CN109575248A - Controlled degradation terpolymer diverting agent, preparation method and application method - Google Patents
Controlled degradation terpolymer diverting agent, preparation method and application method Download PDFInfo
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- CN109575248A CN109575248A CN201811429543.XA CN201811429543A CN109575248A CN 109575248 A CN109575248 A CN 109575248A CN 201811429543 A CN201811429543 A CN 201811429543A CN 109575248 A CN109575248 A CN 109575248A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
- C08G63/06—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from hydroxycarboxylic acids
- C08G63/08—Lactones or lactides
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
- C08G63/06—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from hydroxycarboxylic acids
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/64—Polyesters containing both carboxylic ester groups and carbonate groups
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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
- C09K8/50—Compositions for plastering borehole walls, i.e. compositions for temporary consolidation of borehole walls
- C09K8/504—Compositions based on water or polar solvents
- C09K8/506—Compositions based on water or polar solvents containing organic compounds
- C09K8/508—Compositions based on water or polar solvents containing organic compounds macromolecular compounds
- C09K8/5086—Compositions based on water or polar solvents containing organic compounds macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
Abstract
The invention discloses a kind of controlled degradation terpolymer diverting agents, it includes as three kinds of monomers any in caprolactone, lactide, glycolide, poly (propylene carbonate) dihydric alcohol by terpolymer made of the copolymerization of any molar ratio, the copolymer passes sequentially through heating melting reaction monomers, catalyst or catalyst is added and initiator causes copolyreaction, repeats that precipitating-dissolution purification copolymerization product, being broken for, there is the component of different-grain diameter to prepare in proportion obtains；It is realized when use by additional crystalline fracture agent and/or degradation of promoter and further adjusts degradation time；The controlled degradation terpolymer diverting agent have nontoxic, pressure-bearing pressure it is strong, in aqueous environments 100% it is degradable, degradable after without residue, the characteristics of to reservoir fanout free region；Under 80~150 DEG C of well temperature, the degradable time is adjustable between 0.5h~60d；And the preparation method of the diverting agent and the application method of adjusting degradation time are simple, easy, have good market popularization value.
Description
Technical field
The present invention relates to oilfield prospecting developing underground work technical field, in particular to a kind of controlled degradation ternary is total
Polymers diverting agent, preparation method and application method.
Background technique
With deepening continuously for oil-gas field development, difficulty of construction is increasing, and the requirement to underground work technology is increasingly
Height, such as temporary stall is to fracturing technique, acid fracturing uniform acid distribution technology, oil-gas Layer temporary plugging technique.Wherein, temporary stall is to fracturing technique
It is to be pumped into temporarily stifled diversion agent into target zone under certain condition, using the difference of layer intrinsic permeability, and changes original liquid
Inflow direction achievees the purpose that generate new crack.The core of the technology is breaking agent for chemical temporary-plugging diversion agent.In addition, when needing pressure break to change
When two target zones made are closer and should not descend segmentation tool, using temporary stifled steering technique can reduce pressing crack construction difficulty,
Reduce the usage quantity of segmentation tool, additionally it is possible to improve the transformation efficiency of unit well section, which is improving the same of well yield
When, pressure break cost is effectively reduced.
For Heterogeneous reservoir in carrying out acidification transformation process, acid solution is preferentially acidified that flow resistance is smaller, permeability is higher
Reservoir, and flow resistance is larger, the lower reservoir of permeability because acid solution enter it is unsmooth cause its be acidified correctional effect it is bad.Cause
This, conventional acidulation technology because acid-rock reaction acutely, a large amount of consumption acid due to only can solve pollution and the permeability problems in nearly pit shaft area,
Acid solution cannot achieve the goal the deep hyposmosis area area of floor, it is difficult to uniform acid distribution.In order to effectively in Heterogeneous reservoir
Uniform acid distribution makes injection acid solution reach whole region, realizes maximizing the benefits, and acid fracturing uniform acid distribution technology becomes when previous
Research hotspot common are self-diverting acid technology, fiber ACID FRACTURING TECHNOLOGY, viscous acid and crosslinking technic acid etc., principle are as follows: utilize
High viscosity or plugging characteristics reduce high permeability zone to the absorbability of acid solution, and acid solution turns to the region of tight stratum in turn,
Injection liquid is set to reach whole region, so that maximizing the benefits.
