CN107325299A - A kind of method for preparing water-in-water type non-ionic polyacrylamide - Google Patents
A kind of method for preparing water-in-water type non-ionic polyacrylamide Download PDFInfo
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 48
- 238000000034 method Methods 0.000 title claims abstract description 43
- 229920002401 polyacrylamide Polymers 0.000 title claims abstract description 24
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims abstract description 38
- -1 polypropylene Polymers 0.000 claims abstract description 29
- 238000006243 chemical reaction Methods 0.000 claims abstract description 26
- 239000004743 Polypropylene Substances 0.000 claims abstract description 23
- 229920001155 polypropylene Polymers 0.000 claims abstract description 23
- 150000001408 amides Chemical class 0.000 claims abstract description 21
- 239000002270 dispersing agent Substances 0.000 claims abstract description 18
- 238000003756 stirring Methods 0.000 claims abstract description 16
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 15
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000007788 liquid Substances 0.000 claims abstract description 11
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims abstract description 10
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000003999 initiator Substances 0.000 claims abstract description 10
- 239000010446 mirabilite Substances 0.000 claims abstract description 10
- 239000001301 oxygen Substances 0.000 claims abstract description 10
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 10
- 239000012966 redox initiator Substances 0.000 claims abstract description 9
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 claims abstract description 8
- 229910052921 ammonium sulfate Inorganic materials 0.000 claims abstract description 8
- 235000011130 ammonium sulphate Nutrition 0.000 claims abstract description 8
- 239000003292 glue Substances 0.000 claims abstract description 8
- 239000007787 solid Substances 0.000 claims abstract description 4
- 239000012535 impurity Substances 0.000 claims abstract description 3
- 239000000376 reactant Substances 0.000 claims abstract description 3
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 26
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 13
- 238000002360 preparation method Methods 0.000 claims description 13
- 239000000203 mixture Substances 0.000 claims description 12
- 238000006116 polymerization reaction Methods 0.000 claims description 12
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 8
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical group [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 claims description 8
- 229940079827 sodium hydrogen sulfite Drugs 0.000 claims description 8
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 claims description 8
- MZSDGDXXBZSFTG-UHFFFAOYSA-M sodium;benzenesulfonate Chemical compound [Na+].[O-]S(=O)(=O)C1=CC=CC=C1 MZSDGDXXBZSFTG-UHFFFAOYSA-M 0.000 claims description 7
- 239000002202 Polyethylene glycol Substances 0.000 claims description 4
- 229920001223 polyethylene glycol Polymers 0.000 claims description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 3
- 239000003638 chemical reducing agent Substances 0.000 claims description 3
- 150000001875 compounds Chemical class 0.000 claims description 3
- 239000007800 oxidant agent Substances 0.000 claims description 3
- 230000001590 oxidative effect Effects 0.000 claims description 3
- 238000012805 post-processing Methods 0.000 claims description 3
- 238000010792 warming Methods 0.000 claims description 3
- 229920001285 xanthan gum Polymers 0.000 claims description 3
- 125000002252 acyl group Chemical group 0.000 claims description 2
- 150000001412 amines Chemical class 0.000 claims description 2
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims description 2
- 239000000463 material Substances 0.000 claims description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims 1
- STYCVEYASXULRN-UHFFFAOYSA-N butanimidamide;hydrochloride Chemical compound [Cl-].CCCC(N)=[NH2+] STYCVEYASXULRN-UHFFFAOYSA-N 0.000 claims 1
- 238000004090 dissolution Methods 0.000 abstract description 8
- 230000000694 effects Effects 0.000 abstract description 8
- 239000000470 constituent Substances 0.000 abstract description 7
- 239000006185 dispersion Substances 0.000 abstract description 5
- 239000000243 solution Substances 0.000 description 29
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 14
- 238000001816 cooling Methods 0.000 description 9
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 8
- 239000000839 emulsion Substances 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 7
