JP2008255159A - Method for synthesizing oligomer having on its one end vinylidene-type double bond and/or oligomer having on its both ends vinylidene-type double bonds - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method for continuously synthesizing in high yield and high selectivity an oligomer having on its one end a vinylidene-type double bond and/or an oligomer having on its both ends vinylidene-type double bonds. <P>SOLUTION: The method for synthesizing the oligomer(s) comprises the step of melting polystyrene or a polyolefin at a temperature lower than its thermal decomposition temperature, the step of moving the molten polystyrene or polyolefin via a moving pipe to a thermal decomposition reaction field, the step of thermally decomposing the molten polystyrene or polyolefin under agitation at reduced pressure in an inert gas atmosphere, the step of retrieving nonvolatiles, the step of distilling off volatiles via a distilling-off pipe to a cooling field, the step of collecting the volatiles, and the step of retrieving the volatiles. In the above process, the respective steps are conducted consecutively and made to proceed independently from one another. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to a method for synthesizing an oligomer having a vinylidene type double bond at one end and / or an oligomer having a vinylidene type double bond at both ends.

In recent years, there has been a demand for recycling of resources, and how to recover resources with high yield and high selectivity from petroleum-derived plastic materials has become a problem. Examples of plastic waste include polyethylene and polystyrene. For example, as a method of synthesizing an oligomer from polystyrene, a synthesis method by thermal decomposition of polystyrene is known.
Conventional oligomer synthesis methods based on thermal decomposition of polystyrene require the same steps to be repeated using a distillation column or rectification column, resulting in high costs (Patent Documents 1 to 5).

As a method of synthesizing oligomers, which solves the problem of repeating the same steps, a method of transferring the oligomers generated by thermal decomposition to a cooling vessel with an inert gas flow so that they are not refluxed again to the thermal decomposition reaction vessel. (Patent Documents 6 and 7). This method synthesizes monodisperse terminal-reactive oligomers (monochelix and telechelix) having a single bond and double bonds at both ends that cannot be easily synthesized by ordinary organic synthesis or polymerization. be able to. However, since both methods are batch synthesis methods, there is a problem that the synthesis efficiency is poor and the yield is lowered.
JP 2005-15635 A JP 2005-154509 A JP 2003-47801 A JP 2001-40136 A JP 2001-335658 A Japanese Patent Laid-Open No. 9-291046 JP 2006-316202 A

  The present invention has been made in view of the above-mentioned conventional problems, and an oligomer having a vinylidene type double bond at one end and / or an oligomer having a vinylidene type double bond at both ends are continuously and high. The object is to provide a method for highly selective synthesis in yield.

Specific means for achieving the above object are as follows.
A melting step of melting polystyrene or polyolefin at a melting temperature lower than the thermal decomposition temperature, a moving step of moving the molten polystyrene or molten polyolefin obtained in the melting step to a thermal decomposition reaction field through a moving tube, and the thermal decomposition reaction field Generated under the reduced pressure and the pyrolysis step of thermally decomposing the molten polystyrene or the molten polyolefin while stirring with a stirrer under the introduction of the inert gas into the molten polystyrene or the molten polyolefin, and the thermal decomposition step A non-volatile recovery step for recovering the non-volatile product; a distilling step for distilling the volatile product generated in the thermal decomposition step into a cooling field through the distilling tube; and a volatile property passing through the distilling tube Volatile collection process for collecting the product in a cooling field under reduced pressure, and a volatile recovery process for recovering the volatiles collected in the cooling field. An oligomer having a vinylidene type double bond at one end and / or a vinylidene type at both ends, characterized in that each of the steps is continuously performed and each step is independently performed. This is a method of synthesizing an oligomer having a double bond.

  According to the present invention, since an oligomer having a vinylidene type double bond at one end and / or an oligomer having a vinylidene type double bond at both ends can be continuously synthesized, high yield and high selectivity can be achieved. Can be synthesized and cost-effective.

