CN108342132A - A kind of PVDC coating materials and preparation method thereof with high obstructing performance - Google Patents
A kind of PVDC coating materials and preparation method thereof with high obstructing performance Download PDFInfo
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Abstract
The invention discloses a kind of PVDC coating materials with high obstructing performance, including modified PA films, modified PVDC latex is coated on the outer surface of the modified PA films, the coating inside surfaces of modified PA films there are modified PVDC nanometre glues, and modified PVDC latex includes following raw material：Ultra-pure water, pH value buffering conditioning agent, vinylidene, methacrylate monomer, initiator, dispersant, the thickness of modified PA films is 3.5 4.0 μm, the thickness for the modification PVDC latex being coated on the outer surface of modified PA films is 2.5 3.0 μm, the thickness of the modification PVDC nanometre glues of the coating inside surfaces of modified PA films is 1.5 1.8 μm, PVDC coating materials, continuous interior for 24 hours at atmosheric pressure, oxygen transmission rate is 0.018 0.053ml/mil/100in2, at 100 DEG C of temperature and 90% relative humidity, moisture vapor permeable rate is 0.009 0.012ml/mil/100in2.The technical issues of it is poor that the present invention solves PVDC latex thermal stability, when the heated or room temperature time is longer, easy tos produce double bond conjugation, escapes hydrogen chloride, makes intermolecular generations cavity, barrier property failure.
Description
Technical field
The present invention relates to high barrier coating material technical field, specially a kind of PVDC coatings with high obstructing performance
Material and preparation method thereof.
Background technology
PVDC (chemical name polyvinylidene chloride) is materials with high barrier property is best in plastics package in the world today one
Kind packaging material.It both different from polyvinyl alcohol with moisture absorption increase and so that gas barrier property is drastically declined, also different from nylon membrane by
Moisture barrier property is set to be deteriorated in water imbibition, but the high obstructing performance material that a kind of resistance is wet, choke is all excellent.PVDC has very in foreign countries
Long applicating history.Since nineteen thirties U.S. DOW, chemistry realized industrialized production first, PVDC just has become
The synonym of high-barrier, packaging industry are even more " queen " for being referred to as high barrier material, protect fragrant " princess " for protecting taste.BOPP、
One coated PVDC latex of the basis films such as BOPET, BOPA, CPP, CPE material is handled through special processing technology and be can be obtained pair
The outstanding high obstructing performance of various gases.
But PVDC has that thermal stability is poor as packaging material, it is longer in the heated or room temperature time
When, double bond conjugation is just will produce, hydrogen chloride is escaped, makes intermolecular generation cavity, barrier property is caused to fail.
Invention content
(1) the technical issues of solving
In view of the deficiencies of the prior art, the present invention provides a kind of PVDC coating materials and its system with high obstructing performance
Preparation Method has the advantages that efficiently obstructing, high-efficiency antimicrobial is mould proof and efficient mechanical intensity, solves PVDC latex thermal stability ratio
It is poor, when the heated or room temperature time is longer, double bond conjugation is easy tod produce, hydrogen chloride is escaped, makes intermolecular generation cavity,
The technical issues of barrier property fails.
(2) technical solution
To realize that the above-mentioned purpose efficiently obstructed, the present invention provide the following technical solutions：
A kind of PVDC coating materials with high obstructing performance, including modified PA films, the outer surface of the modified PA films
On be coated with modified PVDC latex, the coating inside surfaces of modified PA films have modified PVDC nanometre glues；
The modified PA films include the raw material of following parts by weight proportioning：70-85 parts of PA films, Nano particles of silicon dioxide
10-15 parts, 0.05-0.08 parts of ammonium hydroxide, 0.4-1 parts of aminopropyl triethoxysilane, mass fraction be 2% piperazine aqueous solution 2-
5 parts, mass fraction be 3% 3-7 parts of triethylamine, mass fraction be 0.25% 10-15 parts of pyromellitic trimethylsilyl chloride, n-hexane
10-15 parts, 50-60 parts of ultra-pure water；
The modified PVDC latex includes the raw material of following parts by weight proportioning：100-150 parts of ultra-pure water, pH value buffering are adjusted
Save 0.05-0.2 parts of agent, 80-90 parts of vinylidene, 10-20 parts of methacrylate monomer, 0.20-0.50 parts of initiator,
0.1-0.2 parts of dispersant；Wherein, pH value buffers one of conditioning agent in Sodium Acid Pyrophosphate, disodium hydrogen phosphate, citric acid
Kind, initiator is selected from azodiisobutyronitrile, azobisisoheptonitrile, one kind of dilauroyl peroxide, and dispersant is selected from Methyl cellulose
One kind in element, hydroxypropyl methyl cellulose, methyl cellulose ether；
The modified PVDC nanometre glues include the raw material of following parts by weight proportioning：5-15 parts of chitosan, 1-3 parts of acetic acid,
4-6 parts of cellulose acetate, 65-70 parts of N-N dimethylformamides, 1-2 parts of nano silver wire, 5-15 parts of glycerine, deionized water 100-
150 parts, 5-10 parts of absolute ethyl alcohol, 0.5-1.5 parts of glycerine；
The thickness of the modified PA films is 3.5-4.0 μm, the modification PVDC latex being coated on the outer surface of modified PA films
Thickness be 2.5-3.0 μm, the thickness of the modification PVDC nanometre glues of the coating inside surfaces of modified PA films is 1.5-1.8 μm；
The PVDC coating materials, continuous interior for 24 hours at atmosheric pressure, oxygen transmission rate 0.018-0.053ml/mil/
100in2, at 100 DEG C of temperature and 90% relative humidity, moisture vapor permeable rate 0.009-0.012ml/mil/100in2；
The density of the PVDC coating materials is 1.52-1.81g/cm, fusing point is 190-220 DEG C, tensile break strength is
85-98MPa, elongation at break >=156%.