- 229910052757 nitrogen Inorganic materials 0.000 description 7
- 239000008367 deionised water Substances 0.000 description 6
- 229910021641 deionized water Inorganic materials 0.000 description 6
- 229920000642 polymer Polymers 0.000 description 6
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 6
- 230000000630 rising effect Effects 0.000 description 6
- 238000009740 moulding (composite fabrication) Methods 0.000 description 5
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 5
- FGRJGEWVJCCOJJ-UHFFFAOYSA-N 2,2-dimethylaziridine Chemical class CC1(C)CN1 FGRJGEWVJCCOJJ-UHFFFAOYSA-N 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- UWNADWZGEHDQAB-UHFFFAOYSA-N 2,5-dimethylhexane Chemical group CC(C)CCC(C)C UWNADWZGEHDQAB-UHFFFAOYSA-N 0.000 description 2
- MPNXSZJPSVBLHP-UHFFFAOYSA-N 2-chloro-n-phenylpyridine-3-carboxamide Chemical compound ClC1=NC=CC=C1C(=O)NC1=CC=CC=C1 MPNXSZJPSVBLHP-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 125000000129 anionic group Chemical group 0.000 description 2
- 125000002091 cationic group Chemical group 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- JEGUKCSWCFPDGT-UHFFFAOYSA-N h2o hydrate Chemical compound O.O JEGUKCSWCFPDGT-UHFFFAOYSA-N 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 239000002893 slag Substances 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 150000001409 amidines Chemical class 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- SRSXLGNVWSONIS-UHFFFAOYSA-N benzenesulfonic acid Chemical compound OS(=O)(=O)C1=CC=CC=C1 SRSXLGNVWSONIS-UHFFFAOYSA-N 0.000 description 1
- 229940092714 benzenesulfonic acid Drugs 0.000 description 1
- 210000000481 breast Anatomy 0.000 description 1
- 229920006317 cationic polymer Polymers 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000006392 deoxygenation reaction Methods 0.000 description 1
- 229910001882 dioxygen Inorganic materials 0.000 description 1
- 230000008030 elimination Effects 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 206010016256 fatigue Diseases 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 238000003475 lamination Methods 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000693 micelle Substances 0.000 description 1
- 239000004531 microgranule Substances 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- 238000004904 shortening Methods 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000007762 w/o emulsion Substances 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/02—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques
- C08J3/03—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques in aqueous media
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F120/00—Homopolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride, ester, amide, imide or nitrile thereof
- C08F120/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F120/52—Amides or imides
- C08F120/54—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide
- C08F120/56—Acrylamide; Methacrylamide
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/38—Polymerisation using regulators, e.g. chain terminating agents, e.g. telomerisation
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2333/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers
- C08J2333/24—Homopolymers or copolymers of amides or imides
- C08J2333/26—Homopolymers or copolymers of acrylamide or methacrylamide
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Dispersion Chemistry (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
The present invention relates to a kind of method for preparing water-in-water type non-ionic polyacrylamide, comprise the following steps：(1) with water by acrylamide, low-molecular polypropylene acid amides, n-butanol, ammonium sulfate, protomere dispersant is configured to solution；(2) under conditions of no oxygen presence, chain-transferring agent, water-soluble azo class initiator, redox initiator are added in the solution that step (1) is prepared, acrylamide is occurred polymerisation；(3) glauber salt is added into the reactant obtained by step (2), reaction system is converted into liquid by frozen glue shape by stirring, then filter and remove solid impurity, obtain water-in-water type non-ionic polyacrylamide.Product prepared by the inventive method has the advantages that active constituent content is high, cheap, dissolution velocity is fast, insoluble matter is low, dispersion effect is good, shelf-stable, has filled up the blank of water-in-water type non-ionic polyacrylamide product.
Description
Technical field
The invention belongs to chemosynthesis technical field, more particularly to a kind of preparation side of water-in-water type nonionic polyacrylamide
Method.
