CN106749897A - A kind of P（AM‑DMDAAC）Synthetic method - Google Patents
A kind of P（AM‑DMDAAC）Synthetic method Download PDFInfo
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- CN106749897A CN106749897A CN201710025931.0A CN201710025931A CN106749897A CN 106749897 A CN106749897 A CN 106749897A CN 201710025931 A CN201710025931 A CN 201710025931A CN 106749897 A CN106749897 A CN 106749897A
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- 238000010189 synthetic method Methods 0.000 title claims abstract description 16
- 239000000178 monomer Substances 0.000 claims abstract description 63
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 17
- 101150096185 PAAS gene Proteins 0.000 claims abstract description 8
- 238000006243 chemical reaction Methods 0.000 claims description 54
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 24
- 239000010453 quartz Substances 0.000 claims description 20
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 18
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 17
- 239000004202 carbamide Substances 0.000 claims description 17
- 239000003999 initiator Substances 0.000 claims description 17
- LXEKPEMOWBOYRF-UHFFFAOYSA-N [2-[(1-azaniumyl-1-imino-2-methylpropan-2-yl)diazenyl]-2-methylpropanimidoyl]azanium;dichloride Chemical group Cl.Cl.NC(=N)C(C)(C)N=NC(C)(C)C(N)=N LXEKPEMOWBOYRF-UHFFFAOYSA-N 0.000 claims description 12
- 229910052757 nitrogen Inorganic materials 0.000 claims description 9
- 238000009738 saturating Methods 0.000 claims description 9
- 238000007789 sealing Methods 0.000 claims description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 9
- 239000011259 mixed solution Substances 0.000 claims description 8
- 238000000746 purification Methods 0.000 claims description 8
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 7
- 239000012153 distilled water Substances 0.000 claims description 7
- 239000000463 material Substances 0.000 claims description 7
- 239000001301 oxygen Substances 0.000 claims description 7
- 229910052760 oxygen Inorganic materials 0.000 claims description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- 239000007788 liquid Substances 0.000 claims description 6
- 238000005406 washing Methods 0.000 claims description 6
- 239000000084 colloidal system Substances 0.000 claims description 5
- 239000000243 solution Substances 0.000 claims description 5
- 239000002253 acid Substances 0.000 claims description 4
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 claims description 3
- 239000012467 final product Substances 0.000 claims description 3
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 3
- 150000003839 salts Chemical class 0.000 claims description 3
- 239000007787 solid Substances 0.000 claims description 3
- 238000003756 stirring Methods 0.000 claims description 3
- 238000001556 precipitation Methods 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims 3
- 210000002700 urine Anatomy 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 6
- 238000000034 method Methods 0.000 abstract description 6
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 22
- 238000003786 synthesis reaction Methods 0.000 description 15
- 230000015572 biosynthetic process Effects 0.000 description 14
- 239000011521 glass Substances 0.000 description 13
- 150000003254 radicals Chemical class 0.000 description 11
- 238000002834 transmittance Methods 0.000 description 11
- 239000000047 product Substances 0.000 description 10
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 5
- 238000010586 diagram Methods 0.000 description 5
- XFOSBZOUUACCCN-UHFFFAOYSA-M dimethyl-bis(prop-2-enyl)azanium;prop-2-enamide;chloride Chemical compound [Cl-].NC(=O)C=C.C=CC[N+](C)(C)CC=C XFOSBZOUUACCCN-UHFFFAOYSA-M 0.000 description 5
- 229910052708 sodium Inorganic materials 0.000 description 5
- 239000011734 sodium Substances 0.000 description 5
- 230000008859 change Effects 0.000 description 4
- GQOKIYDTHHZSCJ-UHFFFAOYSA-M dimethyl-bis(prop-2-enyl)azanium;chloride Chemical compound [Cl-].C=CC[N+](C)(C)CC=C GQOKIYDTHHZSCJ-UHFFFAOYSA-M 0.000 description 4
- 238000004134 energy conservation Methods 0.000 description 4
- 238000005265 energy consumption Methods 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- 230000035484 reaction time Effects 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 3
- 230000033228 biological regulation Effects 0.000 description 3
- 125000002091 cationic group Chemical group 0.000 description 3
- 238000000354 decomposition reaction Methods 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 3
- 229910052753 mercury Inorganic materials 0.000 description 3
- -1 polypropylene Polymers 0.000 description 3
- 239000010802 sludge Substances 0.000 description 3
- 238000012546 transfer Methods 0.000 description 3
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 239000004743 Polypropylene Substances 0.000 description 2
