WO2003095523A1 - Polymere decomposable a la chaleur - Google Patents

Polymere decomposable a la chaleur Download PDF

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Publication number
WO2003095523A1
WO2003095523A1 PCT/JP2003/005725 JP0305725W WO03095523A1 WO 2003095523 A1 WO2003095523 A1 WO 2003095523A1 JP 0305725 W JP0305725 W JP 0305725W WO 03095523 A1 WO03095523 A1 WO 03095523A1
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WO
WIPO (PCT)
Prior art keywords
group
polymer
thermally decomposable
decomposable polymer
organic group
Prior art date
Application number
PCT/JP2003/005725
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English (en)
Japanese (ja)
Inventor
Tamaki Nakano
Original Assignee
Japan Science And Technology Corporation
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Japan Science And Technology Corporation filed Critical Japan Science And Technology Corporation
Priority to JP2004503532A priority Critical patent/JP4457183B2/ja
Publication of WO2003095523A1 publication Critical patent/WO2003095523A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G67/00—Macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing oxygen or oxygen and carbon, not provided for in groups C08G2/00 - C08G65/00

Definitions

  • the present invention relates to a thermally decomposable polymer whose molecular weight is easily reduced by heating, and more particularly to radical generation such as a polymer radical polymerization initiator obtained by promoting polymerization while incorporating oxygen atoms in the polymer main chain.
  • the present invention relates to a thermally decomposable polymer suitable for recycling, such as an adhesive or a removable adhesive, and a method for producing the same.
  • the present inventor accidentally found that the polymerization of dibenzofulvene was carried out in the presence of oxygen, and that the obtained polymer was a thermally decomposable polymer, and reached the present invention. Accordingly, it is an object of the present invention to provide a thermally decomposable polymer whose molecular weight is easily reduced by heating. Disclosure of the invention
  • Ar is an aromatic ring
  • I 1 and R 2 are hydrogen, an alkyl group, —OR, an aromatic group, one N RR, one SR, a halogen, and a group selected from the following groups (provided that R and R ′ Is H or an organic group).
  • R 1 and R 2 may each be introduced as 2 to 4 substituents. In this case, each R 1 or R 2 may be the same or different.
  • 1 ′′ and 1 ′′ are 1 ⁇ or an organic group, and R ′′ and R ′ ′′ may be the same or different.
  • 1 3 ⁇ Pi 1 4 represents hydrogen, an alkyl group, an aromatic group, one CN, or an ester group, X is, - (CH 2) n, an aromatic group, a vinyl group, such as an organic group containing a hetero atom An organic group or a hetero atom, and n is 0, 1 or 2.
  • FIG. 2 is a Raman spectrum diagram of a form-mouth-form-soluble portion of the polymer obtained in Example 1.
  • FIG. 3 is an infrared absorption spectrum diagram of a form-soluble portion of a black hole in the polymer obtained in Example 1.
  • FIG. 2 is an NMR spectrum diagram of a chloroform-soluble portion of the polymer obtained in Example 1.
  • FIG. 2 is a Raman spectrum diagram of a chloroform-insoluble portion of the polymer obtained in Example 1.
  • FIG. 2 is an infrared absorption spectrum diagram of a form-insoluble portion of a polymer in the polymer obtained in Example 1.
  • FIG. 4 is a Raman spectrum diagram of hunoleolene for comparison.
  • FIG. 4 is an NMR spectrum diagram of a polymer form-soluble portion of the polymer obtained in Example 2.
  • FIG. 5 is an NMR spectrum diagram of a form-soluble portion of a polymer in the polymer obtained in Example 3.
  • FIG. 2 is an NMR spectrum diagram of the polymer obtained in Comparative Example 1. BEST MODE FOR CARRYING OUT THE INVENTION
  • the raw material monomer of the thermally decomposable polymer of the present invention has t structural formula 1 represented by structural formula 1
  • R 1 R 2 is hydrogen, an alkyl group, -OR, an aromatic group, one N RR, one SR, a halogen, and a group selected from the following groups (provided that R and R 'is H or an organic group). Further, 2 to 4 R 1 and R 2 may be introduced as substituents, respectively. In this case, each R 1 or R 2 may be the same or different.
  • 1 ′′ and 1 ′ ′′ are ⁇ 1 or an organic group, and R ′′ and R ′′ may be the same or different.
  • Scale 3 ⁇ Pi 1 4 represents hydrogen, an alkyl group, an aromatic group one CN, or an ester group, X is, - (CH 2) n, organic, such as an aromatic group, Bulle group, an organic group containing a hetero atom And n is 0, 1 or 2.
  • examples of the organic group containing a hetero atom include 1 NR— and —C (O) —.
  • R 1 and R 2 alkyl group
  • R 3 and R 4 H, CH 3 or CN
  • R 1 ⁇ Pi R 2 N0 2
  • R 3 ⁇ Pi R 4 H, CH 3 or CN
  • R 1 and R 2 NH 2 , R 3 and R 4 : H, CH 3 , or CN
  • the monomer is reacted in a solid phase or in a condition in which oxygen is dissolved in a solvent under an oxygen or oxygen-containing atmosphere, preferably in an air atmosphere, using the above-mentioned monomer. Is preferred. It is preferable to irradiate light during the reaction.
  • the light irradiated at this time is preferably light having a wavelength of 200 nm to 800 nm, particularly preferably light having a wavelength of 200 nm to 400 nm.
  • the degree of polymerization of the polymer can be adjusted or the thermal decomposition temperature can be controlled by controlling the oxygen concentration, light intensity, reaction time, and the like during the above polymerization reaction.
  • the polymer thus obtained preferably has a heat division angle / temperature of from 20 ° C to 200 ° C.
  • the number average molecular weight of the form-soluble polymer was determined by GPC using a calibration curve prepared with a polystyrene standard sample to be 4640.
  • the number average molecular weight determined using GPC-MALLS was 16,000, The distribution was 2.17.
  • the polymer in the solid state was heated at 100 ° C. for 1 hour, and the number average molecular weight was measured to be 2900 (GPC: converted to polystyrene). When heated at 175 for 1 hour, the number average molecular weight was reduced to 300.
  • the form-insoluble polymer was treated in the same manner at 175 ° C, a part of the soluble polymer having a number average molecular weight of 300 was formed.
  • the Raman spectrum diagram and infrared absorption spectrum diagram of the black form-insoluble polymer were as shown in FIGS. 4 and 5, confirming the presence of one O—O— group.
  • the Raman spectrum of fluorene for comparison is as shown in FIG.
  • Example 2 (polymer synthesis: liquid phase).
  • Hexane solution 13 0 g to previously synthesized dibenzofulvene of (0. 505 g) (concentration is 4 wt. / 0) where blown for 30 seconds air, white precipitate formed.
  • this solution was irradiated with ultraviolet light of 365 nm at 2 mWZ cm 2 for 24 hours, 423 mg of a polymer soluble in chloroform and insoluble in hexane was obtained.
  • the NMR spectrum of this polymer has the same pattern as that of the polymer obtained in Example 1, and has an absorption based on a methylene group hydrogen adjacent to one O—O— group at around 3.5 ppm or around 4 ppm. Was observed (Fig. 3).
  • GPC—MALL S measurements showed that the polymer had a number average molecular weight of 20,000 and a molecular weight distribution of 1.45.
  • the polymer in the solid state was heated at 100 ° C. for 1 hour and the number average molecular weight was measured. The result was 2,000 (GPC: converted to polystyrene). Also 175. Heat at C for 1 hour , The number average molecular weight was reduced to 300.
  • the number-average molecular weight of the chloroform-soluble polymer was determined by GPC using a calibration curve prepared using a polystyrene standard sample, and was 800.
  • the number-average molecular weight determined using GPC-MA LLS was 200.
  • the molecular weight distribution was 1.2. This solid-state polymer was heated at 100 ° C. for 1 hour, and the number average molecular weight was measured. As a result, no change was observed. No change in molecular weight was observed after heating at 175 ° C for 1 hour.
  • the molecular weight of the polymer of the present invention is easily reduced by heating, it can be used as a high-molecular radical polymerization initiator and can be easily disposed.
  • the adhesive strength is reduced by heating, and re-peeling is facilitated, so that an effect of facilitating recycling of the adherend is also produced.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)

Abstract

L'invention concerne un polymère décomposable à la chaleur, caractérisé en ce qu'il est produit par la polymérisation d'un monomère présentant une structure de dibenzofulvène, dans une atmosphère d'oxygène. Ce polymère provoque facilement une réduction de poids moléculaire par chauffage, il est donc utile en tant qu'initiateur de polymérisation de radical à poids moléculaire élevé, et peut être facilement supprimé.
PCT/JP2003/005725 2002-05-08 2003-05-07 Polymere decomposable a la chaleur WO2003095523A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP2004503532A JP4457183B2 (ja) 2002-05-08 2003-05-07 熱分解性ポリマー

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2002-132600 2002-05-08
JP2002132600 2002-05-08

Publications (1)

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WO2003095523A1 true WO2003095523A1 (fr) 2003-11-20

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PCT/JP2003/005725 WO2003095523A1 (fr) 2002-05-08 2003-05-07 Polymere decomposable a la chaleur

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JP (1) JP4457183B2 (fr)
WO (1) WO2003095523A1 (fr)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP5263478B2 (ja) * 2005-04-07 2013-08-14 国立大学法人 奈良先端科学技術大学院大学 光学活性なブロック共重合体、その製造方法及びそのブロック共重合体を用いたクロマトグラフィー用充填剤
US9273179B2 (en) 2013-01-09 2016-03-01 Ricoh Company, Ltd. Decomposable polymer
WO2024142966A1 (fr) * 2022-12-28 2024-07-04 国立大学法人北海道大学 Initiateur mécanoradical polymère et procédé de réaction utilisant un initiateur mécanoradicalaire polymère

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
TAMAKI NAKANO ET AL.: "Dibenzofulvene, a 1,1-diphenylethylene analogue, gives a pi-stacked polymer by anionic, free-radical and cationic catalysts", JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, vol. 123, no. 37, pages 9182 - 9183, XP002971514 *
TAMAKI NAKANO ET AL.: "Solid-state polymerization of dibenzofulvene leading to a copolymer with oxygen", MACROMOLECULES, vol. 36, no. 5, 11 March 2003 (2003-03-11), pages 1433 - 1435, XP002971513 *

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP5263478B2 (ja) * 2005-04-07 2013-08-14 国立大学法人 奈良先端科学技術大学院大学 光学活性なブロック共重合体、その製造方法及びそのブロック共重合体を用いたクロマトグラフィー用充填剤
US9273179B2 (en) 2013-01-09 2016-03-01 Ricoh Company, Ltd. Decomposable polymer
WO2024142966A1 (fr) * 2022-12-28 2024-07-04 国立大学法人北海道大学 Initiateur mécanoradical polymère et procédé de réaction utilisant un initiateur mécanoradicalaire polymère

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JP4457183B2 (ja) 2010-04-28
JPWO2003095523A1 (ja) 2005-09-15

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