Background technology
Polyacrylamide is known as all trades auxiliary agent, in industry-by-industry with more and more extensive.It is general according to state by polypropylene
Acid amides is divided into dry-type, water-in-oil emulsion, water-in-water emulsion type, the major class of aqueous solution type 4.In addition, according to ion characteristic, may be used also
Polyacrylamide can be divided into anionic, cationic, non-ionic and 4 kinds of amphoteric ion type.It is wherein non-ionic in gold
Played an important role in ore deposit, nickel minerals, washed-out sand processing；The speed of dry-type nonionic dissolving is very slow, and general dissolution time is big
In 2 hours；Water-in-oil type nonionic cost is higher, the degradable not shelf-stable of aqueous solution type so that its application in some fields
It is restricted；Water-in-water type product has the characteristics of scattered, dissolving is quick, with low cost, is increasingly widely used.
Wherein, cationic water-in-water emulsion Technical comparing is ripe, but the price of cationic polymer is higher, cause emulsion into
This height；Chinese patent CN105418839A discloses a kind of preparation method of anionic water-in-water type polyacrylamide, but should
PH is adjusted with sodium hydroxide using acrylic acid in method, and pH is higher, is not suitable for water-in-water type non-ionic polyacrylamide
Prepare.In addition, once having proposal in the prior art using acrylamide as monomer, using ammonium sulfate solution as decentralized medium, with azo
Diisobutyl amidine hydrochloride is initiator, using polymethyl acyloxyethyl trimethyl ammonium chloride as dispersant, using scattered poly-
It is legal to be prepared for non-ionic polyacrylamide " water-water " emulsion, but glutinous relative point of the polyacrylamide of this method preparation
Son amount is relatively low, and this method uses ammonium sulfate solution for decentralized medium, and dispersion effect is undesirable, and system is easily formed gel,
In addition, this method uses polymethyl acyloxyethyl trimethyl ammonium chloride for dispersant, reaction cost height (referring to：Liu little Pei,
Wang Junwei, Li Zhongxian, wait dispersion copolymerization methods to prepare non-ionic polyacrylamide " water-water " emulsion [J] chemical research,
2013(6):619-621.)。
The content of the invention
The main object of the present invention is that acquisition active constituent content is high, cheap, dissolution velocity is fast, insoluble matter is low, divided
Scattered effect is good, shelf-stable water-in-water type non-ionic polyacrylamide product emulsion, to solve present in prior art as above
One or more described problem.
The invention provides a kind of method for preparing water-in-water type non-ionic polyacrylamide, methods described includes following step
Suddenly：
(1) solution preparation steps：With water by acrylamide, low-molecular polypropylene acid amides, n-butanol, ammonium sulfate, protomere
Dispersant is configured to solution；
(2) polymerization procedure：Under conditions of no oxygen presence, chain turn is added in the solution that step (1) is prepared
Agent, water-soluble azo class initiator, redox initiator are moved, acrylamide is occurred polymerisation；With
(3) post-processing step：Add glauber salt into the reactant obtained by step (2), by stirring make reaction system by
Frozen glue shape is converted into liquid, then filters and removes solid impurity, obtains water-in-water type non-ionic polyacrylamide.
Preferably, the consumption of each material is：Acrylamide 350-400 parts by weight, low-molecular polypropylene acid amides 3-10 weight
Part, n-butanol 5-10 parts by weight, ammonium sulfate 20-40 parts by weight, protomere dispersant 2-6 parts by weight, water 500-600 parts by weight,
Chain-transferring agent 0.03-0.06 parts by weight, water-soluble azo class initiator 0.1-0.5 parts by weight, redox initiator 0.08-
0.18 parts by weight, glauber salt 5-10 parts by weight.
Preferably, methods described be additionally included in the polymerization process of step (2) controlling reaction temperature 50-55 DEG C it
Between.
Especially, methods described is additionally included in the preparation process of the low-molecular polypropylene acid amides carried out before step (1), should
Preparation process includes following sub-step：
(a) compound concentration is 15wt% acrylamide solution 100-200 parts by weight；
(b) add ammonium persulfate 0.1-0.3 parts by weight in the step (a), isopropanol 3-6 parts by weight, treat ammonium persulfate with
After isopropanol is completely dissolved, be warming up to 55-60 DEG C, and stir be down to after 4-5 hours after normal temperature discharge, be made low-molecular polypropylene
Acid amides；The glutinous equal relative molecular weight of obtained low-molecular polypropylene acid amides is 100-200kg/mol.
