CN101857658B - Copolymer for acid fracturing retarded gel acid and preparation method thereof - Google Patents
Copolymer for acid fracturing retarded gel acid and preparation method thereof Download PDFInfo
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- CN101857658B CN101857658B CN200910081737XA CN200910081737A CN101857658B CN 101857658 B CN101857658 B CN 101857658B CN 200910081737X A CN200910081737X A CN 200910081737XA CN 200910081737 A CN200910081737 A CN 200910081737A CN 101857658 B CN101857658 B CN 101857658B
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Abstract
The invention relates to a copolymer for acid fracturing retarded gel acid and a preparation method thereof. The structural formula of the copolymer is shown in the specifications, wherein m:n:p=95:1:4; and the molecular weight of the copolymer is between 8 and 12 million. The copolymer of the invention has high rigidity, is chain-branched, is a rigid branch chain hydrophobic copolymer and plays an important role in improving the viscosity characteristic of a retarded gel acid system and lowering acid filtration and acid rock reaction speeds.
Description
Technical field
The present invention relates to the petroleum industry acid fracturing and split the field, particularly a kind of multipolymer that is used for acid fracturing retarded gel acid and preparation method thereof.
Background technology
Carbonate rock hydrocarbon reservoir occupies an important position in the distribution of world's hydrocarbon-bearing pool; According in 57 sedimentary basins of nearly 40 countries and regions, having found and developed carbonate rock hydrocarbon reservoir tentatively in the world; Its oil and gas reserves accounts for 48% and 28% of world's oil, gas total reserves respectively, and oil, gas output account for 60% and 30% of world's oil, gas total amount respectively.Since the seventies, China in triumph, North China and basinal facies secondary such as the Liaohe River, Tarim Basin are existing and developed more than 30 Carbonate Burial Hill hydrocarbon-bearing pool, in oil field prospecting exploitation in recent years, have occupied important position.
Split in the field at the carbonate rock hydrocarbon reservoir acid fracturing, slow gel acid is widely used, and result of study shows; Slow gel acid is lower 3-7 times than the speed of response of the hydrochloric acid of conventional same concentrations with the speed of response of limestone, and certain viscosity is arranged, after pressing off the stratum; In the stratum, can evenly advance; Both reduced leak-off, the effect of protection immediate vicinity of wellbore oil reservoir is played on even again corrosion stratum.
The principal element of control acid fracturing effect is the EFFECTIVE RANGE of fissured flow conductivity and acid solution.Acid rock reaction is a heterogeneous reaction process, is mainly accomplished by three steps: 1. H
+Ion is to the scar transmission; 2. H
+Ion and rock react; 3. resultant of reaction leaves the interface, in residual acid solution, transmits.The speed of response of limestone and hydrochloric acid is mainly mass transfer control, and is very fast in the speed of response of solid-liquid interface, thereby the rheology and the heat resistance that improve acid solution are to improve the key of acid fracturing effect.
At present split the slow gel acid used in the field owing to (generally be not more than 50mPa.s under the normal temperature in that viscosity is low at the carbonate rock hydrocarbon reservoir acid fracturing; Generally be not more than 20 mPa.s under 120 ℃ of conditions); Existing bigger gap aspect reduction acid liquid loss and the sour rock speed of response; And the viscosity characteristics of slow gel acid depends on the constructional feature of the employed high molecular polymer of slow gel acid, and therefore being necessary to propose new high molecular polymer improves slow gel acid viscosity.
Summary of the invention:
One of the object of the invention provides a kind of multipolymer that is used for acid fracturing retarded gel acid, and this multipolymer is by two kinds of ammonium salt monomers and free-radical polymerized the forming of acrylic amide process, has the characteristics of good rigidly, collateralization.Multipolymer of the present invention is used for slow gel acid, can improve the temperature resistance and the viscosity of slow gel acid; And thermostability, rheological characteristics are good; Reduce acid liquid loss and carbonatite speed of response, effective.The multipolymer synthesis technique is simple, with low cost and raw material sources are extensive, can be widely used in the technological process that acid fracturing splits.Another object of the present invention provides this preparation method who is used for the multipolymer of acid fracturing retarded gel acid.
The present invention is by there being following technical proposals to realize: a kind of multipolymer that is used for acid fracturing retarded gel acid, this multipolymer are by a kind of formula of using
Methylacryoyloxyethyl trimethyl ammonium chloride structural unit and a kind of formula of using of expression
The expression the dimethyl diallyl ammonium chloride structural unit and use formula
The acrylic amide of expression is 8,000,000 ~ 1,200 ten thousand multipolymer with 95～100:0～5:0～free-radical polymerized molecular weight that forms of 5 mol ratios process, and its structural formula is:
M:n:p=95～100:0～5:0～5 wherein.