- 239000006184 cosolvent Substances 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000009776 industrial production Methods 0.000 description 2
- 229920002401 polyacrylamide Polymers 0.000 description 2
- 229920001155 polypropylene Polymers 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 230000001960 triggered effect Effects 0.000 description 2
- 241000208340 Araliaceae Species 0.000 description 1
- 244000138502 Chenopodium bonus henricus Species 0.000 description 1
- 235000008645 Chenopodium bonus henricus Nutrition 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- 235000005035 Panax pseudoginseng ssp. pseudoginseng Nutrition 0.000 description 1
- 235000003140 Panax quinquefolius Nutrition 0.000 description 1
- 229920002125 Sokalan® Polymers 0.000 description 1
- 125000003368 amide group Chemical group 0.000 description 1
- 235000019270 ammonium chloride Nutrition 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 1
- 235000008434 ginseng Nutrition 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000006698 induction Effects 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 230000033116 oxidation-reduction process Effects 0.000 description 1
- 239000004584 polyacrylic acid Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000013049 sediment Substances 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 238000009281 ultraviolet germicidal irradiation Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/52—Amides or imides
- C08F220/54—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide
- C08F220/56—Acrylamide; Methacrylamide
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/01—Processes of polymerisation characterised by special features of the polymerisation apparatus used
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/46—Polymerisation initiated by wave energy or particle radiation
- C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
Abstract
The invention discloses a kind of P（AM‑DMDAAC）Synthetic method, using AM monomers, DMDAAC monomers and the PAAS as template, initiated polymerization synthesizes P to the method in the presence of low pressure UV（AM‑DMDAAC）.Have the advantages that synthetic effect is good, safe.
Description
Technical field
The invention belongs to technical field of organic synthesis, and in particular to a kind of synthetic method of P (AM-DMDAAC).
Background technology
PAMC (CPAM) is to use extensive sludge conditioner at present.With water quality continuous deterioration and
The continuous increase of displacement, causes sewage load to increase and process depth and increases, and then sludge quantitative change is big.Thus for sun from
Sub- polyacrylamide (CPAM), either its demand or species are all essential.But traditional cation polypropylene acyl
Amine (CPAM) mostly do not concentrate and cause that positive charge density is smaller by cation cell distribution, so as to limit it in sludge dewatering
Application.
For the defect of PAMC (CPAM), people have developed P (AM-DMDAAC) it is i.e. poly- (acrylamide-
Dimethyl diallyl ammonium chloride), the method for synthesis is for typically with acrylamide (AM) monomer, dimethyl diallyl at present
Ammonium chloride (DMDAAC) monomer, low-molecular polypropylene acid sodium (PAAS) is template, and polymerization synthesis P (AM- are triggered by ultraviolet
DMDAAC), ultraviolet synthesis is crucial.
In recent years, ultraviolet light (UV) triggers aqueous solution polymerization technology to cause the attention of scholar, because this method is ring
Guarantor, energy-conservation, and reaction rate are comparatively fast produced.High pressure ultraviolet lamp is mainly 500-1000W using power, and primary waves is a length of
365nm.In addition 120 minutes can be by hydrophobic polymeric method synthesizing cationic polyacrylamide using 200-W lamp and high pressure mercuries.
Additionally, these researchs also reported trigger the modified improvement of lower surface in UV.
However, some new problems occur therewith.Extreme temperature is problem maximum during high-pressure UV triggers, and its record is high
Up to 60-70 DEG C.In addition to ensure polymerisation it is suitable it is constant under conditions of, it is necessary to the complicated condensing plant of addition is reducing
Temperature.Therefore, equipment can increase production cost and in industrial production and operating difficulties.On the other hand, extreme temperature causes polymerization
The crosslinking of thing, further results in the solubility reduction of flocculant.Additionally, high pressure ultraviolet light has penetrability higher, therefore quilt
Think to cause the considerable safety of workshop labourer to threaten, and high pressure ultraviolet light energy consumption is bigger, it is not recommended that in industrial production.
The content of the invention
For deficiencies of the prior art, the present invention provides a kind of synthetic effect good, safe P (AM-
DMDAAC synthetic method).
To achieve these goals, the technical solution adopted by the present invention is as follows：
A kind of synthetic method of P (AM-DMDAAC), it is characterised in that with AM monomers (acrylamide), DMDAAC monomers
(dimethyl diallyl ammonium chloride), urea and the PAAS (PAA) as template, draw in the presence of low pressure UV
Polymerisation is sent out to synthesize P (AM-DMDAAC), i.e., poly- (acrylamide-dimethyl diallyl ammonium chloride).
Specifically include following steps：
1) in wide-mouth bottle add AM monomers and distilled water, then sequentially add PAAS, DMDAAC monomer, urea and
EDTA, then stirs to being completely dissolved, and forms mixed solution.
2) pH value of regulation mixed solution is to 4, then logical nitrogen drives oxygen；Then azo initiator is added in nitrogen atmosphere, and
Continue logical nitrogen 10min, then wide-mouth bottle is sealed, form sealing reaction system.
If pH is because pH value of reaction system is too low for regulation, the amide groups (- CO-NH in polymerization process on AM monomers2)
Intermolecular or intramolecular imidization reaction is susceptible to, is caused polymerizate to be crosslinked or is produced side chain, reduce matrix polymerization
The limiting viscosity of thing；If pH value of reaction system is too high, chain tra nsfer speed can be accelerated, influence chain increases, it is impossible to form pole higher
Limit the polymerizate of viscosity.Therefore regulation system PH=4 may be such that AM is fully utilized.
3) reaction system will be sealed and is placed in wavelength for 253.7nm, power to irradiate more than 1h under the ultraviolet light of 24W, then
More than the sealing reaction system 2h is stood, P (AM-DMDAAC) is in the transparent colloid shape material of sealing reaction system generation.
Its reaction equation be：
In order to further purify, step 4 can also be included)：By P (AM-DMDAAC) solution of transparent colloid shape in distilled water,
And add salt acid for adjusting pH to adjust to pH<2, adding absolute ethyl alcohol carries out washing purification, is precipitated；It is above-mentioned heavy to shred
Form sediment, and with absolute ethyl alcohol carry out washing purification again；Repetition shred, wash purify several times after, be deposited in 60 DEG C by what is obtained
Lower drying obtains final product the P (AM-DMDAAC) of white solid to constant weight.
Wherein：In step 1) in mixed solution in, the mass fraction sum of AM monomers and DMDAAC monomers is 25%, is
Since in the case where monomer gross mass fraction is relatively low, the collision probability of the living radical produced by monomer and ultraviolet light
Reduce, touch opportunity is reduced between monomer and monomer, influence the generation and growth of strand, and reduce the speed of polymerisation
Rate, therefore the limiting viscosity of polymerizate is relatively low；And when monomer gross mass fraction is too high, monomer and monomer, monomer and activity
The probability of contact-impact increases between free radical, causes the speed of polymerisation to be accelerated, and the polymerization reaction heat of generation cannot be timely
Disperse, be also easy to produce chain tra nsfer and chain termination reaction, reduce the limiting viscosity of polymerizate.Additionally, monomer gross mass fraction is too high
The serious crosslinked, branched of the polymerizate molecular structure that also results in, reduces its solubility in water, as shown in Figure 1.
In order to lift the performance of sintetics, DMDAAC monomers are 2 with the mass ratio of AM monomers：3.When DMDAAC mass
When fraction is more than 20%, due to the relatively low DMDAAC too high levels of activity, so that polymerization reaction system is active relatively low, so that
Induction period and the polymerization reaction time for obtaining polymerisation are elongated, monomer may be caused to be polymerized incomplete, and then reduce polymerizate P
(AM-DMDAAC) relative molecular mass, as shown in Figure 2.Therefore monomer ratio is relative influence polymerizate P (AM-DMDAAC)
The key factor of molecular mass, DMDAAC monomers are 2 with the mass ratio of AM monomers：3 are advisable.
The ratio between mass concentration of PAAS and DMDAAC monomers is 1：1.The reaction that adding template can significantly improve DAC is lived
Property so that DAC segments long increase in the strand of synthesis, and in T:The amplitude increased during D=1.0 is maximum.
