WO2005037882A1 - Polymerisate auf basis von n,n-diallylaminderivaten, deren herstellung und verwendung - Google Patents
Polymerisate auf basis von n,n-diallylaminderivaten, deren herstellung und verwendung Download PDFInfo
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- WO2005037882A1 WO2005037882A1 PCT/EP2004/010495 EP2004010495W WO2005037882A1 WO 2005037882 A1 WO2005037882 A1 WO 2005037882A1 EP 2004010495 W EP2004010495 W EP 2004010495W WO 2005037882 A1 WO2005037882 A1 WO 2005037882A1
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- WIPO (PCT)
- Prior art keywords
- acid
- acrylate
- methacrylate
- methyl
- hydrogen
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Classifications
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C229/00—Compounds containing amino and carboxyl groups bound to the same carbon skeleton
- C07C229/02—Compounds containing amino and carboxyl groups bound to the same carbon skeleton having amino and carboxyl groups bound to acyclic carbon atoms of the same carbon skeleton
- C07C229/04—Compounds containing amino and carboxyl groups bound to the same carbon skeleton having amino and carboxyl groups bound to acyclic carbon atoms of the same carbon skeleton the carbon skeleton being acyclic and saturated
- C07C229/06—Compounds containing amino and carboxyl groups bound to the same carbon skeleton having amino and carboxyl groups bound to acyclic carbon atoms of the same carbon skeleton the carbon skeleton being acyclic and saturated having only one amino and one carboxyl group bound to the carbon skeleton
- C07C229/10—Compounds containing amino and carboxyl groups bound to the same carbon skeleton having amino and carboxyl groups bound to acyclic carbon atoms of the same carbon skeleton the carbon skeleton being acyclic and saturated having only one amino and one carboxyl group bound to the carbon skeleton the nitrogen atom of the amino group being further bound to acyclic carbon atoms or to carbon atoms of rings other than six-membered aromatic rings
- C07C229/12—Compounds containing amino and carboxyl groups bound to the same carbon skeleton having amino and carboxyl groups bound to acyclic carbon atoms of the same carbon skeleton the carbon skeleton being acyclic and saturated having only one amino and one carboxyl group bound to the carbon skeleton the nitrogen atom of the amino group being further bound to acyclic carbon atoms or to carbon atoms of rings other than six-membered aromatic rings to carbon atoms of acyclic carbon skeletons
-
- 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
- C08F2/38—Polymerisation using regulators, e.g. chain terminating agents, e.g. telomerisation
-
- 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
- C08F26/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a single or double bond to nitrogen or by a heterocyclic ring containing nitrogen
- C08F26/02—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a single or double bond to nitrogen or by a heterocyclic ring containing nitrogen by a single or double bond to nitrogen
- C08F26/04—Diallylamine
Definitions
- amphiphilic molecules which are used as surfactants in many areas of application, occupy a special place.
- Polyelectrolytes are macromolecular compounds that are wholly or partly made up of ionic or ionizable monomer units. Their property profile is determined both by the chemical structure of the polymer chain as well as by the type, density and strength of the charge as well as the localization of the ionic groups.
- water-soluble polymers as process aids determine technology.
- polyquaternary polymers are used in a large number of industrial areas such as paper production, cosmetics, construction chemicals, detergent and cleaning agent formulations, textile processing, pharmacy and surface coating.
- the polyelectrolytes act as polymeric surfactants, thickeners, solubilizers or dispersion stabilizers.
- polyelectrolytes are called amphoteric polyelectrolytes or polyampholytes.
- polyampholytes can occur as polyacids or polybases.
- cationic charge is permanently present in the form of an aliphatic or aromatic ammonium, sulfonium or phosphonium function and is combined with the basic group in each monomer unit, these zwitterionic compounds are not referred to as polyampholytes, but as polybetaines, since such polymers are different Show behavior in aqueous systems.
- polysulfobetaines, polyphosphobetaines and polycarbobetaines depending on whether the anionic charge is carried by a sulfonate, phosphonate or carboxylate group.
- polycarbobetaines can be obtained in two ways. On the one hand through the synthesis of so-called precursor polymers and subsequent polymer-analogous conversion to the corresponding polycarbobetaines [Al-Muallem et al., Polymer 43, 2002, 4285-4295] or by polymerizing already charged betaine monomers.
