CN102464760B - Copolymer having dithio structure-containing annular groups, its preparation method and application - Google Patents
Copolymer having dithio structure-containing annular groups, its preparation method and application Download PDFInfo
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Abstract
The invention discloses a copolymer having dithio structure-containing annular groups. The copolymer comprises a building block represented by formula (1) and a building block represented by formula (2), wherein, in formula (1), W represents one selected from -CONH2, -COOH and -CON(CH3)2; and in formula (2), R1 represents any one selected from H and C1-C10 alkyl, R2 represents any one selected from C1-C10 alkylene, A represents -O- or -NH-; and X represents dithio structure-containing annular groups of formula (3), in formula (3), R3 and R4 are any one respectively selected from H and C1-C3 alkyl, n represents an integer in the range of 3-10, and the intrinsic viscosity of the copolymer is 1500-3500. The copolymer has excellent salt resistance.
Description
Technical field
The present invention relates to a kind of multipolymer with the cyclic group that contains connection sulphur structure and its preparation method and application.
Background technology
Polyacrylamide (HPAM) is the current main chemical agent for tertiary oil production in oil field, and the I class oil reservoir lower for temperature has good oil displacement efficiency, can greatly improve oil recovery.Yet, the use of HPAM is subject to the impact of operating ambient temperature very large, for burying darker II class, III class oil reservoir, existence due to high temperature and active impurity, the oxygen of trace also can cause the oxidative degradation that polymkeric substance is serious, cause the viscosity of solution sharply to descend, lose stickiness and high molecular chemical characters, lose its use value.This is distinct issues very in II class, the practical application of III class oil reservoir at present.
The kind of the high molecular antioxidative stabilizer of the acrylic amide aqueous solution be can be used for seldom, ubiquity high temperature weak effect, consumption problem large, easy generation chromatographic separation in the polymkeric substance migration process gone back simultaneously.The countermeasure that HPAM manufacturing enterprise adopts at present is mainly the retention of viscosity agent that adds the small molecules thermo-stabilizer and have crosslinked action in the HPAM product, such as hindered phenol, Resorcinol, formaldehyde, alkali metal borohydride, basic metal hyposulfite etc., but effect is all undesirable.Therefore in the urgent need to seeking to be applicable to the stablizer of the anti-oxidant degraded of the new and effective aqueous solution under hot conditions or the heat resistanceheat resistant degraded solution of system.
Current comparatively ideal solution is that the stablizer structure is introduced in the HPAM macromole with the form of chemical bond, thereby solves the problem of chromatographic separation, improves stablizer efficiency, reduces consumption.But, because stablizer is also stopper simultaneously, therefore can not participate in the HPAM polymerization as monomer, and can only after the HPAM polymerization completes, adopt macromolecular reaction, rear grafting stablizer group.But, because HPAM has high viscosity, make the stablizer grafting only be present in HPAM micelle surface, cause grafting efficiency not high, grafting is inhomogeneous.Therefore, also could not enough realize the effective means of chemical graft stablizer at present.
Summary of the invention
The object of the invention is to overcome the problems of the prior art, a kind of multipolymer with the cyclic group that contains connection sulphur structure and its preparation method and application is provided.
The invention provides a kind of multipolymer had containing the cyclic group of connection sulphur structure, wherein, described multipolymer contains the structural unit shown in the structural unit shown in formula (1) and formula (2):
In formula (1), be selected from-CONH of W
2,-COOH and-CON (CH
3)
2In a kind of, in formula (2), R
1For H and C
1-C
10Alkyl in any one, R
2For C
1-C
10Alkylidene group in any one, A is-O-or-NH-, X is the cyclic group containing connection sulphur structure that formula (3) means:
In formula (3), R
3And R
4Be selected from independently of one another H and C
1-C
3Alkyl in any one, and the ring on n carbon atom in any one on R
3Or R
4Quilt and R
2Connected key substitutes; The integer that n is 3-10, the 50-96% of the gross weight that the content of the structural unit shown in formula (1) is the structural unit shown in the structural unit shown in formula (1) and formula (2), be preferably 60-90%; And the intrinsic viscosity of this multipolymer is 1500-3500.
The present invention also provides the preparation method of described multipolymer, and wherein, the method comprises: under the existence of initiator, the compound shown in the compound shown in formula (5) and formula (6) is carried out to aqueous solution polymerization,
In formula (5), W is defined as the aforementioned content of the present invention, in formula (6), and R
1, R
2, A and X defined as the aforementioned content of the present invention.
The present invention also provides the described application of multipolymer in oil-displacing agent had containing the cyclic group of connection sulphur structure.