Hereinafter, the raw materials, products, and synthesis steps used in the synthesis method of the present invention will be described in detail.
-Raw material-
In the synthesis method of the present invention, polystyrene or polyolefin (hereinafter sometimes referred to as “polymer”) is used as a raw material. Polystyrene or polyolefin is not particularly limited, and those having various molecular weights and various structures can be used. Polystyrene or α-polyolefin is preferable, and among them, polystyrene, polyethylene, polyisobutylene, ittactic poly is preferable. (1-butene) and polypropylene can be used more preferably.
In addition, although there is no restriction | limiting in the shape of a polymer, it is preferable that it is a small piece shape when the meltability of a polymer is considered.

-Product-
When the polystyrene or polyolefin is thermally decomposed by the synthesis method of the present invention, an oligomer having a vinylidene type double bond at one end and / or an oligomer having a vinylidene type double bond at both ends can be obtained.
Hereinafter, an oligomer having a vinylidene-type double bond at one end is referred to as “one-end vinylidene-type oligomer” or “monochelix”, and an oligomer having a vinylidene-type double bond at both ends is referred to as “both-end vinylidene-type oligomer” or “telechelix”. May be called. Furthermore, an oligomer having a vinylidene type double bond at one end and / or an oligomer having a vinylidene type double bond at both ends may be collectively referred to as “terminal vinylidene type oligomer”.

  As for the structure of the above monochelix and telechelix, for example, those derived from polypropylene are represented by the following chemical formula.

  In the above chemical formula, m represents the degree of polymerization of the oligomer. m varies depending on the reaction conditions of the thermal decomposition reaction. For example, when monochelix is obtained from polypropylene (molecular weight: 100,000) by the synthesis method of the present invention, m is 2 to 30, and in the case of telechelix, , M is 20 to 1000.

-Synthetic process-
The method for synthesizing a terminal vinylidene type oligomer of the present invention is characterized in that the following steps are continuously performed and the steps are independently performed.
<Melting process>
The raw polymer melts at a temperature lower than the thermal decomposition temperature. Although the temperature of a melting tank changes with raw materials, it is preferable that it is 150-250 degreeC, and it is more preferable that it is 180-230 degreeC. If it is lower than 150 ° C., it may not be sufficiently melted or the viscosity may be increased, and if it is higher than 250 ° C., the polymer may be decomposed.
The melting time depends on the amount and shape of the raw material, but is preferably 30 to 180 minutes. If it is shorter than 30 minutes, it may not melt sufficiently, and if it is longer than 180 minutes, the polymer may be decomposed.
For example, in the case of polystyrene having a molecular weight of 50,000 to 100,000, the melting temperature is preferably 190 to 210 ° C., and the melting time is preferably 30 to 120 minutes.
Moreover, the capacity | capacitance of a melting tank should just be 5 to 10 times or more of the preparation amount of a raw material polymer.

<Transfer process>
The raw material polymer melted in the melting tank is transferred to a decomposition tank, which is a thermal decomposition reaction field of the raw material polymer, through a transfer pipe (hereinafter also referred to as “molten polymer transfer pipe”). The molten polymer moving tube is connected to continuously perform the polymer melting step and the polymer thermal decomposition step, and the melting tank and the molten polymer moving tube are separately independent systems such as openable and closable valves. It is possible to make.
The openable and closable valve (hereinafter also referred to as “open / close valve”) may be of any material and shape as long as the two connected systems can be freely connected or shut off.

The molten polymer moving tube is preferably maintained at the same temperature as the melting tank in order to prevent the molten polymer from being cooled and solidified. That is, it is preferable to hold | maintain at 150-250 degreeC, and it is more preferable that it is 180-230 degreeC.
The method for keeping the molten polymer moving tube at the same temperature as the melting tank is not particularly limited. Generally, the temperature is controlled by winding a ribbon heater around the molten polymer moving tube, or the molten polymer moving tube is insulated. There is a method of covering with material.