Preferably, the quality of the ammonium hydroxide is the 0.5% of the quality of Nano particles of silicon dioxide, aminopropyl-triethoxy silicon
The quality of alkane is the 5-10% of the quality of nano-particle.
Preferably, the pH value buffering conditioning agent is disodium hydrogen phosphate, and initiator is azodiisobutyronitrile, and dispersant is first
Base cellulose ether.
Preferably, the modified PVDC latex includes the raw material of following parts by weight proportioning：120 parts of ultra-pure water, phosphoric acid hydrogen
0.1 part of disodium, 80 parts of vinylidene, 20 parts of methacrylate monomer, 0.35 part of azodiisobutyronitrile, methylcellulose
0.15 part of ether.
Preferably, the modified PVDC nanometre glues include the raw material of following parts by weight proportioning：10 parts of chitosan, acetic acid 2
It is part, 5 parts of cellulose acetate, 65 parts of N-N dimethylformamides, 2 parts of nano silver wire, 10 parts of glycerine, 100 parts of deionized water, anhydrous
10 parts of ethyl alcohol, 1 part of glycerine.
Another technical problem to be solved by the present invention is that providing a kind of system of the PVDC coating materials with high obstructing performance
Preparation Method includes the following steps：
1) preparation of modified PA films
(1) Nano particles of silicon dioxide that 10-15 mass parts grain sizes are 30-60nm is dispersed in 50-60 mass parts
Ultra-pure water in, and be heated to 80-100 DEG C, stir 5-10min, then thereto addition 0.05-0.08 mass parts ammonium hydroxide and
0.4-1 mass parts aminopropyl triethoxysilanes, are sufficiently stirred 6h, are cooled to room temperature, and centrifugation is flushed three times with deionized water,
The substance for not participating in reaction is cleaned, solid is made, puts solid obtained into ball mill ball milling 12h, obtains amino modified
SiO 2 powder；
(2) the amino modified SiO 2 powders of 0.5-1.0g are added into 20-30 mass parts ultra-pure waters, are sufficiently stirred dissolving
Afterwards, the mass fraction of 2-5 mass parts is added as 2% piperazine aqueous solution, after stirring and dissolving, adds the quality of 3-7 mass parts
The triethylamine that score is 3%, after stirring and dissolving, with aqueous phase solution is made；
(3) 10-15 mass parts pyromellitic trimethylsilyl chloride light yellow solid powder is dissolved in 10-15 mass parts n-hexanes,
With obtained organic phase solution；
(4) clean 70-85 mass parts PA films are immersed in aqueous phase solution, immersion is taken out after five minutes, is placed on draught cupboard
In dry, be then immersed in organic phase solution, carry out interface polymerization reaction, taken out after 2 minutes, PA films obtained be placed on
Continue crosslinking 1 minute in 60 DEG C of environment, the modification PA films containing amino modified silica are made；
2) preparation of modified PVDC latex
(1) it is spare to prepare reaction raw materials：In parts by weight, reaction raw materials group becomes 100-150 parts of ultra-pure water, pH value buffering
0.05-0.2 parts of conditioning agent, 80-90 parts of vinylidene, 10-20 parts of methacrylate monomer, initiator 0.20-0.50
Part, 0.1-0.2 parts of dispersant；
(2) pH value buffering conditioning agent aqueous solution and aqueous dispersant are prepared：The pH value of 0.05-0.2 mass parts is buffered
Conditioning agent and the ultra-pure water of 5-8 mass parts are configured to pH value buffering conditioning agent aqueous solution；By the dispersant of 0.1-0.2 mass parts with
The ultra-pure water of 15-35 mass parts is configured to aqueous dispersant；
(3) mix monomer is prepared：By the acrylic acid first of the vinylidene of 80-90 mass parts and 10-20 mass parts
Ester monomer is uniformly mixed, and is configured to mix monomer；
(4) by the ultra-pure water of 80-85 mass parts, pH value buffering conditioning agent aqueous solution, 80% mix monomer, 80% draw
Hair agent, 80% aqueous dispersant be added in polymeric kettle, it is cold dispersion 30 minutes after, risen under 40-100rpm speeds of agitator
Temperature increases speed of agitator to 65-80 DEG C of beginning polymerisation with 3-6rpm/h speed, is increased and is reacted with 3.0 DEG C/h speed
Temperature, remaining mix monomer is continuously added with the speed of 50kg/h, and remaining initiation is continuously added with the speed of 0.5kg/h
Agent continuously adds remaining aqueous dispersant with the speed of 10kg/h, is continuously added with the speed of 50kg/h remaining ultrapure
Water；
(5) after the completion of all remaining reaction raw materials are added, continue to increase speed of agitator with 5rpm/h speed, with 3.0 DEG C/h
Speed increases reaction temperature and terminates polymerisation after polymerisation 2-4h again, and vacuum deviates from residual monomer, cooling discharge, centrifugation,
Drying obtains modified PVDC latex；
3) preparation of modified PVDC nanometre glues
(1) 5-15 mass parts chitosans are taken to be added in the acetic acid solution of 1-3 mass parts, stirring to dissolving, compound concentration is
The chitosan solution of 0.5-1.5%；
(2) 4-6 mass parts cellulose acetates are taken, are added in 65-70 mass parts N-N dimethylformamides, in 70-80 DEG C of water-bath
Then lower stirring is mixed into the acetic acid solution of chitosan, is sufficiently stirred up to dissolving, solution is made to be uniformly mixed；
(3) N-N dimethylformamides are removed with rotary evaporator, obtains chitosan/cellulose acetate plural gel；
(4) 0.5-1.5g chitosans/cellulose acetate plural gel is taken, the deionized water of 100mL is added thereto,
Magnetic agitation makes it dissolve under 70-80 DEG C of oil bath, is configured to binary blend solution；
(5) 1-2 mass parts nano silver wires are taken, is dissolved with 5-10 mass parts absolute ethyl alcohols, is made into nano silver wire solution；
(6) it takes the binary blend solution that 5-15ml prepares to be added in PVDC latex, 0.5-1 mass parts the third three is added dropwise thereto
Alcohol and 0.1-0.2ml nano silver wire solution make it be uniformly mixed with ultrasonic wave, and modified PVDC nanometre glues are made；
4) modified PVDC latex is uniformly coated on the outer surface of modified PA films with blade applicator, controls coating layer thickness
It is 2.5-3.0 μm；
5) modified PVDC nanometre glues are uniformly coated on the inner surface of modified PA films with blade applicator, control applies thickness
Degree is 1.5-1.8 μm；
6) after being coated with, dry curing 12h, obtains PVDC coating materials at 60-85 DEG C.
