CN101857658A - 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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- CN101857658A CN101857658A CN200910081737A CN200910081737A CN101857658A CN 101857658 A CN101857658 A CN 101857658A CN 200910081737 A CN200910081737 A CN 200910081737A CN 200910081737 A CN200910081737 A CN 200910081737A CN 101857658 A CN101857658 A CN 101857658A
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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, have occupied important position in oil field prospecting exploitation in recent years.
Split in the field at the carbonate rock hydrocarbon reservoir acid fracturing; slow gel acid is widely used; 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 finished by three steps: 1. H
+Ion is to the scar transmission; 2. H
+Ion and rock react; 3. resultant of reaction leaves the interface, transmits in residual acid solution.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 20mPa.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 purpose of the present 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 acrylamide 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 acrylamide of expression is with 95～100: the free-radical polymerized molecular weight that forms of 0～5: 0～5 mol ratio process is 8,000,000～1,200 ten thousand multipolymer, and its structural formula is:
M: n: p=95～100: 0～5: 0～5 wherein.
The preparation method of described multipolymer may further comprise the steps:
A, synthesizing of Dimethylaminoethyl Methacrylate: methacrylic acid and dimethylamino-ethanol are joined in the reactor by weight 1: 1.05～1.20, get mixture A, the stopper that adds mixture A total amount 0.05%～0.1%, mix, the catalyzer that adds 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 the homothermic process in 0.6 MPa, be cooled to normal temperature, at 0.4 kPa of following vacuum fractionation, the cut between collecting 90 ℃～94 ℃, the water white liquid that obtains both be Dimethylaminoethyl Methacrylate;
B, methylacryoyloxyethyl trimethyl ammonium chloride synthetic: the Dimethylaminoethyl Methacrylate that step a is obtained, monochloro methane and water are put in the reactor by weight 1: 1.10～1.30: 0.55～0.95 ratio, get mixture B, the stopper that adds mixture B total amount 0.1%～0.15%, the catalyzer that adds mixture B total amount 0.2%～0.4%, be warmed up to 60 ℃～80 ℃, constant temperature is 4～6 hours under stirring, obtain faint yellow clear, the solution of homogeneous both had been the methylacryoyloxyethyl trimethyl ammonium chloride, and methylacryoyloxyethyl trimethyl ammonium chloride active constituent content is not less than 78%;
C; synthesizing of multipolymer: with deionized water; dimethyl diallyl ammonium chloride; acrylamide; the ratio of the methylacryoyloxyethyl trimethyl ammonium chloride 10: 2 by weight proportion～5: 6～12: 73～82 that step b obtains is put in the reactor; 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 successively; catalyzer 2; catalyzer 3; catalyzer 4; catalyzer 5; catalyzer 6; up to blow motionless till; reaction heated up 4～5 hours; after the homo(io)thermism; reactor is squeezed into 40 ℃～50 ℃ hot water; aging 3～4 hours of constant temperature, fragmentation; granulation; dry; pulverizing obtains multipolymer.
Among the step a, described stopper is a MEHQ, and described catalyzer is strong acid or highly basic;
Among the step b, described stopper is a MEHQ, and described catalyzer is Lewis acid or Lewis base;
Among the step c, described catalyzer 1 is an azo class organic compound, and consumption is the 400ppm～800ppm of mixture C total amount; Described catalyzer 2 is hydroxyl or class oxy-compound, and consumption is the 2ppm～20ppm of mixture C total amount; Described catalyzer 3 is the persulphate compounds, and consumption is the 1ppm～15ppm of mixture C total amount; Described catalyzer 4 is a sequestrant, and consumption is the 5ppm～40ppm of mixture C total amount; Described catalyzer 5 is a peralcohol, and consumption is the 0.5ppm～4ppm of mixture C total amount; Described 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, described azo class organic compound is Diisopropyl azodicarboxylate or 2,2'-Azobis(2,4-dimethylvaleronitrile); Described hydroxyl or class oxy-compound are phosphoric acid salt inorganic salt hydroxy-containing compounds or alcohol compound or mercaptoethanol class compounds containing thiol groups; Described persulphate compounds is the positive monovalence inorganic salt compound or the benzoyl peroxide organic compound of persulfuric acid; Described sequestrant is nitrilotriacetic acid or diethylenetriamine pentaacetic acid or citric acid salt sequestrant or tartrates sequestrant or EDTA class sequestrant; Described peralcohol is hydrogen peroxide or Peracetic Acid or tert-butyl peroxide or tertbutanol peroxide; Described 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, every 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 ℃, 170s
-1Under the condition, viscosity can reach 45-60mPa.s, at 90 ℃, 170s
-1Under the condition, viscosity can reach 36-42mPa.s, at 120 ℃, 170s
-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 ℃, 170s
-1Under the condition, viscosity can reach 50-70mPa.s, at 90 ℃, 170s
-1Under the condition, viscosity can reach 45-57mPa.s, at 120 ℃, 170s
-1Under the condition, viscosity can reach 36-45mPa.s, at 160 ℃, 170s
-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 easily molten with water or acid.