The preparation method of said multipolymer may further comprise the steps:
Synthesizing of a, Dimethylaminoethyl Methacrylate: methylacrylic acid and dimethylamino-ethanol are joined in the reaction kettle by weight 1:1.05～1.20, get mixture A, add the stopper of mixture A total amount 0.05%～0.1%; Mix, add the catalyzer of mixture A total amount 0.08%～0.24%, slowly be warming up to 120 degree; The constant temperature condensing reflux is 6～8 hours under stirring; And keep-up pressure in 0.6 MPa in the homothermic process, be cooled to normal temperature, at 0.4 kPa of following vacuum fractionation; Cut between collecting 90 ℃～94 ℃, the water white liquid that obtains both be Dimethylaminoethyl Methacrylate;
Synthesizing of b, methylacryoyloxyethyl trimethyl ammonium chloride: Dimethylaminoethyl Methacrylate, monochloro methane and water that step a obtains are put in the reaction kettle by weight the ratio of 1:1.10～1.30:0.55～0.95; Get mixture B; The stopper that adds mixture B total amount 0.1%～0.15%; Add the catalyzer of mixture B total amount 0.2%～0.4%, be warmed up to 60 ℃～80 ℃, constant temperature is 4～6 hours under stirring; The solution that obtains faint yellow clear, homogeneous both had been the methylacryoyloxyethyl trimethyl ammonium chloride, and methylacryoyloxyethyl trimethyl ammonium chloride active constituent content is not less than 78%;
C, multipolymer synthetic: the methylacryoyloxyethyl trimethyl ammonium chloride that deionized water, dimethyl diallyl ammonium chloride, acrylic amide, step b the are obtained ratio of 10:2～5:6～12:73～82 is by weight proportion put in the reaction kettle; Get mixture C, temperature is controlled in 10 ℃, regulate the pH value 4.2～6.8; Logical nitrogen deoxygenation 20～30 minutes; Under protection of nitrogen gas, add catalyzer 1, catalyzer 2, catalyzer 3, catalyzer 4, catalyzer 5, catalyzer 6 successively, up to blow motionless till, reaction heated up 4～5 hours; After the homo(io)thermism; Reaction kettle is squeezed into 40 ℃～50 ℃ hot water, aging 3～4 hours of constant temperature, and fragmentation, granulation, drying, pulverizing obtain multipolymer.
Among the step a, said stopper is a MEHQ, and said catalyzer is strong acid or highly basic;
Among the step b, said stopper is a MEHQ, and said catalyzer is Lewis acid or Lewis base;
Among the step c, said catalyzer 1 is an azo class organic cpds, and consumption is the 400ppm～800ppm of mixture C total amount; Said catalyzer 2 is hydroxyl or type oxy-compound, and consumption is the 2ppm～20ppm of mixture C total amount; Said catalyzer 3 is the persulphate compounds, and consumption is the 1ppm～15ppm of mixture C total amount; Said catalyzer 4 is a sequestrant, and consumption is the 5ppm～40ppm of mixture C total amount; Said catalyzer 5 is a peroxy compound, and consumption is the 0.5ppm～4ppm of mixture C total amount; Said catalyzer 6 is a reducing metal class mineral compound, and consumption is the 0.4ppm～3.2ppm of mixture C total amount.
Among the step c, said azo class organic cpds is Diisopropyl azodicarboxylate or ABVN; A said hydroxyl or a type oxy-compound are phosphoric acid salt inorganic salt hydroxy-containing compounds or alcohol compound or mercaptoethanol class compounds containing thiol groups; Said persulphate compounds is the positive monovalence inorganic salt compound or the Lucidol organic cpds of persulfuric acid; Said sequestrant is nitrilotriacetic acid or diethylenetriamine pentaacetic acid or citric acid salt sequestrant or tartrates sequestrant or EDTA class sequestrant; Said peroxy compound is hydrogen peroxide or Peracetic Acid or tert-butyl peroxide or tertbutanol peroxide; Said reducing metal class mineral compound is cuprous chloride or chlorination diamino-copper or ferrous sulfate or ferrous ammonium sulphate.
The invention has the beneficial effects as follows: according to industry standard SY/T 5764-1995, SY/T6214-1996 test, each item index has all reached industry standard through technical study institute of Shengli Oil Field Co., Ltd., SINOPEC fracture acidizing research centre in the present invention.
1, thermally-stabilised rheological characteristics is good
The liquid system of 0.8% multipolymer of the present invention in 20%HCL can be used for 140-160 ℃ stratum acid fracturing and splits.At 25 ℃, 170 s
-1Under the condition, viscosity can reach 45-60mPa.s, at 90 ℃, 170 s
-1Under the condition, viscosity can reach 36-42mPa.s, at 120 ℃, 170 s
-1Under the condition, viscosity can reach 24-30mPa.s.
The liquid system of 1.0% multipolymer of the present invention in 20%HCL can be used for 160-180 ℃ stratum.At 25 ℃, 170 s
-1Under the condition, viscosity can reach 50-70mPa.s, at 90 ℃, 170 s
-1Under the condition, viscosity can reach 45-57mPa.s, at 120 ℃, 170 s
-1Under the condition, viscosity can reach 36-45mPa.s, at 160 ℃, 170 s
-1Under the condition, viscosity can reach 24-30mPa.s.
3, slow performance is obvious
The slow rate of the liquid system of multipolymer of the present invention in 20%HCL is greater than 90% (comparing with blank hydrochloric acid).
4, the good filter characteristic of falling
The liquid system of multipolymer of the present invention in 20%HCL reduced the leak-off to the stratum effectively owing to have good rheological characteristics.
5, compatibility is superior
Compatibilities such as multipolymer of the present invention and most inhibiter, emulsion splitter, Fe stabilizer, expansion-resisting agent are good, and are prone to dissolve with water or acid.
For a better understanding of the present invention, further illustrate content of the present invention below in conjunction with instance.
