CN104250380B - 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 PDFInfo
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- CN104250380B CN104250380B CN201310256162.7A CN201310256162A CN104250380B CN 104250380 B CN104250380 B CN 104250380B CN 201310256162 A CN201310256162 A CN 201310256162A CN 104250380 B CN104250380 B CN 104250380B
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- 0 C*C*c1cc(C)cc(OC*)c1 Chemical compound C*C*c1cc(C)cc(OC*)c1 0.000 description 9
- BLARBXSPVIJGSG-SREVYHEPSA-N CCC/C=N\CC Chemical compound CCC/C=N\CC BLARBXSPVIJGSG-SREVYHEPSA-N 0.000 description 1
- ZQONIVAATDHWFA-UHFFFAOYSA-N CCCC[N+]1(C)CC1 Chemical compound CCCC[N+]1(C)CC1 ZQONIVAATDHWFA-UHFFFAOYSA-N 0.000 description 1
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
Technical field
The present invention relates to a kind of dendritic and dendritic monomer and their preparation method and application.
Background technology
In terms of emulsion polymerization, by using suitable surfactant, the emulsion obtaining or reversed-phase emulsion so that applying
The product quality of system obtains qualitative leap, but the surfactant of polyreaction residual also brings a series of problem.At present,
A lot of patent documentations have been had to propose in emulsion polymerization process using some polymerisable surfactants.For example, us4939283
Elaborate a kind of to react, by traditional nonionic surfactant and allyloxy glycidyl ether, the polymerizable surface activity obtaining
Agent, us5296627 elaborates a kind of allyloxy polymerisable surfactant of ethylene end-blocking, and us6649718 elaborates one kind
The polymerisable surfactant being obtained by long-chain epoxyalkane and 1-propenol-3 reaction, us7026418 elaborates that one kind contains and can gather
Close the epoxyalkane of double bond and the copolymer of glycidyl ether as surfactant, cn102489215a discloses a kind of both sexes
Response type surfactant active, cn101982224a discloses a kind of polymerizable surface activity containing pi-allyl or methacrylic
Agent, this polymerizable surfactant carries out etherification reaction by glycidyl ether compound and 1-propenol-3 or methallyl alcohol,
The product obtaining carries out epoxy addition again and obtains.
In Process of Oil Well Drilling, drilling strata is increasingly sophisticated, and exceptional well, ultradeep well and Holes of Complicated Wells quantity increase year by year,
This puts forward higher requirement to drilling fluid.The exploitation of the unconventionaloil pool being representative in shale gas, in order to meet wellbore stability
With the needs of lubrication anti-sticking, external 60%～70% shale gas horizontal well drilling is using oil base drilling fluid system.Because oil base bores
Well liquid high cost, has pollution, therefore water-base drilling fluid is final selection to environmental protection.Research shows, active shale is in high concentration
cacl2Dehydration (or dehydration) phenomenon being occurred in aqueous solution it is seen then that being directed to the needs of shale gas horizontal well drilling, exploring application
Water base cacl2/ polymer drilling fluid, no matter from reduces cost, or the angle of environmental conservation say all very necessary.Due to current
Linear polymer under the conditions of high salinity tackifying ability decline, can not fully meet the needs of drilling well, therefore current water
Base cacl2/ polymer drilling fluid it is important that exploitation be applied to water base cacl2The polymer treatment agent of/polymer drilling fluid.
Content of the invention
It is an object of the invention to provide a kind of dendritic and dendritic monomer and their preparation
Methods and applications, the polymer being obtained by the polymerization of this dendritic monomer can the heatproof improving oil displacement agent effectively resist
Salt ability and rejection ability, can be used in water base cacl2The preparation of/polymer drilling fluid.
The invention provides a kind of dendritic, this dendritic has the structure shown in z- (q) n-y, its
Middle z represents the group that condensation reaction can occur with carboxylic acid halides, and q represents the dendroid constitutional repeating unit of this dendritic, n
Represent the algebraically of this dendritic, be the integer of 2-6, y represents containing so3 -And coo-Group.
Present invention also offers a kind of dendritic monomer, this dendritic monomer has z '-(q) n-y institute
The structure shown, wherein z ' represent the structure shown in following formula (a) and/or formula (b), and q represents the tree of this dendritic monomer
Dendritic constitutional repeating unit, n represents the algebraically of this dendritic monomer, is the integer of 2-6, and y represents containing so3 -And coo-
Group,
r14-r16Identical or different, being each independently h or carbon number is the alkyl of 1-5.
Present invention also offers a kind of preparation method of dendritic, the method comprises the following steps:
(1) preparation has following formula (5) and/or the intermediate of structure shown in formula (6),
In formula (5) and formula (6), r1Represent the alkylidene that carbon number is 1-5, r2-r4Identical or different, independently of one another
It is the alkyl that h or carbon number are 1-5, and n formula (i) r in shown structure1-r4Identical or different independently of one another；
(2) under the conditions of nucleophilic addition, this intermediate is contacted with the unsaturated acid anhydride shown in following formula (7), shape
Become the carboxylic acid amide containing unsaturated bond,
In formula (7), r8-r13Identical or different, the respectively h or carbon number alkyl for 1-5, p and q is identical or different,
It is each independently the integer of 0-5,
(3) under 30-100 DEG C of reaction condition, by step (2) gained contain unsaturated bond carboxylic acid amide and sulfurous acid and/
Or the alkali metal salt contact of sulfurous acid.
Present invention also offers a kind of preparation method of dendritic monomer, the method is included using above-mentioned dendroid
The preparation method of polymer prepares dendritic, then under the conditions of condensation reaction, makes this dendritic and insatiable hunger
Contact with carboxylic acid halides.
Present invention also offers above-mentioned dendritic and dendritic monomer are preparing drilling fluid filtrate reducing
Application in agent, oil displacement agent, fracturing fluid gelatinizer and oil field water treatment agent.
