阅读说明：本技术 官能化的化合物 (Functionalized compounds ) 是由 N·P·泰勒 L·C·福弗尔 P·M·默里 C·诺思 A·沃森 于 2018-11-22 设计创作，主要内容包括：实质上不溶的在其一个或多个羟基处用配体(L)衍生化的具有多糖骨架的化合物,所述配体通过硫原子结合至糖部分,其可以根据宽范围的应用进行定制。该化合物可用作催化剂和从特别是含金属离子的进料中除去污染物。(A substantially insoluble compound having a polysaccharide backbone derivatized at one or more of its hydroxyl groups with a ligand (L) bonded to the sugar moiety through a sulfur atom can be tailored for a wide range of applications.)

1. A compound comprising a substantially insoluble polysaccharide compound selected from cellulose and starch, having a backbone comprising greater than 20 sugar moieties, wherein at least one of the sugar moieties is derivatized at one or more hydroxyl groups thereof with a ligand (L) bonded to the sugar moiety through a sulfur atom, wherein the ligand L is of the formula:

-S(O)_a(CR¹R²)_nX

wherein:

R¹and R²Each specific value of (A) is independently selected from hydrogen, optionally substituted, linear or branched C_1-40Alkyl radical, C_2-40-alkenyl or C_2-40-alkynyl, aryl and C_1-40-an alkylaryl group;

each specific value of a is independently 0 to 2;

n is independently an integer from 1 to 22:

x is selected from:

-CR¹R²R³；

a divalent group linking the two saccharide moieties;

-CR¹R²(CR¹R²)_nC(＝W)R；

-CR¹R²(CR¹Z)_iQ_hCHR¹Z；

-CR¹R²(CR¹Z)_iQ_h[(CHR¹)_nW]_tR¹；

-(CR¹Z)_iQ_hC(＝W)R¹

-CR¹R²(CR¹Z)_iQ_hR³

-OC(＝W)R；

wherein

R is independently selected from H, R¹，-OR¹，-NR¹R²，-NHNR¹R²and-SR¹；R³Is optionally substituted, linear or branched C_1-40Alkyl radical, C_2-40-alkenyl or C_2-40-alkynyl, aryl and C_1-40-an alkylaryl group;

q is independently selected from-C (═ W)¹)W²-and-W²C(＝W¹)-；

W，W¹And W²Independently selected from oxygen, sulfur, -N (R)¹) -and-N (NR)¹R²)；

Z is independently selected from-OR¹，-NR¹R²and-SR¹；

h is independently 0 or 1;

i is independently 0 to 6;

t is independently an integer from 1 to 20;

-[C(＝W)]_h(W(CR¹R²)_m)_nz; and

-S(O)_a-Y

wherein Y is a monovalent end group.

2. The compound according to claim 1 having a solubility in water of less than 5% and desirably less than 1% at standard temperature and pressure.

3. A compound according to claim 1 or 2, wherein the polysaccharide comprises cellulose.

4. A compound according to any one of the preceding claims wherein the sugar moiety is derivatised at a hydroxyl substituent on carbon atom "6" of the sugar moiety.

5. A compound according to any preceding claim, wherein a first part of the sugar moiety is derivatised by ligand L and a second part of the sugar moiety is derivatised at any one or more of the hydroxyl groups on the sugar moiety by a different substituent L ', wherein L' is selected from the group consisting of groups X, R¹，-Z，-(W(CR¹R²)_m)_nZ and a divalent group that forms a cross-linking bridge between two or more sugar moieties.

6. A compound according to any one of the preceding claims, wherein R¹And R²Independently selected from hydrogen, threadC being linear or branched_1-40Alkyl radical, C_2-40-alkenyl or C_2-40-alkynyl, aryl and C_1-40-alkylaryl, m is 1 to 20, a is 0 to 2 and b is 0 to 2.

7. A compound according to claim 6, wherein each CR is¹R²The radical being CH₂。

8. A compound according to any one of the preceding claims, at least part of the group X being selected from- [ CO ] linking two sugar moieties₂(CH₂)_mCO₂]-and- [ CH₂(CH₂)_mCH₂]The divalent group of-and m are independently 1 to 10.

