CN106432575B - A kind of water boiling resistance polyvinylidene emulsions and preparation method thereof - Google Patents

A kind of water boiling resistance polyvinylidene emulsions and preparation method thereof Download PDF

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CN106432575B
CN106432575B CN201610828032.XA CN201610828032A CN106432575B CN 106432575 B CN106432575 B CN 106432575B CN 201610828032 A CN201610828032 A CN 201610828032A CN 106432575 B CN106432575 B CN 106432575B
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mixed
boiling resistance
water boiling
water
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CN106432575A (en
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黄宏存
朱清梅
宋军军
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Hainan Kai Kai Shui New Material Co Ltd
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Hainan Kai Kai Shui New Material Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F214/00—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
    • C08F214/02—Monomers containing chlorine
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B65—CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
    • B65D—CONTAINERS FOR STORAGE OR TRANSPORT OF ARTICLES OR MATERIALS, e.g. BAGS, BARRELS, BOTTLES, BOXES, CANS, CARTONS, CRATES, DRUMS, JARS, TANKS, HOPPERS, FORWARDING CONTAINERS; ACCESSORIES, CLOSURES, OR FITTINGS THEREFOR; PACKAGING ELEMENTS; PACKAGES
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    • C08F2/00—Processes of polymerisation
    • C08F2/12—Polymerisation in non-solvents
    • C08F2/16—Aqueous medium
    • C08F2/22—Emulsion polymerisation
    • C08F2/24—Emulsion polymerisation with the aid of emulsifying agents
    • C08F2/26—Emulsion polymerisation with the aid of emulsifying agents anionic
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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    • C08L27/00—Compositions of 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; Compositions of derivatives of such polymers
    • C08L27/02—Compositions of 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; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L27/04—Compositions of 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; Compositions of derivatives of such polymers not modified by chemical after-treatment containing chlorine atoms
    • C08L27/08—Homopolymers or copolymers of vinylidene chloride
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • 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
    • C09D127/08—Homopolymers or copolymers of vinylidene chloride
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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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    • C09D7/60—Additives non-macromolecular
    • C09D7/61—Additives non-macromolecular inorganic
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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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    • C09K8/60—Compositions for stimulating production by acting on the underground formation
    • C09K8/62—Compositions for forming crevices or fractures
    • C09K8/70—Compositions for forming crevices or fractures characterised by their form or by the form of their components, e.g. foams
    • C09K8/706—Encapsulated breakers
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Abstract

The present invention relates to a kind of water boiling resistance polyvinylidene emulsions, are made by following weight content group lease making seeded emulsion polymerization：Vinylidene chloride 38 42.2%, acrylonitrile 0.4 0.6%, methacrylonitrile 1.2 1.4%, methacrylic acid 1 1.2%, methyl methacrylate 0.3 0.6%, butyl methacrylate 0.2 0.5%, mixed initiator 1.2 1.4%, blended emulsifier 1 1.2%, modified additive 1.5 1.8%, ammonium acetate 0.3 0.5%, frerrous chloride 0.2 0.4%, pH adjusting agent 0.5 0.6%, deionized water 50 51.8%.The lotion has outstanding water boiling resistance performance while keeping high obstructing performance, can be used in water boiling resistance high-barrier packaging, is also applicable to oil exploitation gel breaker peel material.

Description

A kind of water boiling resistance polyvinylidene emulsions and preparation method thereof
Technical field
A kind of water boiling resistance polyvinylidene emulsions of present invention offer and preparation method thereof, belong to polymeric material field.
Background technology
Polyvinylidene chloride is a kind of non-toxic and tasteless, safe and reliable high resistant oxygen, resistance wet stock, also has excellent oil resistant Property, corrosion resistance, protect taste and printing performance, copolymer latex and be widely used in multi-field.In current meat In product processing, it is mainstream to provide the consumer with fresh meat or chilled meat, the following disadvantage of food packaging application generally existing：It provides Food to be reused after consumer oneself boiling, waste time；The food of offer does not pass through high-temperature sterilization and sterilizes, and protects The matter phase is not grown；It packs opaque, can't see packed article.In addition, the high viscosity fracturing fluid used during oil exploitation must pass through Gel breaker thoroughly breaks glue and returns row, to reduce the injury to reservoir, improves oil well output, and gel breaker requires to have to delay brokenly glue Otherwise performance can be extracted in oil and complete preceding glue broken ahead of time, influence yield, it is therefore desirable to which one kind delaying gel breaker, principle To use spraying process to coat one layer of coating on ammonium persulfate surface, which has shielding action to gel breaker and can be certain Under the conditions of rupture, slowly release gel breaker.Gel breaker manufacturer is attempting using polyvinylidene emulsions to broken at present Jelly (main component is ammonium persulfate, potassium peroxydisulfate etc.) is coated, and the gel breaker after cladding can be resistance to 90 within the construction time DEG C boiling (oil exploitation environment), after construction, clad iris action fades away, and broken glue ingredient obtains slow release. Therefore, the water boiling resistance time is more long, and gel breaker slow-release time is extended, and is more conducive to capsule breaker during oil exploitation It uses.
Water boiling resistance at present using packaging material for food made from polyvinylidene emulsions is poor, such as patent The medical packaging that PVDC copolymer emulsions that CN101367898 is related to and its preparation method and application, CN101649015 are related to is inclined The odorless PVDC latex and its preparation side that dichloroethylene copolymer latex and its preparation method and application, CN102250436A are related to A kind of heat-sealing polyvinylidene chloride coating film and its manufacturing method, CN101613582 that method, CN102248729A are related to relate to And aqueous vinylidene chloride base glue used in high-barrier plastic film preparation method, the polyvinylidene chloride glue that the above patent is mentioned The water boiling resistance of breast is poor, cannot meet the use demand of present consumer.
Invention content
Water boiling resistance demand when cannot meet as gel breaker peel material for current polyvinylidene emulsions, this A kind of water boiling resistance polyvinylidene emulsions of invention offer and preparation method thereof, the lotion is for oil exploitation gel breaker packet When covering material can 90 DEG C of environment of water boiling resistance be up to 8 hours, effectively extend the slow-release time of gel breaker；It is additionally useful for barrier food When packaging material can 100 DEG C of water boiling resistance environment 2 hours, and remain to keep good barrier properties energy.
Its innovative point is：(1) resistance of polyvinylidene emulsions can be improved by adjusting compatibility monomer component and content Separating performance；(2) by adding modified additive, (nano hydrotalcite and beta-cyclodextrin are according to 1:2 ratios mix) lotion is changed Property, modified rear stability increase improves water boiling resistance performance, such as separately through nano hydrotalcite modification or separately through beta-cyclodextrin Modified, stabilizing effect is good not as good as the mixed effect of the two, is specifically shown in Table 3；(3) it improves lotion and prepares work Skill, further such that lotion barriering effect obtained and the enhancing of water boiling resistance effect.
It is an object of the present invention to provide a kind of water boiling resistance polyvinylidene emulsions, by following weight content component It is made through seeded emulsion polymerization：
Vinylidene chloride 38-42.2%, acrylonitrile 0.4-0.6%, methacrylonitrile 1.2-1.4%, methacrylic acid 1- 1.2%, methyl methacrylate 0.3-0.6%, butyl methacrylate 0.2-0.5%, mixed initiator 1.2-1.4% are mixed Co-emulsifier 1-1.2%, modified additive 1.5-1.8%, ammonium acetate 0.3-0.5%, frerrous chloride 0.2-0.4%, pH adjusting agent 0.5-0.6%, deionized water 50-51.8%.
The mixed initiator is tert-butyl hydroperoxide and sodium formaldehyde sulphoxylate with 1:1 ratio mixes；
The blended emulsifier is neopelex and secondary sodium alkanesulfonate with 2:1 ratio mixes；
The modified additive is by nano hydrotalcite and beta-cyclodextrin with 1:2 ratios mix；
The pH adjusting agent is potassium hydroxide or triethylamine.
It is a further object to provide a kind of preparation method of water boiling resistance polyvinylidene emulsions, the preparation sides Method uses seeded emulsion polymerization, is as follows：
1. the preparation of raw material：
1) mix monomer is prepared：By 38-42.2% vinylidene chlorides, the acrylonitrile of 0.4-0.6%, 1.2-1.4% methyl Acrylonitrile, 1-1.2% methacrylic acids, 0.3-0.6% methyl methacrylates, 0.2-0.5% butyl methacrylates, stirring 1-1.5h monomer mixture is made；
2) blended emulsifier is prepared：According to 2:1 weight ratio takes neopelex and secondary chain alkyl sulfonic acid respectively Sodium, the two total amount is 1-1.2%, then portions of de-ionized water is added to be dissolved, and then carries out cold dispersion 1-1.5h, and mixing breast is made Agent solution；
3) mixed initiator is prepared：Tert-butyl hydroperoxide is added in portions of de-ionized water to be stirred and is mixed and made into uncle Butyl peroxy hydrogen solution, then sodium formaldehyde sulphoxylate is added to be stirred in portions of de-ionized water and is mixed and made into formaldehyde The adding proportion of conjunction bisulphite sodium solution, tert-butyl hydroperoxide and sodium formaldehyde sulphoxylate is 1:1, the two total amount is 1.2-1.4%；
2. seeding polymerization：
By ammonium acetate 0.3-0.5% and frerrous chloride 0.2-0.4%, produced part blended emulsifier and part go from Sub- water is added in reaction kettle, seals kettle, is led to nitrogen and is replaced 2 times, vacuumizes, and the part mixing that sucking accounts for total mix monomer 3% is single Body heats up 45-50 DEG C as seed monomer, cold dispersion 1h, is pumped into mixed initiator with the charging rate of 5kg/48h, is warming up to 55-58 DEG C of constant temperature；When pressure is down to 0.01-0.03MPa, seeding polymerization terminates, and obtains seed emulsion；
3. emulsion polymerization：
It is continuously pumped into remaining blended emulsifier, mix monomer simultaneously into seed emulsion, is pumped into 10~15h of time, when When pressure is down to 0~-0.01MPa, reaction terminates；1.5-1.8% modified additives are added, open blender, stir 1-1.2h, then It vacuumizes, bottom valve does not open vacuum desorption 1h, and temperature rises to 75 DEG C, keeps 1h, bottom valve is crack, and 0.1MPa is added in desorption 2h afterwards Water vapour, 0.5-0.6%pH conditioning agent tune pH value is added to 2.5-3, filtering obtains polyvinylidene chloride copolymer emulsion.
