CN107602752B - A kind of copolymerization REPVDC alloy solid resin and its preparation method and application - Google Patents
A kind of copolymerization REPVDC alloy solid resin and its preparation method and application Download PDFInfo
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Abstract
The present invention relates to a kind of copolymerization REPVDC alloy solid resins and its preparation method and application, including following components: mix monomer and its dispersing agent, mix monomer initiator, terminator, neutralizer, defoaming agent and deionized water.The present invention is copolymerized by the way that function monomer and vinylidene chloride is added, it can change the crystalline texture of PVDC side chain distortion, become the crystallizable side chain structure of ordered arrangement, to which the intensity, toughness and barrier property of former PVDC be significantly increased, 0.3-3 times of mechanical property raising, heat resistance improve 20-60% and have been assigned Memorability new material on the basis of the original；Preparation process is simple, at low cost, has a good application prospect.
Description
Technical field
The invention belongs to polymeric material field, in particular to a kind of copolymerization REPVDC alloy solid resin and its preparation side
Method and application.
Background technique
A kind of polyvinylidene chloride (abbreviation PVDC) the high molecular material packaging material good as materials with high barrier property, safety
It is nontoxic, it has a wide range of applications in food packaging applications.But PVDC is often exactly thermal stability ratio as packaging material at present
Poor, thermal decomposition temperature is at 100-120 DEG C, when the heated or room temperature time is longer, will generate double bond conjugation, escape chlorine
Change hydrogen, makes intermolecular generation cavity, barrier property failure, when leading to that the additives increase such as addition preservative is also needed to save in food
Between, certain harm is often had to human body.
Summary of the invention
Technical problem to be solved by the invention is to provide a kind of copolymerization REPVDC alloy solid resins and preparation method thereof
And application, the alloy solid resin are copolymerized by the way that function monomer and vinylidene chloride is added, thus it is possible to vary the distortion of PVDC side chain
Crystalline texture, becomes the crystallizable side chain structure of ordered arrangement, so that the intensity, toughness and barrier of former PVDC be significantly increased
Property, 1-3 times of mechanical property raising, heat resistance improve 20-60% and have been assigned memory new material on the basis of the original
Property；Preparation process is simple, at low cost, has a good application prospect.
The present invention provides a kind of copolymerization REPVDC alloy solid resins, by mass percentage, including following components:
Wherein, mix monomer and mix monomer dispersing agent include following components:
Surplus is mix monomer dispersing agent, and the sum of gross mass percentage is 100%.
The rare earth/metallic compound function monomer raw material composition includes mother liquor, alicyclic organic, auxiliary agent and deionized water；
Wherein, mother liquor includes rare earth compound or metallic compound, organic acid, organic amine and deionized water.
Further, the rare earth compound or metallic compound are oxide, hydroxide or the salt of rare earth or metal
One or more of.Wherein, the preferred low oxide of oxide, the preferred carbonate of salt.
Further, the rare earth is lanthanum, cerium, europium, terbium or neodymium element；The metal be zinc, calcium, magnesium, manganese, copper, nickel,
Aluminium, niobium, molybdenum, ruthenium, tungsten, rhenium or hafnium element.
Further, the organic acid is citric acid, in maleic acid, ethylenediamine tetra-acetic acid, succinic acid, adipic acid
It is one or more of.
Further, the organic amine is one of diethylamine, ethylenediamine, allyl amine, diethylenetriamines or several
Kind.
Preferably, the mother liquor is by mass percentage, comprising: rare earth compound or metallic compound 6-9%, organic acid
15%-25%, organic amine 10-20%, surplus are deionized water.
Further, the alicyclic organic is acrylate or epoxy-ester.
Further, the acrylate is one of ethyl acrylate, butyl acrylate, Isooctyl acrylate monomer or several
Kind；The epoxy-ester is one or both of epoxy aliphatic acid methyl ester, epoxy acrylate.
Further, the auxiliary agent includes catalyst and polymerization inhibitor, and the mass ratio of catalyst and polymerization inhibitor is 1:2-5.
Further, the catalyst is p-methyl benzenesulfonic acid；The polymerization inhibitor is hydroquinone, methylnaphthohydroquinone THQ, right
One or more of hydroxyanisol HQMME, p methoxy phenol MEHQ.
Preferably, the raw material forms by mass percentage, including mother liquor 18-28%, alicyclic organic 48-58%, auxiliary agent 0.1
~2%, surplus is deionized water.
