JP3388865B2 - Method for producing isobutylene polymer having olefin group - Google Patents

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a process for producing an isobutylene polymer having an olefin group.

[0002]

2. Description of the Related Art A terminal functional polymer, for example, a polymer having olefin groups at both ends is a photocurable resin, a UV curable resin, an electron beam curable resin, an encapsulating material for electronics,
It is useful as a raw material for adhesives, modifiers, coating agents, sealing agents for construction, etc. One type of end-functional polymer, for example, an isobutylene-based polymer having a chlorine atom bonded to a tertiary carbon at the end is 1,4-bis (α-chloroisopropyl) benzene (hereinafter, simply “p-DCC”). Or 1,3,5-tris (α-chloroisopropyl) benzene (hereinafter simply referred to as “TCC”) as an initiator / chain transfer agent, and boron trichloride as a catalyst by cationic polymerization of isobutylene by the inifer method. It is known to be manufactured (US Pat. No. 4,276,394).

Further, a method is known in which an isobutylene polymer obtained by the inifer method has an olefin group as a crosslinking point. For example, an isobutylene-based polymer having a chlorine atom and a basic compound such as potassium-t-butoxide or sodium ethoxide are heated and refluxed in a tetrahydrofuran (hereinafter referred to as THF) solvent to carry out a dehydrochlorination reaction. There is known a method for obtaining an isopropenyl type olefin terminal by carrying out [Polymer].
Bulletin, 1,575 (1979), Pol
ymer Bulletin, 13, 435 (198
5), U.S. Pat. No. 4,316,973, etc.].

However, assuming that the above-mentioned dehydrochlorination reaction using the THF solvent is carried out on an industrial scale, T
After performing the reaction in HF, THF is distilled off, the isobutylene-based polymer is dissolved in a nonpolar solvent such as hexane, and then the organic layer is washed with water, which is a complicated process. Further, it was revealed by the study of the present inventors that in this step, when the distillation of THF is insufficient, the organic layer becomes an emulsion during washing with water.

An object of the present inventors is to provide a method for carrying out a dehydrochlorination reaction in a system which does not use a solvent such as THF. Further, in the method of heating and refluxing the THF solution, the reaction temperature is about the boiling point of THF (66 ° C.), so the reaction is slow, and it is usually necessary to carry out the reaction for a considerably long time (about 20 hours). There is. Generally, increasing the reaction temperature is effective for increasing the reaction rate, but the boiling point of THF is restricted as long as the THF solvent is used.

[0006]

DISCLOSURE OF THE INVENTION The first object of the present invention is to eliminate the problem of the molecular end without using a solvent such as THF .
Tertiary and to provide a method for dehydrohalogenation of the halogen atom of the isobutylene polymer having a carbon atom and bonded to a halogen atom. Further, a second object of the present inventors is to provide a method for carrying out the above dehydrohalogenation reaction in a short time.

[0007]

Means for Solving the Problems In order to solve the above problems, as a result of intensive investigations by the present inventors, as a result, isobutylene in the presence of various basic compounds even in a system that does not use a solvent such as THF, that is, a solventless system. It was clarified that the dehydrohalogenation reaction of the system-based polymer proceeds to obtain an isobutylene-based polymer having an olefin group.

That is, the present invention relates to a tertiary carbon atom at the molecular end.
The presence of a basic compound dehydrohalogenation reaction of the halogen atom of the isobutylene polymer having a halogen atom bound to atoms, a process for preparing the isobutylene polymer having an olefinic group, which comprises carrying out solvent-free .
Further, the present invention provides the general formula (1):

[0009]

[Chemical 4] (In the formula, R ¹ and R ² represent a monovalent organic group and may be the same or different from each other.) The dehydrochlorination reaction of the group of the isobutylene polymer having a group represented by The present invention relates to a method for producing an isobutylene-based polymer having an olefin group, which is carried out in the presence of a compound without using a solvent.

The present invention also has the general formula (2):

[0011]

[Chemical 5] The method for producing an isobutylene-based polymer having an olefin group is characterized in that the dehydrochlorination reaction of the group having an isobutylene-based polymer represented by is carried out in the presence of a basic compound without a solvent. The present invention also relates to a dehydrochlorination reaction of an isobutylene-based polymer having a group represented by the above general formula (1) or (2), in the presence of a basic compound, without a solvent, at a temperature of 50 ° C or higher and 300 ° C or lower. And a method for producing an isobutylene-based polymer having an olefin group.

In the present invention, the dehydrochlorination reaction of an isobutylene polymer having a group represented by the above general formula (1) or (2) is carried out in the presence of a basic compound without a solvent at a pressure of 1.
The present invention relates to a method for producing an isobutylene-based polymer having an olefin group, which is characterized in that it is performed at 00 Torr or less. Further, the present invention is characterized in that the dehydrochlorination reaction of the isobutylene polymer having a group represented by the above general formula (1) or (2) is carried out in the presence of a basic compound without a solvent. 3):

[0013]

[Chemical 6] Relates to a method for producing an isobutylene polymer having an average of 1.1 or more olefin groups per molecule. In the present invention, the basic compound, as long as it is a generally known basic compound, all can be used, for example, a metal hydride, a metal alkoxide, a metal hydroxide, a metal amide, a metal capable of reacting with a proton, Organometallic compounds or amines are preferred.

As the above-mentioned basic compound, usually, specifically, sodium hydride, potassium hydride, lithium hydride, calcium hydride, sodium t-pentoxide, sodium t-butoxide, potassium t-butoxide, sodium ethoxy are used. Sodium, potassium ethoxide, sodium methoxide, potassium methoxide, sodium hydroxide, potassium hydroxide, lithium hydroxide, sodium amide, potassium amide, sodium, potassium, lithium, butyl lithium, ethyl magnesium bromide, D
BU (1,8-diazabichic [5,4,0] -7-undecene), lutidines, picolines, pyridine, triethylamine and the like are used.

Among these, sodium t-pentoxide, potassium t-butoxide, sodium ethoxide, potassium ethoxide, sodium methoxide, potassium methoxide, sodium hydroxide, potassium hydroxide,
Lithium hydroxide and the like are more preferable. Further, in the present invention, the amount of the basic compound used is usually, relative to the number of moles of the halogen atom contained in the isobutylene polymer,
It is used 0.02 to 50 times, more preferably 2 to 50 times.

Further, the solvent which has been found by the study of the present inventors not to be used is usually a solvent used for an organic reaction, which is neutral or acidic. It shows THF, hexane, toluene, ethanol, methanol, water and the like. Further, in the present invention, the dehydrohalogenation reaction of the halogen atom of the isobutylene polymer having a halogen atom bonded to a tertiary carbon atom at the terminal of the molecule is carried out in the presence of a basic compound without a solvent. The reaction temperature at that time is usually 50 to 300 ° C, and more preferably 80 to 200 ° C. It is possible to increase the reaction rate by raising the reaction temperature, but when the reaction temperature becomes 300 ° C or higher, as a side reaction,
The decomposition reaction of the main chain of the isobutylene polymer will occur.

In the present invention, the dehydrohalogenation reaction may be carried out in an air atmosphere at atmospheric pressure, but in order to avoid reaction with oxygen at a high temperature, a nitrogen atmosphere or 1
It is more preferable to carry out under reduced pressure of 00 Torr or less, particularly 30 Torr or less. Further, in the present invention, the reaction time of the dehydrohalogenation reaction is usually 0.1 to 100.
Although it is time, it is more preferably 1 to 40 hours.

In the present invention, the number average molecular weight (Mn) and Mw of the isobutylene polymer having an olefin group.
/ Mn value is based on polystyrene gel column (Showa Denko KK)
Shodex K-804, mobile phase: chloroform]
It is determined from GPC using (polystyrene conversion value). In the present invention, the number average molecular weight (Mn) determined by GPC is usually 500 to 300,000, preferably 1,000 to 50,000. When Mn is less than 500, the excellent characteristics peculiar to the isobutylene polymer are lost, and when it is more than 300,000, the polymer becomes solid and the workability is extremely deteriorated.

In the present invention, the number (average value) of olefin groups (ie, groups having one carbon-carbon double bond) contained in one molecule of the isobutylene polymer is ¹ H-
It is calculated based on the integrated value of the olefin peak and the main chain peak obtained from NMR and the Mn value obtained from GPC. The amount of olefin groups contained in the isobutylene-based polymer obtained by the method of the present invention is usually 1.1 to 12 in total of vinylene type, vinylidene type, and trisubstituted olefin type, but preferably It is 1.4 to 6. The vinylidene type is particularly preferable, and it is preferable that the average number of isopropenyl groups represented by the general formula (3) is 1.1 or more per molecule. When the number of olefin groups is less than 1.1, a crosslinked product is not formed, and when it is more than 12, the properties of the cured product as an elastic body are lost, which is not preferable.

By the way, in the present invention, the isobutylene-based polymer having a halogen atom bonded to a tertiary carbon atom at the end of the molecule , which is used as a raw material, has the following (A) to
It can be obtained by mixing the components represented by (D) at a low temperature of -10 ° C or lower. (A) Cationic polymerizable monomer containing isobutylene (B) General formula (4):

[0021]

[Chemical 7] (In the formula, R ³ is an a-valent organic group, and a is an integer of 1 to 8. R ⁴ or R ⁵ is a hydrogen atom or a monovalent organic group and may be the same or different. Of course, X represents a halogen atom, an alkoxy group, or an acetoxy group, and when a is 2 or more, a -CR ⁴ R ⁵ X groups may be the same or different. Compound (C) Lewis acid (D) Electron donor component In the present invention, the cationically polymerizable monomer containing isobutylene is not limited to a monomer consisting only of isobutylene, but 50% by weight of isobutylene.
(Hereinafter, simply referred to as "%") means a monomer in which the following is substituted with a cationically polymerizable monomer capable of copolymerizing with isobutylene.

Examples of the cationically polymerizable monomer copolymerizable with isobutylene include olefins having 5 to 12 carbon atoms, conjugated dienes, vinyl ethers, aromatic vinyl compounds, norbornenes, vinylsilanes and the like. Among these, olefins having 5 to 12 carbon atoms and aromatic vinyl compounds are preferable. As the cationically polymerizable monomer copolymerizable with the above isobutylene,
Usually, specifically, 2-butene, 2-methyl-1-butene, 3-methyl-2-butene, pentene, hexene, cyclohexene, vinylcyclohexane, 5-ethylidene norbornene, 5-propylidene norbornene, butadiene, isoprene , Cyclopentadiene, methyl vinyl ether, ethyl vinyl ether, isobutyl vinyl ether, vinylcarbazole, methoxystyrene, ethoxystyrene, t-butoxystyrene, hexenyloxystyrene, styrene, α-methylstyrene, methylstyrene, dimethylstyrene, chloromethylstyrene, chlorostyrene. , Β-pinene, indene, vinyltrichlorosilane, vinylmethyldichlorosilane, vinyldimethylchlorosilane, vinyldimethylmethoxysilane, vinyltrimethylsilane , Divinyldichlorosilane, divinyldimethoxysilane, divinyldimethylsilane, 1,3
-Divinyl-1,1,3,3-tetramethyldisiloxane, trivinylmethylsilane, γ-methacryloyloxypropyltrimethoxysilane, γ-methacryloyloxypropylmethyldimethoxysilane and the like are used.

Of these, 2-butene, cyclopentadiene, 5-ethylidene norbornene, isobutyl vinyl ether, methoxystyrene, styrene, butadiene, isoprene and the like are more preferable. These cationically polymerizable monomers copolymerizable with isobutylene may be used alone or in combination with two or more kinds.

In the present invention, the concentration of the cationically polymerizable monomer containing isobutylene in the batch method is usually 0.1 to 10 mol / l, preferably 0.5 to 6 mol / l. In the present invention, examples of the compound represented by the general formula (4) include general formula (5): AY _n (5) [In the formula, A represents a group having 1 to 4 aromatic rings. Y
Is the general formula (6):

[0025]

[Chemical 8] (In the formula, R ⁶ and R ⁷ are the same or different and each represents a hydrogen atom or a monovalent hydrocarbon group having 1 to 20 carbon atoms. X
Represents a halogen atom, an alkoxy group or an acetoxy group. ) Represents a group bonded to the aromatic ring. n is 1
Indicates an integer of 8. Compounds represented by] the general formula _{(7): BZ m (7} ) wherein, B represents a substituted or unsubstituted hydrocarbon group having 4 to 40 carbon atoms. Z is a halogen atom bonded to a tertiary carbon atom, R ⁸ COO- group (R ⁸ represents a hydrogen atom or an alkyl group of 1 to 5 carbon atoms) or R ⁹ O-group (R ⁹ is hydrogen or C Which represents an alkyl group of the numbers 1 to 5). m represents an integer of 1 to 4. ] And an oligomer having an α-halostyrene unit and the like, but are not limited thereto. These compounds may be used alone or in combination of two or more.

1 in the compound represented by the general formula (5)
The group A having 4 to 4 aromatic rings may be formed by a condensation reaction or may be a non-condensed group. Examples of the group having such an aromatic ring include a phenyl group having 1 to 6 valences, a biphenyl group, a naphthalene group, an anthracene group, a phenanthrene group, a pyrene group and Ph- (CH ₂ ).
_L- Ph group (Ph is a phenyl group, L is an integer of 1 to 10)
Etc., and the group having these aromatic rings has a carbon number of 1
It may be substituted with a straight-chain and / or branched aliphatic hydrocarbon group of ˜20 or a group having a functional group such as a hydroxyl group, an ether group and a vinyl group.

As the compound represented by the general formula (7),
For example, those having a functional group other than Z such as a vinyl group and a silyl group can be used. As the oligomer having an α-halostyrene unit that can be used as an initiator and a chain transfer agent, for example, an oligomer of α-chlorostyrene or α-chlorostyrene and a monomer copolymerizable therewith are copolymerized. Examples thereof include oligomers.

In the present invention, among the compounds represented by the general formula (4), those having two or more halogen atoms, alkoxy groups and acetoxy groups, or halogen atoms, alkoxy groups, acetoxy groups and other reactive functional groups. The use of a compound having a group as an initiator and a chain transfer agent is very effective because the degree of functionalization of the resulting polymer can be increased.

The compound represented by the above general formula (4) is usually, specifically, for example,

[0030]

[Chemical 9]

[0031]

[Chemical 10] Alternatively, an oligomer of α-chlorostyrene is used, but the oligomer is not limited thereto. These compounds are components used as an initiator and a chain transfer agent,
In the present invention, one kind or a mixture of two or more kinds is used. In addition, the number average molecular weight of the resulting isobutylene polymer can be arbitrarily set by adjusting the amounts of these compounds used.

In the present invention, the amount of the compound represented by the general formula (4) used is usually in the range of 0.01 to 20% of the cationically polymerizable monomer containing isobutylene, preferably 0.1. It is in the range of -10%. In the present invention, the Lewis acid is usually a compound represented by MW _P (in the formula, M represents a metal atom, W represents a halogen atom, and P represents an integer of 3 or more), for example, AlCl ₃ , S
nCl ₄ , TiCl ₄ , VCl ₅ , FeCl ₃ , BCl
₃ , and BF _{3 and the} like, and organoaluminum compounds such as Et ₂ AlCl and EtAlCl ₂ are used, but not limited thereto.

A preferable Lewis acid is TiC.
Examples include l ₄ , SnCl ₄ , and BCl ₃ . In addition, in the present invention, the Lewis acid is usually used in a range of 1 to 100 times by mole with respect to the compound represented by the general formula (4), but a preferable amount is in a range of 5 to 30 times by mole. is there.

In the present invention, the electron donor component is
If the number of donors is 15 to 50, conventionally known ones can be widely used. The number of donors is a parameter indicating the strength of various compounds as electron donors (electron donors). For the number of donors of various compounds, see “Donors and Acceptors” [Gutman (Otaki,
Translated by Okada), Academic Publishing Center (1983)]. Preferred electron donor components include, but are not limited to, pyridines, amines, amides or nitriles.

In the present invention, as the electron donor component,
Usually, specifically, 2,6-di-t-butylpyridine,
2-butylpyridine, 2,4,6-trimethylpyridine, 2,6-dimethylpyridine, 2-methylpyridine,
Pyridine, diethylamine, trimethylamine, triethylamine, tributylamine, diethylamine, N,
N-dimethylaniline, aniline, N, N-dimethylformamide, N, N-dimethylacetamide, N, N-
Diethylacetamide, propiononitrile, dimethylsulfoxide, diethyl ether, methyl acetate, ethyl acetate, trimethyl phosphate, tributyl phosphate, hexamethylphosphoric triamide and the like can be used, but preferred is 2,6-di-t- Examples thereof include butyl pyridine, 2,6-dimethyl pyridine, 2-methyl pyridine, pyridine, diethylamine, triethylamine, dimethylformamide, dimethylacetamide, and dimethyl sulfoxide.

In the present invention, the electron donor component is usually used in an amount within the range of 0.01 to 10 times the molar amount of the compound represented by the general formula (4), but preferably 0.2. ˜2 times the molar range. Further, in the present invention, as the polymerization solvent, for example, aliphatic hydrocarbons, aromatic hydrocarbons, halogenated hydrocarbons and the like can be used, and among them, halogenated hydrocarbons, or aliphatic hydrocarbons and halogenated hydrocarbons can be used. Mixed solvents are preferred. As the halogenated hydrocarbon, usually, methyl chloride, methylene chloride, ethyl chloride, dichloroethane, chloroform, trichloroethane, chloroform, trichloroethane, etc.,
As the aliphatic hydrocarbon, propane, pentane,
Hexane, cyclohexane, heptane, octane, etc.
Examples of aromatic hydrocarbons include benzene, toluene, xylene and the like.

As the mixed solvent, various combinations of methyl chloride / hexane, methylene chloride / hexane, methylene chloride / heptane mixed solvent and the like can be used. In the present invention, the polymerization reaction temperature is usually −
The temperature is 120 ° C to -10 ° C, and more preferably -80 ° C to -20 ° C. In the present invention, the polymerization reaction time is usually 1 to 800 minutes, more preferably 10 to 180 minutes.

Further, in the present invention, when carrying out the polymerization reaction, the reaction system is not particularly limited, and a method such as a batch system, a semi-batch system or a continuous system is used to bond with the tertiary carbon atom at the terminal of the molecule.
It is possible to freely obtain the isobutylene polymer having the halogen atom. In addition, the polymerization reaction of the present invention is usually stopped by adding a large amount of alcohols such as methanol, but the present invention is not particularly limited to this method, and any conventional means can be applied.
Further, since the polymerization reaction is stopped by water, when the polymerization solution is washed with water, it is not necessary to perform the stopping reaction again.

[0039]

According to the method of the present invention, an isobutylene polymer having an olefin group can be obtained without using a solvent such as THF. The effects of the present invention are shown below. (1) Since no extra solvent is used, it is possible to reduce raw material costs, eliminate the need for solvent distillation and purification equipment, simplify manufacturing equipment, and reduce equipment costs. (2) By not using THF, the organic phase containing the isobutylene-based polymer does not emulsify during washing with water, so that the unreacted base and the salt produced by the reaction can be easily removed. (3) By omitting the solvent, the reaction temperature is not restricted by the boiling point of the solvent, so that the reaction temperature can be increased and the reaction time can be easily shortened.

[0040]

EXAMPLES Next, the present invention will be further clarified with reference to examples, but the present invention is not limited to the examples. Synthesis Example 1 A 3L pressure vessel equipped with a mechanical stirrer was thoroughly dried and purged with nitrogen, and then 832 mL of methylene chloride and 124-n-hexane, which had been dehydrated in advance with Molecular Sieves 3A.
9 mL, 1,4-bis (α-chloroisopropyl) benzene (hereinafter abbreviated as p-DCC) 1.44 g, and α-picoline 0.23 g were charged. The container was cooled to −70 ° C., and 149 mL of isobutylene monomer weighed in another container was transferred here. While flowing nitrogen gas little by little through the three-way cock, use a dry syringe to remove titanium tetrachloride.
3.7 g was added to initiate polymerization. The reaction was completed by continuing stirring for 2 hours. The reaction solution was poured into 5 L of cold methanol and stirred well to reprecipitate the polymer.
Dissolve the precipitate in 500 mL of n-hexane,
It was washed twice with mL of ion-exchanged water to remove ionic impurities. Vacuum distillation was performed at a temperature of 120 ° C. for 1 hour to obtain an isobutylene polymer having a tertiary carbon-halogen bond at both ends. Hereinafter, the polymer obtained in this synthesis example will be referred to as isobutylene polymer 1.

The analytical values obtained by GPC, NMR and elemental analysis were as follows. However, Fn represents the number of each functional group converted per molecule. Number average molecular weight; 19,700 Molecular weight distribution (Mw / Mn); 1.10 Fn (isopropenyl); 0 Fn (2-methyl-1-propenyl); 0 Example 1 Isobutylene-based heavy obtained in Synthesis Example 1 Combined 3.0 g and sodium methoxide (powder) 0.20 g to 100 m
After kneading in a L eggplant flask, it was attached to an evaporator equipped with an oil bath and the vacuum pressure was reduced to 3
The eggplant flask was rotated while heating at a bath temperature of 160 ° C. while maintaining the temperature at or below Torr. From the start of heating reaction, 2
Sampling was performed after hours and 4 hours. The isobutylene polymer was dissolved in 10 times its amount of hexane, and then the organic phase was washed with 50 mL of water three times. The volatile matter was distilled off to obtain an isobutylene polymer having an olefin group. Table 1 shows the analysis results of the obtained polymer.

[0042]

[Table 1] From Example 1, it was revealed that according to the method of the present invention, an isobutylene polymer having an olefin group can be easily obtained in a short time. Example 2 Isobutylene polymer having chlorine atom [Mn = 430
0, Mw / Mn = 1.9, Fn (isopropenyl) =
0, Fn (2-methyl-1-propenyl) = 0, Fn
(Chlorine) = 2] 2.0 g was added to various basic compounds (8.9
mmol), the isobutylene polymer was dissolved in 30 mL of hexane, and then the organic phase was washed with 50 mL of water three times. The volatile matter was distilled off to obtain an isobutylene polymer having an olefin group. The results are shown in Table 2.

[0043]

[Table 2] From the results of Example 2, it was revealed that various basic compounds are effective for the method of the present invention. Comparative Example 1 Isobutylene polymer having chlorine atom [Mn = 470
0, Mw / Mn = 1.3, Fn (isopropenyl) =
5 g of 0, Fn (2-methyl-1-propenyl) = 0] was dissolved in 115 mL of THF, 4.0 g of potassium t-butoxide (36 mmol) was added, and the mixture was heated under reflux for 40 hours. After the volatile matter was distilled off at 80 ° C. and 3 Torr, the isobutylene polymer was dissolved in 50 mL of hexane and 30 mL of water was added to wash the organic phase with water.
The organic phase has become an emulsion.

Continuation of front page (56) Reference JP-A-4-20501 (JP, A) JP-A-53-42289 (JP, A) (58) Fields investigated (Int.Cl. ⁷ , DB name) C08F 8 / 00-8/50

Claims (6)

(57) [Claims] [Claim 1 wherein said halogen atom of isobutylene polymer having a halogen <br/> emissions atoms bound to tertiary carbon atoms of the molecular ends
The method for producing an isobutylene-based polymer having an olefin group, which comprises carrying out the dehydrohalogenation reaction of 1. in the presence of a basic compound in the absence of a solvent. 2. General formula (1): (In the formula, R ¹ and R ² represent a monovalent organic group and may be the same or different from each other.) The dehydrochlorination reaction of the group of the isobutylene polymer having a group represented by A method for producing an isobutylene-based polymer having an olefin group, which is carried out in the presence of a compound without using a solvent. 3. General formula (2): A method for producing an isobutylene-based polymer having an olefin group, characterized in that the dehydrochlorination reaction of the group having an isobutylene-based polymer represented by is carried out in the presence of a basic compound without a solvent. 4. The method for producing an isobutylene-based polymer having 2 or 3 olefin groups, wherein the dehydrochlorination reaction is carried out at a temperature of 50 ° C. or higher and 300 ° C. or lower. 5. The method for producing an isobutylene-based polymer having an olefin group according to claim 2, 3 or 4, wherein the dehydrochlorination reaction is carried out at a pressure of 100 Torr or less. 6. General formula (3): An isobutylene-based polymer having an average of 1.1 or more olefin groups per molecule represented by the above formula is produced, and the isobutylene-based polymer having an olefin group according to claim 2, 3 or 4 or 5, is produced. Law.