WO2019119248A1 - 基于生物丙烯酰胺和丙烯酸生产阴离子水溶性聚合物的方法 - Google Patents

基于生物丙烯酰胺和丙烯酸生产阴离子水溶性聚合物的方法 Download PDF

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WO2019119248A1
WO2019119248A1 PCT/CN2017/117057 CN2017117057W WO2019119248A1 WO 2019119248 A1 WO2019119248 A1 WO 2019119248A1 CN 2017117057 W CN2017117057 W CN 2017117057W WO 2019119248 A1 WO2019119248 A1 WO 2019119248A1
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acrylic acid
water
bioacrylamide
mol
polymerization
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PCT/CN2017/117057
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English (en)
French (fr)
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法维罗·塞德里克
高军
凌静
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爱森（中国）絮凝剂有限公司
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Priority to CN201780095876.0A priority Critical patent/CN111278876B/zh
Priority to KR1020207016892A priority patent/KR102475632B1/ko
Priority to US16/770,251 priority patent/US11505634B2/en
Priority to PCT/CN2017/117057 priority patent/WO2019119248A1/zh
Priority to EP17935348.7A priority patent/EP3730524B1/en
Priority to FIEP17935348.7T priority patent/FI3730524T3/fi
Publication of WO2019119248A1 publication Critical patent/WO2019119248A1/zh

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    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D21/00—Separation of suspended solid particles from liquids by sedimentation
    • B01D21/01—Separation of suspended solid particles from liquids by sedimentation using flocculating agents
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/52—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
    • C02F1/54—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using organic material
    • C02F1/56—Macromolecular compounds
    • 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
    • C08F2/04—Polymerisation in solution
    • C08F2/10—Aqueous solvent
    • 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
    • C08F220/04—Acids; Metal salts or ammonium salts thereof
    • C08F220/06—Acrylic acid; Methacrylic acid; Metal salts or ammonium salts thereof
    • 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
    • C08F6/00—Post-polymerisation treatments
    • C08F6/02—Neutralisation of the polymerisation mass, e.g. killing the catalyst also removal of catalyst residues

Definitions

  • the present invention relates to a process for producing an anionic water-soluble polymer based on acrylic acid and acrylamide obtained by a biocatalytic reaction.
  • Acrylamide is initially obtained by a sulfuric acid hydrolysis process in which acrylonitrile is heated in the presence of sulfuric acid and water.
  • This method has been replaced by a copper catalyst method in which acrylamide is obtained by directly hydrating acrylonitrile in the presence of a copper catalyst such as copper metal or reduced copper, however, the catalyst method causes side reactions due to severe conditions.
  • bioacrylamide A biocatalytic process in which microbial nitrile hydratase is used to produce high purity acrylamide has been developed.
  • the high purity acrylamide is commonly referred to as bioacrylamide.
  • Acrylamide is widely used as a starting material for the production of water-soluble polymers which can be used, for example, as flocculants in water treatment, sludge dewatering or papermaking processes; or as, for example, in tertiary recovery processes.
  • a thickener in a thickener or cosmetic composition is widely used as a starting material for the production of water-soluble polymers which can be used, for example, as flocculants in water treatment, sludge dewatering or papermaking processes; or as, for example, in tertiary recovery processes.
  • Acrylic acid is also a very common monomer used in combination with acrylamide to produce an anionic water soluble polymer.
  • bioacrylamide is used in place of the term acrylamide obtained by biocatalytic reaction.
  • the present invention provides a process for producing an anionic water-soluble polymer obtained by polymerization of acrylic acid and bioacrylamide, the method comprising the steps of:
  • the oligomeric material can be formed by Michael addition or radical reaction or ionic polymerization.
  • the mass ratio of acrylic acid to water was 95:5 to 70:30 and the bioacrylamide was diluted with water so that the mass ratio of bioacrylamide to water was At 60:40 to 10:90, the amount of oligomers is significantly reduced, thereby allowing the production of an anionic water-soluble polymer with improved solubility and better performance.
  • the neutralization step is preferably carried out such that at least 40%, more preferably at least 50%, of the acrylic functional groups are neutralized.
  • the acrylic functional group can be completely neutralized, and an additional base can be added to achieve an excess of theoretical addition of up to 10% based on the base to completely neutralize the acrylic functional group. Any type of base can be used to neutralize the acrylic functionality. NaOH, KOH and NH 4 OH are preferred.