The present invention provide above-mentioned dendritic and dendritic monomer by with other monomers such as acryloyl
The polymer that amine etc. prepares, can effectively improve heat and salt resistance, rejection ability and the water of drilling fluid polymer treatment agent
Dissolubility.For example, can be seen that at the polymer being obtained using the dendritic monomer of the present invention from the result of table 1 hereinafter
Reason agent, 180 DEG C of api filter losses after aging 16 hours are reduced to 14.5 millis by 89 milliliters when being not added with this dendritic monomer
Rise, reduction rate is up to 83.8%.Rejection ability r1Also bring up to 96.1% by 91.5% when being not added with this dendritic monomer,
Viscosity conservation rate is increased to 34.5% by 15.2%.Due to containing water soluble group, therefore water solublity is also very good.
Specific embodiment
Hereinafter the specific embodiment of the present invention is described in detail.It should be appreciated that it is described herein concrete
Embodiment is merely to illustrate and explains the present invention, is not limited to the present invention.
In the present invention, dendritic, also known as branch fluidized polymer, is to carry poplar bundles primitive on each repetitive
(dendron) linear polymer.
The dendritic of the present invention has the structure shown in z- (q) n-y, and wherein z is represented and can be contracted with carboxylic acid halides
Close the group of reaction, q represents the dendroid constitutional repeating unit of this dendritic, and n represents the generation of this dendritic
Number, is the integer of 2-6, y represents containing so3 -And coo-Group.
Wherein, the group that with carboxylic acid halides, condensation reaction can occur can be well known in the art various can occur with carboxylic acid halides
The group of condensation reaction, preferably z are-oh or-nh2.
In above-mentioned formula, q for various in dendritic construction unit can be able to be for example
Under preferable case, it is following formula (i) shown structure that the dendritic of the present invention has q, and y is for following formula (ii)
The structure of shown structure,
Formula (i) in, r1Represent the alkylidene that carbon number is 1-5, r2-r4Identical or different, it is each independently h or carbon
Atomic number is the alkyl of 1-5, and n formula (i) r in shown structure1-r4Identical or different independently of one another；
Formula (ii) in, r8-r13Identical or different, the respectively h or carbon number alkyl for 1-5, p and q is identical or different,
It is each independently the integer of 0-5, m is h, na or k.
In the present invention, alkyl can be normal chain alkyl (straight chained alkyl) or isomery alkyl (branched alkyl).
In the present invention, alkylidene can be positive structure alkylidene (straight-chain alkyl-sub -) or isomery alkylidene (side chain Asia
Alkyl).
In the present invention, carbon number is the alkylidene of 1-5 is, for example, methylene, ethylidene (- ch2ch2-), propylidene (-
ch2ch2ch2-), isopropylidene (- ch (ch3)ch2- or-ch2ch(ch3) -), butylidene (- ch2ch2ch2ch2-) and its various different
Structure body form, pentylidene (- ch2ch2ch2ch2ch2-) and its various isomeric forms.The present invention is preferably ethylidene.
In the present invention, carbon number is the alkyl of 1-5 can be methyl, ethyl, n-pro-pyl, isopropyl, normal-butyl, isobutyl
Base, the tert-butyl group, n-pentyl or neopentyl.It is preferably methyl and/or ethyl.
According to the dendritic of the present invention, wherein, under preferable case, described dendritic has following formula
(iii) and/or formula (iv) shown structure,
z、r1-r4、r8-r13, m, p and q definition as defined above.
Wherein, (iii) shown polymer is secondary dendritic to formula, and that is, algebraically n is 2；Formula (iv) shown polymer
For three generations's dendritic, that is, algebraically n is 3.Formula (iii) shown polymer and formula (iv) shown polymer can only algebraically be
With it is also possible to z, r1-r13, m, p and q all different.
According to the dendritic of the present invention, wherein, preferably z is oh, r1For ch2ch2, r2-r13It is h, m is na, p
It is 0 with q.
The dendritic monomer being provided according to the present invention, this dendritic monomer has shown in z '-(q) n-y
Structure, wherein z ' represents the structure shown in following formula (a) and/or formula (b), and q represents the branch of this dendritic monomer
Shape constitutional repeating unit, n represents the algebraically of this dendritic monomer, is the integer of 2-6, and y represents containing so3 -And coo-'s
Group,
r14-r16Identical or different, being each independently h or carbon number is the alkyl of 1-5.
According to the dendritic monomer of the present invention, wherein q can be the dendroid of various dendritic monomers
Construction unit, under preferable case, q is following formula (i) shown structure, and y is following formula (ii) shown structure,
Wherein, formula (i) in, r1Represent the alkylidene that carbon number is 1-5, r2-r4Identical or different, it is each independently h
Or carbon number is the alkyl of 1-5, and n formula (i) r in shown structure1-r4Identical or different independently of one another；
Formula (ii) in, r8-r13Identical or different, the respectively h or carbon number alkyl for 1-5, p and q is identical or different,
It is each independently the integer of 0-5, m is h, na or k.
According to the dendritic monomer of the present invention, under preferable case, described dendritic monomer has following
Structure shown in any one in formula (1), formula (2), formula (3) and formula (4),
r1-r4、r8-r16, m, p identical with above-mentioned dendritic with the definition of q.
According to the dendritic monomer of the present invention, wherein particularly preferably described dendritic monomer has above-mentioned
In formula (1) and/or formula (3) structure, and formula (1) and formula (3), r1For ch2ch2, r2-r4、r8-r16It is h, m is na or k, p and q
It is 0 or 1.
