NO861423L - POLYMER ALKYLENE PHOSPHORIC ACID PIPERAZINE ADDITIVES, AND USE OF SUCH. - Google Patents
POLYMER ALKYLENE PHOSPHORIC ACID PIPERAZINE ADDITIVES, AND USE OF SUCH.Info
- Publication number
- NO861423L NO861423L NO861423A NO861423A NO861423L NO 861423 L NO861423 L NO 861423L NO 861423 A NO861423 A NO 861423A NO 861423 A NO861423 A NO 861423A NO 861423 L NO861423 L NO 861423L
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- Prior art keywords
- compound
- hydrogen
- radical
- approx
- solution
- Prior art date
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- 229920000642 polymer Polymers 0.000 title description 7
- 239000000654 additive Substances 0.000 title description 2
- NQQWFVUVBGSGQN-UHFFFAOYSA-N phosphoric acid;piperazine Chemical compound OP(O)(O)=O.C1CNCCN1 NQQWFVUVBGSGQN-UHFFFAOYSA-N 0.000 title 1
- 150000001875 compounds Chemical class 0.000 claims description 17
- 229910052739 hydrogen Inorganic materials 0.000 claims description 12
- 239000001257 hydrogen Substances 0.000 claims description 11
- -1 amine compound Chemical class 0.000 claims description 10
- 239000000047 product Substances 0.000 claims description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- 125000004432 carbon atom Chemical group C* 0.000 claims description 7
- 238000000034 method Methods 0.000 claims description 6
- IMUDHTPIFIBORV-UHFFFAOYSA-N aminoethylpiperazine Chemical compound NCCN1CCNCC1 IMUDHTPIFIBORV-UHFFFAOYSA-N 0.000 claims description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 4
- 125000005843 halogen group Chemical group 0.000 claims description 4
- 150000003254 radicals Chemical class 0.000 claims description 4
- 229910052783 alkali metal Inorganic materials 0.000 claims description 3
- 150000001340 alkali metals Chemical class 0.000 claims description 3
- 150000002894 organic compounds Chemical class 0.000 claims description 3
- GAWIXWVDTYZWAW-UHFFFAOYSA-N C[CH]O Chemical group C[CH]O GAWIXWVDTYZWAW-UHFFFAOYSA-N 0.000 claims description 2
- 239000007795 chemical reaction product Substances 0.000 claims description 2
- 230000002401 inhibitory effect Effects 0.000 claims description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 2
- 150000002431 hydrogen Chemical class 0.000 claims 3
- 239000000243 solution Substances 0.000 claims 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims 1
- 239000007864 aqueous solution Substances 0.000 claims 1
- 230000015572 biosynthetic process Effects 0.000 claims 1
- UEZVMMHDMIWARA-UHFFFAOYSA-M phosphonate Chemical compound [O-]P(=O)=O UEZVMMHDMIWARA-UHFFFAOYSA-M 0.000 claims 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 18
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 12
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 description 10
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 9
- 230000005764 inhibitory process Effects 0.000 description 9
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 8
- 239000002253 acid Substances 0.000 description 8
- 238000010992 reflux Methods 0.000 description 8
- 230000008021 deposition Effects 0.000 description 7
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 7
- 239000003112 inhibitor Substances 0.000 description 7
- 150000001412 amines Chemical class 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 6
- 229920000768 polyamine Polymers 0.000 description 6
- 235000019256 formaldehyde Nutrition 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- IKHGUXGNUITLKF-UHFFFAOYSA-N Acetaldehyde Chemical compound CC=O IKHGUXGNUITLKF-UHFFFAOYSA-N 0.000 description 4
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 4
- NBBJYMSMWIIQGU-UHFFFAOYSA-N Propionic aldehyde Chemical compound CCC=O NBBJYMSMWIIQGU-UHFFFAOYSA-N 0.000 description 4
- 239000011575 calcium Substances 0.000 description 4
- 229910052791 calcium Inorganic materials 0.000 description 4
- 239000011541 reaction mixture Substances 0.000 description 4
- WLOHKZPZHBMVBK-UHFFFAOYSA-N 2-(chloromethyl)oxirane Chemical compound ClCC1CO1.ClCC1CO1 WLOHKZPZHBMVBK-UHFFFAOYSA-N 0.000 description 3
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 description 3
- 239000004593 Epoxy Substances 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 150000001335 aliphatic alkanes Chemical class 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 239000008367 deionised water Substances 0.000 description 3
