrix so that in main chain Duan Shangyu first pre-polymerization
Seemingly, and filling into of follow-up p-phthalic acid mainly prevents response speed from reducing to body phase, and tetrabromo terephthalic acids and 4- bromobenzene
Bromine substituent is mainly incorporated into and connects in section it is ensured that its overall anti-flammability, double (2- ethylhexyls) are to benzene by the addition of acid anhydride
It is too near, in intermolecular interaction that the addition of diacid makes that the polymerization site of tetrabromo terephthalic acids and 4- bromo phthalic anhydride will not lean on
Under the conditions of introduce side-chain radical it is ensured that the uniformity of overall flame performance and stability.
In the preparation process of the 3rd performed polymer, directly by 15 parts of 2- amino p-phthalic acid, 2,2- dimethyl -1,3- third
10 parts of glycol, 150 parts of p-phthalic acid, 180 parts of ethylene glycol are reacted, and because the amount of reaction is less, therefore need be not excessively load
The problem of heart implode, directly participates in reacting, and remaining based on p-phthalic acid and ethylene glycol in the 3rd performed polymer
Want matrix, by adding 2,2-dimethyl-1,3-propanediol, Molecular regulator chain, so that molecular weight product is more uniform, produces simultaneously
The light transmittance of product also can be guaranteed.And the addition of 2- amino p-phthalic acid, introduce amino so that the 3rd performed polymer and
Antibacterial tool is well bonded.Finally make polyester and antibacterial tool is well bonded it is ensured that antibacterial effect
Stable.
Afterwards the first performed polymer, the second performed polymer, the 3rd performed polymer are carried out polyreaction, obtain polyester.
After polyreaction, whole system basic forming, the bromo terephthalic acid's dimethyl ester adding afterwards, 2,2-
Cyclopentadienyl disliked by two fluoro- 1,3- benzos two, magnesium fluosilicate, antibacterial belong to modifying agent, and bromo terephthalic acid's dimethyl ester can be with reaction
The polymer generating is reacted, and improves overall fire resistance, 2,2- bis- fluoro- 1,3- benzos two dislike cyclopentadienyl itself can product whole
The intensity of body, simultaneously close with polyethylene terephthalate in itself structure, therefore there is the preferable compatibility, can
It is evenly distributed between strand, further strengthen overall anti-flammability.The addition of magnesium fluosilicate enables to improve and gathers
The intensity of ester, also can play the effect of a stabilizer simultaneously so that polyester no matter processing or use during can
Embody certain stability.The addition of antibacterial can improve its overall anti-microbial property.
In catalyst adition process, diluted, be prevented from local concentration excessive and lead to the phenomenon reunited of local.
2, the 6- di-tert-butyl-4-methy phenol adding before the reaction is a kind of general antioxidant, with ethylene glycol together
Add container, on the one hand have a cleaning action to reaction vessel, be on the other hand also prevented from polyester during the course of the reaction by
Oxidation.
On antibacterial, from quaternary antibacterial, its quaternary ammonium salt meets on nano silicon.
In the preparation process of antibacterial, nano silicon can be in 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, also can play preferable antibacterial effect during long-time use
Really.
Afterwards it is carried out, chloroform parachlorobenzoyl chloride, Phosphorous chloride. dissolubility preferably, can be taken
Go out, and ethylene glycol then can take out the chloroform of residual, finally cleaned with acetone, can thoroughly take out residuals.
By active nano silicon dioxide and polyethyleneimine, two (trimethyl silicon substrate) phosphinylidyne diimine, polycarbodiimide
Reaction, the group on polyethyleneimine, two (trimethyl silicon substrate) phosphinylidyne diimine, polycarbodiimide is fixed on nano-silica
In SiClx.It is eventually adding glycol dibromide, bromo-n-hexane, bromoacetyl bromide, 1- bromo- 3- methybutane and be 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 more preferably steady on the carrier of nano silicon
Fixed.Wherein react mainly in polyethyleneimine, two (trimethyl silicon substrate) phosphinylidyne diimine, polycarbodiimide and 1,2- dibromo second
React between alkane, bromo-n-hexane, bromoacetyl bromide, 1- bromo- 3- methybutane, the quaternary ammonium salt that reaction generates has stiff stability,
The addition of particularly two (trimethyl silicon substrate) phosphinylidyne diimine, enables to the adhesion of silicon dioxide more preferably, be difficult from receiving
Come off on rice silicon dioxide, the addition of bromoacetyl bromide simultaneously also improves the activity of antibacterial.
Therefore, the thermoplastic polyester material of present invention preparation, while there is preferable anti-flammability, antibiotic property, high intensity,
In time long-time using later, still there is preferable anti-flammability, antibiotic property, high intensity.
By the combination of PP layer and pet layer so that whole composite membrane possesses high barrier, also it is provided with antibacterial simultaneously
Property, the feature of anti-flammability.
Specific embodiment
Embodiment
A kind of high barrier composite membrane, PP plastic pellet and PET particle is added in coextrusion casting film machine and makes
Including the PET/PP film of pet layer and PP layer,
Described PP plastic pellet includes following weight portion composition:
PP:120 parts, 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 following weight portion composition:
P-phthalic acid:1000 parts;Ethylene glycol:600 parts;2- nitroterephthalic acid -4- methyl ester:10 parts, maleic anhydride:
50 parts, 2- methyl -2,4- pentanediol:5 parts, 2,3- dibromo-2-butene-1,4-glycol:5 parts, tetrabromo terephthalic acids:5 parts, double
(2- ethylhexyl) terephthalic acids:8 parts, 4- bromo phthalic anhydride:5 parts, 2- amino p-phthalic acid:15 parts, 2,2- dimethyl -1,3-
Propylene glycol:10 parts, fluoro- 1, the 3- benzo two of 2,2- bis- dislike cyclopentadienyl:3 parts, magnesium fluosilicate:5 parts, 5 parts of antibacterial.
Described PP plastic pellet production method is:Weigh needed raw material according to weight proportion, then under nitrogen protection, will
The each raw material stirring weighing uniformly, 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, stir 2h, be added to extruding pelletization in comminutor and obtain PP plastic pellet.As a further improvement on the present invention:Institute
Stating PET particle production method is:
The synthesis of step 1 first performed polymer:
Step 1-1:200 parts of p-phthalic acid, 140 parts of ethylene glycol are added in reactor, be warming up to 40 DEG C carry out pre-
Mixing;
Step 1-2:50 parts of maleic anhydride, 5 parts of 2,3- dibromo-2-butene-1,4-glycol is added to be warming up to 200~220
Degree Celsius carry out esterification, after reaction 30~50 minutes, add 0.01~0.5 part of Ti/Si series catalysts, continue reaction 10~
30 minutes;
Step 1-3:Add 200 parts of remaining phthalic acid, ethylene glycol 100,10 parts of 2- nitroterephthalic acid -4- methyl ester,
2- methyl -2,5 parts of 4- pentanediol continues reaction and is cooled to 180~200 DEG C, and it is standby that reaction obtains the first performed polymer in 20~40 minutes
With;
Step 2:The preparation of the second performed polymer
Step 2-1:200 parts of p-phthalic acids, 180 parts of ethylene glycol are added in reactor, be warming up to 40 DEG C carry out pre-
Mixing;
Step 2-2:It is warming up to 200~220 degrees Celsius and carries out esterification, after reacting 30~50 minutes, add
0.01~0.5 part of Ti/Si series catalysts, continue reaction 10~30 minutes;
Step 2-3:Add 100 parts of p-phthalic acid, 5 parts of tetrabromo terephthalic acids, double (2- ethylhexyl) terephthalic acids 8
Part, 4- bromo phthalic anhydride, 5 parts, maintain the temperature at 200~220 DEG C and carry out esterification to obtain the second performed polymer within 20~40 minutes standby
With;
Step 3:The preparation of the 3rd performed polymer
Step 3-1:By 15 parts of 2- amino p-phthalic acid, 10 parts of 2,2-dimethyl-1,3-propanediol, p-phthalic acid
150 parts, 180 parts of ethylene glycol be added in reactor, be warming up to 40 DEG C and carry out premixing;
Step 3-2:It is warming up to 200~220 degrees Celsius and carries out esterification, after reacting 30~50 minutes, add Ti/Si system
0.01~0.5 part of catalyst, continues reaction 10~30 minutes;
Step 3-3:Fill into 150 parts of p-phthalic acid, it is standby that sustained response obtains the 3rd performed polymer in 20~40 minutes;
Step 4:First performed polymer, the second performed polymer, the 3rd performed polymer are mixed, temperature control, at 40 DEG C, is carried out
Stirring 1~2 hour, is warming up to 250~280 DEG C, and reaction under 200~300Pa vacuum condition carries out polyreaction in 30~60 minutes;
Step 5:Adjacent 10 parts of bromo terephthalic acid's dimethyl ester, fluoro- 1, the 3- benzo two of 2,2- bis- is added to dislike cyclopentadienyl 3 after completing reaction
Part, 5 parts of magnesium fluosilicate, 5 parts of antibacterial, temperature control, at 100~120 DEG C, after being stirred 30~40 minutes, continues stirring,
Carry out pelletize after being naturally cooling to 50~60 DEG C and obtain plastic pellet;
Step 6:Plastic pellet is filmed.
Described antibacterial is prepared according to following methods:
Step A:In 10g nano silicon, the parachlorobenzoyl chloride of addition 2ml, the 4- bromobutanoylchloride of 1ml, 1ml trichlorine
Change phosphorus, stirring reaction 10~15 hours under the conditions of 20~30 DEG C, activation is carried out to nano silicon;
Step B:After the completion of reaction, mixture is centrifuged, is carried out clearly using chloroform, ethylene glycol, acetone successively
Wash, be dried, obtain activating nano silicon;
Step C:Add 7g polyethyleneimine, 2g bis- (trimethyl silicon substrate) phosphinylidyne two sub- in activation nano silicon
Amine, 1g polycarbodiimide, add 0.1gKOH, stir 15~20 hours under conditions of 85 DEG C;
Step D:React through centrifugation after terminating, and fully washed with methanol, be dried;
Step E:Nano grade silica particles after air-drying are encased in the isobutanol of 20ml, add the 1 of 2ml afterwards,
2- Bromofume, the bromo-n-hexane 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 the completion of reaction, then be added thereto to 5ml potassium iodide, stir 8~12 hours, warp
Cross centrifugation, fully washed with methanol, be then dried to obtain antibacterial.
As a further improvement on the present invention:Described step 1-3:It is initially charged 50 parts of p-phthalic acid, add afterwards
100 parts of ethylene glycol, remaining 150 parts of p-phthalic acids are divided into three parts, every 10 minutes add 50 parts of p-phthalic acids, afterwards plus
Enter ethylene glycol 100,10 parts of 2- nitroterephthalic acid -4- methyl ester, 2- methyl -2,5 parts of 4- pentanediol continue reactions be cooled to 180~
200 DEG C, it is standby that reaction obtains the first performed polymer in 20~40 minutes.
In described step 1-1, step 2-1, step 3-1, before adding raw material, in reaction vessel, first add 2,6- bis- uncle
Butyl -4- methylphenol, adds 50 parts of ethylene glycol, stirs 5~15 minutes, adds leftover materials.Described step 1, step 2,
When adding Ti/Si series catalysts in step 3, first Ti/Si series catalysts are diluted with 50ml ethylene glycol, be added to reaction vessel
In.
