JP2000336152A - Dicyclopentadiene ring-opened polymer having functional group at one end and its production - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the subject polymer at whose one end has a functional group capable of imparting a function such as reactivity, radical polymerizability, flame retardancy and adhesivity to various urachine parts, by subjecting dicyclopentadiene to a ring-opening polymerization in the presence of a specific catalyst and a specific chain transfer agent. SOLUTION: A polymer of formula IV [(n) is 1 to 50 on the average; a double bond is disposed between the No.3 carbon and the No.4 carbon or between the No.4 carbon and the No.5 carbon] is obtained by subjecting dicylopentadiene to a ring-opening metathesis polymerization in the presence of a compound of formula I (M is ruthenium or osmium; X, X1 are each an anionic ligand; L, L1 are each a neutral electron donor group; Q, Q1 are each H or an alkyl, alkenyl or aromatic group which may have a substituent) (for example, a ruthenium carbene complex of formula II) as a catalyst and an allyl compound of the formula: X-CH2-CH=CH2 [X is a group of formula III or a group of the formula: (CH3CH30)3-Si- or the like] (for example, allylglycidyl ether) as a chain transfer agent.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a polymer having at one end a functional group obtained by metathesis ring-opening polymerization of dicyclopentadiene and a method for producing the same. More specifically, a metathesis ring-opening polymer of dicyclopentadiene that can impart functions such as reactivity, radical polymerizability, flame retardancy, and adhesion to various substrates, which is useful for improving the properties of various polymer materials About.

[0002]

2. Description of the Related Art A method of obtaining a polymer by subjecting dicyclopentadiene to metathesis ring-opening polymerization has been known for a long time.
For example, in JP-A-53-24400, a catalyst system comprising a combination of a tungsten catalyst and an organometallic compound of Groups I to IV of the periodic table as an activator is used, and a chain transfer agent (molecular weight) is used. 1-hexene as a regulator)
A method of synthesizing using a chain olefin compound such as 1-octene, styrene, vinyl chloride, and vinyl ether is described.

[0003] Also, Polymer Journal, Vol 27, No.
12, pp 1167-1172 (1995), the number average molecular weight is 1.12 using 1-hexene as a chain transfer agent in the presence of a catalyst system comprising tungsten hexachloride and tetramethyltin as an activator. A method for obtaining a ring-opened linear polymer of × 10 ⁴ dicyclopentadiene is described.

As described above, a ring-opened linear polymer of dicyclopentadiene having a controlled molecular weight can be obtained by using a chain transfer agent. However, in the prior art, the compound used for the chain transfer agent has a functional group. And a compound having a functional group could not be used as a chain transfer agent. The reason was that the catalyst system in which the catalyst component used and the activator were combined easily react with water, air (oxygen) and various functional groups and are deactivated. Therefore, the ring-opened linear polymer of dicyclopentadiene obtained by using a chain olefin compound having no functional group as a chain transfer agent is a so-called hydrocarbon resin having no functional group, and thus its use is limited. Was.

[0005]

SUMMARY OF THE INVENTION An object of the present invention is to provide a dicyclopentadiene having a functional group at one end capable of imparting functions such as reactivity, radical polymerizability, flame retardancy, and adhesion to various equipment. An object of the present invention is to provide a metathesis ring-opened polymer. That is, the present invention provides a metathesis ring-opened polymer of dicyclopentadiene having a glycidyl ether group, methacryloyl group, acid anhydride group, alkoxysilane, tribromophenyl ether, or oxetane functional group at one end.

[0006]

According to the present invention, in the metathesis ring-opening polymerization of dicyclopentadiene, the molecular weight is controlled by using an allyl compound having a functional group in the presence of a ruthenium or osmium carbene complex catalyst, And a ring-opened polymer of dicyclopentadiene having a functional group at one end. The polymer of the present invention is a polymer represented by the general formula [1].

[0007]

Embedded image Wherein n is an average of 1 to 50, and 3 and 4 in the carbon numbers represented by Arabic numerals.
Is a double bond or between carbon numbers 4 and 5 is a double bond. In the production of the polymer of the present invention, a compound represented by the general formula [2] is used as a catalyst with dicyclopentadiene,

[0008]

Embedded image (M is ruthenium or osmium, X and X ₁ are anionic ligands, L and L ₁ are neutral electron donating groups, Q and Q
₁ each independently represents hydrogen, an alkyl group, an alkenyl group or an aromatic group, and the alkyl group, the alkenyl group or the aromatic group may have a substituent. ) And an allyl compound represented by the general formula [3] as a chain transfer agent

[0009]

Embedded image Wherein ring-opening metathesis polymerization is carried out in the presence of

[0010]

DETAILED DESCRIPTION OF THE INVENTION The metathesis polymerization catalyst which can be used in the present invention is different from a catalyst which is a combination of a catalyst component and an activator as conventionally known, and differs from oxygen, moisture and functional groups in the air. By an allyl compound having
This is a catalyst capable of subjecting dicyclopentadiene to metathesis ring-opening polymerization without losing catalytic activity. Preferred as such a metathesis polymerization catalyst are those represented by the general formula [2]:

[0011]

Embedded image In the general formula [2], M represents ruthenium or osmium. X and X ₁ each independently represent an anionic ligand. An anionic ligand is a group that has a negative charge when decoordinated to the central metal. Such groups include, for example, hydrogen, halogen, CF ₃ CO ₂ , C ₃
H ₃ CO ₂ , CFH ₂ CO ₂ , (CH ₃ ) ₃ CO, (C
F ₃ ) ₂ (CH ₃ ) CO, (CF ₃ ) (CH ₃ ) ₂ C
O, an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, a phenyl group, a phenoxy group, a tosyl group, a mesyl group, a trifluoromethanesulfonate group, etc., and particularly preferred are both halogen (particularly, Chlorine). L and L ₁ each independently represent a neutral electron donating group. A neutral electron donating group is one that has a neutral charge when decoordinated to the central metal. Examples of such a group include PR ² R ³ R ⁴ (where R ² is a secondary alkyl group or a cycloalkyl substrate, R ³ and R ⁴ are each independently an aryl group, a C 1-10 Represents a primary alkyl group or a secondary alkyl group or a cycloalkyl group), pyridine, p-fluoropyridine, an imidazolylidene compound, and the like. And L ₁ are both-
P (cyclohexyl) ₃ , -P (cyclopentyl) ₃ ,
Or -P (isopropyl) ₃ . Also,
L and L ₁ may be different from each other. Q and Q
₁ each independently represents hydrogen, an alkyl group, an alkenyl group or an aromatic group. The alkyl group has 1 to 2 carbon atoms.
The alkyl or alkenyl group having 0 to 2 carbon atoms has 2 to 20 carbon atoms.
Examples of the alkenyl group and aromatic group include an aryl group and the like, and the alkyl group, alkenyl group and aromatic group may have a substituent.

Specific examples of the compound (catalyst) represented by the general formula [2] are, for example, ruthenium carbene complexes as shown in formulas (a) to (f).

[0013]

Embedded image

The method of synthesizing the compound (catalyst) is, for example, as follows:
Journal of American Chemical Society Vol. 118,
100 pages (1996) or Organometall
ics Vol. 16, No. 18, p. 3867 (1997
Year), and Organometallics Volume 16, Issue 18, 4
001 (1997).

As the dicyclopentadiene used in the present invention, commercially available dicyclopentadiene can be used. Ordinary commercially available dicyclopentadiene may contain vinylnorbornene, tetrahydroindene, methylvinylnorbornene, methyltetrahydroindene, methyldicyclopentadiene, dimethyldicyclopentadiene, tricyclopentadiene, and the like as impurities. These can be included in a range that does not impair the purpose of the present invention. The commonly used dicyclopentadiene has a purity of 90% by weight or more, preferably 97% by weight or more.

The allyl compound having a functional group used as a chain transfer agent in the present invention includes the following. Allyl glycidyl ether, allyl methacrylate, allyl-2,4,6-tribromophenyl ether, allyltriethoxysilane, allylsuccinic anhydride, 3-allyloxymethyl-3-ethyloxetane. These are all commercially available as industrial chemicals or reagents and can be used as they are.

The molar ratio of dicyclopentadiene to the allyl compound having a functional group used as a chain transfer agent ([dicyclopentadiene] / [allyl compound]) directly defines n in the general formula [1]. That is, the molecular weight of the polymer is suppressed. Although n is changed depending on the purpose of use of the polymer, in the polymer of the present invention, n is 1 to 50,
That is, the allyl compound is charged so that the molar ratio becomes 1 to 50. When the molar ratio is 50 or more, the ratio of the terminal functional group in the obtained polymer becomes small, and it is difficult to exhibit functions such as adhesiveness and flame retardancy.