- 229910021641 deionized water Inorganic materials 0.000 description 3
- 239000000376 reactant Substances 0.000 description 3
- 230000035484 reaction time Effects 0.000 description 3
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- TTZMPOZCBFTTPR-UHFFFAOYSA-N O=P1OCO1 Chemical class O=P1OCO1 TTZMPOZCBFTTPR-UHFFFAOYSA-N 0.000 description 2
- 150000001299 aldehydes Chemical class 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 2
- 229910052794 bromium Inorganic materials 0.000 description 2
- 229940090960 diethylenetriamine pentamethylene phosphonic acid Drugs 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- DUYCTCQXNHFCSJ-UHFFFAOYSA-N dtpmp Chemical compound OP(=O)(O)CN(CP(O)(O)=O)CCN(CP(O)(=O)O)CCN(CP(O)(O)=O)CP(O)(O)=O DUYCTCQXNHFCSJ-UHFFFAOYSA-N 0.000 description 2
- 150000002170 ethers Chemical class 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- CZWSZZHGSNZRMW-UHFFFAOYSA-N 1,2-dibromobutane Chemical compound CCC(Br)CBr CZWSZZHGSNZRMW-UHFFFAOYSA-N 0.000 description 1
- KFUSEUYYWQURPO-UHFFFAOYSA-N 1,2-dichloroethene Chemical compound ClC=CCl KFUSEUYYWQURPO-UHFFFAOYSA-N 0.000 description 1
- YHRUOJUYPBUZOS-UHFFFAOYSA-N 1,3-dichloropropane Chemical compound ClCCCCl YHRUOJUYPBUZOS-UHFFFAOYSA-N 0.000 description 1
- YZNQITSGDRCUKE-UHFFFAOYSA-N 1-chloropropane Chemical compound [CH2]CCCl YZNQITSGDRCUKE-UHFFFAOYSA-N 0.000 description 1
- VILCJCGEZXAXTO-UHFFFAOYSA-N 2,2,2-tetramine Chemical compound NCCNCCNCCN VILCJCGEZXAXTO-UHFFFAOYSA-N 0.000 description 1
- NKWKILGNDJEIOC-UHFFFAOYSA-N 2-(2-chloroethyl)oxirane Chemical compound ClCCC1CO1 NKWKILGNDJEIOC-UHFFFAOYSA-N 0.000 description 1
- LSOXTBBDZHIHDE-UHFFFAOYSA-N 2-(3-chloropropyl)oxirane Chemical compound ClCCCC1CO1 LSOXTBBDZHIHDE-UHFFFAOYSA-N 0.000 description 1
- MMTOSBCMFDNOIY-UHFFFAOYSA-N 2-(chloromethyl)-3-methyloxirane Chemical compound CC1OC1CCl MMTOSBCMFDNOIY-UHFFFAOYSA-N 0.000 description 1
- KKZUMAMOMRDVKA-UHFFFAOYSA-N 2-chloropropane Chemical compound [CH2]C(C)Cl KKZUMAMOMRDVKA-UHFFFAOYSA-N 0.000 description 1
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- ZNSMNVMLTJELDZ-UHFFFAOYSA-N Bis(2-chloroethyl)ether Chemical compound ClCCOCCCl ZNSMNVMLTJELDZ-UHFFFAOYSA-N 0.000 description 1
- 239000004970 Chain extender Substances 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 1
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical class NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 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
- 238000006683 Mannich reaction Methods 0.000 description 1
- 239000004809 Teflon Substances 0.000 description 1
- 229920006362 Teflon® Polymers 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 125000002947 alkylene group Chemical group 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- HRQGCQVOJVTVLU-UHFFFAOYSA-N bis(chloromethyl) ether Chemical compound ClCOCCl HRQGCQVOJVTVLU-UHFFFAOYSA-N 0.000 description 1
- ZTQSAGDEMFDKMZ-UHFFFAOYSA-N butyric aldehyde Natural products CCCC=O ZTQSAGDEMFDKMZ-UHFFFAOYSA-N 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 235000010216 calcium carbonate Nutrition 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 150000001804 chlorine Chemical class 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 150000004985 diamines Chemical class 0.000 description 1
- 239000000539 dimer Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- CUHVTYCUTYWQOR-UHFFFAOYSA-N formaldehyde Chemical compound O=C.O=C CUHVTYCUTYWQOR-UHFFFAOYSA-N 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002366 halogen compounds Chemical class 0.000 description 1
- 150000002367 halogens Chemical group 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 150000002391 heterocyclic compounds Chemical class 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 125000002768 hydroxyalkyl group Chemical group 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 150000002497 iodine compounds Chemical class 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 235000010755 mineral Nutrition 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- LJYRLGOJYKPILZ-UHFFFAOYSA-N murexide Chemical compound [NH4+].N1C(=O)NC(=O)C(N=C2C(NC(=O)NC2=O)=O)=C1[O-] LJYRLGOJYKPILZ-UHFFFAOYSA-N 0.000 description 1
