CN101153102A - Water uptake expansion composition, water uptake expansion material and water uptake expansion packer - Google Patents
Water uptake expansion composition, water uptake expansion material and water uptake expansion packer Download PDFInfo
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- CN101153102A CN101153102A CNA2006101417811A CN200610141781A CN101153102A CN 101153102 A CN101153102 A CN 101153102A CN A2006101417811 A CNA2006101417811 A CN A2006101417811A CN 200610141781 A CN200610141781 A CN 200610141781A CN 101153102 A CN101153102 A CN 101153102A
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- SWPMNMYLORDLJE-UHFFFAOYSA-N n-ethylprop-2-enamide Chemical compound CCNC(=O)C=C SWPMNMYLORDLJE-UHFFFAOYSA-N 0.000 description 1
- YPHQUSNPXDGUHL-UHFFFAOYSA-N n-methylprop-2-enamide Chemical compound CNC(=O)C=C YPHQUSNPXDGUHL-UHFFFAOYSA-N 0.000 description 1
- ODUCDPQEXGNKDN-UHFFFAOYSA-N nitroxyl Chemical compound O=N ODUCDPQEXGNKDN-UHFFFAOYSA-N 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 125000006353 oxyethylene group Chemical group 0.000 description 1
- 239000012188 paraffin wax Substances 0.000 description 1
- 229920002401 polyacrylamide Polymers 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 229920005749 polyurethane resin Polymers 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 239000011241 protective layer Substances 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 230000003014 reinforcing effect Effects 0.000 description 1
- 230000000452 restraining effect Effects 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 150000003377 silicon compounds Chemical class 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- KZOJQMWTKJDSQJ-UHFFFAOYSA-M sodium;2,3-dibutylnaphthalene-1-sulfonate Chemical compound [Na+].C1=CC=C2C(S([O-])(=O)=O)=C(CCCC)C(CCCC)=CC2=C1 KZOJQMWTKJDSQJ-UHFFFAOYSA-M 0.000 description 1
- DAJSVUQLFFJUSX-UHFFFAOYSA-M sodium;dodecane-1-sulfonate Chemical compound [Na+].CCCCCCCCCCCCS([O-])(=O)=O DAJSVUQLFFJUSX-UHFFFAOYSA-M 0.000 description 1
- VQIDGTFLGAAJGI-UHFFFAOYSA-M sodium;prop-1-ene-1-sulfonate Chemical compound [Na+].CC=CS([O-])(=O)=O VQIDGTFLGAAJGI-UHFFFAOYSA-M 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- QAZLUNIWYYOJPC-UHFFFAOYSA-M sulfenamide Chemical compound [Cl-].COC1=C(C)C=[N+]2C3=NC4=CC=C(OC)C=C4N3SCC2=C1C QAZLUNIWYYOJPC-UHFFFAOYSA-M 0.000 description 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 238000005987 sulfurization reaction Methods 0.000 description 1
- 229920003051 synthetic elastomer Polymers 0.000 description 1
- 239000005061 synthetic rubber Substances 0.000 description 1
- 229920001897 terpolymer Polymers 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
- 150000003557 thiazoles Chemical class 0.000 description 1
- 229960002447 thiram Drugs 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- 150000003673 urethanes Chemical class 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
- Sealing Material Composition (AREA)
Abstract
The present invention relates to a water-absorbent expansive composition, the application of the water-absorbent expansive composition, water-absorbent expansive material containing the water-absorbent expansive composition and packers made of the water-absorbent expansive material. The water-absorbent expansive composition of the present invention is made of water-absorbent agent, reaction monomer and surfactant. The water-absorbent agent is a naturally hydrophilic polymer or the derivative; the reaction monomer is monomer containing water-absorbent group such as carboxyl, hydroxyl, ether group, aroylamino, sulfonic group, carboxylate group, sulfonate group, quaternary ammonium salt monomer, or hydrophilic vinyl monomer after hydrolysis. The monomer contains double bonds and can be cross-linked with water-absorbent agent; wherein, the weight content of the water-absorbent agent is 3 portions to 100 portions; the weight content of the reaction monomer is 0 portion to 30 portions; the weight content of the surfactant is 0 portion to 70 portions.
Description
Technical field
The present invention relates to a kind of water uptake expansion composition and application thereof, also relate to the water uptake expansion material and the application thereof that comprise this water uptake expansion composition, and, especially be applicable to the pkr of oil well specific equipment by the pkr that this water uptake expansion material is made.
Background technology
The present invention relates to a kind of packing oil, water layer, adjust the subsurface tool of oil recovery section, this instrument is specially adapted to the more serious producing well of water outlet.When production and well workover, usually the annular space packing between oil pipe and the sleeve pipe or the borehole wall is become upper and lower several sections, control or close some reservoirs.In oil recovery process, the down-hole most permeable zone is carried out shutoff selectively, can realize reducing the purpose of water content in crude oil.For the middle and later periods oil well, entered high water-cut stage, precipitation, the energy-conservation problem that becomes people's first concern, so the research of pkr are heat subjects always.
Retrieve till the end of the year 2005, existing nearly 700 the pkr patents of China are declared, and these pkrs have various uses and principle of work.The Wel packing that adopts has various ways such as mechanical type, waterpower formula, self-sealing at present, and the design of each pkr all has its ingenious part.Most of pkr common drawback are that structure is complicated, the process cost height, and energy consumption is big.
