Macromonomers containing polyisobutene groups, and homopolymers or copolymers thereof

Abstract

The present invention describes novel macromonomers containing polyisobutene groups and homo- or copolymers thereof.

Claims

1. A process for preparing a compound (A) of the formula (I) ##STR00006## in which R.sup.1 to R.sup.5 are each independently selected from the group consisting of hydrogen, C.sub.1-C.sub.20-alkyl, C.sub.1-C.sub.20-alkyloxy and C.sub.5-C.sub.3500-polyisobutyl and C.sub.5-C.sub.3500-polyisobutenyl, R is an alkylene group having 2 to 10 carbon atoms, R.sup.6 is hydrogen or methyl, R.sup.7 is hydrogen, methyl or COOR.sup.8, R.sup.8 is hydrogen or C.sub.1-C.sub.20-alkyl and n is a positive integer from 1 to 50, with the proviso that at least one of the R.sup.1 to R.sup.5 radicals is a C.sub.5-C.sub.3500-polyisobutyl or C.sub.5-C.sub.3500-polyisobutenyl, and is derived from polyisobutene having a content of terminal double bonds of at least 50 mol %, based on the total number of polyisobutene macromolecules, wherein phenols of the formula ##STR00007## are reacted with alkylene carbonates of the formula ##STR00008## followed by a decarboxylation and subsequent esterification with (meth)acrylic acid, crotonic acid, fumaric acid, maleic acid or maleic anhydride, or by transesterification with (meth)acrylic esters, crotonic esters, fumaric esters or maleic esters.

2. The process as claimed in claim 1, wherein the alkylene carbonate is selected from the group consisting of 1,2-ethylene carbonate, 1,3-propylene carbonate and 1,2-propylene carbonate.

3. The process as claimed in claim 1, wherein the stoichiometry of 1 to 2 mol of carbonate:1 mol of phenol.

4. The process as claimed in claim 2, wherein the stoichiometry of 1.2 to 1.5 mol of carbonate:1 mol of phenol.

5. The process as claimed in claim 1, wherein the catalyst is selected from the group consisting of an inorganic salt, tertiary amine, triphenylphosphine, lithium hydride and organic stannate.

6. The process as claimed in claim 1, wherein the reaction is carried out at a temperature of 70 to 200° C.

7. The process as claimed in claim 1, wherein the reaction is carried out at a temperature of 150 to 170° C.

8. The process as claimed in claim 1, wherein the esterification with (meth)acrylic anhydride in the presence of at least one basic catalyst.

9. The process as claimed in claim 1, wherein the transesterification with C.sub.1-4 alkyl ester is a methyl ester, ethyl ester, n-propyl ester, isopropyl ester, n-butyl ester, sec-butyl ester, isobutyl ester or tert-butyl ester.

10. A fuel additive or a lubricant additive which comprises a copolymer comprising, in polymerized form, at least one compound (A) of the formula (I) ##STR00009## in which R.sup.1 to R.sup.5 are each independently selected from the group consisting of hydrogen, C.sub.1-C.sub.20-alkyl, C.sub.1-C.sub.20-alkyloxy and C.sub.5-C.sub.3500-polyisobutyl and C.sub.5-C.sub.3500-polyisobutenyl, R is an alkylene group having 2 to 10 carbon atoms, R.sup.6 is hydrogen or methyl, R.sup.7 is hydrogen, methyl or COOR.sup.8, R.sup.8 is hydrogen or C.sub.1-C.sub.2O-alkyl and n is a positive integer from 1 to 50, with the proviso that at least one of the R.sup.1 to R.sup.5 radicals is a C.sub.5-C.sub.3500-polyisobutyl or C.sub.5-C.sub.3500-polyisobutenyl, and is derived from polyisobutene having a content of terminal double bonds of at least 50 mol %, based on the total number of polyisobutene macromolecules, and at least one monomer (B) selected from the group consisting of (B1) (meth)acrylates other than (A), (B3) alkyl vinyl ethers (B4) styrene and α-methylstyrene and (B7) (meth)acrylamides.

11. The fuel additive or the lubricant additive as claimed in claim 10, wherein the monomer (B1) is methyl (meth)acrylate, ethyl (meth)acrylate, isopropyl (meth)acrylate, n-propyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, sec-butyl (meth)acrylate, tert-butyl (meth)acrylate, n-hexyl (meth)acrylate, n-heptyl (meth)acrylate, n-octyl (meth)acrylate, n-decyl (meth)acrylate, n-dodecyl (meth)acrylate, n-tetradecyl (meth)acrylate, n-hexadecyl (meth)acrylate, n-heptadecyl (meth)acrylate), n-octadecyl (meth)acrylate, n-eicosyl (meth)acrylate, 2-ethylhexyl (meth)acrylate and 2-propylheptyl (meth)acrylate, particular preference to methyl (meth)acrylate, ethyl (meth)acrylate, n-butyl (meth)acrylate, tert-butyl (meth)acrylate and 2-ethylhexyl (meth)acrylate.

12. The fuel additive or the lubricant additive as claimed in claim 10, wherein the proportions of compound (A) in the polymer in polymerized form is at least 1% by weight.

13. The fuel additive or the lubricant additive as claimed in claim 10, wherein the proportions of compound (A) in the polymer in the polymerized form is at least 1% by weight up to 100% by weight but without 100% (the homopolymer).

14. The fuel additive or the lubricant additive as claimed in claim 10, wherein the molecular weight as listed in mass-average molecular weight Mw of the polymers obtained is 5,000 g/mol or more.

15. The fuel additive or the lubricant additive as claimed in claim 10, wherein the molecular weight as listed in mass-average molecular weight Mw of the polymers obtained is 5,000 g/mol up to 1,000,000 g/mol.

16. The fuel additive or the lubricant additive as claimed in claim 10, wherein exactly one of the R.sup.1 to R.sup.5 radicals is C8-C3500-polyisobutyl or C8-C3500-polyisobutenyl.

17. The fuel additive or the lubricant additive as claimed in claim 10, wherein R.sup.3 is a C8-C3500-polyisobutyl or C8-C3500-polyisobutenyl radical and the other radicals are not.

18. The fuel additive or the lubricant additive as claimed in claim 10, wherein the R.sup.1 to R.sup.5 radicals that are not a polyisobutyl or polyisobutenyl radical are selected from the group consisting of hydrogen, methyl and tert-butyl.

19. The fuel additive or the lubricant additive as claimed in claim 10, wherein R is selected from the group consisting of 1,2-ethylene, 1,2-propylene, 1,2-butylene, 1-phenyl-1,2-ethylene and 2-phenyl-1,2-ethylene.

20. The fuel additive or the lubricant additive as claimed in claim 10, wherein n is 1.

Description

EXAMPLES

Analysis

(1) Size exclusion chromatography was conducted in THF+0.1% trifluoroacetic acid at 35° C. and a flow rate of 1 mL/min with a column combination of, if appropriate, a PLgel precolumn and two PLgel MIXED-B columns (I.D. 7.5 mm, length 30 cm, exclusion limit 500-10 000 000 g/mol). Calibration was effected with narrow-distribution polystyrene standards.

Example A

(2) 1775 g of polyisobutene (M.sub.n 1000 g/mol) were dissolved in 360 g of hexane. 345 g of phenol were initially charged in 180 g of toluene in a 4 L HWS vessel with base outlet, and cooled to 16° C. by means of a cooling thermostat. 32.7 g of BF.sub.3-phenol complex were added to the phenol solution. The polyisobutene solution was metered in at 16° C. within 5 h 30 min. The reaction was stirred at room temperature overnight and then terminated with 1 L of methanol. Workup and removal of excess phenol were effected by dilution with hexane and extraction with methanol. Conversion was determined by means of .sup.1H NMR (400 MHz in CDCl.sub.3).

(3) .sup.1H NMR (400 MHz in CDCl.sub.3) δ (ppm)=7.22 (m, 2H), 6.75 (m, 2H), 4.57 (s, 1H), 1.79 (s, 2H), 1.65-0.90 (CH.sub.3 and CH.sub.2, PIB), 0.81 (s, 6H).

Example B

(4) 1380 g of polyisobutene (M.sub.n 2300 g/mol) were dissolved in 400 g of hexane. 113 g of phenol were initially charged under nitrogen in 200 g of toluene in a 4 L HWS vessel with base outlet, and cooled to 19° C. by means of a cooling thermostat. 15.4 g of BF.sub.3-phenol complex were added dropwise to the phenol solution. The polyisobutene solution was metered in at 17-20° C. within 4 h. The reaction was stirred at room temperature for 48 h and then terminated with a methanol/hexane mixture (1 L/500 mL). Workup and removal of excess phenol were effected by extraction with methanol. Conversion was determined by means of .sup.1H NMR (400 MHz in CD.sub.2Cl.sub.2).

Example 1

(5) Transesterification was effected with introduction of lean air in a 4 L jacketed reactor equipped with an anchor stirrer, a lean air inlet, a separating column and a liquid divider. This apparatus was charged with 3383 g of a 30% solution of a monoethoxylated phenol bearing a polyisobutene radical according to example 9 in methyl methacrylate. 0.3 g of methylhydroquinone (MEHQ) and 14.9 g of potassium phosphate were added and the reaction mixture was heated up at a bath temperature of initially 110° C. with introduction of lean air (2 L/h). A pressure of 600 mbar (abs.) was established and an azeotrope of methanol and methyl methacrylate was distilled off continuously, in the course of which a liquid phase temperature at 84° C. to 87° C. was established. The reflux ratio was variable at 10:1 to 20:1 (reflux:efflux). After the reaction had ended, 15 g of Hyflo Super Cel® and 15 g of Ambosol® MP 25 were added to the product, which was filtered through a pressure filter at max. 2 bar, and the reaction mixture was concentrated under reduced pressure. 970 g of product were obtained. Conversion is determined as >99% via TAI NMR, The stabilizer content was 130 ppm MEHQ (determined by HPLC).

(6) .sup.1H NMR (400 MHz in CD.sub.2Cl.sub.2) δ (ppm)=7.28 (m, 2H), 6.83 (m, 2H), 6.11 (m, 1H), 5.58 (m, 1H), 4.46 (m, 2H), 4.20 (m, 2H), 1.94 (s, 3H), 1.82 (s, 2H), 1.65-0.90 (CH.sub.3 and CH.sub.2, PIB), 0.81 (s, 6H).

(7) The fluorine content (determined by combustion IC) was <1 ppm.

Example 2 (Comparative)

(8) Transesterification was effected with introduction of air in a 0.75 L jacketed reactor equipped with an anchor stirrer, an air inlet, a separating column and a liquid divider. This apparatus was initially charged with 50 g of a phenol bearing a polyisobutene radical, obtained analogously to example A, and 600 g of methyl methacrylate. 0.24 g of methylhydroquinone (MEHQ) and 0.75 g of potassium phosphate were added and the reaction mixture was heated up at a bath temperature of 115° C. with introduction of air (0.3 L/h). A pressure of 600 mbar (abs.) was established and MMA with a fraction of methanol was distilled off continuously, in the course of which a liquid phase temperature at 85° C. to 86° C. was established. After 6 h, the reaction mixture was filtered through a pressure filter at max. 2 bar and concentrated under reduced pressure. Conversion was determined via 1H NMR as 2.5%.

Example 3

(9) The reaction was effected in a 500 mL 4-neck round-bottom flask with oil bath heating, thermometer, reflux condenser, air inlet and half-moon Teflon stirrer. 145 g of a monoethoxylated phenol bearing a polyisobutene radical (prepared with 2-methylimidazole as catalyst according to example 9) which had been heated to 60° C. and 33 mg of tert-butylhydroxytoluene were initially charged at a bath temperature of 80° C. With introduction of air (about 0.3 L/h), at a temperature of 95° C., 18.9 g of methacrylic anhydride (94%, stabilized with Topanol® A) were added and the bath temperature was increased to 100° C. After 1.33 h, 80 mg of NaOH were added. After a total of 6 h, conversion was determined as >90% via TAI NMR. A further 1.6 g of methacrylic anhydride were metered in and the mixture was left to react at a bath temperature of 100° C. for a further 3 h. Conversion was now determined as >95% via TAI NMR.

(10) 111 g of the product were admixed with 3 g of n-butanol at 60° C., and the mixture was stirred for 1 h. The product phase was extracted 3× with 30 mL each time of methanol, and the methanolic phases were each removed and discarded. The product phase was concentrated under reduced pressure. The methacrylic acid content was 1% by weight; methacrylic anhydride is no longer found (determined via 1H NMR).

Example 4

(11) The reaction was effected in a 500 mL 4-neck round-bottom flask with oil bath heating, thermometer, reflux condenser, air inlet and half-moon Teflon stirrer. 145 g of a monoethoxylated phenol bearing a polyisobutene radical (prepared with 2-methylimidazole as catalyst according to example 9) which had been heated to 60° C. and 33 mg of tert-butylhydroxytoluene were initially charged at a bath temperature of 80° C. With introduction of air (about 0.3 L/h), at a temperature of 95° C., 19.7 g of methacrylic anhydride (94%, stabilized with Topanol® A) were added. After 2.75 h, 80 mg of NaOH were added and the bath temperature was increased to 100° C. After a total of 5.5 h, the reaction was ended and the product at 80° C. was discharged.

(12) Methacrylic acid was distilled out of the product under reduced pressure at 80° C. down to 2.2 mbar. The sample still comprised 2.3% methacrylic acid (determined via NMR). An about 50% solution in toluene was prepared. The solution was adjusted to a pH>12 with 32% aqueous NaOH and stirred at room temperature for 2 h. 10 g of Bentonit® and 10 g of Hyflo Super Cel® were added. This was followed by filtration through a pressure filter at max. 2 bar and concentration of the product under reduced pressure. Conversion was determined as >95% via TAI NMR. The methacrylic acid content was <0.25% by weight; methacrylic acid is no longer found (determined via NMR).

Example 5

(13) The reaction with ethylene carbonate was effected with introduction of nitrogen (about 0.3 L/h) in a 750 mL jacketed reactor equipped with an anchor stirrer, a gas inlet, a separating column and a liquid divider. This apparatus was initially charged with 230.2 g of a phenol bearing a polyisobutene radical of molar mass 1000 obtained analogously to example A, 21.9 g of ethylene carbonate and 4.1 g of potassium phosphate, and was heated up at a bath temperature of 177-180° C., in the course of which there was evolution of CO.sub.2. The internal temperature was 169-170° C. After 7.5 h, the mixture was cooled down to 60° C. 500 g of methyl methacrylate and 0.1 g of MEHQ were added. The reaction mixture was heated up at a temperature of 115° C. with introduction of air (about 0.3 L/h). A pressure of 600 mbar (abs.) was established and an azeotrope of methanol and methyl methacrylate was distilled off continuously, in the course of which a liquid phase temperature at 84° C. to 87° C. was established. The distillates were collected and analyzed for their methanol content. After the reaction had ended, the product was filtered through a pressure filter at max. 2 bar and the reaction mixture was concentrated under reduced pressure. Conversion was determined as >99% via TAI NMR.

Example 6

(14) The transesterification was effected with introduction of air in a 750 mL jacketed reactor equipped with an anchor stirrer, an air inlet, a separating column and a liquid divider. This apparatus was charged with 990 g of a 29.3% solution of a monoethoxylated phenol bearing a polyisobutene radical according to example 9 (prepared with 2-methylimidazole as catalyst) in methyl methacrylate. 0.495 g of methylhydroquinone (MEHQ) was added and 150 mL of methyl methacrylate were distilled off with introduction of air at bath temperature 95° C. and a reduced pressure of 300 mbar abs.

(15) 150 mL of methyl methacrylate were added and the reaction mixture was heated up at a bath temperature of 120° C. at standard pressure with introduction of air (0.3 L/h). 2.3 g of tetraisopropyl titanate were added and an azeotrope of methanol and methyl methacrylate was distilled off continuously at a bath temperature of 125° C. and a reduced pressure of 700 mbar abs., in the course of which a liquid phase temperature of 90° C. is established.

(16) After the reaction had ended, the reaction mixture was analyzed. Conversion was determined as 14% via TAI NMR.

Example 7

(17) The reaction was effected in a 500 mL 4-neck round-bottom flask with oil bath heating, thermometer, reflux condenser, water separator, air inlet and half-moon Teflon stirrer. 145 g of a monoethoxylated phenol bearing a polyisobutene radical according to example 9 (prepared with 2-methylimidazole as catalyst) which had been heated to 60° C., 100 g of toluene, 10.3 g of methacrylic acid (stabilized with 200 ppm of MEHQ), 0.76 g of p-toluene sulfonic acid monohydrate and 49 mg of MEHQ were initially charged at a bath temperature of 80° C. The reaction mixture was heated up. At a bath temperature of 127° C., the mixture started to boil. The bath temperature was raised to 140° C. in the course of the reaction. A further 1.17 g of p-toluenesulfonic acid monohydrate were added. After a total reaction time of 4.5 h, no water had formed to any significant degree (about 0.2 mL of water). The reaction mixture was cooled down and then, at a liquid phase temperature of 95° C., 7.7 g of methanesulfonic acid and a further 5.1 g of methacrylic acid were added. The bath temperature was adjusted again to 140° C. Within a further 3 h of reaction time, a total of 72% of the expected amount of water was separated out, and no further water distilled over within a further hour (total reaction time then 8.5 h). The reaction was stopped.

Example 9

(18) A phenol bearing a polyisobutene radical obtained analogously to example A (1 eq.) and ethylene carbonate (1.1 eq.) were mixed under a nitrogen atmosphere and heated up to 100° C. 2-Methylimidazole (0.6% by weight) was added and the reaction mixture was gradually heated up to 150° C. within 5 hours until no further evolution of gas was observed. From 140° C., discoloration of the reaction mixture from pale yellow to brown/black was observed. Conversion was monitored by means of .sup.1H NMR spectroscopy.

Example 11

(19) A phenol bearing a polyisobutene radical obtained analogously to example A (1 eq.) and ethylene carbonate (1.3 eq.) were mixed under a nitrogen atmosphere and heated to 170° C. Potassium phosphate (1.46 wt %) was added and the reaction mixture was stirred at 170° C. for 6 hours until no further evolution of gas was observed. No discoloration was observed. Conversion was monitored by means of .sup.1H NMR spectroscopy.

Example 12

(20) A phenol bearing a polyisobutene radical obtained analogously to example B (1 eq.) and ethylene carbonate (1.3 eq.) were mixed under a nitrogen atmosphere and heated to 110° C. Potassium phosphate (1.46% by weight) was added and the reaction mixture was stirred under reduced pressure at 120-170° C. for 48 h.

(21) Conversion was monitored by means of .sup.1H NMR spectroscopy.

Example 13

(22) Transesterification was effected with introduction of lean air in a 4 L jacketed reactor equipped with a multilevel beam stirrer, a lean air inlet, a separating column and a liquid divider. This apparatus was charged with a solution of 450 g of a monoethoxylated phenol bearing a polyisobutene radical according to example 12 in 1500 g of methyl methacrylate. 0.13 g of methylhydroquinone (MEHQ) and 10.5 g of potassium phosphate were added and the reaction mixture was heated up at a bath temperature of initially 115° C. with introduction of lean air (0.5 L/h). A pressure of 600 mbar (abs.) was established and an azeotrope of methanol and methyl methacrylate was distilled off continuously, in the course of which a liquid phase temperature at 84° C. was established. The reflux ratio was 20:1 (reflux:efflux). The bath temperature was lowered to 110° C. in the course of the reaction. After the reaction had ended, the reaction mixture was filtered through a pressure filter at max. 2 bar and concentrated at bath temperature 75° C. under reduced pressure. 449 g of product were obtained. Conversion is determined as >99% via TAI NMR.

Homopolymerizations

Solution Polymerization

Polymerization Example 1

(23) Polymerization was effected under a gentle nitrogen stream in a 4 L jacketed vessel with heating circuit, circulation pump, pilot stirrer, long jacketed coil condenser, anchor stirrer and stirrer motor. 98.17 g of the product from example 3 were initially charged in 391.32 g of orthoxylene and heated up to 80° C. At an internal temperature of 79° C., 0.26 g of tert-butyl acrylate (75%) in 19.63 g of ortho-xylene was metered in within 3 hours. The mixture was then heated up to 90° C. within 15 min, and 0.18 g of tert-butyl peroctoate in 19.63 g of orthoxylene was metered in within 30 min. Conversion was determined by means of .sup.1H NMR as 55%. An M.sub.W of 27 700 g/mol (PDI=12.4) was determined by means of GPC (RI detector) and an M.sub.W of 25 000 g/mol by means of GPC (MALLS).

Miniemulsion Polymerization

Polymerization Example 2

(24) 21.5 g of the product from example 3 were first dissolved in 31.5 g of hexane. 70.88 g of water and 3.68 g of Disponil® FES 27 were premixed in a 250 mL vessel and the macromonomer solution was added gradually. The preemulsion formed was further emulsified with vigorous stirring for 50 min. Subsequently, the preemulsion was treated at the highest level with an ultrasound probe at 400 W and 24 kHz for 2 min. This cooled the emulsion. The miniemulsion was then introduced into a 250 mL stirrer apparatus and inertized by a nitrogen stream at 150 rpm for 10 min. The internal temperature was adjusted to 70° C., and 2.15 g of 10% Cert-butyl hydroperoxide solution were added. Subsequently, 17.2 g of a 2% sodium acetonebisulfite solution were metered in with a feed time of 3 hours.

(25) The molar mass (M.sub.W) of the dispersion obtained was determined by means of GPC (RI detector) as 293 000 g/mol and GPC (UV 275 nm) as 326 000 g/mol.

(26) The molar mass (M.sub.n) of the dispersion obtained was determined by means of GPC (RI detector) as 5720 g/mol and GPC (UV 275 nm) as 6590 g/mol. The low M.sub.n values are attributable here to residual monomers.

Copolymers

Polymerization Example 3

(27) 30 g of the product from example 3 and 30 g of methyl methacrylate were initially charged in 207 g of toluene and heated up to 80° C. 5% of a solution of 4 g of tert-butyl pivalate (75%) in 37.33 g of toluene were metered in within one minute and stirred (150 rpm) at 80° C. for 10 min, before the remaining 95% of the solution were metered in within 4.5 hours. After the metered addition had ended, the mixture was stirred at 80° C. for a further 1.5 hours.

Polymerization Example 4

(28) 45 g of the product from example 3 and 15 g of methyl methacrylate were initially charged in 207 g of toluene and heated up to 80° C. 5% of a solution of 4 g of tert-butyl pivalate (75%) in 37.33 g of toluene were metered in within one minute and stirred (150 rpm) at 80° C. for 10 min, before the remaining 95% of the solution were metered in within 4.5 hours. After the metered addition had ended, the mixture was stirred at 80° C. for a further 1.5 hours.