For a better understanding of the present invention, further illustrate content of the present invention below in conjunction with example.
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 acrylamide of expression is 8,500,000 multipolymer with 95: 1: 4 mol ratio through the free-radical polymerized molecular weight that forms, and its structural formula is:
M: n: p=95 wherein: 1: 4.
As can be seen, in the structural formula of this multipolymer, methylacryoyloxyethyl trimethyl ammonium chloride structural unit has three methyl CH from the structural formula of multipolymer of the present invention
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:
A, synthesizing of Dimethylaminoethyl Methacrylate: methacrylic acid and dimethylamino-ethanol were joined in the reactor by weight 1: 1.05, get mixture A, the MEHQ that adds mixture A total amount 0.05%, mix, the strong acid that adds 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 the homothermic process in 0.6 MPa, be cooled to normal temperature, at 0.4 kPa of following vacuum fractionation, the cut between collecting 90 ℃～94 ℃, the water white liquid that obtains both be Dimethylaminoethyl Methacrylate;
B, methylacryoyloxyethyl trimethyl ammonium chloride synthetic: the Dimethylaminoethyl Methacrylate that step a is obtained, monochloro methane and water are put in the reactor by weight 1.0: 1.10: 0.55 ratio, get mixture B, the MEHQ that adds mixture B total amount 0.1%, the Lewis acid that adds mixture B total amount 0.2%, be warmed up to 60 ℃～80 ℃, constant temperature is 4～6 hours under stirring, obtain faint yellow clear, the solution of 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: with deionized water, dimethyl and the methylacryoyloxyethyl trimethyl ammonium chloride that allyl ammonium chloride, acrylamide, step b obtain 10: 2: 6 by weight proportion: 82 ratio is put in the reactor, 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 2,2'-Azobis(2,4-dimethylvaleronitrile), ethanol, benzoyl peroxide, nitrilotriacetic acid, hydrogen peroxide, chlorination diamino copper successively, up to blow motionless till, reaction heated up 4～5 hours, after the homo(io)thermism, hit the person 40 ℃～50 ℃ hot water of reactor, aging 3～4 hours of constant temperature, fragmentation, granulation, drying, pulverizing obtain multipolymer;
Wherein: the consumption of 2,2'-Azobis(2,4-dimethylvaleronitrile) is the 400ppm of mixture C total amount;
Consumption of ethanol is the 2ppm of mixture C total amount;
The consumption of benzoyl peroxide 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:
A, synthesizing of Dimethylaminoethyl Methacrylate: methacrylic acid and dimethylamino-ethanol were joined in the reactor by weight 1: 1.20, get mixture A, the MEHQ that adds mixture A total amount 0.1%, mix, the strong acid that adds 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 the homothermic process in 0.6 MPa, be cooled to normal temperature, at 0.4 kPa of following vacuum fractionation, the cut between collecting 90 ℃～94 ℃, the water white liquid that obtains both be Dimethylaminoethyl Methacrylate;
B, methylacryoyloxyethyl trimethyl ammonium chloride synthetic: the Dimethylaminoethyl Methacrylate that step a is obtained, monochloro methane and water are put in the reactor by weight 1: 1.30: 0.95 ratio, get mixture B, the MEHQ that adds mixture B total amount 0.15%, the Lewis acid that adds mixture B total amount 0.4%, be warmed up to 60 ℃～80 ℃, constant temperature is 4～6 hours under stirring, obtain faint yellow clear, the solution of 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: with deionized water, dimethyl and the methylacryoyloxyethyl trimethyl ammonium chloride that allyl ammonium chloride, acrylamide, step b obtain 10: 5: 12 by weight proportion: 73 ratio is put in the reactor, 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 2,2'-Azobis(2,4-dimethylvaleronitrile), ethanol, benzoyl peroxide, nitrilotriacetic acid, hydrogen peroxide, chlorination diamino copper successively, up to blow motionless till, reaction heated up 4～5 hours, after the homo(io)thermism, hit the person 40 ℃～50 ℃ hot water of reactor, aging 3～4 hours of constant temperature, fragmentation, granulation, drying, pulverizing obtain multipolymer;
Wherein: the consumption of 2,2'-Azobis(2,4-dimethylvaleronitrile) is the 800ppm of mixture C total amount;
