JP2020169260A - Polyrotaxane having group derived from oxazoline in a part of cyclic molecule, composition having the polyrotaxane, and manufacturing method of the polyrotaxane - Google Patents
Polyrotaxane having group derived from oxazoline in a part of cyclic molecule, composition having the polyrotaxane, and manufacturing method of the polyrotaxane Download PDFInfo
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- JP2020169260A JP2020169260A JP2019071068A JP2019071068A JP2020169260A JP 2020169260 A JP2020169260 A JP 2020169260A JP 2019071068 A JP2019071068 A JP 2019071068A JP 2019071068 A JP2019071068 A JP 2019071068A JP 2020169260 A JP2020169260 A JP 2020169260A
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- polyrotaxane
- cyclic molecule
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- 125000004122 cyclic group Chemical group 0.000 title claims abstract description 79
- IMSODMZESSGVBE-UHFFFAOYSA-N 2-Oxazoline Chemical compound C1CN=CO1 IMSODMZESSGVBE-UHFFFAOYSA-N 0.000 title claims description 15
- 238000004519 manufacturing process Methods 0.000 title claims description 12
- 239000000203 mixture Substances 0.000 title claims description 12
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 claims abstract description 8
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims abstract description 8
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims abstract description 7
- 125000001559 cyclopropyl group Chemical group [H]C1([H])C([H])([H])C1([H])* 0.000 claims abstract description 7
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims abstract description 7
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims abstract description 7
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 claims abstract description 7
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 29
- -1 p-toluenesulfonyl group Chemical group 0.000 claims description 27
- 125000005647 linker group Chemical group 0.000 claims description 19
- 150000001875 compounds Chemical class 0.000 claims description 18
- 230000000903 blocking effect Effects 0.000 claims description 17
- 238000006243 chemical reaction Methods 0.000 claims description 13
- 239000000178 monomer Substances 0.000 claims description 10
- 238000000034 method Methods 0.000 claims description 9
- 125000000217 alkyl group Chemical group 0.000 claims description 7
- 125000000075 primary alcohol group Chemical group 0.000 claims description 7
- YYROPELSRYBVMQ-UHFFFAOYSA-N 4-toluenesulfonyl chloride Chemical compound CC1=CC=C(S(Cl)(=O)=O)C=C1 YYROPELSRYBVMQ-UHFFFAOYSA-N 0.000 claims description 6
- 125000003342 alkenyl group Chemical group 0.000 claims description 6
- 125000004432 carbon atom Chemical group C* 0.000 claims description 6
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 claims description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 3
- 125000002355 alkine group Chemical group 0.000 claims description 3
- 150000005676 cyclic carbonates Chemical class 0.000 claims description 3
- 150000004292 cyclic ethers Chemical group 0.000 claims description 3
- 239000001257 hydrogen Substances 0.000 claims description 3
- 229910052739 hydrogen Inorganic materials 0.000 claims description 3
- 125000004170 methylsulfonyl group Chemical group [H]C([H])([H])S(*)(=O)=O 0.000 claims description 3
- 125000003386 piperidinyl group Chemical group 0.000 claims description 3
- 239000002904 solvent Substances 0.000 abstract description 20
- JQVDAXLFBXTEQA-UHFFFAOYSA-N dibutylamine Chemical group CCCCNCCCC JQVDAXLFBXTEQA-UHFFFAOYSA-N 0.000 description 16
- 239000000463 material Substances 0.000 description 16
- 238000006116 polymerization reaction Methods 0.000 description 16
- 125000000524 functional group Chemical group 0.000 description 14
- 125000001280 n-hexyl group Chemical group C(CCCCC)* 0.000 description 12
- 239000000047 product Substances 0.000 description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 11
- 238000005160 1H NMR spectroscopy Methods 0.000 description 10
- GUXJXWKCUUWCLX-UHFFFAOYSA-N 2-methyl-2-oxazoline Chemical compound CC1=NCCO1 GUXJXWKCUUWCLX-UHFFFAOYSA-N 0.000 description 10
- 238000005259 measurement Methods 0.000 description 10
- 239000007787 solid Substances 0.000 description 10
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- 150000002918 oxazolines Chemical class 0.000 description 9
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 8
- HFHDHCJBZVLPGP-RWMJIURBSA-N alpha-cyclodextrin Chemical compound OC[C@H]([C@H]([C@@H]([C@H]1O)O)O[C@H]2O[C@@H]([C@@H](O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O3)[C@H](O)[C@H]2O)CO)O[C@@H]1O[C@H]1[C@H](O)[C@@H](O)[C@@H]3O[C@@H]1CO HFHDHCJBZVLPGP-RWMJIURBSA-N 0.000 description 8
- 239000002202 Polyethylene glycol Substances 0.000 description 7
- 238000004458 analytical method Methods 0.000 description 7
- 230000015572 biosynthetic process Effects 0.000 description 7
- 229920000773 poly(2-methyl-2-oxazoline) polymer Polymers 0.000 description 7
- 229920000642 polymer Polymers 0.000 description 7
- 238000003786 synthesis reaction Methods 0.000 description 7
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- 229940043377 alpha-cyclodextrin Drugs 0.000 description 5
- 239000007864 aqueous solution Substances 0.000 description 5
- 238000004132 cross linking Methods 0.000 description 5
- 125000004185 ester group Chemical group 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 5
- 125000002088 tosyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1C([H])([H])[H])S(*)(=O)=O 0.000 description 5
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 4
- NQRYJNQNLNOLGT-UHFFFAOYSA-N Piperidine Chemical compound C1CCNCC1 NQRYJNQNLNOLGT-UHFFFAOYSA-N 0.000 description 4
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 4
- ORILYTVJVMAKLC-UHFFFAOYSA-N adamantane Chemical group C1C(C2)CC3CC1CC2C3 ORILYTVJVMAKLC-UHFFFAOYSA-N 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 238000000502 dialysis Methods 0.000 description 4
- 230000000977 initiatory effect Effects 0.000 description 4
- 239000003505 polymerization initiator Substances 0.000 description 4
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
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- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 3
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- 125000001424 substituent group Chemical group 0.000 description 3
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 2
- OALHHIHQOFIMEF-UHFFFAOYSA-N 3',6'-dihydroxy-2',4',5',7'-tetraiodo-3h-spiro[2-benzofuran-1,9'-xanthene]-3-one Chemical compound O1C(=O)C2=CC=CC=C2C21C1=CC(I)=C(O)C(I)=C1OC1=C(I)C(O)=C(I)C=C21 OALHHIHQOFIMEF-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- IRIAEXORFWYRCZ-UHFFFAOYSA-N Butylbenzyl phthalate Chemical compound CCCCOC(=O)C1=CC=CC=C1C(=O)OCC1=CC=CC=C1 IRIAEXORFWYRCZ-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- KCXZNSGUUQJJTR-UHFFFAOYSA-N Di-n-hexyl phthalate Chemical compound CCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCC KCXZNSGUUQJJTR-UHFFFAOYSA-N 0.000 description 2
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 2
- YBGZDTIWKVFICR-JLHYYAGUSA-N Octyl 4-methoxycinnamic acid Chemical compound CCCCC(CC)COC(=O)\C=C\C1=CC=C(OC)C=C1 YBGZDTIWKVFICR-JLHYYAGUSA-N 0.000 description 2
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- 229920002396 Polyurea Polymers 0.000 description 2
- 239000004372 Polyvinyl alcohol Substances 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- 239000006096 absorbing agent Substances 0.000 description 2
- GTDPSWPPOUPBNX-UHFFFAOYSA-N ac1mqpva Chemical compound CC12C(=O)OC(=O)C1(C)C1(C)C2(C)C(=O)OC1=O GTDPSWPPOUPBNX-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 150000008065 acid anhydrides Chemical class 0.000 description 2
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- 239000000654 additive Substances 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
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- PFKFTWBEEFSNDU-UHFFFAOYSA-N carbonyldiimidazole Chemical compound C1=CN=CN1C(=O)N1C=CN=C1 PFKFTWBEEFSNDU-UHFFFAOYSA-N 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
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- 239000002537 cosmetic Substances 0.000 description 2
- DOIRQSBPFJWKBE-UHFFFAOYSA-N dibutyl phthalate Chemical compound CCCCOC(=O)C1=CC=CC=C1C(=O)OCCCC DOIRQSBPFJWKBE-UHFFFAOYSA-N 0.000 description 2
- 239000004205 dimethyl polysiloxane Substances 0.000 description 2
- 150000002009 diols Chemical class 0.000 description 2
- VFHVQBAGLAREND-UHFFFAOYSA-N diphenylphosphoryl-(2,4,6-trimethylphenyl)methanone Chemical compound CC1=CC(C)=CC(C)=C1C(=O)P(=O)(C=1C=CC=CC=1)C1=CC=CC=C1 VFHVQBAGLAREND-UHFFFAOYSA-N 0.000 description 2
- 229920001971 elastomer Polymers 0.000 description 2
- 239000012948 isocyanate Substances 0.000 description 2
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 2
- 150000002513 isocyanates Chemical class 0.000 description 2
- AMXOYNBUYSYVKV-UHFFFAOYSA-M lithium bromide Chemical compound [Li+].[Br-] AMXOYNBUYSYVKV-UHFFFAOYSA-M 0.000 description 2
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- 229960001679 octinoxate Drugs 0.000 description 2
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- 229920000765 poly(2-oxazolines) Polymers 0.000 description 2
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- 125000002221 trityl group Chemical group [H]C1=C([H])C([H])=C([H])C([H])=C1C([*])(C1=C(C(=C(C(=C1[H])[H])[H])[H])[H])C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 description 2
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- PDHSAQOQVUXZGQ-JKSUJKDBSA-N (2r,3s)-2-(3,4-dihydroxyphenyl)-3-methoxy-3,4-dihydro-2h-chromene-5,7-diol Chemical compound C1([C@H]2OC3=CC(O)=CC(O)=C3C[C@@H]2OC)=CC=C(O)C(O)=C1 PDHSAQOQVUXZGQ-JKSUJKDBSA-N 0.000 description 1
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Abstract
Description
本発明は、環状分子の一部にオキサゾリン由来の基を有するポリロタキサン、該ポリロタキサンを有する組成物、及び該ポリロタキサンの製造方法に関する。 The present invention relates to a polyrotaxane having an oxazoline-derived group as part of a cyclic molecule, a composition having the polyrotaxane, and a method for producing the polyrotaxane.
環状分子の開口部が直鎖状分子によって串刺し状に包接されてなる擬ポリロタキサンの両端に、環状分子が脱離しないように封鎖基を配置してなるポリロタキサンは、それを用いた材料が、優れた伸び率、優れた柔軟性などを示すことから種々の材料に応用することが期待されている。
例えば、特許文献１は、有機溶媒に可溶なポリロタキサンを得るために、ポリロタキサンのシクロデキストリンの水酸基の一部又は全部が、−Ｏ−Ｃ３Ｈ６−Ｏ−基と結合したカプロラクトン基（−ＣＯ（ＣＨ２）５−ＯＨ）を有する疎水性修飾ポリロタキサンを開示する。
Polyrotaxane, which is formed by arranging blocking groups at both ends of a pseudo-polyrotaxane in which the openings of cyclic molecules are skewered by linear molecules so that the cyclic molecules do not escape, is made of a material using the same. It is expected to be applied to various materials because it exhibits excellent elongation and excellent flexibility.
For example,
また、特許文献２は、環状分子が比較的長鎖のグラフト鎖を有するポリロタキサンを容易に得る方法を開示する。具体的には、該方法により得られる、ポリロタキサンの環状分子に、リビングラジカル重合開始部位を有するポリロタキサンを開示する。また、その開始部位からラジカル重合性モノマーが重合してなるグラフト鎖、具体的には、（メタ）アクリルモノマーの重合体を有するグラフト鎖を有することを開示する。 Further, Patent Document 2 discloses a method for easily obtaining a polyrotaxane in which a cyclic molecule has a relatively long graft chain. Specifically, the polyrotaxane having a living radical polymerization initiation site in the cyclic molecule of the polyrotaxane obtained by the method is disclosed. Further, it discloses that it has a graft chain obtained by polymerizing a radically polymerizable monomer from the starting site, specifically, a graft chain having a polymer of a (meth) acrylic monomer.
さらに、特許文献３は、種々の溶媒に可溶なポリロタキサンを得るために、ポリロタキサンの環状分子に２種類の低分子量化合物由来の官能基を修飾することを開示する。
Further,
しかしながら、従来のポリロタキサンは、種々の溶媒に可溶とし溶解性を向上させた一方、耐熱性、耐候性に劣る、という問題があった。 However, the conventional polyrotaxane has a problem that it is soluble in various solvents to improve the solubility, but is inferior in heat resistance and weather resistance.
そこで、本発明の目的は、種々の溶媒に可溶であり且つ耐熱性、耐候性に優れたポリロタキサンを提供することにある。
また、本発明の目的は、該ポリロタキサンの製造方法を提供することにある。
Therefore, an object of the present invention is to provide a polyrotaxane that is soluble in various solvents and has excellent heat resistance and weather resistance.
Another object of the present invention is to provide a method for producing the polyrotaxane.
上記目的を達成するために、本発明者は、以下の発明を見出した。
＜１＞ 環状分子の開口部が直鎖状分子によって串刺し状に包接されてなる擬ポリロタキサンの両端に前記環状分子が脱離しないように封鎖基を配置してなるポリロタキサンであって、前記環状分子が下記式Ｉ
（式中、Ｒはメチル基、エチル基、１−プロピル基、２−プロピル基、シクロプロピル基、ブチル基、又はベンジル基を表し；
Ｙは末端基を表し；
ｎは１〜２０、好ましくは２〜１５、より好ましくは４〜１２を表す）
で表す第１の基を有するポリロタキサン。
In order to achieve the above object, the present inventor has found the following invention.
<1> A polyrotaxane in which a blocking group is arranged at both ends of a pseudo-polyrotaxane in which the opening of a cyclic molecule is skewered by a linear molecule so that the cyclic molecule is not detached. The numerator is the following formula I
(In the formula, R represents a methyl group, an ethyl group, a 1-propyl group, a 2-propyl group, a cyclopropyl group, a butyl group, or a benzyl group;
Y represents the terminal group;
n represents 1 to 20, preferably 2 to 15, more preferably 4 to 12)
Polyrotaxane having a first group represented by.
