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4/6/23, 3:19 PM CN103788296A - Cationic polyacrylamide copolymer high-temperature resisting water-in-water dispersion and low-viscosity prepar…
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Cationic polyacrylamide copolymer high-temperature resisting water-in-water dispersion and low-viscosity

preparation method thereof
Abstract
CN103788296A
The invention provides a cationic polyacrylamide copolymer high-temperature resisting water-in-
China
water dispersion liquid and a low-viscosity preparation method thereof. The water packet aqueous
dispersion liquid comprises seed polymers, cationic polyacrylamide copolymers, dispersion
reagents, stabilizing agents and water, wherein the cationic polyacrylamide copolymers are partially Download PDF Find Prior Art Similar
wrapped inside the seed polymers and are partially located outside the seed polymers; the cationic
polyacrylamide copolymers outside the seed polymers are dissolved in water; the surface of the Other languages: Chinese
shells of the seed polymers are coated with the stabilizing agents; the dispersion reagents are
Inventor: 舒鑫, 黄振, 冉千平, 刘加平
dissolved in water. The preparation method is mainly characterized in that when the cationic
polyacrylamide dispersion liquid is prepared, the seed polymers, monomers and the like are firstly
prepared into a seed dispersion liquid, and subsequently components such as an initiator for Worldwide applications
polymerization are added into the prepared seed dispersion liquid so as to polymerize. The problems
2013 CN
that the cationic polyacrylamide copolymer high-temperature resisting water packet aqueous
dispersion liquid is high in viscosity and poor in high-temperature resistance and storage property
are solved. Application CN201310659587.2A events
2013-12-06 Application filed by Sobute New Materials Co Ltd,

Jiangsu Research Institute of Building Science
Co Ltd, Nanjing Bote Building Materials Co Ltd
2013-12-06 Priority to CN201310659587.2A
2014-05-14 Publication of CN103788296A
2016-04-27 Application granted
2016-04-27 Publication of CN103788296B
Status Active
2033-12-06 Anticipated expiration
Info: Patent citations (4), Cited by (2), Legal events, Similar

