WO2000056784A1

WO2000056784A1 - Saturated hydrocarbon polymer having functional group at end and process for producing the same

Info

Publication number: WO2000056784A1
Application number: PCT/JP1999/002693
Authority: WO
Inventors: Takeshi Chiba; Hidenari Tsunemi
Original assignee: Kaneka Corporation
Priority date: 1999-03-19
Filing date: 1999-05-21
Publication date: 2000-09-28

Abstract

Saturated hydrocarbon polymers having hydroxyl groups incorporated at the ends are useful as materials for highly weatherable urethanes. For producing these polymers, a multistage reaction has been necessary in which after completion of polymerization, the polymer ends are converted to olefinic ends and then subjected to hydroboration. A halogen-terminated hydrocarbon polymer obtained by cationic polymerization is reacted with a compound containing both a protected hydroxyl group as a substituent and an unsaturated bond to thereby easily obtain a saturated hydrocarbon polymer having the protected hydroxyl group at each end. This compound can be easily converted into a hydroxyl-terminated polymer by hydrolysis.

Description

TECHNICAL FIELD The present invention relates to a saturated hydrocarbon polymer having a functional group at a terminal and a method for producing the same

The present invention relates to a hydrocarbon-based polymer having a protected hydroxyl group at a terminal, a hydrocarbon-based polymer having a hydroxyl group at a terminal, and methods for producing these. Background art

It is generally known that hydrogenated polybutadiene polyol and polyisoprene polyol synthesized by anionic polymerization can provide a saturated hydrocarbon polymer having a hydroxyl group at a terminal. In living anion polymerization, primary hydroxyl groups can be easily and quantitatively introduced into the terminal by reacting ethylene oxide after the polymerization.

These hydroxyl-terminated polyols easily react with the isocyanate compound to give a urethane-based cured product. It is known that the use of this polymer improves the performance such as weather resistance and chemical resistance, which are problems in urethane compositions containing a polyether-based or polyester-based polyol as a component. However, the durability of urethane compositions using these hydroxyl-terminated polyols as raw materials is not yet sufficient. In addition, when producing a hydroxyl-terminated polyol, there is also a problem that it is necessary to go through a difficult step of hydrogenation.

On the other hand, polyisobutylene obtained by cation polymerization is known as a saturated hydrocarbon-based polymer expected to have high weather resistance. In particular, a reaction for quantitatively introducing a functional group into the terminal of polybutylene by living cationic polymerization is known. J.P.Kennedy et al. First synthesized chlorine-terminated polyisobutylene by living cationic polymerization, and then performed dehydrochlorination of the terminal using ①'BuOK to convert the isopropyl group into a terminal isopropyl group. Derivatives or the reaction of aryltrimethylsilane in the presence of titanium tetrachloride synthesizes polyarylbutylene-terminated polyisobutylene. And the isopropyl group end group or aryl A method is disclosed in which a hydroxyl group is quantitatively introduced into a terminal by reacting a hydrogen-terminated terminal with a hydride-poran reagent such as BH ₃ or 9-BBN and then using hydrogen peroxide (for example, B Ivan, JP Kennedy, and VSC Chang, J. Polym. Sci., Polym. Chem, Ed., 1980, 18.3177 and B. Ivan, and JP Kennedy, Polym. Mater. Sci. Eng., 1988, 58. , 866). J. P. Kennedy et al. Also report that urethane resins obtained by the reaction of hydroxyl-terminated polyisobutylene with a compound having a plurality of isocyanate groups exhibit high weather resistance.

However, this method requires that the chlorine-terminated polyisobutylene obtained by living cationic polymerization be converted to an olefinic terminal and then converted to a hydroxyl group. Furthermore, the raw materials used are very special, and this method is not suitable for producing a saturated hydrocarbon polyol on an industrial scale.

Therefore, the present invention can be synthesized by a one-step reaction from the halogen terminal of a saturated hydrocarbon polymer obtained by cationic polymerization without using a special and expensive reagent such as a hydridoborane reagent. It is an object of the present invention to provide a hydrocarbon polymer having a protected main chain having a protected hydroxyl group at the terminal to give a hydroxyl group to the hydrocarbon chain, and a method for producing the same. Summary of the Invention

The present invention provides a compound obtained by reacting a halogen-terminated hydrocarbon polymer obtained by cationic polymerization forming a carbon-carbon single bond with a compound having a protected hydroxyl group and a carbon-carbon double bond. The present invention relates to a hydrocarbon-based polymer in which a polymer main chain having a protected hydroxyl group at a terminal is a saturated hydrocarbon chain, and a method for producing the same. Furthermore, the polymer main chain having a hydroxyl group at the terminal obtained by deprotecting the obtained hydrocarbon-based polymer in which the obtained polymer main chain having a protected hydroxyl group at the terminal is a saturated hydrocarbon chain is obtained. It relates to a hydrocarbon polymer which is a saturated hydrocarbon chain. Detailed Disclosure of the Invention

Obtained by living cationic polymerization using polymerization initiator (Inifer method) There have been many reports on the reaction of modifying the terminal by reacting another substrate with the terminal of the halogen group of telechelic polyisobutylene. As a method for introducing olefins between chlorine and carbon at the terminal of polyisobutylene, for example, a mixed solvent system of methylene chloride and hexane, using a Lewis acid as a catalyst in 180 ^ to 130, can be used to conjugate or non-conjugate. A system for introducing a conjugated gen to the terminal of a polymer is known (for example, US Pat. No. 5,212,488, Japanese Patent Laid-Open No. 288,309, 1991). For example, in a system in which a conjugated gen such as bushugen is reacted, the terminal becomes an aryl halide terminal which is expected to have high reactivity, and conversion to a terminal hydroxyl group by further deprotection or the like is expected. However, in this method, hydroxyl-terminated polyisobutylene cannot be obtained from halogen-terminated polyisobutylene in one step. Thus, the present inventors have made repeated studies and have completed the present invention.

In the present invention, the hydrocarbon-based polymer in which the main chain of the polymer is a saturated hydrocarbon chain is defined as having a C-C double bond in the main chain obtained by cationic polymerization forming a carbon-carbon single bond. No (that is, saturated) means a hydrocarbon polymer, but the graft group hanging from the main chain may have a C—C double bond. Further, the polymerization initiator used in the cationic polymerization may have a C-C double bond. The structure of a hydrocarbon polymer in which the main chain of the polymer having a protected hydroxyl group at the end is a saturated hydrocarbon chain is represented by the following formula (1):

R ¹ (A-X) _a (1)

(Wherein, R ¹ is a monovalent to tetravalent hydrocarbon group containing a single ring or a plurality of aromatic rings, X is a chlorine group or a bromine group, a is an integer of 1 to 4. A is one kind or two or more kinds. A) is a polymer of a cationic polymerizable monomer, and when a is 2 or more, they may be the same or different.

A compound having a protected hydroxyl group and a carbon-carbon double bond is represented by the formula (2): CH ₂ = C (R ² ) -B—OG (2)

(In the formula, R ² represents hydrogen or a saturated hydrocarbon group having 1 to 18 carbon atoms, B represents a divalent hydrocarbon group having 1 to 30 carbon atoms, and G represents a protecting group for a hydroxyl group.)

It is preferable that they are represented by B in the formula (2) is a divalent hydrocarbon group having 1 to 30 carbon atoms, and has 0 to 5 carbon-carbon double bonds [however, CH ₂ == C (R ² ) — (R ² is the same as above) and / or preferably has 0 to 3 aromatic rings, and B in the formula (2) represents 0 to 3 —CH = More preferably, it has a divalent group represented by CH—.

The compound of the formula (2) includes a compound of the formula (3):

CH ₂ = C (R ² ) one (CH ₂ ) _b — {— CH-CH— (CH ₂ ) _c } _n -OG

(3)

(In the formula, R ² represents hydrogen or a saturated or unsaturated monovalent hydrocarbon group having 1 to 18 carbon atoms, and b and c are integers of 1 to 30 and may be the same or different. And n represents an integer of 0 to 5, and G represents a hydroxyl-protecting group.)

More preferably, it is represented by

The hydrocarbon-based polymer obtained by this method, in which the main chain of the protected hydroxyl-terminated polymer is a saturated hydrocarbon chain, is easily deprotected so that the hydroxyl-terminated polymer main chain is saturated. It can be converted to a hydrocarbon polymer that is a hydrogen chain.

The cationically polymerizable monomer in the above formula (1) is not particularly limited, but preferable monomers include, for example, isobutylene, indene, binene, styrene, methoxystyrene, chlorostyrene and the like.

When the polymer of the present invention is used as a raw material of a curable composition, it is preferable to produce an isobutylene-based polymer which is in a liquid state before crosslinking and can give a rubber-like cured product after crosslinking.

In the isobutylene-based polymer, all of the monomer units may be formed from isobutylene units, or the monomer unit having a copolymer with isobutylene is preferably 50% or less of the isobutylene-based polymer (by weight). %, The same applies hereinafter), more preferably 30% or less, particularly preferably 10% or less.

Examples of such a monomer component include C4 to C12 olefins, vinyl ethers, aromatic vinyl compounds, vinylsilanes, and arylsilanes. Such copolymer components include, for example, 1-butene, 2-butene , 2-methyl-1-butene, 3-methyl-1-butene, pentene, 4-methyl-1-pentene, hexene, vinylcyclohexene, methyl vinyl ether, ethyl vinyl ether, isoptyl vinyl ether, styrene, α —Methylstyrene, dimethylstyrene, monochlorostyrene, dichlorostyrene,) 3-vinylene, indene, pinyltrichlorosilane, vinylmethyldichlorosilane, vinyldimethylchlorosilane, vinyldimethylmethoxysilane, vinyltrimethylsilane, divinyldichlorosilane, divinyl Dimethoxysilane, divinyldimethylsilane, 1,3-divinyl-1,1,3,3-tetramethyldisiloxane, tripinylmethylsilane, tetrabiersilane, aryltrichlorosilane, arylmethyldichlorosilane , Aryldimethylchlorosilane, aryldimethylmethoxysilane, aryltrimethylsilane, diaryldichlorosilane, diaryldimethoxysilane, diaryldimethylsilane, acrylyloxypropyltrimethoxysilane, And methacryloyloxypropylmethyldimethoxysilane.

Further, in order to achieve sufficient strength, weather resistance, gel fraction, etc., when a crosslinkable polymer compound is obtained by a crosslinking reaction, a of the polymer of the formula (1) is preferably a hydrogen atom of 2 or 3 Saturated hydrocarbon polymers having terminal polyisobutylene are preferred.

The protecting group of the compound containing a protected hydroxyl group and a carbon-carbon double bond is not particularly limited as long as it provides a hydroxyl group by deprotection, but is usually an inorganic group having 0 to 54 carbon atoms or Organic group. Preferred protecting groups that can be deprotected under mild conditions include the following.

R ³ -R¾00- R ³ 0- R ^ HCO-

R ³ -M ² - ² X- '

R ³ OR ³ X

R ⁴ -M ³ -XM ^3-

R ³ OR ³ X

R -M ^⁴ - ^ - ⁴ - and XM ⁴ -

R ⁵ OR ⁵ X

(In the formula, R ³ and R \ R ⁵ represent hydrogen or a saturated or unsaturated hydrocarbon group having 1 to 18 carbon atoms, and may be the same or different in a group containing a plurality of R. X is a functional group selected from Cl, Br, and I. M ¹ is a monovalent metal selected from Li, Na, and M ² is selected from Mg, Ca, Sr, and Ba. divalent metal, M ³ is B, a 1, 3-valent metal selected from G a, M ⁴ is T i, Z r, H f , S i, Ge, S n, 4 valent selected from P b Metal.)

Alkyl groups, acyl groups, and RC (O) — groups (where R is a saturated group having 1 to 10 carbon atoms), because of the availability and the difficulty of separating the polymer from the protective group components after deprotection, etc. A hydrocarbon group), a silyl group, and a metal alkoxide; a methyl group, an ethyl group, n- and i-propyl groups, an n-, i- and t-butyl group, a formyl group, an acetyl group, a propionyl group; Even more preferred are a ptyryl group, a benzoyl group, a trimethylsilyl group, and a triphenylsilyl group, and it is particularly preferred that these protecting groups have 0 to 54 carbon atoms.

The compound represented by the above formula (2), which is a substrate to be reacted with the halogen-terminated hydrocarbon polymer, is preferably an olefin having a mono-substituted or 1,1′-monosubstituted terminal-protected hydroxyl group. Although not limited, when G is hydrogen in the above formula (2), aryl alcohol, methallyl alcohol, 3-buten-l-l-ol, 3-methyl-3- Butene-1 1-all, 4 1-pentene 1-olyl, 5-hexene 1-ol j, 6-heptene 1-l, 7-octen 1-ol, 8-nonen-l-ol, 9-decene 1-l 1-ol, 2,5-hexadienol, 2,6-heppugenol, 3,6-heppugenol, 2,7-octagenol, 3,7-octadienol 4,7-octanegenol, 2.8-nonadienol, 3,8-nonadienol, 4,8-nonadienol, 5,8-nonadienol, 2,9-decadienol, 3, Compounds selected from 9-decadienol, 4, 9-decadienol, 5, 9-decadienol or 6,9-decadienol are preferred.

When reacting a compound containing a protected hydroxyl group and an elemental carbon double bond represented by the above formula (2) with a halogen-terminated hydrocarbon polymer obtained by cationic polymerization of the above formula (1), Lewis is used as a catalyst. It is possible to use acids. In this case is not particularly limited as long as Le chair _{acid, T i C l 4, A} 1 C 1 3, BC 1 3, SnC 1 4 has a higher reaction activity, from the viewpoint selectivity is good preferable.

In the present invention, it is possible to use a single or mixed solvent arbitrarily selected from halogenated hydrocarbons, aromatic hydrocarbons, and aliphatic hydrocarbons as the reaction solvent. At least one component selected from methylene chloride, chloroform, 1,1-dichloroethane, 1,2-dichloroethane, n-propyl chloride, and n-butyl chloride as halogenated hydrocarbons due to their reactivity. It is preferred that For the same reason, the aromatic hydrocarbon is preferably toluene, and the aliphatic hydrocarbon is at least one component selected from pentane, n-hexane, cyclohexane, methylcyclohexane, and ethylcyclohexane. Is preferred.

For example, toluene, ethylcyclohexane, or a mixed solvent thereof can be used as a reaction solvent that does not use a halogenated hydrocarbon, which is likely to have an adverse effect on the environment.

The deprotection reaction is not particularly limited, but preferred reactions include a hydrolysis reaction and a thermal decomposition reaction.

The hydrolysis reaction can be performed in either a solvent system or a non-solvent system. The solvent used for the solvent-based reaction is not particularly limited. It is preferable to use a solvent for producing a saturated hydrocarbon polymer having the above. The conditions for performing the hydrolysis may be either acidic or basic conditions, but it is preferable to perform the hydrolysis reaction using a basic aqueous solution in view of the efficiency of the hydrolysis reaction.

The reagent used for the hydrolysis under basic conditions is not particularly limited as long as it is an organic or inorganic basic compound used in a usual hydrolysis reaction. Potassium, lithium hydroxide, calcium hydroxide, magnesium hydroxide, sodium carbonate, potassium carbonate, lithium carbonate, calcium carbonate, magnesium carbonate, sodium acetate, potassium acetate, lithium acetate, calcium acetate, magnesium acetate, potassium t-butoxide, Sodium t-butoxide, potassium methoxide, sodium methoxide and the like are particularly preferred.

In the hydrolysis reaction, the reaction can be efficiently advanced by adding a catalyst. As such a catalyst, any of organic and inorganic catalysts can be used for the reaction. However, an organic salt is preferable because of the ease of the reaction, and a quaternary ammonium salt is particularly preferable. Representative ammonium salts include triethylbenzylammonium chloride, tetramethylammonium chloride, triethylbenzylammonium bromide, trioctylmethylammonium chloride, tributylbenzylammonium chloride, trimethylbenzyl chloride. Ammonia, N-laurylpyridinium chloride, tetra-n-butylammonium hydroxide, tetramethylammonium hydroxide, trimethylbenzylammonium hydroxide, trimethylphenylammonium bromide, tetrabromide Methylammonium, tetraethylammonium bromide. Tetra-n-butylammonium bromide, tetrabutylammonium hydrogen sulfate, N-benzylpicolinium chloride, tetramethylammonium iodide, iodine or tetra-n-butylammonium , N-lauryl-41-picolinidum chloride, N-lauryl-picolinidum chloride and the like.

The production of the saturated hydrocarbon polymer having a protected hydroxyl group at the terminal according to the present invention is performed, for example, as follows. That is, 1 to 4 equivalents of a compound having a protected hydroxyl group and a carbon-carbon double bond represented by the formula (2) are added to a polymer having a halogen group at the terminal represented by the formula (1). , Methylene chloride, 1, 1 —One selected from dichloroethane, 1,2-dichloroethane, n-propyl chloride, n-butyl chloride, toluene, pentane, n-hexane, cyclohexane, methyl cyclohexane, and ethylcyclohexane Dissolves in a solvent consisting of the above components. In the presence of electron donors such as pyridine, 2-methylpyridine, 3-methylpyridine, 4-methylpyridine, 2,6-di-t-butylpyridine, etc., in the temperature range of 110 to 130: _{T i C 1 4, A 1} C 1 B

Was added _{C 1 3, S n C 1} 4 or the like Lewis acid catalyst, by reacting 3 0 minutes to 5 hours, saturated hydrocarbon polymer having a hydroxyl group of interest to the end is obtained.

Here, the process that has reached the present invention will be briefly described.

It is known that a Lewis acid and a compound having a hydroxyl group give a hydrogen halide by reacting. Investigations have shown that contact of a hydroxyl-terminated olefin compound with a Lewis acid generates hydrogen halide, and the addition reaction of the hydrogen halide to the olefin proceeds.

Thus, by protecting the terminal of the olefin substrate with a group which can be easily induced to a hydroxyl group by a deprotection reaction, a side reaction to generate HC1 was suppressed. That is, the hydrogen atom of the hydroxyl group of the olefin compound having a hydroxyl group is

R¾00- R ³ 0- R ^ HCO-

M ¹ R ³ -M ² -R ^ -M ² -XM ^2-

R 3 OR 3 X

^{^{^{R 4 - 3 - 3 X- 3}}} - 4-

(Wherein, R ³ , R ⁴ , and R ⁵ are hydrogen or saturated or unsaturated having 1 to 18 carbon atoms. Represents a hydrocarbon group, and the groups containing a plurality of Rs may be the same or different. X is a functional group selected from Cl, Br and I. M ¹ is a monovalent metal selected from Li, Na, and M ² Mg, a divalent metal selected from Ca, Sr, and Ba, and a trivalent metal selected from M 価 B, A 1, and Ga. metal, M ⁴ is a tetravalent metal selected from among the T i, Z r, H f , S i, Ge, S n, P b. )

The side reaction was suppressed by converting to.

Some hydroxyl protecting groups coordinate to Lewis acids. Since the coordination of the substrate to the catalyst reduces the reaction activity, it is preferable to use a Lewis acid in a molar number equivalent or more to the compound having a hydroxyl group and a carbon-carbon double bond during the addition reaction. Particularly preferred is 1 to 20 equivalents.

The Lewis acid used in the present invention can be used for living cationic polymerization by the inifer method. First, after obtaining a polymer having a halogen group at the terminal by the inifer method, a compound having a protected hydroxyl group and a carbon-carbon double bond, a Lewis acid, By adding an electron donor or the like, a polymer having a protected hydroxyl group at the terminal can be obtained in one pot.

In the formula (1), R ¹ is a residue of a polymerization initiator, and is not particularly limited as long as it is a residue of a monofunctional to tetrafunctional initiator that can be used for the cation cationic polymerization by the inifer method. The number of functional groups of the initiator is preferably 2 or 3. Among these, the compounds having a substituent at the benzyl position shown below are preferable because of their high initiator efficiency during polymerization.

(In the formula, Y represents a chlorine group, a bromine group, a stoxy group, or an acetyl group.) The solvent for the polymerization reaction is not particularly limited. However, after the polymerization reaction, the olefin compound may be produced in one pot after the polymerization reaction. Since it becomes possible, the solvent is preferably the same as the solvent for the reaction for introducing a protected hydroxyl group into the terminal. A single or mixed solvent arbitrarily selected from halogenated hydrocarbons, aromatic hydrocarbons, and aliphatic hydrocarbons can be used as a reaction solvent common to the polymerization reaction and the reaction for introducing a hydroxyl group to a terminal. Among the halogenated hydrocarbons, methylene chloride, chloroform, 1,1-dichloroethane, 1.2-dichloroethane, η-propyl chloride, and η-butyl chloride are used as halogenated hydrocarbons due to their solubility and reactivity under the polymerization conditions of the polymer. Preferably, it is at least one component selected from For the same reason, toluene is preferred as the aromatic hydrocarbon, and at least one component selected from pentane, η-hexane, cyclohexane, methylcyclohexane, and ethylcyclohexane as the aliphatic hydrocarbon. preferable.

In recent years, non-halogenation has become an important technology due to environmental issues.However, even in this system, when a solvent system of toluene and ethylcyclohexane is used, a polymer having a narrow molecular weight distribution due to living cation polymerization is used. In this condition, the addition reaction of the protected olefin compound having a hydroxyl group proceeds rapidly. From the viewpoint of the polymerizability and the solubility of the polymer at a low temperature, the mixing ratio of the solvent is preferably toluene: ethylcyclohexane = 6: 4 to 9: 1 (weight ratio).

The thus-obtained hydrocarbon polymer having a protected hydroxyl-terminated polymer main chain and having a saturated main chain is easily hydrolyzed by a hydrolysis reaction. It can be converted into a union.

In a system in which the protecting group G in the compound represented by the formula (2) or the formula (3) is an alkyl group having 2 or more carbon atoms, a thermal decomposition reaction is effective, and usually 50 to 250 * C The deprotection reaction proceeds by heating under the conditions. In this reaction, the reaction can be made to proceed more easily by adding a catalyst as needed.

As a reaction for generating a hydroxyl group by deprotection, a hydrolysis reaction is effective. The hydrolysis reaction usually proceeds under acidic or basic conditions. At this time, the reaction can be carried out without using a solvent, but the reaction is carried out by dissolving the polymer in an organic solvent. Is preferred.

The reaction can be carried out at a temperature at which a normal hydrolysis reaction is carried out, and the reaction can be carried out at a temperature of from 170 "C to 200 by the presence of a salt and a reaction under a high pressure. The reaction at 0 to 120 is preferable, and the reaction at 50 to 110 is more preferable, from the viewpoints of easy handling and good reactivity.

In the hydrolysis reaction under basic conditions, the reactivity changes depending on the base concentration. Terms have reactivity is Chasse handling good, preferably 10 one ^7-10 ² mode Renault L as the base concentration, 10- ^6-10 ¹ mol ZL is more preferred.

The amount of the catalyst to be added is not particularly limited, but is preferably 0.0001 to 10 times, more preferably 0.01 to 1 times the mol of the hydrolysis substrate in view of the reaction rate and the ease of removing the catalyst. It is more preferred that there be. BEST MODE FOR CARRYING OUT THE INVENTION

Next, the present invention will be further clarified with reference to examples, but the present invention is not limited to the examples.

(Example 1)

A 50 Om 1 separable flask was purged with nitrogen by attaching a three-way cock, a thermocouple, and a stirrer with a vacuum seal. To this, 175m of toluene dehydrated with Molecular Sieves 3A and 21.7ml of ethylcyclohexane were added, and 1,4-bis (11-chloro-1-1-methylethyl) benzene (1.63g, After adding 7.04 mmo 1) and 2-methylpyridine (77.4 mg, 0.83 mmo 1), the mixture was cooled to 70 "C. After cooling, isobutylene monomer (35.5 ml, 598 mmo 1) was introduced. Further, at this temperature, titanium tetrachloride (0.98 m and 8.93 mmo 1) was added to initiate the polymerization, and at this time, the temperature was raised by about 15. The polymerization was completed in about 40 minutes (with the accompanying After the polymerization was completed, 10-acetoxy 1-decene (2.80 g, 14. lmmol) and titanium tetrachloride (5.7 ml, 51.7 mmol 1) were added. After time response Then, the reaction mixture was introduced into 300 ml of ion-exchanged water heated at 80, further transferred to a 1 L separating funnel and shaken. After removing the aqueous layer, the resultant was washed three times with 300 ml of ion-exchanged water, and then the organic layer was isolated. 1 L of acetone was added thereto to reprecipitate a polymer, thereby removing low-molecular compounds. The precipitate was further washed twice with 10 OmI of acetone. The precipitate was further dissolved in 5 OmI of hexane. The solution is transferred to a 300-ml eggplant-shaped flask, and the solvent is distilled off under reduced pressure (at the final l Torr or less) under heating conditions (at 180) in an oil bath, and the target protected hydroxyl group is present at the end. Polysoptylene was obtained.

The functionalization rate of the obtained polyisobutylene was analyzed using NMR.

(NMR)

Gem ini-300, manufactured by Valian Co., Ltd., measuring solvent; carbon tetrachloride heavy acetate = 41 mixed solvent, quantification method; adjacent to the terminal acetyl group based on the signal of the initiator residue (7.2 D prn) Methylene signals (4.OO pm) were compared and quantified. Fn (CH ₂ OCOMe) is the amount of the functional group introduced to the terminal of the polymer, and when introduced quantitatively, it becomes 2.0 with the initiator used this time.

The amount of protected hydroxyl groups introduced into the polymer obtained in Example 1 is as follows: Fn (CH ₂ OCOMe) = 1.48.

(Example 2)

The procedure was performed in the same manner as in Example 1 except that the addition amount of titanium tetrachloride at the time of addition of 10-acetoxy-1-decene was 2.1 ml (19.2 mmo 1). The amount of functional groups introduced into the obtained polymer is as follows: F n (CH ₂ OC〇Me) = 0.78.

(Example 3)

The procedure was performed in the same manner as in Example 1 except that the amount of 10-acetoxy-1-decene was changed to 4.19 g (21.2 mmo 1). The functional group introduction amount of the obtained polymer is as follows: F n (CH ₂ OCOMe) = 1.62.

(Example 4) The procedure was performed in the same manner as in Example 1 except that the addition amount of titanium tetrachloride at the time of addition of 10-acetoxy 1-decene was 11 ml (103.4 mmo 1). The amount of functional groups introduced into the obtained polymer was as follows: F n (CH ₂ OCOMe) = 1.43.

(Example 5)

Example 1 except that the amount of 10-acetoxy 1-decene was 5.60 g (28.2 mmo 1) and the amount of titanium tetrachloride added at the time of adding the compound was 11.4 ml (103.4 mmo 1). The same was done. The functional group introduction amount of the obtained polymer is as follows: F n (CH ₂ OCOMe) = 1.96.

(Example 6)

A 5000 ml separable flask was equipped with a three-way cock, a thermocouple, and a stirrer with a vacuum seal, and the atmosphere was replaced with nitrogen. To this, 1484 ml of toluene dehydrated with Molecular Sieves 3A and 184 ml of ethyl hexane were added, and 1,4_bis (1-chloro-1-methylethyl) benzene (1 3.87 g, 60. Ommo 1) and 2-methylpyridine (657.9 mg, 7.06 mmo 1) were added, and the mixture was cooled to 170. After cooling, isobutylene monomer (299 ml, 3.58 mol) was introduced, and at this temperature, titanium tetrachloride (8.33 ml, 76. Ommo 1) was added to initiate polymerization. At this time, the temperature was raised by about 15 °. The polymerization was completed in about 60 minutes (the exotherm of the reaction system was no longer observed). After completion of the polymerization, 4-acetoxy-2-methyl-1-butene (30.8 g, 24 Ommo 1) and titanium tetrachloride (44.4 ml, 406 mmo 1) were added. After the reaction for 5 hours, 1.5 L of ion-exchanged water heated at 80 was introduced into the reaction mixture, and the mixture was stirred for 20 minutes. After standing, the aqueous layer was removed, 1 L of a 4N aqueous sodium hydroxide solution and 1.5 g of tetrabutylammonium bromide were added, and the mixture was stirred at 100 for 12 hours. After the reaction was completed, the aqueous alkali solution was removed, and the mixture was washed three times with 1 L of ion exchanged water, and then the organic layer was isolated. To this, 10 L of acetone was added to reprecipitate the polymer to remove low molecular weight compounds. The precipitate was further washed twice with 1 L of acetone, and further dissolved in 500 ml of hexane. Make the solution 1 L The solution was transferred to a solvent, and the solvent was distilled off under reduced pressure (at a final pressure of 1 Torr or less) under a heating condition (180) with an oil path to obtain a polyisobutylene having a desired hydroxyl group at the terminal.

The functionalization rate of the obtained polyisobutylene was analyzed using NMR. The amount of hydroxyl groups introduced into the polymer obtained in Example 6 is as follows: F n (CH _z OH) = 1.66 (The analysis method is the same as in Example 1. In addition, the signal of methylene adjacent to the terminal hydroxyl group was used. Is observed at 3.55 ppm).

(Example 7)

The reaction was carried out in the same manner as in Example 3, except that the alkenyl compound to be added was changed from 10-acetoxy-1-decene to oxenyl acetate (4.74 g, 28.2 mmo 1). The functional group introduction amount of the obtained polymer is as follows; Fn (CH ₂ OCME) = 1.70 (The analysis method is the same as in Example 1. The signal of methylene adjacent to the acetoxyl group is 4. Observed at 20 ppm).

(Example 8)

The reaction was carried out in the same manner except that the amounts of the reagents used in Example 6 were changed as follows.

Toluene 592 ml, ethylcyclohexane 73.6 m1, 1,4-bis (1-chloro-1-1-methylethyl) benzene (5.56 g, 24. Ommo 1), 2-methylpyridine (264 mg, 2.83 mmo 1 ), Isobutylene monomer (1 20ml, 1.44mo1)

Titanium chloride (2.52m and 23.Ommol) added during the polymerization reaction.

Oxenyl acetate (32.4 g, 193 mmo 1) and titanium tetrachloride (39.8 ml, 386 mmo 1) added during the alkenyl addition reaction.

1 L of a 2 N aqueous sodium hydroxide solution added during the hydrolysis reaction and 10.0 g of tetrabutylammonium bromide.

The amount of hydroxyl groups introduced into the obtained polymer is as follows: F n (CH _z OH) = 1.90 (The analysis method is the same as in Example 1. The methylene ring adjacent to the terminal hydroxyl group was used. The signal is observed at 4.00 pm).

(Comparative Example 1) Observation of addition reaction of hydrogen halide to olefin by reaction of alkenyl alcohol and Lewis acid

A 20-Om 1 three-necked flask was purged with nitrogen by attaching a three-way cock, a thermocouple, and a stirrer with a vacuum seal. To this, 35 ml of toluene dehydrated with Molecular Sieves 3A and 4.3 ml of methylcyclohexane were added, and 2-methylpyridine (15.5 mg, 0.17 mmo 1) was further added, followed by cooling to 170. After cooling, 9-decene-1-ol (0.87 g, 5.6 mmol) and titanium tetrachloride (1.3 ml, 11.8 mmol) were added. Sampling was performed every 2 hours (final 6 hours), and titanium tetrachloride in the sample was deactivated with pure water. After removal of the aqueous layer, — analysis was performed by NMR. Solvent for measurement; form of heavy-mouth, determination method; sigma of hydrogen chloride adduct to newly generated olefins based on the signal of methylene adjacent to the terminal hydroxyl group (3.55 ppm, triplet, 2H) Areas of null (4.05 ppm, 6-fold, 1 H) were compared and quantified. The amount of 9-decen-1-ol hydrogen chloride adduct formed increased with time as follows.

Table 1 Changes with time in the amount of alkenyl alcohol hydrogen chloride adduct formed

(Comparative Example 2) Addition reaction of hydroxyl group-terminated alkenyl compound to polymer group terminal In Example 1, changed to 9-decene-1-1-ol (2.20 g, 14. lmmo 1) instead of adding 10-acetyl-1-decene The procedure was performed in the same manner as in Example 1 except for the above.

Analysis of the functionalization rate of the obtained polyisobutylene was performed using NMR. Measurement Agent: Carbon tetrachloride Deacetone mixed solvent, Quantitative method: Compare the signal of methylene adjacent to the terminal hydroxyl group (3.45 pm) based on the signal of the initiator residue (7.2 ppm). Quantified. Fn (CH ₂ OH) is the amount of functional group introduced into the polymer terminal. When introduced quantitatively, it becomes 2.0 with the initiator used in this study. The functional group introduction amount of the obtained polymer is as follows: F n (CH ₂ OH) = 1.2

1 Industrial applicability

The polymer obtained by the present invention is a novel saturated hydrocarbon polymer having a functional group which can be easily converted to a hydroxyl group by deprotection at the terminal, and after completion of polymerization, solvent exchange and catalyst removal. It is possible to efficiently introduce hydroxyl groups in one pot without special treatment such as the above.

Claims

The scope of the claims

1. A protected hydroxyl group obtained by the reaction of a halogen-terminated hydrocarbon polymer obtained by cationic polymerization forming a carbon-carbon single bond with a compound having a protected hydroxyl group and a carbon-carbon double bond. A hydrocarbon polymer having a terminal at the terminal and a main chain of the polymer being a saturated hydrocarbon chain.

2. Having a hydroxyl group at the terminal obtained by deprotecting a hydrocarbon polymer having the protected hydroxyl group at the terminal according to claim 1 and having a saturated hydrocarbon chain as a main chain of the polymer; A hydrocarbon polymer in which the polymer main chain is a saturated hydrocarbon chain.

3. The halogen-terminated hydrocarbon polymer obtained by cationic polymerization has the formula (1)

R ¹ (AX) _a (1)

(Wherein, R ¹ is a monovalent to tetravalent hydrocarbon group containing one or more aromatic rings, X is a chlorine group or a bromine group, a is an integer of 1 to 4. A is one kind or two or more kinds. A polymer obtained by polymerizing a cationic polymerizable monomer. When a is 2 or more, they may be the same or different.)

Represented by

A compound having a protected hydroxyl group and a carbon-carbon double bond is represented by the formula (2): CH ₂ == C (R ² ) -B-OG (2)

(In the formula, R ^z represents hydrogen or a saturated hydrocarbon group having 1 to 18 carbon atoms, B represents a divalent hydrocarbon group having 1 to 30 carbon atoms, and G represents a hydroxyl-protecting group.)

2. The hydrocarbon polymer according to claim 1, wherein the polymer has a protected hydroxyl group at its terminal, and the main chain of the polymer is a saturated hydrocarbon chain.

4. Having a protected hydroxyl group at the terminal according to claim 3 and having a hydroxyl group at the terminal obtained by deprotecting a hydrocarbon polymer in which the polymer main chain is a saturated hydrocarbon chain; A hydrocarbon polymer in which the polymer main chain is a saturated hydrocarbon chain.

5. A compound having a protected hydroxyl group and a carbon-carbon double bond is represented by formula (3): CH ₂ = C (R ² ) 1 (CH ₂ ) _b — {-CH-CH- (CH ₂ ) _c } _n -OG

(3)

(In the formula, R ² represents hydrogen or a saturated or unsaturated monovalent hydrocarbon group having 1 to 18 carbon atoms, and b and c are integers of 1 to 30 and may be the same or different. N represents an integer of 0 to 5, and G represents a hydroxyl-protecting group.)

4. The hydrocarbon-based polymer having a protected hydroxyl group at a terminal thereof according to claim 3, wherein the polymer main chain is a saturated hydrocarbon chain.

6. Having a protected hydroxyl group at the terminal according to claim 5 and having a hydroxyl group at the terminal obtained by deprotecting a hydrocarbon-based polymer in which the polymer main chain is a saturated hydrocarbon chain; A hydrocarbon polymer in which the polymer main chain is a saturated hydrocarbon chain.

7. The protected hydroxyl group-terminated terminal hydrocarbon according to claim 3 or 5, wherein the hydrocarbon-based polymer obtained by the cationic polymerization of the formula (1) is an isobutylene-based polymer, and the polymer main chain is saturated. A hydrocarbon polymer that is a hydrocarbon chain.

8. Having a protected hydroxyl group at the terminal of claim 7 and having a hydroxyl group at the terminal obtained by deprotecting a hydrocarbon polymer in which the polymer main chain is a saturated hydrocarbon chain; A hydrocarbon polymer in which the polymer main chain is a saturated hydrocarbon chain.

9. The protected hydroxyl group-terminated terminal polymer according to claim 3 or 5 or 7, wherein a in the formula (1) is 2 or 3, A is polyisobutylene, and X is chlorine. A hydrocarbon polymer that is a natural hydrocarbon chain.

10. Having a hydroxyl group at the terminal end obtained by deprotecting a hydrocarbon-based polymer having the protected hydroxyl group according to claim 9 at the terminal and the polymer main chain being a saturated hydrocarbon chain. And a hydrocarbon polymer wherein the polymer main chain is a saturated hydrocarbon chain. G in the above equation (2) is

R R¾00- R ^-R ^ HCO-

Four

^ 3

^{^{^{M 1 R 3 -M 2 - 2}}} 2

X-M

OR ³ X

R'HD- ³ -XM ^3-

R

R ⁵ OR ⁵

(Wherein, R ³ , R ⁴ , and R ⁵ represent hydrogen or a saturated or unsaturated hydrocarbon group having 1 to 18 carbon atoms, and may be the same or different in a group containing a plurality of Rs. There. 2 X is selected from C 1, B r, is a functional group selected from I. M4 L i, Na, 1 -valent metal selected from, M ² is Mg, C a, S r, B a M 厲 is a trivalent metal selected from M ^ B, A 1, G a, and M ⁴ is a tetravalent metal selected from T i, Z r, H f, S i, Ge, Sn, and P b It is metal.)

10. The hydrocarbon polymer according to claim 3, which is a group selected from the group consisting of: a protected hydroxyl group at the terminal, wherein the polymer main chain is a saturated hydrocarbon chain. 12. The hydroxyl-terminated terminal obtained by deprotecting a hydrocarbon polymer having the protected hydroxyl group according to claim 11 at the terminal and having a saturated hydrocarbon chain as a main chain of the polymer. And a hydrocarbon polymer wherein the polymer main chain is a saturated hydrocarbon chain.

1 3. When the compound represented by the formula (2) is an allylic alcohol or a methallyl alcohol 3-yl, 3-buten-1-ol, 3-methyl-3-butene-1-ol, 4-pentene-1-ol, 5-hexene-1-ol, 6-heptene-1-ol, 7- Octene 1-ol, 8-nonene 1-l-ol, 9-decene-l-l-ol, 10-undecene-l-l-ol, 2,5-hexagenol, 2,6-hexenol, 3 2,6-heptagenol, 2,7-octagenol, 3,7-octanedienol, 4,7-octanegenol, 2,8-nonadienol, 3.8-nonagenol, 4, The hydroxyl group of a compound selected from the group consisting of 8-nonadienol, 5, 8-nonadienol, 2, 9-decadienol, 3, 9-decadienol, 4, 9-decadienol, 5, 9-decadienol and 6, 9-decadienol (3) at least one compound selected from the group of compounds in which (OH group) is an OG group; 7, 9 or 1 1 has terminated a protected hydroxyl group according the polymer main chain saturated hydrocarbon chain der Ru hydrocarbon polymer.

14. Having a protected hydroxyl group at the terminal according to claim 13 and having a hydroxyl group at the terminal obtained by deprotecting a hydrocarbon polymer in which the polymer main chain is a saturated hydrocarbon chain; A hydrocarbon polymer in which the polymer main chain is a saturated hydrocarbon chain.

1 5. As a catalyst in the reaction between a halogen-terminated hydrocarbon polymer obtained by cationic polymerization forming a carbon-carbon single bond and a compound containing a protected hydroxyl group and a carbon-carbon double bond. Claims 1, 3, 5, 7, 9, 1 using a Lewis acid

14. A method for producing a hydrocarbon polymer having the hydroxyl group obtained at the terminal as described in 1 or 13 and having a polymer main chain of a saturated hydrocarbon chain.

1 6. The catalyst is _{T i C 1 4, A 1} C 1 3, BC 1 3 and S n C 1 ₄ is one or more Lewis acid selected from the group consisting of claims 1 5 protected hydroxy as described A method for producing a hydrocarbon-based polymer having a terminal at the terminal and a main chain of the polymer being a saturated hydrocarbon chain.

17. The reaction solvent according to claim 15, wherein the reaction solvent comprises one or more solvents selected from the group consisting of halogenated hydrocarbons, aromatic hydrocarbons, and aliphatic hydrocarbons. A method for producing a hydrocarbon-based polymer having the protected hydroxyl group at the terminal and a polymer main chain comprising a saturated hydrocarbon chain.

18. The halogenated hydrocarbon is at least one substance selected from the group consisting of chromate form, methylene chloride, 1,1-dichloroethane, 1,2-dichloroethane, n-propylic chloride and n-butyl chloride. 18. The process for producing a hydrocarbon polymer according to claim 17, wherein the polymer has a protected hydroxyl group at its terminal and the main chain of the polymer is a saturated hydrocarbon chain. 19. The process for producing a hydrocarbon-based polymer according to claim 17 or 18, wherein the aromatic hydrocarbon is toluene, wherein the protected hydroxyl group-terminated terminal polymer chain is a saturated hydrocarbon chain. .

20. The aliphatic hydrocarbon is at least one substance selected from the group consisting of pentane, n-hexane, cyclohexane, methylcyclohexane, and ethylcyclohexane. A method for producing a hydrocarbon-based polymer having a protected hydroxyl group at the end and a polymer having a main chain of a saturated hydrocarbon chain.

21. The hydrocarbon-based polymer according to claim 17, wherein a mixed solvent of toluene and ethylcyclohexane is used as a reaction solvent, wherein the polymer has a protected hydroxyl group at a terminal and a polymer main chain is a saturated hydrocarbon chain. Manufacturing method of coalescence.