CN109824807B - Preparation method of PDAC (polymer dispersed acrylate) with serialized relative molecular mass and high monomer conversion rate - Google Patents
Preparation method of PDAC (polymer dispersed acrylate) with serialized relative molecular mass and high monomer conversion rate Download PDFInfo
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Abstract
The invention discloses a preparation method of PDAC with serialized relative molecular mass and high monomer conversion rate. The method comprises the steps of taking an industrial product DAC solution as a raw material, adding a metal ion chelating agent and triallylamine hydrochloride containing terminal group double bonds or oligomer thereof with the average polymerization degree of 0-180 in a nitrogen atmosphere, wherein the initial mass fraction range of a monomer is 30.0-60.0%, the mass fraction of a corresponding water-soluble azo initiator in the monomer is 0.85-0.06%, obtaining a series PDAC colloidal product with high monomer conversion rate and incremental relative molecular mass through temperature programming initiation and heat preservation curing, granulating the colloidal product, drying by a fluidized bed, obtaining a series PDAC dry powder with the relative molecular mass of 2.00-14.00 dL/g in a characteristic viscosity meter range, and achieving stability and controllability, and the monomer conversion rate of more than 99.50%.
Description
Technical Field
The invention relates to the technical field of preparation of water-soluble cationic high molecular compounds, and relates to a preparation method of polyacrylic acid oxyethyl trimethyl ammonium chloride (PDAC) by aqueous solution polymerization with serialized relative molecular mass and high monomer conversion rate.
Background
Acryloxyethyltrimethyl ammonium chloride (DAC) is a water-soluble cationic monomer with special function, contains vinyl groups in the molecule, and can perform self homopolymerization or copolymerization with other functional monomers. DAC generates homopolymer Poly (acryloxyethyltrimethyl ammonium chloride, PDAC) through free radical polymerization, and the reaction equation is as follows:
DAC-based polymers play an important role in the application fields of oil exploitation, paper making, daily chemicals, biology, medicine, water treatment and the like, and the annual demand is increasing continuously. In the course of their use in these fields, it has long been recognized that, when the unit structure is determined, products of different relative molecular masses (expressed as the characteristic viscosity) correspond to different molecular chain lengths and thus have different properties and application functions. Therefore, synthesizing a series of relative molecular mass PDAC polymers to meet different requirements of different fields for industrial application of DAC polymers with different relative molecular masses is always a focus and focus of research in the field. However, with the importance of resource utilization and environmental protection in modern economic society, the residual monomer in the polymer not only reduces the utilization rate, but also does not play a role in application, and is often left in the environment after use, possibly causing pollution to various degrees. Therefore, in terms of synthesis angle, how to prepare homopolymer with adjustable relative molecular mass series to meet the requirements of different applications and simultaneously remarkably improve the monomer conversion rate in the polymer is already a new focus and focus of research in the field.
So far, the research on the synthesis process of DAC-based polymers has mostly focused on the copolymerization field, and the research literature on the preparation process of the homopolymer PDAC is less reported. Typical research work to date is as follows.
Reference 1 (praise for Asahi. Low polymerization cationic Polymer development and its use in salt-free dyeing [ D]University of general engineering, 2011.) to obtain a low-polymerization-degree cationic polymer PDAC, a composite initiator (ammonium persulfate and sodium bisulfite) is adopted, the mass fraction of DAC monomer is adjusted to 65%, an appropriate amount of initiator and a small amount of polymerization inhibitor hydroquinone are added, the initiation temperature is 60 ℃, and the constant temperature reaction is carried out for 2 hours. The obtained polymerization product was refined with absolute ethanol and acetone, and dried under vacuum to obtain a pale yellow PDAC solid. The colloidal product was refined to remove some unreacted DAC monomers and oligomers, the refined product was vacuum dried and pulverized to a dry powder, and the product PDAC was found to have a relative molecular mass of 8.7X 105(flow rate 0.5mL/min, GPC measurement), and the structure is characterized by infrared and nuclear magnetism. The document adopts a process mode of high-temperature initiation and constant-temperature polymerization, the reaction time is short, but the high-temperature initiation can cause the reaction rate in a system to be too fast and easy to implode, so that the relative molecular mass of a PDAC product is low. In addition, the document does not investigate the synthesis process of PDAC that serializes relative molecular mass.
Literature reference2 (Jujimei, DAC, DMC polymerization preliminary research [ D)]University of Nanjing physiologist, 2013.) studied the synthesis process of PDAC of high relative molecular mass. The method is characterized in that industrial acryloyloxyethyl trimethyl ammonium chloride (DAC) is used as a raw material, A is used as an initiator, the initiator is added at one time, and a polymerization reaction mode of heating in three steps in the reaction process is adopted, so that the polymerization reaction process conditions are optimized systematically, the polymerization process conditions for preparing PDAC with high relative molecular mass are obtained, and the influence rule of each process factor on the polymerization reaction is explored. The resulting colloidal product PDAC had a maximum intrinsic viscosity of 7.42dL/g and a weight average relative molecular mass of 2.579 xl 06The monomer conversion was 93.56%. The document adopts a three-step heating mode, the reaction is relatively stable, the continuous initiation of an initiator is promoted by increasing the temperature, the residual monomers in a system are further consumed, the characteristic viscosity and the monomer conversion rate of a product are improved, and the characteristic viscosity value is the highest value reported in the existing document on PDAC preparation research. However, this document does not address the study of a PDAC with high monomer conversion for a range of intrinsic viscosities.
Document 3 (a preliminary study of a high and serialized relative molecular mass PDAC preparation process [ D ]. university of tokyo physical engineering, 2017.) studies on a preparation process of a serialized relative molecular mass PDAC. By using Ammonium Persulfate (APS) as an initiator and only controlling the mass fraction (w (DAC): 25.0-53.0%) of the monomer and the amount (m (APS): m (DAC): 0.5-15.0%), PDAC products with the monomer conversion rate of more than 98% and the serial characteristic viscosities of 2.28, 4.38, 5.98, 8.17, 10.05 and 12.49dL/g are obtained, and a polymerization process for preparing PDAC with controllable relative molecular mass is also obtained. The reference obtains a colloidal product of a series of PDACs with characteristic viscosity for the first time through experimental study, and the monomer conversion rate is high. However, the polymerization product of this document is colloidal, which is disadvantageous in storage and transportation, and the polymerization process of this document produces a colloidal product, which is limited in further improvement of the monomer conversion.
The above-described research efforts have focused on how to increase the relative molecular mass of the PDAC product, and there is only one research on the preparation process of PDAC products with higher monomer conversion to range the relative molecular mass. DAC homopolymerization is a polymerization reaction which rapidly grows through a chain reaction and tends to self-accelerate, and how to ensure the smoothness of a polymerization system and the sufficiency of the reaction through the design of a polymerization reaction process mode and the selection of process conditions is the biggest problem faced by researchers. For a long time, the skilled person has been working on overcoming this bottleneck problem, but to date there has been no continuous and intensive research report on improving the relative molecular mass, in particular the preparation of high monomer conversions and the serialization of polymers. The reason for this may be that the existing processes have the following drawbacks.
(1) By adopting a polymerization reaction process mode of constant-temperature polymerization, the system heat release cannot be dispersed in time in the reaction process, the polymerization reaction rate is not stable, implosion is easy to generate, the product PDAC has low characteristic viscosity value and high residual monomer content, namely the monomer conversion rate is low, an organic solvent is required to elute before use, and only one characteristic viscosity product is obtained, as in document 1;
(2) the polymerization reaction of PDAC changes three-step temperature rise from constant temperature polymerization, can realize the staged initiation and polymerization of a reaction system, promote the continuous initiation of an initiator, further consume residual monomers, and improve the characteristic viscosity and the monomer conversion rate of a product; however, there is no study on the serial regulation of relative molecular mass and the improvement of monomer conversion, as in document 2;
(3) the initiator ammonium persulfate generates an acid component after being initiated and decomposed, so that the pH value of the reaction liquid is reduced, the initiation of the ammonium persulfate is automatically accelerated, the initiation process is unstable, and the stable control of the characteristic viscosity of the polymer and the further improvement of the monomer conversion rate are limited, as shown in document 3;
(4) to date, no new process for preparing a PDAC dry powder product with stable and controllable serialized relative molecular mass (expressed by an intrinsic viscosity) and high monomer conversion rate is reported. For example, documents 1, 2 and 3.
The above-mentioned defects are caused by the fact that it is difficult to further increase the monomer conversion rate of the existing series PDAC products with relative molecular mass by the existing process method, and the corresponding obtained products are not favorable for storage, transportation, application and popularization.
Disclosure of Invention
The invention aims to provide a simple, stable and quality-controllable aqueous solution polymerization preparation method of PDAC with serialized relative molecular mass and high monomer conversion rate.
The technical solution for realizing the purpose of the invention is as follows:
the preparation method of the PDAC with the serialized relative molecular mass and the high monomer conversion rate comprises the following specific steps:
taking an industrial DAC monomer solution as a raw material, adding triallylamine hydrochloride or oligomer thereof containing terminal group double bonds and having an average polymerization degree of 0-180 in a nitrogen atmosphere to make the triallylamine hydrochloride or oligomer thereof account for 0.1-5.0% of the mass fraction of the monomer, and adding a metal ion chelating agent and a water-soluble azo initiator accounting for 0.06-0.85% of the mass fraction of the monomer; adjusting the initial mass fraction of the monomer to be 30.0-60.0%; stirring and mixing uniformly, heating the reaction solution, heating by two steps, keeping the temperature at 35-45 ℃ and 55-65 ℃ respectively, polymerizing in a heat preservation manner to obtain a PDAC colloid product, and crushing, granulating and drying the colloid to obtain the PDAC dry powder with serialized relative molecular mass and high monomer conversion rate.
The metal ion chelating agent is tetrasodium ethylene diamine tetraacetate or disodium ethylene diamine tetraacetate, and accounts for 0.005-0.030 percent of the mass fraction of the monomer.
The water-soluble azo initiator is selected from azobisisobutylamidine hydrochloride (V50) or azobisisobutylimidazoline hydrochloride (VA 044).
The polymerization time of the two-step temperature rise is 3.0 plus or minus 0.5 h.
The drying is fluidized bed drying at 70-110 ℃.
The drying time is 1.0 plus or minus 0.5 h.
Compared with the prior art, the invention has the following remarkable advantages:
(1) preparation of PDAC with serialized relative molecular mass and high monomer conversion: according to the kinetic chain length equation (see formula 1) (basis of polymer chemistry and physics, Wei Wu, Shu Qiang, and Yu Yihua Master eds, 2011 edition), the synthesis of the polymer with the relative molecular mass series increasing is obtained, and the following relationship exists between the monomer concentration and the initiator concentration: when the relative molecular mass of the polymer is required to be increased, namely the average polymerization degree is increased by 1.60-1.25 times, and the kinetic chain length is also increased by 1.60-1.25 times, if the concentration of the monomer is regulated and controlled to be increased by (13 +/-3)%, and the corresponding concentration of the initiator is reduced by 50% -18%, a polymerization product with the serialized relative molecular mass and high monomer conversion rate can be obtained. For the PDAC with the serialized relative molecular mass and high monomer conversion rate, when the characteristic viscosity is increased within 2.00-8.00 dL/g, the initial mass fraction of the monomer is increased by 13 +/-3 percent, and the mass ratio of the synchronous initiator in the monomer is decreased by 50-35 percent; when the intrinsic viscosity is increased gradually between 8.00-14.00 dL/g (excluding 8.00), the initial mass fraction of the monomer is regulated and controlled to be increased gradually (13 +/-3)%, and the mass ratio of the synchronous initiator in the monomer is decreased gradually by 30-18%. Therefore, through experimental point exploration, when the mass fraction of the selected monomer is increased from 30.0% to 60.0%, the mass ratio of the corresponding initiator to the monomer is reduced from 0.85% to 0.06%; and then the optimal selection of the polymerization reaction process conditions, temperature and time is combined, so that the preparation of the target PDAC product with the series of characteristic viscosities ranging from 2.00 dL/g to 14.00dL/g and the monomer conversion rate of more than 99.50% is realized. The preparation of the PDAC product with high monomer conversion rate and relative molecular mass in series can obviously improve the utilization rate of raw materials, greatly expand the application range, can be widely applied to multiple fields of oil exploitation, papermaking, mining, textile printing and dyeing, daily chemical industry, water treatment and the like, and provides unique environment-friendly property for the series products due to high monomer conversion rate (less residual monomers).
(2) The compound with weak reactivity and containing terminal group double bonds exists stably at low temperature, the process of a rapid reaction stage in the initial polymerization reaction is not influenced, the compound can participate in the reaction at subsequent high temperature, particularly the drying stage is equivalent to adding a chain extender, residual monomers and polymers are easy to connect, and the characteristic viscosity loss caused by high-temperature degradation is counteracted. The compound containing terminal double bonds can fully play the above role in the process conditions of the invention, thereby further improving the characteristic viscosity of the polymer PDAC and improving the monomer conversion rate.
(3) The azo initiator is adopted, so that the defects that acidic components are generated after persulfate initiator is initiated and decomposed, the pH value of reaction liquid is reduced, and the initiation process is unstable due to automatic acceleration are overcome, and the foundation for stable initiation and relatively stable reaction is laid for further improving the characteristic viscosity and the monomer conversion rate of the polymer.
(4) The invention aims to provide a novel process for preparing a PDAC dry powder product, which has the advantages of stable and controllable serialized relative molecular mass (expressed by the characteristic viscosity) and high monomer conversion rate. The dry powder product has high monomer conversion rate and is convenient for long-distance transportation and long-term storage.
Detailed Description
The technical solution of the present invention is described below with reference to examples.
Example 1
Firstly, adding a monomer aqueous solution of a DAC monomer with the content (calculated by mass fraction, the same below) of 75% into a polymerization reactor, sequentially adding a triallylamine hydrochloride homopolymer with the average polymerization degree of 180 and the mass fraction of (5.00 +/-0.01)% of the monomer, a metal chelating agent ethylene diamine tetraacetic acid tetrasodium solution with the mass ratio of (0.030 +/-0.005)% of the monomer, an azobisisobutylimidazoline hydrochloride (VA044) initiator solution with the mass ratio of (0.85 +/-0.05)% of the monomer and distilled water under the condition of introducing nitrogen and stirring to obtain a reaction solution with the mass fraction of (30.0 +/-2.0%);
secondly, heating the reaction solution to the initiation temperature (35 +/-2) DEG C, and carrying out thermal polymerization reaction (3.0 +/-0.5) h;
thirdly, heating the temperature-rising reaction system to the polymerization temperature (55 +/-2) DEG C, carrying out heat preservation polymerization reaction for (3.0 +/-0.5) h, and stopping heating;
and fourthly, discharging the reaction product obtained by the two-step reaction to obtain a PDAC colloidal product. Then, the gel was pulverized and granulated, and dried in a fluidized bed at (70. + -. 5) ℃ for (1.0. + -. 0.5) hours to obtain a PDAC dry powder, and the PDAC dry powder was measured in 1.0mol/L NaCl solution at (30.0. + -. 0.1) ° C with an Ubbelohde viscometer to obtain an intrinsic viscosity of 2.08dL/g, and the monomer conversion was 99.56% by measuring the residual double bonds with a bromination method.
Example 2
Firstly, adding a monomer aqueous solution of 80% of DAC monomer into a polymerization reactor, sequentially adding triallylamine hydrochloride homopolymer with the average polymerization degree of 140 accounting for (4.50 +/-0.01)% of the mass fraction of the monomer, disodium ethylenediamine tetraacetate solution as a metal chelating agent accounting for (0.010 +/-0.005)% of the mass fraction of the monomer, azodiisobutyronidazoline hydrochloride (VA044) initiator solution accounting for (0.43 +/-0.05)% of the mass fraction of the monomer and distilled water under the condition of introducing nitrogen and stirring to obtain a reaction solution with the mass fraction of the monomer of (35.0 +/-2.0)%;
secondly, heating the reaction solution to the initiation temperature (35 +/-2) DEG C, and carrying out thermal polymerization reaction (3.0 +/-0.5) h;
thirdly, heating the temperature-rising reaction system to the polymerization temperature (60 +/-2) DEG C, carrying out heat preservation polymerization reaction (3.0 +/-0.5) h, and stopping heating;
and fourthly, discharging the reaction product obtained by the two-step reaction to obtain a PDAC colloidal product. Then, the gel was pulverized and granulated, and dried in a fluidized bed at (90. + -. 5) ℃ for (1.0. + -. 0.5) hours to obtain a PDAC dry powder, which was measured in 1.0mol/L NaCl solution at (30.0. + -. 0.1) ℃ with an Ubbelohde viscometer to obtain an intrinsic viscosity of 3.95dL/g, and the residual double bonds were measured by a bromination method to obtain a monomer conversion of 99.60%.
Example 3
Firstly, adding a monomer aqueous solution of 80% of DAC monomer into a polymerization reactor, sequentially adding triallylamine hydrochloride homopolymer with the average polymerization degree of 60 accounting for (3.20 +/-0.01)% of the mass fraction of the monomer, disodium ethylenediamine tetraacetate solution as a metal chelating agent accounting for (0.010 +/-0.005)% of the mass fraction of the monomer, azodiisobutyronidazoline hydrochloride (VA044) initiator solution accounting for (0.25 +/-0.05)% of the mass fraction of the monomer and distilled water under the condition of introducing nitrogen and stirring to obtain a reaction solution with the mass fraction of the monomer of (40.0 +/-2.0)%;
secondly, heating the reaction solution to the initiation temperature (35 +/-2) DEG C, and carrying out thermal polymerization reaction (3.0 +/-0.5) h;
thirdly, heating the temperature-rising reaction system to the polymerization temperature (60 +/-2) DEG C, carrying out heat preservation polymerization reaction (3.0 +/-0.5) h, and stopping heating;
and fourthly, discharging the reaction product obtained by the two-step reaction to obtain a PDAC colloidal product. Then, the gel was pulverized and granulated, and dried in a fluidized bed at (90. + -. 5) ℃ for (1.0. + -. 0.5) hours to obtain a PDAC dry powder, which was measured in 1.0mol/L NaCl solution at (30.0. + -. 0.1) ℃ with an Ubbelohde viscometer to obtain an intrinsic viscosity of 5.85dL/g, and the residual double bonds were measured by a bromination method to obtain a monomer conversion of 99.75%.
Example 4
Firstly, adding a monomer aqueous solution of 80% of DAC monomer into a polymerization reactor, sequentially adding triallylamine hydrochloride homopolymer with the average polymerization degree of 20 accounting for (1.50 +/-0.01)% of the mass fraction of the monomer, disodium ethylenediamine tetraacetate solution as a metal chelating agent accounting for (0.015 +/-0.005)% of the mass fraction of the monomer, azodiisobutyronidazoline hydrochloride (VA044) initiator solution accounting for (0.16 +/-0.05)% of the mass fraction of the monomer and distilled water under the condition of introducing nitrogen and stirring to obtain a reaction solution with the mass fraction of the monomer of (45.0 +/-2.0)%;
secondly, heating the reaction solution to the initiation temperature (35 +/-2) DEG C, and carrying out thermal polymerization reaction (3.0 +/-0.5) h;
thirdly, heating the temperature-rising reaction system to the polymerization temperature (60 +/-2) DEG C, carrying out heat preservation polymerization reaction (3.0 +/-0.5) h, and stopping heating;
and fourthly, discharging the reaction product obtained by the two-step reaction to obtain a PDAC colloidal product. Then, the gel was pulverized and granulated, and dried in a fluidized bed at (100. + -. 5) ℃ for (1.0. + -. 0.5) hours to obtain a PDAC dry powder, which was measured in 1.0mol/L NaCl solution at (30.0. + -. 0.1) ℃ with an Ubbelohde viscometer to obtain an intrinsic viscosity of 8.01dL/g, and the residual double bonds were measured by a bromination method to obtain a monomer conversion of 99.66%.
Example 5
Firstly, adding a monomer aqueous solution of 80 percent of DAC monomer into a polymerization reactor, sequentially adding triallylamine hydrochloride homopolymer with the average polymerization degree of 10 accounting for (0.85 +/-0.01)% of the mass fraction of the monomer, disodium ethylenediamine tetraacetate solution as a metal chelating agent accounting for (0.020 +/-0.005)% of the mass fraction of the monomer and azodiisobutyl amidine hydrochloride (V50) initiator solution accounting for (0.11 +/-0.05)% of the mass fraction of the monomer under the condition of introducing nitrogen and stirring, and adding distilled water to obtain a reaction solution with the mass fraction of the monomer of (50.0 +/-2.0)%;
secondly, heating the reaction solution to the initiation temperature (45 +/-2) DEG C, and carrying out polymerization reaction (3.0 +/-0.5) h at the maintained temperature;
thirdly, heating the temperature-rising reaction system to the polymerization temperature (65 +/-2) DEG C, carrying out heat preservation polymerization reaction for (3.0 +/-0.5) h, and stopping heating;
and fourthly, discharging the reaction product obtained by the two-step reaction to obtain a PDAC colloidal product. Then, the gel was pulverized and granulated, and dried in a fluidized bed at (100. + -. 5) ℃ for (1.0. + -. 0.5) hours to obtain a PDAC dry powder, which was measured in 1.0mol/L NaCl solution at (30.0. + -. 0.1) ℃ with an Ubbelohde viscometer to obtain an intrinsic viscosity of 10.05dL/g, and the residual double bonds were measured by a bromination method to obtain a monomer conversion of 99.76%.
Example 6
Firstly, adding a monomer aqueous solution of 80 percent of DAC monomer into a polymerization reactor, sequentially adding triallylamine hydrochloride homopolymer with the average polymerization degree of 5 accounting for (0.10 +/-0.01)% of the mass fraction of the monomer, disodium ethylenediamine tetraacetate solution as a metal chelating agent accounting for (0.005 +/-0.005)% of the mass fraction of the monomer and azodiisobutyl amidine hydrochloride (V50) solution accounting for (0.08 +/-0.05)% of the mass fraction of the monomer under the condition of introducing nitrogen and stirring, and adding distilled water to obtain a reaction solution with the mass fraction of the monomer of (55.0 +/-2.0)%;
secondly, heating the reaction solution to the initiation temperature (45 +/-2) DEG C, and carrying out polymerization reaction (3.0 +/-0.5) h at the maintained temperature;
thirdly, heating the temperature-rising reaction system to the polymerization temperature (65 +/-2) DEG C, carrying out heat preservation polymerization reaction for (3.0 +/-0.5) h, and stopping heating;
and fourthly, discharging the reaction product obtained by the two-step reaction to obtain a PDAC colloidal product. Then, the gel was pulverized and granulated, and dried in a fluidized bed at (110. + -. 5) ℃ for (1.0. + -. 0.5) hours to obtain a PDAC dry powder, and the PDAC dry powder was measured in 1.0mol/L NaCl solution at (30.0. + -. 0.1) ° C with an Ubbelohde viscometer to obtain an intrinsic viscosity of 12.29dL/g, and the monomer conversion was 99.84% by measuring the residual double bonds with a bromination method.
Example 7
Firstly, adding a monomer aqueous solution containing 85% of DAC monomer into a polymerization reactor, sequentially adding triallylamine hydrochloride accounting for 0.10 +/-0.01% of the mass fraction of the monomer, a metal chelating agent disodium ethylene diamine tetraacetate solution accounting for 0.005 +/-0.005% of the mass fraction of the monomer, an azodiisobutyl amidine hydrochloride (V50) initiator solution accounting for 0.06 +/-0.05% of the mass fraction of the monomer and distilled water under the condition of introducing nitrogen and stirring to obtain a reaction solution accounting for 60.0 +/-2.0% of the mass fraction of the monomer;
secondly, heating the reaction solution to the initiation temperature (45 +/-2) DEG C, and carrying out polymerization reaction (3.0 +/-0.5) h at the maintained temperature;
thirdly, heating the temperature-rising reaction system to the polymerization temperature (65 +/-2) DEG C, carrying out heat preservation polymerization reaction for (3.0 +/-0.5) h, and stopping heating;
and fourthly, discharging the reaction product obtained by the two-step reaction to obtain a PDAC colloidal product. Then, the gel was pulverized and granulated, and dried in a fluidized bed at (110. + -. 5) ℃ for (1.0. + -. 0.5) hours to obtain a PDAC dry powder, and the PDAC dry powder was measured in 1.0mol/L NaCl solution at (30.0. + -. 0.1) ° C with an Ubbelohde viscometer to obtain an intrinsic viscosity of 14.00dL/g, and the monomer conversion was 99.63% by measuring the residual double bonds with a bromination method.
Comparative example 1
This comparative example is essentially the same as example 5, except that the average degree of polymerization of the triallylamine hydrochloride homopolymer added is 320, as follows:
firstly, adding a monomer aqueous solution of 80 percent of DAC monomer into a polymerization reactor, sequentially adding triallylamine hydrochloride homopolymer with the average polymerization degree of 320 accounting for (0.85 +/-0.01)% of the mass fraction of the monomer, disodium ethylenediamine tetraacetate solution as a metal chelating agent accounting for (0.020 +/-0.005)% of the mass fraction of the monomer and azodiisobutyl amidine hydrochloride (V50) initiator solution accounting for (0.11 +/-0.05)% of the mass fraction of the monomer under the condition of introducing nitrogen and stirring, and adding distilled water to obtain a reaction solution with the mass fraction of the monomer of (50.0 +/-2.0)%;
secondly, heating the reaction solution to the initiation temperature (45 +/-2) DEG C, and carrying out polymerization reaction (3.0 +/-0.5) h at the maintained temperature;
thirdly, heating the temperature-rising reaction system to the polymerization temperature (65 +/-2) DEG C, carrying out heat preservation polymerization reaction for (3.0 +/-0.5) h, and stopping heating;
and fourthly, discharging the reaction product obtained by the two-step reaction to obtain a PDAC colloidal product. Then, the gel was pulverized and granulated, and dried in a fluidized bed at (100. + -. 5) ℃ for (1.0. + -. 0.5) hours to obtain a PDAC dry powder, and the PDAC dry powder was measured in 1.0mol/L NaCl solution at (30.0. + -. 0.1) ° C with an Ubbelohde viscometer to obtain an intrinsic viscosity of 5.69dL/g, and the monomer conversion was determined to be 98.07% by measuring the residual double bonds with a bromination method.
Comparative example 2
This comparative example is essentially the same as example 6, except that the mass ratio of the triallylamine hydrochloride homopolymer added to the monomers was (8.00. + -. 0.01)%, and the specific procedure was as follows:
firstly, adding a monomer aqueous solution of 80 percent of DAC monomer into a polymerization reactor, sequentially adding triallylamine hydrochloride homopolymer with the average polymerization degree of 5 accounting for (8.00 +/-0.01)% of the mass fraction of the monomer, disodium ethylenediamine tetraacetate solution as a metal chelating agent accounting for (0.005 +/-0.005)% of the mass fraction of the monomer and azodiisobutyl amidine hydrochloride (V50) solution accounting for (0.08 +/-0.05)% of the mass fraction of the monomer under the condition of introducing nitrogen and stirring, and adding distilled water to obtain a reaction solution with the mass fraction of the monomer of (55.0 +/-2.0)%;
secondly, heating the reaction solution to the initiation temperature (45 +/-2) DEG C, and carrying out polymerization reaction (3.0 +/-0.5) h at the maintained temperature;
thirdly, heating the temperature-rising reaction system to the polymerization temperature (65 +/-2) DEG C, carrying out heat preservation polymerization reaction for (3.0 +/-0.5) h, and stopping heating;
and fourthly, discharging the reaction product obtained by the two-step reaction to obtain a PDAC colloidal product. Then, the gel was pulverized and granulated, and dried in a fluidized bed at (110. + -. 5) ℃ for (1.0. + -. 0.5) hours to obtain a PDAC dry powder, which was measured in 1.0mol/L NaCl solution at (30.0. + -. 0.1) ℃ with an Ubbelohde viscometer to obtain an intrinsic viscosity of 7.12dL/g, and the residual double bonds were measured by a bromination method to obtain a monomer conversion of 98.92%.
Comparative example 3
This comparative example is essentially the same as example 7, except that no triallylamine hydrochloride or homopolymer thereof was added, as follows:
firstly, adding a monomer aqueous solution containing 85 percent of DAC monomer into a polymerization reactor, sequentially adding a metal chelating agent disodium ethylene diamine tetraacetate solution accounting for (0.005 +/-0.005)% of the mass ratio of the monomer and an azodiisobutyl amidine hydrochloride (V50) initiator solution accounting for (0.06 +/-0.05)% of the mass ratio of the monomer under the condition of introducing nitrogen and stirring, and adding distilled water to obtain a reaction solution with the mass fraction of the monomer of (60.0 +/-2.0)%;
secondly, heating the reaction solution to the initiation temperature (45 +/-2) DEG C, and carrying out polymerization reaction (3.0 +/-0.5) h at the maintained temperature;
thirdly, heating the temperature-rising reaction system to the polymerization temperature (65 +/-2) DEG C, carrying out heat preservation polymerization reaction for (3.0 +/-0.5) h, and stopping heating;
and fourthly, discharging the reaction product obtained by the two-step reaction to obtain a PDAC colloidal product. Then, the gel was pulverized and granulated, and dried in a fluidized bed at (110. + -. 5) ℃ for (1.0. + -. 0.5) hours to obtain a PDAC dry powder, which was measured in 1.0mol/L NaCl solution at (30.0. + -. 0.1) ℃ with an Ubbelohde viscometer to obtain an intrinsic viscosity of 10.37dL/g, and the residual double bonds were measured by a bromination method to obtain a monomer conversion of 98.13%.
Claims (7)
1. The preparation method of the PDAC with the serialized relative molecular mass and the high monomer conversion rate is characterized by comprising the following specific steps of:
taking an industrial DAC monomer solution as a raw material, adding triallylamine hydrochloride or oligomer thereof containing terminal group double bonds and having an average polymerization degree of 0-180 in a nitrogen atmosphere to make the triallylamine hydrochloride or oligomer thereof account for 0.1-5.0% of the mass fraction of the monomer, and adding a metal ion chelating agent and a water-soluble azo initiator accounting for 0.06-0.85% of the mass fraction of the monomer; adjusting the initial mass fraction of the monomer to be 30.0-60.0%; stirring and mixing uniformly, heating the reaction solution, heating by two steps, keeping the temperature at 35-45 ℃ and 55-65 ℃ respectively, polymerizing in a heat preservation manner to obtain a PDAC colloid product, and crushing, granulating and drying the colloid to obtain the PDAC dry powder with serialized relative molecular mass and high monomer conversion rate.
2. The method according to claim 1, wherein the metal ion chelating agent is tetrasodium ethylenediaminetetraacetate or disodium ethylenediaminetetraacetate.
3. The preparation method according to claim 1, wherein the metal ion chelating agent is present in an amount of 0.005 to 0.030% by mass based on the monomer.
4. The method of claim 1, wherein the water-soluble azo initiator is selected from the group consisting of azobisisobutylamidine hydrochloride and azobisisobutylimidazoline hydrochloride.
5. The method according to claim 1, wherein the polymerization time at the two-step temperature rise and the holding temperature are both 3.0 ± 0.5 h.
6. The method according to claim 1, wherein the drying is fluidized bed drying at 70-110 ℃.
7. The method of claim 1, wherein the drying time is 1.0 ± 0.5 h.
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