CN107287669A - A kind of alkaline-resisting temperature resistance PVA fibers and application thereof - Google Patents
A kind of alkaline-resisting temperature resistance PVA fibers and application thereof Download PDFInfo
- Publication number
- CN107287669A CN107287669A CN201610225788.5A CN201610225788A CN107287669A CN 107287669 A CN107287669 A CN 107287669A CN 201610225788 A CN201610225788 A CN 201610225788A CN 107287669 A CN107287669 A CN 107287669A
- Authority
- CN
- China
- Prior art keywords
- hydroformylation
- pva fibers
- alkaline
- temperature resistance
- resisting temperature
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Classifications
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
- D01F6/02—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds
- D01F6/14—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds from polymers of unsaturated alcohols, e.g. polyvinyl alcohol, or of their acetals or ketals
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B16/00—Use of organic materials as fillers, e.g. pigments, for mortars, concrete or artificial stone; Treatment of organic materials specially adapted to enhance their filling properties in mortars, concrete or artificial stone
- C04B16/04—Macromolecular compounds
- C04B16/06—Macromolecular compounds fibrous
- C04B16/0616—Macromolecular compounds fibrous from polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds
- C04B16/0641—Polyvinylalcohols; Polyvinylacetates
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K8/00—Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
- C09K8/42—Compositions for cementing, e.g. for cementing casings into boreholes; Compositions for plugging, e.g. for killing wells
- C09K8/46—Compositions for cementing, e.g. for cementing casings into boreholes; Compositions for plugging, e.g. for killing wells containing inorganic binders, e.g. Portland cement
- C09K8/467—Compositions for cementing, e.g. for cementing casings into boreholes; Compositions for plugging, e.g. for killing wells containing inorganic binders, e.g. Portland cement containing additives for specific purposes
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- 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
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- 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
- C09K8/66—Compositions based on water or polar solvents
- C09K8/68—Compositions based on water or polar solvents containing organic compounds
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- 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
- C09K8/84—Compositions based on water or polar solvents
- C09K8/86—Compositions based on water or polar solvents containing organic compounds
- C09K8/88—Compositions based on water or polar solvents containing organic compounds macromolecular compounds
- C09K8/885—Compositions based on water or polar solvents containing organic compounds macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F11/00—Chemical after-treatment of artificial filaments or the like during manufacture
- D01F11/04—Chemical after-treatment of artificial filaments or the like during manufacture of synthetic polymers
- D01F11/06—Chemical after-treatment of artificial filaments or the like during manufacture of synthetic polymers of macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K2208/00—Aspects relating to compositions of drilling or well treatment fluids
- C09K2208/10—Nanoparticle-containing well treatment fluids
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Ceramic Engineering (AREA)
- Textile Engineering (AREA)
- General Chemical & Material Sciences (AREA)
- Structural Engineering (AREA)
- Inorganic Chemistry (AREA)
- Artificial Filaments (AREA)
Abstract
A kind of alkaline-resisting temperature resistance PVA fibers, for 25~35%, PVA fibers, the shrinkage factor S% of its fiber and water temperature T in 120~180 DEG C of water meet following (I) formula to the hydroformylation degree η of the PVA fibers：S<0.16T 18.8 (I), wherein, 120 DEG C<T<180℃.PVA fibers of the present invention have higher temperature tolerance, keep well-pressed in 120~180 DEG C of water, do not decompose, ensure that fiber possesses enough mechanical properties, tensile strength for 6~13cN/dtex at high temperature, at 120 DEG C fibre shrinkage S only up to 0.1%, 180 DEG C of fibre shrinkage S are only up to 9.0%；Alkaline resistance properties is excellent, keep 12 hours fiber quality loss lates to be less than 0.5% in the alkali lye of pH=10, while its good dispersion, mechanical strength are high, fibre 1.0~1.8dtex of density, elongation at break 10~20% under PVA fibers normal temperature of the present invention.
Description
Technical field
The present invention relates to a kind of PVA fibers, more particularly to a kind of high temperature resistant, alkaline-resisting PVA fibers
And application thereof.
Background technology
PVA (polyvinyl alcohol) fiber is the fiber of a class excellent performance, with high intensity, height
The features such as modulus, flatness are spent, and excellent wearability, impact resistance, resistance to corrosion seawater,
Against weather, dispersiveness and the adhesive property good with substrate interface, are widely used as shallow sea seaweed
Breeding net, high-performance rope, tire cord, industry cloth, cement reinforcements, with
And plastics, rubber reinforcement material etc., with wide market potential.
In recent years, domestic and international researcher has persistently carried out numerous studies around PVA fibers.