The amount of the catalyst used is an amount necessary for the reaction to proceed. Although it depends on the type of the catalyst, it is usually 0.001 to 100 parts by weight of dicyclopentadiene.
To 5 parts by weight, preferably 0.01 to 1 part by weight for reasons of economy and continuous reaction.

The polymer to be produced has the general formula [1]
If n is an oligomer having an average of about 1 or 2 in some cases, it can be synthesized without using a solvent, but usually, it does not hinder the metathesis ring-opening polymerization reaction of dicyclopentadiene, and A solvent which dissolves dicyclopentadiene, an allyl compound, and a polymer to be formed and is inert to these is used. Solvents used include aromatic solvents such as toluene, xylene, ethylbenzene, and tetralin; cycloalkane solvents such as cyclohexane, cycloheptane, and cyclooctane; ketone solvents such as acetone, methyl ethyl ketone and cyclohexanone; and dichloromethane and chloroform. Halogen solvents are exemplified.

The amount of the solvent used varies depending on the molecular weight of the polymer to be produced, but is usually used so that the concentration of the substrate is 5 to 70% by weight.

In the atmosphere during the production of the polymer, the reaction proceeds even under air, but it is preferable to make the atmosphere inert with nitrogen, argon or the like.

The reaction temperature for producing the polymer is from 0 to 10
0 ° C., preferably from room temperature (20 ° C.) to 60 ° C. Although the reaction proceeds even at 0 ° C. or lower, the reaction slows down and is not realistic. On the other hand, when the temperature is 100 ° C. or higher, a three-dimensional crosslinked product of dicyclopentadiene is formed as a by-product, which is not preferable because the yield is reduced. This reaction is an exothermic reaction because the nobornene ring of dicyclopentadiene is opened and the strain energy of the ring is released. Therefore, it is preferable to control the reaction temperature by appropriately cooling.

The reaction time varies depending on the amount of the catalyst and the reaction temperature, but is usually 15 minutes to 10 hours. It is preferable to carry out the reaction until the starting material dicyclopentadiene is consumed by the reaction.

(Reaction stopping method) When the raw material dicyclopentadiene is reacted and consumed, the polymerization reaction stops spontaneously, but one end opposite to the one end provided with the functional group of the polymer has The same number of moles of the polymer molecules as in the catalyst are present. If the catalyst is still attached to the polymer end, the polymers may react and gel when the solution in which the polymer is dissolved is concentrated or when the solution in which the polymer is dissolved is concentrated. It is preferred to separate the catalyst from the coalescence. The method of separating the catalyst from the polymer can be achieved by adding a vinyl compound such as ethyl vinyl ether or vinyl acetate in excess of the number of moles of the catalyst using the vinyl compound.

(Post-treatment) After the reaction is completed and the catalyst is separated from the polymer, the reaction solution is poured into a poor solvent such as n-hexane, methanol, water or the like to reprecipitate the polymer. How to dry. Alternatively, a polymer can be obtained by removing the solvent from the reaction solution using a thin film evaporator. It is also possible to modify and react with the next target material in the presence of the solvent.

(Additive; Polymerization Inhibitor) When using an allyl methacrylate as a chain transfer agent to obtain a polymer having a structure in which a methacryloyl group is added to one end, polymerization is inhibited in order to suppress polymerization of the methacryloyl group. It is preferable to add an agent to the reaction system. Examples of the polymerization inhibitor include generally used 4-methoxyphenol and the like, and its amount is 10 to 1,000 ppm of the polymer.

(Additive: Antioxidant) Since the obtained polymer has the same amount of double bonds as the double bond of the starting material dicyclopentadiene, it may be oxidized to form a gel state. is there. Therefore, it is preferable to add an antioxidant to the reaction system. The antioxidant used is not particularly limited as long as it has an antioxidant ability, and preferred examples include a hindered phenol-based antioxidant, and 2,6-di-t-butyl-4-methylphenol,
2,6-di-t-butyl-4-ethylphenol, stearyl-β- (3,5-di-t-butyl-4-hydroxyphenyl) propionate, tetrakis- [methylene-3- (3 ′, 5 ′) -Di-t-butyl-4'-hydroxyphenyl) propionate] methane, 2,2'-methylenebis (4-methyl-6-t-butylphenol),
2,2′-methylenebis (4-ethyl-6-t-butylphenol), 4,4′-methylenebis (2,6-di-
t-butylphenol), 1,3,5-trimethyl-
2,4,6-tris (3,5-di-t-butyl-4-hydroxybenzyl) benzene, 1,3,5-tris (3 ′, 5′-di-t-butyl-4′-hydroxybenzyl) ) -S-Triazine-2,4,6- (1H, 3H,
5H) trione and the like. The addition amount of the antioxidant is usually 10 to 10,000 ppm.

[0028]

Example 1 Synthesis of glycidyl ether-terminated polymer

[0029]

Embedded image Toluene 29 was placed in a 1-liter separable flask equipped with a stirrer, thermometer, nitrogen gas inlet tube and Allin's condenser.
3.5 g of dicyclopentadiene having a purity of 99%.
61 g (1.896 mol) and 43.93 g (0.385 mol) of allyl glycidyl ether were charged (molar ratio =
[Dicyclopentadiene] / [allyl glycidyl ether] = 4.93, substrate concentration = 50.1%), while flowing nitrogen gas at a flow rate of 0.1 l / min.
Cooled to ° C. After removing the ice bath, 0.21% of bis (tricyclohexylphosphine) benzylidyne-ruthenium dichloride represented by the formula (a) was used as a catalyst.
0 g (2.55 × 10 ^-4 mol, dicyclopentadiene 1
0.0838 parts by weight based on 00 parts by weight). At the same time as adding the catalyst, the temperature in the flask rose, and the inside of the flask reached 45 ° C 20 minutes after the start of the reaction. Therefore, the inside of the flask was kept at 45 ° C with an ice bath. Forty minutes after the start of the reaction, the temperature in the flask began to drop, and two minutes after the start of the reaction,
The temperature reached 5 ° C. To separate the catalyst from the polymer, 1.74 g (0.020 mol) of vinyl acetate was added and stirring was continued for 15 minutes. After the completion of the reaction, a minute amount of turbidity was removed by a filtration operation, and then toluene was distilled off with a rotary evaporator to obtain 277 g of a wax-like polymer. The yield was 94%. FIG. 1 shows the result of GPC analysis of this polymer. The number average molecular weight Mn of this polymer in terms of polystyrene was 748, and n was 4.8 on average. The weight average molecular weight Mw is 1,538,
The dispersity (Mw / Mn) of the polymer was 2.06.
The proton nuclear magnetic resonance spectrum ( ¹
H-NMR) is shown in FIG. 3.35 to 3.45 ppm
A peak based on Hd in the following equation (integral value: 8.95),
He-based peak at 3.65 to 3.75 ppm (integral value: 8.49), Hh and H at 4.93 to 5.07 ppm
peak based on i (integral value: 19.66) and 5.20
A peak of a proton bonded to an internal double bond (integral value: 180.88) is observed at about 6.00 ppm. By analyzing this result, it is confirmed that a glycidyl ether group is present at one end of the polymer, and that the polymer of the following formula has n of 4.9.

[0030]

Embedded image

Example 2 Synthesis of methacryloyl-terminated polymer

[0032]

Embedded image Toluene 27 was placed in a 1-liter separable flask equipped with a stirrer, thermometer, nitrogen gas inlet tube and Alin's condenser.
5.7 g, 99% pure dicyclopentadiene 231.
55 g (1.752 mol), 44.19 g (0.3503 mol) of allyl methacrylate to which 250 ppm of a polymerization inhibitor 4-methoxyphenol is added, and 14 mg of an antioxidant 2,6-ditert-butyl-4-methylphenol Charged (molar ratio = [dicyclopentadiene] / [allyl methacrylate] = 5.00, substrate concentration = 50.0%), cooled the inside of the flask to 6 ° C in an ice bath while flowing nitrogen gas at 0.1 l / min. did. After removing the ice bath, 0.197 g (2.39 × 10 ^-4 mol, bis (tricyclohexylphosphine) benzylidene-ruthenium dichloride represented by the formula (a) as a catalyst is used.
0.085 based on 100 parts by weight of dicyclopentadiene
1 part by weight). At the same time as adding the catalyst, the temperature in the flask rose, and 15 minutes after the start of the reaction,
Since the temperature reached ° C, the inside of the flask was kept at 40 ° C with an ice bath.
50 minutes after the start of the reaction, the temperature in the flask began to drop,
The temperature reached 27 ° C. 120 minutes after the start of the reaction. 1.74 g of vinyl acetate to separate the catalyst from the polymer
(0.020 mol) was added and stirring continued for 15 minutes. After the completion of the reaction, a minute amount of turbidity was removed by a filtration operation, and then toluene as a solvent was distilled off using a rotary evaporator to obtain 262 g of a wax-like polymer. The yield was 95%. FIG. 3 shows the result of GPC analysis of this polymer. The number average molecular weight Mn of this polymer was 78 in terms of polystyrene.
2 and n averaged 4.96. The weight average molecular weight Mw is 1,446, and the degree of dispersion of the polymer (Mw /
Mn) was 1.85. FIG. 4 shows a proton nuclear magnetic resonance spectrum ( ¹ H-NMR) of this polymer. 3. a peak based on the methyl group of the methacryloyl group at 1.95 ppm (integral value: 31.5); a peak based on Ha of the following formula at 6.13 ppm (integral value: 11.4);
Peaks based on terminal olefins of Hc and Hd in the following formula (integral value: 22.1) and 5.2 at 90 to 5.07 ppm
A peak of a proton bonded to an internal double bond (integral value: 231.7) is observed at 3 to 6.00 ppm. By analyzing this result, it is confirmed that a methacryloyl group is present at one end of the polymer, and that the polymer of the following formula has n of 5.0.

[0033]

Embedded image

Example 3 Synthesis of acid anhydride terminated polymer

[0035]

Embedded image In a 100 ml three-necked flask equipped with a thermometer and a magnetic rotor, 12.12 g of toluene, 10.01 g (75.7 mmol) of dicyclopentadiene having a purity of 99%, and 2.20 g (15.7 mmol) of allylsuccinic anhydride were charged. (20 ° C.) to give a homogeneous solution. As a catalyst, 8.8 mg (1.07 × 10 ⁻⁵ mol) of bis (tricyclohexylphosphine) benzylidyne ruthenium dichloride represented by the formula (a) was added.
At the same time as adding the catalyst, the temperature in the flask increased, and the temperature in the flask reached 50 ° C. 6 minutes after the start of the reaction. Thereafter, the temperature in the flask gradually decreased, and the temperature in the flask reached 22 ° C. 60 minutes after the start of the reaction. At this point, 0.27 g (3.1 mmol) of vinyl acetate was added and stirred for 15 minutes. After completion of the reaction, a trace amount of turbidity was removed by a filtration operation, and then toluene was distilled off with a rotary evaporator.
11.23 g of a waxy polymer was obtained. 92% yield
Met. The GPC analysis result of this polymer is shown in FIG.
Number average molecular weight Mn of this polymer in terms of polystyrene
Was 780 and n was an average of 4.84. Further, the weight average molecular weight Mw was 2,483, and the degree of dispersion (Mw / Mn) of the polymer was 3.18. Next, FIG. 6 shows a proton nuclear magnetic resonance spectrum ( ¹ H-NMR) of this polymer. 4.90 to 5.07 ppm Hf of the following formula
And a peak based on the terminal olefin of Hg (integral value: 2
0.2) and a peak of a proton bonded to an internal double bond at 5.15 to 6.00 ppm (integral value: 263.9). By analyzing the result, it is confirmed that the polymer represented by the following formula has n of 6.28.

[0036]

Embedded image

Example 4 Synthesis of tribromophenyl ether-terminated polymer

[0038]

Embedded image 15.61 g of toluene, 10.01 g (75.7 mmol) of dicyclopentadiene having a purity of 99% and allyl-2,4,6-tribromophenyl ether 5.6 were placed in a 100 ml three-necked flask equipped with a thermometer and a magnetic rotor.
2 g (15.2 mmol) was charged and stirred at room temperature (22 ° C.) to obtain a homogeneous solution. In addition, a catalyst of the formula (a)
9.1 mg of bis (tricyclohexylphosphine) benzylidyne ruthenium dichloride (1.
11 × 10 ⁻⁵ mol). At the same time as adding the catalyst, the temperature in the flask rose, and reached 44 ° C. 7 minutes after the start of the reaction. Thereafter, the temperature in the flask gradually decreased, and the temperature in the flask reached 23 ° C. 60 minutes after the start of the reaction. At this point, 0.27 g (3.1 mmol) of vinyl acetate was added.
l) Added and stirred for 15 minutes. After completion of the reaction, a trace amount of turbidity was removed by a filtration operation, and then toluene was distilled off with a rotary evaporator to obtain 13.13 g of a waxy polymer. The yield was 84%. FIG. 7 shows the GPC analysis result of this polymer. The number average molecular weight Mn of this polymer in terms of polystyrene was 586, and n was 1.63 on average.
Met. The weight average molecular weight Mw was 1,333, and the degree of dispersion (Mw / Mn) of the polymer was 2.27. Next, FIG. 8 shows a proton nuclear magnetic resonance spectrum ( ¹ H-NMR) of this polymer. A peak based on Ha and Hb of the following formula at 7.64 ppm (integral value: 18.4);
4.45 to 4.72 ppm peaks based on Hc and Hd (integral value: 41.0); 4.90 to 5.07 ppm peaks based on terminal olefins of He and Hf of the following formula (integral value: 36.0). ) And 5.23 to 6.00 ppm of protons bonded to internal double bonds (integral value: 33)
7.4) is observed. By analyzing this result, it is confirmed that tribromophenyl ether is present at one end of the polymer, and that n in the following formula is 3.9.

[0039]

Embedded image

Example 5 Synthesis of oxetane-terminated polymer

[0041]

Embedded image In a 100 ml three-necked flask equipped with a thermometer and a magnetic rotor, 12.42 g of toluene, 10.01 g (75.7 mmol) of dicyclopentadiene having a purity of 99%, and 3
-Allyloxymethyl-3-ethyloxetane 2.38
g (15.2 mmol), (molar ratio = [dicyclopentadiene] / [3-allyloxymethyl-3-ethyloxetane] = 4.97, substrate concentration = 49.9).
%) At room temperature (24 ° C.) to obtain a homogeneous solution. To this, 52.6 mg (6.39 × 10 ⁻⁵ mol, bis (tricyclohexylphosphine) benzylidene ruthenium dichloride of the formula (a) represented by the formula (a), 0.525 parts by weight based on 100 parts by weight of dicyclopentadiene) was added. ) Was added. At the same time as adding the catalyst, the temperature in the flask rose and reached 65 ° C. 4 minutes after the start of the reaction. Thereafter, the temperature in the flask gradually decreased, and the temperature in the flask reached 27 ° C. 40 minutes after the start of the reaction. At this point, 1.36 g (15.8 mmol) of vinyl acetate was added, and 15
Stirred for minutes. After completion of the reaction, a slight amount of turbidity was removed by a filtration operation, and then toluene was distilled off with a rotary evaporator to obtain 10.8 g of a waxy polymer. The yield is 87
%Met. The GPC analysis result of this polymer is shown in FIG. The number average molecular weight Mn of this polymer in terms of polystyrene was 810, and n was 4.95 on average. The weight average molecular weight Mw was 1,474, and the degree of dispersion (Mw / Mn) of the polymer was 1.92. Next, the proton nuclear magnetic resonance spectrum of this polymer ( ¹ H-NM
R) is shown in FIG. 0.83-0.95 ppm 3-
Peak of methyl group based on ethyl oxetane structure (integral value: 32.18), peaks based on terminal olefins of Ha and Hb represented by the following formula at 4.90 to 5.08 ppm (integral value: 19.99) and 5.21 ~ 6.00 ppm of the peak of the proton bonded to the internal double bond (integral value: 20 ppm)
0.73) is observed. By analyzing this result, it is confirmed that an oxetane group is present at one end of the polymer, and that the polymer of the following formula has n of 4.8.

[0042]

Embedded image

Example 6 Synthesis of triethoxysilane-terminated polymer

[0044]

Embedded image In a 100 ml three-necked flask equipped with a thermometer and a magnetic rotor, 13.12 g of toluene, 10.02 g (75.8 mmol) of dicyclopentadiene having a purity of 99%, and 3.11 g (15.2 mmol) of allyltriethoxysilane were added.
l), and (molar ratio = [dicyclopentadiene] /
[Allyltriethoxysilane] = 4.98, substrate concentration =
(50.0%) at room temperature (25 ° C.) to obtain a homogeneous solution. To this, 42.0 mg (5.10 × 10 ⁻⁵ mo) of bis (tricyclohexylphosphine) benzylidyne ruthenium dichloride represented by the formula (a) as a catalyst was added.
1, 0.4 parts per 100 parts by weight of dicyclopentadiene
19 parts by weight). At the same time as adding the catalyst, the temperature in the flask rose and reached 60 ° C. 4 minutes after the start of the reaction.
Thereafter, the temperature in the flask gradually decreased, and the temperature in the flask reached 27 ° C. 50 minutes after the start of the reaction. At this time, 1.05 g (12.2 mmol) of vinyl acetate was added, and the mixture was stirred for 15 minutes. After completion of the reaction, a slight amount of turbidity was removed by a filtration operation, and then toluene was distilled off with a rotary evaporator to obtain 12.1 g of a waxy polymer. The yield was 92%. FIG. 11 shows the GPC analysis result of this polymer. The number average molecular weight Mn of this polymer in terms of polystyrene was 1,056, and n was 6.44 on average. The weight average molecular weight Mw was 1,550, and the degree of dispersion (Mw / Mn) of the polymer was 1.47. Next, a proton nuclear magnetic resonance spectrum of this polymer ⁽¹ H-NMR) in FIG. 3.75-3.93
The peak of a methyl group based on triethoxysilane in ppm (integral value: 28.92), the peak based on the terminal olefin of Ha and Hb in the following formula at 4.90 to 5.07 ppm (integral value: 12.83) and 5 .20 to 6.00 ppm
The peak of the proton bonded to the internal double bond (integral value:
130.88) is observed. By analyzing this result, it is confirmed that a triethoxysilane group is present at one end of the polymer, and that the polymer of the following formula has n of 4.9.

[0045]

Embedded image

[0046]

The metathesis ring-opening polymer of dicyclopentadiene having a functional group at one end and having a controlled molecular weight according to the present invention has reactivity, radical polymerizability, flame retardancy, Since it has functions such as adhesiveness, it is a useful material for improving the characteristics and performance of various polymer materials.

[Brief description of the drawings]

FIG. 1 is a GPC chart of a polymer obtained in Example 1.

FIG. 2 is a ¹ H-NMR spectrum of a polymer obtained in Example 1.

FIG. 3 is a GPC chart of a polymer obtained in Example 2.

FIG. 4 is a ¹ H-NMR spectrum of a polymer obtained in Example 2.

FIG. 5 is a GPC chart of a polymer obtained in Example 3.

FIG. 6 shows a ¹ H-NMR spectrum of a polymer obtained in Example 3.

FIG. 7 is a GPC chart of the polymer obtained in Example 4.

FIG. 8 shows a ¹ H-NMR spectrum of a polymer obtained in Example 4.

FIG. 9 is a GPC chart of the polymer obtained in Example 5.

FIG. 10 shows a ¹ H-NMR spectrum of a polymer obtained in Example 5.

FIG. 11 is a GPC chart of a polymer obtained in Example 6.

FIG. 12 shows a ¹ H-NMR spectrum of a polymer obtained in Example 6.

 ──────────────────────────────────────────────────の Continuing on the front page (72) Inventor Hiromasa Kawai 48 Wadai, Tsukuba, Ibaraki Prefecture Hitachi Chemical Co., Ltd. Tsukuba Development Laboratory Co., Ltd. F term in development laboratory (reference) 4J032 CA38 CB01 CB03 CB12 CD02 CE03 CF03 CG00

Claims (2)

[Claims] 1. A polymer represented by the general formula [1]. Embedded image Wherein n is an average of 1 to 50, and 3 and 4 in the carbon numbers represented by Arabic numerals.
Is a double bond or between carbon numbers 4 and 5 is a double bond. 2. A compound represented by the general formula [2] using dicyclopentadiene as a catalyst: (M is ruthenium or osmium, X and X ₁ are anionic ligands, L and L ₁ are neutral electron donating groups, Q and Q
₁ each independently represents hydrogen, an alkyl group, an alkenyl group or an aromatic group, and the alkyl group, the alkenyl group or the aromatic group may have a substituent. ) And an allyl compound represented by the general formula [3] as a chain transfer agent: The method for producing a polymer according to claim 1, wherein the ring-opening metathesis polymerization is carried out in the presence of: