CN103508913A - Monomer, ternary random copolymer, preparation methods of monomer and ternary random copolymer and application of ternary random copolymer - Google Patents
Monomer, ternary random copolymer, preparation methods of monomer and ternary random copolymer and application of ternary random copolymer Download PDFInfo
- Publication number
- CN103508913A CN103508913A CN201210217033.2A CN201210217033A CN103508913A CN 103508913 A CN103508913 A CN 103508913A CN 201210217033 A CN201210217033 A CN 201210217033A CN 103508913 A CN103508913 A CN 103508913A
- Authority
- CN
- China
- Prior art keywords
- weight
- contact
- monomer
- structural unit
- ternary atactic
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- ZAGHKONXGGSVDV-UHFFFAOYSA-N CCCCC1CCCC1 Chemical compound CCCCC1CCCC1 ZAGHKONXGGSVDV-UHFFFAOYSA-N 0.000 description 1
Images
Landscapes
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
The invention relates to an acrylamide nonionic hydrophilic monomer and a preparation method of the acrylamide nonionic hydrophilic monomer. The acrylamide nonionic hydrophilic monomer has a structure represented in a formula (I). The invention further relates to a ternary random copolymer and a preparation method of the ternary random copolymer. The ternary random copolymer contains a structural unit C, a structural unit D and a structural unit E, wherein the structural unit C is derived from the formula (I), the structural unit D is derived from acrylamide, and the structural unit E is derived from a formula (II). The ternary random copolymer provided by the invention has good aqueous medium thickening capacity, heat resistance and salt tolerance.
Description
Technical field
The present invention relates to a kind of acid/acrylic amide type nonionic hydrophilic monomer and preparation method thereof; A kind of preparation method of ternary atactic copolymer and the ternary atactic copolymer being prepared by the method and described ternary atactic copolymer are as the application of oil-displacing agent.
Background technology
At present, utilize tertiary oil recovery technology to stabilize and increase crude production rate, become the important topic that petroleum industry is needed solution badly.In tertiary oil recovery (EOR) technology, often use the mixing solutions of low-molecular-weight surfactant and polymkeric substance to obtain the displacing fluid of low interfacial tension and high mobility control (high viscosity).Low-molecular-weight surfactant and polymkeric substance, because qualitative difference may be separated from each other when the ground intrastratal flowage, cause tensio-active agent waste in displacement process to increase, and recovery ratio and economic benefit reduce.Meanwhile, existence and the formation temperature of inorganic high-valence cationic constantly raise, and water-mineralizing degree is also more and more high, cause the performance of traditional polymkeric substance-anion surfactant compound system to be difficult to reach the requirement of low interfacial tension and high mobility control.Guarantee that flooding system has sufficiently high viscosity and ultra low interfacial tension under high salinity and higher temperature conditions simultaneously, just need to be in conjunction with the surfactivity of high molecular tackifying ability and low-molecular-weight surfactant.For this reason, on macromolecular chain, introduce the functional group with good surface activity, reach not only tackify but also reduce the effect of interfacial tension, a kind of material plays the effect of polymkeric substance and tensio-active agent bi-material simultaneously, this type of has surface-active macromolecule oil-displacing agent and will solve to a certain extent the chromatographic fractionation effect problem of polymkeric substance-tensio-active agent combination flooding existence, while is due to the thickening property of polymeric surface active agent, make it there is the effect of stable foam, in foam flooding and polynary foam composite flooding, can serve as suds-stabilizing agent, these high-performances make polymeric surface active agent in tertiary oil recovery, have good application prospect.
At present, although solving polymeric surface active agent and have existing certain progress in the problem of high molecular weight and high surface simultaneously, but because the relation understanding to its structure and performance is inadequate, the macromolecular aqueous solution system that relates to physicochemical property is very complicated again, and the research up to now with this field of polymeric surface active agent of ultra-high molecular weight and high surface is still made slow progress.Therefore, the relation of research polymeric surface active agent structure and performance, payes attention to the research and development of novel high polymer tensio-active agent, and the macromolecular compound of synthetic high molecular weight (high viscosity), high surface, has important theory and using value.US4,138,381, US4,463,151, in EP426864A1, adopt respectively alkyl or alkylphenol polyoxyethylene acrylate surface active monomer and acrylamide monomers copolymerization, mainly the association of hydrophobic grouping in water that utilizes surface active monomer, thereby the viscosity of multipolymer is increased substantially, the multipolymer that contains surface active monomer component has better salt tolerance, but amphipathic large monomer component is difficult to assemble to interface in copolymer, therefore, the multipolymer of synthesized surface is active bad.In CN1178802A, acrylamide monomers, surface-active macromonomers and ionic comonomer copolymerization are obtained to terpolymer, this multipolymer viscosity is higher but surfactivity is poor.The people such as the Sun Lili of Southwest Petroleum Institute adopt homogeneous polymerization process, synthesized a kind of novel high polymer surfactant PS 1, this polymeric surface active agent is acrylamide, vinylformic acid, methyl methacrylate copolymer, this polymeric surface active agent reduces capillary ability not as good as low-molecular-weight surfactant, itself and inorganic salt are composite, due to synergistic effect, can produce the compound property that is better than single tensio-active agent, surface tension is even lower, but the temperature resistant antisalt poor-performing of this polymeric surface active agent.It is main raw material that the people such as the Jin Yong of Chengdu Institute of Organic Chemistry, Chinese Academy of Sciences be take tolylene diisocyanate and polyethers, synthesized the non-iron polymerizable polyurethane polymeric surface active agent of a class with two keys, when this polymeric surface active agent can make 25 ℃ of solution when concentration is 0.06mol-L, surface tension is down to 37.6mN-m, under very low concentrations, still can keep good surfactivity simultaneously, in addition, this non-iron polymerizable polyurethane polymeric surface active agent reduces capillary ability and increases along with the increase of hydrophobic segment proportion, but polymerization activity and the heat resistance of this non-iron polymerizable polyurethane polymeric surface active agent are poor.
Summary of the invention
The object of the invention is can not have good viscous water medium ability and the shortcoming of temperature resistant antisalt ability concurrently in order to overcome current polymeric surface active agent, a kind of ternary atactic copolymer that can have good viscous water medium ability and temperature resistant antisalt ability concurrently and its preparation method and application is provided.
The invention provides a kind of acid/acrylic amide type nonionic hydrophilic monomer, wherein, this acid/acrylic amide type nonionic hydrophilic monomer has the structure shown in formula (I),
Wherein, m
1, m
2being the integer of 2-10 independently of one another, is preferably the integer of 3-6 independently of one another.
The present invention also provides a kind of preparation method of acid/acrylic amide type nonionic hydrophilic monomer, and the method comprises the following steps:
(1) polyoxyethylene glycol is carried out in the first organic solvent to first with thionyl chloride and contact, the condition of described the first contact makes to obtain monochloro for polyoxyethylene glycol, and wherein, the polymerization degree of described polyoxyethylene glycol is 2-10;
(2) diethanolamine is carried out in the second organic solvent to second with acrylate chloride and contact, the condition of described the second contact makes to obtain di-alcohol acrylamide;
(3) di-alcohol acrylamide being carried out to the 3rd for polyoxyethylene glycol with monochloro in the 3rd organic solvent contacts, the condition of described the 3rd contact makes to obtain acid/acrylic amide type nonionic hydrophilic monomer, and the structure of described acid/acrylic amide type nonionic hydrophilic monomer as shown in the formula (I);
Wherein, m
1, m
2being the integer of 2-10 independently of one another, is preferably the integer of 3-6 independently of one another.