9. A compound according to any one of the preceding claims, wherein R¹And R²Selected from hydrogen, linear or branched C_1-22Alkyl radical, C_2-22-alkenyl or C_2-22-alkynyl, aryl and C_1-22-alkylaryl and R³Selected from linear or branched C_1-22Alkyl radical, C_2-22-alkenyl or C_2-22-alkynyl, aryl and C_1-22-alkylaryl.

10. A compound according to claim 9, wherein R¹And R²Selected from hydrogen and linear or branched C_1-8-alkyl radical, C_2-8-alkenyl, aryl and C_1-8-alkylaryl and R³Selected from linear or branched C_1-8-alkyl radical, C_2-8-alkenyl, aryl and C_1-8-alkylaryl.

11. A compound according to any one of the preceding claims, wherein the functional group X is selected from:

-S(O)_a(CR¹R²)_nCR¹R²R³；

-S(O)_a(CR¹R²)_nS-Y；

-S(O)_a(CR¹R²)_n-(C＝W)_h(W(CR¹R²)_m)_nZ；

-S(O)_a(CR¹R²)_n(CR¹Z)_iQ_hC(＝W)R¹；

-S(O)_a(CR¹R²)_nCR¹R²(CR¹Z)_iQ_hCHR¹Z；

-S(O)_a(CR¹R²)_nCR¹R²(CR¹Z)Q_h[(CHR¹)_nW]_tR¹

-S(O)_a(CR¹R²)_nCR¹R²(CR¹Z)_iQ_hR³(ii) a And

-S(O)_a(CR¹R²)_nOC(＝W)R¹

wherein:

q is independently selected from-C (═ W)¹)W²-，-W²C(＝W¹)-；

W，W¹And W²Independently selected from oxygen, sulfur, NR¹；

Z is independently selected from-R¹，-OR¹，-NR¹R²and-SR¹(ii) a And

R¹and R²Independently selected from hydrogen, linear or branched C_1-22Alkyl radical, C_2-22-alkenyl and C_2-22-alkynyl, optionally substituted aryl and optionally substituted C_1-22-an alkylaryl group;

R³is optionally substituted, linear or branched C_1-22Alkyl radical, C_2-22-alkenyl or C_2-22-alkynyl, aryl and C_1-22-alkylaryl group

a is independently 0 to 2

h is independently 0 or 1;

i is independently 0 to 6;

m is independently 1 to 6;

n is independently 1 to 6;

t is independently 1 to 20.

12. A compound according to any one of the preceding claims wherein X is selected from-S (CH)₂)_n-CR¹R²R³；-S(CH₂)_nSH；-S(CH₂)_nC(O)(NR¹(CH₂)_m)_nNR¹R²and-S (CH)₂)_n(S(CH₂)_m)_nSH。

13. A compound according to any one of the preceding claims wherein X is selected from-S (CH)₂)_nSH；-S(CH₂)_nC(O)(NR¹(CH₂)_m)_nNR¹R²and-S (CH)₂)_n(S(CH₂)_m)_nSH。

14. A compound according to claim 13, wherein each particular value of n is independently 2 or 3.

15. A process for treating a feed comprising contacting a compound according to any one of claims 1 to 14 with the feed:

i) to effect a chemical reaction by catalytically converting components of the feed to produce a desired product; or

ii) thereby removing a component of the feed or reducing the level thereof to produce a feed which has consumed the removed component.

16. The method of claim 15 which removes or reduces the level of a component of a feed, wherein the component in the feed is a metal species or an anionic species.

17. The method of claim 16, wherein the component is selected from the group consisting of palladium, platinum, rhodium, iridium, ruthenium, gold, nickel, copper, silver, mercury, iron, lead, chromium, cadmium, arsenic, cobalt, arsenate anions, chromate anions, permanganate anions, borate anions, and perchlorate anions.

18. A process according to claim 16 or 17 wherein the level of the component in the feed which has consumed the removed component is at least 10% by weight lower than the level of the component in the feed, based on the level of the component in the feed.

19. A process according to any one of claims 16 to 18 wherein the component is a metal species and is reduced to a level below 500ppm in the feed which has consumed it.

20. A process according to any one of claims 15 to 19 wherein the feed is a water stream.

21. The method of claim 20, wherein the aqueous stream is an alkaline aqueous stream and comprises a component selected from the group consisting of palladium, platinum, rhodium, iridium, ruthenium, gold, nickel, copper, silver, mercury, iron such as fe (iii), lead, chromium, cadmium, arsenic, and cobalt.

22. The method according to any one of claims 15 to 21, wherein the feed is a chemical synthesis process stream or a water stream in an ore-mining process and the contaminant is a heavy metal or a precious metal.

23. Use of a compound according to any one of claims 1 to 14 in an industrial process stream, an ore mining process stream, a chemical synthesis process stream or an electronic component production process stream, wherein the compound reduces the level of metal species in the process stream.

24. A method of preparing a derivatized polysaccharide compound that is substantially water-insoluble, comprising providing a polysaccharide compound having a backbone comprising greater than 20 sugar moieties, derivatizing at least one hydroxyl substituent, and reacting the derivatized hydroxyl substituent with a compound that provides a ligand (L) of the formula:

-S(O)_a(CR¹R²)_nX

whereby the ligand is bound to the sugar moiety through the sulphur atom of the ligand

Wherein:

R¹and R²Each specific value of (A) is independently selected from hydrogen, optionally substituted, linear or branched C_1-40Alkyl radical, C_2-40-alkenyl or C_2-40-alkynyl, aryl and C_1-40-an alkylaryl group;

each specific value of a is independently 0 to 2;

n is independently an integer from 1 to 22, preferably from 1 to 12, especially from 1 to 6, for example 1, 2 or 3:

x is selected from:

-CR¹R²R³；

divalent group linking two sugar moieties, preferably- [ CO ]₂(CH₂)_mCO₂]-or- [ CH₂(CH₂)_mCH₂]And m is independently 1 to 10, preferably 1 to 6, such as 1, 2 or 4;

-CR¹R²(CR¹R²)_nC(＝W)R；

-CR¹R²(CR¹Z)_iQ_hCHR¹Z；

-CR¹R²(CR¹Z)_iQ_h[(CHR¹)_nW]_tR¹；

-(CR¹Z)_iQ_hC(＝W)R¹

-CR¹R²(CR¹Z)_iQ_hR³

-OC(＝W)R；

wherein

R is independently selected from H, R¹，-OR¹，-NR¹R²，-NHNR¹R²and-SR¹；R³Is optionally substituted, linear or branched C_1-40Alkyl radical, C_2-40-alkenyl or C_2-40-alkynyl, aryl and C_1-40-an alkylaryl group;

q independently selectedfrom-C (═ W)¹)W²-and-W²C(＝W¹)-；

W，W¹And W²Independently selected from oxygen, sulfur, -N (R)¹) -and-N (NR)¹R²)；

Z is independently selected from-OR¹，-NR¹R²and-SR¹；

h is independently 0 or 1;

i is independently 0 to 6;

t is independently an integer from 1 to 20, preferably from 1 to 3;

-[C(＝W)]_h(W(CR¹R²)_m)_nz, and preferably in this case R¹And R²Is H and Z is OH or NH₂(ii) a And

-S(O)_a-Y

wherein Y is a monovalent end group, preferably selected from the group consisting of H and X, excluding-S (O)_a-the case of Y.

25. The method according to claim 24, wherein the polysaccharide compound is selected from the group consisting of cellulose, starch, chitin and chitosan.

26. The method according to any one of claims 24 and 25, wherein the derivatizing step comprises tosylation of at least one hydroxyl group of the polysaccharide.

27. The process according to any one of claims 24 to 26, wherein the polysaccharide compound is contacted with a tetrabutylphosphonium hydroxide solution to produce an aqueous solution or dispersion comprising at least 10% by weight of dissolved polysaccharide prior to subjecting it to the derivatizing step.

28. The method according to claim 27, wherein the aqueous solution or dispersion is formed at room temperature and optionally, the hydroxyl derivatization is performed at room temperature.

29. A method of preparing a compound according to any one of claims 1 to 14, comprising contacting a polysaccharide compound having a backbone comprising more than 20 saccharide moieties with a thiol compound under conditions to react the thiol compound with the hydroxyl group at the 6-position of the polysaccharide compound, and contacting a thioether-derivatized compound with a derivatized polysaccharide compound under conditions such that a compound comprising a functional group X as defined in any one of claims 1 to 13 reacts with the derivatized polysaccharide compound, thereby producing a compound according to any one of claims 1 to 14.

30. A capture product comprising a compound as defined in any one of claims 1 to 14, in the form of beads, microcrystalline material, nanofibres or a membrane.

Example 1

Synthetic cellulose tosylate

Cellulose tosylate may be prepared according to the following reaction procedure described in Green chem, 2012, 14, 3126-3131. The dry cellulose (1g) was suspended inWater (26.9m L), then NaOH (2.5g) was added and stirred/shaken until dissolved frozen to a solid (salt/ice bath) and then thawed to a gel at room temperature Once thawed, more water (20.6m L) was added and then NEt was added₃And TsCl, then stirred at room temperature overnight the solid was filtered off and then washed with hot water (300m L) then hot EtOH (150m L) the tosylated cellulose was dried in a vacuum oven at 75-80 ℃, preferably overnight, removing any residual water before use.

Synthetic cellulose tosylate-Et removal₃N and addition of toluene

Aqueous NaOH solution (2.3M, 7.6g) was added to microcrystalline cellulose (0.26g) followed by freezing to a solid (-18 ℃ freezer, typically overnight) thawing to room temperature, then toluene (6M L) and tosyl chloride (1.2g) were added and the mixture stirred vigorously for 3 hours, then ethanol (30M L) was added and the solid material filtered off, then washed with water (30M L), ethanol (20M L), toluene (20M L), ethanol (20M L), and water (20M L). the resulting solid was dried in a vacuum oven at 75 ℃ overnight.

Synthetic cellulose tosylate-removal of complete freezing step

Preparation of a water (430m L) solution of NaOH (40.1g) and cooling to 0 ℃. add microcrystalline cellulose (30g) to the solution and stir at 0 ℃ for 6 hours to disperse, then let the mixture at 0 ℃ without stirring overnight, then restart stirring and add toluene (360m L). cool the mixture back to 0 ℃, then add tosyl chloride (141g) and stir at 0 ℃ for 5 hours, then add methanol (800m L), the reaction mixture stir for 30 minutes, then filter off the solids, the solids are washed with methanol (500m L), water (500m L), methanol (500m L), water (500m L), and methanol (500m L). the resulting solids are dried in a vacuum oven at 55 ℃ overnight.

Synthesis of cellulose tosylate in dimethylacetamide and lithium chloride

Cellulose tosylate can also be prepared according to a non-aqueous reaction scheme, for example as described in Carbohydrateresearch, 1990,208, 183-191. to a stirred suspension of microcrystalline cellulose (1g) and dimethylacetamide (50m L) lithium chloride (4.2g) is added and then stirred overnight, followed by triethylamine (30.1m L), the reaction is cooled to 10 deg.C and then a solution of tosyl chloride (10.3g) in dimethylacetamide is added dropwise to the reaction which is then allowed to stir at 10 deg.C for 24 hours.

During preparation, the tosylated cellulose may be dissolved in a highly polar non-aqueous solvent such as DMSO, DMF or DMAC, with or without L iCl added, depending on the degree of tosylation and the ionic liquid.

Synthesis of cellulose tosylate with tetrabutylphosphonium hydroxide

Cellulose tosylate may also be prepared as follows: the cellulose was dissolved with tetrabutylphosphonium hydroxide at room temperature to provide a solution with high levels of cellulose. The dried cellulose (0.5g) was suspended in tetrabutylphosphonium hydroxide solution (60% wt/wt aqueous, 3g) and stirred until dissolved. The cellulose concentration is 14%, which is higher than what is normally achievable with sodium hydroxide solution, and the reaction can be carried out at room temperature instead of at 0 ℃.

A toluene solution of tosyl chloride was added and stirred vigorously at room temperature for 5 hours methanol (30m L) was added to precipitate a solid substance, which was then filtered, the solid substance was washed with methanol, and the obtained solid was dried overnight with a vacuum oven (65-70 ℃ C.).