Mid-late oilfield development, note adopt it is particularly thorny, between the original heterogeneity of aggravation oil reservoir and well, the difference of interlayer,
Oil layer energy cannot supplement, and absorption well, lost-circulation zone accordingly increase, and generate a large amount of well killing fluids during complete well and workover treatment
Leakage.The exploitation of oil-gas Layer temporary plugging technique solves the problems, such as this, and most popular method is to lose oil gas using diverting agent temporarily leak stopping
Layer, and how to obtain and realize that degradation time is controllable while guaranteeing diverting agent sealing characteristics, it is that current diverting agent was studied
A main problem in journey.
Summary of the invention
The object of the present invention is to provide one kind can in aqueous environments it is 100% degradable, and degradation time is controllable
Controlled degradation terpolymer diverting agent.
It is a further object of the present invention to provide a kind of preparation sides for preparing above-mentioned controlled degradation terpolymer diverting agent
Method.
It is realized controllably it is a further object of the present invention to provide a kind of using above-mentioned controlled degradation terpolymer diverting agent
The application method of degradation.
For this purpose, technical solution of the present invention is as follows:
A kind of controlled degradation terpolymer diverting agent comprising by caprolactone, lactide, glycolide, polymerized thylene carbonate
Any three kinds of reaction monomers are by terpolymer made of the copolymerization of any molar ratio in propyl ester dihydric alcohol.
Wherein, the mole percent of every kind of reaction monomers is 0.1%~99.8%, and the Mole percent of three kinds of reaction monomers
Number is in terms of 100%；The branch number of terpolymer made of corresponding copolymerization is 1~6, is linear chain structure or highly branched chain structure.
In order to meet the requirement for blocking the different size of gap of bottom, which is that terpolymer is prepared as difference
The graininess of partial size and shape, mixture that is powdered and laminar, and forming according to a certain percentage.
It is preferred that controlled degradation terpolymer diverting agent include 0~40 parts by weight length and width be 2~5mm, with a thickness of
The thin slice of 1~2mm, 20~40 parts by weight partial size be 2~8mm elliposoidal bulky grain, 30~50 parts by weight partial size be 20
The partial size of the little particle of~60 mesh and 0~40 parts by weight is the superfines of 100~300 mesh.
Specifically, (1) is right if the terpolymer diverting agent is formed by caprolactone, lactide and glycolide-co
Caprolactone-lactide coglycolide terpolymer, structural formula should be generated are as follows:
Wherein, x, y, z are the molar percentage of three kinds of monomers, 0.1%≤x, y, z≤99.8%, x+y+z=100%； n
For branch number, n=1~6.
(2) if the terpolymer diverting agent is formed by caprolactone, glycolide and poly (propylene carbonate) diol copolymer,
It is then corresponding to generate caprolactone-glycolide-propylene carbonate terpolymer, structural formula are as follows:
Wherein, x, y, z are the molar percentage of three kinds of monomers, 0.1%≤x, y, z≤99.8%, x+y+z=100%； n
For branch number, n=1~6.
(3) if the terpolymer diverting agent is formed by caprolactone, lactide and poly (propylene carbonate) diol copolymer,
It is then corresponding to generate caprolactone-lactide-propylene carbonate terpolymer, structural formula are as follows:
Wherein, x, y, z are the molar percentage of three kinds of monomers, 0.1%≤x, y, z≤99.8%, x+y+z=100%； n
For branch number, n=1~6.
(4) if the terpolymer diverting agent is formed by glycolide, lactide and poly (propylene carbonate) diol copolymer,
It is then corresponding to generate lactide coglycolide-propylene carbonate terpolymer, structural formula are as follows:
Wherein, x, y, z are the molar percentage of three kinds of monomers, 0.1%≤x, y, z≤99.8%, x+y+z=100%； n
For branch number, n=1~6.
It is preferred that the number-average molecular weight of the poly (propylene carbonate) dihydric alcohol is 1000~10000.
A kind of preparation method of controlled degradation terpolymer diverting agent, steps are as follows:
S1, three kinds of reaction monomers are added into reaction flask, are warming up to three kinds of reaction monomers and are heated to molten condition, stirred
Under the conditions of vacuumize, lead to drying nitrogen remove oxygen and moisture；
It is preferred that warming temperature is 80 DEG C；Pumpdown time is 15~20 minutes, and the vacuum degree vacuumized in rear reaction flask is
1~2Torr；
S2, catalyst or catalyst and initiator is added, is warming up to 120~150 DEG C, the reaction was continued 4~8h is obtained anti-
Answer crude product；
When participating in containing poly (propylene carbonate) dihydric alcohol in reaction monomers, since the alcoholic extract hydroxyl group of its own has initiator
Effect, therefore other initiators can not additionally be added；
S3, reacting coarse product is dissolved completely in methylene chloride, after excessive ethyl alcohol is added thereto, it is molten to outwell upper layer
Agent obtains precipitating I；
S4, the dissolution-precipitation process for the S3 that repeats the above steps to precipitating I are multiple, obtain precipitating II, then true at room temperature
Empty drying precipitated II at least 48h is to get arriving terpolymer.
It is preferred that the initiator is small molecule alcohol catalyst, additional amount is three kinds of reaction monomers integral molar quantities
0.01~0.5%.
It is preferred that the small molecule alcohol catalyst be ethylene glycol, propylene glycol, butanediol, pentanediol, trimethylolpropane,
Pentaerythrite, pentitol or dipentaerythritol.
It is preferred that the catalyst be stannous octoate, additional amount be three kinds of reaction monomers integral molar quantities 0.01~
0.1%.
It is preferred that in order to meet the requirement for blocking the different size of gap of bottom, it will be by ternary polymerization made from step S4
Object is prepared as the particle, powder or sheet with different-grain diameter and shape, and composition mixture according to a certain percentage.
A kind of application method that the degradation time realized using the controlled degradation terpolymer diverting agent is controllable, step
It is as follows:
S1,100 parts by weight clear water are weighed as carrying liquid A, or 0.5~0.6 weight is added in 100 parts by weight clear water
The hydroxypropyl guar gum of part is configured to uniform gelled fluid as carrying liquid A；
S2, the degradation of promoter of the crystalline fracture agent of 0~4 parts by weight and/or 0~10 parts by weight is added to carrying liquid A
In, it stirs evenly, obtains carrying liquid B；
S3,5~20 parts by weight terpolymers are added to carrying in liquid B, obtain carrying liquid C after being sufficiently stirred；
S4, carrying liquid C is directly used in fracturing pump note construction.
Wherein, crystalline fracture agent and degradation of promoter can according to need be added after use；Specifically, this is controllable
Degradability terpolymer diverting agent itself can make ternary polymerization made of copolymerization by adjusting the ratio of three kinds of reaction monomers
Object has different degradation times；And according to demand, the addition of crystalline fracture agent can be by changing terpolymer water-soluble
Crystalline state in liquid realizes the purpose of accelerated degradation, that is, changes the solution environmental of terpolymer, make hydrone more easily
It enters in the strand of terpolymer；And the addition of degradation of promoter can equally accelerate the degradation speed of terpolymer
Rate further adjusts degradation by chemical reaction this is because degradation of promoter has the function of destroying ester bond in strand
Rate.
It is preferred that the crystalline fracture agent is ethylenediamine, ethanol amine, diethanol amine, triethanolamine, n-propanolamine, three isopropyls
Hydramine, diisopropanolamine (DIPA), diglycolamine or N butyl diethanol amine.
It is preferred that the degradation of promoter is sodium carbonate, sodium bicarbonate, sodium hydroxide or potassium hydroxide.
Compared with prior art, which passes through the molar ratio of three kinds of synthons
The molecular structures such as example, branch number design terpolymer diverting agent obtained, have nontoxic, environmental protection characteristic, and it can
100% is degradable in aqueous environments, it is degradable after without residue, to reservoir fanout free region；Application method through the invention
It can make terpolymer diverting agent under 80~150 DEG C of well temperature, the degradable time is controllable in 0.5 hour to 2 months,
And the plugging strengths such as its fracture, borehole are high, pressure-bearing difference reaches 20MPa；In addition, the controlled degradation terpolymer temporarily blocks up
The preparation method of agent and the application method for adjusting degradation time are simple, easy, have good market popularization value.
Detailed description of the invention
Fig. 1 is the AO fluorescence photo that osteoblast of rabbit is attached to after cultivating 5 days on the diverting agent product of the preparation of embodiment 1；
Fig. 2 is the AO fluorescence photo that osteoblast of rabbit is attached to after cultivating 5 days on the diverting agent product of the preparation of embodiment 2；
Fig. 3 is the AO fluorescence photo that osteoblast of rabbit is attached to after cultivating 5 days on the diverting agent product of the preparation of embodiment 3；
Fig. 4 is the AO fluorescence photo that osteoblast of rabbit is attached to after cultivating 5 days on the diverting agent product of the preparation of embodiment 4；
Fig. 5 is the AO fluorescence photo that osteoblast of rabbit is attached to after cultivating 5 days on the diverting agent product of the preparation of embodiment 5.
Specific embodiment
With reference to the accompanying drawing and specific embodiment the present invention is described further, but following embodiments are absolutely not to this hair
It is bright to have any restrictions.
Embodiment 1
It is that 99.8% caprolactone, 0.1% lactide and 0.1% glycolide pour into three-neck flask by molar fraction
In, oil bath heating vacuumizes three kinds of reaction monomers under stirring 15 minutes in molten condition to 80 DEG C, and vacuum degree 1 in bottle~
2Torr, while logical drying nitrogen, remove the oxygen and moisture in bottle；Then it is added into three-neck flask and accounts for three kinds of reaction monomers
0.01% ethylene glycol and 0.01% stannous octoate of integral molar quantity, oil bath are warming up to 150 DEG C, the reaction was continued 4h, are reacted
Crude product；Reacting coarse product is dissolved completely in methylene chloride, after excess ethyl alcohol is added thereto, outwell upper layer solvent, obtain
To precipitating I, precipitating I is again dissolved in methylene chloride, after excess ethyl alcohol is added again, outwell upper layer solvent, collect precipitating, weight
Multiple above-mentioned dissolution-precipitation process finally obtains precipitating II, and precipitating II is dried in vacuo 48h at room temperature, obtains straight chain shape
Caprolactone-lactide coglycolide terpolymer.
The reaction equation that ring-opening polymerization generates terpolymer occurs for three kinds of reaction monomers are as follows:
Wherein, it be molar ratio shared by 0.1%, z is 0.1% that molar ratio shared by x, which is molar ratio shared by 99.8%, y,
Branch number n=1 is straight chain shape polymer molecule.
The caprolactone of the straight chain shape-lactide coglycolide terpolymer is prepared by common plastics processing method
Different-grain diameter and powder, specifically, the constituent of the diverting agent are as follows: 20 parts by weight are averaged length and width as 5mm, and thickness is 2mm's
Thin slice, the elliposoidal bulky grain that 30 parts by weight partial sizes are about 5mm, 30 parts by weight partial sizes are about the little particle and 20 weights of 30 mesh
Amount part partial size is about the superfines of 300 mesh, above-mentioned each component is uniformly mixed to get diverting agent product is arrived.
Embodiment 2
It is that 33.3% caprolactone, 33.3% lactide and 33.4% glycolide pour into three-neck flask by molar fraction
In, oil bath heating vacuumizes three kinds of reaction monomers under stirring 15 minutes in molten condition to 80 DEG C, and vacuum degree 1 in bottle~
2Torr, while logical drying nitrogen, remove the oxygen and moisture in bottle；Then it is added into three-neck flask and accounts for three kinds of reaction monomers
0.5% dipentaerythritol and 0.1% stannous octoate of integral molar quantity, oil bath are warming up to 120 DEG C, the reaction was continued 8h, obtain anti-
Answer crude product；Reacting coarse product is dissolved completely in methylene chloride, after excess ethyl alcohol is added thereto, outwell upper layer solvent,
Obtain precipitating I, precipitating I be again dissolved in methylene chloride, after excess ethyl alcohol is added again, outwell upper layer solvent, collect precipitating,
Above-mentioned dissolution-precipitation process is repeated, precipitating II is finally obtained, precipitating II is dried in vacuo 48h at room temperature, is had
There is the caprolactone-lactide coglycolide terpolymer of six branches.
The reaction equation that ring-opening polymerization generates terpolymer occurs for three kinds of reaction monomers are as follows:
Wherein, it is that molar ratio shared by 33.3%, z is that molar ratio shared by x, which is molar ratio shared by 33.3%, y,
33.4%, branch number n=6 are six chain polymer molecules.
The caprolactone of six chains-lactide coglycolide terpolymer is prepared by common plastics processing method
At different-grain diameter and powder, specifically, the constituent of the diverting agent are as follows: elliposoidal big that 30 parts by weight partial sizes are about 8mm
Grain, 50 parts by weight partial sizes are about the little particle of 60 mesh and 20 parts by weight partial sizes are about 100 mesh powders, by above-mentioned each component
It is uniformly mixed to get diverting agent product is arrived.
Embodiment 3
It is that 0.1% caprolactone, 0.1% lactide and 99.8% glycolide pour into three-neck flask by molar fraction
In, oil bath heating vacuumizes three kinds of reaction monomers under stirring 15 minutes in molten condition to 80 DEG C, and vacuum degree 1 in bottle~
2Torr, while logical drying nitrogen, remove the oxygen and moisture in bottle；Then it is added into three-neck flask and accounts for three kinds of reaction monomers
0.1% trimethylolpropane of integral molar quantity and 0.05% stannous octoate, oil bath is warming up to 130 DEG C, the reaction was continued 6h, obtains
To reacting coarse product；Reacting coarse product is dissolved completely in methylene chloride, after excess ethyl alcohol is added thereto, it is molten to outwell upper layer
Agent obtains precipitating I, and precipitating I is again dissolved in methylene chloride, after excess ethyl alcohol is added again, outwell upper layer solvent, it is heavy to collect
It forms sediment, repeats above-mentioned dissolution-precipitation process, finally obtain precipitating II, precipitating II is dried in vacuo 48h at room temperature, is obtained
Caprolactone with three branches-lactide coglycolide terpolymer.
The reaction equation that ring-opening polymerization generates terpolymer occurs for three kinds of reaction monomers are as follows:
Wherein, it is that molar ratio shared by 0.1%, z is that molar ratio shared by x, which is molar ratio shared by 0.1%, y,
99.8%, branch number n=3 are three chain polymer molecules.
The caprolactone of three chains-lactide coglycolide terpolymer is prepared by common plastics processing method
At different-grain diameter and powder, specifically, the constituent of the diverting agent are as follows: 30 parts by weight be averaged length and width be 3mm, with a thickness of 1mm
Thin slice, the elliposoidal bulky grain that 40 parts by weight partial sizes are about 3mm and the little particle that 50 parts by weight partial sizes are about 40 mesh will
Above-mentioned each component is uniformly mixed to arrive diverting agent product.
Embodiment 4
By molar fraction be 33.3% caprolactone, 33.3% glycolide and 33.4% poly (propylene carbonate) dihydric alcohol
(number-average molecular weight 2000) is poured into three-neck flask, and oil bath heating makes three kinds of reaction monomers in molten condition, stirring to 80 DEG C
Under vacuumize 15 minutes, 1~2Torr of vacuum degree in bottle, while logical drying nitrogen removes the oxygen and moisture in bottle；Then to
0.03% stannous octoate for accounting for three kinds of reaction monomers integral molar quantities is added in three-neck flask, oil bath is warming up to 150 DEG C, continues anti-
8h is answered, reacting coarse product is obtained；Reacting coarse product is dissolved completely in methylene chloride, after excess ethyl alcohol is added thereto,
Fall upper layer solvent, obtain precipitating I, precipitating I is again dissolved in methylene chloride, after excess ethyl alcohol is added again, it is molten to outwell upper layer
Precipitating is collected in agent, repeats above-mentioned dissolution-precipitation process, finally obtains precipitating II, and precipitating II is dried in vacuo at room temperature
48h obtains the caprolactone-glycolide-propylene carbonate terpolymer with linear chain structure.
The reaction equation that ring-opening polymerization generates terpolymer occurs for three kinds of reaction monomers are as follows:
Wherein, it is that molar ratio shared by 33.3%, z is that molar ratio shared by x, which is molar ratio shared by 33.3%, y,
33.4%, branch number n=1 are straight chain shape polymer molecule.
Caprolactone-glycolide-propylene carbonate terpolymer of the straight chain shape is passed through into common plastics processing method system
It is standby at different-grain diameter and powder, specifically, the constituent of the diverting agent are as follows: 40 parts by weight be averaged length and width for 4mm, with a thickness of
The thin slice of 2mm, the elliposoidal bulky grain and 30 parts by weight partial sizes that 30 parts by weight partial sizes are about 5mm are about 30 purposes small
Above-mentioned each component is uniformly mixed to get diverting agent product is arrived by grain.
Embodiment 5
It is that (number is equal for 40% caprolactone, 10% lactide and 50% poly (propylene carbonate) dihydric alcohol by molar fraction
Molecular weight is 10000) to pour into three-neck flask, and oil bath heating makes three kinds of reaction monomers in molten condition, stir lower take out to 80 DEG C
Vacuum 15 minutes, 1~2Torr of vacuum degree in bottle, while logical drying nitrogen, remove the oxygen and moisture in bottle；Then to three necks
0.02% stannous octoate for accounting for three kinds of reaction monomers integral molar quantities is added in flask, oil bath is warming up to 150 DEG C, and the reaction was continued
8h obtains reacting coarse product；Reacting coarse product is dissolved completely in methylene chloride, after excess ethyl alcohol is added thereto, outwell
Upper layer solvent obtains precipitating I, and precipitating I is again dissolved in methylene chloride, after excess ethyl alcohol is added again, outwell upper layer solvent,
Precipitating is collected, above-mentioned dissolution-precipitation process is repeated, finally obtains precipitating II, precipitating II is dried in vacuo at room temperature
48h obtains the caprolactone-lactide-propylene carbonate terpolymer with linear chain structure.
The reaction equation that ring-opening polymerization generates terpolymer occurs for three kinds of reaction monomers are as follows:
Wherein, it be molar ratio shared by 10%, z is 50% that molar ratio shared by x, which is molar ratio shared by 40%, y, branch
Chain number n=1 is straight chain shape polymer molecule.
Caprolactone-lactide-propylene carbonate terpolymer of the straight chain shape is passed through into common plastics processing method system
It is standby at different-grain diameter and powder, specifically, the constituent of the diverting agent are as follows: 30 parts by weight be averaged length and width as 5mm, thickness 2mm
Thin slice, the elliposoidal bulky grain that 20 parts by weight partial sizes are about 3mm, 30 parts by weight partial sizes are about the little particle and 20 of 20 mesh
Parts by weight partial size is about 200 mesh powders, above-mentioned each component is uniformly mixed to get diverting agent product is arrived.
Embodiment 6
It is that (number is equal for 10% lactide, 80% glycolide and 10% poly (propylene carbonate) dihydric alcohol by molar fraction
Molecular weight is 500) to pour into three-neck flask, and oil bath heating makes three kinds of reaction monomers in molten condition, stir lower take out very to 80 DEG C
It is 15 minutes, 1~2Torr of vacuum degree in bottle empty, while logical drying nitrogen, remove the oxygen and moisture in bottle；Then it is burnt to three necks
It being added in bottle and accounts for 0.02% stannous octoate of three kinds of reaction monomers integral molar quantities, oil bath is warming up to 150 DEG C, the reaction was continued 8h,
Obtain reacting coarse product；Reacting coarse product is dissolved completely in methylene chloride, after excess ethyl alcohol is added thereto, outwell upper layer
Solvent obtains precipitating I, and precipitating I is again dissolved in methylene chloride, after excess ethyl alcohol is added again, outwell upper layer solvent, collect
Precipitating repeats above-mentioned dissolution-precipitation process, finally obtains precipitating II, and precipitating II is dried in vacuo 48h at room temperature, is obtained
To the lactide coglycolide with linear chain structure-propylene carbonate terpolymer.
The reaction equation that ring-opening polymerization generates terpolymer occurs for three kinds of reaction monomers are as follows:
Wherein, it be molar ratio shared by 80%, z is 10% that molar ratio shared by x, which is molar ratio shared by 10%, y, branch
Number n=1 is straight chain shape polymer molecule.
The lactide coglycolide of the straight chain shape-propylene carbonate terpolymer is passed through into common plastics processing method system
It is standby at different-grain diameter and powder, specifically, the constituent of the diverting agent are as follows: the elliposoidal that 30 parts by weight partial sizes are about 2mm is big
Particle, 30 parts by weight partial sizes be about 40 mesh little particle and 40 parts by weight partial sizes be about 300 mesh superfines, will be above-mentioned
Each component is uniformly mixed to arrive diverting agent product.
Toxicity assessment test is successively carried out to the diverting agent product of Examples 1 to 6 preparation and causes allergic experiment evaluation.
(1) toxicity assessment is tested:
MTT tests the Cytotoxicity evaluation for being frequently used for material, specific experiment method are as follows: prepare Examples 1 to 6
Six kinds of diverting agent products be separately added into six culture dishes containing osteoblast of rabbit, cultivate 1,3 and 5 day, be added MTT examination
Agent, navy blue first a ceremonial jade-ladle, used in libation part can be observed, and the depth of first a ceremonial jade-ladle, used in libation color shows the competent cell quantity of metabolism, finally
Absorbance is measured at 560nm with ELISA instrument, the height of absorbance can reflect the number of competent cell metabolism indirectly
Amount, and blank assay is done to compare.
Experimental result is as shown in table 1 below.
Table 1:
From table 1 it follows that relative to blank group, performance when six kinds of terpolymer diverting agent materials are tested through MTT
Higher absorbance out illustrates that sample does not have cytotoxicity, and shows excellent cell activity.
If Fig. 1~5 are after six kinds of diverting agent products prepared by Examples 1 to 5 are attached to and cultivate 5 days on diverting agent material
AO fluorescence photo.From in Fig. 1~5 it can also be seen that be attached on diverting agent material Oesteoblast growth breeding situation it is good
It is good, do not have cytotoxicity.
In addition, the diverting agent product configuration of Examples 1 to 5 preparation is being carried out abdomen injection to SD rat at suspension
In observations in 7 days of the suspension, it is found that the phenomena of mortality do not occur for the rat of experimental group and negative control group, experimental group rat is not
There is phenomena such as poor state of mind, poor appetite, inactive behavior, every observation index is normal.To the rat body of experimental group
Weight changing value recorded, changes of weight average value be+3.5g, and the changes of weight average value of negative control group rat be+
3.8g, two groups of variations are non-significant variation.As it can be seen that the diverting agent product of Examples 1 to 6 preparation meets acute toxicity grading criteria
In nontoxicity, belong to non-toxic, environmental friendly material.
(2) allergic experiment evaluation is caused:
The experiment method particularly includes: diverting agent product prepared by Examples 1 to 6 is immersed in 72 in 37 DEG C of physiological saline
Hour, obtain extracting solution.0.1 ml of intracutaneous injection extracting solution at the two sides medial border of scapula of experimental group rat is tested in feminine gender
The same area injecting normal saline 0.1ml of group rat is 2% dinitro in the same area injection concentration of positive controls rat
Base fluorobenzene (DNFB) 0.1ml.Local skin reaction in 24,48 and 72 hours is observed after observation injection immediately, and is recorded in detail each
Skin position and the erythema of each observing time and oedema degree.Experimental result is as shown in table 2.
Table 2:
As can be seen that the diverting agent product of Examples 1 to 6 preparation passes through the reaction that experimental group is shown from upper table 2
It is identical as negative control group reaction, do not occur allergic reaction, and then there is allergic reaction in positive controls, illustrate the diverting agent
Product will not cause allergic reaction.
Embodiment 7
A kind of application method of controlled degradation terpolymer diverting agent, steps are as follows:
S1,100 parts by weight clear water are weighed as carrying liquid A；
S2, crystalline fracture agent and/or degradation of promoter are added in carrying liquid A, are stirred evenly, obtain carrying liquid B；
S3,5~20 parts by weight terpolymers are added to carrying in liquid B, obtain carrying liquid C after being sufficiently stirred；
S4, carrying liquid C is directly used in fracturing pump note construction.
Diverting agent product prepared by Examples 1 to 6 is formulated as to the different carryings for being used to pump note construction respectively according to table 3
Liquid C, and the diverting agent product itself for preparing of testing example 1~6 and its prepared carrying liquid C are 100% complete in clear water
The time required to degradable.
Table 3:
As can be seen that the diverting agent product itself of Examples 1 to 6 preparation can pass through three kinds of reactions of allotment from upper table 3
The type and ratio of monomer obtain the diverting agent product with different degradation times, at the same time it can also pass through additional crystalline fracture
The method of agent and/or degradation of promoter further regulates and controls the degradation time of material.
From the test result of table 3 it is found that within the scope of 80~150 DEG C of Applicable temperature, diverting agent product and its preparation
The degradable time for carrying liquid C can regulate and control between 0.5h~60d, and the degradable time for realizing such material is controllable
It adjusts, the time of operation under the operating conditions such as the temporary plugging of lost-circulation zone is needed when being suitable for pressing crack construction, acid fracturing construction and well workover
It asks, i.e., degradation time matches with construction time progress.
Sealing characteristics evaluation is further carried out to ternary using high-temperature and high-pressure filter press.Experimental method are as follows: in cylindrical kettle
Internal bottom be respectively put into be with fracture width 1mm, 3mm and 5mm discoid mold, then using embodiment 1 in table 3~
The diverting agents of 6 preparations carry liquid C and carry out simulated experiments, are 20MPa in pressure difference, when pressure-bearing 30min, the wastage model of simulated experiment
It is trapped among between 15~30mL, and clear water wastage per minute in above-mentioned mold is 1500mL or so, it is seen that the sealing agent product
The sealing characteristics of the carrying liquid C of preparation is excellent, and fracture, borehole etc. all have high-intensitive plugging characteristics；In addition, real by simulation
It tests, core injury recovery rate after the plugged zone that above-mentioned diverting agent carrying liquid C is formed is degradable in 150 DEG C of aqueous environments
Respectively 99.3~100%, it is seen that the sealing agent product is to the basic fanout free region of reservoir.
Claims (10)
1. a kind of controlled degradation terpolymer diverting agent, which is characterized in that it include by caprolactone, lactide, glycolide,
Any three kinds of monomers are by terpolymer made of the copolymerization of any molar ratio in poly (propylene carbonate) dihydric alcohol.
2. controlled degradation terpolymer diverting agent according to claim 1, which is characterized in that the polymerized thylene carbonate third
The number-average molecular weight of ester dihydric alcohol is 1000~10000.
3. a kind of preparation method of controlled degradation terpolymer diverting agent as claimed in claim 1 or 2, feature exist
In steps are as follows:
S1, three kinds of reaction monomers are added into reaction flask, are warming up to three kinds of reaction monomers and are heated to molten condition, stirring condition
Under vacuumize, lead to drying nitrogen remove oxygen and moisture；
S2, catalyst or catalyst and initiator is added, and is warming up to 120~150 DEG C, the reaction was continued 4~8h is reacted
Crude product；
S3, reacting coarse product is dissolved completely in methylene chloride, after excessive ethyl alcohol is added thereto, outwell upper layer solvent,
Obtain precipitating I；
S4, the dissolution-precipitation process for the S3 that repeats the above steps to precipitating I are multiple, obtain precipitating II, then vacuum is dry at room temperature
Dry precipitating II at least 48h to get arrive terpolymer.
4. the preparation method of controlled degradation terpolymer diverting agent according to claim 3, which is characterized in that described
Initiator is small molecule alcohol catalyst, and additional amount is the 0.01~0.5% of three kinds of reaction monomers integral molar quantities.
5. the preparation method of controlled degradation terpolymer diverting agent according to claim 4, which is characterized in that described
Small molecule alcohol catalyst be ethylene glycol, propylene glycol, butanediol, pentanediol, trimethylolpropane, pentaerythrite, pentitol or
Dipentaerythritol.
6. the preparation method of controlled degradation terpolymer diverting agent according to claim 3, which is characterized in that described
Catalyst is stannous octoate, and additional amount is the 0.01~0.1% of three kinds of reaction monomers integral molar quantities.
7. the preparation method of controlled degradation terpolymer diverting agent according to claim 3, which is characterized in that will be through
It crosses terpolymer made from step S4 and is processed as the length for including 0~40 parts by weight and width is 2~5mm, with a thickness of 1~2mm's
Thin slice, 20~40 parts by weight partial size be 2~8mm elliposoidal bulky grain, 30~50 parts by weight partial size be 20~60 purposes
The partial size of little particle and 0~40 parts by weight is the superfines of 100~300 mesh.
8. a kind of application method of controlled degradation terpolymer diverting agent as described in claim 1, which is characterized in that step
It is rapid as follows:
S1,100 parts by weight clear water are weighed as carrying liquid A, or the hydroxyl of 0.5~0.6 parts by weight is added in 100 parts by weight clear water
Propyl guar gum is configured to uniform gelled fluid as carrying liquid A；
S2, the degradation of promoter of the crystalline fracture agent of 0~4 parts by weight, 0~10 parts by weight is added in carrying liquid A, stirring is equal
It is even, it obtains carrying liquid B；
S3,5~20 parts by weight terpolymers are added to carrying in liquid B, obtain carrying liquid C after being sufficiently stirred；
S4, carrying liquid C are directly used in fracturing pump note construction.
9. the application method of controlled degradation terpolymer diverting agent according to claim 8, which is characterized in that described
Crystalline fracture agent is ethylenediamine, ethanol amine, diethanol amine, triethanolamine, n-propanolamine, triisopropanolamine, diisopropanolamine (DIPA), two
At least one of glycol amine, N butyl diethanol amine.
10. the application method of controlled degradation terpolymer diverting agent according to claim 8, which is characterized in that institute
Stating degradation of promoter is at least one of sodium carbonate, sodium bicarbonate, sodium hydroxide, potassium hydroxide.
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| CN110669482A (en) * | 2019-09-18 | 2020-01-10 | 北京易联结科技发展有限公司 | Acidity-controllable rigid temporary plugging agent and preparation method thereof |
| CN111647144A (en) * | 2019-09-20 | 2020-09-11 | 上海浦景化工技术股份有限公司 | Method for adjusting chain structure of polyglycolic acid molecule |
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