The present invention also provides a kind of ternary atactic copolymer, wherein, this ternary atactic copolymer contains derived from structure and is the structural unit C of acid/acrylic amide type nonionic hydrophilic monomer shown in formula I, the structural unit D of derived from acrylamides and derived from structure, is the structural unit E of the hydrophobicity polymerisable monomer shown in formula II, and the gross weight of structural unit of described ternary atactic copolymer of take is benchmark, the content of described structural unit C is 14-43 % by weight, and the content of described structural unit D is 55-70 % by weight; The content of described structural unit E is 2-16 % by weight, and the intrinsic viscosity of described ternary atactic copolymer is 1200-1800mL-g,
Wherein, m
1, m
2be the integer of 2-10 independently of one another, R
1, R
2the alkyl that to be selected from independently of one another H, carbonatoms be 1-12; n
1, n
2be the integer of 3-10 independently of one another.
The present invention also provides a kind of preparation method of ternary atactic copolymer, the method comprises the following steps: in pH value, be under 7-10 and micella copolymerization condition, under the existence of initiator, emulsifying agent and water, make monomer mixture carry out polyreaction, it is 1200-1800mL-g that the condition of polyreaction makes the intrinsic viscosity of the multipolymer that obtains, wherein, described monomer mixture contains the hydrophobicity polymerisable monomer B shown in the acid/acrylic amide type nonionic hydrophilic monomer A shown in acrylamide, formula I and formula II; And the total mass of described monomer mixture of take is benchmark, and the consumption of described monomer A is 14-43 % by weight, and the consumption of described monomers B is 2-16 % by weight, and the consumption of acrylamide is 55-70 % by weight.
The present invention also provides the application as oil-displacing agent of the ternary atactic copolymer that made by aforesaid method and above-mentioned ternary atactic copolymer.
Ternary atactic copolymer provided by the invention has good viscous water medium ability and temperature resistant antisalt ability, has solved to a certain extent the problems such as chromatographic fractionation effect that polymkeric substance-tensio-active agent binary combination flooding exists simultaneously.
Accompanying drawing explanation
The infrared spectrum of the acid/acrylic amide type nonionic hydrophilic monomer that Fig. 1 embodiment of the present invention 1 prepares;
Fig. 2 is the infrared spectrum that the embodiment of the present invention 1 prepares hydrophobicity polymerisable monomer B;
Fig. 3 is ternary atactic copolymer temperature and the apparent viscosity graph of relation that the embodiment of the present invention 1 prepares;
Fig. 4 is ternary atactic copolymer temperature and the apparent viscosity graph of relation that the embodiment of the present invention 2 prepares;
Fig. 5 is ternary atactic copolymer temperature and the apparent viscosity graph of relation that the embodiment of the present invention 3 prepares;
Fig. 6 is binary random copolymer temperature and the apparent viscosity graph of relation that comparative example 1 of the present invention prepares.
Embodiment
According to acid/acrylic amide type nonionic hydrophilic monomer of the present invention, wherein, this acid/acrylic amide type nonionic hydrophilic monomer has the structure shown in formula (I),
Wherein, m
1, m
2being the integer of 2-10 independently of one another, is preferably the integer of 3-6 independently of one another.The limiting examples of the chemical combination shown in formula (I) is:
deng.Be preferably
According to the preparation method of acid/acrylic amide type nonionic hydrophilic monomer of the present invention, the method comprises the following steps:
(1) polyoxyethylene glycol is carried out in the first organic solvent to first with thionyl chloride and contact, the condition of described the first contact makes to obtain monochloro for polyoxyethylene glycol, and wherein, the polymerization degree of described polyoxyethylene glycol is 2-10;
(2) diethanolamine is carried out in the second organic solvent to second with acrylate chloride and contact, the condition of described the second contact makes to obtain di-alcohol acrylamide;
(3) di-alcohol acrylamide being carried out to the 3rd for polyoxyethylene glycol with monochloro in the 3rd organic solvent contacts, the condition of described the 3rd contact makes to obtain acid/acrylic amide type nonionic hydrophilic monomer, and the structure of described acid/acrylic amide type nonionic hydrophilic monomer as shown in the formula (I);
Wherein, m
1, m
2being the integer of 2-10 independently of one another, is preferably the integer of 3-6 independently of one another.
According to the preparation method of acid/acrylic amide type nonionic hydrophilic monomer of the present invention, in step (1), although the mol ratio of various polyoxyethylene glycol and thionyl chloride all can realize object of the present invention, under preferable case, the mol ratio of described polyoxyethylene glycol and thionyl chloride can be 0.8-1.2:1, is preferably 1-1.1:1.Although as long as the condition of described the first contact can access monochloro for polyoxyethylene glycol, there is no particular restriction, and under preferable case, described the first contact comprises two stages of carrying out successively, the reaction conditions of first stage comprises: the temperature of contact is 10-30 ℃, is preferably 20-25 ℃; The time of contact is 0.25-0.75 hour, is preferably 0.5-0.6 hour; The reaction conditions of subordinate phase comprises: the temperature of contact is 100-140 ℃, is preferably 115-125 ℃; The time of contact is 0.5-1.5 hour, is preferably 0.8-1.2 hour.
The preparation method of acid/acrylic amide type nonionic hydrophilic monomer according to the present invention, in step (1), described the first organic solvent can for existing various can be as the organic solvent of reaction media, for example, described the first organic solvent can be selected from one or more in trichloromethane, acetone and dimethyl formamide, is preferably dimethyl formamide.As a rule, it is 20-30 % by weight that the amount that the first organic solvent adds makes the concentration of described polyoxyethylene glycol and thionyl chloride.
The preparation method of acid/acrylic amide type nonionic hydrophilic monomer according to the present invention, in step (1), although the polyoxyethylene glycol of the various polymerization degree all can be realized the object of the invention, preferably, the polymerization degree of described polyoxyethylene glycol can be 2-10, is preferably 3-6.
The preparation method of acid/acrylic amide type nonionic hydrophilic monomer according to the present invention, in order to obtain sterling, method provided by the invention can also be included in step (1) afterwards, step (2) before, by the monochloro obtaining for polyoxyethylene glycol after filtration, washing, extraction, recrystallization and silica gel column chromatography separation method carry out separating-purifying.The mode of filtration, washing, extraction, recrystallization and silica gel column chromatography separation or method can adopt the conventional mode in this area or method.
According to the preparation method of acid/acrylic amide type nonionic hydrophilic monomer of the present invention, in step (2), although the mol ratio of various described diethanolamine and acrylate chloride all can realize object of the present invention, under preferable case, the mol ratio of described diethanolamine and acrylate chloride can be 0.8-1.2:1, is preferably 1-1.1:1.As long as although the condition of described the second contact can access di-alcohol acrylamide, there is no particular restriction, under preferable case, the condition of described the second contact comprises: the temperature of the second contact is 90-130 ℃, and the time of contact is 1-5 hour.