Comparative example:
From commercial PP particle and PET particle, it is added to and carries out extrusion in coextrusion casting film machine and make coextrusion casting film.PP
Particle selects the SFC-650BT curtain coating film special material of the carefree chemistry of Korea S, and PET particle is moulded from 935 BK505 of Dupont
Material particle.
Test, above-mentioned material is all prepared into casting films, and thickness is 200 μm, tests its tensile strength, transparency, antibacterial
Property, fire resistance, do not rub oxygen transmission rate during folding, rub oxygen transmission rate after folding.And in hernia light irradiation 50,100,150,200 hours
Carry out above-mentioned test after test.
Accurately weigh 0.1g sample, be added 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, shaken cultivation 30min under the conditions of 37 DEG C, 200r/min.In triangular flask
Respectively take 0.2mL mixed liquor, after suitably diluting, 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 control group;
B adds the average colony number of antimicrobial sample to be measured.
Staphylococcus aureuses and escherichia coli are selected on the selection of strain.
Table one:Without hernia lamp exposure experiment data
|
Embodiment |
Comparative example |
Tensile strength (N/mm^2) |
253 |
152 |
Flame retardant rating UL 94 index |
V-0 |
V-1 |
Staphylococcus aureuses antibiotic rate % |
96 |
23 |
Escherichia coli antibiotic rate % |
94 |
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:Through 50 hours test datas of hernia light irradiation
Table three:Through 100 hours test datas of hernia light irradiation
|
Embodiment |
Comparative example |
Tensile strength (N/mm^2) |
248 |
111 |
Flame retardant rating UL 94 index |
V-0 |
V-2 |
Staphylococcus aureuses antibiotic rate % |
93 |
12 |
Escherichia coli antibiotic rate % |
92 |
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:Through 150 hours test datas of hernia light irradiation
|
Embodiment |
Comparative example |
Tensile strength (N/mm^2) |
243 |
100 |
Flame retardant rating UL 94 index |
V-0 |
V-2 |
Staphylococcus aureuses antibiotic rate % |
91 |
5 |
Escherichia coli antibiotic rate % |
89 |
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:Through 200 hours test datas of hernia light irradiation
|
Embodiment |
Comparative example |
Tensile strength (N/mm^2) |
235 |
80 |
Flame retardant rating UL 94 index |
V-0 |
V-2 |
Staphylococcus aureuses antibiotic rate % |
90 |
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% |
Make Multi-layer cast film by PET particle and PP plastic pellet being carried out coextrusion casting film machine carrying out extrusion,
Can be by the complementation between bi-material, thus reaching preferable high-barrier, fire-retardant, antibacterial a effect.
It is PP plastic pellet first, PP plastic pellet is sent out by blending and modifying and is prepared, wherein with PP major ingredient, add N,
N '-(4,4 '-methylenediphenyl) BMI, is reacted with PP, adjusts the molecule segment of PP, to strengthen overall
Barrier property.Wherein interpolation trimethylolpropane tris acrylic acid methyl ester. can with the molecule segment of PP have preferably compatible
Agent, simultaneous with oh group, a preferable anti-fog performance can be obtained in the final product.4,4 '-dihydroxy hexichol
The addition of thioether, on the one hand provides hydroxyl to whole system, simultaneously can also be with trimethylolpropane tris acrylic acid methyl ester.
The compatibility is more preferable, the phenyl ring that another aspect sulphur atom two ends connect, it is possible to increase entirely intercept 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, enables to processing and is more prone to.Polyether siloxane copolymer is as defoamer, methyl hydroxyethylcellulose as thickening agent
Add and adjust viscosity, the addition of vinyl three tert-butyl peroxide silane as coupling agent, in step one, first by big portion
The p-phthalic acid dividing, ethylene glycol are added in reaction vessel, carry out a pre-mixing process first, 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 anti-
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, start pet reaction, the amount of ethylene glycol is far longer than p-phthalic acid, one side second in whole reaction system
Glycol is solvent, can reduce and play a diluting effect, so that p-phthalic acid can slowly be gathered with ethylene glycol generation
Ester reacts.