Consumption of ethanol is the 20ppm of mixture C total amount;
The consumption of benzoyl peroxide is the 15ppm of mixture C total amount;
The described 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:
A, synthesizing of Dimethylaminoethyl Methacrylate: methacrylic acid and dimethylamino-ethanol were joined in the reactor by weight 1: 1.15, get mixture A, the MEHQ that adds mixture A total amount 0.08%, mix, the strong acid that adds 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 the homothermic process in 0.6 MPa, be cooled to normal temperature, at 0.4 kPa of following vacuum fractionation, the cut between collecting 90 ℃～94 ℃, the water white liquid that obtains both be Dimethylaminoethyl Methacrylate;
B, methylacryoyloxyethyl trimethyl ammonium chloride synthetic: the Dimethylaminoethyl Methacrylate that step a is obtained, monochloro methane and water are put in the reactor by weight 1: 1.20: 0.75 ratio, get mixture B, the MEHQ that adds mixture B total amount 0.13%, the Lewis acid that adds mixture B total amount 0.3%, be warmed up to 60 ℃～80 ℃, constant temperature is 4～6 hours under stirring, obtain faint yellow clear, the solution of homogeneous both had been the methylacryoyloxyethyl trimethyl ammonium chloride, and methylacryoyloxyethyl trimethyl ammonium chloride active constituent content is not less than 78%;
C, synthesizing of multipolymer: with deionized water, dimethyl and allyl ammonium chloride, acrylamide, the methylacryoyloxyethyl trimethyl ammonium chloride that step b obtains 10: 3: 8 by weight proportion: 79 ratio is put in the reactor, 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 2,2'-Azobis(2,4-dimethylvaleronitrile) successively, ethanol is urged, benzoyl peroxide, nitrilotriacetic acid, hydrogen peroxide, chlorination diamino copper, up to blow motionless till, reaction heated up 4～5 hours, after the homo(io)thermism, hit the person 40 ℃～50 ℃ hot water of reactor, aging 3～4 hours of constant temperature, fragmentation, granulation, dry, pulverizing obtains multipolymer;
Wherein, The consumption of 2,2'-Azobis(2,4-dimethylvaleronitrile) is the 600ppm of mixture C total amount;
Consumption of ethanol is the 10ppm of mixture C total amount;
The consumption of benzoyl peroxide 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:
A, synthesizing of Dimethylaminoethyl Methacrylate: methacrylic acid and dimethylamino-ethanol were joined in the reactor by weight 1: 1.05, get mixture A, the MEHQ that adds mixture A total amount 0.1%, mix, the strong acid that adds 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 the homothermic process in 0.6 MPa, be cooled to normal temperature, at 0.4 kPa of following vacuum fractionation, the cut between collecting 90 ℃～94 ℃, the water white liquid that obtains both be Dimethylaminoethyl Methacrylate;
B, methylacryoyloxyethyl trimethyl ammonium chloride synthetic: the Dimethylaminoethyl Methacrylate that step a is obtained, monochloro methane and water are put in the reactor by weight 1: 1.30: 0.55 ratio, get mixture B, the MEHQ that adds mixture B total amount 0.15%, the Lewis acid that adds mixture B total amount 0.4%, be warmed up to 60 ℃～80 ℃, constant temperature is 4～6 hours under stirring, obtain faint yellow clear, the solution of homogeneous both had been the methylacryoyloxyethyl trimethyl ammonium chloride, and methylacryoyloxyethyl trimethyl ammonium chloride active constituent content is not less than 78%;
C, synthesizing of multipolymer: with deionized water, dimethyl diallyl ammonium chloride, acrylamide, the methylacryoyloxyethyl trimethyl ammonium chloride that step b obtains 10: 2: 6 by weight proportion: 82 ratio is put in the reactor, 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 successively, inferior sodium phosphate, Sodium Persulfate, diethylenetriamine pentaacetic acid, Peracetic Acid, ferrous ammonium sulphate, up to blow motionless till, reaction heated up 4～5 hours, after the homo(io)thermism, hit the person 40 ℃～50 ℃ hot water of reactor, aging 3～4 hours of constant temperature, fragmentation, granulation, dry, pulverizing obtains 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 compound can be azo-bis-isobutyl cyanide or azo two cyanogen in different heptan; Hydroxyl or class 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 benzoyl peroxide organic compound of persulfuric acid; Sequestrant can be nitrilotriacetic acid or diethylenetriamine pentaacetic acid or citric acid salt sequestrant or tartrates sequestrant or EDTA class sequestrant; Peralcohol 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 (8)
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 acrylamide of expression is with 95～100: the free-radical polymerized molecular weight that forms of 0～5: 0～5 mol ratio process is 8,000,000～1,200 ten thousand multipolymer, 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, described preparation method may further comprise the steps:
A, synthesizing of Dimethylaminoethyl Methacrylate: methacrylic acid and dimethylamino-ethanol are joined in the reactor by weight 1: 1.05～1.20, get mixture A, the stopper that adds mixture A total amount 0.05%～0.1%, mix, the catalyzer that adds 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 the homothermic process in 0.6 MPa, be cooled to normal temperature, at 0.4 kPa of following vacuum fractionation, the cut between collecting 90 ℃～94 ℃, the water white liquid that obtains both be Dimethylaminoethyl Methacrylate;
B, methylacryoyloxyethyl trimethyl ammonium chloride synthetic: the Dimethylaminoethyl Methacrylate that step a is obtained, monochloro methane and water are put in the reactor by weight 1: 1.10～1.30: 0.55～0.95 ratio, get mixture B, the stopper that adds mixture B total amount 0.1%～0.15%, the catalyzer that adds mixture B total amount 0.2%～0.4%, be warmed up to 60 ℃～80 ℃, constant temperature is 4～6 hours under stirring, obtain faint yellow clear, the solution of homogeneous both had been the methylacryoyloxyethyl trimethyl ammonium chloride, and methylacryoyloxyethyl trimethyl ammonium chloride active constituent content is not less than 78%;
C; synthesizing of multipolymer: with deionized water; dimethyl diallyl ammonium chloride; acrylamide; the ratio of the methylacryoyloxyethyl trimethyl ammonium chloride 10: 2 by weight proportion～5: 6～12: 73～82 that step b obtains is put in the reactor; 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 successively; catalyzer 2; catalyzer 3; catalyzer 4; catalyzer 5; catalyzer 6; up to blow motionless till; reaction heated up 4～5 hours; after the homo(io)thermism; reactor is squeezed into 40 ℃～50 ℃ hot water; aging 3～4 hours of constant temperature, fragmentation; granulation; dry; pulverizing obtains multipolymer.
3. the preparation method of multipolymer according to claim 2 is characterized in that:
Among the step a, described stopper is a MEHQ, and described catalyzer is strong acid or highly basic;
Among the step b, described stopper is a MEHQ, and described catalyzer is Lewis acid or Lewis base;
Among the step c, described catalyzer 1 is an azo class organic compound, and consumption is the 400ppm～800ppm of mixture C total amount; Described catalyzer 2 is hydroxyl or class oxy-compound, and consumption is the 2ppm～20ppm of mixture C total amount; Described catalyzer 3 is the persulphate compounds, and consumption is the 1ppm～15ppm of mixture C total amount; Described catalyzer 4 is a sequestrant, and consumption is the 5ppm～40ppm of mixture C total amount; Described catalyzer 5 is a peralcohol, and consumption is the 0.5ppm～4ppm of mixture C total amount; Described catalyzer 6 is a reducing metal class mineral compound, and consumption is the 0.4ppm～3.2ppm of mixture C total amount.
4. the preparation method of multipolymer according to claim 3 is characterized in that:
Among the step c, described azo class organic compound is Diisopropyl azodicarboxylate or 2,2'-Azobis(2,4-dimethylvaleronitrile); Described hydroxyl or class oxy-compound are phosphoric acid salt inorganic salt hydroxy-containing compounds or alcohol compound or mercaptoethanol class compounds containing thiol groups; Described persulphate compounds is the positive monovalence inorganic salt compound or the benzoyl peroxide organic compound of persulfuric acid; Described sequestrant is nitrilotriacetic acid or diethylenetriamine pentaacetic acid or citric acid salt sequestrant or tartrates sequestrant or EDTA class sequestrant; Described peralcohol is hydrogen peroxide or Peracetic Acid or tert-butyl peroxide or tertbutanol peroxide; Described reducing metal class mineral compound is cuprous chloride or chlorination diamino copper or ferrous sulfate or ferrous ammonium sulphate.