The preparation method of acid/acrylic amide type nonionic hydrophilic monomer according to the present invention, in step (2), described the second organic solvent can for existing various can be as the organic solvent of reaction media, for example, described the second organic solvent can be selected from one or more in ethyl acetate, sherwood oil and methylene dichloride, is preferably methylene dichloride.As a rule, it is 20-30 % by weight that the amount that the second organic solvent adds makes the concentration of described diethanolamine and acrylate chloride.
The preparation method of acid/acrylic amide type nonionic hydrophilic monomer according to the present invention, in order to obtain sterling, method provided by the invention can also be included in step (2) afterwards, step (3) before, by the di-alcohol acrylamide obtaining after filtration, washing, extraction, recrystallization and silica gel column chromatography separation method carry out separating-purifying.The mode of filtration, washing, extraction, recrystallization and silica gel column chromatography separation or method can adopt the conventional mode in this area or method.
The preparation method of acid/acrylic amide type nonionic hydrophilic monomer according to the present invention, in step (3), although various described di-alcohol acrylamides and monochloro all can be realized object of the present invention for the mol ratio of polyoxyethylene glycol, under preferable case, described di-alcohol acrylamide and monochloro are 1:1.8-2.4 for the mol ratio of polyoxyethylene glycol; As long as although the condition of described the 3rd contact can access acid/acrylic amide type nonionic hydrophilic monomer, there is no particular restriction, under preferable case, described the 3rd contact conditions comprises: the temperature of contact is 30-70 ℃, and the time of contact is 6-10 hour.
The preparation method of acid/acrylic amide type nonionic hydrophilic monomer according to the present invention, in step (3), described the 3rd organic solvent can for existing various can be as the organic solvent of reaction media, for example, described the 3rd organic solvent can be selected from one or more in acetone, ether and methylene dichloride, is preferably methylene dichloride.As a rule, it is 20-30 % by weight for the concentration of polyoxyethylene glycol that the amount that the 3rd organic solvent adds makes described di-alcohol acrylamide and monochloro.
According to the preparation method of acid/acrylic amide type nonionic hydrophilic monomer of the present invention, in the preferred case, this preparation method obtains acid/acrylic amide type nonionic hydrophilic monomer of the present invention through extraction, underpressure distillation after also comprising the 3rd contact.Mode or the method for extraction and underpressure distillation can adopt the conventional mode in this area or method.
According to ternary atactic copolymer of the present invention, wherein, the structural unit D that this ternary atactic copolymer contains structural unit C derived from formula I, derived from acrylamides and derived from the structural unit E of formula II, and the content that the gross weight of structural unit of described terpolymer tensio-active agent of take is structural unit C described in benchmark is 14-43 % by weight, and the content of described structural unit D is 55-70 % by weight; The content of described structural unit E is 2-16 % by weight, and the intrinsic viscosity of described ternary atactic copolymer is 1200-1800mL-g,
Wherein, m
1, m
2be the integer of 2-10 independently of one another, R
1, R
2the alkyl that to be selected from independently of one another H, carbonatoms be 1-12; n
1, n
2be the integer of 3-10 independently of one another.
According to ternary atactic copolymer of the present invention, preferably, the gross weight of structural unit of described ternary atactic copolymer of take is benchmark, and the content of described structural unit C is 24-32 % by weight, the content of described structural unit D is 60-66 % by weight, and the content of described structural unit E is 6-12 % by weight; The intrinsic viscosity of described ternary atactic copolymer is 1230-1750mL-g.
According to the present invention, preferably, m
1, m
2be the integer of 3-6 independently of one another, R
1, R
2the alkyl that to be selected from independently of one another H, carbonatoms be 1-6; n
1, n
2be the integer of 5-8 independently of one another.The ternary atactic copolymer so obtaining is during for the displacement of reservoir oil, and oil displacement efficiency is better.
The limiting examples of the compound shown in formula II is:
According to the preparation method of ternary atactic copolymer of the present invention, wherein, the preparation of the monomers B shown in formula II comprises the following steps:
(i) polypropylene glycol is carried out to the 4th with thionyl chloride in the 4th organic solvent and contact, the condition of described the 4th contact makes to obtain monochloro for polypropylene glycol;
(ii) the compound that is formula III by diethanolamine with structure carries out the 5th and contacts in the 5th organic solvent, and the condition of described the 5th contact makes to obtain the di-alcohol acrylamide of the replacement shown in formula IV;
(iii) the di-alcohol acrylamide of the replacement shown in formula IV is carried out to the 6th for polypropylene glycol with monochloro in the 6th organic solvent and contact, the condition of described the 6th contact makes to obtain the hydrophobicity polymerisable monomer described in formula II,
Wherein, R
1, R
2the alkyl that to be selected from independently of one another H, carbonatoms be 1-12, the polymerization degree of polypropylene glycol is 3-10.Preferably, R
1, R
2the alkyl that to be selected from independently of one another H, carbonatoms be 1-6; The polymerization degree of polypropylene glycol is the integer of 5-8, further preferably, and R
1, R
2be selected from independently of one another hydrogen; The polymerization degree of polypropylene glycol is 5.Limiting examples shown in formula III can be
be preferably
the limiting examples of the compound shown in formula IV can be:
be preferably
According to ternary atactic copolymer of the present invention, wherein, step (i) in, although the mol ratio of various polypropylene glycols and thionyl chloride all can realize object of the present invention, under preferable case, the mol ratio of described polypropylene glycol and thionyl chloride can 0.8-1.2:1, is preferably 1-1.1:1.Although as long as the condition of described the 4th contact can access monochloro for polypropylene glycol, there is no particular restriction, and under preferable case, described the 4th contact comprises two stages of carrying out successively, the reaction conditions of first stage comprises: the temperature of contact is 10-30 ℃, is preferably 20-25 ℃; The time of contact is 0.25-0.75 hour, is preferably 0.5-0.6 hour; The reaction conditions of subordinate phase comprises: the temperature of contact is 100-140 ℃, is preferably 115-125 ℃; The time of contact is 0.5-1.5 hour, is preferably 0.8-1.2 hour.
According to ternary atactic copolymer of the present invention, although the polypropylene glycol of the various polymerization degree all can be realized the object of the invention, preferably, the polymerization degree of polypropylene glycol is 5-8, more preferably 5.
According to ternary atactic copolymer of the present invention, step (i) in, described the 4th organic solvent can for existing various can be as the organic solvent of reaction media, for example, described the 4th organic solvent can be selected from one or more in trichloromethane, dimethyl sulfoxide (DMSO) and dimethyl formamide, is preferably dimethyl formamide.As a rule, it is 20-30 % by weight that the amount that organic solvent adds makes the concentration of described polypropylene glycol and thionyl chloride.
According to the present invention, in order to obtain sterling, method provided by the invention can also be included in step (i) after, step (ii) before, by the monochloro obtaining for polypropylene glycol after filtration, washing, extraction, recrystallization and silica gel column chromatography separation method carry out separating-purifying.The mode of filtration, washing, extraction, recrystallization and silica gel column chromatography separation or method can adopt the conventional mode in this area or method.
According to ternary atactic copolymer of the present invention, wherein, step (ii) in, although the mol ratio of the compound that various diethanolamine and structure are formula III all can realize object of the present invention, under preferable case, described diethanolamine and structure are that the mol ratio of the compound of formula III can be 0.8-1.2:1, are preferably 1-1.1:1; Although as long as the condition of described the 5th contact can access the di-alcohol acrylamide of the replacement shown in formula IV, there is no particular restriction, under preferable case, the condition of described the 5th contact comprises: the temperature of contact is 90-130 ℃, and the time of contact is 1-5 hour.
