CN100547011C - The material and the manufacture method thereof that comprise crosslinked polyrotaxane - Google Patents
The material and the manufacture method thereof that comprise crosslinked polyrotaxane Download PDFInfo
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- CN100547011C CN100547011C CNB2005800132955A CN200580013295A CN100547011C CN 100547011 C CN100547011 C CN 100547011C CN B2005800132955 A CNB2005800132955 A CN B2005800132955A CN 200580013295 A CN200580013295 A CN 200580013295A CN 100547011 C CN100547011 C CN 100547011C
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Abstract
The invention provides a kind of more material that comprises crosslinked polyrotaxane of high swelling property that has, particularly provide a kind of swelling property to change the material that comprises crosslinked polyrotaxane that changes along with pH.In addition, the invention provides under a kind of situation of the electric field change at environment, this electric field is had responsiveness, particularly have the material that comprises crosslinked polyrotaxane of high-speed response.The invention provides a kind of material that comprises crosslinked polyrotaxane, this crosslinked polyrotaxane has the poly-rotaxane of at least 2 molecules, and the ring molecule of the poly-rotaxane of this at least 2 molecule is bonded to each other by chemical bond and forms crosslinked polyrotaxane, straight chain shape molecule is connected on the opening portion of ring molecule and disposes END CAPPED GROUP at two ends of described straight chain shape molecule with puncture shape bag and breaks away to prevent this ring molecule in the described poly-rotaxane, wherein, described ring molecule have hydroxyl (OH), and the group of the part of this hydroxyl with ionic group replace.
Description
Technical field
The present invention relates to comprise poly-rotaxane the be cross-linked to each other material and the manufacture method thereof of the crosslinked polyrotaxane that forms.The present invention be more particularly directed to comprise the material and the manufacture method thereof of crosslinked polyrotaxane, wherein, the contained OH base that ring molecule had is replaced to the group with ionic group in the poly-rotaxane.
Background technology
Poly-rotaxane is following formation: (runner: (axle: axis) two ends (two ends of straight chain shape molecule) that connect the poly-rotaxane of standard that forms with puncture shape bag dispose END CAPPED GROUP in case stop ring shape molecule breaks away to opening portion ratator) by straight chain shape molecule at ring molecule.For example, the use alpha-cylodextrin (below, sometimes cyclodextrin is abbreviated as " CD ") as ring molecule, use polyoxyethylene glycol (below, sometimes abbreviate " PEG " as) as the poly-rotaxane (for example with reference to patent documentation 1) of straight chain shape molecule owing to have various characteristics, so extensively carry out its research in recent years.
In addition, patent documentation 2 discloses and has so-calledly had as the characteristic of slippage gel or slip gel or as the compound that comprises crosslinked polyrotaxane of the characteristic of viscoelastic material.Particularly patent documentation 2 specifically discloses straight chain shape molecule PE G bag and has been connected on formed poly-rotaxane on ring molecule α-CD molecule by the be cross-linked to each other crosslinked polyrotaxane of (combination) of chemical bond.
Wherein, the higher swelling property of material requirements that comprises crosslinked polyrotaxane.For example, the variation that requires the swelling property of crosslinked polyrotaxane to be accompanied by the pH of the variation of the existing environment of crosslinked polyrotaxane, particularly environment and/or ionic strength has the material of bigger variation.In addition, under the situation that the electric field of the existing environment of crosslinked polyrotaxane changes, require this electric field is had responsiveness, particularly has a material of high-speed response.
Patent documentation 1: No. 2810264 communique of Japanese Patent Laid.
Patent documentation 2: No. 3475252 communique of Japanese Patent Laid.
Summary of the invention
The problem that invention will solve
Therefore, the objective of the invention is to address the above problem.
Particularly, the object of the present invention is to provide a kind of more material that comprises crosslinked polyrotaxane of high swelling property that has.The material that comprises crosslinked polyrotaxane that particularly provides a kind of swelling property to change along with the variation of pH and/or ionic strength.
In addition, except above-mentioned purpose, the present invention also aims to provide under a kind of situation of the electric field change at environment this electric field is had responsiveness, particularly has a material that comprises crosslinked polyrotaxane of high-speed response.
Be used to solve the method for problem
The present inventor has carried out meticulous research to achieve these goals, the at least a portion that found that the hydroxyl of the ring molecule by will constituting poly-rotaxane is replaced to the group with ionic group, thereby can control the characteristic of crosslinked polyrotaxane, particularly control swelling property, it is the solvent absorption characteristic, the variation of the swelling property (volume) that causes by pH and/or ionic strength, the behavior variation in electric field atmosphere gas etc.
More specifically, the present inventor finds can solve above-mentioned problem by following invention.
＜1〉a kind of material that comprises crosslinked polyrotaxane, wherein, this crosslinked polyrotaxane has the poly-rotaxane of at least 2 molecules, and the ring molecule of the poly-rotaxane of this at least 2 molecule is bonded to each other by chemical bond and forms crosslinked polyrotaxane, straight chain shape molecule is connected on the opening portion of ring molecule and disposes END CAPPED GROUP at two ends of described straight chain shape molecule with puncture shape bag and breaks away to prevent this ring molecule in the described poly-rotaxane, wherein, described ring molecule have hydroxyl (OH), and the part of this hydroxyl had at least a kind of group of ionic group that is selected from down in the group and replaced: (X represents hydrogen (H) to-COOX base, basic metal and other 1 valency metal),-SO
3X base (X and aforementioned same definition) ,-NH
2Base ,-NH
3X ' the base halide-ions of expression 1 valency (X ') ,-PO
4The base and-HPO
4Base.
＜2〉in above-mentioned＜1〉in, the group with ionic group can replace 10～90% in whole hydroxyls of whole ring molecules, preferably replaces 20～80%, more preferably replaces 30～70%.
＜3〉in above-mentioned＜1〉or＜2 in, the crosslinked polyrotaxane of every 1g absolute dry condition, this material can absorb the above solvent of 1000g, are preferably more than the 2000g, more preferably more than the 4000g.
＜4〉in above-mentioned＜1 〉～＜3 in each, the absorbed water-containing solvent is accompanied by the pH of this solvent and/or the variation of ionic strength, the volume of material can change, for example material is 2 o'clock at pH, and the absolutely dry crosslinked polyrotaxane of every 1g absorbs the above solvent of 5g, is preferably more than the 10g, more preferably more than the 50g, on the other hand, be 10 o'clock at pH, the absolutely dry crosslinked polyrotaxane of every 1g absorbs the above solvent of 500g, be preferably more than the 1000g, more preferably more than the 2000g.In addition, be 10 in ionic strength
-1During mol/L, the absolutely dry crosslinked polyrotaxane of every 1g absorbs the above solvent of 5g, more than being preferably 10g and being, more than the 50g, on the other hand, is 10 in ionic strength more preferably
-3During mol/L, the absolutely dry crosslinked polyrotaxane of every 1g absorbs the above solvent of 200g, is preferably more than the 500g, more preferably more than the 1000g.
＜5〉in above-mentioned＜1 〉～＜4 in each, the absorbed water-containing solvent has absorbed the material of solvent, its shape and/or volume can change according to electric field.Particularly, if ionic group is a cationic, the ring molecule that then has cationic is present in negative pole one side because of the electric field part, thereby the shape of material and/or volume can change, and is for example crooked; If perhaps ionic group is an anionic property, the ring molecule that then has an anionic property is an anodal side because of the electric field part is present in, thereby the shape of material and/or volume take place and can change, and is for example crooked.
＜6〉in above-mentioned＜1 〉～＜5 in each, ring molecule can be cyclodextrin molecular.
＜7〉in above-mentioned＜1 〉～＜5 in each, ring molecule is a cyclodextrin molecular, and this cyclodextrin molecular can be selected from the group that alpha-cylodextrin, beta-cyclodextrin and γ-Huan Hujing form.
＜8〉in above-mentioned＜1 〉～＜7 in each, straight chain shape molecule is selected from the group that polyoxyethylene glycol, polyisoprene, polyisobutene, polyhutadiene, polypropylene glycol, polytetrahydrofuran, polydimethylsiloxane, polyethylene and polypropylene form.
＜9〉in above-mentioned＜1 〉～＜8 in each; END CAPPED GROUP is selected from dinitrobenzene base class, cyclodextrin, diamantane base class, trityl class, fluoresceins, pyrene class, substituted benzene (as substituting group; can enumerate alkyl, alkoxyl group, hydroxyl, halogen, cyano group, alkylsulfonyl, carboxyl, amino, phenyl etc., but be not limited to these.Can there be 1 or a plurality of in substituting group.) can substituted polynuclear aromatic class (as substituting group, can enumerate substituting group same as described above, but be not limited to these.Can there be 1 or a plurality of in substituting group.) and the group formed of steroidal class in.In addition, be preferably selected from the group that dinitrobenzene base class, cyclodextrin, diamantane base class, trityl class, fluoresceins and pyrene class formed, be preferably diamantane base class or trityl class especially.
＜10〉in above-mentioned＜1 〉～＜9 in each, ring molecule is the alpha-cylodextrin molecule, described straight chain shape molecule is a polyoxyethylene glycol.
＜11〉in above-mentioned＜1 〉～＜10 in each, the amount of the cyclodextrin molecular that is connect by bag to greatest extent when described cyclodextrin molecular is connect with puncture shape bag by straight chain shape molecule was made as 1 o'clock, described cyclodextrin molecular with 0.001～0.6, be preferably 0.01～0.5, be more preferably 0.05～0.4 amount puncture shape bag and be connected on the straight chain shape molecule.
＜12〉in above-mentioned＜1 〉～＜9 in each, the poly-rotaxane of at least 2 molecules can pass through the linking agent Chemical bond.
＜13〉in above-mentioned＜1 〉～＜12 in each, the molecular weight of linking agent can be less than 2000, be preferably less than 1000, be more preferably less than 600, most preferably be less than 400.
＜14〉in above-mentioned＜12〉or＜13 in, linking agent can be selected from cyanuryl chloride, trimesoyl chloride, terephthalyl chloride, Epicholorohydrin, dibromobenzene, glutaraldehyde, phenylene diisocyanate, tolylene diisocyanate, divinyl sulfone, 1, in the group that 1 '-phosphinylidyne diimidazole and alkoxyl silicone alkanes are formed.
＜15〉in above-mentioned＜1 〉～＜14 in each, in the poly-rotaxane of at least 2 molecules, at least 1 OH base of at least 1 ring molecule of each poly-rotaxane participates in crosslinked.
＜16〉in above-mentioned＜1 〉～＜15 in each, the molecular weight of straight chain shape molecule is more than 10,000, is preferably more than 20,000, is more preferably more than 3.5 ten thousand.
＜17〉a kind of preparation methods that comprises crosslinked polyrotaxane, it is characterized in that, this preparation methods that comprises crosslinked polyrotaxane comprises: 1) accurate poly-rotaxane preparation section: mix ring molecule and straight chain shape molecule with OH base, preparation straight chain shape molecule is connected on the poly-rotaxane of standard of the opening portion of described ring molecule with puncture shape bag; 2) poly-rotaxane preparation section: two end-capped with the accurate poly-rotaxane of END CAPPED GROUP sealing break away from from the puncture state to prevent described ring molecule, thus the poly-rotaxane of preparation; With 3) crosslinked operation: the ring molecule separately of the poly-rotaxane of at least 2 molecules is bonded to each other by chemical bond and makes the poly-rotaxane of this at least 2 molecule crosslinked,
And the replacement operation that the part of the OH base of described ring molecule is replaced to the group with ionic group is arranged on: A) above-mentioned 1) before the accurate poly-rotaxane preparation section; B) above-mentioned 1) behind the accurate poly-rotaxane preparation section and above-mentioned 2) before the poly-rotaxane preparation section; C) above-mentioned 2) behind the poly-rotaxane preparation section and above-mentioned 3) before the crosslinked operation; And/or D) above-mentioned 3) after the crosslinked operation.
＜18〉a kind of preparation methods that comprises crosslinked polyrotaxane, it is characterized in that, this preparation methods that comprises crosslinked polyrotaxane comprises: 1) accurate poly-rotaxane preparation section: mix cyclodextrin molecular and straight chain shape molecule, preparation straight chain shape molecule is connected on the poly-rotaxane of standard of the opening portion of cyclodextrin molecular with puncture shape bag; 2) poly-rotaxane preparation section: two ends with the accurate poly-rotaxane of END CAPPED GROUP sealing break away from from the puncture state to prevent above-mentioned cyclodextrin molecular, thus the poly-rotaxane of preparation; With 3) crosslinked operation: the cyclodextrin molecular separately of the poly-rotaxane of at least 2 molecules is bonded to each other by chemical bond makes the poly-rotaxane of this at least 2 molecule crosslinked,
And the replacement operation that the part of the OH base of above-mentioned cyclodextrin molecular is replaced to the group with ionic group is arranged on: A) above-mentioned 1) before the accurate poly-rotaxane preparation section; B) above-mentioned 1) behind the accurate poly-rotaxane preparation section and above-mentioned 2) before the poly-rotaxane preparation section; C) above-mentioned 2) behind the poly-rotaxane preparation section and above-mentioned 3) before the crosslinked operation; And/or D) above-mentioned 3) after the crosslinked operation.
＜19〉in above-mentioned＜17〉or＜18 in, replace operation and can be arranged on above-mentioned 2) behind the poly-rotaxane preparation section and above-mentioned 3) before the crosslinked operation.
＜20〉in above-mentioned＜17 〉～＜19 in each, ionic group can be selected from-COOX base (X represents hydrogen (H), basic metal and other 1 valency metal) ,-SO
3X base (X and aforementioned same definition) ,-NH
2Base ,-NH
3X ' the base halide-ions of expression 1 valency (X ') ,-PO
4The base and-HPO
4In the group formed of base at least a kind.
＜21〉in above-mentioned＜17 〉～＜20 in each, the group with ionic group can replace 10～90% in whole hydroxyls of whole ring molecules, preferably replaces 20～80%, more preferably replaces 30～70%.
＜22〉in above-mentioned＜17 〉～＜21 in each, the crosslinked polyrotaxane of every 1g absolute dry condition, material can absorb the above solvent of 1000g, are preferably more than the 2000g, more preferably more than the 4000g.
＜23〉in above-mentioned＜17 〉～＜22 in each, the absorbed water-containing solvent, the volume of material can change along with the p H of this solvent and/or the variation of ionic strength, for example material is 2 o'clock at pH, the absolutely dry crosslinked polyrotaxane of every 1g can absorb the above solvent of 5g, be preferably more than the 10g, more preferably more than the 50g, on the other hand, at pH is 10 o'clock, the absolutely dry crosslinked polyrotaxane of every 1g can absorb the above solvent of 500g, is preferably more than the 1000g, more preferably more than the 2000g.In addition, be 10 in ionic strength
-1During mol/L, the absolutely dry crosslinked polyrotaxane of every 1g can absorb the above solvent of 5g, be preferably more than the 10g, and more than the 50g, on the other hand, be 10 more preferably in ionic strength
-3During mol/L, the absolutely dry crosslinked polyrotaxane of every 1g can absorb the above solvent of 200g, is preferably more than the 500g, more preferably more than the 1000g.
＜24〉in above-mentioned＜17 〉～＜23 in each, and the absorbed water-containing solvent, the shape and/or the volume that have absorbed the material of solvent can change according to electric field.Particularly, if ionic group is a cationic, the ring molecule that then has cationic is present in negative pole one side according to the electric field part, and thus, the shape of material and/or volume can change, and is for example crooked; If perhaps ionic group is an anionic property, the ring molecule that then has anionic property is present in an anodal side according to the electric field part, and thus, the shape of material and/or volume can change, and is for example crooked.
＜25〉in above-mentioned＜17 〉～＜24 in each, ring molecule can be cyclodextrin molecular.
＜26〉in above-mentioned＜17 〉～＜24 in each, ring molecule is a cyclodextrin molecular, and this cyclodextrin molecular can be selected from the group that alpha-cylodextrin, beta-cyclodextrin and γ-Huan Hujing form.
＜27〉in above-mentioned＜17 〉～＜26 in each, straight chain shape molecule is selected from the group that polyoxyethylene glycol, polyisoprene, polyisobutene, polyhutadiene, polypropylene glycol, polytetrahydrofuran, polydimethylsiloxane, polyethylene and polypropylene form.
＜28〉in above-mentioned＜17 〉～＜27 in each; END CAPPED GROUP is selected from dinitrobenzene base class, cyclodextrin, diamantane base class, trityl class, fluoresceins, pyrene class, substituted benzene (as substituting group; can enumerate alkyl, alkoxyl group, hydroxyl, halogen, cyano group, alkylsulfonyl, carboxyl, amino, phenyl etc., but be not limited to these.Can there be 1 or a plurality of in substituting group.), can substituted polynuclear aromatic class (, can enumerate substituting group same as described above, but be not limited to these as substituting group.Can there be 1 or a plurality of in substituting group.) and the group formed of steroidal class in.In addition, be preferably selected from the group that dinitrobenzene base class, cyclodextrin, diamantane base class, trityl class, fluoresceins and pyrene class formed, more preferably diamantane base class or trityl class.
＜29〉in above-mentioned＜17 〉～＜28 in each, ring molecule is the alpha-cylodextrin molecule, described straight chain shape molecule is a polyoxyethylene glycol.
＜30〉in above-mentioned＜17 〉～＜29 in each, the amount of the cyclodextrin molecular that is connect by bag to greatest extent when described cyclodextrin molecular is connect with puncture shape bag by straight chain shape molecule was made as 1 o'clock, described cyclodextrin molecular with 0.001～0.6, be preferably 0.01～0.5, be more preferably 0.05～0.4 amount puncture shape bag and be connected on the straight chain shape molecule.
＜31〉in above-mentioned＜17 〉～＜30 in each, the poly-rotaxane of at least 2 molecules can pass through the linking agent Chemical bond.
＜32〉in above-mentioned＜31〉in, the molecular weight of linking agent can be less than 2000, be preferably less than 1000, be more preferably less than 600, most preferably be less than 400.
＜33〉in above-mentioned＜31〉or＜32 in, linking agent can be selected from cyanuryl chloride, trimesoyl chloride, terephthalyl chloride, Epicholorohydrin, dibromobenzene, glutaraldehyde, phenylene diisocyanate, tolylene diisocyanate, divinyl sulfone, 1, in the group that 1 '-phosphinylidyne diimidazole and alkoxyl silicone alkanes are formed.
＜34〉in above-mentioned＜17 〉～＜33 in each, in the poly-rotaxane of at least 2 molecules, at least 1 OH base of at least 1 ring molecule of each poly-rotaxane can participate in crosslinked.
＜35〉in above-mentioned＜17 〉～＜34 in each, the molecular weight of straight chain shape molecule is more than 10,000, is preferably more than 20,000, is more preferably more than 3.5 ten thousand.
The invention effect
According to the present invention, can provide a kind of more material that comprises crosslinked polyrotaxane of high swelling property that has.The material that comprises crosslinked polyrotaxane that particularly can provide a kind of swelling property to change along with the variation of pH and/or ionic strength.
In addition, except above-mentioned effect,, can also provide under a kind of situation of the electric field change at environment, this electric field is had responsiveness, particularly have the material that comprises crosslinked polyrotaxane of high-speed response according to the present invention.
Description of drawings
Fig. 1 is the synoptic diagram of the change of shape of crosslinked polyrotaxane in electric field of expression embodiment 9.
Fig. 2 is that expression applies the dependent variable of the gel under the voltage condition of 35V and the chart of timing relationship to crosslinked polyrotaxane.
Embodiment
Below the present invention will be described in detail.
The invention provides a kind of material that comprises crosslinked polyrotaxane, wherein, this crosslinked polyrotaxane has the poly-rotaxane of at least 2 molecules, and the ring molecule of the poly-rotaxane of this at least 2 molecule is bonded to each other by chemical bond and forms crosslinked polyrotaxane, straight chain shape molecule is connected on the opening portion of ring molecule and disposes END CAPPED GROUP at two ends of described straight chain shape molecule with puncture shape bag and breaks away to prevent this ring molecule in the described poly-rotaxane, described ring molecule has hydroxyl, and (OH), the part of this hydroxyl is had the group replacement of ionic group.
To the ionic group of material of the present invention, so long as have ionic group, just there is no particular limitation, and ionic group for example can enumerate-COOX base (X represents hydrogen (H), basic metal and other 1 valency metal) ,-SO
3X (X and aforementioned same definition) ,-NH
2Base ,-NH
3X ' the base halide-ions of expression 1 valency (X ') ,-PO
4The base and-HPO
4Bases etc. can be selected from by a kind in these groups of forming at least.
Group with ionic group can replace 10～90% in whole hydroxyls of whole ring molecules, is preferably 20～80%, and more preferably 30～70%.
Material of the present invention produces following effect by having ionic group.That is,, increased hydratability or wetting ability with water, thereby improved solvent absorbing and/or swelling property by having ionic group.
In addition, by changing water contained in the material or changing aqueous pH of institute and/or ionic strength in the material, can change the dispersiveness of ring molecule on straight chain shape molecule with ionic group.Be accompanied by the change of this ring molecule dispersiveness, solvent absorbing and/or swelling property change.Particularly, be under the situation of cationic at ionic group, if pH uprises, then solvent absorbing and/or swelling property reduce.On the other hand, be under the situation of anionic property at ionic group, if p H uprises, then solvent absorbing and/or swelling property increase.
In addition, in electric field, under the situation of configuration material, think to produce following situation by electric field.
For example, by electric field, 1) dispersiveness of ring molecule on straight chain shape molecule with ionic group changes.Because the change of this dispersiveness, the shape and/or the volume of material change.Particularly, be under the situation of cationic at ionic group, the ring molecule part with cationic is present in negative pole one side.On the other hand, be under the situation of anionic property at ionic group, the ring molecule part with anionic property is present in an anodal side.Because such part exists, the shape and/or the volume of material change.More specifically, when the ring molecule part existed, the retractility of crosslinked polyrotaxane was restricted, therefore the part of the local material that exists of ring molecule is shunk, on the other hand, the other parts of material are not shunk, and therefore can cause the change of shape of materials such as material bending.
In addition, 2) electric field of configuration material is to exist under the situation of ionic field, and the ion in the material moves according to electric field, and it is poor to produce partial ionic strength in material.Material is according to ionic strength, and its swelling ratio is different.For example under the bigger situation of ionic strength, the swelling ratio of material is less, and on the other hand, under the less situation of ionic strength, it is big that the swelling ratio of material becomes.Therefore, if it is poor to produce partial ionic strength in material, then partial difference can take place in the swelling ratio of material, can cause the change of shape of materials such as material bending.
Material of the present invention, the crosslinked polyrotaxane of every 1g absolute dry condition can absorb the above solvent of 1000g, is preferably more than the 2000g, more preferably more than the 4000g.
Absorbed water-containing solvent particularly of the present invention, be accompanied by the pH of this solvent and/or the variation of ionic strength, the volume of material can change, and for example material is 2 o'clock at pH, the absolutely dry crosslinked polyrotaxane of every 1g can absorb the above solvent of 5g, be preferably more than the 10g, more preferably more than the 50g, on the other hand, at pH is 10 o'clock, the absolutely dry crosslinked polyrotaxane of every 1g can absorb the above solvent of 500g, is preferably more than the 1000g, more preferably more than the 2000g.In addition, be 10 in ionic strength
-1During mol/L, the absolutely dry crosslinked polyrotaxane of every 1g can absorb the above solvent of 5g, be preferably more than the 10g, and more than the 50g, on the other hand, be 10 more preferably in ionic strength
-3During mol/L, the absolutely dry crosslinked polyrotaxane of every 1g can absorb the above solvent of 200g, is preferably more than the 500g, more preferably more than the 1000g.
In addition, absorbed water-containing solvent of the present invention has absorbed the material of solvent, and its shape and/or volume can change according to electric field.Particularly, if ionic group is a cationic, the ring molecule that then has cationic is present in negative pole one side according to the electric field part, and thus, the shape of material and/or volume can change, for example crooked, if perhaps ionic group is an anionic property, the ring molecule that then has anionic property is present in an anodal side according to the electric field part, thus, the shape of material and/or volume can change, and be for example crooked.
In material of the present invention, ring molecule can be a cyclodextrin molecular.Cyclodextrin molecular can be selected from the group that alpha-cylodextrin, beta-cyclodextrin and γ-Huan Hujing form, and can be the alpha-cylodextrin molecule especially.
In material of the present invention, straight chain shape molecule is selected from the group that polyoxyethylene glycol, polyisoprene, polyisobutene, polyhutadiene, polypropylene glycol, polytetrahydrofuran, polydimethylsiloxane, polyethylene and polypropylene form, and can be polyoxyethylene glycol especially.
The molecular weight of straight chain shape molecule can be more than 10,000, is preferably more than 20,000, is more preferably more than 3.5 ten thousand.
In material of the present invention; END CAPPED GROUP is selected from dinitrobenzene base class, cyclodextrin, diamantane base class, trityl class, fluoresceins, pyrene class, substituted benzene (as substituting group; can enumerate alkyl, alkoxyl group, hydroxyl, halogen, cyano group, alkylsulfonyl, carboxyl, amino, phenyl, but be not limited to these.Can there be 1 or a plurality of in substituting group.), can substituted polynuclear aromatic class (, can enumerate material same as described above, but be not limited to these as substituting group.Can there be 1 or a plurality of in substituting group.) and the group formed of steroidal class in.In addition, be preferably selected from the group that dinitrobenzene base class, cyclodextrin, diamantane base class, trityl class, fluoresceins and pyrene class formed, be preferably diamantane base class or trityl class especially.
In material of the present invention, the bag amount of connecing of ring molecule can be following amount.Promptly, the amount of the cyclodextrin molecular that is connect by bag to greatest extent when cyclodextrin molecular is connect with puncture shape bag by straight chain shape molecule was made as 1 o'clock, and described cyclodextrin molecular can be with 0.001～0.6, be preferably 0.01～0.5, be more preferably 0.05～0.4 amount puncture shape bag is connected on the straight chain shape molecule.During near peaked state, the miles of relative movement of the ring molecule on the straight chain shape molecule has confined tendency in the bag amount of connecing of ring molecule.When miles of relative movement was limited, the degree of the volume change of material had confined tendency, so not preferred.
In addition, the maximum bag amount of connecing of ring molecule can be by the length of straight chain shape molecule and the thickness decision of ring molecule.For example, straight chain shape molecule is that polyoxyethylene glycol, ring molecule are that alpha-cylodextrin divides the period of the day from 11 p.m. to 1 a.m, the maximum bag amount of connecing by experiment try to achieve (with reference to Macromolecules1993,26,5698-5703.In addition, the content of the document is all included in this specification sheets).
In material of the present invention, the poly-rotaxane of at least 2 molecules can pass through the linking agent Chemical bond.
The molecular weight of linking agent can be less than 2000, be preferably less than 1000, be more preferably less than 600, most preferably be less than 400.
Linking agent can be selected from cyanuryl chloride, trimesoyl chloride, terephthalyl chloride, Epicholorohydrin, dibromobenzene, glutaraldehyde, phenylene diisocyanate, tolylene diisocyanate, divinyl sulfone, 1, in the group that 1 '-phosphinylidyne diimidazole and alkoxyl silicone alkanes are formed.
In material of the present invention, in the poly-rotaxane of at least 2 molecules, at least 1 OH base of at least 1 ring molecule of each poly-rotaxane participates in crosslinked.
The material that comprises crosslinked polyrotaxane of the present invention for example can be prepared as follows.It is characterized in that this method comprises: 1) accurate poly-rotaxane preparation section: mix cyclodextrin molecular and straight chain shape molecule, preparation straight chain shape molecule is connected on the poly-rotaxane of standard of the opening portion of cyclodextrin molecular with puncture shape bag; 2) poly-rotaxane preparation section: two ends with the accurate poly-rotaxane of END CAPPED GROUP sealing break away from from the puncture state to prevent described ring molecule, thus the poly-rotaxane of preparation; With 3) crosslinked operation: the ring molecule separately of the poly-rotaxane of at least 2 molecules is bonded to each other by chemical bond and makes the poly-rotaxane of this at least 2 molecule crosslinked,
And the replacement operation that the part of the OH base of cyclodextrin molecular is replaced to the group with ionic group is arranged on: A) above-mentioned 1) before the accurate poly-rotaxane preparation section; B) above-mentioned 1) behind the accurate poly-rotaxane preparation section and above-mentioned 2) before the poly-rotaxane preparation section; C) above-mentioned 2) behind the poly-rotaxane preparation section and above-mentioned 3) before the crosslinked operation; And/or D) above-mentioned 3) after the crosslinked operation.
The part of the OH base that ring molecule had is arranged on above-mentioned A by the replacement operation that ionic group replaces)～interim during D) any, perhaps also can be arranged on A)～D) 2 above periods.
In addition, in above-mentioned preparation method, employed ring molecule, straight chain shape molecule, END CAPPED GROUP etc. can be used above-mentioned material.
The preferred operation that replaces is arranged on 2) behind the poly-rotaxane preparation section and 3) before the crosslinked operation.
Employed condition depends on the ionic group of replacement in the replacement operation, and there is no particular limitation, can use various reaction methods, reaction conditions.For example, with one of above-mentioned carboxyl as under the situation of ionic group, its method can be enumerated the addition of the oxidation of primary hydroxyl, the ether derivantization of primary and secondary hydroxyl (comprising carboxymethylation carboxyethylation etc.), succinyl oxide maleic anhydride and/or its derivative etc., but is not limited to these.
Below, based on embodiment, the present invention will be described in more detail, but the present invention is not limited to present embodiment.
Embodiment 1
The preparation of the poly-rotaxane (carboxymethylation is gathered rotaxane) of＜importing carboxyl 〉
Prepare polyoxyethylene glycol (molecular weight: 35000) bag (the bag amount of connecing: the poly-rotaxane (in addition, END CAPPED GROUP is the diamantane group) that forms of individual α-CD about 25%) that connects 90～100.Dissolving bit by bit adds 10g fines shape sodium hydroxide after 1g should gather rotaxane in 80ml dimethyl sulfoxide (DMSO) (DMSO), and high degree of agitation 1 hour under Ar atmosphere gas makes its homodisperse then, makes and gathers rotaxane preparation liquid.In addition, the solution for preparing dissolving 0.8g monochloro acetate (or monochloro sodium acetate) in the DMSO of 20ml separately.Prepare to drip this solution in the liquid at poly-rotaxane, at room temperature react diel.After reaction finished, dropwise reaction liquid in 300～400ml of high degree of agitation pure water was used in the 50ml 5N hydrochloric acid rapidly and excessive sodium hydroxide.By after using pure water to dialyse to make with extra care sample, lyophilize makes the part quilt-CH of the OH base of α-CD
2Poly-rotaxane (PR-1) 1.19g of the carboxymethylation that the COOH base replaces.
＜import sulfonic poly-rotaxane (sulfoethylization is gathered rotaxane) preparation 1
Make poly-rotaxane similarly to Example 1 and prepare liquid.In addition, the solution for preparing dissolving 1.8g bromoethane sodium in the DMSO of 20m1 separately.Prepare to drip this solution in the liquid at above-mentioned poly-rotaxane, at room temperature react diel.After reaction finished, dropwise reaction liquid in 300～400ml of high degree of agitation pure water was used in the 5N hydrochloric acid of 50ml rapidly and excessive sodium hydroxide.By after using pure water to dialyse to make with extra care sample, lyophilize, make α-CD-the part quilt-(CH of OH base
2)
2-SO
3Poly-rotaxane (PR-2) 0.96g of the sulfoethylization that the Na base replaces.
＜import sulfonic poly-rotaxane (sulfoethylization is gathered rotaxane) preparation 2
Except the molecular weight of polyoxyethylene glycol is 500000, makes poly-rotaxane similarly to Example 1 and prepare liquid (α-CD amount: about 1500, α-CD wraps the amount of connecing: about 25%).In addition, the solution for preparing dissolving 2g bromoethane sodium in the DMSO of 20ml separately.Prepare to drip this solution in the liquid at above-mentioned poly-rotaxane, at room temperature react diel.After reaction finished, dropwise reaction liquid in 300～400ml of high degree of agitation pure water was used in the 5N hydrochloric acid of 50ml rapidly and excessive sodium hydroxide.By after using pure water to dialyse to make with extra care sample, lyophilize, make α-CD-the part quilt-(CH of OH base
2)
2-SO
3The poly-rotaxane of the sulfoethylization that the Na base replaces (PR-2 ') 0.90g.
The preparation of the poly-rotaxane (aminoethylization is gathered rotaxane) that＜importing is amino 〉
Make poly-rotaxane similarly to Example 1 and prepare liquid.In addition, the solution for preparing dissolving 3g bromotrifluoromethane brometo de amonio in the DMSO of 20ml separately.Prepare to drip this solution in the liquid at above-mentioned poly-rotaxane, at room temperature react diel.After reaction finished, dropwise reaction liquid in 300～400ml of high degree of agitation pure water was used in the 5N hydrochloric acid rapidly and excessive sodium hydroxide.By after using pure water to dialyse to make with extra care sample, lyophilize makes the part quilt-(CH of the OH base of α-CD
2)
2-NH
2Poly-rotaxane (PR-3) 0.90g of the aminoethylization that base replaces.
Embodiment 5
＜prepare crosslinked polyrotaxane and characteristic thereof by the poly-rotaxane PR-1 of carboxymethylation 〉
Poly-rotaxane PR-1 is dissolved in the 0.1N NaOH aqueous solution of 1mL with the 250mg carboxymethylation, adds 20 μ L divinylsulfones again, carries out crosslinking reaction.Left standstill 1 hour, and after the affirmation gelation, be impregnated into a large amount of salt solutions repeatedly and (in 0.01～0.1N), remove unreacted reagent and NaOH, make the poly-rotaxane CPR-1 of cross-linked carboxymethylization.
The poly-rotaxane CPR-1 of impregnated crosslinked carboxymethylation makes its swelling in pure water.Pure water around changing repeatedly makes its swelling until reaching balance.Fully after the swelling, on the nylon screen of 120 * 132 sieve meshes, anhydrate branch 10 minutes of drop, gravimetry w1.Resulting swelling thing is carried out lyophilize, gravimetry w2.
Swelling ratio Q (Q=w1/w2) is 2678.
＜prepare crosslinked polyrotaxane and characteristic thereof by the poly-rotaxane PR-2 of sulfoethylization 〉
Poly-rotaxane PR-2 is dissolved among the 0.1N NaOH of 1mL with the 250mg sulfoethylization, adds 20 μ L divinylsulfones again, carries out crosslinking reaction.Left standstill 1 hour, and after the affirmation gelation, be impregnated into a large amount of salt solutions repeatedly and (in 0.01～0.1N), remove unreacted reagent and NaOH, make the poly-rotaxane CPR-2 of crosslinked sulfoethylization.
The poly-rotaxane CPR-2 of impregnated crosslinked sulfoethylization makes its swelling in pure water.Pure water around changing repeatedly makes its swelling until reaching balance.Fully after the swelling, on the nylon screen of 40 sieve meshes, anhydrate branch 10 minutes of drop, gravimetry w1.Resulting swelling thing is carried out lyophilize, gravimetry w2.
Swelling ratio Q (Q=w1/w2) is 851.
Embodiment 7
＜by poly-rotaxane PR-2 ' preparation crosslinked polyrotaxane of sulfoethylization and characteristic thereof 〉
Poly-rotaxane PR-2 ' is dissolved among the DMSO of 1mL with the 150mg sulfoethylization, adds 30mg phosphinylidyne diimidazole again, fully stirs.After the stirring, deaeration was under reduced pressure placed 1～3 day down at 50 ℃, carried out crosslinked.After confirming gelation, be impregnated into a large amount of salt solutions repeatedly and (in 0.01～0.1N), remove unreacted reagent and DMSO, make the poly-rotaxane CPR-2 ' of crosslinked sulfoethylization.
＜by the swelling ratio of the crosslinked polyrotaxane of the poly-rotaxane PR-2 ' preparation of sulfoethylization.The variation that ionic strength is brought 〉
Poly-rotaxane CPR-2 ' is immersed in the NaCl aqueous solution of 1wt%, 0.1wt% and 0.01wt% repeatedly with the crosslinked sulfoethylization that obtains among the embodiment 7, it is swelling to reaches balance.Fully after the swelling, on the nylon screen of 120 * 130 sieve meshes, anhydrate branch 10 minutes of drop, gravimetry w ' 1.Resulting swelling thing is carried out lyophilize or dry at the moisture eliminator of having put into silica gel, measure dry weight w ' 2.Try to achieve liquid absorption w ' and swelling ratio Q ' (weight of the contained liquid of 1g polymkeric substance) according to following formula.
w’＝(w’1-w’2)/(c/100)
Q’＝w’/(w’1-w’)
In the formula, c is the concentration (wt%) of the salt solution of use in each experiment.Resulting swelling ratio Q ' is shown in table 1.
As shown in Table 1, reduce, be ionic strength when diminishing that swelling ratio improves when the concentration of salt solution.
The relation of concentration of table 1. salt solution (ionic concn) and swelling ratio
| The concentration wt% of salt solution | 1 | 0.1 | 0.01 |
| Swelling ratio g/g | 1.70 | 52.3 | 245 |
Embodiment 9
The bending of＜electric field intermediate ion crosslinked polyrotaxane 〉
The ionic crosslinked polyrotaxane CPR-2 that obtains among the embodiment 6 is cut into 2.5 * 2.5 * 24mm or 3 * 4 * 32mm, at the Na of 0.01M
2CO
3Flood in the aqueous solution.As shown in Figure 1, parallel setting is made by the platinum plate in liquid 2 electrodes 1 and 2 are provided with gel 3 in interelectrode central authorities, make that the long limit of gel 3 is parallel with battery lead plate (referring to Fig. 1 (a)).
When counter electrode applied the voltage of 35V, shown in Fig. 1 (b), gel bent with interior at 2 minutes, and two ends are near cathode direction.If continue to apply voltage, then Wan Qu gel reverts to linearity (referring to Fig. 1 (c)) soon, if continue to apply, then bends again, and two ends are near positive extreme direction.
The size and the time relation of the bending the when sample that is cut into 3 * 4 * 32mm is applied the voltage of 35V shown in Figure 2.Wherein, strain (Srain) is defined as 6DY/L
2(to the bending of cathode direction referring to Fig. 1 (b)), wherein, Y (mm) is with to being bent into positive number of cathode direction and the displacement (Deflection) that defines, the width (4mm) that D is gel, the length (32mm) that L is gel.In addition, the displacement Y of the two ends of gel when cathode side is crooked is defined as positive displacement (referring to the Y of Fig. 1 (b)).
Can also know by Fig. 2, when applying voltage,, revert to linearity then, then to the side of the positive electrode bending at first to the cathode side bending.
In addition, in the cathode side bending, if with voltage direction conversely, then test portion moves round about, than the more Zao linearity (Zao about 30 seconds～1 minute) that reverts to of voltage condition that continues to apply a direction at sample.
(comparative example 1)
Shiga et al., J.Appl.Polym.Sci.44,249-253 (1992) and Shiga et al., J.Appl.Polym.Sci.47,113-119 (1993) (in addition, the full content of these documents is introduced in this specification sheets as a reference) put down in writing the electric field (Na of the gel that uses poly-(vinyl alcohol)-polyacrylic acid soda (PVA-PAA gel, diameter is about 8mm, length is the bar-shaped material of 80mm) at 10～30V/cm
2CO
3The aqueous solution) bend in.Strain during known maximum deflection is 0.2, needs about 2 minutes till maximum deflection.
Comparative example 1 and embodiment 9 are compared as can be known, and the both is with the dependent variable (both are about 0.2) of roughly the same degree and with the speed bending of basic identical degree in electric field.Yet, in embodiment 9, can be with lower electric field (embodiment 9:7V/cm; Comparative example 1:30V/cm) produces bending.That is, ionic crosslinked polyrotaxane of the present invention can more easily produce bending.This can think owing to the ring of CD in the ionic crosslinked polyrotaxane of embodiment 9 successfully moves on polymer chain.
Claims (18)
1. material that comprises crosslinked polyrotaxane, this crosslinked polyrotaxane has the poly-rotaxane of at least 2 molecules, and the cyclodextrin molecular of the poly-rotaxane of this at least 2 molecule is bonded to each other by chemical bond and forms crosslinked polyrotaxane, straight chain shape molecule is connected on the opening portion of cyclodextrin molecular and disposes END CAPPED GROUP at two ends of described straight chain shape molecule with puncture shape bag and breaks away to prevent this cyclodextrin molecular in the described poly-rotaxane, wherein, described cyclodextrin molecular has hydroxyl, and the part of this hydroxyl is had at least a kind of group that is selected from down the ionic group in the group and is replaced :-COOX base, wherein, X represents hydrogen, basic metal and other 1 valency metal;-SO
3The X base, wherein, X and aforementioned same definition;-NH
2Base;-NH
3X ' base, wherein, the halide-ions of X ' expression 1 valency;-PO
4Base; With-HPO
4Base.
2. material according to claim 1, wherein, described cyclodextrin molecular is selected from the group that alpha-cylodextrin, beta-cyclodextrin and γ-Huan Hujing form.
3. material according to claim 1, wherein, described group with ionic group replaces 10～90% in whole hydroxyls of whole cyclodextrin moleculars.
4. according to each described material of claim 1～3, wherein, the described crosslinked polyrotaxane of every 1g absolute dry condition, the solvent that described absorbed 1000g is above.
5. according to each described material of claim 1～3, wherein, described crosslinked polyrotaxane absorbs water-containing solvent, is accompanied by the pH of this solvent and/or the variation of ionic strength, and the volume of described crosslinked polyrotaxane changes.
6. according to each described material of claim 1～3, wherein, described crosslinked polyrotaxane absorbs water-containing solvent, the described crosslinked polyrotaxane that absorbs solvent, and its shape and/or volume change according to electric field.
7. according to each described material of claim 1～3, wherein, described straight chain shape molecule is selected from the group that polyoxyethylene glycol, polyisoprene, polyisobutene, polyhutadiene, polypropylene glycol, polytetrahydrofuran, polydimethylsiloxane, polyethylene and polypropylene form.
8. according to each described material of claim 1～3; wherein, described END CAPPED GROUP is selected from the group that dinitrobenzene base class, cyclodextrin, diamantane base class, trityl class, fluoresceins, pyrene class, the optional benzene class that is replaced by 1 or a plurality of alkyl, alkoxyl group, hydroxyl, halogen, cyano group, alkylsulfonyl, carboxyl, amino, phenyl, the optional polynuclear aromatic class that is replaced by 1 or a plurality of alkyl, alkoxyl group, hydroxyl, halogen, cyano group, alkylsulfonyl, carboxyl, amino, phenyl and steroidal class formed.
9. according to each described material of claim 1～3, wherein, described cyclodextrin molecular is the alpha-cylodextrin molecule, and described straight chain shape molecule is a polyoxyethylene glycol.
10. according to each described material of claim 1～3, wherein, the amount of being wrapped the cyclodextrin molecular that connects when described cyclodextrin molecular is connect with puncture shape bag by straight chain shape molecule to greatest extent was made as 1 o'clock, and described cyclodextrin molecular is connected on the straight chain shape molecule with 0.001～0.6 amount puncture shape bag.
11. according to each described material of claim 1～3, wherein, the poly-rotaxane of described at least 2 molecules is by the linking agent Chemical bond.
12. material according to claim 11, wherein, the molecular weight of described linking agent is less than 2000.
13. material according to claim 11, wherein, described linking agent is selected from cyanuryl chloride, trimesoyl chloride, terephthalyl chloride, Epicholorohydrin, dibromobenzene, glutaraldehyde, phenylene diisocyanate, tolylene diisocyanate, divinyl sulfone, 1, in the group that 1 '-phosphinylidyne diimidazole and alkoxyl silicone alkanes are formed.
14. material according to claim 12, wherein, described linking agent is selected from cyanuryl chloride, trimesoyl chloride, terephthalyl chloride, Epicholorohydrin, dibromobenzene, glutaraldehyde, phenylene diisocyanate, tolylene diisocyanate, divinyl sulfone, 1, in the group that 1 '-phosphinylidyne diimidazole and alkoxyl silicone alkanes are formed.
15. according to each described material of claim 1～3, wherein, in the poly-rotaxane of described at least 2 molecules, at least 1 OH base of at least 1 cyclodextrin molecular of each poly-rotaxane participates in crosslinked.
16. according to each described material of claim 1～3, wherein, the molecular weight of described straight chain shape molecule is more than 10,000.
17. a preparation methods that comprises crosslinked polyrotaxane is characterized in that,
This preparation methods that comprises crosslinked polyrotaxane comprises: 1) accurate poly-rotaxane preparation section: mix cyclodextrin molecular and straight chain shape molecule, preparation straight chain shape molecule is connected on the poly-rotaxane of standard of the opening portion of described ring molecule with puncture shape bag; 2) poly-rotaxane preparation section: two ends with the accurate poly-rotaxane of END CAPPED GROUP sealing break away from from the puncture state to prevent described cyclodextrin molecular, thus the poly-rotaxane of preparation; With 3) crosslinked operation: the cyclodextrin molecular separately of the poly-rotaxane of at least 2 molecules is bonded to each other by chemical bond and makes the poly-rotaxane of this at least 2 molecule crosslinked,
And the replacement operation that the part of the OH base of cyclodextrin molecular is replaced to the group with ionic group is arranged on: A) described 1) before the accurate poly-rotaxane preparation section; B) described 1) behind the accurate poly-rotaxane preparation section and described 2) before the poly-rotaxane preparation section; C) described 2) behind the poly-rotaxane preparation section and described 3) before the crosslinked operation; And/or D) described 3) after the crosslinked operation,
Described ionic group is to be selected from-the COOX base, and wherein, X represents hydrogen, basic metal and other 1 valency metal;-SO
3The X base, wherein, X and aforementioned same definition;-NH
2Base;-NH
3X ' base, wherein, the halide-ions of X ' expression 1 valency;-PO
4Base; With-HPO
4In the group formed of base at least a kind.
18. method according to claim 17, wherein, described replacement operation is arranged on described 2) behind the poly-rotaxane preparation section and described 3) before the crosslinked operation.
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| US8785552B2 (en) * | 2008-09-01 | 2014-07-22 | Advanced Softmaterials Inc. | Solvent-free crosslinked polyrotaxane material and process for production of same |
| WO2014196636A1 (en) * | 2013-06-07 | 2014-12-11 | アドバンスト・ソフトマテリアルズ株式会社 | Crosslinking composition having a polyrotaxane and a compound having two or more oxirane groups and/or oxetane groups |
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| US20030171573A1 (en) * | 2002-02-27 | 2003-09-11 | Nobuhiko Yui | Multivalently interactive molecular assembly, capturing agent, drug carrier, calcium chelating agent, and drug enhancer |
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| US20030171573A1 (en) * | 2002-02-27 | 2003-09-11 | Nobuhiko Yui | Multivalently interactive molecular assembly, capturing agent, drug carrier, calcium chelating agent, and drug enhancer |
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