In order to simplify the structure of pkr, investigators are devoted to study the new-type Wel packing of self-expanding formula.Utilize rubber self-expanding principle as CN1452686A (W002120941Al), add protective sleeve and reinforcing member; CN1236857A makes the self-sealing packing element by C3-C7 hydrocarbon derivative net high-polymer; CN2386189Y is made of a water-swellable packing element and a sleeve assembly; CN1249390 utilizes water-swellable glue bowl and kit to constitute; The CN1330205A packing element becomes big by the molten back of paraffin volume and expands; CN2119498V utilizes the agent of the interior injection of packing element heat expansion to form; CN2617909Y is made of a packing element and a cover mating parts; U.S.6073692 utilizes waterpower or mechanical force to cause the cross-sectional shape change and expands; U.S.4886117 causes expansion by in-hole fluid pressure; The sealing-ring that U.S.4753444 is made up of poly-aryl ketones etc., when being subjected to longitudinal pressure the footpath outwards button realize sealing; U.S.4137970 is the elastomerics of being made by sodium dichromate 99, glycerine, glycol ether ethylene glycol, polyacrylamide.Be similar to above-mentioned numerous pkr that has packing element, still need supporting subassembly, outer power pressurization, or swelling agent is heated the volume change product at pressure.Packing element of wherein mentioning or glue bowl do not disclose any technology contents such as rubber kind, component, moulding process.Under the high temperature of its tangible down-hole harshness, high pressure, acid, alkali, oil, water, the vapour Working environment, not any hydro-expansive rubber (abbreviating WSR as) can both bear, only carry " hydro-expansive rubber " six words, there is not embodiment to support again, there are not experimental data, processing parameter, performance index etc., can't confirm whether this technological method can finish described invention task, how does not know actual effect, those skilled in the art can't reproduce this technology.Because " hydro-expansive rubber " exists kind difference, manufacture craft difference, expansion principle difference, and a series of difference such as expansion multiplying power, acid and alkali-resistance ability, oil resistant steam ability, heat-resisting ability, precipitate degree, mechanical Strong degree, only mention hydro-expansive rubber, can't implement.The WSR that has is when down-hole liquid soaks, and short-term will become sticky and lose use value.
It is few to relate to the WSR patent, makes water-absorbing resin as CN1563155A by Soxylat A 25-7 (methyl) acrylate and other monomer copolymerization, again with chloroprene rubber mixing; CN1172117A is by natural rubber (NR), high water absorbency polymer, the following lignocellulose powder of 3mm rolling; CN1450105A and CN1421465A, be respectively concrete compound lithium hydroxide and sodium hydroxide and unsaturated carboxylic acid are added in the rubber mixing, alkali and carboxylic acid reaction in mixing, thus make the water sucting rubber of poly-metallic salts of unsaturated carboxylate modification; CN12263490C forms A, B component with polyether glycol, tolylene diisocyanate, isoprene-isobutylene rubber etc.; Te Kaiping 4-363499 is made up of sponge-like polyurethane resin etc.
In the technical paper retrieval, also reveal some WSR method for makings, (J). polymer material science and engineering, 2001,17 (4): 101-104. has mentioned sodium polyacrylate-styrene-butadiene rubber(SBR) blend and has prepared the water sucting rubber method; (J). chemical fertilizer design, 2002,40 (5): 15-18. has mentioned with NR, sodium polyacrylate, has contained the segmented copolymer of polyoxyethylene block, uses the mechanical blending method; (J). Chinese railway science, 2001,22 (4): 69-73. has introduced the applicable cases of hydrophilic polyurethane and vulcanization of rubber thing; (J). the Hubei chemical industry, 2001,5:11-13. has introduced crosslinking sodium polyacrylate and NR refining; (J). rubber industry, 1999,46 (6): 353-355. prepares with the physical blending method with acrylate resin and rubber.But the paper of current stage, in order to protect the innovative point of oneself, key component is often underground.
WSR succeeded in developing the end of the seventies, was to be base material with rubber, included hydroaropic substance or made rubber have hydrophilic radical, made rubber have a kind of type material of water-swelling property.Expand when it is characterized in that absorbing water, produce the swelling pressure, during pressurization, water can not be extruded, and the elasticity of rubber self forms the double seal effect in addition.
Chemical graft process is meant hydrophilic polymer such as polyethylene oxide, poly(propylene oxide), polyoxyethylene glycol etc. is had particular functional group's elastomerics with some, as chlorosulfonated polyethylene, by process meanses such as solution reactions, hydrophilic radical or segment such as hydroxyl, carboxyl, ether etc. are grafted on the rubber, make wetting ability rubber.Its main drawback is: 1. complex process, to use, consume solvent as solution reaction.2. percentage of grafting is low, and water absorbent rate is low.3. need make earlier hydrophilic polymer again with grafting rubbers, be the reaction between the macromole.
Chemical graft process is because complex process, percentage of grafting is low, rate of expansion is low and do not see suitability for industrialized production report.
The physical blending method is simple, with low cost owing to method for making, rate of expansion is high, and is applied.The physical blending method is that mixing adding water-absorbing resin forms in rubber.Mostly rubber is general natural rubber (NR), chloroprene rubber (CR), styrene-butadiene rubber(SBR) (SBR), terpolymer EP rubber (EPDM) etc.Water-absorbing resin is meant the polymkeric substance that contains hydrophilic radical in its structure, can be synthetic system, also can be the natural polymer graft copolymer.But there is following main drawback in this method:
1. normally particulate state or fine powder of water-absorbing resin is difficult for being uniformly dispersed in rubber.
2. water-absorbing resin and rubber lack avidity, easily separate out when rubber swelling.
Therefore, people attempt:
1. that water-absorbing resin is pulverized is very thin, mentions in the document being preferably in below the 100 μ m, better less than 50 μ m.
2. add expanding material in the prescription, components such as tackifier have been received certain effect, but how to prevent that water-absorbing resin from separating out the emphasis that this problem is still the WSR scientific research when expanding.
The general water-retaining agent of normal See, the same as the natural polymer graft copolymer with synthetic system, all be rigid macromolecule resin with certain degree of hardness.No matter how carefully be ground to, be still granular.Suppose it is spheric, diameter is at 100 μ m, and volumetric expansion is 500 times after suction, and the about 0.8mm of diameter then need not any instrument, and it is clear that human eye just can be seen.After cutting rubber, can see original very thin water-absorbent resin powder, become bigger gel particle, many ground are embedded in the rubber, are easy to be extruded by the caoutchouc elasticity convergent force, and the pimple injustice can appear in rubber surface.
