CN104250380A - Dendritic polymer, dendritic polymer monomer, and preparation methods and application of two - Google Patents

Dendritic polymer, dendritic polymer monomer, and preparation methods and application of two Download PDF

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CN104250380A
CN104250380A CN201310256162.7A CN201310256162A CN104250380A CN 104250380 A CN104250380 A CN 104250380A CN 201310256162 A CN201310256162 A CN 201310256162A CN 104250380 A CN104250380 A CN 104250380A
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formula
branch
shape polymer
structure shown
monomer
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CN104250380B (en
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王中华
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China Petroleum and Chemical Corp
Drilling Engineering Technology Research Institute of Sinopec Zhongyuan Petroleum Engineering Co Ltd
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China Petroleum and Chemical Corp
Drilling Engineering Technology Research Institute of Sinopec Zhongyuan Petroleum Engineering Co Ltd
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Priority to US14/314,756 priority patent/US9475894B2/en
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Abstract

The invention discloses a dendritic polymer, dendritic polymer monomer, and preparation methods and application of the two. The dendritic polymer monomer has the structure of Z'-(Q)n-Y, wherein the Z' has the structure shown as a formula (a) and/or a formula (b), Q represents the dendritic repeated structure unit of the dendritric polymer monomer, n represents the generation quantity of the dendritric polymer monomer and is an integer of 2-6, Y represents a group containing SO3- and COO-, and R2-R4 are same or different and independently represent H or an alkyl with the carbon atom number of 1-5. The monomer can be used as a copolymerization monomer for preparing a hyperbranched polymer for oil fields, the obtained hyperbranched polymer can be used as a drilling-fluid inhibitive filtrate reducer, a flocculating agent, an encapsulating agent, a temperature-resistant salt-resistant polymer oil displacement agent, a fracturing-fluid thickening agent and the like, and the monomer also can be used to prepare other-purpose water-soluble polymers and inner surfactant for emulsion polymerization.

Description

A kind of branch-shape polymer and branch-shape polymer monomer and its preparation method and application
Technical field
The present invention relates to a kind of branch-shape polymer and branch-shape polymer monomer and their preparation method and application.
Background technology
In letex polymerization, by using suitable tensio-active agent, the emulsion obtained or reversed-phase emulsion, make the quality product of application system obtain qualitative leap, but the tensio-active agent that polyreaction remains also brings a series of problem.At present, a lot of patent documentation has been had to propose in emulsion polymerization process, use some polymerisable surfactant.Such as, US4939283 has set forth a kind of polymerisable surfactant be obtained by reacting by traditional nonionogenic tenside and allyloxy glycidyl ether, US5296627 has set forth a kind of allyloxy polymerisable surfactant of ethene end-blocking, US6649718 has set forth a kind of polymerisable surfactant be obtained by reacting by long-chain epoxy alkane and vinyl carbinol, US7026418 has set forth a kind of multipolymer of the epoxy alkane and glycidyl ether that contain polymerizable double bond as tensio-active agent, CN102489215A discloses a kind of amphoteric reaction type tensio-active agent, CN101982224A discloses a kind of polymerisable surfactant containing allyl group or methacrylic, this polymerizable surfactant carries out etherification reaction by glycidyl ether compound and vinyl carbinol or methallyl alcohol, the product obtained carries out epoxy addition again and obtains.
In Process of Oil Well Drilling, drilling strata is increasingly sophisticated, and exceptional well, ultra deep well and Holes of Complicated Wells quantity increase year by year, and this has higher requirement to drilling fluid.Be the exploitation of the unconventionaloil pool of representative at shale gas, in order to meet the needs of wellbore stability and lubricate and sticking control, the shale gas horizontal well drilling of external 60% ~ 70% adopts oil base drilling fluid system.Because oil base drilling fluid cost is high, have pollution to environmental protection, therefore water-base drilling fluid is final selection.Research shows, active shale is at high density CaCl 2dehydration (or dehydration) phenomenon can be there is in the aqueous solution, visible, for the needs of shale gas horizontal well drilling, explore water-based CaCl 2/ polymer drilling fluid, no matter from reducing costs, or the angle of environment protection is said all very necessary.Because current linear polymer tackifying ability under high salinity condition declines, the needs of drilling well can not be met completely, therefore current water base CaCl 2the emphasis of/polymer drilling fluid is that exploitation is applicable to water base CaCl 2the polymer treatment agent of/polymer drilling fluid.
Summary of the invention
The object of the present invention is to provide a kind of branch-shape polymer and branch-shape polymer monomer and their preparation method and application, the polymkeric substance obtained by this branch-shape polymer monomer polymerization can the temperature resistant antisalt ability of raising oil-displacing agent effectively and rejection ability, can be used in water base CaCl 2the preparation of/polymer drilling fluid.
The invention provides a kind of branch-shape polymer, this branch-shape polymer has the structure shown in Z-(Q) n-Y, wherein Z represent can with the group of carboxylic acid halides generation condensation reaction, Q represents the dendroid repeated structural unit of this branch-shape polymer, n represents the algebraically of this branch-shape polymer, for the integer of 2-6, Y represents containing SO 3 -and COO -group.
Present invention also offers a kind of branch-shape polymer monomer, this branch-shape polymer monomer has the structure shown in Z '-(Q) n-Y, wherein Z ' represents the structure shown in following formula (a) and/or formula (b), Q represents the dendroid repeated structural unit of this branch-shape polymer monomer, n represents the algebraically of this branch-shape polymer monomer, for the integer of 2-6, Y represents containing SO 3 -and COO -group,
R 14-R 16identical or different, independently of one another for H or carbonatoms are the alkyl of 1-5.