＜２＞ 上記＜１＞において、Ｙが、−ＯＨ基、−ＮＲ１Ｒ２基（Ｒ１、Ｒ２は、それぞれ独立に炭素数１〜１０の直鎖又は分岐鎖のアルキル基、アルケニル基又はアルキン基（アルキル基、アルケニル基又はアルキン基中の一部の水素がＯＨ基、ＣＮ基又はＮＨ２基で置換されていてもよい）を表す）、−Ｎ３基、及びピペリジン基からなる群から選ばれる１種の基であるのがよい。−ＮＲ１Ｒ２基として、例えば−Ｎ（ＣＨ２ＣＨ２ＯＨ）２基、−Ｎ（ＣＨ２ＣＨ３）２、−Ｎ（ＣＨ２ＣＨ２ＣＨ３）、−Ｎ（ＣＨ２ＣＨ２ＣＨ２ＣＨ３）２、−Ｎ（ＣＨ２ＣＨ２ＣＨ２ＣＨ２ＣＨ３）２、−Ｎ（ＣＨ２ＣＨ２ＣＨ２ＣＨ２ＣＨ２ＣＨ３）２、−Ｎ（ＣＨ２ＣＨ２ＣＨ２ＣＨ２ＣＨ２ＣＨ２ＣＨ３）２、−Ｎ（ＣＨ２ＣＨ２ＣＨ２ＣＨ２ＣＨ２ＣＨ２ＣＨ２ＣＨ３）２、−Ｎ（ＣＨ２ＣＨ（ＣＨ３）ＣＨ３）２、−Ｎ（ＣＨ２ＣＨ（ＣＨ３）ＣＨ３）２、−Ｎ（ＣＨ２ＣＨ（ＣＨ２ＣＨ３）ＣＨ２ＣＨ２ＣＨ２ＣＨ３）２、−Ｎ（ＣＨ２ＣＨＣＨ２）２基、−Ｎ（ＣＨ２ＣＨ２ＣＮ）２基、−Ｎ（Ｃ３Ｈ６ＮＨ２）２基、−ＮＨＣＨ２ＣＨ２ＮＨ２基、−Ｎ（ＣＨ２ＣＣＨ）２基などを挙げることができるがこれらに限定されない。Ｙは、−ＯＨ基、−Ｎ（ＣＨ２ＣＨ２ＣＨ２ＣＨ３）２基、及び−Ｎ（ＣＨ２ＣＨ２ＯＨ）２基からなる群から選ばれる１種の基であるのが好ましい。
＜３＞ 上記＜１＞又は＜２＞において、第１の基が、オキサゾリンモノマー又はその誘導体由来であるのがよい。具体的には、第１の基が、オキサゾリンモノマー又はその誘導体の開環重合で重合されてなるのがよい。
<2> In <1> above, Y is an -OH group and -NR 1 R 2 groups (R 1 and R 2 are linear or branched alkyl groups and alkenyl groups having 1 to 10 carbon atoms, respectively. Alternatively, it comprises an alkin group (representing an alkyl group, an alkenyl group or a part of hydrogen in the alkin group may be substituted with an OH group, a CN group or an NH 2 group), -N 3 groups, and a piperidine group. It should be one type of group selected from the group. -NR 1 as R 2 groups, for example -N (CH 2 CH 2 OH) 2 group, -N (CH 2 CH 3) 2, -N (CH 2 CH 2 CH 3), - N (CH 2 CH 2 CH 2 CH 3 ) 2 , -N (CH 2 CH 2 CH 2 CH 2 CH 3 ) 2 , -N (CH 2 CH 2 CH 2 CH 2 CH 2 CH 3 ) 2 , -N (CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 3 ) 2 , -N (CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 3 ) 2 , -N (CH 2 CH (CH 3 ) CH 3 ) 2 , -N ( CH 2 CH (CH 3 ) CH 3 ) 2 , -N (CH 2 CH (CH 2 CH 3 ) CH 2 CH 2 CH 2 CH 3 ) 2 , -N (CH 2 CH CH 2 ) 2 units, -N (CH) 2 CH 2 CN) 2 units, -N (C 3 H 6 NH 2 ) 2 units, -NHCH 2 CH 2 NH 2 units, -N (CH 2 CCH) 2 units, etc., but are not limited thereto. .. Y is, -OH group, -N (CH 2 CH 2 CH 2 CH 3) 2 group, and is preferably one group selected from -N (CH 2 CH 2 OH) group consisting of 2 groups.
<3> In the above <1> or <2>, the first group is preferably derived from an oxazoline monomer or a derivative thereof. Specifically, the first group may be polymerized by ring-opening polymerization of an oxazoline monomer or a derivative thereof.
＜４＞ 上記＜１＞〜＜３＞のいずれかにおいて、環状分子が水酸基を有し、該水酸基に代えて、又は該水酸基と反応させて前記第１の基を設けるのがよい。
＜５＞ 上記＜４＞において、第１の基は、環状分子の水酸基の２％以上、好ましくは５％以上、より好ましくは１５％以上、最も好ましくは３０％以上で設けられるのがよい。
＜６＞ 上記＜１＞〜＜５＞のいずれかにおいて、第１の基が、第１の連結基を介して環状分子に結合するのがよい。
該第１の連結基として、−ＣＨ２−ＣＨ２−、−ＣＨ２−ＣＨ２−ＣＨ２−、−ＣＨ２ＣＨ（ＯＨ）−ＣＨ２−、−ＣＨ２−ＣＨ２−ＣＨ２−ＣＨ２−、−ＣＯ−ＣＨ２−ＣＨ２−、−ＣＯ−Ｃ（ＣＨ３）２−ＣＨ２−、−ＣＯ−ＣＨ（ＯＨ）−ＣＨ２−、−ＣＯ−ＣＨ２−ＣＨ２−ＣＨ２−ＣＨ２−ＣＨ２−、−ＣＯ−ＣＨ２−ＣＨ２−ＣＨ２−ＣＨ（ＣＨ３）−を挙げることができるがこれらに限定されない。
<4> In any of the above <1> to <3>, it is preferable that the cyclic molecule has a hydroxyl group, and the first group is provided in place of the hydroxyl group or by reacting with the hydroxyl group.
<5> In the above <4>, the first group is preferably provided at 2% or more, preferably 5% or more, more preferably 15% or more, and most preferably 30% or more of the hydroxyl groups of the cyclic molecule.
<6> In any of the above <1> to <5>, it is preferable that the first group is bonded to the cyclic molecule via the first linking group.
As a linking group of said 1, -CH 2 -CH 2 -, - CH 2 -CH 2 -CH 2 -, - CH 2 CH (OH) -CH 2 -, - CH 2 -CH 2 -CH 2 -CH 2 -, - CO-CH 2 -CH 2 -, - CO-C (CH 3) 2 -CH 2 -, - CO-CH (OH) -CH 2 -, - CO-CH 2 -CH 2 -CH 2 -CH 2 -CH 2 -, - CO -CH 2 -CH 2 -CH 2 -CH (CH 3) - can be exemplified without limitation.
＜７＞ 上記＜１＞〜＜６＞のいずれかのポリロタキサンを有する組成物。
＜８＞ 上記＜１＞〜＜６＞のいずれかのポリロタキサンを含有する成形体。
＜９＞ 上記＜８＞において、成形体１００ｗｔ％中、上記ポリロタキサンの量が０．１〜５０ｗｔ％、好ましくは０．３〜３０ｗｔ％、より好ましくは０．５〜２０ｗｔ％、最も好ましくは１〜１５ｗｔ％であるのがよい。
<7> A composition having the polyrotaxane according to any one of <1> to <6> above.
<8> A molded product containing any of the above <1> to <6> polyrotaxane.
<9> In <8>, the amount of the polyrotaxane in 100 wt% of the molded product is 0.1 to 50 wt%, preferably 0.3 to 30 wt%, more preferably 0.5 to 20 wt%, and most preferably 1. It should be ~ 15 wt%.
＜１０＞ Ｉ）環状分子の開口部が直鎖状分子によって串刺し状に包接されてなる擬ポリロタキサンの両端に前記環状分子が脱離しないように封鎖基を配置してなるポリロタキサンであって、前記環状分子が下記式ＩＩ
（式ＩＩ中、Ｚはｐ−トルエンスルホニル基（Ｔｓ基）又はメシル基（Ｍｓ基）、好ましくはＴｓ基を表す。
Ｘは、単結合又は第１の連結基を表す。第１の連結基としての−Ｘ−は、−ＣＨ２−ＣＨ２−、−ＣＨ２−ＣＨ２−ＣＨ２−、−ＣＨ２ＣＨ（ＯＨ）−ＣＨ２−、−ＣＨ２−ＣＨ２−ＣＨ２−ＣＨ２−、−ＣＯ−ＣＨ２−ＣＨ２−、−ＣＯ−Ｃ（ＣＨ３）２−ＣＨ２−、−ＣＯ−ＣＨ（ＯＨ）−ＣＨ２−、−ＣＯ−ＣＨ２−ＣＨ２−ＣＨ２−ＣＨ２−ＣＨ２−、−ＣＯ−ＣＨ２−ＣＨ２−ＣＨ２−ＣＨ（ＣＨ３）−からなる群から選択される１種であるのがよい）
で表される第２の基を有する第Ｉのポリロタキサンを準備する工程；
ＩＩ）前記第Ｉのポリロタキサンに式ＩＩＩ（式ＩＩＩ中、Ｒは、メチル基、エチル基、１−プロピル基、２−プロピル基、シクロプロピル基、ブチル基、又はベンジル基を表す）で表されるオキサゾリン誘導体を反応させて、式ＩＶ（式ＩＶ中、Ｘ、Ｚ及びＲは上述と同じ定義を有し、ｎは１〜２０を表す）で表される第３の基を有する第ＩＩのポリロタキサンを得る工程；及び
ＩＩＩ）前記第ＩＩのポリロタキサンを反応させて式Ｖ（式中、Ｘ、Ｒ及びｎは上述と同じ定義を有し、Ｙは末端基を表す。Ｙは、上述と同じ定義を有する。）で表される第４の基を有する第ＩＩＩのポリロタキサンを得る工程；
を有することにより、
環状分子の開口部が直鎖状分子によって串刺し状に包接されてなる擬ポリロタキサンの両端に前記環状分子が脱離しないように封鎖基を配置してなるポリロタキサンであって、前記環状分子が式Ｖで表される第４の基を有するポリロタキサンを得る、式Ｖで表される第４の基を有する第ＩＩＩのポリロタキサンの製造方法。
<10> I) A polyrotaxane in which a blocking group is arranged at both ends of a pseudo-polyrotaxane in which the opening of a cyclic molecule is skewered by a linear molecule so that the cyclic molecule is not detached. The cyclic molecule is the following formula II
(In Formula II, Z represents a p-toluenesulfonyl group (Ts group) or a mesyl group (Ms group), preferably a Ts group.
X represents a single bond or a first linking group. As the -X- first linking group, -CH 2 -CH 2 -, - CH 2 -CH 2 -CH 2 -, - CH 2 CH (OH) -CH 2 -, - CH 2 -CH 2 - CH 2 -CH 2 -, - CO -CH 2 -CH 2 -, - CO-C (CH 3) 2 -CH 2 -, - CO-CH (OH) -CH 2 -, - CO-CH 2 -CH 2 −CH 2 −CH 2 −CH 2 −, −CO−CH 2 −CH 2 −CH 2 −CH (CH 3 ) − It is preferable to be one selected from the group consisting of −)
The step of preparing the first polyrotaxane having the second group represented by;
II) The polyrotaxane of the first I is represented by the formula III (in the formula III, R represents a methyl group, an ethyl group, a 1-propyl group, a 2-propyl group, a cyclopropyl group, a butyl group, or a benzyl group). The oxazoline derivative is reacted with a third group having a third group represented by the formula IV (in the formula IV, X, Z and R have the same definitions as described above and n represents 1 to 20). Steps to Obtain Polyrotaxane; and III) Reacting the above-mentioned II polyrotaxane to formula V (in the formula, X, R and n have the same definitions as above, Y represents a terminal group; Y is the same as above. A step of obtaining a third polyrotaxane having a fourth group represented by);
By having
A polyrotaxan in which a blocking group is arranged at both ends of a pseudo-polyrotaxane in which the opening of a cyclic molecule is skewered by a linear molecule so that the cyclic molecule is not detached, and the cyclic molecule is of the formula. A method for producing a third polyrotaxane having a fourth group represented by the formula V, which obtains a polyrotaxan having a fourth group represented by V.