(3) advantageous effect
Compared with prior art, the present invention provides a kind of with the PVDC coating materials of high obstructing performance and its preparation side
Method has following advantageous effect：
1, the modification containing amino modified silica is made by the surface-crosslinked modification in PA films in the PVDC coating materials
PA films, the modification PA films obtained containing amino modified silica have higher tensile break strength than conventional PA films, together
When in modified PA film surfaces introduce silica, silica is photocatalyst medium, and photocatalyst will produce class under the irradiation of light
Like photosynthetic light-catalyzed reaction, oxidability extremely strong free hydroxy and active oxygen are produced, there is very strong photooxidation
Change restoring function, it is oxidable to decompose various organic compounds and part inorganic matter, the cell membrane and solidification virus of bacterium can be destroyed
Protein, bacterium and decomposing organic pollutant can be killed, organic pollution is resolved into free of contamination water and carbon dioxide, have
There are extremely strong sterilization and antimildew function.
2, the PVDC coating materials, by adding methyl cellulose ether in PVDC latex, methyl cellulose ether is a kind of
Dispersant is that a kind of in the molecule while having the interfacial agents of two kinds of opposite natures of lipophile and hydrophily, Methyl cellulose
Plain ether can not only disperse vinylidene and methacrylate monomer, make vinylidene and methyl acrylate list
Body mixing is more uniform, and can prevent vinylidene and methacrylate monomer from sedimentation and cohesion occurs, and makes partially
Polymerization effect between dichloroethylene monomer and methacrylate monomer is more preferable, and it is poor to solve PVDC latex thermal stability,
When the heated or room temperature time is longer, double bond conjugation is easy tod produce, hydrogen chloride is escaped, makes intermolecular generation cavity, barrier
Property failure the technical issues of.
3, PVDC coating materials, by being made in PVDC latex addition chitosan and cellulose acetate and nano silver wire
Modified PVDC nanometre glues can increase the viscosity of PVDC latex, cellulose acetate has since chitosan is as a kind of thickener
Higher transparency and stronger crushing resistance, can enhance the extension at break performance of PVDC latex, and nano silver wire has stronger
Anti-microbial property, therefore, modified PVDC nanometre glues also have excellent antibacterial performance and machine while with significant barrier property
Tool performance.
4, PVDC coating materials, by the modified PVDC latex of coating on the outer surface of modified PA films, in modified PA
The coating inside surfaces of film are modified PVDC nanometre glues, realize PVDC coating materials with the same of significant high obstructing performance
When, it may have significant antibacterial and mouldproof performance and higher tensile break strength and better extension at break performance.
5, the preparation method of the PVDC coating materials, by preparing modified PA films, modified PVDC latex and modification respectively
PVDC nanometre glues, then coating is modified PVDC latex on the outer surface of modified PA films, on the inner surface of modified PA films
The modified PVDC nanometre glues of coating, the preparation method of PVDC coating materials are simple and efficient, and can considerably improve PVDC coating materials
The production efficiency of material.
Specific implementation mode
Below in conjunction with the embodiment of the present invention, technical solution in the embodiment of the present invention is clearly and completely retouched
It states, it is clear that described embodiments are only a part of the embodiments of the present invention, instead of all the embodiments.Based on the present invention
In embodiment, every other implementation obtained by those of ordinary skill in the art without making creative efforts
Example, shall fall within the protection scope of the present invention.
Embodiment one：
(1) Nano particles of silicon dioxide that 10 mass parts grain sizes are 30nm is dispersed in the ultra-pure water of 50 mass parts
In, and 80 DEG C are heated to, 5min is stirred, then adds three ethoxy of 0.05 mass parts ammonium hydroxide and 0.4 mass parts aminopropyl thereto
Base silane is sufficiently stirred 6h, is cooled to room temperature, and centrifugation is flushed three times with deionized water, cleans the substance for not participating in reaction, system
Solid is obtained, solid obtained is put into ball mill ball milling 12h, obtains amino modified SiO 2 powder；
(2) the amino modified SiO 2 powders of 0.5g are added into 20 mass parts ultra-pure waters, after being sufficiently stirred dissolving, are added
The piperazine aqueous solution that the mass fraction of 2 mass parts is 2%, after stirring and dissolving, the mass fraction for adding 3 mass parts is 3%
Triethylamine, after stirring and dissolving, with aqueous phase solution is made；
(3) 10 mass parts pyromellitic trimethylsilyl chloride light yellow solid powder are dissolved in 10 mass parts n-hexanes, with obtained
Organic phase solution；
(4) 70 clean mass parts PA films are immersed in aqueous phase solution, immersion is taken out after five minutes, is placed in draught cupboard
It dries, is then immersed in organic phase solution, carry out interface polymerization reaction, taken out after 2 minutes, PA films obtained are placed on 60
Continue crosslinking 1 minute in DEG C environment, the modification PA films containing amino modified silica are made；
(5) ultra-pure water of the citric acid of 0.05 mass parts and 5 mass parts is configured to aqueous citric acid solution；By 0.1 mass
The hydroxypropyl methyl cellulose of part and the ultra-pure water of 15 mass parts are configured to hydroxypropyl methyl cellulose aqueous solution；
(6) methacrylate monomer of the vinylidene of 80 mass parts and 10 mass parts is uniformly mixed, is prepared
At mix monomer；
(7) by the ultra-pure water of 80 mass parts, aqueous citric acid solution, 80% mix monomer, 80% dilauroyl peroxide,
80% hydroxypropyl methyl cellulose aqueous solution is added in polymeric kettle, it is cold dispersion 30 minutes after, risen under 40rpm speeds of agitator
Temperature increases speed of agitator to 65 DEG C of beginning polymerisations with 3rpm/h speed, and reaction temperature is increased with 3.0 DEG C/h speed,
Remaining mix monomer is continuously added with the speed of 50kg/h, remaining peroxidating 12 is continuously added with the speed of 0.5kg/h
Acyl is continuously added remaining hydroxypropyl methyl cellulose aqueous solution with the speed of 10kg/h, is continuously added with the speed of 50kg/h
Remaining ultra-pure water；
(8) after the completion of all remaining reaction raw materials are added, continue to increase speed of agitator with 5rpm/h speed, with 3.0 DEG C/h
Speed increases reaction temperature and terminates polymerisation after polymerisation 2h again, and vacuum deviates from residual monomer, and cooling discharge, is done centrifugation
It is dry to obtain modified PVDC latex；
(9) 5 mass parts chitosans are taken to be added in the acetic acid solution of 1 mass parts, stirring to dissolving, compound concentration 0.5%
Chitosan solution；
(10) 4 mass parts cellulose acetates are taken, is added in 65 mass parts N-N dimethylformamides, is stirred under 70 DEG C of water-baths
Until dissolving, is then mixed into the acetic acid solution of chitosan, is sufficiently stirred, solution is made to be uniformly mixed；
(11) N-N dimethylformamides are removed with rotary evaporator, obtains chitosan/cellulose acetate plural gel；
(12) 0.5g chitosans/cellulose acetate plural gel is taken, the deionized water of 100mL is added thereto, at 70 DEG C
Magnetic agitation makes it dissolve under oil bath, is configured to binary blend solution；
(13) 1 mass parts nano silver wire is taken, is dissolved with 5 mass parts absolute ethyl alcohols, is made into nano silver wire solution；
(14) the binary blend solution that 5ml prepares is taken to be added in PVDC latex, be added dropwise thereto 0.5 mass parts glycerine and
0.1ml nano silver wire solution makes it be uniformly mixed with ultrasonic wave, and modified PVDC nanometre glues are made；
(15) modified PVDC latex is uniformly coated on the outer surface of modified PA films with blade applicator, control applies thickness
Degree is 2.5 μm；
(16) modified PVDC nanometre glues are uniformly coated on the inner surface of modified PA films with blade applicator, control coating
Thickness is 1.5 μm；
(17) after being coated with, dry curing 12h, obtains PVDC coating materials at 60 DEG C.
Embodiment two：
(1) Nano particles of silicon dioxide that 12 mass parts grain sizes are 50nm is dispersed in the ultra-pure water of 55 mass parts
In, and 90 DEG C are heated to, 8min is stirred, then adds three ethoxy of 0.08 mass parts ammonium hydroxide and 0.8 mass parts aminopropyl thereto
Base silane is sufficiently stirred 6h, is cooled to room temperature, and centrifugation is flushed three times with deionized water, cleans the substance for not participating in reaction, system
Solid is obtained, solid obtained is put into ball mill ball milling 12h, obtains amino modified SiO 2 powder；
(2) the amino modified SiO 2 powders of 0.8g are added into 25 mass parts ultra-pure waters, after being sufficiently stirred dissolving, are added
The piperazine aqueous solution that the mass fraction of 4 mass parts is 2%, after stirring and dissolving, the mass fraction for adding 5 mass parts is 3%
Triethylamine, after stirring and dissolving, with aqueous phase solution is made；
(3) 15 mass parts pyromellitic trimethylsilyl chloride light yellow solid powder are dissolved in 10-15 mass parts n-hexanes, are prepared
Obtain organic phase solution；
(4) 80 clean mass parts PA films are immersed in aqueous phase solution, immersion is taken out after five minutes, is placed in draught cupboard
It dries, is then immersed in organic phase solution, carry out interface polymerization reaction, taken out after 2 minutes, PA films obtained are placed on 60
Continue crosslinking 1 minute in DEG C environment, the modification PA films containing amino modified silica are made；
(5) ultra-pure water of the disodium hydrogen phosphate of 0.1 mass parts and 6 mass parts is configured to disodium hydrogen phosphate aqueous solution；It will
The methyl cellulose ether of 0.15 mass parts and the ultra-pure water of 20 mass parts are configured to methyl cellulose ether aqueous solution；
(6) methacrylate monomer of the vinylidene of 85 mass parts and 15 mass parts is uniformly mixed, is prepared
At mix monomer；
(7) ultra-pure water of 85 mass parts, disodium hydrogen phosphate aqueous solution, 80% mix monomer, 80% azo two is different
Butyronitrile, 80% methyl cellulose ether aqueous solution be added in polymeric kettle, it is cold dispersion 30 minutes after, 40-100rpm stirring turn
It is warming up to 70 DEG C of beginning polymerisations under speed, while speed of agitator is increased with 5rpm/h speed, is increased and is reacted with 3.0 DEG C/h speed
Temperature, remaining mix monomer is continuously added with the speed of 50kg/h, and remaining azo two is continuously added with the speed of 0.5kg/h
Isobutyronitrile is continuously added remaining methyl cellulose ether aqueous solution with the speed of 10kg/h, is continuously added with the speed of 50kg/h
Remaining ultra-pure water；
(8) after the completion of all remaining reaction raw materials are added, continue to increase speed of agitator with 5rpm/h speed, with 3.0 DEG C/h
Speed increases reaction temperature and terminates polymerisation after polymerisation 2-4h again, and vacuum deviates from residual monomer, cooling discharge, centrifugation,
Drying obtains modified PVDC latex；
(9) 10 mass parts chitosans are taken to be added in the acetic acid solution of 2 mass parts, to dissolving, compound concentration is 1% for stirring
Chitosan solution；
(10) 5 mass parts cellulose acetates are taken, is added in 70 mass parts N-N dimethylformamides, is stirred under 75 DEG C of water-baths
Until dissolving, is then mixed into the acetic acid solution of chitosan, is sufficiently stirred, solution is made to be uniformly mixed；
(11) N-N dimethylformamides are removed with rotary evaporator, obtains chitosan/cellulose acetate plural gel；
(12) 1g chitosans/cellulose acetate plural gel is taken, the deionized water of 100mL is added thereto, in 75 DEG C of oil
The lower magnetic agitation of bath makes it dissolve, and is configured to binary blend solution；
(13) 1.5 mass parts nano silver wires are taken, is dissolved with 8 mass parts absolute ethyl alcohols, is made into nano silver wire solution；
(14) it takes the binary blend solution that 10ml is prepared to be added in PVDC latex, 0.8 mass parts glycerine is added dropwise thereto
With 0.15ml nano silver wire solution, so that it is uniformly mixed with ultrasonic wave, modified PVDC nanometre glues are made；
(15) modified PVDC latex is uniformly coated on the outer surface of modified PA films with blade applicator, control applies thickness
Degree is 3.0 μm；
(16) modified PVDC nanometre glues are uniformly coated on the inner surface of modified PA films with blade applicator, control coating
Thickness is 1.6 μm；
(17) after being coated with, dry curing 12h, obtains PVDC coating materials at 80 DEG C.
Embodiment three：
(1) Nano particles of silicon dioxide that 15 mass parts grain sizes are 60nm is dispersed in the ultra-pure water of 60 mass parts
In, and 100 DEG C are heated to, 10min is stirred, then adds three ethoxy of 0.08 mass parts ammonium hydroxide and 1 mass parts aminopropyl thereto
Base silane is sufficiently stirred 6h, is cooled to room temperature, and centrifugation is flushed three times with deionized water, cleans the substance for not participating in reaction, system
Solid is obtained, solid obtained is put into ball mill ball milling 12h, obtains amino modified SiO 2 powder；
(2) the amino modified SiO 2 powders of 1.0g are added into 30 mass parts ultra-pure waters, after being sufficiently stirred dissolving, are added
The piperazine aqueous solution that the mass fraction of 5 mass parts is 2%, after stirring and dissolving, the mass fraction for adding 7 mass parts is 3%
Triethylamine, after stirring and dissolving, with aqueous phase solution is made；
(3) 15 mass parts pyromellitic trimethylsilyl chloride light yellow solid powder are dissolved in 15 mass parts n-hexanes, with obtained
Organic phase solution；
(4) 85 clean mass parts PA films are immersed in aqueous phase solution, immersion is taken out after five minutes, is placed in draught cupboard
It dries, is then immersed in organic phase solution, carry out interface polymerization reaction, taken out after 2 minutes, PA films obtained are placed on 60
Continue crosslinking 1 minute in DEG C environment, the modification PA films containing amino modified silica are made；
(5) ultra-pure water of the Sodium Acid Pyrophosphate of 0.2 mass parts and 8 mass parts is configured to Sodium Acid Pyrophosphate water
Solution；The ultra-pure water of the methylcellulose of 0.2 mass parts and 35 mass parts is configured to methylated cellulose aqueous solution；
(6) methacrylate monomer of the vinylidene of 90 mass parts and 20 mass parts is uniformly mixed, is prepared
At mix monomer；
(7) by the ultra-pure water of 85 mass parts, Sodium Acid Pyrophosphate aqueous solution, 80% mix monomer, 80% azo
Two different heptonitriles, 80% methylated cellulose aqueous solution be added in polymeric kettle, it is cold dispersion 30 minutes after, in 100rpm speeds of agitator
Under be warming up to 80 DEG C beginning polymerisations, while with 6rpm/h speed increase speed of agitator, with 3.0 DEG C/h speed increase reaction temperature
Degree, continuously adds remaining mix monomer, it is different continuously to add remaining azo two with the speed of 0.5kg/h with the speed of 50kg/h
Heptonitrile, remaining methylated cellulose aqueous solution is continuously added with the speed of 10kg/h, and residue is continuously added with the speed of 50kg/h
Ultra-pure water；
(8) after the completion of all remaining reaction raw materials are added, continue to increase speed of agitator with 5rpm/h speed, with 3.0 DEG C/h
Speed increases reaction temperature and terminates polymerisation after polymerisation 4h again, and vacuum deviates from residual monomer, and cooling discharge, is done centrifugation
It is dry to obtain modified PVDC latex；
(9) 15 mass parts chitosans are taken to be added in the acetic acid solution of 3 mass parts, stirring to dissolving, compound concentration 1.5%
Chitosan solution；
(10) 6 mass parts cellulose acetates are taken, is added in 70 mass parts N-N dimethylformamides, is stirred under 80 DEG C of water-baths
Until dissolving, is then mixed into the acetic acid solution of chitosan, is sufficiently stirred, solution is made to be uniformly mixed；
(11) N-N dimethylformamides are removed with rotary evaporator, obtains chitosan/cellulose acetate plural gel；
(12) 1.5g chitosans/cellulose acetate plural gel is taken, the deionized water of 100mL is added thereto, at 80 DEG C
Magnetic agitation makes it dissolve under oil bath, is configured to binary blend solution；
(13) 2 mass parts nano silver wires are taken, is dissolved with 10 mass parts absolute ethyl alcohols, is made into nano silver wire solution；
(14) the binary blend solution that 15ml prepares is taken to be added in PVDC latex, be added dropwise thereto 1 mass parts glycerine and
0.2ml nano silver wire solution makes it be uniformly mixed with ultrasonic wave, and modified PVDC nanometre glues are made；
(15) modified PVDC latex is uniformly coated on the outer surface of modified PA films with blade applicator, control applies thickness
Degree is 3.0 μm；
(16) modified PVDC nanometre glues are uniformly coated on the inner surface of modified PA films with blade applicator, control coating
Thickness is 1.8 μm；
(17) after being coated with, dry curing 12h, obtains PVDC coating materials at 85 DEG C.
Experimental example：
High-barrier coating material made from embodiment 1, embodiment 2, embodiment 3 is continuous interior for 24 hours at atmosheric pressure, it surveys
Oxygen transmission rate is tried, at 100 DEG C of temperature and 90% relative humidity, tests moisture vapor permeable rate, experimental results are shown in Table 1.
Criterion：High barrier material refers to continuous interior for 24 hours at atmosheric pressure, and oxygen transmission rate is less than 0.1ml/mil/
100in2；At 100 DEG C of temperature and 90% relative humidity, moisture vapor permeable rate is less than or equal to 0.03ml/mil/100in2；
Table 1
| Oxygen transmission rate (ml/mil/100in2) | Moisture vapor permeable rate (ml/mil/100in2) | |
| Embodiment 1 | 0.053 | 0.009 |
| Embodiment 2 | 0.018 | 0.011 |
| Embodiment 3 | 0.029 | 0.012 |
The beneficial effects of the invention are as follows：It can be obtained by table 1, embodiment 1, embodiment 2 and the oxygen transmission rate of embodiment 3 are distinguished
For 0.053ml/mil/100in2、0.018ml/mil/100in2With 0.029ml/mil/100in2Respectively less than 0.1ml/mil/
100in2, embodiment 1, embodiment 2 and the moisture vapor permeable rate of embodiment 3 are respectively 0.009ml/mil/100in2、0.011ml/mil/
100in2With 0.012ml/mil/100in2Respectively less than 0.03ml/mil/100in2, therefore, the oxygen transmission rate of PVDC coating materials with
Two performance indicators of moisture vapor permeable rate meet the criterion of high barrier material.
Typical case：
(1) Nano particles of silicon dioxide that 12 mass parts grain sizes are 50nm is dispersed in the ultra-pure water of 55 mass parts
In, and 90 DEG C are heated to, 8min is stirred, then adds three ethoxy of 0.08 mass parts ammonium hydroxide and 0.8 mass parts aminopropyl thereto
Base silane is sufficiently stirred 6h, is cooled to room temperature, and centrifugation is flushed three times with deionized water, cleans the substance for not participating in reaction, system
Solid is obtained, solid obtained is put into ball mill ball milling 12h, obtains amino modified SiO 2 powder；
(2) the amino modified SiO 2 powders of 0.8g are added into 25 mass parts ultra-pure waters, after being sufficiently stirred dissolving, are added
The piperazine aqueous solution that the mass fraction of 4 mass parts is 2%, after stirring and dissolving, the mass fraction for adding 5 mass parts is 3%
Triethylamine, after stirring and dissolving, with aqueous phase solution is made；
(3) 15 mass parts pyromellitic trimethylsilyl chloride light yellow solid powder are dissolved in 10-15 mass parts n-hexanes, are prepared
Obtain organic phase solution；
(4) 80 clean mass parts PA films are immersed in aqueous phase solution, immersion is taken out after five minutes, is placed in draught cupboard
It dries, is then immersed in organic phase solution, carry out interface polymerization reaction, taken out after 2 minutes, PA films obtained are placed on 60
Continue crosslinking 1 minute in DEG C environment, the modification PA films containing amino modified silica are made；
(5) ultra-pure water of the disodium hydrogen phosphate of 0.1 mass parts and 6 mass parts is configured to disodium hydrogen phosphate aqueous solution；It will
The methyl cellulose ether of 0.15 mass parts and the ultra-pure water of 20 mass parts are configured to methyl cellulose ether aqueous solution；
(6) methacrylate monomer of the vinylidene of 85 mass parts and 15 mass parts is uniformly mixed, is prepared
At mix monomer；
(7) ultra-pure water of 85 mass parts, disodium hydrogen phosphate aqueous solution, 80% mix monomer, 80% azo two is different
Butyronitrile, 80% methyl cellulose ether aqueous solution be added in polymeric kettle, it is cold dispersion 30 minutes after, 40-100rpm stirring turn
It is warming up to 70 DEG C of beginning polymerisations under speed, while speed of agitator is increased with 5rpm/h speed, is increased and is reacted with 3.0 DEG C/h speed
Temperature, remaining mix monomer is continuously added with the speed of 50kg/h, and remaining azo two is continuously added with the speed of 0.5kg/h
Isobutyronitrile is continuously added remaining methyl cellulose ether aqueous solution with the speed of 10kg/h, is continuously added with the speed of 50kg/h
Remaining ultra-pure water；
(8) after the completion of all remaining reaction raw materials are added, continue to increase speed of agitator with 5rpm/h speed, with 3.0 DEG C/h
Speed increases reaction temperature and terminates polymerisation after polymerisation 2-4h again, and vacuum deviates from residual monomer, cooling discharge, centrifugation,
Drying obtains modified PVDC latex；
(9) 10 mass parts chitosans are taken to be added in the acetic acid solution of 2 mass parts, to dissolving, compound concentration is 1% for stirring
Chitosan solution；
(10) 5 mass parts cellulose acetates are taken, is added in 70 mass parts N-N dimethylformamides, is stirred under 75 DEG C of water-baths
Until dissolving, is then mixed into the acetic acid solution of chitosan, is sufficiently stirred, solution is made to be uniformly mixed；
(11) N-N dimethylformamides are removed with rotary evaporator, obtains chitosan/cellulose acetate plural gel；
(12) 1g chitosans/cellulose acetate plural gel is taken, the deionized water of 100mL is added thereto, in 75 DEG C of oil
The lower magnetic agitation of bath makes it dissolve, and is configured to binary blend solution；
(13) 1.5 mass parts nano silver wires are taken, is dissolved with 8 mass parts absolute ethyl alcohols, is made into nano silver wire solution；
(14) it takes the binary blend solution that 10ml is prepared to be added in PVDC latex, 0.8 mass parts glycerine is added dropwise thereto
With 0.15ml nano silver wire solution, so that it is uniformly mixed with ultrasonic wave, modified PVDC nanometre glues are made；
(15) modified PVDC latex is uniformly coated on the outer surface of modified PA films with blade applicator, control applies thickness
Degree is 3.0 μm；
(16) modified PVDC nanometre glues are uniformly coated on the inner surface of modified PA films with blade applicator, control coating
Thickness is 1.6 μm；
(17) after being coated with, dry curing 12h, obtains PVDC coating materials at 80 DEG C.
