CN100341909C - Method for synthesizing hydrophobic association water-soluble polymer by adopting template copolymerization method - Google Patents
Method for synthesizing hydrophobic association water-soluble polymer by adopting template copolymerization method Download PDFInfo
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- 230000002209 hydrophobic effect Effects 0.000 title claims abstract description 82
- 238000000034 method Methods 0.000 title claims abstract description 34
- 238000007334 copolymerization reaction Methods 0.000 title claims abstract description 25
- 229920003169 water-soluble polymer Polymers 0.000 title claims abstract description 14
- 230000002194 synthesizing effect Effects 0.000 title abstract description 4
- 239000000178 monomer Substances 0.000 claims abstract description 68
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 17
- 229920001577 copolymer Polymers 0.000 claims abstract description 16
- 239000003999 initiator Substances 0.000 claims abstract description 15
- 238000006243 chemical reaction Methods 0.000 claims abstract description 14
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 34
- 229920000642 polymer Polymers 0.000 claims description 23
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 claims description 21
- 229910052757 nitrogen Inorganic materials 0.000 claims description 17
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 16
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 15
- 230000008569 process Effects 0.000 claims description 14
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 9
- 230000018044 dehydration Effects 0.000 claims description 8
- 238000006297 dehydration reaction Methods 0.000 claims description 8
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- 238000001291 vacuum drying Methods 0.000 claims description 8
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- LSXWFXONGKSEMY-UHFFFAOYSA-N di-tert-butyl peroxide Chemical compound CC(C)(C)OOC(C)(C)C LSXWFXONGKSEMY-UHFFFAOYSA-N 0.000 claims description 6
- 230000003407 synthetizing effect Effects 0.000 claims description 6
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical group OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 4
- 239000003513 alkali Substances 0.000 claims description 4
- 125000003118 aryl group Chemical group 0.000 claims description 4
- 239000004342 Benzoyl peroxide Substances 0.000 claims description 3
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 claims description 3
- YIVJZNGAASQVEM-UHFFFAOYSA-N Lauroyl peroxide Chemical compound CCCCCCCCCCCC(=O)OOC(=O)CCCCCCCCCCC YIVJZNGAASQVEM-UHFFFAOYSA-N 0.000 claims description 3
- 229920002125 Sokalan® Polymers 0.000 claims description 3
- 235000019400 benzoyl peroxide Nutrition 0.000 claims description 3
- YQHLDYVWEZKEOX-UHFFFAOYSA-N cumene hydroperoxide Chemical compound OOC(C)(C)C1=CC=CC=C1 YQHLDYVWEZKEOX-UHFFFAOYSA-N 0.000 claims description 3
- 150000004985 diamines Chemical class 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 3
- 239000004584 polyacrylic acid Substances 0.000 claims description 3
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Substances [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 3
- 235000015320 potassium carbonate Nutrition 0.000 claims description 3
- 235000017550 sodium carbonate Nutrition 0.000 claims description 3
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 3
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 3
- 229920002554 vinyl polymer Polymers 0.000 claims description 3
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 2
- XMNIXWIUMCBBBL-UHFFFAOYSA-N 2-(2-phenylpropan-2-ylperoxy)propan-2-ylbenzene Chemical compound C=1C=CC=CC=1C(C)(C)OOC(C)(C)C1=CC=CC=C1 XMNIXWIUMCBBBL-UHFFFAOYSA-N 0.000 claims description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical group [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 2
- 125000003368 amide group Chemical group 0.000 claims description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 2
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 2
- 238000006392 deoxygenation reaction Methods 0.000 claims description 2
- KFIGICHILYTCJF-UHFFFAOYSA-N n'-methylethane-1,2-diamine Chemical compound CNCCN KFIGICHILYTCJF-UHFFFAOYSA-N 0.000 claims description 2