  • the water used is preferably distilled water or purified water.
  • the aqueous solution of bioacrylamide does not comprise acrylamide that is not obtained by biocatalytic reaction.
  • the solution preferably comprises bioacrylamide, water and up to 1% by weight of a stabilizer.
  • the aqueous solution of bioacrylamide mixed with the dilute solution of acrylic acid comprises 15% to 45% by weight of bioacrylamide.
  • the mass ratio of acrylic acid to water in the diluted solution of acrylic acid is preferably from 93:7 to 80:20, preferably from 92:8 to 85:15, before mixing the diluted solution of acrylic acid with the aqueous solution of bioacrylamide.
  • a very preferred mass ratio is 90:10.
  • the mass ratio of bioacrylamide to water in the diluted solution of bioacrylamide is preferably from 60:40 to 20:80, preferably 60, before mixing the diluted solution of bioacrylamide with the diluted solution of acrylic acid. 40 to 30:70. A very preferred ratio is from 55:45 to 45:55.
  • the molar ratio of acrylic acid and its salt in the monomer mixture before polymerization is preferably from 5 mol% to 95 mol%, more preferably from 10 mol% to 70 mol%, even more preferably 20 mol, based on the total moles of the monomers in the monomer mixture before polymerization. % to 50 mol%.
  • the molar ratio of bioacrylamide in the monomer mixture before polymerization is preferably from 5 mol% to 95 mol%, more preferably from 30 mol% to 90 mol%, even more preferably 50 mol%, based on the total moles of the monomers in the monomer mixture before polymerization. Up to 80 mol%.
  • the molar ratio of the monomers corresponds to the number of moles of the monomers / the total number of moles of monomers in the monomer mixture x 100%.
  • the manner in which the monomer mixture is polymerized is not limited to a specific polymerization type.
  • Polymerization techniques known to those skilled in the art may be used, such as solution polymerization, gel polymerization, inverse emulsion polymerization, which may or may not be followed by a spray drying step, or may or may not be post-hydrolyzed or Co-hydrolysis polymerization.
  • the polymerization reaction is usually a radical polymerization reaction.
  • free radical polymerization including free radical polymerization by means of an ultraviolet initiator, an azo initiator, a redox initiator or a thermal initiator, and a controlled radical polymerization (CRP) technique or a template polymerization technique.
  • an ultraviolet initiator an azo initiator, a redox initiator or a thermal initiator
  • CRP controlled radical polymerization
  • additional monomers can be used in combination with bioacrylamide and acrylic acid.
  • These monomers can be selected from the following list:
  • Nonionic monomers methacrylamide, N,N-dimethylacrylamide, N-vinylpyrrolidone, N-vinylformamide, methacrylate of polyethylene glycol, diacetone acrylamide, N -isopropylacrylamide, 2-hydroxyethyl acrylate, 2,3-dihydroxypropyl acrylate, 2-hydroxyethyl methacrylate, 2,3-dihydroxypropyl methacrylate,
  • Anionic monomers unsalted, partially salted or fully salted 2-acrylamido-2-methylpropanesulfonic acid (ATBS), methacrylic acid, itaconic acid, maleic acid,
  • ATBS 2-acrylamido-2-methylpropanesulfonic acid
  • methacrylic acid methacrylic acid
  • itaconic acid maleic acid
  • DADMAC diallyldimethylammonium chloride
  • DAMEA dialkylaminoethyl acrylate
  • DAMEMA dialkylaminoethyl methacrylate
  • acrylamidodialkylamino Propyl methacrylamidodialkylaminopropyl, and acidified or quaternary ammonium salts thereof.
  • structurants for example polyethylenically unsaturated monomers having at least two unsaturated functional groups (for example vinyl, allyl, acrylic and epoxy functional groups), and mention may be made, for example, of methylenebispropene Amides (MBA), triallylamine, or macroinitiators such as polyperoxides, polyazo compounds, and transfer polymerization agents such as polythiol polymers.
  • MWA methylenebispropene Amides
  • macroinitiators such as polyperoxides, polyazo compounds, and transfer polymerization agents such as polythiol polymers.
  • the amount is such that the polymer obtained by the process of the invention is still water soluble.