The urea of addition is urea liquid that mass fraction is 3 ‰.Urea concentration is with product limiting viscosity relation curve such as
Shown in Fig. 3.Because when a small amount of urea is added, can as cosolvent, appropriate cosolvent as assistant reducing agent, by ginseng
Plus oxidation-reduction process, be conducive to kinetic chain length to increase, so as to improve the relative molecular mass of product；When urea concentration is too high
When, the probability of chain tra nsfer will be increased, the growth of chain free radical is hindered, it is unfavorable for the raising of product relative molecular mass.Therefore,
Urea concentration takes 0.3 ‰ preferably.
Step 2) in the azo initiator that adds be V-50 or Va-044, addition is the matter of AM monomers and DMDAAC monomers
The 0.07% of amount sum.This is that, due to the negligible amounts of the free radical produced when V-50 concentration is relatively low, chain is increased one
Fixed inhibitory action.With the increase of V-50 concentration, gel effect causes the inherent viscosity of polymer to continue to increase.From Fig. 4
It can be found that we are with the increase of initiator concentration, and the limiting viscosity of polymer is raised rapidly, when initiator concentration is
When 0.07%, the limiting viscosity of polymer reaches maximum, starts gradually to reduce afterwards.Because if initiator concentration is too low,
The living radical for then producing is less, and chain increasess slowly in polymerisation, causes polymerizate limiting viscosity not high；If initiator
Concentration is more than 0.07%, then excessive living radical, polymerization rate can be produced to accelerate, and a large amount of reaction heat of generation cannot
Disperse in time, make strand more easy fracture, cause the reduction of polymer limiting viscosity.Therefore initiator concentration should preferably take 0.07%.
The time that logical nitrogen drives oxygen is no less than 5min.This is, in order to fully remove the oxygen in reactor, to prevent amino and double
The groups such as key are oxidized.
In order to improve the yield of synthetic product, the material of described wide-mouth bottle is quartz.Because quartz glass has most preferably
Saturating ultra violet light resistance energy and saturating visible ray and near infrared light performance, therefore the light transmittance of quartz reactor is far longer than glass
The light transmittance of reactor, and light intensity higher contributes to light trigger energy absorption, decomposes and produces free radical, so as to trigger polymerization
Reaction so that product yield and inherent viscosity increase, therefore in an experiment using quartz reactor advantageously in entering for testing
OK.Further, since low pressure mercury lamp power is less than high-pressure sodium lamp power, and low pressure UV triggers lower temperature of reaction system also more
Low, lower using low pressure UV energy consumption, product synthesis is complete, more development space.Can be with as reaction vessels using quartz
Ensure that it triggers in low pressure UV and be issued to enough reaction requirements, and the big P (AM- of inherent viscosity can be obtained
DMDAAC), preparation more energy-conservation, also safer is made.
Compared with prior art, the present invention has the advantages that：
1st, synthetic effect is good.The present invention use low pressure UV and quartz reactor, due to quartz glass have it is optimal
Saturating ultra violet light resistance energy and saturating visible ray and near infrared light performance, therefore the light transmittance of quartz reactor to be far longer than glass anti-
The light transmittance of device is answered, and light intensity higher contributes to light trigger energy absorption, decomposes and produces free radical, so as to trigger polymerization anti-
Should so that product yield and inherent viscosity increase, and this causes the better quality of synthetic product.
2nd, yield is high.There is light transmittance very high as reaction vessels due to using quartz, irradiated in low pressure UV,
Through the energy required for making decomposition of initiator produce enough free radicals can be reached so that the comparing that reaction is carried out is complete.
3rd, safety, energy-conservation.Low pressure mercury lamp power is less than high-pressure sodium lamp power, and low pressure UV triggers lower reaction system temperature
Degree is also lower, lower using low pressure UV energy consumption, while low pressure UV influences less to people, security is higher, is easy to
Promoted the use of in workshop.
Brief description of the drawings
The limiting viscosity relation curve of the mass fraction sum of Fig. 1 monomers and the P (AM-DMDAAC) of synthesis；
Fig. 2 is the limiting viscosity relation curve of DMC mass fractions and the P (AM-DMDAAC) of synthesis；
Fig. 3 is the limiting viscosity relation curve of urea concentration and the P (AM-DMDAAC) of synthesis；
Fig. 4 is the limiting viscosity relation curve of initiator concentration and the P (AM-DMDAAC) of synthesis；
Fig. 5 is the influence comparison diagram of Fig. 1 quartz reactors and glass reactor to conversion ratio；
Fig. 6 is the influence comparison diagram of quartz reactor and glass reactor to inherent viscosity；
Fig. 7 is influence comparison diagram of the ultraviolet light-initiated lower light application time of high-low pressure to system temperature；
Fig. 8 is influence comparison diagram of the high-low pressure UV Light time to inherent viscosity；
Fig. 9 is the influence comparison diagram of high-low pressure UV Light time conversion ratio.
Specific embodiment
The present invention is described in further detail with reference to specific embodiment.
Embodiment one
Using AM monomers (acrylamide), DMDAAC monomers (, dimethyl diallyl ammonium chloride) and as the PAAS of template
(PAA), initiated polymerization synthesizes P (AM-DMDAAC) in the presence of low pressure UV, i.e., poly- (acrylamide-
Dimethyl diallyl ammonium chloride).Wherein reaction with wide-mouth bottle quartz material be respectively adopted carry out parallel reality with glass material
Test to consider quartz and influence of the glass to conversion ratio and inherent viscosity, specific step is：
1) to AM monomers and distilled water is added in wide-mouth bottle, PAAS, DMDAAC monomer, EDTA and urea are then sequentially added
(60mg urea being added in 20ml distilled water, obtain the urea liquid that concentration is 3 ‰), then stirs to being completely dissolved, and is formed
Mixed solution.
2) pH value of mixed solution can be adjusted to 4 with hydrochloric acid and NaOH, then logical nitrogen drives oxygen；Then in nitrogen atmosphere
Middle addition azo initiator, and continue logical nitrogen 10min, then wide-mouth bottle is sealed, form sealing reaction system.
3) reaction system will be sealed and is placed in wavelength for 253.7nm, power to irradiate more than 1h under the ultraviolet light of 24W, then
More than the sealing reaction system 2h is stood, P (AM-DMDAAC) is in the transparent colloid shape material of sealing reaction system generation.
Its reaction equation be：
4)：By P (AM-DMDAAC) solution of transparent colloid shape in distilled water, and salt acid for adjusting pH is added to adjust to pH<2, then
Adding absolute ethyl alcohol carries out washing purification, is precipitated；
To shred above-mentioned precipitation, and with absolute ethyl alcohol carry out washing purification again；Repetition shred, wash purification 3 times after, general
Obtain be deposited in 60 DEG C at dry to constant weight, obtain final product the P (AM-DMDAAC) of white solid.
Wherein：In step 1) in mixed solution in, the mass fraction sum of AM monomers and DMDAAC monomers is 25%.
DMDAAC monomers are 2 with the mass ratio of AM monomers：3.The ratio between mass concentration of PAAS and DMDAAC monomers is 1：1.
Step 2) in the azo initiator that adds be V-50 or Va-044, addition is the matter of AM monomers and DMDAAC monomers
The 0.07% of amount sum.The time that logical nitrogen drives oxygen is no less than 5min.Azo initiator is V-50 or Va-044, and addition is that AM is mono-
The 0.07% of the quality sum of body and DMDAAC monomers.The urea of addition is solution that mass concentration is 3 ‰.
In the polymerization, the translucency of reactor and the quantity of free radical are related, thus for synthesis P (DMDAAC)
Conversion ratio and inherent viscosity have considerable influence.Keep other conditions constant, when temperature is room temperature, in PH=4, total monomer quality point
Number content is 25% (cationic monomer DMDAAC accounts for total monomer 40%), masterplate and cationic monomer DMDAAC concentration ratios T:D=
1：1, initiator concentration is 0.7 ‰ (accounting for total monomer content), and urea concentration is 3 ‰ (accounting for total monomer content), PAAS (polyacrylic acid
Sodium) under masterplate, measure light application time is for the conversion ratio of synthesis P (AM-DMDAAC) and the influence situation of inherent viscosity.From figure
5th, understand in 6, with the increase of light application time, the conversion ratio and inherent viscosity of synthesis P (AM-DMDAAC) all increase therewith, and
The conversion ratio and inherent viscosity for synthesizing P (AM-DMDAAC) in quartz reactor are above glass reactor synthesis P (AM-
DMDAAC conversion ratio) and inherent viscosity, and when reacted between more than 60min after, synthesis P (AM-DMDAAC) conversion ratio and
Inherent viscosity does not continue to increase, and tends towards stability.Wherein, turning for P (AM-DMDAAC) is synthesized in 60min, in quartz reactor
Rate is up to 97.5%, and inherent viscosity is up to 8.05dL*g-1.And in 60min, P (AM- are synthesized in glass reactor
DMDAAC conversion ratio) is up to 89%, and inherent viscosity is up to 9.65dL*g-1.Because quartz glass has optimal saturating purple
Outer optical property and saturating visible ray and near infrared light performance.May certify that the light transmittance of quartz reactor is far longer than glass reaction
The light transmittance of device, and light intensity higher contributes to light trigger energy absorption, decomposes and produces free radical, so as to trigger polymerization anti-
Should, product yield and inherent viscosity increase.According to the consideration of conversion ratio, inherent viscosity and energy-conservation, same recipe is being used
Under the premise of, it is more excellent using quartz reactor.