In sum, the special-purpose WSR of pkr should be based on following consideration:
1. the selection principle of rubber is the erosion that can bear harsh Working environments such as down-hole high temperature, high pressure.
2. the selection of water-absorbing material answers water absorbent rate big, is difficult for separating out.
3. anti-correct selection of analysing agent.
The new term that the present invention uses first " prevents analysing agent ", and its definition is: can prevent the class material that water-absorbing material is separated out from WSR.From generalized concept, " anti-analyse agent " should be: can prevent suction or oil absorption material, separate out from expanding material and the auxiliary agent dosed.
4.WSR preparation technology is simple, packer construction is simple, manufacturing is simple.
5.WSR water-swelling multiplying power, speed of expansion can satisfy the shutoff requirement of pkr.
Because WSR only under bound state, fully expand by the suction back, just can produce the swelling pressure to constraint face, realize sealing purpose, swelling capacity is big more, and then sealing property is good more.
For this reason, the present invention is the superpower WSR of preparation, open a new technological line, creatively used the composition of the tensio-active agent of the unsaturated reaction monomers of the multifunctional reactive group of Mierocrystalline cellulose and derivative water-retaining agent thereof/have/optional, add in the rubber (or other macromolecular material) as swelling agent, because the synergy of component makes the controlled WSR of expansion multiplying power (or other water-swelling macromolecular material).
Summary of the invention
Purpose of the present invention aims to provide a kind of novel water uptake expansion composition, and this water uptake expansion composition can use as water absoption expanding agent, thereby increases the water-swelling multiplying power of water uptake expansion material, and the suction back is difficult for separating out from water uptake expansion material.Each component of this water uptake expansion composition acts synergistically mutually, can obtain the controlled water uptake expansion material of expansion multiplying power.
Another object of the present invention aims to provide a kind of water uptake expansion material that adopts above-mentioned water uptake expansion composition as swelling agent, and it comprises water swelling rubber, water-swelling rubber and plastic material and water-swelling plastics etc.The high magnification expansion can take place after meeting water in these water uptake expansion materials.
Another purpose of the present invention aims to provide a kind of pkr that adopts water uptake expansion material of the present invention to make, and especially is applicable to the special-purpose pkr of oil well.High magnification takes place when the water uptake expansion material in the pkr is met water expand, its expansion multiplying power and speed can satisfy the shutoff requirement of pkr, thereby reach plugging action.
In order to realize the foregoing invention purpose, an aspect of of the present present invention provides a kind of water uptake expansion composition, and it is made up of water-retaining agent, reaction monomers and tensio-active agent, and wherein said water-retaining agent is a natural hydrophilic macromolecular compound or derivatives thereof; Described reaction monomers is the vinyl monomer that contains possess hydrophilic property after the monomer of suction basic carboxyl, hydroxyl, ether, amido, amino, sulfonic group, carboxylate group, sulphonate-base or quaternary ammonium salt monomer or the hydrolysis, described monomer contains two keys, can take place crosslinked with water-retaining agent; Wherein the weight content of water-retaining agent is 3-100 part; The weight content of reaction monomers is 0-30 part; The weight content of tensio-active agent is 0-70 part.
Water uptake expansion composition of the present invention can be used as the water absoption expanding agent in the water uptake expansion material, and described water uptake expansion material is selected from elastomerics or inelastic body.Being used for elastomerics of the present invention can include but not limited to, and as rubber etc., inelastic body include but not limited to, as plastics, rubber and plastic material etc.
In water uptake expansion material, the invention provides a kind of water swelling rubber, it comprises water uptake expansion composition of the present invention, rubber and vulcanizing agent, and the weight content of wherein said rubber is 100 parts, and the weight content of vulcanizing agent is 0.6-20 part.
In water uptake expansion material, the invention provides a kind of water-swelling rubber and plastic material, it comprises water uptake expansion composition of the present invention, rubber and plastic material and vulcanizing agent, and the weight content of wherein said rubber and plastic material is 100 parts, and the weight content of vulcanizing agent is 0.6-20 part.
In water uptake expansion material, the invention provides a kind of water-swelling plastics, it comprises water uptake expansion composition of the present invention, plastics and linking agent, and the weight content of wherein said plastics is 100 parts, and the weight content of linking agent is 0.6-20 part.
Another aspect of the present invention provides a kind of water uptake expansion packer, it is made up of the tube core expansion sleeve outer with being coated on this tube core, wherein, described expansion sleeve is made as water swelling rubber, water-swelling rubber and plastic material or water-swelling plastics by water uptake expansion material of the present invention.
Water-absorbing material of the present invention, can be used for preparing various sealing members as water swelling rubber, water-swelling rubber and plastic material or water-swelling plastics, it includes but not limited to, as the circle of sealing usefulness, pad, bar, sheet, expansion sleeve etc., makes it have super-strong moisture absorbing swelling capacity and the anti-property separated out.
Water uptake expansion material of the present invention, pkr as water swelling rubber, water-swelling rubber and plastic material or the preparation of water-swelling plastics, can be used as Wel packing, in use, when running into water, expansion sleeve absorbs water automatically to produce and expands, and it is big that volume becomes, thereby the borehole wall of sealing oil well or the annular space between sleeve pipe and the oil pipe have been realized the selectivity in interval, stratum is isolated.