  • the present invention also provides an anionic water-soluble polymer which is prepared from acrylic acid and acrylamide obtained by a biocatalytic reaction and obtained by the method of the present invention.
  • the weight average molecular weight of the polymer according to the invention is preferably from 1,500,000 g/mol to 30,000,000 g/mol.
  • the weight average molecular weight is measured by gel permeation chromatography (GPC).
  • the polymers according to the invention obtained by the process of the invention have better solubility than the polymers obtained by other methods, under otherwise identical conditions.
  • the solubility was measured by mixing the polymer in powder form in distilled water at a concentration of 3 g/l for 30 minutes at 25 ° C, and using the resulting mixture for a Filter Ratio (FR) test. Filtration ratio testing is well known and used in the oil and gas industry. The lower the FR value, the better the solubility. A filtration ratio of 1 to 1.5 indicates good solubility.
  • the "filtration ratio" (FR) is determined by a test as described herein, which involves injecting an aqueous polymer solution through a filter at a constant pressure.
  • the FR was determined by dividing the difference between the time when the measured filtration volume was 300 mL and the time when the filtration volume was 200 mL divided by the time when the filtration volume was 200 mL and the time when the filtration volume was 100 mL.
  • the filtration ratio test was carried out as follows.
  • the polymer solution (3 g/l) obtained as described above was filtered through a 5 ⁇ m nuclear pore membrane under a constant pressure of 2 bar.
  • a membrane or filter (Whatman Nuclepor, 47 mm diameter, polycarbonate type, thickness 7 ⁇ m to 22 ⁇ m) was inserted into a Sartorius SM16249 filter unit (bottom). Record the time relative to the filter volume.
  • the difference between the time when FR corresponds to the time when the filtration volume is 300 mL and the time when the filtration volume is 200 mL divided by the time when the filtration volume is 200 mL and the time when the filtration volume is 100 mL
  • the time accuracy is 0.1 second.
  • the polymers according to the invention also exhibit better properties, for example in terms of flocculation. Without being bound by any theory, the polymer according to the invention appears to have a better anionic charge distribution along the polymer chain due to the reduced amount of oligomeric species and improved control of polymer polydispersity, allowing for more Uniform performance and better performance.
  • the invention also provides the use of the polymers of the invention in water treatment, sludge dewatering, papermaking processes, agricultural, cosmetic and cleaning compositions, textile processes, oil and gas recovery processes, mining operations.
  • the polymer of the examples was prepared from acrylamide based on 75 mol% total moles of monomers and acrylic acid based on 25 mol% total moles of monomers.
  • the acrylic acid was diluted with distilled water at different mass ratios as shown in Table 1.
  • the bioacrylamide is diluted as needed prior to mixing with the diluted acrylic acid.
  • the diluted acrylic acid and the diluted bioacrylamide are mixed.
  • the acrylic acid was then completely neutralized with NaOH while cooling to maintain the temperature at 0 °C to 5 °C.
  • the solution was cooled to 0 ° C and transferred to an insulated vessel (Dewar, Dewar).
  • a temperature probe was introduced in an insulated vessel (Dewar) to record the temperature rise during the polymerization reaction.
  • the solution was sparged with nitrogen over 30 minutes.
  • An initiator is introduced into the solution.
  • the choice of initiator is adapted to the pH of the solution and the type of monomer to be polymerized. In this example, 5 ppm of sodium persulfate and 5 ppm of sodium sulfite were added to initiate polymerization.
  • the viscosity in the adiabatic reactor (Dewar) increased and the nitrogen sparging was stopped.
  • the temperature was raised to 90 ° C, and polymerization was carried out for 3 hours to obtain a gel.
  • the obtained gel was cut and granulated using a granulator having a mesh to obtain gel particles having a diameter of 6 mm or less. These gel particles were dried overnight in an oven at 50 °C.
  • the obtained dry powder was ground and sieved to obtain a white powder having a particle diameter of 1 mm or less.
  • the resulting polymer has a weight average molecular weight of from about 10,000,000 g/mol to 15,000,000 g/mol.
  • the polymer solution was prepared by mixing the polymer in powder form in distilled water at a concentration of 5 g/l for 30 minutes at 25 °C.
  • the flocculation test was carried out by mixing the resulting solution with red mud having a solid content of 15% by weight.