documents, Priority and Related Applications
External links: Espacenet, Global Dossier, Discuss
Claims (6) Hide Dependent
1. a cationic polyacrylamide high-temperature resistant water bag aqueous dispersions, it is characterized in that: its composition comprises seed polymer, cationic
polyacrylamide, point phase reagent, stablizer, He Shui, wherein cationic polyacrylamide part is wrapped in seed polymer, part is present in seeding polymerization beyond the
region of objective existence, and the cationic polyacrylamide of seeding polymerization beyond the region of objective existence is partially dissolved in water; Stabilizer
package is overlying on the case surface of seed polymer, and phase-splitting agent dissolves is in water; Mass ratio between said components is:
Seed polymer: account for the 1-10% of system total mass,
Cationic polyacrylamide: account for system total mass 1-20%, and the ratio of its total mass and seed polymer total mass is not more than 8,
Stablizer: account for the 5-20% of seed polymer and cationic polyacrylamide total mass,
Divide phase reagent: account for the 15-37% of system total mass,
Water: surplus is water;
Described seed polymer is a kind of of polymkeric substance shown in following general formula (1) or more than a kind of arbitrary combination, its weight average molecular
weight range is 5 × 10 5-2 × 10 6,
Wherein, R 1represent H or CH 3, R 2with R 3for one of combining below: H and CH (CH 3) CH 3; CH 2cH 3with CH 2cH 3; H and CH (CH 2oH) CH 2cH 3;
Described stablizer is a kind of of polymkeric substance shown in following general formula (2) or more than a kind of arbitrary combination, its weight average molecular
weight range is 5 × 10 4-1 × 10 6;
Wherein radicals X represents O or NH, and Y represents CH 2cH 2, CH 2cH 2cH 2or CH 2cH (OH) CH 2, R 4and R 7represent H or CH 3, R 5with R 6for one of combining below: H
and CH (CH 3) CH 3; CH 2cH 3with CH 2cH 3; H and CH (CH 2oH) CH 2cH 3, R 8and R 9represent independently of one another CH 3or CH 2cH 3, R 10represent H, CH 3, CH 2cH 3or
CH 2c 6h 5.In general formula, b and c meet and are related to 0≤b/c≤1/9;
Divide phase reagent by leading point phase reagent and helping phase-splitting reagent to form, it is one or both mixture of ammonium sulfate and sodium sulfate that
described master divides phase reagent, and the total mass concentration that ammonium sulfate and sodium sulfate account for dispersion liquid system is 14.5-35%, and
https://patents.google.com/patent/CN103788296A/en 1/15
wherein sodium sulfate quality concentration range is 0-3%; The described point phase reagent that helps is that sodium-chlor and Lithium Sulphate mix with arbitrary
proportion, and the total mass concentration that Lithium Sulphate and sodium-chlor account for dispersion liquid system is 0.5-2%;
Described cationic polyacrylamide is obtained by non-ionic monomer and cationic monomer copolymerization, and the 65-100%(that wherein non-ionic monomer accounts for
monomer integral molar quantity is not containing 100%), cationic monomer accounts for the 0-35%(of monomer integral molar quantity not containing 0%);
Described non-ionic monomer is a kind of of monomer shown in following general formula (3) or more than a kind of any mixing:
R 11represent H or CH 3, R 12and R 13represent independently respectively H or the alkyl containing 1-3 C atom;
Described cationic monomer is a kind of of monomer shown in following general formula (4) or more than a kind of any mixing:
Wherein group A represents O or NH, and B represents CH 2cH 2, CH 2cH 2cH 2or CH 2cH (OH) CH 2, R 14represent H or CH 3, R 15and R 16represent independently of one
another CH 3or CH 2cH 3, R 17represent H, CH 3, CH 2cH 3or CH 2c 6h 5.
2. the preparation method of cationic polyacrylamide high-temperature resistant water bag aqueous dispersions claimed in claim 1, is characterized in that comprising
the steps:
(1) aqueous solution of monomer, point phase reagent, stablizer and seed polymer is joined in reactor, add water, under polymerization temperature, fully stir and make to
reach dissolving/partition equilibrium, obtain the seed dispersion liquid of white opacity shape containing monomer, be reaction solution;
(2) under polymerization temperature, pass into rare gas element to the reaction solution of having prepared and remove O 2, keep inert atmosphere;
(3) in reaction solution, add the aqueous dispersions that contains whole initiators to form reaction system, and the aqueous dispersions of initiator account for 1% of
end reaction system total mass mark; After adding initiator aqueous dispersions, start timing, reach under polymerizing condition and react after required time,
time remove
inert atmosphere protection, cooling stopped reaction, obtains described cationic polyacrylamide high-temperature resistant water bag aqueous dispersions.
3. the preparation method of cationic polyacrylamide high-temperature resistant water bag aqueous dispersions according to claim 2, is characterized in that: in step (1),
each amounts of components of reaction solution meets the following conditions: the ratio that in reaction solution, each composition accounts for reaction system total
mass is:
Monomer 1-20%,
Divide phase reagent 15-37%,
Seed polymer 1-10%;
And the ratio of monomer total mass and seed polymer total mass is not more than 8; Stablizer is the 5-20% of seed polymer and monomer total mass; Ammonium
sulfate and sodium sulfate total mass concentration are 14.5-35%, and wherein sodium sulfate quality concentration range is 0-3%; Lithium Sulphate and sodium-chlor
total mass concentration are 0.5-2%.
4. according to the preparation method of the cationic polyacrylamide high-temperature resistant water bag aqueous dispersions described in claim 2 or 3, it is
characterized in that: when stablizer weight average molecular weight range used is 5 × 10 4-5 × 10 5time
time, the total mass concentration that ammonium sulfate and
sodium sulfate account for reaction system is 20-30%, wherein sodium sulfate quality concentration range is 0-3%; Lithium Sulphate and sodium-chlor total mass
concentration are 0.5-2%.
characterized in that: stablizer is 5-15% with respect to the mass content of seed polymer.
characterized in that: in step (3), initiator used is the mixing of following a kind of system or multiple system:
Thermolysis initiator system: azo azo di-isopropyl imidazoline salt hydrochlorate VA044, azo di-isopropyl imidazoline salt hydrochlorate V50 or Diisopropyl
azodicarboxylate AIBN; Organo-peroxide class diisobutyl superoxide TBP;
Or redox initiation system: hydrogen peroxide (H 2o 2) with vitamins C (VC), persulphate in a kind of and Sulfates at a low price in one, ammonium persulphate and
Sodium Pyrosulfite and take ferrous sulfate as core ductant; Described persulphate refers to ammonium persulphate, Sodium Persulfate and Potassium Persulphate;
Described low price Sulfates refers to S-WAT, sodium bisulfite, Sodium Pyrosulfite, rongalite; The consumption of oxygenant and reductive agent meets
oxygenant/reductive agent (mol ratio) between 0.5-2.0;
Initiator amount is the 0.001-0.05% of monomer integral molar quantity, and redox system is calculated with the lower side's integral molar quantity of molar weight in
Oxidizing and Reducing Agents.
Description
A kind of cationic polyacrylamide high-temperature resistant water bag aqueous dispersions and low viscosity preparation method thereof
Technical field
The invention belongs to the preparing technical field of cation type water-soluble polymer dispersion, relate in particular to a kind of low viscosity preparation method of
cationic polyacrylamide high-temperature resistant water bag aqueous dispersions.
Background technology
The constructional feature of polyacrylamide uniqueness and complete range of product make it to be widely applied in the every field of national economy, enjoy the title
of " all trades auxiliary agent ".In China, the application of polyacrylamide in oil, water treatment and the large field of papermaking three is even more important.
Current existing Polyacrylamide multipolymer industrial process comprises solution polymerization, inverse suspension polymerization and inverse emulsion
polymerization.The product that the production method of solution polymerization obtains is powder, outside the high viscosity problem in production process, similar
with inverse suspension polymerization, owing to finally need to drying granulation, unavoidably need to introduce drying-granulating equipment, increasing production
cost, in producing, produce dust simultaneously, also there is problems such as dissolving difficulty in final product.And inverse suspension polymerization and reverse
emulsion polymerization are aborning in a large number with an organic solvent and tensio-active agent, itself easily produces secondary pollution to environment.In
order to overcome above defect, people have developed aqueous dispersion polymerization (aqueous dispersion polymerization, also be referred to as the water
polymerization of water bag or double-aqueous phase polymerization) preparation method, directly preparing product and without aftertreatment of this method,
production efficiency is high, products therefrom dissolves fast, and itself is without organic solvent, thereby environmental friendliness.
In recent ten years, about the existing more research of preparation method of the water bag aqueous dispersions of cationic polyacrylamide.European patent EP
0183466 and EP0657478, U.S. Pat A4929655 and USA5006590 have all described in the aqueous solution that contains multivalent anions salt and polymer stabilizer,
obtain water-in-water emulsion by acrylamide, acrylyl oxy-ethyl-trimethyl salmiac and the copolymerization of acrylyl oxy-ethyl dimethyl benzyl ammonium chloride, but its
system viscosity in the process of preparation is very high, to stirring and conducting heat, high requirement is all proposed.
CN1884324A reduces acrylamide solubleness by introducing hydrophobic monomer copolymerization, and polyacrylamide is separated out in time
time, adopts cationic
polymers and polymerized polyalcohol one package stabilizer to improve stabilising effect simultaneously.CN101016352A adopts the cationic monomer that contains
benzyl to reduce acrylamide solubleness; CN1709945A adopts the one package stabilizer of addition polymerization cationic polymers and condensation polymerization
cationic polymers, because condensation polymer molecular weight is low, therefore has better stabilising effect.The core concept that CN1286866C adopts inorganic
salt and the shared one package stabilizer CN100516100C of water-soluble polymer to feed intake according to substep, introduces a small amount of hydrophobic
monomer, has prepared the lower polyacrylamide dispersion liquid of viscosity.
Above method all belongs to traditional water bag water polymerization process, the key of its polymerization process is, the polymer chain forming by radical
polymerization is Precipitation from system in time
time, form primary particle, adsorb rapidly stablizer simultaneously, form stable emulsion particle, avoid causing gel
because system viscosity explodes, so all belong to " auto-polymerization nucleation " method, be that solution polymerization first occurs in polymerization process, in
the time reaching polymkeric substance phase-splitting critical molecular weight, polymer chain is separated out nucleation (primary particle) from solution.In the
category of the method, investigators are from shortening the phase-splitting time and improving the aspects such as condition of phase separation water bag aqueous
dispersions synthetic carried out to improvement in various degree, in to a certain degree, controlled final product viscosity, improved molecular weight of product and
dispersion liquid solid content.
But, exist with ... " auto-polymerization nucleation " process, still there is the following problem to be solved that has in these class methods:
(1) tradition " auto-polymerization nucleation " method building-up process medium viscosity is larger, is unfavorable for producing.According to bibliographical
information (European Polymer Journal, 42,2006,1284-1297), the preparation process of water bag aqueous dispersions comprises the process of being separated out to
phase-splitting by solution polymerization, and polymericular weight and concentration that in this process, the viscosity of dispersion liquid system is dissolved in by
solution phase determine.Water bag aqueous dispersions divides phase time
time, existing certain transformation efficiency, and now in solution, polymer concentration is
higher, and molecular weight (even can reach 10 near critical molecular weight 6).So tradition " auto-polymerization nucleation " water bag aqueous dispersions
