CN1458177A - Technology for preparing itaconic acid-propenoic acid copolymer from fermented liquid - Google Patents
Technology for preparing itaconic acid-propenoic acid copolymer from fermented liquid Download PDFInfo
- Publication number
- CN1458177A CN1458177A CN 02110331 CN02110331A CN1458177A CN 1458177 A CN1458177 A CN 1458177A CN 02110331 CN02110331 CN 02110331 CN 02110331 A CN02110331 A CN 02110331A CN 1458177 A CN1458177 A CN 1458177A
- Authority
- CN
- China
- Prior art keywords
- acid
- itaconic acid
- technology
- acid copolymer
- propenoic
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 229920001577 copolymer Polymers 0.000 title claims abstract description 31
- 238000005516 engineering process Methods 0.000 title claims abstract description 23
- 239000007788 liquid Substances 0.000 title claims abstract description 7
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 claims abstract description 53
- 238000000855 fermentation Methods 0.000 claims abstract description 33
- 230000004151 fermentation Effects 0.000 claims abstract description 33
- 239000003999 initiator Substances 0.000 claims abstract description 17
- NIXOWILDQLNWCW-UHFFFAOYSA-N Acrylic acid Chemical compound OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000000178 monomer Substances 0.000 claims abstract description 6
- 238000006243 chemical reaction Methods 0.000 claims abstract description 5
- 238000007334 copolymerization reaction Methods 0.000 claims abstract description 5
- 239000000463 material Substances 0.000 claims abstract description 4
- 235000014347 soups Nutrition 0.000 claims description 29
- 239000003795 chemical substances by application Substances 0.000 claims description 12
- 239000007787 solid Substances 0.000 claims description 11
- 238000006116 polymerization reaction Methods 0.000 claims description 10
- 238000005342 ion exchange Methods 0.000 claims description 7
- 230000002829 reductive effect Effects 0.000 claims description 7
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 5
- 239000011777 magnesium Substances 0.000 claims description 5
- 229910052749 magnesium Inorganic materials 0.000 claims description 5
- LCPVQAHEFVXVKT-UHFFFAOYSA-N 2-(2,4-difluorophenoxy)pyridin-3-amine Chemical compound NC1=CC=CN=C1OC1=CC=C(F)C=C1F LCPVQAHEFVXVKT-UHFFFAOYSA-N 0.000 claims description 4
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 4
- YYRMJZQKEFZXMX-UHFFFAOYSA-N calcium;phosphoric acid Chemical compound [Ca+2].OP(O)(O)=O.OP(O)(O)=O YYRMJZQKEFZXMX-UHFFFAOYSA-N 0.000 claims description 4
- 239000012141 concentrate Substances 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 4
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 claims description 4
- 239000002994 raw material Substances 0.000 claims description 4
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Substances [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 claims description 4
- 239000002426 superphosphate Substances 0.000 claims description 4
- 239000011734 sodium Substances 0.000 claims description 3
- LSNNMFCWUKXFEE-UHFFFAOYSA-L sulfite Chemical compound [O-]S([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-L 0.000 claims description 3
- DHCDFWKWKRSZHF-UHFFFAOYSA-L thiosulfate(2-) Chemical compound [O-]S([S-])(=O)=O DHCDFWKWKRSZHF-UHFFFAOYSA-L 0.000 claims description 3
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 2
- 239000004160 Ammonium persulphate Substances 0.000 claims description 2
- 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 claims description 2
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical compound SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 claims description 2
- CMEWLCATCRTSGF-UHFFFAOYSA-N N,N-dimethyl-4-nitrosoaniline Chemical compound CN(C)C1=CC=C(N=O)C=C1 CMEWLCATCRTSGF-UHFFFAOYSA-N 0.000 claims description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 2
- 239000004159 Potassium persulphate Substances 0.000 claims description 2
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical compound OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 claims description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 2
- 239000003513 alkali Substances 0.000 claims description 2
- 150000001412 amines Chemical class 0.000 claims description 2
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 2
- 235000019395 ammonium persulphate Nutrition 0.000 claims description 2
- LSXWFXONGKSEMY-UHFFFAOYSA-N di-tert-butyl peroxide Chemical compound CC(C)(C)OOC(C)(C)C LSXWFXONGKSEMY-UHFFFAOYSA-N 0.000 claims description 2
- 239000012933 diacyl peroxide Substances 0.000 claims description 2
- GRWZHXKQBITJKP-UHFFFAOYSA-N dithionous acid Chemical compound OS(=O)S(O)=O GRWZHXKQBITJKP-UHFFFAOYSA-N 0.000 claims description 2
- 229910021645 metal ion Inorganic materials 0.000 claims description 2
- MPNNOLHYOHFJKL-UHFFFAOYSA-N peroxyphosphoric acid Chemical compound OOP(O)(O)=O MPNNOLHYOHFJKL-UHFFFAOYSA-N 0.000 claims description 2
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 claims description 2
- 239000011591 potassium Substances 0.000 claims description 2
- 229910052700 potassium Inorganic materials 0.000 claims description 2
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 claims description 2
- 235000019394 potassium persulphate Nutrition 0.000 claims description 2
- 229910052708 sodium Inorganic materials 0.000 claims description 2
- 229910052725 zinc Inorganic materials 0.000 claims description 2
- 239000011701 zinc Substances 0.000 claims description 2
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 abstract description 9
- 238000000034 method Methods 0.000 abstract description 7
- 239000003599 detergent Substances 0.000 abstract description 5
- 239000002455 scale inhibitor Substances 0.000 abstract description 5
- -1 scale remover Substances 0.000 abstract description 3
- 239000002270 dispersing agent Substances 0.000 abstract 1
- 238000010526 radical polymerization reaction Methods 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 16
- 229920000642 polymer Polymers 0.000 description 10
- 239000000126 substance Substances 0.000 description 10
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 239000011575 calcium Substances 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 5
- 229910052791 calcium Inorganic materials 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- 239000006185 dispersion Substances 0.000 description 4
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 4
- 229920000141 poly(maleic anhydride) Polymers 0.000 description 4
- 230000009466 transformation Effects 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 230000003301 hydrolyzing effect Effects 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 229920002126 Acrylic acid copolymer Polymers 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- 241000040710 Chela Species 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 229920002125 Sokalan® Polymers 0.000 description 2
- 125000002091 cationic group Chemical group 0.000 description 2
- 239000000470 constituent Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000000706 filtrate Substances 0.000 description 2
- 239000008233 hard water Substances 0.000 description 2
- 230000005764 inhibitory process Effects 0.000 description 2
- 235000013980 iron oxide Nutrition 0.000 description 2
- 235000012204 lemonade/lime carbonate Nutrition 0.000 description 2
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000004584 polyacrylic acid Substances 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 description 2
- 238000002834 transmittance Methods 0.000 description 2
- JSYPRLVDJYQMAI-ODZAUARKSA-N (z)-but-2-enedioic acid;prop-2-enoic acid Chemical compound OC(=O)C=C.OC(=O)\C=C/C(O)=O JSYPRLVDJYQMAI-ODZAUARKSA-N 0.000 description 1
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 1
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000001110 calcium chloride Substances 0.000 description 1
- 229910001628 calcium chloride Inorganic materials 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 125000002843 carboxylic acid group Chemical group 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 239000011790 ferrous sulphate Substances 0.000 description 1
- 235000003891 ferrous sulphate Nutrition 0.000 description 1
- 229910052588 hydroxylapatite Inorganic materials 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- VBMVTYDPPZVILR-UHFFFAOYSA-N iron(2+);oxygen(2-) Chemical class [O-2].[Fe+2] VBMVTYDPPZVILR-UHFFFAOYSA-N 0.000 description 1
- 229910000359 iron(II) sulfate Inorganic materials 0.000 description 1
- 239000001095 magnesium carbonate Substances 0.000 description 1
- 235000014380 magnesium carbonate Nutrition 0.000 description 1
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 description 1
- 229960001708 magnesium carbonate Drugs 0.000 description 1
- 229910000021 magnesium carbonate Inorganic materials 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 description 1
- XYJRXVWERLGGKC-UHFFFAOYSA-D pentacalcium;hydroxide;triphosphate Chemical compound [OH-].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O XYJRXVWERLGGKC-UHFFFAOYSA-D 0.000 description 1
- JRKICGRDRMAZLK-UHFFFAOYSA-L persulfate group Chemical group S(=O)(=O)([O-])OOS(=O)(=O)[O-] JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 description 1
- 229920001444 polymaleic acid Polymers 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000003352 sequestering agent Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
Landscapes
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
The present invention provides technology of preparing itaconic acid-propenoic acid copolymer from fermented liquid. With the fermented liquid for producing itaconic acid via biological fermentation as material, and through ionic exchange, concentration, copolymerization with propenoic acid in the presence of initiator, itaconic acid-propenoic acid copolymer solution is prepared. Using the fermented liquid as initial material can lower the cost greatly, and the free radical polymerization process solves the demerit of hard homopolymerization of itaconic acid. The process has less residual monomer and high conversion rate. The copolymer may be used as scale inhibitor, scale remover, dispersant, detergent assistant, etc.