The multipolymer had containing the cyclic group that joins the sulphur structure provided by the invention is the temperature resistant antisalt polymkeric substance with temperature response stabilising characteristic, and can be used as the use of polymer flooding thickening material.The described multipolymer with the cyclic group that contains connection sulphur structure can solve stablizer of the prior art and can not participate in polymerization, and stopper chromatographic separation easily occurs and the problems such as inefficacy in annotating collecting process.Tracing it to its cause, may be that described multipolymer has lower apparent viscosity in the low temperature process of injection allocation of ground, reduces the injection allocation energy consumption; Under the stratum high-temperature working conditions, the thermal destruction activation by self, produce thermally-stabilised group, forms and have the thermally-stabilised structure that catches the short free radical performance of going out.Along with the prolongation of thermal aging time, the viscosity of described polymkeric substance improves gradually, and the viscosity retention rate is greater than 1, presents aging tackified phenomenon, has embodied excellent saline-alkaline tolerance.Simultaneously, its thermally-stabilised reaction product also can improve the salt tolerant hydrophilicity of oil-displacing agent, enlarges the kinetics volume simultaneously, has further increased the viscosity of polymer oil-displacing agent.
Embodiment
According to the present invention, the described multipolymer had containing the cyclic group that joins the sulphur structure contains the structural unit shown in the structural unit shown in formula (1) and formula (2):
In formula (1), can be selected from-CONH of W
2,-COOH and-CON (CH
3)
2In a kind of;
In formula (2), R
1Can be H and C
1-C
10Alkyl in any one, be preferably H and C
1-C
6Alkyl in any one, more preferably in situation, R
1Can be selected from a kind of in hydrogen, methyl, ethyl, propyl group, sec.-propyl, butyl and isobutyl-,
R
2Can be C
1-C
10Alkylidene group in any one, be preferably C
2-C
6Alkylidene group in any one, more preferably in situation, R
2Can be selected from a kind of in methylene radical, ethylidene, propylidene, isopropylidene, butylidene, isobutylidene, pentylidene and hexylidene,
A can for-O-or-NH-,
X is the cyclic group containing connection sulphur structure that formula (3) means:
In formula (3), R
3And R
4Can be selected from independently of one another H and C
1-C
3Alkyl in any one, and the ring on n carbon atom in any one on R
3Or R
4Quilt and R
2Connected key substitutes, and the cyclic group that should contain connection sulphur structure can be by any one carbon atom on ring and the R in formula (2)
2Bond connected, can be with connection sulphur structure in the adjacent carbon atom of sulphur, can be also with connection sulphur structure in the sulphur carbon atom of being separated by; The integer that n is 3-10.
In formula (2), the major function radicals X is the cyclic group containing connection sulphur structure, in its process of low temperature polymerization at HPAM, and homeostasis and there is no inhibition, in hot environment, homolysis can occur and produce two-S free radical scavenger (S-S bond energy: 226kJ/mol in connection sulphur ring; C-S bond energy: 259kJ/mol; C-C bond energy: 347kJ/mol), and become thermo-stabilizer; Simultaneously ,-S possesses chain transfer, can shift formation by chain crosslinked, and performance retention of viscosity agent performance.
More preferably, in situation, X is the cyclic group containing connection sulphur structure that formula (4) means:
In formula (4), R
5Can be H and C
1-C
3Alkyl in any one, be connected with R
5Carbon on key and R
2Key connects; R
6And R
7Can be selected from independently of one another H and C
1-C
3Alkyl in any one; The integer that m is 2-5.
Under most preferred case, according to the specific embodiment of the present invention, X is selected from any one in following cyclic group:
According to polymkeric substance provided by the invention, wherein, the content of the structural unit shown in formula (1) can be the 50-96% of the gross weight of the structural unit shown in the structural unit shown in formula (1) and formula (2); Under preferable case, the 60-90% of the gross weight that the content of the structural unit shown in formula (1) is the structural unit shown in the structural unit shown in formula (1) and formula (2).
According to the present invention, the intrinsic viscosity of described multipolymer is 1500-3500, is preferably 1800-3300.Described intrinsic viscosity can record according to method well known in the art.
According to the present invention, to be 1500 mg/litre, the salinity described aqueous copolymers solution that is 32868mg/L can, for being greater than 1 to 12, be preferably 4-11 the apparent viscosity of 85 ℃ to concentration.
In the present invention, described salinity refers to the total content of the salt in water, described salt such as carbonate, hydrocarbonate, muriate, vitriol, the nitrate of the metals such as calcium, magnesium, iron, aluminium and manganese; And various sodium salts.Salinity in the present invention is according to the gravimetric determination of stipulating in China-styled Certain Industry Field standard SL79-1994.
According to the present invention, the described preparation method with polymkeric substance of the cyclic group that contains connection sulphur structure comprises: under the existence of initiator, the compound shown in the compound shown in formula (5) and formula (6) is carried out to aqueous solution polymerization,
In formula (5), W is defined as the aforementioned content of the present invention, in formula (6), and R
1, R
2, A and X defined as the aforementioned content of the present invention.
The method according to this invention, wherein, the weight ratio of the compound shown in the compound shown in water, formula (5), formula (6) and initiator can be 1000: (80-450): (20-50): (1-3), under preferable case, the weight ratio of the compound shown in the compound shown in water, formula (5), formula (6) and initiator can be 1000: (100-260): (20-40): (1-3).