According to ternary atactic copolymer of the present invention, step (ii) in, described the 5th organic solvent can for existing various can be as the organic solvent of reaction media, for example, described the 5th organic solvent can be selected from one or more in ethyl acetate, sherwood oil and methylene dichloride, is preferably methylene dichloride.As a rule, it is 20-30 % by weight that the amount that the 5th organic solvent adds makes the concentration of the compound that described diethanolamine and structure are formula III.
According to ternary atactic copolymer of the present invention, wherein, step (iii) in, although the di-alcohol acrylamide of the replacement shown in various formula IV and monochloro all can be realized object of the present invention for the mol ratio of polypropylene glycol, under preferable case, the di-alcohol acrylamide of the replacement shown in described formula IV and monochloro can be 1:1.8-2.4 for the mol ratio of polypropylene glycol, are preferably 1:2-2.2; As long as although the condition of described the 6th contact can access the hydrophobic monomer shown in formula II, there is no particular restriction, under preferable case, the condition of described the 6th contact comprises: the temperature of contact is 30-70 ℃, and the time of contact is 6-10 hour.
According to ternary atactic copolymer of the present invention, step (iii) in, described the 6th organic solvent can for existing various can be as the organic solvent of reaction media, for example, described the 6th organic solvent can be selected from one or more in acetone, ether and methylene dichloride, is preferably methylene dichloride.As a rule, it is 20-30 % by weight for the concentration of polypropylene glycol that the amount that the 6th organic solvent adds makes the di-alcohol acrylamide of described replacement and monochloro.
According to ternary atactic copolymer of the present invention, in the preferred case, this preparation method obtains hydrophobicity polymerisable monomer shown in formula II of the present invention through extraction, underpressure distillation after also comprising the 6th contact.Mode or the method for extraction and underpressure distillation can adopt the conventional mode in this area or method.
According to the preparation method of ternary atactic copolymer of the present invention, the method comprises the following steps: in pH value, be under 7-10 and micella copolymerization condition, under the existence of initiator, emulsifying agent and water, make monomer mixture carry out polyreaction, it is 1200-1800mL-g that the condition of polyreaction makes the intrinsic viscosity of the multipolymer that obtains, wherein, described monomer mixture contains the hydrophobic monomer B shown in the acid/acrylic amide type nonionic hydrophilic monomer A shown in acrylamide, formula (I) and formula II; And the gross weight of described monomer mixture of take is benchmark, and the consumption of described monomer A is 14-43 % by weight, and the consumption of described monomers B is 2-16 % by weight, and the consumption of acrylamide is 55-70 % by weight.Preferably, the consumption of described monomer A is 24-32 % by weight, and the consumption of described monomers B is 6-12 % by weight, and the consumption of acrylamide is 60-66 % by weight, and it is 1230-1750mL-g that the condition of polyreaction makes the intrinsic viscosity of the multipolymer that obtains.
According to the preparation method of ternary atactic copolymer of the present invention, the present invention does not have particular requirement to the condition of micella copolymerization, the micella copolymerization condition of prior art all can realize the object of the invention, preferably, described micella copolymerization condition comprises: polymerization temperature is 0 ℃ to 40 ℃, is preferably 0 ℃ to 35 ℃; Polymerization time is 5-15 hour, is preferably 9-12 hour.
According to the preparation method of ternary atactic copolymer of the present invention, wherein, the gross weight of described monomer mixture of take is benchmark, and the consumption of described initiator is 0.01-0.1 % by weight; The present invention is not particularly limited described initiator, and the initiator using in various micella copolymerizations of the prior art all can be realized object of the present invention, and preferably, described initiator is selected from any two kinds in radical polymerization initiator; Described radical polymerization initiator comprises azo-initiator, peroxide initiator and redox class initiator; Described azo-initiator is selected from one or more in azo-bis-iso-dimethyl, azo-bis-isobutyrate hydrochloride, Cellmic C 121, azo di-isopropyl imidazoline salt hydrochlorate, azo isobutyl cyano group methane amide, azo dicyclohexyl formonitrile HCN, azo dicyano valeric acid, azo di-isopropyl tetrahydroglyoxaline, Diisopropyl azodicarboxylate, 2,2'-Azobis(2,4-dimethylvaleronitrile) and 2,2'-Azobis(2,4-dimethylvaleronitrile); Described peroxide initiator is selected from hydrogen peroxide, ammonium persulphate, Sodium Persulfate, Potassium Persulphate, one or more in benzoyl peroxide and the benzoyl peroxide tert-butyl ester; Described redox class initiator is selected from one or more in sodium bisulfite-Potassium Persulphate, S-WAT-Potassium Persulphate, sodium bisulfite-ammonium persulphate, S-WAT-ammonium persulphate, Sodium Persulfate-thiocarbamide and Tetramethyl Ethylene Diamine-ammonium persulphate.
According to the preparation method of ternary atactic copolymer of the present invention, the gross weight of described monomer mixture of take is benchmark, and the consumption of described emulsifying agent is 200-500 % by weight; Wherein, the present invention is not particularly limited described emulsifying agent, the emulsifying agent using in various micella copolymerization of the prior art all can be realized object of the present invention, preferably, described emulsifying agent is selected from one or more in OP-10, NP-10 and Sodium dodecylbenzene sulfonate, is preferably Sodium dodecylbenzene sulfonate.
According to the preparation method of ternary atactic copolymer of the present invention, the present invention is not particularly limited the concentration of described monomer mixture, and preferably, the concentration of described monomer mixture is 15-30 % by weight, is preferably 20-25 % by weight.
According to the preparation method of ternary atactic copolymer of the present invention, in order further to promote the carrying out of polyreaction, adopting pH adjusting agent to regulate the pH value of reaction system is 7-10, and in the preferred case, the pH value of reaction system is adjusted within the scope of 7.5-9.5.The present invention does not have particular requirement to the kind of described pH value conditioning agent, the various pH adjusting agents that the pH value of reaction system can be adjusted to 7-10 of prior art all can realize the present invention, for example, described pH adjusting agent can be one or more in sodium hydroxide, sodium carbonate, salt of wormwood and ammoniacal liquor, is preferably sodium hydroxide.
In the preparation method of ternary atactic copolymer of the present invention, in order to suppress the generation of side reaction, improve the transformation efficiency of reaction, in the preferred case, described polyreaction is carried out under inert conditions, such as guaranteeing that polymerization reaction system is inert atmosphere by pass into the mode of the rare gas elementes such as nitrogen or argon gas in reaction system.
According to the present invention, in order to increase the solvability of each material in polymerization reaction system, under preferable case, also contain small molecules chain-transfer agent in described polymerization reaction system, described small molecules chain-transfer agent can be selected from one or more in urea, thiocarbamide, quadrol, formic acid and ammonia three propionic acid amides.The gross weight of described monomer mixture of take is benchmark, and the consumption of described small molecules chain-transfer agent can be 0.01-1 % by weight conventionally.