Preferably, the pH value of solution in step (1) is adjusted to 3.5-4；And/or adjust the temperature of solution in step (1)
Save as 15-18 DEG C.
Preferably, described protomere dispersant be the number-average molecular weight of 5-8 parts by weight be 6kg/mol polyethylene glycol,
The mixture of the xanthans of 3-5 parts by weight and the water of 15-20 parts by weight.
Preferably, described chain-transferring agent is that mass ratio is 2：(0.8-1)：Benzene sulfonic acid sodium salt, n-butanol and the water of (7-10)
Mixture.
Preferably, oxidant is ammonium persulfate in described redox initiator, and reducing agent is sodium hydrogensulfite；With/
Or described water-soluble azo class initiator is azo-bis-isobutyrate hydrochloride.
The present invention at least has the advantages that compared with prior art：
1st, product prepared by the inventive method has cheap, dissolubility good, and dispersion effect is good, shelf-stable, dissolving speed
The features such as spending fast, can dissolve complete in 6min, hence it is evident that energy consumption caused by shortening dissolution time and reduction dissolved product, improve
Production efficiency, reduces waste.
2nd, the inventive method improves the active constituent content of product to 35-40%, significantly reduces cost of transportation.
3rd, the low-molecular polypropylene acid amides being related in the inventive method is served during water-in-water type emulsion is formed
The effect of stabilizer, while low-molecular polypropylene acid amides has certain dispersion effect in water-in-water type emulsion course of reaction, it is low
Molecular polypropylene acid amides can play synergy with protomere dispersant.
4th, the protomere dispersant effect used in the inventive method is good, can overcome polymerisation hardly possible control, easily
Occur to gather cruelly, product is easily layered, and is difficult flowing, it is easy to the deficiency formed in terms of gel.
Embodiment
, below will be in the embodiment of the present invention to make the purpose, technical scheme and advantage of the embodiment of the present invention clearer
Technical scheme be clearly and completely described, it is clear that described embodiment be the present invention a part of embodiment, without
It is whole embodiments.Based on the embodiment in the present invention, those of ordinary skill in the art are not making creative work
Under the premise of the every other embodiment that is obtained, belong to the scope of protection of the invention.
Specifically, the invention provides a kind of method for preparing water-in-water type non-ionic polyacrylamide, methods described bag
Include following steps：
(1) solution preparation steps：With 500-600 parts by weight (such as 500,510,520,530,540,550,560,570,
580th, 590 or 600 parts by weight) water is by 350-400 parts by weight (such as the parts by weight of 350,360,370,380,390 or 400) propylene
Acid amides, 3-10 parts by weight (parts by weight of such as 3,4,5,6,7,8,9 or 10) low-molecular polypropylene acid amides, 5-10 parts by weight are (for example
5th, 6,7,8,9 or 10 parts by weight) n-butanol, 20-40 parts by weight (parts by weight of such as 20,25,30,35 or 40) ammonium sulfate, 2-6 weights
Amount part (parts by weight of such as 2,3,4,5 or 6) protomere dispersant is configured to solution, and regulates the temperature and pH of prepared solution
Value；The water is preferably deionized water, and the temperature of the solution is preferably 15-18 DEG C (such as 15 DEG C, 16 DEG C, 17 DEG C or 18
DEG C), the pH value of the solution is preferably 3.5-4 (such as 3.5,3.6,3.7,3.8,3.9 or 4), and the pH value of the solution is with weak
Acid is adjusted, and is preferably adjusted with acetic acid, oxalic acid or phosphoric acid.
(2) polymerization procedure：Under conditions of no oxygen presence, 0.03- is added in the solution that step (1) is prepared
0.06 parts by weight (parts by weight of such as 0.03,0.04,0.05 or 0.06) chain-transferring agent, 0.1-0.5 parts by weight (such as 0.1,0.2,
0.3rd, 0.4 or 0.5 parts by weight) water-soluble azo class initiator, 0.08-0.18 parts by weight (such as 0.08,0.09,0.10,
0.11st, 0.12,0.13,0.14,0.15,0.16,0.17 or 0.18 parts by weight) redox initiator initiation acrylamide polymerization
Reaction；In the course of the polymerization process, reaction temperature can rise, according to one preferred embodiment, pass through cooling in the course of the polymerization process
And the method controlling reaction temperature being stirred continuously is between 50-55 DEG C.Specifically, when reaction temperature rises to 55 DEG C, open
Cooling, and by being stirred continuously radiating, it is 50-55 DEG C to control temperature fluctuation range, temperature, which no longer rises, after cooling is closed is considered as
Reaction terminates.The condition that described no oxygen is present, can be by being passed through rare gas into reaction unit (such as reactor)
(such as nitrogen, helium or argon gas) reaches the purpose of deoxygenation, specifically, and nitrogen 40min can be passed through into reactor and eliminates oxygen
Gas.
(3) post-processing step：Reaction temperature obtains gum polymers after no longer rising, and 5-10 weights are added in step (2)
Part (parts by weight of such as 5,6,7,8,9 or 10) glauber salt is measured, being stirred continuously makes reaction system be converted into liquid by frozen glue shape, cooling
To normal temperature (such as 25 DEG C), solid residue is filtered out, water-in-water type non-ionic polyacrylamide is obtained.
According to a preferred embodiment, methods described is additionally included in the low-molecular polypropylene acyl carried out before step (1)
The preparation of amine, comprises the following steps：
(a) compound concentration is the 15wt% acrylamide solution 100-200 parts by weight (weight of such as 100,150 or 200
Part)；
(b) ammonium persulfate 0.1-0.3 parts by weight (parts by weight of such as 0.1,0.2 or 0.3), isopropyl are added in step (a)
Alcohol 3-6 parts by weight (3,4,5 or 6 parts by weight), after ammonium persulfate and isopropanol are completely dissolved, are warming up to 55-60 DEG C, and machinery
Stirring is down to after normal temperature and discharged for 4-5 hours after (such as 4 hours, 4.5 hours or 5 hours), and glutinous equal relative molecular weight is made and is
100-200kg/mol low-molecular polypropylene acid amides.
According to a preferred embodiment, described protomere dispersant is the 5-8 parts by weight (weight of such as 5,6,7 or 8
Part) number-average molecular weight be 6kg/mol polyethylene glycol, 3-5 parts by weight (parts by weight of such as 3,4 or 5) xanthans and 15-20 weight
The mixture of part (parts by weight of such as 15,16,17,18,19 or 20) water.
According to a preferred embodiment, described chain-transferring agent is that mass ratio is 2：(0.8-1)：(7-10) (such as 2:
0.8:7、2:0.8:8、2:0.8:9、2:0.8:10、2:0.9:7、2:0.9:8、2:0.9:9、2:0.9:10、2:1:7、2:1:8、
2:1:9 or 2:1:10) mixture of benzene sulfonic acid sodium salt, n-butanol and water.
According to a preferred embodiment, oxidant is ammonium persulfate in described redox initiator, and reducing agent is
Sodium hydrogensulfite and/or described water-soluble azo class initiator are azo-bis-isobutyrate hydrochloride.
Embodiment 1
With 590 parts by weight of deionized water by 380 parts by weight propylene acid amides, 7 parts by weight low-molecular polypropylene acid amides, 8 weight
It is transferred in reactor and stirs after part n-butanol, 30 parts sulfuric acid ammoniums, 4 parts by weight protomere dispersant wiring solution-formings, adjusts
Solution temperature is saved to 16 DEG C, regulation solution ph then passes to nitrogen 40min and eliminate oxygen, add 0.03 parts by weight to 3.5
(mass ratio is 2 to chain-transferring agent:1:The mixture of 7 benzene sulfonic acid sodium salt, n-butanol and water), the NSC 18620 salt of 0.4 parts by weight azo two
Hydrochlorate, 0.1 parts by weight ammonium persulfate, 0.08 parts by weight sodium hydrogensulfite trigger polymerization, and temperature rises to 55 DEG C and opens cooling, no
Disconnected mixing control temperature fluctuation range is 50-55 DEG C.Reaction temperature obtains gum polymers after no longer rising, add 6 parts by weight
Glauber salt, continue to stir no longer reduces to system viscosity, reaction system is converted into liquid by frozen glue shape, is cooled to normal temperature, filters
Residue is gone to produce product water-in-water type non-ionic polyacrylamide.
The technique products obtained therefrom active constituent content is 37.7%, equal relative molecular weight is sticked for 14000kg/mol, under normal temperature
Dissolution time is 5min, and insolubles content is 0.01%.
Embodiment 2
With 600 parts by weight of deionized water by 400 parts by weight propylene acid amides, 10 parts by weight low-molecular polypropylene acid amides, 7 weight
It is transferred in reactor and stirs after part n-butanol, 40 parts sulfuric acid ammoniums, 5 parts by weight protomere dispersant wiring solution-formings, adjusts
Solution temperature is saved to 16 DEG C, regulation solution ph then passes to nitrogen 40min and eliminate oxygen, add 0.05 parts by weight chain to 4
(mass ratio is 2 to transfer agent:1:The mixture of 7 benzene sulfonic acid sodium salt, n-butanol and water), the NSC 18620 hydrochloric acid of 0.35 parts by weight azo two
Salt, 0.1 parts by weight ammonium persulfate, 0.08 parts by weight sodium hydrogensulfite trigger polymerization, and temperature rises to 55 DEG C and opens cooling, constantly
Mixing control temperature fluctuation range is 50-55 DEG C.Reaction temperature obtains gum polymers after no longer rising, add 8 parts by weight member
Bright powder, continue to stir no longer reduces to system viscosity, and reaction system is converted into liquid by frozen glue shape, is cooled to normal temperature, filters off residual
Slag produces product water-in-water type non-ionic polyacrylamide.
The technique products obtained therefrom active constituent content is 38.3%, equal relative molecular weight is sticked for 9500kg/mol, under normal temperature
Dissolution time is 5min, and insolubles content is 0.01%.
Embodiment 3
With 500 parts by weight of deionized water by 350 parts by weight propylene acid amides, 3 parts by weight low-molecular polypropylene acid amides, 5 weight
It is transferred in reactor and stirs after part n-butanol, 20 parts sulfuric acid ammoniums, 2 parts by weight protomere dispersant wiring solution-formings, adjusts
Solution temperature is saved to 16 DEG C, regulation solution ph then passes to nitrogen 40min and eliminate oxygen, add 0.04 parts by weight chain to 4
(mass ratio is 2 to transfer agent:1:The mixture of 7 benzene sulfonic acid sodium salt, n-butanol and water), the NSC 18620 hydrochloric acid of 0.45 parts by weight azo two
Salt, 0.1 parts by weight ammonium persulfate, 0.08 parts by weight sodium hydrogensulfite trigger polymerization, and temperature rises to 55 DEG C and opens cooling, constantly
Mixing control temperature fluctuation range is 50-55 DEG C.Reaction temperature obtains gum polymers after no longer rising, add 10 parts by weight member
Bright powder, continue to stir no longer reduces to system viscosity, and reaction system is converted into liquid by frozen glue shape, is cooled to normal temperature, filters off residual
Slag produces product water-in-water type non-ionic polyacrylamide.
The technique products obtained therefrom active constituent content is 39.7%, equal relative molecular weight is sticked for 11000kg/mol, under normal temperature
Dissolution time is 6min, and insolubles content is 0.01%.
Embodiment 4-9 is carried out by the way of substantially the same manner as Example 1, and difference is as shown in table 1 below.
Table 1：Embodiment 4-9 composition of raw materials and product effect.
Comparative example 1
The preparation method be the same as Example 1 of comparative example 1 is substantially the same, and difference is：
PH is differed with embodiment 1, and pH value is 6.5 in comparative example 1, and concrete scheme is as follows：
With 590 parts by weight of deionized water by 380 parts by weight propylene acid amides, 7 parts by weight low-molecular polypropylene acid amides, 8 weight
It is transferred in reactor and stirs after part n-butanol, 30 parts sulfuric acid ammoniums, 4 parts by weight protomere dispersant wiring solution-formings, adjusts
Solution temperature is saved to 16 DEG C, regulation solution ph then passes to nitrogen 40min and eliminate oxygen, add 0.03 parts by weight to 6.5
(mass ratio is 2 to chain-transferring agent:1:The mixture of 7 benzene sulfonic acid sodium salt, n-butanol and water), the NSC 18620 salt of 0.4 parts by weight azo two
Hydrochlorate, 0.1 parts by weight ammonium persulfate, 0.08 parts by weight sodium hydrogensulfite trigger polymerization, and temperature rises to 55 DEG C and opens cooling, no
Disconnected mixing control temperature fluctuation range is 50-55 DEG C.Reaction temperature obtains gum polymers after no longer rising, add 6 parts by weight
Glauber salt, continue to stir no longer reduces to system viscosity, reaction system is converted into liquid.
Viscosity is too big during the course of the reaction for comparative example 1, gel state, in course of reaction between polyacrylamide microgranule
Bad dispersibility, can not be converted into uniform liquid phase, but be changed into small micelle shape liquid after adding glauber salt by gel state.
Comparative example 2
The preparation method be the same as Example 1 of comparative example 2 is substantially the same, and difference is：
Directly use Aqueous Solutions of Polyethylene Glycol for dispersant in comparative example 2, concrete scheme is as follows：
With 590 parts by weight of deionized water by 380 parts by weight propylene acid amides, 7 parts by weight low-molecular polypropylene acid amides, 8 weight
Part n-butanol, 30 parts sulfuric acid ammoniums, 4 parts per weight dispersing agents (the poly- second that the number-average molecular weight that concentration is 33wt% is 6kg/mol
Two alcohol solutions) be transferred in reactor after wiring solution-forming and stir, regulation solution temperature to 16 DEG C, regulation solution ph to
3.5, then pass to nitrogen 40min and eliminate oxygen, adding 0.03 parts by weight chain-transferring agent, (mass ratio is 2:1:7 benzene sulfonic acid
The mixture of sodium, n-butanol and water), 0.4 parts by weight azo-bis-isobutyrate hydrochloride, 0.1 parts by weight ammonium persulfate, 0.08 weight
Part sodium hydrogensulfite triggers polymerization, and temperature rises to 55 DEG C and opens cooling, is stirred continuously and controls temperature fluctuation range for 50-55
℃.Reaction temperature obtains gum polymers after no longer rising, add 6 parts by weight glauber salt, continues to stir to system viscosity no longer
Reduction, makes reaction system be converted into liquid by frozen glue shape, is cooled to normal temperature, and elimination residue produces product water-in-water type nonionic and gathered
Acrylamide.
The technique products obtained therefrom active constituent content is 37.7%, equal relative molecular weight is sticked for 12000kg/mol, under normal temperature
Dissolution time is 5min, and insolubles content is 0.01%, the bad stability of the technique products obtained therefrom, breast occurs after placing 20 days
Liquid lamination.
Finally it should be noted that：The above embodiments are merely illustrative of the technical solutions of the present invention, rather than its limitations；Although
The present invention is described in detail with reference to the foregoing embodiments, it will be understood by those within the art that：It still may be used
To be modified to the technical scheme described in foregoing embodiments, or equivalent substitution is carried out to which part technical characteristic；
And these modification or replace, do not make appropriate technical solution essence depart from various embodiments of the present invention technical scheme spirit and
Scope.
Claims (10)
1. a kind of method for preparing water-in-water type non-ionic polyacrylamide, it is characterised in that methods described comprises the following steps：
(1) solution preparation steps：With water by acrylamide, low-molecular polypropylene acid amides, n-butanol, ammonium sulfate, protomere disperses
Agent is configured to solution；
(2) polymerization procedure：No oxygen presence under conditions of, in the solution that step (1) is prepared add chain-transferring agent,
Water-soluble azo class initiator, redox initiator, make acrylamide occur polymerisation；With
(3) post-processing step：Glauber salt is added into the reactant obtained by step (2), reaction system is made by frozen glue by stirring
Shape is converted into liquid, then filters and removes solid impurity, obtains water-in-water type non-ionic polyacrylamide.