  • the amount used is 500 g/dmt, which corresponds to the amount of polymer in dry form/solids content in red mud. This unit is widely used in the mining industry.
  • the results are expressed in terms of the amount of purified water (ml) after 24 hours. For each test, an appropriate volume of polymer solution was added to 200 g of red mud, and then the entire mixture was manually mixed until flocculation and water release were observed, and then placed until 24 hours to obtain a purified water release amount (ml).
  • Table 1 summarizes the results of the solubility test and the flocculation test
  • the water release corresponds to the total amount of water released.
  • the amount of purified water (NWR) corresponds to the total amount of water recovered in the flocculation test (in ml) minus the amount of water from the polymer solution used to flocculate the red mud.
  • CE refers to the comparative example.
  • E refers to an embodiment in accordance with the present invention.
  • the FR was significantly lower when the polymer was prepared according to the method of the present invention.
  • the polymers of Examples 3, 4, 5 and 8 have an FR value of 1 to 1.5, which means that their solubility is very good, and the solubility with respect to Comparative Examples 1, 2, 6, 7, and 9 (FR value is higher than 1.5). And better than 1.9 to 2.7).
  • the polymer obtained by the method of the present invention has a higher water release amount.
  • the NWR of Examples 3, 4, 5 and 8 was higher than 14 ml and was 14.1 ml to 16.5 ml.
  • the polymers of Comparative Examples 1, 2, 6, 7, and 9 had an NWR of less than 13 ml and ranged from 11.2 ml to 12.9 ml.
  • Table 2 summarizes the results of solubility testing and flocculation testing of polymers prepared using different acrylamides.
