JP2006316202A - Terminal reactive oligomer having terminal vinylidene group - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a reactive oligomer having terminal vinylidene groups. <P>SOLUTION: The reactive oligomer having terminal vinylidene groups is a heat decomposition product of a propylene-α-olefin random copolymer and has 1.5-1.9 average terminal vinylidene groups per molecule, 1,000-100,000 number average molecular weight (Mn) and ≤2.5 dispersion (Mw/Mn) of molecular distribution. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to a terminal reactive oligomer having a terminal vinylidene group having a terminal vinylidene group.

  Propylene-based copolymers, especially propylene / α-olefin random copolymers, are used to improve impact resistance, compatibilizers, sealants, and other properties. Has been developed and is commercially available (Patent Document 1).

  If a reactive group having further chemical reactivity, such as a double bond, a hydroxyl group, a carboxyl group, or the like can be introduced into the molecule of the propylene / α-olefin random copolymer having such excellent properties, other monomers and By adding reactivity with polymers, development of new applications can be greatly expected.

However, it is extremely difficult to introduce a functional group into a specific position of a polymer chain by actually using a polymerization reaction or a polymer reaction even with the current technology. The present inventors proposed a method for producing an α · ω-diene-oligomer by thermal decomposition of a polymer material containing poly (α-olefin), and exemplified poly (1-butene) as the polymer material. However, at this time, only propylene oligomers having double bonds at both ends were obtained by thermal decomposition of isotactic polypropylene (Patent Document 2, Non-Patent Document 1). In addition, only after that, only polyisobutylene having an oligoisobutylene having double bonds at both ends was obtained by thermal decomposition of polyisobutylene.
JP 2003-73426 A Japanese Patent Laid-Open No. 55-084302 Macromolecules, 28, 7973 (1995); Polymer Journal, 28, 817 (1996)

  An object of the present invention is to provide a terminal-reactive oligomer in which both ends are vinylidene groups.

  As a result of diligent research to achieve the above-mentioned problems, the present inventors use a conventionally known propylene / α-olefin random copolymer as a raw material, and a highly controlled pyrolysis method, The present invention was completed by discovering that it can be decomposed as a terminal reactive oligomer having a desired molecular weight and having a novel structure having vinylidene groups at both ends thereof.

  That is, the present invention is a thermal decomposition product of a propylene / α-olefin random copolymer having an average number of terminal vinylidene groups per molecule of 1.5 to 1.8 and a number average molecular weight (Mn) of 1,000 to 1,000. The present invention relates to a terminal-reactive oligomer having a terminal vinylidene group, characterized by having a dispersity (Mw / Mn) of 100,000 and a molecular weight distribution of 2.5 or less. Furthermore, the present invention relates to a terminal reactive oligomer having a terminal vinylidene group, wherein the α-olefin is ethylene, 1-butene, pentene, or hexene. Moreover, this invention relates to the terminal reactive oligomer which has a terminal vinylidene group whose content of the said alpha olefin is arbitrary quantity.

  The present invention also includes a highly controlled pyrolysis process for producing such terminally reactive oligomers.

  The oligomer according to the present invention has a characteristic structure in which a vinylidene group is present at both ends while maintaining the structure of a conventionally known propylene / α-olefin random copolymer used as a raw material. Therefore, the oligomer according to the present invention retains the excellent properties of a conventionally known propylene / α-olefin random copolymer used as a raw material, and can also exhibit a large chemical reactivity due to vinylidene groups at both ends.

(Propylene / α-olefin random copolymer)
The propylene / α-olefin random copolymer, which is a raw material used in the present invention, means a polymer in which propylene and an α-olefin are randomly copolymerized. Furthermore, about an alpha olefin monomer, there is no restriction | limiting about the kind (% by weight, mol%) with respect to the kind and propylene monomer. In the present invention, the α-olefin monomer has 2, 4 to 8 carbon atoms. More specifically, examples of the α-olefin include ethylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, and 1-octene. The α-olefin content is preferably in the range of 1 to 30 mol%, more preferably in the range of 1 to 10 mol%. In particular, when the α-olefin is 1-butene, a 1-butene content in the range of 0.1 to 99.9 mol% can be used. More particularly, when the α-olefin is ethylene, the ethylene content is preferably in the range of 1 to 10 mol%. When the α-olefin is 1-pentene to 1-octene, the 1-pentene to 1-octene content is preferably in the range of 1 to 10 mol%.

In the present invention, these propylene / α-olefin random copolymers that can be used as raw materials can be produced by a conventionally known method, and commercially available products can be used as they are. In particular, as a conventionally known production method, it is preferable to use a propylene / α-olefin random copolymer obtained by a method using a metallocene catalyst or a Ziegler-Natta catalyst. The molecular structure of the raw material propylene / α-olefin random copolymer may differ depending on the production method, but can be analyzed in detail by conventionally known structural analysis methods for various polymer compounds. Specifically, the microstructure of the propylene monomer and α-olefin monomer forming the polymer chain is analyzed in detail by nuclear magnetic resonance absorption spectra (hereinafter referred to as “NMR”) of hydrogen ( ¹ H) and carbon ( ¹³ C). be able to.

(Terminal reactive oligomer having a terminal vinylidene group)
The terminal-reactive oligomer having a terminal vinylidene group of the present invention is an oligomer obtained by thermally decomposing a propylene / α-olefin random copolymer, which is a raw material described above, under a highly controlled condition. The chain structure is characterized by essentially maintaining the molecular structure of the starting polymer. Such a structure can be confirmed by detailed analysis by a conventionally known structure analysis method for various polymer compounds. Specifically, the microstructure of the propylene monomer and α-olefin monomer forming the oligomer chain is analyzed in detail by nuclear magnetic resonance absorption spectra (hereinafter referred to as “NMR”) of hydrogen ( ¹ H) and carbon ( ¹³ C). It can be seen that the molecular structure in the chain of the oligomer of the present invention substantially retains the molecular structure of the propylene / α-olefin random copolymer as the raw material.

  The terminal reactive oligomer of the present invention is characterized in that both terminal groups are vinylidene groups. When the case where both ends are completely vinylidene groups is 2.0, the double bond average value of the terminal reactive oligomer of the present invention is in the range of 1.5 to 1.8. Whether both terminal groups are vinylidene groups can be qualitatively and quantitatively measured using various chemical structure analysis means. In particular, it is possible to analyze in detail from the actual measurement value and theoretical value of NMR.

The structure of the vinylidene end group of the terminal reactive oligomer of the present invention depends on the type of raw material used. Specifically, when the α-olefin is described as CH ₂ ═CH—R, the main vinylidene group structure is derived from propylene monomer-derived —CH ₂ —C (CH ₃ ) ═CH ₂ , α-olefin-derived and a _{-CH 2 -C (R) = CH} 2. For example, when α- olefin is 1-butene, terminal groups of the resulting oligomer, _-CH 2 -C _(CH 3) derived from propylene monomer = and CH _{2, -CH} 2 -C-derived 1-butene _{(C 2} the H ₅₎ = CH _2.

  Further, the molecular weight of the terminal reactive oligomer of the present invention is not particularly limited. Oligomers having various molecular weights can be obtained by setting various conditions for the highly controlled pyrolysis method described below. Specifically, in the following formula (1) showing the oligomer of the present invention expressed excluding the terminal group,

ｎは１〜５、ｋは１〜５、さらにはｍは２０〜２,０００なる範囲のオリゴマーを得ることが可能である。また分子量、分子量分布の分散度測定は通常公知の種々の測定方法により求めることができる。具体的には適当な溶媒と充填剤カラムを用いてゲルパーミエイションクロマトグラフ（ＧＰＣ）が挙げられる。また分子量分布の分散度(Ｍw／Ｍn)は２.５以下、好ましくは２.０以下である。ＭnおよびＭw／Ｍnは熱分解時間の経過と共に急速に低下し、最終的にほぼ一定の値、Ｍnは約１０００に、Ｍn／Ｍwは約１.５に収束する。

It is possible to obtain an oligomer in which n is 1 to 5, k is 1 to 5, and m is 20 to 2,000. The molecular weight and the molecular weight distribution can be measured by various known measuring methods. Specifically, gel permeation chromatograph (GPC) is mentioned using a suitable solvent and a filler column. 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 1.5.

(Highly controlled pyrolysis method)
The terminal reactive oligomer of the present invention can be obtained by thermally decomposing a propylene / α-olefin copolymer as a raw material. In this case, it is preferable to highly control heating conditions (temperature, time), atmospheric gas, and pressure. By appropriately changing and optimizing these pyrolysis reaction conditions, it is possible to efficiently obtain a product having a desired molecular weight according to the raw material used. The reactor is not limited in size and shape as long as these conditions are satisfied, and may be a so-called batch reactor or a continuous reactor.

  The reactor is made of a material that can withstand heating conditions, and the raw materials in the reactor are heated by an external heating device in an inert gas atmosphere under reduced pressure. It is preferable to have a collecting device for collecting outside the reaction device. The heating temperature is preferably controlled in the range of 300 to 500 ° C. with a standard deviation of ± 5 ° C. The heating means is not particularly limited, but an external electric furnace, a metal bath, etc. can be used. Further, any inert gas may be used as long as undesirable side reactions can be suppressed or the generated volatile low-molecular product can be efficiently sent to the collection device. Specific examples include nitrogen gas and argon gas. There is no particular limitation on the flow rate of the inert gas, and a product having a desired molecular weight can be efficiently obtained according to the raw material to be used by appropriately changing and optimizing the flow rate. The collector is provided with a cooling means so that the pressure of the reaction system can be controlled to a high degree. If necessary, it is also possible to use a low-molecular product collected in a collection device.

  The reaction is preferably carried out under reduced pressure, but can be optimized as appropriate in order to efficiently obtain raw materials to be used and products having a desired molecular weight. Specifically, it is in the range of 1 to 4 mmHg. It is preferable to use an appropriate pressure reducing device having a sufficient exhaust capacity for highly controlling the pressure reducing force.

  In the thermal decomposition reaction, a raw material polymer is placed in a reaction vessel, and after the vessel is sealed, an inert gas is introduced and maintained at a predetermined pressure with a decompression device. The post-reaction vessel is started to be heated by a heating furnace. The temperature inside the reaction vessel is monitored, it is confirmed that the predetermined temperature is reached, and the temperature is maintained. Along with the thermal decomposition, low molecular weight volatile components are collected from the reaction vessel into the collection device. After performing the thermal decomposition reaction for a predetermined time, the reaction vessel is separated from the heating furnace and left to cool. Dissolve the solid product in the apparatus with a suitable solvent. In this case, examples of the solvent include xylene. The product can be separated by removing the solvent, or it can be introduced into a suitable solvent and separated as a solid.

  EXAMPLES Hereinafter, although an Example demonstrates this invention further in detail, this invention is not limited to these Examples.

Example 1 Thermal Decomposition of Propylene / (1-Butene) Random Copolymer Propylene / (1-butene) random copolymer (trade name: TAFMER, manufactured by Mitsui Chemicals, average molecular weight 150,000) 1.0 kg Was collected, and the pressure was reduced to about 2 mmHg to replace N ₂ , and then heated to a predetermined temperature (330 ° C., 350 ° C., 370 ° C., 390 ° C.) under N ₂ aeration. The temperature was adjusted to a predetermined thermal decomposition time (1, 2, 2.5, 3, 3.5 hours), and the volatile components produced under the reaction conditions were dissolved in chloroform and recovered. The residue in the decomposition vessel 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. Each reaction condition and the resulting product are summarized in Table 1.

From the infrared absorption spectrum (IR spectrum), ¹ H-NMR, and ¹³ C-NMR spectrum of the recovered thermal decomposition product, it was confirmed that the thermal decomposition product was an oligomer having a terminal vinylidene group. The presence of a terminal vinylidene group is shown from a ¹³ C-NMR spectrum. Further, the average number of terminal vinylidene groups (fTVD value) per molecule of the pyrolysis product was calculated based on the signal intensity ratio between the side chain methyl group of the terminal vinylidene group and the saturated terminal methyl group. The side chain methyl group and ethyl group of the terminal vinylidene group and the saturated terminal methyl group and ethyl group were confirmed in the vicinity of 20.5, 10.6, 12.6 and 12.2 ppm by HMDS, respectively, and the fTVD value calculated based on the signal intensity ratio was 1.5. It was about ~ 1.8. Further, the structure of the pyrolysis product almost retained the structure of the raw material.

  Further, the number average molecular weight (Mn) and the degree of dispersion of molecular weight distribution (Mw / Mn) were calculated by GPC.

  Table 1 further shows DSC measurement results of the thermal decomposition products obtained under each condition. The endothermic peak shifted to the low temperature side as the decomposition time passed, and the glass transition temperature gradually shifted from the raw material −17 ° C. to −30 ° C. to the low temperature side.

  Although not shown in the table, the ft value of the obtained pyrolyzate was in the range of 1.5 to 1.8. There was a tendency for the molecular weight to increase as the molecular weight decreased.

(Example 2) Thermal decomposition of propylene / ethylene random copolymer 1.0 kg of propylene / ethylene random copolymer (trade name: WINTEC, manufactured by Nippon Polychem Co., Ltd., average molecular weight 220,000) was collected in a decomposition kettle and decompressed to about 2 mmHg. Then, N _{2 was} substituted, and then heated to a predetermined temperature (330 ° C., 360 ° C., 390 ° C.) under N ₂ aeration. The temperature was adjusted to a predetermined thermal decomposition time (1, 2, 3, 3.5, 4, 5, 6 hours), and the volatile components produced under the reaction conditions were dissolved in 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. Each reaction condition and the resulting product are summarized in Table 2.

From the infrared absorption spectrum (IR spectrum), ¹ H-NMR, and ¹³ C-NMR spectrum of the recovered thermal decomposition product, it was confirmed that the thermal decomposition product was an oligomer having a terminal vinylidene group. Further, the average number of terminal vinylidene groups (fTVD value) per molecule of the pyrolysis product was calculated based on the signal intensity ratio between the side chain methyl group of the terminal vinylidene group and the saturated terminal methyl group. The side chain methyl group and the saturated terminal methyl group of the terminal vinylidene group were confirmed in the vicinity of 20.5 and 12.6 ppm on the basis of HMDS, respectively, and the fTVD value calculated based on the signal intensity ratio was about 1.5 to 1.8. Further, the structure of the pyrolysis product almost retained the structure of the raw material. Further, the number average molecular weight (Mn) and the degree of dispersion of molecular weight distribution (Mw / Mn) were calculated by GPC.

  Table 2 further shows the DSC measurement results of the thermal decomposition products obtained under each condition. As the decomposition time passed, the endothermic peak shifted to the low temperature side, and the glass transition temperature gradually shifted from -13 ° C to -30 ° C of the raw material.

    Although not shown in the table, the ft value of the obtained pyrolyzate was in the range of 1.6 to 1.9. There was a tendency for the molecular weight to increase as the molecular weight decreased.

Example 3 Thermal Decomposition of Propylene Random Copolymer 1.0 g of propylene random copolymer (random polypropylene) was collected in a two-necked flask, reduced to about 2 mmHg and purged with N ₂ , and then at a predetermined temperature (390 ° C. under N 2 aeration). ). The temperature was adjusted to a predetermined pyrolysis time (1, 2 hours), 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. Each reaction condition and the resulting product are summarized in Table 3.

From the infrared absorption spectrum (IR spectrum), ¹ H-NMR, and ¹³ C-NMR spectrum of the recovered thermal decomposition product, it was confirmed that the thermal decomposition product was an oligomer having a terminal vinylidene group. The side chain methyl group and the saturated terminal methyl group of the terminal vinylidene group were confirmed at around 20.5 and 12.6 ppm, respectively, based on HMDS, and the fTVD value calculated based on the signal intensity ratio was about 1.5 to 1.8. Further, the structure of the pyrolysis product almost retained the structure of the raw material. In addition, the average number of terminal vinylidene groups (f _TVD value) per molecule of the thermal decomposition product was calculated based on the signal intensity ratio of the side chain methyl group of the terminal vinylidene group to the saturated terminal methyl group. Further, the number average molecular weight (Mn) and the degree of dispersion of molecular weight distribution (Mw / Mn) were calculated by GPC.

  Table 3 further shows DSC measurement results of the thermal decomposition products obtained under each condition. As the decomposition time passed, the endothermic peak shifted to the low temperature side, and no clear glass transition temperature (Tg) was exhibited.

  Since the terminal reactive oligomer of the present invention has a double bond at the terminal, other olefins such as ethylene, propylene and isoprene, diolefins such as butadiene and isoprene, and vinylic double bonds such as styrene, acrylate and methacrylate. It is possible to copolymerize with the monomer having the above, and to incorporate and modify the characteristics of the propylene / (α-olefin) random copolymer in the copolymer. Further, since it is possible to introduce a functional group such as a hydroxyl group or a carboxy group at the terminal using a terminal vinylidene group, it can be used as a raw material for synthesizing various functional polymers and derivatives. Since the oligomer having a terminal vinylidene group of the present invention has a rich terminal double bond, it can be used as a starting material for various polymer modifications and functional polymers. Is extremely large.

Claims (4)

  Thermal decomposition product of propylene / α-olefin random copolymer having an average number of terminal vinylidene groups per molecule of 1.5 to 1.9, a number average molecular weight (Mn) of 1,000 to 100,000, and a molecular weight distribution The terminal reactive oligomer having a terminal vinylidene group, wherein the dispersity (Mw / Mn) is 2.5 or less.   The terminal reactive oligomer which has a terminal vinylidene group of Claim 1 whose said alpha olefin is ethylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene.   The terminal reactive oligomer which has a terminal vinylidene group of Claim 1 whose content of the said alpha olefin is 0.1-99.9 mol%.   The terminal reactive oligomer which has a terminal vinylidene group of Claim 1 whose said alpha olefin is ethylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene.