CN101397351A - Hydrophobic modified cationic polyacrylamide, preparation method and use thereof - Google Patents
Hydrophobic modified cationic polyacrylamide, preparation method and use thereof Download PDFInfo
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- CN101397351A CN101397351A CNA2007101755028A CN200710175502A CN101397351A CN 101397351 A CN101397351 A CN 101397351A CN A2007101755028 A CNA2007101755028 A CN A2007101755028A CN 200710175502 A CN200710175502 A CN 200710175502A CN 101397351 A CN101397351 A CN 101397351A
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Abstract
The invention belongs to the field of functional polymer, which relates to the hydrophobic modified cationic polyacrylamide comprising hydrophobic units, the function thereof, and the synthetic method for preparing the hydrophobic modified cationic polyacrylamide comprising hydrophobic units by homogeneous aqueous solution copolymerization. The invention prepares a multifunctional organic polymer flocculant by introducing an appropriate hydrophobic group in the hydrophobic modified cationic polyacrylamide (multifunctional organic polymer flocculant). The molecular weight of the hydrophobic modified cationic polyacrylamide prepared by the invention is in the scope of 2 multiplied by 10<6> to 1 multiplied by 10<7>, and the structural formula is shown as above, wherein, x, y and z are equal to 1, H or CH3 is independent in R1 and R3, and R2 is the alkyl with more than 3 and less than 16 alkyl groups or naphthenic base.
Description
Technical field
The invention belongs to the functional polymer polymer arts, relate to the dewatered modified cation polyacrylamide and the purposes that contain hydrophobic units, and the homogeneous phase aqueous solution copolymerization prepares the synthetic method of the dewatered modified cation polyacrylamide of hydrophobic units.
Background technology
Polymeric flocculant is a kind ofly suspended substance in the water, colloid or solute can be formed flocculation sediment, or making its functional polymer that is suspended in liquid level, they have a very important role in the application aspect industry such as trade effluent, sanitary sewage disposal, papermaking mining and the biological medicine.Polymeric flocculant experienced from the non-ionic type to the anionic, the development of cationic and amphoteric, and cationic high-molecular flocculant also has sterilization, higher flocculation efficiency, to advantages such as many suspended solids dehydrations are fast, effective, be one of emphasis of domestic and international flocculation agent exploitation in recent years.The design of polymeric flocculant at present is mainly cationic monomer diallyldimethylammonChloride Chloride (DMDAAC), methylacryoyloxyethyl trimethyl ammonium chloride (DMC), multipolymer (some problems of relevant cation polymeric flocculant of acrylyl oxy-ethyl-trimethyl salmiac (DAC) etc. and acrylamide (AM), meticulous and specialty chemicals, 2002,21,3～6).And nearest discover that hydrophobic grouping is introduced this family macromolecule can be played and strengthen such high molecular flocculating effect.
Because the deliquescent problem of hydrophobic monomer, the process for copolymerization of hydrophilic monomer and hydrophobic monomer employing at present is mainly three kinds: (1) mixing solutions polymerization, and promptly hydrophilic and hydrophobic two kinds of monomers all are dissolved in homogeneous phase copolymerization in the mixed solvent; (2) micella copolymerization, the hydrophobic monomer solubilising carries out copolymerization in the micella that tensio-active agent forms; (3) dispersion polymerization, promptly hydrophobic monomer directly is dispersed in and carries out heterogeneous copolymerization in the water.Preceding two kinds of polymerization processs have used organic solvent and tensio-active agent to pollute environment, and dispersion polymerization usually hydrophobic monomer reaction not exclusively, poor product quality.
Therefore, for the production technique of development environment close friendization, must improve aforesaid method.
Summary of the invention
One of purpose of the present invention provides the dewatered modified cation polyacrylamide.
Two of the object of the invention provides a kind of hydrophobic monomer inclusion complex that can be used to prepare the dewatered modified cation polyacrylamide.
Three of purpose of the present invention provides the method that a kind of copolymerization prepares the dewatered modified cation polyacrylamide, can remove the use of organic solvent or tensio-active agent from, reduces the pollution to environment.
Four of the object of the invention provides the method for preparing the hydrophobic monomer inclusion complex, and hydrophobic monomer is converted into hydrophilic monomer, adopts the inclusion effect of cyclodextrin that hydrophobic monomer is converted into hydrophilic monomer, can realize this polymerization of class monomer in the aqueous solution; The hydrophobic monomer inclusion complex for preparing has well water-soluble, and solubleness can satisfy the requirement of the hydrophobic monomer concentration of polymerization needs more than 5%.
Five of purpose of the present invention provides the purposes of dewatered modified cation polyacrylamide.
Dewatered modified cation polyacrylamide of the present invention (polymeric flocculant) is obtained by a small amount of hydrophobic monomer inclusion complex and acrylamide (AM) and cationic monomer aqueous solution copolymerization, be the water-soluble good hydrophobic modified cation of class polyacrylamide, its molecular weight is 2 * 10
6～1 * 10
7Scope, structural formula can be expressed as follows (P-1, P-2):
x＝y＝z＝1
R
1, R
3Independently be H or CH
3
R
2Be the alkyl number greater than 3 less than 16 alkyl, or cycloalkyl;
(P-1)
Or
x＝y＝z＝1
R
4, R
6Independently be H or CH
3
R
5Be (CH
2)
nOr (CH
2CH
2O)
m, m wherein, n is respectively 1～6 integer;
Ph is C
6H
5
(P-2)
The synthetic method of dewatered modified cation polyacrylamide of the present invention is to adopt the method for copolymerization:
In reaction vessel, add hydrophobic monomer inclusion complex, acrylamide monomer, cationic monomer, the dissolving back feeds high purity nitrogen in reaction vessel, the logical nitrogen time is 20～40 minutes, add initiator then, continued logical nitrogen 10～15 minutes, heat up naturally and carry out polymerization, preferably carry out polymerization, obtain transparent polymeric articles at 20～60 ℃; Use the acetone precipitation purifying then, hydrophobic monomer inclusion complex and unreacted monomer can be removed, vacuum-drying obtains the dewatered modified cation polyacrylamide to constant weight under 30～60 ℃ of temperature.
In polymerization system, 65～89.9mol% that acrylamide monomer accounts for the total monomer amount is good, and 10～30mol% that cationic monomer (PB) accounts for the total monomer amount is good, and 0.1～5mol% that hydrophobic monomer inclusion complex (PA or PC) accounts for the total monomer amount is good.Initiator content is that 0.1～2.0wt% of monomer total amount is good.
Used initiator is water-soluble radical initiator among the present invention, as hydrogen peroxide, persulphate or water-soluble azo etc., or the redox system of formations such as a kind of and reductive agent triethylamine in the described water-soluble radical initiator or Tetramethyl Ethylene Diamine, both mass ratioes are 1:1.
Described persulphate is ammonium persulphate or Potassium Persulphate etc.
Described water-soluble azo is azo two NSC 18620 salt or azo two (methylpent hydrochlorate) etc.
Described cationic monomer is methylacryoyloxyethyl trimethyl ammonium chloride or acrylyl oxy-ethyl-trimethyl salmiac.
By introducing the hydrophobic monomer inclusion complex, can associate mutually among the present invention, help polymer interchain bridging action, the flocculating effect of polymkeric substance is increased by the hydrophobic interaction of flexible alkyl chains or end group phenyl ring.Though this water insoluble of class hydrophobic monomer inclusion complex is dissolved in organic solvent in addition, but since they content is seldom in multipolymer, so by acrylamide monomer, cationic monomer with contain the multipolymer that the hydrophobic monomer inclusion complex of hydrophobic monomer forms on a small quantity and still keep well water-soluble, play certain hydrophobic interaction simultaneously again.
Employed hydrophobic monomer inclusion complex is the hydrophobic monomer inclusion complex that is formed by the cyclic dextrin clathrate hydrophobic monomer under certain conditions in the homogeneous phase copolymerization of the present invention, inclusion effect by cyclodextrin becomes water-soluble monomer with the hydrophobic monomer modification, removed the use of organic solvent or tensio-active agent from, avoided the pollution to environment, cyclodextrin can carry out recycle and reuse simultaneously.This hydrophobic monomer inclusion complex is water-soluble good, can be used for polyreaction.Be fit to the hydrophobic monomer of this technology, comprise following broad variety.
(1) long-chain hydrophobic monomer molecule (PA)
(2) the short alkyl chain hydrophobic molecule (PC) of benzene end group
The preparation method of hydrophobic monomer inclusion complex of the present invention is, according to geometrical shape, size and the polarity of hydrophobic monomer, selects suitable water-soluble good cyclodextrin or derivatives thereof for use, and adopting altogether, molten legal system is equipped with inclusion complex.Cyclodextrin and hydrophobic monomer all are dissolved in the mixed solvent of water/organic solvent or with in a kind of organic solvent.At first hydrophobic monomer and cyclodextrin or derivatives thereof are dissolved in the mixed solvent of the water/organic solvent in the container or in the organic solvent for the ratio of 1:1～1:3 in molar ratio, this container is placed on the vibrator, about continuous oscillation at normal temperatures 3～15 hours, whether detect the inclusion reaction with thin layer chromatography complete, rotary evaporation removes and desolvates then, product vacuum-drying under the temperature about 30 ℃～50 ℃ obtains the hydrophobic monomer inclusion complex product of solid, water soluble.If will be further purified, solid product can be dissolved in the distilled water again, through handling with lyophilize behind the membrane filtration, can obtain pure Powdered hydrophobic monomer inclusion complex.Obtain water-soluble good hydrophobic monomer inclusion complex and can be directly used in polyreaction.
Cyclodextrin used in the aforesaid method can comprise methyl flamprop, hydroxyethyl cyclodextrin or hydroxypropyl cyclodextrin etc. for all water-soluble good cyclodextrin.
The present invention has prepared a class multifunctional organic polymer flocculant by introduced suitable hydrophobic grouping in dewatered modified cation polyacrylamide (multifunctional organic polymer flocculant).The introducing of suitable hydrophobic grouping can promote the flocculation of suspended substance by intermolecular association.
Its molecular weight of dewatered modified cation polyacrylamide of the present invention's preparation is 2 * 10
6～1 * 10
7Scope, showing in the aqueous solution has good throwing out to kaolin families or dye class sewage.Simultaneously oil field class sewage, sanitary sewage etc. there is same action effect.
Description of drawings
Fig. 1 embodiment of the invention 1,4,5 dewatered modified cation concentration of polyacrylamide are to the influence of Kaolin clay suspension settling velocity.
Embodiment
Embodiment 1:
(1) hydrophobic monomer inclusion complex Me-β-CD/PA
(Me-β-CD) inclusion hydrophobic monomer PA (methacrylic tert-butyl acrylate) forms water-soluble good hydrophobic monomer inclusion complex in water, is that 2:1 prepares according to the molar ratio of Me-β-CD/PA to adopt methyl flamprop.Me-β-CD (0.04mol) and PA (0.02mol) are dissolved in the 100ml methanol solution, place on the vibrator concussion of continuous oscillation room temperature at normal temperatures 10 hours with filling the container that mixes back solution.Behind the evaporate to dryness methanol solvate, obtain solid hydrophobic monomer inclusion complex, 30 ℃ in vacuum drying oven dry 5 hours.
(2) dewatered modified cation polyacrylamide (P-1) is synthetic
Adopt H
2O is that solvent carries out the homogeneous phase copolymerization, and adding hydrophobic monomer inclusion complex 1.25g (0.0004mol), cationic monomer methylacryoyloxyethyl trimethyl ammonium chloride 3.99g (0.019mol) and acrylamide 7.18g (0.10mol) are dissolved in the 40ml water in reaction vessel.In reactor, feed high purity nitrogen 30 minutes, add initiator (m
Ammonium persulphate/ m
Tetramethyl Ethylene Diamine=1:2) ammonium persulphate 0.011g, Tetramethyl Ethylene Diamine 0.022g continued logical nitrogen after 20 minutes, natural intensification polymerization, polymerization conversion keeps more than 95%.Polymerisate is removed cyclodextrin and unreacted monomer with acetone reprecipitation twice, and the polymer samples behind the purifying is dried to constant weight under 45 ℃ of vacuum.The hydrophobic body molar content of the dewatered modified cation polyacrylamide that obtains is 0.33%, and the positively charged ion molar content is 15.8%, and the acrylamide molar content is 83.87%, and polymericular weight is 6.7 * 10
6The dewatered modified cation concentration of polyacrylamide to the influence of Kaolin clay suspension settling velocity as shown in Figure 1.
Embodiment 2:
Adopt the method among the embodiment 1 to prepare the hydrophobic monomer inclusion complex.According to the method for embodiment 1, adjust following processing condition, other is identical with embodiment 1, the preparation polymkeric substance.The terpolymer of hydrophobic monomer content and cation mono body burden system (P-1).The hydrophobic monomer molar content is 0.3% in the dewatered modified cation polyacrylamide that obtains, and the cationic monomer molar content is 10%, and the acrylamide molar content is 89.7%, and polymericular weight is 8.3 * 10
6This base polymer shows in the aqueous solution has good throwing out to kaolin families or dye class sewage.Simultaneously oil field class sewage, sanitary sewage etc. there is same action effect.
Embodiment 3:
Adopt the method among the embodiment 1 to prepare the hydrophobic monomer inclusion complex.According to the method for embodiment 1, adjust following processing condition, other is identical with embodiment 1, the preparation polymkeric substance.Adjust hydrophobic body burden and cationic monomer (acrylyl oxy-ethyl-trimethyl salmiac) content and prepare terpolymer (P-1).The hydrophobic monomer molar content is 5% in the dewatered modified cation polyacrylamide that obtains, and the cationic monomer molar content is 30%, and the acrylamide molar content is 65%, and polymericular weight is 5.6 * 10
6
Embodiment 4: dewatered modified cation polyacrylamide (P-2) synthetic
(1) hydrophobic monomer inclusion complex Me-β-CD/PC
(Me-β-CD) inclusion hydrophobic monomer (benzene tripropoxy acrylate) forms water-soluble good hydrophobic monomer inclusion complex in water, is that 3:1 prepares according to the molar ratio of Me-β-CD/PC to adopt methyl flamprop.Me-β-CD (0.06mol) and PC (0.02mol) are dissolved in the 100ml butanediol solution, place on the vibrator concussion of continuous oscillation room temperature at normal temperatures 10 hours with filling the container that mixes back solution.Behind the evaporate to dryness methanol solvate, obtain solid hydrophobic monomer inclusion complex, 40 ℃ in vacuum drying oven dry 4 hours.
(2) hydrophobic modified cationic block terpolymer (P-2) is synthetic
Adopt H
2O is that solvent carries out the homogeneous phase copolymerization, adds hydrophobic monomer inclusion complex, cationic monomer methylacryoyloxyethyl trimethyl ammonium chloride and acrylamide and be dissolved in the 100ml water in reaction vessel.In reactor, feed high purity nitrogen 35 minutes, add initiator azo two NSC 18620 salt 0.011g, continue logical nitrogen after 20 minutes, natural intensification polymerization.The hydrophobic monomer molar content is 0.3% in the dewatered modified cation polyacrylamide that obtains, and the cationic monomer molar content is 10%, and the acrylamide molar content is 89.7%, and polymericular weight is 7.5 * 10
6The dewatered modified cation concentration of polyacrylamide to the influence of Kaolin clay suspension settling velocity as shown in Figure 1.
Embodiment 5:
Method prepares hydrophobic body inclusion complex (PC) (benzene triethoxy acrylate) among the employing embodiment 4.According to method among the embodiment 4, adjust following processing condition, other is identical with embodiment 1, the preparation polymkeric substance.Add two (methylpent hydrochlorate) 0.013g of initiator azo, adjust the terpolymer (P-2) of hydrophobic body burden and cationic monomer (acrylyl oxy-ethyl-trimethyl salmiac) content system.The hydrophobic monomer molar content is 5% in the dewatered modified cation polyacrylamide that obtains, and the cationic monomer molar content is 30%, and the acrylamide molar content is 65%, and polymericular weight is 5.3 * 10
6This base polymer shows in the aqueous solution has good throwing out to kaolin families or dye class sewage.Simultaneously oil field class sewage, sanitary sewage etc. there is same action effect.
Claims (10)
1. a dewatered modified cation polyacrylamide is characterized in that, this dewatered modified cation polyacrylamide has following structure:
x＝y＝z＝1
R
1, R
3Independently be H or CH
3
R
2Be the alkyl number greater than 3 less than 16 alkyl, or cycloalkyl;
Or
x＝y＝z＝1
R
4, R
6Independently be H or CH
3
R
5Be (CH
2)
nOr (CH
2CH
2O)
m, m wherein, n is respectively 1～6 integer;
Ph is C
6H
5
2. dewatered modified cation polyacrylamide according to claim 1 is characterized in that the molecular weight of described dewatered modified cation polyacrylamide is 2 * 10
6～1 * 10
7Scope.
3. the synthetic method of a dewatered modified cation polyacrylamide according to claim 1 and 2 is characterized in that:
In reaction vessel, add hydrophobic monomer inclusion complex, acrylamide monomer, cationic monomer, the dissolving back feeds high purity nitrogen in reaction vessel, the logical nitrogen time is 20～40 minutes, add initiator then, continue logical nitrogen 10～15 minutes, and heated up naturally and carry out polymerization, obtain transparent dewatered modified cation polyacrylamide polymers product.
4. synthetic method according to claim 3, it is characterized in that: in polymerization system, acrylamide monomer accounts for 65～89.9mol% of total monomer amount, and cationic monomer accounts for 10～30mol% of total monomer amount, and the hydrophobic monomer inclusion complex accounts for 0.1～5mol% of total monomer amount.
5. according to claim 3 or 4 described synthetic methods, it is characterized in that: described initiator content is 0.1～2.0wt% of monomer total amount.
6. synthetic method according to claim 5 is characterized in that: described initiator is hydrogen peroxide, persulphate or the water-soluble azo in the water-soluble radical initiator; Or the redox system of a kind of and reductive agent triethylamine in the described water-soluble radical initiator or Tetramethyl Ethylene Diamine formation, both mass ratioes are 1:1.
7. synthetic method according to claim 3 is characterized in that: described cationic monomer is methylacryoyloxyethyl trimethyl ammonium chloride or acrylyl oxy-ethyl-trimethyl salmiac.
8. hydrophobic monomer inclusion complex that is used to prepare claim 1 or 2 described dewatered modified cation polyacrylamides, it is characterized in that: described hydrophobic monomer inclusion complex is the hydrophobic monomer inclusion complex that is formed by the cyclic dextrin clathrate hydrophobic monomer, and described hydrophobic monomer structure is:
(1) long-chain hydrophobic monomer molecule
Or
(2) the short alkyl chain hydrophobic molecule of benzene end group
9. the synthetic method of a hydrophobic monomer inclusion complex according to claim 8, it is characterized in that: described hydrophobic monomer inclusion complex is by hydrophobic monomer and cyclodextrin or derivatives thereof are dissolved in the mixed solvent of the water/organic solvent in the container or in the organic solvent for the ratio of 1:1～1:3 in molar ratio, this container is placed on the vibrator, continuous oscillation at normal temperatures 3～15 hours, after reacting completely, evaporation removes and desolvates, product vacuum-drying under 30 ℃～50 ℃ temperature obtains the hydrophobic monomer inclusion complex product of solid, water soluble.
10. the purposes of a dewatered modified cation polyacrylamide according to claim 1 and 2, it is characterized in that: described dewatered modified cation polyacrylamide can have throwing out to kaolin families or dye class sewage in the aqueous solution; Or oil field class sewage, sanitary sewage there is throwing out.
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