In addition,, in order to regulate the molecular weight of the polymkeric substance obtaining, under preferable case, in described polymerization reaction system, also contain molecular weight regulator.Described molecular weight regulator refers to the larger material of chain transfer constant in polymerization system.In polymerization process, only need add a small amount of described molecular weight regulator just can reduce the molecular weight of polymerisate, and also can be by regulating the consumption of described molecular weight regulator to control the molecular weight of described polymerisate.The kind of described molecular weight regulator and consumption are conventionally known to one of skill in the art, and for example, described molecular weight regulator can be selected from one or more in ethylenediamine tetraacetic acid (EDTA) (EDTA), diethylenetriamine pentaacetic acid and poly-hydroxyl acrylic.The gross weight of described monomer mixture of take is benchmark, and the consumption of described molecular weight regulator can be 0.01-1 % by weight conventionally.
The ternary atactic copolymer that the present invention also provides above-mentioned method to make.
In addition, application according to ternary atactic copolymer of the present invention as polymer oil-displacing agent, ternary atactic copolymer of the present invention can be applicable to oil reservoir after high temperature and high salt oil deposit and polymer flooding as polymer oil-displacing agent, further improves oil recovery factor in tertiary oil recovery.
Below by specific embodiment, the present invention is further described in detail.
In comparative example and embodiment, reagent used is commercially available chemically pure reagent.
The dissolution time of multipolymer is measured by GB12005.8-89; The intrinsic viscosity of multipolymer is measured according to GB12005.1-89 polyacrylamide For Intrinsic Viscosity Measurements method: with Ubbelohde viscometer, measure (the NaCl solution of 10 % by weight) at 25 ℃; Viscosity molecular weight is according to formula M=([η]-K)
1 α, K=4.5 * 10 wherein
-3, α=0.80 calculates; Brookfield DV-III viscometer for the apparent viscosity of multipolymer, with 1500mg-L concentration, is that 30000mg-L, rotating speed are 6rmin at 75 ℃, salinity
-1condition under measure; Surface tension adopts Dataphysics DCAT21 surface tension instrument to measure, and experimental temperature is 30.0 ℃.
(1) acid/acrylic amide type nonionic hydrophilic monomer A's is synthetic
Induction stirring is being housed, thermometer, reflux condensing tube, drying tube, in the three-necked flask of constant pressure funnel, the polyoxyethylene glycol (polymerization degree is 5) that adds 23.8g, 0.1mol dimethyl formamide, under induction stirring, in 20 ℃, through constant pressure funnel, slowly add 0.1mol thionyl chloride, polyoxyethylene glycol wherein, dimethyl formamide, pressing 1:1:1 mol ratio with thionyl chloride feeds in raw material, after reaction 0.5h, be warming up to 120 ℃ of reaction 1h, after cooling by the frozen water solution of the saturated sodium carbonate of reaction product impouring 100ml, with sherwood oil, divide 3 extractions, washing sherwood oil 3 times, on Rotary Evaporators, be spin-dried for sherwood oil, underpressure distillation again, collection temperature is 56-60 ℃, pressure is 168Pa component, obtain monochloro for polyoxyethylene glycol, productive rate 53%.Structure with infrared spectroscopy (infrared spectra or nuclear-magnetism) to monochloro for polyoxyethylene glycol characterizes, wherein, and IR (KBr) :-OH (3430); CH
2-(2853,1420); C-O-C-(1105); C-Cl (696), the appearance at these peaks has obtained intermediate monochloro for polyoxyethylene glycol.
The diethanolamine that adds 0.1mol in the three-necked flask that electric mixer and reflux condensing tube are housed, the methylene dichloride of 50mL, by constant pressure funnel, slowly drip the acrylate chloride of 0.1mol, it is reinforced that wherein diethanolamine and acrylate chloride are pressed 1:1 mol ratio, return stirring reaction 3h in 110 ℃ of oil baths.Cooling, add water and stir, reaction product to be filtered, washing, is placed in cable type extractor according extraction using alcohol 10h, takes out and dries the dry di-alcohol acrylamide, productive rate 60% of obtaining of final vacuum.With infrared spectroscopy, di-alcohol acrylamide is characterized, wherein, IR (KBr): C=C-H (3020); CH
2-(2918,2850,1428); C=O (1653); C=C (1602);-C-N (1410); C-O-C-(1135), the appearance explanation at these peaks has generated intermediate di-alcohol acrylamide.
In the three-necked flask that electric mixer and reflux condensing tube are housed, add 0.1mol di-alcohol acrylamide, 100mL methylene dichloride, with sodium hydroxide, the pH value of reaction system is adjusted to 9.5, with constant pressure funnel, slowly add 0.2mol monochloro for polyoxyethylene glycol, di-alcohol acrylamide and monochloro are pressed 1:2 mol ratio for polyoxyethylene glycol and are fed in raw material, at 40 ℃ of temperature, react 8h, obtain acid/acrylic amide type nonionic hydrophilic monomer A, productive rate 85%.The infrared spectrum of monomer A as shown in Figure 1.Wherein, IR (KBr) :-OH (3432cm
-1; CH
2-(2850cm
-1, 1428cm
-1); C=O (1651cm
-1); C=C (1602cm
-1);-C-N (1130cm
-1); C-O-C-(1112cm
-1), the appearance explanation at these peaks has generated target product monomer A.
(2) preparation of hydrophobicity polymerisable monomer B
Induction stirring is being housed, thermometer, reflux condensing tube, drying tube, in the 100mL three-necked flask of constant pressure funnel, add 0.05mol polypropylene glycol (polymerization degree is 5), dimethyl formamide 10mL, under induction stirring, in 20 ℃, through constant pressure funnel, slowly add 0.06mol thionyl chloride, after dropwising reaction 0.5h after, be warming up to 120 ℃ of reaction 1h, after cooling in the frozen water solution of impouring 50ml saturated sodium carbonate, with 300mL sherwood oil, divide 3 extractions, washing sherwood oil 3 times, on Rotary Evaporators, be spin-dried for sherwood oil, underpressure distillation again, collect 184-186 ℃, pressure is the component under 532Pa, obtain monochloro for polypropylene glycol, productive rate 75%.With infrared spectroscopy, to monochloro, the structure for polypropylene glycol characterizes, wherein, and IR (KBr) :-OH (3451cm
-1); CH
3-, CH
2-, CH-(2931cm
-1, 2853cm
-1, 1420cm
-1); C-O-C-(1105cm
-1); C-Cl (696cm
-1), illustrate and obtained intermediate monochloro for polypropylene glycol.
The diethanolamine that adds 0.1mol in the three-necked flask that electric mixer and reflux condensing tube are housed, the methylene dichloride of 50mL, by constant pressure funnel, slowly drip the acrylate chloride of 0.1mol, it is reinforced that wherein diethanolamine and acrylate chloride are pressed 1:1 mol ratio, return stirring reaction 3h in 110 ℃ of oil baths.Cooling, add water and stir, reaction product to be filtered, washing, is placed in cable type extractor according extraction using alcohol 10h, takes out and dries the dry di-alcohol acrylamide, productive rate 60% of obtaining of final vacuum.
In the three-necked flask that electric mixer and reflux condensing tube are housed, add 0.1mol di-alcohol acrylamide and 100mL methylene dichloride, in pH value, for 9.5-10.5, with constant pressure funnel, slowly add 0.2mol monochloro for polypropylene glycol, di-alcohol acrylamide and monochloro are pressed 1:2 mol ratio for polypropylene glycol and are fed in raw material, under temperature 50 C, react 8h, obtain hydrophobicity polymerisable monomer B, productive rate 80%.
Hydrophobicity polymerisable monomer B through infrared spectrum as shown in Figure 2.Wherein, IR (KBr) :-OH (3442); CH
3-, CH
2-, CH-(2916,2852,1432); C=O (1653); C=C (1612);-C-N (1133); C-O-C-(1121).Illustrate and obtained target product monomers B.
(3) preparation of ternary atactic copolymer
Terpolymer PEAM-1 is prepared in the monomer A that step (1) in employing the present embodiment and (2) prepare respectively and monomers B and acrylamide (AM) copolymerization.
Adopt micella process for copolymerization, in the polyreaction bottle of 150mL, add 15.5g acrylamide, 8g acid/acrylic amide type nonionic hydrophilic monomer A, 1.5g hydrophobicity polymerisable monomer B and 2g Sodium dodecylbenzene sulfonate, add 73mL distilled water (total monomer concentration is 25 % by weight) simultaneously, be stirred well to clear solution, add sodium hydroxide regulation system pH value to 9, then reactor is placed in to ice bath, pass into volumetric concentration and be 99.99% high pure nitrogen deoxygenation in 30 minutes, then add successively 20mg urea and 4mg ammonium persulphate and 4mg sodium bisulfite (accounting for the 40ppm of reaction system gross weight), continue to pass into high pure nitrogen 10 minutes, keeping bath temperature is 10 ℃ of reactions 12 hours, obtain the transparent ternary atactic copolymer with viscosity, with acetone precipitation, purify after twice of ternary atactic copolymer, at 50 ℃ of temperature, vacuum-drying is to constant weight, obtain ternary atactic copolymer PEAM-1.
The intrinsic viscosity of this ternary atactic copolymer PEAM-1 is 1388mL.g
-1, viscosity-average molecular weight is 636 * 10
4, surface tension is 36.3mN/m.The simulated formation water that is 10000mg/L by oil field salinity configuration polymers soln, is 1500mg/L at polymer solution concentration, shearing rate 7.34s
-1condition under, polymers soln apparent viscosity variation with temperature curve is shown in Fig. 3.The simulated formation water configuration polymers soln that ，Yong oil field salinity is 10000mg/L as can be seen from Figure 3, when polymer solution concentration is 1500mg/L, is 7.34s in shearing rate
-1condition under, in the time of 25 ℃, the apparent viscosity of the polymers soln of this concentration can reach 20.9mPa.s, and the apparent viscosity in the time of 90 ℃ is 6.9mPa.s, illustrates that the ternary atactic copolymer PEAM-1 obtaining has good temperature resistant antisalt ability and viscous water medium ability.
Except following steps difference, all the other are with embodiment 1.
(3) preparation of ternary atactic copolymer
Adopt micella process for copolymerization, in the polyreaction bottle of 150mL, add 16.5g acrylamide, 6g acid/acrylic amide type nonionic hydrophilic monomer A, 2.5g hydrophobicity polymerisable monomer B and 3g Sodium dodecylbenzene sulfonate, add 72mL distilled water (total monomer concentration is 25 % by weight) simultaneously, be stirred well to clear solution, add sodium hydroxide regulation system pH value to 9.3, then reactor is placed in to ice bath, pass into volumetric concentration and be 99.99% high pure nitrogen deoxygenation in 30 minutes, then add successively 25mg urea and 8mg ammonium persulphate and 4mg sodium bisulfite (accounting for the 40ppm of reaction system gross weight), continue to pass into high pure nitrogen 10 minutes, keeping bath temperature is 5 ℃ of reactions 12 hours, obtain the transparent ternary atactic copolymer with viscosity, with acetone precipitation, purify after twice of ternary atactic copolymer, at 50 ℃ of temperature, vacuum-drying is to constant weight, obtain ternary atactic copolymer PEAM-2.
The intrinsic viscosity of this ternary atactic copolymer PEAM-2 is 1669mL.g
-1, viscosity-average molecular weight is 870 * 10
4, surface tension is 37.5mN/m.The simulated formation water that is 10000mg/L by oil field salinity configuration polymers soln, is 1500mg/L at polymer solution concentration, shearing rate 7.34s
-1condition under, polymers soln apparent viscosity variation with temperature curve is shown in Fig. 4.The simulated formation water configuration polymers soln that ，Yong oil field salinity is 10000mg/L as can be seen from Figure 4, polymer solution concentration is 1500mg/L, at shearing rate 7.34s
-1condition under, in the time of 25 ℃, the apparent viscosity of the polymers soln of this concentration can reach 21.5mPa.s, and in the time of 90 ℃, its apparent viscosity is 8.8mPa.s, illustrates that the ternary atactic copolymer PEAM-2 obtaining has good temperature resistant antisalt ability and viscous water medium ability.
Except following steps difference, all the other are with embodiment 1.
(3) preparation of ternary atactic copolymer
Adopt micella process for copolymerization, in the polyreaction bottle of 150mL, add 15g acrylamide, 7g acid/acrylic amide type nonionic hydrophilic monomer A, 3g hydrophobicity polymerisable monomer B and 3g Sodium dodecylbenzene sulfonate, add 72mL distilled water (total monomer concentration is 25 % by weight) simultaneously, be stirred well to clear solution, add sodium hydroxide regulation system pH value to 9.5, then reactor is placed in to ice bath, pass into volumetric concentration and be 99.99% high pure nitrogen deoxygenation in 30 minutes, then add successively 30mg urea and 2mg ammonium persulphate and 2mg sodium bisulfite (accounting for the 40ppm of reaction system gross weight), continue to pass into high pure nitrogen 10 minutes, keeping bath temperature is 0 ℃ of reaction 12 hours, obtain the transparent ternary atactic copolymer with viscosity, with acetone precipitation, purify after twice of ternary atactic copolymer, at 50 ℃ of temperature, vacuum-drying is to constant weight, obtain ternary atactic copolymer PEAM-3.
The intrinsic viscosity of this ternary atactic copolymer PEAM-3 is 1773mL.g
-1, viscosity-average molecular weight is 936 * 10
4, surface tension is 38.9mN/m.The simulated formation water that is 10000mg/L by oil field salinity configuration polymers soln, is 1500mg/L at polymer solution concentration, shearing rate 7.34s
-1condition under, polymers soln apparent viscosity variation with temperature curve is shown in Fig. 5.As can be seen from Figure 5, this non-ionic (polymeric surfactant) PEAM-3 obtaining has good temperature resistant antisalt ability, the simulated formation water that is 10000mg/L by oil field salinity configuration polymers soln, polymer solution concentration is 1500mg/L, shearing rate 7.34s
-1condition under, its apparent viscosity in the time of 25 ℃ of the polymers soln of this concentration can reach 22.7mPa.s, in the time of 90 ℃, its apparent viscosity still can reach 10.3mPa.s, illustrates that the ternary atactic copolymer PEAM-3 obtaining has good temperature resistant antisalt ability and viscous water medium ability.
Comparative example 1
In the polyreaction bottle of 150mL, the polymeric unit 6.38g acrylamide adding, 18.62g acrylamide group methyl propanesulfonate, add 73mL distilled water (total monomer concentration is 25 % by weight) simultaneously, be stirred well to clear solution, add auxiliary agent urea 10mg, simultaneously by 3.6g sodium hydroxide regulation system pH value to 8.0, then reactor is placed in to ice bath, pass into volumetric concentration and be 99.99% high pure nitrogen deoxygenation in 30 minutes, then add successively 4mg ammonium persulphate and 4mg sodium bisulfite (accounting for the 40ppm of reaction system gross weight), continue to pass into high pure nitrogen 10 minutes, keeping bath temperature is 10 ℃ of reactions 12 hours, obtain the transparent polymkeric substance with viscosity, with twice of acetone precipitation purified polymer, at 50 ℃ of temperature, vacuum-drying is to constant weight, obtain copolymer P (AM-AMPS).
