JP4125884B2 - Oligo (1-butene) with terminal vinylidene group - Google Patents

Description

[0001]
BACKGROUND OF THE INVENTION
The present invention relates to oligo (1-butene) having a novel terminal vinylidene group, more specifically, oligo (1-butene) having vinylidene groups at both ends and one end obtained by highly controlled pyrolysis of poly (1-butene). Butene).
[0002]
[Technical background]
1-butene is obtained as a by-product in the production of isobutylene and butadiene, but the polymer poly (1-butene) has different characteristics from polyisobutylene, polybutadiene, and polypropylene having a monomer unit having one less carbon atom. As shown, the application is limited and the production volume is extremely small.
[0003]
By introducing a functional group such as a double bond, a hydroxyl group or a carboxyl group at the terminal of poly (1-butene) and adding reactivity with other monomers or polymers, the poly (1-butene) We can expect the development of new applications that take advantage of these characteristics. However, it is extremely difficult to introduce a functional group at a specific position of a polymer chain using a polymer reaction.
[0004]
The present inventors have proposed a method for producing an α · ω-diene-oligomer by thermal decomposition of a polymer material containing poly (α-olefin) in JP-A-55-084302. As an example, polybutene was used. However, at this time, it has only been proved that propylene oligomers having double bonds at both ends can be obtained by thermal decomposition of isotactic polypropylene (Macromolecules, 28, 7973 (1995); Polymer Journal). 28, 817 (1996)), and only after that, oligostyrene having double bonds at both ends was obtained by thermal decomposition of polystyrene (Polymer, 37, 3697 (1996)).
[0005]
[Problems to be solved by the invention]
The object of the present invention is to provide an oligo (1-butene) having a double bond at the end of the 1-butene chain, that is, a vinylidene group.
[0006]
[Means for Solving the Problems]
As a result of intensive studies to achieve the above object, the present inventors have found that, as in the case of the isotactic polypropylene, by thermal decomposition of poly (1-butene) under controlled conditions, 1- The inventors have found that an oligomer having a vinylidene group at the end of a butene chain can be obtained in a high yield, thereby completing the present invention.
[0007]
The present invention is a thermal decomposition product of poly (1-butene),
The following general formula (1)
[Chemical 3]
And oligo (1-butene) having vinylidene groups at both ends represented by formula (2):
[Formula 4]
The number of average terminal vinylidene groups per molecule including oligo (1-butene) having a vinylidene group at one end represented by the formula: 1.53 to 1.75, number average molecular weight (Mn) of 1000 to 5000, molecular weight An oligo (1-butene) having a terminal vinylidene group, characterized in that the dispersity (Mw / Mn) of the distribution is 2.5 or less.
[0008]
DETAILED DESCRIPTION OF THE INVENTION
In the present invention, an oligo (1-butene) having vinylidene groups at both ends represented by the general formula (1) and an oligo (1-1-butene) having vinylidene groups at one end represented by the general formula (2). Butene) was obtained as a thermal decomposition product of poly (1-butene), and was calculated based on the average number of terminal vinylidene groups per molecule (f _TVD ) calculated based on the ¹³ C-nuclear magnetic resonance (NMR) spectrum shown in FIG. Value) is obtained as a mixture of 1.53 to 1.75, the number average molecular weight (Mn) by the gel permeation chromatograph (GPC) shown in FIG. 5 is 1000 to 5000, and the degree of dispersion (Mw) / Mn) is 2.5 or less, and the stereoregularity of poly (1-butene) before thermal decomposition is maintained very well.
[0009]
The oligo (1-butene) having a terminal vinylidene group is obtained by subjecting the raw material poly (1-butene) to a temperature of 300 to 450 ° C., preferably 350 to 400 ° C. under an inert gas such as nitrogen and argon. It is obtained by thermal decomposition for 30 to 240 minutes, preferably 40 to 180 minutes while removing volatile components.
[0010]
The average number of terminal vinylidene groups (f _TVD value) per molecule of the pyrolysis product is the production of oligo (1-butene) having vinylidene groups at both ends and oligo (1-butene) having a double bond at one end. It represents a ratio, and when the thermal decomposition temperature of the raw material poly (1-butene) is constant, it varies between 1.53 and 1.75 as the thermal decomposition time elapses.
[0011]
The number average molecular weight (Mn) of the thermal decomposition product is 1000 to 5000, preferably 1000 to 2500, and the degree of dispersion (Mw / Mn) of the molecular weight distribution is 2.5 or less, preferably 2.0 or less. Mn and Mw / Mn rapidly decrease with the lapse of the pyrolysis time, and finally converge to a substantially constant value, Mn to about 1000 and Mn / Mw to about 1.8. And the thermal decomposition product does not show a clear glass transition point (Tg).
[0012]
Since the oligo (1-butene) having a terminal vinylidene group according to the present invention has a terminal double bond, other olefins such as ethylene, propylene and isoprene, diolefins such as butadiene and isoprene, styrene, acrylate and methacrylate, etc. Copolymerization with monomers having a vinylic double bond is possible, and the properties of poly (1-butene) can be incorporated and modified in these copolymers.
[0013]
In addition, since it is possible to introduce a functional group such as a hydroxyl group or a carboxy group at the end of the 1-butene chain using a terminal vinylidene group, it can be used as a raw material for synthesizing various functional polymers and derivatives. Can do.
[0014]
【Example】
The invention is explained in more detail by means of examples.
[0015]
Synthesis Example Thermal Decomposition of Isotactic Poly (1-butene) 1.0 g of isotactic poly (1-butene) (sample name: P2000, manufactured by Mitsui Chemicals, Inc.) was collected in a two-necked flask. The pressure was reduced to ₂ mmHg to replace N ₂ , and then the mixture was heated to 370 ° C. under N ₂ aeration. The pyrolysis time was adjusted to 30 minutes, 45 minutes, 60 minutes, 90 minutes, 120 minutes, 150 minutes and 180 minutes, and volatile components produced under the reaction conditions were absorbed into chloroform and recovered. The residue in the flask after the elapse of the thermal decomposition time was dissolved by heating with xylene, and then subjected to hot filtration to drop the filtrate dropwise into methanol. The produced precipitate was collected by suction filtration and dried under reduced pressure.
[0016]
From the infrared absorption spectrum (IR spectrum) and ¹ H-NMR spectrum of the recovered thermal decomposition product, it was confirmed that the thermal decomposition product was an isotactic oligo (1-butene) having a terminal vinylidene group.
The IR spectrum of the pyrolysis product is shown in FIG. 1, and the ¹ H-NMR spectrum is shown in FIGS. 2 (a) and 2 (b).
[0017]
Further, the ¹³ C-NMR spectrum of the pyrolysis product shows the presence of a terminal vinylidene group and a saturated terminal methyl group, and the pyrolysis product is an oligo (1 having vinylidene groups at both ends represented by the general formula (1). -Butene) and an oligo (1-butene) having a vinylidene group at one end represented by the general formula (2) were confirmed. The average number of terminal vinylidene groups (f _TVD value) per molecule of the thermal decomposition product calculated based on the signal intensity ratio between the side chain methyl group of the terminal vinylidene group and the saturated terminal methyl group is 1.53-1 depending on the thermal decomposition time. It varied between .75. ^{The 13} C-NMR spectrum is shown in FIGS. 3 (a), 3 (b) and 3 (c), and the change in f _TVD value with the decomposition time is shown in FIG. 4.
[0018]
The GPC of the pyrolysis product has a number average molecular weight (Mn) and a molecular weight distribution dispersity (Mw / Mn) that decrease rapidly with the elapse of the pyrolysis time, Mn to 1000 and Mw / Mn to 1.8. Showed convergence. Changes in Mn and Mw / Mn with decomposition time are shown in FIG.