The mix monomer dispersing agent by mass percentage, including following components:
Further, the dispersing agent is polyvinyl alcohol.
Further, the pH adjusting agent is ammonium hydrogen carbonate or ammonium hydroxide.
Further, the molecular weight regulator is beta -mercaptoethanol.
The mix monomer initiator by mass percentage, including following components:
Emulsifier 0.1-0.3%；
Wetting agent 0.1-0.3%；
Initiator 15-20%；
Surplus is deionized water, and the sum of gross mass percentage is 100%.
Further, the initiator is dicetyl peroxydicarbonate ethylhexyl EHP or di-isopropyl peroxydicarbonate
IPP。
Further, the emulsifier is non-ionic fatty acid polyglycol ethylene oxide ether.
Further, the wetting agent is anionic fluorochemical surfactant or siliceous anionic surfactant.
Further, the terminator is diethyl hydroxylamine DEHA.
Further, the neutralizer is sodium hydroxide.
Further, the defoaming agent is silanes, preferably organic silicon defoamer.
The present invention also provides a kind of preparation methods for being copolymerized REPVDC alloy solid resin, comprising:
(1) according to the ratio, vinylidene chloride is first added in a kettle, adds acrylated phosphate, is added after stirring dilute
Soil/metallic compound function monomer, Isooctyl acrylate monomer and acrylonitrile is eventually adding the stirring of mix monomer dispersing agent, is divided
Throwaway body；
(2) according to the ratio, first reaction kettle is vacuumized, inflated with nitrogen, heated deionized water is then first added, is then added
Dispersed monomer and mix monomer initiator are added terminator and terminate reaction, be eventually adding neutralizer and defoaming agent after being stirred to react
Cooling discharge is to get copolymerization REPVDC alloy solid resin.
Preparation method is specific as follows:
1. the pre-dispersed technique of monomer:
(1) vinylidene chloride is first poured into monomer reaction kettle (No. 1 kettle) by formula metering, adds propylene acid phosphoric acid
Ester, revolving speed are 200-300 revs/min, spare after sealing is placed 12-24 hours after stirring 20-30 minutes.
(2) it by after the monomer filtering in No. 1 kettle, squeezes into monomer mixing kettle (No. 2 kettles), then press formula rate for function list
Body, Isooctyl acrylate monomer, acrylonitrile are driven into No. 2 kettles, 200-300 revs/min of revolving speed be stirred continuously it is spare.
(3) mix monomer dispersing agent is formulated into Scattered Kettle (No. 3 kettles) by formula rate, revolving speed is 400-500 revs/min
Clock is stirred continuously, and after stirring 20-30 minutes, then by the mix monomer in No. 2 kettles, is calculated, has been beaten by Mean Speed within 90 minutes,
It is driven into No. 3 kettles to get dispersed monomer.
2. initiator emulsifying process:
According to formula rate, water, emulsifier, wetting agent are first added in initiator kettle (No. 4 kettles), revolving speed 400-
500 revs/min, be stirred continuously, then initiator be added drop-wise in No. 4 kettles, calculated according to Mean Speed, drip off within 90 minutes to get
Mix monomer initiator.
3. hot deionized water:
Deionized water is added in hot water kettle (No. 5 kettles), and is stirred continuously, revolving speed is 300-400 revs/min, if
± 0.2 DEG C of normal temperature (50-55 DEG C) for determining polymerization parameter is heated and is kept the temperature spare.
4. terminator:
It prepares in reaction terminating agent kettle (No. 6 kettles) in the ratio of 50% terminator and 50% deionized water, and constantly stirs
It mixes, revolving speed is 300-400 revs/min.
5. neutralizer:
In the ratio of 35% neutralizer and 65% deionized water, material is formulated into and is neutralized in kettle, and be stirred continuously, turned
Speed is 300-400 revs/min.
6. polymeric kettle (No. 7 kettles): three floor stirring slurry
(1) Ion Cleaning polymeric kettle is spent.
(2) after kettle inner wall surface is dry, anti-blocking agent is coated；Tu Yici anti-blocking agent, can be 3-5 times with repeated polymerization.
(3) kettle inner wall is heated to 65 DEG C, heat preservation after forty minutes, cools down spare.
