CN106432576A - Polyvinylidene chloride emulsion used as gel breaker capsule coating material and preparation method thereof - Google Patents
Polyvinylidene chloride emulsion used as gel breaker capsule coating material and preparation method thereof Download PDFInfo
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- 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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- C09K8/00—Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
- C09K8/60—Compositions for stimulating production by acting on the underground formation
- C09K8/62—Compositions for forming crevices or fractures
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- C09K8/00—Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
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- 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
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Abstract
The invention relates to a polyvinylidene chloride emulsion used as a gel breaker capsule coating material. The polyvinylidene chloride emulsion is prepared by polymerizing the following components in percentage by weight with a seed emulsion: 34.4-41% of vinylidene chloride, 0.4-0.6% of vinyl cyanide, 1.2-1.5% of methacrylonitrile, 0.8-1.4% of methacrylic acid, 0.3-0.7% of methyl methacrylate, 0.2-0.5% of butyl methacrylate, 0.9-1.5% of mixed initiators, 0.9-1.2% of mixed emulsifiers, 1.3-1.5% of nano modification additives, 0.2-0.4% of ammonium acetate, 0.3-0.5% of ferrous chloride, 0.5-0.8% of a pH regulator and 52-55% of deionized water. The emulsion has high barrier performance and has high boiling resistance; the boiling resistant time in the environment at the temperature of 90 DEG C can last for 8 hours; the emulsion is applicable to boiling-resistant barrier packaging and is especially applicable to coating of gel breakers for oil exploitation; the slow release time can be effectively prolonged.
Description
Technical field
The present invention provides a kind of gel breaker peel material polyvinylidene emulsions and preparation method thereof, belongs to macromolecule material
Material field.
Background technology
During oil exploitation, generally wear pressure principle using liquid and aqueous fracturing fluid is injected oil reservoir, so that oil reservoir is forced out
One or several level or vertical crack, thus accelerate crude oil from flow in fracture to oil well in carry out subsequent extracted.And water
Base fracturing fluid is the fracturing fluid being made into water as solvent or decentralized medium, is broadly divided into viscous water fracturing fluid, aqueous gel pressure break
This is several for liquid, oil-in-water fracturing fluid, water-base foam fracturing fluid.Wherein, viscous water fracturing fluid, thickening agent will be dissolved in water and is made into,
Because viscosity ratio water is high, be conducive to taking sand and reduce leak-off, and during flow at high speed, the low advantage of frictional ratio water, application at present is more
Extensively.After gelled waterfrac fluid viscosity is higher, and solid-carrying performance is stronger, and the success rate of construction is higher, but construction terminates, high viscous pressure break
Liquid must thoroughly break glue using capsule breaker as early as possible and return row, to reduce the injury to reservoir.Therefore, capsule breaker concentration must
Must be sufficiently large, the compound of birdsing of the same feather flock together of the guar gum in fracturing fluid just can be made to break glue completely, can reduce the injury to stratum, improve oil well and produce
Amount.But common gel breaker dissolves in a liquid, with fluid loss leak-off in stratum it is impossible to effectively break glue, and broken glue speed
Rate is too fast should not to be controlled, and cause fracturing fluid viscosity premature loss in construction, ultimately result in and sand fallout, sand plug in pressing crack construction,
Lead to construct unsuccessfully when serious.Therefore, the early stage viscosity reduction for solving fracturing fluid breaks the difficult contradiction of glue with the later stage, needs one kind to prolong
Slow gel breaker, using spraying coating process in one layer of coating of ammonium persulfate Surface coating, this coating has shielding action simultaneously to gel breaker
Can rupture under certain condition, discharge gel breaker, thus reaching the purpose delaying brokenly glue.
In trial, using polyvinylidene emulsions, to gel breaker, (main component is persulfuric acid for current gel breaker manufacturer
Ammonium, potassium peroxydisulfate etc.) coated, the gel breaker after cladding can boil (oil exploitation environment) by resistance to 90 DEG C of water within the engineering time,
After construction terminates, clad iris action fades away, and broken glue composition is slowly discharged.Therefore, the water boiling resistance time is more long, breaks
Jelly slow-release time is extended, and is more conducive to the use of capsule breaker during oil exploitation.But existing cladding gel breaker
Product is only resistant to 90 DEG C of water and boils 2 hours of environment, limits the oil exploitation engineering time it is impossible to obtain large-scale application.
Content of the invention
Can not meet as water boiling resistance demand during gel breaker peel material for current polyvinylidene emulsions, this
Invention offer is a kind of can be up to 8 hours polyvinylidene emulsions and preparation method thereof by 90 DEG C of environment of water boiling resistance, the broken glue of cladding
Effectively slow-release time can be extended after agent, widen oil exploitation application.
Its innovative point is：(1) pass through to adjust compatibility monomer component and content can improve the resistance of polyvinylidene emulsions
Separating performance；(2) (nano hydrotalcite and nano titanium oxide are according to 4 to pass through to add nano modification auxiliary agent:3 ratio mixing) to emulsion
It is modified, modified rear stability increases, improve water boiling resistance performance, such as modified or separately through receiving separately through nano hydrotalcite
Rice is titania modified, and its stabilizing effect is all good not as the two mixed effect, is specifically shown in Table 3；(3) improve breast
Liquid preparing process, further such that the emulsion barriering effect being obtained and water boiling resistance effect strengthen.
It is an object of the present invention to provide a kind of gel breaker peel material polyvinylidene emulsions, it is by following weight
Content groups lease making seeded emulsion polymerization is obtained：
Vinylidene chloride 34.4-41%, acrylonitrile 0.4-0.6%, methacrylonitrile 1.2-1.5%, methacrylic acid
0.8-1.4%, methyl methacrylate 0.3-0.7%, butyl methacrylate 0.2-0.5%, mixed initiator 0.9-
1.5%, blended emulsifier 0.9-1.2%, nano modification auxiliary agent 1.3-1.5%, ammonium acetate 0.2-0.4%, frerrous chloride 0.3-
0.5%, pH adjusting agent 0.5-0.8%, deionized water 52-55%.
Described mixed initiator is TBHP and sodium formaldehyde sulphoxylate with 1:1 ratio mixing；
Described blended emulsifier is neopelex and secondary sodium alkanesulfonate with 2:1 ratio mixing；
Described nano modification auxiliary agent is with 4 by nano hydrotalcite and nano titanium oxide:3 ratio mixing；
Described pH adjusting agent is potassium hydroxide or triethylamine.
It is a further object to provide a kind of preparation method of gel breaker peel material polyvinylidene emulsions,
This preparation method adopts seeded emulsion polymerization, and it comprises the following steps that：
1. the preparation of raw material：
1) mix monomer is prepared：By 34.4-41% vinylidene chloride, the acrylonitrile of 0.4-0.6%, 1.2-1.5% methyl
Acrylonitrile, 0.8-1.4% methacrylic acid, 0.3-0.7% methyl methacrylate, 0.2-0.5% butyl methacrylate, stir
Mix 1-1.5h, make monomer mixture；
2) blended emulsifier is prepared：According to 2:1 part by weight takes neopelex and secondary chain alkyl sulfonic acid respectively
Sodium, the two total amount be 0.9-1.2%, then plus portions of de-ionized water dissolved, then carry out cold dispersion 1-1.5h, make mixing
Emulsifier solution；
3) mixed initiator is prepared：TBHP is added in portions of de-ionized water and is stirred being mixed and made into uncle
Butyl peroxy hydrogen solution, then sodium formaldehyde sulphoxylate is added in portions of de-ionized water is stirred being mixed and made into formaldehyde
Close bisulphite sodium solution, the adding proportion of TBHP and sodium formaldehyde sulphoxylate is 1:1, the two total amount is
0.9-1.5%；
2. seeding polymerization：
By ammonium acetate 0.2-0.4% and frerrous chloride 0.3-0.5%, produced part blended emulsifier and part go from
Sub- water is added in reactor, seals kettle, logical nitrogen displacement 2 times, vacuumizes, suck account for total mix monomer 3% part mixing single
Body as seed monomer, cold dispersion 1h, 45-50 DEG C of intensification, mixed initiator is pumped into 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 in seed emulsion simultaneously, pump into time 10～15h, when
When pressure is down to 0～-0.01MPa, reaction terminates；Add 1.3-1.5% nano modification auxiliary agent, open mixer, stir 1-
1.2h, then vacuumize, vacuum desorption 1h do not opened by bottom valve, and temperature rises to 75 DEG C, keeps 1h, and bottom valve is crack, and desorption 2h adds afterwards
The water vapour of 0.1MPa, adds 0.5-0.8%pH conditioning agent to adjust pH value to 2.5-3, filters, obtain polyvinylidene chloride copolymerization breast
Liquid.
Table 1 present invention is obtained the traditional performance of polyvinylidene chloride
| Polyvinylidene emulsions performance indications of the present invention | Method of testing or standard | |
| Solid content (%) | 48.5-50.8 | GB1725-79 |
| Surface tension (mN/m) | ≤41 | GB1725-79 |
| Viscosity (mPa s) | ≤12 | U.S.'s BROOKFIELD viscosimeter |
| PH value | 2.5-3 | PHS-3C precision pH meter |
| Density (g/cm3) | 1.24-1.26 | Density Measuring Instrument |
The traditional performance that the present invention is obtained polyvinylidene emulsions is shown in Table 1.And water resistance to contrast in terms of two, first
Referring initially to GB/T10004-1998, as saturating in coating shedding situation, oxygen before and after being boiled by the coating film water that test is formed by emulsion
The change of the performances such as excess, water vapour transit dose, to characterize the water boiling resistance of emulsion；In addition, when being applied to oil exploitation, bag
After covering gel breaker, under the conditions of 90 DEG C of water boil, the broken glue time characterizes water boiling resistance.Therefore, test the present invention be obtained poly- inclined two
Vinyl chloride emulsion and conventional polyvinylidene emulsions specific performance, and accordingly contrast, the results are shown in Table 2.
Table 2 present invention is obtained polyvinylidene emulsions and conventional polyvinylidene emulsions water boiling resistance performance comparison
Remarks：The preparation of conventional polyvinylidene emulsions is with reference to patent application 201210572049.5.
Before and after table 3 nano modification, different polyvinylidene emulsions is typically referred to as scale value contrast
Remarks：In polyvinylidene emulsions A compared with polyvinylidene emulsions of the present invention, remove only nano-silica
Change titanium component, remaining component and content, production technology all same；Gather inclined two chloroethenes with the present invention in polyvinylidene emulsions B
Alkene emulsion is compared, and remove only nano hydrotalcite component, remaining component and content, production technology all same；Polyvinylidene chloride
In emulsion C compared with polyvinylidene emulsions of the present invention, only eliminate nano hydrotalcite and nanometer titanium dioxide titanium component simultaneously,
Remaining component and content, production technology all same；When coating shedding situation, oxygen transit dose, water vapour permeability, water boil brokenly glue
Between testing standard or method identical with table 2.
Contrasted from table 2, polyvinylidene emulsions are obtained using the present invention, after BOPP base material is coated with and through 90
DEG C water boils 8 hours, and more conventional polyvinylidene emulsions are compared, and water boils before and after's coating and all do not fall off, and barriering effect has carried
Height, barrier property does not decline to a great extent；After cladding oil exploitation gel breaker, outward appearance is good, using conventional polyvinylidene chloride
Cladding gel breaker, starts to occur crack after 90 DEG C of water boil 2 hours, and water boiling resistance breaks the glue time only 2 hours, and system of the present invention
Crack after 90 DEG C of water boil 8 hours not yet in the gel breaker obtaining polyvinylidene chloride cladding, but is further continued for water and boils, and crack is gradually
Occur, you can water boiling resistance broke the glue time up to 8 hours, effectively extended the broken glue time of gel breaker.
In addition, being contrasted by table 3, change separately through nano hydrotalcite modification with separately through nano titanium oxide
Property, the water boiling resistance performance after the barrier property of the polyvinylidene chloride obtaining, cladding gel breaker is all passed through the two than the present invention and is closed
The polyvinylidene emulsions performance of reason mixture post-modification is weak.In addition, individually adding nano hydrotalcite or independent interpolation nanometer two
Titanium oxide all increases than the polyvinylidene emulsions barrier property and water boiling resistance performance not passing through nano modification.Nanometer changes
It is favorably improved barrier property and the water boiling resistance performance of polyvinylidene emulsions after property.
Summary contrasts, and the present invention is obtained the more conventional product of polyvinylidene chloride to be had compared with much progress, barrier property and resistance to
Water boils performance raising and essentially consists in nano modification means, and the modified effect after two kinds of nano material rational mixtures is much higher than one
Plant the modification of nano material.The present invention is obtained polyvinylidene emulsions and can be used for, in water boiling resistance barrier package, being particularly suited for
Oil exploitation gel breaker peel material.
Specific embodiment
Embodiment 1：
1. the preparation of raw material：
1) mix monomer is prepared：By 5.16kg vinylidene chloride, the acrylonitrile of 0.09kg, 0.225kg methacrylonitrile,
0.21kg methacrylic acid, 0.105kg methyl methacrylate, 0.075kg butyl methacrylate, stir 1h, make
5.865kg monomer mixture；
2) blended emulsifier is prepared：Take neopelex 0.12kg and secondary sodium alkanesulfonate 0.06kg respectively,
Again plus 1kg deionized water is dissolved, then carry out cold dispersion 1h, make 1.18kg mixing and emulsifying agent solution；
3) mixed initiator is prepared：0.1125kg TBHP is added in 1kg deionized water and is stirred mixing
TBHP solution is made in conjunction, then 0.1125kg sodium formaldehyde sulphoxylate is added in 1kg deionized water carries out
Stirring is mixed and made into sodium formaldehyde sulphoxylate solution, and two preparing kind solution carries out being mixed and made into 2.225kg mixing initiation again
Agent；
2. seeding polymerization：
By 0.06kg ammonium acetate and 0.075kg frerrous chloride, produced 0.8kg blended emulsifier and 3kg deionized water
It is added in reactor, seals kettle, logical nitrogen displacement 2 times, vacuumize, suck 0.176kg mix monomer as seed monomer, cold point
Scattered 1h, heats up 45 DEG C, pumps into 2.225kg mixed initiator with the charging rate of 5kg/48h, be 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 in seed emulsion simultaneously, and 2.25kg deionized water, pump
Angle of incidence 15h, when pressure is down to -0.01MPa, reaction terminates；Add 0.129kg nano hydrotalcite and 0.096kg nanometer two
Two kinds of mixed modified additives of titanium oxide, open mixer, stir 1h, then vacuumize, vacuum desorption 1h do not opened by bottom valve, temperature
Degree rises to 75 DEG C, keeps 1h, and bottom valve is crack, desorption 2h, adds the water vapour of 0.1MPa afterwards, adds 0.12kg potassium hydroxide to adjust pH
It is worth to 2.9, filter, obtain polyvinylidene chloride copolymer emulsion.
Prepared polyvinylidene emulsions, solid content is 45%, surface tension 41mN/m, viscosity 12mPa s, density
1.24g/cm3；With coating weight as 2.4g/m on BOPP base material2Be coated, boil 8 hours through 90 DEG C of water, record water boil forward and backward
OTR oxygen transmission rate be respectively 2.8,19.5ml/ 24h, moisture-vapor transmission be respectively 5,5.5g/ 24h；Using this
After emulsion cladding oil exploitation gel breaker, can it be 8 hours the water boiling resistance time.Through performance verification, the product water that the present invention is obtained
Remain to keep good barrier property after boiling, apply and extend water in oil exploitation gel breaker and boil brokenly the glue time.
Embodiment 2：
1. the preparation of raw material：
1) mix monomer is prepared：By 10.74kg vinylidene chloride, the acrylonitrile of 0.15kg, 0.42kg methacrylonitrile,
0.36kg methacrylic acid, 0.18kg methyl methacrylate, 0.12kg butyl methacrylate, stir 1.1h, make
11.97kg monomer mixture；
2) blended emulsifier is prepared：Take neopelex 0.22kg and secondary sodium alkanesulfonate 0.11kg respectively,
Again plus 1.5kg deionized water is dissolved, then carry out cold dispersion 1.2h, make 1.53kg mixing and emulsifying agent solution；
3) mixed initiator is prepared：0.195kg TBHP is added in 1.5kg deionized water and is stirred mixing
TBHP solution is made in conjunction, then 0.195kg sodium formaldehyde sulphoxylate is added in 1.5kg deionized water carries out
Stirring is mixed and made into sodium formaldehyde sulphoxylate solution, and two preparing kind solution carries out being mixed and made into 3.39kg mixing initiation again
Agent；
2. seeding polymerization：
0.09kg ammonium acetate and 0.12kg frerrous chloride, produced 1.0kg blended emulsifier and 8kg deionized water are added
Enter in reactor, seal kettle, logical nitrogen displacement 2 times, vacuumize, suck 0.176kg mix monomer as seed monomer, cold dispersion
1h, heats up 46 DEG C, pumps into 3.39kg mixed initiator with the charging rate of 5kg/48h, be warming up to 57 DEG C of constant temperature；When pressure is down to
During 0.02MPa, seeding polymerization terminates, and obtains seed emulsion；
3. emulsion polymerization：
It is continuously pumped into remaining blended emulsifier, mix monomer, mixed initiator, and 3.97kg in seed emulsion simultaneously
Deionized water, pumps into time 10h, and when pressure is down to 0MPa, reaction terminates；Add 0.129kg nano hydrotalcite and 0.096kg
Two kinds of mixed modified additives of nano titanium oxide, open mixer, stir 1h, then vacuumize, and bottom valve is not opened vacuum and taken off
Inhale 1h, temperature rises to 75 DEG C, keep 1h, bottom valve is crack, desorption 2h, add the water vapour of 0.1MPa afterwards, add 0.21kg tri- second
Amine adjusts pH value to 3, filters, obtains polyvinylidene chloride copolymer emulsion.
Prepared polyvinylidene emulsions, solid content is 45.1%, surface tension 40mN/m, and viscosity 11mPa s is close
Degree 1.25g/cm3；With coating weight as 2.4g/m on BOPP base material2Be coated, boil 8 hours through 90 DEG C of water, record water boil before,
OTR oxygen transmission rate afterwards is respectively 3,20ml/ 24h, and moisture-vapor transmission is respectively 4.8,5.2g/ 24h；Using this
After emulsion cladding oil exploitation gel breaker, can it be 8 hours the water boiling resistance time.Through performance verification, the product water that the present invention is obtained
Remain to keep good barrier property after boiling, apply and extend water in oil exploitation gel breaker and boil brokenly the glue time.
Embodiment 3：
1. the preparation of raw material：
1) mix monomer is prepared：By 18.85kg vinylidene chloride, the acrylonitrile of 0.2kg, 0.65kg methacrylonitrile,
0.55kg methacrylic acid, 0.25kg methyl methacrylate, 0.15kg butyl methacrylate, stir 1h, make 20.65kg
Monomer mixture；
2) blended emulsifier is prepared：Take neopelex 0.33kg and secondary sodium alkanesulfonate 0.17kg respectively,
Again plus 3kg deionized water is dissolved, then carry out cold dispersion 1.3h, make 3.5kg mixing and emulsifying agent solution；
3) mixed initiator is prepared：0.35kg TBHP is added and is stirred in 3kg deionized water mixing
Make TBHP solution, then 0.35kg sodium formaldehyde sulphoxylate is added in 3kg deionized water is stirred
It is mixed and made into sodium formaldehyde sulphoxylate solution, two preparing kind solution carries out being mixed and made into 6.7kg mixed initiator again；
2. seeding polymerization：
0.1kg ammonium acetate and 0.15kg frerrous chloride, produced 1.8kg blended emulsifier and 10kg deionized water are added
Enter in reactor, seal kettle, logical nitrogen displacement 2 times, vacuumize, suck 0.6195kg mix monomer as seed monomer, cold point
Scattered 1h, heats up 48 DEG C, pumps into 6.7kg mixed initiator with the charging rate of 5kg/48h, be warming up to 57 DEG C of constant temperature；Work as pressure drop
During to 0.03MPa, seeding polymerization terminates, and obtains seed emulsion；
3. emulsion polymerization：
It is continuously pumped into remaining blended emulsifier, mix monomer in seed emulsion simultaneously, and 7.95kg deionized water, pump
Angle of incidence 12h, when pressure is down to -0.01MPa, reaction terminates；Add 0.372kg nano hydrotalcite and 0.278kg nanometer two
Two kinds of mixed modified additives of titanium oxide, open mixer, stir 1h, then vacuumize, vacuum desorption 1h do not opened by bottom valve, temperature
Degree rises to 75 DEG C, keeps 1h, and bottom valve is crack, desorption 2h, adds the water vapour of 0.1MPa afterwards, adds 0.3kg potassium hydroxide to adjust pH
It is worth to 2.63, filter, obtain polyvinylidene chloride copolymer emulsion.
Prepared polyvinylidene emulsions, solid content is 46.1%, surface tension 41mN/m, and viscosity 10mPa s is close
Degree 1.24g/cm3；With coating weight as 2.4g/m on BOPP base material2Be coated, boil 8 hours through 90 DEG C of water, record water boil before,
OTR oxygen transmission rate afterwards is respectively 2.5,18ml/ 24h, and moisture-vapor transmission is respectively 4.6,5.4g/ 24h；Use
After this emulsion cladding oil exploitation gel breaker, can it be 8 hours the water boiling resistance time.Through performance verification, the product that the present invention is obtained
Water remains to keep good barrier property after boiling, and applies and extends water in oil exploitation gel breaker and boil brokenly the glue time.
Embodiment 4：
1. the preparation of raw material：
1) mix monomer is prepared：By 22.86kg vinylidene chloride, the acrylonitrile of 0.36kg, 0.84kg methacrylonitrile,
0.6kg methacrylic acid, 0.24kg methyl methacrylate, 0.24kg butyl methacrylate, stir 1.3h, make
25.14kg monomer mixture；
2) blended emulsifier is prepared：Take neopelex 0.36kg and secondary sodium alkanesulfonate 0.18kg respectively,
Again plus 4kg deionized water is dissolved, then carry out cold dispersion 1.5h, make 4.54kg mixing and emulsifying agent solution；
3) mixed initiator is prepared：0.33kg TBHP is added and is stirred in 4kg deionized water mixing
Make TBHP solution, then 0.33kg sodium formaldehyde sulphoxylate is added in 4kg deionized water is stirred
It is mixed and made into sodium formaldehyde sulphoxylate solution, two preparing kind solution carries out being mixed and made into 8.66kg mixed initiator again；
2. seeding polymerization：
By 0.18kg ammonium acetate and 0.24kg frerrous chloride, produced 2.0kg blended emulsifier and 10kg deionized water
It is added in reactor, seals kettle, logical nitrogen displacement 2 times, vacuumize, suck 0.7542kg mix monomer as seed monomer, cold
Dispersion 1h, heats up 47 DEG C, pumps into 8.66kg mixed initiator with the charging rate of 5kg/48h, be 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 in seed emulsion simultaneously, and 9.98kg deionized water, pump
Angle of incidence 13h, when pressure is down to 0MPa, reaction terminates；Add 0.48kg nano hydrotalcite and 0.36kg nano titanium oxide
Two kinds of mixed modified additives, open mixer, stir 1h, then vacuumize, vacuum desorption 1h do not opened by bottom valve, and temperature rises to
75 DEG C, keep 1h, bottom valve is crack, desorption 2h, afterwards the water vapour of addition 0.1MPa, addition 0.42kg triethylamine tune pH value to 2.8,
Filter, obtain polyvinylidene chloride copolymer emulsion.
Prepared polyvinylidene emulsions, solid content is 46.7%, surface tension 39mN/m, and viscosity 12mPa s is close
Degree 1.26g/cm3；With coating weight as 2.4g/m on BOPP base material2Be coated, boil 8 hours through 90 DEG C of water, record water boil before,
OTR oxygen transmission rate afterwards is respectively 2.7,15ml/ 24h, and moisture-vapor transmission is respectively 4.5,5g/ 24h；Using this
After emulsion cladding oil exploitation gel breaker, can it be 8 hours the water boiling resistance time.Through performance verification, the product water that the present invention is obtained
Remain to keep good barrier property after boiling, apply and extend water in oil exploitation gel breaker and boil brokenly the glue time.
Embodiment 5：
1. the preparation of raw material：
1) mix monomer is prepared：By 29.475kg vinylidene chloride, the acrylonitrile of 0.375kg, 0.975kg metering system
Nitrile, 0.675kg methacrylic acid, 0.3kg methyl methacrylate, 0.225kg butyl methacrylate, stir 1.4h, make
32.025kg monomer mixture；
2) blended emulsifier is prepared：Take neopelex 0.5kg and secondary sodium alkanesulfonate 0.25kg respectively, then
Plus 5kg deionized water is dissolved, then carry out cold dispersion 1.4h, make 5.75kg mixing and emulsifying agent solution；
3) mixed initiator is prepared：0.45kg TBHP is added in 4.5kg deionized water and is stirred mixing
TBHP solution is made in conjunction, then 0.45kg sodium formaldehyde sulphoxylate is added in 4.5kg deionized water carries out
Stirring is mixed and made into sodium formaldehyde sulphoxylate solution, and two preparing kind solution carries out being mixed and made into 9.9kg mixed initiator again；
2. seeding polymerization：
By 0.3kg ammonium acetate and 0.375kg frerrous chloride, produced 3.0kg blended emulsifier and 10kg deionized water
It is added in reactor, seals kettle, logical nitrogen displacement 2 times, vacuumize, suck 0.961kg mix monomer as seed monomer, cold point
Scattered 1h, heats up 48 DEG C, pumps into 9.9kg mixed initiator with the charging rate of 5kg/48h, be warming up to 57 DEG C of constant temperature；Work as pressure drop
During to 0.01MPa, seeding polymerization terminates, and obtains seed emulsion；
3. emulsion polymerization：
It is continuously pumped into remaining blended emulsifier, mix monomer in seed emulsion simultaneously, and 15.075kg deionized water,
Pump into time 14h, when pressure is down to -0.01MPa, reaction terminates；Add 0.643kg nano hydrotalcite and 0.482kg nanometer
Two kinds of mixed modified additives of titanium dioxide, open mixer, stir 1h, then vacuumize, vacuum desorption 1h do not opened by bottom valve,
Temperature rises to 75 DEG C, keeps 1h, and bottom valve is crack, desorption 2h, adds the water vapour of 0.1MPa afterwards, adds 0.45kg potassium hydroxide to adjust
PH value, to 3, filters, obtains polyvinylidene chloride copolymer emulsion.
Prepared polyvinylidene emulsions, solid content is 47.9%, surface tension 41mN/m, and viscosity 11mPa s is close
Degree 1.25g/cm3；With coating weight as 2.4g/m on BOPP base material2Be coated, boil 8 hours through 90 DEG C of water, record water boil before,
OTR oxygen transmission rate afterwards is respectively 2.2,13.5ml/ 24h, and moisture-vapor transmission is respectively 5,5.3g/ 24h；Use
After this emulsion cladding oil exploitation gel breaker, can it be 8 hours the water boiling resistance time.Through performance verification, the product that the present invention is obtained
Water remains to keep good barrier property after boiling, and applies and extends water in oil exploitation gel breaker and boil brokenly the glue time.
Embodiment 6：
1. the preparation of raw material：
1) mix monomer is prepared：By 41kg vinylidene chloride, the acrylonitrile of 0.4kg, 1.2kg methacrylonitrile, 0.8kg first
Base acrylic acid, 0.3kg methyl methacrylate, 0.2kg butyl methacrylate, stir 1.5h, make the mixing of 43.9kg monomer
Thing；
2) blended emulsifier is prepared：Take neopelex 0.6kg and secondary sodium alkanesulfonate 0.3kg respectively, then
Plus 6kg deionized water is dissolved, then carry out cold dispersion 1.5h, make 6.9kg mixing and emulsifying agent solution；
3) mixed initiator is prepared：0.45kg TBHP is added and is stirred in 5kg deionized water mixing
Make TBHP solution, then 0.45kg sodium formaldehyde sulphoxylate is added in 5kg deionized water is stirred
It is mixed and made into sodium formaldehyde sulphoxylate solution, two preparing kind solution carries out being mixed and made into 10.9kg mixed initiator again；
2. seeding polymerization：
0.2kg ammonium acetate and 0.3kg frerrous chloride, produced 4.9kg blended emulsifier and 12kg deionized water are added
Enter in reactor, seal kettle, logical nitrogen displacement 2 times, vacuumize, suck 1.317kg mix monomer as seed monomer, cold dispersion
1h, heats up 50 DEG C, pumps into 10.9kg mixed initiator with the charging rate of 5kg/48h, be warming up to 58 DEG C of constant temperature；When pressure is down to
During 0.03MPa, seeding polymerization terminates, and obtains seed emulsion；
3. emulsion polymerization：
It is continuously pumped into remaining blended emulsifier, mix monomer in seed emulsion simultaneously, and 24kg deionized water, pump into
Time 15h, when pressure is down to 0MPa, reaction terminates；Add 0.743kg nano hydrotalcite and 0.557kg nano titanium oxide
Two kinds of mixed modified additives, open mixer, stir 1h, then vacuumize, vacuum desorption 1h do not opened by bottom valve, and temperature rises to
75 DEG C, keep 1h, bottom valve is crack, desorption 2h, afterwards the water vapour of addition 0.1MPa, addition 0.5kg triethylamine tune pH value to 2.5,
Filter, obtain polyvinylidene chloride copolymer emulsion.
Prepared polyvinylidene emulsions, solid content is 48%, surface tension 39mN/m, viscosity 10mPa s, density
1.26g/cm3；With coating weight as 2.4g/m on BOPP base material2Be coated, boil 8 hours through 90 DEG C of water, record water boil forward and backward
OTR oxygen transmission rate be respectively 2.6,18ml/ 24h, moisture-vapor transmission be respectively 4.9,5.4g/ 24h；Using this
After emulsion cladding oil exploitation gel breaker, can it be 8 hours the water boiling resistance time.Through performance verification, the product water that the present invention is obtained
Remain to keep good barrier property after boiling, apply and extend water in oil exploitation gel breaker and boil brokenly the glue time.
Claims (7)
1. a kind of gel breaker peel material polyvinylidene emulsions it is characterised in that：By following weight content group lease making seed
Emulsion polymerization is obtained：Vinylidene chloride 34.4-41%, acrylonitrile 0.4-0.6%, methacrylonitrile 1.2-1.5%, metering system
0.8-1.4%, methyl methacrylate 0.3-0.7%, butyl methacrylate 0.2-0.5%, mixed initiator 0.9-
1.5%, blended emulsifier 0.9-1.2%, nano modification auxiliary agent 1.3-1.5%, ammonium acetate 0.2-0.4%, frerrous chloride 0.3-
0.5%, pH adjusting agent 0.5-0.8%, deionized water 52-55%.
2. a kind of gel breaker peel material polyvinylidene emulsions according to claim 1 it is characterised in that：Described
Mixed initiator is TBHP and sodium formaldehyde sulphoxylate with 1:1 ratio mixing.
3. a kind of gel breaker peel material polyvinylidene emulsions according to claim 1 it is characterised in that：Described
Blended emulsifier is neopelex and secondary sodium alkanesulfonate with 2:1 ratio mixing.
4. a kind of gel breaker peel material polyvinylidene emulsions according to claim 1 it is characterised in that：Described
Nano modification auxiliary agent is with 4 by nano hydrotalcite and nano titanium oxide:3 ratio mixing.
5. a kind of gel breaker peel material polyvinylidene emulsions according to claim 1 it is characterised in that：Described
PH adjusting agent is potassium hydroxide or triethylamine.
6. the preparation method of a kind of gel breaker peel material polyvinylidene emulsions according to claim 1, using kind
Sub- emulsion polymerization is it is characterised in that comprise the following steps that：
(1) preparation of raw material：
1) mix monomer is prepared：By 34.4-41% vinylidene chloride, the acrylonitrile of 0.4-0.6%, 1.2-1.5% metering system
Nitrile, 0.8-1.4% methacrylic acid, 0.3-0.7% methyl methacrylate, 0.2-0.5% butyl methacrylate, stir 1-
1.5h, makes monomer mixture；
2) blended emulsifier is prepared：According to 2:1 part by weight takes neopelex and secondary sodium alkanesulfonate respectively, and two
Person's total amount be 0.9-1.2%, then plus portions of de-ionized water dissolved, then carry out cold dispersion 1-1.5h, make mixing and emulsifying
Agent solution；
3) mixed initiator is prepared：TBHP is added in portions of de-ionized water and is stirred being mixed and made into the tert-butyl group
Hydrogenperoxide steam generator, then sodium formaldehyde sulphoxylate is added in portions of de-ionized water is stirred being mixed formaldehyde and closes time
The adding proportion of sodium bisulfate, TBHP and sodium formaldehyde sulphoxylate is 1:1, the two total amount is 0.9-
1.5%；
(2) seeding polymerization：
By ammonium acetate 0.2-0.4% and frerrous chloride 0.3-0.5%, produced part blended emulsifier and portions of de-ionized water
It is added in reactor, seals kettle, logical nitrogen displacement 2 times, vacuumize, suck and account for the part mix monomer of total mix monomer 3% and make
For seed monomer, cold dispersion 1h, 45-50 DEG C of intensification, mixed initiator is pumped into 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 in seed emulsion simultaneously, pump into time 10～15h, work as pressure
When being down to 0～-0.01MPa, reaction terminates；Add 1.3-1.5% nano modification auxiliary agent, open mixer, stir 1-1.2h, then
Vacuumize, vacuum desorption 1h do not opened by bottom valve, temperature rises to 75 DEG C, keep 1h, bottom valve is crack, desorption 2h, add 0.1MPa afterwards
Water vapour, add 0.5-0.8%pH conditioning agent to adjust pH value to 2.5-3, filter, obtain polyvinylidene chloride copolymer emulsion.
7. a kind of gel breaker peel material polyvinylidene emulsions according to claim 1 purposes it is characterised in that：
Can be used for water boiling resistance barrier package coating, also can be used for oil exploitation gel breaker peel material.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN107699211A (en) * | 2017-09-27 | 2018-02-16 | 南通瑞普埃尔生物工程有限公司 | Oil recovery auxiliary agent is sustained emulsion and preparation method thereof with vinylidene chloride |
| CN111961450A (en) * | 2019-05-20 | 2020-11-20 | 中国石油天然气股份有限公司 | Capsule gel breaker and preparation method thereof |
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| CN102936309A (en) * | 2012-10-29 | 2013-02-20 | 浙江巨化股份有限公司电化厂 | Boiling-resistant PVDC (polyvinyl dichloride) water-based emulsion |
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| CN102850866A (en) * | 2012-08-31 | 2013-01-02 | 海南必凯水性涂料有限公司 | High oxygen resistance polyvinylidenechloride emulsion for coating, and preparation method thereof |
| 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 |
| CN102936309A (en) * | 2012-10-29 | 2013-02-20 | 浙江巨化股份有限公司电化厂 | Boiling-resistant PVDC (polyvinyl dichloride) water-based emulsion |
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| CN111961450A (en) * | 2019-05-20 | 2020-11-20 | 中国石油天然气股份有限公司 | Capsule gel breaker and preparation method thereof |
| CN111961450B (en) * | 2019-05-20 | 2022-08-05 | 中国石油天然气股份有限公司 | Capsule gel breaker and preparation method thereof |
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