According to the present invention provide a kind of dendritic preparation method, when described dendritic have above-mentioned
Formula (iii) and/or formula (iv) shown structure when, the method comprises the following steps:
(1) preparation has following formula (5) and/or the intermediate of structure shown in formula (6),
In formula (5) and formula (6), r1Represent the alkylidene that carbon number is 1-5, r2-r4Identical or different, independently of one another
It is the alkyl that h or carbon number are 1-5, and n formula (i) r in shown structure1-r4Identical or different independently of one another；
(2) under the conditions of nucleophilic addition, this intermediate is contacted with the unsaturated acid anhydride shown in following formula (7), shape
Become the carboxylic acid amide containing unsaturated bond,
In formula (7), r8-r13Identical or different, the respectively h or carbon number alkyl for 1-5, p and q is identical or different,
It is each independently the integer of 0-5,
(3) under 30-100 DEG C of reaction condition, by step (2) gained contain unsaturated bond carboxylic acid amide and sulfurous acid and/
Or the alkali metal salt contact of sulfurous acid.
Formula (5) and/or the intermediate of structure shown in formula (6) can be obtained by means commonly known in the art, such as formula
(5) intermediate of structure shown in can pass through the unsaturated acids Arrcostab shown in following formula and z-r1-nh2Amine occur Michael
Additive reaction, then makes this Michael addition reaction product and nh2-r1-nh2There is condensation reaction in alkyl diamine, then make again
State condensation reaction products and sequentially repeat above-mentioned Michael addition reaction and condensation reaction, be derived from that there is the poly- of dendritic structure
Compound intermediate, the corresponding required algebraically of number of times of repetition.
Wherein z, r1、r14-r16As defined above, it is former that r ' is preferably carbon
Subnumber is the alkyl of 1-5, more preferably methyl or ethyl.
Described Michael addition reaction is preferably carried out in the presence of solvent, and described solvent is preferably methanol, ethanol, isopropanol
One or more of with the tert-butyl alcohol.
The condition of described Michael addition reaction can include temperature and be 25-55 DEG C, and the time is 3-7 hour, and preferably 4-6 is little
When.
Described condensation reaction is preferably carried out in the presence of solvent, and described solvent is preferably methanol, ethanol, isopropanol and tertiary fourth
One or more of alcohol.
The condition of described condensation reaction can include temperature and be 10-60 DEG C, and the time is 20-35 hour, and preferably 24-30 is little
When.
As a example intermediate shown in below by formula (5d), the preparation of this intermediate to be described.
A preferred embodiment of the invention, the intermediate shown in described formula (5d) can be by including following steps
Rapid method is being obtained:
(i) add acrylic acid methyl ester., ethanolamine and solvent such as methanol in a kettle., first in 10-25 DEG C and logical shielding gas
Body such as n2In the case of stirring 10-60min after be warming up to 30-40 DEG C holding 3-7h, then vacuum distillation to remove organic solvent, obtain
Product to structure as shown in formula (5a).
(ii) the product of structure shown in formula (5a) and organic solvent such as methanol are added in reactor, stir at 10-40 DEG C
Under the conditions of, Deca ethylenediamine, then reacts 20-35h, then vacuum distillation to remove organic solvent, that is, obtains at this temperature
Intermediate product shown in formula (5b) structure.
(iii) the intermediate product of structure shown in formula (5b) and organic solvent such as methanol are added in reactor, 10-40 DEG C is stirred
Under the conditions of mixing, Deca acrylic acid methyl ester., reacts 20-35h, vacuum distillation removes organic solvent, obtains structure as shown in formula (5c)
Intermediate product.
(iv) the intermediate product of modus ponens (5c) structure and organic solvent such as methanol add in reactor, 10-40 DEG C of stirring bar
Under part, Deca ethylenediamine, reacts 20-35h, vacuum distillation, to remove methanol, obtains the intermediate product as shown in formula (d) structure.
Repeat the above steps (iii) (iv) can increase a generation with step, so obtain with formula (6) counter structure shown in
Intermediate.
In formula (5) and formula (6), r1-r4Situation for other substituent groups is referred to said method and to prepare, as long as selecting
Corresponding raw material.
Preparation in accordance with the present invention, when each step solvent for use phase it is also possible to not remove solvent and direct
Carry out the reaction of next step.
In step (2), unsaturated acid anhydride can be represented with formula formula.
Wherein, r8-r13And p with q is identical with definition above.
Under preferable case, described unsaturated acid anhydride is maleic anhydride.
Step (2) nucleophilic addition condition includes temperature and is 60-100 DEG C more preferably 80 DEG C, and the time is 4-20 hour.
Step (2) is preferably carried out under agitation, further preferably in organic solvent such as amide solvent and/or halo
Alkane solvents, still more preferably for n, n- dimethylformamide, n, n- dimethyl acetylamide, dichloromethane, chloroform,
Carry out in the presence of one or more of dichloroethanes, toluene.Described unsaturated acid anhydride is preferably fed by Deca mode.
The reaction of step (3) is preferably carried out in the presence of solvent, and described solvent is preferably amide solvent and/or alkyl halide
Varsol, more preferably n, n- dimethylformamide, n, n- dimethyl acetylamide, dichloromethane, chloroform, dichloro
One or more of ethane, toluene.The organic solvent of the organic solvent of step (2) and step (3) can be identical or different, excellent
Select the organic solvent of step (2) identical with the organic solvent of step (3).Further preferably step (2) product without point
From the reaction directly carrying out step (3).
The described catalytic condition of step (3) can include temperature and be 30-70 DEG C, and the time is 3-20 hour.During reaction
Between can by double bond disappear be defined.Can (the chemical books that may be referred to routine be it is also possible to reference by way of bromination addition
Close in " gb/t10533-2000 water treatment agent polyacrylic acid " and " gb/t10535-1997 water treatment agent hydrolytic polymaleic anhydride "
In the method for free acrylic acid or bromine number, with reference in " gb/t10533-2000 water treatment agent polyacrylic acid " in the embodiment of the present invention
Method with regard to free acrylic acid or bromine number) judging that double bond disappears.
After the completion of step (3) reaction, gained mixture is filtered and steam organic solvent, be subsequently adding at activated carbon adsorption
Reason 14-28 hour, to go the removal of impurity, then filters activated carbon, the solution obtaining vacuum dehydration obtains final product goal tree dendritic polymerization
Thing.
The preparation method of the dendritic monomer being provided according to the present invention, the method includes preparing using said method
Dendritic, then under the conditions of condensation reaction, makes this dendritic contact with unsaturated carboxylic acid halides.
The reaction that dendritic is contacted with unsaturated carboxylic acid halides is preferably carried out in the presence of solvent, and the condition of contact is permissible
It is 0-20 DEG C including temperature, the time is 0.5-10h.
A preferred embodiment of the invention, the preparation method of described dendritic monomer can include as
Lower step: above-mentioned dendritic, organic solvent and the sour agent of bundle are added equipped with the reaction bulb of chiller, is cooled to 5
DEG C about, then it is slowly added into unsaturated carboxylic acid halides (in adition process, temperature is less than 15 DEG C), after unsaturated carboxylic acid halides adds, in about
0.5-8h is reacted at 10 DEG C.Reactant is stood, separates organic faciess, wash for several times with saturated sodium bicarbonate solution neutralization, with anhydrous
Sodium sulfate is dried, and steams organic solvent and obtains final product crude product, crude product is further purified, the product obtaining final product polymer grade is dendroid
Polymer monomer.
Described unsaturation carboxylic acid halides can be unsaturated acyl chlorides and/or unsaturated acylbromide, the carbon atom of described unsaturation carboxylic acid halides
Number is preferably 3-6, and the especially unsaturated carboxylic acid halides of the present invention is acryloyl chloride and/or methacrylic chloride.
Described bundle acid agent can be various alkaline matters, preferably various nitrogen-containing organic compounds, more preferably first
One or more of amine, ethamine, propylamine, dimethylamine, diethylamine, triethylamine, three n-pro-pyl amine, tri-n-butyl amine, pyridine.
Dendritic: organic solvent: the sour agent of bundle: the mol ratio of unsaturated carboxylic acid halides is preferably 1:18-22:1.0-1.1:
1.0-1.05.
Each reaction being related to due to above-mentioned preparation method is the organic chemical reactionses of routine, and the Direction of Reaction clearly and
Uniquely, therefore can determine the carrying out of above-mentioned reaction by reaction raw materials and reaction condition, and need not individually product be carried out
Characterize.It is of course also possible to by various conventional meanses are for example infrared, the means such as nuclear-magnetism, mass spectrum determine various intermediate products, intermediate
Synthesis with target product.
Present invention also offers above-mentioned dendritic and dendritic monomer prepare filtrate reducer for drilling fluid,
Application in oil displacement agent, fracturing fluid gelatinizer and oil field water treatment agent.
The filtrate reducer for drilling fluid prepared using the dendritic of the present invention and dendritic monomer, the displacement of reservoir oil
Agent, fracturing fluid gelatinizer and oil field water treatment agent have temperature resistance, salt resistance and rejection ability.Trace it to its cause it may be possible to because this
The dendritic monomer of bright offer, in molecule contain be easy to be polymerized acryloxy, on monomer molecule chain contain amido,
Carboxyl and sulfonic group etc., can obtain dissaving polymer, as additive for drilling fluid during when autohemagglutination or with other monomers copolymerization
When, due to the dissaving structure of polymer, the stability under the thickening of polymer and high temperature can be improved, hyperbranched polymeric monomer divides
Amido and carboxyl, sulfonic group etc. is contained, the dissaving polymer being obtained with other monomers copolymerization with it is in drilling fluid in subchain
There is the ability of good thickening, filtrate reducing and suppression shale or clay hydration swelling.Due to the present invention obtain polymerisable
Dendritic monomer has surface-active action, therefore can be added in emulsion polymerization using conventional method, as
Internal emulsifying agent.The dendritic monomer that the present invention provides has in water-soluble polymer and inverse emulsion polymer synthesis
Wide application prospect.
With reference to specific embodiment, the present invention will be further described.
Preparation example 1
The synthesis of intermediate.
Be first according to routine method synthetic intermediate:
(i) add acrylic acid methyl ester., ethanolamine and methanol according to mol ratio 1:0.5:15 in a kettle., in room temperature and logical
n2In the case of be warming up to 35 DEG C of holding 4h after stirring 30min, then vacuum distillation removing methanol, obtains tying as shown in formula (5a)
The product of structure.
(ii) than 1:3, the product of structure shown in formula (5a) and methanol are added in reactor according to weight, 25 DEG C of stirring bars
Under part, Deca ethylenediamine (mol ratio with the product of structure shown in formula (5a) is 1:1.05) reacts 24h, then vacuum distillation afterwards
To remove methanol, that is, obtain the intermediate product shown in formula (5b) structure.
(iii) the intermediate product of structure shown in formula (5b) and methanol are added in reactor than 1:3 according to weight, 25 DEG C are stirred
Under the conditions of mixing, Deca acrylic acid methyl ester., reacts 24h, vacuum distillation removes methanol, obtains the middle product of structure as shown in formula (5c)
Thing.
(iv) add in reactor according to weight than the intermediate product of 1:3 modus ponens (5c) structure and methanol, 25 DEG C of stirring bars
Under part, Deca ethylenediamine, reacts 24h, vacuum distillation, to remove methanol, obtains the intermediate as shown in formula (5d) structure.
Preparation example 2
The synthesis of intermediate.
Be first according to routine method synthetic intermediate:
(i) add acrylic acid methyl ester., ethanolamine and methanol according to mol ratio for 1:0.50:10 in a kettle., in room temperature
With logical n2In the case of stirring 30min after be warming up to 35 DEG C holding 4h, then vacuum distillation to remove methanol, obtain as above-mentioned formula
(5a) product of structure shown in.
(ii) than 1:3.5, the product of structure shown in formula (5a) and methanol are added in reactor according to weight, 25 DEG C of stirrings
Under the conditions of, Deca ethylenediamine (mol ratio with the product of structure shown in formula (5a) is 1:1.0) reacts 24h afterwards, and then decompression is steamed
Evaporate to remove methanol, as above stated the intermediate product shown in formula (5b) structure.
(iii) than 1:3.5, the intermediate product of structure shown in formula (5b) and methanol are added in reactor according to weight, 25 DEG C
Under stirring condition, Deca acrylic acid methyl ester., reacts 24h, vacuum distillation removes methanol, obtains in structure as shown in above-mentioned formula (5c)
Between product.
(iv) add in reactor according to weight than the intermediate product of 1:3.5 modus ponens (5c) structure and methanol, 25 DEG C of stirrings
Under the conditions of, Deca ethylenediamine, reacts 24h, vacuum distillation, to remove methanol, obtains the middle product as shown in above-mentioned formula (5d) structure
Thing.
(v) the intermediate product of structure shown in formula (5d) and methanol are added in reactor than 1:3.5 according to weight, 25 DEG C are stirred
Under the conditions of mixing, Deca acrylic acid methyl ester., reacts 24h, vacuum distillation removes methanol, obtains intermediate product as following formula (6e) (with formula
(5c) it is similar to, but algebraically adds 1).
(vi) (v) the intermediate product of gained and methanol add in reactor to take step according to weight than 1:3.5,25 DEG C of stirrings
Under the conditions of, Deca ethylenediamine, reacts 24h, vacuum distillation, to remove methanol, obtains the intermediate shown in formula (6f).
Embodiment 1
This embodiment is used for dendritic and dendritic monomer and preparation method thereof are described.
(1) the prepared intermediate product of formula (5d) structure of 74.5 grams of preparation examples 1 and 180 milliliters of n, n- dimethyl acetylamide are taken
Add in reactor, under 25 DEG C of stirring conditions, Deca is dissolved in 100 milliliters of n, n- dimethyl by 39.2 grams of maleic anhydrides (ma)
The solution of acetamide, is warming up to 80 DEG C, reacts 20 hours.
(2) and then add the sodium sulfite aqueous solution of 336 gram mass fractions 15% at 30 DEG C in above-mentioned product,
Reaction disappears (judging by bromination addition process) to double bond in 20 hours.Filter, steam organic solvent.Add at activated carbon adsorption
Reason 24 hours, then filters activated carbon, the solution obtaining vacuum dehydration obtains as the hyperbranched product of following formula (i-1) structure:
Wherein:
(3) according to the hyperbranched product of step (2) gained: organic solvent (dichloromethane): the sour agent (triethylamine) of bundle: propylene
Acyl chlorides is 1:18:1:1(mol ratio) ratio, the hyperbranched product of step (2) gained, organic solvent and the sour agent of bundle are added dress
Have in the reaction bulb of chiller, be cooled to 5 DEG C, be then slowly added into acryloyl chloride and (be dissolved in advance in solvent, in adition process
Temperature is less than 15 DEG C), after acryloyl chloride adds, react 0.5 hour at 10 DEG C.Reactant is stood, separates organic faciess, use
Saturated sodium bicarbonate solution neutralization is washed for several times, with anhydrous sodium sulfate drying, steams organic solvent and obtains final product crude product, crude product is entered
One step purification, obtains final product the dendritic monomeric products of the polymer grade shown in formula (1-1), wherein r1For ch2ch2, r2-r4、r8-
r13It is h, m is na, p and q is 0.
Wherein, the definition of r with r1 is identical with above-mentioned formula (i-1).
Embodiment 2
This embodiment is used for dendritic and dendritic monomer and preparation method thereof are described.
(1) the prepared intermediate product of formula (5d) structure of 74.5 grams of preparation examples 1 and 150 milliliters of n, n- dimethylformamide are taken
Add in reactor, under 30 DEG C of stirring conditions, Deca is dissolved in 110 milliliters of n, n- diformazan by 39.2 grams of maleic anhydrides (ma)
Base formamide solution, is warming up to 90 DEG C, reacts 8 hours.
(2) and then add the potassium sulfite aqueous solution of 421 gram mass fractions 15% at 70 DEG C in above-mentioned product,
Reaction disappears (judging by bromination addition process) to double bond in 3 hours.Filter, steam organic solvent.Add at activated carbon adsorption
Reason 24 hours, then filters activated carbon, and the solution obtaining vacuum dehydration obtains the hyperbranched of as shown in following formula (i-2) structure
Product:
Wherein:
(3) according to the hyperbranched product of step (2) gained: organic solvent (n, n- dimethyl acetylamide): the sour agent (pyrrole of bundle
Pyridine): acryloyl chloride be 1:20:1.05:1.02(mol ratio) ratio, by the hyperbranched product of step (2) gained, organic solvent
Sour agent etc. adds equipped with the reaction bulb of chiller, being cooled to 8 DEG C with bundle, is then slowly added into methacrylic chloride (in advance
It is dissolved in solvent, in adition process, temperature is less than 15 DEG C), after methacrylic chloride adds, react 0.5 hour at 10 DEG C.
Reactant is stood, separates organic faciess, washed for several times with saturated sodium bicarbonate solution neutralization, with anhydrous sodium sulfate drying, steamed
Machine solvent obtains final product crude product, and crude product is further purified, and obtains final product the dendritic monomer of the polymer grade shown in formula (2-2)
Product, wherein r1For ch2ch2, r2-r4、r8-r13It is h, m is k, p and q is 0.
The definition of r with r1 is identical with above-mentioned formula (i-2).
Embodiment 3
This embodiment is used for dendritic and dendritic monomer and preparation method thereof are described.
(1) the prepared intermediate product of formula (5d) structure of 74.5 grams of preparation examples 1 and 150 milliliters of n, n- dimethyl acetylamide are taken
Add in reactor, under 25 DEG C of stirring conditions, Deca is dissolved in 150 milliliters of n, n- dimethyl second by 56.9 grams of 3- hexene diacid acid anhydride
Amide solution, is warming up to 80 DEG C, reacts 18 hours.
(2) state the sodium sulfite aqueous solution adding 336 gram mass fractions 15% in product then up, react to double
Key disappears (judging by bromination addition process).Filter, steam organic solvent.Add activated carbon adsorption process 24 hours, then
Filter activated carbon, the solution obtaining vacuum dehydration obtain the hyperbranched product of structure as shown in following formula (i-3):
Wherein:
(3) according to the hyperbranched product of step (2) gained: organic solvent (toluene): the sour agent (triethylamine) of bundle: propylene acylbromide
For 1:22:1.1:1.05(mol ratio) ratio, the hyperbranched product of step (2) gained, organic solvent and the sour agent of bundle etc. are added
Enter equipped with the reaction bulb of chiller, being cooled to 0 DEG C, be then slowly added into propylene acylbromide and (be dissolved in advance in solvent, added
In journey, temperature is less than 15 DEG C), after propylene acylbromide adds, react 0.5 hour at 10 DEG C.Reactant is stood, separates organic
Phase, is washed for several times with saturated sodium bicarbonate solution neutralization, with anhydrous sodium sulfate drying, steams organic solvent and obtain final product crude product, will be thick
Product is further purified, and obtains final product the dendritic monomeric products of the polymer grade shown in formula (2-3), wherein r1For ch2ch2,
r2-r4、r8-r13It is h, m is na, p and q is 1.
The definition of r with r1 is identical with formula (i-3).
Embodiment 4
This embodiment is used for dendritic and dendritic monomer and preparation method thereof are described.
(1) the prepared intermediate shown in formula (6f) of 82.85 grams of preparation examples 2 and 200 milliliters of n, n- dimethyl acetylamide are taken
Add in reactor, under 25 DEG C of stirring conditions, Deca is dissolved in 120 milliliters of n, n- dimethyl by 39.2 grams of maleic anhydrides (ma)
The solution of acetamide, is warming up to 80 DEG C, reacts 15 hours.
(2) and then add the sodium sulfite aqueous solution of 336 gram mass fractions 15% at 35 DEG C in above-mentioned product,
Reaction disappears (judging by bromination addition process) to double bond in 18 hours.Filter, steam organic solvent.Add at activated carbon adsorption
Reason 24 hours, then filters activated carbon, and the solution obtaining vacuum dehydration obtains the hyperbranched of as shown in following formula (i-4) structure
Product:
Wherein:
(3) according to the hyperbranched product of step (2) gained: organic solvent (dichloromethane): the sour agent (triethylamine) of bundle: propylene
Acyl chlorides is 1:18:1:1(mol ratio) ratio, the hyperbranched product of step (2) gained, organic solvent and the sour agent of bundle etc. are added
Equipped with the reaction bulb of chiller, being cooled to 5 DEG C, then it is slowly added into acryloyl chloride and (is dissolved in advance in solvent, adition process
Middle temperature is less than 15 DEG C), after acryloyl chloride adds, react 0.5 hour at 10 DEG C.Reactant is stood, separates organic faciess,
Washed for several times with saturated sodium bicarbonate solution neutralization, with anhydrous sodium sulfate drying, steam organic solvent and obtain final product crude product, by crude product
It is further purified, obtain final product the dendritic monomeric products of the polymer grade shown in formula (2-4), wherein r1For ch2ch2, r2-r4、
r8-r13It is h, m is na, p and q is 0.
The definition of r with r1 is identical with formula (i-4).
Test case 1
The sodium hydroxide of 200ml water, 0.05 mole is added reactor, after its dissolving, adds 0.05 mole of 2- propylene
The ph value of system, after stirring, is adjusted to by amide groups -2- methyl propane sulfonic acid with mass fraction 20% sodium hydroxide solution
10.0, it is subsequently adding dendritic monomer, 0.05 mole of 3- acrylamido propyl group two prepared by 0.25 mole of embodiment 1
Methyl propane sulfonic acid ammonium, 0.65 mole percent acrylamide, stirring makes it dissolve to obtain reaction mixture；Reaction mixture is gone to polymerization
In reactor, add 0.10 gram of Ammonium persulfate., 0.10 gram of sodium sulfite under agitation, the initial temperature of polyreaction is 60
DEG C, maintain polyreaction 45 minutes, obtain gel elasticity product；After the gel obtaining elastomeric shear, at 120 DEG C
Dry, pulverize and obtain final product polymer for drilling fluid inorganic agent.
Temperature-resistant anti-salt ability using filtrate reducing aptitude tests above-mentioned polymer treatment agent in compound saline.Complex salt used
The preparation of water base slurry: add 15.75g sodium chloride, 1.75g anhydrous calcium chloride, 4.6g magnesium chloride, 52.5g in 350ml distilled water
Calcium bentonite (Weifang Hao Da bentonite company limited produces, industrial goods) and 3.15g natrium carbonicum calcinatum, high-speed stirred 20min, room
Temperature places aging 24h, obtains compound salt-water basic slurry.The sample of 1.5 weight % is added, high-speed stirred 5 minutes, then 180 during evaluation
DEG C roll aging 16h, be cooled to room temperature, with zns type drilling fluid filter press measure drilling fluid filter loss.180 DEG C of rollings starched by base
Api filter loss after aging 16h is 228 milliliters.
Test rejection ability and the absorbability of above-mentioned polymer treatment agent using shale rolling rate of recovery method.Method is such as
Under:
Primary recovery r1: accurately weigh 50 grams of landwaste sample (m), add the polymerization to be measured of 350 milliliters of mass fractions 0.3%
In thing solution, it is then placed in ageing can, sealing, after rolling 16h in 120 DEG C, cooling, reclaim landwaste with 40 mesh sieves, in 100 ± 5
It is dried to permanent matter at DEG C, weigh (m1), calculate primary recovery r1.Primary recovery reacts water in inorganic agent aqueous solution for the shale
Change deployment conditions, primary recovery r1Higher, then rejection ability is stronger.
Secondary returning yield r2: will once reclaim gained landwaste (m1) put in 350 milliliters of clear water, after rolling 2h at 120 DEG C
Cooling, reclaims landwaste with 40 mesh sieves, is dried to permanent matter at 100 ± 5 DEG C, weighs (m2), calculate secondary returning yield r2.Secondary recovery
Stable case in clear water for the landwaste obtaining once is reclaimed in rate reaction, and secondary returning yield is higher, shows inorganic agent absorbability
Stronger.
Landwaste used is bright 9-5 well 2695m landwaste (6～10 mesh).The response rate of the clear water (without sample) of landwaste is
49.5%.
Computing formula:
Wherein r is relative recovery, and it reflects absorbability on shale for the polymer, and the bigger absorption of its value is stronger.
Dissolubility adopts prepares mass fraction 0.5% aqueous solutions of polymers, according to formation homogeneous aqueous solution (i.e. no under room temperature
Polymer swellable particles) the high-speed stirred time judge.Process is: takes 398 milliliters of water, adds 2 grams of samples under high velocity agitation,
Then proceed to stir, to mixing time reach 3min when, took off observation dissolution phenomena every 30 seconds, until be completely dissolved, record
The mixing time being completely dissolved.
cacl2Tackifying ability in solution adopts the cacl of mass fraction 0.3% polymer2Aqueous solution (cacl2Mass fraction
20%) and distilled water solution viscosity ratio, that is, viscosity conservation rate investigating:
Above-mentioned test result is as shown in table 1 below.
Test case 2
The sodium hydroxide of 95ml water, 0.15 mole is added reactor, after its dissolving, adds 0.15 mole of 2- acryloyl
Amido -2- methyl propane sulfonic acid adds reactor, after stirring, with the potassium hydroxide solution of mass fraction 10% by the ph of system
Value is adjusted to 7.0, is subsequently adding dendritic monomer, 0.30 mole of 3- acrylamide prepared by 0.05 mole of embodiment 2
Base propyl-dimethyl propane sulfonic acid ammonium, 0.25 mole percent acrylamide, stirring makes it dissolve to obtain reaction mixture；By reaction mixture
Go in polymerization reaction kettle, add 0.30 gram of Ammonium persulfate., 0.30 gram of sodium sulfite, the initial temperature of polyreaction under agitation
Spend for 40 DEG C, maintain polyreaction 90 minutes, obtain gel elasticity product；After the gel obtaining elastomeric shear, in
Dry at 100 DEG C, pulverize and obtain final product polymer for drilling fluid inorganic agent.
Method according to test case 1 carries out performance test, and result is as shown in table 1 below.
Test case 3
The sodium hydroxide of 185ml water, 0.1 mole is added reactor, after its dissolving, adds 0.10 mole of 2- acryloyl
Amido -2- methyl propane sulfonic acid adds reactor, after stirring, with the sodium hydroxide solution of mass fraction 15% by the ph of system
Value is adjusted to 8.0, is subsequently adding dendritic monomer, 0.30 mole of 3- acrylamide prepared by 0.20 mole of embodiment 3
Base propyl group (2- hydroxyl) diallyidimethylammonium chloride, 0.30 mole percent acrylamide, stirring makes it dissolve to obtain reaction mixture；Will
Reaction mixture goes in polymerization reaction kettle, adds 0.35 gram of potassium peroxydisulfate, 0.35 gram of sodium sulfite under agitation, and polymerization is anti-
The initial temperature answered is 45 DEG C, maintains polyreaction 60 minutes, obtains gel elasticity product；By the gel obtaining elastomer
After shearing, dry at 110 DEG C, pulverize and obtain final product polymer for drilling fluid inorganic agent.
Method according to above-mentioned test case 1 carries out performance test, and result is as shown in table 1 below.
Test case 4
The sodium hydroxide of 180ml water, 0.1 mole is added reactor, after its dissolving, adds 0.10 mole of 2- acryloyl
Amido -2- methyl propane sulfonic acid adds reactor, after stirring, with the potassium hydroxide solution of mass fraction 12% by the ph of system
Value is adjusted to 8.0, is subsequently adding dendritic monomer, 0.35 mole of 3- acrylamide prepared by 0.20 mole of embodiment 4
Base propyl-dimethyl propane sulfonic acid ammonium, 0.30 mole percent acrylamide, stirring makes it dissolve to obtain reaction mixture；By reactant mixture
Go in polymer reactor, add 0.35 gram of Ammonium persulfate., 0.35 gram of sodium sulfite under agitation, polyreaction initial
Temperature is 45 DEG C, maintains polyreaction 60 minutes, obtains gel elasticity product；After the gel obtaining elastomeric shear,
Dry at 120 DEG C, pulverize and obtain final product polymer for drilling fluid inorganic agent.
Method according to above-mentioned test case 1 carries out performance test, and result is as shown in table 1 below.
Reference test case 1
Method according to embodiment 1 prepares polymer for drilling fluid inorganic agent, except for the difference that, is added without embodiment 1 and prepares
Dendritic monomer carry out polyreaction, obtain reference polymer for drilling fluid inorganic agent.According to above-mentioned test case 1
Method carries out performance test, and result is as shown in table 1 below.
Table 1
Note: the api filter loss after 180 DEG C of aging 16h of rolling starched by base is 228 milliliters.The clear water (without sample) of landwaste
The response rate is 49.5%.
At the polymer that the result explanation of table 1 is obtained with other monomers cooperation using the dendritic monomer of the present invention
Reason agent had both had stronger temperature-resistant anti-salt ability, had good rejection ability again, and product good water solubility.
The preferred embodiment of the present invention described in detail above, but, the present invention is not limited in above-mentioned embodiment
Detail, in the range of the technology design of the present invention, multiple simple variant can be carried out to technical scheme, this
A little simple variant belong to protection scope of the present invention.
It is further to note that each particular technique feature described in above-mentioned specific embodiment, in not lance
In the case of shield, can be combined by any suitable means.In order to avoid unnecessary repetition, the present invention to various can
The compound mode of energy no longer separately illustrates.
Additionally, combination in any can also be carried out between the various different embodiment of the present invention, as long as it is without prejudice to this
The thought of invention, it equally should be considered as content disclosed in this invention.
Claims (10)
1. a kind of dendritic, this dendritic has the structure shown in z- (q) n-y, and wherein z represents can be with acyl
There is the group of condensation reaction in halogen, be oh or nh2；Q represents the dendroid constitutional repeating unit of this dendritic, is following
Structure shown in formula (i)；N represents the algebraically of this dendritic, is the integer of 2-6；Y represents containing so3 -And coo-Group,
Structure shown in following formula (ii),
In formula (i), r1Represent the alkylidene that carbon number is 1-5, r2-r4Identical or different, it is each independently h or carbon atom
The alkyl for 1-5 for the number, and the r in structure shown in n formula (i)1-r4Identical or different independently of one another；
In formula (ii), r8-r13Identical or different, the respectively h or carbon number alkyl for 1-5, p and q is identical or different, each
It independently is the integer of 0-5, m is h, na or k.
2. dendritic according to claim 1, wherein, described dendritic have following formula (iii) and/
Or structure shown in formula (iv),
z、r1-r4、r8-r13, m, p identical with claim 1 with the definition of q.
3. dendritic according to claim 1 and 2, wherein, z is oh, r1For ch2ch2, r2-r4、r8-r13It is
H, m are na, p and q is 0.
4. a kind of dendritic monomer, this dendritic monomer has the structure shown in z '-(q) n-y, wherein z ' table
Show the structure shown in following formula (a) and/or formula (b), q represents the dendroid constitutional repeating unit of this dendritic monomer,
Structure shown in following formula (i)；N represents the algebraically of this dendritic monomer, is the integer of 2-6；Y represents containing so3 -With
coo-Group, be structure shown in following formula (ii)；
r14-r16Identical or different, being each independently h or carbon number is the alkyl of 1-5；
Wherein, in formula (i), r1Represent the alkylidene that carbon number is 1-5, r2-r4Identical or different, it is each independently h or carbon
Atomic number is the alkyl of 1-5, and the r in structure shown in n formula (i)1-r4Identical or different independently of one another；
In formula (ii), r8-r13Identical or different, the respectively h or carbon number alkyl for 1-5, p and q is identical or different, each
It independently is the integer of 0-5, m is h, na or k.
5. dendritic monomer according to claim 4, wherein, described dendritic monomer has following formula
(1), the structure shown in any one in formula (2), formula (3) and formula (4),
r1-r4、r8-r16, m, p identical with claim 4 with the definition of q.
6. dendritic monomer according to claim 5, wherein, this dendritic monomer have formula (1) and/
Or in structure, and formula (1) and formula (3) shown in formula (3), r1For ch2ch2, r2-r4、r8-r13It is h, m is na, p and q is 0.
7. a kind of preparation method of dendritic, the method comprises the following steps:
(1) preparation has following formula (5) and/or the intermediate of structure shown in formula (6),
In formula (5) and formula (6), z, r1-r4Definition identical with claim 6,
(2) under the conditions of nucleophilic addition, this intermediate is contacted with the unsaturated acid anhydride shown in following formula (7), formation contains
The carboxylic acid amide of unsaturated bond,
In formula (7), r8-r13, p with q definition identical with claim 4,
(3) under 30-100 DEG C of reaction condition, step (2) gained is contained carboxylic acid amide and sulfurous acid and/or the Asia of unsaturated bond
The alkali metal salt contact of sulphuric acid.
8. method according to claim 7, wherein, described unsaturated acid anhydride is maleic anhydride.
9. a kind of preparation method of dendritic monomer, the method is included using described in any one in claim 7-8
Method prepare dendritic, then under the conditions of condensation reaction, so that this dendritic is contacted with unsaturated carboxylic acid halides.
10. described in any one in the dendritic described in any one and claim 4-6 in claim 1-3
Dendritic monomer answering in preparing filtrate reducer for drilling fluid, oil displacement agent, fracturing fluid gelatinizer and oil field water treatment agent
With.
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| CN106520085B (en) * | 2016-11-03 | 2018-06-26 | 中国石油大学(华东) | A kind of dendritic polyether shale inhibitor and preparation method and application |
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| CN108070367A (en) * | 2017-12-22 | 2018-05-25 | 长江大学 | A kind of sulfonate modified hyperbranched surfactant and preparation method |
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| CN110938414B (en) * | 2019-11-25 | 2022-07-12 | 长江大学 | Temperature-resistant anti-collapse multi-polymer filtrate reducer and preparation method thereof |
| CN111592654B (en) * | 2020-04-14 | 2022-02-01 | 西南石油大学 | Shale intercalation inhibitor prepared from environment-friendly hyperbranched polyamino acid |
| CN115386047A (en) * | 2022-07-15 | 2022-11-25 | 北京伸恒能源科技有限公司 | Polymer for high-temperature-resistant saline-water-based fracturing fluid thickening agent of oil-gas well |
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