text: as a result of extensive studies , the present inventors have been succeeded in obtaining functionalized resins , represented by the following general formula ( i ) from a starting material polyallylamine , economical production of which had been accomplished first by one ( harada ) of the present inventors . ## str2 ## [ in formula [ i ], x represents the formula : ( wherein t is 0 or 1 and l is an integer of 1 to 20 ), n ≧ 10 , o & lt ; j & lt ; 1 , u = 1 or 2 , and m = 0 or 1 , with the proviso that t and m are not simultaneously 0 .] the resins represented by the above formula [ i ] are roughly divided into the following three types of polymers : ## str3 ## the above polymer a is obtained by reacting polyallkylamine with n . n - phthaloylglutamic 1 , 5 - anhydride represented by the formula : ## str4 ## or with n , n - phthaloylapartic 1 , 4 - anhydride represented by the formula : ## str5 ## and then treating the intermediate product with hydrous hydrazine such as hydrazine hydrate . of these two n , n - phthaloylamino acid anhydrides , n , n - phthaloylaspartic 1 , 4 - anhydride [ iv ] reacts at the sites of both α - and β - carbonyl groups and hence it is difficult to effectively introduce intended α - amino acid moieties in side chains . therefore , the use of this amino acid anhydride is disadvantageous compared with the use of n , n - phthaloylglutamic 1 , 5 - anhydride [ iii ] which reacts only at the γ - carboxyl group , and the polymers produced by using the former anhydride have restricted applications . it is also possible that the γ - carboxyl group of glutamic acid or the β - carboxyl group of aspartic acid is activated by some methods other than the above . for example , the amino acid can be converted into an ester ( active ester ) by reacting with p - nitrophenol , pentachlorophenol or n - hydroxysuccinimide , or can be converted into the acid halide , and thereafter the product ( ester or acid halide ) can be reacted with polyamines of the general formula [ i ] ( m = 0 ). in this case , the α - amino acid moieties should be protected so as not to participate in said reaction . for the protection reactions and the protecting agents there can be utilized techniques which are utilized in the synthesis of peptides . although being obtainable also according to the above mentioned methods using the ester or acid halide , the functionalized resin [ i ] of the invention is better synthesized through the route in which compound [ iii ] or [ iv ] is used , because the above mentioned methods using the ester or acid halide require the complication of operations for the temporary protection of α - amino acid moieties . the polymer b is obtained by reacting polyallylamine with a phthaloylamino acid , acid chloride thereof , or an acid anhydride ( including asymmetric acid anhydrides derived from phthaloyl amino acid and other carboxylic acid ), followed by treating the intermediate product with hydrous hydrazine such as hydrazine hydrate . the polymer c is obtained by reacting the thus obtained polymer b with the compound such as n , n - phthaloylglutamic 1 , 5 - anhydride ( iii ) and n , n - phthaloylaspartic 1 , 4 - anhydride ( iv ), followed by treating the intermediate product with hydrous hydrazine such as hydrazine hydrate . the functionalized resin [ i ] of the invention can be used to recover heavy metals dissolved in water or to resolve racemates of amino acid or the like , by taking advantage of the metal chelating function of the α - amino acid structural parts thereof . for use in such purposes , a functionalized resin [ i ] can be produced according to the process of the invention from an crosslinked polyallylamine . the following examples illustrate the invention , but it is not limited to these examples . polyallylamine used in the following examples was prepared from polyallylamine hydrochloride which had been synthesized according to the process described in japanese patent application no . 54988 / 83 . that is , an aqueous solution of polyallylamine was prepared by passing an aqueous solution of 20 % polyallylamine hydrochloride through a strong - basic ion exchange resin column . in most of the following experiments the aqueous solution of polyallylamine was used as such , but in other experiments a pure polyallylamine obtained by freeze - drying of the aqueous solution was used in the form of methanolic solution . ( 1 ) in a solution of na 2 co 3 ( 51 . 5 g ) in water ( 350 ml ) at 5 ° c . was dissolved l - glutamic acid ( 29 . 4 g ). carboethoxy phthalimide ( 59 . 6 g ) was added to the solution and suspended therein and thereafter reacted at 350 ° c . for 30 - 40 minutes . then the solution was freed from insoluble matter , adjusted to ph 2 . 5 with 6n - hcl , and allowed to stand at 0 ° c . the resulting precipitate was filtered , and recrystallized from water to give n , n - phthaloylglutamic acid , yield 35 . 7 g , 64 . 4 %; specific rotation [ α ] d 25 =- 48 . 6 ° ( c = 1 , dioxane ). ( 2 ) to phthaloylglutamic acid ( 27 . 7 g ) obtained in ( 1 ) above was added acetic anhydride ( 40 ml ) and they were reacted at 40 °- 42 ° c . for 3 hours . then acetic anhydride ( 10 ml ) was further added to react for 3 additional hours . after reaction , the resultant mixture was allowed to cool , washed well with ether - petroleum ether , and dried under reduced pressure to give phthaloylglutamic 1 , 5 - anhydride , yield 21 . 8 g , 84 . 2 %; specific rotation [ α ] d 25 =- 44 . 5 ° ( c = 1 . 75 , dioxane ). following the procedure of reference example 1 , there were obtained n , n - phthaloyl aspartic acid and 1 , 4 - anhydride thereof from aspartic acid . ( i ) a solution of polyallylamine hydrochloride ( 4 . 68 g ) in water ( 50 ml ) was passed through an amberlite - 402 column to prepare an aqueous solution of polyallylamine . this solution was concentrated to a volume of about 10 ml , and acetic acid of 9 times the volume of the solution was added . then n , n - phthaloylglutamic 1 , 5 - anhydride ( 12 . 96 g ) from reference example 1 was added to the mixture and they are reacted at 60 °- 65 ° c . for 1 . 5 hours . the reaction mixture was then allowed to cool , and poured into ethyl acetate . the formed precipitate was collected by filtration , and dried to give poly [ γ - allylamine ( n - phthaloyl ) glutamic acid ] ( 11 . 26 g ). ir absorption spectrum to this polymer showed absorptions at 1700 cm - 1 and 1640 cm - 1 assigned to c = 0 and nhco , respectively . the specific rotation [ α ] d 25 was - 35 . 5 ° ( c = 1 , dmso ). the molar fraction of phthaloylglutamic acid attached was about 50 %, as determined from ir and uv absorption spectra and specific rotation . from the above data , this polymer is concluded to have the following structure : ## str6 ## ( ii ) after poly [ γ - allylamide ( n - phthaloyl ) glutamic acid ) ( 1 . 0 g ) from ( 1 ) above was dissolved in dmso ( 50 ml ) by heating , hydrazine hydrate ( 10 g ) was added thereto , and the mixture was stirred at room temperature for 22 hours . the formed precipitate was filtered , washed with dmso and then with water , and dissolved in 1n - hcl ( 19 ml ) at room temperature . the solution was poured into acetone , and the formed precipitate was collected by filtration , and dried to give poly ( γ - allylamideglutamic acid )( 0 . 65 g ). ir absorption spectrum of this polymer showed absorptions at 1720 cm - 1 and 1640 cm - 1 assigned to c = 0 and nhco , respectively . the specific rotation [ α ] d 25 was 14 . 1 °( c = 1 , h 2 o ). uv absorption spectroscopy and proton nmr absorption spectroscopy indicated that the polymer had no aromatic nucleus . from these results , it is concluded that the polymer has the following structure : ## str7 ## ( i ) a mixture of phthalic anhydride ( 500 g ) and β - alanine ( 267 g ) was fused by heating at 200 ° c . for 15 minutes , and poured into water ( 1500 ml ). the formed precipitate was collected by filtration , and recrystallized from ethanol to give phthaloyl - β - alanine ( hereinafter referred to as pht - βala ), yield 537 g , 81 . 6 %. then pht - βala ( 43 . 9 g ) was mixed with thionyl chloride ( 82 ml ) and they were reacted by heating at 50 ° c . for 30 minutes . the resultant mixture was allowed to cool , and the excess of thionyl chloride was distilled off . the residue , solidified entirely , was purified with petroleum ether to give n - phthaloyl - β - alanine chloride ( hereinafter referred to as pht - βalacl ), yield 45 . 8 g , 96 . 4 %. a solution of pht - βalacl ( 45 . 8 g ) in acetone was added dropwise to a mixture of a 13 . 6 % aqueous polyallylamine solution ( 81 . 7 g ), triethylamine ( 21 . 6 g ), and acetic acid ( 247 ml ) under cooling with ice , and they were reacted for 6 hours . then the acetone was removed by distillation under reduced pressure , and the residue was poured into ethyl acetate ( 3000 ml ). the formed precipitate was collected , and purified with methanol - ethyl acetate to give poly [ β - allylamide ( n - phthaloylamino ) β - alanine ], yield 39 . 0 g . the resin was treated with conc . hcl and with acetone , and filtered and dried . results of ir absorption spectroscopy ( absorptions at about 1700 cm - 1 and about 1640 cm - 1 assigned to c = 0 and nhco , respectively ), uv absorption spectroscopy ( an absorption in 200 - 250 nm assigned to phthaloyl groups ), and elementary analysis have revealed that this resin is n - phthaloyl - polyamidepolyamine having the following structure : ## str8 ## ( ii ) phthaloyl - containing polyamidepolyamine ( 10 . 0 g ) from ( i ) above was dispersed in dmso ( 100 ml ), and hydrazine hydrate ( 50 ml ) was added thereto and they were reacted at 60 ° c . for 10 hours . then the resulting precipitate was filtered , and dissolved in a mixture of conc . hcl ( 20 ml ) and water ( 10 ml ). the solution was poured into acetone ( 500 ml ), and the precipitated polymer was filtered and dried . ir absorption spectrum of this polymer ( absorptions at about 1700 cm - 1 and about 1640 cm - 1 assigned to c = 0 and nhco , respectively ) and uv absorption spectrum thereof ( no absorption assigned to the phenyl group was observed ) have indicated that this polymer is concluded to be a polyamine having the following structure : ## str9 ## ( i - a ) n - phthaloylglycine chloride ( hereinafter referred to as pht - gly - cl ) ( 22 . 4 g ) prepared according to the procedure of example 2 -( i ) was dissolved in acetone ( 40 ml ). the solution was added dropwise to a mixture of a 13 . 6 % aqueous polyallylamine solution ( 42 . 0 g ), triethylamine ( 10 . 1 g ), and acetic acid ( 126 ml ). then a resin ( 16 . 5 g ) was obtained in the same manner as in example 2 -( i ), yield 16 . 5 g . ( i - b ) to pht - gly - cl ( 22 . 7 g ) and acetic acid ( 6 . 0 g ) dissolved in tetrahydrofuran ( 130 ml ) was added dropwise triethylamine ( 14 ml ). regardless of immediate appearance of a precipitate , the reaction was continued overnight . the resulting precipitate was filtered , and the filtrate containing glycylacetic anhydride was used as such in the next step . acetic acid ( 100 ml ) was added to a solution of polyallylamine hydrochloride ( 9 . 4 g ) in water ( 30 ml ). regardless of immediate precipitation of a polymer , a solution of triethylamine ( 10 . 1 g ) in acetic acid ( 50 ml ) was added to the mixture , giving a homogeneous solution [ a triethylamine - treated polyallylamine solution ( paa - et 3 n solution )]. on addition of the above solution of glycylacetic anhydride to the paa - et 3 n solution , a polymer precipitated immediately . after 3 - hour continuation of the reaction , the precipitate was filtered , and dissolved in a mixture of conc . hcl ( 20 ml ) and water ( 20 ml ). the solution was poured into acetone ( 1500 ml ), and the formed precipitate was filtered and dried . ( i - c ) to pht - gly - cl ( 24 . 6 g ) and phthaloylglycine ( 22 . 6 g ) dissolved in tetrahydrofuran ( 200 ml ) was added dropwise triethylamine ( 15 . 4 ml ) under cooling with ice . while a precipitate appeared simultaneously with the addition , the reaction was continued for 1 - 2 hours . then the precipitate was filtered , and the filtrate containing diphthaloylglycine was used as such in the next step . a solution ( 50 ml ) of triethylamine ( 10 . 1 g ) in acetic acid was added to a dispersion of polyallylamine hydrochloride ( 9 . 4 g ) in acetic acid ( 100 ml ). then water ( 30 ml ) was added to the mixture to form a homogeneous solution . on addition of a solution of diphthaloylglycine anhydride in tetrahydrofuran to the resulting solution , a polymer precipitated immediately . the reaction was continued at room temprature . then the supernatant was removed by decantation , and the residue was washed with tetrahydrofuran and then with ethyl acetate and dissolved in conc . hcl ( 40 ml ). the polymer was reprecipitated from the solution with acetone ( 1500 ml ). ir absorption spectrum ( absorptions at about 1700 cm - 1 and about 1640 cm - 1 assigned to c = 0 and nhco , respectively ) and uv absorption spectrum ( an absorption in 200 - 250 nm assigned to phthaloyl groups ) of the resins prepared in ( i - a ), ( i - b ), and ( i - c ) have revealed that all the resins are n - phthaloyl - polyamidepolyamines of the following structure : ## str10 ## ( ii ) each ( 10 . 0 g ) of the phthaloyl - containing polyamidepolyamines obtained in ( i - a ), ( i - b ), and ( i - c ) was dispersed in dmso ( 100 ml ) and reacted with hydrazine hydrate ( 50 ml ) at 60 ° c . for 10 hours . then the precipitate was filtered , and dissolved in a mixture of conc . hcl ( 20 ml ) and water ( 10 ml ). the solution was poured in acetone ( 500 ml ), and the precipitated polymer was filtered and dried . from ir absorption spectrum of the thus obtained polymers ( absorptions at about 1700 cm - 1 and about 1640 cm - 1 assigned to c ═ o and nhco , respectively ) and uv absorption spectrum thereof ( no absorption assigned to the phenyl group was observed ), these polymers are concluded to be polyamines having the following structure : ## str11 ## ( i ) a mixture of phthalic anhydride ( 148 g ) and γ - amino - n - butyric acid ( 103 g ) was fused by heating at 180 ° c . for 5 minutes and then at 200 ° c . for 5 minutes , and poured into water ( 750 ml ) to obtain n . sup . γ - phthaloylamino - n - butyric acid , yield 191 . 8 g , 82 . 2 %. this acid ( 35 . 0 g ) was reacted with thionyl chloride ( 62 ml ) at 50 ° c . for 40 minutes . after reaction , the excess of thionyl chloride was distilled off . after addition of petroleum ether to the residue and cooling thereof , n . sup . γ - phthaloylamino - n - butyric acid chloride was obtained , yield 36 . 9 g , 97 . 6 %. the n . sup . γ - phthaloylamino - n - butyric acid chloride ( 36 . 9 g ) as such was added to a mixture of a 13 . 6 % aqueous polyallylamine solution ( 61 . 3 g ), triethylamine ( 14 . 8 g ), and acetic acid ( 184 ml ). the acid chloride was dissolved not immediately but gradually and completely in about 20 minutes from the addition , forming a homogeneous solution . the resultant solution was poured into ethyl acetate ( 1500 ml ). the formed precipitate was filtered , and dissolved in a mixture of conc . hcl ( 50 ml ) and water ( 20 ml ). the solution was poured into acetone ( 1000 ml ), and the formed precipitate was collected by filtration , yield 20 . 2 g . from ir absorption spectrum of the thus obtained resin ( absorptions at about 1700 cm - 1 and about 1640 cm - 1 assigned to c ═ o and nhco , respectively ) and uv absorption spectrum thereof ( an absorption in 200 - 250 nm assigned to phthaloyl groups ), the resin is concluded to be an n - phthaloyl - polyamide polyamine having the following structure : ## str12 ## ( ii ) phthaloyl - containing polyamide polyamine ( 10 . 0 g ) from ( i ) above was dispersed in dmso ( 100 ml ) and reacted with hydrazine hydrate ( 50 ml ) at 60 ° c . for 100 hours . then the resulting precipitate was filtered , and dissolved in a mixture of conc . hcl ( 20 ml ) and water ( 10 ml ). the solution was poured into acetone ( 500 ml ), and the precipitated polymer was filtered and dried . from ir absorption spectrum of the thus obtained polymer ( absorptions at about 1700 cm - 1 and about 1640 cm - 1 assigned to c ═ o and nhco , respectively ) and uv absorption spectrum thereof ( no absorption assigned to the phenyl group was observed ), this polymer is concluded be a polyamine having the following structure : ## str13 ## ( i ) a mixture of phthalic anhydride ( 62 . 1 g ) and ε - amino - n - caproic acid ( 50 g ) was fused by heating at 180 ° c . for 10 minutes , and poured into water ( 750 ml ) to give n . sup . ε - phthaloylamino - n - caproic acid , yield 96 . 1 g , 96 . 5 %. then n . sup . ε - phthaloylamino - n - caproic acid ( 39 . 2 g ) was reacted with thionyl chloride ( 62 ml ) at 50 ° c . for 5 minutes . thereafter the excess of thionyl chloride was distilled off . petroleum ether was added to the residue , and the mixture was cooled to give n . sup . ε - phthaloylamino - n - caproyl chloride , yield 39 . 9 g , 95 . 1 %. a solution of n . sup . ε - phthaloylamino - n - caproyl chloride ( 39 . 9 g ) in acetone was added to a mixture of a 13 . 6 % aqueous polyallylamine solution ( 60 . 0 g ), triethylamine ( 14 . 5 g ), and acetic acid ( 181 ml ). after this reaction , a polymer was obtained by the same post - treatment as in example 4 ( i ), yield 22 . 1 g . from ir absorption spectrum of the obtained resin ( absorptions at about 1700 cm - 1 and about 1640 cm - 1 assigned to c ═ o and nhco , respectively ) and uv absorption spectrum thereof ( an absorption in 200 - 250 nm assigned to phthaloyl groups ), the resin has been confirmed to be n - phthaloyl - polyamidepolyamine having the following structure : ## str14 ## ( ii ) phthaloyl - containing polyamide polyamine ( 10 . 0 g ) from ( i ) above was dispersed in dmso ( 100 ml ), and reacted with hydrazine hydrate ( 50 ml ) at 60 ° c . for 10 hours . then , the resulting precipitate was filtered , and dissolved in a mixture of conc . hcl ( 20 ml ) and water ( 10 ml ). the solution was poured into acetone ( 500 ml ), and the precipitated polymer was filtered and dried . from ir absorption spectrum of the obtained polymer ( absorptions at about 1700 cm - 1 and about 1640 cm - 1 assigned to c ═ o and nhco , respectively ) and uv absorption spectrum thereof ( no absorption assigned to the phenyl group was observed ), the polymer is concluded to be a polyamine having the following structure : ## str15 ## each ( 5 g ) of polyamine hydrochlorides ( b - 1 ), ( b - 2 ), ( b - 3 ), and ( b - 4 ) prepared in examples 2 , 3 , 4 , and 5 , respectively , was dissolved in water ( 50 - 80 ml ), and passed through an amberlite - 402 column to give an aqueous polyamine solution . this solution , after concentration to a volume of 10 - 20 ml , was reacted with n , n - phthaloylglutamic 1 , 5 - anhydride ( 1 . 1 equivalent to the amino groups ) at 60 °- 65 ° c . for 1 - 3 hours . then , the reaction mixture was allowed to cool , and poured into ethyl acetate . the formed precipitate was filtered , and treated with conc . hcl - acetone . in this way , there were obtained polyamine hydrochlorides which have phthaloylglutamic acid moieties in side chains of different lengths . from ir absorption spectra of the thus obtained polymers ( absorptions at about 1700 cm - 1 and about 1640 cm - 1 polymers ( absorptions at about 1700 cm - 1 and about p1640 cm - 1 assigned to c ═ o and nhco , respectively ) and uv absorption spectra thereof ( an absorption in 200 - 250 nm assigned to phthaloyl groups ), it has proved that these polymers have the following respective structures : __________________________________________________________________________starting specific rotationmaterialstructure of product [ α ]. sub . d . sup . 25 ( c = 1 , __________________________________________________________________________ dmso )( b - 1 ) ## str16 ## - 32 . 3 °( b - 2 ) ## str17 ## - 34 . 1 °( b - 3 ) ## str18 ## - 31 . 0 °( b - 4 ) ## str19 ## - 28 . 6 ° __________________________________________________________________________ ( ii ) each ( 1 . 5 g ) of resins ( c - 1 &# 39 ;), ( c - 2 &# 39 ;), ( c - 3 &# 39 ;) and ( c - 4 &# 39 ;) prepared in ( i ) above was dissolved in dmso ( 50 ml ) by heating , and mixed with hydrazine hydrate by stirring at room temperature for 24 hours . the formed precipitate was filtered , washed with dmso and then with water , and dissolved in 1n - hcl ( 20 ml ). the solution was poured into acetone , and the formed precipitate was filtered and dried . in this way , there were obtained resins ( 0 . 7 - 0 . 8 g ) to which glutamic acid moieties were attached . ir absorption spectra of these polymers ( absorptions at about 1700 cm - 1 and about 1640 cm - 1 assigned to c ═ o and nhco , respectively ) and uv absorption spectra thereof ( the absorption peak assigned to the phenyl group which was observed in the spectra of the resins prepared in ( i ) above had disappeared ) have indicated that the intended removal of phthaloyl groups was completely carried out in the preparation of these polymers . __________________________________________________________________________starting specific rotationmaterial [ α ]. sub . d . sup . 25 ( c = 1 , h . sub . 2__________________________________________________________________________ o )( c - 1 &# 39 ;) ## str20 ## 13 . 0 °( c - 2 &# 39 ;) ## str21 ## 13 . 6 °( c - 3 &# 39 ;) ## str22 ## 12 . 8 °( c - 4 &# 39 ;) ## str23 ## 12 . 5 ° __________________________________________________________________________