CN109824807A - The preparation method of seriation relative molecular mass and high monomer conversion ratio PDAC - Google Patents
The preparation method of seriation relative molecular mass and high monomer conversion ratio PDAC Download PDFInfo
- Publication number
- CN109824807A CN109824807A CN201910074984.0A CN201910074984A CN109824807A CN 109824807 A CN109824807 A CN 109824807A CN 201910074984 A CN201910074984 A CN 201910074984A CN 109824807 A CN109824807 A CN 109824807A
- Authority
- CN
- China
- Prior art keywords
- monomer
- pdac
- preparation
- polymerization
- relative molecular
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Abstract
The invention discloses the preparation methods of a kind of seriation relative molecular mass and high monomer conversion ratio PDAC.The method is using industrial goods DAC solution as raw material, under nitrogen atmosphere, the triallyl amine hydrochloride or its oligomer of the double bond containing end group that metal ion chelation agent and average degree of polymerization are 0~180 is added, monomer initial mass fraction range is 30.0%~60.0%, the mass fraction that corresponding water-soluble azo class initiator accounts for monomer is 0.85%~0.06%, caused by temperature programming, keep the temperature the mode of curing, obtain the incremental high monomer conversion ratio PDAC colloid product of seriation relative molecular mass, colloid product is through being granulated, fluidized bed drying, serial relative molecular mass is obtained with feature viscosmeter range as 2.00~14.00dL/g, it is stably and controllable, monomer conversion is 99.50% or more PDAC dry powder.
Description
Technical field
The present invention relates to the preparation technical fields of water-soluble cationic high-molecular compound, are related to a kind of opposite point of seriation
The aqueous solution polymerization preparation method of protonatomic mass and high monomer conversion ratio polyacrylamide oxy-ethyl-trimethyl salmiac (PDAC).
Background technique
Acrylyl oxy-ethyl-trimethyl salmiac (Acryloyloxyethyl trimethyl ammonium
Chloride, abbreviation DAC) it is a kind of water-soluble cationic monomer with specific function, contain vinyl group in molecule, it can
Carry out the homopolymerization of itself or the copolyreaction with other functional monomers.DAC generates homopolymer by Raolical polymerizable and gathers
Acrylyl oxy-ethyl-trimethyl salmiac (Poly acryloyloxyethyl trimethyl ammonium chloride, letter
Claim PDAC), reaction equation is as follows:
It is led using DAC as the polymer of base in the application such as oil exploitation, papermaking, household chemicals, biology, medicine and water process
Domain plays an important role, and annual requirement constantly increases.In the application process in these fields, for a long time, it is considered that,
After cellular construction determines, it is long that the product of different relative molecular masses (being indicated with feature viscosity) corresponds to different chain elements
Degree, to have different property and application function.Therefore, seriation relative molecular mass PDAC polymer is synthesized to meet not
The different demands that same domain applies different relative molecular mass DAC polymer industryizatioies are always the hot spot of the area research
And emphasis.However, the attention with modern economy society to the utilization of resources and environmental protection, in polymer, the residual of monomer is not only
Make the reduction of its utilization rate, and it does not play a role generally in the application, often remains on environment after use again, it is possible to cause
Different degrees of pollution.Therefore, for synthetic degree of angle, expire how to prepare the relative molecular mass adjustable homopolymer of series
Foot difference while needs of purposes, significantly improve monomer conversion in polymer, be the new hot spot of the area research and
Emphasis.
So far, it focuses mostly on by the Macroscopic single crystal technical study of base of DAC in copolymerization art, to its homopolymer PDAC
Study on Preparation document report it is less.Up to now representational research work is as follows.
Document 1 (development of Teng Xiaoxu low polymerization degree cationic polymer and its application Dalian [D] in salt-free dyeing
Polytechnics, 2011.) in order to obtain low polymerization degree cationic polymer PDAC, using composite initiator (ammonium persulfate and sulfurous
Sour hydrogen sodium), adjusting DAC monomer mass score is 65%, and appropriate initiator and a small amount of hydroquinone of polymerization retarder, initiation temperature is added
It is 60 DEG C, isothermal reaction 2h.Obtained polymerizate is dry under vacuum through dehydrated alcohol and acetone refining, has obtained faint yellow
PDAC solid.Colloid product eliminates some unreacted DAC monomers and oligomer, refined products warp in subtractive process
It is dried in vacuo and smashes into dry powder, measuring product PDAC relative molecular mass is 8.7 × 105(flow velocity 0.5mL/min, GPC survey
Examination), and its structure is characterized using infrared, nuclear-magnetism.The document is caused using high temperature, the technology mode of constant temperature polymerization, instead
It is shorter between seasonable, but to will lead to reaction rate in system too fast for high temperature initiation, is easy to happen implode, leads to its PDAC product phase
It is lower to molecular mass.In addition, the document does not study the synthesis technology of the PDAC of seriation relative molecular mass.
Document 2 (Ju Jiumei .DAC, DMC polymerization technology Primary Study [D] Institutes Of Technology Of Nanjing, 2013.) is to high phase
The synthesis technology of the PDAC of molecular mass is studied.It is with industrial goods acrylyl oxy-ethyl-trimethyl salmiac (DAC)
Raw material uses A for initiator, take initiator be added at one time-reaction process in the heating of point three steps polymerization reaction mode, it is right
Polymerization technology condition has carried out system optimization, has obtained the polymerization process condition for preparing higher relative molecular mass PDAC,
And each technological factor has been probed into the affecting laws of polymerization reaction.Gained colloid product PDAC highest feature k value is
7.42dL/g, average weight-molecular mass are 2.579 × l06, monomer conversion 93.56%.The document is heated up using three steps
Mode, react more steady, by improving temperature, promote initiator persistently to cause, the remnants in further consumption system are single
Body improves the feature viscosity and monomer conversion of product, and its feature k value is in existing document about PDAC preparation research
The peak of report.But the document does not study the PDAC of seriation feature viscosity high monomer conversion ratio.
(the Nanjing Primary Study [D] the science and engineering of Wang Minglong high and seriation relative molecular mass PDAC preparation process of document 3
University, 2017.) preparation process of seriation relative molecular mass PDAC is studied.Ammonium persulfate (APS) is used to draw
Agent is sent out, control monomer mass score (w (DAC)=25.0%~53.0%) and initiator amount (m (APS): m (DAC) are only passed through
=0.5%~15.0%), obtained monomer conversion greater than 98%, seriation feature viscosity is respectively 2.28,4.38,5.98,
8.17, the PDAC product of 10.05,12.49dL/g, while having obtained preparing the controllable PDAC polymerization technique of relative molecular mass.
The document obtains the colloid product of seriation feature viscosity PDAC by experimental study for the first time, and monomer conversion is higher.But
The polymerizate of the document is colloid, is unfavorable for storing and transport, while being glue using made from the polymerization technique of the document
Body product further increases monomer conversion and is restricted.
Above-mentioned research work focuses mostly in terms of the relative molecular mass for how improving PDAC product, only one pass
In the Study on Preparation of the relatively high monomer conversion ratio PDAC product of seriation relative molecular mass.DAC homopolymerization is one
Via chain reaction rapid growth and the polymerization reaction that there is autoacceleration to be inclined to, how by the design of polymerization technology mode and
The adequacy of process conditions selected to guarantee the steady of polymerization system and reaction is the greatest problem that researcher faces.For a long time with
Coming, those skilled in the art have been devoted to the bottleneck that research overcomes problem, but are improving its relative molecular mass so far,
Lasting in-depth study report is had no in terms of especially preparing high monomer conversion ratio and serial fluidized polymer.Its reason may be existing
With the presence of the following defect of technique.
(1) the polymerization technology mode of constant temperature polymerization is used, system heat release cannot scatter in time in reaction process, polymerize
Reaction rate is unstable, is easy to produce implode, causes product PDAC feature k value low, and residual monomer content is high, i.e., monomer turns
Rate is low, needs to be eluted with organic solvent before use, a kind of feature viscosity products is only obtained, such as document 1；
(2) polymerization reaction of PDAC from constant temperature polymerize change three steps heating, it can be achieved that reaction system segmentation cause and polymerization,
Promote initiator persistently to cause, further consumes residual monomer, improve the feature viscosity and monomer conversion of product；But not
Have and seriation regulation is carried out to relative molecular mass and improves the research of monomer conversion, such as document 2；
(3) initiator ammonium persulfate generates acidic components after causing and decomposing, and reduces reacting liquid pH value, can automatically speed up
The initiation of ammonium persulfate keeps elicitation procedure unstable, to limit the control of feature viscosity stablization and monomer conversion of polymer
Rate further improves, such as document 3；
(4) up to now, there is not yet having seriation relative molecular mass (expression of available feature viscosity) stably and controllable
The report of the PDAC power-product new preparation process high with monomer conversion.For example, document 1,2 and 3.
Drawbacks described above causes up to now, to be difficult to make existing seriation relative molecular mass by prior art method
PDAC product further increases monomer conversion ratio, and corresponding products obtained therefrom is unfavorable for storage transport, application.
Summary of the invention
The purpose of the present invention is to provide a kind of simple and stables, quality controllable seriation relative molecular mass and high monomer
The aqueous solution polymerization preparation method of conversion ratio PDAC.
The technical solution for realizing the aim of the invention is as follows:
The preparation method of seriation relative molecular mass and high monomer conversion ratio PDAC, the specific steps are as follows:
Using industrial goods DAC monomer solution as raw material, under nitrogen atmosphere, it is 0~180 containing end group pair that average degree of polymerization, which is added,
The triallyl amine hydrochloride of key or its oligomer, make it account for monomer mass score 0.1%~5.0%, and metal ion is added
Chelating agent and the water-soluble azo class initiator for accounting for monomer mass score 0.06%~0.85%；Adjust monomer initial mass score
It is 30.0%~60.0%；It is uniformly mixed, heats reaction solution, heated up using two steps, temperature is respectively 35~45 DEG C and 55
~65 DEG C, heat preservation polymerization, obtain PDAC colloid product, colloid through crush be granulated, drying, obtain seriation relative molecular mass and
The PDAC dry powder of high monomer conversion ratio.
The metal ion chelation agent is tetrasodium ethylenediamine tetraacetate or disodium ethylene diamine tetraacetate, accounts for monomer mass
Score 0.005%~0.030%.
The water-soluble azo class initiator is selected from two isobutyl imidazoles of azo diisobutyl amidine hydrochloride (V50) or azo
Quinoline hydrochloride (VA044).
The heat preservation polymerization time of the two steps heating is 3.0 ± 0.5h.
The drying is to dry in 70~110 DEG C of fluidized bed at elevated.
The drying time is 1.0 ± 0.5h.
Compared with prior art, the present invention its remarkable advantage is:
(1) preparation of seriation relative molecular mass and high monomer conversion ratio PDAC: according to kinetic chain length equation (see formula
1) (" Chemistry and Physics of Polymers basis ", Wei Wuji, Yu Qiang, Cui Yihua chief editor, 2011 editions) calculates it is found that obtaining for opposite
The synthesis of the incremental polymer of molecular mass series, there are following relationships for monomer and initiator concentration: when the phase for requiring polymer
Molecular mass is incremented by, i.e., average degree of polymerization is incremented by 1.60~1.25 times, when kinetic chain length is also incremented by 1.60~1.25 times, such as
Fruit regulates and controls monomer concentration and is incremented by (13 ± 3) %, corresponding initiator concentration successively decrease 50%~18% when, can get opposite point of seriation
The polymerizate of protonatomic mass and high monomer conversion ratio.And for seriation relative molecular mass and high monomer conversion ratio PDAC and
Speech, when feature viscosity is incremented by between 2.00~8.00dL/g, regulation monomer initial mass score is incremented by (13 ± 3) %, together
Step initiator accounts for monomer weight ratio and successively decreases 50%~35%；When feature viscosity 8.00~14.00dL/g (not including 8.00) it
Between when being incremented by, regulation monomer initial mass score is incremented by (13 ± 3) %, synchronous initiator account for monomer weight ratio successively decrease 30%~
18%.Therefore, being tested a point exploration can obtain, and when selecting monomer mass score to rise to 60.0% from 30.0%, draw accordingly
Hair agent accounts for monomer weight ratio and is reduced to 0.06% from 0.85%；In conjunction with the optimization choosing of polymerization technology Conditions Temperature, time
It selects, so that realizing series of features viscosity range is the target of 2.00~14.00dL/g, monomer conversion greater than 99.50%
The preparation of PDAC product.The preparation of the high monomer conversion ratio PDAC product of seriation relative molecular mass can be such that its raw material utilizes
Rate significantly improves, and the scope of application has biggish expansion, can be more broadly used for oil exploitation, papermaking, mining, textile printing and dyeing,
The multiple fields such as daily-use chemical industry and water process, and high monomer conversion ratio (residual monomer is few) is again unique to the offer of seriation product
Environmental-friendly property.
(2) present invention makes it at low temperature using the addition of the compound of the weak double bond containing end group of reactivity, and stabilization is deposited
, do not influence to start the process in fast reaction stage when polymerization reaction, and reaction can be participated under subsequent high temperature, it is especially dry
It in the dry stage, is equivalent to and joined chain extender, be easily attached residual monomer and polymer, offset feature viscosity caused by high temperature degradation
Loss.The compound of the double bond containing end group can more fully play its above-mentioned effect in process conditions of the invention, thus into
One step improves the feature viscosity of polymer P DAC, improves monomer conversion.
(3) azo initiator is used, acidic components are generated after avoiding persulfate initiator from causing decomposition, make reaction solution pH
Value reduces, and automatically speeds up the deficiency for keeping elicitation procedure unstable, is that feature viscosity and the monomer conversion of polymer are further
Raising, which is established, stablizes initiation, guarantees the relatively stable basis of reaction.
(4) target of the present invention is with seriation relative molecular mass (expression of available feature viscosity) stably and controllable and monomer
The PDAC power-product new preparation process of high conversion rate.Power-product, not only monomer conversion is high, and convenient for long-distance transport and
Long term storage.
Specific embodiment
Technical solution of the present invention is described below with reference to embodiment.
Embodiment 1
The monomer for the DAC monomer that content (based on mass fraction, similarly hereinafter) is 75% is added in the first step in polymer reactor
Aqueous solution, lead to nitrogen gas stirring under the conditions of, sequentially add average degree of polymerization be 180, account for monomer mass score be (5.00 ±
0.01) the triallyl amine hydrochloride homopolymer of % accounts for the metal-chelator second that monomer weight ratio is (0.030 ± 0.005) %
Four sodium solution of ethylenediamine tetraacetic acid (EDTA) and account for monomer weight ratio be (0.85 ± 0.05) % two isobutyl imidazoline hydrochloride of azo
(VA044) initiator solution adds distilled water, obtains the reaction solution that monomer mass score is (30.0 ± 2.0) %；
Second step, heat temperature raising reaction solution to initiation temperature (35 ± 2) DEG C keep the temperature polymerization reaction (3.0 ± 0.5) h；
Third step reheats temperature reaction system to polymerization temperature (55 ± 2) DEG C, keeps the temperature polymerization reaction (3.0 ± 0.5) h,
Stop heating；
Reaction product through two-step reaction is discharged, obtains PDAC colloid product by the 4th step.Then, colloid is made through crushing
Grain dries (1.0 ± 0.5) h on (70 ± 5) DEG C fluidized bed at elevated, obtains PDAC dry powder, in 1.0mol/L NaCl solution,
Determination of ubbelohde viscometer is used at (30.0 ± 0.1) DEG C, is acquired feature viscosity and is 2.08dL/g, measures residual double bonds with bromination method,
Acquiring monomer conversion is 99.56%.
Embodiment 2
The monomer solution for the DAC monomer that content is 80% is added in the first step in polymer reactor, leads to nitrogen gas stirring item
Under part, sequentially adding average degree of polymerization is 140, accounts for the triallyl amine hydrochloride that monomer mass score is (4.50 ± 0.01) %
Homopolymer accounts for metal-chelator disodium ethylene diamine tetra-acetic acid solution and Zhan Danti that monomer weight ratio is (0.010 ± 0.005) %
Mass ratio is azo two isobutyl imidazoline hydrochloride (VA044) initiator solution of (0.43 ± 0.05) %, adds distilled water, obtains
Monomer mass score is the reaction solution of (35.0 ± 2.0) %；
Second step, heat temperature raising reaction solution to initiation temperature (35 ± 2) DEG C keep the temperature polymerization reaction (3.0 ± 0.5) h；
Third step reheats temperature reaction system to polymerization temperature (60 ± 2) DEG C, keeps the temperature polymerization reaction (3.0 ± 0.5) h,
Stop heating；
Reaction product through two-step reaction is discharged, obtains PDAC colloid product by the 4th step.Then, colloid is made through crushing
Grain dries (1.0 ± 0.5) h on (90 ± 5) DEG C fluidized bed at elevated, obtains PDAC dry powder, in 1.0mol/L NaCl solution,
Determination of ubbelohde viscometer is used at (30.0 ± 0.1) DEG C, is acquired feature viscosity and is 3.95dL/g, measures residual double bonds with bromination method,
Acquiring monomer conversion is 99.60%.
Embodiment 3
The monomer solution for the DAC monomer that content is 80% is added in the first step in polymer reactor, leads to nitrogen gas stirring item
Under part, sequentially adding average degree of polymerization is 60, accounts for the triallyl amine hydrochloride that monomer mass score is (3.20 ± 0.01) %
Homopolymer accounts for metal-chelator disodium ethylene diamine tetra-acetic acid solution and Zhan Danti that monomer weight ratio is (0.010 ± 0.005) %
Mass ratio is azo two isobutyl imidazoline hydrochloride (VA044) initiator solution of (0.25 ± 0.05) %, adds distilled water, obtains
Monomer mass score is the reaction solution of (40.0 ± 2.0) %；
Second step, heat temperature raising reaction solution to initiation temperature (35 ± 2) DEG C keep the temperature polymerization reaction (3.0 ± 0.5) h；
Third step reheats temperature reaction system to polymerization temperature (60 ± 2) DEG C, keeps the temperature polymerization reaction (3.0 ± 0.5) h,
Stop heating；
Reaction product through two-step reaction is discharged, obtains PDAC colloid product by the 4th step.Then, colloid is made through crushing
Grain dries (1.0 ± 0.5) h on (90 ± 5) DEG C fluidized bed at elevated, obtains PDAC dry powder, in 1.0mol/L NaCl solution,
Determination of ubbelohde viscometer is used at (30.0 ± 0.1) DEG C, is acquired feature viscosity and is 5.85dL/g, measures residual double bonds with bromination method,
Acquiring monomer conversion is 99.75%.
Embodiment 4
The monomer solution for the DAC monomer that content is 80% is added in the first step in polymer reactor, leads to nitrogen gas stirring item
Under part, sequentially adding average degree of polymerization is 20, accounts for the triallyl amine hydrochloride that monomer mass score is (1.50 ± 0.01) %
Homopolymer accounts for metal-chelator disodium ethylene diamine tetra-acetic acid solution and Zhan Danti that monomer weight ratio is (0.015 ± 0.005) %
Mass ratio is azo two isobutyl imidazoline hydrochloride (VA044) initiator solution of (0.16 ± 0.05) %, adds distilled water, obtains
Monomer mass score is the reaction solution of (45.0 ± 2.0) %；
Second step, heat temperature raising reaction solution to initiation temperature (35 ± 2) DEG C keep the temperature polymerization reaction (3.0 ± 0.5) h；
Third step reheats temperature reaction system to polymerization temperature (60 ± 2) DEG C, keeps the temperature polymerization reaction (3.0 ± 0.5) h,
Stop heating；
Reaction product through two-step reaction is discharged, obtains PDAC colloid product by the 4th step.Then, colloid is made through crushing
Grain dries (1.0 ± 0.5) h on (100 ± 5) DEG C fluidized bed at elevated, obtains PDAC dry powder, in 1.0mol/L NaCl solution,
Determination of ubbelohde viscometer is used at (30.0 ± 0.1) DEG C, is acquired feature viscosity and is 8.01dL/g, measures residual double bonds with bromination method,
Acquiring monomer conversion is 99.66%.
Embodiment 5
The monomer solution for the DAC monomer that content is 80% is added in the first step in polymer reactor, leads to nitrogen gas stirring item
Under part, sequentially adding average degree of polymerization is 10, accounts for the triallyl amine hydrochloride that monomer mass score is (0.85 ± 0.01) %
Homopolymer accounts for metal-chelator disodium ethylene diamine tetra-acetic acid solution and Zhan Danti that monomer weight ratio is (0.020 ± 0.005) %
Mass ratio is azo diisobutyl amidine hydrochloride (V50) initiator solution of (0.11 ± 0.05) %, adds distilled water, obtains monomer
Mass fraction is the reaction solution of (50.0 ± 2.0) %；
Second step, heat temperature raising reaction solution to initiation temperature (45 ± 2) DEG C keep the temperature polymerization reaction (3.0 ± 0.5) h；
Third step reheats temperature reaction system to polymerization temperature (65 ± 2) DEG C, keeps the temperature polymerization reaction (3.0 ± 0.5) h,
Stop heating；
Reaction product through two-step reaction is discharged, obtains PDAC colloid product by the 4th step.Then, colloid is made through crushing
Grain dries (1.0 ± 0.5) h on (100 ± 5) DEG C fluidized bed at elevated, obtains PDAC dry powder, in 1.0mol/L NaCl solution,
Determination of ubbelohde viscometer is used at (30.0 ± 0.1) DEG C, is acquired feature viscosity and is 10.05dL/g, measures residual double bonds with bromination method,
Acquiring monomer conversion is 99.76%.
Embodiment 6
The monomer solution for the DAC monomer that content is 80% is added in the first step in polymer reactor, leads to nitrogen gas stirring item
Under part, sequentially adding average degree of polymerization is 5, and it is equal to account for the triallyl amine hydrochloride that monomer mass score is (0.10 ± 0.01) %
Polymers accounts for metal-chelator disodium ethylene diamine tetra-acetic acid solution and account for monomer matter that monomer weight ratio is (0.005 ± 0.005) %
Amount adds distilled water, obtains monomer matter than azo diisobutyl amidine hydrochloride (V50) initiator solution for being (0.08 ± 0.05) %
Measure the reaction solution that score is (55.0 ± 2.0) %；
Second step, heat temperature raising reaction solution to initiation temperature (45 ± 2) DEG C keep the temperature polymerization reaction (3.0 ± 0.5) h；
Third step reheats temperature reaction system to polymerization temperature (65 ± 2) DEG C, keeps the temperature polymerization reaction (3.0 ± 0.5) h,
Stop heating；
Reaction product through two-step reaction is discharged, obtains PDAC colloid product by the 4th step.Then, colloid is made through crushing
Grain dries (1.0 ± 0.5) h on (110 ± 5) DEG C fluidized bed at elevated, obtains PDAC dry powder, in 1.0mol/L NaCl solution,
Determination of ubbelohde viscometer is used at (30.0 ± 0.1) DEG C, is acquired feature viscosity and is 12.29dL/g, measures residual double bonds with bromination method,
Acquiring monomer conversion is 99.84%.
Embodiment 7
The monomer solution for the DAC monomer that content is 85% is added in the first step in polymer reactor, leads to nitrogen gas stirring item
Under part, sequentially adding average degree of polymerization is 0, accounts for the triallyl amine hydrochloride that monomer mass score is (0.10 ± 0.01) %,
Account for the metal-chelator disodium ethylene diamine tetra-acetic acid solution and account for monomer weight ratio that monomer weight ratio is (0.005 ± 0.005) %
For azo diisobutyl amidine hydrochloride (V50) initiator solution of (0.06 ± 0.05) %, add distilled water, obtains monomer mass point
Number is the reaction solution of (60.0 ± 2.0) %；
Second step, heat temperature raising reaction solution to initiation temperature (45 ± 2) DEG C keep the temperature polymerization reaction (3.0 ± 0.5) h；
Third step reheats temperature reaction system to polymerization temperature (65 ± 2) DEG C, keeps the temperature polymerization reaction (3.0 ± 0.5) h,
Stop heating；
Reaction product through two-step reaction is discharged, obtains PDAC colloid product by the 4th step.Then, colloid is made through crushing
Grain dries (1.0 ± 0.5) h on (110 ± 5) DEG C fluidized bed at elevated, obtains PDAC dry powder, in 1.0mol/L NaCl solution,
Determination of ubbelohde viscometer is used at (30.0 ± 0.1) DEG C, is acquired feature viscosity and is 14.00dL/g, measures residual double bonds with bromination method,
Acquiring monomer conversion is 99.63%.
Comparative example 1
This comparative example is substantially the same manner as Example 5, it is unique unlike the triallyl amine hydrochloride homopolymer that is added
Average degree of polymerization is 320, the specific steps are as follows:
The monomer solution for the DAC monomer that content is 80% is added in the first step in polymer reactor, leads to nitrogen gas stirring item
Under part, sequentially adding average degree of polymerization is 320, accounts for the triallyl amine hydrochloride that monomer mass score is (0.85 ± 0.01) %
Homopolymer accounts for metal-chelator disodium ethylene diamine tetra-acetic acid solution and Zhan Danti that monomer weight ratio is (0.020 ± 0.005) %
Mass ratio is azo diisobutyl amidine hydrochloride (V50) initiator solution of (0.11 ± 0.05) %, adds distilled water, obtains monomer
Mass fraction is the reaction solution of (50.0 ± 2.0) %；
Second step, heat temperature raising reaction solution to initiation temperature (45 ± 2) DEG C keep the temperature polymerization reaction (3.0 ± 0.5) h；
Third step reheats temperature reaction system to polymerization temperature (65 ± 2) DEG C, keeps the temperature polymerization reaction (3.0 ± 0.5) h,
Stop heating；
Reaction product through two-step reaction is discharged, obtains PDAC colloid product by the 4th step.Then, colloid is made through crushing
Grain dries (1.0 ± 0.5) h on (100 ± 5) DEG C fluidized bed at elevated, obtains PDAC dry powder, in 1.0mol/L NaCl solution,
Determination of ubbelohde viscometer is used at (30.0 ± 0.1) DEG C, is acquired feature viscosity and is 5.69dL/g, measures residual double bonds with bromination method,
Acquiring monomer conversion is 98.07%.
Comparative example 2
This comparative example is substantially the same manner as Example 6, unique the difference is that the triallyl amine hydrochloride homopolymer being added accounts for
Monomer weight ratio is (8.00 ± 0.01) %, the specific steps are as follows:
The monomer solution for the DAC monomer that content is 80% is added in the first step in polymer reactor, leads to nitrogen gas stirring item
Under part, sequentially adding average degree of polymerization is 5, and it is equal to account for the triallyl amine hydrochloride that monomer mass score is (8.00 ± 0.01) %
Polymers accounts for metal-chelator disodium ethylene diamine tetra-acetic acid solution and account for monomer matter that monomer weight ratio is (0.005 ± 0.005) %
Amount adds distilled water, obtains monomer matter than azo diisobutyl amidine hydrochloride (V50) initiator solution for being (0.08 ± 0.05) %
Measure the reaction solution that score is (55.0 ± 2.0) %；
Second step, heat temperature raising reaction solution to initiation temperature (45 ± 2) DEG C keep the temperature polymerization reaction (3.0 ± 0.5) h；
Third step reheats temperature reaction system to polymerization temperature (65 ± 2) DEG C, keeps the temperature polymerization reaction (3.0 ± 0.5) h,
Stop heating；
Reaction product through two-step reaction is discharged, obtains PDAC colloid product by the 4th step.Then, colloid is made through crushing
Grain dries (1.0 ± 0.5) h on (110 ± 5) DEG C fluidized bed at elevated, obtains PDAC dry powder, in 1.0mol/L NaCl solution,
Determination of ubbelohde viscometer is used at (30.0 ± 0.1) DEG C, is acquired feature viscosity and is 7.12dL/g, measures residual double bonds with bromination method,
Acquiring monomer conversion is 98.92%.
Comparative example 3
This comparative example is substantially the same manner as Example 7, it is unique unlike the triallyl amine hydrochloride that is added without or its
Polymers, the specific steps are as follows:
The monomer solution for the DAC monomer that content is 85% is added in the first step in polymer reactor, leads to nitrogen gas stirring item
Under part, sequentially add account for monomer weight ratio be (0.005 ± 0.005) % metal-chelator disodium ethylene diamine tetra-acetic acid solution and
Azo diisobutyl amidine hydrochloride (V50) initiator solution that monomer weight ratio is (0.06 ± 0.05) % is accounted for, adds distilled water, obtains
The reaction solution for being (60.0 ± 2.0) % to monomer mass score；
Second step, heat temperature raising reaction solution to initiation temperature (45 ± 2) DEG C keep the temperature polymerization reaction (3.0 ± 0.5) h；
Third step reheats temperature reaction system to polymerization temperature (65 ± 2) DEG C, keeps the temperature polymerization reaction (3.0 ± 0.5) h,
Stop heating；
Reaction product through two-step reaction is discharged, obtains PDAC colloid product by the 4th step.Then, colloid is made through crushing
Grain dries (1.0 ± 0.5) h on (110 ± 5) DEG C fluidized bed at elevated, obtains PDAC dry powder, in 1.0mol/L NaCl solution,
Determination of ubbelohde viscometer is used at (30.0 ± 0.1) DEG C, is acquired feature viscosity and is 10.37dL/g, measures residual double bonds with bromination method,
Acquiring monomer conversion is 98.13%.
Claims (7)
1. the preparation method of seriation relative molecular mass and high monomer conversion ratio PDAC, which is characterized in that specific step is as follows:
Using industrial goods DAC monomer solution as raw material, under nitrogen atmosphere, the double bond containing end group that average degree of polymerization is 0~180 is added
Triallyl amine hydrochloride or its oligomer, make it account for monomer mass score 0.1%~5.0%, and metal ion-chelant is added
Agent and the water-soluble azo class initiator for accounting for monomer mass score 0.06%~0.85%；Adjusting monomer initial mass score is
30.0%~60.0%；It being uniformly mixed, heats reaction solution, heated up using two steps, temperature is respectively 35~45 DEG C and 55~
65 DEG C, heat preservation polymerization obtains PDAC colloid product, and colloid is granulated through crushing, and drying obtains seriation relative molecular mass and height
The PDAC dry powder of monomer conversion.
2. preparation method according to claim 1, which is characterized in that the metal ion chelation agent is ethylenediamine tetrem
Sour four sodium or disodium ethylene diamine tetraacetate.
3. preparation method according to claim 1, which is characterized in that the metal ion chelation agent accounts for monomer mass point
Number 0.005%~0.030%.
4. preparation method according to claim 1, which is characterized in that the water-soluble azo class initiator is selected from azo
Two isobutyl imidazoline hydrochloride of diisobutyl amidine hydrochloride or azo.
5. preparation method according to claim 1, which is characterized in that the heat preservation polymerization time of the described two steps heating is
3.0±0.5h。
6. preparation method according to claim 1, which is characterized in that the drying is in 70~110 DEG C of fluidized bed at elevated
Drying.
7. preparation method according to claim 1, which is characterized in that the drying time is 1.0 ± 0.5h.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910074984.0A CN109824807B (en) | 2019-01-25 | 2019-01-25 | Preparation method of PDAC (polymer dispersed acrylate) with serialized relative molecular mass and high monomer conversion rate |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910074984.0A CN109824807B (en) | 2019-01-25 | 2019-01-25 | Preparation method of PDAC (polymer dispersed acrylate) with serialized relative molecular mass and high monomer conversion rate |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN109824807A true CN109824807A (en) | 2019-05-31 |
| CN109824807B CN109824807B (en) | 2021-02-12 |
Family
ID=66862434
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201910074984.0A Active CN109824807B (en) | 2019-01-25 | 2019-01-25 | Preparation method of PDAC (polymer dispersed acrylate) with serialized relative molecular mass and high monomer conversion rate |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN109824807B (en) |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1675256A (en) * | 2002-08-15 | 2005-09-28 | 西巴特殊化学水处理有限公司 | High molecular weight cationic polymers obtained by post-polymerization crosslinking reaction |
| CN105017453A (en) * | 2014-04-30 | 2015-11-04 | 南京理工大学 | Preparing method for PDMC with high monomer conversion rate and serialized relative molecular mass |
| CN108329421A (en) * | 2018-01-02 | 2018-07-27 | 江苏富淼科技股份有限公司 | A kind of emulsifier for alkenyl succinic anhydride emulsification |
-
2019
- 2019-01-25 CN CN201910074984.0A patent/CN109824807B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1675256A (en) * | 2002-08-15 | 2005-09-28 | 西巴特殊化学水处理有限公司 | High molecular weight cationic polymers obtained by post-polymerization crosslinking reaction |
| CN105017453A (en) * | 2014-04-30 | 2015-11-04 | 南京理工大学 | Preparing method for PDMC with high monomer conversion rate and serialized relative molecular mass |
| CN105017453B (en) * | 2014-04-30 | 2017-08-04 | 南京理工大学 | The preparation method of high monomer conversion ratio and seriation relative molecular mass PDMC |
| CN108329421A (en) * | 2018-01-02 | 2018-07-27 | 江苏富淼科技股份有限公司 | A kind of emulsifier for alkenyl succinic anhydride emulsification |
Non-Patent Citations (2)
| Title |
|---|
| 唐莉: ""高且系列化相对分子质量PDMC制备工艺的初步研究"", 《中国优秀硕士论文全文数据库》 * |
| 王明龙: ""高且系列化相对分子质量PDAC制备工艺的初步研究"", 《中国优秀硕士论文全文数据库》 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN109824807B (en) | 2021-02-12 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US3804881A (en) | Polymerization using varying monomer concentration | |
| EP2555921B1 (en) | Regulated and continuous polymerization of polycarboxylic acid monomers | |
| CZ293475B6 (en) | Method of preparing a branched polymer, the branched polymer per se and articles produced therefrom | |
| Chernykh et al. | Living carbocationic polymerization of a vinyl ether monomer derived from soybean oil, 2-(vinyloxy) ethyl soyate | |
| CN102443090A (en) | Synthetic method for fluororubber | |
| CN105061774B (en) | A kind of paper making intensifier and preparation method thereof | |
| CN105017453B (en) | The preparation method of high monomer conversion ratio and seriation relative molecular mass PDMC | |
| CN114524929A (en) | Preparation method of carbon dioxide-based quadripolymer | |
| CN105801831B (en) | A kind of unsaturated quaternary ammonium salt polyethers, preparation method and applications | |
| US3352838A (en) | Methylolated urea and melamine etherified with butanol and polyethyleneglycol as emulsion polymerization agents | |
| US3280218A (en) | Graft polymers of ethylenimine onto a polyacrylic or polymethacrylic acid backbone | |
| CN109824807A (en) | The preparation method of seriation relative molecular mass and high monomer conversion ratio PDAC | |
| US2878237A (en) | Mercapto dibasic acids as regulators for the polymerization of acrylic acids, amidesand salts | |
| US2640819A (en) | Process for polymerizing styrene and maleic compounds | |
| CN103304714A (en) | Preparation method of instant ultra-high molecular weight polyacrylamide dry powder | |
| US5629395A (en) | Process for producing cross-linked polymer containing carboxyl group | |
| CN109763380B (en) | Wet strength agent for papermaking and preparation method thereof | |
| CN108864345A (en) | A kind of synthetic method of Ultra-low molecular weight polyvinyl alcohol | |
| CN109897142A (en) | A kind of hyperbranched cationic polymer emulsion and its application in sludge dewatering | |
| CN109135712A (en) | A kind of shale gas fracturing fluid instant water-in-water emulsion friction reducer and preparation method thereof | |
| US6828393B1 (en) | Rate matched copolymerization | |
| CN109880004A (en) | The preparation method of high molecular weight polypropylene acyloxyethyl trimethyl ammonium chloride | |
| CN105949365B (en) | A kind of pearl hyperviscosity water-soluble cationic polymer and preparation method thereof | |
| CN1146579C (en) | Process for preparing water-soluble styrenelacrylic resins by continuous bulk polymerization | |
| CN106279468A (en) | Inverse emulsion polymerization method and for its surface activator composition |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |