Method of producing (meth)acryloyl-terminated polyisobutylene polymer

Abstract

A method for producing a (meth)acryloyl-terminated polyisobutylene polymer includes a step 1 of polymerizing an isobutylene monomer under the presence of a Lewis acid catalyst to prepare a halogen-terminated polyisobutylene polymer (B), a step 2 of reacting the halogen-terminated polyisobutylene polymer (B) with a compound (C) having a halogen group and a phenoxy group under the presence a Lewis acid catalyst to prepare a halogenated phenoxyalkyl-terminated polyisobutylene polymer (D), and a step 3 of reacting the halogenated phenoxyalkyl-terminated polyisobutylene polymer (D) with an acrylic acid compound (E) to prepare the (meth)acryloyl-terminated polyisobutylene polymer (A).

Claims

1. A method for producing a (meth)acryloyl-terminated polyisobutylene polymer (A) represented by the following general formula (1), ##STR00014## wherein R.sup.1 represents a monovalent or multivalent aromatic hydrocarbon group, or a monovalent or multivalent aliphatic hydrocarbon group, A represents a polyisobutylene polymer, R.sup.2 represents a divalent saturated hydrocarbon group having 2 to 6 carbons and having no heteroatom, each of R.sup.3 and R.sup.4 represents a hydrogen, a monovalent hydrocarbon having 1 to 20 carbons, or an alkoxy group, R.sup.5 represents a hydrogen or a methyl group, and n represents natural number, the method comprising: a step 1 of polymerizing an isobutylene monomer under the presence of a Lewis acid catalyst to prepare a polyisobutylene polymer (B) represented by the following general formula (2), ##STR00015## wherein R.sup.1, A, and n are the same as in the general formula (1), and Z represents a chlorine, a bromine, an iodine, an acetoxy group, or a methoxy group; a step 2 of reacting the polyisobutylene polymer (B) with a compound (C) having a halogen group and a phenoxy group as represented by the following general formula (3) under the presence of a Lewis acid catalyst to prepare a halogenated phenoxyalkyl-terminated polyisobutylene polymer (D) represented by the following general formula (4), wherein a ratio of a total molar amount of the Lewis acid catalyst to a molar amount of the compound (C) having a halogen group and a phenoxy group is 3.3 or less, ##STR00016## wherein R.sup.2, R.sup.3, and R.sup.4 are the same as in the general formula (1), and X represents a chlorine, a bromine, or an iodine, ##STR00017## wherein R.sup.1, R.sup.2, R.sup.3, R.sup.4, A, and n are the same as in the general formula (1), and X is the same as in the general formula (3); and a step 3 of reacting the halogenated phenoxyalkyl-terminated polyisobutylene polymer (D) with an acrylic acid compound (E) represented by the following general formula (5) to prepare the (meth)acryloyl-terminated polyisobutylene polymer (A), ##STR00018## wherein R.sup.5 represents a hydrogen or a methyl group, and Y represents a hydrogen, a lithium, a sodium, a potassium, a rubidium, or a cesium.

2. The method according to claim 1, wherein a reaction solvent is used in the step 3, and wherein the reaction solvent is at least one solvent selected from the group consisting of a halogenated hydrocarbon, a linear saturated hydrocarbon, a cyclic saturated hydrocarbon, and an aromatic hydrocarbon.

3. The method according to claim 1, wherein a reaction solvent is used in the step 3, and wherein the reaction solvent is a halogenated hydrocarbon, or a mixed solvent of a halogenated hydrocarbon and a linear saturated hydrocarbon.

4. The method according to claim 1, wherein a reaction solvent is used in the step 3, and wherein the reaction solvent is an aromatic hydrocarbon, or a mixed solvent of an aromatic hydrocarbon and a linear saturated hydrocarbon or a cyclic saturated hydrocarbon.

5. The method according to claim 1, wherein the step 3 is carried out under the presence of at least one compound selected from the group consisting of an ammonium salt, a phosphonium salt, and a crown ether.

6. The method according to claim 5, wherein the ammonium salt comprises one or less of a methyl group as a substituent on a nitrogen atom.

7. The method according to claim 1, further adding an aprotic amphiphilic solvent in the step 3.

8. The method according to claim 1, wherein a content of water is 1000 ppm or less in the step 3.

9. The method according to claim 1, wherein the (meth)acryloyl-terminated polyisobutylene polymer has a number average molecular weight of 8000 to 500000 as measured by size exclusion chromatography.

10. The method according to claim 1, wherein in the chemical formula 5, Y represents a lithium, a sodium, a potassium, a rubidium, or a cesium.

Description

EXAMPLES

(1) Next, one or more embodiments of the present invention will be described in detail with reference to Examples, but the present invention is not limited thereto. In addition, each of measurement method and evaluation method is explained before describing Example.

(2) (Molecular Weight Measurement)

(3) In the following Examples, number average molecular weight, weight average molecular weight and molecular weight distribution (ratio of weight average molecular weight to number average molecular weight) were calculated by standard polystyrene conversion method using size permeation chromatography (SEC). In this measurement, LCModule 1 manufactured by Waters was used as an SEC system, a column filled with a polystyrene crosslinked gel (Shodex GPCK-804; manufactured by Showa Denko K.K.) was used as a GPC column (stationary phase), and chloroform was used as a mobile phase.

(4) (APHA Measurement: Hazen Color Number)

(5) The Hazen color number was measured according to ISO 6721-2: 2004 to obtain the APHA value. For the measurement, a SC-P spectrophotometer manufactured by Suga Test Instruments Co., Ltd. was used.

(6) (Number of Introduced (Meth)Acryloyl Group)

(7) The number of (meth)acryloyl groups introduced at the end of the (meth) acryloyl-terminated polyisobutylene polymer was determined in the following manner. First, from the number average molecular weight Mn of the polymer determined by the above molecular weight measurement (GPC measurement), the number of protons derived from the methyl group in the polyisobutylene contained in one molecule of the polymer was determined. Next, .sup.1H NMR measurement was carried out, and the peak integral value of the proton was determined from the NMR chart. The number of (meth)acryloyl groups introduced in one molecule of the polymer was determined by using the number and the peak integral value of protons and the peak integral value of the vinyl proton derived from the (meth)acryloyl group obtained from the NMR chart.

(8) (Number of Halogenated Phenoxyalkyl Groups Introduced)

(9) The number of halogenated phenoxyalkyl groups introduced at the end of the halogenated phenoxyalkyl-terminated polyisobutylene polymer was determined in the following manner. First, from the number average molecular weight Mn of the polymer determined by the above molecular weight measurement (GPC measurement), the number of protons derived from the methyl group in the polyisobutylene contained in one molecule of the polymer was determined. Next, .sup.1H NMR measurement was carried out, and the peak integral value of the proton was determined from the NMR chart. Using the number and the peak integral value of protons and the peak integral value of the proton at the a position of the halogen group and the oxygen atom in the halogenated phenoxyalkyl group determined from the NMR chart, the number of halogenated phenoxyalkyl groups in one molecule of the polymer was determined.

Example 1

Production of Acryloyl-Terminated Polyisobutylene Polymer (Component P-1)

(10) After replacing the inside of a 500 mL separable flask with nitrogen, 17 g of n-hexane (dried with molecular sieves) and 209 g of butyl chloride (dried with molecular sieves) were added, and a mixture was cooled to 70 C. while stirring under a nitrogen atmosphere. Subsequently, 140 mL (1.48 mol) of isobutylene, 2.00 g (8.65 mmol) of p-dicumyl chloride and 0.201 g (1.99 mmol) of triethylamine were added. After the reaction mixture was cooled to 70 C., 0.66 mL (6.06 mmol) of titanium tetrachloride was added to initiate polymerization. After the initiation of polymerization, the residual isobutylene concentration was measured by gas chromatography, and when the residual amount of isobutylene was less than 0.5%, 3.65 g (18.2 mmol) of 2-phenoxyethyl bromide (-bromophenetole) and 3.79 mL (34.6 mmol) of titanium tetrachloride were added. After stirring at 75 C. for 3 hours, the reaction solution was poured into another separable flask that contains a mixture of 478 g of water and 265 g of a mixed solvent of n-hexane and butyl chloride (mixture ratio of n-hexane:butyl chloride=9:1, v/v) at 50 C. while stirring. Thereafter, the reaction mixture was kept stirred at 50 C. for 1 hour to deactivate the catalyst. After standing still for 30 minutes, the aqueous phase was discharged. Next, the organic phase was washed with 478 g of a 0.5 wt % sodium sulfate solution for 1 hour at 50 C. and then the mixture was stood still for next 30 minutes. Thereafter, the aqueous phase was taken out. The same procedure was repeated again to obtain the purified organic phase.

(11) To this organic phase, 9.52 g (86.5 mmol) of potassium acrylate and 0.88 g (2.73 mmol) of tetrabutylammonium bromide were added and stirring was continued at 50 C. for 24 hours. Thereafter, the organic phase was washed with 478 g of deionized water at 50 C. three times to take out the purified organic phase.

(12) To the organic phase, 0.18 g of 4-methoxyphenol was added, and the solvent was evaporated under reduced pressure to obtain an acryloyl-terminated polyisobutylene polymer P-1. The molecular weight (standard polystyrene) of P-1 was found to be number average molecular weight Mn of 11,998, molecular weight distribution Mw/Mn of 1.23, introduction number of acryloyl groups of 1.6, and APHA of 10.

Example 2

Production of Acryloyl-Terminated Polyisobutylene Polymer (Component P-2)

(13) After replacing the inside of a 500 mL separable flask with nitrogen, 17 g of n-hexane (dried with molecular sieves) and 209 g of butyl chloride (dried with molecular sieves) were added, and a mixture was cooled to 70 C. while stirring under a nitrogen atmosphere. Subsequently, 140 mL (1.48 mol) of isobutylene, 2.00 g (8.65 mmol) of p-dicumyl chloride and 0.201 g (1.99 mmol) of triethylamine were added. After the reaction mixture was cooled to 70 C., 0.76 mL (6.92 mmol) of titanium tetrachloride was added to initiate polymerization. After the initiation of polymerization, the residual isobutylene concentration was measured by gas chromatography, and when the residual amount of isobutylene was less than 0.5%, 3.15 ml (19.9 mmol) of 3-phenoxypropyl bromide and 2.85 ml (26.0 mmol) of titanium tetrachloride were added. After stirring at 75 C. for 3 hours, the reaction solution was poured into another separable flask that contains a mixture of 478 g of water and 265 g of a mixed solvent of n-hexane and butyl chloride (mixture ratio of n-hexane:butyl chloride=9:1, v/v) at 50 C. while stirring. Thereafter, the reaction mixture was kept stirred at 50 C. for 1 hour to deactivate the catalyst. After standing still for 30 minutes, the aqueous phase was discharged. Next, the organic phase was washed with 478 g of a 0.5 wt % sodium sulfate solution for 1 hour at 50 C. and then the mixture was stood still for next 30 minutes. Thereafter, the aqueous phase was taken out. The same procedure was repeated again to obtain the purified organic phase.

(14) To this organic phase, 9.52 g (86.5 mmol) of potassium acrylate and 0.88 g (2.73 mmol) of tetrabutylammonium bromide were added and stirring was continued at 50 C. for 24 hours. Thereafter, the organic phase was washed with 478 g of deionized water at 50 C. three times to take out the purified organic phase.

(15) To this organic phase, 0.18 g of 4-methoxyphenol was added, and the solvent was evaporated under reduced pressure to obtain an acryloyl-terminated polyisobutylene polymer P-2. The molecular weight (standard polystyrene) of P-2 was found to be number average molecular weight Mn of 12,370, molecular weight distribution Mw/Mn of 1.26, introduction number of acryloyl groups of 1.6, and APHA of 20.