The synthetic copolymer P (AM-AMPS) obtaining of acrylamide and acrylamide group methyl propanesulfonate (mol ratio 1:1), its intrinsic viscosity is 1612mL.g
-1, viscosity-average molecular weight is 823 * 10
4, surface tension is 65.9mN/m.
The simulated formation water that is 10000mg/L by oil field salinity configuration copolymer P (AM-AMPS) solution, is 1500mg/L in this copolymer strength of solution, shearing rate 7.34s
-1condition under, polymers soln apparent viscosity variation with temperature curve is shown in Fig. 6.The simulated formation water configuration binary random copolymer solution that ，Yong oil field salinity is 10000mg/L as can be seen from Figure 6, binary random copolymer strength of solution is 1500mg/L, at shearing rate 7.34s
-1condition under, in the time of 25 ℃, its apparent viscosity is 16.8mPa.s, in the time of 90 ℃, its apparent viscosity is 4.7mPa.s.
Claims (16)
1. an acid/acrylic amide type nonionic hydrophilic monomer, is characterized in that, this acid/acrylic amide type nonionic hydrophilic monomer has the structure shown in formula (I),
Wherein, m
1, m
2being the integer of 2-10 independently of one another, is preferably the integer of 3-6 independently of one another.
2. a preparation method for acid/acrylic amide type nonionic hydrophilic monomer, the method comprises the following steps:
(1) polyoxyethylene glycol is carried out in the first organic solvent to first with thionyl chloride and contact, the condition of described the first contact makes to obtain monochloro for polyoxyethylene glycol, and wherein, the polymerization degree of described polyoxyethylene glycol is 2-10;
(2) diethanolamine is carried out in the second organic solvent to second with acrylate chloride and contact, the condition of described the second contact makes to obtain di-alcohol acrylamide;
(3) di-alcohol acrylamide being carried out to the 3rd for polyoxyethylene glycol with monochloro in the 3rd organic solvent contacts, the condition of described the 3rd contact makes to obtain acid/acrylic amide type nonionic hydrophilic monomer, and the structure of described acid/acrylic amide type nonionic hydrophilic monomer as shown in the formula (I);
Wherein, m
1, m
2being the integer of 2-10 independently of one another, is preferably the integer of 3-6 independently of one another.
3. preparation method according to claim 2, wherein, in step (1), the mol ratio of described polyoxyethylene glycol and thionyl chloride is 0.8-1.2:1; Described the first contact comprises two stages of carrying out successively, and the reaction conditions of first stage comprises: the temperature of contact is 10-30 ℃, and the time of contact is 0.25-0.75 hour; The reaction conditions of subordinate phase comprises: the temperature of contact is 100-140 ℃, and the time of contact is 0.5-1.5 hour.
4. preparation method according to claim 2, wherein, in step (2), the mol ratio of described diethanolamine and acrylate chloride is 0.8-1.2:1; The condition of described the second contact comprises: the temperature of the second contact is 90-130 ℃, and the time of contact is 1-5 hour.
5. preparation method according to claim 2, wherein, in step (3), described di-alcohol acrylamide and monochloro are 1:1.8-2.4 for the mol ratio of polyoxyethylene glycol; Described the 3rd contact conditions comprises: the temperature of contact is 30-70 ℃, and the time of contact is 6-10 hour.
6. a ternary atactic copolymer, it is characterized in that, this ternary atactic copolymer contains derived from structure and is the structural unit C of acid/acrylic amide type nonionic hydrophilic monomer shown in formula I, the structural unit D of derived from acrylamides and derived from structure, is the structural unit E of the hydrophobicity polymerisable monomer shown in formula II, and the gross weight of structural unit of described ternary atactic copolymer of take is benchmark, the content of described structural unit C is 14-43 % by weight, and the content of described structural unit D is 55-70 % by weight; The content of described structural unit E is 2-16 % by weight, and the intrinsic viscosity of described ternary atactic copolymer is 1200-1800mL/g,
Wherein, m
1, m
2be the integer of 2-10 independently of one another, R
1, R
2the alkyl that to be selected from independently of one another H, carbonatoms be 1-12; n
1, n
2be the integer of 3-10 independently of one another.
7. ternary atactic copolymer according to claim 6, wherein, the gross weight of structural unit of described ternary atactic copolymer of take is benchmark, the content of described structural unit C is 24-32 % by weight, the content of described structural unit D is 60-66 % by weight, and the content of described structural unit E is 6-12 % by weight; The intrinsic viscosity of described ternary atactic copolymer is 1230-1750mL/g.
8. ternary atactic copolymer according to claim 6, wherein, m
1, m
2be the integer of 3-6 independently of one another, R
1, R
2the alkyl that to be selected from independently of one another H, carbonatoms be 1-6; n
1, n
2be the integer of 5-8 independently of one another.
9. the preparation method of a ternary atactic copolymer, the method comprises the following steps: in pH value, be under 7-10 and micella copolymerization condition, under the existence of initiator and emulsifying agent and water, make monomer mixture carry out polyreaction, it is 1200-1800mL/g that the condition of polyreaction makes the intrinsic viscosity of the multipolymer that obtains, wherein, described monomer mixture contains the hydrophobicity polymerisable monomer B shown in acrylamide, acid/acrylic amide type nonionic hydrophilic monomer A claimed in claim 1 and formula II; And the gross weight of described monomer mixture of take is benchmark, and the consumption of described monomer A is 14-43 % by weight, and the consumption of described monomers B is 2-16 % by weight, and the consumption of acrylamide is 55-70 % by weight.
10. preparation method according to claim 9, wherein, take described monomer mixture as benchmark, the consumption of described monomer A is 24-32 % by weight, the consumption of described monomers B is 6-12 % by weight, the consumption of acrylamide is 60-66 % by weight, and it is 1230-1750mL/g that the condition of polyreaction makes the intrinsic viscosity of the multipolymer that obtains.
11. preparation methods according to claim 9, wherein, described micella copolymerization condition comprises: polymerization temperature is 0 ℃ to 40 ℃; Polymerization time is 5-15 hour.
12. preparation methods according to claim 9, wherein, the gross weight of described monomer mixture of take is benchmark, the consumption of described initiator is 0.01-0.1 % by weight; Described initiator is selected from azo-initiator, peroxide initiator and redox class initiator at least two kinds; Described azo-initiator is selected from one or more in azo two isopropylformic acid diformazan nitrogen isobutyl cyano group methane amides, azo dicyclohexyl formonitrile HCN, azo dicyano valeric acid, azo di-isopropyl miaow ester, azo-bis-isobutyrate hydrochloride, Cellmic C 121, azo di-isopropyl imidazoline salt hydrochlorate, even azoles quinoline, Diisopropyl azodicarboxylate, 2,2'-Azobis(2,4-dimethylvaleronitrile) and 2,2'-Azobis(2,4-dimethylvaleronitrile); Described peroxide initiator is selected from hydrogen peroxide, ammonium persulphate, Sodium Persulfate, Potassium Persulphate, one or more in benzoyl peroxide and the benzoyl peroxide tert-butyl ester; Described redox class initiator is selected from one or more in sodium bisulfite-Potassium Persulphate, S-WAT-Potassium Persulphate, sodium bisulfite-ammonium persulphate, S-WAT-ammonium persulphate, Sodium Persulfate-thiocarbamide and Tetramethyl Ethylene Diamine-ammonium persulphate; The gross weight of described monomer mixture of take is benchmark, and the consumption of described emulsifying agent is 200-500 % by weight; Described emulsifying agent is selected from one or more in OP-10, NP-10 and Sodium dodecylbenzene sulfonate, is preferably Sodium dodecylbenzene sulfonate.