- WO 00/14053 describes the synthesis of the polymers from a water-soluble, hydrolysis-stable amphoteric monomer based on dimethylaminopropyl methacrylamide (DMAPMA).
- DMAPMA dimethylaminopropyl methacrylamide
- Polymers based on diallyl compounds are primarily polycarbobetaines starting from diallylammonium compounds with subsequent cyclization polymerization [Favresse et al., Polymer 42 (2001) 2755-2766].
- ampholytic polymers based on diallylamine and substituted diallylamines can be anionic, cationic or zwitterionic.
- Al-Muallem et al. [Polymer 43 (2002) 1041-1050] describe the synthesis of N, N-diallyl-N-carboethoxymethylamine or pentylamine by reacting diallylamine with chloroacetic acid or 1-chlorohexanoic acid ethyl ester with the addition of potassium carbonate.
- Laschewsky et al. synthesize ethyl 2- (N, N-diallylamino) valerate by nucleophilic substitution.
- Polymers based on diallylamine and substituted diallylamines are used, for example, for the production of flocculants and ion exchange resins and in fiber and paper technology.
- Ammonium salts are polymerized, since the uncharged form cannot be “readily” polymerized under the conditions of free radical polymerization.
- This further functional group is preferably a proanionic, particularly preferably a carboxyl group.
- R ⁇ R 2 are independently hydrogen or -CC 4 alkyl with compounds of general formula II, H HR 3rd
- R 3 is COOR 4 , CN, CHO, SO 3 H, PO (OH) 2 or CONR 5 R 6 and
- R 4 , R 5 and R 6 independently of one another are hydrogen or C 1 to C 18 -alkyl, are reacted and the Michael adducts are then radically polymerized, optionally in the presence of one or more radically copolymerizable monomers.
- diallylamine derivatives of the formula I in which R 1 , R 2 are, for example, hydrogen, methyl, ethyl, n-propyl, 1-methylethyl, n-butyl, 1-methylpropyl, 2-methylpropyl or 1, 1-dimethylethyl independently of one another the compounds are diallylamine, 2-methylldiallylamine or bis (2-methylallyl) amine, 2-ethyldiallylamine, bis (2-ethylallyl) amine, 2-isopropyldiallylamine, bis (2-isopropylallyl) amine, 2-tert-butyldiallylamine or bis (2-tert-butylallyl) amine is preferred.
- N, N-diallylamine is particularly preferred.
- Compounds of the general formula II are, for example, acrylic acid, acrylic acid esters such as methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, t-butyl acrylate, isobutyl acrylate, 2-ethylhexyl acrylate and stearyl arylate, furthermore acrylonitrile, acrolein, vinylsulfonic acid, vinylphosphonic acid, acrylamide, naphtha Butylacrylamide and N-octylacrylamide.
- Preferred compound of the general formula II is acrylic acid.
- Monomers for copolymerization with the reaction products according to the invention from compounds of the general formula I and compounds of the general formulas II include acrylic acid, methacrylic acid, maleic acid, fumaric acid, crotonic acid, itaconic acid, maleic anhydride and its half-ester, methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, n- Butyl acrylate, n-butyl methacrylate, t-butyl acrylate, t-butyl methacrylate, isobutyl acrylate, isobutyl methacrylate, 2-ethylhexyl acrylate, stearyl arylate, stearyl methacrylate, N-butyl acrylamide, N-octyl acrylate, 2-hydroxyethyl acrylate, hydroxypropyl acrylate, 2-hydroxyethyl methacrylate, hydroxyl acrylate,
- methyl, ethyl, butyl or dodecyl vinyl ether vinyl formamide, vinyl methylacetamide, vinylamine, 1-vinylimidazole, 1-vinyl-2-methylimidazole, N, N- Dimethylaminomethyl methacrylate and N- [3- (dimethylamino) propyl] methacrylamide; 3-methyl-1-vinylimidazolium chloride, 3-methyl-1-vinylimidazolium methyl sulfate, N, N-dimethylaminoethyl methacrylate, N- [3- (dimethylamino) propyl] methacrylamide, methyl sulfate or diethyl sulfate.
- the monomers bearing amino groups can be present in quaternized form.
- the present invention furthermore relates to a process for the preparation of the polymers, starting from the compounds of the formulas I and II.
- the process according to the invention comprises the reaction of a compound of general formula I with at least one compound of general formula II in the sense of a Michael addition.
- the preferred molar ratio I to II is 1: 1, but an excess of one of the components can also be used.
- An example of a surplus is 1 to 1, 1 or 1.1 to 1.
- the Michael addition can take place with or without a solvent, depending on the miscibility of the pure substances.
- Water alcohols such as methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, tert-butanol, ethers such as diethyl ether, tert-butyl methyl ether, tetrahydrofuran, dioxane, aliphatic table hydrocarbons such as pentane, hexane, heptane, cyclopentane, cyclohexane, aromatic hydrocarbons such as benzene, toluene, ethylbenzene, o-xylene, m-xylene, p-xylene, ketones such as acetone, amides such as N, N- Dimethylformamide, N, N-dimethylacetamide, chlorinated hydrocarbons such as dichloromethane, chloroform or 1, 1, 2,2-
- a preferred embodiment is the reaction without a solvent.
- the products obtained from the Michael addition can be isolated in a manner known per se.
- Michael addition is usually carried out at temperatures between -20 and + 50 ° C, preferably between -10 and + 30 ° C.
- the invention furthermore relates to the products of the formula III obtained from this reaction
- R 1 and R 2 independently of one another are hydrogen or d to C 4 -alkyl
- R 3 is COOR 4 , CN, CHO, SO 3 H, PO (OH) 2 or CONR 5 R 6 and R 4 , R 5 and R 6 independently of one another are hydrogen or C 1 to C 18 -alkyl, it also being possible for the nitrogen to be quaternized by protonation.
- the inventive method further includes the polymerization of the products of formula III.
- the compounds of the general formula III according to the invention can be isolated or used for the polymerization without further working up.
- the compounds of the general formula III according to the invention can be converted into homopolymers or, in the presence of one or more free-radically copolymerizable monomers, into copolymers.
- the polymerization is a radical polymerization, which is preferably carried out in solution.
- Possible solvents are all solvents customary for polymerization reactions.
- the preferred solvent is water.
- the radical polymerization is carried out in a manner known per se with the exclusion of oxygen, for example by flowing through an inert gas and, if appropriate, under an inert gas atmosphere, nitrogen being preferably used as the inert gas.
- Water-soluble and water-insoluble initiators can be used as initiators for the radical polymerization.
- Typical initiators are peroxides, hydroperoxides, peroxodisulfates, percarbonates, peroxide esters, hydrogen peroxide and azo compounds.
- Examples include hydrogen peroxide, dibenzoyl peroxide, dicyclohexyl peroxidicarbonate, dilauroyl peroxide, methyl ethyl ketone peroxide, di-tert-butyl hydroperoxide, acetyl acetone peroxide, tert-butyl hydroperoxide, cumene hydroperoxide, tert-butyl perneodecanoate, tert-amyl perpivalate, tert-butyl perpivalate, tert-butyl perbenzoate, lithium, sodium, potassium and ammonium peroxodisulfate.
- Water-soluble azo compounds such as, for example, azobisisobutyronitrile, 2,2'-azobis [2- (5-methyl-2-imidazolin-2-yl) propane] dihydrochloride, 2,2'-azobis [2- (2- imidazolin-2-yl) propane] dihydrochloride, 2,2'-azobis [2- (2-imidazolin-2-yl) propane disulfate dihydrate, 2,2'-azobis (2-methylpropionamide) dihydrochloride, 2,2'- Azobis [2- (3,4,5,6-tetrahydropyrimidin-2-yl) propane] dihydrochloride, 2,2'-azobis [2- (2-imidazolin-2-yl) propane], 4,4'-azo -bis- (4-cyanvaleric acid), 1, 1 '-azo-bis- (cyclohexanecarboxylic acid nitrile), 2,2'-azobis (isobutyric acid amidine) dihydrochloride, 2,2
- the initiators can be used alone or as mixtures. Examples of such mixtures are binary mixtures such as e.g. Mixtures of hydrogen peroxide and sodium peroxodisulfate. Water-soluble initiators are preferably used for the polymerization in aqueous medium.
- redox initiator systems can be used as polymerization initiators.
- Such redox initiator systems contain at least one peroxide-containing compound in combination with a redox coinitiator such as, for example, reducing sulfur compounds such as bisulfites, sulfites, thiosulfates, dithionites and tetrahionates of alkali metals and ammonium compounds.
- peroxodisulfates with alkali metal or ammonium bisulfites can be used, e.g. Ammonium peroxodisulfate and ammonium disulfite.
- the proportions of peroxide-containing compound to redox coinitiator are in the range from 30: 1 to 0.05: 1.
- additional transition metal catalysts can be used, for example salts of iron, cobalt, nickel, copper, vanadium and manganese.
- Suitable salts are, for example, iron (II) sulfate, cobalt (II) chloride, nickel (II) sulfate, or copper (I) chloride.
- the reducing transition metal salt is usually used in a concentration in the range from 0.1 ppm to approx. 1000 ppm.
- Combinations of hydrogen peroxide with iron (II) salts can be used, such as 0.5 to 30% hydrogen peroxide and 0.1 to 500 ppm Mohr's salt.
- redox coinitiators and / or transition metal catalysts can be used in combination with the abovementioned initiators, for example benzoin, dimethylaniline, ascorbic acid and organically soluble complexes of heavy metals, such as copper, cobalt, iron, manganese, nickel and Chrome.
- the amounts of redox coinitiators or transition metal catalysts usually used are about 0.1 to about 1000 ppm, based on the amounts of monomers used.
- water-soluble azo initiators hydrogen peroxide, sodium persulfate, potassium persulfate or ammonium persulfate are used.
- initiators are water-soluble azo initiators; 2,2'-azobis [2- (2-imidazolin-2-yl) propane] dihydrochloride (trade name: VA-044) is very particularly preferred.
- the amounts of initiator are generally between 0.5 and 10% by weight, based on the total mass of monomer. Preferred amounts are 1 to 6% by weight, particularly preferred are 2 to 4% by weight.
- the molar proportion of compound III, based on the total amount of monomers is in the range from 5 to 95 mol%, preferably in the range from 20 to 80 mol%. %, particularly preferably in the range from 45 to 55 mol%.
- the polymerization can be carried out in a temperature range between 30 and 90 ° C., preferably between 40 and 70 ° C., very particularly preferably between 55 and 65 ° C.
- the homopolymerization of monomers of the general formula III can be carried out without or with the addition of acid. In the absence of hydrolysis-sensitive substituents, it is preferably carried out in the presence of acids.
- Suitable acids are hydrochloric acid, sulfuric acid, phosphoric acid, nitric acid, perchloric acid, methanesulfonic acid, p-toluenesulfonic acid, benzenesulfonic acid, trifluoro- acetic acid, trifluoromethanesulfonic acid, formic acid, acetic acid, chloroacetic acid,
- Hydrochloric acid, sulfuric acid and phosphoric acid are particularly suitable, hydrochloric acid is very particularly suitable.
- the homopolymerization of monomers of the general formula III in aqueous solution can preferably be carried out at acid concentrations in the range from 0 to 70 mol%. Molar concentrations greater than 5 mol% are particularly preferred, very particularly preferably greater than 30 mol%.
- copolymerization of monomers of the general formula III with the monomers accessible by hydrolysis is advantageously carried out in a buffered aqueous solution.
- the sum of the concentrations of the monomers in the solution are between 15 and 85%, preferably between 25 and 75%, particularly preferably between 40 and 60%.
- the properties such as the molecular weight (M w , M n ) of the polymers according to the invention depend on the reaction conditions chosen.
- the reaction conditions initiator amount, initiator type, course of initiator addition, use of acid, type and amount of acid, solids content of the polymerization solution, temperature, reaction time, post-polymerization with repeated addition of initiator or duration of the post-polymerization may be mentioned as influencing variables.
- the yields are between 40 and 95% depending on the reaction conditions chosen.
- the molecular weights M w are in the range between 10,000 and 300,000, in particular between 30,000 and 200,000.
- the polymers according to the invention can be used in a variety of ways, for example in cosmetic and pharmaceutical compositions, foods, surfactants and cleaning agents.
- the polymers according to the invention can be used in the petroleum industry, pulp processing, paint production and textile industry.
- Example 1 N, N-diallyl-3-aminopropionic acid
- a monomer solution containing 200 g of N, N-diallyl-3-aminopropionic acid, 67.5 g of 32% hydrochloric acid and 32.5 g of water was heated to 60 ° C. under a nitrogen atmosphere.
- the polymerization was then started by adding 10% of an 8% aqueous initiator solution of VA-044 (2,2'-azobis [2- (2-imidazolin-2-yl) propane] dihydrochloride) (the total amount of initiator is 4 wt .-% based on the total amount of monomer).
- Another 60% initiator solution was added dropwise over 3 hours. After a further 2 hours with stirring, the remaining initiator solution was added over a period of 1 hour, the temperature was finally raised to 80 ° C. and the mixture was stirred for another 3 hours.
- the polymer was obtained in a yield of 93%.
- Dependence of the yield of poly (N, N-diallyl-3-aminopropionic acid) on the acid concentration is the total amount of
- the polymers mentioned in Table 2 were prepared essentially analogously to the reaction described in Example 2, the amount of acid being varied. Further reaction conditions: The concentration of the acid is based on the amount of monomer. Weight fraction of all monomers 50%, weight fraction catalyst VA-0444%, night Polymerization time 1 h, temperature 60 ° C, 10 vol% of the initiator solution added at the beginning of the reaction
- the polymers mentioned in Table 4 were prepared essentially analogously to the reaction described in Example 2, the temperature being varied. Further reaction conditions: 50% by weight of all monomers, 2% by weight of catalyst VA-044, post-polymerization time 1 h, 25% by volume of the initiator solution added at the start of the reaction, hydrochloric acid, acid concentration 50% based on the amount of monomer. Table 4:
- the polymers mentioned in Table 5 were prepared essentially analogously to the reaction described in Example 2, the amount of initiator being varied. Further reaction conditions: weight fraction of all monomers 50%, post-polymerization time 1 h, temperature 60 ° C., 10% by volume of the initiator solution added at the beginning of the reaction, hydrochloric acid, acid concentration 50% based on the amount of monomer.
- the polymers mentioned in Table 6 were prepared essentially analogously to the reaction described in Example 2, the temperature and the addition of initiator being varied. Further reaction conditions: weight fraction of the monomers 50%, weight fraction catalyst VA-0442%, post-polymerization time 1 h, amount of acid based on the amount of monomer 50%,
- a common 50% aqueous solution of 169 g of N, N-diallyl-3-aminopropionic acid and 71 g of acrylamide (molar ratio 1: 1) and a 4% aqueous initiator solution of VA-044 (9.6 g dissolved in 480 ml water) were prepared in a dropping funnel. 20% of the monomer solution was dropped into the reaction vessel and heated to 60 ° C. The reaction was started by adding 20% of the initiator solution. The remaining monomer solution was then added dropwise over four hours, the remaining initiator solution over five hours. The reaction mixture was then stirred at 80 ° C. for another hour. A slightly yellowish solution was obtained with a polymer yield of 85%.
- DPA N, N-diallyl-3-aminopropionic acid
- AAM acrylamide
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- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
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Abstract
Description
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Priority Applications (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CA002539157A CA2539157A1 (en) | 2003-09-29 | 2004-09-18 | Polymers based on n,n-diallylamine derivatives, their production and use |
US10/573,838 US20070004889A1 (en) | 2003-09-29 | 2004-09-18 | Polymers based on n,n-diallylamine derivatives their production and use |
JP2006529996A JP2007506852A (ja) | 2003-09-29 | 2004-09-18 | N,n−ジアリルアミン誘導体を基礎とするポリマー、該ポリマーの製造及び使用 |
EP04765386A EP1670837A1 (de) | 2003-09-29 | 2004-09-18 | Polymerisate auf basis von n,n-diallylaminderivaten, deren herstellung und verwendung |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE10345602.3 | 2003-09-29 | ||
DE10345602 | 2003-09-29 |
Publications (1)
Publication Number | Publication Date |
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WO2005037882A1 true WO2005037882A1 (de) | 2005-04-28 |
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Application Number | Title | Priority Date | Filing Date |
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PCT/EP2004/010495 WO2005037882A1 (de) | 2003-09-29 | 2004-09-18 | Polymerisate auf basis von n,n-diallylaminderivaten, deren herstellung und verwendung |
Country Status (7)
Country | Link |
---|---|
US (1) | US20070004889A1 (de) |
EP (1) | EP1670837A1 (de) |
JP (1) | JP2007506852A (de) |
KR (1) | KR20070029629A (de) |
CN (1) | CN1860143A (de) |
CA (1) | CA2539157A1 (de) |
WO (1) | WO2005037882A1 (de) |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2008038077A (ja) * | 2006-08-09 | 2008-02-21 | Kao Corp | 洗浄剤組成物 |
JP2010031238A (ja) * | 2008-06-23 | 2010-02-12 | Hakuto Co Ltd | 多分岐化合物及びその製造方法並びに感光性樹脂組成物及びその硬化物 |
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KR100874219B1 (ko) * | 2006-11-03 | 2008-12-15 | 한국과학기술원 | 계면활성제막이 표면에 고착된 탄소나노튜브의 제조방법 및 그의 제조 방법 |
KR101762469B1 (ko) * | 2010-04-19 | 2017-07-27 | 니토 보세키 가부시기가이샤 | 디알릴아민 아세트산염 중합체의 제조 방법 |
US9396997B2 (en) * | 2010-12-10 | 2016-07-19 | Infineon Technologies Ag | Method for producing a semiconductor component with insulated semiconductor mesas |
WO2014196950A1 (en) * | 2013-06-03 | 2014-12-11 | General Electric Company | Polymer coagulants |
CN104193938A (zh) * | 2014-09-17 | 2014-12-10 | 利达科技(福建)有限公司 | 一种磺酸盐二元醇亲水扩链剂及其制备方法 |
JP7226317B2 (ja) * | 2017-08-04 | 2023-02-21 | 日東紡績株式会社 | 電解めっき液添加剤及びその用途 |
CN109722062A (zh) * | 2018-12-21 | 2019-05-07 | 英德科迪颜料技术有限公司 | 一种核壳结构透明氧化铁包覆颜料的制备方法 |
CN111925464B (zh) * | 2020-07-24 | 2023-04-07 | 安徽大学 | 具有高密度离子功能基团的阴离子交换膜及制备方法 |
CN112812224B (zh) * | 2021-02-03 | 2022-09-27 | 中国海洋石油集团有限公司 | 一种聚驱采出水用可降解清水剂及其制备方法 |
CN112920303B (zh) * | 2021-03-31 | 2023-02-28 | 安徽大学 | 二维阳离子交换聚合物的一种制备方法 |
CN113929801B (zh) * | 2021-12-07 | 2023-06-27 | 东营宝莫环境工程有限公司 | 一种超高温度酸化压裂用稠化剂的制备方法 |
CN117682957A (zh) * | 2022-08-22 | 2024-03-12 | 华为技术有限公司 | 配体化合物、复合物及其应用 |
Citations (1)
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WO2003022898A1 (en) * | 2001-09-06 | 2003-03-20 | Hercules Incorporated | Amphoteric polymer resins that increase the rate of sizing development |
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US4591625A (en) * | 1984-11-26 | 1986-05-27 | University Of Southern Mississippi | Monomer and polymers containing 4-aminopyridine |
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2004
- 2004-09-18 CA CA002539157A patent/CA2539157A1/en not_active Abandoned
- 2004-09-18 JP JP2006529996A patent/JP2007506852A/ja not_active Withdrawn
- 2004-09-18 KR KR1020067006054A patent/KR20070029629A/ko not_active Application Discontinuation
- 2004-09-18 WO PCT/EP2004/010495 patent/WO2005037882A1/de not_active Application Discontinuation
- 2004-09-18 CN CNA2004800283575A patent/CN1860143A/zh active Pending
- 2004-09-18 US US10/573,838 patent/US20070004889A1/en not_active Abandoned
- 2004-09-18 EP EP04765386A patent/EP1670837A1/de not_active Withdrawn
Patent Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2003022898A1 (en) * | 2001-09-06 | 2003-03-20 | Hercules Incorporated | Amphoteric polymer resins that increase the rate of sizing development |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2008038077A (ja) * | 2006-08-09 | 2008-02-21 | Kao Corp | 洗浄剤組成物 |
JP2010031238A (ja) * | 2008-06-23 | 2010-02-12 | Hakuto Co Ltd | 多分岐化合物及びその製造方法並びに感光性樹脂組成物及びその硬化物 |
Also Published As
Publication number | Publication date |
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CN1860143A (zh) | 2006-11-08 |
US20070004889A1 (en) | 2007-01-04 |
JP2007506852A (ja) | 2007-03-22 |
CA2539157A1 (en) | 2005-04-28 |
EP1670837A1 (de) | 2006-06-21 |
KR20070029629A (ko) | 2007-03-14 |
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