Example 3

Production of Acryloyl-Terminated Polyisobutylene Polymer (Component P-3)

(16) After replacing the inside of a 500 mL separable flask with nitrogen, 17 g of n-hexane (dried with molecular sieves) and 209 g of butyl chloride (dried with molecular sieves) were added, and a mixture was cooled to 70 C. while stirring under a nitrogen atmosphere. Subsequently, 140 mL (1.48 mol) of isobutylene, 2.00 g (8.65 mmol) of p-dicumyl chloride and 0.201 g (1.99 mmol) of triethylamine were added. After the reaction mixture was cooled to 70 C., 0.76 mL (6.92 mmol) of titanium tetrachloride was added to initiate polymerization. After the initiation of polymerization, the residual isobutylene concentration was measured by gas chromatography, and when the residual amount of isobutylene was less than 0.5%, 4.56 g (19.9 mmol) of 4-phenoxybutyl bromide and 2.85 mL (26.0 mmol) of titanium tetrachloride were added. After stirring at 75 C. for 3 hours, the reaction solution was poured into another separable flask that contains a mixture of 478 g of water and 265 g of a mixed solvent of n-hexane and butyl chloride (mixture ratio of n-hexane:butyl chloride=9:1, v/v) at 50 C. while stirring. Thereafter, the reaction mixture was kept stirred at 50 C. for 1 hour to deactivate the catalyst. After standing still for 30 minutes, the aqueous phase was discharged. Next, the organic phase was washed with 478 g of a 0.5 wt % sodium sulfate solution for 1 hour at 50 C. and then the mixture was stood still for next 30 minutes. Thereafter, the aqueous phase was taken out. The same procedure was repeated again to obtain the purified organic phase.

(17) To this organic phase, 9.52 g (86.5 mmol) of potassium acrylate and 0.88 g (2.73 mmol) of tetrabutylammonium bromide were added and stirring was continued at 50 C. for 24 hours. Thereafter, the organic phase was washed with 478 g of deionized water at 50 C. three times to take out the purified organic phase.

(18) To the organic phase, 0.18 g of 4-methoxyphenol was added, and the solvent was evaporated under reduced pressure to obtain an acryloyl-terminated polyisobutylene polymer P-3. The molecular weight (standard polystyrene) of P-3 was found to be number average molecular weight Mn of 12,877, molecular weight distribution Mw/Mn of 1.21, introduction number of acryloyl group of 1.5, and APHA of 10.

Comparative Example 1

Production of Acryloyl-Terminated Polyisobutylene Polymer (Component Q-1)

(19) After replacing the inside of a 500 mL separable flask with nitrogen, 14 g of n-hexane (dried with molecular sieves) and 163 g of butyl chloride (dried with molecular sieves) were added, and a mixture was cooled to 70 C. while stirring under a nitrogen atmosphere. Next, 109 mL (1.16 mol) of isobutylene, 1.56 g (6.75 mmol) of p-dicumyl chloride and 0.157 g (1.55 mmol) of triethylamine were added. After the reaction mixture was cooled to 70 C., 0.39 mL (3.58 mmol) of titanium tetrachloride was added to initiate polymerization. After the initiation of polymerization, the residual isobutylene concentration was measured by gas chromatography, and when the residual amount of isobutylene was less than 0.5%, 5.19 g (27.0 mmol) of phenoxyethyl acrylate and 9.62 mL (87.7 mmol) of titanium tetrachloride were added.

(20) After stirring at 75 C. for 3 hours, the reaction solution was poured into another separable flask that contains a mixture of 530 g of a 0.2 wt % sodium sulfate aqueous solution 194 g of a mixed solution of n-hexane and butyl chloride (mixing ratio of n-hexane:butyl chloride=1:9, v/v) at 50 C. while stirring.

(21) Thereafter, the reaction mixture was kept stirred at 50 C. for 1 hour to deactivate the catalyst. After standing still for 30 minutes, the aqueous phase was discharged. Next, the organic phase was washed with a mixture of 530 g of deionized water and 34.7 g of a 48 wt % sodium hydroxide solution at 50 C. for 1 hour. Then, the mixture was allowed to stand for 30 minutes, and the aqueous phase was discharged. Next, the organic phase was washed with 478 g of a 0.2 wt % sodium sulfate solution for 1 hour at 50 C. and then the mixture was stood still for next 30 minutes. Thereafter, the aqueous phase was taken out. The same procedure was repeated again to obtain the purified organic phase.

(22) Since the organic phase taken out was cloudy, purification with pressure filtration (filter cloth: PE-1-P01 H-202 manufactured by EATON Co., Ltd, filtering aid: Radiolite R100S manufactured by Showa Chemical Industry Co., Ltd., filter aid amount: 8 g per 200 g of organic phase, nitrogen pressure: 0.04 MPa) was repeated three times.

(23) To 400 g of the organic phase subjected to filtration, 0.100 g of 4-methoxyphenol was added and the solvent was evaporated under reduced pressure to obtain an acryloyl-terminated polyisobutylene polymer Q-1. The molecular weight (standard polystyrene) of Q-1 was found to be number average molecular weight Mn of 13,433, molecular weight distribution Mw/Mn of 1.36, introduction number of acryloyl groups of 1.40, and APHA of 100.

Comparative Example 2

Production of Acryloyl-Terminated Polyisobutylene Polymer (Component Q-2)

(24) Comparative Example 2 was carried out in the same manner as in Comparative Example 1 except that 2.98 g (15.5 mmol) of phenoxyethyl acrylate and 2.42 mL (22.1 mmol) of titanium tetrachloride were used in the functionalization reaction, to prepare an acryloyl-terminated polyisobutylene polymer Q-2. The introduction number of acryloyl group of Q-2 was 0.1, and this value was not practical and was very low.

Comparative Example 3

Production of Acryloyl-Terminated Polyisobutylene Polymer (Component Q-3)

(25) Comparative Example 3 was carried out in the same manner as in Comparative Example 1 except that 4.49 mL (40.9 mmol) of titanium tetrachloride was used in the functionalization reaction to prepare an acryloyl-terminated polyisobutylene polymer Q-3. The introduction number of the acryloyl group of Q-3 was 0.3, and this value was not practical and was a very low.

(26) TABLE-US-00001 TABLE 1 Comparative Comparative Comparative Example 1 Example 2 Example 3 Example 4 Example 1 Example 2 Example 3 Molar amount of Lew is acid polymerization 6.06 6.92 6.92 15.5 3.58 3.58 3.58 catalyst used (mmol) (A) functionalization reaction 34.6 26.0 26.0 38.8 87.7 15.5 40.9 Molar amount of compound (C) having halogen group 18.2 19.9 19.9 23.2 27.0 15.5 27.0 and phenoxy group (mmol) (B) [1] Ratio of total molar amount of Lew is acid catalyst to 2.23 1.65 1.65 2.34 3.38 1.23 1.65 molar amount of compound (C) (A)/(B) Amount (g) of Lew is acid catalyst used in production of 0.0877 0.0707 0.0705 0.103 0.253 0.071 0.123 1 g of polymer Introduction number of acryloyl group 1.6 1.6 1.5 1.8 1.4 0.1 0.3 [1] Comparative Examples 1 to 3 indicates an amount of phenoxyethylacrylate

Example 4

(27) Production of Acryloyl-Terminated Polyisobutylene Polymer (Component P-4)

(28) After replacing the inside of a 500 mL separable flask with nitrogen, 49 g of ethylcyclohexane (dried with molecular sieves) and 155 g of toluene (dried with molecular sieves) were added, and a mixture was cooled to 70 C. while stirring under a nitrogen atmosphere. Then 125 mL (1.33 mmol) of isobutylene, 1.79 g (7.74 mmol) of p-dicumyl chloride and 0.248 mL (1.78 mmol) of triethylamine were added. After the reaction mixture was cooled to 70 C., 1.70 mL (15.5 mmol) of titanium tetrachloride was added to initiate polymerization. After the initiation of polymerization, the residual isobutylene concentration was measured by gas chromatography, and when the residual amount of isobutylene was less than 0.5%, 3.68 mL (23.2 mmol) of 3-phenoxypropyl bromide and 4.25 mL (38.8 mmol) of titanium tetrachloride were added. After stirring at 75 C. for 3 hours, the reaction solution was poured into another separable flask that contains a mixture of 242 g of water and 350 g of a mixed solvent of ethylcyclohexane and toluene (toluene:ethylcyclohexane=7.4:2.6, v/v mixing ratio) at 50 C. while stirring. Thereafter, the reaction mixture was kept stirred at 50 C. for 1 hour to deactivate the catalyst. After standing still for 30 minutes, the aqueous phase was discharged. Next, the organic phase was washed with 242 g of deionized water for 1 hour at 50 C. and then the mixture was stood still for next 30 minutes. Thereafter, the aqueous phase was taken out. The same procedure was repeated another three times to obtain the purified organic phase.

(29) To this organic phase, 8.52 g (77.4 mmol) of potassium acrylate and 1.00 g (3.10 mmol) of tetrabutylammonium bromide were added and stirring was continued at 50 C. for 24 hours. Thereafter, the organic phase was washed with 500 g of deionized water at 50 C. three times to obtain the purified organic phase.

(30) The extracted organic phase was subjected to pressure filtration (filter cloth: PE-1-P01H-202 manufactured by EATON Co., Ltd. filtration aid: Radiolite R100S manufactured by Showa Chemical Industry Co., Ltd., filter aid amount: 4 g per 200 g of organic phase, nitrogen pressure: 0.04 MPa), and the organic phase was purified.

(31) To 200 g of the organic phase subjected to filtration, 0.050 g of 4-methoxyphenol was added and the solvent was evaporated under reduced pressure to obtain an acryloyl-terminated polyisobutylene polymer P-4. The molecular weight (standard polystyrene) of P-4 was found to be number average molecular weight Mn of 11,965, molecular weight distribution Mw/Mn of 1.41, introduction number of acryloyl groups of 1.80, and APHA of 30.

(32) The experiments described in the patent documents 1 and 2 were carried out in Comparative Example 1. In this case, the amount of Lewis acid catalyst required to produce 1 g of polymer as defined by (the weight of the titanium tetrachloride catalyst used in the manufacture)/(theoretical yield of the resin) was 0.253 g.

(33) In contrast, in the methods described in Examples 1 to 3, the amount of Lewis acid catalyst required to produce 1 g of polymer was 0.0877 g in Example 1, the amount of Lewis acid catalyst required to produce 1 g of polymer was 0.0707 g in Example 2, and the amount of Lewis acid catalyst required to produce 1 g of polymer was 0.0705 g in Example 3.

(34) In Examples 1 to 3, the amount of the Lewis acid catalyst used in the production of the (meth) acryloyl-terminated polyisobutylene polymer was 35% in Example 1, and 28% in Examples 2 and 3, compared with that in Comparative Example 1, indicating that the amount of Lewis acid catalyst required is very small.

(35) In addition, these titanium catalysts undergo hydrolysis in the catalyst deactivation step and become titanium residues including titanium dioxide, titanium hydroxide and the like. However, these are removed from the polymer as aqueous phase is dispensed. These titanium species are insoluble in water and generally are separated from wastewater and discarded as solids. When a large amount of titanium catalyst is used at the time of production, the amount of waste from titanium residues also increases. Therefore, there are concerns that productivity decreases in the case where the treatment takes time and the environmental burden also increases. However, these concerns can be greatly reduced according to embodiments of the present invention.

(36) In Comparative Example 1, a filtration step is necessary for removing the catalyst residue, whereas in embodiments of the present invention, as shown in Examples 1 to 3, a polymer excellent in transparency can be obtained by merely washing the polymer solution with water. Thus, according to embodiments of the present invention, it is possible to simplify the post-treatment process.

(37) Furthermore, in Comparative Example 1, it was difficult to remove the titanium catalyst used in a large amount, so that the obtained resin had a high APHA value of 100, whereas the polymers in Examples 1 to 3 have a relatively low APHA value of 10 to 20. Therefore, according to embodiments of the present invention, a polymer excellent in transparency can be obtained.

(38) On the other hand, as shown in Comparative Examples 2 to 3, when the amount of the titanium catalyst to be used is reduced in the conventionally known production method, the number of the acryloyl group introduced at a terminal of the polymer is drastically reduced. In these cases, the curing rate and mechanical properties of the curable composition may not be practical.

(39) As shown in Example 4, when a mixed solvent of an aromatic hydrocarbon and a linear saturated hydrocarbon or a cyclic saturated hydrocarbon is used as a reaction solvent, an acryloyl-terminated polyisobutylene polymer having a high introduction number of an acryloyl group can be obtained while maintaining excellent transparency (APHA).

(40) In the mixed solvent of the halogenated hydrocarbon and the linear saturated hydrocarbon used in Examples 1 to 3, an acryloyl-terminated polyisobutylene polymer having introduction number of a functional group of 1.5 to 1.6 is obtained. Although the number of introduced functional groups is sufficiently high to such an extent that there is no problem in practical use, and in order to obtain higher cured physical properties (for example, modulus) and higher curing rate, it may be desired that acryloyl-terminated polyisobutylene polymers have more high introduction number of a functional group. In order to meet the requirement, it is useful to use a mixed solvent of the aromatic hydrocarbon and the linear saturated hydrocarbon or the cyclic saturated hydrocarbon as a reaction solvent as shown in Example 4.

Production Example 1

Production of Halogenated Phenoxyalkyl-Terminated Polyisobutylene Polymer (Component R-1)

(41) After replacing the inside of a 500 mL separable flask with nitrogen, 12 g of n-hexane (dried with molecular sieves) and 150 g of butyl chloride (dried with molecular sieves) were added, and a mixture was cooled to 70 C. while stirring under a nitrogen atmosphere. Subsequently, 100 mL (1.06 mol) of isobutylene, 1.43 g (6.19 mmol) of p-dicumyl chloride and 0.144 g (1.42 mmol) of triethylamine were added. After the reaction mixture was cooled to 70 C., 0.47 mL (4.33 mmol) of titanium tetrachloride was added to initiate polymerization. After the initiation of polymerization, the residual isobutylene concentration was measured by gas chromatography, and 3.11 g (15.5 mmol) of 2-phenoxyethyl bromide (-bromophenetole) and 1.70 mL (15.5 mmol) of titanium tetrachloride were added when the residual amount of isobutylene was less than 0.5%. After stirring at 75 C. for 3 hours, the reaction solution was poured into another separable flask that contains a mixture of 500 g of water, and 180 g of a mixed solution of n-hexane and butyl chloride (mixing ratio of butyl chloride:n-hexane=9:1, v/v) at 50 C. while stirring. Thereafter, the reaction mixture was kept stirred at 50 C. for 1 hour to deactivate the catalyst. After standing still for 30 minutes, the aqueous phase was discharged. Next, the organic phase was washed with 478 g of a 0.5 wt % sodium sulfate solution for 1 hour at 50 C. and then the mixture was stood still for next 30 minutes. Thereafter, the aqueous phase was taken out. The same procedure was repeated again to obtain the organic phase containing the reaction mixture.

(42) In order to analyze the polymer obtained in Production Example 1, 20 ml of the reaction mixture was weighed, and the solvent was evaporated under reduced pressure to obtain a halogenated phenoxyalkyl-terminated polyisobutylene polymer R-1. The molecular weight (standard polystyrene) of R-1 was found to have number average molecular weight Mn of 12,724, molecular weight distribution Mw/Mn of 1.49, and introduction number of a halogenated phenoxyalkyl group of 1.7.

(43) Next, an experiment was conducted to evaluate the catalytic ability of various phase transfer catalysts using the polymer solution obtained in Production Example 1. Here, the reaction temperature was 60 C. and the reaction time was 24 hours, respectively, and the catalytic ability of each phase transfer catalyst was examined by comparing introduction numbers of acryloyl group of the polymer obtained under the conditions.

Example 5

(44) Next, to 6 g of the solution of the polymer R-1 obtained in Production Example 1 (measured value: polymer concentration of 17.7 wt %), 0.0919 g (8.3510.sup.4 mol) of potassium acrylate, and 0.0163 g (5.8610.sup.5 mol, 1.53 parts by weight based on 100 parts by weight of the polymer) of tetrabutylammonium chloride were added and reacted at 60 C. for 24 hours. After the reaction, about 5 ml of the reaction solution was reprecipitated by adding it to a mixed solvent of acetone and methanol (mixing ratio of acetone/methanol=20 ml/20 ml) to isolate an acryloyl-terminated polyisobutylene polymer P-5. The introduction number of the acryloyl group was 1.5.

Example 6

(45) Acryloylation was carried out in the same manner as in Example 5 except that 0.0189 g (5.8610.sup.5 mol, 1.78 parts by weight relative to 100 parts by weight of the polymer) of tetrabutylammonium bromide was used as a phase transfer catalyst to obtain an acryloyl-terminated polyisobutylene polymer P-6. The introduction number of acryloyl groups was 1.6.

Example 7

(46) Acryloylation was carried out in the same manner as in Example 5 except that 0.0216 g (5.8610.sup.5 mol, 2.04 parts by weight relative to 100 parts by weight of the polymer) of tetrabutylammonium iodide was used as a phase transfer catalyst to obtain an acryloyl-terminated polyisobutylene polymer P-7. The introduction number of the acryloyl group was 1.4.

Example 8

(47) Acryloylation was carried out in the same manner as in Example 5 except that 0.0320 g (5.8610.sup.5 mol, 3.02 parts by weight relative to 100 parts by weight of the polymer) of tetraoctylammonium bromide was used as a phase transfer catalyst to obtain an acryloyl-terminated polyisobutylene polymer P-8. The introduction number of acryloyl groups was 1.6.

Example 9

(48) Acryloylation was carried out in the same manner as in Example 5 except that 0.0265 g (5.8610.sup.5 mol, 2.49 parts by weight relative to 100 parts by weight of the polymer) of tributyldodecylphosphonium bromide was used as a phase transfer catalyst to obtain an acryloyl-terminated polyisobutylene polymer P-9. The introduction number of acryloyl groups was 1.6.

Example 10

(49) Acryloylation was carried out in the same manner as in Example 5 except that 0.0199 g (5.8610.sup.5 mol, 1.87 parts by weight relative to 100 parts by weight of the polymer) of tetrabutylphosphonium bromide was used as the phase transfer catalyst to obtain an acryloyl-terminated polyisobutylene polymer P-10. The introduction number of acryloyl groups was 1.6.

(50) Next, in order to further investigate the catalytic ability of the phase transfer catalyst, the acryloylation reaction rates were compared by reacting at 60 C. for 4 hours using various phase transfer catalysts, and stopping a reaction after 4 hours. After completion of the reaction for 4 hours, the phase transfer catalyst giving a high introduction number of acryloyl group is highly active and can be suitably used in embodiments of the present invention.

Production Example 2

Production of Halogenated Phenoxyalkyl-Terminated Polyisobutylene Polymer (Component R-2)

(51) After replacing the inside of a 500 mL separable flask with nitrogen, 17 g of n-hexane (dried with molecular sieves) and 209 g of butyl chloride (dried with molecular sieves) were added, and a mixture was cooled to 70 C. while stirring under a nitrogen atmosphere. Subsequently, 140 mL (1.48 mol) of isobutylene, 2.00 g (8.65 mmol) of p-dicumyl chloride and 0.201 g (1.99 mmol) of triethylamine were added. After the reaction mixture was cooled to 70 C., 0.66 mL (6.06 mmol) of titanium tetrachloride was added to initiate polymerization. After the initiation of polymerization, the residual isobutylene concentration was measured by gas chromatography, and when the residual amount of isobutylene was less than 0.5%, 4.35 g (21.6 mmol) of 2-phenoxyethyl bromide (-bromophenetole) and 1.90 nit (17.3 mmol) of titanium tetrachloride were added. After stirring at 75 C. for 3 hours, the reaction solution was poured into another separable flask that contains a mixture of 478 g of water and 265 g of a mixed solution of n-hexane and butyl chloride (mixing ratio of butyl chloride:n-hexane=9:1, v/v) at 50 C. while stirring. Thereafter, the reaction mixture was kept stirred at 50 C. for 1 hour to deactivate the catalyst. After standing still for 30 minutes, the aqueous phase was discharged. Next, the organic phase was washed with 478 g of a 0.5 wt % sodium sulfate solution for 1 hour at 50 C. and then the mixture was stood still for next 30 minutes. Thereafter, the aqueous phase was taken out. The same procedure was repeated again to obtain the organic phase containing the reaction mixture.

(52) In order to analyze the polymer obtained in Production Example 2, 20 ml of the reaction mixture was weighed and the solvent was evaporated under reduced pressure to obtain a halogenated phenoxyalkyl-terminated polyisobutylene polymer R-2. The molecular weight of R-2 (standard polystyrene) had number average molecular weight Mn of 11,360, molecular weight distribution Mw/Mn of 1.28, and introduction number of halogenated phenoxyalkyl terminal was 1.6.

Example 11

(53) Next, to 10 g of the solution of the polymer R-2 obtained in Production Example 2 (measured value: polymer concentration of 15.0 wt %), 0.145 g (1.3210.sup.3 mol) of potassium acrylate, and 0.0150 g (4.6510.sup.5 mol, 1.00 part by weight based on 100 parts by weight of the polymer) of tetrabutylammonium chloride were added, and the mixture was reacted at 60 C. for 4 hours. After the reaction, about 5 ml of the reaction solution was reprecipitated by adding it to a mixed solvent of acetone and methanol (mixing ratio of acetone/methanol=20 ml/20 ml) to isolate an acryloyl-terminated polyisobutylene polymer P-11. The introduction number of acryloyl groups was 0.66.

Example 12

(54) Acryloylation was carried out in the same manner as in Example 11 except that 0.0188 g (4.6510.sup.5 mol, 1.25 parts by weight relative to 100 parts by weight of the polymer) of methyltrioctylammonium bromide was used as the phase transfer catalyst to obtain an acryloyl-terminated isobutylene polymer P-12. The introduction number of the acryloyl group was 0.54.

Example 13

(55) Acryloylation was carried out in the same manner as in Example 11 except that 0.0294 g (4.6510.sup.5 mol, 1.96 parts by weight relative to 100 parts by weight of the polymer) of dimethyldioctadecylammonium bromide was used as the phase transfer catalyst to obtain an acryloyl-terminated polyisobutylene polymer P-13. The introduction number of acryloyl groups was 0.41.

Example 14

(56) Acryloylation was carried out in the same manner as in Example 11 except that 0.0162 g (4.6510.sup.5 mol, 1.08 parts by weight based on 100 parts by weight of the polymer) of trimethyloctadecylammonium chloride was used as the phase transfer catalyst to obtain an acryloyl-terminated polyisobutylene polymer P-14. The introduction number of acryloyl groups was 0.41.

Example 15

(57) Acryloylation was carried out in the same manner as in Example 11 except that 0.0130 g (4.6510.sup.5 mol, 0.87 parts by weight relative to 100 parts by weight of the polymer) of decyltrimethylammonium bromide was used as a phase transfer catalyst to obtain an acryloyl-terminated polyisobutylene polymer P-15. The introduction number of acryloyl groups was 0.10.

(58) As results of the above Examples 11 to 12, the catalyst having one methyl group or no methyl group as the substituent on the nitrogen atom of the ammonium salt has high catalytic activity in the acryloylation reaction. On the other hand, as shown in Examples 13 to 15, those containing two or more methyl groups as substituents on the nitrogen atom of the ammonium salt have catalytic activity. However, these are relatively lower activity than other ammonium salts.

(59) Although this reason is not necessarily clarified, when the phase transfer catalyst has more hydrophobicity and lower hydrophilicity, the dissolution into the organic phase and the approach to the halogenated phenoxyalkyl terminated polyisobutylene polymer become advantageous.

(60) Therefore, those having a substituent that makes the phase transfer catalyst more hydrophobic are effective in embodiments of the present invention, and for example, those having a large number of carbon atoms can be suitably used as a substituent on the ammonium salt.

(61) Next, in order to investigate the effect of adding the aprotic amphiphilic solvent, various aprotic amphiphilic solvents were added and the reaction was carried out. Here, the reaction was terminated at 60 C. for 4 hours, and the evaluation was carried out by comparing the number of acryloyl groups introduced into the polymer at that time.

Production Example 3

Production of Halogenated Phenoxyalkyl-Terminated Polyisobutylene Polymer (Component R-3)

(62) After replacing the inside of a 500 mL separable flask with nitrogen, 17 g of n-hexane (dried with molecular sieves) and 209 g of butyl chloride (dried with molecular sieves) were added, and a mixture was cooled to 70 C. while stirring under a nitrogen atmosphere. Subsequently, 140 mL (1.48 mol) of isobutylene, 2.00 g (8.65 mmol) of p-dicumyl chloride and 0.201 g (1.99 mmol) of triethylamine were added. After the reaction mixture was cooled to 70 C., 0.76 mL (6.92 mmol) of titanium tetrachloride was added to initiate polymerization.

(63) After the initiation of polymerization, the residual isobutylene concentration was measured by gas chromatography, and when the residual amount of isobutylene was less than 0.5%, 3.15 ml (19.9 mmol) of 3-phenoxypropyl bromide and 2.85 ml (26.0 mmol) of titanium tetrachloride were added. After stirring at 75 C. for 3 hours, the reaction solution was poured into another separable flask that contains a mixture of 478 g of water and 265 g of a mixed solution of n-hexane and butyl chloride (mixing ratio of butyl chloride:n-hexane=9:1, v/v) at 50 C. while stirring. Thereafter, the reaction mixture was kept stirred at 50 C. for 1 hour to deactivate the catalyst. After standing still for 30 minutes, the aqueous phase was discharged. Next, the organic phase was washed with 478 g of a 0.5 wt % sodium sulfate solution for 1 hour at 50 C. and then the mixture was stood still for next 30 minutes. Thereafter, the aqueous phase was taken out. The same procedure was repeated again to obtain the organic phase containing the reaction mixture.

(64) In order to analyze the polymer obtained in Production Example 3, 20 ml of the reaction mixture was weighed, and the solvent was evaporated under reduced pressure to obtain a halogenated phenoxyalkyl-terminated polyisobutylene polymer R-3. The molecular weight (standard polystyrene) of R-3 had number average molecular weight Mn of 13,036, molecular weight distribution Mw/Mn of 1.20, and introduction number of halogenated phenoxyalkyl groups of 1.8.

Example 16

(65) Next, to 10 g of the solution of the polymer R-3 obtained in Production Example 3 (measured value: polymer concentration of 15.0 wt %), 0.127 g (1.1510.sup.3 mol) of potassium acrylate, and 0.0150 g (4.6510.sup.5 mol, 1.00 parts by weight based on 100 parts by weight of the polymer) of tetrabutylammonium bromide were added, and the mixture was reacted at 60 C. for 4 hours. After the reaction, about 5 ml of the reaction solution was reprecipitated by adding it to a mixed solvent of acetone and methanol (mixing ratio of acetone/methanol=20 ml/20 ml) to isolate an acryloyl-terminated polyisobutylene polymer P-16. The introduction number of acryloyl groups was 0.79.

Example 17

(66) Further, to 10 g of a solution of the polymer R-3 obtained in Production Example 3 (measured value: polymer concentration of 15.0 wt %), 0.127 g (1.1510.sup.3 mol) of potassium acrylate, and 0.0150 g (4.6510.sup.5 mol, 1.00 parts by weight based on 100 parts by weight of the polymer) of tetrabutylammonium chloride, 0.5 g (33.3 parts by weight based on 100 parts by weight of the polymer) of N,N-dimethylacetamide were added, and the mixture was reacted at 60 C. for 4 hours. After the reaction, about 5 ml of the reaction solution was reprecipitated by adding it to a mixed solvent of acetone and methanol (mixing ratio of acetone/methanol=20 ml/20 ml) to isolate an acryloyl-terminated polyisobutylene polymer P-17. The introduction number of the acryloyl group was 1.51.

Example 18

(67) Acryloylation was carried out in the same manner as in Example 17 except that 0.5 g of N,N-dimethylformamide (33.3 parts by weight based on 100 parts by weight of the polymer) was used as the aprotic amphiphilic solvent to obtain an acryloyl-terminated polyisobutylene polymer P-18. The introduction number of the acryloyl group was 1.26.

Example 19

(68) Acryloylation was carried out in the same manner as in Example 17 except that 0.5 g of dimethylsulfoxide (33.3 parts by weight based on 100 parts by weight of the polymer) was used as the aprotic amphiphilic solvent to obtain an acryloyl-terminated polyisobutylene polymer P-19. The introduction number of the acryloyl group was 1.46.

Example 20

(69) Acryloylation was carried out in the same manner as in Example 17 except that 0.5 g of acetone (33.3 parts by weight based on 100 parts by weight of the polymer) was used as the aprotic amphiphilic solvent to obtain an acryloyl-terminated polyisobutylene polymer P-20. The introduction number of the acryloyl group was 0.81.

Example 21

(70) Acryloylation was carried out in the same manner as in Example 17 except that 0.5 g of tetrahydrofuran (33.3 parts by weight based on 100 parts by weight of the polymer) was used as the aprotic amphiphilic solvent to obtain an acryloyl-terminated polyisobutylene polymer P-21. The introduction number of acryloyl groups was 1.40.

Example 22

(71) Acryloylation was carried out in the same manner as in Example 17 except that 0.5 g of acetonitrile (33.3 parts by weight based on 100 parts by weight of the polymer) was used as the aprotic amphiphilic solvent to obtain an acryloyl-terminated polyisobutylene polymer P-22. The introduction number of acryloyl groups was 1.49.

Example 23

(72) Acryloylation was carried out in the same manner as in Example 17 except that 0.3 g of dimethylacetamide (20 parts by weight based on 100 parts by weight of the polymer) was used as the aprotic amphiphilic solvent to obtain an acryloyl-terminated polyisobutylene polymer P-23. The introduction number of the acryloyl group was 1.52.

Example 24

(73) Acryloylation was carried out in the same manner as in Example 17 except that 0.1 g of dimethylacetamide (6.7 parts by weight based on 100 parts by weight of the polymer) was used as the aprotic amphiphilic solvent to obtain an acryloyl-terminated polyisobutylene polymer P-24. The introduction number of the acryloyl group was 1.52.

Example 25

(74) Acryloylation was carried out in the same manner as in Example 17 except that 0.025 g of dimethylacetamide (1.67 parts by weight based on 100 parts by weight of the polymer) was used as the aprotic amphiphilic solvent to obtain an acryloyl-terminated polyisobutylene polymer P-25. The introduction number of the acryloyl group was 1.51.

Reference Example 1

(75) Acryloylation was carried out in the same manner as in Example 17 except that 0.5 g of methanol (33.3 parts by weight based on 100 parts by weight of the polymer) was used as the protic amphiphilic solvent instead of the aprotic amphiphilic solvent to obtain an acryloyl-terminated polyisobutylene polymer S-1. The introduction number of acryloyl groups was 0.01, and the acryloylation reaction was very slow.

Reference Example 2

(76) Acryloylation was carried out in the same manner as in Example 17 except that 0.5 g of ethanol (33.3 parts by weight based on 100 parts by weight of the polymer) was used as the protic amphiphilic solvent instead of the aprotic amphiphilic solvent to obtain an acryloyl-terminated polyisobutylene polymer S-2. The introduction number of the acryloyl group was 0.02, and the progress of the acryloylation reaction was very slow.

Reference Example 3

(77) Acryloylation was carried out in the same manner as in Example 17 except that 0.027 g of acrylic acid (1.8 parts by weight based on 100 parts by weight of the polymer) was used as the protic amphiphilic solvent instead of the aprotic amphiphilic solvent to obtain an acryloyl-terminated polyisobutylene polymer S-3. The introduction number of the acryloyl group was 0.01, and the progress of the acryloylation reaction was very slow.

Example 26

Production of Acryloyl-Terminated Polyisobutylene Polymer (Component P-26)

(78) After replacing the inside of a 500 mL separable flask with nitrogen, 17 g of n-hexane (dried with molecular sieves) and 209 g of butyl chloride (dried with molecular sieves) were added, and a mixture was cooled to 70 C. while stirring under a nitrogen atmosphere. Subsequently, 140 mL (1.48 mol) of isobutylene, 2.00 g (8.65 mmol) of p-dicumyl chloride and 0.201 g (1.99 mmol) of triethylamine were added. After the reaction mixture was cooled to 70 C., 0.76 mL (6.92 mmol) of titanium tetrachloride was added to initiate polymerization. After the initiation of polymerization, the residual isobutylene concentration was measured by gas chromatography, and when the residual amount of isobutylene was less than 0.5%, 3.15 g (19.9 mmol) of 3-phenoxypropyl bromide and 2.85 mL (26.0 mmol) of titanium tetrachloride were added. After stirring at 75 C. for 3 hours, the reaction solution was poured into another separable flask that contains a mixture of 478 g of water and 265 g of a mixed solvent of n-hexane and butyl chloride (mixing ratio: n-hexane:butyl chloride=1:9, v/v) at 50 C. while stirring. Thereafter, the reaction mixture was kept stirred at 50 C. for 1 hour to deactivate the catalyst. After standing still for 30 minutes, the aqueous phase was discharged. Next, the organic phase was washed with 478 g of a 0.5 wt % sodium sulfate solution for 1 hour at 50 C. and then the mixture was stood still for next 30 minutes. Thereafter, the aqueous phase was taken out. The same procedure was repeated again to obtain the organic phase.

(79) To this organic phase, 9.52 g (86.5 mmol) of potassium acrylate, 0.88 g (2.73 mmol) of tetrabutylammonium bromide, and 1.50 g of N,N-dimethylacetamide (1.70 parts by weight based on the theoretical yield of the polymer) were added and stirring was continued at 50 C. for 13 hours. Thereafter, 478 g of deionized water was added to the solution and the mixture was kept stirring at 50 C. for 1 hour. After standing for 30 minutes, the aqueous phase was discharged and the organic phase was washed with 478 g of water twice and separated.

(80) To the organic phase, 0.18 g of 4-methoxyphenol was added, and the solvent was evaporated under reduced pressure to obtain an acryloyl-terminated polyisobutylene polymer P-26. The molecular weight (standard polystyrene) of P-26 was found to be number average molecular weight Mn of 12,938, molecular weight distribution Mw/Mn of 1.19, introduction number of acryloyl group of 1.6, and APHA of 50.

(81) From the results of Examples 16 to 26 and Reference Examples 1 to 3 as described above, by allowing an aprotic amphiphilic solvent to coexist, the acryloylation reaction can be remarkably promoted and the productivity of the (meth) acryloyl-terminated polyisobutylene polymer can be increased. On the other hand, a protic amphiphilic solvent such as methanol, ethanol or acrylic acid inhibits the acryloylation reaction, indicating that the progress of the reaction is very slow.

(82) Next, the influence of water in the system on the acryloylation reaction was investigated.

Example 27

(83) Acryloylation was carried out in the same manner as in Example 17 except that 0.025 g of dimethylacetamide (1.67 parts by weight based on 100 parts by weight of the polymer) was used as the aprotic amphiphilic solvent and the reaction time was 2 hours to obtain an acryloyl-terminated polyisobutylene polymer P-27. The introduction number of the acryloyl group was 1.19. The polymer solution used in this example was obtained in Production Example 3 and its water content was 530 ppm.

Example 28

(84) To 50 g of the polymer solution obtained in Production Example 3 was added about 10 of magnesium sulfate, and stirring was continued at room temperature for 1 hour. Thereafter, the magnesium sulfate was filtered off and the water content of the obtained filtrate was measured to be 153 ppm.

(85) Acryloylation reaction was carried out for 2 hours in the same manner as in Example 26 except that the polymer solution thus obtained was used to obtain an acryloyl-terminated polyisobutylene polymer P-28. The introduction number of acryloyl groups was 1.44.

(86) From the results of Examples 27 and 28 as described above, in the acryloylation reaction, the reaction proceeds more rapidly as the water content decreases in the system. Therefore, when high productivity is desired, it may be preferable that the content of water in the reaction system is small.

(87) Next, investigation was carried out using crown ether as a phase transfer catalyst. From Example 29 below, the crown ether can also be suitably used as the phase transfer catalyst.

Example 29

(88) To a reaction system, 10 g of the solution of the polymer R-3 obtained in Production Example 3 (measured value: polymer concentration of 15.0 wt %), 0.127 g (1.1510.sup.3 mol) of potassium acrylate, and 0.123 g of 18-crown-6-ether (4.6510.sup.4 mol, 8.2 parts by weight based on 100 parts by weight of the polymer) were added and reacted at 60 C. for 4 hours. After the reaction, about 5 ml of the reaction solution was reprecipitated by adding it to a mixed solvent of acetone and methanol (mixing ratio of acetone/methanol=20 ml/20 ml) to isolate an acryloyl-terminated polyisobutylene polymer P-29. The introduction number of the acryloyl group was 1.33.

(89) Although the disclosure has been described with respect to only a limited number of embodiments, those skilled in the art, having benefit of this disclosure, will appreciate that various other embodiments may be devised without departing from the scope of the present invention. Accordingly, the scope of the invention should be limited only by the attached claims.