  • the polymer prepared by using bioacrylamide according to the present invention can obtain better performance than the polymer prepared by reacting a copper catalyst to obtain acrylamide.
  • Table 3 summarizes the results of solubility testing and flocculation testing of polymers prepared using different concentrations of bioacrylamide solution
  • the polymer prepared according to the present invention obtained better performance than the polymer prepared by using a bioacrylamide solution having a mass ratio of 80:20.

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  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
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Abstract

一种用于生产阴离子水溶性聚合物的方法，所述聚合物通过丙烯酸和通过生物催化反应获得的丙烯酰胺的聚合反应而获得，所述方法包括以下步骤：通过将丙烯酸和水混合来制备丙烯酸稀释溶液，其中丙烯酸与水的质量比为95:5至70:30；制备生物丙烯酰胺与水的稀释溶液，其中生物丙烯酰与水的质量比为60:40至10:90；混合所述丙烯酸稀释溶液和生物丙烯酰胺的所述稀释溶液；混合部分或全部中和丙烯酸的酸性官能团；以及使所得混合物聚合。

Description

基于生物丙烯酰胺和丙烯酸生产阴离子水溶性聚合物的方法 技术领域
本发明涉及基于丙烯酸和通过生物催化反应获得的丙烯酰胺生产阴离子水溶性聚合物的方法。
背景技术
丙烯酰胺最初通过其中在硫酸和水的存在下加热丙烯腈的硫酸水解方法来获得。该方法已经被铜催化剂方法代替，在铜催化剂方法中，丙烯酰胺通过在铜催化剂如铜金属、还原铜的存在下使丙烯腈直接水合来获得，但是，该催化剂方法由于苛刻条件引起副反应。
开发了其中使用微生物腈水合酶来生产高纯度丙烯酰胺的生物催化方法。所述高纯度丙烯酰胺通常称为生物丙烯酰胺(bioacrylamide)。
丙烯酰胺被广泛用作生产水溶性聚合物的起始材料，所述水溶性聚合物可以用作例如水处理、污泥脱水或造纸工艺中的絮凝剂；或者用作例如三次采油工艺中的增稠剂或化妆品组合物中的增稠剂。
丙烯酸也是与丙烯酰胺组合使用以生产阴离子水溶性聚合物的非常常见的单体。
尽管基于丙烯酰胺和丙烯酸的阴离子水溶性聚合物取得了很大的改进，但是仍然需要改善这些聚合物的溶解度和性能。
发明内容
出乎意料地发现，在将丙烯酸与稀释的生物丙烯酰胺混合之前用水以特定比例稀释丙烯酸实现了这些目标。
在本发明中，术语“生物丙烯酰胺”用于替代术语通过生物催化反应获得的丙烯酰胺。
本发明提供了一种用于生产阴离子水溶性聚合物的方法，所述聚合物通过丙烯酸和生物丙烯酰胺的聚合反应而获得，所述方法包括以 下步骤：
-通过将丙烯酸和水混合来制备丙烯酸稀释溶液，其中丙烯酸与水的质量比为95:5至70:30；
-制备生物丙烯酰胺与水的稀释溶液，其中生物丙烯酰胺与水的质量比为60:40至10:90；
-将所述丙烯酸稀释溶液与生物丙烯酰胺的所述稀释溶液混合；
-部分或全部中和丙烯酸的酸官能团；
-使所得混合物聚合。
发现在将生物丙烯酰胺和丙烯酸混合时，形成低聚物。最常见的低聚物是丙烯酸的二聚物和三聚物。这些低聚物对于用生物丙烯酰胺和丙烯酸制成的聚合物的品质是不利的。低聚物质可通过迈克尔加成(Michael addition)或自由基反应或离子聚合来形成。
出乎意料地发现，当在使丙烯酸和生物丙烯酰胺混合之前用水稀释丙烯酸使得丙烯酸与水的质量比为95:5至70:30并用水稀释生物丙烯酰胺使得生物丙烯酰胺与水的质量比为60:40至10:90时，低聚物的量显著减少，进而允许产生具有提高的溶解度和更好性能的阴离子水溶性聚合物。
优选地进行中和步骤使得至少40％，更优选至少50％的丙烯酸官能团被中和。丙烯酸官能团可以被完全中和，并且可以添加额外的碱以达到基于碱的理论添加量过量多至10％，从而完全中和丙烯酸官能团。可以使用任何种类的碱来中和丙烯酸官能团。NaOH、KOH和NH 4OH是优选的。
所使用的水优选为蒸馏水或纯化水。
在一个优选实施方案中，生物丙烯酰胺的水溶液不包含不是通过生物催化反应获得的丙烯酰胺。所述溶液优选地包含生物丙烯酰胺、水和多至1重量％的稳定剂。
在一个优选实施方案中，与丙烯酸稀释溶液混合的生物丙烯酰胺的水溶液包含15重量％至45重量％的生物丙烯酰胺。
根据本发明，在将丙烯酸稀释溶液与生物丙烯酰胺的水溶液混合 之前，丙烯酸稀释溶液中的丙烯酸与水的质量比优选为93:7至80:20，优选为92:8至85:15。非常优选的质量比为90:10。
根据本发明，在将生物丙烯酰胺的稀释溶液与丙烯酸的稀释溶液混合之前，生物丙烯酰胺的稀释溶液中的生物丙烯酰胺与水的质量比优选为60:40至20:80，优选为60:40至30:70。非常优选的比例为55:45至45:55。
基于聚合前单体混合物中单体的总摩尔数，聚合前单体混合物中的丙烯酸及其盐的摩尔比率优选为5mol％至95mol％，更优选为10mol％至70mol％，甚至更优选为20mol％至50mol％。
基于聚合前单体混合物中单体的总摩尔数，聚合前单体混合物中的生物丙烯酰胺的摩尔比率优选为5mol％至95mol％，更优选为30mol％至90mol％，甚至更优选为50mol％至80mol％。
单体的摩尔比率对应于所述单体的摩尔数/单体混合物中单体的摩尔总数×100％。
根据本发明，单体混合物聚合的方式不限于特定的聚合反应类型。可以使用本领域技术人员已知的聚合反应技术，例如溶液聚合反应、凝胶聚合反应、反相乳液聚合反应，其可以或可以不后接喷洒干燥步骤，或者可以或可以不后接后水解或共水解聚合反应。
在本发明的方法中，所有的这些聚合技术都允许生产高品质的聚合物，但是根据本发明，凝胶聚合反应是优选的，因为其给予更高的性能。然后将凝胶切割，研磨并干燥，获得粉末。
聚合反应通常是自由基聚合反应。对于自由基聚合反应，包括借助于紫外线引发剂、偶氮引发剂、氧化还原引发剂或热引发剂的自由基聚合反应，以及受控自由基聚合反应(CRP)技术或模板聚合反应技术。
在本发明的方法中，可以与生物丙烯酰胺和丙烯酸组合使用另外的单体。这些单体可以选自以下列表：
-非离子单体：甲基丙烯酰胺、N,N-二甲基丙烯酰胺、N-乙烯基吡咯烷酮、N-乙烯基甲酰胺、聚乙二醇的甲基丙烯酸酯、双丙酮丙烯 酰胺、N-异丙基丙烯酰胺、丙烯酸2-羟乙酯、丙烯酸2,3-二羟丙酯、甲基丙烯酸2-羟乙酯、甲基丙烯酸2,3-二羟丙酯，
-阴离子单体：未成盐的、部分成盐的或完全成盐的2-丙烯酰胺基-2-甲基丙磺酸(ATBS)、甲基丙烯酸、衣康酸、马来酸，
-阳离子单体：二烯丙基二甲基氯化铵(DADMAC)、丙烯酸二烷基氨基乙酯(DAMEA)和甲基丙烯酸二烷基氨基乙酯(DAMEMA)、丙烯酰胺基二烷基氨基丙基、甲基丙烯酰胺基二烷基氨基丙基、及其酸化盐或季铵盐。
还可以使用结构剂，例如具有至少两个不饱和官能团(例如乙烯基、烯丙基、丙烯酸类和环氧官能团)的多烯键式不饱和单体，并且可以提及例如亚甲基双丙烯酰胺(MBA)、三烯丙基胺，或者大分子引发剂如多过氧化物、多偶氮化合物和转移聚合剂如聚硫醇聚合物。
当使用结构剂时，其量使得通过本发明的方法获得的聚合物仍然是水溶性的。
本发明还提供了用丙烯酸和通过生物催化反应获得的丙烯酰胺制备并且通过本发明的方法获得的阴离子水溶性聚合物。
根据本发明的聚合物的重均分子量优选为1500000g/mol至30000000g/mol。重均分子量通过凝胶渗透色谱(GPC)来测量。
在其他条件相同的情况下，通过本发明的方法获得的根据本发明的聚合物与通过其他方法获得的聚合物相比具有更好的溶解度。
溶解度通过以下来测量：在25℃下将粉末形式的聚合物在蒸馏水中以3g/l的浓度混合30分钟，并用所得混合物进行过滤比(Filter Ratio，FR)测试。过滤比测试是众所周知的并且在油气行业中使用。FR值越低，溶解度越好。1至1.5的过滤比值表示良好的溶解度。
根据本发明的“过滤比”(FR)通过如本文所述的测试来确定，该测试包括在恒定压力下注射聚合物水溶液通过过滤器。FR通过测得的过滤体积为300mL时的时间与过滤体积为200mL时的时间之差除以过滤体积为200mL时的时间与过滤体积为100mL时的时间之差来确定。
过滤比测试如下进行。在2巴的恒定压力下使如前所述获得的聚合物溶液(3g/l)过滤通过5μm核孔膜。将膜或过滤器(Whatman Nuclepor，47mm直径，聚碳酸酯型，厚度为7μm至22μm)插入Sartorius SM16249过滤装置(底部)中。记录相对于过滤体积的时间。FR对应于过滤体积为300mL时的时间与过滤体积为200mL时的时间之差除以过滤体积为200mL时的时间与过滤体积为100mL时的时间之差
Figure PCTCN2017117057-appb-000001
其中，
t 300ml＝在恒定压力下获得300ml滤液所需的时间
t 200ml＝在恒定压力下获得200ml滤液所需的时间
t 100ml＝在恒定压力下获得100ml滤液所需的时间
时间精度为0.1秒。
根据本发明的聚合物还显示出例如在絮凝方面更好的性能。不受任何理论的限制，根据本发明的聚合物似乎由于低聚物质的量减少而具有较好的沿聚合物链的阴离子电荷分布，并且改善了对聚合物多分散性的控制，从而允许更均匀的表现和更好的性能。
本发明还提供了本发明的聚合物在水处理、污泥脱水、造纸工艺、农业、化妆品和清洁组合物、纺织工艺、油气回收工艺、采矿作业中的用途。
具体实施方式
现在将通过以下实施例更详细地说明本发明。
实施例
实施例的聚合物由基于单体总摩尔数为75mol％的丙烯酰胺和基于单体总摩尔数为25mol％的丙烯酸制得。用蒸馏水以如表1所示的不同质量比稀释丙烯酸。生物丙烯酰胺在与稀释的丙烯酸混合之前根据需要进行稀释。将稀释的丙烯酸和稀释的生物丙烯酰胺混合。然后 在冷却以保持温度为0℃至5℃的情况下用NaOH完全中和丙烯酸。
将溶液冷却至0℃并转移至绝热容器(杜瓦瓶，Dewar)。在绝热容器(杜瓦瓶)中引入温度探针以记录聚合反应期间的温度升高。在30分钟内用氮气喷射该溶液。向溶液中引入引发剂。引发剂的选择适于溶液的pH以及待聚合单体的类型。在该实施例中，添加5ppm的过硫酸钠和5ppm的亚硫酸钠以引发聚合反应。
5分钟后，绝热反应器(杜瓦瓶)中的粘度增加，停止氮气喷射。温度升至90℃，并且聚合反应进行3小时以获得凝胶。将所得凝胶切割，使用具有网格的造粒机进行造粒，获得直径6mm以下的凝胶颗粒。将这些凝胶颗粒在50℃的烘箱中干燥过夜。将获得的干燥粉末研磨并进行筛分，获得粒径为1mm以下的白色粉末。
所得聚合物的重均分子量为约10000000g/mol至15000000g/mol。
溶解度测试通过如前所述的过滤比来完成。结果归纳在表1中。
絮凝测试
在25℃下通过在蒸馏水中以5g/l的浓度混合粉末形式的聚合物30分钟来制备聚合物溶液。通过将所得溶液与固体含量为15重量％的赤泥混合来进行絮凝测试。用量为500克/干吨，其对应于干燥形式的聚合物的量/赤泥中的固体含量。该单位广泛用于矿业领域。结果以24小时后的净水释放量(ml)来表示。对于每个测试，将适当体积的聚合物溶液添加到200g赤泥中，然后手动混合整个混合物直到观察到絮凝和水释放，然后放置直到24小时获得净水释放量(ml)。
表1 归纳了溶解度测试和絮凝测试的结果
Figure PCTCN2017117057-appb-000002
Figure PCTCN2017117057-appb-000003
水释放对应于释放的水的总量。净水释放量(NWR)对应于絮凝测试期间回收的水的总量(以ml计)减去来自用于絮凝赤泥的聚合物溶液的水的量。
CE是指对比例。
E是指根据本发明的实施例。
根据表1中示出的数据，当根据本发明的方法制备聚合物时，FR显著较低。实施例3、4、5和8的聚合物的FR值为1至1.5，这意味着它们的溶解度非常好，并且与对比例1、2、6、7和9的溶解度(FR值高于1.5且为1.9至2.7)相比更好。
结果清楚地表明，根据本发明的方法导致溶解度的显著提高。
根据表1中示出的数据，用本发明的方法获得的聚合物的净水释放量更高。实施例3、4、5和8的NWR高于14ml并且为14.1ml至16.5ml。相比之下，对比例1、2、6、7和9的聚合物的NWR低于13ml并且为11.2ml至12.9ml。
结果清楚地表明，根据本发明的方法导致絮凝的显著改善。
进行以下测试以比较用生物丙烯酰胺制备的聚合物与用由铜催化剂获得的丙烯酰胺制备的聚合物。以分别与实施例3、4和5完全相同的成分和方法制备实施例10、11和12的聚合物，不同之处在于在实施例10、11和12中，用由铜催化剂反应获得的丙烯酰胺代替生物丙烯酰胺。进行如前所述相同的测试并获得以下结果并归纳在下表2中。
