CN108219163B - Preparation method of instant poly dimethyl diallyl ammonium chloride dry powder - Google Patents

Preparation method of instant poly dimethyl diallyl ammonium chloride dry powder Download PDF

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CN108219163B
CN108219163B CN201611157520.9A CN201611157520A CN108219163B CN 108219163 B CN108219163 B CN 108219163B CN 201611157520 A CN201611157520 A CN 201611157520A CN 108219163 B CN108219163 B CN 108219163B
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dry powder
pdmdaac
ammonium chloride
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diallyl ammonium
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CN108219163A (en
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张跃军
王明龙
王廷福
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Nanjing University of Science and Technology
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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    • C08J2339/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a single or double bond to nitrogen or by a heterocyclic ring containing nitrogen; Derivatives of such polymers

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Abstract

The invention discloses a preparation method of instant poly dimethyl diallyl ammonium chloride dry powder. The method takes a series of PDMDAAC colloids with characteristic viscosity values as raw materials, the colloidal particles with certain sizes are prepared by granulation and are placed in a dryer, the time for reaching the turning point of a constant speed and speed reduction drying stage and the time required by the speed reduction drying stage in the drying process are designed according to the solid content of the PDMDAAC colloids, and a series of PDMDAAC dry powder products with the monomer conversion rate of more than 98.00 percent and the solid content of more than 89.00 percent and the characteristic viscosity values of 1.4-3.6dL/g are obtained by adopting a drying mode of two-stage temperature programming, so that the dry powder products have no side reactions such as crosslinking and degradation, and the characteristic viscosity values are improved and are easy to dissolve. The PDMDAAC dry powder preparation process is energy-saving and environment-friendly, and the prepared poly dimethyl diallyl ammonium chloride instant dry powder is convenient to store and transport and easy to realize industrial mass production.

Description

Preparation method of instant poly dimethyl diallyl ammonium chloride dry powder
Technical Field
The invention relates to a preparation technology of cationic polymer dry powder, in particular to a preparation method of poly dimethyl diallyl ammonium chloride (PDMDAAC) instant dry powder.
Background
Poly dimethyl diallyl ammonium Chloride (PDMDAAC) is obtained by homopolymerization of dimethyl diallyl ammonium Chloride (DMDAAC), and has the advantages of controllable relative molecular mass, high cation degree, high stability, good water solubility and the like, so that the poly dimethyl diallyl ammonium Chloride (PDMDAAC) is widely applied to the fields of papermaking, coal mining, petroleum exploitation, textile printing and dyeing, medicines, biology, daily chemicals, water treatment and the like. The preparation process of the PDMDAAC dry powder is concerned due to inconvenient transportation, storage and use of the PDMDAAC jelly obtained by aqueous solution free radical polymerization.
The literature on the preparation of homopolymer PDMDAAC colloid is more at home and abroad, but the reports on the dry powder preparation process are few, and the reports on the PDMDAAC dry powder preparation process with the serialized characteristic viscosity value are not found. The related research work representative up to now is as follows.
Document 1(Rene H, et al. high molecular weight positioning polymers, preparation method and uses thereof of [ P ]. US: 20040030039A 1,2004-12-12.) A polymer was obtained by reversed phase suspension polymerization using t-butyl peroxide or azo V50 as an initiator at w (DMDAAC) 67% to 77%, and then the product was isolated and dried at 50 ℃ for 24 hours to obtain a dry powder having a particle size mainly distributed around 350. mu.m. The process uses industrial monomer as raw material, selects oil phase as continuous phase, and uses surfactant to make suspension polymerization to obtain the product whose relative molecular mass is high and its form is dry powder, and when the mass fraction of product solution is 20%, the apparent viscosity is maximally 97000cps (Brookfield measurement, but its specific measurement temperature and solvent are not described). However, the viscosity of the solution system can be greatly increased due to the bead string effect of the water-soluble polymer and the surfactant in the polymerization process, so that the accuracy of measuring the characteristic viscosity value of the PDMDAAC product is influenced to a certain extent. This study is the only report in the literature that has been prepared for the preparation of powdered PDMDAAC product.
Document 2 (Queriai Fei. instant powdery PDA preparation process preliminary research [ D ]. Nanjing: Nanjing university of physical and chemical industries, 2008.) 10% cationicity PDA (a copolymer of acrylamide and DMDAAC as a cationic monomer) colloid obtained by an aqueous solution polymerization method is used as a raw material, the characteristic viscosity of the colloid is 15.6dL/g, an auxiliary agent and a simulation single-screw extrusion granulator are used for granulation, a drying auxiliary agent formula and a drying process are studied, the colloid is dried at 80 ℃ for 10min, and then dried at 70 ℃ for 70min, so that 10% cationicity powdery PDA with the characteristic viscosity of 11.3dL/g and the dissolution time of 5h can be obtained; and 10 percent cationic powdery PDA with the characteristic viscosity of 11.7dL/g and the dissolution time of 6 h. The intrinsic viscosity of 10% cationic powdery PDA obtained in this study is the highest reported in the literature, but the product is a cationic copolymer.
The dry powder polymer has the advantages of convenient transportation and storage, and the like, and better meets the application requirements of various industrial fields, so the preparation of the dry powder polymer becomes one of the focuses in the field in recent years. DMDAAC-based homopolymers and copolymers are widely used due to their unique properties. In research work, better results are obtained in the preparation of DMDAAC-based copolymer dry powder by adjusting process methods and conditions, but the dry powder preparation process of the homopolymer PDMDAAC is only limited by reports of a suspension polymerization method, and the synthesized dry powder product has relatively low characteristic viscosity and impurities. The reason is that the existing process generally has the following defects:
(1) the preparation of copolymer dry powder products by inverse suspension polymerization requires separation, washing, drying and other procedures, which are complicated, and the obtained products not only have low accuracy of characteristic viscosity values, but also have limited application range due to the inclusion of additives such as emulsifiers and the like, as in document 1;
(2) in the preparation process of the dry powder copolymer, the product is easy to generate side reactions such as degradation, crosslinking and the like, so that the characteristic viscosity loss is caused, the dissolution time is prolonged, and the dissolution needs 5 hours, as shown in document 2;
(3) the preparation process of the PDMDAAC dry powder product obtained by an aqueous solution polymerization method is not reported, and the preparation of the PDMDAAC dry powder with a series of characteristic viscosity values is not reported, such as documents 1 and 2.
The above drawbacks make it difficult to obtain PDMDAAC instant dry powder products of a range of characteristic viscosities with reference to or application of existing processes to date.
Disclosure of Invention
The invention aims to provide a preparation method of PDMDAAC instant dry powder with simple and stable process, low preparation cost and serial characteristic viscosity.
The technical solution for realizing the purpose of the invention is as follows:
a preparation method of PDMDAAC instant dry powder takes PDMDAAC colloid with a characteristic viscosity value of 1.0-3.5dL/g and a solid content of 57.60% -69.30% as a raw material, granules are granulated to obtain PDMDAAC colloidal particles, the colloidal particles are dried in a two-stage temperature programming mode, firstly, the colloidal particles are maintained for 20-50min at 60 +/-5 ℃ in a constant-speed drying stage, then, the colloidal particles are maintained for 80-100min at 75-100 ℃ in a later speed reduction drying stage, and the colloidal particles are ground after the drying is finished, so that the PDMDAAC dry powder with the characteristic viscosity value of 1.4-3.6dL/g is obtained.
Wherein the size of the PDMDAAC colloidal particles is 2 multiplied by 20-6 multiplied by 50 mm.
Compared with the prior art, the invention has the following remarkable advantages:
(1) the temperature designed in the constant-speed drying stage is similar to the later-stage reaction temperature in the process optimization in the colloid preparation, so that the colloid product can be further cured, the characteristic viscosity value and the monomer conversion rate of the PDMDAAC dry powder product compared with the colloid raw material are obviously improved, the improvement range of the characteristic viscosity value is 2.0-35.0%, and the monomer conversion rate reaches more than 98.00%.
(2) According to a drying rate curve, in combination with the difference of solid contents of PDMDAAC colloid, the time required for each sample to reach the turning point of the constant speed and speed reduction drying stage in the drying process is also different, and a drying mode of programmed temperature rise is adopted. Designing two-stage temperature programming: in the constant-speed drying stage, the lower temperature is kept and constant, most of water is transferred out, side reactions such as crosslinking and degradation are avoided, and the lower the solid content of the colloid is, the longer the corresponding maintaining time of the stage is; in the speed reduction drying stage, the moisture in the material is greatly reduced, and the moisture conditions of side reactions such as crosslinking and degradation are weakened, so that the temperature of the material can be increased by properly increasing the drying temperature, the migration rate of the moisture in the material is accelerated, and the drying rate is increased.
(3) The grain size design of the colloidal particles is convenient for granulation of an industrial extruder and drying in a short time, and prevents polymer molecules in the colloid from being heated and decomposed.
(4) The obtained series PDMDAAC dry powder product with the characteristic viscosity value of 1.4-3.6dL/g has the solid content of more than 89.00 percent, the particle size is mainly distributed at about 350 mu m, the dry powder product has no crosslinking and degradation and is very easy to dissolve in water and is completely dissolved within 10min under the stirring at room temperature.
(5) The drying process is simple and convenient, can be used for continuous preparation, and is beneficial to industrial production.
Drawings
FIG. 1 is a graph of solids content versus time for an initial constant rate drying stage for gels of varying intrinsic viscosity.
Detailed Description
The present invention will be described in more detail with reference to the following examples and the accompanying drawings.
Example 1
A preparation method of PDMDAAC instant dry powder comprises the following steps:
step one, adopting PDMDAAC colloid obtained by an aqueous solution polymerization method as a raw material, wherein the solid content is 57.67%, the intrinsic viscosity is 1.06dL/g, and the monomer conversion rate is 96.67%;
secondly, taking the colloid product, and granulating according to the design requirement to prepare granular colloidal particles with the size of (2 multiplied by 20) mm;
thirdly, adjusting the airflow drying box of the fixed bed to the drying initial temperature T1The temperature is (60 + -5) deg.C, placing the vessel containing granular colloidal particles into a drying oven, maintaining for (50 + -5) min, adjusting the temperature of the blast drying oven to the late drying period T2Maintaining at 100 + -5 deg.C for 100 + -5 min, and drying for 150 + -5 min;
fourthly, putting the dried product into a grinder for grinding, and screening dry powder particles by a sieve with the aperture of 0.46mm-0.30 mm. According to the national standard GB/T12005.2-1989 of the method for measuring the solid content of polyacrylamide, the solid content is measured to be 93.25 percent, and the polyacrylamide is prepared into (1.5 +/-0.1) multiplied by 10-3The dissolution time was measured in g/mL of an aqueous solution to be (6. + -. 1) min. According to the method for determining intrinsic viscosity of polyacrylamide under the national standard GB/T12005.1-1989, the intrinsic viscosity is determined by a Ubbelohde viscometer in 1mol/L NaCl aqueous solution at (30 +/-0.1) DEG C, the intrinsic viscosity is calculated to be 1.40dL/g by a single-point method, the intrinsic viscosity is increased by 32.08 percent compared with that of a colloid raw material, and the monomer conversion rate is calculated to be 98.69 percent by determining residual double bonds according to a bromination method which is a method for determining the content of residual acrylamide in polyacrylamide under the national standard GB/T12005.3-1989.
Example 2
A preparation method of PDMDAAC instant dry powder comprises the following steps:
firstly, adopting PDMDAAC colloid obtained by an aqueous solution polymerization method as a raw material, wherein the solid content of the colloid is 62.97%, the intrinsic viscosity of the colloid is 1.89dL/g, and the monomer conversion rate is 95.88%;
secondly, taking the colloid product, and granulating according to the design requirement to prepare granular colloidal particles with the size of (6 multiplied by 50);
thirdly, adjusting the airflow drying box of the fixed bed to the drying initial temperature T1The temperature is (60 + -5) deg.C, placing the vessel containing granular colloidal particles into a drying oven, maintaining for (40 + -5) min, adjusting the temperature of the blast drying oven to the late drying period T2Maintaining at 90 + -5 deg.C for 90 + -5 min, and dryingThe time t is (130 +/-5) min;
fourthly, putting the dried product into a grinder for grinding, and screening dry powder particles by a sieve with the aperture of 0.46mm-0.30 mm. According to the national standard GB/T12005.2-1989 of the method for measuring the solid content of polyacrylamide, the solid content is measured to be 91.20 percent, and the polyacrylamide is prepared into (1.5 +/-0.1) multiplied by 10-3The dissolution time was measured to be (8. + -. 1) min in g/mL of the aqueous solution. According to the method for determining intrinsic viscosity of polyacrylamide under the national standard GB/T12005.1-1989, the intrinsic viscosity is determined by an Ubbelohde viscometer in 1mol/L NaCl aqueous solution at (30 +/-0.1) DEG C, the intrinsic viscosity is calculated to be 2.40dL/g by a single-point method, the intrinsic viscosity is improved by 26.98 percent compared with that of a colloid raw material, and the monomer conversion is calculated to be 98.63 percent by determining residual double bonds according to a bromination method which is a method for determining the content of residual acrylamide in polyacrylamide under the national standard GB/T12005.3-1989.
Example 3
A preparation method of PDMDAAC instant dry powder comprises the following steps:
step one, adopting PDMDAAC colloid obtained by an aqueous solution polymerization method as a raw material, wherein the solid content is 68.20%, the intrinsic viscosity is 2.92dL/g, and the monomer conversion rate is 96.18%;
secondly, taking the colloid product, and granulating according to the design requirement to prepare granular colloidal particles with the size of (4 multiplied by 35) mm;
thirdly, adjusting the airflow drying box of the fixed bed to the drying initial temperature T1The temperature is (60 + -5) deg.C, placing the vessel containing granular colloidal particles into a drying oven, maintaining for (30 + -5) min, adjusting the temperature of the blast drying oven to the late drying period T2Maintaining at 80 + -5 deg.C for 90 + -5 min, and drying for 120 + -5 min;
fourthly, putting the dried product into a grinder for grinding, and screening dry powder particles by a sieve with the aperture of 0.46mm-0.30 mm. According to the national standard GB/T12005.2-1989 of the method for measuring the solid content of polyacrylamide, the solid content is measured to be 94.31 percent, and the polyacrylamide is prepared into (1.5 +/-0.1) multiplied by 10-3The dissolution time was measured to be (8. + -. 1) min in g/mL of the aqueous solution. According to the method for measuring the intrinsic viscosity of polyacrylamide under the national standard GB/T12005.1-1989, the intrinsic viscosity is calculated by a single-point method under the temperature of 30 +/-0.1 ℃ in 1mol/L NaCl aqueous solution by using a Ubbelohde viscometer3.22dL/g, the characteristic viscosity value is improved by 10.27 percent compared with the colloid raw material, and the monomer conversion rate is 98.76 percent by measuring the residual double bonds according to the bromination method of the residual acrylamide content measuring method in the polyacrylamide of the national standard GB/T12005.3-1989.
Example 4
A preparation method of PDMDAAC instant dry powder comprises the following steps:
step one, adopting PDMDAAC colloid obtained by an aqueous solution polymerization method as a raw material, wherein the solid content is 69.30 percent, the intrinsic viscosity is 3.43dL/g, and the monomer conversion rate is 96.45 percent;
secondly, taking the colloid product, and granulating according to the design requirement to prepare granular colloidal particles with the size of (4 multiplied by 35) mm;
thirdly, adjusting the airflow drying box of the fixed bed to the drying initial temperature T1The temperature is (60 + -5) deg.C, placing the vessel containing granular colloidal particles into a drying oven, maintaining for (20 + -5) min, adjusting the temperature of the blast drying oven to the late drying period T2Maintaining at 75 + -5 deg.C for 80 + -5 min, and drying for 100 + -5 min;
fourthly, putting the dried product into a grinder for grinding, and screening dry powder particles by a sieve with the aperture of 0.46mm-0.30 mm. According to the national standard GB/T12005.2-1989 of the method for measuring the solid content of polyacrylamide, the solid content is measured to be 94.40 percent, and the polyacrylamide is prepared into (1.5 +/-0.1) multiplied by 10-3The dissolution time was measured to be (9. + -. 1) min in g/mL of the aqueous solution. According to the method for determining intrinsic viscosity of polyacrylamide under the national standard GB/T12005.1-1989, the intrinsic viscosity is determined by an Ubbelohde viscometer in 1mol/L NaCl aqueous solution at (30 +/-0.1) DEG C, the intrinsic viscosity is calculated to be 3.52dL/g by a single-point method, the intrinsic viscosity is increased by 2.62 percent compared with that of a colloid raw material, and the monomer conversion rate is calculated to be 98.86 percent by determining residual double bonds according to a bromination method which is a method for determining the content of residual acrylamide in polyacrylamide under the national standard GB/T12005.3-1989.
TABLE 1 relationship of colloidal solid content to initial constant-speed drying stage time
Figure BDA0001180911420000051
Table 1 and fig. 1 show the relationship between the colloid solids content and the initial constant rate drying stage time, it can be seen that the lower the colloid solids content, the longer the initial constant rate drying stage time should be.

Claims (1)

1. A preparation method of instant poly dimethyl diallyl ammonium chloride dry powder is characterized in that poly dimethyl diallyl ammonium chloride colloid with the characteristic viscosity value of 1.0-3.5dL/g and the solid content of 57.60% -69.30% is used as a raw material, granulation is carried out to obtain poly dimethyl diallyl ammonium chloride colloid particles, the colloid particles are dried in a two-stage temperature programming mode, the colloid particles are firstly maintained for 20-50min at the temperature of 60 +/-5 ℃ in a constant-speed drying stage, then maintained for 80-100min at the temperature of 75-100 ℃ in a later speed reduction drying stage, and crushed after drying is finished, so that the poly dimethyl diallyl ammonium chloride dry powder with the characteristic viscosity value of 1.4-3.6dL/g is obtained, and the size of the poly dimethyl diallyl ammonium chloride colloid particles is 2 x 20-6 x 50 mm.
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