It although an embodiment of the present invention has been shown and described, for the ordinary skill in the art, can be with
Understanding without departing from the principles and spirit of the present invention can carry out these embodiments a variety of variations, modification, replace
And modification, the scope of the present invention is defined by the appended.
Claims (6)
1. a kind of PVDC coating materials with high obstructing performance, including modified PA films, which is characterized in that the modified PA films
Modified PVDC latex is coated on outer surface, the coating inside surfaces of modified PA films there are modified PVDC nanometre glues；
The modified PA films include the raw material of following parts by weight proportioning：70-85 parts of PA films, Nano particles of silicon dioxide 10-15
Part, 0.05-0.08 parts of ammonium hydroxide, 0.4-1 parts of aminopropyl triethoxysilane, mass fraction be 2% 2-5 parts of piperazine aqueous solution,
10-15 parts of pyromellitic trimethylsilyl chloride that 3-7 parts of the triethylamine that mass fraction is 3%, mass fraction are 0.25%, n-hexane 10-15
Part, 50-60 parts of ultra-pure water；
The modified PVDC latex includes the raw material of following parts by weight proportioning：100-150 parts of ultra-pure water, pH value buffer conditioning agent
0.05-0.2 parts, 80-90 parts of vinylidene, 10-20 parts of methacrylate monomer, 0.20-0.50 parts of initiator, dispersion
0.1-0.2 parts of agent；Wherein, the one kind of pH value buffering conditioning agent in Sodium Acid Pyrophosphate, disodium hydrogen phosphate, citric acid,
Initiator be selected from azodiisobutyronitrile, azobisisoheptonitrile, one kind of dilauroyl peroxide, dispersant be selected from methylcellulose,
One kind in hydroxypropyl methyl cellulose, methyl cellulose ether；
The modified PVDC nanometre glues include the raw material of following parts by weight proportioning：5-15 parts of chitosan, 1-3 parts of acetic acid, acetic acid
4-6 parts of cellulose, 65-70 parts of N-N dimethylformamides, 1-2 parts of nano silver wire, 5-15 parts of glycerine, deionized water 100-150
Part, 5-10 parts of absolute ethyl alcohol, 0.5-1.5 parts of glycerine；
The thickness of the modified PA films is 3.5-4.0 μm, the thickness for the modification PVDC latex being coated on the outer surface of modified PA films
Degree is 2.5-3.0 μm, and the thickness of the modification PVDC nanometre glues of the coating inside surfaces of modified PA films is 1.5-1.8 μm；
The PVDC coating materials, continuous interior for 24 hours at atmosheric pressure, oxygen transmission rate 0.018-0.053ml/mil/100in2,
At 100 DEG C of temperature and 90% relative humidity, moisture vapor permeable rate 0.009-0.012ml/mil/100in2；
The density of the PVDC coating materials is 1.52-1.81g/cm, fusing point is 190-220 DEG C, tensile break strength 85-
98MPa, elongation at break >=156%.
2. a kind of PVDC coating materials with high obstructing performance according to claim 1, which is characterized in that the ammonium hydroxide
Quality be Nano particles of silicon dioxide quality 0.5%, the quality of aminopropyl triethoxysilane is the matter of nano-particle
The 5-10% of amount.
3. a kind of PVDC coating materials with high obstructing performance according to claim 1, which is characterized in that the pH value
Buffering conditioning agent is disodium hydrogen phosphate, and initiator is azodiisobutyronitrile, and dispersant is methyl cellulose ether.
4. a kind of PVDC coating materials with high obstructing performance according to claim 1, which is characterized in that the modification
PVDC latex includes the raw material of following parts by weight proportioning：120 parts of ultra-pure water, 0.1 part of disodium hydrogen phosphate, vinylidene
80 parts, 20 parts of methacrylate monomer, 0.35 part of azodiisobutyronitrile, 0.15 part of methyl cellulose ether.
5. a kind of PVDC coating materials with high obstructing performance according to claim 1, which is characterized in that the modification
PVDC nanometre glues include the raw material of following parts by weight proportioning：10 parts of chitosan, 2 parts of acetic acid, 5 parts of cellulose acetate, N-N diformazans
65 parts of base amide, 2 parts of nano silver wire, 10 parts of glycerine, 100 parts of deionized water, 10 parts of absolute ethyl alcohol, 1 part of glycerine.
6. a kind of preparation method of the PVDC coating materials with high obstructing performance, which is characterized in that include the following steps：
1) preparation of modified PA films
(1) Nano particles of silicon dioxide that 10-15 mass parts grain sizes are 30-60nm is dispersed in the super of 50-60 mass parts
In pure water, and it is heated to 80-100 DEG C, stirs 5-10min, then adds 0.05-0.08 mass parts ammonium hydroxide and 0.4-1 thereto
Mass parts aminopropyl triethoxysilane, is sufficiently stirred 6h, is cooled to room temperature, and centrifugation is flushed three times with deionized water, is cleaned not
The substance of reaction is participated in, solid is made, puts solid obtained into ball mill ball milling 12h, obtains amino modified titanium dioxide
Si powder；
(2) the amino modified SiO 2 powders of 0.5-1.0g are added into 20-30 mass parts ultra-pure waters, after being sufficiently stirred dissolving,
The mass fraction of 2-5 mass parts is added as 2% piperazine aqueous solution, after stirring and dissolving, adds the mass fraction of 3-7 mass parts
For 3% triethylamine, after stirring and dissolving, with aqueous phase solution is made；
(3) 10-15 mass parts pyromellitic trimethylsilyl chloride light yellow solid powder is dissolved in 10-15 mass parts n-hexanes, is prepared
Obtain organic phase solution；
(4) clean 70-85 mass parts PA films are immersed in aqueous phase solution, immersion is taken out after five minutes, is placed in draught cupboard and is dried in the air
It is dry, it is then immersed in organic phase solution, carries out interface polymerization reaction, taken out after 2 minutes, PA films obtained are placed on 60 DEG C
Continue crosslinking 1 minute in environment, the modification PA films containing amino modified silica are made；
2) preparation of modified PVDC latex
(1) it is spare to prepare reaction raw materials：In parts by weight, reaction raw materials group becomes 100-150 parts of ultra-pure water, and pH value buffering is adjusted
0.05-0.2 parts of agent, 80-90 parts of vinylidene, 10-20 parts of methacrylate monomer, 0.20-0.50 parts of initiator, point
0.1-0.2 parts of powder；
(2) pH value buffering conditioning agent aqueous solution and aqueous dispersant are prepared：The pH value of 0.05-0.2 mass parts is buffered and is adjusted
The ultra-pure water of agent and 5-8 mass parts is configured to pH value buffering conditioning agent aqueous solution；By the dispersant and 15- of 0.1-0.2 mass parts
The ultra-pure water of 35 mass parts is configured to aqueous dispersant；
(3) mix monomer is prepared：By the methyl acrylate list of the vinylidene of 80-90 mass parts and 10-20 mass parts
Body is uniformly mixed, and is configured to mix monomer；
(4) by the ultra-pure water of 80-85 mass parts, pH value buffering conditioning agent aqueous solution, 80% mix monomer, 80% initiation
Agent, 80% aqueous dispersant be added in polymeric kettle, it is cold dispersion 30 minutes after, heat up under 40-100rpm speeds of agitator
To 65-80 DEG C of beginning polymerisation, while speed of agitator is increased with 3-6rpm/h speed, reaction temperature is increased with 3.0 DEG C/h speed
Degree, continuously adds remaining mix monomer with the speed of 50kg/h, remaining initiator is continuously added with the speed of 0.5kg/h,
Remaining aqueous dispersant is continuously added with the speed of 10kg/h, remaining ultra-pure water is continuously added with the speed of 50kg/h；
(5) after the completion of all remaining reaction raw materials are added, continue to increase speed of agitator with 5rpm/h speed, with 3.0 DEG C/h speed
It increases reaction temperature and terminates polymerisation after polymerisation 2-4h again, vacuum deviates from residual monomer, cooling discharge, centrifugation, drying
Obtain modified PVDC latex；
3) preparation of modified PVDC nanometre glues
(1) 5-15 mass parts chitosans are taken to be added in the acetic acid solution of 1-3 mass parts, stirring to dissolving, compound concentration 0.5-
1.5% chitosan solution；
(2) 4-6 mass parts cellulose acetates are taken, is added in 65-70 mass parts N-N dimethylformamides, is stirred under 70-80 DEG C of water-bath
It mixes up to dissolving, is then mixed into the acetic acid solution of chitosan, is sufficiently stirred, solution is made to be uniformly mixed；
(3) N-N dimethylformamides are removed with rotary evaporator, obtains chitosan/cellulose acetate plural gel；
(4) 0.5-1.5g chitosans/cellulose acetate plural gel is taken, the deionized water of 100mL is added thereto, in 70-80
Magnetic agitation makes it dissolve under DEG C oil bath, is configured to binary blend solution；
(5) 1-2 mass parts nano silver wires are taken, is dissolved with 5-10 mass parts absolute ethyl alcohols, is made into nano silver wire solution；
(6) the binary blend solution that 5-15ml prepares is taken to be added in PVDC latex, be added dropwise thereto 0.5-1 mass parts glycerine and
0.1-0.2ml nano silver wire solution makes it be uniformly mixed with ultrasonic wave, and modified PVDC nanometre glues are made；
4) modified PVDC latex is uniformly coated on the outer surface of modified PA films with blade applicator, control coating layer thickness is
2.5-3.0μm；
5) modified PVDC nanometre glues are uniformly coated on the inner surface of modified PA films with blade applicator, control coating layer thickness is
1.5-1.8μm；
6) after being coated with, dry curing 12h, obtains PVDC coating materials at 60-85 DEG C.
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| CN113371323A (en) * | 2021-07-30 | 2021-09-10 | 四川新升塑胶实业有限公司 | High-barrier plastic container, preparation method and spraying equipment |
| US11560487B2 (en) | 2020-09-22 | 2023-01-24 | Swimc Llc | Coating compositions containing low molecular weight chitosan composition |
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