WO2000056784A1 - Polymere d'hydrocarbures satures ayant un groupe fonctionnel en extremite et procede de production d'un tel polymere - Google Patents

Polymere d'hydrocarbures satures ayant un groupe fonctionnel en extremite et procede de production d'un tel polymere Download PDF

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Publication number
WO2000056784A1
WO2000056784A1 PCT/JP1999/002693 JP9902693W WO0056784A1 WO 2000056784 A1 WO2000056784 A1 WO 2000056784A1 JP 9902693 W JP9902693 W JP 9902693W WO 0056784 A1 WO0056784 A1 WO 0056784A1
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polymer
hydrocarbon
hydroxyl group
group
terminal
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Japanese (ja)
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Takeshi Chiba
Hidenari Tsunemi
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Kaneka Corp
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Kaneka Corp
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F8/00—Chemical modification by after-treatment
    • C08F8/12—Hydrolysis

Definitions

  • 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.
  • hydrogenated polybutadiene polyol and polyisoprene polyol synthesized by anionic polymerization can provide a saturated hydrocarbon polymer having a hydroxyl group at a terminal.
  • primary hydroxyl groups can be easily and quantitatively introduced into the terminal by reacting ethylene oxide after the polymerization.
  • 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.
  • polyisobutylene obtained by cation polymerization is known as a saturated hydrocarbon-based polymer expected to have high weather resistance.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • hydroxyl-terminated polyisobutylene cannot be obtained from halogen-terminated polyisobutylene in one step.
  • 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.
  • 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 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.
  • 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
  • G represents a protecting group for a hydroxyl group.
  • 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
  • R 2 represents hydrogen or a saturated or unsaturated monovalent hydrocarbon group having 1 to 18 carbon atoms
  • b and c are integers of 1 to 30 and may be the same or different.
  • n represents an integer of 0 to 5
  • G represents a hydroxyl-protecting group.
  • 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.
  • 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.
  • 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.
  • Such a monomer component examples 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, ⁇ —Methylstyrene, dimethylstyrene, monochlorostyrene, dichlorostyrene,) 3-vinylene, indene, pinyltrichlorosilane, vinylmethyldichlorosilane, vinyldimethylchlorosilane, vinyldimethylmethoxysilane, vinyltrimethylsilane, divinyldichlorosilane, divinyl Dimeth
  • 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 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.
  • G is hydrogen in the above formula (2)
  • Lewis 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.
  • a single or mixed solvent arbitrarily selected from halogenated hydrocarbons, aromatic hydrocarbons, and aliphatic hydrocarbons as the reaction solvent.
  • 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.
  • 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.
  • the reaction can be efficiently advanced by adding a catalyst.
  • a catalyst any of organic and inorganic catalysts can be used for the reaction.
  • 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.
  • 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.
  • 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
  • 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 ⁇ 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.
  • 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.
  • 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.
  • the compounds having a substituent at the benzyl position shown below are preferable because of their high initiator efficiency during polymerization.
  • 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.
  • halogenated hydrocarbons methylene chloride, chloroform, 1,1-dichloroethane, 1.2-dichloroethane, ⁇ -propyl chloride, and ⁇ -butyl chloride are used as halogenated hydrocarbons due to their solubility and reactivity under the polymerization conditions of the polymer.
  • it is at least one component selected from
  • toluene is preferred as the aromatic hydrocarbon
  • pentane, ⁇ -hexane, cyclohexane, methylcyclohexane, and ethylcyclohexane as the aliphatic hydrocarbon.
  • 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.
  • 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.
  • a hydrolysis reaction is effective as a reaction for generating a hydroxyl group by deprotection.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • the functionalization rate of the obtained polyisobutylene was analyzed using NMR.
  • the signal of methylene adjacent to the terminal hydroxyl group was used. Is observed at 3.55 ppm).
  • 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).
  • 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.
  • 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.
  • 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.
  • 9-decene-1-ol (0.87 g, 5.6 mmol
  • titanium tetrachloride 1.3 ml, 11.8 mmol
  • 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.

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  • Chemical & Material Sciences (AREA)
  • General Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
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Abstract

L'invention se rapporte à des polymères d'hydrocarbures saturés portant en leurs extrémités des groupes fonctionnels, qui s'avèrent utiles en tant que matières premières pour les uréthannes présentant une grande résistance aux intempéries. Pour ces polymères, il est nécessaire de mettre en oeuvre une réaction à étapes multiples dans laquelle, à la fin de la polymérisation, les extrémités des polymères sont converties en extrémités oléfiniques puis soumises à une hydroboration. On fait réagir un polymère d'hydrocarbure à terminaison halogène obtenu par polymérisation cationique avec un composé contenant à la fois un groupe hydroxyle protégé en tant que substituant et une liaison insaturée dans le but de produire facilement un polymère d'hydrocarbure saturé portant un groupe hydroxyle protégé en chacune de ses extrémités. Ce composé peut être facilement converti par hydrolyse en polymère à terminaison hydroxyle.
PCT/JP1999/002693 1999-03-19 1999-05-21 Polymere d'hydrocarbures satures ayant un groupe fonctionnel en extremite et procede de production d'un tel polymere Ceased WO2000056784A1 (fr)

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JP11/75087 1999-03-19
JP7508799 1999-03-19

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Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH01103605A (ja) * 1987-08-10 1989-04-20 General Electric Co <Ge> テレキーリックポリイソブチレンおよびブロックコポリマー誘導体

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH01103605A (ja) * 1987-08-10 1989-04-20 General Electric Co <Ge> テレキーリックポリイソブチレンおよびブロックコポリマー誘導体

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
B. IVAN, J.P. KENNEDY, V.S.C. CHANG., J. POLYM. SCI. POLYM. CHEM. ED.,, vol. 18, 1980, pages 3177 - 3191, XP002926329 *

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