polymerization system viscosity will reach high level (viscosity is far above final product) near phase separation point, and pole-climbing or gelatin phenomenon now very
easily occur.Just may obtain after this dispersion liquid product of good fluidity, although the method for existing bibliographical information can obtain final product
dispersion liquid, these methods all inevitably cause larger viscosity in process of production, and this is disadvantageous for production.
(2) the macroion degree cationic polyacrylamide water bag aqueous dispersions viscosity that prepared by tradition " auto-polymerization nucleation " method is large,
and mobility is not good, and storge quality is poor.The different solubility of the polyacrylamide copolymer of different ions degree in point phase system, the
solubleness that ion degree is little is little, easily phase-splitting; And the high solubleness of ion degree is large, in point phase time solution, polymer concentration is
high, and molecular weight is large, and phase-splitting is difficulty comparatively.
In addition, the synthetic dispersion liquid of traditional method is at low temperature normal temperature (0-30 ℃) good fluidity, comparatively stable, when this and low
temperature, polymerization-filling thing solubleness is low closely related, but polymkeric substance (comprising polyacrylamide) can be partially dissolved in point
phase system in the time of high temperature, cause viscosity further to raise, easily there is gelatin phenomenon, thereby its storge quality affected by temperature
fluctuation larger, this is tradition " auto-polymerization nucleation " method shortcoming that cannot overcome, thereby is difficult to prepare good fluidity, macroion
degree polyacrylamide water bag aqueous dispersions that stability is high.
(3) tradition " auto-polymerization nucleation " method prepare height admittedly containing in low ion degree cationic polyacrylamide water bag aqueous dispersions
process easily due to stability deficiency gel (with reference to Journal of Applied Polymer Science, 83,2002,1397-1405).According to contriver's result of study, when its
reason is that phase-splitting particle surface does not reach adsorption equilibrium, surface is only contained partially stabilized dose, remaining surface is exposed,
because low ion degree polyacrylamide copolymer surface charge amount is lower, sterically hindered lower with electrical charge rejection between phase-splitting
particle, between particle, easily there is coalescence (thereby falling low surface energy to reduce surface-area), the macrobead that final coalescence obtains can not
be fully stable by stablizer, thus gel.
Summary of the invention
For solving the problem that cationic polyacrylamide water bag aqueous dispersions preparation process medium viscosity is high and high temperature resistant
memory property is poor, the invention provides a kind of cationic polyacrylamide high-temperature resistant water bag aqueous dispersions and low viscosity
preparation method thereof.
Cationic polyacrylamide high-temperature resistant water bag aqueous dispersions of the present invention and low viscosity preparation method's thereof core feature
is: while preparing cationic polyacrylamide dispersion liquid, first seed polymer, monomer etc. are prepared into seed dispersion liquid, then the components such as the
required initiator of polymerization are added in the seed dispersion liquid having prepared and carry out polymerization.Wherein, described seed polymer is the
polymkeric substance that possesses lowest critical solution temperature, lowest critical solution temperature or can be referred to as minimum phase separation
temperature, and it has negative solubility temperature coefficient; Be under polymerizing condition without through any chemical reaction, seed polymer Yin Wendu
raises the polymkeric substance of phase-splitting just can occur in reaction system, after phase-splitting, formation is received the particle of micro-meter scale and is
present in system, is " seed ".
Described monomer reaches swelling equilibrium before polymerization in seed dispersion liquid; Auto-polymerization reaction starts, and initiator is that swellable
enters seed, trigger monomer polymerization in seed and outside seed.According to contriver's result of study, the interior monomer concentration of this polymerization
system " seed " " seed " is outer high, that is the distribution of organic molecule polymerization single polymerization monomer in organic polymer is higher than the
distribution in outside inorganic salt solution (in " seed " inside and outside monomer concentration---unit mass, contained pair of key mole number ratio is generally
greater than 1.5), also (AIChE J.2011 similar document, 9,2493-2504) report, in double-aqueous phase polymerization whole process, disperse phase, be equivalent to "
seed ", inner acrylamide monomer concentration is higher than external phase.In the present invention, from polymerization initially, polymerization take in seed as main,
the degree of solution polymerization regeneration polymer seeds is lower, thereby can effectively reduce in solution phase, namely " seed " outer solvent polymerization
substrate concentration.For macroion degree and low ion degree polyacrylamide copolymer, because its overwhelming majority is wrapped in seed hulls, be subject to
ambient conditions influence degree little, the viscosity of system and stability mainly determines by kind of a subshell, thereby guaranteed low viscosity and the stability
of system.
Because seed polymer is the polymkeric substance with lowest critical solution temperature, in the aqueous solution, under low temperature, can dissolve completely,
when temperature raises, polymkeric substance can be separated out to form and be received micron particle from solution.After polymerization completes, intraseminal
polyacrylamide copolymer is wrapped in seed polymer, and its free stripping is hindered, along with temperature raises, seed polymer shell can not dissolve, and in shell,
polyacrylamide is also difficult to ooze out, and dispersion liquid heat-resisting ability significantly rises.Accordingly, in the time of low temperature, because seed
polymer shell can be partly dissolved because solubleness increases, thereby make system have certain rising in the viscosity of low temperature.
Cationic polyacrylamide high-temperature resistant water bag aqueous dispersions of the present invention, its composition comprises seed polymer, cationic
polyacrylamide, point phase reagent, stablizer, He Shui, wherein cationic polyacrylamide part is wrapped in seed polymer, part is present in seeding polymerization
beyond the region of objective existence, and the cationic polyacrylamide of seeding polymerization beyond the region of objective existence is partially dissolved in
water; Stabilizer package is overlying on the case surface of seed polymer, and phase-splitting agent dissolves is in water; Mass ratio between said components is:
Seed polymer: account for the 1-10% of system total mass,
Cationic polyacrylamide: account for system total mass 1-20%, and the ratio of its total mass and seed polymer total mass is not more than 8,
Stablizer: account for the 5-20% of seed polymer and cationic polyacrylamide total mass,
Divide phase reagent: account for the 15-37% of system total mass,
Water: surplus is water;
Described seed polymer is a kind of of polymkeric substance shown in following general formula (1) or more than a kind of arbitrary combination, its weight average
molecular weight range is 5 × 10 5-2 × 10 6,
Wherein, R 1represent H or CH 3, R 2with R 3for one of combining below: H and CH (CH 3) CH 3; CH 2cH 3with CH 2cH 3; H and CH (CH 2oH) CH 2cH 3; General formula (1)
has only illustrated the monomeric species and the ratio that form this polymkeric substance, does not limit the mode of connection between adjacent monomer, this
structure comprised between monomer, formed with backbone c atoms mode of connection polymkeric substance.
Described seed polymer can be by the aqueous solution polymerization preparation of corresponding monomer; Weight-average molecular weight is lower than 5 × 10
5seed polymer is difficult to directly phase-splitting formation " seed " from system under polymerization temperature; Weight-average molecular weight is higher than 2 ×
10 6the flocculation of easily building bridge between multiple dispersion liquid particulates makes dispersion liquid coalescence precipitation.
Described stablizer is a kind of of polymkeric substance shown in following general formula (2) or more than a kind of arbitrary combination, its weight average molecular
weight range is 5 × 10 4-1 × 10 6.Molecular weight is lower than 5 × 10 4stablizer easily from product dispersion liquid microparticle surfaces come off, and its electrical
charge rejection and sterically hindered less, is difficult to stable dispersions particulate; Molecular weight is higher than 1 × 10 6dispersion liquid viscosity is larger, and
the flocculation of easily building bridge between multiple dispersion liquid particulates makes dispersion liquid coalescence precipitation.
Wherein radicals X represents O or NH, and Y represents CH 2cH 2, CH 2cH 2cH 2or CH 2cH (OH) CH 2, R 4and R 7represent H or CH 3, R 5with R 6for one of combining
below: H and CH (CH 3) CH 3; CH 2cH 3with CH 2cH 3; H and CH (CH 2oH) CH 2cH 3, R 8and R 9represent independently of one another CH 3or CH 2cH 3, R 10represent H,
CH 3, CH 2cH 3or CH 2c 6h 5.In general formula, a and b meet and are related to 0≤b/c≤1/9; General formula (2) has only illustrated the monomeric species and the ratio
that form this polymkeric substance, do not limit the mode of connection between adjacent monomer, also not limiting polymkeric substance is block polymer structures,
this structure comprised between these two kinds of monomers with random order and arbitrarily backbone c atoms mode of connection formed polymkeric substance.
Divide phase reagent by leading point phase reagent and helping phase-splitting reagent to form, it is one or both mixture of ammonium sulfate and sodium sulfate that
described master divides phase reagent, and the total mass concentration that ammonium sulfate and sodium sulfate account for dispersion liquid system is 14.5-35%,
and wherein sodium sulfate quality concentration range is 0-3%; The described point phase reagent that helps is that sodium-chlor and Lithium Sulphate mix with
arbitrary proportion, and the total mass concentration that Lithium Sulphate and sodium-chlor account for dispersion liquid system is 0.5-2%.
The phase-splitting of seed polymer in reaction system caused by two factors, determinative is temperature, cofactor is namely inorganic salt of point phase reagent, and
point phase reagent can further reduce the solubleness of seed polymer, thereby makes seed polymer phase-splitting under lower temperature.
Described cationic polyacrylamide is obtained by non-ionic monomer and cationic monomer copolymerization, and the 65-100%(that wherein non-ionic monomer
accounts for monomer integral molar quantity is not containing 100%), cationic monomer accounts for the 0-35%(of monomer integral molar quantity not containing 0%);
Described non-ionic monomer is a kind of of monomer shown in following general formula (3) or more than a kind of any mixing:
R 11represent H or CH 3, R 12and R 13represent independently respectively H or the alkyl containing 1-3 C atom;
Described cationic monomer is a kind of of monomer shown in following general formula (4) or more than a kind of any mixing:
Wherein group A represents O or NH, and B represents CH 2cH 2, CH 2cH 2cH 2or CH 2cH (OH) CH 2, R 14represent H or CH 3, R 15and R 16represent independently of one
another CH 3or CH 2cH 3, R 17represent H, CH 3, CH 2cH 3or CH 2c 6h 5.
The low viscosity preparation method of cationic polyacrylamide high-temperature resistant water bag aqueous dispersions of the present invention, comprises the
steps:
(1) aqueous solution of monomer, point phase reagent, stablizer and seed polymer is joined in reactor, add water, under polymerization temperature, fully stir and make to
reach dissolving/partition equilibrium, obtain the seed dispersion liquid of white opacity shape containing monomer, be reaction solution;
(2) under polymerization temperature, pass into rare gas element (as N to the reaction solution of having prepared 2) remove O 2, keep inert atmosphere;
(3) in reaction solution, add the aqueous dispersions that contains whole initiators to form reaction system, and the aqueous dispersions of initiator account for 1% of
end reaction system total mass mark; After adding initiator aqueous dispersions, start timing, reach under polymerizing condition and react after required time,
time remove
inert atmosphere protection, cooling stopped reaction, obtains described cationic polyacrylamide high-temperature resistant water bag aqueous dispersions.
Seed polymer in step (1) must be mixed with the aqueous solution and use, in the reaction solution that seed polymer strength of solution should be prepared higher than
step (1) herein, seed polymer accounts for the total mass mark of seed polymer and water: the seed polymer solution obtaining by aqueous solution polymerization can
directly use in the time preparing dispersion liquid, or wherein after polymer purification, being mixed with the aqueous solution uses, so can significantly shorten when
preparation is reaction solution containing the seed dispersion liquid of monomer and reach and dissolve the partition equilibrium time used, can obtain comparatively
stable seed dispersion liquid simultaneously.
Described initiator dispersion concentration is in order to guarantee that the water yield of bringing into while adding seed polymer solution is no more than the total
Water that reaction solution prepared by step (1) contains.
In order to make building-up process milder, be that in preparation process, the viscosity of reaction system is lower, the stability of product dispersion liquid is better, and
in step (1), each amounts of components of reaction solution meets the following conditions: the ratio that in reaction solution, each composition accounts for reaction
system total mass is:
Monomer 1-20%,
Divide phase reagent 15-37%,
Seed polymer 1-10%;
And the ratio of monomer total mass and seed polymer total mass is not more than 8; Stablizer is the 5-20% of seed polymer and monomer total mass; Ammonium
sulfate and sodium sulfate total mass concentration are 14.5-35%, and wherein sodium sulfate quality concentration range is 0-3%; Lithium Sulphate and sodium-chlor
total mass concentration are 0.5-2%.
It should be noted that especially working as stablizer weight average molecular weight range used is 5 × 10 4-5 × 10 5time
time, the total mass concentration that ammonium
sulfate and sodium sulfate account for reaction system is 20-30%, wherein sodium sulfate quality concentration range is 0-3%; Lithium Sulphate and sodium-chlor total
mass concentration are 0.5-2%.
When stablizer is 5-15% with respect to the total mass content of seed polymer and monomer, polymerization process viscosity is lower, and high viscosity is not higher
than 500cP, and products therefrom dispersion liquid mobility is better, and its viscosity is not higher than 150cP.
In step (3), initiator used is the mixing of following a kind of system or multiple system:
Thermolysis initiator system: azo azo di-isopropyl imidazoline salt hydrochlorate VA044, azo di-isopropyl imidazoline salt hydrochlorate V50 or Diisopropyl
azodicarboxylate AIBN; Organo-peroxide class diisobutyl superoxide TBP;
Or redox initiation system: hydrogen peroxide (H 2o 2) with vitamins C (VC), persulphate in a kind of and Sulfates at a low price in one, ammonium persulphate and
Sodium Pyrosulfite and take ferrous sulfate as core ductant; Described persulphate refers to ammonium persulphate, Sodium Persulfate and Potassium Persulphate;
Described low price Sulfates refers to S-WAT, sodium bisulfite, Sodium Pyrosulfite, rongalite; The consumption of oxygenant and reductive agent meets
oxygenant/reductive agent (mol ratio) between 0.5-2.0;
Initiator amount is the 0.001-0.05% of monomer integral molar quantity, and redox system is calculated with the lower side's integral molar quantity of molar weight in
Oxidizing and Reducing Agents.
Initiator amount may produce following situation lower than 0.001% monomer molar amount: (1) transformation efficiency is lower; (2) due to the O of micro-seepage
2cause reaction terminating Deng species; (3) allowed to reaction, its repeatability is poor.
For thermal decomposition initiating, can directly once add, also can slowly evenly add, the time is no more than 3h; For redox initiator, first required quality reductive
agent is added to polymerization system, then oxidizing agent solution is slowly evenly added to polymerization system, the control joining day is no less than 15min, is
no more than 3h.Because the existence of transformation period, thermal decomposition initiating elicitation procedure is relatively mild, so can once add, also can
slowly evenly add, and once adds and has slight gel effect.But for redox initiation system, general activation energy is lower, if once add initiation, not only can be on the
low side because of the too low transformation efficiency that makes of later stage number of free radical, number of free radical is too high in early days easily causes
more serious gel effect to make polymerization viscosity excessive.
Being suitable for kick off temperature (polymerization temperature) is 20-50 ℃, this area researchist can judge according to other documents and use experience the
suitable kick off temperature of initiator used, redox initiation system kick off temperature approaches normal temperature, and thermolysis initiator system kick off
temperature can determine according to its transformation period.
Because polymerization time is longer, transformation efficiency is higher, so more than polymerization time is generally 10h; And in order to guarantee that reaction does
not have monomer to proceed polymerization (otherwise easily causing system viscosity to increase) while end, generally carry out the sufficiently long time.Wherein,
time the
redox initiation system time is slightly short compared with thermolysis initiator system polymerization time.
time
In a word, the low viscosity preparation method of cationic polyacrylamide high-temperature resistant water bag aqueous dispersions of the present invention, in its
polymerisation run, " auto-polymerization nucleation " degree is lower, so whole polymerisation run viscosity is low and steady, polymerization process peak viscosity is
no more than 1000cP; And can prepare good fluidity, the lower stable storing of normal temperature (0-30 ℃), 25 ℃ can store the cationic polyacrylamide water bag
aqueous dispersions that exceedes a year; The viscosity of described cationic polyacrylamide water bag aqueous dispersions is no more than 500cP, under optimal
conditions generally not higher than 150cP.
It should be noted that, during lower than 25 ℃, temperature reduces this dispersion liquid viscosity may have liter to a certain extent, but still good fluidity, and with
respect to prior synthesizing method gained dispersion liquid, this dispersion liquid is more high temperature resistant, at 40-50 ℃, viscosity changes relatively little, its
viscosity rises to some extent, but generally not higher than 1000cP, especially for the low ion degree of high copolymer solid content (cationic polyacrylamide effective
constituent is not less than 15wt%) (mole ion degree 0%-2%, containing 0%) and macroion degree (mole ion degree 30-35%) polyacrylamide dispersion liquid.
Embodiment
In order to make object of the present invention, technical scheme and advantage clearer, below in conjunction with embodiment, the present invention is further
elaborated.
In addition, because high solids content (the cationic polyacrylamide virtual mass content that polymerization obtains is not less than 15%) dispersion liquid viscosity is
higher than low-solid content dispersion liquid (the cationic polyacrylamide virtual mass content that polymerization obtains is lower than 15%), under corresponding
synthesis condition, the building-up process of low-solid content dispersion liquid will be milder, and product viscosity is lower.So for the present invention is more
effectively described, following instance describes and contrasts mainly with the preparation of high solids content dispersion liquid.
In following embodiment and comparative example, enumerate unit used and be mass parts.
1 is dissolved with preparation and the sign of the seed dispersion liquid of monomer
Below only enumerated several seed dispersion liquids as embodiment explanation, the seed dispersion liquid that in the present invention, indication is dissolved with
monomer is including, but not limited to following kind:
Stablizer 1: 0.85 part of NIPA (NIPAM) and 99.15 parts of acrylyl oxy-ethyl dimethyl benzene ammonio methacrylates (DMPhC) are mixed with to the aqueous solution, by
HCl adjusting pH to 6,970 parts of gross weights.Logical N wherein 2except O 2after 0.5 hour, be warming up to 35 ℃, N 230 parts of the aqueous solution that under
protection, evenly dropping contains 60 ‰ parts of VA044 wherein, control time for adding is 30min, drips reaction and is warming up to 50 ℃ after 24 hours, continues
reaction 6 hours.Stop heating, remove N 2protection, is cooled to room temperature, and P (NIPAM-co-DMPhC) the seed polymer molecular weight of gained mole
cationic degree 98% is 7.7 × 10 4, by stand-by the vacuum-drying of gained stabiliser solution (ST2-1).Change monomer and initiator amount ratio, in the adjusting
aqueous solution, monomer concentration all can the different seed polymer of synthetic molecular weight.Other monomers use conditions of similarity can prepare
respective seed polymkeric substance (reaction conditions is in table 2).
Stablizer 2: lead to N in the aqueous solution that contains 60 parts of DMPhC (570 parts) 2except O 2after 0.5 hour, be warming up to 50 ℃, N 2under protection, evenly
drip wherein 30 parts of aqueous solution that contain 24 ‰ parts of V50, control time for adding is 30min, drips reaction 24 hours, is warming up to 80 ℃, continues
reaction 6 hours.Stop heating, remove N 2protection, is cooled to room temperature, and gained PDMPhC molecular weight is 1.8 × 10 5(measuring method is
viscosimetry, same to document: Polymer, 1984,25,1317-1322), by stand-by the vacuum-drying of gained stabiliser solution (ST2-5).Change monomer and initiator
amount ratio, in the adjusting aqueous solution, monomer concentration all can the different stablizer of synthetic molecular weight.Other monomers use conditions of
similarity can prepare corresponding stablizer (reaction conditions is in table 1).
Seed polymer: by 100 parts of NIPAM and 2.0 ‰ parts of H 2o 2be mixed with the aqueous solution, regulate its pH=6,470 parts of gross weights with HCl.Logical N
2except O 230min, keeps 20 ℃ of temperature, N 230 parts of the aqueous solution that under protection, evenly dropping contains 7.4 ‰ parts of vitamins Cs (VC)
wherein, time for adding is controlled at 30min, drips isothermal reaction 12 hours, stops N 2protection, is cooled to room temperature.Molecular weight determination is
a part PC method (same to document: Polymer, 2012,53,5010-5015), and gained NIPAM homopolymer molecular weight is 5.9 × 10 5.This solution (SP2-1) directly uses
in follow-up synthesizing.Change monomer and initiator amount ratio, in the adjusting aqueous solution, monomer concentration all can the different seed polymer of
synthetic molecular weight.Other monomers use conditions of similarity can prepare respective seed polymkeric substance (reaction conditions is in table 2).
Take 52 parts of (NH 4) 2sO 4, 3 parts of Li 2sO 4p (NIPAM-co-DMPhC) stablizer (ST2-1) with 2.7 parts of synthesizeds, adds 75.3 parts of H 2in O, then add wherein 25
parts of synthesized P (AM-co-DMC) seed polymer solution (SP2-1), under 40 ℃, 300rpm mechanical stirring condition, be fully uniformly mixed 30min and make seed
dispersion liquid.In this seed dispersion liquid, add 0.24 part of DMC and 39.76 parts of acrylamides (AM), continue constant temperature stirring 30min and make the
seed dispersion liquid (for Embodiment C 1) that is dissolved with monomer.Other seed dispersion liquids that are dissolved with monomer can be according to same
operation method preparation (condition that feeds intake is in Table 3A and 3C).
Monomer is at " seed " concentration determination (method with reference to AIChE J.2011,9, the 2493-2504 of solution phase mutually and outside " seed ";
J.Appl.Polym.Sci.2009,112,2859-2867):
Get the seed dispersion liquid that is dissolved with monomer, centrifugal (12000rpm/10min) separates, and takes respectively 0.2g left and right upper strata m 1(be
generally " seed " phase, density ratio salts solution is low) and the m of lower floor 2(clear, salts solution phase) (unit is g), fully dissolves with 50mL water, adds the
KBr/KBrO that 20mL6mol/L hydrochloric acid and 20mL concentration are 0.2mol/L 3mixing solutions (molar concentration rate KBr/KBrO 3=5/1), mix, after dark place
reaction 30min, add the KI aqueous solution of 20mL massfraction 20%, with the Na of 0.1mol/L 2s 2o 3the I that standardized solution titration generates 2amount, Na
used 2s 2o 3standardized solution volume is designated as respectively V 1and V 2(Unit/mL), the Br that two keys consume in sample in prediction on such basis
2amount, thus extrapolate double bond content and concentration:
" seed " internal double bond concentration
0.2mol · 𝐿-1 × time 1 / 2 - 0.1mol · 𝐿-1 ×

time 0.02𝐿 × time 𝑉1 / 1000 ×
time 1 / 2
𝐶SE =
𝑚1 / 1000
The two key concentration of " seed " outer solution phase
-1 -1
0.2mol · 𝐿 ×
time 0.02𝐿 ×
time 1 / 2 - 0.1mol · 𝐿 ×
time 𝑉2 / 1000 ×
time 1 / 2
𝐶SO = 𝑚2 / 1000
Part dispersion liquid measurement result is in Table 3B, monomer distribution concentration between solution phase outside " seed " phase and " seed " is dominant
mutually with " seed " as seen herein, so about more than a kind of seed polymer, do not measure more than the system of a kind of polymerization non-ionic monomer
and unnecessary a kind of polymerization plasma type monomer, can predict in these systems " seed " mutually two key concentration also higher than " seed " outer
solution phase.
Synthetic and the sign of 2 cationic polyacrylamide water bag aqueous dispersions
Universal synthesis method:
Seed polymer dispersion liquid logical N under polymerization temperature of monomer will be dissolved with 2except O 230min, N 2under protective condition, add
wherein the solution (or dispersion liquid) containing required quality initiator: for thermal decomposition initiating, can directly once add, also can slowly evenly add, the
time is no more than 3h; For redox initiator, first required quality reductive agent is added to polymerization system, then oxidizing agent solution is slowly evenly added to
polymerization system, the control joining day is no less than 15min, is no more than 3h.Following examples and comparative example (total polymerization liquid weight
is 200 parts), the initiation component for initiation reaction finally adding is all formulated as 2 parts of aqueous dispersions.
time, stop heating, be cooled to 20 ℃, remove N 2protection, can obtain required

Add fashionable timing from initiator, under polymerization temperature, react required time
cationic polyacrylamide water bag aqueous dispersions.
The monitoring of polymerization process medium viscosity is for using syringe abstraction reaction liquid every 15min, measure (Nirun SNB-1 intelligence Brookfield
viscometer with Brookfield viscometer, 29# rotor, viscosity adopts 10rpm rotating speed lower than 10000cP, viscosity adopts 1rpm rotating speed higher than
10000cP).Molecular weight of product is measured with reference to stablizer and seed polymer.
Embodiment C 1(thermal decomposition initiating): will under 40 ℃ of mechanical stirring conditions, lead to N according to the prepared seed dispersion liquid that is
dissolved with monomer of consumption in table 2 2except O 230min, N 2disposablely wherein under protective condition add 2 parts of aqueous solution that contain
3.0 ‰ parts of VA044, certainly adding, reaction is stirred and is carried out 30h, stops stirring and N 2protection; cooling can make cationic degree 0.2%, effective solid
content (synthesizing cationic polyacrylamide; containing stablizer and seed polymer) 20% oyster white P (AM-co-DMC) water bag aqueous dispersions; peak viscosity
244.1cP in reaction process; final product viscosity is 54.6cP(25 ℃), molecular weight 10.4 × 10 6, normal temperature (25 ℃) can store 1 year above (relevant nature is
in table 4).
Embodiment C 4(redox initiator): to according to adding 6 ‰ parts of VC and stirring and dissolving at 25 ℃ in the prepared seed dispersion liquid that is dissolved with
monomer of consumption in table 2.Keep 25 ℃ and mechanical stirring, wherein logical N 2except O 230min, N 2under protective condition, evenly drip wherein 2 parts
and contain 0.97 ‰ part of H 2o 2the aqueous solution, control time for adding is 60min.From dripping, reaction is stirred and is carried out 12h, stops stirring and N
2protection; cooling can make cationic degree 0.5%, effective solid content (synthesizing cationic polyacrylamide; containing stablizer and seed polymer) 20% oyster
white P (AM-co-DEAC) water bag aqueous dispersions; peak viscosity 270.5cP in reaction process; final product viscosity is 161.3cP(25 ℃), molecular weight 13.6 × 10 6,
normal temperature (25 ℃) can store 1 year above (relevant nature is in table 4).
Embodiment C 13(mixed stabilizer, mixed seeds polymkeric substance, mix monomer and mixed initiator): to according to adding 1.2 ‰ parts of Sodium Pyrosulfites
(SMBS) and stirring and dissolving at 35 ℃ in the prepared seed dispersion liquid that is dissolved with monomer of consumption in table 3.Keep 35 ℃ and mechanical
stirring, wherein logical N 2except O 230min, N 2under protective condition, slowly evenly add wherein (can use peristaltic pump) 2 parts of aqueous solution that contain
1.2 ‰ parts of APS and 1.0 ‰ parts of VA044, the control joining day is 15min.From initiator adds, reaction is stirred and is carried out 30h, stops stirring and N
2protection; cooling can make cationic degree 0.2%, effective solid content (synthesizing cationic polyacrylamide; containing stablizer and seed polymer) 18% oyster
white P (AM-co-DMAM-co-DAC-co-DMC) water bag aqueous dispersions; peak viscosity 361.8cP in reaction process; final product viscosity is 125.7cP(25 ℃), molecular
weight 10.4 × 10 6, normal temperature (25 ℃) can store 1 year above (relevant nature is in table 4).
Other embodiment (in Table 3A and 3C) carry out according to above embodiment step, and relevant nature is in table 4.
Because stablizer structure is similar with character, seed polymer structure is similar with character, non-ionic monomer structure is similar with character, cation mono
body structure is similar with character, has only enumerated two kinds of stablizers, two kinds of seed polymers, two kinds of non-ionic monomers, two kinds of cationic
monomers and the mode more than a kind of initiator system of using herein.Only need phase application quantity will be revised for the reaction system more than two
kinds of similar species, its reactive mode is identical, and those skilled in the art can be directly release the preparation method of water bag aqueous dispersions while
simultaneously using more than two kinds of similar species successively according to general polyreaction embodiment.
3 comparative examples
The polymerizing condition of comparative example is selected with reference to embodiment: compare with corresponding embodiment, in comparative example
polymerization process, do not use seed polymer, so stablizer actual amount is a little less than embodiment (having removed the stablizer part of calculating according
to seed polymer consumption), other conditions are identical with embodiment.
In addition, for the effective resistance to elevated temperatures of the synthetic dispersion liquid of explanation the inventive method, under the prerequisite of epimere
explanation, comparative example adopts low-solid content formula synthetic (and high solid will cause having can not get efficiency high temperature resistance and
contrast product because of synthetic viscosity is too high containing formula).
Take stablizer, inorganic salt, water, monomer and the initiation component 1 of aequum, mutually mix, under polymerization temperature, fully stir (mechanical stirring)
and dissolve.
Keep temperature, in above-mentioned solution, lead to N 2except O 230min, N 2under protective condition, add wherein the solution (or dispersion liquid) that causes
component 2 containing required quality: for thermal decomposition initiating, can directly once add, also can evenly drip, the time is no more than 3h; For redox initiator,
first required quality reductive agent is added to polymerization system, then oxidizing agent solution is evenly added dropwise to polymerization system, control time for
adding and be no less than 15min, be no more than 3h.Following examples and comparative example (total polymerization liquid weight is 200 parts), the initiation
component for initiation reaction finally adding is all formulated as 2 parts of aqueous dispersions.Add fashionable timing from initiator, under polymerization
temperature, react required time
time, stop heating, remove N 2protection, can obtain required cationic polyacrylamide water bag aqueous dispersions.The monitoring of
polymerization process medium viscosity is for using syringe abstraction reaction liquid every 15min, measure (Nirun SNB-1 intelligence Brookfield viscometer with
Brookfield viscometer, 29# rotor, viscosity adopts 10rpm rotating speed lower than 10000cP, viscosity adopts 1rpm rotating speed higher than 10000cP).Molecular
weight of product is measured with reference to stablizer and seed polymer.
Comparative example D2(redox initiator): take 7.44 parts of ST2-3 stablizers, 52 parts of (NH 4) 2sO 4, 3 parts of Li 2sO 4, 97.56 parts of H 2o, 30.72 parts of NIPAM, 9.28
parts of DAC and 2.2 ‰ parts of NaHSO 3(SBS) mix mutually abundant stirring and dissolving (mechanical stirring) at 35 ℃.In above-mentioned solution, lead to N
2except O 230min, N 2under protective condition, evenly add wherein 2 parts of aqueous solution initiation reactions containing 4 ‰ parts of APS, the control joining day
is 15min, from initiator adds, stirs polyase 13 0h, stops stirring and N 2protection; cooling can make cationic degree 15%, effective solid content (synthesizing cationic
polyacrylamide; containing stablizer and seed polymer) 20% oyster white P (NIPAM-co-DAC) water bag aqueous dispersions; peak viscosity 7523cP in reaction process;
final product viscosity is 1876cP(25 ℃); product is compared with thickness, molecular weight 12.1 × 10 6, normal temperature (25 ℃) can store six months, and
(relevant nature is in table 6) afterwards can slowly lose flowability.
Comparative example D3(thermal decomposition initiating): take 5.52 parts of ST2-5 stablizers, 44 parts of (NH 4) 2sO 4, 2 parts of Na 2sO 4, 4 parts of NaCl, 108.48
parts of H 2o, 15.79 parts of DMAM see appendix 1 with 20.21 parts of DEAC() mix mutually abundant stirring and dissolving (mechanical stirring) at 45 ℃.In above-
mentioned solution, lead to N 2except O 230min, N 2under protective condition, once add wherein 2 parts of aqueous solution initiation reactions containing 15.2 ‰ parts
of V50.From initiator adds and starts, stir polymerization 12h, stop stirring and N 2protection; cooling can make cationic degree 35%, effective solid content (synthesizing
cationic polyacrylamide; containing stablizer and seed polymer) 18% oyster white P (DMAM-co-DEAC) water bag aqueous dispersions; in reaction process, peak viscosity
exceedes 100000cP(and occurs rod climbing phenomenon); final product viscosity is 47380cP(25 ℃); product is thickness very, molecular weight 7.1 × 10 6, normal
temperature (25 ℃) is placed gel (relevant nature is in table 6) after a day.
Comparative example D7(mixed stabilizer, mix monomer and mixed initiator): take 3.0 parts of ST2-2 stablizers, 5.4 parts of ST2-5 stablizers, 52 parts of (NH 4) 2sO 4, 3
parts of Li 2sO 4, 2 parts of NaCl, 32.27 parts of H 2o, 11.12 parts of AM, 7.08 parts of NIPAM, 5.07 parts of DMPhC, 16.73 parts of AMPH mix mutually with 9.0 ‰ parts
of vitamins Cs (VC), abundant stirring and dissolving (mechanical stirring) at 20 ℃.In above-mentioned solution, lead to N 2except O 230min, N 2under protective
condition, slowly evenly add wherein (can use peristaltic pump) 1mL to contain 1.45 ‰ parts of H 2o 2the aqueous solution and 1mL containing the aqueous dispersions
of 2.0 ‰ parts of TBP, control time for adding 15min.From dropping starts, stir polymerization 12h, stop stirring and N 2protection; cooling can make cationic degree 30%,
effective solid content (synthesizing cationic polyacrylamide; containing stablizer and seed polymer) 20% oyster white P (AM-co-NIPAM-co-DMPhC-co-AMPH) water bag
aqueous dispersions; in reaction process, peak viscosity exceedes 100000cP; final product viscosity is 36670cP(25 ℃); product is thickness very, molecular weight 8.3 ×
10 6, normal temperature (25 ℃) is placed gel (relevant nature is in table 6) after a day.
Other comparative examples (in Table 5A and 5B) are carried out according to above comparative example step, and relevant nature is in table 6.
Below in all forms the abbreviation of monomer and initiator all with reference to annex 1, awt% refers to massfraction, and mol% refers to molar fraction.
Synthesizing of table 1 stablizer (Stablizer, ST)
Synthesizing of continued 1 stablizer (Stablizer, ST)
Synthesizing of table 2 seed polymer (Seed Polymer, SP)
Synthesizing of continued 2 seed polymers (Seed Polymer, SP)
Synthesizing of table 3A cationic polyacrylamide water bag aqueous dispersions
Synthesizing of continued 3A cationic polyacrylamide water bag aqueous dispersions
a"-" refers to regulate pH.
bfor redox system, component 1 is reductive agent component, and "-" refers to without this component; Component 2 is oxidant constituents.
dinitiation method: I is for once adding, and II, III and IV refer to respectively evenly drip 15min, 60min and 180min.
The concentration determination (under polymerization temperature) of monomer solution phase outside seed phase and seed before table 3B polymerization
Synthesizing of table 3C cationic polyacrylamide water bag aqueous dispersions
Synthesizing of continued 3C cationic polyacrylamide water bag aqueous dispersions
Renew the synthetic of table 3C cationic polyacrylamide water bag aqueous dispersions
asT refers to Stablizer, stablizer; SP refers to Seed Polymer, seed polymer.
binitiation method: cause component 1 and directly add in reaction system, cause component 2 for initiated polymerization, initiation method label is for component 2:I
for once adding herein, and II, III and IV refer to respectively evenly drip 15min, 60min and 180min.
The sign of table 4 cationic polyacrylamide water bag aqueous dispersions
Synthetic (comparative example) of table 5A cationic polyacrylamide water bag aqueous dispersions
Synthetic (comparative example) of continued 5A cationic polyacrylamide water bag aqueous dispersions
a"-" refers to regulate pH.
bfor redox system, this is reductive agent component, and "-" refers to without this component.
cfor redox system, this is oxidant constituents.
dinitiation method: component 1 directly adds in reaction system, component 2 is for initiated polymerization, and initiation method label is for component 2:I for once
adding herein, and II, III and IV refer to respectively evenly drip 15min, 60min and 180min.
Synthetic (comparative example) of table 5B cationic polyacrylamide water bag aqueous dispersions
Synthetic (comparative example) of continued 5B cationic polyacrylamide water bag aqueous dispersions
Renew synthetic (comparative example) of table 5B cationic polyacrylamide water bag aqueous dispersions
ainitiation method: component 1 directly adds in reaction system, component 2 is for initiated polymerization, and initiation method label is for component 2:I for once
adding herein, and II, III and IV refer to respectively evenly drip 15min, 60min and 180min.
bthis is design reaction time

times, partial reaction gel midway when actually operating.
The sign (comparative example) of table 6 cationic polyacrylamide water bag aqueous dispersions
a"-" refers to measure.
b"-" refers to measure.
c"-" refers to be not suitable for store.
In annex 1 polymerizing condition, the abbreviation of monomer used and initiator represents
Patent Citations (4)
Publication number Priority date Publication date Assignee Title
CN101735388A * 2009-12-25 2010-06-16 同济大学 Preparation method of water-in-water cation polyacrylamide
WO2010139683A1 * 2009-06-04 2010-12-09 Basf Se Fine-particle, cationic, aqueous polymer dispersions, method for the production
thereof, and use thereof
CN102286128A * 2009-12-31 2011-12-21 中国科学院成都有机化学有 Cationic hydrophobically associated polyacrylamide water-in-water emulsion
限公司
CN103044622A * 2012-10-30 2013-04-17 江苏博特新材料有限公司 Preparation method of water-in-water type cationic polyacrylamide emulsion
Family To Family Citations
* Cited by examiner, † Cited by third party
Cited By (2)
Publication number Priority date Publication date Assignee Title
CN111533836A * 2020-05-13 2020-08-14 常州大学 Self-initiated free radical polymerization of N-isopropylacrylamide
Family To Family Citations
WO2022094171A1 * 2020-10-30 2022-05-05 Kemira Oyj Stable cationic polyacrylamide dispersions and use thereof in papermaking
* Cited by examiner, † Cited by third party, ‡ Family to family citation
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Priority And Related Applications
Priority Applications (1)
Application Priority date Filing date Title
CN201310659587.2A 2013-12-06 2013-12-06 A kind of cationic polyacrylamide high-temperature resistant water bag aqueous dispersions and low viscosity
preparation method thereof
Applications Claiming Priority (1)
Application Filing date Title
CN201310659587.2A 2013-12-06 A kind of cationic polyacrylamide high-temperature resistant water bag aqueous dispersions and low viscosity preparation method
thereof
Legal Events
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2014-05-14 C06 Publication
2014-05-14 PB01 Publication
2014-06-11 C10 Entry into substantive examination
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2014-06-25 C41 Transfer of patent application or patent right or utility model
2014-06-25 TA01 Transfer of patent application right Effective date of registration: 20140529
Address after: Jiangning District of Nanjing City, Jiangsu province 211103 Li Quan Lu
No. 69
Applicant after: Jiangsu Subute New Materials Co., Ltd.
Applicant after: Nanjing Bote Building Materials Co., Ltd.
Address before: Jiangning District of Nanjing City, Jiangsu province 211103 Li Quan Lu
No. 69
Applicant before: Jiangsu Subute New Materials Co., Ltd.
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2020-12-18 CP02 Change in the address of a patent holder
2020-12-18 CP02 Change in the address of a patent holder Address after: No.6 shuiyougang, Gulou District, Nanjing City, Jiangsu Province 210013
Patentee after: JIANGSU SUBOTE NEW MATERIALS Co.,Ltd.
Patentee after: JIANGSU BOTE NEW MATERIALS Co.,Ltd.
Address before: Jiangning District of Nanjing City, Jiangsu province 211103 Li Quan Lu
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Concepts
machine-extracted Download Filter table
Name Image Sections Count Query match
dispersion title,claims,abstract,description 119 0.000
cationic group title,claims,abstract,description 83 0.000
polyacrylamide title,claims,abstract,description 78 0.000
water title,claims,abstract,description 76 0.000
preparation method title,claims,abstract,description 26 0.000
polymer claims,abstract,description 88 0.000
polymerization reaction claims,abstract,description 73 0.000
liquid claims,abstract,description 59 0.000
initiator claims,abstract,description 39 0.000
chemical reaction reagent claims,abstract,description 22 0.000
stabilizer claims,abstract,description 12 0.000
monomer claims,description 75 0.000
chemical reaction claims,description 57 0.000
solution claims,description 50 0.000
aqueous solution claims,description 24 0.000
initiatory claims,description 22 0.000
mixture claims,description 19 0.000
stirring claims,description 18 0.000
substance claims,description 18 0.000
lithium sulfate claims,description 16 0.000
sodium-chlor claims,description 15 0.000
na2so4 claims,description 14 0.000
sodium sulfate claims,description 14 0.000
sodium sulphate claims,description 14 0.000
chemical substances by application claims,description 13 0.000
nucleation claims,description 13 0.000
reduced claims,description 9 0.000
Ammonium sulfate claims,description 8 0.000
ammonium sulfate claims,description 8 0.000
ammonium sulphate claims,description 8 0.000
cooling claims,description 8 0.000
mixing claims,description 7 0.000
oxidant agent claims,description 7 0.000
vitamin C claims,description 7 0.000
vitamin C claims,description 7 0.000
Ammonium persulfate claims,description 6 0.000
ammonium persulphate claims,description 6 0.000
sodium bisulfite claims,description 6 0.000
polymerizing claims,description 5 0.000
sodium metabisulphite claims,description 5 0.000
Ammonium persulphate claims,description 4 0.000
Azobisisobutyronitrile claims,description 4 0.000
Sodium persulfate claims,description 4 0.000
atmosphere claims,description 4 0.000
copolymerization reaction claims,description 4 0.000
hydrogen peroxide claims,description 4 0.000
persulfate group claims,description 4 0.000
sulfuric acid derivatives claims,description 4 0.000
thermolysis claims,description 4 0.000
partition claims,description 3 0.000
2,5-Dimethylhexane claims,description 2 0.000
Iron(II) sulfate claims,description 2 0.000
Potassium persulfate claims,description 2 0.000
Potassium persulphate claims,description 2 0.000
Rongalite claims,description 2 0.000
Sodium sulfite claims,description 2 0.000
alkyl group claims,description 2 0.000
carbon atoms claims,description 2 0.000
ferrous sulphate claims,description 2 0.000
ferrous sulphate claims,description 2 0.000
gas claims,description 2 0.000
iron(II) sulfate claims,description 2 0.000
potassium persulphate claims,description 2 0.000
propan-2-yl (NE)-N-propan-2-yloxycarbonyliminocarbamate claims,description 2 0.000
reducing agent claims,description 2 0.000
sodium bisulfite claims,description 2 0.000
sodium hydrogen sulphite claims,description 2 0.000
Show all concepts from the description section
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4/6/23, 3:19 PM CN103788296A - Cationic polyacrylamide copolymer high-temperature resisting water-in-water dispersion and low-viscosity prepar…

Cationic polyacrylamide copolymer high-temperature resisting water-in-water dispersion and low-viscosity

2013-12-06 Application filed by Sobute New Materials Co Ltd,

2013-12-06 Priority to CN201310659587.2A

2014-05-14 Publication of CN103788296A

2016-04-27 Application granted

2016-04-27 Publication of CN103788296B

2033-12-06 Anticipated expiration

Info: Patent citations (4), Cited by (2), Legal events, Similar

External links: Espacenet, Global Dossier, Discuss

Claims (6) Hide Dependent

Seed polymer: account for the 1-10% of system total mass,

Water: surplus is water;

Divide phase reagent 15-37%,

Seed polymer 1-10%;

Summary of the invention

Seed polymer: account for the 1-10% of system total mass,

Water: surplus is water;

Divide phase reagent 15-37%,

Seed polymer 1-10%;

2amount, thus extrapolate double bond content and concentration:

" seed " internal double bond concentration

0.2mol &CenterDot; 𝐿-1 &times; time 1 / 2 - 0.1mol &CenterDot; 𝐿-1 &times;

Universal synthesis method:

time, stop heating, be cooled to 20 ℃, remove N 2protection, can obtain required

Synthesizing of table 1 stablizer (Stablizer, ST)

Synthesizing of continued 1 stablizer (Stablizer, ST)

Synthesizing of table 2 seed polymer (Seed Polymer, SP)

Synthesizing of continued 2 seed polymers (Seed Polymer, SP)

Synthesizing of table 3A cationic polyacrylamide water bag aqueous dispersions

Synthesizing of continued 3A cationic polyacrylamide water bag aqueous dispersions

a"-" refers to regulate pH.

Synthesizing of table 3C cationic polyacrylamide water bag aqueous dispersions

Synthesizing of continued 3C cationic polyacrylamide water bag aqueous dispersions

asT refers to Stablizer, stablizer; SP refers to Seed Polymer, seed polymer.

The sign of table 4 cationic polyacrylamide water bag aqueous dispersions

a"-" refers to regulate pH.

cfor redox system, this is oxidant constituents.

bthis is design reaction time

a"-" refers to measure.

b"-" refers to measure.

c"-" refers to be not suitable for store.

Patent Citations (4)

Publication number Priority date Publication date Assignee Title

CN101735388A * 2009-12-25 2010-06-16 同济大学 Preparation method of water-in-water cation polyacrylamide

Family To Family Citations

* Cited by examiner, † Cited by third party

Publication number Priority date Publication date Assignee Title

CN111533836A * 2020-05-13 2020-08-14 常州大学 Self-initiated free radical polymerization of N-isopropylacrylamide

Family To Family Citations

* Cited by examiner, † Cited by third party, ‡ Family to family citation

Publication Publication Date Title

CN102464781B 2013-02-27 Thermothickening terpolymer, its preparation method and application

CN103044622B 2015-01-07 Preparation method of water-in-water type cationic polyacrylamide emulsion

CN104356292B 2016-08-17 A kind of preparation method of PAMC aqueous emulsion product

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Priority Applications (1)

0.2mol · 𝐿-1 × time 1 / 2 - 0.1mol · 𝐿-1 ×