JP2005132760A - Oligomer complexing at both ends - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To obtain a new oligomer complexing at both ends, containing a complexing group at one end or both ends. <P>SOLUTION: The oligomer complexing at both ends contains crown ether groups represented by the formula (n is an integer of 2-100; R is a 1-3C alkyl group or a phenyl group) at both ends. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

  The present invention relates to an oligomer having a complex-forming group at both ends. The present invention also relates to a both-end complex-forming oligomer and a polymer obtained by polymerization by complex formation at both ends.

  The present inventors reported that an olefin oligomer having a functional vinylidene double bond at one or both ends can be obtained by highly controlled pyrolysis of polyolefin such as polypropylene and polystyrene (for example, Non-Patent Document 1). reference).

  Furthermore, the present inventors have found that a copolymer is formed between the maleated oligoolefin and various monomers by introducing a maleic group at one or both ends (for example, see Patent Document 1).

In addition, the present inventors have succeeded in finding a photopolymerization / dissociation reversible telechelic oligomer having an anthracene group as a photofunctional group at one or both ends and a production method thereof. It has also been found that this photopolymerization / dissociation reversible telechelic oligomer occurs reversibly depending on the wavelength of actinic rays irradiated by anthracene dimerization and dissociation (for example, see Patent Document 2).
JP 2002-161141 JP 2000-220413 A Macromolechles, 28, 7973 (1995)

  An object of the present invention is to find a novel both-end complex-forming oligomer having a complexable group at one end or both ends and a polymer polymerized by complexing with the same.

  The inventors of the present invention have intensively studied to achieve such an object, and an oligomer having a crown ether group bonded as a complex-forming group at one or both ends is complexed with a terminal diamino compound and polymerized to form a high molecular weight polymer. The present invention has been completed by finding out that coalescence is provided.

  The complex-forming oligomer according to the present invention is an oligomer having a crown ether group at both ends. More specifically, it has a structure represented by the following formula.

（式中、ｎは２〜１００の正数であり、Ｒは炭素数１〜３のアルキル基またはフェニル基を表す。）で表される光重合／解離可逆性テレケリックオリゴマーである。また上式ではクラウンエーテルが１８−クラウン−６の場合が示されているが、その他のサイズのクラウンエーテルも含まれる。

(Wherein n is a positive number of 2 to 100 and R represents an alkyl group having 1 to 3 carbon atoms or a phenyl group.), A photopolymerization / dissociation reversible telechelic oligomer. In the above formula, the crown ether is 18-crown-6, but other sizes of crown ethers are also included.

  The present invention further relates to a polymer polymerized by complex formation between a crown ether-ammonium ion between such a complex-forming oligomer and a compound having an amino group at both ends. One specific example thereof has a structure of a repeating unit represented by the following formula.

  Since the complex-forming oligomer according to the present invention has a crown ether group at both ends thereof, the complex-forming reaction proceeds with the terminal diamine compound to polymerize, thereby giving a high molecular weight polymer.

(Complex-forming oligomer)
The complex-forming oligomer of the present invention has an oligomer structure substituted at the terminal portion with a substituent capable of complex formation. Although there is no restriction | limiting in particular about the repeating monomer which comprises this oligomer, and a repeating number, An alpha olefin monomer is mentioned as a preferable monomer. Particularly preferred are aliphatic olefins such as ethylene, propylene, 1-butylene and 1-pentene, and aromatic olefins such as styrene and alkyl-substituted styrene.

  The number of repeating monomers is not particularly limited, but is preferably in the range of 1 to 100, and more preferably 10 to 50.

The substituent capable of complex formation is not particularly limited, but may be any one of a set of functional groups capable of performing a known complex formation reaction. Specific examples include a complex formation reaction between crown ether and ammonium ions. In this case, the substituent capable of complex formation may be a crown ether group or an ammonium group. In the present invention, examples of the substituent capable of complex formation include crown ether. Examples of the atoms for complex formation include oxygen, nitrogen, and sulfur, but oxygen is preferred. The size of the crown ether is not particularly limited, but a crown ether having 4 to 10 oxygen atoms is preferable. Specifically, 12-crown-4, 13-crown-4, 14-crown-4, 15-crown-5, 16-crown-5, 17-crown-5, 18-crown-6, 20-crown -6, 21-crown-7, 24-crown-8, 27-crown-9, 30-crown-10. In the present invention, complex formation with a diamine compound is preferred. In this case, 18-crown-6 and 20-crown-6 are preferred.
The bond between these complex-forming groups and the oligomer is not particularly limited, but is preferably a covalent bond in consideration of scientific stability. Specifically, various types of conventionally known reaction forms capable of forming a covalent bond between the functional group possessed by the substituent having a complex-forming group and the functional group possessed by the terminal of the oligomer can be selected. . For this purpose, it is also possible to optimize the reactivity by chemically modifying both ends of the oligomer.

  In the present invention, it is particularly preferable to form a compound having a complex-forming substituent having an amino group and form an imide bond with both ends of the oligomer, as will be described in the following examples. In order to form such an imide bond, it is preferable that both ends of the oligomer are maleic anhydride groups. For the introduction of maleic anhydride groups, it is preferred that both ends of the oligomer are vinylidene groups as starting materials. For this purpose, various oligomers in which both ends are vinylidene groups can be used. A specific reaction example is shown by the following formula.

  Such various oligomers having both vinylidene groups at their ends can be obtained from various polymers by a highly-controlled pyrolysis method by a conventionally known method. Olefin oligomers obtained by highly controlled pyrolysis of polyolefins, such as propylene oligomers, maintain the stereoregularity of polypropylene before pyrolysis very well, so that the properties depending on their stereostructure are also maintained. ing.

  Specifically, the reaction between an oligomer having a maleic anhydride group at both ends and a crown ether having an amino group is shown.

（錯形成による重合及び重合体）
クラウンエーテルは、アンモニウムイオンとの間に錯形成することが知られているが、本発明のオリゴマーは両末端にクラウンエーテル基を有することから、アンモニウムイオンとの間に錯形成可能である。

(Polymerization and polymer by complex formation)
Although it is known that a crown ether forms a complex with an ammonium ion, the oligomer of the present invention has a crown ether group at both ends, so that it can form a complex with an ammonium ion.

  Furthermore, when the oligomer of the present invention is an organic compound such as an amino compound and ammonium ions can be produced, it can be complexed with the produced ammonium ions. Preferred examples of the compound having an amino group for obtaining the oligomer of the present invention and a high molecular weight polymer include diamino compounds having amino groups at both ends. If there are amino groups at both ends, there are no particular restrictions on the group that binds them. It may be aliphatic, aromatic, or a group in which they coexist. In the present invention, it is particularly preferable to use polymethylenediamine.

  It is also known that the complex formation reaction may be affected by the solvent. Therefore, complex formation requires selection of a complex-forming group and selection of an appropriate solvent for the complex formation. In particular, complex formation between ammonium ions and crown ethers depends on the nature of the solvent.

  When the complexing reaction proceeds sufficiently, a high molecular weight polymer is formed, and an appropriate reaction time is required to complete the polymerization.

  Since the obtained polymer is polymerized by complex formation, in order to further isolate the polymer, conditions that do not cause dissociation opposite to complex formation are necessary. For this purpose, a method of precipitating in a poor solvent for polymer isolation is preferred. In addition, for the measurement of the physicochemical properties of the obtained polymer, it is necessary to select the polarity of the measurement solvent, and a solvent that does not proceed with dissociation should be selected. In the case of complex formation between a crown ether and a polymethylene diammonium ion, the use of a polar solvent such as THF is not preferable because dissociation proceeds. Examples of the nonpolar solvent include halogen-based aromatic solvents.

  Examples will be described in more detail below.

Synthesis of maleated oligopropylene (iPP-MA) Synthesis was performed according to the following reaction formula.

  Oligopropylene having vinylidene bonds at both ends with number average molecular weight Mn 1600 (n = 38), dispersity Mw / Mn 1.73, average terminal vinylidene double bond number 1.78, obtained by highly controlled pyrolysis of isotactic polypropylene The molar ratio of (iPP-TVD) / maleic anhydride / antioxidant was set to 1/42 / 1.68, and the reaction was performed by stirring and holding at 190 ° C. for 24 hours in a decalin solvent under a nitrogen gas atmosphere.

  After completion of the reaction, the reaction solution was filtered into A seton while hot filtration to precipitate a polymer. The polymer was filtered and dried under reduced pressure to obtain maleated oligopropylene (iPP-MA).

Crown etherification (iPPv-Crown)
The addition reaction of aminobenzocrown ether (ABC) was synthesized according to the following reaction formula.

  This was carried out by heating for 4 hours in a molten state (190 ° C.) under reduced pressure at a molar ratio of iPPv-MA: A.B.C. = 1: 2 (iPPv-Crown = 320 mg, A.B.C. = 250 mg). Subsequently, the reaction mixture was dissolved in toluene (50 ml) and added dropwise to methanol (700 ml) to perform reprecipitation, and the generated precipitate was collected and dried by heating under vacuum to obtain iPPv-Crown (recovery rate, 50wt% (± 10wt%)).

1 and 2 show a 1H-NMR spectrum and a GPC curve, respectively. In particular, from the result of ¹ H-NMR (FIG. 1), a signal derived from ABC can be confirmed in the vicinity of 3.7 to 4.2 ppm. From the intensity ratio of the proton of the methyl group in the main chain to the proton in the crown ether of ABC, the reaction Was found to be progressing almost quantitatively.

Complex formation of iPPv-Crown and diamine In a container, iPPv-Crown and 1,6-hexamethylenediamine (diamine) are mixed with a THF solution of iPPv-Crown and diamine so that the molar ratio is 1:10. A 1N / HCl aqueous solution was prepared and mixed, and stirred at room temperature for 24 hours to carry out the reaction. After the reaction, water and toluene are added and separated into two phases, an organic phase and an aqueous phase. After stirring for 24 hours, the precipitate generated at the liquid-liquid interface is collected by suction filtration and then in a two-phase state for a predetermined time. After allowing to stand, the organic phase and the aqueous phase were separated by filtration, the solvent was distilled off, and the recovered materials were dried by heating under vacuum.

About 30 wt% of the iPPv-Crown charged in the reaction was recovered, and the precipitate was confirmed to be unreacted iPPv-Crown by ¹ H-NMR and THF-GPC.

Regarding the time of standing in the two-phase state, after filtration by suction, the solvent was immediately distilled off from the organic phase and the recovered material was iPPv-Crown + (NH ₃ ⁺ ) ₂ C ₆ H ₁₀ (1). What was recovered by evaporation was iPPv-Crown + (NH ₃ ⁺ ) ₂ C ₆ H ₁₀ (2). The recovered amount was about 60 wt% of the charged iPPv-Crown. As a result of each ¹ H-NMR (FIG. 3) and GPC measurement (FIG. 4), signals resulting from complex formation of iPPv-Crown and diamine were confirmed by ¹ H-NMR. Moreover, a new peak appeared on the high molecular weight side by high temperature GPC. iPPv-Crown + (NH ₃ ⁺ ) ₂ C ₆ H ₁₀ (1) showed a slight peak of unreacted iPPv-Crown that did not form a complex, but iPPv-Crown + (NH ₃ ⁺ ) ₂ C ₆ H _{In 10} (2), the unreacted peak almost disappeared. The peak on the high molecular weight side in GPC is a polymer produced by complex formation.

On the other hand, the components recovered from the aqueous phase reached about 150 wt% of the charged diamine, but they were all diamine by ¹ H-NMR and THF-GPC, and almost all of the unreacted diamine was converted to the aqueous phase. It was confirmed that it was dissolved. The reason why the recovery rate of the diamine in the aqueous phase exceeds 100% is considered to be because the diamine has become a hydrate.

  Since the both-end complex-forming oligomer according to the present invention has a crown ether group at both ends, complex formation occurs with an appropriate diamine compound. Further, such complex formation proceeds continuously to give a new polymer having a high molecular weight.

FIG. 1 shows the ¹ H-NMR spectrum of crown etherification (iPPv-Crown).

FIG. 2 shows the results of high temperature GPC of crown etherification (iPPv-Crown).

FIG. 3 shows a ¹ H-NMR spectrum of a complex of iPPv-Crown and a diamine.

FIG. 4 shows the result of high temperature GPC of the complex of iPPv-Crown and diamine.

Claims (2)

A both-end complex-forming oligomer represented by the following formula.

(In the formula, n is a positive number of 2 to 100, and R represents an alkyl group having 1 to 3 carbon atoms or a phenyl group.)   A polymer comprising the both-end complex-forming oligomer according to claim 1 and polymethylenediamine.

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