Description
Technical field
The present invention relates to the technology of methylene-succinic acid and acrylic acid copolymer, specifically is the technology that is prepared itaconic acid-propenoic acid copolymer by the fermentation soup.
Background technology
The domestic report of relevant process for polymerization of itaconic acid is less, and the difficult homopolymerization of methylene-succinic acid is in common knowledge for everybody.In addition, the higher development that limits its purposes of methylene-succinic acid price.As the invention disclosed patent application on October 14 in 1992 of Chinese patent communique: process for polymerization of itaconic acid, application number: 92102091, its technical scheme is: be placed with in the container of water when complete neutral monomer solution and initiator solution are joined beginning, be enough to carry out promptly can to generate the polymerization of itaconic acid thing by high conversion under the temperature of polyreaction, transformation efficiency is higher, but owing to consume a large amount of alkali cost is raise.
The production of relevant polycarboxylic acid polymkeric substance both at home and abroad and use morely as polyacrylic acid, hydrolytic polymaleic anhydride, vinylformic acid-maleic acid etc., is widely used in Scale inhibitors, dispersion agent, washing auxiliary detergent, chela and agent etc.Because hydrolytic polymaleic anhydride needs polymerization in organic solvent, pollute greatlyyer, and domestic its polymericular weight is less, someone studies vinylformic acid and toxilic acid aqueous solution copolymerization, and carboxyl is than polyacrylic acid content height on its polymer chain, and is better dispersed, and chela and calcium, magnesium value are higher, reach 200mg/g as the calcium chelating value, pollute also for a short time, but from reactivity ratio, vinylformic acid is 18.05, toxilic acid is 0.0085, and polymerization effect is bad.
Summary of the invention
Characteristics of the present invention are that with the fermentation soup in the methylene-succinic acid production be starting raw material, reduce its cost greatly, and the characteristics of the difficult homopolymerization of methylene-succinic acid have been solved with acrylic acid copolymer, transformation efficiency is higher, its reactivity ratio is respectively: vinylformic acid is 1.89, methylene-succinic acid is 0.52, and polymerization effect is good, carboxylic acid group's content height on the molecular chain.
Concrete grammar of the present invention is: the fermentation soup of producing in the methylene-succinic acid with biological fermentation process is a raw material, after ion-exchange, concentrating, carries out copolymerization with vinylformic acid in the presence of initiator, prepares itaconic acid-propenoic acid copolymer solution.
The described technology for preparing itaconic acid-propenoic acid copolymer by the fermentation soup, the itaconic acid fermentation soup is passed through ion exchange column, remove magnesium wherein, zinc and other metal ion, after to be concentrated into the methylene-succinic acid mass content be 5%～40%, join in the reactor under the insulation, steady temperature is between 30～100 ℃, add initiator solution with uniform feed rate, vinylformic acid, wherein active initiator content (is benchmark with the monomer mass) is 0%～20%, vinylformic acid (is benchmark with the methylene-succinic acid quality) add-on is 5%～200%, add material back restir for some time, about 0.5～3 hour, prepare itaconic acid-propenoic acid copolymer solution.
Describedly prepare the technology of itaconic acid-propenoic acid copolymer by the fermentation soup, the fermentation soup also can concentrate earlier, after pass through ion exchange column.
Describedly prepare the technology of itaconic acid-propenoic acid copolymer by the fermentation soup, initiator is selected from the combination of following wherein one or more oxygenants: Sodium Persulfate, ammonium persulphate, Potassium Persulphate, peroxophosphoric acid sodium, potassium superphosphate, ammonium superphosphate, hydrogen peroxide and tert-butyl peroxide, diacyl peroxide; Or itself and single the kind or the combination of multiple reductive agent: sulphite, hydrosulphite, phosphite, thiosulphate, sulfurous acid, mercaptan, ferrous salt, amine are (as N, accelerine) etc., with oxygenant or and the water-soluble respectively aqueous solution that is prepared into of reductive agent, form initiator system.Its concentration is 0.5～30%.Suitable oxygenant is a persulphate, evenly adds in polyreaction, and reductive agent is sulphite, thiosulphate, ferrous salt.
