GB1572285A - Creación de Inventos y Patentes con Inteligencia Artificial

GB1572285A – Heavy metal ion adsorbents
– Google Patents

GB1572285A – Heavy metal ion adsorbents
– Google Patents
Heavy metal ion adsorbents

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Publication number
GB1572285A

GB1572285A
GB3784/78A
GB378478A
GB1572285A
GB 1572285 A
GB1572285 A
GB 1572285A
GB 3784/78 A
GB3784/78 A
GB 3784/78A
GB 378478 A
GB378478 A
GB 378478A
GB 1572285 A
GB1572285 A
GB 1572285A
Authority
GB
United Kingdom
Prior art keywords
metal ion
heavy metal
amino
ion adsorbent
polystyrene
Prior art date
1977-03-09
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.)

Expired

Application number
GB3784/78A
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)

TABUSHI I

Original Assignee
TABUSHI I
Priority date (The priority date 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 date listed.)
1977-03-09
Filing date
1978-01-31
Publication date
1980-07-30

1977-03-09
Priority claimed from JP2488477A
external-priority
patent/JPS53109886A/en

1977-03-09
Priority claimed from JP2488577A
external-priority
patent/JPS53111090A/en

1977-03-09
Priority claimed from JP2488677A
external-priority
patent/JPS53111091A/en

1978-01-31
Application filed by TABUSHI I
filed
Critical
TABUSHI I

1980-07-30
Publication of GB1572285A
publication
Critical
patent/GB1572285A/en

Status
Expired
legal-status
Critical
Current

Links

Espacenet

Global Dossier

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239000003463
adsorbent
Substances

0.000
title
claims
description
13

229910001385
heavy metal
Inorganic materials

0.000
title
claims
description
12

239000004793
Polystyrene
Substances

0.000
claims
description
35

229920002223
polystyrene
Polymers

0.000
claims
description
21

LFQSCWFLJHTTHZ-UHFFFAOYSA-N
Ethanol
Chemical compound

CCO
LFQSCWFLJHTTHZ-UHFFFAOYSA-N
0.000
claims
description
19

229920003002
synthetic resin
Polymers

0.000
claims
description
15

239000000057
synthetic resin
Substances

0.000
claims
description
15

229910021645
metal ion
Inorganic materials

0.000
claims
description
8

PPBRXRYQALVLMV-UHFFFAOYSA-N
Styrene
Chemical compound

C=CC1=CC=CC=C1
PPBRXRYQALVLMV-UHFFFAOYSA-N
0.000
claims
description
6

229920005989
resin
Polymers

0.000
claims
description
4

239000011347
resin
Substances

0.000
claims
description
4

NIXOWILDQLNWCW-UHFFFAOYSA-N
2-Propenoic acid
Natural products

OC(=O)C=C
NIXOWILDQLNWCW-UHFFFAOYSA-N
0.000
claims
description
2

SMZOUWXMTYCWNB-UHFFFAOYSA-N
2-(2-methoxy-5-methylphenyl)ethanamine
Chemical compound

COC1=CC=C(C)C=C1CCN
SMZOUWXMTYCWNB-UHFFFAOYSA-N
0.000
claims
1

239000003795
chemical substances by application
Substances

0.000
claims
1

229920002554
vinyl polymer
Polymers

0.000
claims
1

OKKJLVBELUTLKV-UHFFFAOYSA-N
Methanol
Chemical compound

OC
OKKJLVBELUTLKV-UHFFFAOYSA-N
0.000
description
21

150000001875
compounds
Chemical class

0.000
description
18

XLYOFNOQVPJJNP-UHFFFAOYSA-N
water
Substances

O
XLYOFNOQVPJJNP-UHFFFAOYSA-N
0.000
description
14

VEXZGXHMUGYJMC-UHFFFAOYSA-N
Hydrochloric acid
Chemical compound

Cl
VEXZGXHMUGYJMC-UHFFFAOYSA-N
0.000
description
12

HEMHJVSKTPXQMS-UHFFFAOYSA-M
Sodium hydroxide
Chemical compound

[OH-].[Na+]
HEMHJVSKTPXQMS-UHFFFAOYSA-M
0.000
description
12

150000002500
ions
Chemical class

0.000
description
11

239000000203
mixture
Substances

0.000
description
11

HEDRZPFGACZZDS-UHFFFAOYSA-N
Chloroform
Chemical compound

ClC(Cl)Cl
HEDRZPFGACZZDS-UHFFFAOYSA-N
0.000
description
10

WYURNTSHIVDZCO-UHFFFAOYSA-N
Tetrahydrofuran
Chemical compound

C1CCOC1
WYURNTSHIVDZCO-UHFFFAOYSA-N
0.000
description
10

125000004122
cyclic group
Chemical group

0.000
description
9

PXHVJJICTQNCMI-UHFFFAOYSA-N
nickel
Substances

[Ni]
PXHVJJICTQNCMI-UHFFFAOYSA-N
0.000
description
9

239000000243
solution
Substances

0.000
description
8

239000013078
crystal
Substances

0.000
description
7

239000007864
aqueous solution
Substances

0.000
description
6

239000007795
chemical reaction product
Substances

0.000
description
6

-1
cyclic diamides
Chemical class

0.000
description
6

238000000921
elemental analysis
Methods

0.000
description
6

238000010438
heat treatment
Methods

0.000
description
6

229910052751
metal
Inorganic materials

0.000
description
6

239000002184
metal
Substances

0.000
description
6

238000006722
reduction reaction
Methods

0.000
description
6

239000002904
solvent
Substances

0.000
description
6

238000001179
sorption measurement
Methods

0.000
description
6

OFOBLEOULBTSOW-UHFFFAOYSA-L
Malonate
Chemical compound

[O-]C(=O)CC([O-])=O
OFOBLEOULBTSOW-UHFFFAOYSA-L
0.000
description
5

230000015572
biosynthetic process
Effects

0.000
description
5

229910052739
hydrogen
Inorganic materials

0.000
description
5

239000000047
product
Substances

0.000
description
5

238000003756
stirring
Methods

0.000
description
5

238000003786
synthesis reaction
Methods

0.000
description
5

YLQBMQCUIZJEEH-UHFFFAOYSA-N
tetrahydrofuran
Natural products

C=1C=COC=1
YLQBMQCUIZJEEH-UHFFFAOYSA-N
0.000
description
5

VILCJCGEZXAXTO-UHFFFAOYSA-N
2,2,2-tetramine
Chemical compound

NCCNCCNCCN
VILCJCGEZXAXTO-UHFFFAOYSA-N
0.000
description
4

238000004458
analytical method
Methods

0.000
description
4

AGGKEGLBGGJEBZ-UHFFFAOYSA-N
tetramethylenedisulfotetramine
Chemical compound

C1N(S2(=O)=O)CN3S(=O)(=O)N1CN2C3
AGGKEGLBGGJEBZ-UHFFFAOYSA-N
0.000
description
4

229960001124
trientine
Drugs

0.000
description
4

UHOVQNZJYSORNB-UHFFFAOYSA-N
Benzene
Chemical compound

C1=CC=CC=C1
UHOVQNZJYSORNB-UHFFFAOYSA-N
0.000
description
3

ZMXDDKWLCZADIW-UHFFFAOYSA-N
N,N-Dimethylformamide
Chemical compound

CN(C)C=O
ZMXDDKWLCZADIW-UHFFFAOYSA-N
0.000
description
3

KWYUFKZDYYNOTN-UHFFFAOYSA-M
Potassium hydroxide
Chemical compound

[OH-].[K+]
KWYUFKZDYYNOTN-UHFFFAOYSA-M
0.000
description
3

229910052799
carbon
Inorganic materials

0.000
description
3

229920001429
chelating resin
Polymers

0.000
description
3

238000006243
chemical reaction
Methods

0.000
description
3

125000004218
chloromethyl group
Chemical group

[H]C([H])(Cl)*

0.000
description
3

KTVIXTQDYHMGHF-UHFFFAOYSA-L
cobalt(2+) sulfate
Chemical class

[Co+2].[O-]S([O-])(=O)=O
KTVIXTQDYHMGHF-UHFFFAOYSA-L
0.000
description
3

238000001816
cooling
Methods

0.000
description
3

239000010949
copper
Substances

0.000
description
3

125000004177
diethyl group
Chemical group

[H]C([H])([H])C([H])([H])*

0.000
description
3

239000012153
distilled water
Substances

0.000
description
3

238000001819
mass spectrum
Methods

0.000
description
3

238000002844
melting
Methods

0.000
description
3

230000008018
melting
Effects

0.000
description
3

150000002739
metals
Chemical class

0.000
description
3

238000000655
nuclear magnetic resonance spectrum
Methods

0.000
description
3

239000000843
powder
Substances

0.000
description
3

239000002244
precipitate
Substances

0.000
description
3

239000011541
reaction mixture
Substances

0.000
description
3

239000000126
substance
Substances

0.000
description
3

MYRTYDVEIRVNKP-UHFFFAOYSA-N
1,2-Divinylbenzene
Chemical compound

C=CC1=CC=CC=C1C=C
MYRTYDVEIRVNKP-UHFFFAOYSA-N
0.000
description
2

LTMRRSWNXVJMBA-UHFFFAOYSA-L
2,2-diethylpropanedioate
Chemical compound

CCC(CC)(C([O-])=O)C([O-])=O
LTMRRSWNXVJMBA-UHFFFAOYSA-L
0.000
description
2

XJUZRXYOEPSWMB-UHFFFAOYSA-N
Chloromethyl methyl ether
Chemical compound

COCCl
XJUZRXYOEPSWMB-UHFFFAOYSA-N
0.000
description
2

RTZKZFJDLAIYFH-UHFFFAOYSA-N
Diethyl ether
Chemical compound

CCOCC
RTZKZFJDLAIYFH-UHFFFAOYSA-N
0.000
description
2

KEAYESYHFKHZAL-UHFFFAOYSA-N
Sodium
Chemical compound

[Na]
KEAYESYHFKHZAL-UHFFFAOYSA-N
0.000
description
2

239000003957
anion exchange resin
Substances

0.000
description
2

150000001721
carbon
Chemical group

0.000
description
2

238000007265
chloromethylation reaction
Methods

0.000
description
2

229910001429
cobalt ion
Inorganic materials

0.000
description
2

XLJKHNWPARRRJB-UHFFFAOYSA-N
cobalt(2+)
Chemical compound

[Co+2]
XLJKHNWPARRRJB-UHFFFAOYSA-N
0.000
description
2

DIOQZVSQGTUSAI-UHFFFAOYSA-N
decane
Chemical compound

CCCCCCCCCC
DIOQZVSQGTUSAI-UHFFFAOYSA-N
0.000
description
2

238000001035
drying
Methods

0.000
description
2

125000006575
electron-withdrawing group
Chemical group

0.000
description
2

125000004435
hydrogen atom
Chemical group

[H]*

0.000
description
2

125000001841
imino group
Chemical group

[H]N=*

0.000
description
2

238000000034
method
Methods

0.000
description
2

239000012046
mixed solvent
Substances

0.000
description
2

229910052759
nickel
Inorganic materials

0.000
description
2

229910001453
nickel ion
Inorganic materials

0.000
description
2

239000012074
organic phase
Substances

0.000
description
2

238000007363
ring formation reaction
Methods

0.000
description
2

239000007787
solid
Substances

0.000
description
2

125000001424
substituent group
Chemical group

0.000
description
2

125000000547
substituted alkyl group
Chemical group

0.000
description
2

JIAARYAFYJHUJI-UHFFFAOYSA-L
zinc dichloride
Chemical compound

[Cl-].[Cl-].[Zn+2]
JIAARYAFYJHUJI-UHFFFAOYSA-L
0.000
description
2

VEFLKXRACNJHOV-UHFFFAOYSA-N
1,3-dibromopropane
Chemical compound

BrCCCBr
VEFLKXRACNJHOV-UHFFFAOYSA-N
0.000
description
1

UWMHHZFHBCYGCV-UHFFFAOYSA-N
2,3,2-tetramine
Chemical compound

NCCNCCCNCCN
UWMHHZFHBCYGCV-UHFFFAOYSA-N
0.000
description
1

CQPGDDAKTTWVDD-UHFFFAOYSA-N
4-bromobutanenitrile
Chemical compound

BrCCCC#N
CQPGDDAKTTWVDD-UHFFFAOYSA-N
0.000
description
1

NWWWGAKVHCSAEU-UHFFFAOYSA-N
5-bromopentanenitrile
Chemical compound

BrCCCCC#N
NWWWGAKVHCSAEU-UHFFFAOYSA-N
0.000
description
1

OKTJSMMVPCPJKN-UHFFFAOYSA-N
Carbon
Chemical compound

[C]
OKTJSMMVPCPJKN-UHFFFAOYSA-N
0.000
description
1

229910000570
Cupronickel
Inorganic materials

0.000
description
1

IAZDPXIOMUYVGZ-UHFFFAOYSA-N
Dimethylsulphoxide
Chemical compound

CS(C)=O
IAZDPXIOMUYVGZ-UHFFFAOYSA-N
0.000
description
1

PIICEJLVQHRZGT-UHFFFAOYSA-N
Ethylenediamine
Chemical compound

NCCN
PIICEJLVQHRZGT-UHFFFAOYSA-N
0.000
description
1

241000256835
Polistes
Species

0.000
description
1

239000004372
Polyvinyl alcohol
Substances

0.000
description
1

241001558496
Talpa caeca
Species

0.000
description
1

238000010521
absorption reaction
Methods

0.000
description
1

125000003368
amide group
Chemical group

0.000
description
1

125000004202
aminomethyl group
Chemical group

[H]N([H])C([H])([H])*

0.000
description
1

238000009835
boiling
Methods

0.000
description
1

QHIWVLPBUQWDMQ-UHFFFAOYSA-N
butyl prop-2-enoate;methyl 2-methylprop-2-enoate;prop-2-enoic acid
Chemical compound

OC(=O)C=C.COC(=O)C(C)=C.CCCCOC(=O)C=C
QHIWVLPBUQWDMQ-UHFFFAOYSA-N
0.000
description
1

125000004432
carbon atom
Chemical group

0.000
description
1

125000003178
carboxy group
Chemical group

[H]OC(*)=O

0.000
description
1

238000010531
catalytic reduction reaction
Methods

0.000
description
1

239000003638
chemical reducing agent
Substances

0.000
description
1

229940061627
chloromethyl methyl ether
Drugs

0.000
description
1

229920001577
copolymer
Polymers

0.000
description
1

YOCUPQPZWBBYIX-UHFFFAOYSA-N
copper nickel
Chemical compound

[Ni].[Cu]
YOCUPQPZWBBYIX-UHFFFAOYSA-N
0.000
description
1

125000004093
cyano group
Chemical group

*C#N

0.000
description
1

150000001923
cyclic compounds
Chemical class

0.000
description
1

238000003795
desorption
Methods

0.000
description
1

238000010790
dilution
Methods

0.000
description
1

239000012895
dilution
Substances

0.000
description
1

229960001760
dimethyl sulfoxide
Drugs

0.000
description
1

238000000605
extraction
Methods

0.000
description
1

239000000706
filtrate
Substances

0.000
description
1

125000000524
functional group
Chemical group

0.000
description
1

JEGUKCSWCFPDGT-UHFFFAOYSA-N
h2o hydrate
Chemical compound

O.O
JEGUKCSWCFPDGT-UHFFFAOYSA-N
0.000
description
1

238000002329
infrared spectrum
Methods

0.000
description
1

239000002198
insoluble material
Substances

0.000
description
1

239000003456
ion exchange resin
Substances

0.000
description
1

229920003303
ion-exchange polymer
Polymers

0.000
description
1

239000012280
lithium aluminium hydride
Substances

0.000
description
1

238000005259
measurement
Methods

0.000
description
1

JOUIQRNQJGXQDC-AXTSPUMRSA-N
namn
Chemical group

O1[C@@H](COP(O)([O-])=O)[C@H](O)[C@@H](O)[C@@H]1[N+]1=CC=CC(C(O)=O)=C1
JOUIQRNQJGXQDC-AXTSPUMRSA-N
0.000
description
1

125000001997
phenyl group
Chemical group

[H]C1=C([H])C([H])=C(*)C([H])=C1[H]

0.000
description
1

239000002798
polar solvent
Substances

0.000
description
1

238000006116
polymerization reaction
Methods

0.000
description
1

229920002451
polyvinyl alcohol
Polymers

0.000
description
1

AOHJOMMDDJHIJH-UHFFFAOYSA-N
propylenediamine
Chemical compound

CC(N)CN
AOHJOMMDDJHIJH-UHFFFAOYSA-N
0.000
description
1

238000007670
refining
Methods

0.000
description
1

239000013535
sea water
Substances

0.000
description
1

239000002594
sorbent
Substances

0.000
description
1

239000007858
starting material
Substances

0.000
description
1

239000002351
wastewater
Substances

0.000
description
1

239000011592
zinc chloride
Substances

0.000
description
1

235000005074
zinc chloride
Nutrition

0.000
description
1

Classifications

C—CHEMISTRY; METALLURGY

C07—ORGANIC CHEMISTRY

C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS

C07C255/00—Carboxylic acid nitriles

C—CHEMISTRY; METALLURGY

C07—ORGANIC CHEMISTRY

C07D—HETEROCYCLIC COMPOUNDS

C07D257/00—Heterocyclic compounds containing rings having four nitrogen atoms as the only ring hetero atoms

C07D257/02—Heterocyclic compounds containing rings having four nitrogen atoms as the only ring hetero atoms not condensed with other rings

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

C08F8/00—Chemical modification by after-treatment

C08F8/30—Introducing nitrogen atoms or nitrogen-containing groups

C08F8/32—Introducing nitrogen atoms or nitrogen-containing groups by reaction with amines

Description

PATENT SPECIFICATION
( 21) Application No 3784 i 78 ( 11) 1 572 285 ( 22) Filed 31 Jan 1978 ( 31) Convention Application No’s 521024884 ( 32) Filed 9 Mar 1977 52/024885 52/024886 ( 33) Japal ( PI) ( 44) Complete Specification Published 30) Juil 1980 ( 51) INT CL’ C 071) 257 M( 2 13011) 15 i 04 C 08 F, 8/0 fl C 011 h 1162 ( 52) Index at Acceptance C 2 C 178 X 20 Y 215 246 250 252 25 Y 30)5 30 Y 321 320 32 Y 351 352 366 368 451 45 Y 020) 62 Y 635 638 650 650 AA MC MD) NI, CI A Gil (; 221 ( 9 P)2 A I C’ 251 327 406 A (‘.1 A F All AT CR (C 3 W209 215 301 C 3 Y Bl N) 13180 13218 13260111 ( ( 54) HEAVY ME Tl AL ION AD)SORBENT 15 ( 71) 1 1 WA() TABL-USI I a citizen of J Iapan of’ No 15-27 3-chornc Maidashi.
I iah-u Fuikuoka-shi i l 1 ‘uktokaiken Japan do hecreby declare the invention for which I pray that a patent max,1 be igranlted to me and thle method by which it is to be performed to bie parllticuilarily described in and bv thle following statement:-
The invention relates to adlsorbents for heavv mectal ions.
The invention provides heavy metal ion adsorbents of the general formula:
(C.L 12 (CH 2) ((iN Ni Il i 5 wherein i’ im and N are each 2 or 3 R represents anl r-amino substituted alkyl group having from 4 to 6 carbon atomns andie A represents al hydrogen atom or a synthetic resin residue.
Pr’eferred ()-aminiiio substituted alkv 11 groups R are oj-am-ino-nibutvl and rn)-amino-iipentvl Inl addition, namn substituted alkyl groups containing side chains can be used.
Some compounds represented Lw thle general formula ( 1) are given below:
CN NIH j y CH 2 c 12 C 2 CI 2 ‘2 (I) ( 1 I) n 4 A ^ 1 n _Will :z 1 572 285 (III) 5 u N NN K CH 2 CN 2 CH 2 CH 2 NH 2 Q 2; (PS) 10 _.H (PS) NH (IV) 15 CH 2 CH 2 CH 2 Ci 22 NN 2 wherein (PS) represents polystyrene, and 20 Hlf < 2 @C C-(PS) Qx N (V) 25 NU(V Y CH 2 CH 2 CH 2 CH 2 NH 2 3 Oy 30 wherein (PS) represents polystyrene. Heavy metal ion adsorbents of the general formula (I) in which A represents a hydrogen atom can be synthesized by various procedures In general, they are synthesized by reacting a linear tetramine with an o-cvanoalkyl malonate, and reducing the resulting cyclic product. Preferred linear tetramines include triethylene-tetramine, 1,4,8,11tetraazaundecane and 1.59 13-tetraazatridecane Of these compounds 1 4,8,11-tetraazaundecane, for example, can be obtained by reacting ethylenediamine and 1,3-dibromopropane in the presence of potassium hydroxide in ethanol. Preferred w-cyanoalkyl malonates include diethyl o-cyanobutyl malonate, which can be 40 formed by reacting diethyl malonate with 1-cyano-4-bromobutane. The reaction of the tetramine and the (o-cyanoalkyl malonate may be effected by dissolving them in a polar solvent such as methanol, ethanol, dimethyl formamide or dimethyl sulphoxide while heating under atmospheric pressure over a period of from 3 to 5 days 45 This cyclization yields cyclic diamides represented by the general formula (VI): /(C)2 '. NN >NN N () (VI)N wherein { m and N are each 2 or 3 and R’ represents an o-cyano substituted alkyl group 55 having from 3 to 5 carbon atoms (excluding the carbon atom of the cyano group) The cyclic compounds thus obtained may be recrystallized from ethanol, isolated and then reduced.
Reduction may be carried out using reducing agents such as lithium aluminium hydride or diborane or bv catalytic reduction 6 The, reduction converts the ring amido group (-NHCO) into a methyleneimino group 60 (-NHCH 2) and the o-cvano group (-CN) into an aminomethyl group (-CH 2 NH 2) to give compounds of the general formula I.
3 1 572 2853 Compounds represented by formula (VI) which are formed by the above cyclization reaction are given below:
(N NH 5 AN NO (VII) CH 2 C 92 C 2 CN 10 ?fl) (VIII) 15 N Nit H 2 CN 2 CN 2 CN 20 Reduction of the compound (VII) yields the compound (II), and reduction of the compound (VIII) yields the compound (III).
Heavy metal ion adsorbents of the general formula (I) in which A represents a synthetic 25 resin residue may be produced by reacting a tetramine with an wcyanoalkyl malonate as described above, and either reducing the resulting cyclic product and bonding a synthetic resin to the reduction product or as is preferred, bonding a synthetic resin to the resulting cyclic product and reducing the compound thus obtained.
Svnthetic resins suitable for use in this invention are those having strong electron 30 withdrawing groups or capable of introducing strong electron withdrawing groups For example styrene based synthetic resins, acrylic acid based synthetic resins and polyvinyl alcohol resins can be used Of these synthetic resins, those containing benzene nuclei in the structure thereof are particularly preferred These preferred synthetic resins are, for example polystyrene and a copolymer of styrene and divinyl benzene They are usually 35 used as ion exchange resins.
Chemical bonding of the above described cyclic reaction product and synthetic resin is achieved bv reacting the imino group (=NH) contained in the cyclic reaction product with a strong electron withdrawing group such as -Cl -Br, -I, -COOH -COOR or -SO 3 R which is present in the synthetic resin or introduced therein Of these synthetic resins, polystyrene 40 with chloromethyl groups introduced therein as functional groups is most preferred in effecting the chemical bonding with the cyclic reaction products Reaction conditions under which the chemical bonding is carried out are not especially limited, and it is sufficient to stir the above cyclic reaction product and the synthetic resin at room temperature or at elevated temperatures After the above reaction if necessary reduction can be carried out 45 In this wav synthetic resins to which cvclic tetramines containing a specific substituent are bonded as represented by formulae (IV) and (V), can be obtained.
Of the heavv metal ion adsorbents of the invention cyclic tetramines represented by formula ( 11) or ( 111) have excellent selective adsorption characteristics for heavy metal ions, and furthermore their selectivities among heavy metal ions are excellent The presence of 50 the specific substituent at the ring carbon atom increases the adsorption speeds of heavy metal ions and makes the adsorption and desorption markedly easy Those heavy metal ion adsorbents prepared by chemically bonding a cyclic tetramine to a synthetic resin such as polystyrene as represented by formula (IV) or (V) are insoluble in water, and thus they will find a wide variety of applications 55 Thus the heavv metal ion adsorbents of the invention can be extensively and effectively used in a wide variety of applications such as treatment of waste water, refining of metals, extraction of useful metals from sea water and concentration of metals in isotope dilution analysis.
1 572 285 1 572 285 The following Examples illustrate the invention.
EXAMPLE 1 ( 1) Synthesis of Diethyl 3-Cvanopropvl malonate To a 1-litre three necked flask equipped with a stirrer, a condenser with a drying tube, 5 and a dropping funnel were charged 500 ml of anhydrous ethanol and 23 g ( 1 mole) of sodium metal After the sodium metal was completely dissolved, 165 g ( 1 03 moles) of diethyl malonate was added through the dropping funnel at 50 C Then, 148 g ( 1 mole) of 3-cyanopropylbromide was added through the dropping funnel The reaction mixture was refluxed under heating for 3 hours After the major portion of the solvent had been distilled 10 off 400 ml of water was added to the residue and the organic phase was isolated On distilling the organic phase under reduced pressure, 186 g of diethyl 3cyanopropyl malonate having a boiling point of 135 C/4 mm Hg was obtained (yield 82 %) The infrared spectrum showed peaks at 2250 cm-‘ and 1740 cm-‘.
15 ( 2) Synthesis of’ 3-( 3-(C’vanopropvl)-2 4-dioxo-1,5,8,11tetraazacyclotridecane To a 2-litre three necked flask equipped with a cooler and a stirring device were charged 14.6 g ( O 1 mole) of triethylene-tetramine and a solution prepared by dissolving 22 7 g ( 0 1 mole) of diethvl 3-cyanopropyl malonate (prepared as above described) in 1 litre of 95 % ethanol The resulting mixture was refluxed under heating and stirring for 5 days The 20 major portion of ethanol was distilled away from the reaction mixture under reduced pressure The residues were cooled and the crystals which precipitated were gathered.
These crystals were recrystallized from ethanol Thus 6 9 g ( 0 025 mole) of crystals of 3-( 3-cyanopropyl)-2,4-dioxo-1 5,8,11-tetraazacyclotridecane was obtained (yield 25 %).
Analysis of the crystals obtained gave the following results: 25 ( 1) Melting Point: 196-198 C ( 2) Elemental Analysis: C 13 H 2302 Ns 30 Found(%) Calculated ( 9 C 55 49 55 52 35 H 8 61 8 19 N 24 56 24 91 4 O 40 ( 3) Peaks of Mass Spectrum: m/e: (MA), 238 ( 4) NMR Spectrum (heavy methanol solvent, TMS base):
h (ppm) 3 48-3 90 ( 2 H m), 3 28 ( 1 H, t J= 7 0 Hz), 2 95-3 20 ( 2 H, m), 2 73 ( 8 H m), 2 58 ( 2 H, t, J= 7 0 Hz)1 90 ( 4 Hm) 45 ( 3) Synthesis of 3-( 4-Amino-n-butvl)-1,5,811-tetraazacyclotridecane To 30 ml of a solution of diborane ( 18 m mole) in tetrahydrofuran was added little by little 5 m mole of 3-( 3-cyanopropyl)-24-dioxo-1,5,8,11tetraazacyclotridecane prepared as above described The mixture was allowed to stand for 30 minutes, and the tetrahydrofuran 50 was distilled off by heating for 5 hours To the residue was added 20 ml of 6 N hydrochloric acid, and the resulting mixture was heated for 3 hours Then, the solvent was distilled off under reduced pressure The residue was further dissolved in a mixed solvent of ethanol and water ( 5:1) by heating, and then it was cooled The hydrochloric acid salt of 3-( 4-amino-n-butvl)-1,58 11-tetraaza-cyclotridecane precipitated 55 A column was charged with about 400 ml of an anionic exchange resin (Amberlite IRA-400) which had been washed with an aqueous solution of sodium hydroxide, and with water «Amberlite» is a Trade Mark A solution prepared by dissolving the above hydrochloric acid salt in about 150 ml of water was passed through the column followed by about 500 ml of water Water was distilled off from the eluate and 3-( 4amino-n-butyl) 60 1.5,8,11-tetraazacvclotridecane was obtained in high yield.
EXAMPLE 2 ( 1) Synthesis of Chloromethvl Polvstvrene A round bottom flask equipped with a stirring device was charged with 20 g of 65 A A 4 1 572 285 polystyrene having T a degree of polymerization of 1 600 to 1,800 and 124 g ( 1 54 mole) of chloromethvl methyl ether The polystyrene was dissolved in the ether by stirring at room temperature To tihe solution was added 3 14 g ( O 023 mole) of anhydrous zinc chloride powder, and the resulting mixture was stirred at room temperature ( 20 C) for 10) hours The major portion of the unllreacted excess chloromethyl methyl ether was distilled off from the 5 reaction mixture at lt)10 C under reduced pressure To the residue was added 150 ml of chloroform, and the mixture was filtered to remove insoluble material 3 ( 10 ml of methanol was added to the filtrate, and the resulting precipitate was filtered off On drying the precipitate at 60 C under reduced pressure 15 g of chloromethyl polystyrene was dissolved in heavy chloroform for measurement of its degree of chloromethylation NMR 10 spectroscopv showed that its degree of chloromethylation per phenyl ring of the starting material was 60 %.
( 2) Bonding of 3-( 3-( ‘ anoprol)y)-24-dioxo-l 5,8, ltetraazacvclotridecane and (Chlororeethll Polist’rene 15 In 30 ml of chloroform was dissolved O 89 g of chloromethyl polystyrene (containing 4 m.mole of chloromethvl group) prepared as above described To this solution was added 1.124 g ( 4 m mole) of 3-( 3-cvanopropyl)-2 4-dioxo-1, 5,8 11tetraazacyclotridecane prepared as described inl Example I and the resulting mixture was stirred at room temperature for 48 hours An insoluble reaction product precipitated The precipitate was filtered off 20 washed with a O IN aqueous hydrochloric acid, distilled water () IN aqueous sodium hydroxide distilled water, chloroform and methanol in that order, and dried under reduced pressure at 80 C for 12 hours As a result, there was obtained 1 3 g of a white solid compound in which polystyrene was chemically bonded to 3-( 3-cyanopropyl)2,4-dioxo1 5 8 1 1-tetraazacyclotridecane 25 ( 3) Redc’tion of 3-( 3-(‘Cvanopropyl) -2 4-dioxo 5,8, 11tet’aazac(vclotridecane bonded to Polhstyrene 500 me of the compound prepared as above described was pulverized to from 11)) to 200 mesh added little bv little to 30 ml of a solution of diborane ( 14 m mole) inll tetrahydrofuran 30 under cooling allowed to stand at room temperature for 30 minutes and then heated to C and maintained at that temperature for 5 hours The tetrahydrofuran was distilled off.
To the residue was added 30 ml of 6 N aqueous hydrochloric acid, and the resulting mixture was heated to 70 C and maintained at that temperature for 3 hours The reaction product was filtered off, washed with water IN aqueous sodium hydroxide, distilled water, 35 chloroform and finally methanol in that order, and dried under reduced pressure at 80 C for 12 hours 3-( 4-Amino-n-butvl) 1 5 8,11 -tetraazacyclotridecane bonded to polystyrene was obtained as a white solid ( 30) mg) Elemental analysis of the product gave its composition as C 74 91 %: H 9 49 %: N 9 35 %.
From these results, it was calculated that 3 ( 4-amino-n-butyl)-l 5,8,11 40 tetraazacvclotridecane (m mole)/polystyrene (g) = 1 34 Furthermore, it was found that the introduction ratio of 3-( 4-amino-nz-butyl)-1 5,8,11tetraazacyclotridecane to chloromethylated stvrene unit was 43 %.
( 4) Metal Adsorp)tion Test 45 An amount of 3-( 4-amino-n-butyl)-1 5 8 1 1-tetraazacyclotridecane chemically bonded to polystyrene equivalent to 0) 18 m mole of 3-( 4-amino-nt-butyl)-1 5,8,11tetraazacvclotridecane was pulverized to from 100 to 200 mesh 134 mg of this pulverised compound was added to each of 3 ml of O 02 mole aqueous solutions of copper nickel and cobalt sulphates After equilibrium at 25 C was attained, the concentration of the 50 remaining metal ion was measured by the atomic absorption The results obtained are shown in Table 1.
TABLE 1
55 Metal Initial Residual Ion Concentration Concentration (ppm) (ppm) Cu 2 + 1270 1 5 after 24 hours 6 Ni 2 + 1174 0 25 after 96 hours Co 2 + 1180 2 5 after 96 hours ( 5) 100 mesh powder of 3-( 4-amino-n-butyl)-1,5,8 11tetraazacyclotridecane chemically 1 572 285 bonded to polystyrene, was added to each of 3 ml of O ( 02 mole aqueous solutions of nickel and cobalt sulphates in an amount equivalent to 0 09 m mole of 3-( 4amino-n-butyl)1,5,8 1-tetraazacvclotridecane The half-life period of metal ion remaining in the aqueous solution was measured at 25 C T’he results are as follows:
5 Nickel ion 30 minutes Cobalt ion 30 minutes 10 EXAMPLE 3 (I) Svnthesis of 3-( 3-C:vanoprw)yl) -2, 4-dioxo-15, 8,12tetraazacyclotetradecane Part ( 2) of Example I was repeated save that N,N’-bis-( 2-aminoethyl)-1 3 15 propvlenediamine was used in place of triethylene tetramine 3-( 3-Cyanopropyl)-2,4dioxo-1 5 8 12-tetraazacyclotetra decane was obtained in a yield of 30 %.
Analysis gave the following results:
20 ( 1) Melting Point: 178-180 o C ( 2) Elemental Analysis: C 14 H 2 S 02 Ns 25 Found (%) Calculated (%) C 57 00 56 92 H 8 68 8 53 30 N 23 50 23 71 ( 3) Peaks of Mass Spectrum: m/e 295 (MW) 35 ( 4) NMR Spectrum (heavy methanol solvent, TMS base) (ppm) 7 50 ( 2 H, broad), 3.60-3 05 ( 4 H m), 3 20 ( 1 H, t J= 6 Hz) 2 70 ( 8 H m), 2 41 ( 2 H, s), 2 00 ( 2 H, m), 1 70 ( 4 Hm), 1 41 ( 2 Ht J= 6 Hz) 40 ( 2) Synthesis of 3-( 4-Aminlo-n-butvl)-l 5 8, 12tetraazacyclotetradecane 3-( 3-Cyanopropyl)-24-dioxo 1 5 8 12-tetraazacyclotetradecane ( 5 m mole), prepared as above described was added little by little, under cooling, to 30 ml of a solution of diborane ( 18 m mole) in tetrahvdrofuran allowed to stand for 30 minutes and then heated for 5 45 hours to distill off the tetrahydrofuran To the residue was added 20 ml of 6 N hydrochloric acid The mixture was heated for 3 hours and the solvent was distilled off under reduced pressure The residue was dissolved in a mixed solvent of ethanol and water ( 5:1) by heating On cooling the solution obtained above, the hydrochloric acid salt precipitated.
About 40 ()0 ml of an anion exchange resin (Amberlite IRA-400), which had been washed 50 with an aqueous solution of sodium hydroxide and with water, was charged to a column.
The above hydrochloric acid salt dissolved in about 150 ml of water was passed through the column followed by about 500 ml of water On distilling off the water from the eluate obtained, colorless crystals were obtained in a yield of 70 %.
I 572 285 Analysis of these crystals gave thile following results:
( 1) Melting Point:
132-133 C ( 2) Elemental Analysis:
C 14 H 33 Ns 5 HO Calculated (%) N 24 19 ( 3) Peaks of Mass Spectrum:
m/e: 271 (M +) ( 4) NMR Spectrum (helavy methanol solvent, TMS base) 6 (ppm) 2 90-2 5 () ( 5 H m), 1 72 ( 2 H q) 2 30 ( 611 s) 1 36 ( 6 H s J= 6 Hz) These results are consistent with the crystals being 3-( 4-amino-n-butyl)1,58,12tetraazazcvclotetradecane.
( 3) Mletal Adsorption Test A compound in which 3-( 4-amino-n-butvl)-1 5 8,12tetraazacyclotetradecane was chemicallv bonded to polystyrene was formed as described in Parts ( 2) and ( 3) of Example 2 except that 3-( 3-cvaliopropvl)-2 4-dioxo-1 5 8 12tetraazacvclotetradecane prepared as above described, was used Using this compound the adsorption test described in Part ( 4) of Example 2 wvas conducted The results obtained are shown in Table 2.
TABLE 2
Metal Ion Cu 2 + Ni 2 + Co 2 + Initial Concentration (ppm) 1270 1174 1180 Residual Concentration (ppm) 2.5 18 Elemental analysis of the compound gave its composition as C, 74 52 %; H, 8 72 %; N, 9 76 %r.
From these results it was calculated that 3-( 4-amino-n-butyl)-1,5,8,12tetraazacvclotetradecane (m inole)ipolvstvrene (g)= 1 35 Furthermore, it was found that the introduction ratio of 3-( 4-amino-ni-butyl)-1 5 8 12tetraazacyclotetradecane to chloromniethlvlated stvrene unit was 45 C%.
( 4) 100 mesh powder of 3-( 4-amino-n-butvl)-1 58 12tetraazacyclotetradecane chemically bonded to polystyrene was added to each of 3 ml of 0 02 mole aqueous solutions of nickel and cobalt sulphates in amounts equivalent to 0 09 m mole of 3-( 4-aminon-butyl)-1,5 8,12tetraazacvclotetradecane The half-life period of metal ions remaining in the aqueous was measured at 25 C The results are as follows:
Nickel ion Cobalt ion 1 hour 1 hour EXAMIPLE 4 A compound in which 3-( 4-amino-n-butvl)-1 5 9 13-tetraazacvclohexadecane was chemically bonded to polystyrene was synthesized in the manner described in Examples 1 and 2 except that N N’-lis( 3-aminopropy 1)-1 3-propylenediamine was used in place of triethylene-tetramine.
Found (c%) C 59 17 H 11 93 58.09 12.19 24.20 8 1 572 285 8 The compound obtained is represented by the following formula:
Kr’>,i 2 -; CH 1 -(PS)5 /’2 ‘X test (PS) 5 ( 1 IM 3 SIN H)Z l 10 CHI 2 CH 2 CH 2 C I 2 ci 2 wherein (PS) is polystyrene.
Using this compoundt the adsorption test described in Part ( 4) of Example 2 was 15 conducted The results obtained are shown in Table 3.
TABLE 3
Metal Initial Residual 20 Ion Concentration (ppm) Concentration (ppm) Cu 2 + 1270 3 6 Ni 2 + 1174 10 25 Co 2 + 1180 19 Elemental analysis of the compound gave its composition as C 77 23 %, H 8 20 %: N, 8 4)% From these results it was calculated that 3-( 4-amino-n-butyl)-15,9, 13 30 tetraazacvclohlexadecane (m mole)/polvstvrene (g)= 1 20 Further, it was found that the introduction ratio of 3-( 4-amino-n-butvl)-1 5 9,13tetraazacyclohexadecane to chloronilethlvlated stvrene unit was 375 %.

Claims (9)

WHAT I CLAIM IS:-

1 A heavv metal ion adsorbent of the general formula I as herein defined 35

2 3-( 4-Amino-n-butvl) 1 5 8 11 -tetraazacvclotridecane.

3 3-( 4-Amino-n-butvl) 1 5 8 12-tetraazacvclotetradecane.

4 3-( 4-Amino-n-butyl) 1

5 9 13-tetraazacvclohexadecane.
A heavv metal ion adsorbent according to claim 1 in which A represents a styrene based svnthetic resin residue an acrylic acid based synthetic resin residue or a polyvinyl 40 alcohol based synthetic resin residue.

6 A heavy metal ion adsorbent of the formula KU/ad 22 (t PS} -‘» (Ph) 45 L J 50 CH 2 CH 2 CH 2 C If 2 RH 2 wherein (PS) represents polystyrene.

7 A heavy metal ion adsorbent of the formula: 55 C 1 (PS) & MCH P) NH 60 y 22 C 2 CH 2 N 2 CH 2 CH 2 CH 2 CH 2 NH 2 wherein (PS) represents polystyrene.
1 572 2 X 5 9 1 572 285 9

8 A heavy metal ion adsorbent of the formula:
t N to (PS) 5 HN 14 10 CH 2 CH 2 CH 2 CH 2 NH 2 wherein (PS) represents polystyrene.

9 A heavy metal ion adsorbent as claimed in claim 1 substantially as described herein with reference to any one of the Examples 15 SERJEANTS, Chartered Patent Agents, The Crescent, Leicester 20 Printed for Her Majesty’s Stationery Office, by Croydon Printing Company Limited, Croydon, Surrey, 1980.
Published by The Patent Office, 25 Southampton Buildings, London, WC 2 A l AY,from which copies may be obtained.

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A kind of compound resin and preparation method thereof and recovery method to palladium in nitric acid medium

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2021-08-31
中国工程物理研究院核物理与化学研究所
Composite resin, preparation method thereof and method for recovering palladium in nitric acid medium

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