13. preparation methods according to claim 9, wherein, the concentration of described monomer mixture is 15-30 % by weight, is preferably 20-25 % by weight.
14. preparation methods according to claim 9, wherein, the pH value of reaction system is adjusted to 7.5-9.5; Described pH adjusting agent is selected from one or more in sodium hydroxide, sodium carbonate and ammoniacal liquor, is preferably sodium hydroxide.
15. ternary atactic copolymers that make according to the method described in any one in claim 9-14.
Ternary atactic copolymer described in 16. claims 6,7,8 or 15 is as the application of polymer oil-displacing agent.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210217033.2A CN103508913B (en) | 2012-06-27 | 2012-06-27 | Monomer, ternary random copolymer, preparation methods of monomer and ternary random copolymer, and application of ternary random copolymer |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210217033.2A CN103508913B (en) | 2012-06-27 | 2012-06-27 | Monomer, ternary random copolymer, preparation methods of monomer and ternary random copolymer, and application of ternary random copolymer |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103508913A true CN103508913A (en) | 2014-01-15 |
| CN103508913B CN103508913B (en) | 2015-05-13 |
Family
ID=49892400
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201210217033.2A Active CN103508913B (en) | 2012-06-27 | 2012-06-27 | Monomer, ternary random copolymer, preparation methods of monomer and ternary random copolymer, and application of ternary random copolymer |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103508913B (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108929669A (en) * | 2018-08-17 | 2018-12-04 | 西南石油大学 | Recyclable clean fracturing fluid thickening agent and preparation method thereof, recovery method and high temperature resistant clean fracturing fluid |
| CN113563542A (en) * | 2021-09-24 | 2021-10-29 | 山东诺尔生物科技有限公司 | Polyacrylamide copolymer, polymer profile control agent and preparation method thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1993011174A1 (en) * | 1991-12-06 | 1993-06-10 | Pier Giorgio Righetti | New formulations for polyacrylamide matrices in electrokinetic and chromatographic methodologies |
| CN101432324A (en) * | 2006-05-02 | 2009-05-13 | 巴斯夫欧洲公司 | Copolymers as scale inhibitors |
-
2012
- 2012-06-27 CN CN201210217033.2A patent/CN103508913B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1993011174A1 (en) * | 1991-12-06 | 1993-06-10 | Pier Giorgio Righetti | New formulations for polyacrylamide matrices in electrokinetic and chromatographic methodologies |
| CN101432324A (en) * | 2006-05-02 | 2009-05-13 | 巴斯夫欧洲公司 | Copolymers as scale inhibitors |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108929669A (en) * | 2018-08-17 | 2018-12-04 | 西南石油大学 | Recyclable clean fracturing fluid thickening agent and preparation method thereof, recovery method and high temperature resistant clean fracturing fluid |
| WO2020034292A1 (en) * | 2018-08-17 | 2020-02-20 | 西南石油大学 | Recyclable clean fracturing fluid thickening agent, preparation method for same, recycling method therefore, and high temperature-resistant clean fracturing fluid |
| CN108929669B (en) * | 2018-08-17 | 2020-07-28 | 西南石油大学 | Recoverable clean fracturing fluid thickening agent, preparation method and recovery method thereof, and high-temperature-resistant clean fracturing fluid |
| US10894761B2 (en) | 2018-08-17 | 2021-01-19 | Southwest Petroleum University | Recyclable clean fracturing fluid thickener, preparation method and recovery method thereof, and high-temperature resistant clean fracturing fluid |
| CN113563542A (en) * | 2021-09-24 | 2021-10-29 | 山东诺尔生物科技有限公司 | Polyacrylamide copolymer, polymer profile control agent and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN103508913B (en) | 2015-05-13 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US10570239B1 (en) | Surface-active two-tailed hydrophobic associated polymer and preparation method thereof | |
| CN102372806B (en) | Initiator composition used for synthesizing polyacrylamide capable of displacing oil | |
| CN104693374A (en) | Functional polymer with surface activity as well as preparation method and application thereof | |
| CN115368505B (en) | Temperature-resistant and salt-resistant water-soluble hydrophobically associating polymer oil displacement agent and preparation method thereof | |
| CN104693351A (en) | Functional polymer with surface activity as well as preparation method and application thereof | |
| CN101928556A (en) | Five-membered copolymer fluid loss agent and preparation method thereof | |
| CN103113518A (en) | Viscosifier for drilling fluid and preparation method thereof | |
| CN103242818A (en) | AM (acrylamide)/NaAA (sodium acrylic acid)/AMPL (N-allyl morpholinium) ternary copolymer oil displacement agent and synthesis method thereof | |
| CN103555311A (en) | AM/NaAA/APO (acrylamide/sodium acrylate/N-allylphenoxyacetamide) ternary polymer flooding agent and synthesis method | |
| CN104311449A (en) | Alkenyl-branched monomers and preparation method thereof | |
| CN103435750A (en) | Hydrophobic associated polymer containing capsaicin activated monomer and preparation method thereof | |
| CN103508913B (en) | Monomer, ternary random copolymer, preparation methods of monomer and ternary random copolymer, and application of ternary random copolymer | |
| CN102453478A (en) | Temperature-resistance salt-tolerance macromolecular surfactant for oil field, preparation method and application thereof | |
| CN103508917B (en) | Monomer, binary random copolymer, preparation methods of monomer and binary random copolymer and application of binary random copolymer | |
| CN103508914B (en) | Hydrophobic polymerizable monomer and oil-displacing agent composition as well as preparation method thereof | |
| CN102807503B (en) | Polymerizable monomer with surface activity and tackifying copolymer with surface activity as well as preparation methods and application thereof | |
| CN102453252A (en) | Acrylamide macromonomer and comb type copolymer and preparation method and application thereof | |
| CN105038733A (en) | High-temperature-resistant polymer tackifier for drilling fluid and preparation method for high-temperature-resistant polymer tackifier | |
| CN104974301A (en) | Polymer having surface activity function, preparation method and application thereof | |
| CN110790862B (en) | Acrylamide copolymer and preparation method and application thereof | |
| CN112724314A (en) | Oil displacing polymer, its preparation process and application as polymer oil displacing agent | |
| CN105461598A (en) | Acrylamide monomer, acrylamide copolymer and preparation method therefor and applicationthereof | |
| CN106589232A (en) | Hydrophobic association acrylamide copolymer and preparing method | |
| CN105085309B (en) | A kind of preparation method and application of polymerisable monomer | |
| CN106478463B (en) | A kind of temperature-resistant anti-salt monomer and polymer and its preparation method and application |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |