CN101490091B

CN101490091B - Method for producing cellulose acetals

Info

Publication number: CN101490091B
Application number: CN200780025838.4A
Authority: CN
Inventors: K·马松内; V·施泰格曼; G·德安多拉; W·摩尔曼; M·威兹斯坦; W·冷
Original assignee: BASF SE; Universitaet Siegen
Current assignee: BASF SE; Universitaet Siegen
Priority date: 2006-07-07
Filing date: 2007-06-28
Publication date: 2012-12-12
Anticipated expiration: 2027-06-28
Also published as: DE102006031810A1; CN101490091A; ZA200900853B

Abstract

The present invention describes a method for producing acetals of poly-, oligo- or disaccharides by dissolving them in at least one ionic liquid and then reacting them with a vinylether. The resulting acetalized poly- or oligosaccharides can be cross-linked by treatment with acid. The present invention relates also to acetals of poly-, oligo- or disaccharides and cross-linked poly- or oligosaccharides.

Description

The method of production of cellulose acetal

The invention describes a kind of preparation through the method that Mierocrystalline cellulose and vinyl ether reacted prepare the Mierocrystalline cellulose acetal and new Mierocrystalline cellulose acetal in ionic liquid.

Mierocrystalline cellulose is most important renewable raw materials and is the for example important source material of textiles, paper and supatex fabric industry.

It also (comprises ether of cellulose such as methylcellulose gum and CMC 99.5 as derivatived cellulose and modifier; Based on the organic acid cellulose ester; For example rhodia, cellulose butyrate, and based on the cellulose ester of mineral acid, for example nitrocellulose etc.) raw material.These verivates and modifier have many purposes, for example are used for textiles, food, building and topcoating industry.Rhodia is especially interesting here.Still be desirable to provide cellulosic other verivates, to satisfy the requirement of above-mentioned industry.

By J.Polymer Science, 51 173 (1961) (T.Fujimura etc.) known fiber cellulose fiber can be handled and formation semi-acetal and acetal with oxalic dialdehyde or LUTARALDEHYDE.In the method, the cellulosic fibre introducing is comprised in the bath of dialdehyde.Therefore this method is heterogeneous reaction, and it receives the quality influence of used cellulosic fibre to a great extent and compares with fiber core (if words that semi-acetalization/acetalation takes place there), and the semi-acetal and the acetal formation that increase take place at cellulose surface.

Yet, hope to provide " evenly " acetalized fiber plain, it is not crosslinked and dissolve in conventional organic solvent such as ether, ester, ketone, alcohol or the hydrocarbon.

This purpose is through being dissolved in Mierocrystalline cellulose in the ionic liquid and making it and vinyl ether reaction realizes.In addition, found new Mierocrystalline cellulose acetal.

For the purpose of the present invention, ionic liquid is preferably:

(A) salt of general formula (I):

[A] _n ⁺ [Y] ^n- ?(I)，

Wherein n is 1,2,3 or 4, [A] ⁺Be quaternary ammonium cation, oxygen positively charged ion, sulfonium cation Huo phosphonium cation and [Y] ^N-Be monovalence, divalence, trivalent or quadrivalent anion;

(B) mixing salt of general formula (II):

[A ¹] ⁺[A ²] ⁺[Y] ^N-(IIa), n=2 wherein;

[A ¹] ⁺[A ²] ⁺[A ³] ⁺[Y] ^N-(IIb), n=3 wherein; Or

[A ¹] ⁺[A ²] ⁺[A ³] ⁺[A ⁴] ⁺[Y] ^N-(IIc), n=4 wherein,

[A wherein ¹] ⁺, [A ²] ⁺, [A ³] ⁺[A ⁴] ⁺Be independently selected from [A] ⁺The group of being mentioned and [Y] ^N-Such as (A) following definition.

Ionic liquid preferably has the fusing point less than 180 ℃.Fusing point is preferably-50 ℃ to 150 ℃ especially, and is especially-20 ℃ to 120 ℃, extra preferably less than 100 ℃.

The used ionic liquid of the present invention is an organic cpds, and promptly this ion liquid at least one positively charged ion or negatively charged ion comprise organic group.

Be fit to form ion liquid positively charged ion [A] ⁺Compound for example known by DE 102 02 838 A1.Therefore, this compounds can comprise oxygen, phosphorus, sulphur or especially nitrogen-atoms, for example at least one nitrogen-atoms, preferably 1-10 nitrogen-atoms, especially preferably 1-5 nitrogen-atoms, very especially preferably 1-3 nitrogen-atoms, especially 1 or 2 nitrogen-atoms.Suitable, also can comprise other heteroatomss such as oxygen, sulphur or phosphorus atom.Nitrogen-atoms is the suitable carrier of positive charge in the ion liquid positively charged ion, and proton or alkyl can be in balance be forwarded on the negatively charged ion and produced the electroneutral molecule by it.

If nitrogen-atoms is the carrier of positive charge in the ion liquid positively charged ion, then can at first produce positively charged ion through the nitrogen-atoms of quaternized for example amine or nitrogen heterocyclic in ion liquid synthesizing.Quaternized can carrying out through the alkylation of nitrogen-atoms.Depend on used alkylating reagent, obtain having the salt of different anions.When can not be quaternized in itself during the required negatively charged ion of formation, this can carry out in another step of synthetic.For example begin, can make the reaction of this halogenide and Lewis acid, form coordination anion by this halogenide and Lewis acid by ammonium halide.As replacement, can use required negatively charged ion displacement halogen ion.This can be through adding metal-salt with the metal halide of deposition formation, by ionite or through realizing with strong acid displacement halogen ion (releasing hydrogen halide).Suitable method for example is described in Angew.Chem.2000, in 112, the 3926-3945 pages or leaves and the document wherein quoted.

For example can be used for the suitable alkyl of quaternized amine or azepine ring nitrogen is C ₁-C ₁₈Alkyl, preferred C ₁-C ₁₀Alkyl, preferred especially C ₁-C ₆Alkyl, very special preferable methyl.Alkyl can not be substituted or have one or more identical or different substituting groups.

Preferably comprise at least one 5 or 6 element heterocycles, especially compound of 5 element heterocycles, this heterocycle has at least one nitrogen-atoms and suitable words oxygen or sulphur atom.The compound that equally especially preferably comprises at least one 5 or 6 element heterocycle, this heterocycle have 1,2 or 3 nitrogen-atoms and sulphur or Sauerstoffatom, very especially preferably have the compound of two nitrogen-atoms.Further preferred aromatic heterocycle.

Preferred especially compound has less than 1000g/mol, very especially preferably less than 500g/mol, especially less than the molecular weight of 350g/mol.

In addition, be preferably selected from the positively charged ion of formula (IIIa)-(IIIw) compound:

And the oligopolymer that comprises these structures.

Other suitable positively charged ions are general formula (IIIx) and compound (IIIy):

And the oligopolymer that comprises these structures.

In following formula (IIIa)-(IIIy),

● radicals R is hydrogen or has 1-20 carbon atom and can not be substituted or by 1-5 heteroatoms or functional group at interval or substituted saturated or unsaturated, acyclic or cyclic aliphatic, aromatics or araliphatic organic carbonaceous group; With

● radicals R ¹-R ⁹Separately independently of each other for hydrogen, sulfo group or have 1-20 carbon atom and can not be substituted or rolled into a ball interval or substituted saturated or unsaturated, acyclic or cyclic aliphatic, aromatics or araliphatic organic carbonaceous group by 1-5 heteroatoms or suitable functional groups, wherein in following formula (III) with the radicals R of carbon atom bonding (and not with heteroatoms bonding) ¹-R ⁹Extraly can be halogen or functional group; Or

Two are selected from R ¹-R ⁹Adjacent group can also form together and have 1-30 carbon atom and can not be substituted or at interval or substituted saturated or unsaturated, acyclic or cyclic aliphatic, aromatics or araliphatic divalence organic carbonaceous group by 1-5 heteroatoms or functional group.

At radicals R and R ¹-R ⁹Definition in, possible heteroatoms is that all can substitute-CH in form in principle ₂-group ,-the CH=group ,-C ≡ group or=heteroatoms of C=group.Comprise heteroatoms as if this carbon-containing group, then preferred oxygen, nitrogen, sulphur, phosphorus and silicon.Preferred group especially is-O-,-S-,-SO-,-SO ₂-,-NR '-,-N=,-PR '-,-PR ' ₃With-SiR ' ₂-, radicals R ' be the remainder of carbon-containing group wherein.Radicals R in the following formula (III) therein ¹-R ⁹Under the situation of carbon atom bonding (and not with heteroatoms bonding), they also can be directly via this heteroatoms bonding.

Suitable functional groups group be in principle all can with carbon atom or heteroatoms bonding and not with the functional group of vinyl ether reaction.Suitable instance is=O (especially being carbonyl) ,-NR ₂' ,=NR ' and-CN (cyanic acid).Functional group and heteroatoms can also direct neighbors, thereby also comprise the combination of a plurality of adjacent atoms, for example-O-(ether) ,-S-(thioether) ,-COO-(ester) or-CONR '-(teritary amide), for example two-C ₁-C ₄Alkylamino, C ₁-C ₄Carbalkoxy or C ₁-C ₄Alkoxyl group.Radicals R ' be the remainder of this carbon-containing group.

Can mention fluorine, chlorine, bromine and iodine as halogen.

Radicals R is preferably:

● can not be substituted or by one or more halogens, phenyl, cyanic acid and/or C ₁-C ₆Carbalkoxy replaces and has altogether the not branching or the branching C of 1-20 carbon atom ₁-C ₁₈Alkyl; Methyl for example; Ethyl; The 1-propyl group; The 2-propyl group; The 1-butyl; The 2-butyl; 2-methyl isophthalic acid-propyl group; 2-methyl-2-propyl group; The 1-amyl group; The 2-amyl group; The 3-amyl group; The 2-methyl-1-butene base; 3-methyl isophthalic acid-butyl; 2-methyl-2-butyl; 3-methyl-2-butyl; 2; 2-dimethyl--1-propyl group; The 1-hexyl; The 2-hexyl; The 3-hexyl; 2-methyl-1-pentene base; 3-methyl-1-pentene base; 4-methyl-1-pentene base; 2-methyl-2-amyl group; 3-methyl-2-amyl group; 4-methyl-2-amyl group; 2-methyl-3-amyl group; 3-methyl-3-amyl group; 2; 2-dimethyl--1-butyl; 2; 3-dimethyl--1-butyl; 3; 3-dimethyl--1-butyl; 2-ethyl-1-butyl; 2; 3-dimethyl--2-butyl; 3; 3-dimethyl--2-butyl; The 1-heptyl; The 1-octyl group; The 1-nonyl; The 1-decyl; The 1-undecyl; The 1-dodecyl; The 1-tetradecyl; The 1-hexadecyl; The 1-octadecyl; Benzyl; The 3-phenyl propyl; The 2-cyano ethyl; 2-(methoxycarbonyl) ethyl; 2-(ethoxycarbonyl) ethyl; 2-(positive butoxy carbonyl) ethyl; Trifluoromethyl; Difluoromethyl; Methyl fluoride; Pentafluoroethyl group; Seven fluoropropyls; Seven fluorine sec.-propyls; Nine fluorine butyl; Nine fluorine isobutyl-s; 11 fluorine amyl groups and 11 fluorine isopentyl

● glycol, butyleneglycol and have 1-100 unitary oligopolymer, all above-mentioned groups have C ₁-C ₈Alkyl is as end group, for example R ^AO-(CHR ^B-CH ₂-O) _m-CHR ^B-CH ₂-or R ^AO-(CH ₂CH ₂CH ₂CH ₂O) _m-CH ₂CH ₂CH ₂CH ₂-, R wherein ^AAnd R ^BBe preferably methyl or ethyl and m separately and be preferably 0-3, especially 3-oxa-butyl, 3-oxa-amyl group, 3,6-dioxaheptyl, 3,6-dioxa octyl group, 3; 6,9-trioxa decyl, 3,6,9-trioxa undecyl, 3; 6,9,12-four oxa-tridecyls and 3; 6,9,12-four oxa-tetradecyls;

● vinyl;

● 1-propylene-1-base, 1-propylene-2-base and 1-propylene-3-base; With

● N, N-two-C ₁-C ₆Alkylamino such as N, N-dimethylamino and N, N-diethylin.

Radicals R is preferably not branching and unsubstituted C especially ₁-C ₁₈Alkyl; Like methyl, ethyl, 1-propyl group, 1-butyl, 1-amyl group, 1-hexyl, 1-heptyl, 1-octyl group, 1-decyl, 1-dodecyl, 1-tetradecyl, 1-hexadecyl, 1-octadecyl, 1-propylene-3-base; Especially methyl, ethyl, 1-butyl and 1-octyl group, perhaps CH ₃O-(CH ₂CH ₂O) _m-CH ₂CH ₂-and CH ₃CH ₂O-(CH ₂CH ₂O) _m-CH ₂CH ₂-, wherein m is 0-3.

Preferred group R ¹-R ⁹Be independently of each other separately:

● hydrogen;

● halogen;

● suitable functional groups group;

● can choose wantonly by suitable functional groups group, aryl, alkyl, aryloxy, alkoxyl group, halogen, heteroatoms and/or heterocyclic substituted and/or by one or more oxygen and/or sulphur atom and/or one or more replacement or unsubstituted imino-C at interval ₁-C ₁₈Alkyl;

● can choose wantonly by suitable functional groups group, aryl, alkyl, aryloxy, alkoxyl group, halogen, heteroatoms and/or heterocyclic substituted and/or by one or more oxygen and/or sulphur atom and/or one or more replacement or unsubstituted imino-C at interval ₂-C ₁₈Alkenyl;

● can choose wantonly by the C of suitable functional groups group, aryl, alkyl, aryloxy, alkoxyl group, halogen, heteroatoms and/or heterocyclic substituted ₆-C ₁₂Aryl;

● can choose wantonly by the C of suitable functional groups group, aryl, alkyl, aryloxy, alkoxyl group, halogen, heteroatoms and/or heterocyclic substituted ₅-C ₁₂Naphthenic base;

● can choose wantonly by the C of suitable functional groups group, aryl, alkyl, aryloxy, alkoxyl group, halogen, heteroatoms and/or heterocyclic substituted ₅-C ₁₂Cycloalkenyl group; Or

● can choose wantonly by suitable functional groups group, aryl, alkyl, aryloxy, alkoxyl group, halogen, heteroatoms and/or heterocyclic substituted 5 or 6 Yuans contain oxygen-, nitrogen-and/or thia ring; Or

Two adjacent groups form together:

● can choose wantonly by suitable functional groups group, aryl, alkyl, aryloxy, alkoxyl group, halogen, heteroatoms and/or heterocyclic substituted and can choose wantonly by one or more oxygen and/or sulphur atom and/or one or more replacement or unsubstituted imino-unsaturated, saturated or aromatic ring at interval.

Can choose wantonly by the C of suitable functional groups group, aryl, alkyl, aryloxy, alkoxyl group, halogen, heteroatoms and/or heterocyclic substituted ₁-C ₁₈Alkyl is preferably methyl, ethyl, 1-propyl group, 2-propyl group, 1-butyl, 2-butyl, 2-methyl isophthalic acid-propyl group (isobutyl-), 2-methyl-2-propyl group (tertiary butyl), 1-amyl group, 2-amyl group, 3-amyl group, 2-methyl-1-butene base, 3-methyl isophthalic acid-butyl, 2-methyl-2-butyl, 3-methyl-2-butyl, 2; 2-dimethyl--1-propyl group, 1-hexyl, 2-hexyl, 3-hexyl, 2-methyl-1-pentene base, 3-methyl-1-pentene base, 4-methyl-1-pentene base, 2-methyl-2-amyl group, 3-methyl-2-amyl group, 4-methyl-2-amyl group, 2-methyl-3-amyl group, 3-methyl-3-amyl group, 2; 2-dimethyl--1-butyl, 2; 3-dimethyl--1-butyl, 3; 3-dimethyl--1-butyl, 2-ethyl-1-butyl, 2; 3-dimethyl--2-butyl, 3; 3-dimethyl--2-butyl, heptyl, octyl group, 2-ethylhexyl, 2; 4; 4-tri-methyl-amyl, 1; 1; 3; 3-tetramethyl butyl, 1-nonyl, 1-decyl, 1-undecyl, 1-dodecyl, 1-tridecyl, 1-tetradecyl, 1-pentadecyl, 1-hexadecyl, 1-heptadecyl, 1-octadecyl, cyclopentyl-methyl, 2-cyclopentyl ethyl, 3-cyclopentyl propyl group, cyclohexyl methyl, 2-cyclohexyl ethyl, 3-cyclohexyl propyl group, benzyl (phenyl methyl), diphenyl methyl (diphenyl-methyl), trityl group, 1-phenylethyl, 2-phenylethyl, 3-phenyl propyl, α; α-Er Jiajibianji, p-methylphenyl methyl, 1-(to butyl phenyl) ethyl, p-chlorobenzyl, 2; The 4-dichloro benzyl, to methoxy-benzyl, m-oxethyl benzyl, 2-cyano ethyl, 2-cyanic acid propyl group, 2-methoxycarbonyl ethyl, 2-ethoxycarbonyl-ethyl, 2-butoxy carbonyl propyl group, 1,2-two (methoxycarbonyl) ethyl, methoxyl group, oxyethyl group, formyl radical, 1,3-dioxolane-2-base, 1; 3-diox-2-base, 2-methyl isophthalic acid; 3-dioxolane-2-base, 4-methyl isophthalic acid, 3-dioxolane-2-base, 2-dimethylaminoethyl, 2-dimethylamino-propyl, 3-dimethylamino-propyl, 4-dimethylamino butyl, 6-dimethylamino hexyl, 2-phenoxy ethyl, 2-phenoxy propyl, 3-phenoxy propyl, 4-phenoxy butyl, 6-phenoxy hexyl, 2-methoxy ethyl, 2-methoxy-propyl, 3-methoxy-propyl, 4-methoxyl group butyl, 6-methoxyl group hexyl, 2-ethoxyethyl group, 2-ethoxycarbonyl propyl, 3-ethoxycarbonyl propyl, 4-oxyethyl group butyl, 6-oxyethyl group hexyl, ethanoyl, C _mF _{2 (m-a)+(1-b)}H _2a+b, wherein m is 1-30,0≤a≤m and b=0 or 1 (CF for example ₃, C ₂F ₅, CH ₂CH ₂-C _(m-2)F _{2 (m-2)+1}, C ₆F ₁₃, C ₈F ₁₇, C ₁₀F ₂₁, C ₁₂F ₂₅), chloromethyl, 2-chloroethyl, trichloromethyl, 1,1-dimethyl--2-chloroethyl, methoxymethyl, 2-butoxyethyl group, diethoxymethyl, diethoxy ethyl, 2-isopropoxy ethyl, 2-butoxy propyl group, 2-octyloxy ethyl, 2-methoxyl group sec.-propyl, 2-(methoxycarbonyl) ethyl, 2-(ethoxycarbonyl) ethyl, 2-(positive butoxy carbonyl) ethyl, butylthio methyl, 2-dodecyl sulfenyl ethyl, 2-thiophenyl ethyl, 5-methoxyl group-3-oxa-amyl group, 8-methoxyl group-3; 6-dioxa octyl group, 11-methoxyl group-3; 6,9-trioxa undecyl, 7-methoxyl group-4-oxa-heptyl, 11-methoxyl group-4,8-dioxa undecyl, 15-methoxyl group-4; 8; 12-trioxa pentadecyl, 9-methoxyl group-5-oxa-nonyl, 14-methoxyl group-5,10-dioxa tetradecyl, 5-oxyethyl group-3-oxa-amyl group, 8-oxyethyl group-3,6-dioxa octyl group, 11-oxyethyl group-3; 6; 9-trioxa undecyl, 7-oxyethyl group-4-oxa-heptyl, 11-oxyethyl group-4,8-dioxa undecyl, 15-oxyethyl group-4,8; 12-trioxa pentadecyl, 9-oxyethyl group-5-oxa-nonyl or 14-oxyethyl group-5,10-oxa-tetradecyl.

Can choose wantonly by suitable functional groups group, aryl, alkyl, aryloxy, alkoxyl group, halogen, heteroatoms and/or heterocyclic substituted and/or by one or more oxygen and/or sulphur atom and/or one or more replacement or unsubstituted imino-C at interval ₂-C ₁₈Alkenyl is preferably vinyl, 2-propenyl, 3-crotonyl, cis-2-butene base, trans-2-butene base or C _mF _{2 (m-a)-(1-b)}H _2a-b, wherein m≤30,0≤a≤m and b=0 or 1.

Can choose wantonly by the C of suitable functional groups group, aryl, alkyl, aryloxy, alkoxyl group, halogen, heteroatoms and/or heterocyclic substituted ₆-C ₁₂Aryl is preferably phenyl, tolyl, xylyl, Alpha-Naphthyl, betanaphthyl, 4-xenyl, chloro-phenyl-, dichlorophenyl, trichlorophenyl, difluorophenyl, aminomethyl phenyl, 3,5-dimethylphenyl, trimethylphenyl, ethylphenyl, diethylammonium phenyl, isopropyl phenyl, tert-butyl-phenyl, dodecylphenyl, p-methoxy-phenyl, Dimethoxyphenyl, ethoxyl phenenyl, hexyloxy phenyl, methyl naphthyl, sec.-propyl naphthyl, chloronaphthyl, methylnaphthyl, oxyethyl group naphthyl, 2; 6-3,5-dimethylphenyl, 2; 4; 6-trimethylphenyl, 2; 6-Dimethoxyphenyl, 2; 6-dichlorophenyl, 4-bromophenyl, 2-nitrophenyl, 4-nitrophenyl, 2; 4-dinitrophenyl, 2,6-dinitrophenyl, 4-dimethylamino phenyl, 4-acetylphenyl, methoxy ethyl phenyl, ethoxyl methyl phenyl, thiotolene base, sec.-propyl thienyl or tertiary butyl thienyl or C ₆F _(5-a)H _a, 0≤a≤5 wherein.

Can choose wantonly by the C of suitable functional groups group, aryl, alkyl, aryloxy, alkoxyl group, halogen, heteroatoms and/or heterocyclic substituted ₅-C ₁₂Naphthenic base is preferably cyclopentyl, cyclohexyl, ring octyl group, cyclo-dodecyl, methylcyclopentyl, dimethylcyclopentyl, methylcyclohexyl, Dimethylcyclohexyl, diethylammonium cyclohexyl, butyl cyclohexyl, methoxyl group cyclohexyl, dimethoxy cyclohexyl, diethoxy cyclohexyl, butylthio cyclohexyl, chloro cyclohexyl, dichloro cyclohexyl, dichloro cyclopentyl, C _mF _{2 (m-a)-(1-b)}H _2a-b, wherein m≤30,0≤a≤m and b=0 or 1, saturated or unsaturated bicyclic system such as norcamphyl or norbornene.

Can choose wantonly by the C of suitable functional groups group, aryl, alkyl, aryloxy, alkoxyl group, halogen, heteroatoms and/or heterocyclic substituted ₅-C ₁₂Cycloalkenyl group is preferably 3-cyclopentenyl, 2-cyclohexenyl, 3-cyclohexenyl, 2,5-cyclohexadienyl or C _nF _{2 (m-a)-3 (1-b)}H _2a-3b, wherein m≤30,0≤a≤m and b=0 or 1.

Can choose wantonly by suitable functional groups group; Aryl; Alkyl; Aryloxy; Alkoxyl group; Halogen; Heteroatoms and/or heterocyclic substituted 5 or 6 Yuans contain oxygen-; Nitrogen-and/or the thia ring be preferably furyl; Thienyl; Pyrryl; Pyridyl; Indyl benzoxazolyl; Dioxolyl dioxine base; Benzimidazolyl-; Benzothiazolyl; The lutidine base; The toluquinoline base; Dimethyl pyrrole; The methoxyl group furyl; Dimethoxy-pyridine base or difluoro pyridine base.

If two adjacent groups form together and can choose wantonly by suitable functional groups group, aryl, alkyl, aryloxy, alkoxyl group, halogen, heteroatoms and/or heterocyclic substituted and/or can choose wantonly by one or more oxygen and/or sulphur atom and/or one or more replacement or unsubstituted imino-unsaturated, saturated or aromatic ring at interval, then they are preferably formed trimethylene, 1; 4-butylidene, 1; 5-pentylidene, 2-oxa--trimethylene, 1-oxa--trimethylene, 2-oxa--1; 3-propylidene, 1-oxa--1; 3-propenylidene, 3-oxa--pentamethylene, 1-azepine-propenylene, 1-C ₁-C ₄Alkyl-1-azepine-propenylene, 1,4-fourth-1,3-diene subunit, 1-azepine-1,4-fourth-1,3-diene subunit or 2-azepine-1,4-fourth-1,3-diene subunit.

If above-mentioned group comprises oxygen and/or sulphur atom and/or replacement or unsubstituted imino-, then the number to oxygen and/or sulphur atom and/or imino-has no restriction.Usually in this group, be no more than 5, preferably be no more than 4, very particularly preferably be no more than 3.

If above-mentioned group comprises heteroatoms, then between any two heteroatomss, there are at least one carbon atom, preferably at least two carbon atoms usually.

Special preferred group R ¹-R ⁹Be independently of each other separately:

● hydrogen;

● can not be substituted or by one or more H, halogen, phenyl, cyanic acid and/or C ₁-C ₆Carbalkoxy replaces and has altogether the not branching or the branching C of 1-20 carbon atom ₁-C ₁₈Alkyl; For example methyl, ethyl, 1-propyl group, 2-propyl group, 1-butyl, 2-butyl, 2-methyl isophthalic acid-propyl group, 2-methyl-2-propyl group, 1-amyl group, 2-amyl group, 3-amyl group, 2-methyl-1-butene base, 3-methyl isophthalic acid-butyl, 2-methyl-2-butyl, 3-methyl-2-butyl, 2; 2-dimethyl--1-propyl group, 1-hexyl, 2-hexyl, 3-hexyl, 2-methyl-1-pentene base, 3-methyl-1-pentene base, 4-methyl-1-pentene base, 2-methyl-2-amyl group, 3-methyl-2-amyl group, 4-methyl-2-amyl group, 2-methyl-3-amyl group, 3-methyl-3-amyl group, 2; 2-dimethyl--1-butyl, 2; 3-dimethyl--1-butyl, 3; 3-dimethyl--1-butyl, 2-ethyl-1-butyl, 2; 3-dimethyl--2-butyl, 3,3-dimethyl--2-butyl, 1-heptyl, 1-octyl group, 1-nonyl, 1-decyl, 1-undecyl, 1-dodecyl, 1-tetradecyl, 1-hexadecyl, 1-octadecyl, benzyl, 3-phenyl propyl, 2-cyano ethyl, 2-(methoxycarbonyl) ethyl, 2-(ethoxycarbonyl) ethyl, 2-(positive butoxy carbonyl) ethyl, trifluoromethyl, difluoromethyl, methyl fluoride, pentafluoroethyl group, seven fluoropropyls, seven fluorine sec.-propyls, nine fluorine butyl, nine fluorine isobutyl-s, 11 fluorine amyl groups and 11 fluorine isopentyl;

● glycol, butyleneglycol and have 1-100 unitary oligopolymer, all above-mentioned groups have C ₁-C ₈Alkyl is as end group, for example R ^AO-(CHR ^B-CH ₂-O) _m-CHR ^B-CH ₂-or R ^AO-(CH ₂CH ₂CH ₂CH ₂O) _m-CH ₂CH ₂CH ₂CH ₂-, R wherein ^AAnd R ^BBe preferably methyl or ethyl and n separately and be preferably 0-3, especially 3-oxa-butyl, 3-oxa-amyl group, 3,6-dioxaheptyl, 3,6-dioxa octyl group, 3; 6,9-trioxa decyl, 3,6,9-trioxa undecyl, 3; 6,9,12-four oxa-tridecyls and 3; 6,9,12-four oxa-tetradecyls;

● vinyl;

● 1-propylene-1-base, 1-propylene-2-base and 1-propylene-3-base; With

● N, N-two-C ₁-C ₆Alkylamino such as N, N-dimethylamino and N, N-diethylin;

Wherein when IIIw is III, R ³Be not hydrogen.

Very special preferred group R ¹-R ⁹Be hydrogen or C separately independently of each other ₁-C ₁₈Alkyl such as methyl, ethyl, 1-butyl, 1-amyl group, 1-hexyl, 1-heptyl, 1-octyl group, phenyl, 2-cyano ethyl, 2-(methoxycarbonyl) ethyl, 2-(ethoxycarbonyl) ethyl, 2-(positive butoxy carbonyl) ethyl, N; N-dimethylamino, N, N-diethylin, chlorine or CH ₃O-(CH ₂CH ₂O) _m-CH ₂CH ₂-and CH ₃CH ₂O-(CH ₂CH ₂O) _m-CH ₂CH ₂-, wherein m is 0-3.