Describedly prepare the technology of itaconic acid-propenoic acid copolymer by the fermentation soup, the reductive agent in the initiator can join before polymerization in the methylene-succinic acid solution, also can evenly add in the reaction system in polymerization.
Describedly prepare the technology of itaconic acid-propenoic acid copolymer by the fermentation soup, initiator and acrylic acid reinforced time are 0.5～5 hour.
The described technology for preparing itaconic acid-propenoic acid copolymer by the fermentation soup, the itaconic acid-propenoic acid copolymer solution of gained is the liquid of solid content about 5%～80%, but also behind the concentrate drying sheet or powdery solid, available bases is (as sodium hydroxide, potassium hydroxide, ammonia etc.) after the neutralization, the reconcentration drying is sheet or powdery solid.
According to initiator and other condition difference,, be fit to different purposes by the inventive method synthetic polymkeric substance for molecular weight is 300～20000 series product (number-average molecular weight).This polymkeric substance can be used for Scale inhibitors, scale remover, sequestrant, dispersion agent, washing auxiliary detergent etc.This polymkeric substance has good dispersing property to ferric oxide etc., can effectively stop the formation of dirts layers such as lime carbonate, magnesiumcarbonate, silicate, hydroxylapatite and adheres to, and the calcium chelating value can reach more than the 240mg/g, and the magnesium chelating value can reach more than 200.
Embodiment
Example 1: a certain amount of itaconic acid fermentation soup is passed through cationic exchange coloum, the back is concentrated into solid content under negative pressure be 35% methylene-succinic acid solution, get this solution 300mL and join in the 500mL four-hole round-bottomed flask, get ferrous sulfate 0.1g and add wherein dissolving, and feed nitrogen.Respectively 4g Sodium Persulfate and 4g S-WAT are dissolved in the 50mL water, 90 ℃ down and 70g vinylformic acid join simultaneously in the flask, add restir 1 hour in 3 hours.Cooling obtains 392mL scarlet polymers soln.
Resulting polymers solution transformation efficiency is 97.8% (is benchmark with the methylene-succinic acid), and unpolymerized remaining methylene-succinic acid monomer is 2.2%.Resulting polymers density is 1.21g/mL (25 ℃), and solid content is 42.3%, and number-average molecular weight is 900.
The test of resulting polymers scale inhibition performance: contain Ca
2+250mg/L, HCO
3 -250mg/L (in lime carbonate) hard water preparation: get NaHCO
30.21g and CaCl
20.2775g be dissolved in the 200mL distilled water, be diluted with water to 1000mL.This polymkeric substance and commercially available hydrolytic polymaleic anhydride are joined respectively in this hard water of 500mL, making its effective constituent concentration is 8mg/L, stirs 8 hours cooled and filtered down at 80 ℃, with calcium contents in the EDTA filtrates tested, scale inhibition performance is respectively 99.80% and 99.75%.
The test of resulting polymers dispersing iron oxide: get 0.0880gFeSO
47H
2O, 100mL0.25mol/L Na
2B
4O
7, 40.8mL1mol/LHCl is made into 2000mL solution, and wherein polymkeric substance effective constituent is 10mg/L, and 70 ℃ of following constant temperature 6 hours, cooling was left standstill.Getting this polymkeric substance equally compares with commercially available hydrolyzed polymaleic anhydride, the cooling back adds the solution non-oxidation iron precipitation of this polymkeric substance, is 88.7% with spectrophotometer at 650nm place its transmittance of test, and the solution of adding polymaleic acid has a large amount of red iron oxides precipitations, and its transmittance is 100%.
Example 2: by cationic exchange coloum, the back is concentrated into solid content under negative pressure be 39% methylene-succinic acid solution with a certain amount of itaconic acid fermentation soup, gets this solution 300mL and join in the 500mL four-hole round-bottomed flask, and feed nitrogen.Respectively 4g Sodium Persulfate and 6g S-WAT are dissolved in the 50mL water, 70 ℃ down and 80g vinylformic acid join simultaneously in the flask, add restir 1 hour in 2 hours.Cooling obtains the faint yellow polymers soln of 405mL.
Resulting polymers solution transformation efficiency is 99.7% (is benchmark with the methylene-succinic acid), and unpolymerized remaining methylene-succinic acid monomer is 0.3%.Resulting polymers density is 1.19g/mL (25 ℃), and solid content is 41.6%, and number-average molecular weight is 2000.
Resulting polymers is stung the test of the value of closing: get a certain amount of polymkeric substance, solid content is about 0.2g, add water 100mL, regulate pH to 10 with sodium hydroxide, get 20mL0.05M calcium chloride and add, and be diluted to 250mL, in 35 ℃ of following constant temperature 20 minutes, cooled and filtered is got filtrate analysis, and calculating the calcium chelating value is 256mg/g.To sting the value of closing be 180mg/g with record magnesium with quadrat method.
The application of gained multipolymer aspect Scale inhibitors, scale remover, dispersion agent and washing auxiliary detergent, more specifically saying so with soup in the itaconic acid fermentation production is raw material, after ion-exchange, concentrating, the polymkeric substance that makes with this method is fit to do Scale inhibitors, dispersion agent, scale remover, washing auxiliary detergent etc.
Describedly prepare the technology of itaconic acid-propenoic acid copolymer by the fermentation soup, the methylene-succinic acid finished product can be mixed with 5%～40% the aqueous solution, carries out copolymerization.
Claims (10)
1, a kind of technology for preparing itaconic acid-propenoic acid copolymer by the fermentation soup, it is characterized in that: the fermentation soup of producing in the methylene-succinic acid with biological fermentation process is a raw material, after ion-exchange, concentrating, in the presence of initiator, carry out copolymerization, prepare itaconic acid-propenoic acid copolymer solution with vinylformic acid.
2, as claimed in claim 1ly prepare the technology of itaconic acid-propenoic acid copolymer, it is characterized in that adopting following steps by the fermentation soup:
(a) the fermentation soup of biological fermentation process being produced in the methylene-succinic acid passes through ion exchange column, removes wherein metal ion such as magnesium, zinc;
(b) aforesaid liquid is evaporated to contain the methylene-succinic acid amount be 5%～40%;
(c) add initiator solution, vinylformic acid with uniform feed rate, wherein active initiator content (is benchmark with the monomer mass) is 0%～20%, and vinylformic acid (is benchmark with the methylene-succinic acid quality) add-on is 5%～200%
(d) entire reaction course maintains the temperature at 30～100 ℃, reacts 0.5～3 hour after adding material again, prepares itaconic acid-propenoic acid copolymer solution.
3, according to claim 1ly prepare the technology of itaconic acid-propenoic acid copolymer by the fermentation soup, it is characterized in that: the fermentation soup also can concentrate earlier, after pass through ion exchange column.
4, according to claim 1ly prepare the technology of itaconic acid-propenoic acid copolymer by the fermentation soup, it is characterized in that: initiator is selected from the combination of following wherein one or more oxygenants: Sodium Persulfate, ammonium persulphate, Potassium Persulphate, peroxophosphoric acid sodium, potassium superphosphate, ammonium superphosphate, hydrogen peroxide and tert-butyl peroxide, diacyl peroxide; Or itself and single the kind or the combination of multiple reductive agent: sulphite, hydrosulphite, phosphite, thiosulphate, sulfurous acid, mercaptan, ferrous salt, amine (as N, accelerine) etc., wherein oxygenant evenly adds in polyreaction.
5. describedly prepare the technology of itaconic acid-propenoic acid copolymer by the fermentation soup according to claim 1,4, it is characterized in that: the reductive agent in the initiator joins before polymerization in the methylene-succinic acid solution.
6. describedly prepare the technology of itaconic acid-propenoic acid copolymer by the fermentation soup according to claim 1,4, it is characterized in that: the reductive agent in the initiator evenly adds in the reaction system in polymerization.
7. according to claim 1ly prepare the technology of itaconic acid-propenoic acid copolymer by the fermentation soup, it is characterized in that: initiator and acrylic acid reinforced time are 0.5～5 hour.
8. according to claim 1ly prepare the technology of itaconic acid-propenoic acid copolymer by the fermentation soup, it is characterized in that: the itaconic acid-propenoic acid copolymer solution of gained is the liquid of solid content 5%～80%.
9. according to claim 1ly prepare the technology of itaconic acid-propenoic acid copolymer, it is characterized in that by the fermentation soup: but be sheet or powdery solid behind the itaconic acid-propenoic acid copolymer solution concentrate drying of gained.