Concrete embodiment:
Embodiment 1:
Present embodiment provides the multipolymer that an example is used for acid fracturing retarded gel acid, and this multipolymer is by a kind of formula of using
Methylacryoyloxyethyl trimethyl ammonium chloride structural unit and a kind of formula of using of expression
The expression the dimethyl diallyl ammonium chloride structural unit and use formula
The acrylic amide of expression is 8,500,000 multipolymer with the mol ratio of 95:1:4 through the free-radical polymerized molecular weight that forms, and its structural formula is:
M:n:p=95:1:4 wherein.
Can find out that from the structural formula of multipolymer of the present invention in the structural formula of this multipolymer, methylacryoyloxyethyl trimethyl ammonium chloride structural unit has three methyl CH
3, and the dimethyl diallyl ammonium chloride structural unit has a five-ring
Multipolymer of the present invention has been Duoed a methyl CH than the polymkeric substance that is used for acid fracturing retarded gel acid of prior art
3With a five-ring.Therefore, this multipolymer good rigidly and collateralization are a kind of rigidity collateralization hydrophobic copolymers, and this multipolymer reaches the viscosity characteristics that improves slow gel acid system and playing an important role aspect reduction acid liquid loss and the sour rock speed of response.
Embodiment 2:
A kind of preparation method of multipolymer may further comprise the steps:
Synthesizing of a, Dimethylaminoethyl Methacrylate: methylacrylic acid and dimethylamino-ethanol are joined in the reaction kettle by weight 1:1.05, get mixture A, add the MEHQ of mixture A total amount 0.05%; Mix, add the strong acid of mixture A total amount 0.08%, slowly be warming up to 120 degree; Constant temperature condensing reflux 6～8 hours; And keep-up pressure in 0.6 MPa in the homothermic process, be cooled to normal temperature, at 0.4 kPa of following vacuum fractionation; Cut between collecting 90 ℃～94 ℃, the water white liquid that obtains both be Dimethylaminoethyl Methacrylate;
Synthesizing of b, methylacryoyloxyethyl trimethyl ammonium chloride: Dimethylaminoethyl Methacrylate, monochloro methane and water that step a obtains are put in the reaction kettle by weight the ratio of 1.0:1.10:0.55; Get mixture B; The MEHQ that adds mixture B total amount 0.1%; Add the Lewis acid of mixture B total amount 0.2%, be warmed up to 60 ℃～80 ℃, constant temperature is 4～6 hours under stirring; The solution that obtains faint yellow clear, homogeneous both had been the methylacryoyloxyethyl trimethyl ammonium chloride, and methylacryoyloxyethyl trimethyl ammonium chloride active constituent content is not less than 78%;
C, multipolymer synthetic: the methylacryoyloxyethyl trimethyl ammonium chloride that deionized water, dimethyl diallyl ammonium chloride, acrylic amide, step b the are obtained ratio of 10:2:6:82 is by weight proportion put in the reaction kettle; Get mixture C; Temperature is controlled in 10 ℃, regulates the pH value 6.80.Logical nitrogen deoxygenation 20～30 minutes; Under protection of nitrogen gas, add ABVN, ethanol, Lucidol, nitrilotriacetic acid, hydrogen peroxide, chlorination diamino-copper successively, up to blow motionless till, reaction heated up 4～5 hours; After the homo(io)thermism; Reaction kettle is squeezed into 40 ℃～50 ℃ hot water, aging 3～4 hours of constant temperature, and fragmentation, granulation, drying, pulverizing obtain multipolymer;
Wherein: the consumption of ABVN is the 400ppm of mixture C total amount;
Consumption of ethanol is the 2ppm of mixture C total amount;
The consumption of Lucidol is the 1ppm of mixture C total amount;
The consumption of nitrilotriacetic acid is the 5ppm of mixture C total amount;
The consumption of hydrogen peroxide is the 0.5ppm of mixture C total amount;
The consumption of chlorination diamino-copper is the 0.4ppm of mixture C total amount.
Embodiment 3:
A kind of preparation method of multipolymer may further comprise the steps:
Synthesizing of a, Dimethylaminoethyl Methacrylate: methylacrylic acid and dimethylamino-ethanol are joined in the reaction kettle by weight 1:1.20, get mixture A, add the MEHQ of mixture A total amount 0.1%; Mix, add the strong acid of mixture A total amount 0.24%, slowly be warming up to 120 degree; Constant temperature condensing reflux 6～8 hours; And keep-up pressure in 0.6 MPa in the homothermic process, be cooled to normal temperature, at 0.4 kPa of following vacuum fractionation; Cut between collecting 90 ℃～94 ℃, the water white liquid that obtains both be Dimethylaminoethyl Methacrylate;
Synthesizing of b, methylacryoyloxyethyl trimethyl ammonium chloride: Dimethylaminoethyl Methacrylate, monochloro methane and water that step a obtains are put in the reaction kettle by weight the ratio of 1:1.30:0.95; Get mixture B; The MEHQ that adds mixture B total amount 0.15%; Add the Lewis acid of mixture B total amount 0.4%, be warmed up to 60 ℃～80 ℃, constant temperature is 4～6 hours under stirring; The solution that obtains faint yellow clear, homogeneous both had been the methylacryoyloxyethyl trimethyl ammonium chloride, and methylacryoyloxyethyl trimethyl ammonium chloride active constituent content is not less than 78%;
C, multipolymer synthetic: the methylacryoyloxyethyl trimethyl ammonium chloride that deionized water, dimethyl diallyl ammonium chloride, acrylic amide, step b the are obtained ratio of 10:5:12:73 is by weight proportion put in the reaction kettle; Get mixture C; Temperature is controlled in 10 ℃, regulates the pH value 4.2.Logical nitrogen deoxygenation 20～30 minutes; Under protection of nitrogen gas, add ABVN, ethanol, Lucidol, nitrilotriacetic acid, hydrogen peroxide, chlorination diamino-copper successively, up to blow motionless till, reaction heated up 4～5 hours; After the homo(io)thermism; Reaction kettle is squeezed into 40 ℃～50 ℃ hot water, aging 3～4 hours of constant temperature, and fragmentation, granulation, drying, pulverizing obtain multipolymer;
Wherein: the consumption of ABVN is the 800ppm of mixture C total amount;
Consumption of ethanol is the 20ppm of mixture C total amount;
The consumption of Lucidol is the 15ppm of mixture C total amount;
The said consumption of nitrilotriacetic acid is the 40ppm of mixture C total amount;
The consumption of hydrogen peroxide is the 4ppm of mixture C total amount;
The consumption of chlorination diamino-copper is the 3.2ppm of mixture C total amount.