Present invention also offers a kind of preparation method of branch-shape polymer, the method comprises the following steps:
(1) preparation has the intermediate of structure shown in following formula (5) and/or formula (6),
In formula (5) and formula (6), R 1represent that carbonatoms is the alkylidene group of 1-5, R 2-R 4identical or different, independently of one another for H or carbonatoms are the alkyl of 1-5, and the R in structure shown in n formula (I) 1-R 4identical or different independently of one another;
(2) under nucleophilic addition condition, the unsaturated acid anhydride shown in this intermediate with following formula (7) is contacted, forms the carboxylic acid amide containing unsaturated link(age),
In formula (7), R 8-R 13identical or different, separately for H or carbonatoms are the alkyl of 1-5, p and q is identical or different, is the integer of 0-5 independently of one another,
(3) under 30-100 DEG C of reaction conditions, the carboxylic acid amide of step (2) gained containing unsaturated link(age) is contacted with an alkali metal salt of sulfurous acid and/or sulfurous acid.
Present invention also offers a kind of preparation method of branch-shape polymer monomer, the method comprises and adopts the preparation method of above-mentioned branch-shape polymer to prepare branch-shape polymer, then under condensation reaction condition, this branch-shape polymer is contacted with unsaturated carboxylic acid halides.
Present invention also offers above-mentioned branch-shape polymer and branch-shape polymer monomer is preparing the application in filtrate reducer for drilling fluid, oil-displacing agent, fracturing fluid gelatinizer and oil-field water treatment agent.
Above-mentioned branch-shape polymer provided by the invention and the branch-shape polymer monomer polymkeric substance by preparing as acrylamide etc. with other monomers, effectively can improve the heat and salt resistance of drilling fluid polymer treatment agent, rejection ability and water-soluble.Such as, as can be seen from the result of hereinafter table 1, adopt the polymer treatment agent that branch-shape polymer monomer of the present invention is obtained, 180 DEG C of API filtrations after aging 16 hours are reduced to 14.5 milliliters by 89 milliliters when not adding this branch-shape polymer monomer, and reduced rate is up to 83.8%.Rejection ability R 1also bring up to 96.1% by 91.5% when not adding this branch-shape polymer monomer, viscosity conservation rate is elevated to 34.5% by 15.2%.Due to containing water soluble group, therefore water-soluble also very good.
Embodiment
Below the specific embodiment of the present invention is described in detail.Should be understood that, embodiment described herein, only for instruction and explanation of the present invention, is not limited to the present invention.
In the present invention, branch-shape polymer, also known as poplar bundles polymkeric substance, is the linear polymer with poplar bundles primitive (dendron) on each repeating unit.
Branch-shape polymer of the present invention has the structure shown in Z-(Q) n-Y, wherein Z represent can with the group of carboxylic acid halides generation condensation reaction, Q represents the dendroid repeated structural unit of this branch-shape polymer, and n represents the algebraically of this branch-shape polymer, for the integer of 2-6, Y represents containing SO 3 -and COO -group.
Wherein, can with the group of carboxylic acid halides generation condensation reaction can be well known in the art various can with the group of carboxylic acid halides generation condensation reaction, preferred Z is-OH or-NH 2.
In above-mentioned formula, Q can be various in dendritic structural unit, such as, can be
Under preferable case, it is structure shown in following formula (I) that branch-shape polymer of the present invention has Q, and Y is the structure of structure shown in following formula (II),
In formula (I), R 1represent that carbonatoms is the alkylidene group of 1-5, R 2-R 4identical or different, independently of one another for H or carbonatoms are the alkyl of 1-5, and the R in structure shown in n formula (I) 1-R 4identical or different independently of one another;
In formula (II), R 8-R 13identical or different, separately for H or carbonatoms are the alkyl of 1-5, p and q is identical or different, is the integer of 0-5 independently of one another, and M is H, Na or K.
In the present invention, alkyl can be normal chain alkyl (straight chained alkyl), also can be isomery alkyl (branched-chain alkyl).
In the present invention, alkylidene group can be positive structure alkylidene group (straight-chain alkyl-sub-), also can be isomery alkylidene group (branched alkylidene).
In the present invention, carbonatoms is the alkylidene group of 1-5 is such as methylene radical, ethylidene (-CH 2cH 2-), propylidene (-CH 2cH 2cH 2-), isopropylidene (-CH (CH 3) CH 2-or-CH 2cH (CH 3)-), butylidene (-CH 2cH 2cH 2cH 2-) and various isomeric forms, pentylidene (-CH 2cH 2cH 2cH 2cH 2-) and various isomeric forms.The present invention is preferably ethylidene.
In the present invention, carbonatoms is the alkyl of 1-5 can be methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, isobutyl-, the tertiary butyl, n-pentyl or neo-pentyl.Be preferably methyl and/or ethyl.
According to branch-shape polymer of the present invention, wherein, under preferable case, described branch-shape polymer has structure shown in following formula (III) and/or formula (IV),
Z, R 1-R 4, R 8-R 13, M, p be identical with above-mentioned definition with the definition of q.
Wherein, polymkeric substance shown in formula (III) be two generation branch-shape polymer, namely algebraically n is 2; Shown in formula (IV), polymkeric substance is The Trees of Three Generations dendritic polymer, and namely algebraically n is 3.Shown in formula (III), polymkeric substance can only algebraically be different with formula (IV) Suo Shi for polymkeric substance, also can Z, R 1-R 13, M, p and q be all different.
According to branch-shape polymer of the present invention, wherein, preferred Z is OH, R 1for CH 2cH 2, R 2-R 13be H, M is that Na, p and q are 0.
According to branch-shape polymer monomer provided by the invention, this branch-shape polymer monomer has the structure shown in Z '-(Q) n-Y, wherein Z ' represents the structure shown in following formula (a) and/or formula (b), Q represents the dendroid repeated structural unit of this branch-shape polymer monomer, n represents the algebraically of this branch-shape polymer monomer, for the integer of 2-6, Y represents containing SO 3 -and COO -group,
R 14-R 16identical or different, independently of one another for H or carbonatoms are the alkyl of 1-5.
According to branch-shape polymer monomer of the present invention, wherein Q can be the branch shape structural unit of various branch-shape polymer monomer, and under preferable case, Q is structure shown in following formula (I), and Y is structure shown in following formula (II),
Wherein, in formula (I), R 1represent that carbonatoms is the alkylidene group of 1-5, R 2-R 4identical or different, independently of one another for H or carbonatoms are the alkyl of 1-5, and the R in structure shown in n formula (I) 1-R 4identical or different independently of one another;
In formula (II), R 8-R 13identical or different, separately for H or carbonatoms are the alkyl of 1-5, p and q is identical or different, is the integer of 0-5 independently of one another, and M is H, Na or K.
According to branch-shape polymer monomer of the present invention, under preferable case, described branch-shape polymer monomer has the structure shown in any one in following formula (1), formula (2), formula (3) and formula (4),
R 1-R 4, R 8-R 16, M, p be identical with above-mentioned branch-shape polymer with the definition of q.
According to branch-shape polymer monomer of the present invention, wherein particularly preferably described branch-shape polymer monomer has above-mentioned formula (1) and/or formula (3) structure, and in formula (1) and formula (3), R 1for CH 2cH 2, R 2-R 4, R 8-R 16be H, M is that Na or K, p and q are 0 or 1.
According to the preparation method of a kind of branch-shape polymer provided by the invention, when described branch-shape polymer has structure shown in above-mentioned formula (III) and/or formula (IV), the method comprises the following steps:
(1) preparation has the intermediate of structure shown in following formula (5) and/or formula (6),
In formula (5) and formula (6), R 1represent that carbonatoms is the alkylidene group of 1-5, R 2-R 4identical or different, independently of one another for H or carbonatoms are the alkyl of 1-5, and the R in structure shown in n formula (I) 1-R 4identical or different independently of one another;
(2) under nucleophilic addition condition, the unsaturated acid anhydride shown in this intermediate with following formula (7) is contacted, forms the carboxylic acid amide containing unsaturated link(age),
In formula (7), R 8-R 13identical or different, separately for H or carbonatoms are the alkyl of 1-5, p and q is identical or different, is the integer of 0-5 independently of one another,
(3) under 30-100 DEG C of reaction conditions, the carboxylic acid amide of step (2) gained containing unsaturated link(age) is contacted with an alkali metal salt of sulfurous acid and/or sulfurous acid.
The intermediate of formula (5) and/or the shown structure of formula (6) can come to obtain by means commonly known in the art, and the intermediate of such as, shown in formula (5) structure can pass through the unsaturated acid alkyl ester shown in following formula and Z-R 1-NH 2amine generation Michael reaction, then make this Michael reaction product and NH 2-R 1-NH 2alkyl diamine generation condensation reaction, and then make above-mentioned condensation reaction products sequentially repeat above-mentioned Michael reaction and condensation reaction, obtain the intermediate polymer with dendritic structure thus, the algebraically needed for number of times correspondence of repetition.
wherein Z, R 1, R 14-R 16identical with above-mentioned definition, it is the alkyl of 1-5 that R ' is preferably carbonatoms, more preferably methyl or ethyl.
Described Michael reaction is preferably carried out in the presence of solvent, described solvent be preferably in methyl alcohol, ethanol, Virahol and the trimethyl carbinol one or more.
It is 25-55 DEG C that the condition of described Michael reaction can comprise temperature, and the time is 3-7 hour, preferred 4-6 hour.
Described condensation reaction is preferably carried out in the presence of solvent, described solvent be preferably in methyl alcohol, ethanol, Virahol and the trimethyl carbinol one or more.
It is 10-60 DEG C that the condition of described condensation reaction can comprise temperature, and the time is 20-35 hour, is preferably 24-30 hour.
The preparation of this intermediate is described for the intermediate shown in formula (5d) below.
A preferred embodiment of the invention, the intermediate shown in described formula (5d) can be obtained by the method comprised the steps:
(I) add methyl acrylate, thanomin and solvent in a kettle. as methyl alcohol, first at 10-25 DEG C and logical shielding gas as N 2be warming up to 30-40 DEG C after stirring 10-60min in situation and keep 3-7h, then underpressure distillation is to remove organic solvent, obtains the product such as formula structure (5a) Suo Shi.
(II) product of structure formula (5a) Suo Shi and organic solvent such as methyl alcohol are added in reactor, under 10-40 DEG C of agitation condition, drip quadrol, then react 20-35h at this temperature, then underpressure distillation is to remove organic solvent, namely obtains the intermediate product shown in formula (5b) structure.
(III) intermediate product of structure formula (5b) Suo Shi and organic solvent such as methyl alcohol are added in reactor, under 10-40 DEG C of agitation condition, drip methyl acrylate, reaction 20-35h, underpressure distillation removing organic solvent, must such as formula the intermediate product of structure (5c) Suo Shi.
(IV) intermediate product of modus ponens (5c) structure and organic solvent such as methyl alcohol add in reactor, under 10-40 DEG C of agitation condition, drip quadrol, and reaction 20-35h, underpressure distillation, to remove methyl alcohol, obtains such as formula the intermediate product shown in (d) structure.
Repetition above-mentioned steps (III) and step (IV) can increase a generation, and then obtain and the intermediate shown in formula (6) counter structure.
In formula (5) and formula (6), R 1-R 4for other substituent situations can be prepared with reference to aforesaid method, as long as select corresponding raw material.
Preparation in accordance with the present invention, when each step solvent for use is identical, also directly can not carry out next step reaction except desolventizing.
In step (2), unsaturated acid anhydride can represent with following formula structural formula.
Wherein, R 8-R 13and p with q is identical with definition above.
Under preferable case, described unsaturated acid anhydride is maleic anhydride.
It is 60-100 DEG C more preferably 80 DEG C that step (2) nucleophilic addition condition comprises temperature, and the time is 4-20 hour.
Step (2) is preferably carried out under agitation, further preferred at organic solvent as amide solvent and/or halogenated alkanes solvents, further be preferably N, carry out under one or more existence in dinethylformamide, N,N-dimethylacetamide, methylene dichloride, trichloromethane, ethylene dichloride, toluene.Described unsaturated acid anhydride feeds in raw material preferably by dropping mode.
The reaction of step (3) is preferably carried out in the presence of solvent, described solvent is preferably amide solvent and/or halogenated alkanes solvents, one or more more preferably in DMF, N,N-dimethylacetamide, methylene dichloride, trichloromethane, ethylene dichloride, toluene.The organic solvent of step (2) and the organic solvent of step (3) can be identical or different, and the organic solvent of preferred steps (2) is identical with the organic solvent of step (3).The reaction product of further preferred steps (2) is without being separated the reaction directly carrying out step (3).
It is 30-70 DEG C that the described catalytic condition of step (3) can comprise temperature, and the time is 3-20 hour.Reaction times can disappear with double bond and be as the criterion.The mode can passing through bromination addition (can with reference to the chemical books of routine, also can with reference to the method about free vinylformic acid or bromine number in " GB/T10533-2000 water conditioner polyacrylic acid " and " GB/T10535-1997 water conditioner hydrolytic polymaleic anhydride ", with reference to the method about free vinylformic acid or bromine number in " GB/T10533-2000 water conditioner polyacrylic acid " in the embodiment of the present invention) judge that double bond disappears.
Gained mixture to filter after having reacted and steams organic solvent by step (3), then adds charcoal absorption process 14-28 hour, and to remove impurity, then filtering gac, by the solution for vacuum dehydration obtained, obtains goal tree dendritic polymer.
According to the preparation method of branch-shape polymer monomer provided by the invention, the method comprises employing aforesaid method and prepares branch-shape polymer, then under condensation reaction condition, this branch-shape polymer is contacted with unsaturated carboxylic acid halides.
The reaction that branch-shape polymer contacts with unsaturated carboxylic acid halides is preferably carried out in the presence of solvent, and it is 0-20 DEG C that the condition of contact can comprise temperature, and the time is 0.5-10h.
A preferred embodiment of the invention, the preparation method of described branch-shape polymer monomer can comprise the steps: above-mentioned branch-shape polymer, organic solvent and bundle acid agent to add to be equipped with in the reaction flask of refrigerating unit, be cooled to about 5 DEG C, then unsaturated carboxylic acid halides (in adition process, temperature is no more than 15 DEG C) is slowly added, after unsaturated carboxylic acid halides adds, at about 10 DEG C, react 0.5-8h.Reactant is left standstill, separates organic phase, wash for several times with saturated sodium bicarbonate solution neutralization, with anhydrous sodium sulfate drying, steam organic solvent and namely obtain crude product, crude product is further purified, obtain product and the branch-shape polymer monomer of polymerization-grade.
Described unsaturated carboxylic acid halides can be unsaturated acyl chlorides and/or unsaturated acylbromide, and the carbonatoms of described unsaturated carboxylic acid halides is preferably 3-6, and the unsaturated especially carboxylic acid halides of the present invention is acrylate chloride and/or methacrylic chloride.
The sour agent of described bundle can be various alkaline matter, is preferably various nitrogen-containing organic compound, one or more more preferably in methylamine, ethamine, propylamine, dimethylamine, diethylamine, triethylamine, three n-propyl amine, tri-n-butyl amine, pyridine.
Branch-shape polymer: organic solvent: restraint sour agent: the mol ratio of unsaturated carboxylic acid halides is preferably 1:18-22:1.0-1.1:1.0-1.05.
Each reaction related to due to above-mentioned preparation method is conventional organic chemical reactions, and the Direction of Reaction is clear and definite and unique, therefore can be determined the carrying out of above-mentioned reaction by reaction raw materials and reaction conditions, and without the need to characterizing product separately.Certainly, also can by various conventional means as the means such as infrared, nuclear-magnetism, mass spectrum determine the synthesis of various intermediate product, intermediate and target product.
Present invention also offers above-mentioned branch-shape polymer and branch-shape polymer monomer is preparing the application in filtrate reducer for drilling fluid, oil-displacing agent, fracturing fluid gelatinizer and oil-field water treatment agent.
The filtrate reducer for drilling fluid, oil-displacing agent, fracturing fluid gelatinizer and the oil-field water treatment agent that use branch-shape polymer of the present invention and branch-shape polymer monomer to prepare have temperature resistance, anti-salt and rejection ability.Trace it to its cause, may be because branch-shape polymer monomer provided by the invention, containing the acryloxy being easy to be polymerized in molecule, containing amido on monomer molecule chain, carboxyl and sulfonic group etc., hyperbranched polymer can be obtained when autohemagglutination or with during other monomer copolymerizations, during as additive for drilling fluid, due to the dissaving structure of polymkeric substance, the stability under the thickening of polymkeric substance and high temperature can be improved, containing amido and carboxyl on hyperbranched polymeric monomer molecular chain, sulfonic group etc., the hyperbranched polymer obtained with itself and other monomer copolymerization has good thickening in drilling fluid, the ability of filtrate reducing and suppression shale or clay hydration swelling.The polymerisable branch-shape polymer monomer obtained due to the present invention has surface-active action, and conventional method therefore can be adopted to join in letex polymerization, as internal emulsifying agent.Branch-shape polymer monomer provided by the invention has wide application prospect in water-soluble polymers and inverse emulsion polymer synthesis.
Below in conjunction with specific embodiment, the present invention will be further described.
Preparation example 1
The synthesis of intermediate.
First conventionally synthetic intermediate:
(I) methyl acrylate, thanomin and methyl alcohol is added according to mol ratio 1:0.5:15 in a kettle., at room temperature and logical N 2be warming up to 35 DEG C after stirring 30min in situation and keep 4h, then underpressure distillation is to remove methyl alcohol, obtains the product such as formula structure (5a) Suo Shi.
(II) according to weight ratio 1:3, the product of structure formula (5a) Suo Shi and methyl alcohol are added in reactor, under 25 DEG C of agitation conditions, drip quadrol (be 1:1.05 with the mol ratio of the product of structure formula (5a) Suo Shi) and react 24h afterwards, then underpressure distillation is to remove methyl alcohol, namely obtains the intermediate product shown in formula (5b) structure.
(III) add in reactor according to weight ratio 1:3 by the intermediate product of structure formula (5b) Suo Shi and methyl alcohol, under 25 DEG C of agitation conditions, drip methyl acrylate, reaction 24h, underpressure distillation removing methyl alcohol, must such as formula the intermediate product of structure (5c) Suo Shi.
(IV) add in reactor according to the intermediate product of weight ratio 1:3 modus ponens (5c) structure and methyl alcohol, under 25 DEG C of agitation conditions, drip quadrol, reaction 24h, underpressure distillation, to remove methyl alcohol, obtains such as formula the intermediate shown in (5d) structure.
Preparation example 2
The synthesis of intermediate.
First conventionally synthetic intermediate:
(I) be that 1:0.50:10 adds methyl acrylate, thanomin and methyl alcohol according to mol ratio in a kettle., at room temperature and logical N 2be warming up to 35 DEG C after stirring 30min in situation and keep 4h, then underpressure distillation is to remove methyl alcohol, obtains the product of structure as Suo Shi above-mentioned formula (5a).
(II) according to weight ratio 1:3.5, the product of structure formula (5a) Suo Shi and methyl alcohol are added in reactor, under 25 DEG C of agitation conditions, drip quadrol (be 1:1.0 with the mol ratio of the product of structure formula (5a) Suo Shi) and react 24h afterwards, then underpressure distillation is to remove methyl alcohol, namely obtains the intermediate product as shown in above-mentioned formula (5b) structure.
(III) according to weight ratio 1:3.5, the intermediate product of structure formula (5b) Suo Shi and methyl alcohol are added in reactor, under 25 DEG C of agitation conditions, drip methyl acrylate, reaction 24h, underpressure distillation removing methyl alcohol, must as Suo Shi above-mentioned formula (5c) intermediate product of structure.
(IV) add in reactor according to the intermediate product of weight ratio 1:3.5 modus ponens (5c) structure and methyl alcohol, under 25 DEG C of agitation conditions, drip quadrol, reaction 24h, underpressure distillation, to remove methyl alcohol, obtains the intermediate product as shown in above-mentioned formula (5d) structure.
(V) according to weight ratio 1:3.5, the intermediate product of structure formula (5d) Suo Shi and methyl alcohol are added in reactor, under 25 DEG C of agitation conditions, drip methyl acrylate, reaction 24h, underpressure distillation removing methyl alcohol, must as shown in the formula the intermediate product of (6e) (similar with formula (5c), but algebraically adds 1).
(VI) get the intermediate product of step (V) gained according to weight ratio 1:3.5 and methyl alcohol adds in reactor, under 25 DEG C of agitation conditions, drip quadrol, reaction 24h, underpressure distillation, to remove methyl alcohol, obtains the intermediate shown in formula (6f).
Embodiment 1
This embodiment is for illustration of branch-shape polymer and branch-shape polymer monomer and preparation method thereof.
(1) intermediate product and 180 milliliters of N of obtained formula (5d) structure of 74.5 grams of preparation examples 1 are got, N-N,N-DIMETHYLACETAMIDE adds in reactor, under 25 DEG C of agitation conditions, drip and be dissolved in 100 milliliters of N by 39.2 grams of MALEIC ANHYDRIDE (MA), the solution of N-N,N-DIMETHYLACETAMIDE, be warming up to 80 DEG C, react 20 hours.
(2) at 30 DEG C, in above-mentioned reaction product, then add the sodium sulfite aqueous solution of 336 gram mass marks 15%, reaction 20 is little disappears (being judged by bromination additive process) up to double bond.Filter, steam organic solvent.Add charcoal absorption process 24 hours, then filtering gac, by the solution for vacuum dehydration obtained, obtain the hyperbranched product as shown in the formula (I-1) structure:
Wherein:
(3) according to the hyperbranched product of step (2) gained: organic solvent (methylene dichloride): restraint sour agent (triethylamine): acrylate chloride is 1:18:1:1(mol ratio) ratio, the hyperbranched product of step (2) gained, organic solvent and bundle acid agent being added is equipped with in the reaction flask of refrigerating unit, be cooled to 5 DEG C, then slowly add acrylate chloride (to be dissolved in advance in solvent, in adition process, temperature is no more than 15 DEG C), after acrylate chloride adds, react 0.5 hour at 10 DEG C.Reactant is left standstill, separates organic phase, wash for several times with saturated sodium bicarbonate solution neutralization, with anhydrous sodium sulfate drying, steam organic solvent and namely obtain crude product, crude product is further purified, obtain the branch-shape polymer monomeric products of the polymerization-grade shown in formula (1-1), wherein R 1for CH 2cH 2, R 2-R 4, R 8-R 13be H, M is that Na, p and q are 0.
Wherein, the definition of R with R1 is identical with above-mentioned formula (I-1).
Embodiment 2
This embodiment is for illustration of branch-shape polymer and branch-shape polymer monomer and preparation method thereof.
(1) intermediate product and 150 milliliters of N of obtained formula (5d) structure of 74.5 grams of preparation examples 1 are got, dinethylformamide adds in reactor, under 30 DEG C of agitation conditions, dropping is dissolved in the N of 110 milliliters by 39.2 grams of MALEIC ANHYDRIDE (MA), dinethylformamide solution, be warming up to 90 DEG C, react 8 hours.
(2) at 70 DEG C, in above-mentioned reaction product, then add the potassium sulfite aqueous solution of 421 gram mass marks 15%, reaction 3 is little disappears (being judged by bromination additive process) up to double bond.Filter, steam organic solvent.Add charcoal absorption process 24 hours, then filtering gac, by the solution for vacuum dehydration obtained, obtain the hyperbranched product as shown in the formula structure (I-2) Suo Shi:
Wherein:
(3) according to the hyperbranched product of step (2) gained: organic solvent (N, N-N,N-DIMETHYLACETAMIDE): restraint sour agent (pyridine): acrylate chloride is 1:20:1.05:1.02(mol ratio) ratio, the hyperbranched product of step (2) gained, organic solvent and bundle acid agent etc. being added is equipped with in the reaction flask of refrigerating unit, be cooled to 8 DEG C, then slowly add methacrylic chloride (to be dissolved in advance in solvent, in adition process, temperature is no more than 15 DEG C), after methacrylic chloride adds, react 0.5 hour at 10 DEG C.Reactant is left standstill, separates organic phase, wash for several times with saturated sodium bicarbonate solution neutralization, with anhydrous sodium sulfate drying, steam organic solvent and namely obtain crude product, crude product is further purified, obtain the branch-shape polymer monomeric products of the polymerization-grade shown in formula (2-2), wherein R 1for CH 2cH 2, R 2-R 4, R 8-R 13be H, M is that K, p and q are 0.
The definition of R with R1 is identical with above-mentioned formula (I-2).
Embodiment 3
This embodiment is for illustration of branch-shape polymer and branch-shape polymer monomer and preparation method thereof.
(1) intermediate product and 150 milliliters of N of obtained formula (5d) structure of 74.5 grams of preparation examples 1 are got, N-N,N-DIMETHYLACETAMIDE adds in reactor, under 25 DEG C of agitation conditions, drip and be dissolved in 150 milliliters of N by the 3-hexene diacid acid anhydride of 56.9 grams, N-dimethylacetamide solution, be warming up to 80 DEG C, react 18 hours.
(2) in above-mentioned reaction product, then add the sodium sulfite aqueous solution of 336 gram mass marks 15%, react to double bond disappearance (being judged by bromination additive process).Filter, steam organic solvent.Add charcoal absorption process 24 hours, then filtering gac, by the solution for vacuum dehydration obtained, obtain the hyperbranched product as shown in the formula structure (I-3) Suo Shi:
Wherein:
(3) according to the hyperbranched product of step (2) gained: organic solvent (toluene): restraint sour agent (triethylamine): propylene acylbromide is 1:22:1.1:1.05(mol ratio) ratio, the hyperbranched product of step (2) gained, organic solvent and bundle acid agent etc. being added is equipped with in the reaction flask of refrigerating unit, be cooled to 0 DEG C, then slowly add propylene acylbromide (to be dissolved in advance in solvent, in adition process, temperature is no more than 15 DEG C), after propylene acylbromide adds, react 0.5 hour at 10 DEG C.Reactant is left standstill, separates organic phase, wash for several times with saturated sodium bicarbonate solution neutralization, with anhydrous sodium sulfate drying, steam organic solvent and namely obtain crude product, crude product is further purified, obtain the branch-shape polymer monomeric products of the polymerization-grade shown in formula (2-3), wherein R 1for CH 2cH 2, R 2-R 4, R 8-R 13be H, M is that Na, p and q are 1.
The definition of R with R1 is identical with formula (I-3).
Embodiment 4
This embodiment is for illustration of branch-shape polymer and branch-shape polymer monomer and preparation method thereof.
(1) the obtained intermediate shown in formula (6f) of 82.85 grams of preparation examples 2 and 200 milliliters of N are got, N-N,N-DIMETHYLACETAMIDE adds in reactor, under 25 DEG C of agitation conditions, drip and be dissolved in 120 milliliters of N by 39.2 grams of MALEIC ANHYDRIDE (MA), the solution of N-N,N-DIMETHYLACETAMIDE, be warming up to 80 DEG C, react 15 hours.
(2) at 35 DEG C, in above-mentioned reaction product, then add the sodium sulfite aqueous solution of 336 gram mass marks 15%, reaction 18 is little disappears (being judged by bromination additive process) up to double bond.Filter, steam organic solvent.Add charcoal absorption process 24 hours, then filtering gac, by the solution for vacuum dehydration obtained, obtain the hyperbranched product as shown in the formula structure (I-4) Suo Shi:
Wherein:
(3) according to the hyperbranched product of step (2) gained: organic solvent (methylene dichloride): restraint sour agent (triethylamine): acrylate chloride is 1:18:1:1(mol ratio) ratio, the hyperbranched product of step (2) gained, organic solvent and bundle acid agent etc. being added is equipped with in the reaction flask of refrigerating unit, be cooled to 5 DEG C, then slowly add acrylate chloride (to be dissolved in advance in solvent, in adition process, temperature is no more than 15 DEG C), after acrylate chloride adds, react 0.5 hour at 10 DEG C.Reactant is left standstill, separates organic phase, wash for several times with saturated sodium bicarbonate solution neutralization, with anhydrous sodium sulfate drying, steam organic solvent and namely obtain crude product, crude product is further purified, obtain the branch-shape polymer monomeric products of the polymerization-grade shown in formula (2-4), wherein R 1for CH 2cH 2, R 2-R 4, R 8-R 13be H, M is that Na, p and q are 0.
The definition of R with R1 is identical with formula (I-4).
Test case 1
200ml water, the sodium hydroxide of 0.05 mole are added reactor, after it dissolves, add 0.05 mole of 2-acrylamide-2-methylpro panesulfonic acid, after stirring, with massfraction 20% sodium hydroxide solution, the pH value of system is adjusted to 10.0, then add the branch-shape polymer monomer of 0.25 mole of embodiment 1 preparation, 0.05 mole of 3-acrylamido propyl-dimethyl propanesulfonic acid ammonium, 0.65 mole percent acrylamide, stirring makes it dissolve and obtains reaction mixture; Gone to by reaction mixture in polymerization reaction kettle, under agitation add 0.10 gram of ammonium persulphate, 0.10 gram of sodium bisulfite, the starting temperature of polyreaction is 60 DEG C, maintains polyreaction 45 minutes, obtains gel elasticity product; By after the gel elastomeric shear that obtains, dry at 120 DEG C, pulverize and obtain polymer for drilling fluid treatment agent.
Adopt the temperature resistant antisalt ability of the above-mentioned polymer treatment agent of filtrate reducing aptitude tests in compound salt solution.The preparation of compound salt-water basic slurry used: add 15.75g sodium-chlor in 350ml distilled water, 1.75g Calcium Chloride Powder Anhydrous, 4.6g magnesium chloride, (Weifang Hao Da wilkinite company limited produces 52.5g calcium bentonite, industrial goods) and 3.15g anhydrous sodium carbonate, high-speed stirring 20min, room temperature places aging 24h, obtains compound salt-water basic slurry.Add the sample of 1.5 % by weight during evaluation, high-speed stirring 5 minutes, then at 180 DEG C of aging 16h that roll, be cooled to room temperature, measure the filter loss of drilling fluid with ZNS type drilling fluid filter press.The API filtration that base is starched after 180 DEG C of aging 16h that roll is 228 milliliters.
Shale rolling rate of recovery method is adopted to test rejection ability and the adsorptive power of above-mentioned polymer treatment agent.Method is as follows:
Primary recovery R 1: accurately take 50 grams of landwaste sample (m), add in the polymers soln to be measured of 350 milliliters of massfractions 0.3%, then put into digestion tank, sealing, after 120 DEG C of rolling 16h, cooling, reclaims landwaste with 40 mesh sieves, at 100 ± 5 DEG C, is dried to permanent matter, weighs (m 1), calculate primary recovery R 1.The aquation deployment conditions of primary recovery reaction shale in the treatment agent aqueous solution, primary recovery R 1higher, then rejection ability is stronger.
Secondary returning yield R 2: once will reclaim gained landwaste (m 1) put into 350 milliliters of clear water, lower the temperature after the 2h that rolls at 120 DEG C, reclaim landwaste with 40 mesh sieves, at 100 ± 5 DEG C, be dried to permanent matter, weigh (m 2), calculate secondary returning yield R 2.Secondary returning yield reaction once reclaims the stable case of landwaste in clear water obtained, and secondary returning yield is higher, shows that treatment agent adsorptive power is stronger.
Landwaste used is bright 9-5 well 2695m landwaste (6 ~ 10 order).The rate of recovery of the clear water (not containing sample) of landwaste is 49.5%.
Calculation formula:
R 1 = m 1 m × 100 % , R 2 = m 2 m 1 × 100 % , R = R 2 R 1 × 100 %
Wherein R is relative recovery, and the adsorptive power of its reflection polymkeric substance on shale, the larger absorption of its value is stronger.
Solvability prepares massfraction 0.5% aqueous solutions of polymers under adopting room temperature, and the high-speed stirring time according to forming homogeneous aqueous solution's (i.e. non-polymer swellable particles) judges.Process is: get 398 ml waters, adds 2 grams of samples under high velocity agitation, then continues to stir, and when reaching 3min to churning time, takes off observation dissolution phenomena every 30 seconds, until dissolve completely, records consoluet churning time.
CaCl 2tackifying ability in solution adopts the CaCl of massfraction 0.3% polymkeric substance 2the aqueous solution (CaCl 2massfraction 20%) and distilled water solution viscosity ratio, namely viscosity conservation rate is investigated:
Above-mentioned test result is as shown in table 1 below.
Test case 2
95ml water, the sodium hydroxide of 0.15 mole are added reactor, after it dissolves, add 0.15 mole of 2-acrylamide-2-methylpro panesulfonic acid add reactor, after stirring, with the potassium hydroxide solution of massfraction 10%, the pH value of system is adjusted to 7.0, then add the branch-shape polymer monomer of 0.05 mole of embodiment 2 preparation, 0.30 mole of 3-acrylamido propyl-dimethyl propanesulfonic acid ammonium, 0.25 mole percent acrylamide, stirring makes it dissolve and obtains reaction mixture; Gone to by reaction mixture in polymerization reaction kettle, under agitation add 0.30 gram of ammonium persulphate, 0.30 gram of sodium bisulfite, the starting temperature of polyreaction is 40 DEG C, maintains polyreaction 90 minutes, obtains gel elasticity product; By after the gel elastomeric shear that obtains, dry at 100 DEG C, pulverize and obtain polymer for drilling fluid treatment agent.
Carry out performance test according to the method for test case 1, result is as shown in table 1 below.
Test case 3
185ml water, the sodium hydroxide of 0.1 mole are added reactor, after it dissolves, add 0.10 mole of 2-acrylamide-2-methylpro panesulfonic acid add reactor, after stirring, with the sodium hydroxide solution of massfraction 15%, the pH value of system is adjusted to 8.0, then add the branch-shape polymer monomer of 0.20 mole of embodiment 3 preparation, 0.30 mole of 3-acrylamido propyl group (2-hydroxyl) diallyidimethylammonium chloride, 0.30 mole percent acrylamide, stirring makes it dissolve and obtains reaction mixture; Gone to by reaction mixture in polymerization reaction kettle, under agitation add 0.35 gram of Potassium Persulphate, 0.35 gram of sodium bisulfite, the starting temperature of polyreaction is 45 DEG C, maintains polyreaction 60 minutes, obtains gel elasticity product; By after the gel elastomeric shear that obtains, dry at 110 DEG C, pulverize and obtain polymer for drilling fluid treatment agent.
Carry out performance test according to the method for above-mentioned test case 1, result is as shown in table 1 below.
Test case 4
180ml water, the sodium hydroxide of 0.1 mole are added reactor, after it dissolves, add 0.10 mole of 2-acrylamide-2-methylpro panesulfonic acid add reactor, after stirring, with the potassium hydroxide solution of massfraction 12%, the pH value of system is adjusted to 8.0, then add the branch-shape polymer monomer of 0.20 mole of embodiment 4 preparation, 0.35 mole of 3-acrylamido propyl-dimethyl propanesulfonic acid ammonium, 0.30 mole percent acrylamide, stirring makes it dissolve and obtains reaction mixture; Gone to by reaction mixture in polymer reactor, under agitation add 0.35 gram of ammonium persulphate, 0.35 gram of sodium bisulfite, the starting temperature of polyreaction is 45 DEG C, maintains polyreaction 60 minutes, obtains gel elasticity product; By after the gel elastomeric shear that obtains, dry at 120 DEG C, pulverize and obtain polymer for drilling fluid treatment agent.
Carry out performance test according to the method for above-mentioned test case 1, result is as shown in table 1 below.
Reference test case 1
Polymer for drilling fluid treatment agent is prepared according to the method for embodiment 1, unlike, the branch-shape polymer monomer not adding embodiment 1 preparation carries out polyreaction, obtains reference polymer for drilling fluid treatment agent.Carry out performance test according to the method for above-mentioned test case 1, result is as shown in table 1 below.
Table 1
Note: the API filtration that base is starched after 180 DEG C of aging 16h that roll is 228 milliliters.The rate of recovery of the clear water (not containing sample) of landwaste is 49.5%.
The result of table 1 illustrates and adopts branch-shape polymer monomer of the present invention to coordinate with other monomers obtained polymer treatment agent both to have stronger temperature resistant antisalt ability, has again good rejection ability, and product good water solubility.
More than describe the preferred embodiment of the present invention in detail; but the present invention is not limited to the detail in above-mentioned embodiment, within the scope of technical conceive of the present invention; can carry out multiple simple variant to technical scheme of the present invention, these simple variant all belong to protection scope of the present invention.
It should be noted that in addition, each the concrete technical characteristic described in above-mentioned embodiment, in reconcilable situation, can be combined by any suitable mode.In order to avoid unnecessary repetition, the present invention illustrates no longer separately to various possible array mode.
In addition, also can carry out arbitrary combination between various different embodiment of the present invention, as long as it is without prejudice to thought of the present invention, it should be considered as content disclosed in this invention equally.

Claims (12)

1. a branch-shape polymer, this branch-shape polymer has the structure shown in Z-(Q) n-Y, wherein Z represent can with the group of carboxylic acid halides generation condensation reaction, Q represents the dendroid repeated structural unit of this branch-shape polymer, n represents the algebraically of this branch-shape polymer, for the integer of 2-6, Y represents containing SO 3 -and COO -group.
2. branch-shape polymer according to claim 1, wherein, Z is OH or NH 2, Q is structure shown in following formula (I), and Y is structure shown in following formula (II),
In formula (I), R 1represent that carbonatoms is the alkylidene group of 1-5, R 2-R 4identical or different, independently of one another for H or carbonatoms are the alkyl of 1-5, and the R in structure shown in n formula (I) 1-R 4identical or different independently of one another;
In formula (II), R 8-R 13identical or different, separately for H or carbonatoms are the alkyl of 1-5, p and q is identical or different, is the integer of 0-5 independently of one another, and M is H, Na or K.
3. branch-shape polymer according to claim 2, wherein, described branch-shape polymer has structure shown in following formula (III) and/or formula (IV),
Z, R 1-R 4, R 8-R 13, M, p be identical with claim 2 with the definition of q.
4. the branch-shape polymer according to Claims 2 or 3, wherein, Z is OH, R 1for CH 2cH 2, R 2-R 4, R 8-R 13be H, M is that Na, p and q are 0.
5. a branch-shape polymer monomer, this branch-shape polymer monomer has the structure shown in Z '-(Q) n-Y, wherein Z ' represents the structure shown in following formula (a) and/or formula (b), Q represents the dendroid repeated structural unit of this branch-shape polymer monomer, n represents the algebraically of this branch-shape polymer monomer, for the integer of 2-6, Y represents containing SO 3 -and COO -group,
R 14-R 16identical or different, independently of one another for H or carbonatoms are the alkyl of 1-5.
6. branch-shape polymer monomer according to claim 5, wherein, Q is structure shown in following formula (I), and Y is structure shown in following formula (II),
Wherein, in formula (I), R 1represent that carbonatoms is the alkylidene group of 1-5, R 2-R 4identical or different, independently of one another for H or carbonatoms are the alkyl of 1-5, and the R in structure shown in n formula (I) 1-R 4identical or different independently of one another;
In formula (II), R 8-R 13identical or different, separately for H or carbonatoms are the alkyl of 1-5, p and q is identical or different, is the integer of 0-5 independently of one another, and M is H, Na or K.
7. branch-shape polymer monomer according to claim 6, wherein, described branch-shape polymer monomer has the structure shown in any one in following formula (1), formula (2), formula (3) and formula (4),
R 1-R 4, R 8-R 16, M, p be identical with claim 6 with the definition of q.
8. branch-shape polymer monomer according to claim 7, wherein, this branch-shape polymer monomer has structure shown in formula (1) and/or formula (3), and in formula (1) and formula (3), R 1for CH 2cH 2, R 2-R 13be H, M is that Na, p and q are 0.
9. a preparation method for branch-shape polymer, the method comprises the following steps:
(1) preparation has the intermediate of structure shown in following formula (5) and/or formula (6),
In formula (5) and formula (6), Z, R 1-R 4definition identical with claim 6,
(2) under nucleophilic addition condition, the unsaturated acid anhydride shown in this intermediate with following formula (7) is contacted, forms the carboxylic acid amide containing unsaturated link(age),
In formula (7), R 8-R 13, p with q definition identical with claim 6,
(3) under 30-100 DEG C of reaction conditions, the carboxylic acid amide of step (2) gained containing unsaturated link(age) is contacted with an alkali metal salt of sulfurous acid and/or sulfurous acid.
10. method according to claim 9, wherein, described unsaturated acid anhydride is maleic anhydride.
The preparation method of 11. 1 kinds of branch-shape polymer monomers, the method that the method comprises in employing claim 9-10 described in any one prepares branch-shape polymer, then under condensation reaction condition, this branch-shape polymer is contacted with unsaturated carboxylic acid halides.
Branch-shape polymer monomer in branch-shape polymer in 12. claim 1-4 described in any one and claim 5-8 described in any one is preparing the application in filtrate reducer for drilling fluid, oil-displacing agent, fracturing fluid gelatinizer and oil-field water treatment agent.
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