＜１１＞ 上記＜１０＞のＩＩＩ）工程において、前記第ＩＩのポリロタキサンと、水、ＮＨＲ１Ｒ２（式中、Ｒ１及びＲ２は、各々独立に、上述と同じ定義を有する。）、−Ｎ３基を有する化合物、及びピペリジンからなる群から選ばれる１種と反応させるのがよい。なお、ＮＨＲ１Ｒ２として、例えば、ＮＨ（ＣＨ２ＣＨ２ＯＨ）２、ＮＨ（ＣＨ２ＣＨ３）２、ＮＨ（ＣＨ２ＣＨ２ＣＨ３）、ＮＨ（ＣＨ２ＣＨ２ＣＨ２ＣＨ３）２、ＮＨ（ＣＨ２ＣＨ２ＣＨ２ＣＨ２ＣＨ３）２、ＮＨ（ＣＨ２ＣＨ２ＣＨ２ＣＨ２ＣＨ２ＣＨ３）２、ＮＨ（ＣＨ２ＣＨ２ＣＨ２ＣＨ２ＣＨ２ＣＨ２ＣＨ３）２、ＮＨ（ＣＨ２ＣＨ２ＣＨ２ＣＨ２ＣＨ２ＣＨ２ＣＨ２ＣＨ３）２、ＮＨ（ＣＨ２ＣＨ（ＣＨ３）ＣＨ３）２、ＮＨ（ＣＨ２ＣＨ（ＣＨ３）ＣＨ３）２、ＮＨ（ＣＨ２ＣＨ（ＣＨ２ＣＨ３）ＣＨ２ＣＨ２ＣＨ２ＣＨ３）２、ＮＨ（ＣＨ２ＣＨＣＨ２）２、ＮＨ（ＣＨ２ＣＨ２ＣＮ）２、ＮＨ（Ｃ３Ｈ６ＮＨ２）２、ＮＨＣＨ２ＣＨ２ＮＨ２、ＮＨ（ＣＨ２ＣＣＨ）２を挙げることができるがこれらに限定されない。 <11> In the step III) of the above <10>, the polyrotaxane of the second II, water, NHR 1 R 2 (in the formula, R 1 and R 2 have the same definitions as described above independently). It is preferable to react with one selected from the group consisting of a compound having three −N groups and piperidine. As NHR 1 R 2 , for example, NH (CH 2 CH 2 OH) 2 , NH (CH 2 CH 3 ) 2 , NH (CH 2 CH 2 CH 3 ), NH (CH 2 CH 2 CH 2 CH 3 ) 2 , NH (CH 2 CH 2 CH 2 CH 2 CH 3 ) 2 , NH (CH 2 CH 2 CH 2 CH 2 CH 2 CH 3 ) 2 , NH (CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 3) ) 2 , NH (CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 3 ) 2 , NH (CH 2 CH (CH 3 ) CH 3 ) 2 , NH (CH 2 CH (CH 3 ) CH 3 ) 2 , NH (CH 2 CH (CH 2 CH 3 ) CH 2 CH 2 CH 2 CH 3 ) 2 , NH (CH 2 CH CH 2 ) 2 , NH (CH 2 CH 2 CN) 2 , NH (C 3 H 6 NH) 2 ) 2 , NHCH 2 CH 2 NH 2 , NH (CH 2 CCH) 2 can be mentioned, but is not limited thereto.
＜１２＞ 上記＜１０＞又は＜１１＞において、Ｉ−２） 前記工程Ｉ）の第２の基を有する第Ｉのポリロタキサンは、環状分子の開口部が直鎖状分子によって串刺し状に包接されてなる擬ポリロタキサンの両端に前記環状分子が脱離しないように封鎖基を配置してなるポリロタキサンであって前記環状分子が−Ｘ−ＯＨ（式中、Ｘは上記と同じ定義を有する）で表される第１級アルコール基を有する第ＩａのポリロタキサンとＺＣｌ（式中、Ｚは上記と同じ定義を有する）とを反応して得られるのがよい。
＜１３＞ 上記＜１２＞において、−Ｘ−ＯＨで表される第１級アルコール基が、下記式ＩＩａで表される基であり、ＺＣｌがＴｓＣｌであるのがよい。
<12> In the above <10> or <11>, the opening of the cyclic molecule of the first polyrotaxane having the second group of I-2) step I) is included in a skewer shape by the linear molecule. It is a polyrotaxan obtained by arranging a blocking group at both ends of the pseudo-polyrotaxane so that the cyclic molecule does not desorb, and the cyclic molecule is -X-OH (in the formula, X has the same definition as above). It is preferably obtained by reacting the polyrotaxane of Ia having the represented primary alcohol group with ZCl (in the formula, Z has the same definition as above).
<13> In the above <12>, the primary alcohol group represented by −X—OH is the group represented by the following formula IIa, and ZCl is preferably TsCl.
＜１４＞ 上記＜１２＞又は＜１３＞において、Ｉ−１）前記工程Ｉ−２）の−Ｘ−ＯＨ（式中、Ｘは上記と同じ定義を有する）で表される第１級アルコール基を有する第Ｉａのポリロタキサンは、環状分子の開口部が直鎖状分子によって串刺し状に包接されてなる擬ポリロタキサンの両端に前記環状分子が脱離しないように封鎖基を配置してなるポリロタキサンであって前記環状分子が水酸基を有するポリロタキサンにエチレンオキシド、環状カルボナート、Ｔ−Ｘ’−ＯＨ（式中、Ｔは、炭素数２〜４の環状エーテル基、Ｃｌ基、Ｂｒ基、又はＩ基を表し、Ｘ’は、第２の連結基を表す）で表される化合物を反応して得られるのがよい。
＜１５＞ 上記＜１４＞において、Ｔ−Ｘ−ＯＨで表される化合物が下記式ＩＩｂで表される化合物であるのがよい。
<14> In the above <12> or <13>, a primary alcohol group represented by −X—OH (in the formula, X has the same definition as above) in I-1) the step I-2). The polyrotaxane of the Ia th is a polyrotaxan obtained by arranging a blocking group at both ends of a pseudo-polyrotaxane in which the opening of the cyclic molecule is squeezed by a linear molecule so that the cyclic molecule is not detached. Polyrotaxane in which the cyclic molecule has a hydroxyl group represents ethylene oxide, cyclic carbonate, TX'-OH (in the formula, T represents a cyclic ether group having 2 to 4 carbon atoms, a Cl group, a Br group, or an I group). , X'represents a second linking group) and is preferably obtained by reacting with a compound.
<15> In the above <14>, the compound represented by TX-OH is preferably the compound represented by the following formula IIb.
本発明により、種々の溶媒に可溶であり且つ耐熱性、耐候性に優れたポリロタキサンを提供することができる。
また、本発明により、該ポリロタキサンの製造方法を提供することができる。
INDUSTRIAL APPLICABILITY According to the present invention, it is possible to provide a polyrotaxane that is soluble in various solvents and has excellent heat resistance and weather resistance.
In addition, the present invention can provide a method for producing the polyrotaxane.
以下、本願に記載する発明を詳細に説明する。
本発明は、環状分子の一部にオキサゾリン由来の基を有するポリロタキサン、該ポリロタキサンを有する組成物、及び該ポリロタキサンの製造方法を提供する。以下、順に説明する。
Hereinafter, the invention described in the present application will be described in detail.
The present invention provides a polyrotaxane having an oxazoline-derived group as part of a cyclic molecule, a composition having the polyrotaxane, and a method for producing the polyrotaxane. Hereinafter, they will be described in order.
＜環状分子の一部にオキサゾリン由来の基を有するポリロタキサン＞
本発明は、環状分子の一部にオキサゾリン由来の基を有するポリロタキサンを提供する。具体的には、本発明は、環状分子の開口部が直鎖状分子によって串刺し状に包接されてなる擬ポリロタキサンの両端に前記環状分子が脱離しないように封鎖基を配置してなるポリロタキサンであって、前記環状分子が下記式Ｉで表す第１の基を有するポリロタキサンを提供する。
式中、Ｒはメチル基、エチル基、１−プロピル基、２−プロピル基、シクロプロピル基、ブチル基、又はベンジル基を表す。
Ｙは末端基を表す。特に、Ｙは、−ＯＨ基、−ＮＲ１Ｒ２基（Ｒ１、Ｒ２は、それぞれ独立に炭素数１〜１０の直鎖又は分岐鎖のアルキル基、アルケニル基又はアルキン基（アルキル基、アルケニル基又はアルキン基中の一部の水素がＯＨ基、ＣＮ基又はＮＨ２基で置換されていてもよい）を表す）、−Ｎ３基、及びピペリジン基からなる群から選ばれる１種の基であるのがよい。
−ＮＲ１Ｒ２基として、例えば−Ｎ（ＣＨ２ＣＨ２ＯＨ）２基、−Ｎ（ＣＨ２ＣＨ３）２、−Ｎ（ＣＨ２ＣＨ２ＣＨ３）、−Ｎ（ＣＨ２ＣＨ２ＣＨ２ＣＨ３）２、−Ｎ（ＣＨ２ＣＨ２ＣＨ２ＣＨ２ＣＨ３）２、−Ｎ（ＣＨ２ＣＨ２ＣＨ２ＣＨ２ＣＨ２ＣＨ３）２、−Ｎ（ＣＨ２ＣＨ２ＣＨ２ＣＨ２ＣＨ２ＣＨ２ＣＨ３）２、−Ｎ（ＣＨ２ＣＨ２ＣＨ２ＣＨ２ＣＨ２ＣＨ２ＣＨ２ＣＨ３）２、−Ｎ（ＣＨ２ＣＨ（ＣＨ３）ＣＨ３）２、−Ｎ（ＣＨ２ＣＨ（ＣＨ３）ＣＨ３）２、−Ｎ（ＣＨ２ＣＨ（ＣＨ２ＣＨ３）ＣＨ２ＣＨ２ＣＨ２ＣＨ３）２、−Ｎ（ＣＨ２ＣＨＣＨ２）２基、−Ｎ（ＣＨ２ＣＨ２ＣＮ）２基、−Ｎ（Ｃ３Ｈ６ＮＨ２）２基、−ＮＨＣＨ２ＣＨ２ＮＨ２基、−Ｎ（ＣＨ２ＣＣＨ）２基などを挙げることができるがこれらに限定されない。
Ｙは、−ＯＨ基、−Ｎ（ＣＨ２ＣＨ２ＣＨ２ＣＨ３）２基、及び−Ｎ（ＣＨ２ＣＨ２ＯＨ）２基からなる群から選ばれる１種の基であるのが好ましい。
ｎは１〜２０、好ましくは２〜１５、より好ましくは４〜１２を表す。
<Polyrotaxane having an oxazoline-derived group as part of the cyclic molecule>
The present invention provides a polyrotaxane having an oxazoline-derived group as part of a cyclic molecule. Specifically, the present invention is a polyrotaxane in which a blocking group is arranged at both ends of a pseudo-polyrotaxane in which the opening of a cyclic molecule is skewered by a linear molecule so that the cyclic molecule is not detached. Provided is a polyrotaxane in which the cyclic molecule has a first group represented by the following formula I.
In the formula, R represents a methyl group, an ethyl group, a 1-propyl group, a 2-propyl group, a cyclopropyl group, a butyl group, or a benzyl group.
Y represents a terminal group. In particular, Y is a -OH group and -NR 1 R 2 groups (R 1 and R 2 are linear or branched alkyl groups having 1 to 10 carbon atoms, respectively, alkenyl groups or alkyne groups (alkyl groups, respectively). A part of the hydrogen in the alkenyl group or the alkyne group may be substituted with an OH group, a CN group or an NH 2 group)), -N 3 groups, and one selected from the group consisting of a piperidine group. It should be a group.
-NR 1 as R 2 groups, for example -N (CH 2 CH 2 OH) 2 group, -N (CH 2 CH 3) 2, -N (CH 2 CH 2 CH 3), - N (CH 2 CH 2 CH 2 CH 3 ) 2 , -N (CH 2 CH 2 CH 2 CH 2 CH 3 ) 2 , -N (CH 2 CH 2 CH 2 CH 2 CH 2 CH 3 ) 2 , -N (CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 3 ) 2 , -N (CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 3 ) 2 , -N (CH 2 CH (CH 3 ) CH 3 ) 2 , -N ( CH 2 CH (CH 3 ) CH 3 ) 2 , -N (CH 2 CH (CH 2 CH 3 ) CH 2 CH 2 CH 2 CH 3 ) 2 , -N (CH 2 CH CH 2 ) 2 units, -N (CH) 2 CH 2 CN) 2 units, -N (C 3 H 6 NH 2 ) 2 units, -NHCH 2 CH 2 NH 2 units, -N (CH 2 CCH) 2 units, etc., but are not limited thereto. ..
Y is, -OH group, -N (CH 2 CH 2 CH 2 CH 3) 2 group, and is preferably one group selected from -N (CH 2 CH 2 OH) group consisting of 2 groups.
n represents 1 to 20, preferably 2 to 15, more preferably 4 to 12.
該ポリロタキサンの製造方法において後述するが、第１の基が、オキサゾリンモノマー又はその誘導体から由来するのがよく、具体的には、第１の基が、オキサゾリンモノマー又はその誘導体の開環重合で重合されてなるのがよい。
また、後述するように、環状分子が水酸基を有し、該水酸基に代えて、又は該水酸基と反応させて前記第１の基を設けるのがよい。
環状分子が水酸基を有する場合、第１の基は、該環状分子の水酸基の２％以上、好ましくは５％以上、より好ましくは１５％以上、最も好ましくは３０％以上が置換されて設けられるのがよい。
As will be described later in the method for producing the polyrotaxane, the first group is preferably derived from an oxazoline monomer or a derivative thereof, and specifically, the first group is polymerized by ring-opening polymerization of the oxazoline monomer or a derivative thereof. It should be done.
Further, as will be described later, it is preferable that the cyclic molecule has a hydroxyl group, and the first group is provided in place of the hydroxyl group or by reacting with the hydroxyl group.
When the cyclic molecule has a hydroxyl group, the first group is provided by substituting 2% or more, preferably 5% or more, more preferably 15% or more, and most preferably 30% or more of the hydroxyl group of the cyclic molecule. Is good.
第１の基は、連結基を介して環状分子に結合してもよい。
連結基を設けることにより、例えば、以下の効果を奏することができる。（１）上記ポリロタキサンの製造方法において後述するが、重合開始点となる化合物と反応できる官能基を連結基に備えることができる；（２）重合開始点となる化合物が環状分子に設けやすくなり、その導入量を効率よく制御することができる；（３）連結基を設け且つその種類を変化させることにより、上記ポリロタキサンの製造方法において使用する溶媒、反応条件に適応させることができる；など。
該連結基として、−ＣＨ２−ＣＨ２−、−ＣＨ２−ＣＨ２−ＣＨ２−、−ＣＨ２ＣＨ（ＯＨ）−ＣＨ２−、−ＣＨ２−ＣＨ２−ＣＨ２−ＣＨ２−、−ＣＯ−ＣＨ２−ＣＨ２−、−ＣＯ−Ｃ（ＣＨ３）２−ＣＨ２−、−ＣＯ−ＣＨ（ＯＨ）−ＣＨ２−、−ＣＯ−ＣＨ２−ＣＨ２−ＣＨ２−ＣＨ２−ＣＨ２−、−ＣＯ−ＣＨ２−ＣＨ２−ＣＨ２−ＣＨ（ＣＨ３）−を挙げることができるがこれらに限定されない。
The first group may be attached to the cyclic molecule via a linking group.
By providing the connecting group, for example, the following effects can be obtained. (1) As will be described later in the above method for producing polyrotaxane, the linking group can be provided with a functional group capable of reacting with the compound as the polymerization initiation point; (2) the compound as the polymerization initiation point can be easily provided in the cyclic molecule. The amount of the introduction can be efficiently controlled; (3) by providing a linking group and changing the type thereof, it can be adapted to the solvent and reaction conditions used in the above-mentioned method for producing polyrotaxane.
As the linking group, -CH 2 -CH 2 -, - CH 2 -CH 2 -CH 2 -, - CH 2 CH (OH) -CH 2 -, - CH 2 -CH 2 -CH 2 -CH 2 -, -CO-CH 2 -CH 2 -, - CO-C (CH 3) 2 -CH 2 -, - CO-CH (OH) -CH 2 -, - CO-CH 2 -CH 2 -CH 2 -CH 2 -CH 2 -, - CO-CH 2 -CH 2 -CH 2 -CH (CH 3) - can be exemplified without limitation.
以下、ポリロタキサンを構成する「環状分子」、「直鎖状分子」、「封鎖基」について説明する。なお、これらは従来公知のものを用いることができる。
＜＜環状分子＞＞
本発明のポリロタキサンの環状分子は、環状であり、開口部を有し、直鎖状分子によって串刺し状に包接されるものであれば、特に限定されない。
環状分子は、上述の任意の連結基を介して第１の基を有する。
環状分子は、上記第１の基以外の基を有してもよい。例えば、上記第１の基以外の基として、フェニル基、ベンジルカルバモイル基、フェニルエチルカルバモイル基、ベンジルエステル基、ブチルベンジルエステル基などを挙げることができるがこれらに限定されない。
環状分子として、例えば、α−シクロデキストリン、β−シクロデキストリン及びγ−シクロデキストリンからなる群から選択されるのがよい。
例えば、α−シクロデキストリンなどの−ＯＨ基の一部を、上述の任意の連結基、及び／又は上述の第１の基で置換してもよく、上記第１の基以外の基で置換されてもよい。
Hereinafter, the "cyclic molecule", the "linear molecule", and the "blocking group" constituting the polyrotaxane will be described. As these, conventionally known ones can be used.
<< Cyclic molecule >>
The cyclic molecule of the polyrotaxane of the present invention is not particularly limited as long as it is cyclic, has an opening, and is skewered by a linear molecule.
The cyclic molecule has a first group via any of the linking groups described above.
The cyclic molecule may have a group other than the first group. For example, examples of the group other than the first group include, but are not limited to, a phenyl group, a benzyl carbamoyl group, a phenylethyl carbamoyl group, a benzyl ester group, and a butyl benzyl ester group.
The cyclic molecule is preferably selected from, for example, the group consisting of α-cyclodextrin, β-cyclodextrin and γ-cyclodextrin.
For example, a part of the -OH group such as α-cyclodextrin may be substituted with any of the above-mentioned linking groups and / or the above-mentioned first group, and is substituted with a group other than the above-mentioned first group. You may.
＜＜直鎖状分子＞＞
本発明のポリロタキサンの直鎖状分子は、用いる環状分子の開口部に串刺し状に包接され得るものであれば、特に限定されない。
例えば、直鎖状分子として、ポリビニルアルコール、ポリビニルピロリドン、ポリ（メタ）アクリル酸、セルロース系樹脂（カルボキシメチルセルロース、ヒドロキシエチルセルロース、ヒドロキシプロピルセルロース等）、ポリアクリルアミド、ポリエチレンオキサイド、ポリエチレングリコール、ポリプロピレングリコール、ポリビニルアセタール系樹脂、ポリビニルメチルエーテル、ポリアミン、ポリエチレンイミン、カゼイン、ゼラチン、でんぷん等及び／またはこれらの共重合体、ポリエチレン、ポリプロピレン、およびその他オレフィン系単量体との共重合樹脂などのポリオレフィン系樹脂、ポリエステル樹脂、ポリ塩化ビニル樹脂、ポリスチレンやアクリロニトリル−スチレン共重合樹脂等のポリスチレン系樹脂、ポリメチルメタクリレートや（メタ）アクリル酸エステル共重合体、アクリロニトリル−メチルアクリレート共重合樹脂などのアクリル系樹脂、ポリカーボネート樹脂、ポリウレタン樹脂、塩化ビニル−酢酸ビニル共重合樹脂、ポリビニルブチラール樹脂等；及びこれらの誘導体又は変性体、ポリイソブチレン、ポリテトラヒドロフラン、ポリアニリン、アクリロニトリル−ブタジエン−スチレン共重合体（ＡＢＳ樹脂）、ナイロンなどのポリアミド類、ポリイミド類、ポリイソプレン、ポリブタジエンなどのポリジエン類、ポリジメチルシロキサンなどのポリシロキサン類、ポリスルホン類、ポリイミン類、ポリ無水酢酸類、ポリ尿素類、ポリスルフィド類、ポリフォスファゼン類、ポリケトン類、ポリフェニレン類、ポリハロオレフィン類、並びにこれらの誘導体からなる群から選ばれるのがよい。例えばポリエチレングリコール、ポリイソプレン、ポリイソブチレン、ポリブタジエン、ポリプロピレングリコール、ポリテトラヒドロフラン、ポリジメチルシロキサン、ポリエチレン、ポリプロピレン、ポリビニルアルコール及びポリビニルメチルエーテルからなる群から選ばれるのがよい。特にポリエチレングリコールであるのがよい。
<< Linear molecule >>
The linear molecule of the polyrotaxane of the present invention is not particularly limited as long as it can be skewered into the opening of the cyclic molecule used.
For example, as linear molecules, polyvinyl alcohol, polyvinylpyrrolidone, poly (meth) acrylic acid, cellulose-based resins (carboxymethyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose, etc.), polyacrylamide, polyethylene oxide, polyethylene glycol, polypropylene glycol, polyvinyl. Acetal resins, polyvinyl methyl ethers, polyamines, polyethyleneimines, caseins, gelatins, starches and / or copolymers thereof, copolymers of polyethylene, polypropylene, and other olefin monomers, and other polyolefin resins. Polyester resin, polyvinyl chloride resin, polystyrene resin such as polystyrene and acrylonitrile-styrene copolymer resin, polymethylmethacrylate and (meth) acrylic acid ester copolymer, acrylic resin such as acrylonitrile-methylacrylate copolymer resin, polycarbonate Resins, polyurethane resins, vinyl chloride-vinyl acetate copolymer resins, polyvinyl butyral resins, etc .; and derivatives or modified products thereof, polyisobutylene, poly tetrahydrofuran, polyaniline, acrylonitrile-butadiene-styrene copolymer (ABS resin), nylon, etc. Polyamides, polyimides, polyisoprenes, polydiene such as polybutadiene, polysiloxanes such as polydimethylsiloxane, polysulfones, polyimines, polyanacetic acetic acids, polyureas, polysulfides, polyphosphazenes, polyketones. , Polyphenylenes, polyhaloolefins, and derivatives thereof are preferably selected. For example, it may be selected from the group consisting of polyethylene glycol, polyisobutylene, polyisobutylene, polybutadiene, polypropylene glycol, polytetrahydrofuran, polydimethylsiloxane, polyethylene, polypropylene, polyvinyl alcohol and polyvinyl methyl ether. Especially polyethylene glycol is preferable.
直鎖状分子は、その重量平均分子量が１，０００以上、好ましくは３，０００〜１００，０００、より好ましくは６，０００〜５０，０００であるのがよい。
本願の、ポリロタキサンにおいて、（環状分子、直鎖状分子）の組合せが、（α−シクロデキストリン由来、ポリエチレングリコール由来）であるのがよい。
The weight average molecular weight of the linear molecule is preferably 1,000 or more, preferably 3,000 to 100,000, and more preferably 6,000 to 50,000.
In the polyrotaxane of the present application, the combination of (cyclic molecule, linear molecule) is preferably (derived from α-cyclodextrin, derived from polyethylene glycol).
＜＜封鎖基＞＞
本発明のポリロタキサンの封鎖基は、擬ポリロタキサンの両端に配置され、用いる環状分子が脱離しないように作用する基であれば、特に限定されない。
例えば、封鎖基として、ジニトロフェニル基類、シクロデキストリン類、アダマンタン基類、トリチル基類、フルオレセイン類、シルセスキオキサン類、ピレン類、置換ベンゼン類（置換基として、アルキル、アルキルオキシ、ヒドロキシ、ハロゲン、シアノ、スルホニル、カルボキシル、アミノ、フェニルなどを挙げることができるがこれらに限定されない。置換基は１つ又は複数存在してもよい。）、置換されていてもよい多核芳香族類（置換基として、上記と同じものを挙げることができるがこれらに限定されない。置換基は１つ又は複数存在してもよい。）、及びステロイド類からなる群から選ばれるのがよい。なお、ジニトロフェニル基類、シクロデキストリン類、アダマンタン基類、トリチル基類、フルオレセイン類、シルセスキオキサン類、及びピレン類からなる群から選ばれるのが好ましく、より好ましくはアダマンタン基類又はシクロデキストリン類であるのがよい。
<< Blockade Group >>
The blocking group of the polyrotaxane of the present invention is not particularly limited as long as it is a group arranged at both ends of the pseudopolyrotaxane and acts to prevent the cyclic molecule used from being detached.
For example, as a blocking group, dinitrophenyl groups, cyclodextrins, adamantan groups, trityl groups, fluoresceins, silsesquioxanes, pyrenes, substituted benzenes (as substituents, alkyl, alkyloxy, hydroxy, Halogen, cyano, sulfonyl, carboxyl, amino, phenyl and the like can be mentioned, but the present invention is not limited to these. One or more substituents may be present), and optionally substituted polynuclear aromatics (substitution). As the group, the same group as above can be mentioned, but the group is not limited thereto. One or more substituents may be present), and it is preferable to be selected from the group consisting of steroids. It is preferable to select from the group consisting of dinitrophenyl groups, cyclodextrins, adamantane groups, trityl groups, fluoresceins, silsesquioxanes, and pyrenes, and more preferably adamantane groups or cyclodextrins. It should be kind.
本発明のポリロタキサンは、式Ｉで表される第１の基を有することにより、溶媒に対する溶解性を向上させることができる。また、ポリロタキサンの材料としての特性を変化させることもできる。さらに、エチレンイミンの重合体部により親水性を付与させながら、アシル部位（ＲＣ＝Ｏ）のＲにより親水性の程度を容易に制御することができる。式Ｉにおけるｎは、重合体部の重合度を表すが、該ｎによりポリロタキサンの修飾量を可変とすることができ、溶解性、相溶性の制御を行うことができる。また、Ｙ、即ち末端基の存在により、反応、架橋するのに必要な官能基の付与が容易にできる。
つまり、本発明のポリロタキサンは、式Ｉで表される第１の基を有することにより、溶解性、相溶性を制御し、反応に必要な官能基の量も同時に制御することができる。
なお、本発明のポリロタキサンは、エステル基を有さないのが好ましい。エステル基を有さないことにより、エステル結合に由来する加水分解性への耐性を有するポリロタキサン及び該ポリロタキサンを有する材料を提供することができる。
The polyrotaxane of the present invention can improve the solubility in a solvent by having a first group represented by the formula I. In addition, the properties of polyrotaxane as a material can be changed. Further, the degree of hydrophilicity can be easily controlled by the R of the acyl moiety (RC = O) while imparting hydrophilicity by the polymer portion of ethyleneimine. Although n in the formula I represents the degree of polymerization of the polymer portion, the modification amount of polyrotaxane can be made variable by the n, and the solubility and compatibility can be controlled. Further, the presence of Y, that is, a terminal group, facilitates the addition of functional groups necessary for reaction and cross-linking.
That is, the polyrotaxan of the present invention has the first group represented by the formula I, so that the solubility and compatibility can be controlled, and the amount of the functional group required for the reaction can be controlled at the same time.
The polyrotaxane of the present invention preferably does not have an ester group. By not having an ester group, it is possible to provide a polyrotaxane having resistance to hydrolyzability derived from an ester bond and a material having the polyrotaxane.
なお、式Ｖで表される第４の基におけるｎは、オキサゾリン由来の鎖の平均重合度を表すが、該ｎは、次のように１Ｈ−ＮＭＲ測定により算出することができる。
平均重合度の算出の一例として、後述の実施例２で得られるＰＲ−ｇ−ＰＯＸ−２により説明する。図１は、ＰＲ−ｇ−ＰＯＸ−２の１Ｈ−ＮＭＲの測定結果を示す。
２．０ｐｐｍのＮ−ＣＨ３基の−ＣＨ３プロトンの積分値をｔとし、０．８ｐｐｍに示されるる側鎖末端ジブチルアミンの−ＣＨ３のプロトンの積分値をｐとする場合、以下の関係式で重合度ｎを算出することができる。
ｎ＝（ｔ／３）／（ｐ／６）
図１の場合、０．８ｐｐｍの積分値を６とすると、２．０ｐｐｍの積分値２２．６になるため、重合度ｎは（２４．３／３）／（６／６）＝８．１となる。
なお、上述したとおり、ｎは、１〜２０、好ましくは２〜１８、より好ましくは３〜１０であるのがよい。
The n in the fourth group represented by the formula V represents the average degree of polymerization of the chain derived from oxazoline, and the n can be calculated by 1 H-NMR measurement as follows.
As an example of calculating the average degree of polymerization, PR-g-POX-2 obtained in Example 2 described later will be described. FIG. 1 shows the measurement results of 1 H-NMR of PR-g-POX-2.
The integral value of -CH 3 protons of N-CH 3 groups 2.0ppm and t, the integral value of the indicated Ruru side chain terminal dibutylamine -CH 3 protons to 0.8ppm case of a p, the following The degree of polymerization n can be calculated by the relational expression.
n = (t / 3) / (p / 6)
In the case of FIG. 1, if the integral value of 0.8 ppm is 6, the integral value of 2.0 ppm is 22.6, so that the degree of polymerization n is (24.3 / 3) / (6/6) = 8.1. It becomes.
As described above, n is preferably 1 to 20, preferably 2 to 18, and more preferably 3 to 10.
＜本発明のポリロタキサンを有する組成物＞
本発明は、上述の環状分子の一部にオキサゾリン由来の基を有するポリロタキサン；を有する組成物を提供する。
該組成物は、上述の環状分子の一部にオキサゾリン由来の基を有するポリロタキサン以外の成分を有することができる。
上記ポリロタキサン以外の成分として、上記ポリロタキサン以外のポリロタキサン、ポリロタキサン以外のポリマー又は該ポリマーを形成するモノマー又はオリゴマー、溶媒などを挙げることができるが、これらの限定されない。
また、本発明の組成物から形成される成形体が、所望の特性を備えるための各種成分を挙げることができる。該各種成分として、酸化防止剤、ＵＶ吸収剤、架橋剤、架橋助剤、界面活性剤、乳化剤、可塑剤、重合開始剤、重合禁止剤、ポリマー微粒子、シリカ、アルミナなどの金属酸化物、表面調整剤、難燃剤を挙げることができるが、これらに限定されない。
<Composition having the polyrotaxane of the present invention>
The present invention provides a composition having a polyrotaxane having an oxazoline-derived group as part of the above-mentioned cyclic molecule.
The composition can have components other than polyrotaxane having an oxazoline-derived group as part of the above-mentioned cyclic molecule.
Examples of components other than the polyrotaxane include, but are not limited to, polyrotaxane other than the polyrotaxane, a polymer other than the polyrotaxane, a monomer or oligomer forming the polymer, and a solvent.
In addition, various components for allowing the molded product formed from the composition of the present invention to have desired properties can be mentioned. As the various components, antioxidants, UV absorbers, cross-linking agents, cross-linking aids, surfactants, emulsifiers, plasticizers, polymerization initiators, polymerization inhibitors, polymer fine particles, metal oxides such as silica and alumina, and surfaces. Modulators and flame retardants can be mentioned, but are not limited thereto.
＜＜本発明のポリロタキサン以外の成分＞＞
上記ポリロタキサン以外のポリロタキサンとして、上述の環状分子の一部にオキサゾリン由来の基を有さないポリロタキサンを挙げることができる。
ポリロタキサン以外のポリマーとして、ポリエーテル、ポリエステル、ポリカルボナート、ポリアクリレート、ポリウレタン、ポリウレア、ポリシロキサン、ポリオレフィン、ポリアミド、ポリアミド酸、ポリエン、ポリビニルエーテル、ポリビニルエステル及びこれらの共重合体、又はこれらの変性体を挙げることができるがこれらに限定されない。
<< Ingredients other than polyrotaxane of the present invention >>
Examples of the polyrotaxane other than the above-mentioned polyrotaxane include a polyrotaxane having no oxazoline-derived group as a part of the above-mentioned cyclic molecule.
Polymers other than polyrotaxane include polyether, polyester, polycarbonate, polyacrylate, polyurethane, polyurea, polysiloxane, polyolefin, polyamide, polyamic acid, polyene, polyvinyl ether, polyvinyl ester and copolymers thereof, or modifications thereof. The body can be raised, but not limited to these.
可塑剤として、フタル酸ジブチル、フタル酸ジ−２−エチルヘキシル、フタル酸ブチルベンジル、フタル酸ジヘキシル、アジピン酸ジオクチル、アジピン酸ビス（２−エチルヘキシル）、トリメリット酸トリス（２−エチルヘキシル）、リン酸トリクレジルなどを挙げることができるが、これらに限定されない。 As plasticizers, dibutyl phthalate, di-2-ethylhexyl phthalate, butylbenzyl phthalate, dihexyl phthalate, dioctyl adipate, bis (2-ethylhexyl) adipate, tristrimeritate (2-ethylhexyl), phosphate Examples include, but are not limited to, tricresyl.
架橋剤として、塩化シアヌル、トリメソイルクロリド、テレフタロイルクロリド、エピクロロヒドリン、ジブロモベンゼン、グルタールアルデヒド、脂肪族多官能イソシアネート、芳香族多官能イソシアネート、ジイソシアン酸トリレイン、ヘキサメチレンジイソシアネート、ジビニルスルホン、１，１’−カルボニルジイミダゾール、エチレンジアミン四酢酸二無水物、meso-ブタン-1,2,3,4-テトラカルボン酸二無水物などの酸無水物類、多官能酸ヒドラジン類、多官能カルボイミド類、アルコキシシラン類、およびそれらの誘導体を挙げることができるが、これらに限定されない。 As a cross-linking agent, cyanul chloride, trimeoyl chloride, terephthaloyl chloride, epichlorohydrin, dibromobenzene, glutaaldehyde, aliphatic polyfunctional isocyanate, aromatic polyfunctional isocyanate, trilein diisosocyanate, hexamethylene diisocyanate, divinyl sulfone , 1,1'-carbonyldiimidazole, ethylenediamine tetraacetate dianhydride, meso-butane-1,2,3,4-tetracarboxylic acid dianhydride and other acid anhydrides, polyfunctional acid hydrazines, polyfunctional Carboximides, alkoxysilanes, and derivatives thereof can be mentioned, but are not limited thereto.
ＵＶ吸収剤として、パラジメチルアミノ安息香酸２−エチルヘキシル、サリチル酸２−エチルヘキシル、２、４−ジヒドロキシベンゾフェノン、２−ヒドロキシ−４−ｎ−オクチルベンゾフェノン、２−（２’−ヒドロキシ−５’−ｔ−ブチルフェニル）ベンゾトリアゾール、ビス（２、２、６、６−テトラメチル−４−ピペリジル）−セバケート、パラメトキシケイ皮酸２エチルヘキシル、パラメトキシケイヒ酸イソプロピル、メトキシケイヒ酸エチルヘキシル、メトキシケイヒ酸オクチルなどを挙げることができるが、これらに限定されない。 As UV absorbers, 2-ethylhexyl paradimethylaminobenzoate, 2-ethylhexyl salicylate, 2,4-dihydroxybenzophenone, 2-hydroxy-4-n-octylbenzophenone, 2- (2'-hydroxy-5'-t- Butylphenyl) benzotriazole, bis (2,2,6,6-tetramethyl-4-piperidyl) -sevacate, diethylhexyl paramethoxysilicate, isopropyl paramethoxysilicate, ethylhexyl methoxycinnamate, octyl methoxycinnamate, etc. However, it is not limited to these.
光重合開始剤は、2,4,6-トリメチルベンゾイル-ジフェニル-ホスフィンオキシド（Lucirin（登録商標） TPO）などのベンゾイルホスフィンオキシド化合物；又はビス（2,4,6-トリメチルベンゾイル）-フェニルホスフィンオキシド（Irgacure（登録商標）819）などのビスアシルホスフィンオキシド化合物；1-ヒドロキシシクロヘキシルフェニルケトン（Irgacure（登録商標）184）などの1-ヒドロキシフェニルケトンなどを挙げることができるが、これらに限定されない。 The photopolymerization initiator is a benzoylphosphine oxide compound such as 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide (Lucirin® TPO); or bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide. Bisacylphosphine oxide compounds such as (Irgacure® 819); 1-hydroxyphenylketones such as 1-hydroxycyclohexylphenylketone (Irgacure® 184), and the like, but are not limited thereto.
熱重合開始剤としては、過酸化ベンゾイル、ラウロイルパーオキサイド、ｔ−ブチルパーオキシイソブチレート、ｔ−ブチルパーオキシ−２−エチルヘキサノエート、ｔ−ブチルパーオキシネオデカノエート、ｔ−へキシルパーオキシピバレート、ジイソプロピルパーオキシジカーボネート、ビス（４−ｔ−ブチルシクロヘキシル）パーオキシジカーボネート等の有機過酸化物系重合開始剤；２，２’−アゾビスイソブチロニトリル、２，２’−アゾビス（２，４−ジメチルバレロニトリル）、２，２’−アゾビス（４−メトキシ−２，４−ジメチルバレロニトリル）等のアゾ系重合開始剤を挙げることができるが、これらに限定されない。
溶媒として、メタノール、エタノール、イソプロピルアルコール、水、ジメチルホルムアミド、ジメチルアセトアミド、Ｎ−メチルピロリドン、アセトニトリルを挙げることができるがこれらに限定されない。
Examples of the thermal polymerization initiator include benzoyl peroxide, lauroyl peroxide, t-butylperoxyisobutyrate, t-butylperoxy-2-ethylhexanoate, t-butylperoxyneodecanoate, and t-. Organic peroxide-based polymerization initiators such as xylperoxypivalate, diisopropylperoxydicarbonate, and bis (4-t-butylcyclohexyl) peroxydicarbonate; 2,2'-azobisisobutyronitrile, 2, Examples of azo-based polymerization initiators such as 2'-azobis (2,4-dimethylvaleronitrile) and 2,2'-azobis (4-methoxy-2,4-dimethylvaleronitrile) can be mentioned, but are limited thereto. Not done.
Examples of the solvent include, but are not limited to, methanol, ethanol, isopropyl alcohol, water, dimethylformamide, dimethylacetamide, N-methylpyrrolidone, and acetonitrile.
＜本発明のポリロタキサンを含有する成形体＞
本発明は、上述のポリロタキサンを含有する成形体を提供する。
本発明の成形体は、該成形体の重量を１００ｗｔ％とした場合、本発明のポリロタキサンの量は、１００ｗｔ％中、０．１〜５０ｗｔ％、好ましくは０．３〜３０ｗｔ％、より好ましくは０．５〜２０ｗｔ％、最も好ましくは１〜１５ｗｔ％であるのがよい。
<Molded product containing the polyrotaxane of the present invention>
The present invention provides a molded product containing the above-mentioned polyrotaxane.
In the molded product of the present invention, when the weight of the molded product is 100 wt%, the amount of polyrotaxane of the present invention is 0.1 to 50 wt%, preferably 0.3 to 30 wt%, more preferably 0.3 to 50 wt% in 100 wt%. It is preferably 0.5 to 20 wt%, most preferably 1 to 15 wt%.
成形体として、上述のポリロタキサン同士の架橋体；上述のポリロタキサンとポリロタキサン以外の材料との架橋体；などを挙げることができる。
上述のポリロタキサンとポリロタキサン以外の材料との架橋体を形成するために、上述のポリロタキサン及びポリロタキサン以外の材料の双方に、双方が反応できる官能基を有し、該官能基同士が反応して架橋するのがよい。また、官能基同士が架橋剤を介して反応する場合も考えられる。官能基として、水酸基、アミノ基、チオール基、イソシアネート基、エポキシ基、カルボン酸基、酸無水物基、ラジカル重合性基などが挙げられる。
Examples of the molded product include a crosslinked product between the above-mentioned polyrotaxanes; a crosslinked product between the above-mentioned polyrotaxane and a material other than the polyrotaxane;
In order to form a crosslinked product of the above-mentioned polyrotaxane and a material other than polyrotaxane, both the above-mentioned polyrotaxane and the material other than polyrotaxane have functional groups capable of reacting with each other, and the functional groups react with each other to crosslink. Is good. It is also possible that the functional groups react with each other via a cross-linking agent. Examples of the functional group include a hydroxyl group, an amino group, a thiol group, an isocyanate group, an epoxy group, a carboxylic acid group, an acid anhydride group, and a radically polymerizable group.
これらの官能基は、上述のポリロタキサン、特に式Ｉで表される第１の基のＹ上に設けるか、連結基を有する場合には該連結基に有するか、環状分子が備える他の基に有する、などであるのがよい。例えば、官能基をＹ上に設ける場合であってＹがジエタノールアミン由来の基である場合、末端にＯＨ基を有することとなり、該ＯＨ基が上述の架橋反応の際の官能基として作用することができる。また、例えば、末端にＯＨ基を有するＹだけでなく、該ＯＨ基をラジカル重合性基などへと置換し、該ラジカル重合性基を、架橋反応の際の官能基として作用させることもできる。 These functional groups are provided on the above-mentioned polyrotaxane, particularly Y of the first group represented by the formula I, or if it has a linking group, it is contained in the linking group, or it is contained in another group contained in the cyclic molecule. It is better to have. For example, when a functional group is provided on Y and Y is a group derived from diethanolamine, it has an OH group at the terminal, and the OH group may act as a functional group in the above-mentioned cross-linking reaction. it can. Further, for example, not only Y having an OH group at the terminal but also the OH group can be substituted with a radically polymerizable group or the like so that the radically polymerizable group can act as a functional group in the cross-linking reaction.
上述のような双方が反応できる官能基を有する場合の他、架橋剤の種類、具体的には反応できる官能基が複数ある架橋剤を用いることにより、上述のポリロタキサンとポリロタキサン以外の材料との架橋体を形成することができる。
そのような架橋剤の例として、例えば、ポリイソシアネート化合物、多官能性カルボキシル化合物、多官能性酸無水物などを挙げることができるがこれらに限定されない。
上記ポリロタキサンを有する材料の架橋反応は、溶媒中または無溶媒で行うことができる。溶媒として、用途、加工方法に依存するが、公知の有機溶媒、水系溶媒、水などを使用することができる。
In addition to the case where both have a functional group capable of reacting as described above, by using a type of cross-linking agent, specifically, a cross-linking agent having a plurality of functional groups capable of reacting, the above-mentioned polyrotaxane and a material other than polyrotaxane can be crosslinked. Can form a body.
Examples of such cross-linking agents include, but are not limited to, polyisocyanate compounds, polyfunctional carboxyl compounds, polyfunctional acid anhydrides and the like.
The cross-linking reaction of the material having polyrotaxane can be carried out in a solvent or without a solvent. As the solvent, known organic solvents, aqueous solvents, water and the like can be used, although it depends on the application and the processing method.
本発明のポリロタキサン、該ポリロタキサンを有する組成物、ポリロタキサンを含有する成形体は、その特性から、種々の応用がある。応用として、例えば、粘着剤・接着剤、耐キズ性膜、防振・制振・免振材料、吸音材量、塗料、コーティング剤、シール材、インク添加物・バインダー、電気絶縁材料、電気・電子部品材料、光学材料、摩擦制御剤、化粧品材料、ゴム添加剤、発泡材料、樹脂改質・強靭化剤、樹脂の相溶化剤、電解質材料、レオロジー制御剤、増粘剤、繊維、医療用生体材料、化粧品材料、機械・自動車材料、建築材料、衣料・スポーツ用品などを挙げることができるがこれらに限定されない。 The polyrotaxane of the present invention, the composition having the polyrotaxane, and the molded article containing the polyrotaxane have various applications due to their characteristics. Applications include, for example, adhesives / adhesives, scratch-resistant films, anti-vibration / anti-vibration / anti-vibration materials, amount of sound absorbing material, paints, coating agents, sealing materials, ink additives / binders, electrical insulation materials, electricity / Electronic parts materials, optical materials, friction control agents, cosmetic materials, rubber additives, foam materials, resin modifiers / toughening agents, resin compatibilizers, electrolyte materials, rheology control agents, thickeners, fibers, medical use Biomaterials, cosmetic materials, machinery / automobile materials, building materials, clothing / sporting goods, etc. can be mentioned, but are not limited thereto.
＜本発明のポリロタキサンの製造方法＞
本発明のポリロタキサンは、例えば、次のような方法により製造することができる。
即ち、
Ｉ）環状分子の開口部が直鎖状分子によって串刺し状に包接されてなる擬ポリロタキサンの両端に前記環状分子が脱離しないように封鎖基を配置してなるポリロタキサンであって、前記環状分子が下記式ＩＩ
（式ＩＩ中、Ｚはｐ−トルエンスルホニル基（Ｔｓ基）又はメシル基（Ｍｓ基）、好ましくはＴｓ基を表す。
Ｘは、単結合又は第１の連結基を表す。第１の連結基としての−Ｘ−は、−ＣＨ２−ＣＨ２−、−ＣＨ２−ＣＨ２−ＣＨ２−、−ＣＨ２ＣＨ（ＯＨ）−ＣＨ２−、−ＣＨ２−ＣＨ２−ＣＨ２−ＣＨ２−、−ＣＯ−ＣＨ２−ＣＨ２−、−ＣＯ−Ｃ（ＣＨ３）２−ＣＨ２−、−ＣＯ−ＣＨ（ＯＨ）−ＣＨ２−、−ＣＯ−ＣＨ２−ＣＨ２−ＣＨ２−ＣＨ２−ＣＨ２−、−ＣＯ−ＣＨ２−ＣＨ２−ＣＨ２−ＣＨ（ＣＨ３）−からなる群から選択される１種であるのがよい）
で表される第２の基を有する第Ｉのポリロタキサンを準備する工程；
ＩＩ）前記第Ｉのポリロタキサンに式ＩＩＩ（式ＩＩＩ中、Ｒは、メチル基、エチル基、１−プロピル基、２−プロピル基、シクロプロピル基、ブチル基、又はベンジル基を表す）で表されるオキサゾリン誘導体を反応させて、式ＩＶ（式ＩＶ中、Ｘ、Ｚ及びＲは上述と同じ定義を有し、ｎは１〜２０を表す）で表される第３の基を有する第ＩＩのポリロタキサンを得る工程；及び
ＩＩＩ）前記第ＩＩのポリロタキサンを反応させて式Ｖ（式中、Ｘ、Ｒ及びｎは上述と同じ定義を有し、Ｙは末端基を表し、上述と同じ定義を有する。）で表される第４の基を有する第ＩＩＩのポリロタキサンを得る工程；
を有することにより、本発明のポリロタキサンを、具体的には、環状分子の開口部が直鎖状分子によって串刺し状に包接されてなる擬ポリロタキサンの両端に前記環状分子が脱離しないように封鎖基を配置してなるポリロタキサンであって、前記環状分子が式Ｖで表される第４の基を有する第ＩＩＩのポリロタキサンを得ることができる。
<Method for producing polyrotaxane of the present invention>
The polyrotaxane of the present invention can be produced, for example, by the following method.
That is,
I) A polyrotaxane obtained by arranging a blocking group at both ends of a pseudo-polyrotaxane in which the opening of a cyclic molecule is skewered by a linear molecule so that the cyclic molecule is not detached. Is the following formula II
(In Formula II, Z represents a p-toluenesulfonyl group (Ts group) or a mesyl group (Ms group), preferably a Ts group.
X represents a single bond or a first linking group. As the -X- first linking group, -CH 2 -CH 2 -, - CH 2 -CH 2 -CH 2 -, - CH 2 CH (OH) -CH 2 -, - CH 2 -CH 2 - CH 2 -CH 2 -, - CO -CH 2 -CH 2 -, - CO-C (CH 3) 2 -CH 2 -, - CO-CH (OH) -CH 2 -, - CO-CH 2 -CH 2 −CH 2 −CH 2 −CH 2 −, −CO−CH 2 −CH 2 −CH 2 −CH (CH 3 ) − It is preferable to be one selected from the group consisting of −)
The step of preparing the first polyrotaxane having the second group represented by;
II) The polyrotaxane of the first I is represented by the formula III (in the formula III, R represents a methyl group, an ethyl group, a 1-propyl group, a 2-propyl group, a cyclopropyl group, a butyl group, or a benzyl group). The oxazoline derivative is reacted with a third group having a third group represented by the formula IV (in the formula IV, X, Z and R have the same definitions as described above and n represents 1 to 20). Step of obtaining polyrotaxane; and III) Reacting the polyrotaxane of the second II with the formula V (in the formula, X, R and n have the same definition as described above, Y represents a terminal group and has the same definition as described above. A step of obtaining a third polyrotaxane having a fourth group represented by.);
By having the polyrotaxane of the present invention, specifically, the cyclic molecule is sealed at both ends of the pseudopolyrotaxane in which the opening of the cyclic molecule is skewered by the linear molecule so that the cyclic molecule is not detached. It is possible to obtain a third polyrotaxane in which the cyclic molecule has a fourth group represented by the formula V, which is a polyrotaxane having a group arranged therein.
工程Ｉ）は、環状分子が下記式ＩＩで表される第２の基を有する第Ｉのポリロタキサンを準備する工程である。
第Ｉのポリロタキサンは、次のように得ることができる。
Ｉ−１）環状分子の開口部が直鎖状分子によって串刺し状に包接されてなる擬ポリロタキサンの両端に前記環状分子が脱離しないように封鎖基を配置してなるポリロタキサンであって前記環状分子が水酸基を有するポリロタキサンにエチレンオキシド、環状カルボナート、Ｔ−Ｘ’−ＯＨ（式中、Ｔは、炭素数２〜４の環状エーテル基、Ｃｌ基、Ｂｒ基、又はＩ基を表し、Ｘ’は、第２の連結基を表す）で表される化合物を反応させて、−Ｘ−ＯＨ（式中、Ｘは上記と同じ定義を有する）で表される第１級アルコール基を有する第Ｉａのポリロタキサンを得るのがよい。
なお、Ｔ−Ｘ−ＯＨで表される化合物が下記式ＩＩｂで表される化合物であり、得られる−Ｘ−ＯＨ（式中、Ｘは上記と同じ定義を有する）で表される第１級アルコール基が下記式ＩＩａで表される基であるのがよい。
Step I) is a step of preparing the first polyrotaxane in which the cyclic molecule has a second group represented by the following formula II.
The polyrotaxane I can be obtained as follows.
I-1) A polyrotaxane in which a blocking group is arranged at both ends of a pseudo-polyrotaxane in which the opening of a cyclic molecule is skewered by a linear molecule so that the cyclic molecule is not detached. Polyrotaxane in which the molecule has a hydroxyl group, ethylene oxide, cyclic carbonate, TX'-OH (in the formula, T represents a cyclic ether group having 2 to 4 carbon atoms, a Cl group, a Br group, or an I group, and X'is , A compound represented by (representing a second linking group) is reacted to form a first Ia having a primary alcohol group represented by -X-OH (where X has the same definition as above). It is better to get polyrotaxane.
The compound represented by TX-OH is a compound represented by the following formula IIb, and the obtained first-class compound represented by -X-OH (in the formula, X has the same definition as above). The alcohol group is preferably a group represented by the following formula IIa.
工程Ｉ−１）は、用いるポリロタキサン、用いるＴ−Ｘ’−ＯＨに依存するが、例えば常圧から加圧下、常温から１５０℃の加熱下、触媒存在下、溶剤中という条件下で行うのがよい。 Step I-1) depends on the polyrotaxane used and TX'-OH used, but for example, it is carried out under the conditions of normal pressure to pressurization, heating from normal temperature to 150 ° C., presence of a catalyst, and solvent. Good.
次いで、Ｉ−２） 得られた第Ｉａのポリロタキサンを、ＺＣｌ（式中、Ｚは上記と同じ定義を有する）と反応させることにより、第Ｉのポリロタキサンを得ることができる。
ここで、ＺＣｌとして、ＴｓＣｌであることが好ましい。
工程Ｉ−１）は、用いる第Ｉａのポリロタキサン、用いるＺＣｌに依存するが、例えば常圧下、常温から８０℃の加熱下、塩基触媒下、溶媒中という条件下で行うのがよい。
Next, I-2) The obtained polyrotaxane of Ia can be reacted with ZCl (where Z has the same definition as above) to obtain the polyrotaxane of Ia.
Here, it is preferable that ZCl is TsCl.
Step I-1) depends on the polyrotaxane of Ia used and ZCl used, but it is preferable to carry out the step I-1) under the conditions of, for example, normal pressure, heating from room temperature to 80 ° C., base catalyst, and solvent.
工程ＩＩ）は、上記式ＩＩで表される第２の基を有する第Ｉのポリロタキサンに式ＩＩＩで表されるオキサゾリン誘導体を反応させて、式ＩＶで表される第３の基を有する第ＩＩのポリロタキサンを得る工程である。
工程ＩＩ）は、換言すると、重合開始点としてのＺ基（ＺはＴｓ又はＭｓを表す）に、モノマーであるオキサゾリン誘導体を反応させて、該オキサゾリン誘導体から形成されるオキサゾリウムカチオンの誘導体が活性種となり、リビング重合、好ましくはリビングカチオン重合を行う工程である。
式ＩＩＩで表されるオキサゾリン誘導体として、２−メチル−２−オキサゾリン、２−エチル−２−オキサゾリン、２−プロピル−２−オキサゾリン、２−イソプロピル−２−オキサゾリン、２−シクロプロピル−２−オキサゾリン、２−ブチル−２−オキサゾリンなどを挙げることができるがこれらに限定されない。なお、オキサゾリン誘導体を２種類以上混合して使用し、ランダム共重合ポリオキサゾリンを得てもよい。また、一種類のオキサゾリン誘導体を反応させてから、異なる種類のオキサゾリンを次に反応させ、ブロック共重合ポリオキサゾリンを得てもよい。
工程ＩＩ）は、用いる第Ｉのポリロタキサン、用いるオキサゾリン誘導体に依存するが、常圧下、５０℃から１５０℃の加熱下、溶媒中という条件下で行うことができる。
In step II), the oxazoline derivative represented by the formula III is reacted with the polyrotaxan I having the second group represented by the above formula II, and the second group having the third group represented by the formula IV is reacted. This is a step of obtaining the polyrotaxane of.
In step II), in other words, the Z group (Z represents Ts or Ms) as the polymerization initiation point is reacted with the oxazoline derivative as a monomer to obtain an oxazoline cation derivative formed from the oxazoline derivative. It is a step of becoming an active species and performing living polymerization, preferably living cationic polymerization.
As the oxazoline derivative represented by the formula III, 2-methyl-2-oxazoline, 2-ethyl-2-oxazoline, 2-propyl-2-oxazoline, 2-isopropyl-2-oxazoline, 2-cyclopropyl-2-oxazoline , 2-Butyl-2-oxazoline and the like, but are not limited thereto. Random copolymerized polyoxazoline may be obtained by mixing two or more kinds of oxazoline derivatives. Alternatively, one type of oxazoline derivative may be reacted and then a different type of oxazoline may be reacted next to obtain a block copolymer polyoxazoline.
Step II) depends on the first polyrotaxane used and the oxazoline derivative used, but can be carried out under normal pressure, heating at 50 ° C. to 150 ° C., and in a solvent.
工程ＩＩＩ）は、前記第ＩＩのポリロタキサンから、式Ｖで表される第４の基を有する第ＩＩＩのポリロタキサンを得る工程である。
換言すると、工程ＩＩＩ）は、上記工程ＩＩ）の重合反応を停止させる工程ということができる。
重合反応を停止させる化合物、即ちＹとなる化合物として、水（詳細には水とアルカリ）、
ＮＨＲ１Ｒ２（式中、Ｒ１及びＲ２は、各々独立に、上述と同じ定義を有する。）、−Ｎ３基を有する化合物、及びピペリジンからなる群から選ばれる１種と反応させるのがよい。
なお、ＮＨＲ１Ｒ２として、例えば、ＮＨ（ＣＨ２ＣＨ２ＯＨ）２、ＮＨ（ＣＨ２ＣＨ３）２、ＮＨ（ＣＨ２ＣＨ２ＣＨ３）、ＮＨ（ＣＨ２ＣＨ２ＣＨ２ＣＨ３）２、ＮＨ（ＣＨ２ＣＨ２ＣＨ２ＣＨ２ＣＨ３）２、ＮＨ（ＣＨ２ＣＨ２ＣＨ２ＣＨ２ＣＨ２ＣＨ３）２、ＮＨ（ＣＨ２ＣＨ２ＣＨ２ＣＨ２ＣＨ２ＣＨ２ＣＨ３）２、ＮＨ（ＣＨ２ＣＨ２ＣＨ２ＣＨ２ＣＨ２ＣＨ２ＣＨ２ＣＨ３）２、ＮＨ（ＣＨ２ＣＨ（ＣＨ３）ＣＨ３）２、ＮＨ（ＣＨ２ＣＨ（ＣＨ３）ＣＨ３）２、ＮＨ（ＣＨ２ＣＨ（ＣＨ２ＣＨ３）ＣＨ２ＣＨ２ＣＨ２ＣＨ３）２、ＮＨ（ＣＨ２ＣＨＣＨ２）２、ＮＨ（ＣＨ２ＣＨ２ＣＮ）２、ＮＨ（Ｃ３Ｈ６ＮＨ２）２、ＮＨＣＨ２ＣＨ２ＮＨ２、ＮＨ（ＣＨ２ＣＣＨ）２を挙げることができるがこれらに限定されない。
Step III) is a step of obtaining a third polyrotaxane having a fourth group represented by the formula V from the second polyrotaxane.
In other words, step III) can be said to be a step of stopping the polymerization reaction of step II).
As a compound that stops the polymerization reaction, that is, a compound that becomes Y, water (specifically, water and alkali),
React with one selected from the group consisting of NHR 1 R 2 (in the formula, R 1 and R 2 each independently have the same definition as above), a compound having -N 3 groups, and piperidine. Is good.
As NHR 1 R 2 , for example, NH (CH 2 CH 2 OH) 2 , NH (CH 2 CH 3 ) 2 , NH (CH 2 CH 2 CH 3 ), NH (CH 2 CH 2 CH 2 CH 3 ) 2 , NH (CH 2 CH 2 CH 2 CH 2 CH 3 ) 2 , NH (CH 2 CH 2 CH 2 CH 2 CH 2 CH 3 ) 2 , NH (CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 3) ) 2 , NH (CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 3 ) 2 , NH (CH 2 CH (CH 3 ) CH 3 ) 2 , NH (CH 2 CH (CH 3 ) CH 3 ) 2 , NH (CH 2 CH (CH 2 CH 3 ) CH 2 CH 2 CH 2 CH 3 ) 2 , NH (CH 2 CH CH 2 ) 2 , NH (CH 2 CH 2 CN) 2 , NH (C 3 H 6 NH) 2 ) 2 , NHCH 2 CH 2 NH 2 , NH (CH 2 CCH) 2 can be mentioned, but is not limited thereto.
本発明の製造方法は、上記の工程以外の工程を設けてもよい。
例えば、上記工程ＩＩＩ）後に、得られた第ＩＩＩのポリロタキサンをさらに修飾する工程を設けてもよい。例えば、第ＩＩＩのポリロタキサンの末端基Ｙをさらに修飾してもよい。
The manufacturing method of the present invention may be provided with steps other than the above steps.
For example, after the above step III), a step of further modifying the obtained third polyrotaxane may be provided. For example, the terminal group Y of the third polyrotaxane may be further modified.
（実施例）
以下、実施例に基づいて、本発明をさらに詳細に説明するが、本発明は本実施例に限定されるものではない。
各化合物の分析装置
１Ｈ−ＮＭＲ測定は、４００ＭＨｚ ＪＥＯＬ ＪＮＭ−ＡＬ４００（日本電子株式会社製）によって測定した。
分子量、分子量分布の測定は、ＴＯＳＯＨ ＨＬＣ−８２２０ＧＰＣ装置で行った。カラム：ＴＳＫガードカラムＳｕｐｅｒ ＡＷ−ＨとＴＳＫｇｅｌ Ｓｕｐｅｒ ＡＷＭ−Ｈ（２本連結）、溶離液：ジメチルスルホキシド（ＤＭＳＯ）／０．０１Ｍ ＬｉＢｒ、カラムオーブン：５０℃、流速：０．５ｍｌ／ｍｉｎ、試料濃度を約０．２ｗｔ／ｖｏｌ％、注入量：２０μｌ、前処理：０．２μｍフィルターでろ過、スタンダード分子量：ＰＥＯ、の条件下で測定した。
水酸基価、酸価の測定は、ＪＩＳ ００７０−１９９２に準ずる方法で測定した。
ガスクロマトグラフ（ＧＣ）は、島津製作所製のＧＣ−２０１４で測定した。
ＵＶスペクトルは、ダイオードアレイ分光光度計Agilent８４５３（Agilent Technology製）によって測定した。
熱分析、熱分解温度は、差動型示差熱天秤ＴＧ８１２０−１Ｃ（リガク製）で測定し、評価した。
(Example)
Hereinafter, the present invention will be described in more detail based on Examples, but the present invention is not limited to the present Examples.
Analyzer for each compound
1 1 H-NMR measurement was measured by 400 MHz JEOL JNM-AL400 (manufactured by JEOL Ltd.).
The molecular weight and the molecular weight distribution were measured by the TOSOH HLC-8220GPC device. Column: TSK guard column Super AW-H and TSKgel Super AWM-H (two connected), eluent: dimethyl sulfoxide (DMSO) / 0.01M LiBr, column oven: 50 ° C., flow rate: 0.5 ml / min, sample The concentration was measured under the conditions of about 0.2 wt / vol%, injection volume: 20 μl, pretreatment: filtration with a 0.2 μm filter, and standard molecular weight: PEO.
The hydroxyl value and acid value were measured by a method according to JIS 0070-1992.
The gas chromatograph (GC) was measured by GC-2014 manufactured by Shimadzu Corporation.
The UV spectrum was measured by a diode array spectrophotometer Agilent 8453 (manufactured by Agilent Technologies).
Thermal analysis and thermal decomposition temperature were measured and evaluated with a differential differential thermal balance TG8120-1C (manufactured by Rigaku).
＜合成例１：未修飾ポリロタキサンＸ１の調製＞
直鎖状分子：ポリエチレングリコール（Ｍｗ：２０，０００）、環状分子：α−シクロデキストリン（以下、単に「α−ＣＤ」と略記する場合がある）、封鎖基：アダマンタン基からなるポリロタキサン（以下、単に「ＡＰＲ２０」又は「未修飾ポリロタキサンＸ１」と略記する場合がある）（重量平均分子量Ｍｗ＝６５，０００）をＷＯ２００５／０５２０２６又はＷＯ２０１３／１４７３０１に記載されている方法で作製した。
なお、１Ｈ−ＮＭＲ測定によって計算されたＡＰＲ２０の包接率は２７％であった。ここで、包接率は、α−ＣＤがポリエチレングリコールにより串刺し状に包接される際にα−ＣＤが最大限に包接される量を１として得た（Macromolecules 1993, 26, 5698-5703を参照のこと。なお、この文献の内容はすべて本明細書に組み込まれる）。
ＧＰＣにより平均重量分子量Ｍｗは６５，０００であった。
<Synthesis Example 1: Preparation of unmodified polyrotaxane X1>
Linear molecule: Polyethylene glycol (Mw: 20,000), Cyclic molecule: α-cyclodextrin (hereinafter, may be simply abbreviated as “α-CD”), Closing group: Polyrotaxane consisting of adamantane group (hereinafter, hereafter. (Sometimes abbreviated simply as "APR20" or "unmodified polyrotaxane X1") (weight average molecular weight Mw = 65,000) was made by the method described in WO2005 / 052026 or WO2013 / 147301.
The inclusion rate of APR20 calculated by 1 1 H-NMR measurement was 27%. Here, the inclusion rate was obtained by setting the amount of α-CD to be maximally included when α-CD was skewered with polyethylene glycol (Macromolecules 1993, 26, 5698-5703). (Note that the entire contents of this document are incorporated herein by reference).
The average weight molecular weight Mw was 65,000 by GPC.
＜合成例２：グリシドール修飾ポリロタキサンＧＡＰＲの合成＞
ポリロタキサンＡＰＲ２０ ５ｇを反応容器に入れ、その後、１．５Ｎ ＮａＯＨ水溶液２５ｇを入れて溶解させた。得られた溶液を撹拌、氷浴で冷やしながら、グリシドール２５ｇをゆっくり滴下し、一晩攪拌した。その後、６Ｎ塩酸を用いて反応水溶液を中和した。得られた水溶液を透析チューブにより３日間透析を行った。次いで水溶液を凍結乾燥で乾燥し、白色粉末固体を６．３ｇ得て、グリシドール修飾ポリロタキサンであるＧＡＰＲを得た。なお、透析チューブによる透析の代わりに、得られた反応水溶液をメタノールに注ぎ、固体を析出させた後、得られた固体をさらに純粋で洗浄し、乾燥しても同様なＧＡＰＲが得られた。
ＧＰＣで分析した結果、重量平均分子量Ｍｗ＝６８，０００であった。滴定による水酸基価を測定した結果、６９３ｍｇＫＯＨ／ｇであった。
<Synthesis Example 2: Synthesis of Glycidol-Modified Polyrotaxane GAPR>
5 g of polyrotaxane APR20 was placed in a reaction vessel, and then 25 g of a 1.5N NaOH aqueous solution was added and dissolved. While stirring the obtained solution and cooling it in an ice bath, 25 g of glycidol was slowly added dropwise, and the mixture was stirred overnight. Then, the reaction aqueous solution was neutralized with 6N hydrochloric acid. The obtained aqueous solution was dialyzed against a dialysis tube for 3 days. The aqueous solution was then lyophilized to give 6.3 g of a white powder solid to give GAPR, a glycidol-modified polyrotaxane. Instead of dialysis with a dialysis tube, the obtained reaction aqueous solution was poured into methanol to precipitate a solid, and then the obtained solid was further washed with pure water and dried to obtain the same GAPR.
As a result of analysis by GPC, the weight average molecular weight was Mw = 68,000. As a result of measuring the hydroxyl value by titration, it was 693 mgKOH / g.
＜合成例３：トシル基修飾ポリロタキサンＴｓＧＡＰＲの合成＞
反応容器にグリシドール修飾ポリロタキサンＧＡＰＲ ３ｇ及びピリジン２０ｍｌを入れ、ＧＡＰＲを溶解させた。得られた溶液を含む容器を氷水で冷却しながら、ピリジン１０ｍｌに溶解したトシルクロリド４．３ｇをゆっくり滴下し、撹拌しながら５時間反応させた。反応液を水３００ｍｌに注ぎ、反応生成物を析出させ、遠心分離機で固体を分離した。得られた固体を１Ｎ ＨＣｌで洗浄した後、数回純水で洗浄後、遠心分離機で固体を回収し、乾燥させ、トシル基で修飾されたポリロタキサンＴｓＧＡＰＲ ７．８ｇを得た。
ＧＰＣで分析した結果、Ｍｗ＝１１３，８００、Ｍｗ／Ｍｎ＝１．３であった。ＵＶ分光法の測定により、導入されたトシル基の量が３．９ｍｍｏｌ／ｇであった。
<Synthesis Example 3: Synthesis of Tosyl Group-Modified Polyrotaxane TsGAPR>
3 g of glycidol-modified polyrotaxane GAPR and 20 ml of pyridine were placed in a reaction vessel to dissolve GAPR. While cooling the container containing the obtained solution with ice water, 4.3 g of tosyl lolide dissolved in 10 ml of pyridine was slowly added dropwise, and the mixture was reacted for 5 hours with stirring. The reaction solution was poured into 300 ml of water to precipitate the reaction product, and the solid was separated by a centrifuge. The obtained solid was washed with 1N HCl, washed with pure water several times, and then recovered with a centrifuge and dried to obtain 7.8 g of polyrotaxane TsGAPR modified with a tosyl group.
As a result of analysis by GPC, Mw = 113,800 and Mw / Mn = 1.3. The amount of tosyl group introduced was 3.9 mmol / g as measured by UV spectroscopy.
（実施例１）
８０℃、２時間減圧乾燥したトシル基修飾ポリロタキサンＴｓＧＡＰＲ １．０ｇを１８．２ｇのＤＭＦに溶解し、８０℃、窒素ブローしながら、２−メチル−２−オキサゾリン１．７ｇを加えて一晩反応させた。その後、ジブチルアミン１．１ｇを添加し、さらに一晩反応を継続した。反応液を水で薄めて、透析膜で透析を２日間行い、凍結乾燥し、白色固体（ＰＲ−ｇ−ＰＯＸ−１）１．２ｇを得た。
ＧＰＣ測定により、Ｍｗ＝３９９，０００、Ｍｗ／Ｍｎ＝１．５であった。１Ｈ−ＮＭＲ分析により、ＣＤにポリ（２−メチル−２−オキサゾリン）側鎖を有し、側鎖末端に−Ｎ（ＣＨ２ＣＨ２ＣＨ２ＣＨ３）２基が付与されたことが分かり、ポリ（２−メチル−２オキサゾリン）の側鎖の重合度ｎは約４．０であった。
(Example 1)
1.0 g of tosyl group-modified polyrotaxane TsGAPR dried under reduced pressure at 80 ° C. for 2 hours was dissolved in 18.2 g of DMF, and 1.7 g of 2-methyl-2-oxazoline was added while blowing nitrogen at 80 ° C. and reacted overnight. I let you. Then, 1.1 g of dibutylamine was added, and the reaction was continued overnight. The reaction mixture was diluted with water, dialyzed against a dialysis membrane for 2 days, and freeze-dried to obtain 1.2 g of a white solid (PR-g-POX-1).
By GPC measurement, Mw = 399,000 and Mw / Mn = 1.5. By 1 H-NMR analysis, CD to have a poly (2-methyl-2-oxazoline) side chains, -N its side chain end (CH 2 CH 2 CH 2 CH 3) shows that the 2 group is assigned , The degree of polymerization n of the side chain of poly (2-methyl-2oxazoline) was about 4.0.
（実施例２）
実施例１の２−メチル−２−オキサゾリン「１．７ｇ」及びジブチルアミン「１．１ｇ」の代わりに、２−メチル−２−オキサゾリン「３．４ｇ」及びジブチルアミン「２．１ｇ」を用いた以外、実施例１と同様にして、白色固体（ＰＲ−ｇ−ＰＯＸ−２）１．８ｇを得た。
ＧＰＣ測定により、Ｍｗ＝６２８，０００、Ｍｗ／Ｍｎ＝１．７であった。１Ｈ−ＮＭＲ分析により、ポリ（２−メチル−２−オキサゾリン）の側鎖の重合度ｎは約８．１であった。水酸基価を測定した結果、８０ｍｇＫＯＨ／ｇであった。
(Example 2)
Instead of 2-methyl-2-oxazoline "1.7 g" and dibutylamine "1.1 g" in Example 1, 2-methyl-2-oxazoline "3.4 g" and dibutylamine "2.1 g" were used. In the same manner as in Example 1, 1.8 g of a white solid (PR-g-POX-2) was obtained.
By GPC measurement, Mw = 628,000 and Mw / Mn = 1.7. 1 By 1 H-NMR analysis, the degree of polymerization n of the side chain of poly (2-methyl-2-oxazoline) was about 8.1. As a result of measuring the hydroxyl value, it was 80 mgKOH / g.
（実施例３）
実施例１の２−メチル−２−オキサゾリン「１．７ｇ」及びジブチルアミン「１．１ｇ」の代わりに、２−メチル−２−オキサゾリン「６．８ｇ」及びジブチルアミン「４．１ｇ」を用いた以外、実施例１と同様にして、白色固体（ＰＲ−ｇ−ＰＯＸ−３）２．８ｇを得た。
ＧＰＣ測定により、Ｍｗ＝５１０，０００、Ｍｗ／Ｍｎ＝２．５であった。１Ｈ−ＮＭＲ分析により、ポリ（２−メチル−２−オキサゾリン）の側鎖の重合度ｎは約７．８であった。水酸基価を測定した結果、５３ｍｇＫＯＨ／ｇであった。
(Example 3)
2-Methyl-2-oxazoline "6.8 g" and dibutylamine "4.1 g" were used in place of 2-methyl-2-oxazoline "1.7 g" and dibutylamine "1.1 g" of Example 1. A white solid (PR-g-POX-3) of 2.8 g was obtained in the same manner as in Example 1.
By GPC measurement, Mw = 510,000 and Mw / Mn = 2.5. 1 By 1 H-NMR analysis, the degree of polymerization n of the side chain of poly (2-methyl-2-oxazoline) was about 7.8. As a result of measuring the hydroxyl value, it was 53 mgKOH / g.
（実施例４）
実施例１のジブチルアミン１．１ｇの代わりに、ジアタノールアミン０．８４ｇを使用する以外、実施例１と同様にして、白色固体（ＰＲ−ｇ−ＰＯＸ−４）１．４ｇを得た。
ＧＰＣ測定により、Ｍｗ＝３２１，０００、Ｍｗ／Ｍｎ＝２．６であった。１Ｈ−ＮＭＲ分析により、ＣＤにポリ（２−メチル−２−オキサゾリン）側鎖を有し、側鎖末端に−Ｎ（ＣＨ２ＣＨ２ＯＨ）２基が付与されたことが分かり、ポリ（２−メチル−２−オキサゾリン）の側鎖の重合度ｎは約８．０であった。
(Example 4)
1.4 g of a white solid (PR-g-POX-4) was obtained in the same manner as in Example 1 except that 0.84 g of diatanolamine was used instead of 1.1 g of dibutylamine of Example 1.
By GPC measurement, Mw = 321,000 and Mw / Mn = 2.6. By 1 H-NMR analysis, CD to have a poly (2-methyl-2-oxazoline) side chains, see that -N in the side chain end (CH 2 CH 2 OH) 2 group is assigned, poly ( The degree of polymerization n of the side chain of 2-methyl-2-oxazoline) was about 8.0.
（実施例５）
実施例１のジブチルアミン１．１ｇの代わりに、水４ｇ及び炭酸ナトリウム４．２４ｇを使用する以外、実施例１と同様にして、白色固体（ＰＲ−ｇ−ＰＯＸ−５）２．１ｇを得た。
ＧＰＣ測定により、Ｍｗ＝４６２，０００、Ｍｗ／Ｍｎ＝２．９であった。１Ｈ−ＮＭＲ分析により、ＣＤにポリ（２−メチル−２−オキサゾリン）側鎖を有し、側鎖末端に−ＯＨ基が付与されたことが分かり、ポリ（２−メチル−２−オキサゾリン）の側鎖の重合度ｎは約８．０であった。
(Example 5)
2.1 g of a white solid (PR-g-POX-5) was obtained in the same manner as in Example 1 except that 4 g of water and 4.24 g of sodium carbonate were used instead of 1.1 g of dibutylamine of Example 1. It was.
By GPC measurement, Mw = 462,000 and Mw / Mn = 2.9. 1 1 H-NMR analysis revealed that the CD had a poly (2-methyl-2-oxazoline) side chain and a -OH group was added to the side chain end, and poly (2-methyl-2-oxazoline). The degree of polymerization n of the side chain of No. 1 was about 8.0.
（実施例６）
実施例２で得られたＰＲ−ｇ−ＰＯＸ−２を用いて、各種溶媒への溶解性を測定した。その結果を表１に示す。なお、溶解性について、１０ｗｔ％の濃度で、５℃、２５℃及び６０℃で行った。
表１における評価◎、○及び×は次のとおりである。
◎：溶解して透明；
○：溶解して濁る；
×：不溶物がある。
(Example 6)
The solubility in various solvents was measured using the PR-g-POX-2 obtained in Example 2. The results are shown in Table 1. The solubility was carried out at a concentration of 10 wt% at 5 ° C., 25 ° C. and 60 ° C.
Evaluations ⊚, ◯ and × in Table 1 are as follows.
⊚: Melted and transparent;
◯: Melts and becomes cloudy;
X: There is an insoluble matter.
（比較例１）
合成例１で得られた未修飾ポリロタキサンＸ１を用いて、実施例６と同様に、各種溶媒への溶解性を測定した。その結果についても、表１に示す。
(Comparative Example 1)
Using the unmodified polyrotaxane X1 obtained in Synthesis Example 1, the solubility in various solvents was measured in the same manner as in Example 6. The results are also shown in Table 1.
（比較例２）
合成例２で得られたＧＡＰＲを用いて、実施例６と同様に、各種溶媒への溶解性を測定した。その結果についても、表１に示す。
(Comparative Example 2)
Using the GAPR obtained in Synthesis Example 2, the solubility in various solvents was measured in the same manner as in Example 6. The results are also shown in Table 1.
表１から次のことがわかる。即ち、本発明のポリロタキサンは、ジクロロメタン、クロロホルム、メタノールなどのアルコール系、水、アセトニトリル、ジメチルホルムアミド、ジメチルアセトアミド、Ｎ−メチルピロリドンなど、一般的に用いられる溶媒への溶解性が向上したことがわかる。 The following can be seen from Table 1. That is, it can be seen that the polyrotaxane of the present invention has improved solubility in alcohol-based solvents such as dichloromethane, chloroform and methanol, and commonly used solvents such as water, acetonitrile, dimethylformamide, dimethylacetamide and N-methylpyrrolidone. ..
（実施例７）
実施例２で得られたポリロタキサンＰＲ−ｇ−ＰＯＸ−２ ０．６２ｇ、分子量５３０のポリカプロラクトンジオール０．２２ｇ、両末端イソシアネート基変性したポリカプロラクトンジオール（分子量５３０のプレポリマー）０．３１ｇ、ジブチルジラウリル酸スズ０．７ｍｇ、メチルセロソルブ０．９６ｇを均一に混合し、基板に塗布し、１５０℃、３ｈ加熱架橋したところ、柔軟性のある透明なエラストマーシートを得た。
(Example 7)
Polyrotaxane PR-g-POX-2 0.62 g obtained in Example 2, polycaprolactone diol having a molecular weight of 530, 0.22 g, polycaprolactone diol modified with isocyanate groups at both ends (prepolymer having a molecular weight of 530), 0.31 g, dibutyl 0.7 mg of tin dilaurylate and 0.96 g of methyl cellosolve were uniformly mixed, applied to a substrate, and crosslinked by heating at 150 ° C. for 3 hours to obtain a flexible transparent elastomer sheet.
（実施例８）
実施例３で得られたＰＲ−ｇ−ＰＯＸ−３を用いて、空気中におけるＴＧ／ＤＴＡ熱分析を行い、室温から５００℃まで、加熱速度５℃／分で、質量の５％減量、１０％減量の温度を測定した。その結果を表２に示す。
(Example 8)
Using the PR-g-POX-3 obtained in Example 3, TG / DTA thermal analysis was performed in air, and the mass was reduced by 5% from room temperature to 500 ° C. at a heating rate of 5 ° C./min, 10 % Weight loss temperature was measured. The results are shown in Table 2.
（比較例３）
α−シクロデキストリンの水酸基の一部を２−ヒドロキシプロピル基で修飾し、その後、ε−カプロラクトンモノマーでグラフト重合したポリカプロラクトン（ポリエステル）側鎖を有するポリロタキサン、ＳＨ３４００Ｐ（アドバンスト・ソフトマテリアルズ製）を用いて、実施例８と同様な測定を行った。その結果を表２に示す。
表２から、エステル結合をもたない実施例８のポリロタキサンは、エステル結合を有する比較例３のポリロタキサンよりも、分解温度が高くなり、耐熱性、耐候性に優れることがわかる。また、実施例３で得られたＰＲ−ｇ−ＰＯＸ−３を含む実施例で得られたポリロタキサンは、エステル基を有さないポリロタキサンであるので、エステル結合に由来する加水分解性への耐性を有する材料を提供することができる。
(Comparative Example 3)
SH3400P (manufactured by Advanced Soft Materials), a polyrotaxane having a polycaprolactone (polyester) side chain in which a part of the hydroxyl group of α-cyclodextrin is modified with a 2-hydroxypropyl group and then graft-polymerized with ε-caprolactone monomer is used. Using it, the same measurement as in Example 8 was performed. The results are shown in Table 2.
From Table 2, it can be seen that the polyrotaxane of Example 8 having no ester bond has a higher decomposition temperature than the polyrotaxane of Comparative Example 3 having an ester bond, and is excellent in heat resistance and weather resistance. Further, since the polyrotaxane obtained in the example containing PR-g-POX-3 obtained in Example 3 is a polyrotaxane having no ester group, it is resistant to hydrolyzability derived from the ester bond. The material to have can be provided.
Claims (14)
（式中、Ｒはメチル基、エチル基、１−プロピル基、２−プロピル基、シクロプロピル基、ブチル基、又はベンジル基を表し；
Ｙは末端基を表し；
ｎは１〜２０を表す）
で表す第１の基を有するポリロタキサン。
(In the formula, R represents a methyl group, an ethyl group, a 1-propyl group, a 2-propyl group, a cyclopropyl group, a butyl group, or a benzyl group;
Y represents the terminal group;
n represents 1 to 20)
Polyrotaxane having a first group represented by.
ＩＩ）前記第Ｉのポリロタキサンに式ＩＩＩ（式ＩＩＩ中、Ｒは、メチル基、エチル基、１−プロピル基、２−プロピル基、シクロプロピル基、ブチル基、又はベンジル基を表す）で表されるオキサゾリン誘導体を反応させて、式ＩＶ（式ＩＶ中、Ｘ、Ｚ及びＲは上述と同じ定義を有し、ｎは１〜２０を表す）で表される第３の基を有する第ＩＩのポリロタキサンを得る工程；及び
ＩＩＩ）前記第ＩＩのポリロタキサンを反応させて式Ｖ（式中、Ｘ、Ｒ及びｎは上述と同じ定義を有し、Ｙは末端基を表す）で表される第４の基を有する第ＩＩＩのポリロタキサンを得る工程；
を有することにより、環状分子の開口部が直鎖状分子によって串刺し状に包接されてなる擬ポリロタキサンの両端に前記環状分子が脱離しないように封鎖基を配置してなるポリロタキサンであって、前記環状分子が式Ｖで表される第４の基を有するポリロタキサンを得る、式Ｖで表される第４の基を有する第ＩＩＩのポリロタキサンの製造方法。
II) The polyrotaxane of the first I is represented by the formula III (in the formula III, R represents a methyl group, an ethyl group, a 1-propyl group, a 2-propyl group, a cyclopropyl group, a butyl group, or a benzyl group). In the formula IV, X, Z and R have the same definitions as described above, and n represents 1 to 20 of the second II having a third group represented by the reaction. Step of obtaining a polyrotaxan; and III) The fourth polyrotaxan represented by the formula V (wherein X, R and n have the same definitions as described above and Y represents a terminal group) by reacting the polyrotaxan of the second II. Step of obtaining a third polyrotaxane having a group of;
A polyrotaxan obtained by arranging a blocking group at both ends of a pseudo-polyrotaxane in which the opening of a cyclic molecule is skewered by a linear molecule so that the cyclic molecule is not detached. A method for producing a third polyrotaxane having a fourth group represented by the formula V, wherein the cyclic molecule obtains a polyrotaxan having a fourth group represented by the formula V.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2008108411A1 (en) * | 2007-03-06 | 2008-09-12 | Advanced Softmaterials, Inc. | Polyrotaxanes and material having polyrotaxane, crosslinked polyrotaxanes and material having the crosslinked polyrotaxane, and processes for producing these |
| WO2009136618A1 (en) * | 2008-05-07 | 2009-11-12 | アドバンスト・ソフトマテリアルズ株式会社 | Polyrotaxane, crosslinked structure comprising polyrotaxane and polymer, and processes for producing these |
| JP4521875B2 (en) * | 2005-08-31 | 2010-08-11 | 日産自動車株式会社 | Hydrophobic modified polyrotaxane |
| JP2012172083A (en) * | 2011-02-22 | 2012-09-10 | Sumitomo Chemical Co Ltd | Polyrotaxane and curable composition |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP4521875B2 (en) * | 2005-08-31 | 2010-08-11 | 日産自動車株式会社 | Hydrophobic modified polyrotaxane |
| WO2008108411A1 (en) * | 2007-03-06 | 2008-09-12 | Advanced Softmaterials, Inc. | Polyrotaxanes and material having polyrotaxane, crosslinked polyrotaxanes and material having the crosslinked polyrotaxane, and processes for producing these |
| WO2009136618A1 (en) * | 2008-05-07 | 2009-11-12 | アドバンスト・ソフトマテリアルズ株式会社 | Polyrotaxane, crosslinked structure comprising polyrotaxane and polymer, and processes for producing these |
| JP2012172083A (en) * | 2011-02-22 | 2012-09-10 | Sumitomo Chemical Co Ltd | Polyrotaxane and curable composition |
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