表2 归纳了使用不同丙烯酰胺制备的聚合物的溶解度测试和絮凝测试的结果
Figure PCTCN2017117057-appb-000004
Figure PCTCN2017117057-appb-000005
*通过铜催化剂反应获得的丙烯酰胺
结果证明了根据本发明用生物丙烯酰胺制备的聚合物与用由铜催化剂反应获得丙烯酰胺制备的聚合物相比获得更好的性能。
进行以下测试以比较根据本发明的用具有50:50的质量比的生物丙烯酰胺溶液制备的聚合物与用具有80:20的质量比的生物丙烯酰胺溶液制备的聚合物。以分别与实施例3、4和5完全相同的成分和方法制备实施例13、14和15的聚合物，不同之处在于在实施例13、14和15中，用具有80:20质量比的生物丙烯酰胺溶液代替根据本发明的具有50:50质量比的生物丙烯酰胺溶液。进行如前所述相同的测试并获得以下结果并归纳在下表3中。
表3 归纳了使用不同浓度的生物丙烯酰胺溶液制备的聚合物的溶解度测试和絮凝测试的结果
结果证明了根据本发明制备的聚合物与用具有80:20质量比的生物丙烯酰胺溶液制备的聚合物相比获得更好的性能。

Claims (12)

  1. 一种用于生产阴离子水溶性聚合物的方法，所述聚合物通过丙烯酸和生物丙烯酰胺的聚合反应获得，所述方法包括以下步骤：
    -通过将丙烯酸和水混合来制备丙烯酸稀释溶液，其中丙烯酸与水的质量比为95:5至70:30；
    -制备生物丙烯酰胺和水的稀释溶液，其中生物丙烯酰胺与水的质量比为60:40至10:90；
    -将所述丙烯酸稀释溶液与生物丙烯酰胺的所述稀释溶液混合；
    -部分或全部中和丙烯酸的酸官能团；
    -使所得混合物聚合。
  2. 根据权利要求1所述的方法，其中丙烯酸与水的质量比为93:7至80:20，优选为92:8至85:15。
  3. 根据前述权利要求中任一项所述的方法，其中在生物丙烯酰胺的所述稀释溶液与所述丙烯酸稀释溶液混合之前，在生物丙烯酰胺的所述稀释溶液中生物丙烯酰胺与水的质量比为60:40至20:80，优选60:40至30:70，甚至更优选55:45至45:50混合。
  4. 根据前述权利要求中任一项所述的方法，其中进行中和步骤使得至少40％的丙烯酸官能团被中和。
  5. 根据前述权利要求中任一项所述的方法，其中丙烯酸官能团被完全中和。
  6. 根据前述权利要求中任一项所述的方法，其中所述水为蒸馏水或纯化水。
  7. 根据前述权利要求中任一项所述的方法，其中，基于聚合前单体混合物中单体的总摩尔数，聚合前单体混合物中的丙烯酸的摩尔比率为5mol％至95mol％，优选为10mol％至70mol％，更优选为20mol％至50mol％。
  8. 根据前述权利要求中任一项所述的方法，其中，基于聚合前单体混合物中单体的总摩尔数，聚合前单体混合物中的通过生物催化反应获得的丙烯酰胺的摩尔比率为5mol％至95mol％，优选为30 mol％至90mol％，更优选为50mol％至80mol％。
  9. 根据前述权利要求中任一项所述的方法，其中聚合反应是凝胶聚合反应。
  10. 根据前述权利要求中任一项所述的方法，其中与丙烯酸和通过生物催化反应获得的丙烯酰胺组合使用另外的单体，所述单体选自以下列表：
    -非离子单体：甲基丙烯酰胺、N,N-二甲基丙烯酰胺、N-乙烯基吡咯烷酮、N-乙烯基甲酰胺、聚乙二醇的甲基丙烯酸酯、双丙酮丙烯酰胺、N-异丙基丙烯酰胺、丙烯酸2-羟乙酯、丙烯酸2,3-二羟丙酯、甲基丙烯酸2-羟乙酯、甲基丙烯酸2,3-二羟丙酯，
    -阴离子单体：未成盐的、部分成盐的或完全成盐的2-丙烯酰胺基-2-甲基丙磺酸(ATBS)、甲基丙烯酸、衣康酸、马来酸，
    -阳离子单体：二烯丙基二甲基氯化铵(DADMAC)、丙烯酸二烷基氨基乙酯(DAMEA)和甲基丙烯酸二烷基氨基乙酯(DAMEMA)、丙烯酰胺基二烷基氨基丙基、甲基丙烯酰胺基二烷基氨基丙基、及其酸化盐或季铵盐。
  11. 一种通过权利要求1至10所述的方法获得的阴离子水溶性聚合物。
  12. 一种根据权利要求11所述的聚合物在水处理、污泥脱水、造纸工艺、农业、化妆品和清洁组合物、纺织工艺、油气回收工艺、采矿作业中的用途。
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