<Thermal decomposition process>
The molten raw material polymer is set to the thermal decomposition temperature of the raw material polymer, and is thermally decomposed by stirring under reduced pressure in a decomposition tank into which an inert gas is introduced. The decomposition tank is connected to the molten polymer moving pipe, and an open / close valve is provided between the decomposition tank and the molten polymer moving pipe. The on-off valve is as described above.
The temperature of the decomposition tank (hereinafter sometimes referred to as “decomposition tank temperature”) depends on the raw material polymer, but is preferably 300 to 450 ° C.,
It is more preferable to set it as 350-400 degreeC. When the temperature is lower than 300 ° C., the raw polymer may not cause a thermal decomposition reaction, and when the temperature is higher than 450 ° C., the thermal decomposition product may be colored.
Although the time required for decomposition (hereinafter sometimes referred to as “decomposition time”) depends on the structure and amount of the raw material polymer, it is preferably 30 to 360 minutes. If it is shorter than 30 minutes, the molecular weight of the thermal decomposition product may not be sufficiently lowered, and if it is longer than 360 minutes, the thermal decomposition product may be colored. The time required for decomposition specifically refers to the time from when the molten polymer is completely put into the decomposition tank until the thermal decomposition product is taken out from the decomposition tank.

  For example, in the case of polystyrene having a molecular weight of 10,000 to 1,000,000, the decomposition tank temperature is preferably 330 to 390 ° C., and the decomposition time is preferably 30 to 360 minutes.

The molecular weight of the terminal vinylidene-type oligomer of the nonvolatile product produced by the thermal decomposition reaction can be adjusted by adjusting the decomposition tank temperature and the decomposition time.
Although depending on the raw material, in order to synthesize a terminal vinylidene type oligomer having a molecular weight of about 5000, it is preferable to set the decomposition tank temperature to 370 to 400 ° C. and the decomposition time to 150 to 210 minutes. On the other hand, in order to synthesize a terminal vinylidene type oligomer having a molecular weight of about 3000, it is preferable to set the decomposition tank temperature to 370 to 400 ° C. and the decomposition time to 210 to 270 minutes.

The molten raw material polymer needs to be sufficiently stirred in order to cause the thermal decomposition reaction to proceed uniformly. The stirring can be performed by introducing an inert gas into the molten polymer and generating bubbles in addition to the stirring by a stirrer.
The inert gas is not particularly limited as long as it does not inhibit the thermal decomposition reaction of the raw material polymer, and nitrogen gas, argon gas, helium gas and the like are preferably used. Furthermore, water vapor can also be used.

  In the decomposition tank, in order to quickly discharge the volatile product obtained by the thermal decomposition reaction from the decomposition tank, the pressure in the system is preferably reduced to 1 to 4 mmHg. In addition, the inert gas introduced into the raw polymer also plays a role of discharging volatile products from the decomposition tank. In order for the inert gas to exhibit such a volatile component discharge function, the flow rate of the inert gas is preferably set to 10 to 1000 ml / min.

<Nonvolatile matter recovery process>
Of the products obtained by the thermal decomposition reaction, non-volatile products are discharged from the decomposition tank to the kettle residue receiver. By providing the kettle residue receiver separately from the decomposition tank, it is possible to recover the non-volatile product from the kettle residue receiver while continuing the thermal decomposition reaction of the polymer. An open / close valve is provided between the decomposition tank and the pot receiver, and the system in the decomposition tank and the system in the pot receiver can be made independent.
The temperature in the pot residue receiver is preferably set to the same temperature and pressure as in the decomposition tank. When recovering the non-volatile product, set the inside of the pot receiver to room temperature and normal pressure.

<Distillation process>
On the other hand, among the products obtained by the thermal decomposition reaction, volatile products are discharged through a distillation pipe to a volatile collection tank as a cooling field. It is preferable to hold | maintain the said distilling pipe at 300-400 degreeC, and it is more preferable to hold | maintain at 350-400 degreeC. If it is higher than 300 ° C., the volatile product can be transferred to the volatile collection tank as a gas, and if it is lower than 400 ° C., the secondary reaction of the volatile product can be suppressed.
The method for maintaining the distilling pipe at the above-mentioned temperature is not particularly limited, but in general, the temperature is controlled by winding a ribbon heater around at least a part of the distilling pipe, or at least the distilling pipe is used. There is a method of covering a part with a heat insulating material.
In the distilling step, it is preferable to maintain the pressure in the system at the same pressure as in the decomposition tank.

<Volatile matter collection process>
Volatile products that have passed through the distillation pipe are collected in a volatile collection tank in a cooling field. The volatile matter collecting tank is preferably cooled to -20 to -30 ° C and depressurized to 1 to 4 mmHg so that volatile products can be easily collected. If the temperature in the tank is −20 ° C. or lower, the volatile product can be collected as a solid.
An on-off valve is provided between the molten polymer transfer tube and the volatile collection tank so that the system of the polymer thermal decomposition reaction field and the cooling field can be made independent. The on-off valve is as described above.

  In order to efficiently collect the volatile product in the cooling field, it is preferable to provide a condenser for cooling the volatile product between the distillation pipe and the cooling field. The condenser is preferably kept at 0 to 100 ° C. by flowing a refrigerant. As the refrigerant, water is usually used, but alcohol may be used when kept at a low temperature, and oil may be used when kept at a high temperature.

<Volatile recovery process>
Volatile products collected in the volatile collection tank can be collected by moving to the volatile collection tank and bringing the inside of the volatile collection tank to room temperature and normal pressure. An open / close valve is provided between the volatile matter collecting tank and the volatile matter collecting tank. As a result, the cooling and collection of the volatile product produced by the thermal decomposition reaction of the polymer and the recovery can be performed independently, and the volatile product can be recovered while continuing the thermal decomposition reaction. It becomes possible.

  As described above, by connecting containers for performing each process, a series of processes can be continuously performed, and each process can be performed by closing an on-off valve provided between the containers. Each can proceed independently. By such a method, a terminal vinylidene type oligomer can be synthesized continuously from a polymer.

The process for synthesizing the terminal vinylidene type oligomer of the present invention will be described with reference to FIG. In addition, the said synthetic | combination process of this invention is not limited to the following content.
As shown in FIG. 1, the bottom of the melting tank 1 is connected to the molten polymer moving tube 10, and the molten polymer in the melting tank can move to the moving tube 10 from the bottom of the melting tank 1. ing. Further, the molten polymer moving tube 10 is connected to the upper part of the decomposition tank 2. The melting tank 1 is heated by an oil heater (not shown), and a ribbon heater (not shown) is wound around the molten polymer moving tube 10 to keep the temperature.
The raw material polymer is melted by holding the melting tank 1 at 180 to 250 ° C., and the molten polymer is cooled by moving the molten polymer to the decomposition tank 2 through the molten polymer moving tube 10 set to 180 to 250 ° C. -It becomes possible to move to the decomposition tank 2 continuously without solidifying.

  An opening / closing valve 12a is provided on the side of the molten polymer moving tube 10 on the melting tank 1 so that the system of the melting tank 1 and the molten polymer moving tube 10 can be made independent. In addition, an on-off valve 12b is provided on the side of the decomposition tank 2 of the molten polymer moving pipe 10 so that the system of the molten polymer moving pipe 10 and the decomposition tank 2 can be made independent of each other. Thus, by setting each system in an independent state, it is possible to melt the next raw material polymer in the melting tank 1 while proceeding with the thermal decomposition reaction of the raw material polymer in the decomposition tank 2.

The decomposition tank 2 can heat the polymer with an electric heater (not shown). After confirming that the on-off valve 12c provided at the bottom of the decomposition tank 2 is closed, the molten polymer is transferred to the decomposition tank 2 that has been set to the melting temperature of the raw material polymer in advance, and then the molten polymer transfer pipe 10 The on-off valve 12b is closed. The molten polymer is agitated by a stirrer 8 and bubbles of inert gas 9 introduced from a tube inserted into the molten polymer. Furthermore, after opening the on-off valve 12f which will be described later and confirming that the on-off valve 12g is closed, the inside of the decomposition tank 2 is depressurized to 1 to 4 mmHg to 300 to 450 ° C. which is the thermal decomposition temperature of the molten polymer. As the temperature rises, the thermal decomposition reaction of the polymer begins to proceed.
The inside of the decomposition tank 2 is depressurized by using a vacuum pump 7a directly connected to a volatile collection tank 5 described later, and the pressure in the tank is confirmed by a pressure gauge such as a manometer (not shown) installed in the decomposition tank 2.

As shown in FIG. 1, a distillation pipe 11 is connected to the upper part of the decomposition tank 2 and communicates with a volatile collection tank 5 in a cooling field. As described above, the vacuum pump 7 a is connected to the upper part of the volatile matter collecting tank 5. A ribbon heater (not shown) is wound around the distilling tube 11 over the entire range so that the temperature can be controlled. A condenser 4 is connected between the distilling tube 11 and the volatile matter collection tank 5, and an open / close valve 12 f is provided between the condenser 4 and the volatile matter collection tank 5.
On the other hand, the bottom part of the decomposition tank 2 is connected to the pot residue receiver 3 through a pipe, and an opening / closing valve 12c is provided on the decomposition tank 2 side of the pipe and an opening / closing valve 12d is provided on the pot residue receiver 3 side. ing. In addition, a vacuum pump 7b is connected between the decomposition tank 2 and the pot receiver 3, and an open / close valve 12e is provided on a pipe leading to the vacuum pump 7b.

  Among the products obtained by the thermal decomposition reaction of the raw polymer, volatile products pass through the distillation pipe 11 connected to the upper part of the decomposition tank 2 at any time by the suction of the vacuum pump 7a during the thermal decomposition reaction. And discharged from the decomposition tank 2. On the other hand, the system of the pot residue receiver 3 is opened by the vacuum pump 7b by opening the on-off valves 12d and 12e so that the pressure in the system is the same as that in the tank of the decomposition tank 2 independently of the decomposition tank 2. The pressure is reduced to 4 mmHg. After the pot rest 3 has been depressurized, the on-off valves 12e and 12d are closed.

  After completion of the thermal decomposition reaction, the on-off valve 12f is closed, and the on-off valve 12c and the on-off valve 12d are opened, whereby the non-volatile product obtained by the pyrolysis reaction is discharged to the pot residue receiver 3. After closing the on-off valve 12d, the system of the pot receiver 3 is brought to room temperature and normal pressure, and the nonvolatile product is recovered. As the non-volatile product, a terminal vinylidene type oligomer having a molecular weight of 1,000 to tens of thousands can be obtained.

The distillation pipe 11 connected to the upper part of the decomposition tank 2 is set to 300 to 400 ° C. so that volatile components generated by the thermal decomposition reaction do not cause a secondary reaction. The condenser 4 connected to the distillation pipe 11 is caused to flow 10-30 ° C. water to cool the volatile product.
The volatile collection tank 5 connected to the condenser 4 can be cooled by a temperature control device (not shown). Further, the bottom of the volatile matter collecting tank 5 is connected to the volatile matter collecting tank 6 by a pipe. An opening / closing valve 12g is provided on the volatile matter collecting tank 5 side of the tube, and an opening / closing valve 12h is provided on the volatile matter collecting tank 6 side. A vacuum pump 7c is provided between the volatile matter collecting tank 5 and the volatile matter collecting tank 6, and an opening / closing valve 12i is provided on a pipe communicating with the vacuum pump 7c.

  As described above, when the thermal decomposition reaction is started, the on-off valve 12g provided at the bottom of the volatile matter collecting tank 5 is closed. Moreover, the volatile matter collection tank 5 sets the temperature in the tank to -20 to -30 ° C in advance, and the vacuum inside the tank is reduced to 1 to 4 mmHg by the vacuum pump 7a connected to the volatile matter collection tank 5, It is possible to collect volatile components generated by the thermal decomposition reaction.

  On the other hand, the inside of the system of the volatile matter collecting tank 6 is decompressed to 1 to 4 mmHg by the vacuum pump 7a independently of the volatile matter collecting tank 5 by opening the on-off valves 12h and 12i. After the volatile matter recovery tank 6 is decompressed, the on-off valves 12h and 12i are closed.

After completion of the thermal decomposition reaction, the on-off valve 12f is closed, and the on-off valves 12g and 12h are opened, so that the volatile products collected in the volatile collection tank 5 are discharged to the volatile collection tank 6. Thereafter, the on-off valve 12h is closed, and the volatile product is recovered by bringing the inside of the volatile matter recovery tank 6 to room temperature and normal pressure. As a volatile product, a one-end vinylidene type oligomer having a molecular weight of several hundreds can be obtained.
The volatile product and non-volatile product obtained by the synthesis method of the present invention are distilled as necessary and recovered as a terminal vinylidene type oligomer.

  In the examples described later, except for numerical conditions such as set temperature and pressure, the same equipment as described above was used, and the equipment was operated in the same manner as described above.

  Hereinafter, the present invention will be described more specifically with reference to examples. The materials, reagents, ratios, equipment, operations, and the like shown in the following examples can be appropriately changed without departing from the scope of the present invention. Therefore, the scope of the present invention is not limited to the following examples. Unless otherwise specified, “%” and “parts” represent “% by mass” and “parts by mass”, and the molecular weight indicates the weight average molecular weight.

Example 1
2 kg of polystyrene (molecular weight 183,000) was charged into a melting tank having a capacity of 10,000 ml, and the inside of the melting tank was set to 200 ° C. After confirming that the polystyrene was sufficiently melted, it was moved to the decomposition tank through a molten polymer moving tube set at 200 ° C. Nitrogen gas was introduced into the molten polystyrene at a flow rate of 100 ml / min and stirred with a stirrer. The inside of the decomposition tank was depressurized to 2 mmHg, and the decomposition tank temperature was raised to 390 ° C. to initiate the thermal decomposition reaction. The decomposition time was 120 minutes.
As a result, it was possible to recover 220 g of monokelix (one-end vinylidene type oligomer) having a molecular weight of 11,600 as a nonvolatile product and 1,600 g of monochelix having a molecular weight of 200 as a volatile product. Little telechelix was produced. The breakdown of all monochelics as the volatile product was monomer: dimer: trimer: tetramer or higher multimer = 50: 15: 30: 5 [% by mass].

(Example 2)
The same procedure as in Example 1 was performed except that the polypropylene shown in Table 1 was used as a raw material, and the decomposition bath temperature and decomposition time shown in Table 1 were used.
As a result, the non-volatile products and volatile products shown in Table 2 could be recovered.

(Example 3)
The same procedure as in Example 1 was performed except that isotactic poly (1-butene) shown in Table 1 was used as a raw material and the decomposition bath temperature and decomposition time shown in Table 1 were used.
As a result, the non-volatile products and volatile products shown in Table 2 could be recovered.

Example 4
The same procedure as in Example 1 was carried out except that the polypropylene-1-butene random copolymer shown in Table 1 was used as the raw material, and the decomposition bath temperature and decomposition time shown in Table 1 were used.
As a result, the non-volatile products and volatile products shown in Table 2 could be recovered.

In Table 1 below, R ¹ , R ² and n correspond to R ¹ , R ² and n in the following general formula (1).

<Measurement of f _TVD value>
^The f _TVD value was determined for the product obtained by the pyrolysis reaction by ¹³ C-NMR measurement. The f _TVD value represents the average number of double bonds per molecule, and the closer the f _TVD value is to 2, the more the composition of telechelics (telechelics in all non-volatile products or all volatile products). ) Is high. For example, in a non-volatile product, if the f _TVD value is 1.8, the composition is statistically estimated to be telechelics: monochelics: saturated component = 81: 18: 9 [mass%]. . Further, when the f _TVD value is 1.7, telechelix: monochelix: saturated component = 73: 25: 2 [mass%].

<Identification of product structure>
The product obtained by the pyrolysis reaction was confirmed as follows.
(1) Structure identification of volatile product of polystyrene The composition of styrene monomer, dimer and trimer was determined by GC and GPC. The result was 50: 15: 30: 5 mass%. Monomers, dimers and trimers were isolated and purified by distillation, and the structure was determined by ¹ H-NMR measurement.
^{In 1} H-NMR measurement, the styrene dimer detects protons of the benzene ring at 7.5 to 7.1 ppm, two protons of vinylidene double bonds at 5.30 ppm and 5.29 ppm, and 2. The main chain methylene proton was detected at 80 ppm. In the styrene trimer, a proton of a benzene ring is detected at 7.5 to 7.0 ppm, two protons of vinylidene are detected at 5.15 ppm and 4.88 ppm, and a methylene proton of the main chain is detected at 2.81 ppm. The main chain methine proton was detected at 2.68 ppm, the α-position methylene proton of vinylidene was detected at 2.37 ppm, and the γ-position methylene proton of vinylidene was detected at 2.03 ppm and 1.88 ppm.
Further, in the ¹³ C-NMR measurement, the f _TVD value was determined by using the intensity ratio between the unsaturated terminal and the saturated terminal methylene carbon detected at 114 ppm and 34 ppm, respectively.

(2) Identifying the structure of non-volatile products of polypropylene
^{By 13} C-NMR, methyl, methine, and methylene carbons of an isotactic chain of propylene were detected at 19.8 ppm, 27.1 ppm, and 44.7 ppm. In addition, the methyl carbon of the n-propyl group which is a saturated terminal and the vinylidene group which is an unsaturated terminal was detected at 12.4 ppm and 20.6 ppm. The f _TVD value was determined using this intensity ratio.

(3) Isotactic poly (1-butene) non-volatile product structure identification The f _TVD value was determined in the same manner as the polypropylene structure identification. ^{By 13} C-NMR, methyl of 1-butene isotactic chain, methylene of side chain, methylene carbon of methine and main chain were detected at 8.8 ppm, 25.8 ppm, 33.1 ppm and 38.3 ppm, respectively. In addition, a vinylidene group methyl carbon which is an unsaturated terminal and a methyl carbon of an n-butyl group which is a saturated terminal were detected at 10.7 ppm and 12.1 ppm, respectively, and an f _TVD value was obtained from this intensity ratio.

(4) Structure identification of propylene-1-butene random copolymer As in the case of structure identification of the polypropylene and structure identification of the isotactic poly (1-butene), in ¹³ C-NMR, polypropylene and isotactic Both peaks of tic poly (1-butene) were detected. The f _TVD value was determined by the intensity ratio of each unsaturated end to saturated end.

(5) In each measurement for specifying the structure of the product, “TOSOH HLC-8220 GPC manufactured by Tosoh Corporation” is used for GPC measurement, and “TOSOH HLC-821 manufactured by Tosoh Corporation” is used for high-temperature GPC measurement. GPC / HT ”was used,“ JEOL-EC500 ”manufactured by JEOL Ltd. was used for ¹ H-NMR measurement and ¹³ C-NMR measurement, and“ HP6890 ”manufactured by HEWLETT PACKARD was used for GC measurement.

Table 2 shows the yield (mass%) and molecular weight of each nonvolatile product and volatile product obtained by the thermal decomposition reaction of Examples 1 to 4, and the f _TVD value obtained by the above measurement. Table 2 shows the composition (% by mass) of telechelics for non-volatile products and the composition (% by mass) of monochelics for volatile products.

It is a figure which shows an example of the synthetic | combination process of the terminal vinylidene type oligomer of this invention.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Melting tank 2 Decomposition tank 3 Kettle receiver 4 Condenser 5 Volatile collection tank 6 Volatile collection tank 7a-7c Vacuum pump 8 Stirrer 9 Inert gas 10 Molten polymer moving pipe 11 Distillation pipe 12a-12i On-off valve

Claims (1)

A melting step of melting polystyrene or polyolefin at a melting temperature lower than the pyrolysis temperature;
A moving step of moving the molten polystyrene or molten polyolefin obtained in the melting step to a pyrolysis reaction field through a moving tube;
A thermal decomposition step of thermally decomposing the molten polystyrene or the molten polyolefin while stirring with a stirrer under reduced pressure of the thermal decomposition reaction field and introduction of an inert gas into the molten polystyrene or the molten polyolefin;
A non-volatile recovery step of recovering the non-volatile product generated in the pyrolysis step;
A distilling step of distilling the volatile product produced in the pyrolysis step into a cooling field through a distilling tube;
A volatile collection step of collecting a volatile product that has passed through the distillation pipe in a cooling field under reduced pressure;
A volatile recovery step of recovering volatiles collected in the cooling field;
An oligomer having a vinylidene-type double bond at one end and / or a vinylidene-type double at both ends, characterized in that each of the steps is continuously performed and each of the steps proceeds independently. A method of synthesizing an oligomer having a bond.

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