[0019]
Further, in the DSC curve of the pyrolysis product, the endothermic peak shifted to the low temperature side as the decomposition time passed, and no clear glass transition temperature (Tg) was shown. The weight loss starting temperature in the TG curve was similar to that of sample P2000. The DSC curve according to the decomposition time is shown in FIG. 6, the TG curve is shown in FIG. 7, and the yield of the thermal decomposition product is shown in FIG.
[0020]
Example Maleation of terminal vinylidene group Mole obtained in the above synthesis example was oligo (1-butene) / maleic anhydride / butylhydroxytoluene (BHT) having a terminal vinylidene group of 3000. The molar ratio was 1/10/0. And a reaction was carried out in a decahydronaphthalene solvent at 180 ° C. for 24 hours in a nitrogen gas atmosphere. After completion of the reaction, the reaction solution was poured into acetone while hot filtration, and the resulting precipitate was filtered with suction and dried under reduced pressure.
[0021]
In the IR spectrum of the reaction product obtained above, the absorption peak derived from the terminal vinylidene group of the oligo (1-butene) having the starting vinylidene group disappeared, and the absorption peak derived from the acid anhydride was newly observed. The reaction product was confirmed to be a terminal maleated oligo (1-butene). The IR spectrum of the terminal maleated oligo (1-butene) is shown in FIG.
[0022]
【The invention's effect】
The oligo (1-butene) having a terminal vinylidene group according to the present invention can be used as a raw material for the modification of various polymers and the production of functional polymers because the terminal double bond is highly reactive. The industrial significance in the field is extremely large.
[Brief description of the drawings]
FIG. 1 IR spectra of pyrolysis products of poly (1-butene) (oligo (1-butene) having terminal vinylidene groups and terminal maleated oligo (1-butene)). In the figure, iPB-TVD : oligo (1-butene) having a terminal vinylidene group, iPB-MA : terminal maleated oligo (1-butene) .
FIG. 2 is a ¹ H-NMR spectrum of a thermal decomposition product of poly (1-butene) (an oligo (1-butene) having a terminal vinylidene group).
FIG. 3 is a ¹³ C-NMR spectrum of a thermal decomposition product of poly (1-butene) (oligo (1-butene) having a terminal vinylidene group).
FIG. 4 is a graph _showing the average number of terminal vinylidene groups (f _TVD value) vs. thermal decomposition time curve of a thermal decomposition product of poly (1-butene) (oligo (1-butene) having a terminal vinylidene group).
FIG. 5: Number average molecular weight (Mn) of poly (1-butene) pyrolysis product (oligo (1-butene) having a terminal vinylidene group) and dispersity of molecular weight distribution (Mw / Mn) vs. pyrolysis time curve.
FIG. 6 is a DSC curve of a thermal decomposition product of poly (1-butene) (oligo (1-butene) having a terminal vinylidene group).
FIG. 7 is a TG curve of a thermal decomposition product of poly (1-butene) (an oligo (1-butene) having a terminal vinylidene group).
FIG. 8: Yield vs. pyrolysis time curve of poly (1-butene) pyrolysis product (oligo (1-butene) with terminal vinylidene groups).

Claims (1)

A thermal decomposition product of poly (1-butene), which is represented by the following general formula (1), oligo (1-butene) having vinylidene groups at both ends, and the following general formula (2) Including oligo (1-butene) having a vinylidene group at one end, the average number of terminal vinylidene groups per molecule (f _TVD value) is 1.53 to 1.75, the number average molecular weight (Mn) is 1000 to 5000, The oligo (1-butene) mixture having a terminal vinylidene group having a molecular weight distribution dispersity (Mw / Mn) of 2.5 or less is used to make a hydroxyl group, a carboxyl group, or an acid anhydride group using the terminal vinylidene group. Functionalized oligo (1-butene) mixture obtained by introducing (wherein n and m in the formula are numbers with which the number average molecular weight of the oligo (1-butene) mixture is 1000 to 5000) .