Embodiment 4:
A kind of preparation method of multipolymer may further comprise the steps:
Synthesizing of a, Dimethylaminoethyl Methacrylate: methylacrylic acid and dimethylamino-ethanol are joined in the reaction kettle by weight 1:1.15, get mixture A, add the MEHQ of mixture A total amount 0.08%; Mix, add the strong acid of mixture A total amount 0.15%, slowly be warming up to 120 degree; Constant temperature condensing reflux 6～8 hours; And keep-up pressure in 0.6 MPa in the homothermic process, be cooled to normal temperature, at 0.4 kPa of following vacuum fractionation; Cut between collecting 90 ℃～94 ℃, the water white liquid that obtains both be Dimethylaminoethyl Methacrylate;
Synthesizing of b, methylacryoyloxyethyl trimethyl ammonium chloride: Dimethylaminoethyl Methacrylate, monochloro methane and water that step a obtains are put in the reaction kettle by weight the ratio of 1:1.20:0.75; Get mixture B; The MEHQ that adds mixture B total amount 0.13%; Add the Lewis acid of mixture B total amount 0.3%, be warmed up to 60 ℃～80 ℃, constant temperature is 4～6 hours under stirring; The solution that obtains faint yellow clear, homogeneous both had been the methylacryoyloxyethyl trimethyl ammonium chloride, and methylacryoyloxyethyl trimethyl ammonium chloride active constituent content is not less than 78%;
C, multipolymer synthetic: the methylacryoyloxyethyl trimethyl ammonium chloride that deionized water, dimethyl diallyl ammonium chloride, acrylic amide, step b the are obtained ratio of 10:3:8:79 is by weight proportion put in the reaction kettle; Get mixture C, temperature is controlled in 10 ℃, regulate the pH value 5.8; Logical nitrogen deoxygenation 20～30 minutes; Under protection of nitrogen gas, add ABVN, ethanol, Lucidol, nitrilotriacetic acid, hydrogen peroxide, chlorination diamino-copper successively, up to blow motionless till, reaction heated up 4～5 hours; After the homo(io)thermism; Reaction kettle is squeezed into 40 ℃～50 ℃ hot water, aging 3～4 hours of constant temperature, and fragmentation, granulation, drying, pulverizing obtain multipolymer;
Wherein, The consumption of ABVN is the 600ppm of mixture C total amount;
Consumption of ethanol is the 10ppm of mixture C total amount;
The consumption of Lucidol is the 8ppm of mixture C total amount;
The consumption of nitrilotriacetic acid is the 20ppm of mixture C total amount;
The consumption of hydrogen peroxide is the 3ppm of mixture C total amount;
The consumption of chlorination diamino-copper is the 2.4ppm of mixture C total amount.
Embodiment 5:
A kind of preparation method of multipolymer may further comprise the steps:
Synthesizing of a, Dimethylaminoethyl Methacrylate: methylacrylic acid and dimethylamino-ethanol are joined in the reaction kettle by weight 1:1.05, get mixture A, add the MEHQ of mixture A total amount 0.1%; Mix, add the strong acid of mixture A total amount 0.24%, slowly be warming up to 120 degree; Constant temperature condensing reflux 6～8 hours; And keep-up pressure in 0.6 MPa in the homothermic process, be cooled to normal temperature, at 0.4 kPa of following vacuum fractionation; Cut between collecting 90 ℃～94 ℃, the water white liquid that obtains both be Dimethylaminoethyl Methacrylate;
Synthesizing of b, methylacryoyloxyethyl trimethyl ammonium chloride: Dimethylaminoethyl Methacrylate, monochloro methane and water that step a obtains are put in the reaction kettle by weight the ratio of 1:1.30:0.55; Get mixture B; The MEHQ that adds mixture B total amount 0.15%; Add the Lewis acid of mixture B total amount 0.4%, be warmed up to 60 ℃～80 ℃, constant temperature is 4～6 hours under stirring; The solution that obtains faint yellow clear, homogeneous both had been the methylacryoyloxyethyl trimethyl ammonium chloride, and methylacryoyloxyethyl trimethyl ammonium chloride active constituent content is not less than 78%;
C, multipolymer synthetic: the methylacryoyloxyethyl trimethyl ammonium chloride that deionized water, dimethyl diallyl ammonium chloride, acrylic amide, step b the are obtained ratio of 10:2:6:82 is by weight proportion put in the reaction kettle; Get mixture C, temperature is controlled in 10 ℃, regulate the pH value 6.2; Logical nitrogen deoxygenation 20～30 minutes; Under protection of nitrogen gas, add Diisopropyl azodicarboxylate, inferior sodium phosphate, Sodium Persulfate, diethylenetriamine pentaacetic acid, Peracetic Acid, ferrous ammonium sulphate successively, up to blow motionless till, reaction heated up 4～5 hours; After the homo(io)thermism; Reaction kettle is squeezed into 40 ℃～50 ℃ hot water, aging 3～4 hours of constant temperature, and fragmentation, granulation, drying, pulverizing obtain multipolymer;
Wherein: the consumption of Diisopropyl azodicarboxylate is the 400ppm of mixture C total amount;
The consumption of inferior sodium phosphate is the 8ppm of mixture C total amount;
The consumption of Sodium Persulfate is the 1ppm of mixture C total amount;
The consumption of diethylenetriamine pentaacetic acid is the 5ppm of mixture C total amount;
The consumption of Peracetic Acid is the 2.0ppm of mixture C total amount;
The consumption of ferrous ammonium sulphate is the 1.6ppm of mixture C total amount.
In 4 preparation method embodiment of above-mentioned multipolymer, azo class organic cpds can be azo-bis-isobutyl cyanide or azo two cyanogen in different heptan; A hydroxyl or a type oxy-compound can be phosphoric acid salt inorganic salt hydroxy-containing compounds or alcohol compound or mercaptoethanol class compounds containing thiol groups; The persulphate compounds can be the positive monovalence inorganic salt compound or the Lucidol organic cpds of persulfuric acid; Sequestrant can be nitrilotriacetic acid or diethylenetriamine pentaacetic acid or citric acid salt sequestrant or tartrates sequestrant or EDTA class sequestrant; Peroxy compound can be hydrogen peroxide or Peracetic Acid or tert-butyl peroxide or tertbutanol peroxide; Reducing metal class mineral compound can be cuprous chloride or chlorination diamino-copper or ferrous sulfate or ferrous ammonium sulphate.
Claims (6)
1. a multipolymer that is used for acid fracturing retarded gel acid is characterized in that, this multipolymer is by a kind of formula of using
Methylacryoyloxyethyl trimethyl ammonium chloride structural unit and a kind of formula of using of expression
The expression the dimethyl diallyl ammonium chloride structural unit and use formula
The acrylic amide of expression is 8,000,000 ~ 1,200 ten thousand multipolymer with 95～100:0～5:0～free-radical polymerized molecular weight that forms of 5 mol ratios process, and its structural formula is:
M:n:p=95～100:0～5:0～5 wherein.
2. the preparation method of the described multipolymer of claim 1 is characterized in that, said preparation method may further comprise the steps:
Synthesizing of a, Dimethylaminoethyl Methacrylate: methylacrylic acid and dimethylamino-ethanol are joined in the reaction kettle by weight 1:1.05～1.20, get mixture A, add the stopper of mixture A total amount 0.05%～0.1%; Mix, add the catalyzer of mixture A total amount 0.08%～0.24%, slowly be warming up to 120 degree; The constant temperature condensing reflux is 6～8 hours under stirring; And keep-up pressure in 0.6 MPa in the homothermic process, be cooled to normal temperature, at 0.4 kPa of following vacuum fractionation; Cut between collecting 90 ℃～94 ℃, the water white liquid that obtains both be Dimethylaminoethyl Methacrylate; Said stopper is a MEHQ, and said catalyzer is strong acid or highly basic;
Synthesizing of b, methylacryoyloxyethyl trimethyl ammonium chloride: Dimethylaminoethyl Methacrylate, monochloro methane and water that step a obtains are put in the reaction kettle by weight the ratio of 1:1.10～1.30:0.55～0.95; Get mixture B; The stopper that adds mixture B total amount 0.1%～0.15%; Add the catalyzer of mixture B total amount 0.2%～0.4%, be warmed up to 60 ℃～80 ℃, constant temperature is 4～6 hours under stirring; The solution that obtains faint yellow clear, homogeneous both had been the methylacryoyloxyethyl trimethyl ammonium chloride, and methylacryoyloxyethyl trimethyl ammonium chloride active constituent content is not less than 78%; Said stopper is a MEHQ, and said catalyzer is Lewis acid or Lewis base;
C, multipolymer synthetic: the methylacryoyloxyethyl trimethyl ammonium chloride that deionized water, dimethyl diallyl ammonium chloride, acrylic amide, step b the are obtained ratio of 10:2～5:6～12:73～82 is by weight proportion put in the reaction kettle; Get mixture C, temperature is controlled in 10 ℃, regulate the pH value 4.2～6.8; Logical nitrogen deoxygenation 20～30 minutes; Under protection of nitrogen gas, add catalyzer 1, catalyzer 2, catalyzer 3, catalyzer 4, catalyzer 5, catalyzer 6 successively, up to blow motionless till, reaction heated up 4～5 hours; After the homo(io)thermism; Reaction kettle is squeezed into 40 ℃～50 ℃ hot water, aging 3～4 hours of constant temperature, and fragmentation, granulation, drying, pulverizing obtain multipolymer; Said catalyzer 1 is Diisopropyl azodicarboxylate or ABVN, and consumption is the 400ppm～800ppm of mixture C total amount; Said catalyzer 2 is phosphoric acid salt inorganic salt hydroxy-containing compounds or alcohol compound or mercaptoethanol class compounds containing thiol groups, and consumption is the 2ppm～20ppm of mixture C total amount; Said catalyzer 3 is the positive monovalence inorganic salt compound or the Lucidol organic cpds of persulfuric acid, and consumption is the 1ppm～15ppm of mixture C total amount; Said catalyzer 4 is nitrilotriacetic acid or diethylenetriamine pentaacetic acid or citric acid salt sequestrant or tartrates sequestrant or EDTA class sequestrant, and consumption is the 5ppm～40ppm of mixture C total amount; Said catalyzer 5 is hydrogen peroxide or Peracetic Acid or tert-butyl peroxide or tertbutanol peroxide, and consumption is the 0.5ppm～4ppm of mixture C total amount; Said catalyzer 6 is cuprous chloride or chlorination diamino-copper or ferrous sulfate or ferrous ammonium sulphate, and consumption is the 0.4ppm～3.2ppm of mixture C total amount.
3. the preparation method of multipolymer according to claim 2 is characterized in that, said preparation method may further comprise the steps:
Synthesizing of a, Dimethylaminoethyl Methacrylate: methylacrylic acid and dimethylamino-ethanol are joined in the reaction kettle by weight 1:1.05, get mixture A, add the MEHQ of mixture A total amount 0.05%; Mix, add the strong acid of mixture A total amount 0.08%, slowly be warming up to 120 degree; Constant temperature condensing reflux 6～8 hours; And keep-up pressure in 0.6 MPa in the homothermic process, be cooled to normal temperature, at 0.4 kPa of following vacuum fractionation; Cut between collecting 90 ℃～94 ℃, the water white liquid that obtains both be Dimethylaminoethyl Methacrylate;
Synthesizing of b, methylacryoyloxyethyl trimethyl ammonium chloride: Dimethylaminoethyl Methacrylate, monochloro methane and water that step a obtains are put in the reaction kettle by weight the ratio of 1.0:1.10:0.55; Get mixture B; The MEHQ that adds mixture B total amount 0.1%; Add the Lewis acid of mixture B total amount 0.2%, be warmed up to 60 ℃～80 ℃, constant temperature is 4～6 hours under stirring; The solution that obtains faint yellow clear, homogeneous both had been the methylacryoyloxyethyl trimethyl ammonium chloride, and methylacryoyloxyethyl trimethyl ammonium chloride active constituent content is not less than 78%;
C, multipolymer synthetic: the methylacryoyloxyethyl trimethyl ammonium chloride that deionized water, dimethyl diallyl ammonium chloride, acrylic amide, step b the are obtained ratio of 10:2:6:82 is by weight proportion put in the reaction kettle; Get mixture C; Temperature is controlled in 10 ℃, regulates the pH value 6.80; Logical nitrogen deoxygenation 20～30 minutes; Under protection of nitrogen gas, add ABVN, ethanol, Lucidol, nitrilotriacetic acid, hydrogen peroxide, chlorination diamino-copper successively, up to blow motionless till, reaction heated up 4～5 hours; After the homo(io)thermism; Reaction kettle is squeezed into 40 ℃～50 ℃ hot water, aging 3～4 hours of constant temperature, and fragmentation, granulation, drying, pulverizing obtain multipolymer;
Wherein: the consumption of ABVN is the 400ppm of mixture C total amount;
Consumption of ethanol is the 2ppm of mixture C total amount;
The consumption of Lucidol is the 1ppm of mixture C total amount;
The consumption of nitrilotriacetic acid is the 5ppm of mixture C total amount;
The consumption of hydrogen peroxide is the 0.5ppm of mixture C total amount;
The consumption of chlorination diamino-copper is the 0.4ppm of mixture C total amount.
4. the preparation method of multipolymer according to claim 2 is characterized in that, said preparation method may further comprise the steps:
Synthesizing of a, Dimethylaminoethyl Methacrylate: methylacrylic acid and dimethylamino-ethanol are joined in the reaction kettle by weight 1:1.20, get mixture A, add the MEHQ of mixture A total amount 0.1%; Mix, add the strong acid of mixture A total amount 0.24%, slowly be warming up to 120 degree; Constant temperature condensing reflux 6～8 hours; And keep-up pressure in 0.6 MPa in the homothermic process, be cooled to normal temperature, at 0.4 kPa of following vacuum fractionation; Cut between collecting 90 ℃～94 ℃, the water white liquid that obtains both be Dimethylaminoethyl Methacrylate;
Synthesizing of b, methylacryoyloxyethyl trimethyl ammonium chloride: Dimethylaminoethyl Methacrylate, monochloro methane and water that step a obtains are put in the reaction kettle by weight the ratio of 1:1.30:0.95; Get mixture B; The MEHQ that adds mixture B total amount 0.15%; Add the Lewis acid of mixture B total amount 0.4%, be warmed up to 60 ℃～80 ℃, constant temperature is 4～6 hours under stirring; The solution that obtains faint yellow clear, homogeneous both had been the methylacryoyloxyethyl trimethyl ammonium chloride, and methylacryoyloxyethyl trimethyl ammonium chloride active constituent content is not less than 78%;
C, multipolymer synthetic: the methylacryoyloxyethyl trimethyl ammonium chloride that deionized water, dimethyl diallyl ammonium chloride, acrylic amide, step b the are obtained ratio of 10:5:12:73 is by weight proportion put in the reaction kettle; Get mixture C; Temperature is controlled in 10 ℃, regulates the pH value 4.2; Logical nitrogen deoxygenation 20～30 minutes; Under protection of nitrogen gas, add ABVN, ethanol, Lucidol, nitrilotriacetic acid, hydrogen peroxide, chlorination diamino-copper successively, up to blow motionless till, reaction heated up 4～5 hours; After the homo(io)thermism; Reaction kettle is squeezed into 40 ℃～50 ℃ hot water, aging 3～4 hours of constant temperature, and fragmentation, granulation, drying, pulverizing obtain multipolymer;
Wherein: the consumption of ABVN is the 800ppm of mixture C total amount;
Consumption of ethanol is the 20ppm of mixture C total amount;
The consumption of Lucidol is the 15ppm of mixture C total amount;
The said consumption of nitrilotriacetic acid is the 40ppm of mixture C total amount;
The consumption of hydrogen peroxide is the 4ppm of mixture C total amount;
The consumption of chlorination diamino-copper is the 3.2ppm of mixture C total amount.
5. the preparation method of multipolymer according to claim 2 is characterized in that, said preparation method may further comprise the steps:
Synthesizing of a, Dimethylaminoethyl Methacrylate: methylacrylic acid and dimethylamino-ethanol are joined in the reaction kettle by weight 1:1.15, get mixture A, add the MEHQ of mixture A total amount 0.08%; Mix, add the strong acid of mixture A total amount 0.15%, slowly be warming up to 120 degree; Constant temperature condensing reflux 6～8 hours; And keep-up pressure in 0.6 MPa in the homothermic process, be cooled to normal temperature, at 0.4 kPa of following vacuum fractionation; Cut between collecting 90 ℃～94 ℃, the water white liquid that obtains both be Dimethylaminoethyl Methacrylate;
Synthesizing of b, methylacryoyloxyethyl trimethyl ammonium chloride: Dimethylaminoethyl Methacrylate, monochloro methane and water that step a obtains are put in the reaction kettle by weight the ratio of 1:1.20:0.75; Get mixture B; The MEHQ that adds mixture B total amount 0.13%; Add the Lewis acid of mixture B total amount 0.3%, be warmed up to 60 ℃～80 ℃, constant temperature is 4～6 hours under stirring; The solution that obtains faint yellow clear, homogeneous both had been the methylacryoyloxyethyl trimethyl ammonium chloride, and methylacryoyloxyethyl trimethyl ammonium chloride active constituent content is not less than 78%;
C, multipolymer synthetic: the methylacryoyloxyethyl trimethyl ammonium chloride that deionized water, dimethyl diallyl ammonium chloride, acrylic amide, step b the are obtained ratio of 10:3:8:79 is by weight proportion put in the reaction kettle; Get mixture C, temperature is controlled in 10 ℃, regulate the pH value 5.8; Logical nitrogen deoxygenation 20～30 minutes; Under protection of nitrogen gas, add ABVN, ethanol, Lucidol, nitrilotriacetic acid, hydrogen peroxide, chlorination diamino-copper successively, up to blow motionless till, reaction heated up 4～5 hours; After the homo(io)thermism; Reaction kettle is squeezed into 40 ℃～50 ℃ hot water, aging 3～4 hours of constant temperature, and fragmentation, granulation, drying, pulverizing obtain multipolymer;
Wherein, The consumption of ABVN is the 600ppm of mixture C total amount;
Consumption of ethanol is the 10ppm of mixture C total amount;
The consumption of Lucidol is the 8ppm of mixture C total amount;
The consumption of nitrilotriacetic acid is the 20ppm of mixture C total amount;
The consumption of hydrogen peroxide is the 3ppm of mixture C total amount;
The consumption of chlorination diamino-copper is the 2.4ppm of mixture C total amount.
6. the preparation method of multipolymer according to claim 2 is characterized in that, said preparation method may further comprise the steps:
Synthesizing of a, Dimethylaminoethyl Methacrylate: methylacrylic acid and dimethylamino-ethanol are joined in the reaction kettle by weight 1:1.05, get mixture A, add the MEHQ of mixture A total amount 0.1%; Mix, add the strong acid of mixture A total amount 0.24%, slowly be warming up to 120 degree; Constant temperature condensing reflux 6～8 hours; And keep-up pressure in 0.6 MPa in the homothermic process, be cooled to normal temperature, at 0.4 kPa of following vacuum fractionation; Cut between collecting 90 ℃～94 ℃, the water white liquid that obtains both be Dimethylaminoethyl Methacrylate;
Synthesizing of b, methylacryoyloxyethyl trimethyl ammonium chloride: Dimethylaminoethyl Methacrylate, monochloro methane and water that step a obtains are put in the reaction kettle by weight the ratio of 1:1.30:0.55; Get mixture B; The MEHQ that adds mixture B total amount 0.15%; Add the Lewis acid of mixture B total amount 0.4%, be warmed up to 60 ℃～80 ℃, constant temperature is 4～6 hours under stirring; The solution that obtains faint yellow clear, homogeneous both had been the methylacryoyloxyethyl trimethyl ammonium chloride, and methylacryoyloxyethyl trimethyl ammonium chloride active constituent content is not less than 78%;
C, multipolymer synthetic: the methylacryoyloxyethyl trimethyl ammonium chloride that deionized water, dimethyl diallyl ammonium chloride, acrylic amide, step b the are obtained ratio of 10:2:6:82 is by weight proportion put in the reaction kettle; Get mixture C, temperature is controlled in 10 ℃, regulate the pH value 6.2; Logical nitrogen deoxygenation 20～30 minutes; Under protection of nitrogen gas, add Diisopropyl azodicarboxylate, inferior sodium phosphate, Sodium Persulfate, diethylenetriamine pentaacetic acid, Peracetic Acid, ferrous ammonium sulphate successively, up to blow motionless till, reaction heated up 4～5 hours; After the homo(io)thermism; Reaction kettle is squeezed into 40 ℃～50 ℃ hot water, aging 3～4 hours of constant temperature, and fragmentation, granulation, drying, pulverizing obtain multipolymer;
Wherein: the consumption of Diisopropyl azodicarboxylate is the 400ppm of mixture C total amount;
The consumption of inferior sodium phosphate is the 8ppm of mixture C total amount;
The consumption of Sodium Persulfate is the 1ppm of mixture C total amount;
The consumption of diethylenetriamine pentaacetic acid is the 5ppm of mixture C total amount;
The consumption of Peracetic Acid is the 2.0ppm of mixture C total amount;
The consumption of ferrous ammonium sulphate is the 1.6ppm of mixture C total amount.
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| CN103788290A (en) * | 2012-10-29 | 2014-05-14 | 中国石油化工股份有限公司 | Acrylamide copolymer, and preparation method and application thereof |
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| CN104388075A (en) * | 2014-10-27 | 2015-03-04 | 中国石油集团渤海钻探工程有限公司 | Gelatinizing agent for acidification of high temperature carbonatite and preparing method of gelatinizing agent |
| CN104650287A (en) * | 2015-02-13 | 2015-05-27 | 荆州市天合科技化工有限公司 | Novel powder cationic polymer for preventing clay from hydration swelling |
| CN105001849A (en) * | 2015-07-02 | 2015-10-28 | 西南石油大学 | Hydrophobically associated type cation acid solution retardant and preparation method thereof |
| CN105713594A (en) * | 2016-01-21 | 2016-06-29 | 西安石油大学 | Viscous acid and preparation method thereof |
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| CN107619660B (en) * | 2017-11-02 | 2020-04-14 | 中国石油化工股份有限公司 | Gelled acid thickener and preparation method thereof |
| CN108164642A (en) * | 2017-12-29 | 2018-06-15 | 山东诺尔生物科技有限公司 | A kind of acid fracturing operation gelling agent and preparation method thereof |
| CN110093148A (en) * | 2019-04-10 | 2019-08-06 | 南通科益化工有限公司 | A kind of hydrochlorate reaction reduction of speed agent and preparation method thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4726906A (en) * | 1984-11-23 | 1988-02-23 | Calgon Corporation | Polymers for use as filtration control aids in drilling muds |
| CN101161691A (en) * | 2007-11-28 | 2008-04-16 | 湖北省化学研究院 | Dispersion polymeric acrylamide emulsion and its application in oil field produced liquid treatment |
| CN101220263A (en) * | 2007-12-11 | 2008-07-16 | 北京希涛高分子聚合物研究所 | Water-based fracturing fluid gelatinizer and producing method thereof |
-
2009
- 2009-04-09 CN CN200910081737XA patent/CN101857658B/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4726906A (en) * | 1984-11-23 | 1988-02-23 | Calgon Corporation | Polymers for use as filtration control aids in drilling muds |
| CN101161691A (en) * | 2007-11-28 | 2008-04-16 | 湖北省化学研究院 | Dispersion polymeric acrylamide emulsion and its application in oil field produced liquid treatment |
| CN101220263A (en) * | 2007-12-11 | 2008-07-16 | 北京希涛高分子聚合物研究所 | Water-based fracturing fluid gelatinizer and producing method thereof |
Non-Patent Citations (3)
| Title |
|---|
| Li-Ying Tian et al.."Solution Properties of a Hyamine Based on N,N-Dimethyl Diallyl Ammonium Chloride–Acrylamide Copolymer".《Journal of Applied Polymer Science》.2002,第90卷(第3期),765-771. * |
| Li-YingTianetal.."SolutionPropertiesofaHyamineBasedonN N-Dimethyl Diallyl Ammonium Chloride–Acrylamide Copolymer".《Journal of Applied Polymer Science》.2002 |
| 赵修太等."反相乳液法合成高温酸化胶凝剂的研究".《钻井液与完井液》.2007,第24卷(第6期),58-61,65. |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103788290A (en) * | 2012-10-29 | 2014-05-14 | 中国石油化工股份有限公司 | Acrylamide copolymer, and preparation method and application thereof |
| CN103788290B (en) * | 2012-10-29 | 2016-06-29 | 中国石油化工股份有限公司 | A kind of acrylamide based copolymer and its preparation method and application |
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