5. the preparation method of multipolymer according to claim 4 is characterized in that, described preparation method may further comprise the steps:
A, synthesizing of Dimethylaminoethyl Methacrylate: methacrylic acid and dimethylamino-ethanol were joined in the reactor by weight 1: 1.05, get mixture A, the MEHQ that adds mixture A total amount 0.05%, mix, the strong acid that adds 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 the homothermic process in 0.6 MPa, be cooled to normal temperature, at 0.4 kPa of following vacuum fractionation, the cut between collecting 90 ℃～94 ℃, the water white liquid that obtains both be Dimethylaminoethyl Methacrylate;
B, methylacryoyloxyethyl trimethyl ammonium chloride synthetic: the Dimethylaminoethyl Methacrylate that step a is obtained, monochloro methane and water are put in the reactor by weight 1.0: 1.10: 0.55 ratio, get mixture B, the MEHQ that adds mixture B total amount 0.1%, the Lewis acid that adds mixture B total amount 0.2%, be warmed up to 60 ℃～80 ℃, constant temperature is 4～6 hours under stirring, obtain faint yellow clear, the solution of 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: with deionized water, dimethyl and the methylacryoyloxyethyl trimethyl ammonium chloride that allyl ammonium chloride, acrylamide, step b obtain 10: 2: 6 by weight proportion: 82 ratio is put in the reactor, 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 2,2'-Azobis(2,4-dimethylvaleronitrile), ethanol, benzoyl peroxide, nitrilotriacetic acid, hydrogen peroxide, chlorination diamino copper successively, up to blow motionless till, reaction heated up 4～5 hours, after the homo(io)thermism, hit the person 40 ℃～50 ℃ hot water of reactor, aging 3～4 hours of constant temperature, fragmentation, granulation, drying, pulverizing obtain multipolymer;
Wherein: the consumption of 2,2'-Azobis(2,4-dimethylvaleronitrile) is the 400ppm of mixture C total amount;
Consumption of ethanol is the 2ppm of mixture C total amount;
The consumption of benzoyl peroxide 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.
6. the preparation method of multipolymer according to claim 4 is characterized in that, described preparation method may further comprise the steps:
A, synthesizing of Dimethylaminoethyl Methacrylate: methacrylic acid and dimethylamino-ethanol were joined in the reactor by weight 1: 1.20, get mixture A, the MEHQ that adds mixture A total amount 0.1%, mix, the strong acid that adds 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 the homothermic process in 0.6 MPa, be cooled to normal temperature, at 0.4 kPa of following vacuum fractionation, the cut between collecting 90 ℃～94 ℃, the water white liquid that obtains both be Dimethylaminoethyl Methacrylate;
B, methylacryoyloxyethyl trimethyl ammonium chloride synthetic: the Dimethylaminoethyl Methacrylate that step a is obtained, monochloro methane and water are put in the reactor by weight 1: 1.30: 0.95 ratio, get mixture B, the MEHQ that adds mixture B total amount 0.15%, the Lewis acid that adds mixture B total amount 0.4%, be warmed up to 60 ℃～80 ℃, constant temperature is 4～6 hours under stirring, obtain faint yellow clear, the solution of 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: with deionized water, dimethyl and the methylacryoyloxyethyl trimethyl ammonium chloride that allyl ammonium chloride, acrylamide, step b obtain 10: 5: 12 by weight proportion: 73 ratio is put in the reactor, 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 2,2'-Azobis(2,4-dimethylvaleronitrile), ethanol, benzoyl peroxide, nitrilotriacetic acid, hydrogen peroxide, chlorination diamino copper successively, up to blow motionless till, reaction heated up 4～5 hours, after the homo(io)thermism, hit the person 40 ℃～50 ℃ hot water of reactor, aging 3～4 hours of constant temperature, fragmentation, granulation, drying, pulverizing obtain multipolymer;
Wherein: the consumption of 2,2'-Azobis(2,4-dimethylvaleronitrile) is the 800ppm of mixture C total amount;
Consumption of ethanol is the 20ppm of mixture C total amount;
The consumption of benzoyl peroxide is the 15ppm of mixture C total amount;
The described 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.