Whole pet reaction is divided into and first prepares three kinds of different performed polymers, again three kinds of different performed polymers are carried out afterwards
Polycondensation reaction, obtains polyester, and it is high to have molecular weight uniform, physical property stability, simultaneously because the group introducing various functions is point
Step is polymerized, and so, interference each other is also considerably reduced, and obtains more stable effect.
In step 1, for the preparation of the first performed polymer, the first performed polymer using p-phthalic acid and ethylene glycol as matrix,
First most p-phthalic acid, ethylene glycol are added in reaction vessel, carry out a pre-mixing process first, rise simultaneously
, to 40 DEG C, it is more uniform to enable to its premixing for temperature, promotes intermolecular free motion.Can effectively prevent from adding suddenly
The reaction raw materials of volume can occur the phenomenon being excessively polymerized.Add maleic anhydride, the bromo- 2-butylene-Isosorbide-5-Nitrae-two of 2,3- bis- afterwards
Alcohol adjusts the group on segment.Maleic anhydride can increase the flexibility of overall segment, the length of Molecular regulator chain, ensure that
Segment has preferable tensile strength, and 2,3- dibromo-2-butene-1,4-glycols can participate in reacting, and bromine substituent is incorporated into
Even in section, it is possible to increase overall fire resistance.Maleic anhydride, 2,3- dibromo-2-butene-1,4-glycol have preferably simultaneously
The compatibility so that the product obtaining during the course of the reaction is more uniform.Add remaining after reaction a period of time
P-phthalic acid, ethylene glycol, 2- nitroterephthalic acid -4- methyl ester, 2- methyl -2,4- pentanediol.Enable bromine substituent position
In segment relatively centered on position, prevent from being affected, p-phthalic acid, subsequently filling into of ethylene glycol can increase reaction speed
Degree is so that reaction will not slow down it is ensured that production efficiency.The addition of 2- nitroterephthalic acid -4- methyl ester can consume portion simultaneously
While dividing ethylene glycol, amino and nitro can be introduced in whole system, the weatherability of whole system can be strengthened, also simultaneously
With phenyl group, the overall compatibility can be improved with whole system similar compatibility, therefore, it is possible to bring preferable uniformity,
Avoid the lifting of Local Property.2- methyl -2, the addition of 4- pentanediol can cellular construction on Molecular regulator chain so that
After obtaining the first performed polymer, the first performed polymer can have the more preferable compatibility, so that final polyester is had more simultaneously
Good weatherability.
In step 2, equally adopt using p-phthalic acid and ethylene glycol as matrix so that in main chain Duan Shangyu first pre-polymerization
Seemingly, and filling into of follow-up p-phthalic acid mainly prevents response speed from reducing to body phase, and tetrabromo terephthalic acids and 4- bromobenzene
Bromine substituent is mainly incorporated into and connects in section it is ensured that its overall anti-flammability, double (2- ethylhexyls) are to benzene by the addition of acid anhydride
It is too near, in intermolecular interaction that the addition of diacid makes that the polymerization site of tetrabromo terephthalic acids and 4- bromo phthalic anhydride will not lean on
Under the conditions of introduce side-chain radical it is ensured that the uniformity of overall flame performance and stability.
In the preparation process of the 3rd performed polymer, directly by 15 parts of 2- amino p-phthalic acid, 2,2- dimethyl -1,3- third
10 parts of glycol, 150 parts of p-phthalic acid, 180 parts of ethylene glycol are reacted, and because the amount of reaction is less, therefore need be not excessively load
The problem of heart implode, directly participates in reacting, and remaining based on p-phthalic acid and ethylene glycol in the 3rd performed polymer
Want matrix, by adding 2,2-dimethyl-1,3-propanediol, Molecular regulator chain, so that molecular weight product is more uniform, produces simultaneously
The light transmittance of product also can be guaranteed.And the addition of 2- amino p-phthalic acid, introduce amino so that the 3rd performed polymer and
Antibacterial tool is well bonded.Finally make polyester and antibacterial tool is well bonded it is ensured that antibacterial effect
Stable.
Afterwards the first performed polymer, the second performed polymer, the 3rd performed polymer are carried out polyreaction, obtain polyester.
After polyreaction, whole system basic forming, the bromo terephthalic acid's dimethyl ester adding afterwards, 2,2-
Cyclopentadienyl disliked by two fluoro- 1,3- benzos two, magnesium fluosilicate, antibacterial belong to modifying agent, and bromo terephthalic acid's dimethyl ester can be with reaction
The polymer generating is reacted, and improves overall fire resistance, 2,2- bis- fluoro- 1,3- benzos two dislike cyclopentadienyl itself can product whole
The intensity of body, simultaneously close with polyethylene terephthalate in itself structure, therefore there is the preferable compatibility, can
It is evenly distributed between strand, further strengthen overall anti-flammability.The addition of magnesium fluosilicate enables to improve and gathers
The intensity of ester, also can play the effect of a stabilizer simultaneously so that polyester no matter processing or use during can
Embody certain stability.The addition of antibacterial can improve its overall anti-microbial property.
In catalyst adition process, diluted, be prevented from local concentration excessive and lead to the phenomenon reunited of local.
2, the 6- di-tert-butyl-4-methy phenol adding before the reaction is a kind of general antioxidant, with ethylene glycol together
Add container, on the one hand have a cleaning action to reaction vessel, be on the other hand also prevented from polyester during the course of the reaction by
Oxidation.
On antibacterial, from quaternary antibacterial, its quaternary ammonium salt meets on nano silicon.
In the preparation process of antibacterial, nano silicon can be in 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, also can play preferable antibacterial effect during long-time use
Really.
Afterwards it is carried out, chloroform parachlorobenzoyl chloride, Phosphorous chloride. dissolubility preferably, can be taken
Go out, and ethylene glycol then can take out the chloroform of residual, finally cleaned with acetone, can thoroughly take out residuals.
By active nano silicon dioxide and polyethyleneimine, two (trimethyl silicon substrate) phosphinylidyne diimine, polycarbodiimide
Reaction, the group on polyethyleneimine, two (trimethyl silicon substrate) phosphinylidyne diimine, polycarbodiimide is fixed on nano-silica
In SiClx.It is eventually adding glycol dibromide, bromo-n-hexane, bromoacetyl bromide, 1- bromo- 3- methybutane and be 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 more preferably steady on the carrier of nano silicon
Fixed.Wherein react mainly in polyethyleneimine, two (trimethyl silicon substrate) phosphinylidyne diimine, polycarbodiimide and 1,2- dibromo second
React between alkane, bromo-n-hexane, bromoacetyl bromide, 1- bromo- 3- methybutane, the quaternary ammonium salt that reaction generates has stiff stability,
The addition of particularly two (trimethyl silicon substrate) phosphinylidyne diimine, enables to the adhesion of silicon dioxide more preferably, be difficult from receiving
Come off on rice silicon dioxide, the addition of bromoacetyl bromide simultaneously also improves the activity of antibacterial.
Therefore, the thermoplastic polyester material of present invention preparation, while there is preferable anti-flammability, antibiotic property, high intensity,
In time long-time using later, still there is preferable anti-flammability, antibiotic property, high intensity.
By the combination of PP layer and pet layer so that whole composite membrane possesses high barrier, also it is provided with antibacterial simultaneously
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 belonging 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
Should be regarded as protection scope of the present invention.