2. according to the method described in claim 1, it is characterised in that the consumption of each material is as follows：Acrylamide 350-400 weight
Part, low-molecular polypropylene acid amides 3-10 parts by weight, n-butanol 5-10 parts by weight, ammonium sulfate 20-40 parts by weight, protomere dispersant
2-6 parts by weight, water 500-600 parts by weight, chain-transferring agent 0.03-0.06 parts by weight, water-soluble azo class initiator 0.1-0.5 weights
Measure part, redox initiator 0.08-0.18 parts by weight, glauber salt 5-10 parts by weight.
3. according to the method described in claim 1, it is characterised in that methods described is additionally included in the polymerisation mistake of step (2)
Controlling reaction temperature is between 50-55 DEG C in journey.
4. according to the method in any one of claims 1 to 3, it is characterised in that methods described be additionally included in step (1) it
The preparation process of the low-molecular polypropylene acid amides of preceding progress, the preparation process includes following sub-step：
(a) compound concentration is 15wt% acrylamide solution 100-200 parts by weight；
(b) ammonium persulfate 0.1-0.3 parts by weight are added in step (a), isopropanol 3-6 parts by weight treat ammonium persulfate and isopropyl
After alcohol is completely dissolved, 55-60 DEG C is warming up to, and stirs to be down to after 4-5 hours after normal temperature and discharges, low-molecular polypropylene acyl is made
Amine.
5. method according to claim 4, it is characterised in that：Glutinous relative point of obtained low-molecular polypropylene acid amides
Son amount is 100-200kg/mol.
6. according to the method in any one of claims 1 to 3, it is characterised in that：By the solution prepared in step (1)
PH value is adjusted to 3.5-4；And/or
It it is 15-18 DEG C by the temperature adjustment for the solution prepared in step (1).
7. according to the method described in claim 1, it is characterised in that：Described protomere dispersant is equal for the number of 5-8 parts by weight
The mixture of the water of polyethylene glycol, the xanthans of 3-5 parts by weight and 15-20 parts by weight that molecular weight is 6kg/mol.
8. according to the method described in claim 1, it is characterised in that：Described chain-transferring agent is that mass ratio is 2：(0.8-1)：
The mixture of the benzene sulfonic acid sodium salt of (7-10), n-butanol and water.
9. according to the method described in claim 1, it is characterised in that：Oxidant in described redox initiator is over cure
Sour ammonium, reducing agent is sodium hydrogensulfite.
10. according to the method described in claim 1, it is characterised in that：Described water-soluble azo class initiator is that azo two is different
Butanimidamide, monohydrochloride.
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| US20090269323A1 (en) * | 2007-09-18 | 2009-10-29 | Syracuse University Technology Transfer And Industrial Development Office | Non-amphiphile-based water-in-water emulsion and uses thereof |
| CN102321208A (en) * | 2011-06-20 | 2012-01-18 | 四川大学 | Water-in-water polymer dispersion and preparation method thereof |
| CN105418839A (en) * | 2015-11-17 | 2016-03-23 | 山东诺尔生物科技有限公司 | Preparation method of anion water-in-water type polyacrylamide |
| CN106497537A (en) * | 2016-10-25 | 2017-03-15 | 长江大学 | A kind of while " two-in-one " hydraulic fracturing liquid system with drag reduction and solid-carrying performance |
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|---|---|---|---|---|
| US20090269323A1 (en) * | 2007-09-18 | 2009-10-29 | Syracuse University Technology Transfer And Industrial Development Office | Non-amphiphile-based water-in-water emulsion and uses thereof |
| CN102321208A (en) * | 2011-06-20 | 2012-01-18 | 四川大学 | Water-in-water polymer dispersion and preparation method thereof |
| CN105418839A (en) * | 2015-11-17 | 2016-03-23 | 山东诺尔生物科技有限公司 | Preparation method of anion water-in-water type polyacrylamide |
| CN106497537A (en) * | 2016-10-25 | 2017-03-15 | 长江大学 | A kind of while " two-in-one " hydraulic fracturing liquid system with drag reduction and solid-carrying performance |
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