10. according to claim 1ly prepare the technology of itaconic acid-propenoic acid copolymer, it is characterized in that by the fermentation soup: the itaconic acid-propenoic acid copolymer solution of gained with in the alkali and after, the reconcentration drying is sheet or powdery solid.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 02110331 CN1458177A (en) | 2002-05-15 | 2002-05-15 | Technology for preparing itaconic acid-propenoic acid copolymer from fermented liquid |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 02110331 CN1458177A (en) | 2002-05-15 | 2002-05-15 | Technology for preparing itaconic acid-propenoic acid copolymer from fermented liquid |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN1458177A true CN1458177A (en) | 2003-11-26 |
Family
ID=29426289
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 02110331 Pending CN1458177A (en) | 2002-05-15 | 2002-05-15 | Technology for preparing itaconic acid-propenoic acid copolymer from fermented liquid |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1458177A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105209508A (en) * | 2013-03-15 | 2015-12-30 | 路博润先进材料公司 | Itaconic acid polymers |
-
2002
- 2002-05-15 CN CN 02110331 patent/CN1458177A/en active Pending
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105209508A (en) * | 2013-03-15 | 2015-12-30 | 路博润先进材料公司 | Itaconic acid polymers |
| CN110105480A (en) * | 2013-03-15 | 2019-08-09 | 路博润先进材料公司 | Polymerization of itaconic acid object |
| JP2020090687A (en) * | 2013-03-15 | 2020-06-11 | ルブリゾル アドバンスド マテリアルズ， インコーポレイテッド | Itaconic acid polymer |
| JP7065135B2 (en) | 2013-03-15 | 2022-05-11 | ルブリゾル アドバンスド マテリアルズ， インコーポレイテッド | Itaconic acid polymer |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101700937B (en) | Composite scale inhibitor | |
| JPH0372502A (en) | Preparation of maleic acid (co)polymer salt with improved biodegradability and its use | |
| CN102225976A (en) | Method for preparing polyacrylic acid dispersing agents by adopting acrylic acid waste water as raw material | |
| CN102910745B (en) | A fluorescent tracer green environment-friendly polyethylene glycol water treatment agent and preparation method thereof | |
| CN102516476A (en) | Synthesis of amphiphilic ionic high polymer soil conditioner | |
| CN102108111B (en) | Polyitaconic acid and its preparation method | |
| US4668735A (en) | Process for producing polymaleate | |
| CN103570145A (en) | Preparation method of olefin ether and unsaturated carboxylic acid copolymer anti-sludging agent | |
| CN1511793A (en) | Polynary itaconic acid copolymer as high efficiency anti-sludging agent and preparing method | |
| CN102127188A (en) | Preparation method of polyacrylamide with ultrahigh molecular weight | |
| CN105566560A (en) | Structure-oriented composite initiator system and acrylamide polymer and preparation method and application thereof | |
| CN101200523B (en) | A method for preparing polymer solution from pulping waste liquor | |
| CN116693073A (en) | Degradable high-efficiency silica scale inhibitor and preparation method thereof | |
| CN1458177A (en) | Technology for preparing itaconic acid-propenoic acid copolymer from fermented liquid | |
| CN1746198A (en) | Preparation of high molecular weight anion polyacrylamide | |
| CN1314720C (en) | Preparation method of high molecular weight amphoteric high molecule | |
| CN102417593B (en) | Biodegradable water treatment agent asparamido polyepoxy succinic acid and preparation method thereof | |
| CN102391491A (en) | Biodegradable water treatment agent p-sulfonicphenylaminopolyepoxysuccinic acid and preparation method thereof | |
| CN1063800C (en) | Adhesive for metal powdered ore prilling (block) | |
| CN100460426C (en) | A kind of acrylic acid acrylamide copolymer antiscaling dispersant and preparation method thereof | |
| CN109851699B (en) | Method for catalyzing water-phase polymerization of alkene monomers by using hydrogen peroxide/resin | |
| CN106045068B (en) | A kind of polymerization species barium strontium calcium antisludging agent and preparation method thereof | |
| CN106928942A (en) | Fluid loss additive for boring fluid AM/AA/ hydrolyzed polyacrylonitrile ammonium salt copolymer aquas and preparation method thereof | |
| CN102807285B (en) | Environment-friendly branched polyether water treatment agent and preparation method thereof | |
| CN113698549B (en) | Hyperbranched polymer, preparation method, application and washing product thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C02 | Deemed withdrawal of patent application after publication (patent law 2001) | ||
| WD01 | Invention patent application deemed withdrawn after publication |