CN200510057435, a kind of method for preparing high performance polyvinyl alcohel fiber, using by nitrogenous
The composite modifier and polyvinyl alcohol of compound, hydrophily auxiliary additive and water composition are divided
Hydrogen bond is combined between son, modified polyvinylalcohol is prepared, in extrusion-spinning equipment to modified poly ethylene
Alcohol carries out melting as-spun fibre, and polyvinyl alcohol as-spun fibre is dried again through multistage stretching, and heat is fixed
Type prepares high-performance polyethylene alcohol.A kind of wearability PVA acetal fibres of CN200610021470
And its production and use, using 100 parts of polyvinyl alcohol, 2-6 parts of additives, 400-900
Part deionized water prepares the fine and close wear polyvinyl alcohol fiber of cortex construction through wet spinning.
CN201110300982.2, a kind of PVA fibers and its preparation method and application, using spinning head
Specification is that≤5000 holes, aperture are that 0.125-0.2mm, discharge-amount are 1000-1300ml/min
Equipment and wet-dry change technique, the line density for preparing vinal is
6.0-10.0dtex.CN201110238175.2, a kind of high intensity, high-modulus, high-melting-point
PVA content 15-17wt%, boric acid in PVA fibers and its manufacture method, the spinning solution of use
Contain in content 1.2-1.6wt%, sulfuric acid copper content 0.05-0.1wt%, the spinning coagulation bath of use
Sodium hydroxide 15-50g/L, boric acid 5-1515-50g/L, prepare PVA fibre strengths >=
13.5cN/dtex, modulus >=320cN/dtex, just fusing point >=108 DEG C.CN201310251768,
A kind of preparation method of polyvinyl alcohol filament yarn fiber, discloses polyvinyl alcohol spin dope preparation,
Metering, spinning, solidification, secondary solidification is washed, and drying oils, and winds for the first time, heat
Plate stretching, is twisted, for the second time the production technology such as winding.
In actual applications, it has been found that need one kind can high temperature resistant, again can be alkaline-resisting
PVA fibers, however conventional PVA fibers in an environment of high temperature can significant shrinkage even decompose,
Mechanical property it cannot be guaranteed that, therefore there is the defect of non-refractory.In existing disclosed technology also
Do not find to can solve the problem that the technical scheme of PVA fibre fire resistants, more both do not meet high temperature resistant
And alkaline-resisting technical scheme.
The content of the invention
An object of the present invention is to provide a kind of alkaline-resisting temperature resistance PVA fibers.
The second object of the present invention is to provide a kind of new use of above-mentioned alkaline-resisting temperature resistance PVA fibers
On the way.
What the object of the invention was achieved through the following technical solutions：
A kind of alkaline-resisting temperature resistance PVA fibers, the hydroformylation degree η of the PVA fibers is 25~35%,
PVA fibers the shrinkage factor S% of fiber and water temperature T in 120~180 DEG C of water are met following (I)
Formula：
S ＜ 0.16T-18.8 (I), wherein, 120 DEG C of 180 DEG C of ＜ T ＜.
Inventor has found, meets above-mentioned hydroformylation degree and the PVA fibers of shrinkage factor, resistance to elevated temperatures
Protrude, while alkali resistance is good.
Specifically, the polyvinyl alcohol raw material that PVA fibers of the present invention are used in preparing is the degree of polymerization
1000~3000, alcoholysis degree 80~99.5 (mol) % polyvinyl alcohol, dissolved through PVA,
The process systems such as spinneret, coagulating bath solidification, damp and hot stretching, hot-stretch, sizing and secondary hydroformylation
It is standby to form.
Preferably, above-mentioned secondary hydroformylation process is first time dialdehyde hydroformylation, hydroformylation liquid temperature degree
For 55~85 DEG C, 10~90 minutes hydroformylation time, monoaldehyde hydroformylation, hydroformylation liquid are used for the second time
Temperature is 60~85 DEG C, 20~80 minutes hydroformylation time, twice hydroformylation process interval 8~12
Hour.
Further, above-mentioned dialdehyde be glyoxal, MDA, butanedial, glutaraldehyde, oneself two
One or more in aldehyde, terephthalaldehyde, the monoaldehyde be formaldehyde, acetaldehyde, propionic aldehyde,
One or more in butyraldehyde.
It is highly preferred that above-mentioned dialdehyde is glutaraldehyde, above-mentioned monoaldehyde is formaldehyde.
Second of prioritization scheme of above-mentioned hydroformylation process is that dialdehyde is glutaraldehyde and glyoxal
The mol ratio of composition, glutaraldehyde and glyoxal be 5~7: 3~5, monoaldehyde be formaldehyde and
The mol ratio of the composition of acetaldehyde, formaldehyde and acetaldehyde is 5~8: 2~6.
Further, above-mentioned dialdehyde hydroformylation liquid is made up of dialdehyde, the concentrated sulfuric acid, zinc chloride and water,
Wherein binary aldehyde concentration is 40~90g/L, and concentrated sulfuric acid concentration is 150~270g/L, zinc chloride
Concentration is 30~90g/L；The monoaldehyde hydroformylation liquid is by monoaldehyde, the concentrated sulfuric acid, sodium sulphate
With water composition, wherein unitary aldehyde concentration is 30~80g/L, and concentrated sulfuric acid concentration is 100~220g/L,
Sodium sulfate concentration is 80~250g/L.
Application of the above-mentioned PVA fibers in reinforcing oil well agent is prepared；Preferably, above-mentioned PVA is fine
Tie up the application in aqua type reinforcing oil well agent is prepared.
Application of the above-mentioned PVA fibers in oil field diverting agent is prepared；Preferably, above-mentioned PVA is fine
Tie up the application in aqua type oil field diverting agent is prepared.
Application of the above-mentioned PVA fibers in oil field fracturing fluid is prepared；Preferably, above-mentioned PVA is fine
Tie up the application in aqua type oil field fracturing fluid is prepared.
Application of the above-mentioned PVA fibers in cement is prepared.
Alkaline-resisting temperature resistance type PVA fibers of the present invention, are temporarily blocked up and oil for reinforcing oil well, oil field
Field pressure break field, is especially suitable for the agent of aqua type reinforcing oil well, oil field diverting agent and oil field pressure
Split in liquid, when reinforcing oil well agent, oil field diverting agent and oil field fracturing fluid are in acid, alkalescence, also may be used
To apply well.In addition, alkaline-resisting temperature resistance type PVA fibers of the present invention are also applied to cement
In, play a part of enhancing strength of cement and toughness.
Alkaline-resisting temperature resistance type PVA fibers of the present invention are used as taking sand fiber in oil field fracturing fluid.
Alkaline-resisting temperature resistance type PVA fibers of the present invention are used as the conveying of transport high temperature highly pressurised liquid
Pipeline reinforcing material etc..
The present invention has the advantages that：
PVA fibers of the present invention have higher temperature tolerance, are kept in 120~180 DEG C of water
It is well-pressed, do not decompose, it is ensured that fiber possesses enough mechanical properties, tensile strength and is at high temperature
6~13cN/dtex, at 120 DEG C fibre shrinkage S only up to 0.1%, 180 DEG C of fibers receive
Shrinkage S is only up to 9.0%；Alkaline resistance properties is excellent, holding 12 hours in pH=10 alkali lye
Fiber quality loss late is less than 0.5%, while its good dispersion, mechanical strength are high, the present invention
1.0~1.8dtex of fine density, elongation at break 10~20% under PVA fiber normal temperature.
PVA fibers of the present invention are used in the preparation of aqua type oil field fracturing fluid so that its sand carrying effect
Good, the row of returning greatly shortens the time, generally wants two or three talent drained, has used the present invention
After PVA fibers less than 2 hours it is drained with regard to that can return；The row's of returning silt content significantly lowers, up to 10~
30%；Oil gas field amount of increase in production is up to 30-50%.PVA fibers of the present invention are used for aqua type oil field
In prepared by diverting agent, the Oil/gas Well crossed in pressure break is used, it is therefore an objective to block old crack, is split new
Crack, the effect with PVA fibers is：More than pressure rise 6MPA, well production increment 2
More than times.
Brief description of the drawings
Fig. 1：The hydroformylation degree test device figure of alkaline-resisting temperature resistance type PVA fibers of the present invention,
In figure, 1-250ml three-necked bottles, 2- conical flasks, 3- electric furnaces, 4- electric furnaces, 5-1L
Brown volumetric flask, 6- condenser pipes, 7- bulb tubes, 8- screw clips, 9- spring clips,
10- glass stoppers.
Fig. 2：Shrinkage factor curve of the fiber made from embodiment 3 in different temperatures hot water, its
Middle serial 1 represents S=0.16T-18.8 curves, and series 2 is measured value.
Embodiment
The present invention is specifically described below by embodiment, it is necessary to it is pointed out here that be
The present embodiment is served only for that the present invention is further described, it is impossible to be interpreted as to present invention protection
The limitation of scope, the person skilled in the art in the field can be according to the content of the invention described above to this
Some nonessential modifications and adaptations are made in invention.Below in an example, fiber tension is strong
Degree, elongation at break, modulus, single fiber line density, the shrinkage factor S of fiber, the hydroformylation of fiber
The numerical value for spending the loss late of η, fiber in alkali lye is determined using following methods.
Fibre tensile strength, line density, elongation at break, the measure of modulus, with reference to GB/T14462
- 1993 perform.
Fibre shrinkage S measure：
Using that can bear the scale test of 120-180 DEG C of temperature, fibre length 30mm, fiber is complete
It is immersed in entirely in water, to reading in 2 minutes to 2.5 minutes from being put into water fiber.
The calculation formula of fibre shrinkage：
l0：Fiber original length, mm；
l1：Length after filament contraction, mm.
Fiber hydroformylation degree η measure：
Measuring principle：A certain amount of fiber is swelled in sulfuric acid in still-process, by the aldehyde in fiber
Separate out, then with excessive a kind of crystallization for being insoluble in water of sodium hydrogensulfite generation in receiving flask
Thing.Titrated with iodine standard solution and neutralize excessive sodium hydrogensulfite, after neutralization plus sodium carbonate make with
The sodium hydrogensulfite that aldehyde is combined, which is dissociated, to be come.Finally, dripped with 0.020mol/L iodine standard solutions
Determine the sodium hydrogensulfite of separate out, you can try to achieve aldehyde from the volume of iodine standard solution used
Content.Its whole is considered as into formaldehyde when calculating the aldehyde for calibrating and to be calculated.It distills
Device is as shown in Figure 1.
Hydroformylation degree η calculation formula is as follows：
The substance withdrawl syndrome of iodine standard solution, mol/L；
The volume of the iodine standard solution of consumption, mL；
m0：Absolute dry mass after fiber oil removing, g.
Mass loss rate measurement of the fiber in alkaline solution：PH=10 alkali is prepared with NaOH
Property solution, fiber produced by the present invention is totally submerged in alkaline solution, soak 12 hours
Fiber is pulled out afterwards and dried 3 hours in 100 DEG C of baking ovens again, by measuring the front and rear fiber of immersion
It is of poor quality, calculate fiber loss late.
Embodiment 1：By the degree of polymerization 1500, the PVA successively dissolvings of alcoholysis degree 95% (mol),
Spinneret, coagulating bath solidification, damp and hot stretching, thermal finalization, then carry out two by fiber at normal temperatures
Secondary hydroformylation.Hydroformylation is carried out with glutaraldehyde for the first time, hydroformylation liquid is by glutaraldehyde, the concentrated sulfuric acid, chlorination
Zinc and water composition, wherein glutaraldehyde concentration are 80g/L, and concentrated sulfuric acid concentration is 220g/L, chlorination
Zinc concentration is 30g/L, and hydroformylation liquid temperature degree is 75 DEG C, 45 minutes hydroformylation time, second of use
Formaldehyde hydroformylation, hydroformylation liquid is made up of formaldehyde, the concentrated sulfuric acid, sodium sulphate and water, wherein concentration of formaldehyde
For 40g/L, concentrated sulfuric acid concentration is 180g/L, and sodium sulfate concentration is 120g/L, hydroformylation liquid temperature
Spend for 65 DEG C, 30 minutes hydroformylation time, twice hydroformylation process interval 9 hours.
Alkaline-resisting temperature resistance type PVA fibers are finally made, its test index for details see attached table 1 produces this
Product in reinforcing oil well, oil field temporarily stifled, oil field compression fracture for improving oil gas field yield, the product
It is additionally operable in cement enhancing.
Embodiment 2：By the degree of polymerization 2000, the PVA successively dissolvings of alcoholysis degree 90% (mol),
Spinneret, coagulating bath solidification, damp and hot stretching, thermal finalization, then carry out secondary hydroformylation by fiber.
The dialdehyde that first time hydroformylation is used is the composition of glutaraldehyde and glyoxal, and hydroformylation liquid is by penta 2
Aldehyde, glyoxal, the concentrated sulfuric acid, zinc chloride and water composition, wherein glutaraldehyde and glyoxal is in hydroformylation
Total concentration in liquid is 90g/L, and concentrated sulfuric acid concentration is 180g/L, and zinc oxide concentration is 60g/L,
Hydroformylation liquid temperature degree is 65 DEG C, 25 minutes hydroformylation time, and the mol ratio of glutaraldehyde and glyoxal is
7: 3, second aldehyde is the composition of formaldehyde and acetaldehyde, hydroformylation liquid by formaldehyde, acetaldehyde,
The concentrated sulfuric acid, sodium sulphate and water are constituted, and the wherein total concentration of formaldehyde and acetaldehyde in hydroformylation liquid is
60g/L, concentrated sulfuric acid concentration is 140g/L, and sodium sulfate concentration is 170g/L, and hydroformylation liquid temperature degree is
70 DEG C, 50 minutes hydroformylation time, the mol ratio of formaldehyde and acetaldehyde is 6: 5, twice hydroformylation work
Skill interval 10 hours.
Alkaline-resisting temperature resistance type PVA fibers are finally made, its test index for details see attached table 1 produces this
Product in reinforcing oil well, oil field temporarily stifled, oil field compression fracture for improving oil gas field yield, the product
It is additionally operable in cement enhancing.
Embodiment 3：By the degree of polymerization 2400, the PVA successively dissolvings of alcoholysis degree 99.5% (mol),
Spinneret, coagulating bath solidification, damp and hot stretching, thermal finalization, then carry out two by fiber at normal temperatures
Secondary hydroformylation.The aldehyde that first time hydroformylation is used is the composition of glutaraldehyde and hexandial, hydroformylation liquid by
Glutaraldehyde, hexandial, the concentrated sulfuric acid, zinc chloride and water composition, wherein glutaraldehyde and hexandial exist
Total concentration in hydroformylation liquid is 50g/L, and concentrated sulfuric acid concentration is 170g/L, and zinc oxide concentration is
80g/L, hydroformylation liquid temperature degree is 80 DEG C, 35 minutes hydroformylation time, glutaraldehyde and hexandial
Mol ratio is 7: 3, and second of aldehyde is the composition of formaldehyde and butyraldehyde, and hydroformylation liquid is by first
Aldehyde, butyraldehyde, the concentrated sulfuric acid, sodium sulphate and water composition, wherein formaldehyde and butyraldehyde are in hydroformylation liquid
Total concentration is 70g/L, and concentrated sulfuric acid concentration is 160g/L, and sodium sulfate concentration is 130g/L, aldehyde
It is 65 DEG C to change liquid temperature degree, 90 minutes hydroformylation time, and the mol ratio of formaldehyde and butyraldehyde is 8: 3,
Hydroformylation process interval 11 hours twice.
Alkaline-resisting temperature resistance type PVA fibers are finally made, its test index for details see attached table 1 produces this
Product in reinforcing oil well, oil field temporarily stifled, oil field compression fracture for improving oil gas field yield, the product
It is additionally operable in cement enhancing.
Embodiment 4：By the degree of polymerization 1900, the PVA successively dissolvings of alcoholysis degree 98% (mol),
Spinneret, coagulating bath solidification, damp and hot stretching, thermal finalization, then carry out two by fiber at normal temperatures
Secondary hydroformylation.Hydroformylation is carried out with glutaraldehyde for the first time, hydroformylation liquid is by glutaraldehyde, the concentrated sulfuric acid, chlorination
Zinc and water composition, wherein glutaraldehyde concentration are 70g/L, and concentrated sulfuric acid concentration is 190g/L, chlorination
Zinc concentration is 70g/L, and hydroformylation liquid temperature degree is 65 DEG C, 60 minutes hydroformylation time, second of use
Formaldehyde hydroformylation, hydroformylation liquid is made up of formaldehyde, the concentrated sulfuric acid, sodium sulphate and water, wherein concentration of formaldehyde
For 30g/L, concentrated sulfuric acid concentration is 200g/L, and sodium sulfate concentration is 160g/L, hydroformylation liquid temperature
Spend for 55 DEG C, 70 minutes hydroformylation time, twice hydroformylation process interval 9 hours.
Alkaline-resisting temperature resistance type PVA fibers are finally made, its test index for details see attached table 1 produces this
Product in reinforcing oil well, oil field temporarily stifled, oil field compression fracture for improving oil gas field yield, the product
It is additionally operable in cement enhancing.
Embodiment 5：By the degree of polymerization 2000, the PVA successively dissolvings of alcoholysis degree 99.5% (mol),
Spinneret, coagulating bath solidification, damp and hot stretching, thermal finalization, then carry out two by fiber at normal temperatures
Secondary hydroformylation.The aldehyde that first time hydroformylation is used is the composition of glutaraldehyde and glyoxal, hydroformylation liquid by
Glutaraldehyde, glyoxal, the concentrated sulfuric acid, zinc chloride and water composition, wherein glutaraldehyde and glyoxal exist
Total concentration in hydroformylation liquid is 80g/L, and concentrated sulfuric acid concentration is 200g/L, and zinc oxide concentration is
60g/L, hydroformylation liquid temperature degree is 75 DEG C, 40 minutes hydroformylation time, glutaraldehyde and glyoxal
Mol ratio is 6: 3, and second of aldehyde is the composition of formaldehyde and acetaldehyde, and hydroformylation liquid is by first
Aldehyde, acetaldehyde, the concentrated sulfuric acid, sodium sulphate and water composition, wherein formaldehyde and acetaldehyde are in hydroformylation liquid
Total concentration is 75g/L, and concentrated sulfuric acid concentration is 200g/L, and sodium sulfate concentration is 180g/L, aldehyde
It is 55 DEG C to change liquid temperature degree, 60 minutes hydroformylation time, and the mol ratio of formaldehyde and acetaldehyde is 6: 4,
Hydroformylation process interval 11 hours twice.
Alkaline-resisting temperature resistance type PVA fibers are finally made, its test index for details see attached table 1 produces this
Product in reinforcing oil well, oil field temporarily stifled, oil field compression fracture for that can improve oil gas field yield, the product
It is additionally operable in cement enhancing.
Subordinate list 1
Fiber product made from one embodiment is taken in addition, appointing, the fiber product as made from embodiment 4,
Its shrinkage factor value in different temperatures hot water is tested, the pass between shrinkage factor and water temperature is drawn out
It is curve, refers to Figure of description 2.
Claims (8)
1. a kind of alkaline-resisting temperature resistance PVA fibers, it is characterised in that the hydroformylation degree η of the PVA fibers is that 25~35%, PVA fibers the shrinkage factor S% of its fiber and water temperature T in 120~180 DEG C of water meet following (I) formula：
S<0.16T-18.8 (I), wherein, 120 DEG C<T<180℃.
2. alkaline-resisting temperature resistance PVA fibers as claimed in claim 1, it is characterised in that：The polyvinyl alcohol raw material that the PVA fibers are used in preparing is the degree of polymerization 1000~3000, alcoholysis degree 80~99.5（mol）% polyvinyl alcohol, dissolves, spinneret, coagulating bath solidification, damp and hot stretching, hot-stretch, sizing and secondary hydroformylation process are prepared from through PVA.
3. alkaline-resisting temperature resistance PVA fibers as claimed in claim 2, it is characterised in that：The secondary hydroformylation process is first time dialdehyde hydroformylation, and hydroformylation liquid temperature degree is 55~85 DEG C, 10~90 minutes hydroformylation time, use monoaldehyde hydroformylation for the second time, hydroformylation liquid temperature degree is 60~85 DEG C, 20~80 minutes hydroformylation time, twice hydroformylation process interval 8~12 hours.
4. alkaline-resisting temperature resistance PVA fibers as claimed in claim 3, it is characterised in that：The dialdehyde is the one or more in glyoxal, MDA, butanedial, glutaraldehyde, hexandial, terephthalaldehyde, and the monoaldehyde is the one or more in formaldehyde, acetaldehyde, propionic aldehyde, butyraldehyde.
5. alkaline-resisting temperature resistance PVA fibers as claimed in claim 4, it is characterised in that：The dialdehyde is glutaraldehyde, and the monoaldehyde is formaldehyde.
6. alkaline-resisting temperature resistance PVA fibers as claimed in claim 3, it is characterised in that：The dialdehyde hydroformylation liquid is made up of dialdehyde, the concentrated sulfuric acid, zinc chloride and water, and wherein binary aldehyde concentration is 40~90g/L, and concentrated sulfuric acid concentration is 150~270g/L, and zinc oxide concentration is 30~90 g/L；The monoaldehyde hydroformylation liquid is made up of monoaldehyde, the concentrated sulfuric acid, sodium sulphate and water, and wherein unitary aldehyde concentration is 30~80g/L, and concentrated sulfuric acid concentration is 100~220g/L, and sodium sulfate concentration is 80~250 g/L.
7. the purposes of alkaline-resisting temperature resistance PVA fibers as described in any one of claim 1~6, it is characterised in that：Application of the alkaline-resisting temperature resistance type PVA fibers in reinforcing oil well agent, oil field diverting agent, oil field fracturing fluid or cement is prepared.
8. the purposes of alkaline-resisting temperature resistance PVA fibers as claimed in claim 7, it is characterised in that：Application of the alkaline-resisting temperature resistance type PVA fibers in the agent of aqua type reinforcing oil well, aqua type oil field diverting agent or aqua type oil field fracturing fluid is prepared.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610225788.5A CN107287669A (en) | 2016-04-12 | 2016-04-12 | A kind of alkaline-resisting temperature resistance PVA fibers and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610225788.5A CN107287669A (en) | 2016-04-12 | 2016-04-12 | A kind of alkaline-resisting temperature resistance PVA fibers and application thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN107287669A true CN107287669A (en) | 2017-10-24 |
Family
ID=60093133
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610225788.5A Pending CN107287669A (en) | 2016-04-12 | 2016-04-12 | A kind of alkaline-resisting temperature resistance PVA fibers and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN107287669A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113981564A (en) * | 2021-11-15 | 2022-01-28 | 中国石油大学(北京) | Sand-carrying fiber and preparation and application thereof |
Citations (17)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH10226958A (en) * | 1997-02-14 | 1998-08-25 | Kuraray Co Ltd | Production of polyvinyl alcohol base synthetic fiber |
| CN101456707A (en) * | 2008-12-30 | 2009-06-17 | 北京科技大学 | Fiber reinforcement fine aggregate glued stone concrete light partition board and method for producing the same |
| CN101643534A (en) * | 2009-09-08 | 2010-02-10 | 无锡新宏泰电器科技股份有限公司 | Marbling polyester molding compound for medium-high voltage appliances and preparation method thereof |
| CN101812744A (en) * | 2009-08-10 | 2010-08-25 | 上海全宇生物科技遂平制药有限公司 | Formalizing method of high-strength and high-modulus polyvinyl alcohol fiber |
| CN102925133A (en) * | 2012-10-16 | 2013-02-13 | 中国石油天然气股份有限公司 | Fracturing fluid for controlling extension of fracture and fracturing method |
| CN102952534A (en) * | 2012-10-16 | 2013-03-06 | 中国石油天然气股份有限公司 | Low-damage fracturing fluid and fracturing method |
| CN103031611A (en) * | 2011-09-30 | 2013-04-10 | 中国石油化工集团公司 | Polyvinyl alcohol fiber and preparation method as well as application thereof |
| CN103388189A (en) * | 2012-05-10 | 2013-11-13 | 中国石油化工集团公司 | Fine-denier or superfine-denier polyvinyl alcohol fiber and preparation method thereof |
| CN103694976A (en) * | 2013-12-18 | 2014-04-02 | 四川省博仁达石油科技有限公司 | Fiber temporary plugging agent for acidizing and fracturing |
| CN103725277A (en) * | 2013-12-18 | 2014-04-16 | 四川省博仁达石油科技有限公司 | Fibre compound temporary plugging agent |
| CN103774266A (en) * | 2012-10-26 | 2014-05-07 | 中国石油化工集团公司 | Preparation method of polyvinyl formal fiber |
| CN104099074A (en) * | 2014-06-10 | 2014-10-15 | 中国石油集团川庆钻探工程有限公司工程技术研究院 | Volume fracturing reconstruction crack plugging agent and water plugging construction method |
| CN104405360A (en) * | 2014-10-27 | 2015-03-11 | 中石化胜利油田分公司采油工艺研究院 | Fracturing method capable of improving sand-carrying performance of fracturing liquid |
| CN104449621A (en) * | 2014-12-18 | 2015-03-25 | 中国石油大学(华东) | Efficient well-cementing flushing fluid system |
| CN104694113A (en) * | 2015-02-13 | 2015-06-10 | 中国石油天然气股份有限公司 | Method for improving sand-carrying capacity of fracturing fluid and fiber-containing fracturing fluid |
| CN104727800A (en) * | 2015-01-22 | 2015-06-24 | 中国石油集团川庆钻探工程有限公司长庆井下技术作业公司 | Temporary blocking turnaround fracturing method based on surface modified polyvinyl alcohol fibers |
| CN104962275A (en) * | 2015-05-29 | 2015-10-07 | 中国石油天然气股份有限公司 | Fiber-reactive aqueous fracturing fluid for compact reservoir transformation, and use method thereof |
-
2016
- 2016-04-12 CN CN201610225788.5A patent/CN107287669A/en active Pending
Patent Citations (17)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH10226958A (en) * | 1997-02-14 | 1998-08-25 | Kuraray Co Ltd | Production of polyvinyl alcohol base synthetic fiber |
| CN101456707A (en) * | 2008-12-30 | 2009-06-17 | 北京科技大学 | Fiber reinforcement fine aggregate glued stone concrete light partition board and method for producing the same |
| CN101812744A (en) * | 2009-08-10 | 2010-08-25 | 上海全宇生物科技遂平制药有限公司 | Formalizing method of high-strength and high-modulus polyvinyl alcohol fiber |
| CN101643534A (en) * | 2009-09-08 | 2010-02-10 | 无锡新宏泰电器科技股份有限公司 | Marbling polyester molding compound for medium-high voltage appliances and preparation method thereof |
| CN103031611A (en) * | 2011-09-30 | 2013-04-10 | 中国石油化工集团公司 | Polyvinyl alcohol fiber and preparation method as well as application thereof |
| CN103388189A (en) * | 2012-05-10 | 2013-11-13 | 中国石油化工集团公司 | Fine-denier or superfine-denier polyvinyl alcohol fiber and preparation method thereof |
| CN102925133A (en) * | 2012-10-16 | 2013-02-13 | 中国石油天然气股份有限公司 | Fracturing fluid for controlling extension of fracture and fracturing method |
| CN102952534A (en) * | 2012-10-16 | 2013-03-06 | 中国石油天然气股份有限公司 | Low-damage fracturing fluid and fracturing method |
| CN103774266A (en) * | 2012-10-26 | 2014-05-07 | 中国石油化工集团公司 | Preparation method of polyvinyl formal fiber |
| CN103694976A (en) * | 2013-12-18 | 2014-04-02 | 四川省博仁达石油科技有限公司 | Fiber temporary plugging agent for acidizing and fracturing |
| CN103725277A (en) * | 2013-12-18 | 2014-04-16 | 四川省博仁达石油科技有限公司 | Fibre compound temporary plugging agent |
| CN104099074A (en) * | 2014-06-10 | 2014-10-15 | 中国石油集团川庆钻探工程有限公司工程技术研究院 | Volume fracturing reconstruction crack plugging agent and water plugging construction method |
| CN104405360A (en) * | 2014-10-27 | 2015-03-11 | 中石化胜利油田分公司采油工艺研究院 | Fracturing method capable of improving sand-carrying performance of fracturing liquid |
| CN104449621A (en) * | 2014-12-18 | 2015-03-25 | 中国石油大学(华东) | Efficient well-cementing flushing fluid system |
| CN104727800A (en) * | 2015-01-22 | 2015-06-24 | 中国石油集团川庆钻探工程有限公司长庆井下技术作业公司 | Temporary blocking turnaround fracturing method based on surface modified polyvinyl alcohol fibers |
| CN104694113A (en) * | 2015-02-13 | 2015-06-10 | 中国石油天然气股份有限公司 | Method for improving sand-carrying capacity of fracturing fluid and fiber-containing fracturing fluid |
| CN104962275A (en) * | 2015-05-29 | 2015-10-07 | 中国石油天然气股份有限公司 | Fiber-reactive aqueous fracturing fluid for compact reservoir transformation, and use method thereof |
Non-Patent Citations (5)
| Title |
|---|
| 梅自强: "《纺织工业中的表面活性剂》", 30 April 2001, 中国石化出版社 * |
| 水佑人等: "《维尼纶制造工艺》", 29 February 1964, 中国财政经济出版社 * |
| 沈新元: "《化学纤维手册》", 30 September 2008, 中国纺织出版社 * |
| 祖立武: "《化学纤维成型工艺学》", 30 September 2014, 哈尔滨工业大学出版社 * |
| 赵祥森等: "高耐热水性聚乙烯醇纤维的制备与结构性能研究", 《合成纤维工业》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113981564A (en) * | 2021-11-15 | 2022-01-28 | 中国石油大学(北京) | Sand-carrying fiber and preparation and application thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| EP3284861B1 (en) | Method for preparing salt-resistant and detergent-resistant seaweed fiber | |
| CN103031611B (en) | A kind of vinal and its preparation method and application | |
| CN100398707C (en) | Method for preparing meta aromatic polyamide fiber | |
| CN101161880A (en) | Method for preparing polyacrylonitrile-based carbon fiber precursor fiber | |
| CN109569322B (en) | Super-hydrophilic and underwater super-oleophobic cellulose membrane and preparation method thereof | |
| CN106277805B (en) | A kind of mineral wool and preparation method thereof | |
| CN104371096B (en) | A kind of water-soluble polyester of sea-island fibre and preparation method thereof | |
| ATE417951T1 (en) | METHOD FOR PRODUCING POLYARENAZOLE YARN | |
| CN102660791A (en) | Old clothes recovery method | |
| CN104562282A (en) | Fishing net thread suitable for being used in seawater | |
| CN107287674B (en) | A kind of solubility fine-denier PVA fiber and application thereof | |
| CN103469343B (en) | A kind of method improving the Interaction Force of fento in aramid fiber | |
| CN107964804A (en) | Dipped aramid cord twists with the fingers leaching production technology | |
| CN104963030B (en) | A kind of corrosion-resistant high-toughness high-strength composite fibre and its production technology | |
| CN107287668B (en) | A kind of heat-resistance type PVA fiber and application thereof | |
| CN107287669A (en) | A kind of alkaline-resisting temperature resistance PVA fibers and application thereof | |
| CN103060940B (en) | A kind of preparation method of medium modulus vinal | |
| JP5741815B2 (en) | Carbon fiber precursor acrylic fiber bundle and carbon fiber bundle | |
| CN103276469B (en) | Production method of concrete reinforced and toughened PVA (polyvinyl alcohol) fiber | |
| CN110230130B (en) | Preparation method of high-strength medium-modulus carbon fiber precursor | |
| WO2012017453A1 (en) | High luster acrylic fiber and process for manufacturing the same | |
| CN106426975B (en) | A kind of preparation process of compound fishing rod | |
| CN114196165A (en) | Preparation method of modified jute fiber reinforced bio-based epoxy resin composite material | |
| CN103314142B (en) | The preparation of copolymer fibre and drying | |
| CN111501383B (en) | Novel basalt fiber composite rib and preparation method and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| WD01 | Invention patent application deemed withdrawn after publication | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20171024 |