Preferred very especially pyridinium ion (IIIa) be following those, wherein

● radicals R ¹-R ⁵One of be methyl, ethyl or chlorine and remaining radicals R ¹-R ⁵The hydrogen of respectively doing for oneself;

● R ³Be dimethylamino and remaining radicals R ¹, R ², R ⁴And R ⁵The hydrogen of respectively doing for oneself;

● all radicals R ¹-R ⁵Be hydrogen;

● R ¹And R ²Or R ²And R ³Be 1,4-fourth-1,3-diene subunit and remaining radicals R ¹, R ², R ⁴And R ⁵The hydrogen of respectively doing for oneself;

And especially following those, wherein

● R ¹-R ⁵The hydrogen of respectively doing for oneself; Or

● radicals R ¹-R ⁵One of be methyl or ethyl and remaining radicals R ¹-R ⁵The hydrogen of respectively doing for oneself.

As preferred very especially pyridinium ion (IIIa); Can mention 1-picoline, 1-ethylpyridine, 1-(1-butyl) pyridine, 1-(1-hexyl) pyridine, 1-(1-octyl group) pyridine, 1-(1-hexyl) pyridine, 1-(1-octyl group) pyridine, 1-(1-dodecyl) pyridine, 1-(1-tetradecyl) pyridine, 1-(1-hexadecyl) pyridine, 1; 2-lutidine, 1-ethyl-2-picoline, 1-(1-butyl)-2-picoline, 1-(1-hexyl)-2-picoline, 1-(1-octyl group)-2-picoline, 1-(1-dodecyl)-2-picoline, 1-(1-tetradecyl)-2-picoline, 1-(1-hexadecyl)-2-picoline, 1-methyl-2-ethylpyridine, 1; 2-parvoline, 1-(1-butyl)-2-ethylpyridine, 1-(1-hexyl)-2-ethylpyridine, 1-(1-octyl group)-2-ethylpyridine, 1-(1-dodecyl)-2-ethylpyridine, 1-(1-tetradecyl)-2-ethylpyridine, 1-(1-hexadecyl)-2-ethylpyridine, 1; 2-dimethyl--5-ethylpyridine, 1,5-diethylammonium-2-picoline, 1-(1-butyl)-2-methyl-3-ethylpyridine, 1-(1-hexyl)-2-methyl-3-ethylpyridine, 1-(1-octyl group)-2-methyl-3-ethylpyridine, 1-(1-dodecyl)-2-methyl-3-ethylpyridine, 1-(1-tetradecyl)-2-methyl-3-ethylpyridine and 1-(1-hexadecyl)-2-methyl-3-ethylpyridine.

Preferred very especially pyridazine ion (IIIb) be following those, wherein

● R ¹-R ⁴The hydrogen of respectively doing for oneself; Or

● radicals R ¹-R ⁴One of be methyl or ethyl and remaining radicals R ¹-R ⁴The hydrogen of respectively doing for oneself.

Preferred very especially pyridinium ion (IIIc) be following those, wherein

● R ¹Be hydrogen, methyl or ethyl and R ²-R ⁴Be hydrogen or methyl separately independently of each other; Or

● R ¹Be hydrogen, methyl or ethyl, R ²And R ⁴Methyl and R respectively do for oneself ³Be hydrogen.

Preferred very especially pyrazine ion (IIId) be following those, wherein

● R ¹Be hydrogen, methyl or ethyl and R ²-R ⁴Be hydrogen or methyl separately independently of each other;

● R ¹Be hydrogen, methyl or ethyl, R ²And R ⁴Methyl and R respectively do for oneself ³Be hydrogen;

● R ¹-R ⁴The methyl of respectively doing for oneself; Or

● R ¹-R ⁴Respectively do for oneself methyl or hydrogen.

Preferred very especially imidazol ion (IIIe) be following those, wherein

● R ¹Be hydrogen, methyl, ethyl, 1-propyl group, 1-butyl, 1-amyl group, 1-hexyl, 1-octyl group, 1-propylene-3-base or 2-cyano ethyl and R ²-R ⁴Be hydrogen, methyl or ethyl separately independently of each other.

As preferred very especially imidazol ion (IIIe), can mention 1-Methylimidazole, 1-ethyl imidazol(e), 1-(1-butyl) imidazoles, 1-(1-octyl group) imidazoles, 1-(1-dodecyl) imidazoles, 1-(1-tetradecyl) imidazoles, 1-(1-hexadecyl) imidazoles, 1,3-methylimidazole, 1-ethyl-3-Methylimidazole, 1-(1-butyl)-3-Methylimidazole, 1-(1-butyl)-3-ethyl imidazol(e), 1-(1-hexyl)-3-Methylimidazole, 1-(1-hexyl)-3-ethyl imidazol(e), 1-(1-hexyl)-3-NSC 158165,1-(1-octyl group)-3-Methylimidazole, 1-(1-octyl group)-3-ethyl imidazol(e), 1-(1-octyl group)-3-NSC 158165,1-(1-dodecyl)-3-Methylimidazole, 1-(1-dodecyl)-3-ethyl imidazol(e), 1-(1-dodecyl)-3-NSC 158165,1-(1-dodecyl)-3-octyl group imidazoles, 1-(1-tetradecyl)-3-Methylimidazole, 1-(1-tetradecyl)-3-ethyl imidazol(e), 1-(1-tetradecyl)-3-NSC 158165,1-(1-tetradecyl)-3-octyl group imidazoles, 1-(1-hexadecyl)-3-Methylimidazole, 1-(1-hexadecyl)-3-ethyl imidazol(e), 1-(1-hexadecyl)-3-NSC 158165,1-(1-hexadecyl)-3-octyl group imidazoles, 1; 2-methylimidazole, 1,2,3-tri-methylimidazolium, 1-ethyl-2; 3-methylimidazole, 1-(1-butyl)-2,3-methylimidazole, 1-(1-hexyl)-2,3-methylimidazole, 1-(1-octyl group)-2; 3-methylimidazole, 1; 4-methylimidazole, 1,3,4-tri-methylimidazolium, 1; 4-dimethyl--3-ethyl imidazol(e), 1; 4-dimethyl--3-NSC 158165,1,4-dimethyl--3-octyl group imidazoles, 1,4; 5-tri-methylimidazolium, 1; 3,4,5-tetramethyl-imidazoles, 1; 4; 5-trimethylammonium-3-ethyl imidazol(e), 1,4,5-trimethylammonium-3-NSC 158165,1; 4,5-trimethylammonium-3-octyl group imidazoles and 1-(third-1-alkene-3-yl)-3-Methylimidazole.

Preferred very especially pyrazoles ion (IIIf), (IIIg) and (IIIg ') be following those, wherein

● R ¹Be hydrogen, methyl or ethyl and R ²-R ⁴Be hydrogen or methyl separately independently of each other.

Preferred very especially pyrazoles ion (IIIh) be following those, wherein

● R ¹-R ⁴Be hydrogen or methyl separately independently of each other.

Preferred very especially 1-pyrazoline ion (IIIi) be following those, wherein

● R ¹-R ⁶Be hydrogen or methyl separately independently of each other.

Preferred very especially 2-pyrazoline ion (IIIj) and (IIIj ') be following those, wherein

● R ¹Be hydrogen, methyl, ethyl or phenyl and R ²-R ⁶Be hydrogen or methyl separately independently of each other.

Preferred very especially 3-pyrazoline ion (IIIk) and (IIIk ') be following those, wherein

● R ¹And R ²Be hydrogen, methyl, ethyl or phenyl and R separately independently of each other ³-R ⁶Be hydrogen or methyl separately independently of each other.

Preferred very especially tetrahydroglyoxaline ion (IIIl) be following those, wherein

● R ¹And R ²Be hydrogen, methyl, ethyl, 1-butyl or phenyl separately independently of each other, R ³And R ⁴Be hydrogen, methyl or ethyl and R separately independently of each other ⁵And R ⁶Be hydrogen or methyl separately independently of each other.

Preferred very especially tetrahydroglyoxaline ion (IIIm) and (IIIm ') be following those, wherein

● R ¹And R ²Be hydrogen, methyl or ethyl and R separately independently of each other ³-R ⁶Be hydrogen or methyl separately independently of each other.

Preferred very especially tetrahydroglyoxaline ion (IIIn) and (IIIn ') be following those, wherein

● R ¹-R ³Be hydrogen, methyl or ethyl and R separately independently of each other ⁴-R ⁶Be hydrogen or methyl separately independently of each other.

Preferred very especially thiazole ion (IIIo) and (IIIo ') Yi Ji oxazole ion (IIIp) be following those, wherein

● R ¹Be hydrogen, methyl, ethyl or phenyl and R ²And R ³Be hydrogen or methyl separately independently of each other.

Preferred very especially 1,2,4-three oxazolinium ions (IIIq), (IIIq ') and (IIIq ") be following those, wherein

● R ¹And R ²Be hydrogen, methyl, ethyl or phenyl and R separately independently of each other ³Be hydrogen, methyl or phenyl.

Preferred very especially 1,2,3-triazoles ion (IIIr), (IIIr ') and (IIIr ") be following those, wherein

● R ¹Be hydrogen, methyl or ethyl and R ²And R ³Be hydrogen or methyl or R separately independently of each other ²And R ³Be 1 together, 4-fourth-1,3-diene subunit.

Preferred very especially tetramethyleneimine ion (IIIs) be following those, wherein

● R ¹Be hydrogen, methyl, ethyl or phenyl and R ²-R ⁹Separately independently of each other for being hydrogen or methyl.

Preferred very especially imidazolidine ion (IIIt) be following those, wherein

● R ¹And R ⁴Be hydrogen, methyl, ethyl or phenyl and R separately independently of each other ²And R ³And R ⁵-R ⁸Be hydrogen or methyl separately independently of each other.

Preferred very especially ammonium ion (IIIu) be following those, wherein

● R ¹-R ³Be C separately independently of each other ₁-C ₁₈Alkyl; Or

● R ¹And R ²Be pentamethylene or 3-oxa--pentamethylene and R together ³Be C ₁-C ₁₈Alkyl or 2-cyano ethyl.

As preferred very especially ammonium ion (IIIu), can mention methyl three (1-butyl) ammonium, N, N-lupetidine and N, N-thebaine.

Through being diethylammonium-n-butylamine, diethylammonium-tert-butylamine, diethylammonium n-pentyl amine, diethylhexyl amine, diethylammonium octyl amine, diethylammonium (2-ethylhexyl) amine, di butylamine, di n-pentyl amine, di hexyl amine, di octyl amine, di (2-ethylhexyl) amine, diisopropyl ethyl amine, di-isopropyl n-propyl amine, di-isopropyl butylamine, di-isopropyl amylamine, di-isopropyl hexyl amine, di-isopropyl octyl amine, di-isopropyl (2-ethylhexyl) amine, di-n-butyl ethylamine, di-n-butyl n-propyl amine, di-n-butyl n-pentyl amine, di-n-butyl hexyl amine, di-n-butyl octyl amine, di-n-butyl (2-ethylhexyl) amine, N-n-butylpyrrolioine, N-sec.-butyl tetramethyleneimine, N-tertiary butyl tetramethyleneimine, N-n-pentyl tetramethyleneimine, N with the quaternized tertiary amine instance that derives the quaternary ammonium ion of general formula (IIIu) of said radicals R; N-dimethylcyclohexylam,ne, N; N-diethylammonium cyclo-hexylamine, N; N-di-n-butyl cyclo-hexylamine, N-n-propyl piperidines, N-sec.-propyl piperidines, N-normal-butyl piperidines, N-sec.-butyl piperidines, N-tertiary butyl piperidines, N-n-pentyl piperidines, N-normal-butyl morpholine, N-sec.-butyl morpholine, N-tertiary butyl morpholine, N-n-pentyl morpholine, N-benzyl-N-ethylaniline, N-benzyl-N-n-propyl aniline, N-benzyl-N-isopropyl aniline, N-benzyl-N-n-butyl aniline, N; N-dimethyl--para-totuidine, N; N-diethylammonium-para-totuidine, N, N-di-n-butyl-para-totuidine, diethylammonium benzyl amine, di benzyl amine, di-n-butyl benzyl amine, diethylammonium phenyl amine, di phenyl amine and di-n-butyl phenyl amine.

The quaternary ammonium ion of preferred general formula (IIIu) be can through by said radicals R quaternized and go out by following tertiary amines derived those; For example diisopropyl ethyl amine, diethylammonium tert-butylamine, di-isopropyl butylamine, di-n-butyl n-pentyl amine, N, N-di-n-butyl cyclo-hexylamine and the tertiary amine that is derived from the amyl group isomer.

Preferred especially tertiary amine is di-n-butyl n-pentyl amine and the tertiary amine that is derived from the amyl group isomer.The tertiary amine that further preferably has 3 identical groups is a triallylamine.

Preferred very especially guanidinium ion (IIIv) ' be following those, wherein

● R ¹-R ⁵The methyl of respectively doing for oneself.

As preferred very especially guanidinium ion (IIIv), can mention N, N, N ', N ', N ", N " hexamethyl guanidine.

Preferred very especially cholinium ion (IIIw) be following those, wherein

● R ¹And R ²Be methyl, ethyl, 1-butyl or 1-octyl group and R separately independently of each other ³Be methyl, ethyl or ethanoyl;

● R ¹Be methyl, ethyl, 1-butyl or 1-octyl group, R ²Be group-CH ₂-CH ₂-OR ⁴And R ³And R ⁴Be methyl, ethyl or ethanoyl separately independently of each other; Or

● R ¹Be group-CH ₂-CH ₂-OR ⁴, R ²Be group-CH ₂-CH ₂-OR ⁵And R ³-R ⁵Be methyl, ethyl or ethanoyl separately independently of each other.

Preferred especially cholinium ion (IIIw) be following those, R wherein ³Be selected from methyl, ethyl, ethanoyl, 5-methoxyl group-3-oxa-amyl group, 8-methoxyl group-3,6-dioxa octyl group, 11-methoxyl group-3,6; 9-trioxa undecyl, 7-methoxyl group-4-oxa-heptyl, 11-methoxyl group-4,8-dioxa undecyl, 15-methoxyl group-4,8; 12-trioxa pentadecyl, 9-methoxyl group-5-oxa-nonyl, 14-methoxyl group-5,10-oxa-tetradecyl, 5-oxyethyl group-3-oxa-amyl group, 8-oxyethyl group-3,6-dioxa octyl group, 11-oxyethyl group-3; 6; 9-trioxa undecyl, 7-oxyethyl group-4-oxa-heptyl, 11-oxyethyl group-4,8-dioxa undecyl, 15-oxyethyl group-4,8; 12-trioxa pentadecyl, 9-oxyethyl group-5-oxa-nonyl and 14-oxyethyl group-5,10-oxa-tetradecyl.

Very the other You Xuan of Te De Phosphonium ion (IIIx) be following those, wherein

● R ¹-R ³Be C separately independently of each other ₁-C ₁₈Alkyl, especially butyl, isobutyl-, 1-hexyl or 1-octyl group.

In above-mentioned heterocycle positively charged ion, preferred pyridinium ion, pyrazoline ion, pyrazoles ion, tetrahydroglyoxaline ion and imidazol ion.Also preferred ammonium ion.

Preferred especially 1-picoline, 1-ethylpyridine, 1-(1-butyl) pyridine, 1-(1-hexyl) pyridine, 1-(1-octyl group) pyridine, 1-(1-hexyl) pyridine, 1-(1-octyl group) pyridine, 1-(1-dodecyl) pyridine, 1-(1-tetradecyl) pyridine, 1-(1-hexadecyl) pyridine, 1; 2-lutidine, 1-ethyl-2-picoline, 1-(1-butyl)-2-picoline, 1-(1-hexyl)-2-picoline, 1-(1-octyl group)-2-picoline, 1-(1-dodecyl)-2-picoline, 1-(1-tetradecyl)-2-picoline, 1-(1-hexadecyl)-2-picoline, 1-methyl-2-ethylpyridine, 1; 2-parvoline, 1-(1-butyl)-2-ethylpyridine, 1-(1-hexyl)-2-ethylpyridine, 1-(1-octyl group)-2-ethylpyridine, 1-(1-dodecyl)-2-ethylpyridine, 1-(1-tetradecyl)-2-ethylpyridine, 1-(1-hexadecyl)-2-ethylpyridine, 1; 2-dimethyl--5-ethylpyridine, 1; 5-diethylammonium-2-picoline, 1-(1-butyl)-2-methyl-3-ethylpyridine, 1-(1-hexyl)-2-methyl-3-ethylpyridine, 1-(1-octyl group)-2-methyl-3-ethylpyridine, 1-(1-dodecyl)-2-methyl-3-ethylpyridine, 1-(1-tetradecyl)-2-methyl-3-ethylpyridine, 1-(1-hexadecyl)-2-methyl-3-ethylpyridine, 1-Methylimidazole, 1-ethyl imidazol(e), 1-(1-butyl) imidazoles, 1-(1-octyl group) imidazoles, 1-(1-dodecyl) imidazoles, 1-(1-tetradecyl) imidazoles, 1-(1-hexadecyl) imidazoles, 1,3-methylimidazole, 1-ethyl-3-Methylimidazole, 1-(1-butyl)-3-Methylimidazole, 1-(1-hexyl)-3-Methylimidazole, 1-(1-octyl group)-3-Methylimidazole, 1-(1-dodecyl)-3-Methylimidazole, 1-(1-tetradecyl)-3-Methylimidazole, 1-(1-hexadecyl)-3-Methylimidazole, DMIZ 1,2 dimethylimidazole, 1; 2; 3-tri-methylimidazolium, 1-ethyl-2,3-methylimidazole, 1-(1-butyl)-2,3-methylimidazole, 1-(1-hexyl)-2; 3-methylimidazole, 1-(1-octyl group)-2; 3-methylimidazole, 1,4-methylimidazole, 1,3; 4-tri-methylimidazolium, 1; 4-dimethyl--3-ethyl imidazol(e), 3-NSC 158165,1,4-dimethyl--3-octyl group imidazoles, 1,4; 5-tri-methylimidazolium, 1; 3,4,5-tetramethyl-imidazoles, 1; 4; 5-trimethylammonium-3-ethyl imidazol(e), 1,4,5-trimethylammonium-3-NSC 158165,1; 4,5-trimethylammonium-3-octyl group imidazoles and 1-(third-1-alkene-3-yl)-3-Methylimidazole.

As negatively charged ion, can use all negatively charged ion in principle.

Ion liquid negatively charged ion [Y] ^N-For example be selected from following group:

● the halogen ion of following formula and halogen contained compound group:

F ^-、Cl ^-、Br ^-、I ^-、BF ₄ ^-、PF ₆ ^-、CF ₃SO ₃ ^-、(CF ₃SO ₃) ₂N ^-、CF ₃CO ₂ ^-、CCl ₃CO ₂ ^-、CN ^-、SCN ^-、OCN ^-

● sulfate radical, inferior sulfate radical and the sulfonate radical of following general formula:

SO ₄ ^2-、HSO ₄ ^-、SO ₃ ^2-、HSO ₃ ^-、R ^aOSO ₃ ^-、R ^aSO ₃ ^-

● the phosphate radical of following general formula:

PO ₄ ^3-、HPO ₄ ^2-、H ₂PO ₄ ^-、R ^aPO ₄ ^2-、HR ^aPO ₄ ^-、R ^aR ^bPO ₄ ^-

● the phosphonate radical and the phospho acid root (phosphinate) of following general formula:

R ^aHPO ₃ ^-、R ^aR ^bPO ₂ ^-、R ^aR ^bPO ₃ ^-

● the orthophosphite of following general formula:

PO ₃ ^3-、HPO ₃ ^2-、H ₂PO ₃ ^-、R ^aPO ₃ ^2-、R ^aHPO ₃ ^-、R ^aR ^bPO ₃ ^-

● the phosphonous acid root and the Hypophosporous Acid, 50 root (phosphinite) of following general formula:

R ^aR ^bPO ₂ ^-、R ^aHPO ₂ ^-、R ^aR ^bPO ^-、R ^aHPO ^-

● the carboxylate radical of following general formula:

R ^aCOO ^-

● the borate of following general formula:

BO ₃ ^3-、HBO ₃ ^2-、H ₂BO ₃ ^-、R ^aR ^bBO ₃ ^-、R ^aHBO ₃ ^-、R ^aBO ₃ ^2-、B(OR ^a)(OR ^b)(OR ^c)(OR ^d) ^-、B(HSO ₄) ^-、B(R ^aSO ₄) ^-

● the organic boronic root (boronate) of following general formula:

R ^aBO ₂ ^2-、R ^aR ^bBO ^-

● the silicate and the silicon ester group of following general formula:

SiO ₄ ^4-、HSiO ₄ ^3-、H ₂SiO ₄ ^2-、H ₃SiO ₄ ^-、R ^aSiO ₄ ^3-、R ^aR ^bSiO ₄ ^2-、R ^aR ^bR ^cSiO ₄ ^-、HR ^aSiO ₄ ^2-、H ₂R ^aSiO ₄ ^-、HR ^aR ^bSiO ₄ ^-

● the alkyl silane and the aryl-silane salt group of following general formula:

R ^aSiO ₃ ^3-、R ^aR ^bSiO ₂ ^2-、R ^aR ^bR ^cSiO ^-、R ^aR ^bR ^cSiO ₃ ^-、R ^aR ^bR ^cSiO ₂ ^-、R ^aR ^bSiO ₃ ^2-

● carboxylic imide, two (alkylsulfonyl) imide and the alkylsulfonyl imide group of following general formula:

● the methide group of following general formula:

Here, R ^a, R ^b, R ^cAnd R ^dBe hydrogen, C separately independently of each other ₁-C ₃₀Alkyl, can choose wantonly by one or more non-adjacent oxygen and/or sulphur atom and/or one or more replacement or unsubstituted imino-C at interval ₂-C ₁₈Alkyl, C ₆-C ₁₄Aryl, C ₅-C ₁₂Naphthenic base or 5 or 6 Yuans heterocycles that contain oxygen, nitrogen and/or sulphur; Wherein two in them can also form together and can choose wantonly by one or more oxygen and/or sulphur atom and/or one or more the replacement or substituted imino-unsaturated, saturated or aromatic ring at interval, and wherein said group separately can be extra by suitable functional groups group, aryl, alkyl, aryloxy, alkoxyl group, halogen, heteroatoms and/or heterocyclic substituted.

Here, can choose wantonly by the C of suitable functional groups group, aryl, alkyl, aryloxy, alkoxyl group, halogen, heteroatoms and/or heterocyclic substituted ₁-C ₁₈Alkyl for example is methyl, ethyl, propyl group, sec.-propyl, normal-butyl, sec.-butyl, the tertiary butyl, amyl group, hexyl, heptyl, octyl group, 2-ethylhexyl, 2; 4; 4-tri-methyl-amyl, decyl, dodecyl, tetradecyl, heptadecyl, octadecyl, 1; 1-dimethyl propyl, 1; 1-dimethylbutyl, 1; 1; 3; 3-tetramethyl butyl, benzyl, 1-phenylethyl, α, α-Er Jiajibianji, diphenyl-methyl, p-methylphenyl methyl, 1-(to butyl phenyl) ethyl, p-chlorobenzyl, 2,4-dichloro benzyl, to methoxy-benzyl, m-oxethyl benzyl, 2-cyano ethyl, 2-cyanic acid propyl group, 2-methoxycarbonyl ethyl, 2-ethoxycarbonyl-ethyl, 2-butoxy carbonyl propyl group, 1; 2-two-(methoxycarbonyl) ethyl, 2-methoxy ethyl, 2-ethoxyethyl group, 2-butoxyethyl group, diethoxymethyl, diethoxy ethyl, 1; 3-dioxolane-2-base, 1,3-diox-2-base, 2-methyl isophthalic acid, 3-dioxolane-2-base, 4-methyl isophthalic acid; 3-dioxolane-2-base, 2-isopropoxy ethyl, 2-butoxy propyl group, 2-octyloxy ethyl, chloromethyl, trichloromethyl, trifluoromethyl, 1; 1-dimethyl--2-chloroethyl, 2-methoxyl group sec.-propyl, 2-ethoxyethyl group, butylthio methyl, 2-dodecyl sulfenyl ethyl, 2-thiophenyl ethyl, 2,2,2-trifluoroethyl, 2-dimethylaminoethyl, 2-dimethylamino-propyl, 3-dimethylamino-propyl, 4-dimethylamino butyl, 6-dimethylamino hexyl, 2-phenoxy ethyl, 2-phenoxy propyl, 3-phenoxy propyl, 4-phenoxy butyl, 6-phenoxy hexyl, 2-methoxy ethyl, 2-methoxy-propyl, 3-methoxy-propyl, 4-methoxyl group butyl, 6-methoxyl group hexyl, 2-ethoxyethyl group, 2-ethoxycarbonyl propyl, 3-ethoxycarbonyl propyl, 4-oxyethyl group butyl or 6-oxyethyl group hexyl.

Can choose wantonly by one or more non-adjacent oxygen and/or sulphur atom and/or one or more replacement or unsubstituted imino-C at interval ₂-C ₁₈Alkyl for example is 5-methoxyl group-3-oxa-amyl group, 8-methoxyl group-3,6-dioxa octyl group, 11-methoxyl group-3,6; 9-trioxa undecyl, 7-methoxyl group-4-oxa-heptyl, 11-methoxyl group-4,8-dioxa undecyl, 15-methoxyl group-4,8; 12-trioxa pentadecyl, 9-methoxyl group-5-oxa-nonyl, 14-methoxyl group-5,10-oxa-tetradecyl, 5-oxyethyl group-3-oxa-amyl group, 8-oxyethyl group-3,6-dioxa octyl group, 11-oxyethyl group-3; 6; 9-trioxa undecyl, 7-oxyethyl group-4-oxa-heptyl, 11-oxyethyl group-4,8-dioxa undecyl, 15-oxyethyl group-4,8; 12-trioxa pentadecyl, 9-oxyethyl group-5-oxa-nonyl or 14-oxyethyl group-5,10-oxa-tetradecyl.

If two group Cheng Huan, then these groups can form the condensed structural unit together, for example 1; 3-propylidene, tetramethylene, 2-oxa--trimethylene, 1-oxa--1; 3-propylidene, 2-oxa--propenylene, 1-azepine-propenylene, 1-C ₁-C ₄Alkyl-1-azepine-propenylene, 1,4-fourth-1,3-diene subunit, 1-azepine-1,4-fourth-1,3-diene subunit or 2-azepine-1,4-fourth-1,3-diene subunit.

The number of non-adjacent oxygen and/or sulphur atom and/or imino-does not receive any restriction in principle or receives this group automatically or the unitary limitation of size of ring texture.Usually in each group, exist to be no more than 5, preferably be no more than 4, very especially preferably be no more than 3.In addition, between any two heteroatomss, there are at least one carbon atom, preferably at least two carbon atoms usually.

Replacement and unsubstituted imino-for example can be imino-, methyl-imino, sec.-propyl imino-, normal-butyl imino-or tertbutylimido.

Term " functional group " for example refers to following groups: N, N-two (C ₁-C ₄Alkyl) carboxylic acid amides, two (C ₁-C ₄Alkyl) amino, C ₁-C ₄Carbalkoxy, cyanic acid or C ₁-C ₄Alkoxyl group.Here, C ₁-C ₄Alkyl is methyl, ethyl, propyl group, sec.-propyl, normal-butyl, sec.-butyl or the tertiary butyl.

Can choose wantonly by the C of suitable functional groups group, aryl, alkyl, aryloxy, alkoxyl group, halogen, heteroatoms and/or heterocyclic substituted ₆-C ₁₄Aryl for example is phenyl, tolyl, xylyl, Alpha-Naphthyl, betanaphthyl, 4-xenyl, chloro-phenyl-, dichlorophenyl, trichlorophenyl, difluorophenyl, aminomethyl phenyl, 3,5-dimethylphenyl, trimethylphenyl, ethylphenyl, diethylammonium phenyl, isopropyl phenyl, tert-butyl-phenyl, dodecylphenyl, p-methoxy-phenyl, Dimethoxyphenyl, ethoxyl phenenyl, hexyloxy phenyl, methyl naphthyl, sec.-propyl naphthyl, chloronaphthyl, methylnaphthyl, oxyethyl group naphthyl, 2; 6-3,5-dimethylphenyl, 2; 4; 6-trimethylphenyl, 2; 6-Dimethoxyphenyl, 2; 6-dichlorophenyl, 4-bromophenyl, 2-or 4-nitrophenyl, 2,4-or 2,6-dinitrophenyl, 4-dimethylamino phenyl, 4-acetylphenyl, methoxy ethyl phenyl or ethoxyl methyl phenyl.

Can choose wantonly by the C of suitable functional groups group, aryl, alkyl, aryloxy, alkoxyl group, halogen, heteroatoms and/or heterocyclic substituted ₅-C ₁₂Naphthenic base for example is cyclopentyl, cyclohexyl, ring octyl group, cyclo-dodecyl, methylcyclopentyl, dimethylcyclopentyl, methylcyclohexyl, Dimethylcyclohexyl, diethylammonium cyclohexyl, butyl cyclohexyl, methoxyl group cyclohexyl, dimethoxy cyclohexyl, diethoxy cyclohexyl, butylthio cyclohexyl, chloro cyclohexyl, dichloro cyclohexyl, the saturated or unsaturated bicyclic system of dichloro cyclopentyl such as norcamphyl or norbornene.

5 or 6 Yuans heterocycles that contain oxygen, nitrogen and/or sulphur for example are furyl, thienyl, pyrryl, pyridyl, indyl, benzoxazolyl, dioxolyl 、 dioxine base, benzimidazolyl-, benzothiazolyl, lutidine base, toluquinoline base, dimethyl pyrrole, methoxyl group furyl, dimethoxy-pyridine base, difluoro pyridine base, thiotolene base, sec.-propyl thienyl or tertiary butyl thienyl.

Preferred anionic surfactants is selected from halogen ion and halogen contained compound group, sulfate radical, inferior sulfate radical and sulfonate radical, phosphate radical and carboxylate radical, especially halogen ion and halogen contained compound group, carboxylate radical, SO ₄ ^2-, SO ₃ ^2-, R ^aOSO ₃ ^-And R ^aSO ₃ ^-And PO ₄ ^3-And R ^aR ^bPO ₄ ^-, especially preferred halogen ion and halogen contained compound group.

Preferred anionic surfactants is halogen ion such as cl ions, bromide anion, iodide ion especially, SCN ^-, OCN ^-, CN ^-, acetate moiety, propionate, benzoate anion, C ₁-C ₄Alkyl sulfate, R ^a-COO ^-, R ^aSO ₃ ^-, R ^aR ^bPO ₄ ^-, methanesulfonate, tosylate or two (C ₁-C ₄Alkyl) phosphate radical.

Special preferred anionic surfactants is Cl ^-, CH ₃COO ^-, C ₂H ₅COO ^-, C ₆H ₅COO ^-, CH ₃SO ₃ ^-, (CH ₃O) ₂PO ₂ ^-(C ₂H ₅O) ₂PO ₂ ^-

Especially preferred negatively charged ion is a cl ions.

In another preferred embodiment, use ionic liquid as shown in the formula I, wherein:

[A] _n ⁺Be 1-Methylimidazole, 1-ethyl imidazol(e), 1-(1-butyl) imidazoles, 1-(1-octyl group) imidazoles, 1-(1-dodecyl) imidazoles, 1-(1-tetradecyl) imidazoles, 1-(1-hexadecyl) imidazoles, 1,3-methylimidazole, 1-ethyl-3-Methylimidazole, 1-(1-butyl)-3-Methylimidazole, 1-(1-butyl)-3-ethyl imidazol(e), 1-(1-hexyl)-3-Methylimidazole, 1-(1-hexyl)-3-ethyl-imidazoles, 1-(1-hexyl)-3-NSC 158165,1-(1-octyl group)-3-Methylimidazole, 1-(1-octyl group)-3-ethyl imidazol(e), 1-(1-octyl group)-3-NSC 158165,1-(1-dodecyl)-3-Methylimidazole, 1-(1-dodecyl)-3-ethyl imidazol(e), 1-(1-dodecyl)-3-NSC 158165,1-(1-dodecyl)-3-octyl group imidazoles, 1-(1-tetradecyl)-3-Methylimidazole, 1-(1-tetradecyl)-3-ethyl imidazol(e), 1-(1-tetradecyl)-3-NSC 158165,1-(1-tetradecyl)-3-octyl group imidazoles, 1-(1-hexadecyl)-3-Methylimidazole, 1-(1-hexadecyl)-3-ethyl imidazol(e), 1-(1-hexadecyl)-3-NSC 158165,1-(1-hexadecyl)-3-octyl group imidazoles, DMIZ 1,2 dimethylimidazole, 1; 2,3-tri-methylimidazolium, 1-ethyl-2,3-methylimidazole, 1-(1-butyl)-2; 3-methylimidazole, 1-(1-hexyl)-2; 3-methylimidazole, 1-(1-octyl group)-2,3-methylimidazole, 1,4-methylimidazole, 1; 3; 4-tri-methylimidazolium, 1,4-dimethyl--3-ethyl imidazol(e), 1,4-dimethyl--3-NSC 158165,1; 4-dimethyl--3-octyl group imidazoles, 1; 4,5-tri-methylimidazolium, 1,3; 4; 5-tetramethyl-imidazoles, 1,4,5-trimethylammonium-3-ethyl imidazol(e), 1; 4; 5-trimethylammonium-3-NSC 158165,1,4,5-trimethylammonium-3-octyl group imidazoles and 1-(third-1-alkene-3-yl)-3-Methylimidazole; And

[Y] ^N+Be Cl ^-, CH ₃COO ^-, C ₂H ₅COO ^-, C ₆H ₅COO ^-, CH ₃SO ₃ ^-, (CH ₃O) ₂PO ₂ ^-Or (C ₂H ₅O) ₂PO ₂ ^-

In another preferred embodiment, use its negatively charged ion to be selected from HSO ₄ ^-, HPO ₄ ^2-, H ₂PO ₄ ^-And HR ^aPO ₄ ^-Especially HSO ₄ ^-Ionic liquid.

Especially use ionic liquid as shown in the formula I, wherein:

[A] _n ⁺Be 1-Methylimidazole, 1-ethyl imidazol(e), 1-(1-butyl) imidazoles, 1-(1-octyl group) imidazoles, 1-(1-dodecyl) imidazoles, 1-(1-tetradecyl) imidazoles, 1-(1-hexadecyl) imidazoles, 1,3-methylimidazole, 1-ethyl-3-Methylimidazole, 1-(1-butyl)-3-Methylimidazole, 1-(1-butyl)-3-ethyl imidazol(e), 1-(1-hexyl)-3-Methylimidazole, 1-(1-hexyl)-3-ethyl-imidazoles, 1-(1-hexyl)-3-NSC 158165,1-(1-octyl group)-3-Methylimidazole, 1-(1-octyl group)-3-ethyl imidazol(e), 1-(1-octyl group)-3-NSC 158165,1-(1-dodecyl)-3-Methylimidazole, 1-(1-dodecyl)-3-ethyl imidazol(e), 1-(1-dodecyl)-3-NSC 158165,1-(1-dodecyl)-3-octyl group imidazoles, 1-(1-tetradecyl)-3-Methylimidazole, 1-(1-tetradecyl)-3-ethyl imidazol(e), 1-(1-tetradecyl)-3-NSC 158165,1-(1-tetradecyl)-3-octyl group imidazoles, 1-(1-hexadecyl)-3-Methylimidazole, 1-(1-hexadecyl)-3-ethyl imidazol(e), 1-(1-hexadecyl)-3-NSC 158165,1-(1-hexadecyl)-3-octyl group imidazoles, DMIZ 1,2 dimethylimidazole, 1; 2,3-tri-methylimidazolium, 1-ethyl-2,3-methylimidazole, 1-(1-butyl)-2; 3-methylimidazole, 1-(1-hexyl)-2; 3-methylimidazole, 1-(1-octyl group)-2,3-methylimidazole, 1,4-methylimidazole, 1; 3; 4-tri-methylimidazolium, 1,4-dimethyl--3-ethyl imidazol(e), 1,4-dimethyl--3-NSC 158165,1; 4-dimethyl--3-octyl group imidazoles, 1; 4,5-tri-methylimidazolium, 1,3; 4; 5-tetramethyl-imidazoles, 1,4,5-trimethylammonium-3-ethyl imidazol(e), 1; 4; 5-trimethylammonium-3-NSC 158165,1,4,5-trimethylammonium-3-octyl group imidazoles or 1-(third-1-alkene-3-yl)-3-Methylimidazole; And

[Y] ^N+Be HSO ₄ ^-

In the methods of the invention, use the ionic liquid of a kind of formula I or the ion liquid mixture of formula I.The preferred ionic liquid that uses a kind of formula I.

In another embodiment of the present invention, can use the ionic liquid of a kind of formula II or the ion liquid mixture of formula II.The preferred ionic liquid that uses a kind of formula II.

In another embodiment of the present invention, can use the ion liquid mixture of formula I and formula II.

For the purpose of the present invention, vinyl ether is the vinyl ether of formula IV:

Wherein each group has following meanings:

R ^X, R ^YHydrogen, C respectively do for oneself ₁-C ₃₀Alkyl, C ₂-C ₃₀Alkenyl, C ₂-C ₃₀Alkynyl, C ₃-C ₁₂Naphthenic base, C ₅-C ₁₂Cycloalkenyl group, aryl or heterocyclic radical, wherein back seven groups can be chosen wantonly and be substituted;

R ^ZBe C ₁-C ₃₀Alkyl, C ₂-C ₃₀Alkenyl, C ₂-C ₃₀Alkynyl, C ₃-C ₁₂Naphthenic base, C ₅-C ₁₂Cycloalkenyl group, aryl or heterocyclic radical, wherein these seven groups can be chosen wantonly and be substituted;

Or

R ^XAnd R ^YForm together and choose substituted-(CH wantonly ₂) _o-X _p-(CH ₂) _q-or-the CH=CH-CH=CH-chain, wherein

X be O, S, S (=O), S (=O) ₂Or N (C ₁-C ₄Alkyl);

O, q respectively do for oneself 1,2,3,4,5 or 6;

P is 0 or 1;

Or

R ^XAnd R ^ZForm together and choose substituted-(CH wantonly ₂) _r-Y _s-(CH ₂) _t-chain, wherein

Y be O, S, S (=O), S (=O) ₂Or N (C ₁-C ₄Alkyl);

R, t respectively do for oneself 1,2,3,4,5 or 6;

S is 0 or 1.

Optional substituted C ₁-C ₃₀Alkyl R ^X, R ^YAnd R ^ZEspecially be unsubstituted C ₁-C ₃₀Alkyl or by the C of suitable functional groups group, aryl, alkyl, aryloxy, alkoxyl group, naphthenic base, halogen, heteroatoms and/or heterocyclic substituted ₁-C ₃₀Alkyl, preferred C ₁-C ₃₀Alkyl; Like methyl, ethyl, 1-propyl group, 2-propyl group, 1-butyl, 2-butyl, 2-methyl isophthalic acid-propyl group, 2-methyl-2-propyl group, 1-amyl group, 2-amyl group, 3-amyl group, 2-methyl-1-butene base, 3-methyl isophthalic acid-butyl, 2-methyl-2-butyl, 3-methyl-2-butyl, 2; 2-dimethyl--1-propyl group, 1-hexyl, 2-hexyl, 3-hexyl, 2-methyl-1-pentene base, 3-methyl-1-pentene base, 4-methyl-1-pentene base, 2-methyl-2-amyl group, 3-methyl-2-amyl group, 4-methyl-2-amyl group, 2-methyl-3-amyl group, 3-methyl-3-amyl group, 2; 2-dimethyl--1-butyl, 2; 3-dimethyl--1-butyl, 3; 3-dimethyl--1-butyl, 2-ethyl-1-butyl, 2,3-dimethyl--2-butyl, 3,3-dimethyl--2-butyl, heptyl, octyl group, 2-ethylhexyl, 2; 4; 4-tri-methyl-amyl, 1,1,3; 3-tetramethyl butyl, 1-nonyl, 1-decyl, 1-undecyl, 1-dodecyl, 1-tridecyl, 1-tetradecyl, 1-pentadecyl, 1-hexadecyl, 1-heptadecyl, 1-octadecyl and 1-eicosyl, special preferable methyl, ethyl, 1-propyl group, 1-butyl, 1-decyl, 1-dodecyl, 1-tetradecyl or 1-hexadecyl; Or preferably by the C of suitable functional groups group, aryl, alkyl, aryloxy, alkoxyl group, naphthenic base, halogen, heteroatoms and/or heterocyclic substituted ₁-C ₃₀Alkyl; For example cyano methyl, 2-cyano ethyl, 2-cyanic acid propyl group, methoxycarbonyl methyl, 2-methoxycarbonyl ethyl, ethoxycarbonylmethyl group, 2-ethoxycarbonyl-ethyl, 2-(butoxy carbonyl) ethyl, 2-butoxy carbonyl propyl group, 1; 2-two (methoxycarbonyl) ethyl, formyl radical, dimethylamino methyl, 2-dimethylaminoethyl, 2-dimethylamino-propyl, 3-dimethylamino-propyl, 4-dimethylamino butyl, 6-dimethylamino hexyl, phenoxymethyl, 2-phenoxy ethyl, 2-phenoxy propyl, 3-phenoxy propyl, 4-phenoxy butyl, 6-phenoxy hexyl, methoxymethyl, 2-methoxy ethyl, 2-methoxy-propyl, 3-methoxy-propyl, 4-methoxyl group butyl, 6-methoxyl group hexyl, ethoxyl methyl, 2-ethoxyethyl group, 2-ethoxycarbonyl propyl, 3-ethoxycarbonyl propyl, 4-oxyethyl group butyl, 6-oxyethyl group hexyl, 2-butoxyethyl group, 2-isopropoxy ethyl, 2-butoxy propyl group, 2-octyloxy ethyl, 2-methoxyl group sec.-propyl, dimethoxy-methyl, diethoxymethyl, 2; 2-diethoxymethyl, 2; 2-diethoxy ethyl, ethanoyl, propionyl group, C _mF _{2 (m-a)+(1-b)}H _2a+b, wherein m is 1-30,0≤a≤m and b=0 or 1 (CF for example ₃, C ₂F ₅, CH ₂CH ₂-C _(m-2)F _{2 (m-2)+1}, C ₆F ₁₃, C ₈F ₁₇, C ₁₀F ₂₁, C ₁₂F ₂₅), chloromethyl, 2-chloroethyl, trichloromethyl, 1,1-dimethyl--2-chloroethyl, methylthiomethyl, ethylmercapto group methyl, butylthio methyl, 2-dodecyl sulfenyl ethyl, 2-thiophenyl ethyl, 5-methoxyl group-3-oxa-amyl group, 8-methoxyl group-3; 6-dioxa octyl group, 11-methoxyl group-3,6,9-trioxa undecyl, 7-methoxyl group-4-oxa-heptyl, 11-methoxyl group-4; 8-dioxa undecyl, 15-methoxyl group-4,8,12-trioxa pentadecyl, 9-methoxyl group-5-oxa-nonyl, 14-methoxyl group-5; 10-dioxa tetradecyl, 5-oxyethyl group-3-oxa-amyl group, 8-oxyethyl group-3; 6-dioxa octyl group, 11-oxyethyl group-3,6,9-trioxa undecyl, 7-oxyethyl group-4-oxa-heptyl, 11-oxyethyl group-4; 8-dioxa undecyl, 15-oxyethyl group-4; 8,12-trioxa pentadecyl, 9-oxyethyl group-5-oxa-nonyl or 14-oxyethyl group-5,10-oxa-tetradecyl.

Optional substituted C ₂-C ₃₀Alkenyl R ^X, R ^YAnd R ^ZEspecially unsubstituted C ₂-C ₃₀Alkenyl or by the C of suitable functional groups group, aryl, alkyl, aryloxy, alkoxyl group, naphthenic base, halogen, heteroatoms and/or heterocyclic substituted ₂-C ₃₀Alkenyl, preferred C ₂-C ₃₀Alkenyl, for example vinyl, 2-propenyl, 3-crotonyl, cis-2-butene base or trans-2-butene base, preferred vinyl or 2-propenyl especially; Or preferably by the C of suitable functional groups group, aryl, alkyl, aryloxy, alkoxyl group, naphthenic base, halogen, heteroatoms and/or heterocyclic substituted ₂-C ₃₀Alkenyl, for example C _mF _{2 (m-a)-(1-b)}H _2a-b, wherein m≤30,0≤a≤m and b=0 or 1.

Optional substituted C ₂-C ₃₀Alkynyl R ^X, R ^YAnd R ^ZEspecially unsubstituted C ₂-C ₃₀Alkynyl or by the C of suitable functional groups group, aryl, alkyl, aryloxy, alkoxyl group, naphthenic base, halogen, heteroatoms and/or heterocyclic substituted ₂-C ₃₀Alkynyl; Preferred C ₂-C ₃₀Alkynyl such as ethynyl, 1-propine-3-base, 1-propine-1-base or 3-methyl isophthalic acid-propine-3-base, preferred especially ethynyl or 1-propine-3-base.

Optional substituted C ₃-C ₁₂Naphthenic base R ^X, R ^YAnd R ^ZEspecially unsubstituted C ₃-C ₈Naphthenic base or by the C of suitable functional groups group, aryl, alkyl, aryloxy, alkoxyl group, naphthenic base, halogen, heteroatoms and/or heterocyclic substituted ₃-C ₁₂Naphthenic base, preferred C ₃-C ₁₂Naphthenic base; For example cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, ring octyl group, cyclo-dodecyl, methylcyclopentyl, dimethylcyclopentyl, methylcyclohexyl, Dimethylcyclohexyl, diethylammonium cyclohexyl or butyl cyclohexyl and bicyclic system such as norcamphyl, preferred cyclopentyl or cyclohexyl; Or preferably by the C of suitable functional groups group, aryl, alkyl, aryloxy, alkoxyl group, naphthenic base, halogen, heteroatoms and/or heterocyclic substituted ₃-C ₁₂Naphthenic base, for example methoxyl group cyclohexyl, dimethoxy cyclohexyl, diethoxy cyclohexyl, butylthio cyclohexyl, chloro cyclohexyl, dichloro cyclohexyl, dichloro cyclopentyl, C _mF _{2 (m-a)-(1-b)}H _2a-b, wherein m≤30,0≤a≤m and b=0 or 1.

Optional substituted C ₅-C ₁₂Cycloalkenyl group R ^X, R ^YAnd R ^ZEspecially unsubstituted C ₃-C ₈Cycloalkenyl group or by the C of suitable functional groups group, aryl, alkyl, aryloxy, alkoxyl group, naphthenic base, halogen, heteroatoms and/or heterocyclic substituted ₃-C ₈Cycloalkenyl group, preferred C ₃-C ₈Cycloalkenyl group, for example 3-cyclopentenyl, 2-cyclohexenyl, 3-cyclohexenyl, 2,5-cyclohexadienyl, and bicyclic system such as norcamphyl, preferred especially 3-cyclopentenyl, 2-cyclohexenyl or 3-cyclohexenyl; Or preferably by the C of suitable functional groups group, aryl, alkyl, aryloxy, alkoxyl group, naphthenic base, halogen, heteroatoms and/or heterocyclic substituted ₃-C ₈Cycloalkenyl group, for example C _nF _{2 (m-a)-3 (1-b)}H _2a-3b, wherein m≤12,0≤a≤m and b=0 or 1.

Optional substituted aryl R ^X, R ^YAnd R ^ZEspecially unsubstituted C ₆-C ₁₂Aryl or by the C of suitable functional groups group, aryl, alkyl, aryloxy, alkoxyl group, naphthenic base, halogen, heteroatoms and/or heterocyclic substituted ₆-C ₁₂Aryl, preferred C ₆-C ₁₂Aryl, for example phenyl, Alpha-Naphthyl or betanaphthyl, especially preferably phenyl; Or preferably by the C of suitable functional groups group, aryl, alkyl, aryloxy, alkoxyl group, naphthenic base, halogen, heteroatoms and/or heterocyclic substituted ₆-C ₁₂Aryl; For example tolyl, xylyl, 4-xenyl, chloro-phenyl-, dichlorophenyl, trichlorophenyl, difluorophenyl, aminomethyl phenyl, 3,5-dimethylphenyl, trimethylphenyl, ethylphenyl, diethylammonium phenyl, isopropyl phenyl, tert-butyl-phenyl, dodecylphenyl, p-methoxy-phenyl, Dimethoxyphenyl, ethoxyl phenenyl, hexyloxy phenyl, methyl naphthyl, sec.-propyl naphthyl, chloronaphthyl, methylnaphthyl, oxyethyl group naphthyl, 2; 6-3,5-dimethylphenyl, 2; 4; 6-trimethylphenyl, 2,6-Dimethoxyphenyl, 2,6-dichlorophenyl, 4-bromophenyl, 2-nitrophenyl, 4-nitrophenyl, 2; 4-dinitrophenyl, 2,6-dinitrophenyl, 4-dimethylamino phenyl, 4-acetylphenyl, methoxy ethyl phenyl, ethoxyl methyl phenyl, thiotolene base, sec.-propyl thienyl or tertiary butyl thienyl or C ₆F _(5-a)H _a, 0≤a≤5 wherein, preferred especially 4-tolyl.

The optional especially unsubstituted heteroaryl of substituted heterocyclic radical or by the heteroaryl of suitable functional groups group, aryl, alkyl, aryloxy, alkoxyl group, naphthenic base, halogen, heteroatoms and/or heterocyclic substituted; 5 or 6 Yuans heteroaryls that preferably comprise oxygen, nitrogen and/or sulphur atom, for example furyl, thienyl, pyrryl, pyridyl, indyl, benzoxazolyl, dioxolyl, dioxine base, benzimidazolyl-or benzothiazolyl; Or preferably comprise oxygen, nitrogen and/or sulphur atom and by 5 or 6 Yuans heteroaryls of suitable functional groups group, aryl, alkyl, aryloxy, alkoxyl group, naphthenic base, halogen, heteroatoms and/or heterocyclic substituted, for example picolyl, lutidine base, toluquinoline base, dimethyl pyrrole, methoxyl group furyl, dimethoxy-pyridine base, chloro-pyridine base or difluoro pyridine base.

If R ^XAnd R ^YForm together and choose substituted-(CH wantonly ₂) _o-X _p-(CH ₂) _q-or-CH=CH-CH=CH-chain, then preferred-(CH ₂) _o-X _p-(CH ₂) _q-or-the CH=CH-CH=CH-chain, especially-(CH ₂) _o-(CH ₂) _q-chain, particularly-(CH ₂) ₅-or-(CH ₂) ₆-, or C ₁-C ₄Alkyl is substituted-(CH ₂) _o-X _p-(CH ₂) _q-or C ₁-C ₄Alkyl is substituted-CH=CH-CH=CH-chain, especially C ₁-C ₄Alkyl is substituted-(CH ₂) _o-(CH ₂) _q-chain, particularly C ₁-C ₄Alkyl is substituted-(CH ₂) ₅-or-(CH ₂) ₆-chain.

If R ^XAnd R ^ZForm together and choose substituted-(CH wantonly ₂) _r-Y _s-(CH ₂) _t-chain, then preferred-(CH ₂) _r-X _s-(CH ₂) _t-chain, preferred-(CH especially ₂) _r-(CH ₂) _t-chain, especially-(CH ₂) ₂-,-(CH ₂) ₃-or-(CH ₂) ₄-, especially preferably-(CH ₂) ₃-, or C ₁-C ₄Alkyl is substituted-(CH ₂) _r-Y _s-(CH ₂) _t-chain, preferred especially C ₁-C ₄Alkyl is substituted-(CH ₂) _r-(CH ₂) _t-chain, especially C ₁-C ₄Alkyl is substituted-(CH ₂) ₂-,-(CH ₂) ₃-or-(CH ₂) ₄-chain, especially preferred C ₁-C ₄Alkyl is substituted-(CH ₂) ₃-chain.

In embodiments of the invention, use each group wherein to have the vinyl ether of the formula IV of following meanings:

R ^XBe hydrogen or C ₁-C ₁₈Alkyl, preferred hydrogen or C ₁-C ₆Alkyl; Preferred especially hydrogen, methyl or ethyl;

Especially preferred hydrogen;

R ^YBe hydrogen;

R ^ZBe C ₁-C ₁₈Alkyl, preferred C ₁-C ₆Alkyl; Special preferable methyl, ethyl, 1-propyl group, 2-propyl group, 1-butyl, 2-butyl, 2-methyl isophthalic acid-propyl group, 2-methyl-2-propyl group.

In another embodiment, use each group wherein to have the vinyl ether of the formula IV of following meanings:

R ^XBe 1-decyl, 1-dodecyl, 1-tetradecyl or 1-hexadecyl;

R ^YBe hydrogen;

R ^XAnd R ^ZFormation-(CH together ₂) _r-(CH ₂) _t-chain, preferred-(CH ₂) ₂-,-(CH ₂) ₃-or-(CH ₂) ₄-chain, preferred-(CH especially ₂) ₃-chain;

R ^YBe hydrogen.

In Mierocrystalline cellulose acetalation of the present invention, can use the Mierocrystalline cellulose in wide region source with the form of rich cellulose, for example from cotton, flax, ramie, wheat straw, bacterium etc. or from timber or bagasse.

Yet the inventive method not only can be used to prepare the Mierocrystalline cellulose acetal, and can be used for preparing polysaccharide, oligose and disaccharides acetal and verivate thereof usually.The instance of polysaccharide comprises Mierocrystalline cellulose and semicellulose and starch, glycogen, VISOSE and tunicin.Other instances are polycondensates of D-fructose, inulin for example, and especially chitin, WOT Recovery Floc T and alginic acid.Sucrose is the instance of disaccharides.Suitable derivatived cellulose is those of DS＜3; Comprise ether of cellulose such as methylcellulose gum and CMC 99.5, cellulose ester such as rhodia, cellulose butyrate, Mierocrystalline cellulose silyl ether such as Mierocrystalline cellulose trimethyl silyl ether; And nitrocellulose, DS＜3 in each case.Be described in accordingly here and use similarly.

In one embodiment of the invention, make polysaccharide such as Mierocrystalline cellulose, semicellulose, starch, glycogen, VISOSE, tunicin, inulin, chitin or alginic acid, preferred cellulose is through the inventive method reaction.

In another embodiment of the present invention, disaccharides such as sucrose are reacted through the inventive method.

In another embodiment of the present invention; Make the derivatived cellulose reaction of DS＜3 through the inventive method; For example ether of cellulose such as methylcellulose gum or CMC 99.5, cellulose ester such as rhodia, cellulose butyrate, Mierocrystalline cellulose silyl ether such as Mierocrystalline cellulose trimethyl silyl ether; Or nitrocellulose, DS＜3 in each case.Here preferably use ether of cellulose such as methylcellulose gum and CMC 99.5, cellulose ester such as rhodia, cellulose butyrate and nitrocellulose.

Mierocrystalline cellulose is also referred to as " cellulosic acetalation " for the purpose of the present invention with the reaction that the vinyl ether of formula IV forms corresponding Mierocrystalline cellulose acetal; This can illustrate that as follows wherein " OH " is that cellulosic hydroxy functional group and " Cell " are the remainder of cellulosic molecule.

In the methods of the invention, the solution of preparation Mierocrystalline cellulose in ionic liquid.Here cellulosic concentration can change in wide region.Usually be 0.1-50 weight % based on this total solution weight, preferred 0.2-40 weight %, preferred especially 0.3-30 weight %, preferred very especially 0.5-20 weight %.

This dissolving program can be carried out under room temperature or heating, but temperature will be higher than ion liquid fusing point or softening temperature, is generally 0-200 ℃, and preferred 20-180 ℃, preferred 50-150 ℃ especially.Yet, can also be through brute force stirring or mixing or the combination accelerate dissolution of passing through to introduce microwave or ultrasonic energy or passing through these.

Vinyl ether with formula IV adds in the gained solution then.

The vinyl ether of formula IV can directly add or add as the solution in ionic liquid or suitable solvent.Suitable solvent for example is ethers such as ether, MTBE, THF Huo diox, or ketone such as dimethyl ketone, or halogenated hydrocarbon such as methylene dichloride, trichloromethane or ethylene dichloride.The quantity of solvent that is used for the vinyl ether of dissolution type IV should make and cellulosic deposition when feeding in raw material, not occur.Used ionic liquid is preferably Mierocrystalline cellulose itself and is dissolved in wherein those as stated.

If the vinyl ether of formula IV is gaseous state, then it can be used as in the solution of gas introducing Mierocrystalline cellulose in ionic liquid.

In particular embodiment, the vinyl ether of formula IV directly adds.

In another particular embodiment, the vinyl ether of formula IV adds as the solution in ionic liquid, and preferred especially use also is used for the ionic liquid of dissolving cellulos.

In another embodiment, the vinyl ether of premix ionic liquid and formula IV and Mierocrystalline cellulose is dissolved in this mixture.

Can also one or more other solvents be added in the reaction mixture or with the vinyl ether of ionic liquid or formula IV and introduce.Here possible solvent is to influence cellulosic deliquescent solvent sharply, for example non-proton dipole solvent such as methyl-sulphoxide, N, N,N-DIMETHYLACETAMIDE or tetramethylene sulfone.In addition, can extra adding nitrogenous base such as pyridine etc.

In particular embodiment; Reaction mixture comprises gross weight based on reaction mixture less than 5 weight % any solvent wherein except the vinyl ether of ionic liquid and formula IV has been dissolved in; Preferably less than 2 weight %, especially less than other solvents of 0.1 weight % and/or extra nitrogenous base.

Can also in the presence of catalyzer, carry out the inventive method.Appropriate catalyst here for example is acetate, propionic salt, benzoate, muriate, vitriol and the nitrate salt of mercury (II) salt such as mercury (II); Or acetate, propionic salt, muriate, nitrate salt and the benzoate of palladium (II) salt such as palladium (II) and with 1,10-phenanthroline monohydrate blended palladium (II) salt.Catalyzer usually based on the vinyl ether of formula IV with 20mol% at the most, the amount of preferred 5mol% is at the most used.

The reactivity that depends on the vinyl ether of used ionic liquid and used formula IV, this reaction preferred 20-180 ℃, is especially carried out under 50-150 ℃ the temperature usually at ion liquid fusing point to 200 ℃.

Vinyl ether at formula IV is being under the situation of liquid or solid under the temperature of reaction, and this reaction is carried out under environmental stress usually.Yet, also possibly advantageously under superatmospheric pressure, carry out sometimes, particularly when using the vinyl ether of volatile formula IV.Usually, this is reflected in the air and carries out.Yet, can also be at rare gas element (i.e. N for example ₂), carry out under rare gas or its mixture.

Vinyl ether at formula IV is being under the gasiform situation under the temperature of reaction, maybe be is advantageously carrying out this reaction under the autogenous pressure under the desired reaction temperature or be higher than under the pressure of autogenous pressure of reaction system carrying out this reaction at reaction mixture.

Yet, also possibly advantageously react the also vinyl ether of excessive use gasiform formula IV with the vinyl ether that is gasiform formula IV under temperature of reaction and environmental stress.

Vinyl ether is set as the function of cellulosic required substitution value with respect to used cellulosic consumption, reaction times and suitable words temperature of reaction in each case.

For example, if will the complete acetalation of on average being made up of u anhydroglucose unit of Mierocrystalline cellulose then be required the vinyl ether of the normal formula IV of 3u.Here the preferred vinyl ether (n that uses stoichiometric formula IV _{Vinyl ether}/ n _{Anhydroglucose unit}=3) or excessive use, be preferably based on the excessive 1000mol% at the most of u.

If will be with the Mierocrystalline cellulose part acetalation of on average forming by u anhydroglucose unit, the then common correspondingly consumption (n of the vinyl ether of adjustable type IV _{Vinyl ether}/ n _{Anhydroglucose unit}＜3).Ratio n _{Vinyl ether}/ n _{Anhydroglucose unit}More little, under the identical in other respects condition and same reaction under the time the plain average substitution degree of acetalized fiber more little.

In addition, can be when reaching required acetalation degree through from reaction mixture, isolating the plain acetalation that stop of acetalized fiber.This for example can through add excessive water or wherein plain insoluble but another suitable solvent that ionic liquid is prone to dissolve of acetalized fiber carry out, this solvent for example is a lower alcohol, like methyl alcohol, ethanol, propyl alcohol or butanols, or ketone, like metacetone etc., or its mixture.The selection of suitable solvent is also by corresponding substitution value on the Mierocrystalline cellulose and substituting group decision.Preferred excessive water or the methyl alcohol of using.

Reaction mixture is usually through precipitating the acetalized fiber element and leaching the acetalized fiber element and aftertreatment as stated.Ionic liquid can pass through ordinary method, the vinyl ether through steam removing volatile constituent such as precipitation agent or excessive formula IV or its hydrolysate etc. and reclaimed by filtrating.Residual ionic liquid can be used further in the inventive method.If in this reaction, use catalyzer, then this remains in the liquid phase and with ionic liquid recycling usually.In another embodiment, the vinyl ether of excessive formula IV can also remain in the ionic liquid and can be used further in the inventive method.

Yet; Can also reaction mixture introduced in the water or introduces another suitable solvent, the plain insoluble but ionic liquid of acetalized fiber be prone to dissolve in this solvent, and said solvent for example is a lower alcohol; Like methyl alcohol, ethanol, propyl alcohol or butanols; Or ketone such as metacetone etc., or its mixture, and depend on that specific embodiments obtains for example plain fiber, the film of acetalized fiber.The selection of suitable solvent is also by cellulosic corresponding substitution value and substituting group decision.Aftertreatment is filtrated as stated.

In addition, when reaching required acetalation degree, can also acetalation stopped and carrying out aftertreatment through reaction mixture.Aftertreatment can be carried out through aforesaid method.

Acetalation can also through distillation, stripping or use with ionic liquid form the biphase SX from reaction mixture, remove the formula IV that still exists vinyl ether and preset time point stop.

In another embodiment of the present invention, make the vinyl ether reaction of two kinds or more kinds of formula IV.The mode that at this moment, can be similar to said procedure is used the mixture of the vinyl ether of two kinds of (or more kinds of) formula IV.Yet, can also at first use first vinyl ether of formula IV to react to DS=a (＜3), use second vinyl ether of formula IV to react then, wherein a＜b≤3 to DS=b.

In this embodiment, obtain wherein cellulosic OH group by two (or more a plurality of) different O-CH (OR ^Z) (CHCR ^XR ^Y) group replaces the acetalized fiber of (as the function of the vinyl ether of used formula IV) plain.

If the circulation ionic liquid, then this ionic liquid can comprise 15 weight % at the most, preferably 10 weight %, the above-mentioned precipitation agent of 5 weight % especially at the most at the most.Yet, according to circumstances possibly use the vinyl ether of suitably excessive formula IV this moment.

This method can be in batches, semicontinuous or carry out continuously.

The present invention also provides polysaccharide, oligose or the disaccharides or derivatives thereof of acetalation; Especially acetalized fiber is plain; It can pass through polysaccharide, oligose or disaccharides or derivatives thereof; Especially Mierocrystalline cellulose is with the reaction and obtaining in the ionic liquid of formula I or II or its mixture of the vinyl ether of formula IV, in the vinyl ether of formula IV

Y be O, S, S (=O), S (=O) ₂Or N (C ₁-C ₄Alkyl);

R, t respectively do for oneself 1,2,3,4,5 or 6;

S is 0 or 1;

With

R ^YBe hydrogen, C ₁-C ₃₀Alkyl, C ₂-C ₃₀Alkenyl, C ₂-C ₃₀Alkynyl, C ₃-C ₁₂Naphthenic base, C ₅-C ₁₂Cycloalkenyl group, aryl or heterocyclic radical, wherein back seven groups can be chosen wantonly and be substituted.

Can be through for example being fit to produce moulded product, fiber and film and coating by vinyl ether acetalation polysaccharide or oligose, the especially Mierocrystalline cellulose of formula IV acetalation polysaccharide obtained by the method for the present invention or oligose, especially acetalized fiber element.Particularly advantageous is can the solubilized form processed products, changes into insoluble cross-linked form then.

Can also be through with s.t. acetalation polysaccharide or oligose, plain and crosslinked acetalation polysaccharide or the oligose that obtains by aforesaid method, especially acetalized fiber element of acetalized fiber especially.Can use inorganic or organic acid or its mixture as acid.

In a particular embodiment, this crosslinked utilization is plain with the acetalized fiber that obtains as stated as shown in the formula the vinyl ether reaction of IV through Mierocrystalline cellulose, and wherein each group has following meanings:

Or R ^XAnd R ^YForm together and choose substituted-(CH wantonly ₂) _o-X _p-(CH ₂) _q-or-the CH=CH-CH=CH-chain, wherein

X be O, S, S (=O), S (=O) ₂Or N (C ₁-C ₄Alkyl);

O, q respectively do for oneself 1,2,3,4,5 or 6;

P is 0 or 1.

In a particular embodiment, this crosslinked utilization is plain with the acetalized fiber that obtains as shown in the formula the reaction of the vinyl ether of IV through Mierocrystalline cellulose, and wherein each group has following meanings:

R ^XBe hydrogen or C ₁-C ₁₈Alkyl, preferred hydrogen or C ₁-C ₆Alkyl; More preferably hydrogen, methyl or ethyl; Hydrogen very preferably;

R ^YBe hydrogen;

R ^ZBe C ₁-C ₁₈Alkyl, preferred C ₁-C ₆Alkyl; More preferably methyl, ethyl, 1-propyl group, 2-propyl group, 1-butyl, 2-butyl, 2-methyl isophthalic acid-propyl group, 2-methyl-2-propyl group.

In another particular embodiment, this crosslinked utilization is plain with the acetalized fiber that obtains as shown in the formula the reaction of the vinyl ether of IV through Mierocrystalline cellulose, and wherein each group has following meanings:

R ^XBe 1-decyl, 1-dodecyl, 1-tetradecyl or 1-hexadecyl;

R ^YBe hydrogen;

Representative examples of mineral pigments is haloid acid such as HF, HCl, HBr or HI, high hydracid such as HClO ₄, hydracid such as HClO ₃, sulfur acid such as H ₂SO ₄, many sulfuric acid or H ₂SO ₃, nitrogen acid such as HNO ₃, or phosphoric acid such as H ₃PO ₄, Tripyrophosphoric acid or H ₃PO ₃Preferred haloid acid such as HCl or HBr, the H of using ₂SO ₄, HNO ₃Or H ₃PO ₄, especially HCl, H ₂SO ₄Or H ₃PO ₄

The organic acid instance is a carboxylic acid, as

● C ₁-C ₆Alkanoic acid, for example acetate, propionic acid, normal butane carboxylic acid or PIVALIC ACID CRUDE (25),

● dicarboxylicacid or poly carboxylic acid, for example succsinic acid, toxilic acid or fumaric acid,

● hydroxycarboxylic acid, for example oxyacetic acid, lactic acid, toxilic acid or Hydrocerol A,

● halogenated carboxylic acid, for example C ₁-C ₆The halogenated alkane carboxylic acid, for example fluoro acetate, chloracetic acid, monobromo-acetic acid, difluoroacetic acid, dichloro acetic acid, chlorine gifblaar poison, trifluoroacetic acid, trichoroacetic acid(TCA), 2-chloropropionic acid, perfluorinated acid or perfluorinated butane carboxylic acid,

● aromatic carboxylic acid, for example aryl carboxylic acid such as phenylformic acid;

Or sulfonic acid, as

● C ₁-C ₆Alkansulfonic acid, for example methylsulfonic acid or ethyl sulfonic acid,

● halogenosulfonic acid, for example C ₁-C ₆Halogenated alkane sulfonic acid such as trifluoromethanesulfonic acid,

● aromatic sulfonic acid, for example aryl sulfonic acid such as Phenylsulfonic acid or 4-aminomethyl phenyl sulfonic acid.

Preferably use C as organic acid ₁-C ₆Alkanoic acid, for example acetate or propionic acid, halogenated carboxylic acid, for example C ₁-C ₆The halogenated alkane carboxylic acid, like fluoro acetate, chloracetic acid, difluoroacetic acid, dichloro acetic acid, chlorine gifblaar poison, trifluoroacetic acid, trichoroacetic acid(TCA) or perfluorinated acid, or sulfonic acid such as C ₁-C ₆Alkansulfonic acid, for example methylsulfonic acid or ethyl sulfonic acid, halogenosulfonic acid, for example C ₁-C ₆Halogenated alkane sulfonic acid such as trifluoromethanesulfonic acid, or aryl sulfonic acid such as Phenylsulfonic acid or 4-aminomethyl phenyl sulfonic acid.Preferred acetate, chlorine gifblaar poison, trifluoroacetic acid, perfluorinated acid, methylsulfonic acid, trifluoromethanesulfonic acid or the 4-aminomethyl phenyl sulfonic acid of using.

Crosslinked can carrying out in every way.

In one embodiment, the Mierocrystalline cellulose acetal directly is applied on the inactive surfaces, for example uses, then through for example making the steam flow of acetate, HCl gas etc. cross the vapour cure that appropriate acid is used on this surface that scribbles the Mierocrystalline cellulose acetal as film.Concentration that this is sour and treatment time and treatment temp are set as the function of required degree of crosslinking.When reaching required degree of crosslinking, with the gained cross-linked cellulose with its insoluble therein solvent rinsing.Water or for example lower alcohol such as methyl alcohol, ethanol, propyl alcohol or butanols or ketone, metacetone etc. for example, or its mixture is fit to this purpose.This rinsing program can be carried out on the used inactive surfaces of beginning, but also can take out the gained formed body from inactive surfaces, then this formed body of rinsing.

In another embodiment, the Mierocrystalline cellulose acetal being dissolved in it dissolves in the solvent wherein.The solvent that is fit to this purpose is usually at the described ionic liquid of beginning.Yet, depend on acetal type, plain DS and the DP of acetalized fiber, can also use solvent such as aromatic hydrocarbon, like benzene, hydrochloric ether is like methylene dichloride, chloroform, 1,2-ethylene dichloride, ketone such as acetone, metacetone or ether such as THF or diox.Directly or with the solution form should acid add in this solution then.Crosslinked Mierocrystalline cellulose precipitates this moment usually.If situation is not like this, then adds crosslinked Mierocrystalline cellulose and be insoluble to solvent wherein.The solvent of suitable this purpose is water and lower alcohol such as methyl alcohol, ethanol, propyl alcohol or butanols, especially methyl alcohol especially.

In particular embodiment of the present invention, the reaction mixture that in the reaction of the vinyl ether of Mierocrystalline cellulose and formula IV, obtains with above-mentioned s.t..

In another embodiment, as stated the Mierocrystalline cellulose acetal being dissolved in it dissolves in the solvent wherein.Then this solution is introduced that water or crosslinked Mierocrystalline cellulose are insoluble to wherein but this solvent is soluble in wherein and has been added with another suitable solvent (for example lower alcohol such as methyl alcohol, ethanol, propyl alcohol or butanols or the ketone of acid; Like metacetone etc., or its mixture) in and depend on that this embodiment for example obtains the fiber of cross-linked cellulose, film etc.

In particular embodiment of the present invention, the reaction mixture that in the vinyl ether reaction of Mierocrystalline cellulose and formula IV, obtains is used above-mentioned s.t..

The consumption of acid is 0.001-10mol% based on the anhydroglucose unit number of used Mierocrystalline cellulose acetal.Preferred catalytic amount, the especially 0.1-0.001mol% of using.

This is crosslinked usually at 200 ℃ at the most, preferred 0-150 ℃, especially carries out under 10-100 ℃ the temperature.In specific embodiments, this is crosslinked at room temperature to carry out.

The cross-linked cellulose that is obtained by this method is new and is provided by the present invention equally.

Plain crosslinked (a) the intermolecular acetal that possibly cause forming of aforesaid acetalized fiber; Therefore it be bonded together various " cellulose chains "; And/or cause forming (b) intramolecularly acetal, promptly between the various anhydroglucose unit of " cellulose chain ", form acetal.This can be explained that wherein R representes H or CH (OR by following formula ^z)-CHR ^xR ^yAnd wherein intermolecular or intramolecularly bridge joint is not fixed in the position of giving an example, but can take place in other positions of specific anhydroglucose unit yet:

The following example explanation the present invention.

Preliminary explanation:

With Avicel PH 101 (Microcrystalline Celluloses; DP=463) 105 ℃ and 0.05 millibar of following dried overnight.

When stirring with this ionic liquid 120 ℃ and 0.05 millibar of following dried overnight.

All embodiment carry out under anhydrous argon gas atmosphere.

The average substitution degree DS of acetalized fiber element is by determination of elemental analysis.

Abbreviation:

BMIM Cl chlorination 1-butyl-3-Methylimidazole

BMMIM Cl chlorination 1-butyl-2, the 3-methylimidazole

DHP 3,4-dihydro (2H) pyrans

The AGU anhydroglucose unit

The DS average substitution degree

Embodiment 1:

Universal method

5-15ml BMIM Cl is placed the 25ml flask and when stirring under the temperature that table 1 is put down in writing, adds Avicel PH 101.After obtaining clear solution, under this temperature, add vinyl ether and suitable words catalyzer.Reaction mixture after the time that stirring table 1 is put down in writing under this temperature, is being cooled off this mixture and in vigorous stirring, adding methyl alcohol.The deposition that suction strainer forms is also dry under 70 ℃ and 0.05 millibar.

Table 1

Vinyl ether (IV)	The amount of vinyl ether [mmol]	n _(AGU)∶n _(vinyl _Ether)[mol/mol]	Catalyzer	Temperature [℃]	Reaction times [h]	Productive rate [%]	DS	Solvability
									Vinyl n-butyl ether	62.90	1∶19	Pd ^a)	80	29	71.4	2.32	CHCl ₃
Vinyl n-butyl ether	38.44	1∶18	Hg ^b)	90	74	82.6	2.24
									Vinyl isobutyl ether	73.00	1∶18	Pd ^a)	80	73	59.1	2.31 ^c)	CHCl ₃
DHP	54.68	1∶15	-	90	51	54.5	1.69 ^c)	CHCl ₃
									Vinyl n-butyl ether ^d)	5.09	1∶3	Pd ^a)	80	12	74.7	1.10 ^c)	CH ₃OH
Vinyl n-butyl ether ^d)	5.99	1∶3	Hg ^b)	80	18	71.2	1.51 ^c)	CH ₃OH

^A)Based on AGU is that the acetate Pd (II)+based on AGU of 5mol% is 1 of 5mol%, 10-phenanthroline monohydrate

^B)Based on AGU is the mercuric acetate (II) of 5mol%

^C)DS by the NMR spectrographic determination

^D)In this embodiment, make water replace methyl alcohol to carry out aftertreatment.

Embodiment 2

At room temperature the product (table 1 last column) with 0.5g embodiment 1 test 6 is dissolved in the 10ml methyl alcohol.Adding 0.01g concentration is 96% sulfuric acid under this temperature.In whipping process, form white precipitate immediately.With its suction strainer, wash 3 times (using 20ml methyl alcohol) at every turn and under 60 ℃ and 0.05 millibar, be dried to constant weight after 2 hours.

This product is insoluble to all conventional solvents (THF 、 diox, toluene, ETHYLE ACETATE, N, methyl-sulphoxide, methyl alcohol etc.).According to ultimate analysis, this product is for having 1.5 (＞CH-CH ₃) Mierocrystalline cellulose of bridge/AGU.

Embodiment 3:

In round-bottomed flask, add BMMIM Cl and under agitation add Avicel PH101 in 120 ℃.Obtain after the clear solution, add 16.55mmol DHP (n down at 120 ℃ _(AGU): n _(vinyl _Ether)[mol/mol]=1: 5) and be the acetate Pd (II) of 5mol% and be 1 of 5mol% based on AGU, 10-phenanthroline monohydrate based on AGU.Reaction mixture is being cooled off this mixture and under vigorous stirring, introducing methyl alcohol after 4 hours in stirring under 120 ℃.The deposition that suction strainer forms is also dry under 70 ℃ and 0.05 millibar.The DS that the Mierocrystalline cellulose acetal that so obtains has (by the NMR spectrographic determination) is 0.6 and dissolves in the methyl-sulphoxide.

Claims

1. the acetalation method of a polysaccharide, wherein polysaccharide is dissolved at least a ionic liquid and with the vinyl ether reaction, wherein with Mierocrystalline cellulose as polysaccharide, and said ionic liquid or its mixture are selected from formula I compound:

Wherein

N is 1,2,3 or 4;

[A] ⁺Be quaternary ammonium cation, oxygen

Positively charged ion, sulfonium cation or Positively charged ion; And

[Y] ^N-Be monovalence, divalence, trivalent or quadrivalent anion;

Or formula II compound:

[A ¹] ⁺[A ²] ⁺[Y] ^N-(IIa), n=2 wherein;

[A ¹] ⁺[A ²] ⁺[A ³] ⁺[Y] ^N-(IIb), n=3 wherein; Or

[A ¹] ⁺[A ²] ⁺[A ³] ⁺[A ⁴] ⁺[Y] ^N-(IIc), n=4 wherein,

Wherein

[A ¹] ⁺, [A ²] ⁺, [A ³] ⁺[A ⁴] ⁺Be independently selected from [A] ⁺The group of being mentioned; [Y] ^N-As above define.

2. according to the process of claim 1 wherein [A] ⁺For being selected from the positively charged ion of (IIIa)-(IIIy) compound:

And the oligopolymer that comprises these structures, wherein

● radicals R is hydrogen or has 1-20 carbon atom and can not be substituted or by 1-5 heteroatoms or suitable functional groups group at interval or substituted saturated or unsaturated, acyclic or cyclic aliphatic, aromatics or araliphatic organic carbonaceous group, wherein said suitable functional groups group refer to can with carbon atom or heteroatoms bonding and not with the functional group of vinyl ether reaction; With

● radicals R ¹-R ⁹Separately independently of each other for hydrogen, sulfo group or have 1-20 carbon atom and can not be substituted or rolled into a ball interval or substituted saturated or unsaturated, acyclic or cyclic aliphatic, aromatics or araliphatic organic carbonaceous group by 1-5 heteroatoms or suitable functional groups, wherein in following formula (III) with carbon atom bonding and not with the radicals R of heteroatoms bonding ¹-R ⁹Extraly can be halogen or suitable functional groups group, wherein said suitable functional groups group refer to can with carbon atom or heteroatoms bonding and not with the functional group of vinyl ether reaction; Or

Two are selected from R ¹-R ⁹Adjacent group can also form together and have 1-30 carbon atom and can not be substituted or at interval or substituted saturated or unsaturated, acyclic or cyclic aliphatic, aromatics or araliphatic divalence organic carbonaceous group by 1-5 heteroatoms or functional group, wherein said functional group refer to can with carbon atom or heteroatoms bonding and not with the functional group of vinyl ether reaction;

Wherein when IIIw is III, R ³Be not hydrogen.

3. according to the method for claim 2, wherein [Y] ^N-For being selected from following negatively charged ion:

● the halogen ion of following formula and halogen contained compound group:

● the phosphate radical of following general formula:

● the phosphonate radical and the phospho acid root of following general formula:

R ^aHPO ₃ ^-、R ^aR ^bPO ₂ ^-、R ^aR ^bPO ₃ ^-

● the orthophosphite of following general formula:

● the phosphonous acid root and the Hypophosporous Acid, 50 root of following general formula:

R ^aR ^bPO ₂ ^-、R ^aHPO ₂ ^-、R ^aR ^bPO ^-、R ^aHPO ^-

● the carboxylate radical of following general formula:

R ^aCOO ^-

● the borate of following general formula:

● the organic boronic root of following general formula:

R ^aBO ₂ ^2-、R ^aR ^bBO ^-

● the silicate and the silicon ester group of following general formula:

● the methide group of following general formula:

Radicals R wherein ^a, R ^b, R ^cAnd R ^dBe hydrogen, C separately independently of each other ₁-C ₃₀Alkyl, can choose wantonly by one or more non-adjacent oxygen and/or sulphur atom and/or one or more replacement or unsubstituted imino-C at interval ₂-C ₁₈Alkyl, C ₆-C ₁₄Aryl, C ₅-C ₁₂Naphthenic base or 5 or 6 yuan of heterocycles that contain oxygen, nitrogen and/or sulphur; Wherein two in them can also form together and can choose wantonly by one or more oxygen and/or sulphur atom and/or one or more the replacement or substituted imino-unsaturated, saturated or aromatic ring at interval; Wherein said group separately can be extra by suitable functional groups group, aryl, alkyl, aryloxy, alkoxyl group, halogen, heteroatoms and/or heterocyclic substituted, wherein said suitable functional groups group refer to can with carbon atom or heteroatoms bonding and not with the functional group of vinyl ether reaction.

4. according to the method for claim 3, wherein [A] ⁺For being selected from compound III a, IIIe, IIIf; The positively charged ion of IIIg, IIIg ', IIIh, IIIi, IIIj, IIIj ', IIIk, IIIk ', IIIl, IIIm, IIIm ', IIIn and IIIn '.

5. according to the method for claim 2, wherein [A] ⁺For being selected from the positively charged ion of compound III a, IIIe and IIIf.

6. according to the method for claim 4, wherein [Y] ^N-For being selected from halogenide and halogen contained compound group, carboxylate radical, SO ₄ ^2-, SO ₃ ^2-, R ^aOSO ₃ ^-And R ^aSO ₃ ^-And PO ₄ ^3-And R ^aR ^bPO ₄ ^-Negatively charged ion.

7. according to the process of claim 1 wherein [Y] ^N-Be cl ions.

8. according to each method among the claim 1-7, wherein with formula IV compound as vinyl ether:

Wherein each group has following meanings:

R ^ZBe C ₁-C ₃₀Alkyl, C ₂-C ₃₀Alkenyl, C ₂-C ₃₀Alkynyl, C ₃-C ₁₂Naphthenic base, C ₅-C ₁₂Ring

Thiazolinyl, aryl or heterocyclic radical, wherein these seven groups can be chosen wantonly and be substituted;

Or

X be O, S, S (=O), S (=O) ₂Or N (C ₁-C ₄Alkyl);

O, q respectively do for oneself 1,2,3,4,5 or 6;

P is 0 or 1;

Or

Y be O, S, S (=O), S (=O) ₂Or N (C ₁-C ₄Alkyl);

R, t respectively do for oneself 1,2,3,4,5 or 6;

S is 0 or 1.

9. according to Claim 8 method, each group of the vinyl ether of its Chinese style IV has following meanings:

R ^XBe hydrogen or C ₁-C ₁₈Alkyl;

R ^YBe hydrogen;

R ^ZBe C ₁-C ₁₈Alkyl.

10. according to the method for claim 9, R wherein ^XBe hydrogen or C ₁-C ₆Alkyl.

11. according to the method for claim 9, wherein R ^ZBe C ₁-C ₆Alkyl.

12. method according to Claim 8, each group of the vinyl ether of its Chinese style IV has following meanings:

R ^XBe 1-decyl, 1-dodecyl, 1-tetradecyl or 1-hexadecyl;

R ^YBe hydrogen;

R ^ZBe C ₁-C ₁₈Alkyl.

13. according to the method for claim 12, wherein R ^ZBe C ₁-C ₆Alkyl.

14. method according to Claim 8, each group of the vinyl ether of its Chinese style IV has following meanings:

R ^XAnd R ^ZFormation-(CH together ₂) _r-(CH ₂) _t-chain;

R ^YBe hydrogen.

15. according to the method for claim 14, wherein R ^XAnd R ^ZFormation-(CH together ₂) ₂-,-(CH ₂) ₃-or-(CH ₂) ₄-chain.

16. according to each method among the claim 1-7, wherein the concentration of polysaccharide in said ionic liquid is 0.1-50 weight % based on said total solution weight.

17. method according to Claim 8, wherein the concentration of polysaccharide in said ionic liquid is 0.1-50 weight % based on said total solution weight.

18., carry out under the wherein said temperature that is reflected at said ion liquid fusing point to 200 ℃ according to each method among the claim 1-7.

19. method is according to Claim 8 carried out under the wherein said temperature that is reflected at said ion liquid fusing point to 200 ℃.

20., carry out under the wherein said temperature that is reflected at said ion liquid fusing point to 200 ℃ according to the method for claim 16.

21. according to each method among the claim 1-7, the vinyl ether of wherein said formula IV based on the hydroxy number of polysaccharide with stoichiometric quantity or excessive use.

22. method according to Claim 8, the vinyl ether of wherein said formula IV based on the hydroxy number of polysaccharide with stoichiometric quantity or excessive use.

23. according to the method for claim 16, the vinyl ether of wherein said formula IV based on the hydroxy number of polysaccharide with stoichiometric quantity or excessive use.

24. according to the method for claim 18, the vinyl ether of wherein said formula IV based on the hydroxy number of polysaccharide with stoichiometric quantity or excessive use.

25. a method for preparing cross-linked cellulose, wherein Mierocrystalline cellulose is dissolved at least a ionic liquid according to each method among the claim 1-24 and with vinyl ether reaction and the product that obtains in this way with s.t..

26. according to the method for claim 25, the plain reaction product with vinyl ether of de-fibering wherein.

27. according to the method for claim 25, wherein Mierocrystalline cellulose is used s.t. with the reaction product of vinyl ether without separating.

28. according to each method among the claim 25-27, wherein with HCl, H ₂SO ₄, H ₃PO ₄, acetate, chlorine gifblaar poison, trifluoroacetic acid, perfluorinated acid, methylsulfonic acid or trifluoromethanesulfonic acid be as acid.