CN108410280A - A kind of preparation method of coating PVDC water-based emulsions - Google Patents
A kind of preparation method of coating PVDC water-based emulsions Download PDFInfo
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- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D127/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Coating compositions based on derivatives of such polymers
- C09D127/02—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Coating compositions based on derivatives of such polymers not modified by chemical after-treatment
- C09D127/04—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Coating compositions based on derivatives of such polymers not modified by chemical after-treatment containing chlorine atoms
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- C08F265/00—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00
- C08F265/04—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00 on to polymers of esters
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- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
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Abstract
The invention discloses a kind of preparation methods being coated with aqueous PVDC lotions, including：(1) it is spare to prepare reaction raw materials；(2) initiator solution is configured；(3) premixed liquid is configured；(4) seeded emulsion polymerization；(5) PVDC emulsion polymerizations；(6) desorption of lotion.The obtained PVDC water-based emulsions of method of the present invention, which are coated in the stiff sheet such as PVC, PET, nylon, PCT, is made composite hard sheet, has excellent in cushion effect, is not likely to produce crackle, good barrier property, harmful substance will not be dissolved out, can be in direct contact with drug, the advantages that high yellowing-resistant ability of thermal stability is strong.
Description
Technical field
The invention belongs to polymeric material fields, and in particular to a kind of preparation method of coating PVDC water-based emulsions.
Background technology
The stiff sheet such as PVC, PET, nylon, PCT have thickness uniformly, good seal performance, heat seal it is fast, it is easily molded, cheap,
Uvioresistant and radioresistance, have been widely used for the exterior and interior packing of the drugs such as tablet, capsule, injection, oral solution, but PVC,
The defects of stiff sheet such as PET, nylon, PCT lead to drug oxidizable failure there are barrier property difference.PVDC is as a kind of plastics package
Material have it is portable, harmful substance will not be dissolved out can be in direct contact with food and medicine, is high barrier, cheap and facilitate popularization
The advantages that, have been widely used for drug and food packaging applications.Food and drug packing field all widely use at present
PVDC lotions, by PVDC emulsion coatings on the materials such as PVC, PET, nylon, PCT, hence it is evident that improve the barrier property of these materials
And so that these materials is become environmentally protective, can directly with food and drug contact.
Such as China Patent Publication No. CN102876149A, publication date on January 16th, 2013, denomination of invention：A kind of coating use
Tack polyvinylidene emulsions and preparation method thereof.Preparation method is：(1) vinylidene chloride 45-60% is taken respectively, third
Five kinds of monomers of olefin(e) acid 1-3%, butyl acrylate 2-5%, ethyl methacrylate 0.5-5%, acrylonitrile 0.5-3%, chain cause
Agent 0.3-0.5%, emulsifier 0.1-1%, antifoaming agent 0.1-0.5% and softened water 35.5-37%.Preparation method is：(1) respectively
Take vinylidene chloride 45-60%, acrylic acid 1-3%, butyl acrylate 2-5%, ethyl methacrylate 0.5-5%, acrylonitrile
Five kinds of monomers of 0.5-3%, chain initiator 0.3-0.5%, emulsifier 0.1-1%, antifoaming agent 0.1-0.5% and softened water 35.5-
37%, it is positioned in separate Raw material pail, successively adds the above monomer of the one third for accounting for each total amount, auxiliary agent and softened water
Enter and mixed into reaction kettle, open stirring, mixing speed is 120-200 revs/min, is slowly warmed to 55-70 DEG C, carries out pre-polymerization
It closes, then successively continuously equably adds remaining monomer, chain initiator, emulsifier, antifoaming agent and softened water in 1 hour
It is complete, continue stirring 1-2 hours, the modification PVDC copolymer emulsions that solid content is 63-64.5% are obtained after cooling and standings；(2) it takes
Modified PVDC copolymer emulsions obtained are stated, is put into a rustless steel container, opens stirring, mixing speed is set as 120 revs/min
Clock, then the amino silicane coupling agent of 0.5-5% is taken, slipping agent 3-5%, antitack agent 3-5%, softened water 13.5-20% are added
In PVDC copolymer emulsions, stirring timing starts, and sets mixing time as 1 hour, and last filtering and discharging obtains coating and uses
Tack PVDC lotions.Shortcoming is complex process, cumbersome, and product thermal stability, yellowing-resistant energy force difference are not suitable for work
Industryization mass produces.
For another example China Patent Publication No. CN107573452A, publication date on January 12nd, 2018, denomination of invention：A kind of copolymerization
REPVDC alloy emulsions and its preparation method and application, including seed emulsion.Copolymerization REPVDC alloy emulsions are applied to steel knot
The aqueous heavy antisepsis of structure, food packaging or birds, beasts and eggs, preserving fruit and vegetable utilizing.Shortcoming is complex process, cumbersome, and a large amount of rare earths help
The addition of agent increases cost, affects product thermal stability height and yellowing-resistant ability.
For another example China Patent Publication No. CN105153345A, publication date on December 16th, 2015, denomination of invention：It is a kind of aqueous
The preparation method of environment protecting tableware PVDC lotions.A kind of disclosure of the invention preparation method of environment protecting tableware with PVDC lotions, is adopted
With the mode of substep core-shell emulsion polymerization, the intrinsic strength of polymer itself is improved, while cross-linking monomer is added, improves breast
The crosslinking degree of liquid forms uniform reticular structure after being allowed to film forming.Modified function acrylic emulsion, further improves breast
Film forming, alcohol resistance energy, oil resistivity, high temperature resistant deformation nature and follow-up tableware of the liquid on fibre tableware after lamination are being stored
Anti-yellowing property in the process.Shortcoming is that preparation method step is more, difficult to control, is not suitable for industrialization large-scale production.
Invention content
In order to overcome the deficiencies of existing technologies, present invention offer is a kind of simple for process, and reaction is mild, is suitable for industrialized painting
The preparation method of cloth PVDC water-based emulsions, the PVDC water-based emulsions that method of the invention is prepared are coated on PVC, PET, Buddhist nun
Composite hard sheet is made in the stiff sheet such as dragon, PCT, have it is excellent in cushion effect, be not likely to produce crackle, good barrier property will not dissolve out
The advantages that evil substance, can be in direct contact with drug, and the high yellowing-resistant ability of thermal stability is strong.
In order to solve the above-mentioned technical problem, the technical solution adopted by the present invention is：A kind of aqueous PVDC lotions of coating
Preparation method includes the following steps：
(1) it is spare to prepare reaction raw materials
In parts by weight, reaction raw materials group becomes：1~5 part of seed monomer, 45~55 parts of vinylidene chloride (VDC) monomer, altogether
4~10 parts of polycondensation monomer, 0.01~0.05 part of initiator, 0.1~0.5 part of seed emulsifier, 0.5~3 part of emulsifier, other auxiliary agents
0.01~0.05 part, 0.001~0.01 part of modified additive, 35~40 parts of deionized water；
(2) initiator solution is configured：The initiator for accounting for seed monomer quality 0.2~0.5% is configured with deionized water
At a concentration of 0.1~1% seeded emulsion polymerization initiator solution, remaining initiator is configured to concentration with deionized water
It is spare for 0.2~0.8% emulsion polymerization initiator solution；
(3) premixed liquid is configured：By vinylidene chloride monomer, comonomer, emulsifier, other auxiliary agents and 10~35% go from
Sub- water disperses 5~30min under 2~10 DEG C, 100~200rpm speeds of agitator, obtains premixed liquid, spare；
(4) seeded emulsion polymerization：Seed monomer, seed emulsifier and remaining deionized water are put into polymeric kettle,
Under 100~200rpm speeds of agitator after pre-dispersed 5~30 minutes, step (2) is added and configures obtained seeded emulsion polymerization with drawing
Hair agent aqueous solution is reacted, and reaction temperature is 70~85 DEG C, and reaction was completed after 1~2h of reaction, obtains seed emulsion；
(5) PVDC emulsion polymerizations：Under 90~120rpm speeds of agitator, it is added in the seed emulsion obtained to step (4)
The emulsion polymerization initiator solution and step (3) that step (2) configuration obtains configure obtained premixed liquid, 50~65
After reacting 6~12h at DEG C, 70~85 DEG C of 0.5~2.5h of heat preservation are warming up to, PVDC lotions are obtained；
(6) desorption of lotion：Modified additive is added in the PVDC lotions obtained to step (5), -0.04~-
0.02Mpa blasts nitrogen into PVDC lotions under 60~75 DEG C and 15~30rpm speeds of agitator and carries out desorption, and the desorption time is 1
~4h, desorption complete postcooling, filtering to get to product.
As the preferred embodiment of the present invention, can before the PVDC emulsion polymerizations with nitrogen to polymeric kettle into line replacement
And vacuumize, the pressure vacuumized is -0.08~-0.06Mpa.
As the preferred embodiment of the present invention, the comonomer is preferably methyl acrylate, ethyl acrylate, propylene
Acid butyl ester, methyl methacrylate, ethyl methacrylate, hydroxy-ethyl acrylate, vinylacetate, acrylic acid-2-ethyl oneself
The mixture of one or more of ester, acrylonitrile, methacrylonitrile, acrylic acid, methacrylic acid, itaconic acid, the copolymerization
Monomer is more preferably methyl acrylate, ethyl acrylate, butyl acrylate, methyl methacrylate, ethyl methacrylate, third
The mixture of one or more of olefin(e) acid hydroxyl ethyl ester, vinylacetate, acrylic acid-2-ethyl caproite, acrylic acid, itaconic acid.
Persulfuric acid salt initiator can be selected in the present invention, and the initiator is preferably ammonium persulfate, sodium peroxydisulfate, persulfuric acid
The mixture of one or more of potassium.
Anion emulsifier can be selected in the seed emulsifier of the present invention, and the seed emulsifier is preferably dodecyl sulphate
Sodium, pentadecyl sodium sulphate, sodium stearyl sulfate, neopelex, Pentadecylbenzene sulfonic acid sodium, octadecyl sulphur
One or more of sour sodium, alcohol ether carboxylate, dodecyl carboxylic acid potassium, pentadecyl carboxylic acid sodium, octadecyl carboxylic acid potassium
Mixture, the seed emulsifier are more preferably lauryl sodium sulfate, pentadecyl sodium sulphate, sodium stearyl sulfate, ten
The mixing of one or more of five sodium alkyl benzene sulfonates, alcohol ether carboxylate, pentadecyl carboxylic acid sodium, octadecyl carboxylic acid potassium
Object.
Anion emulsifier can be selected in the emulsifier of the present invention, and the emulsifier is preferably lauryl sodium sulfate, 15
Sodium alkyl sulfate, sodium stearyl sulfate, neopelex, Pentadecylbenzene sulfonic acid sodium, sodium stearyl sulfonate, alcohol
One kind in ether carboxylate, dodecyl carboxylic acid potassium, pentadecyl carboxylic acid sodium, pentadecyl carboxylic acid potassium, octadecyl carboxylic acid sodium
Or several mixture.The emulsifier is more preferably lauryl sodium sulfate, sodium stearyl sulfate, Pentadecylbenzene sulfonic acid
One or more of sodium, alcohol ether carboxylate, dodecyl carboxylic acid potassium, pentadecyl carboxylic acid potassium, octadecyl carboxylic acid sodium are mixed
Close object.
As the preferred embodiment of the present invention, other described auxiliary agents be preferably sodium bicarbonate, saleratus, ammonium acetate,
One or several kinds of mixtures in glacial acetic acid.
As the preferred embodiment of the present invention, the modified additive is preferably dimethicone, polysiloxanes, benzyl carbinol
The mixture of one or more of oleate, tributyl phosphate, Laurate alcohol ester phenylacetate, polyvinylether.
The dosage of seed emulsifier and emulsifier has shadow larger impact, dosage too big the size of the grain size of latex particle
Then latex particle grain size is smaller, good emulsion stability, on the contrary then the grain size of latex particle is larger, and stability of emulsion is poor, therefore this
The parts by weight of seed emulsifier are 0.1~0.5 part, preferably 0.3~0.4 part in invention；Emulsifier parts by weight be 0.5~
The grain size of 3.0 parts, preferably 1.2~2.5 parts, the latex particle of PVDC lotions obtained both ensured between 140-190nm
Emulsion intercalation method, and saved cost.
PVDC polymer is crystalline polymer, and after PVDC starts crystallization, hardness and barrier property all can be with
The increase of crystallinity and increase, but toughness and impact strength can be reduced with the increase of crystallinity, when being processed into finished product
Crackle is will produce, to lose obstructing capacity.The content of VDC is higher in PVDC polymer, its final crystallinity is also higher, barrier
Performance is also better, but impact strength can be lower.Therefore, the parts by weight of VDC monomers are 45~55 parts in the present invention, preferably
48-52 parts, it not only ensure that the barrier property of film made from lotion but also taken into account its impact strength.
The molecular weight of PVDC polymer has a great impact to the property of polymer, and the molecular weight of polymer is higher, PVDC
The intensity and mechanical property of polymer can improve, and impact strength can also improve.Reaction temperature to the molecular weight of polymer have compared with
The molecular weight of big influence, polymer is reduced with the increase of reaction temperature.Therefore, selective redox system is in the present invention
Initiation system reduces reaction temperature, has not only ensured the higher molecular weight of polymer, but also the reaction time will not be made long.
The thermal stability of pure PVDC polymer is poor, when heating or encountering alkali, active metal and lewis acid, very
It is easy dehydrochlorination and forms conjugated double bond.When there are a conjugated double bonds in system, formation is more on main chain soon
The method of unsaturated unit, generally use copolymerization blocks this fall out effect.It is general when unsaturated unit is more than 4, polymer
It is possible to change colour.Here selection VDC monomers are copolymerized with other monomers.Assuming that comonomer is uniformly nested in PVDC strands
In, VDC contents are higher, and the content of comonomer is lower, then VDC chain lengths are higher in corresponding PVDC strands, it is easier
The unsaturated unit that unit number is more than 4 is formed, thermal stability is poorer, and barrier property is not up to if the content of VDC monomers is too low
To requirement.Therefore, the parts by weight of VDC monomers are 45~55 parts in the present invention, and comonomer is 4~10 parts, both ensure that breast
The barrier property of film made from liquid has taken into account its thermal stability again.
The type and dosage of other auxiliary agents directly affect above-mentioned initiator free radical activity and vinylidene chloride monomer it is steady
It is qualitative.Other auxiliary agents in the present invention can use the one or more of sodium bicarbonate, saleratus, ammonium acetate, glacial acetic acid, excellent
Select sodium bicarbonate.Other auxiliary dosages too great Yi reduces initiator activity, and dosage is too small, reduces the stabilization of vinylidene chloride monomer
Property, therefore, the present invention in other auxiliary agents parts by weight be 0.01~0.05 part, preferably 0.03~0.04.
It by monomer, emulsifier or seed emulsifier and is gone using pre-emulsifying method when seeded emulsion polymerization and PVDC emulsion polymerizations
Ionized water elder generation pre-emulsification allows they are first pre-dispersed uniformly to add in polymeric kettle, this makes monomer once energy in entrance polymeric kettle
Reaction is participated at once, will not be accumulated, this so that reaction process is steady, will not concentrate heat release, and reaction is caused to be difficult to control.
Speed of agitator also has a significant effect to reaction, if speed of agitator is too fast, the high speed shear of agitating paddle can destroy latex
Particle leads to gel on agitating paddle, or even can be demulsified；If speed of agitator is too low, causes material to be difficult to be uniformly dispersed, cause list
The accumulation of body causes to concentrate heat release, makes runaway reaction.The emulsion polymerization stage selects 90~120rpm of speed of agitator in the present invention,
It is preferred that 100~110rpm.
The present invention influences the factor of polymerisation, optimization by optimizing polymeric reaction temperature, speed of agitator, feeding mode etc.
Polymerization, the PVDC water-based emulsions that method of the invention is prepared are coated in the stiff sheet such as PVC, PET, nylon, PCT and make
At composite hard sheet, the performances such as impact strength, barrier property, thermal stability and the yellowing-resistant of stiff sheet are improved.
Compared with prior art, advantages of the present invention is：
1, method of the invention is easy to operate, and polymerization process is mild and steady, without strongly exothermic phenomenon, is suitable for scale and gives birth to
Production；
2, properties of product are excellent, and between 140~190nm, solid content exists PVDC water-based emulsions grain size produced by the present invention
Between 59.8~61.1%, for viscosity between 23.2~25.7mPa.S, surface tension is particularly suitable between 38.5~46.6
Composite hard sheet is made in being coated in the stiff sheet such as PVC, PET, nylon, PCT, have it is excellent in cushion effect, be not likely to produce crackle, hinder
It is good every property, harmful substance will not be dissolved out, can be in direct contact with drug, the advantages that high yellowing-resistant ability of thermal stability is strong.
Specific implementation mode
More specific description is carried out to the present invention by the following examples, but the present invention is not limited to the embodiment described.
Embodiment 1
A kind of preparation method being coated with aqueous PVDC lotions, includes the following steps：
(1) it is spare to prepare reaction raw materials
Composition of raw materials is as follows：
(2) initiator solution is configured：The ammonium persulfate (APS) for weighing 0.005kg, over cure is made into 2kg deionized waters
Sour aqueous ammonium I, it is spare；It is water-soluble to be made into sodium pyrosulfite with 3kg deionized waters for the sodium pyrosulfite (SMBS) for weighing 0.02kg
Liquid, it is spare；0.017kg ammonium persulfates (APS) are weighed, ammonium persulfate aqueous solution II is made into 3kg deionized waters, it is spare；
(3) premixed liquid is configured：By the vinylidene chloride monomer of 49.51kg, the propylene of the methyl acrylate of 2.91kg, 2.91kg
The dodecyl of acid butyl ester, the itaconic acid of 2.33kg, the acrylic acid of 0.58kg, the sodium stearyl sulfate of 0.41kg, 0.41kg
Carboxylic acid potassium, the Pentadecylbenzene sulfonic acid sodium of 0.82kg, the sodium bicarbonate of 0.02kg, the ammonium acetate of 0.02kg and 7.2kg deionizations
Water input mixes liquid bath, disperses 30min under 5 DEG C, 170rpm speeds of agitator, obtains premixed liquid, spare；
(4) seeded emulsion polymerization：By the methyl methacrylate of 0.875kg, the butyl acrylate of 0.7kg, 0.07kg
The deionization of acrylic acid, the acrylonitrile of 0.105kg, 0.07kg lauryl sodium sulfate, the alcohol ether carboxylate of 0.07kg and 23kg
Water is put into polymeric kettle, under 100rpm speeds of agitator after pre-dispersed 30 minutes, the temperature of polymeric kettle is risen to 75 DEG C, step is added
Suddenly the ammonium persulfate aqueous solution I that (2) configuration obtains is reacted, and reaction was completed after reaction 1.5h, obtains seed emulsion；
(5) PVDC emulsion polymerizations：Polymeric kettle displacement is vacuumized afterwards twice with nitrogen, pressure is -0.08Mpa, is vacuumized
Polymeric kettle temperature is adjusted to 55 DEG C after the completion, step (2) is added and configures obtained metabisulfite solution, ammonium persulfate water
The premixed liquid that solution II and step (3) configuration obtain is reacted, and control speed of agitator is 110rpm, after reacting 12h, is risen
Temperature obtains PVDC lotions to 70 DEG C of heat preservation 2h；
(6) desorption of lotion：In the PVDC lotions obtained to step (5) be added 0.002kg dimethicone and
The polyvinylether of 0.002kg, it is entire de- by the outlet of nitrogen tube not in PVDC lotions liquid level hereinafter, blast nitrogen and vacuumize
Pressure control is in -0.02Mpa during suction, and at 65 DEG C, speed of agitator 20rpm, the desorption time is 4h for temperature control, and desorption is complete
It is filtered to get to product at postcooling.The performance parameter of lotion is shown in Table 1.
Embodiment 2
A kind of preparation method being coated with aqueous PVDC lotions, includes the following steps：
(1) it is spare to prepare reaction raw materials
Composition of raw materials is as follows：
(2) initiator solution is configured：The ammonium persulfate (APS) for weighing 0.017kg, was configured to 2kg deionized waters
Ammonium sulfate solution I, it is spare；The sodium pyrosulfite (SMBS) for weighing 0.01kg, sodium pyrosulfite is configured to 3kg deionized waters
Aqueous solution, it is spare；0.008kg ammonium persulfates (APS) are weighed, ammonium persulfate aqueous solution II is configured to 3kg deionized waters, it is standby
With；
(3) premixed liquid is configured：By the vinylidene chloride monomer of 49.2kg, the acrylic acid-2-ethyl caproite of 1.7kg, 2.5kg
The alcohol of methyl methacrylate, the itaconic acid of 2.5kg, the acrylic acid of 0.57kg, the lauryl sodium sulfate of 0.34kg, 0.34kg
Ether carboxylate, 0.34kg dodecyl carboxylic acid potassium, the sodium bicarbonate of 0.02kg, the glacial acetic acid of 0.005kg and 5.55kg go from
Sub- water input mixes liquid bath, disperses 25min under 2 DEG C, 100rpm speeds of agitator, obtains premixed liquid, spare；
(4) seeded emulsion polymerization：By the methyl acrylate of 1.36kg, the propylene of the butyl acrylate of 0.85kg, 0.17kg
Acid, the methyl methacrylate of 1.02kg, 0.1kg pentadecyls sodium sulphate, the alcohol ether carboxylate of 0.2kg, 0.1kg octadecyls
The deionized water of carboxylic acid potassium and 25kg are put into polymeric kettle, at speed of agitator 150rpm after pre-dispersed 15 minutes, by polymeric kettle
Temperature rise to 75 DEG C, the ammonium persulfate aqueous solution I configured in step (2) is added and is reacted, reacts after 1.8h that reaction was completed,
Obtain seed emulsion；
(5) PVDC emulsion polymerizations：Polymeric kettle displacement is vacuumized afterwards twice with nitrogen, pressure is -0.08Mpa, is vacuumized
The temperature of polymeric kettle is adjusted to 50 DEG C after the completion, step (2) is added and configures obtained metabisulfite solution and persulfuric acid
The premixed liquid that aqueous ammonium II and step (3) configuration obtain is reacted, and control speed of agitator is 120rpm, after reacting 6h,
75 DEG C of heat preservation 1h are warming up to, PVDC lotions are obtained；
(6) desorption of lotion：In the PVDC lotions obtained to step (5) be added 0.003kg Laurate alcohol ester phenylacetate and
The polyvinylether of 0.002kg, it is entire de- by the outlet of nitrogen tube not in PVDC lotions liquid level hereinafter, blast nitrogen and vacuumize
Pressure control is between -0.03Mpa during suction, speed of agitator 25rpm, and at 60 DEG C, the desorption time is 3h, is taken off for temperature control
Postcooling filtering is sucked into get to product.The performance parameter of lotion is shown in Table 1.
Embodiment 3
A kind of preparation method being coated with aqueous PVDC lotions, includes the following steps：
(1) it is spare to prepare reaction raw materials
Composition of raw materials is as follows：
(2) initiator solution is configured：The ammonium persulfate for weighing 0.007kg is configured to ammonium persulfate with deionized water 2kg
Aqueous solution I, it is spare；It is water-soluble to be configured to sodium pyrosulfite with deionized water 3kg for the sodium pyrosulfite (SMBS) for weighing 0.014kg
Liquid, it is spare；0.012kg ammonium persulfates (APS) are weighed, the ammonium persulfate aqueous solution II being configured to deionized water 3kg is spare；
(3) premixed liquid is configured：By the vinylidene chloride monomer of 49.6kg, the ethyl methacrylate of 1.7kg, 0.6kg third
The pentadecyl carboxylic of e pioic acid methyl ester, the itaconic acid of 1.1kg, the vinylacetate of 2.9kg, the alcohol ether carboxylate of 0.7kg, 0.7kg
Sour potassium, the saleratus of 0.02kg, the ammonium acetate of 0.01kg and 4.4kg deionized water input mix liquid bath, at 10 DEG C, 190rpm
Disperse 20min under speed of agitator, obtains premixed liquid, it is spare；
(4) seeded emulsion polymerization：By the methyl methacrylate of 1.26kg, the vinylacetate of 0.61kg, 0.06kg
Acrylic acid, the methacrylonitrile of 0.1kg, 0.09kg sodium stearyl sulfates, 0.09kg Pentadecylbenzene sulfonic acids sodium and 26kg are gone
Ionized water is put into polymeric kettle, at speed of agitator 200rpm it is pre-dispersed after five minutes, polymeric kettle temperature is risen to 80 DEG C, is added
The ammonium persulfate aqueous solution I configured in step (2) is reacted, and reaction was completed after reaction 1.6h, obtains seed emulsion；
(5) PVDC emulsion polymerizations：Polymeric kettle displacement is vacuumized afterwards twice with nitrogen, pressure is -0.065Mpa, is vacuumized
The temperature of polymeric kettle is adjusted to 60 DEG C after the completion, step (2) is added and configures obtained metabisulfite solution and persulfuric acid
The premixed liquid that aqueous ammonium II and step (3) configuration obtain is reacted, and control speed of agitator is 100rpm, reacts 10h
Afterwards, 80 DEG C of heat preservation 0.5h are warming up to, PVDC lotions are obtained；
(6) desorption of lotion：In the PVDC lotions obtained to step (5) be added 0.003kg benzyl carbinol oleate and
The tributyl phosphate of 0.003kg, by the outlet of nitrogen tube not in PVDC lotions liquid level hereinafter, blasting nitrogen and vacuumizing, entirely
Pressure control is between -0.025Mpa in desorption process, speed of agitator 15rpm, and temperature control is in 75 DEG C, desorption time
1h, cold filtration is to get to product after the completion of desorption.The performance parameter of lotion is shown in Table 1.
Embodiment 4
A kind of preparation method being coated with aqueous PVDC lotions, includes the following steps：
(1) it is spare to prepare reaction raw materials
Composition of raw materials is as follows：
(2) initiator solution is configured：The ammonium persulfate for weighing 0.013kg is configured to ammonium persulfate with deionized water 2kg
Aqueous solution I, it is spare；It is water-soluble to be configured to sodium pyrosulfite with deionized water 3kg for the sodium pyrosulfite (SMBS) for weighing 0.014kg
Liquid；0.012kg ammonium persulfates (APS) are weighed, ammonium persulfate aqueous solution II is configured to deionized water 3kg；
(3) premixed liquid is configured：By the vinylidene chloride monomer of 52kg, the ethyl methacrylate of 1.74kg, 0.58kg third
The pentadecyl carboxylic of e pioic acid methyl ester, the itaconic acid of 1.13kg, the vinylacetate of 2.9kg, the alcohol ether carboxylate of 1.7kg, 0.7kg
Sour potassium, the saleratus of 0.02kg, the ammonium acetate of 0.01kg and 10.4kg deionized water input mix liquid bath, at 8 DEG C, 200rpm
Disperse 15min under speed of agitator, obtains premixed liquid, it is spare；
(4) seeded emulsion polymerization：By the methyl acrylate of 1.86kg, the ethyl acetate of 0.74kg, 0.11kg acrylic acid,
The acrylonitrile of 0.14kg, the deionized water input of 0.1kg sodium stearyl sulfates, 0.2kg Pentadecylbenzene sulfonic acids sodium and 20kg
In polymeric kettle, at speed of agitator 180rpm it is pre-dispersed after ten minutes, the temperature of polymeric kettle is risen to 85 DEG C, step (2) is added
The ammonium persulfate aqueous solution I of middle configuration is reacted, and reaction was completed after reaction 1.75h, obtains seed emulsion；
(5) PVDC emulsion polymerizations：Polymeric kettle displacement is vacuumized afterwards twice with nitrogen, pressure is -0.065Mpa, is vacuumized
The temperature of polymeric kettle is adjusted to 65 DEG C after the completion, step (2) is added and configures obtained metabisulfite solution and persulfuric acid
The premixed liquid that aqueous ammonium II and step (3) configuration obtain is reacted, and control speed of agitator is 90rpm, after reacting 8h,
85 DEG C of heat preservation 0.5h are warming up to, PVDC lotions are obtained；
(6) desorption of lotion：In the PVDC lotions obtained to step (5) be added 0.003kg benzyl carbinol oleate and
The tributyl phosphate of 0.003kg, by the outlet of nitrogen tube not in PVDC lotions liquid level hereinafter, blasting nitrogen and vacuumizing, entirely
Pressure control is in -0.04Mpa in desorption process, and speed of agitator 30rpm, at 70 DEG C, the desorption time is 2h, desorption for temperature control
Cold filtration is to get to product after the completion.The performance parameter of lotion is shown in Table 1.
Embodiment 5
A kind of preparation method being coated with aqueous PVDC lotions, includes the following steps：
(1) it is spare to prepare reaction raw materials
Composition of raw materials is as follows：
(2) initiator solution is configured：The ammonium persulfate for weighing 0.009kg is configured to ammonium persulfate with deionized water 2kg
Aqueous solution I, it is spare；Weighing the sodium pyrosulfite (SMBS) of 0.018kg, with deionized water 3kg to be configured to sodium pyrosulfite water-soluble
Liquid, it is spare；It weighs 0.015kg ammonium persulfates (APS) and is configured to ammonium persulfate aqueous solution II with deionized water 3kg, it is spare；
(3) premixed liquid is configured：By the vinylidene chloride monomer of 53.7kg, the acrylic acid of 1.15kg ethyl acrylates, 0.57kg
The octadecyl carboxylic of hydroxyl ethyl ester, the itaconic acid of 1.15kg, the vinylacetate of 1.15kg, the alcohol ether carboxylate of 0.7kg, 0.7kg
Sour sodium, the saleratus of 0.01kg, the sodium bicarbonate of 0.01kg, the deionized water input of the ammonium acetate of 0.02kg and 12.4kg are mixed
Liquid bath disperses 10min under 9 DEG C, 160rpm speeds of agitator, obtains premixed liquid, spare；
(4) seeded emulsion polymerization：By the methyl methacrylate of 1.62kg, acetic acid hydroxyalkyl vinyl ester, the 0.07kg of 0.58kg
Acrylic acid, the acrylonitrile of 0.46kg, the pentadecyl sodium sulphate of 0.1kg, the pentadecyl carboxylic acid sodium of 0.2kg and going for 18kg
Ionized water is put into polymeric kettle, at speed of agitator 120rpm it is pre-dispersed after twenty minutes, polymeric kettle temperature is risen to 70 DEG C, is added
The ammonium persulfate aqueous solution I configured in step (2) is reacted, and reaction was completed after reaction 1.65h, obtains seed emulsion；
(5) PVDC emulsion polymerizations：Polymeric kettle displacement is vacuumized afterwards twice with nitrogen, pressure is -0.07Mpa, is vacuumized
Polymeric kettle temperature is adjusted to 55 DEG C after the completion, step (2) is added and configures obtained metabisulfite solution and ammonium persulfate water
The premixed liquid that solution II and step (3) configuration obtain is reacted, and control speed of agitator is 110rpm, after reacting 9h, heating
To 70 DEG C of heat preservation 2.5h, PVDC lotions are obtained；
(6) desorption of lotion：In the PVDC lotions obtained to step (5) be added 0.002kg benzenephosphonic acid tributyl and
The polysiloxanes of 0.003kg, it is entire de- by the outlet of nitrogen tube not in PVDC lotions liquid level hereinafter, blast nitrogen and vacuumize
Pressure control is in -0.03Mpa during suction, and speed of agitator 20rpm, at 70 DEG C, the desorption time is 3.5h, desorption for temperature control
Cold filtration is to get to product after the completion.The performance parameter of lotion is shown in Table 1.
Comparative example
The product being prepared according to the method for China Patent Publication No. CN104114585A embodiments 1.
Performance test：
1, the making of impact resistance evaluation PVDC/PVC composite hard sheets
Corona discharge Treatment is passed through on PVC stiff sheet (thick bottom is about 250um) surface, one layer of 2g/m is applied in surface face2It is viscous
Mixture (adhesive is that polyurethane is dissolved in the solution formed in ethyl acetate), heated-air drying 20S, face applies 80g/m2Embodiment 1
~5 and comparative example made from aqueous PVDC lotions, then pass through infrared drying, that is, complete impact resistance evaluation PVDC/PVC
The making of composite hard sheet.
Impact resistance is executed by YBB00222005-2015 standards.Performance evaluation the results are shown in Table 2 and table 3.
2, the making of barrier property evaluation PVDC/PVC composite hard sheets
Corona discharge Treatment is passed through on PVC stiff sheet (thick bottom is about 250um) surface, one layer of 2g/m is applied in surface face2It is viscous
Mixture (adhesive is that polyurethane is dissolved in the solution formed in ethyl acetate), heated-air drying 20S, face applies 80g/m2Embodiment 1
~5 and comparative example made from aqueous PVDC lotions, then pass through infrared drying, be then placed in drying chamber and cure 48h in 50 DEG C,
Complete the making of barrier property evaluation PVDC/PVC composite hard sheets.
Steam penetrating capacity detection method presses GB1037-1988《Plastic film and sheet material water vapor permeability test method cup
Formula method》Standard executes；Oxygen presses GB/T1038-2000 through quantity measuring method《Plastic film and the experiment of thin slice gas-premeable
Method pressure differential method》Standard executes.Evaluation results are shown in Table 4.
3, the making of Evaluation of Thermal Stability PVDC/PVC composite hard sheets
One layer of 2g/m is applied in surface face2Adhesive (adhesive be polyurethane be dissolved in formed in ethyl acetate it is molten
Liquid), heated-air drying 20S, face applies 80g/m2Then aqueous PVDC lotions made from Examples 1 to 5 and comparative example pass through infrared ray
It is dry, that is, complete the making of Evaluation of Thermal Stability PVDC/PVC composite hard sheets.
Evaluation of Thermal Stability test method：PVDC/PVC composite sheets are placed certain time at different temperatures, observe table
Face color whether changes.Evaluation results are shown in Table 5.
Aqueous PVDC emulsion properties parameter made from 1 Examples 1 to 5 of table and comparative example
The impact resistance test result (PVDC lotions room temperature 2 weeks) of 2 PVDC/PVC composite hard sheets of table
The impact resistance test result (PVDC lotions room temperature March) of 3 PVDC/PVC composite hard sheets of table
The barrier property test result of 4 PVDC/PVC composite hard sheets of table
5 PVDC/PVC composite hard sheet heat stability testing results of table
Claims (9)
1. a kind of preparation method being coated with aqueous PVDC lotions, which is characterized in that include the following steps：
(1) it is spare to prepare reaction raw materials
In parts by weight, reaction raw materials group becomes：1~5 part of seed monomer, 45~55 parts of vinylidene chloride monomer, comonomer 4~
10 parts, 0.01~0.05 part of initiator, 0.1~0.5 part of seed emulsifier, 0.5~3 part of emulsifier, other auxiliary agents 0.01~
0.05 part, 0.001~0.01 part of modified additive, 35~40 parts of deionized water；
(2) initiator solution is configured：The initiator for accounting for seed monomer quality 0.2~0.5% is configured to deionized water dense
Degree is 0.1~1% seeded emulsion polymerization initiator solution, remaining initiator is configured to deionized water a concentration of
0.2~0.8% emulsion polymerization initiator solution, it is spare；
(3) premixed liquid is configured：By vinylidene chloride monomer, comonomer, emulsifier, other auxiliary agents and 10~35% deionization
Water disperses 5~30min under 2~10 DEG C, 100~200rpm speeds of agitator, obtains premixed liquid, spare；
(4) seeded emulsion polymerization：Seed monomer, seed emulsifier and remaining deionized water are put into polymeric kettle, 100~
Under 200rpm speeds of agitator after pre-dispersed 5~30 minutes, step (2) is added and configures obtained seeded emulsion polymerization initiator water
Solution is reacted, and reaction temperature is 70~85 DEG C, and reaction was completed after 1~2h of reaction, obtains seed emulsion；
(5) PVDC emulsion polymerizations：Under 90~120rpm speeds of agitator, step is added in the seed emulsion obtained to step (4)
(2) the emulsion polymerization initiator solution and step (3) that configuration obtains configure obtained premixed liquid, at 50~65 DEG C
After reacting 6~12h, 70~85 DEG C of 0.5~2.5h of heat preservation are warming up to, PVDC lotions are obtained；
(6) desorption of lotion：Modified additive is added in the PVDC lotions obtained to step (5), in -0.04~-0.02Mpa, 60
Nitrogen is blasted under~75 DEG C and 15~30rpm speeds of agitator into PVDC lotions and carries out desorption, the desorption time is 1~4h, desorption
Postcooling, filtering are completed to get to product.
2. the preparation method according to claim 1 for being coated with aqueous PVDC lotions, which is characterized in that in PVDC breasts
Liquid polymerize preceding nitrogen and into line replacement and is vacuumized to polymeric kettle, and the pressure vacuumized is -0.08~-0.06Mpa.
3. the preparation method according to claim 1 for being coated with aqueous PVDC lotions, which is characterized in that the seed monomer
For methyl acrylate, ethyl acrylate, butyl acrylate, methyl methacrylate, hydroxy-ethyl acrylate, acetic acid hydroxyalkyl vinyl ester,
Vinylacetate, ethyl acetate, acrylic acid-2-ethyl caproite, acrylonitrile, methacrylonitrile, acrylic acid, methacrylic acid, clothing
The mixture of one or more of health acid.
4. the preparation method according to claim 1 for being coated with aqueous PVDC lotions, which is characterized in that the comonomer
For methyl acrylate, ethyl acrylate, butyl acrylate, methyl methacrylate, ethyl methacrylate, acrylic acid hydroxyl second
In ester, vinylacetate, acrylic acid-2-ethyl caproite, acrylonitrile, methacrylonitrile, acrylic acid, methacrylic acid, itaconic acid
One or more of mixtures.
5. the preparation method according to claim 1 for being coated with aqueous PVDC lotions, which is characterized in that the initiator is
The mixture of one or more of ammonium persulfate, sodium peroxydisulfate, potassium peroxydisulfate.
6. the preparation method according to claim 1 for being coated with aqueous PVDC lotions, which is characterized in that the seed emulsification
Agent is lauryl sodium sulfate, pentadecyl sodium sulphate, sodium stearyl sulfate, neopelex, pentadecyl benzene
Sodium sulfonate, sodium stearyl sulfonate, alcohol ether carboxylate, dodecyl carboxylic acid potassium, pentadecyl carboxylic acid sodium, octadecyl carboxylic acid potassium
One or more of mixture.
7. the preparation method according to claim 1 for being coated with aqueous PVDC lotions, which is characterized in that the emulsifier is
Lauryl sodium sulfate, pentadecyl sodium sulphate, sodium stearyl sulfate, neopelex, Pentadecylbenzene sulfonic acid
Sodium, sodium stearyl sulfonate, alcohol ether carboxylate, dodecyl carboxylic acid potassium, pentadecyl carboxylic acid sodium, pentadecyl carboxylic acid potassium, ten
The mixture of one or more of eight sodium carboxylates.
8. the preparation method according to claim 1 for being coated with aqueous PVDC lotions, which is characterized in that other described auxiliary agents
For one or several kinds of mixtures in sodium bicarbonate, saleratus, ammonium acetate, glacial acetic acid.
9. the preparation method according to claim 1 for being coated with aqueous PVDC lotions, which is characterized in that the modified additive
For one kind in dimethicone, polysiloxanes, benzyl carbinol oleate, tributyl phosphate, Laurate alcohol ester phenylacetate, polyvinylether
Or several mixture.
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| CN112778461A (en) * | 2020-12-31 | 2021-05-11 | 山东华夏神舟新材料有限公司 | Preparation method of aqueous PVDF resin dispersion emulsion |
| CN112940014A (en) * | 2021-02-03 | 2021-06-11 | 浙江工业大学 | Thiophene derivative and synthesis method and application thereof |
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