According to method provided by the invention, described initiator can be selected from the initiator of various routines known in the field, and for example, described initiator can be azo-type initiator and/or oxidation-reduction type initiator; Wherein, described azo-type initiator can and be preferably Diisopropyl azodicarboxylate and/or 2,2'-Azobis(2,4-dimethylvaleronitrile); Described oxidation-reduction type initiator can and be preferably Potassium Persulphate-S-WAT initiator and/or ammonium sulfate-sodium bisulfite initiator.
The method according to this invention, the condition of described polymerization can comprise starting polymerization temperature and polymerization time, the selectable range of the temperature of starting polymerization is wider, the more high generation that more is beneficial to polyreaction of its starting polymerization temperature, but considering of comprehensive cost and effect, the temperature of described starting polymerization can be 0-70 ℃.The prolongation of polymerization time is conducive to the abundant copolymerization of described two monomers, but the long amplitude of the improvement to its performance of polymerization time not obvious, and therefore, polymerization time can be 5-10 hour, is preferably 6-8 hour.
In addition, under preferable case, when selecting described azo-type initiator, the temperature of described starting polymerization is preferably 40-70 ℃; When selecting described oxidation-reduction type initiator, the temperature of described polymerization is preferably 0-30 ℃.
Polymerization system pH value is preferably neutrality or weakly alkaline, and described pH value is preferably 7.7-10, more preferably 8.5-9.5.Can adopt conventional method to regulate the pH of polymerization system, for example, can adopt sodium hydroxide or potassium hydroxide aqueous solution to regulate the pH value.
According to the present invention, the described preparation method with compound of the cyclic group that contains connection sulphur structure comprises: under the existence of solvent and stopper and under the condensation reaction condition, the first reactant is contacted with the second reactant; Described the first reactant is the compound shown in following general formula (4), and described the second reactant is the compound shown in following general formula (5):
In general formula (4), R
2With X, as the aforementioned content of the present invention, defined, Y can for-OH or-NH
2
In general formula (5), R
1As the aforementioned content of the present invention is defined, Z can for-Cl or-OH;
And Y is-during OH, Z is-Cl that Y is-NH
2The time, Z is-OH.
According to a kind of embodiment of the present invention, the Y in the first reactant is-OH that the Z in the second reactant is-Cl.Y in the first reactant is-OH, Z in the second reactant is-during Cl, as long as the mol ratio of described the first reactant and the second reactant with and the condition of condensation reaction guarantee to make C in the first reactant (4) and the D in the second reactant (5) that condensation reaction occurs and connect by-O-key key, so above-mentioned mole when the selectable range of condition is wider.
According to above-mentioned embodiment of the present invention, under preferable case, the mol ratio of the first reactant and the second reactant can be 1: 1-3, more preferably 1: 1-2.
The condition of described condensation reaction comprises the temperature of reaction and the time of reaction, and the temperature of reaction can be 40-70 ℃, is preferably 50-60 ℃; The time of reaction can be 4-8 hour, is preferably 5-7 hour.
The kind of described stopper and consumption can be conventional kind known in those skilled in the art and consumption, and its effect is mainly that the Raolical polymerizable of vinyl monomer is stopped fully; Under preferable case, the mol ratio of described stopper and the first reactant is 0.005-0.02: 1, and 0.01-0.02 more preferably: 1.
Described Z is-selectable range of the second reactant of Cl is wider, in the present invention, described the second reactant can be preferably selected from least one in acrylate chloride, methacrylic chloride, ethyl propylene acyl chlorides, propyl group acrylate chloride, butyl acrylate chloride, amyl group acrylate chloride and hexyl acrylate chloride.
According to another embodiment of the present invention, the Y in the first reactant is-NH
2, the Z in the second reactant is-OH.Y in the first reactant is-NH
2Z in the second reactant is-during OH, as long as the mol ratio of described the first reactant and the second reactant with and the condition of condensation reaction guarantee to make Y in the first reactant (4) and the Z in the second reactant (5) that condensation reaction occurs and connect by-NH-key key, so above-mentioned mole when the selectable range of condition is wider.
According to above-mentioned embodiment of the present invention, under preferable case, the mol ratio of the first reactant and the second reactant is 1: 1-3 is preferably 1: 1-2.
The condition of described condensation reaction comprises the reaction mixture reflux that will contain solvent, stopper, the first reactant and the second reactant, and the time of described reflux can be 1-5 hour.Under preferable case, in order to impel described reaction, more easily carry out and improve reaction efficiency, also contain catalyzer in reaction mixture.In the method the consumption of catalyzer is not particularly limited, only can promotes the carrying out of reaction to get final product, under preferable case, the mol ratio of the first reactant and catalyzer can be 0.1-0.5: 1, and described catalyzer can be the vitriol oil or sodium hydroxide usually.
The kind of described stopper and consumption can be conventional kind known in those skilled in the art and consumption; Under preferable case, the mol ratio of stopper and the first reactant can be 0.005-0.02: 1, and 0.01-0.02 more preferably: 1.
Described Z is-selectable range of the second reactant of OH is wider, in the present invention, described the second reactant can be preferably selected from least one in vinylformic acid, methacrylic acid, ethylacrylic acid, propyl group vinylformic acid, butylacrylic acid, amyl group vinylformic acid and hexyl vinylformic acid.
According to above-mentioned two kinds of embodiments of the present invention, in order further to impel described reaction, to positive dirction, carry out, the first reactant and contacting under the existence that also is included in acid binding agent of the second reactant are carried out, the kind of described acid binding agent and the selectable range of consumption are wider, can be various can adsorber acid or can with the material of acid-respons, for example, described acid binding agent can be selected from least one in triethylamine, sodium hydroxide and salt of wormwood.In the method the consumption of acid binding agent is not particularly limited, as long as can promote the carrying out of reaction, under the preferable case, the mol ratio of the first reactant and acid binding agent can be 1: 1-1.5, more preferably 1: 1.1-1.4.Described stopper is preferably selected from least one in Resorcinol, p methoxy phenol and benzoquinones.Described solvent is preferably selected from least one in acetone, benzene, toluene and hexanaphthene, and its consumption only guaranteed reactant that makes fully dissolves and gets final product, and generally, the mol ratio of the first reactant and solvent can 1: 1-15.
Below will to the present invention, be further described in detail by specific embodiment.
The first reactant 6 in following embodiment, 8-bis-thiophene octylames (sulphur octylame), 6,8-bis-thiophene octanols (sulphur octanol), 6,9-bis-thiophene nonyl alcohols, 6,9-bis-thiophene nonyl amines are all purchased from the permanent far company of scientific and technological development limited liability company in Nanjing; The second reactant methacrylic acid, methacrylic chloride, acrylate chloride, and hydroquinone of polymerization retarder and acid binding agent triethylamine are all purchased from Beijing Chemical Plant.
Acrylamide in following embodiment, vinylformic acid and Dimethylaminoethyl Methacrylate are all purchased from Beijing Chemical Plant.
Preparation Example 1
The present embodiment is for illustrating compound with the cyclic group that contains connection sulphur structure provided by the invention and preparation method thereof.
In the there-necked flask that thermometer, agitator, reflux exchanger are housed, in amount of substance, add 1 part of sulphur octylame (formal name used at school: 6,8-bis-thiophene octylames), 10 parts of solvent toluenes and 0.01 part of hydroquinone of polymerization retarder, be heated to 60 ℃ it is all dissolved after, then add successively 2 parts of methacrylic acids and 0.1 part of vitriol oil (mass percent concentration is 98%).First reflux approximately, about 3 hours, is then loaded onto water trap, carries out azeotropic dehydration.After separating 0.7 part of water, the temperature maintained in there-necked flask is 120 ℃.When observing amount and theoretical value when suitable (1 part of water), stopped reaction, be cooled to room temperature, and unreacted vinylformic acid and solvent are removed in underpressure distillation.After catalyzer and stopper are removed in the silicagel column separation, obtain the Compound C 1 (acrylamide monomers) as the cyclic group containing connection sulphur structure of structural formula (I), yield 85.2%.
H1-NMR before and after reaction shows, the peak position (chemical shift 2.69ppm) and the integral area that are positioned at the hydrogen above the C of the connection S on 6,8 do not change, and illustrates that the Cloud Distribution of S does not change or is offset, and join the sulphur structure and do not destroy.
Preparation Example 2
The present embodiment is for illustrating compound with the cyclic group that contains connection sulphur structure provided by the invention and preparation method thereof.
In the there-necked flask that thermometer, agitator, reflux exchanger are housed, in amount of substance, after adding 0.01 part of hydroquinone of polymerization retarder, add successively 1 part of sulphur octanol (formal name used at school: 6,8-bis-thiophene octanols), 1.2 parts of triethylamines, 10 parts of toluene solvants, be warming up to 50 ℃, then (three's mol ratio is 1: 1.2: 2 to add 2 parts of methacrylic chlorides in dropping funnel, methacrylic chloride is excessive), drip about 1 hour, dropwise 50 ℃ of insulations 8 hours.The salt that after reaction finishes, the elimination reaction generates, underpressure distillation, except desolventizing and excessive acyl chlorides, then pour product into beaker, the NaOH aqueous solution that is 5% with mass percent concentration washes away Resorcinol and a small amount of vinylformic acid, then washes with water for several times, until neutral, vacuum-drying, obtain the Compound C 2 (acrylic ester monomer) as the cyclic group containing connection sulphur structure of structural formula (II), yield 90.4%.
H1-NMR before and after reaction shows, the peak position (chemical shift 2.69ppm) and the integral area that are positioned at the hydrogen above the C of the connection S on 6,8 do not change, and illustrates that the Cloud Distribution of S does not change or is offset, and join the sulphur structure and do not destroy.
Preparation Example 3
The present embodiment is for illustrating compound with the cyclic group that contains connection sulphur structure provided by the invention and preparation method thereof.