7. material recycle kettle (No. 8 kettles)
Operating procedure: suspension method batch polymerization processes
(1) it after sealing No. 7 kettles, vacuumizes, wash kettle inflated with nitrogen three times, be evacuated down to-0.080-- 0.100Mpa again.
(2) it is squeezed into hot deionized water 25-40% (No. 7 kettle total measurement (volume)s) to No. 7 kettles, setting reaction normal temperature 50-55 ±
0.2 DEG C, start to stir, rate is 500-800/ minutes, heat preservation.
(3) when temperature is raised to certain value, emulsified monomer 35-55% (No. 7 kettle total measurement (volume)s) is squeezed into No. 7 kettles
(4) when temperature is raised to certain value, starting that emulsification initiator is added dropwise, dripping quantity is 6-9% (No. 7 kettle total measurement (volume)s),
It calculates 4-6 hours and drips off by average drop rate.
(5) when pressure reduction is to≤0.050Mpa, terminator 1-2% is added in conversion ratio >=85% of REPVDC resin
(No. 7 kettle total measurement (volume)s) opens No. 7 bottoms after five minutes and connect discharge valve with No. 8 kettles, while No. 8 kettles start to vacuumize, and make object
Material enters No. 8 kettles and starts to be stirred continuously after material pours into thoroughly, and revolving speed is 500-800 revs/min；No. 7 kettle valves are closed at this time
Door, then hot deionized water and emulsified monomer are squeezed into again, repeat above-mentioned circulation.
(6) No. 8 kettles are warming up to 50-70 DEG C, open bottom and take off dilute nitrogen valve and kettle top portion vacuum-pumping valve, starts to take off
It is dilute, unreacted monomer is recycled by condenser and is stored, it is next with new monomer in the ratio reuse of 1:10.
(7) take off it is 1-3 hours dilute after, neutralizer 0.1-0.2% are added dropwise to No. 8 kettles, stop being added dropwise when pH=6-7；It drips again
Add defoaming agent 0.1-0.2% (material gross mass), after stirring 3-5 minutes are still, cooling discharge.
(8) by material by centrifuge in after leather hard, then use deionized water, one of rinsing material passes through centrifuge
Dehydration, drying machine are dry, are exactly REPVDC alloy solid resin.
The present invention also provides a kind of application for being copolymerized REPVDC alloy solid resin, the alloy solid resin is applied to
Medicine, cosmetics, the Packaging Bottle of field of food, packing box, packaging bag, to avoid use or the food, fruits and vegetables of preservative
Or the preservative film of birds, beasts and eggs, the fresh-keeping function being able to achieve under normal temperature condition.
The alloy solid resin of rare earth/metallic compound and vinylidene chloride of the present invention, the alloy solid resin property are excellent
It is specific as follows in the performance of PVF polyvinylidenechloride:
(1) by the thermal stability factor of PVDC by 100-110 DEG C, 150 DEG C are increased to greater than, 140 DEG C of the fusing point greater than PVDC；
Solve the problems, such as that existing pure PVDC resin is unable to blown film, injection molding.
(2) crystalline texture that PVDC side chain can be distorted after rare earth, metal ion is added, is changed to the side chain of ordered arrangement
Crystalline texture, so that the intensity, toughness and barrier property of PVDC be greatly improved.
(3) preservative film, food flexible packing, fermented liquid food packaging bottle, the medicine bottle, cosmetics of pure PVDC resin are realized
The industrialization of bottle etc., reduces or prevents the use of food preservative.
Since rare earth element is abbreviated as " RE " in English, " RE " has the meaning traced back, remanufactured again, institute again in English
Rare earth/metal alloy PVDC of this copolymerization is named as REPVDC with the difference in order to distinguish existing PVDC material.
Beneficial effect
The present invention is copolymerized by the way that function monomer and vinylidene chloride is added, thus it is possible to vary the crystallization knot of PVDC side chain distortion
Structure, becomes the crystallizable side chain structure of ordered arrangement, so that the intensity, toughness and barrier property of former PVDC, green wood be significantly increased
1-3 times of mechanical property raising, heat resistance improve 20-60% and have been assigned Memorability material on the basis of the original；Prepare work
Skill is simple, at low cost, has a good application prospect.
Specific embodiment
Present invention will be further explained below with reference to specific examples.It should be understood that these embodiments are merely to illustrate the present invention
Rather than it limits the scope of the invention.In addition, it should also be understood that, after reading the content taught by the present invention, those skilled in the art
Member can make various changes or modifications the present invention, and such equivalent forms equally fall within the application the appended claims and limited
Range.
The formula of function monomer in embodiment is as follows:
Mother liquor formula is as follows:
| Title | Deionized water | Citric acid | Lanthanum carbonate | Diethylamine |
| Mass percent | 61.20% | 21.70% | 6.30% | 10.80% |
Function monomer formula is as follows:
| Title | Deionized water | Mother liquor | P-methyl benzenesulfonic acid | Hydroquinone | Ethyl acrylate |
| Mass percent | 25.20% | 24.60% | 0.20% | 0.68% | 49.32% |
This formula is only for example, function monomer required for can preparing according to actual demand in practical operation.
Embodiment 1
The formula for present embodiments providing a kind of REPVDC alloy solid resin is as follows:
Mix monomer:
| Title | Function monomer | Isooctyl acrylate monomer | Acrylonitrile | Vinylidene chloride | Acrylated phosphate |
| Percentage (%) | 6.60 | 4.20 | 1.40 | 73.23 | 1.80 |
Mix monomer dispersing agent:
Mix monomer initiator:
Terminator:
| Title | Deionized water | Diethyl hydroxylamine DEHA |
| Percentage (%) | 50 | 50 |
Neutralizer:
| Title | Deionized water | Sodium hydroxide |
| Percentage (%) | 65 | 35 |
Defoaming agent:
| Title | Deionized water | Silane |
| Percentage (%) | 65 | 35 |
Surplus is deionized water.
Preparation process is as follows:
(1) it after sealing No. 7 kettles, vacuumizes, wash kettle inflated with nitrogen three times, be evacuated down to-0.080-- 0.100Mpa again.
(2) it is squeezed into hot deionized water 30% (No. 7 kettle total measurement (volume)s) to No. 7 kettles, sets 60 ± 0.2 DEG C of reaction normal temperature,
Start to stir, rate is 500-800/ minutes, heat preservation.
(3) when temperature is raised to 50 DEG C, emulsified monomer 50% (No. 7 kettle total measurement (volume)s) is squeezed into No. 7 kettles
(4) when temperature is raised to 55 DEG C, start that emulsification initiator is added dropwise, dripping quantity is 7% (No. 7 kettle total measurement (volume)), by flat
Equal drop rate, which calculates 4-6 hours, to be dripped off.
(5) when pressure reduction is to≤0.050Mpa, terminator 2% (7 is added in conversion ratio >=85% of REPVDC resin
Number kettle total measurement (volume)), No. 7 bottoms are opened after five minutes and connect discharge valve with No. 8 kettles, while No. 8 kettles start to vacuumize, and make material
Into No. 8 kettles, after material pours into thoroughly, start to be stirred continuously, revolving speed is 500-800 revs/min；No. 7 kettle valves are closed at this time,
Squeeze into hot deionized water 30%, emulsified monomer 50% again again.Repeat above-mentioned circulation.
(6) No. 8 kettles are warming up to 60 DEG C, open bottom and take off dilute nitrogen valve and kettle top portion vacuum-pumping valve, start to take off it is dilute,
Unreacted monomer is recycled by condenser and is stored, it is next with new monomer in the ratio reuse of 1:10.
(7) take off it is 1-3 hours dilute after, 0.13% neutralizers are added dropwise to No. 8 kettles, stop being added dropwise when pH=6-7；It is added dropwise and disappears again
Infusion 0.1% (material gross mass), after stirring 3-5 minutes are still, cooling discharge.
(8) by material by centrifuge in after leather hard, then use deionized water, one of rinsing material passes through centrifuge
Dehydration, drying machine are dry to get REPVDC alloy solid resin.
The good barrier property of the present embodiment REPVDC alloy solid resin, intensity is general, and suitable injection molding is slim, stress is lesser
Packing container；The resin molecular weight that this preparation process obtains is small.
Embodiment 2
The formula for present embodiments providing a kind of REPVDC alloy solid resin is as follows:
Mix monomer:
| Title | Function monomer | Isooctyl acrylate monomer | Acrylonitrile | Vinylidene chloride | Acrylated phosphate |
| Percentage (%) | 8.20 | 4.80 | 2.0 | 65.74 | 1.80 |
Mix monomer dispersing agent:
Mix monomer initiator:
Terminator:
| Title | Deionized water | Diethyl hydroxylamine DEHA |
| Percentage (%) | 50 | 50 |
Neutralizer:
| Title | Deionized water | Sodium hydroxide |
| Percentage (%) | 65 | 35 |
Defoaming agent:
| Title | Deionized water | Silane |
| Percentage (%) | 65 | 35 |
Surplus is deionized water.
Preparation process is as follows:
(1) it after sealing No. 7 kettles, vacuumizes, wash kettle inflated with nitrogen three times, be evacuated down to-0.080-- 0.100Mpa again.
(2) it is squeezed into hot deionized water 30% (No. 7 kettle total measurement (volume)s) to No. 7 kettles, sets 55 ± 0.2 DEG C of reaction normal temperature,
Start to stir, rate is 500-800/ minutes, heat preservation.
(3) when temperature is raised to 45 DEG C, emulsified monomer 50% (No. 7 kettle total measurement (volume)s) is squeezed into No. 7 kettles
(4) when temperature is raised to 50 DEG C, start that emulsification initiator is added dropwise, dripping quantity is 7% (No. 7 kettle total measurement (volume)), by flat
Equal drop rate, which calculates 4-6 hours, to be dripped off.
(5) when pressure reduction is to≤0.050Mpa, terminator 2% (7 is added in conversion ratio >=85% of REPVDC resin
Number kettle total measurement (volume)), No. 7 bottoms are opened after five minutes and connect discharge valve with No. 8 kettles, while No. 8 kettles start to vacuumize, and make material
Into No. 8 kettles, after material pours into thoroughly, start to be stirred continuously, revolving speed is 500-800 revs/min；No. 7 kettle valves are closed at this time,
Squeeze into hot deionized water 30%, emulsified monomer 50% again again.Repeat above-mentioned circulation.
(6) No. 8 kettles are warming up to 60 DEG C, open bottom and take off dilute nitrogen valve and kettle top portion vacuum-pumping valve, start to take off it is dilute,
Unreacted monomer is recycled by condenser and is stored, it is next with new monomer in the ratio reuse of 1:10.
(7) take off it is 1-3 hours dilute after, 0.13% neutralizers are added dropwise to No. 8 kettles, stop being added dropwise when pH=6-7；It is added dropwise and disappears again
Infusion 0.1% (material gross mass), after stirring 3-5 minutes are still, cooling discharge.
(8) by material by centrifuge in after leather hard, then use deionized water, one of rinsing material passes through centrifuge
Dehydration, drying machine are dry to get REPVDC alloy solid resin.
The barrier property of the present embodiment REPVDC alloy solid resin is preferable, and intensity is good, is suitble to injection molding thicker, stress biggish
Packing container；The resin molecular weight that this preparation process obtains is medium.
Embodiment 3
The formula for present embodiments providing a kind of REPVDC alloy solid resin is as follows:
Mix monomer:
| Title | Function monomer | Isooctyl acrylate monomer | Acrylonitrile | Vinylidene chloride | Acrylated phosphate |
| Percentage (%) | 10.00 | 5.00 | 2.00 | 63.51 | 1.41 |
Mix monomer dispersing agent:
Mix monomer initiator:
Terminator:
| Title | Deionized water | Diethyl hydroxylamine DEHA |
| Percentage (%) | 50 | 50 |
Neutralizer:
| Title | Deionized water | Sodium hydroxide |
| Percentage (%) | 65 | 35 |
Defoaming agent:
| Title | Deionized water | Silane |
| Percentage (%) | 65 | 35 |
Surplus is deionized water.
Preparation process is as follows:
(1) it after sealing No. 7 kettles, vacuumizes, wash kettle inflated with nitrogen three times, be evacuated down to-0.080-- 0.100Mpa again.
(2) it is squeezed into hot deionized water 30% (No. 7 kettle total measurement (volume)s) to No. 7 kettles, sets 50 ± 0.2 DEG C of reaction normal temperature,
Start to stir, rate is 500-800/ minutes, heat preservation.
(3) when temperature is raised to 40 DEG C, emulsified monomer 50% (No. 7 kettle total measurement (volume)s) is squeezed into No. 7 kettles
(4) when temperature is raised to 45 DEG C, start that emulsification initiator is added dropwise, dripping quantity is 7% (No. 7 kettle total measurement (volume)), by flat
Equal drop rate, which calculates 4-6 hours, to be dripped off.
(5) when pressure reduction is to≤0.050Mpa, terminator 2% (7 is added in conversion ratio >=85% of REPVDC resin
Number kettle total measurement (volume)), No. 7 bottoms are opened after five minutes and connect discharge valve with No. 8 kettles, while No. 8 kettles start to vacuumize, and make material
Into No. 8 kettles, after material pours into thoroughly, start to be stirred continuously, revolving speed is 500-800 revs/min；No. 7 kettle valves are closed at this time,
Squeeze into hot deionized water 30%, emulsified monomer 50% again again.Repeat above-mentioned circulation.
(6) No. 8 kettles are warming up to 60 DEG C, open bottom and take off dilute nitrogen valve and kettle top portion vacuum-pumping valve, start to take off it is dilute,
Unreacted monomer is recycled by condenser and is stored, it is next with new monomer in the ratio reuse of 1:10.
(7) take off it is 1-3 hours dilute after, 1.5% neutralizers are added dropwise to No. 8 kettles, stop being added dropwise when pH=6-7；It is added dropwise and disappears again
Infusion 0.1% (material gross mass), after stirring 3-5 minutes are still, cooling discharge.
(8) by material by centrifuge in after leather hard, then use deionized water, one of rinsing material passes through centrifuge
Dehydration, drying machine are dry to get REPVDC alloy solid resin.
Preferable, the good toughness of the present embodiment REPVDC alloy solid resin is suitble to blown film；The resin that this preparation process obtains
Molecular weight is big.
Test result is as follows for the alloy solid resin property of Examples 1 to 3:
Claims (14)
1. a kind of copolymerization REPVDC alloy solid resin, it is characterised in that: by mass percentage, including following components:
Wherein, mix monomer and mix monomer dispersing agent include following components:
Surplus is mix monomer dispersing agent, and the sum of gross mass percentage is 100%；
The rare earth/metallic compound function monomer raw material composition includes mother liquor, organic ester, auxiliary agent and deionized water；Wherein,
Mother liquor is by mass percentage, comprising: rare earth compound or metallic compound 6-9%, organic acid 15%-25%, organic amine 10-
20%, surplus is deionized water；The organic ester is acrylate；The auxiliary agent includes catalyst and polymerization inhibitor；
The organic acid is one or more of citric acid, maleic acid, ethylenediamine tetra-acetic acid, succinic acid, adipic acid；
The organic amine is one or more of diethylamine, ethylenediamine, allyl amine, diethylenetriamines.
2. a kind of copolymerization REPVDC alloy solid resin according to claim 1, it is characterised in that: the rare earth compound
Or metallic compound is one or more of rare earth or oxide, hydroxide or the carbonate of metal.
3. a kind of copolymerization REPVDC alloy solid resin according to claim 1 or 2, it is characterised in that: the rare earth is
Lanthanum, cerium, europium, terbium or neodymium element；The metal is zinc, calcium, magnesium, manganese, copper, nickel, aluminium, niobium, molybdenum, ruthenium, tungsten, rhenium or hafnium element.
4. a kind of copolymerization REPVDC alloy solid resin according to claim 1, it is characterised in that: the acrylate is
One or more of ethyl acrylate, butyl acrylate, Isooctyl acrylate monomer.
5. a kind of copolymerization REPVDC alloy solid resin according to claim 1, it is characterised in that: the catalyst is pair
Toluenesulfonic acid；The polymerization inhibitor is hydroquinone, methylnaphthohydroquinone THQ, p-hydroxyanisole HQMME, p methoxy phenol
One or more of MEHQ.
6. a kind of copolymerization REPVDC alloy solid resin according to claim 1, it is characterised in that: the rare earth/metal
The raw material of compound function monomer forms by mass percentage, including mother liquor 18-28%, organic ester 48-58%, auxiliary agent 0.1~
2%, surplus is deionized water.
7. a kind of copolymerization REPVDC alloy solid resin according to claim 1, it is characterised in that: the mix monomer point
Powder by mass percentage, including following components:
8. a kind of copolymerization REPVDC alloy solid resin according to claim 7, it is characterised in that: the dispersing agent is poly-
Vinyl alcohol；The pH adjusting agent is ammonium hydrogen carbonate or ammonium hydroxide；The molecular weight regulator is beta -mercaptoethanol.