- 229910052760 oxygen Inorganic materials 0.000 claims description 2
- JRKICGRDRMAZLK-UHFFFAOYSA-L persulfate group Chemical group S(=O)(=O)([O-])OOS(=O)(=O)[O-] JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 claims description 2
- 229920001444 polymaleic acid Polymers 0.000 claims description 2
- 229910052717 sulfur Inorganic materials 0.000 claims description 2
- GJBRNHKUVLOCEB-UHFFFAOYSA-N tert-butyl benzenecarboperoxoate Chemical compound CC(C)(C)OOC(=O)C1=CC=CC=C1 GJBRNHKUVLOCEB-UHFFFAOYSA-N 0.000 claims description 2
- 229910052500 inorganic mineral Inorganic materials 0.000 claims 1
- 239000011707 mineral Substances 0.000 claims 1
- 235000010755 mineral Nutrition 0.000 claims 1
- 239000007864 aqueous solution Substances 0.000 abstract description 9
- 238000006116 polymerization reaction Methods 0.000 abstract description 8
- 230000000694 effects Effects 0.000 abstract description 7
- 230000008719 thickening Effects 0.000 abstract description 6
- 230000007935 neutral effect Effects 0.000 abstract description 5
- 150000003254 radicals Chemical class 0.000 abstract description 5
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- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 abstract 1
- 239000000126 substance Substances 0.000 description 16
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- 230000001105 regulatory effect Effects 0.000 description 6
- 229920000371 poly(diallyldimethylammonium chloride) polymer Polymers 0.000 description 4
- RIYWSTHXFWOZAG-UHFFFAOYSA-N 2-ethoxy-3-prop-2-enoyloxybenzoic acid Chemical compound C(C=C)(=O)OC=1C(=C(C(=O)O)C=CC1)OCC RIYWSTHXFWOZAG-UHFFFAOYSA-N 0.000 description 3
- 125000003010 ionic group Chemical group 0.000 description 3
- 229920002401 polyacrylamide Polymers 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
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- LNETULKMXZVUST-UHFFFAOYSA-N 1-naphthoic acid Chemical compound C1=CC=C2C(C(=O)O)=CC=CC2=C1 LNETULKMXZVUST-UHFFFAOYSA-N 0.000 description 1
- FGRJGEWVJCCOJJ-UHFFFAOYSA-N 2,2-dimethylaziridine Chemical class CC1(C)CN1 FGRJGEWVJCCOJJ-UHFFFAOYSA-N 0.000 description 1
- LCPVQAHEFVXVKT-UHFFFAOYSA-N 2-(2,4-difluorophenoxy)pyridin-3-amine Chemical compound NC1=CC=CN=C1OC1=CC=C(F)C=C1F LCPVQAHEFVXVKT-UHFFFAOYSA-N 0.000 description 1
- UNVGUCSMZRAQPQ-UHFFFAOYSA-N 2-(4-aminophenoxy)ethyl prop-2-enoate Chemical compound Nc1ccc(OCCOC(=O)C=C)cc1 UNVGUCSMZRAQPQ-UHFFFAOYSA-N 0.000 description 1
- ZKFOEDSYSPDTEB-UHFFFAOYSA-N 2-prop-2-enoyloxybenzoic acid Chemical compound OC(=O)C1=CC=CC=C1OC(=O)C=C ZKFOEDSYSPDTEB-UHFFFAOYSA-N 0.000 description 1
- RKAUIQHSMZCPIR-UHFFFAOYSA-N C(C=C)(=O)OC=1C(=C(C#N)C=CC1)OCC Chemical compound C(C=C)(=O)OC=1C(=C(C#N)C=CC1)OCC RKAUIQHSMZCPIR-UHFFFAOYSA-N 0.000 description 1
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- DILRJUIACXKSQE-UHFFFAOYSA-N n',n'-dimethylethane-1,2-diamine Chemical compound CN(C)CCN DILRJUIACXKSQE-UHFFFAOYSA-N 0.000 description 1
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Abstract
The invention belongs to the field of functional polymers, and particularly relates to a hydrophobically associating water-soluble polymer and a method for synthesizing the high-efficiency instant hydrophobically associating water-soluble polymer by using a template polymerization method. An ionic polymer is added into a reaction system as a template, ionic monomers are pre-assembled on the template, and water-soluble monomers AM are dissolved in the aqueous solution body. When water-soluble initiator is adopted to initiate monomer to carry out free radical copolymerization reaction, neutral monomer AM in aqueous solution is initiated to polymerize firstly, then when macromolecular free radicals touch a template, ionic monomer assembled on the template is initiated to polymerize, a section of hydrophobic monomer chain segment is generated on a molecular chain, then the hydrophobic monomer chain segment enters body water to initiate AM polymerization, and a section of AM chain segment is generated on the molecular chain, and the steps are repeated for multiple times, so that the obtained copolymer has a multi-block-shaped structure, the molecular weight is 105～107The range, structure as follows, has good water solubility and shows good thickening effect in water or saline solution.
Description
Technical field
The invention belongs to filed of functional, particularly hydrophobic associated water-soluble polymer, and the method that adopts the instant hydrophobic associated water-soluble polymer of template copolymerization process synthesizing efficient.
Background technology
Hydrophobic associated water-soluble polymer is a kind of functional polymer that contains a small amount of hydrophobic body, they are easy to pass through hydrophobic association in the aqueous solution, produce physical crosslinking, make solution property generation cataclysm, increase on foot as soltion viscosity, viscosity is constantly descended, and removing shearing action again can reinstatement.This hydrophobic associated water-soluble polymer adopts the preparation of micellar copolymerization method usually.
In recent years, hydrophobic associated water-soluble polymer is because of its unique molecule self-assembly behavior and SOLUTION PROPERTIES people's attention extremely.Usually, the content of hydrophobic components is very low in this base polymer molecular structure, and they are attached on the main chain of water-soluble polymers in the mode of side chain or end group.In the aqueous solution, when polymkeric substance surpasses finite concentration, because the molecule interchain interacts, hydrophobic association can take place, this physical crosslinking effect is owing to have reversibility, make this type of polymers soln have the particular rheological properties energy, thereby have important use and be worth, particularly in tertiary oil recovery, water-based paint, weaving, papermaking, aspects such as mining and medicine preparation have shown application prospects (" Water soluble polymers:Synthesis, Solution Properties and Application " S W Shalaby, Charles L.McCormick, G B Butter Eds, ACS.Sym.Ser.467,1991, water-soluble polymers synthetic, SOLUTION PROPERTIES and application, American Chemical Society's proceeding, 467,1991 years).
Up to the present, the most effective synthetic method of hydrophobic associated water-soluble polymer is exactly a micellar copolymerization, and this method is owing to need to use a large amount of tensio-active agents, and this has increased cost on the one hand, brings negative impact also on the other hand polymkeric substance on using; In synthetic most hydrophobic association polymer in the past, because the existence of hydrophobic monomer, the solubility property of product in water is very poor.Template copolymerization (Template Copolymerization) is to introduce a kind of polymkeric substance that is called template in copolymerization system, this template polymer can interact with a kind of monomer or the monomer oligopolymer in the system, so the introducing of template polymer can change the kinetics and the microstructure of product of copolymerization.For example, in the copolymerization system of a kind of neutral monomer and ion monomer composition, the ionic polymer that adds a kind of opposite charges is as template, the ionic polymer of this opposite charges will be undertaken compound by charge effect and ion monomer, cause the pre-assembling of ion monomer on template, in copolymerization process, at first neutral monomer is carried out polymerization in the solution body, then growing chain causes ion monomer and carries out polymerization along template, on polymer molecular chain, add the ion monomer block, by this reaction repeated process, the product of gained and the polymer phase that does not have template to participate in are than having long monomeric unit sequence, and the long sequential structure of this many blocks property brings the character of uniqueness to polymkeric substance.
Summary of the invention
One of purpose of the present invention provides the synthetic method of the instant type water solubility copolymer of a kind of hydrophobic association, promptly adopt the template copolymerization process for synthetizing hydrophobic associated polymkeric substance, it is few that this method has a template consumption, the product solubility property is good, the characteristics that thickening effectiveness is high, and do not need aftertreatment directly to use.
Two of purpose of the present invention provides and adopts the enforcement means of template copolymerization process as molecular designing, constructs a kind of novel many block-wise acrylamide hydrophobically associating water soluble multipolymer.
Three of purpose of the present invention provides a class and is fit to the hydrophobic monomer that has ion hydrotropy group that template copolymerization prepares hydrophobic associated polymer.
The present invention adopts the template copolymerization process for synthetizing hydrophobic associated polymkeric substance first, and the template used amount of this method seldom and does not need aftertreatment directly to use, and therefore has easy to makely, and process is simple, the advantage that cost is low.Simultaneously, hydrophobic monomer contains ionic group, has improved the solvability of polymkeric substance in the aqueous solution.
The present invention by template synthetic hydrophobic associating water-soluble copolymer by water-soluble monomer acrylamide and the hydrophobic monomer that contains ionic group on a small quantity form, its molecular structural formula is as follows:
In the water-soluble hydrophobic associated copolymer chain, neutral monomer acrylamide (AM) content (x) is 90～99.9mol%, and the content of ionic hydrophobic monomer (y) is 0.1～10mol%.The molecular weight of polymkeric substance is 10
5～10
7Scope.
The ionic hydrophobic monomer that is fit to the template copolymerization process for synthetizing hydrophobic associated polymkeric substance is the hydrophobic monomer that a class contains ionic end groups, belong to vinyl monomer, they are connected with hydrophobic body (G) through intermediate chain (Z) by the active group on the vinyl (A), ion or ionizable group (B) are positioned at the end of the chain of hydrophobic body (G), and chemical structural formula is as follows:
In the formula: R be selected from H or-CH
3
A is selected from
O or S.
Z is selected from
n
1=0～3,
n
2=0～10
2Or
n
3=0～10
3
G is selected from aryl, cycloalkyl, many aromatic rings or greasiness ring.
B is selected from carboxyl, amido or ammonium.
In ionic hydrophobic monomer structure, the R group relates to the rigidity of main chain, and the hydrophobic body (G) on the side chain is connected with active group (A) on the main chain by intermediate chain (Z), the effect of intermediate chain helps the interaction of hydrophobic body G on the one hand, the hydrophobic/hydrophilic character that simultaneously also can regulate side chain, the ionic end groups of hydrophobic body (B) mainly for hydrophobic monomer is assembled on the template polymer molecular chain in advance by electrostatic interaction, increases the water-soluble of polymkeric substance simultaneously again.Merit attention, selecting active group A, intermediate chain Z when hydrophobic body G and ionic group B, must guarantee that polymkeric substance has enough hydrophobic association effects, has good water-solubility simultaneously again.In order to guarantee that polymkeric substance has good solvability, general hydrophobic monomer content is lower, still has very high hydrophobic association effect in order to make polymkeric substance under lower hydrophobic monomer content, makes hydrophobic body form the block-wise structure usually in polymkeric substance.Adopt the template copolymerization process, can realize this purpose very easily, obtain hydrophobic associated polymer efficiently.
The used template of the present invention is an Ionomer, can also can be anionic polymer for positively charged ion, and its molecular weight is several thousand to several ten thousand.Template polymer can be polyacrylic acid, polymethyl acrylic acid, PAH, polyethyene diamine, poly-N-methyl ethylenediamine, poly-N, N-dimethyl-ethylenediamine or polymaleic acid.
The template copolymerization method that the present invention adopts belongs to the radical-type polymerization mode, in water solution system, carry out, so use water-soluble radical initiator, as hydrogen peroxide, persulphate, isopropyl benzene hydroperoxide, tertbutyl peroxide, dicumyl peroxide, ditertiary butyl peroxide, peroxidized t-butyl perbenzoate, benzoyl peroxide, dilauroyl peroxide, water-soluble azo compounds or their any mixture, as ditertiary butyl peroxide and the azo two NSC 18620 salt mixture by weight 1/1.
Template copolymerization process synthesizing efficient hydrophobic associated polymer, be different from common process for copolymerization, in reaction system, add a kind of Ionomer as template, make ionic comonomer on template, assemble arrangement in advance, and water-soluble monomer AM is dissolved in the aqueous solution body.When adopting the water soluble starter trigger monomer to carry out free radical copolymerization, at first cause neutral monomer AM polymerization in the aqueous solution, work as macromolecular radical subsequently and run into template, just cause the ion monomer polymerization that is assembled on the template, on molecular chain, generate one section hydrophobic monomer segment, enter then and cause the AM polymerization in the body water, on molecular chain, generate one section AM segment, so repeatedly repeat, the multipolymer of gained has many block-wise structure.
In the template copolymerization reaction system, monomer total mass concentration 1～45wt% is good with 5～25wt% especially.The ratio of ionic hydrophobic monomer and acrylamide is 0.1～10mol%, is good with 0.5～5mol% especially.The ratio of the amount of template polymer and ionic hydrophobic monomer is that 10～200mol%, especially 50～150mol% are good.The pH of reaction system is very big to the influence of reaction, and general pH value of solution is 5.5～9, and preferably 6～8.The consumption of initiator is 0.01～5wt% of monomer mass, and preferably 0.1～3wt% is good.Because polymer template content seldom, its existence does not influence the solvability of hydrophobic copolymer, and polymer template has opposite electric charge with the hydrophobic copolymer intermediate ion, can form associated complex in solution, and this has further increased the hydrophobicity of multipolymer again.
The method of template copolymerization process for synthetizing hydrophobic associated water-soluble multipolymer of the present invention is as follows:
In reactor, add acrylamide, ionic hydrophobic monomer, template polymer, deionized water successively, monomeric total mass concentration is 1～45wt% in the reaction system, the ratio of ionic hydrophobic monomer and acrylamide is 0.1～10mol%, the ratio of template polymer and ionic hydrophobic monomer is 10～200mol%, adds inorganic alkali solution and regulates pH to 5.5～9.In reactor, feed the high pure nitrogen deoxygenation, the logical nitrogen time is 20～40 minutes, add initiator then, initiator amount is 0.01～5wt% of monomer total mass, continues logical nitrogen 5～15 minutes, under 40～70 ℃ of temperature, reacted 10～20 hours, obtain transparent or semitransparent gel product, add acetone then, make the product dehydration, vacuum-drying obtains hydrophobic associating water-soluble copolymer to constant weight under 30～60 ℃ of temperature.
Described alkali is selected from sodium hydroxide, potassium hydroxide, yellow soda ash, salt of wormwood.
Its molecular weight of the hydrophobic associating water-soluble copolymer that the present invention makes is 10
5～10
7Scope has well water-solublely, demonstrates good thickening effectiveness in water or salt brine solution.The viscosity of this hydrophobic associated copolymer solution is non-linear increase with polymer concentration, and viscosity amplification can reach 1～3 order of magnitude.Fig. 1 is by acrylamide and the concentration of aqueous solution of ionic hydrophobic monomer acryloyl-oxy ethoxy benzonitrile acid copolymer and the relation curve of viscosity, when polymer concentration increases to certain value, because the hydrophobic association effect has taken place, makes soltion viscosity raise suddenly.And the non-hydrophobic associated polymer polyacrylamide (PAM) that does not contain hydrophobic body is much smaller with the increase viscosity increase amplitude of concentration.
In addition, the content of hydrophobic body has material impact to the thickening power of multipolymer in this hydrophobic associated copolymer.As shown in Figure 2, along with the increase of hydrophobic monomer content, the thickening effectiveness of aqueous copolymers solution increases.Because this analog copolymer aqueous solution has very high viscosity, is class thickening material efficiently, can be used for tertiary oil recovery, water-borne coatings, printing ink, makeup, pharmaceutical preparation, weaving, printing and dyeing, papermaking, aspects such as mining.
Description of drawings
Fig. 1. the embodiment of the invention 1 water-soluble hydrophobic associated copolymer soltion viscosity and polyacrylamide solution viscosity correlation curve.
Fig. 2. the embodiment of the invention 2,3, the correlation curve of 4,6 water-soluble hydrophobic associated copolymer soltion viscosities and hydrophobic body burden.
Embodiment
Embodiment 1
In reactor, add 40g (0.56mol) acrylamide, 0.13g (0.00056mol) to the acryloyl-oxy ethoxybenzoic acid, 0.105g (0.0011mol) poly diallyldimethylammonium chloride, the 50ml deionized water, regulating pH with sodium hydroxide is 6.5, violent stirring makes reactants dissolved, fed high purity nitrogen 30 minutes to reactor, add initiator azo-bis-isobutyrate hydrochloride 0.2g (0.5wt% amount of monomer), continued logical nitrogen 10 minutes, keep 50 ℃ of reactions of temperature 15 hours, obtain the transparence gel, this gel is added the acetone dehydration, and vacuum-drying obtains containing the multipolymer of hydrophobic monomer to constant weight under 50 ℃ of temperature then, its hydrophobic monomer content is 0.1mol%, and polymericular weight is 7.3 * 10
6The dissolution time that does not have under stirring is 10 hours.
Embodiment 2
In reactor, add 1.34g (0.0189mol) acrylamide, 0.5g (0.0021mol) to the acryloyl-oxy ethoxybenzoic acid, 0.02g (0.00021mol) poly diallyldimethylammonium chloride, the 50ml deionized water, regulating pH with sodium hydroxide is 7.5, violent stirring makes reactants dissolved, fed high purity nitrogen 30 minutes to reactor, add initiator Sodium Persulfate 0.055g (3wt% amount of monomer), continued logical nitrogen 10 minutes, keep 40 ℃ of reactions of temperature 15 hours, obtain the transparence gel, this gel is added the acetone dehydration, and vacuum-drying obtains multipolymer to constant weight under 50 ℃ of temperature then, its hydrophobic monomer content is 10mol%, and polymericular weight is 5.95 * 10
5The dissolution time that does not have under stirring is 10 hours.
Embodiment 3
In the reactor first, add 10g (0.14mol) acrylamide, 0.5g (0.0021mol) to the acryloyl-oxy ethoxybenzoic acid, 0.20g (0.0021mol) poly diallyldimethylammonium chloride, the 50ml deionized water, regulating pH with yellow soda ash is 7.0, violent stirring makes reactants dissolved, fed high purity nitrogen 30 minutes to reactor, add initiator isopropyl benzene hydroperoxide and each 0.05g of tertbutyl peroxide (1wt% amount of monomer), continued logical nitrogen 10 minutes, keep 50 ℃ of reactions of temperature 15 hours, obtain the transparence gel, this gel is added the acetone dehydration, and vacuum-drying obtains multipolymer to constant weight under 50 ℃ of temperature then, wherein hydrophobic monomer content is 1.5mol%, and polymericular weight is 5.17 * 10
6The dissolution time that does not have under stirring is 10 hours.
Embodiment 4
In reactor, add 10g (0.14mol) acrylamide, 1.0g (0.0052mol) to the acryloyl-oxy phenylformic acid, 0.58g (0.0062mol) poly diallyldimethylammonium chloride, the 50ml deionized water, regulating pH with potassium hydroxide is 9.0, violent stirring makes reactants dissolved, fed high purity nitrogen 30 minutes to reactor, add initiator dilauroyl peroxide 0.165g (1.5wt% amount of monomer), continued logical nitrogen 10 minutes, keep 50 ℃ of reactions of temperature 15 hours, obtain the transparence gel, this gel is added the acetone dehydration, and vacuum-drying obtains multipolymer to constant weight under 50 ℃ of temperature then, its hydrophobic monomer content is 3.6mol%, and polymericular weight is 5.67 * 10
6The dissolution time that does not have under stirring is 10 hours.
Embodiment 5
In reactor, add 10g (0.14mol) acrylamide, 1.0g (0.0048mol) to the acryloyl-oxy phenetidine, 2.76g (0.038mol) polyacrylic acid, the 50ml deionized water, regulating pH with salt of wormwood is 6.0, violent stirring makes reactants dissolved, fed high purity nitrogen 30 minutes to reactor, add initiator benzoyl peroxide 0.33g (3wt% amount of monomer), continued logical nitrogen 10 minutes, keep 50 ℃ of reactions of temperature 15 hours, obtain the transparence gel, this gel is added the acetone dehydration, and vacuum-drying obtains multipolymer to constant weight under 50 ℃ of temperature then, its hydrophobic monomer content is 3.3mol%, and polymericular weight is 5.32 * 10
6The dissolution time that does not have under stirring is 10 hours.
Embodiment 6
In reactor, add 10g (0.14mol) acrylamide, 0.3g (0.00073mol) 4-acryloyl-oxy oxyethyl group naphthoic acid, 0.047g (0.0011mol) polyethyene diamine, the 50ml deionized water, regulating pH with sodium hydroxide is 8.0, violent stirring makes reactants dissolved, fed high purity nitrogen 30 minutes to reactor, add initiator azo-bis-isobutyrate hydrochloride 0.0515g (0.5wt% amount of monomer), continued logical nitrogen 10 minutes, keep 50 ℃ of reactions of temperature 15 hours, obtain the transparence gel, this gel is added the acetone dehydration, and vacuum-drying obtains multipolymer to constant weight under 50 ℃ of temperature then, its hydrophobic monomer content is 0.52mol%, and polymericular weight is 4.03 * 10
6The dissolution time that does not have under stirring is 10 hours.
Claims (8)
1. method that adopts template copolymerization process for synthetizing hydrophobic associated water-soluble polymer is characterized in that:
In reactor, add acrylamide, ionic hydrophobic monomer, template polymer, deionized water successively, monomeric total mass concentration is 1～45wt% in the reaction system, the ratio of ionic hydrophobic monomer and acrylamide is 0.1～10mol%, the ratio of template polymer and ionic hydrophobic monomer is 10～200mol%, adds inorganic alkali solution and regulates pH to 5.5～9; In reactor, feed the high pure nitrogen deoxygenation, add initiator then, initiator amount is 0.01～5wt% of monomer total mass, continue logical nitrogen, under 40～70 ℃ of temperature, react, obtain transparent or semitransparent gel product, add acetone then, make the product dehydration, vacuum-drying obtains hydrophobic associating water-soluble copolymer to constant weight under 30～60 ℃ of temperature;
Described template polymer is selected from polyacrylic acid, polymethyl acrylic acid, PAH, polyethyene diamine, poly-N-methyl ethylenediamine, poly-N, a kind of in N-dimethyl-ethylenediamine or the polymaleic acid;
Described ionic hydrophobic monomer is the vinyl monomer that a class contains ionic end groups, and its structure is:
In the formula: R be selected from H or-CH
3
A is selected from
O or S;
Z is selected from
n
1=0～3,
n
2=0～10
2Or
n
3=0～10
3
G is selected from aryl, cycloalkyl, many aromatic rings or greasiness ring;
B is selected from carboxyl, amido or ammonium.
2. method according to claim 1 is characterized in that: the ratio of described ionic hydrophobic monomer and acrylamide is 0.5～5mol%.
3. method according to claim 1 is characterized in that: the ratio of described template polymer and ionic hydrophobic monomer is 50～150mol%.
4. method according to claim 1 is characterized in that: the consumption of described initiator is 0.1～3% of a monomer mass.
5. according to claim 1 or 4 described methods, it is characterized in that: described initiator is selected from hydrogen peroxide, persulphate, isopropyl benzene hydroperoxide, tertbutyl peroxide, dicumyl peroxide, ditertiary butyl peroxide, peroxidized t-butyl perbenzoate, benzoyl peroxide, dilauroyl peroxide, water-soluble azo compounds or their any mixture.
6. method according to claim 1 is characterized in that: described monomer total mass concentration is 5～25%.
7. method according to claim 1 is characterized in that: the pH of described reaction system is 6～8.
8. method according to claim 1 is characterized in that: described mineral alkali is selected from sodium hydroxide, potassium hydroxide, yellow soda ash or salt of wormwood.
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| CN101724132B (en) * | 2008-10-22 | 2011-11-16 | 中国科学院理化技术研究所 | Cationic polyacrylamide with micro-block structure and synthesis method adopting template copolymerization method |
| CN102060965B (en) * | 2009-11-11 | 2012-07-04 | 中国科学院理化技术研究所 | Preparation method of partially hydrolyzed polyacrylamide with improved temperature resistance and salt resistance |
| CN101885805B (en) * | 2010-05-28 | 2012-07-18 | 中国海洋石油总公司 | Cationic polymer for increasing and/or stabilizing viscosity of hydrophobic association type polymer oil-displacing agent |
| CN103159888B (en) * | 2013-03-29 | 2015-08-05 | 南京大学 | Primary amine groups resin of a kind of acrylic acid series Large Copacity trapping cupric ion and preparation method thereof |
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| CN1302797A (en) * | 2000-07-19 | 2001-07-11 | 西南石油学院 | Non-ionic hydrophobic monomer and its preparing process |
| CN1405266A (en) * | 2002-10-28 | 2003-03-26 | 四川大学 | Method for preparing oil-displacing agent of high-tack-producing hydrophobic association polymer |
| CN1511856A (en) * | 2002-12-30 | 2004-07-14 | 中国科学院理化技术研究所 | Hydrophobic association polymer containing benzene end group short alkyl chain and its synthesis method and use |
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| CN1302797A (en) * | 2000-07-19 | 2001-07-11 | 西南石油学院 | Non-ionic hydrophobic monomer and its preparing process |
| CN1405266A (en) * | 2002-10-28 | 2003-03-26 | 四川大学 | Method for preparing oil-displacing agent of high-tack-producing hydrophobic association polymer |
| CN1511856A (en) * | 2002-12-30 | 2004-07-14 | 中国科学院理化技术研究所 | Hydrophobic association polymer containing benzene end group short alkyl chain and its synthesis method and use |
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