Embodiment two
Using AM monomers (acrylamide), DMDAAC monomers (, dimethyl diallyl ammonium chloride) and as the PAAS of template
(PAA), initiated polymerization synthesizes P (AM-DMDAAC) in the presence of low pressure UV, i.e., poly- (acrylamide-
Dimethyl diallyl ammonium chloride).Its reaction condition is identical with embodiment one, the difference is that only two groups of experiment condition difference
For one group uses high pressure ultraviolet light (wavelength 365nm, power 500W), glass jar, another group uses low pressure UV (wavelength
257.3nm, power 24W) and quartzy wide-mouth bottle, and the ultraviolet light-initiated lower light application time of high-low pressure is considered in this way to system temperature
The influence of degree, the influence of high-low pressure UV Light time conversion ratio.
As seen from Figure 7, with the increase in reaction time, the temperature of reaction system is all significantly increased, its mesohigh
It is ultraviolet it is light-initiated under system temperature change it is more violent.To after 60min between when reacted, two kinds are triggered lower system temperatures to become
In stabilization, illustrate that synthetic reaction is all basically completed, in course of reaction, the ultraviolet light-initiated lower body system temperature of high pressure is reached as high as 68
DEG C or so, low pressure UV triggers lower system temperature to reach as high as 34 DEG C or so, and both differ obvious.Because quartz glass has
Optimal saturating ultra violet light resistance energy and saturating visible ray and near infrared light performance so that the light transmittance of quartz reactor is far longer than glass
The light transmittance of glass reactor, even if so quartzy low pressure mercury lamp power exports energy less than high-pressure sodium lamp power under similar time
Difference, but because quartz reactor has more preferable light transmittance, its energy utilization rate is higher so that both react the complete time
In 60min or so, substantially always.Thus can Preliminary conclusion, use low pressure UV trigger and quartz reactor, energy profit
Higher with rate, energy consumption is lower, more development space.
As shown in Figure 8, increased with the increase of time using the inherent viscosity of high pressure ultraviolet light and low pressure UV, when anti-
When reaching 60min between seasonable, inherent viscosity has reached 9.85,11.8dL/g.Increase later with the reaction time is almost unchanged.
It is respectively less than obtained by low pressure UV in the identical time using the product performance viscosity of high pressure ultraviolet light.Use high pressure
The temperature of ultraviolet light is high, and the big calorimetric of polymerisation generation can cause that chain propagation reaction terminates earlier, and the big calorimetric for producing
Can be broken the chain for having generated, so being that the chain for obtaining is shorter, molecular weight is smaller, and inherent viscosity is small.Use low pressure UV
The inherent viscosity that irradiation is obtained is higher.
Embodiment three
Using AM monomers (acrylamide), DMDAAC monomers (, dimethyl diallyl ammonium chloride) and as the PAAS of template
(PAA), initiated polymerization synthesizes P (AM-DMDAAC) in the presence of low pressure UV, i.e., poly- (acrylamide-
Dimethyl diallyl ammonium chloride).Its reaction condition is identical with embodiment two, the difference is that only two groups of experiment condition difference
For one group uses high pressure ultraviolet light (wavelength 365nm, power 500W), glass jar, another group uses low pressure UV (wavelength
257.3nm, power 24W) and quartzy wide-mouth bottle, and consider the high-low pressure UV Light time in this way to inherent viscosity and turn
The influence of rate.
As shown in Figure 9, increased with the increase of time using the conversion ratio of high pressure ultraviolet light and low pressure UV, work as reaction
When time reaches 60min, conversion ratio has reached 98%, 97.6%.Increase later with the reaction time is almost unchanged.Make simultaneously
It is substantially the same in the identical time with the conversion ratio of high pressure ultraviolet light and low pressure UV.This is due to using quartz as anti-
Answering vessel has light transmittance very high, and in low pressure UV irradiation, having been able to reach makes decomposition of initiator generation free enough
Energy required for base so that the comparing that reaction is carried out is complete.The energy discharged using high pressure ultraviolet light can be than using
The height of low pressure UV so that decomposition of initiator more completely, make conversion ratio more slightly higher, but increasing degree very little, it is logical
Cross this cost on the premise of big energy to increase the conversion ratio of very little be substantially unreasonable and uneconomic.
The above embodiment of the present invention is only example to illustrate the invention, and is not to implementation of the invention
The restriction of mode.For those of ordinary skill in the field, other can also be made not on the basis of the above description
With the change and variation of form.Here all of implementation method cannot be exhaustive.It is every to belong to technical scheme
The obvious change amplified out changes row still in protection scope of the present invention.
Claims (10)
1. a kind of P（AM-DMDAAC）Synthetic method, it is characterised in that using AM monomers, DMDAAC monomers, urea and as mould
The PAAS of plate, initiated polymerization synthesizes P in the presence of low pressure UV（AM-DMDAAC）.
2. P according to claim 1（AM-DMDAAC）Synthetic method, it is characterised in that comprise the following steps：
1）To AM monomers and distilled water is added in wide-mouth bottle, PAAS, DMDAAC monomer, urea and EDTA are then sequentially added, so
After stir to being completely dissolved, form mixed solution；
2）The pH value of mixed solution is adjusted to 4, then logical nitrogen drives oxygen；Then azo initiator is added in nitrogen atmosphere, and is continued
Logical nitrogen 10min, then wide-mouth bottle is sealed, form sealing reaction system；
3）Reaction system will be sealed and be placed in wavelength for 253.7nm, power to irradiate more than 1h under the ultraviolet light of 24W, then stood
More than the sealing reaction system 2h, P is in the transparent colloid shape material of sealing reaction system generation（AM-DMDAAC）.
3. P according to claim 2（AM-DMDAAC）Synthetic method, it is characterised in that also including step 4）：Will be saturating
The P of bright colloidal（AM-DMDAAC）Solution adds salt acid for adjusting pH to adjust to pH in distilled water<2, add absolute ethyl alcohol and enter
Row washing purification, is precipitated；
To shred above-mentioned precipitation, and with absolute ethyl alcohol carry out washing purification again；Repetition shred, wash purification several times after, general
Obtain be deposited in 60 DEG C at dry to constant weight, obtain final product the P of white solid（AM-DMDAAC）.
4. P according to claim 2（AM-DMDAAC）Synthetic method, it is characterised in that in step 1）In mixing it is molten
In liquid, the mass fraction sum of AM monomers and DMDAAC monomers is 25%.
5. P according to claim 2（AM-DMDAAC）Synthetic method, it is characterised in that in step 1）In mixing it is molten
In liquid, DMDAAC monomers are 2 with the mass ratio of AM monomers：3.
6. P according to claim 2（AM-DMDAAC）Synthetic method, it is characterised in that in step 1）In mixing it is molten
In liquid, the ratio between mass concentration of PAAS and DMDAAC monomers is 1：1.
7. P according to claim 2（AM-DMDAAC）Synthetic method, it is characterised in that step 2）The azo of middle addition
Initiator is V-50 or Va-044, and addition is the 0.7% of the quality sum of AM monomers and DMDAAC monomers.
8. P according to claim 2（AM-DMDAAC）Synthetic method, it is characterised in that step 2）In lead to nitrogen and drive oxygen
Time is no less than 5min.
9. P according to claim 2（AM-DMDAAC）Synthetic method, it is characterised in that the material of described wide-mouth bottle
It is quartz.
10. P according to claim 2（AM-DMDAAC）Synthetic method, it is characterised in that step 1）The urine of middle addition
Element is urea liquid that mass fraction is 3 ‰.
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