7. the preparation method of multipolymer according to claim 4 is characterized in that, described preparation method may further comprise the steps:
A, synthesizing of Dimethylaminoethyl Methacrylate: methacrylic acid and dimethylamino-ethanol were joined in the reactor by weight 1: 1.15, get mixture A, the MEHQ that adds mixture A total amount 0.08%, mix, the strong acid that adds 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 the homothermic process in 0.6 MPa, be cooled to normal temperature, at 0.4 kPa of following vacuum fractionation, the cut between collecting 90 ℃～94 ℃, the water white liquid that obtains both be Dimethylaminoethyl Methacrylate;
B, methylacryoyloxyethyl trimethyl ammonium chloride synthetic: the Dimethylaminoethyl Methacrylate that step a is obtained, monochloro methane and water are put in the reactor by weight 1: 1.20: 0.75 ratio, get mixture B, the MEHQ that adds mixture B total amount 0.13%, the Lewis acid that adds mixture B total amount 0.3%, be warmed up to 60 ℃～80 ℃, constant temperature is 4～6 hours under stirring, obtain faint yellow clear, the solution of homogeneous both had been the methylacryoyloxyethyl trimethyl ammonium chloride, and methylacryoyloxyethyl trimethyl ammonium chloride active constituent content is not less than 78%;
C, synthesizing of multipolymer: with deionized water, dimethyl and allyl ammonium chloride, acrylamide, the methylacryoyloxyethyl trimethyl ammonium chloride that step b obtains 10: 3: 8 by weight proportion: 79 ratio is put in the reactor, 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 2,2'-Azobis(2,4-dimethylvaleronitrile) successively, ethanol is urged, benzoyl peroxide, nitrilotriacetic acid, hydrogen peroxide, chlorination diamino copper, up to blow motionless till, reaction heated up 4～5 hours, after the homo(io)thermism, hit the person 40 ℃～50 ℃ hot water of reactor, aging 3～4 hours of constant temperature, fragmentation, granulation, dry, pulverizing obtains multipolymer;
Wherein, The consumption of 2,2'-Azobis(2,4-dimethylvaleronitrile) is the 600ppm of mixture C total amount;
Consumption of ethanol is the 10ppm of mixture C total amount;
The consumption of benzoyl peroxide 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.
8. the preparation method of multipolymer according to claim 4 is characterized in that, described preparation method may further comprise the steps:
A, synthesizing of Dimethylaminoethyl Methacrylate: methacrylic acid and dimethylamino-ethanol were joined in the reactor by weight 1: 1.05, get mixture A, the MEHQ that adds mixture A total amount 0.1%, mix, the strong acid that adds 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 the homothermic process in 0.6 MPa, be cooled to normal temperature, at 0.4 kPa of following vacuum fractionation, the cut between collecting 90 ℃～94 ℃, the water white liquid that obtains both be Dimethylaminoethyl Methacrylate;
B, methylacryoyloxyethyl trimethyl ammonium chloride synthetic: the Dimethylaminoethyl Methacrylate that step a is obtained, monochloro methane and water are put in the reactor by weight 1: 1.30: 0.55 ratio, get mixture B, the MEHQ that adds mixture B total amount 0.15%, the Lewis acid that adds mixture B total amount 0.4%, be warmed up to 60 ℃～80 ℃, constant temperature is 4～6 hours under stirring, obtain faint yellow clear, the solution of homogeneous both had been the methylacryoyloxyethyl trimethyl ammonium chloride, and methylacryoyloxyethyl trimethyl ammonium chloride active constituent content is not less than 78%;
C, synthesizing of multipolymer: with deionized water, dimethyl diallyl ammonium chloride, acrylamide, the methylacryoyloxyethyl trimethyl ammonium chloride that step b obtains 10: 2: 6 by weight proportion: 82 ratio is put in the reactor, 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 successively, inferior sodium phosphate, Sodium Persulfate, diethylenetriamine pentaacetic acid, Peracetic Acid, ferrous ammonium sulphate, up to blow motionless till, reaction heated up 4～5 hours, after the homo(io)thermism, hit the person 40 ℃～50 ℃ hot water of reactor, aging 3～4 hours of constant temperature, fragmentation, granulation, dry, pulverizing obtains 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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