- 239000013618 particulate matter Substances 0.000 description 1
- 229920001281 polyalkylene Polymers 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 239000002455 scale inhibitor Substances 0.000 description 1
- 238000004448 titration Methods 0.000 description 1
- FQDIANVAWVHZIR-OWOJBTEDSA-N trans-1,4-Dichlorobutene Chemical compound ClC\C=C\CCl FQDIANVAWVHZIR-OWOJBTEDSA-N 0.000 description 1
Landscapes
- Materials For Medical Uses (AREA)
- Saccharide Compounds (AREA)
- Polymers With Sulfur, Phosphorus Or Metals In The Main Chain (AREA)
Description
Anvendelse av metylenfosfonsyresubstituerte alkylenpoly-aminer for metallionekontroll ved mindre enn støkiometriske mengder ble foreslått i US-patentskrift 2.609.390 (Bersworth) Use of methylenephosphonic acid substituted alkylene polyamines for metal ion control at less than stoichiometric amounts was suggested in US Patent 2,609,390 (Bersworth)
i 1952. Senere ble et vanndispergerbart polymert amin-gelati-neringsmiddel som inkluderte alkylenfosfonat-derivater angitt å ha "terskel"-effekter for avsetningsinhiberende formål (se US-patent 3.331.773), idet denne betegnelse anvendes for å be-skrive anvendelse av midlet i mindre enn støkiometriske mengder. Diamin- og polyamin-metylenfosfonatderivatene angis og kreves be-skyttet i henholdsvis US-patent 3.336.221 og 3.434.969. Noen av de produkter som er åpenbart i disse to patenter er tilgjengelige kommersielt og anbefales som avsetningsinhibitorer når de påføres i terskelmengder. in 1952. Later, a water dispersible polymeric amine gelatinizer which included alkylene phosphonate derivatives was stated to have "threshold" effects for scale inhibiting purposes (see US Patent 3,331,773), this term being used to describe the use of the agent in less than stoichiometric amounts. The diamine and polyamine methylene phosphonate derivatives are specified and claimed to be protected in US patent 3,336,221 and 3,434,969, respectively. Some of the products disclosed in these two patents are available commercially and are recommended as scale inhibitors when applied in threshold amounts.
Noan andre patenter som åpenbarer heterocykliske nitrogen-holdige forbindelser som er nyttige gelatineringsmidler og kan anvendes i terskelmengder, er US-patenter 3.674.804; 3.720.498; 3.743.603; 3.859.211 og 3.954.761. Noen av de forbindelser som er inkludert deri er heterocykliske forbindelser med følgende formler: hvor R er hydrogen eller alkyl og M er hydrogen, alkalimetall, ammonium- eller di- eller trietanolamin-radikal; Some other patents that disclose heterocyclic nitrogen-containing compounds that are useful gelatinizing agents and can be used in threshold amounts are US Patents 3,674,804; 3,720,498; 3,743,603; 3,859,211 and 3,954,761. Some of the compounds included therein are heterocyclic compounds of the following formulas: wherein R is hydrogen or alkyl and M is hydrogen, alkali metal, ammonium or di- or triethanolamine radical;
Metylenfosfonater av polyalkylenpolyaminer, åpenbart i US-patent 4.051.110, lages ved å omsette di- eller polyaminer med et kjedeforlengelsesmiddel som f.eks. et dihalogenid eller et epoksyhalogenid, f.eks. etylendiklorid eller epiklorhydrin og deretter med fosforsyre og formaldehyd. Således omsettes f.eks. trietylentetraamin med epiklorhydrin i et tilnærmet molforhold 1:1; deretter omsettes produktet med forsforsyre og formaldehyd i nærvær av saltsyre. Det resulterende metylenfosfonerte polyamin er nyttig i små mengder som avsetningsinhibitor, idet det anvendes i konsentrasjoner av 20-50 ppm. Methylene phosphonates of polyalkylene polyamines, disclosed in US Patent 4,051,110, are made by reacting di- or polyamines with a chain-extending agent such as a dihalide or an epoxy halide, e.g. ethylene dichloride or epichlorohydrin and then with phosphoric acid and formaldehyde. Thus, e.g. triethylenetetramine with epichlorohydrin in an approximate 1:1 molar ratio; the product is then reacted with phosphoric acid and formaldehyde in the presence of hydrochloric acid. The resulting methylenephosphonated polyamine is useful in small amounts as a deposition inhibitor, being used in concentrations of 20-50 ppm.
Polymetylenfosfonsyrederivater av polymerer av N-aminoetylpiperazin har nå vist seg å være overlegne avsetningsinhibitorer og kan anvendes i terskelmengder. Polymethylenephosphonic acid derivatives of polymers of N-aminoethylpiperazine have now been shown to be superior deposition inhibitors and can be used in threshold amounts.
Polymerene i henhold til oppfinnelsen lages ved å omsette N-aminetylpiperazin (AEP) med en dihalogen- eller epoksyhalogenforbindelse og etterpå omsette den polymer som derved er dannet med fosforsyre og et alkanal (aldehyd) ved lav pH-verdi, vanligvis tilveiebragt ved nærvær av en mineralsyre, f.eks. saltsyre. N-aminetylpiperazin har følgende strukturformel: The polymers according to the invention are made by reacting N-aminetylpiperazine (AEP) with a dihalogen or epoxyhalogen compound and then reacting the resulting polymer with phosphoric acid and an alkanal (aldehyde) at a low pH value, usually provided in the presence of a mineral acid, e.g. hydrochloric acid. N-aminetylpiperazine has the following structural formula:
og kan betegnes som 1-(2-aminoetyl)-piperazin. Heretter vil forbindelsen bli forkortet "AEP". and can be designated as 1-(2-aminoethyl)-piperazine. Hereafter, the connection will be abbreviated "AEP".
AEP kan omsettes med hvilket som helst antall av dihalogen-eller epoksyhalogenforbindelser slik at det dannes en dimer eller polymer. Ethvert egnet epoksyhalogenalkan (epihalogenhydrin) AEP can be reacted with any number of dihalogen or epoxyhalogen compounds to form a dimer or polymer. Any suitable epoxyhaloalkane (epihalohydrin)
kan omsettes, idet 1,2-epoksy-3-klorpropan (epiklorhydrin) foretrekkes. Generelt vil epoksyhalogenforbindelsen ha 3-10 karbonatomer. Andre epiklorhydrintypeforbindelser inkluderer: 1,2-epoksy-4-klorbutan, 2,3-epoksy-4-klorbutan, 1,2-epoksy-5-klorpentan, 2,2-epoksy-5-klorpentan etc. Generelt foretrekkes klorderivatene, selv om de tilsvarende brom- eller iodforbind-elser kan anvendes. Blandinger av epoksyhalogenalkaner kan også anvendes. can be reacted, with 1,2-epoxy-3-chloropropane (epichlorohydrin) being preferred. In general, the epoxy halogen compound will have 3-10 carbon atoms. Other epichlorohydrin type compounds include: 1,2-epoxy-4-chlorobutane, 2,3-epoxy-4-chlorobutane, 1,2-epoxy-5-chloropentane, 2,2-epoxy-5-chloropentane, etc. In general, the chlorine derivatives are preferred, even whether the corresponding bromine or iodine compounds can be used. Mixtures of epoxyhaloalkanes can also be used.
Dihalogenider som har 1-20 karbonatomer kan anvendes. Dihalides having 1-20 carbon atoms can be used.
Mettede dihalogenider med formel X(CH„) X, hvor X kan være Saturated dihalides of formula X(CH„) X, where X can be
3 zn 3 zn
klor, brom, iod eller kombinasjoner derav og hvor n er et helt tall fra 1 til ca. 10, fortrinnsvis 2 til 6, kan anvendes. Således kan f.eks. diklormetan (metylenklorid), 1,2-dikloretan (etylendiklorid), 1,2- eller 1,3-diklorpropan, 1,4- eller chlorine, bromine, iodine or combinations thereof and where n is an integer from 1 to approx. 10, preferably 2 to 6, can be used. Thus, e.g. dichloromethane (methylene chloride), 1,2-dichloroethane (ethylene dichloride), 1,2- or 1,3-dichloropropane, 1,4- or
1,2-dibrombutan og lignende anvendes. 1,2-dibromobutane and the like are used.
Aralkylendihalogenider kan også anvendes som har formelen X-H2C-Ar-CH2-X hvor Ar er Aralkylene dihalides can also be used which have the formula X-H2C-Ar-CH2-X where Ar is
hvor R kan være hydrogen, halogen, alkyl, med 1-4 karbonatomer, hydroksyl og hydroksyalkyl, med 1-4 karbonatomer, og X er et halogenatom. where R can be hydrogen, halogen, alkyl, with 1-4 carbon atoms, hydroxyl and hydroxyalkyl, with 1-4 carbon atoms, and X is a halogen atom.
Dihalogenalkylenetere kan også anvendes, f.eks. bis(klormetyl)-eter eller bis(kloretyl)eter. Formler for slike etere inkluderer ogsåtDihaloalkylene ethers can also be used, e.g. bis(chloromethyl) ether or bis(chloroethyl) ether. Formulas for such ethers also include
X-CH„CH„ (0CHoCHo) X hvor n er 1-3 og X-CH„CH„ (0CHoCHo) X where n is 1-3 and
hvor X er et halogenatom. where X is a halogen atom.
Dihalogenidene kan også være umettet. Således kan 1,2-dikloreten, 1,4-diklor-2-buten og lignende anvendes. The dihalides may also be unsaturated. Thus, 1,2-dichloroethene, 1,4-dichloro-2-butene and the like can be used.
Betingelsene for å fremstille polymeren er å anvende reaktantene i en mengde av fra ca. 0,2 til ca. 1 mol av kjede-forlengerforbindelsen, fortrinnsvis ca. 0,25 til ca. 0,6, dvs. diepoksy-, dihalogen- eller epoksyhalogenforbindelsen, pr. mol av AEP. Reaksjonstemperaturen er fra ca. 50 til ca. 100°C, fortrinnsvis 70-80°C, ved et trykk som er tilstrekkelig til å opp-rettholde reaktantene i flytende fase. The conditions for producing the polymer are to use the reactants in an amount of from approx. 0.2 to approx. 1 mol of the chain-extender compound, preferably approx. 0.25 to approx. 0.6, i.e. the diepoxy, dihalogen or epoxyhalogen compound, per moles of AEP. The reaction temperature is from approx. 50 to approx. 100°C, preferably 70-80°C, at a pressure sufficient to maintain the reactants in liquid phase.
Fosfonometyleringen (Mannich-reaksjon) utføres deretter på produktet i nærvær av en sterk syre for å holde pH-verdien på mindre enn 1. The phosphonomethylation (Mannich reaction) is then performed on the product in the presence of a strong acid to keep the pH at less than 1.
Mens reaksjonen vil skride frem ved temperaturer over et bredt område, dvs. fra 85 til 150°C, foretrekkes det at reak-sjonsmiljøet holdes under tilbakeløpskjøling. Reaksjonen utføres fortrinnsvis ved atmosfæretrykk, selv om underatmosfærisk og over-atmosfærisk trykk kan benyttes om så ønskes. Reaksjonstidene vil variere i avhengighet av en rekke variable, men den foretrukne reaksjonstid er 1-5 timer, og den mest foretrukne reaksjonstid er 2-4 timer. While the reaction will proceed at temperatures over a wide range, ie from 85 to 150°C, it is preferred that the reaction environment be maintained under reflux. The reaction is preferably carried out at atmospheric pressure, although sub-atmospheric and above-atmospheric pressure can be used if desired. The reaction times will vary depending on a number of variables, but the preferred reaction time is 1-5 hours, and the most preferred reaction time is 2-4 hours.
Selv om fosforsyren og alkanet kan tilsettes sammen eller separat Although the phosphoric acid and the alkane can be added together or separately
i hvilken som helst rekkefølge til reaksjonsblandingen, foretrekkes det å tilsette fosforsyren til polyaminet og deretter langsomt å tilsette alkanalet under tilbakeløpsbetingelser. in any order to the reaction mixture, it is preferred to add the phosphoric acid to the polyamine and then slowly add the alkane under reflux conditions.
Tilnærmet ekvimolare mengder av alkanal og fosforsyre anvendes for fosfonometyleringen av aminet. Overskudd av enten alkanalet eller syren kan benyttes, selv om store overskudd av hver av disse ville være uøkonomisk. Den foretrukne prosess vil anvende en mengde av alkanal som er ekvivalent med de aminhydro-genatomer som er tilgjengelige og et svakt støkiometrisk overskudd av fosforsyren. Approximately equimolar amounts of alkanol and phosphoric acid are used for the phosphonomethylation of the amine. Excesses of either the alkane or the acid can be used, although large excesses of each would be uneconomical. The preferred process will use an amount of alkanol equivalent to the amine hydrogen atoms available and a slight stoichiometric excess of the phosphoric acid.
Selv om metanal (formaldehyd) foretrekkes, kan andre alkan-aler (aldehyder) anvendes istedenfor metanal, f.eks. etanal (acetaldehyd), propanal (propionaldehyd), og lignende, hvor alkanalet kan inneholde en rett eller forgrenet kjede med opp til 10 karbonatomer. Although methanal (formaldehyde) is preferred, other alkanals (aldehydes) can be used instead of methanal, e.g. ethanal (acetaldehyde), propanal (propionaldehyde), and the like, where the alkanal can contain a straight or branched chain with up to 10 carbon atoms.
Således kan forbindelsene i henhold til oppfinnelsen være representert ved følgende formel: Thus, the compounds according to the invention can be represented by the following formula:
A-f BA) m A-f BA) m
hvor A er et organisk radikal med formel where A is an organic radical of formula
hvor Z er hydrogen, hydroksyetyl, hydroksypropyl, eller BA hvor M er hydrogen, et alkalimetall eller ammonium, og hvor B er et toverdig radikal som stammer fra en dihalogen-, diepoksy- eller halogenepoksy-organisk forbindelse som har én av de følgende strukturformler: hvor n er 1-10, n<1>er 1-3, og hvor R er hydrogen eller metyl og R' er hydrogen, et alkylradikal eller et hydroksyalkylradikal med 1-4 karbonatomer, et hydroksyradikal eller et halogenatom, m er 1-10 og minst 50% av Z-gruppene er grupper. Foretrukne forbindelser i henhold til oppfinnelsen er slike hvor B-andelen stammer fra 1,2-epoksy-3-klorpropan (epiklorhydrin) eller 1,2-dikloretan, hvor m er 1 eller 2, Z-andelen er where Z is hydrogen, hydroxyethyl, hydroxypropyl, or BA where M is hydrogen, an alkali metal or ammonium, and where B is a divalent radical originating from a dihalo, diepoxy or haloepoxy organic compound having one of the following structural formulas: where n is 1-10, n<1> is 1-3, and where R is hydrogen or methyl and R' is hydrogen, an alkyl radical or a hydroxyalkyl radical with 1-4 carbon atoms, a hydroxy radical or a halogen atom, m is 1- 10 and at least 50% of the Z groups are groups. Preferred compounds according to the invention are those where the B part originates from 1,2-epoxy-3-chloropropane (epichlorohydrin) or 1,2-dichloroethane, where m is 1 or 2, the Z part is
og M er H, Na eller NH^. and M is H, Na or NH 2 .
De følgende eksempler illustrerer oppfinnelsen. The following examples illustrate the invention.
Eksempel 1 Example 1
Et N-aminetylpiperazin (AEP)-basert amin ble fremstilt ved An N-amineethylpiperazine (AEP)-based amine was prepared by
å omsette 22,7 g N-aminoetylpiperazin (0,176 mol), 9,8 g 1,2-dikloretan (DCE) (0,099 mol) og 17,5 g avionisert vann (DCE/AEP -molforhold = 0,56) i en 500 ml rundbunnet reaksjons-kolbe utstyrt med vanndrevet tilbakeløpskjøler, mekanisk rører, termometer med temperaturregulator og tilsetningstrakt. Reaksjonsproduktet ble deretter fosfonometylert ved å tilsette tilnærmet 75 g konsentrert saltsyre og 32,6 g (0,40 mol) fosforsyre til den vandige aminløsning, og reaksjonsblandingen ble oppvarmet til tilbakeløp og holdt slik i en time. 37%ig vandig metanal-løsning (28,1 g - 0,35 mol) ble tilsatt gjennom tilsetnings-trakten i løpet av 1 1/2 time. Reaksjonsblandingen ble oppvarmet under tilbakeløp i 3 timer til og så avkjølt. Produktet ble vurdert ved avsetningsinhiberingstesten (se forskrift for dette i det følgende) og sammenlignet med dietylentriaminpentametylen-fosfonsyre (DETA-MPA), en kommersielt tilgjengelig organo-fosfonsyre. Resultatene er angitt i tabell I. to react 22.7 g of N-aminoethylpiperazine (0.176 mol), 9.8 g of 1,2-dichloroethane (DCE) (0.099 mol) and 17.5 g of deionized water (DCE/AEP molar ratio = 0.56) in a 500 ml round-bottomed reaction flask equipped with water-driven reflux cooler, mechanical stirrer, thermometer with temperature regulator and addition funnel. The reaction product was then phosphonomethylated by adding approximately 75 g of concentrated hydrochloric acid and 32.6 g (0.40 mol) of phosphoric acid to the aqueous amine solution, and the reaction mixture was heated to reflux and held for one hour. 37% aqueous methanal solution (28.1 g - 0.35 mol) was added through the addition funnel over 1 1/2 hours. The reaction mixture was heated under reflux for another 3 hours and then cooled. The product was assessed by the deposition inhibition test (see regulations for this below) and compared to diethylenetriaminepentamethylene-phosphonic acid (DETA-MPA), a commercially available organo-phosphonic acid. The results are shown in Table I.
Eksempel A ( for sammenligning) Example A (for comparison)
100 g avionisert vann og 32,7 g (0,25 mol) av 98%ig N-aminetylpiperazin ble veid inn i en 500 ml rundbunnet reaksjons-kolbe utstyrt med vanndrevet tilbakeløpskjøler, mekanisk rører, termometer med temperaturregulator og tilsetningstrakt. Tilnærmet 90 g konsentrert saltsyre og 73,5 g (0,90 mol) fosforsyre ble tilsatt til den vandige aminløsning. Oppvarmning og tilbakeløps-kjøling ble utført som i eksempel 1, og så ble 63,3 g (0,78 mol) av 37%ig vandig metanal tilsatt gjennom en tilsetningstrakt i løpet av 1 1/2 timer. Reaksjonsblandingen ble oppvarmet under tilbakeløp som i eksempel 1 og avkjølt. Avsetningsinhiberings-resultater, ved anvendelse av følgende testmetode, er vist i tabell I. 100 g of deionized water and 32.7 g (0.25 mol) of 98% N-aminoethylpiperazine were weighed into a 500 ml round bottom reaction flask equipped with a water driven reflux cooler, mechanical stirrer, thermometer with temperature controller and addition funnel. Approximately 90 g of concentrated hydrochloric acid and 73.5 g (0.90 mol) of phosphoric acid were added to the aqueous amine solution. Heating and reflux cooling were carried out as in Example 1, and then 63.3 g (0.78 mol) of 37% aqueous methanal was added through an addition funnel over 1 1/2 hours. The reaction mixture was heated under reflux as in Example 1 and cooled. Deposition inhibition results, using the following test method, are shown in Table I.
Testmetode (avsetningsinhibering) Test method (deposition inhibition)
<*>Indikatoren er en 0,2%ig løsning av ammoniumpurpurat i etylenglykol. <*>The indicator is a 0.2% solution of ammonium purpurate in ethylene glycol.
Inhibitorløsninger ble fremstilt av de forbindelser som skulle vurderes, slik at en løsning med 1% aktivt (i form av syre) produkt ble dannet. Inhibitor solutions were prepared from the compounds to be evaluated, so that a solution with 1% active (in the form of acid) product was formed.
Metode Method
Til en 4-ounce (118 ml) flaske med vid åpning ble det tilsatt 50 ml av løsning A og en 1 tommes (25,4 mm) teflonbelagt magnetisk rørestav. Til løsning A ble det under røring tilsatt 0,1 ml av den l%ige løsning av den forbindelse som skulle testes. To a 4-ounce (118 ml) wide mouth bottle was added 50 ml of solution A and a 1 inch (25.4 mm) Teflon-coated magnetic stir bar. To solution A, 0.1 ml of the 1% solution of the compound to be tested was added while stirring.
Røringen ble fortsatt i tilnærmet 1 minutt, og så ble The stirring was continued for approximately 1 minute, and then it was
50 ml av løsning B tilsatt og røringen fortsatt i 3 minutter til. Rørestaven ble tatt vekk, flasken korket, merket og anbragt i et 80°C tørkeskap i 24 timer. Etter at de 24 timer var gått, ble prøven tatt ut av tørkeskapet, og 5 ml av væsken ble ekstrahert (partikkelformig materiale ble unngått) og filtrert gjennom en 4 um glassfritte. Til den filtrerte prøve ble det tilsatt 2 ml av IN NaOH og 4 dråper av 0,2% "Murexide"-indikatorløsning. 50 ml of solution B added and stirring continued for a further 3 minutes. The stirring rod was removed, the bottle corked, labeled and placed in an 80°C drying cabinet for 24 hours. After the 24 hours had passed, the sample was removed from the drying cabinet and 5 ml of the liquid was extracted (particulate matter was avoided) and filtered through a 4 µm glass frit. To the filtered sample was added 2 ml of 1N NaOH and 4 drops of 0.2% "Murexide" indicator solution.
Ca. 70 ml avionisert vann ble tilsatt og løsningen titrert med 0,01M EDTA inntil farven forandret seg fra rosa til fiolett. About. 70 ml of deionized water was added and the solution titrated with 0.01M EDTA until the color changed from pink to violet.
Den totale kalsiumkonsentrasjon er 0,01M etter at 50 ml av løsning A var blandet med 50 ml av løsning B. Hvis alt kalsium forblir i løsning i den 24 timers periode ved 80°C, så vil konsentrasjonen fremdeles være 0,01M, og dette representerer 100% inhibering av CaCO^. Avhengig av ytelsen til den inhibitor som skal vurderes, vil noe CaC03 bli utfelt, og dette etterlater mindre løselig kalsium. Titreringen måler mengden av løselig kalsium som er igjen i løsning etter 24 timer ved 80°C. Denne mengde divideres med den totale mengde som opprinnelig ble tilsatt, og resultatet multipliseres med 100 slik at man får prosent inhibering. The total calcium concentration is 0.01M after 50 ml of solution A has been mixed with 50 ml of solution B. If all the calcium remains in solution during the 24 hour period at 80°C, then the concentration will still be 0.01M, and this represents 100% inhibition of CaCO^. Depending on the performance of the inhibitor being evaluated, some CaCO3 will precipitate, leaving less soluble calcium. The titration measures the amount of soluble calcium that remains in solution after 24 hours at 80°C. This amount is divided by the total amount that was originally added, and the result is multiplied by 100 so that you get percent inhibition.
Konsentrasjonen av inhibitor som ble anvendt i avsetningsinhiberingstesten var 10 ppm (aktiv syre) basert på total vekt av løsning. The concentration of inhibitor used in the deposition inhibition test was 10 ppm (active acid) based on total weight of solution.
I de følgende eksempler ble det anvendt forskjellige molforhold mellom 1,2-dikloretan (DCE)/AEP. Fremgangsmåten fra eksempel 1 ble fulgt, med unntagelse av reaktantforholdene. Igjen ble det anvendt 10 ppm av inhibitoren. Resultatene er gjengitt i Tabell II. In the following examples, different molar ratios of 1,2-dichloroethane (DCE)/AEP were used. The procedure from Example 1 was followed, with the exception of the reactant ratios. Again, 10 ppm of the inhibitor was used. The results are reproduced in Table II.
Det fremgår av dataene i de ovenstående tabeller at AEP-trimetylenfosfonsyre (eksempel A) bare har liten evne til å inhibere avsetning, 46% sammenlignet med 37% for ingen inhibitor. Det kan også sees at de produkter som dannes ved anvendelse av molforhold (DEC/AEP) på fra ca. 0,2 til ca. 0,8 etter fosfono-metylering gir et uventet resultat i sammenligning med den fosfonometylerte DETA og AEP. Det bør også bemerkes at når det dannes høyere polymerer, slik som i tabell II, eksempel 5, er inhibering bare litt bedre enn for AEP-monomeren, men er bedre er intet additiv i det hele tatt. It appears from the data in the above tables that AEP-trimethylenephosphonic acid (Example A) has only a small ability to inhibit deposition, 46% compared to 37% for no inhibitor. It can also be seen that the products that are formed by applying molar ratios (DEC/AEP) of from approx. 0.2 to approx. 0.8 after phosphonomethylation gives an unexpected result in comparison with the phosphonomethylated DETA and AEP. It should also be noted that when higher polymers are formed, such as in Table II, Example 5, inhibition is only slightly better than for the AEP monomer, but is better is no additive at all.
Eksempel 6 Example 6
1,2-epoksy-3-klorpropan (epiklorhydrin) ble brukt istedenfor 1,2-dikloretan i eksempel 1 ved et molforhold epoksy/amin på 0,50. Det resulterende metylenfosfonerte produkt ved 10 ppm ga 96% inhibering i avsetningsinhiberingstesten. 1,2-Epoxy-3-chloropropane (epichlorohydrin) was used instead of 1,2-dichloroethane in Example 1 at an epoxy/amine molar ratio of 0.50. The resulting methylenephosphonated product at 10 ppm gave 96% inhibition in the deposit inhibition test.
De fosfonometylerte produkter i henhold til oppfinnelsen anvendes i mengder som er mindre enn de støkiometriske, dvs. "terskelmengder". Den nøyaktige mengde vil være avhengig av konsentrasjonen av metallioner som det er ønskelig å regulere, men så lave mengder som 0,1 ppm eller så høye som 500 ppm kan anvendes, basert på vekten av løsning. The phosphonomethylated products according to the invention are used in amounts that are smaller than the stoichiometric, i.e. "threshold amounts". The exact amount will depend on the concentration of metal ions it is desired to control, but amounts as low as 0.1 ppm or as high as 500 ppm can be used, based on the weight of solution.
Claims (7)
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PCT/US1984/001273 WO1986001192A1 (en) | 1982-09-27 | 1984-08-14 | Polymeric alkylenephosphoric acid piperazine derivatives as scale inhibitors |
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1986
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