The traditional performance of the obtained polyvinylidene chloride of 1 present invention of table
Polyvinylidene emulsions performance indicator of the present invention Test method or standard
Solid content (%) 47.8-50.3 GB1725-79
Surface tension (mN/m) ≤41.8 GB1725-79
Viscosity (mPas) ≤11.6 U.S.'s BROOKFIELD viscosimeters
PH value 2.2-2.8 PHS-3C precision pH meters
Density (g/cm3) 1.20-1.28 Densimeter
The traditional performance that polyvinylidene emulsions are made in the present invention is included in table 1.Its water boiling resistance performance is next pair in terms of two Than referring initially to GB/T10004-1998, by testing the coated film formed by lotion before and after 100 DEG C of boilings such as coating shedding The variation of the performances such as situation, oxygen transit dose, water vapour transit dose, to characterize the water boiling resistance of lotion；In addition, when being applied to stone When oil exploitation, after coating gel breaker, gel breaking time under the conditions of 90 DEG C of boilings characterizes water boiling resistance.After tested, of the invention Polyvinylidene emulsions obtained are shown in Table 2 with conventional polyvinylidene emulsions specific performance comparison.
The obtained polyvinylidene emulsions of 2 present invention of table and conventional polyvinylidene emulsions water boiling resistance performance comparison
Remarks：The preparation of conventional polyvinylidene emulsions is with reference to patent application 201210572049.5.
Different polyvinylidene emulsions is typically referred to as scale value comparison before and after 3 nano modification of table
Remarks：In polyvinylidene emulsions A compared with polyvinylidene emulsions of the present invention, beta-cyclodextrin is removed only Component, remaining component and content, production technology all same；It is newborn with polyvinylidene chloride of the present invention in polyvinylidene emulsions B Liquid phase ratio, removes only nano hydrotalcite component, remaining component and content, production technology all same；Polyvinylidene emulsions C In compared with polyvinylidene emulsions of the present invention, only simultaneously eliminate nano hydrotalcite and beta-cyclodextrin component, remaining component And content, production technology all same；The test of coating shedding situation, oxygen transit dose, water vapour permeability, boiling gel breaking time Standard or method are identical with table 2.
It is compared by table 2 it is found that using the obtained polyvinylidene emulsions of the present invention, after being coated on BOPP base materials and is passed through 100 DEG C of boilings 2 hours, more conventional polyvinylidene emulsions are compared, and coating is not fallen off before and after boiling, and barriering effect is It improves, barrier property does not decline to a great extent；After coating oil exploitation gel breaker, appearance is good, gathers inclined two chloroethene using conventional Alkene coats gel breaker, starts crack occur after 2-3 hour in 90 DEG C of boilings, and water boiling resistance gel breaking time is only 2-3 hours, and Invention is made the gel breaker of polyvinylidene chloride cladding and does not occur crack yet after 5.5-7 hours in 90 DEG C of boilings, but is further continued for water It boils, crack gradually appears, you can water boiling resistance gel breaking time longest effectively extended the gel breaking time of gel breaker up to 7 hours.
In addition, being compared by table 3 it is found that modified and be modified separately through beta-cyclodextrin separately through nano hydrotalcite, obtain Water boiling resistance performance after the barrier property of the polyvinylidene chloride arrived, cladding gel breaker passes through the two rational mixture than the present invention The polyvinylidene emulsions performance of post-modification is weak.In addition, individually adding nano hydrotalcite or individually adding beta-cyclodextrin ratio not It is increased by modified polyvinylidene emulsions barrier property and water boiling resistance performance.Modified help to improve is gathered partially The barrier property and water boiling resistance performance of dichloroethylene lotion.
In summary it compares, the more conventional product of polyvinylidene chloride, which is made, in the present invention has compared with much progress, barrier property and resistance to The raising of boiling performance essentially consists in modified method, and the modified effect after two kinds of modified material rational mixtures is much higher than a kind of material The modification of material.Polyvinylidene emulsions water boiling resistance excellent performance is made in the present invention, can be used in water boiling resistance high-barrier packaging, also It is applicable to oil exploitation gel breaker peel material.
Specific implementation mode
Embodiment 1：
1. the preparation of raw material：
1) mix monomer is prepared：By 5.7kg vinylidene chlorides, the acrylonitrile of 0.09kg, 0.21kg methacrylonitriles, 0.18kg methacrylic acids, 0.09kg methyl methacrylates, 0.075kg butyl methacrylates stir 1h, are made 6.345kg monomer mixture；
2) blended emulsifier is prepared：Neopelex 0.12kg and secondary sodium alkanesulfonate 0.06kg are taken respectively, Again plus 1kg deionized waters are dissolved, and then carry out cold dispersion 1h, and 1.18kg mixing and emulsifying agent solutions are made；
3) mixed initiator is prepared：0.105kg tert-butyl hydroperoxide is added in 1kg deionized waters and is stirred mixing Tert-butyl hydroperoxide solution is made, then 0.105kg sodium formaldehyde sulphoxylates are added in 1kg deionized waters and are stirred It is mixed and made into sodium formaldehyde sulphoxylate solution, two prepared kind solution carries out being mixed and made into 2.21kg mixed initiators again；
2. seeding polymerization：
By 0.075kg ammonium acetates and 0.06kg frerrous chlorides, produced 0.6kg blended emulsifiers and 2.5kg deionizations Water is added in reaction kettle, seals kettle, is led to nitrogen and is replaced 2 times, vacuumizes, and sucking 0.19kg mix monomers are cold as seed monomer Disperse 1h, heats up 45 DEG C, 2.21kg mixed initiators are pumped into the charging rate of 5kg/48h, are warming up to 55 DEG C of constant temperature；Work as pressure When being down to 0.01MPa, seeding polymerization terminates, and obtains seed emulsion；
3. emulsion polymerization：
It is continuously pumped into remaining blended emulsifier, mix monomer and 2.27kg deionized waters simultaneously into seed emulsion, is pumped Angle of incidence 15h, when pressure is down to -0.01MPa, reaction terminates；0.09kg nano hydrotalcites and 0.18kg beta-cyclodextrins is added Two kinds of mixed modified additives open blender, stir 1h, then vacuumize, bottom valve does not open vacuum desorption 1h, and temperature rises to 75 DEG C, 1h is kept, bottom valve is crack, desorption 2h, the rear water vapour that 0.1MPa is added, addition 0.09kg triethylamine tune pH value to 2.8, Filtering, obtains polyvinylidene chloride copolymer emulsion.
Polyvinylidene emulsions obtained, solid content 48.2%, surface tension 41.8mN/m, viscosity 11.6mPa S, density 1.22g/cm3；With coating weight it is 2.4g/m on BOPP base materials2It is coated, through 100 DEG C of boilings 2 hours, measures water Boil forward and backward OTR oxygen transmission rate be respectively 2.9,10.6ml/ ㎡ for 24 hours, moisture-vapor transmission is respectively 5.5,6.3g/ ㎡ 24h；After coating oil exploitation gel breaker using the lotion, it is 6 hours to be resistant to 90 DEG C of boiling times.Through performance verification, this hair It remains to keep good barrier property after bright product boiling obtained, applies and extend the broken glue of boiling in oil exploitation gel breaker Time.
Embodiment 2：
1. the preparation of raw material：
1) mix monomer is prepared：By 11.67kg vinylidene chlorides, the acrylonitrile of 0.18kg, 0.39kg methacrylonitriles, 0.33kg methacrylic acids, 0.15kg methyl methacrylates, 0.15kg butyl methacrylates stir 1.1h, are made 12.87kg monomer mixtures；
2) blended emulsifier is prepared：Neopelex 0.22kg and secondary sodium alkanesulfonate 0.11kg are taken respectively, Again plus 1.5kg deionized waters are dissolved, and then carry out cold dispersion 1.2h, and 1.53kg mixing and emulsifying agent solutions are made；
3) mixed initiator is prepared：It is mixed by being stirred in 0.21kg tert-butyl hydroperoxide addition 1.5kg deionized waters Tert-butyl hydroperoxide solution is made in conjunction, then 0.21kg sodium formaldehyde sulphoxylates are added in 1.5kg deionized waters and are carried out It is stirred and sodium formaldehyde sulphoxylate solution is made, two prepared kind solution carries out being mixed and made into 3.42kg mixing initiations again Agent；
2. seeding polymerization：
0.12kg ammonium acetates and 0.12kg frerrous chlorides, produced 1.0kg blended emulsifiers and 9kg deionized waters are added Enter into reaction kettle, seal kettle, lead to nitrogen and replace 2 times, vacuumize, sucking 0.386kg mix monomers are as seed monomer, cold dispersion 1h heats up 46 DEG C, is pumped into 3.42kg mixed initiators with the charging rate of 5kg/48h, is warming up to 57 DEG C of constant temperature；When pressure is down to When 0.02MPa, seeding polymerization terminates, and obtains seed emulsion；
3. emulsion polymerization：
It is continuously pumped into remaining blended emulsifier, mix monomer and 1.95kg deionized waters simultaneously into seed emulsion, is pumped Angle of incidence 10h, when pressure is down to -0.01MPa, reaction terminates；0.17kg nano hydrotalcites and 0.34kg beta-cyclodextrins is added Two kinds of mixed modified additives open blender, stir 1h, then vacuumize, bottom valve does not open vacuum desorption 1h, and temperature rises to 75 DEG C, 1h is kept, bottom valve is crack, desorption 2h, and 0.18kg potassium hydroxide tune pH value is added extremely in the rear water vapour that 0.1MPa is added 2.6, filtering obtains polyvinylidene chloride copolymer emulsion.
Polyvinylidene emulsions obtained, solid content 48.5%, surface tension 41.5mN/m, viscosity 10mPas, Density 1.28g/cm3；With coating weight it is 2.4g/m on BOPP base materials2It is coated, through 100 DEG C of boilings 2 hours, measures boiling Forward and backward OTR oxygen transmission rate be respectively 3,10.2ml/ ㎡ for 24 hours, moisture-vapor transmission be respectively 5.8,6.5g/ ㎡ for 24 hours；Make After coating oil exploitation gel breaker with the lotion, it is 5.5 hours to be resistant to 90 DEG C of boiling times.Through performance verification, system of the present invention Product boiling after remain to keep good barrier property, apply extended in oil exploitation gel breaker boiling break glue when Between.
Embodiment 3：
1. the preparation of raw material：
1) mix monomer is prepared：By 19.8kg vinylidene chlorides, the acrylonitrile of 0.25kg, 0.65kg methacrylonitriles, 0.55kg methacrylic acids, 0.25kg methyl methacrylates, 0.2kg butyl methacrylates stir 1h, it is mono- that 21.7kg are made Body mixture；
2) blended emulsifier is prepared：Neopelex 0.33kg and secondary sodium alkanesulfonate 0.17kg are taken respectively, Again plus 3kg deionized waters are dissolved, and then carry out cold dispersion 1.3h, and 3.5kg mixing and emulsifying agent solutions are made；
3) mixed initiator is prepared：0.35kg tert-butyl hydroperoxide is added in 3kg deionized waters and is stirred mixing Tert-butyl hydroperoxide solution is made, then 0.35kg sodium formaldehyde sulphoxylates are added in 3kg deionized waters and are stirred It is mixed and made into sodium formaldehyde sulphoxylate solution, two prepared kind solution carries out being mixed and made into 6.7kg mixed initiators again；
2. seeding polymerization：
By 0.25kg ammonium acetates and 0.15kg frerrous chlorides, produced 1.8kg blended emulsifiers and 10kg deionized waters It is added in reaction kettle, seals kettle, lead to nitrogen and replace 2 times, vacuumize, sucking 0.651kg mix monomers are as seed monomer, cold point 1h is dissipated, heats up 48 DEG C, 6.7kg mixed initiators is pumped into the charging rate of 5kg/48h, are warming up to 57 DEG C of constant temperature；Work as pressure drop When to 0.03MPa, seeding polymerization terminates, and obtains seed emulsion；
3. emulsion polymerization：
It is continuously pumped into remaining blended emulsifier, mix monomer and 6.55kg deionized waters simultaneously into seed emulsion, is pumped Angle of incidence 12h, when pressure is down to -0.01MPa, reaction terminates；0.29kg nano hydrotalcites and 0.56kg beta-cyclodextrins is added Two kinds of mixed modified additives open blender, stir 1h, then vacuumize, bottom valve does not open vacuum desorption 1h, and temperature rises to 75 DEG C, 1h is kept, bottom valve is crack, desorption 2h, the rear water vapour that 0.1MPa is added, addition 0.3kg triethylamine tune pH value to 2.5, Filtering, obtains polyvinylidene chloride copolymer emulsion.
Polyvinylidene emulsions obtained, solid content 48.9%, surface tension 40.5mN/m, viscosity 11.6mPa S, density 1.20g/cm3；With coating weight it is 2.4g/m on BOPP base materials2It is coated, through 100 DEG C of boilings 2 hours, measures water Boil forward and backward OTR oxygen transmission rate be respectively 3.6,12.4ml/ ㎡ for 24 hours, moisture-vapor transmission is respectively 6.1,7.2g/ ㎡ 24h；After coating oil exploitation gel breaker using the lotion, it is 7 hours to be resistant to 90 DEG C of boiling times.Through performance verification, this hair It remains to keep good barrier property after bright product boiling obtained, applies and extend the broken glue of boiling in oil exploitation gel breaker Time.
Embodiment 4：
1. the preparation of raw material：
1) mix monomer is prepared：By 24.3kg vinylidene chlorides, the acrylonitrile of 0.36kg, 0.84kg methacrylonitriles, 0.6kg methacrylic acids, 0.24kg methyl methacrylates, 0.24kg butyl methacrylates stir 1.3h, are made 26.58kg monomer mixtures；
2) blended emulsifier is prepared：Neopelex 0.44kg and secondary sodium alkanesulfonate 0.22kg are taken respectively, Again plus 4kg deionized waters are dissolved, and then carry out cold dispersion 1.5h, and 4.66kg mixing and emulsifying agent solutions are made；
3) mixed initiator is prepared：0.39kg tert-butyl hydroperoxide is added in 4kg deionized waters and is stirred mixing Tert-butyl hydroperoxide solution is made, then 0.39kg sodium formaldehyde sulphoxylates are added in 4kg deionized waters and are stirred It is mixed and made into sodium formaldehyde sulphoxylate solution, two prepared kind solution carries out being mixed and made into 8.78kg mixed initiators again；
2. seeding polymerization：
By 0.18kg ammonium acetates and 0.24kg frerrous chlorides, produced 2.0kg blended emulsifiers and 12kg deionized waters It is added in reaction kettle, seals kettle, lead to nitrogen and replace 2 times, vacuumize, sucking 0.7974kg mix monomers are cold as seed monomer Disperse 1h, heats up 47 DEG C, 8.78kg mixed initiators are pumped into the charging rate of 5kg/48h, are warming up to 56 DEG C of constant temperature；Work as pressure When being down to 0.01MPa, seeding polymerization terminates, and obtains seed emulsion；
3. emulsion polymerization：
It is continuously pumped into remaining blended emulsifier, mix monomer and 6.42kg deionized waters simultaneously into seed emulsion, is pumped Angle of incidence 14h, when pressure is down to -0.01MPa, reaction terminates；0.28kg nano hydrotalcites and 0.56kg beta-cyclodextrins is added Two kinds of mixed modified additives open blender, stir 1h, then vacuumize, bottom valve does not open vacuum desorption 1h, and temperature rises to 75 DEG C, 1h is kept, bottom valve is crack, desorption 2h, and 0.3kg potassium hydroxide tune pH value is added extremely in the rear water vapour that 0.1MPa is added 2.2, filtering obtains polyvinylidene chloride copolymer emulsion.
Polyvinylidene emulsions obtained, solid content 49.3%, surface tension 39.8mN/m, viscosity 10.7mPa S, density 1.25g/cm3；With coating weight it is 2.4g/m on BOPP base materials2It is coated, through 100 DEG C of boilings 2 hours, measures water Boil forward and backward OTR oxygen transmission rate be respectively 3.5,11.8ml/ ㎡ for 24 hours, moisture-vapor transmission is respectively 5.9,6.8g/ ㎡ 24h；After coating oil exploitation gel breaker using the lotion, it is 6.5 hours to be resistant to 90 DEG C of boiling times.Through performance verification, originally It remains to keep good barrier property after invention product boiling obtained, applies that extend boiling in oil exploitation gel breaker broken The glue time.
Embodiment 5：
1. the preparation of raw material：
1) mix monomer is prepared：By 30.975kg vinylidene chlorides, the acrylonitrile of 0.3kg, 0.975kg methacrylonitriles, 0.75kg methacrylic acids, 0.225kg methyl methacrylates, 0.225kg butyl methacrylates stir 1.4h, are made 33.45kg monomer mixtures；
2) blended emulsifier is prepared：Neopelex 0.5kg and secondary sodium alkanesulfonate 0.25kg are taken respectively, then Add 5kg deionized waters to be dissolved, then carry out cold dispersion 1.4h, 5.75kg mixing and emulsifying agent solutions are made；
3) mixed initiator is prepared：It is mixed by being stirred in 0.45kg tert-butyl hydroperoxide addition 4.5kg deionized waters Tert-butyl hydroperoxide solution is made in conjunction, then 0.45kg sodium formaldehyde sulphoxylates are added in 4.5kg deionized waters and are carried out It is stirred and sodium formaldehyde sulphoxylate solution is made, two prepared kind solution carries out being mixed and made into 9.9kg mixed initiators again；
2. seeding polymerization：
0.3kg ammonium acetates and 0.3kg frerrous chlorides, produced 3.0kg blended emulsifiers and 15kg deionized waters are added Enter into reaction kettle, seal kettle, lead to nitrogen and replace 2 times, vacuumize, sucking 1.0035kg mix monomers are as seed monomer, cold point 1h is dissipated, heats up 48 DEG C, 9.9kg mixed initiators is pumped into the charging rate of 5kg/48h, are warming up to 57 DEG C of constant temperature；Work as pressure drop When to 0.01MPa, seeding polymerization terminates, and obtains seed emulsion；
3. emulsion polymerization：
It is continuously pumped into remaining blended emulsifier, mix monomer and 8.725kg deionized waters simultaneously into seed emulsion, It is pumped into time 13h, when pressure is down to -0.01MPa, reaction terminates；0.375kg nano hydrotalcites and 0.75kg β-ring paste is added Smart two kinds of mixed modified additives, open blender, stir 1h, then vacuumize, bottom valve does not open vacuum desorption 1h, temperature liter To 75 DEG C, 1h is kept, bottom valve is crack, desorption 2h, and 0.45kg triethylamine tune pH value is added extremely in the rear water vapour that 0.1MPa is added 2.3, filtering obtains polyvinylidene chloride copolymer emulsion.
Polyvinylidene emulsions obtained, solid content 49.7%, surface tension 40.4mN/m, viscosity 11.0mPa S, density 1.26g/cm3；With coating weight it is 2.4g/m on BOPP base materials2It is coated, through 100 DEG C of boilings 2 hours, measures water Boil forward and backward OTR oxygen transmission rate be respectively 3.2,11.9ml/ ㎡ for 24 hours, moisture-vapor transmission is respectively 5.8,6.6g/ ㎡ 24h；After coating oil exploitation gel breaker using the lotion, it is 6 hours to be resistant to 90 DEG C of boiling times.Through performance verification, this hair It remains to keep good barrier property after bright product boiling obtained, applies and extend the broken glue of boiling in oil exploitation gel breaker Time.
Embodiment 6：
1. the preparation of raw material：
1) mix monomer is prepared：By 42.2kg vinylidene chlorides, the acrylonitrile of 0.4kg, 1.2kg methacrylonitriles, 1kg first Base acrylic acid, 0.3kg methyl methacrylates, 0.2kg butyl methacrylates stir 1.5h, and the mixing of 45.3kg monomers is made Object；
2) blended emulsifier is prepared：Neopelex 0.6kg and secondary sodium alkanesulfonate 0.4kg are taken respectively, then Add 6kg deionized waters to be dissolved, then carry out cold dispersion 1.5h, 7kg mixing and emulsifying agent solutions are made；
3) mixed initiator is prepared：0.6kg tert-butyl hydroperoxide is added in 5kg deionized waters and is stirred mixing system At tert-butyl hydroperoxide solution, then 0.6kg sodium formaldehyde sulphoxylates are added in 5kg deionized waters and are stirred mixing Sodium formaldehyde sulphoxylate solution is made, two prepared kind solution carries out being mixed and made into 11.2kg mixed initiators again；
2. seeding polymerization：
0.3kg ammonium acetates and 0.2kg frerrous chlorides, produced 5kg blended emulsifiers and 18kg deionized waters are added Into reaction kettle, kettle is sealed, leads to nitrogen and replaces 2 times, vacuumize, sucking 1.359kg mix monomers are as seed monomer, cold dispersion 1h heats up 50 DEG C, is pumped into 11.2kg mixed initiators with the charging rate of 5kg/48h, is warming up to 58 DEG C of constant temperature；When pressure is down to When 0.03MPa, seeding polymerization terminates, and obtains seed emulsion；
3. emulsion polymerization：
It is continuously pumped into remaining blended emulsifier, mix monomer and 16kg deionized waters simultaneously into seed emulsion, is pumped into Time 11h, when pressure is down to -0.01MPa, reaction terminates；0.5kg nano hydrotalcites are added and two kinds of 1kg beta-cyclodextrins are mixed Modified additive after conjunction opens blender, stirs 1h, then vacuumize, and bottom valve does not open vacuum desorption 1h, and temperature rises to 75 DEG C, 1h is kept, bottom valve is crack, desorption 2h, the rear water vapour that 0.1MPa is added, addition 0.5kg potassium hydroxide tune pH value to 2.4, mistake Filter, obtains polyvinylidene chloride copolymer emulsion.
Polyvinylidene emulsions obtained, solid content 50%, surface tension 40.2mN/m, viscosity 11.3mPas, Density 1.27g/cm3；With coating weight it is 2.4g/m on BOPP base materials2It is coated, through 100 DEG C of boilings 2 hours, measures boiling Forward and backward OTR oxygen transmission rate be respectively 6.0,7.0ml/ ㎡ for 24 hours, moisture-vapor transmission be respectively 5.8,6.9g/ ㎡ for 24 hours； After coating oil exploitation gel breaker using the lotion, it is 6 hours to be resistant to 90 DEG C of boiling times.Through performance verification, system of the present invention Product boiling after remain to keep good barrier property, apply extended in oil exploitation gel breaker boiling break glue when Between.

Claims (6)

1. a kind of water boiling resistance polyvinylidene emulsions, it is characterised in that：By following weight content group lease making seeded emulsion polymerization It is made：Vinylidene chloride 38-42.2%, acrylonitrile 0.4-0.6%, methacrylonitrile 1.2-1.4%, methacrylic acid 1- 1.2%, methyl methacrylate 0.3-0.6%, butyl methacrylate 0.2-0.5%, mixed initiator 1.2-1.4% are mixed Co-emulsifier 1-1.2%, modified additive 1.5-1.8%, ammonium acetate 0.3-0.5%, frerrous chloride 0.2-0.4%, pH adjusting agent 0.5-0.6%, deionized water 50-51.8%；The modified additive is by nano hydrotalcite and beta-cyclodextrin with 1:2 ratios are mixed It closes.
2. water boiling resistance polyvinylidene emulsions according to claim 1, it is characterised in that：The mixed initiator is Tert-butyl hydroperoxide and sodium formaldehyde sulphoxylate are with 1:1 ratio mixes.
3. water boiling resistance polyvinylidene emulsions according to claim 1, it is characterised in that：The blended emulsifier is Neopelex and secondary sodium alkanesulfonate are with 2:1 ratio mixes.
4. water boiling resistance polyvinylidene emulsions according to claim 1, it is characterised in that：The pH adjusting agent is hydrogen Potassium oxide or triethylamine.
5. the preparation method of water boiling resistance polyvinylidene emulsions according to claim 1, using seeded emulsion polymerization, It is characterized in that：
It is as follows：
(1) preparation of raw material：
1) mix monomer is prepared：By 38-42.2% vinylidene chlorides, the acrylonitrile of 0.4-0.6%, 1.2-1.4% metering systems Nitrile, 1-1.2% methacrylic acids, 0.3-0.6% methyl methacrylates, 0.2-0.5% butyl methacrylates stir 1- Monomer mixture is made in 1.5h；
2) blended emulsifier is prepared：According to 2:1 weight ratio takes neopelex and secondary sodium alkanesulfonate respectively, and two Person's total amount is 1-1.2%, then portions of de-ionized water is added to be dissolved, and then carries out cold dispersion 1-1.5h, blended emulsifier is made Solution；
3) mixed initiator is prepared：Tert-butyl hydroperoxide is added in portions of de-ionized water to be stirred and is mixed and made into tertiary butyl Hydrogenperoxide steam generator, then sodium formaldehyde sulphoxylate is added in portions of de-ionized water to be stirred and is mixed and made into formaldehyde conjunction time The adding proportion of sodium bisulfate, tert-butyl hydroperoxide and sodium formaldehyde sulphoxylate is 1:1, the two total amount is 1.2- 1.4%；
(2) seeding polymerization：
By ammonium acetate 0.3-0.5% and frerrous chloride 0.2-0.4%, produced part blended emulsifier and portions of de-ionized water It is added in reaction kettle, seals kettle, lead to nitrogen and replace 2 times, vacuumize, the part mix monomer that sucking accounts for total mix monomer 3% is made For seed monomer, cold dispersion 1h heats up 45-50 DEG C, is pumped into mixed initiator with the charging rate of 5kg/48h, is warming up to 55-58 DEG C constant temperature；When pressure is down to 0.01-0.03MPa, seeding polymerization terminates, and obtains seed emulsion；
(3) emulsion polymerization：
It is continuously pumped into remaining blended emulsifier, mix monomer simultaneously into seed emulsion, 10~15h of time is pumped into, works as pressure When being down to 0~-0.01MPa, reaction terminates；1.5-1.8% modified additives are added, open blender, stir 1-1.2h, then take out true Sky, bottom valve do not open vacuum desorption 1h, and temperature rises to 75 DEG C, keeps 1h, and bottom valve is crack, desorption 2h, the rear water that 0.1MPa is added 0.5-0.6%pH conditioning agent tune pH value is added to 2.5-3 in steam, and filtering obtains polyvinylidene chloride copolymer emulsion.
6. a kind of purposes of water boiling resistance polyvinylidene emulsions according to claim 1, it is characterised in that：It can be used for resistance to In boiling high-barrier packaging, it is also applicable to oil exploitation gel breaker peel material.
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CN102924643A (en) * 2012-10-29 2013-02-13 浙江巨化股份有限公司电化厂 Preparation method of steaming-resisting and boiling-resisting poly(vinylidene chloride) (PVDC) waterborne emulsion
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