Detailed Description Of The Invention
The invention provides a kind of water uptake expansion composition, it is made up of water-retaining agent, reaction monomers and tensio-active agent, and described water-retaining agent is a natural hydrophilic macromolecular compound or derivatives thereof; Described reaction monomers is the vinyl monomer that contains possess hydrophilic property after the monomer of suction basic carboxyl, hydroxyl, ether, amido, amino, sulfonic group, carboxylate group, sulphonate-base or quaternary ammonium salt monomer or the hydrolysis, described monomer contains two keys, can take place crosslinked with water-retaining agent; Wherein the weight content of water-retaining agent is 3-100 part; The weight content of reaction monomers is 0-30 part; The weight content of tensio-active agent is 0-70 part.Water-retaining agent in the water uptake expansion composition of the present invention is a natural hydrophilic macromolecular compound or derivatives thereof, the preferred cellulose or derivatives thereof.This natural hydrophilic macromolecular compound and derivative thereof can comprise, but be not limited to following compounds, as carboxymethyl cellulose (CMC), methylcellulose gum (MC), Natvosol (HEC), hydroxyethylmethyl-cellulose (HEMC), hydroxypropylcellulose (HPC), Vltra tears (HPMC), carboxymethyl hydroxyethyl cellulose (CMHEC) etc.The weight content of the water-retaining agent in this water uptake expansion composition is 3-100 part, is preferably 7-80 part, more preferably 15-60 part.
Reaction monomers in the water uptake expansion composition of the present invention be contain suction base as the monomer of carboxyl, hydroxyl, ether, amide group, amino, sulfonic group, carboxylate group, sulphonate-base or quaternary ammonium salt monomer or hydrolysis after the vinyl monomer of possess hydrophilic property, described monomer contains two keys, can take place crosslinked with water-retaining agent.The reaction monomers that the present invention uses can include, but are not limited to following compounds, as contains carboxylic monomer, (methyl) vinylformic acid, maleic acid etc.; Carboxylic acid dehydrate monomer is as MALEIC ANHYDRIDE; The carboxylate salt monomer is as (methyl) sodium acrylate, sodium maleate; The sulfonic group monomer is as (methyl) propene sulfonic acid; Sulfonate monomer is as the propene sulfonic acid sodium salt; The hydroxyl monomer is as (methyl) vinylcarbinol; Contain the ether monomer, as many oxyethylene oxidation propylene glycol list propylene ether; The amide-containing monomer, N-ethyl acrylamide as (methyl) acrylamide, N-alkyl acrylamide class, N, the N of N-dialkyl group acrylic amide, the N-DMAA, N-hydroxyethyl methacrylamide, the N hydroxymethyl acrylamide of N-hydroxyalkyl acrylic amide, N, the N of N-dihydroxyalkyl acrylic amide, N-dihydroxy ethyl Methacrylamide; The quaternary ammonium salt monomer, as N, N, N-trimethylammonium-N acrylamide ethyl oxide ammonium chloride; After the hydrolysis hydrophilic monomer, as (methyl) methyl acrylate of the lower alkyl esters class of vinyl unsaturated carboxylic acid; The monomer of cyano-containing is as (methyl) vinyl cyanide etc.Preferred monomer is the nontoxic monomer in the acrylic amide.The weight content of the reaction monomers in the water uptake expansion composition is preferably 0.5-30 part, more preferably 4-20 part, more preferably 7-15 part.
The tensio-active agent that is used for water uptake expansion composition of the present invention can be ionic, non-ionic type, polymer etc.The tensio-active agent that the present invention uses can include, but are not limited to following compounds, as sodium lauryl sulphate (SDS), Sodium dodecylbenzene sulfonate (SDBS), sodium laurylsulfonate (DS), the sodium dibutyl naphthalene sulfonate of ionic; Non-ionic type, as polyethenoxy ether class, ceteth (CPE) etc. for example.Consider preferred ion type tensio-active agent, more preferably anion surfactant from material form, operation difficulty or ease, cost, result of use etc. are many-sided.The weight content of tensio-active agent is preferably 4-70 part, more preferably 8-55 part, more preferably 11-20 part.
Be to be noted that the scope that the present invention provides is a preferable range, exceed upper range, when for example tensio-active agent is 80 parts, still can be used in the composition, and play the water-swelling effect, just this effect of tensio-active agent is more obvious.
The present invention also provides a kind of water swelling rubber, and this water swelling rubber comprises water uptake expansion composition of the present invention, rubber and vulcanizing agent, and the weight content of wherein said rubber is 100 parts, and the weight content of vulcanizing agent is 0.6-20 part.
The rubber matrix that is fit to WSR of the present invention is unrestricted, can select natural rubber or synthetic rubber for use, polarity or non-polar rubber, as NR, polyisoprene rubber (IR), SBR, CR, cis-1,4-polybutadiene rubber (BR), (ternary) ethylene-propylene rubber(EPR) (E) PDM, (hydrogenation) paracril ((H) NBR), viton (FKM), trifluoropropyl siloxane (FVMQ), urethanes (PU), epichlorohydrin rubber (ECO), chlorinated polyethylene rubber (CM), chlorosulfonated polyethylene rubber (CSM) etc., preferred (H) NBR.
The present invention's vulcanizing agent applicatory and/or vulcanization accelerator get final product by the configuration of general routine techniques, and suitable vulcanizing agent is sulphur (S) and organic compounds containing sulfur, and organic peroxyization, amine etc.Tetraethylthiuram disulfide of sulfurous organic compound class etc. for example.The diisopropylbenzene(DIPB) of organo-peroxide class (DCP), ditertiary butyl peroxide (DTBP), dibenzoyl peroxide (BPO), 2.5-dimethyl-2.5-di-t-butyl peroxide hexane (DBPH) etc.Preferred S, DCP, preferable amount is 0.6-20 part, further preferable amount is 1-10 part, further preferred 1.5-6 part.
The present invention also can use various rubber to make the conventional additives in field as required, as promotor, anti-aging agent, softening agent, filler etc.The kind and the consumption of these additives are not particularly limited, and those of ordinary skills can select according to conventional knowledge.
Promotor applicatory has the tetramethyl-thiuram disulfide (TM monex TD) of thiurams, thiazoles 2-benzothiazolyl mercaptan (captax), dibenzothiazyl disulfide (DM) arranged, sulfenamide N cyclohexyl 2 benzothiazole sulfenamide (accelerant CZ), guanidine class such as vulkacit D (vulkacit D) etc. are arranged.Preferable amount is 0.5-5 part.
Anti-aging agent applicatory can be selected from aldehyde amine reactant such as aldol-alpha-naphthylamine (antioxidant A P), the ketoamine reactant is as 2,2,4-trimethylammonium-1,2-dihyaroquinoline polymkeric substance (anti-aging agent RD), arylamines such as N-Phenyl beta naphthylamine (antioxidant D), N-sec.-propyl-N '-diphenyl-para-phenylene diamine (anti-aging agent IPPD), alkylarylamine such as N-cyclohexyl-P-nethoxyaniline (anti-aging agent CMA), (replacement) phenol such as p-tert-butylphenol, thiophenols such as thiobis (two-sec.-amyl sec-pentyl secondary amyl phenol) etc., preferable range is 1-6 part.
Promoting agent and filler can be selected from carbon black (HAF), silicon compounds such as white carbon black, potter's clay, talcum powder, mica etc., carbonate such as lime carbonate, metal oxides such as titanium dioxide, magnesium oxide, zinc oxide etc.The stearic acid (salt) of fatty oil system etc.Preferred carbon black 3-60 part, further preferred 10-40 part.Zinc oxide 3-5 part, stearic acid (salt) 0.5-5.Magnesium oxide 2-5 part, white carbon black 3-40 part.Cloud is 4-16 part part not.Potter's clay 4-20 part.Other additive has the preferred 1-2 part of sodium-chlor, the preferred 0.5-6 part of N-(4-anilino phenyl) maleimide.Coumarone (solid coumarone resin) 2-8 part.The preferred 0.5-5 part of N-4-(anilino phenyl) methacrylic acid amino.N, the N '-preferred 0.5-5 part of a penylene bismaleimides.
Water swelling rubber of the present invention, production cost is low, and processing characteristics is stable, and physical and mechanical properties is good.Overcome water wetted material in rubber, disperse uneven, disadvantage such as separate out easily.
The present invention also provides the method for preparing water swelling rubber of the present invention, and wherein water-retaining agent and/or reaction monomers and/or tensio-active agent directly are added in the rubber, react in vulcanization of rubber process.
WSR of the present invention, can obtain by conventional method for preparing rubber, it is mixing to adopt mill or Banbury mixer that each combination is carried out, and melting temperature is at 35-55 ℃, and the time is at 10-50min, roll spacing 4-6mm, become the 1-2mm thin-pass, adopt vulcanizing press or vulcanizing boiler to vulcanize then, curing temperature is at 145-185 ℃, time makes the super-strong moisture absorbing expanded rubber at 2-50min.
The invention provides water-swelling rubber and plastic material, it comprises water uptake expansion composition of the present invention, rubber and plastic material and vulcanizing agent, and the weight content of wherein said rubber and plastic material is 100 parts, and the weight content of vulcanizing agent is 0.6-20 part.
In addition, the present invention also provides the water-swelling plastics, and it comprises water uptake expansion composition of the present invention, plastics and linking agent, and the weight content of wherein said plastics is 100 parts, and the weight content of linking agent is 0.6-20 part.Described plastics are selected from thermoplastics, as ethene-vinyl acetate (EVA), arborescens chlorinatedpolyethylene (CPE) or chlorosulfonated polyethylene (CSM).
Water uptake expansion material of the present invention, can be used for preparing sealing member as water swelling rubber, water-swelling rubber and plastic material or water-swelling plastics, can be made into the sealing member of various forms, shape, as sealing member, circle, pad, bar, sheet etc., can be used on the place that all need seal, as aspects such as various cementing tools, equipment, pipeline, instrument, instrument, subway, tunnel, dam, aqueduct, foundation works, building, mining industry, well, oil well engineerings.
Water uptake expansion material of the present invention can also be used to make pkr as water swelling rubber, water-swelling rubber and plastic material or water-swelling plastics.Especially, utilize the pkr of water swelling rubber of the present invention or the manufacturing of water-swelling rubber and plastic material to have super-strong moisture absorbing swelling capacity and the anti-property separated out, can be used for preparing Wel packing.
Pkr is made up of the tube core expansion sleeve outer with being coated on tube core.Expansion sleeve is promptly made by water swelling rubber of the present invention or water-swelling rubber and plastic material.Tube core and expansion sleeve can cement and be sulfided into integral body, as a kind of selection mode, tube core and rubber swelling cover also can overlap dress up relative can active state.
Sulfuration all-in-one-piece operating process is as follows: at first with tube core through alkali lye degreasing, cleaning, phosphatization, flushing, 150 ℃, 30min drying, after being cooled to room temperature, coating out nurse falls to restraining tackiness agent stand-by, with made rubber unvulcanizate, extension overlays on the tube core that coats tackiness agent, in vulcanizing press or vulcanizing boiler, according to the common vulcanization process of rubber, vulcanize according to the processing condition that provide.
When down-hole application, Wel packing of the present invention becomes the part of flow string, when running into water, expansion sleeve suction automatically produces expansion, and it is big that volume becomes, thereby the borehole wall of sealing oil well or the annular space between sleeve pipe and the oil pipe have been realized the selectivity in interval, stratum is isolated.
Because the pkr of the automatic water-swelling that the present invention makes just coats expansion sleeve outside tube core, do not have subassembly, does not have the active accessory, does not have special back-up coat, protective layer, does not need control, auxiliary ligand cover system from ground to the down-hole.Because simple in structure, manufacturing process is simple, so low cost of manufacture.Have simple installation in addition, process cost is low, advantages such as save energy.
Embodiment
Launch to various aspects of the present invention by the following examples to be described in detail, it should be noted that these embodiment are to the evidence of further explaination of the present invention, invention effect and giving an example of manufacture method, and limit the scope of the invention never in any form.
Embodiment 1: prepare WSR of the present invention
A. with 55 parts of 30 parts of 100 parts of 100 parts of HNBR, CMC, NMA, SDBS, S1 part, 30 parts of 10 parts of DCP, HAF, 5 parts of stearic acid, 0.5 part of Zinic stearas, 0.5 part of captax, 2 parts of TMTD, 1 part of antioxidant D, IPPD3 part, 20 parts of white carbon blacks, 3 parts of Methacrylamides of N-(4-anilino phenyl), 3 parts in zinc oxide, 2 parts in magnesium oxide, 7 parts on mica, in Banbury mixer or mill, temperature 50-55 ℃, operation 10-15min, roll spacing 4-6mm, become the 1-2mm thin-pass, mixing even, sheet about mill, naturally cooling.
B. after at room temperature parking 17h, put into mould, use the vulcanizing press sulfidization molding, remain on 180 ℃ * 5min * 10MPa, make the WSR test piece.
Its main performance index is as follows:
A. hardness (Shao A): 90 degree b. tensile strength: 8.32MPa
C. tensile yield: 50% d. setafter break: 0%
E. weight expansion multiplying power: 59.8% (in deionized water, soaking 48h).
Embodiment 2: prepare WSR of the present invention
A. with 15 parts of 60 parts of 20 parts of 70 parts of 20 parts of 80 parts of 100 parts of NBR, CMC, NMA, SDBS, DCP, HAF, 3 parts of stearic acid, 5 parts of vulkacit Ds, 2 parts of IPPD, 3 parts of white carbon blacks, 3 parts of Methacrylamides of N-(4-anilino phenyl), 6 parts of maleimides of N-(4-anilino phenyl), 4 parts in zinc oxide, potter's clay in Banbury mixer or mill, temperature 45-50 ℃, operation 10-15min, roll spacing 4-6mm, become the 1-2mm thin-pass, mixing even, sheet about mill, naturally cooling.
B. after at room temperature parking 17h, put into mould, use the vulcanizing press sulfidization molding, remain on 170 ℃ * 5min * 10MPa, make the WSR test piece.
Its main performance index is as follows:
A. hardness (Shao A): 88 degree b. tensile strength 5.58MPa
C. tensile yield: 30% d. setafter break 0%
E. weight expansion multiplying power: 23.7% (in deionized water, soaking 48h).
Embodiment 3: prepare WSR of the present invention
A. with 40 parts of 6 parts of 20 parts of 7 parts of 25 parts of 100 parts of NR, CMC, AM, SDS, DCP, HAF, 1 part of stearic acid, 3 parts of accelerant CZs, 2 parts of antioxidant Ds, 5 parts of Methacrylamides of N-(4-anilino phenyl), N, N '-0.5 part of a penylene bismaleimides, 5 parts in magnesium oxide, 10 parts in potter's clay, 4 parts on mica, in Banbury mixer or mill, temperature 35-40 ℃, operation 10-15min, roll spacing 4-6mm becomes the 1-2mm thin-pass, mixing even, sheet about mill, naturally cooling.
B. after at room temperature parking 17h, put into mould, use the vulcanizing press sulfidization molding, remain on 170 ℃ * 10min * 10MPa, make the WSR test piece,
Its main performance index is as follows:
A. hardness (Shao A): 60 degree b. tensile strength: 5.71MPa
C. tensile yield: 200% d. setafter break: 0%
E. weight expansion multiplying power: 26.1% (in deionized water, soaking 48h).
Embodiment 4: prepare WSR of the present invention
A. with 20 parts of 4 parts of 11 parts of 15 parts of 50 parts of 20 parts of 80 parts of NBR, EPDM, CMC, NMA, DS, DCP, HAF, 5 parts of stearic acid, 0.5 part of captax, 2 parts of IPPD, (Gu) 8 parts of coumarones, 4 parts in potter's clay, 4 parts of maleimide amine amides of N-(4-anilino phenyl), 3 parts in zinc oxide, N, N,-1.5 parts of penylene bismaleimidess, mica 10hr, in Banbury mixer or mill, temperature 45-55 ℃, operation 10-15min, roll spacing 4-6mm becomes the 1-2mm thin-pass, mixing even, sheet about mill, naturally cooling.
B. after at room temperature parking 17h, put into mould, use the vulcanizing press sulfidization molding, remain on 170 ℃ * 5min * 10MPa, make the WSR test piece.
Its main performance index is as follows:
A. hardness (Shao A): 82 degree b. tensile strength: 5.74MPa
C. tensile yield: 175% d. setafter break: 5%
E. weight expansion multiplying power: 58.0% (in deionized water, soaking 48h).
Embodiment 5: prepare WSR of the present invention
A. with 10 parts of 2 parts of 8 parts of 15 parts of 60 parts of 100 parts of NBR, CMC, MeAA, SDS, DCP, HAF, 0.5 part of stearic acid, 0.5 part of Zinic stearas, 6 parts of 1 part of TMTD, IPPD, (Gu) 2 parts of coumarones, 1 part of maleimide amine amide of N-(4-anilino phenyl), 2 parts in magnesium oxide, N, N '-3 parts of penylene bismaleimidess, 16 parts on mica, in Banbury mixer or mill, temperature 50-55 ℃, operation 10-15min, mixing even, roll spacing 4-6mm becomes the 1-2mm thin-pass, sheet about mill, naturally cooling.
B. after at room temperature parking 17h, put into mould, use the vulcanizing press sulfidization molding, remain on 180 ℃ * 5min * 10MPa, make the WSR test piece.
Its main performance index is as follows:
A. hardness (Shao A): 66 degree b. tensile strength: 4.18MPa
C. tensile yield: 625% d. setafter break: 30%
E. weight expansion multiplying power: 170.7% (in deionized water, soaking 48h).
Embodiment 6: prepare WSR of the present invention
A. with 3 parts of 0.6 part of 4 parts of 7 parts of 15 parts of 100 parts of HNBR, CMC, NMA, SDBS, S, HAF, 3 parts of stearic acid, 4 parts of 2 parts of TM monex TD, anti-aging agent IPPD, 8 parts of white carbon blacks, 0.5 part of maleimide of N-(4-anilino phenyl), 3 parts in zinc oxide, 1.5 parts of N-(4-anilino phenyl) Methacrylamides, in Banbury mixer or mill, temperature 50-55 ℃, operation 10-15min, roll spacing 4-6mm becomes the 1-2mm thin-pass, mixing even, sheet about mill, naturally cooling.
B. after at room temperature parking 17h, put into mould, use the vulcanizing press sulfidization molding, remain on 180 ℃ * 5min * 10MPa, make the WSR test piece.
Its main performance index is as follows:
A. hardness (Shao A): 32 degree b. tensile strength: 3.10MPa
C. tensile yield: 1050% d. setafter break: 120%
E. weight expansion multiplying power: 44.0% (in deionized water, soaking 48h).
Embodiment 7: prepare WSR of the present invention
A. with 2 parts of 15 parts of 4 parts of 15 parts of 7 parts of 100 parts of NBR, CMC, HEC, NMA, SDS, DCP, HAF10 part, 2 parts of Zinic stearass, 2 parts of vulkacit Ds, 4 parts of antioxidant Ds, (Gu) 3 parts of coumarones,, 5 parts in zinc oxide, 20 parts in potter's clay, 1 part in sodium-chlor, in Banbury mixer or mill, temperature 45-55 ℃, operation 10-15min, roll spacing 4-6mm becomes the 1-2mm thin-pass, mixing even, sheet about mill, naturally cooling.
B. after at room temperature parking 17h, put into mould, use the vulcanizing press sulfidization molding, remain on 170 ℃ * 5min * 10MPa, make the WSR test piece.
Its main performance index is as follows:
A. hardness (Shao A): 64 degree b. tensile strength: 5.94MPa
C. tensile yield: 1000% d. setafter break: 20%
E. weight expansion multiplying power: 32.4% (in deionized water, soaking 48h).
Embodiment 8: prepare WSR of the present invention
A. with 25 parts of 3 parts of 8 parts of 4 parts of 0.5 part of 35 parts of 3 parts of 100 parts of NBR, CMC, HEC, NMA, AM, DS, DCP, HAF, 2 parts of stearic acid, 2 parts of captaxs, 6 parts of antioxidant Ds, (Gu) 5 parts of coumarones, 40 parts of white carbon blacks, 0.5 part of Methacrylamide of N-(4-anilino phenyl), 3 parts in zinc oxide, 2 parts in sodium-chlor, in Banbury mixer or mill, temperature 45-55 ℃, operation 10-15min, roller 4-6mm becomes the 1-2mm thin-pass, mixing even, sheet about mill, naturally cooling.
B. after at room temperature parking 17h, put into mould, use the vulcanizing press sulfidization molding, remain on 170 ℃ * 5min * 10MPa, make the WSR test piece.
Its main performance index is as follows:
A. hardness (Shao A): 90 degree b. tensile strength: 13.86MPa
C. tensile yield: 500% d. setafter break: 50%
E. weight expansion multiplying power: 43.1% (in deionized water, soaking 48h).
Embodiment 9: prepare WSR of the present invention
A. with 10 parts of 10 parts of 90 parts of HNBR, NBR, HAF, 1 part of stearic acid, 1 part of Zinic stearas, 4 parts in zinc oxide, 4 parts in magnesium oxide, 13 parts of white carbon blacks, 0.5 part on mica, 0.5 part of TM monex TD, 0.5 part of captax, 2 parts of 4 parts of DCP, ANPM, 60 parts of CMC, HA-81 part, 10 parts of NMA, 11 parts of SDBS, in Banbury mixer or mill, temperature 45-55 ℃, operation 10-15min, it is logical that roll spacing 4-6mm becomes the 1-2mm book, mixing even, sheet about mill, naturally cooling.
B. after at room temperature parking 17h, put into mould, use the vulcanizing press sulfidization molding, remain on 170 ℃ * 5min * 10MPa, make the WSR test piece.
Its main performance index is as follows:
A. hardness (Shao A): 72 degree b. tensile strength: 9MPa
C. tensile yield: 500% d. setafter break: 35%
E. weight expansion multiplying power: 127% (in deionized water, soaking 48h).
Embodiment 10: prepare WSR of the present invention
Use NBR100phr, DCP2.0phr, white carbon black 6.0phr, the consumption of pressing table 1 adds CMC, and the result when suction reaches balance sees Table 1 data.
| Embodiment | CMC phr | Stretching Strong degree MPa | Elongation at break % | Weight expansion multiplying power % |
| 1 2 3 4 | 0 10 60 80 | 1.21 1.31 0.63 0.98 | 220 240 260 220 | - 153.05 740.42 760.34 |
Along with the increase of CMC consumption, the rubber effective content reduces in the WSR composition, and stretching Strong degree descends, and swelling capacity significantly strengthens.When the parts by weight of CMC are zero among the embodiment 1, in the test duration, almost can not detect the changes in weight of test piece.
Embodiment 11: prepare water-swelling rubber and plastic material of the present invention
A. with 0.5 part of 1.5 parts of 90 parts of 10 parts of EVA, NR, DCP, S, 10 parts of white carbon blacks, Zn04 part, 1 part of stearic acid, 1 part of Zinic stearas, 10 parts of 50 parts of CMC, SDBS, 2 parts of TM monex TD, 2 parts of IPPD, in Banbury mixer or mill, temperature 55-65 ℃ of operation 10-15min, roll spacing 4-6mm becomes the 1-2mm thin-pass, mixing even, sheet about mill, naturally cooling.
B. after at room temperature parking 17h, put into mould, use the vulcanizing press sulfidization molding, remain on 165 ℃ * 16min * 10MPa, make the WSR test piece.
Its main performance index is as follows:
A. hardness (Shao A): 33 degree b. tensile strength: 6.2MPa
C. tensile yield: 625% d. setafter break: 20%
E. weight expansion multiplying power: 32.6% (in deionized water, soaking 22h).
Embodiment 12: prepare water-swelling rubber and plastic material of the present invention
A. with 10 parts of 90 parts of NBR, PF, 5 parts of carbon blacks, 0.5 part of 1 part of S, DCP,
2 parts of TM monex TD, Zn03 part, 1.5 parts of stearic acid, 12 parts of 55 parts of CMC, SDS, 5 parts in potter's clay, 0.2 part of hexamethylenetetramine, in Banbury mixer or mill, temperature 55-65 ℃ of operation 10-15min, roll spacing 4-6mm becomes the 1-2mm thin-pass, mixing even, sheet about mill, naturally cooling.
B. after at room temperature parking 17h, put into mould, use the vulcanizing press sulfidization molding, remain on 160 ℃ * 16min * 10MPa, make the WSR test piece.
Its main performance index is as follows:
A. hardness (Shao A): 68 degree b. tensile strength: 4.3MPa
C. tensile yield: 340% d. setafter break: 8%
E. weight expansion multiplying power: 48.6% (in deionized water, soaking 22h).
Embodiment 13: prepare water-swelling plastics of the present invention
A. with 30 parts of 60 parts of 100 parts of EVA, CMC, DS, 2 parts of DCP, in Banbury mixer or mill, operate 10-15min for temperature 55-65 ℃, roll spacing 4-6mm becomes the 1-2mm thin-pass, and is mixing even, sheet about mill, naturally cooling.
B. after at room temperature parking 17h, put into mould, use the vulcanizing press sulfidization molding, remain on 100 ℃ * 10min * 10MPa, make the WSR test piece.
Its main performance index is as follows:
A. hardness (Shao A): 78 degree b. tensile strength: 2.1MPa
C. tensile yield: 50% d. setafter break: 5%
E. weight expansion multiplying power: 49.9% (in deionized water, soaking 22h).
Embodiment 14: prepare water-swelling plastics of the present invention
A. with 2 parts of 15 parts of 55 parts of 100 parts of arborescens CPE, CMC, SDBS, NMA, DCP1.5 part in Banbury mixer or mill, temperature 60-65 ℃ of operation 11-15min, roll spacing 4-6mm becomes the 1-2mm thin-pass, mixing evenly, at mill sheet up and down, naturally cooling.
B. after at room temperature parking 17h, put into mould, use the vulcanizing press sulfidization molding, remain on 150 ℃ * 40min * 10MPa, make test piece.
Its main performance index is as follows:
A. hardness (Shao A): 85 degree b. tensile strength: 7.5MPa
C. tensile yield: 40% d. setafter break: 3%
E. weight expansion multiplying power: 35% (in deionized water, soaking 22h).
Embodiment 15: prepare water-swelling plastics of the present invention
1.5 parts of 55 parts of 100 parts of A.CSM, CMC, 15 parts of 10 parts of HEC, SDBS, 2 parts of NMA, DCP in Banbury mixer or mill, temperature 60-65 ℃ of operation 11-15min, roll spacing 4-6mm, become the 1-2mm thin-pass, mixing even, sheet about mill, naturally cooling.
B. after at room temperature parking 17h, put into mould, use the vulcanizing press sulfidization molding, remain on 150 ℃ * 40min * 10MPa, make test piece.
Its main performance index is as follows:
A. hardness (Shao A): 60 degree b. tensile strength: 3.7MPa
C. tensile yield: 515% d. setafter break: 40%
E. weight expansion multiplying power: 85.2% (in deionized water, soaking 22h).
Claims (9)
1. water uptake expansion composition, it is made up of water-retaining agent, reaction monomers and tensio-active agent, and described water-retaining agent is a natural hydrophilic macromolecular compound or derivatives thereof; Described reaction monomers is the vinyl monomer that contains possess hydrophilic property after the monomer of suction basic carboxyl, hydroxyl, ether, amido, amino, sulfonic group, carboxylate group, sulphonate-base or quaternary ammonium salt monomer or the hydrolysis, described monomer contains two keys, can take place crosslinked with water-retaining agent; Wherein the weight content of water-retaining agent is 3-100 part; The weight content of reaction monomers is 0-30 part; The weight content of tensio-active agent is 0-70 part.
2. the described water uptake expansion composition of claim 1 is as the application of the water absoption expanding agent in the water uptake expansion material.
3. application according to claim 2, wherein said water uptake expansion material is selected from elastomerics or inelastic body.
4. water swelling rubber, it comprises the described water uptake expansion composition of claim 1, rubber and vulcanizing agent, and the weight content of wherein said rubber is 100 parts, and the weight content of vulcanizing agent is 0.6-20 part.
5. water-swelling rubber and plastic material, it comprises the described water uptake expansion composition of claim 1, rubber and plastic material and vulcanizing agent, and the weight content of wherein said rubber and plastic material is 100 parts, and the weight content of vulcanizing agent is 0.6-20 part.
6. water-swelling plastics, it comprises the described water uptake expansion composition of claim 1, plastics and linking agent, and the weight content of wherein said plastics is 100 parts, and the weight content of linking agent is 0.6-20 part.
7. method for preparing the described water swelling rubber of claim 4, wherein water-retaining agent and/or reaction monomers and/or tensio-active agent directly are added in the rubber, react in vulcanization of rubber process.
8. any described water swelling rubber of claim 4-6, water-swelling rubber and plastic material or the water-swelling plastics application in the preparation sealing member.
9. water uptake expansion packer, it is by tube core and be coated on the outer expansion sleeve of this tube core and form, and wherein, described expansion sleeve is made by any described water swelling rubber, water-swelling rubber and plastic material or water-swelling plastics among the claim 4-6.
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Effective date of registration: 20190905 Address after: 13th Floor, Block C, Yuanda Center, No. 5 Huizhong Road, Chaoyang District, Beijing 100101 Patentee after: STARSE Energy and Technology (Group) Co., Ltd. Address before: 100101 C05-06, 20th floor, Block C, Yuanda Center, No. 5 Huizhong Road, Chaoyang District, Beijing Co-patentee before: Yi Qizun Patentee before: Yi Huian |