In the there-necked flask that thermometer, agitator, reflux exchanger are housed, in amount of substance, after adding 0.01 part of hydroquinone of polymerization retarder, add successively 1 part 6,9-bis-thiophene nonyl alcohols, 1.2 parts of triethylamines, 10 parts of toluene solvants, be warming up to 50 ℃, then in dropping funnel, adds 2 parts of acrylate chlorides (three's mole proportioning is 1: 1.2: 2), drip about 1 hour, dropwise 50 ℃ of insulations 8 hours.The salt that after reaction finishes, the elimination reaction generates, underpressure distillation, except desolventizing and excessive acyl chlorides, then pour product into beaker, with the NaOH aqueous solution of mass concentration 5%, wash away Resorcinol and a small amount of vinylformic acid, then wash with water for several times, until neutral, vacuum-drying, obtain the Compound C 3 (acrylic ester monomer) as the cyclic group containing connection sulphur structure of structural formula (III), yield 91.6%.
H1-NMR before and after reaction shows, the peak position (chemical shift 2.69ppm) and the integral area that are positioned at 6,9 hydrogen above the C that connects S do not change.The Cloud Distribution that S is described does not change or skew, and connection sulphur structure is not destroyed.
Preparation Example 4
The present embodiment is for illustrating compound with the cyclic group that contains connection sulphur structure provided by the invention and preparation method thereof.
In the there-necked flask that thermometer, agitator, reflux exchanger are housed, in amount of substance, add 6 of 1 part of amount of substance, 9-bis-thiophene nonyl amines, 10 parts of solvent toluenes and 0.01 part of hydroquinone of polymerization retarder, be heated to 60 ℃ it is all dissolved after, then add successively 1.5 parts of methacrylic acids and 0.1 part of vitriol oil (mass percent concentration is 98%).Reflux approximately, about 3 hours, is then loaded onto water trap, carries out azeotropic dehydration.After separating 0.7 part of water, the temperature maintained in there-necked flask is 120 ℃.When observing amount and theoretical value when suitable (1 part of water), stopped reaction, be cooled to room temperature, and unreacted vinylformic acid and solvent are removed in underpressure distillation.After catalyzer and stopper are removed in the silicagel column separation, obtain the Compound C 4 (acrylamide monomers) as the cyclic group containing connection sulphur structure of structural formula (IV), yield 878%.
H1-NMR before and after reaction shows, the peak position (chemical shift 2.69ppm) and the integral area that are positioned at 6,9 hydrogen above the C that connects S do not change.The Cloud Distribution that S is described does not change or skew, and connection sulphur structure is not destroyed.
Preparation Example 5
The present embodiment is for illustrating compound with the cyclic group that contains connection sulphur structure provided by the invention and preparation method thereof.
Method according to embodiment 1 prepares described compound, different, in amount of substance, add 1 part of sulphur octylame, 10 parts of solvent xylenes and 0.02 part of stopper benzoquinones, be heated to 70 ℃ it is all dissolved after, then add successively 1 part of propyl group vinylformic acid and 0.5 part of trolamine.Obtain Compound C 5.
Embodiment 1
The present embodiment has the preparation containing the multipolymer of the cyclic group that joins the sulphur structure for explanation.
Under agitation, the Compound C 1 that the acrylamide that is 180 parts by mass fraction (AM), the Preparation Example 1 of 20 parts make is dissolved in the water of 1000 parts.Under room temperature (25 ℃), the aqueous solution was led to the nitrogen deoxygenation after 30 minutes, the pH value of regulating the aqueous solution with sodium hydroxide is 9.2, under agitation add the initiator potassium persulfate of 0.01 part, the sodium bisulfite of 0.02 part, be 5 ℃ of reactions 6 hours in normal pressure (0.01MPa) starting temperature, obtain rubbery polymer product 1.
The polymer product drying, granulation, the pulverizing that obtain are obtained to temperature resistant antisalt oil-displacing agent product.
By elemental microanalysis method, record: 90% of the gross weight of the structural unit that the content of the structural unit of acrylamide is acrylamide structural unit and Compound C 1.
Embodiment 2
The present embodiment has the preparation containing the multipolymer of the cyclic group that joins the sulphur structure for explanation.
Under agitation, the Compound C 1 that the acrylamide that is 120 parts by mass fraction (AM), vinylformic acid (AA) and the Preparation Example 1 of 10 parts of 60 parts make is dissolved in the water of 1000 parts.Under room temperature (25 ℃), the aqueous solution was led to the nitrogen deoxygenation after 30 minutes, regulator solution pH value to 9, the initiator ammonium persulfate and the 0.01 part of sodium bisulfite that under agitation add 0.01 part, be 10 ℃ of reactions 7 hours in normal pressure (0.01MPa) starting temperature, obtain gum polymers solution product sample 2.The polymer product drying, granulation, the pulverizing that obtain are obtained to temperature resistant antisalt oil-displacing agent product.
By elemental microanalysis method, record: the content of the content of the structural unit of acrylamide, acrylic acid structure unit be respectively acrylamide structural unit and acrylic acid structure unit and Compound C 1 structural unit gross weight 63.2% and 31.6%.
Embodiment 3
The present embodiment has the preparation containing the multipolymer of the cyclic group that joins the sulphur structure for explanation.
Under agitation, the Compound C 3 that the acrylamide that is 150 parts by mass fraction (AM), 100 parts of Dimethylaminoethyl Methacrylate (DMAM) and the Preparation Example 3 of 10 parts make is dissolved in the water of 1000 parts.Under room temperature (25 ℃), the aqueous solution was led to the nitrogen deoxygenation after 30 minutes, regulator solution pH value to 7.92, the initiator 2 that under agitation adds 0.015 part, two (the 2-methyl-prop amidine) hydrochlorides (AIBA) of 2-azo, be 50 ℃ of reactions 6 hours in normal pressure (0.01MPa) starting temperature, obtain gum polymers solution product sample 3.The polymer product drying, granulation, the pulverizing that obtain are obtained to temperature resistant antisalt oil-displacing agent product.
By elemental microanalysis method, record: the content of the content of the structural unit of acrylamide, Dimethylaminoethyl Methacrylate structural unit be respectively acrylamide structural unit and Dimethylaminoethyl Methacrylate structural unit and Compound C 3 structural unit gross weight 57.7% and 38.3%.
Embodiment 4
The present embodiment has the preparation containing the multipolymer of the cyclic group that joins the sulphur structure for explanation.
Under agitation, the Compound C 1 that the acrylamide that is 150 parts by mass fraction (AM), 50 parts of Dimethylaminoethyl Methacrylate (DMAM) and the Preparation Example 1 of 20 parts make is dissolved in the water of 1000 parts.Under room temperature (25 ℃), by the logical nitrogen deoxygenation of the aqueous solution after 30 minutes, regulator solution pH value to 9.4, under agitation add the initiator Diisopropyl azodicarboxylate of 0.02 part, be 40 ℃ of reactions 6 hours in normal pressure (0.01MPa) starting temperature, obtain gum polymers solution product sample 4.The polymer product drying, granulation, the pulverizing that obtain are obtained to temperature resistant antisalt oil-displacing agent product.
By elemental microanalysis method, record: the content of the content of the structural unit of acrylamide, Dimethylaminoethyl Methacrylate structural unit be respectively acrylamide structural unit and Dimethylaminoethyl Methacrylate structural unit and Compound C 1 structural unit gross weight 68.2% and 22.7%.
Embodiment 5
The present embodiment has the preparation containing the multipolymer of the cyclic group that joins the sulphur structure for explanation.
Under agitation, the Compound C 1 that the acrylamide that is 150 parts by mass fraction (AM), 100 parts of Dimethylaminoethyl Methacrylate (DMAM) and the Preparation Example 1 of 20 parts make is dissolved in the water of 1000 parts.Under room temperature (25 ℃), the aqueous solution was led to the nitrogen deoxygenation after 30 minutes, regulator solution pH value to 9, under agitation add the Sodium Persulfate of 0.01 part and 0.01 part of sodium bisulfite as redox initiator, be 0 ℃ of reaction 6 hours in normal pressure (0.01MPa) starting temperature, obtain gum polymers solution product sample 5.The polymer product drying, granulation, the pulverizing that obtain are obtained to temperature resistant antisalt oil-displacing agent product.
By elemental microanalysis method, record: the content of the content of the structural unit of acrylamide, Dimethylaminoethyl Methacrylate structural unit be respectively acrylamide structural unit and Dimethylaminoethyl Methacrylate structural unit and Compound C 3 structural unit gross weight 55.5% and 37%.
Embodiment 6
The present embodiment has the preparation containing the multipolymer of the cyclic group that joins the sulphur structure for explanation.
Have the multipolymer containing the cyclic group of connection sulphur structure according to the preparation of the method for embodiment 1, different, the Compound C 1 that the acrylamide that is 100 parts by mass fraction (AM), the Preparation Example 1 of 30 parts make is dissolved in the water of 1000 parts.The consumption of initiator potassium persulfate is that 0.05 part, the consumption of sodium bisulfite initiator are 0.05 part.Obtain gum polymers solution product sample 6.The polymer product drying, granulation, the pulverizing that obtain are obtained to temperature resistant antisalt oil-displacing agent product.
By elemental microanalysis method, record: the gross weight of the structural unit that the content of the structural unit of acrylamide is acrylamide structural unit and Compound C 1 76.9%).
Embodiment 7
The present embodiment has the preparation containing the multipolymer of the cyclic group that joins the sulphur structure for explanation.
Have the multipolymer containing the cyclic group of connection sulphur structure according to the preparation of the method for embodiment 1, different, the Compound C 2 that the acrylamide that is 180 parts by mass fraction (AM), the Preparation Example 2 of 20 parts make is dissolved in the water of 1000 parts.Obtain gum polymers solution product sample 7.The polymer product drying, granulation, the pulverizing that obtain are obtained to temperature resistant antisalt oil-displacing agent product.
By elemental microanalysis method, record: 90% of the gross weight of the structural unit that the content of the structural unit of acrylamide is acrylamide structural unit and Compound C 2.
Embodiment 8
The present embodiment has the preparation containing the multipolymer of the cyclic group that joins the sulphur structure for explanation.
Have the multipolymer containing the cyclic group of connection sulphur structure according to the preparation of the method for embodiment 1, different, the Compound C 5 that the acrylamide that is 80 parts by mass fraction (AM), the Preparation Example 5 of 50 parts make is dissolved in the water of 1000 parts.Obtain gum polymers solution product sample 8.The polymer product drying, granulation, the pulverizing that obtain are obtained to temperature resistant antisalt oil-displacing agent product.
By elemental microanalysis method, record: the gross weight of the structural unit that the content of the structural unit of acrylamide is acrylamide structural unit and Compound C 5 61.5%).
EXPERIMENTAL EXAMPLE 1-8
The performance test of thickening material product prepared by embodiment 1-8 for explanation by this EXPERIMENTAL EXAMPLE.
Intrinsic viscosity adopts GB GB/T 1632-93 testing method test (adopt Ubbelohde viscometer, one point method is measured intrinsic viscosity).
By temperature-resistant salt-resistant thickening agent product and the conventional polypropylene acid amides KYPAM-6A (purchased from Beijing permanent agglomerated masses Products Co., Ltd) obtained, carry out Performance Ratio under the same conditions, that is, carry out apparent viscosity test (the salt solution preparation 1500mg/L polymers soln of salinity 32868mg/L, divalent ion concentration 800mg/L under the high temperature and high salt environment on BrookfieldDV-III type rotational rheometer.Shearing rate shear rate 7.34/S, 85 ℃ of probe temperatures).By the test apparent viscosity, calculate the performance that apparent viscosity retention ratio is estimated opposing anaerobic high temperature ageing.
Table 1 is under room temperature (25 ℃), and under the different digestion time conditions under 85 ℃, the viscosity data of the temperature-resistant salt-resistant thickening agent product water solution of 1500mg/L concentration.
Table 1
(copolymer concentration is 1500mg/L, and salinity is 32868mg/L, and divalent ion concentration is 800mg/L, shear rate 7.34/S) (* means precipitation, can't measure)
From can find out in data in table 1, in the situation that there is bigger difference in molecular weight, the multipolymer obtained according to method of the present invention viscosity at room temperature is not high and aging initial viscosity is not high, and along with the prolongation of thermal aging time, viscosity improves gradually, and viscosity retention rate (retention rate=aging rear apparent viscosity/initial apparent viscosity) is greater than 1, presents aging tackified phenomenon, compare with traditional polyacrylamide amine product, fully demonstrated its excellent saline-alkaline tolerance.
Claims (25)
1. the multipolymer had containing the cyclic group of connection sulphur structure, is characterized in that, described multipolymer contains the structural unit shown in the structural unit shown in formula (1) and formula (2):
In formula (1), be selected from-CONH of W
2,-COOH and-CON (CH
3)
2In a kind of, in formula (2), R
1For H and C
1-C
6Alkyl in any one, R
2For C
1-C
10Alkylidene group in any one, A is-O-or-NH-, X is selected from following any one containing in the cyclic group of connection sulphur structure:
2. multipolymer according to claim 1, wherein, the 60-90% of the gross weight that the content of the structural unit shown in formula (1) is the structural unit shown in the structural unit shown in formula (1) and formula (2).
3. multipolymer according to claim 1, wherein, in formula (2), R
2For C
2-C
6Alkylidene group in any one.
4. multipolymer according to claim 3, wherein, R
1Be selected from a kind of in hydrogen, methyl, ethyl, propyl group and butyl; R
2Be selected from a kind of in ethylidene, propylidene, butylidene, pentylidene and hexylidene.
5. a preparation method who has containing the multipolymer of the cyclic group that joins the sulphur structure, is characterized in that, the method comprises: under the existence of initiator, the compound shown in the compound shown in formula (5) and formula (6) is carried out to aqueous solution polymerization,
In formula (5), W is defined as claim 1, and in formula (6), A and X are defined as claim 1, R
1As claim 1 or 4 are defined, R
2As any one in claim 1,3 and 4 is defined.
6. method according to claim 5, wherein, the weight ratio of the compound shown in the compound shown in water, formula (5), formula (6) and initiator is 1000:(80-450): (10-50): (0.01-3).
7. method according to claim 6, wherein, the weight ratio of the compound shown in the compound shown in water, formula (5), formula (6) and initiator is 1000:(100-260): (10-30): (0.01-0.1).
8. method according to claim 5, wherein, the condition of polymerization comprises that the starting polymerization temperature is 0-70 ℃, and polymerization time is 5-10 hour, and the pH value is 7.7-10.
9. method according to claim 5, wherein, initiator is azo-type initiator and/or oxidation-reduction type initiator; Described azo-type initiator is Diisopropyl azodicarboxylate and/or 2,2'-Azobis(2,4-dimethylvaleronitrile); Described oxidation-reduction type initiator is Potassium Persulphate-S-WAT initiator and/or ammonium sulfate-sodium bisulfite initiator.
10. method according to claim 5, wherein, the preparation method of the compound shown in formula (6) comprises: under the existence of solvent and stopper and under the condensation reaction condition, the first reactant is contacted with the second reactant; Described the first reactant is the compound shown in formula (7), and described the second reactant is the compound shown in formula (8):
In general formula (7), R
2As any one in claim 1,3 and 4 is defined, X is defined as claim 1, Y is-OH or-NH
2
In general formula (8), R
1As claim 1 or 4 are defined, Z is-Cl or-OH;
And when Y be-during OH, Z is-Cl, when Y is-NH
2The time, Z is-OH.
11. method according to claim 10, wherein, the Y in the first reactant is-OH that the Z in the second reactant is-Cl that the mol ratio of the first reactant and the second reactant is 1:1-3; The mol ratio of stopper and the first reactant is 0.005-0.02:1.
12. method according to claim 11, wherein, the mol ratio of the first reactant and the second reactant is 1:1-2; The mol ratio of stopper and the first reactant is 0.01-0.02:1.
13. method according to claim 11, wherein, the condition of condensation reaction comprises that the temperature of reaction is 50-60 ℃, and the time of reaction is 4-8 hour.
14., according to the described method of claim 11 or 12, wherein, the first reactant and contacting under the existence of acid binding agent of the second reactant are carried out, the mol ratio of the first reactant and acid binding agent is 1:1-1.5.
15. method according to claim 14, wherein, the mol ratio of the first reactant and acid binding agent is 1:1.1-1.4.
16. method according to claim 14, wherein, described acid binding agent is selected from least one in triethylamine, trolamine and quadrol.
17. according to the described method of claim 11 or 12, wherein, described the second reactant is selected from least one in acrylate chloride, methacrylic chloride, ethyl propylene acyl chlorides, propyl group acrylate chloride, butyl acrylate chloride, amyl group acrylate chloride and hexyl acrylate chloride.
18. method according to claim 10, wherein, the Y in the first reactant is-NH
2, the Z in the second reactant is-OH that the mol ratio of the first reactant and the second reactant is 1:1-3; The mol ratio of stopper and the first reactant is 0.005-0.02:1.
19. method according to claim 18, wherein, the mol ratio of the first reactant and the second reactant is 1:1-2; The mol ratio of stopper and the first reactant is 0.01-0.02:1.
20. method according to claim 18, wherein, the condition of condensation reaction comprises the reaction mixture reflux that will contain solvent, stopper, the first reactant and the second reactant, and the time of described reflux is 1-5 hour.
21. method according to claim 18, wherein, also contain catalyzer in reaction mixture.
22. method according to claim 21, wherein, the mol ratio of the first reactant and catalyzer is 0.1-0.5:1, and described catalyzer is the vitriol oil or sodium hydroxide.
23., according to the described method of any one in claim 18-20, wherein, described the second reactant is selected from least one in vinylformic acid, methacrylic acid, ethylacrylic acid, propyl group vinylformic acid, butylacrylic acid, amyl group vinylformic acid and hexyl vinylformic acid.
24. method according to claim 10, wherein, described stopper is selected from least one in Resorcinol, p methoxy phenol and benzoquinones, and described solvent is selected from least one in acetone, benzene, toluene and hexanaphthene.
25. the described application of multipolymer in oil-displacing agent had containing the cyclic group of connection sulphur structure of any one in claim 1-4.
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|---|---|---|---|---|
| US4681912A (en) * | 1984-06-07 | 1987-07-21 | Institut Francais Du Petrole | Process for manufacturing inverse microlatices of watersoluble copolymers, the resultant inverse microlatices and their use for improving the production of hydrocarbons |
| CN101037493A (en) * | 2007-03-31 | 2007-09-19 | 中国石油大学(华东) | Cation polypropylene amides gel micro-ball and preparation method thereof |
| CN101157741A (en) * | 2007-09-28 | 2008-04-09 | 东营顺通化工（集团）有限公司 | Synthesis technology of high molecular weight temperature-tolerant anti-salt polyacrylamide |
| CN101293944A (en) * | 2008-04-03 | 2008-10-29 | 成都理工大学 | High adhesion-promotion salt resistant water-soluble copolymer, preparation method and application thereof |
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2010
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4681912A (en) * | 1984-06-07 | 1987-07-21 | Institut Francais Du Petrole | Process for manufacturing inverse microlatices of watersoluble copolymers, the resultant inverse microlatices and their use for improving the production of hydrocarbons |
| CN101037493A (en) * | 2007-03-31 | 2007-09-19 | 中国石油大学(华东) | Cation polypropylene amides gel micro-ball and preparation method thereof |
| CN101157741A (en) * | 2007-09-28 | 2008-04-09 | 东营顺通化工（集团）有限公司 | Synthesis technology of high molecular weight temperature-tolerant anti-salt polyacrylamide |
| CN101293944A (en) * | 2008-04-03 | 2008-10-29 | 成都理工大学 | High adhesion-promotion salt resistant water-soluble copolymer, preparation method and application thereof |
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