9. a kind of copolymerization REPVDC alloy solid resin according to claim 1, it is characterised in that: the mix monomer draws
Send out agent by mass percentage, including following components:
Emulsifier 0.1-0.3%；
Wetting agent 0.1-0.3%；
Initiator 15-20%；
Surplus is deionized water, and the sum of gross mass percentage is 100%.
10. a kind of copolymerization REPVDC alloy solid resin according to claim 9, it is characterised in that: the initiator is
Dicetyl peroxydicarbonate ethylhexyl EHP or di-isopropyl peroxydicarbonate IPP.
11. a kind of copolymerization REPVDC alloy solid resin according to claim 7 or 9, it is characterised in that: the emulsifier
For non-ionic fatty acid polyglycol ethylene oxide ether；The wetting agent is anionic fluorochemical surfactant or siliceous anionic surface
Activating agent.
12. a kind of copolymerization REPVDC alloy solid resin according to claim 1, it is characterised in that: the terminator is
Diethyl hydroxylamine DEHA；The neutralizer is sodium hydroxide；The defoaming agent is silanes.
13. a kind of preparation method of copolymerization REPVDC alloy solid resin as described in claim 1, comprising:
(1) according to the ratio, vinylidene chloride is first added in a kettle, adds acrylated phosphate, rare earth/gold is added after stirring
Belong to compound function monomer, Isooctyl acrylate monomer and acrylonitrile, is eventually adding the stirring of mix monomer dispersing agent, it is single to obtain dispersion
Body；
(2) according to the ratio, first reaction kettle is vacuumized, inflated with nitrogen, heated deionized water is then first added, dispersion is then added
Monomer and mix monomer initiator are added terminator and terminate reaction, be eventually adding neutralizer and defoaming agent cooling after being stirred to react
Discharging is to get copolymerization REPVDC alloy solid resin.
14. a kind of application of copolymerization REPVDC alloy solid resin as described in claim 1, it is characterised in that: the alloy
Hard resin is applied to medicine, cosmetics, the Packaging Bottle of field of food, packing box, packaging bag or food, fruits and vegetables or birds, beasts and eggs
Preservative film.
Priority Applications (5)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710936339.6A CN107602752B (en) | 2017-10-10 | 2017-10-10 | A kind of copolymerization REPVDC alloy solid resin and its preparation method and application |
| JP2020539123A JP2020536163A (en) | 2017-10-10 | 2018-03-23 | Rare earth / metal compound functional monomer and its manufacturing method, application |
| EP18867107.7A EP3677601B1 (en) | 2017-10-10 | 2018-03-23 | Rare earth/metal compound functional monomer and preparation method therefor and application thereof |
| PCT/CN2018/080192 WO2019071920A1 (en) | 2017-10-10 | 2018-03-23 | Rare earth/metal compound functional monomer and preparation method therefor and application thereof |
| US16/845,039 US11472941B2 (en) | 2017-10-10 | 2020-04-09 | Functional monomer comprising rare earth/metal compound, preparation method thereof, and method of using the same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710936339.6A CN107602752B (en) | 2017-10-10 | 2017-10-10 | A kind of copolymerization REPVDC alloy solid resin and its preparation method and application |
Publications (2)
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| CN101649015A (en) * | 2009-08-27 | 2010-02-17 | 浙江野风塑胶有限公司 | Polyvinylidene chloride (PVDC) copolymer latex for medicine packaging as well as preparation method and application thereof |
| CN104028312A (en) * | 2013-12-20 | 2014-09-10 | 江苏佳华新材料科技有限公司 | A preparing method of a rare earth catalytic cracking double-metal deactivator |
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| CN101649015A (en) * | 2009-08-27 | 2010-02-17 | 浙江野风塑胶有限公司 | Polyvinylidene chloride (PVDC) copolymer latex for medicine packaging as well as preparation method and application thereof |
| CN104028312A (en) * | 2013-12-20 | 2014-09-10 | 江苏佳华新材料科技有限公司 | A preparing method of a rare earth catalytic cracking double-metal deactivator |
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Effective date of registration: 20210709 Address after: No. 1919, panchuan Road, Baoshan District, Shanghai, 200949 Patentee after: ANTAINENG (SHANGHAI) HIGH-MOLECULAR MATERIAL Co.,Ltd. Address before: 1919 panchuan Road, Baoshan District, Shanghai, 201900 Patentee before: SHANGHAI LUFENG PROMOTER Co.,Ltd. |