Preparation of diesters of (meth)acrylic acid from epoxides

Abstract

The invention relates to a method for preparation of diesters from anhydrides of carboxylic acids.

Claims

1. A process for preparation of a diester of general Formula (I): ##STR00016## wherein: R.sup.1 is a hydrogen atom or a methyl group; R.sup.2 to R.sup.6 are independently selected from hydrogen atoms or optionally substituted aliphatic or aromatic substituents having up to 17 carbon atoms; wherein the process comprises at least process step (a): (a) reacting a (meth)acrylic anhydride of general Formula (II): ##STR00017## with an epoxide of general Formula (III): ##STR00018## to deliver a product mixture comprising the diester of general Formula (I); wherein the reaction is carried out in the presence of a catalyst in combination with a co-catalyst, wherein: the catalyst comprises a first catalyst, a second catalyst or a combination of both, and: the first catalyst is a halide of magnesium or a trifluoromethanesulfonate of a rare earth element; and the second catalyst is a chromium (III) salt; the co-catalyst is selected from the group consisting of: a tertiary amine; a quaternary ammonium salt; a tertiary phosphine; and a quaternary phosphonium salt.

2. The process of claim 1, wherein: R.sup.1 is a hydrogen atom, R.sup.2 is a vinyl group, and the (meth)acrylic anhydride of formula (II) is acrylic acid anhydride; or alternatively: R.sup.1 is a methyl group, R.sup.2 is a 1-methylvinyl group and the (meth)acrylic anhydride of formula (II) is methacrylic acid anhydride.

3. The process of claim 1, wherein the optionally substituted aliphatic or aromatic substituents having up to 17 carbon atoms are selected from the group consisting of: optionally substituted alkyl, cycloalkyl, alkenyl, or alkadienyl substituents having up to 17 carbon atoms optionally substituted with one substituent R.sup.7 selected from: a halogen atom, —CN, —SCN, —OCN, and —NCO.

4. The process of claim 1, wherein the epoxide of general Formula (III) is selected from the group consisting of: ethylene oxide; propylene oxide; 1-hexene oxide; cyclohexene oxide; cyclopentene oxide; 1-butene oxide; 2-butene oxide; isobutene oxide; styrene oxide; and glycidyl methacrylate.

5. The process of claim 1, wherein process step (a) is carried out in the presence of the first catalyst, the second catalyst and the co-catalyst.

6. The process of claim 1, wherein the co-catalyst is a quaternary ammonium salt.

7. The process of claim 1, wherein the co-catalyst is selected from the group consisting of: tetrabutylammonium chloride; tetrabutylammonium bromide; tetraethylammonium chloride; tetrabutylammonium acetate; tetramethylammonium chloride; tetrapentylammonium bromide; cetyl-trimethylammonium bromide; 1-butyl-3-methyl-imidazolyl chloride; cetylpyridinium chloride; and triethylbenzylammonium chloride.

8. The process of claim 1, wherein the second catalyst is a chromium (III) carboxylate.

9. The process of claim 8, wherein the chromium (III) carboxylate is selected from the group consisting of: chromium (III) 2-ethylhexanoate; chromium (III) heptanoate; chromium (III) acetate; and chromium (III) methacrylate.

10. The process of claim 1, wherein the total amount of the first catalyst in process step (a) is between 0.001 mol.-% and 10 mol.-%, based on the amount of the epoxide of general Formula (III).

11. The process of claim 1, wherein the total amount of the second catalyst in process step (a) is between 0.001 mol.-% and 10 mol.-%, based on the amount of the epoxide of general Formula (III).

12. The process of claim 1, wherein the total amount of the co-catalyst in process step (a) is between 0.001 mol.-% and 10 mol.-%, based on the amount of the epoxide of general Formula (III).

13. The process of claim 1, wherein the molar ratio anhydride of the general Formula (II): epoxide of the general Formula (III) in process step (a) is between 5:1 and 1:0.1.

14. The process of claim 1, wherein the temperature during process step (a) is in the range 20° C. to 140° C.

15. The process of claim 1, wherein the process is carried out in the presence of at least 10 mol % excess of the anhydride.

16. The process of claim 15, further comprising process steps (b) and (c) which are carried out after process step (a): (b) adding an auxiliary alcohol to the product mixture obtained in process step (a) to form a product mixture comprising the diester of the general Formula (I) and an ester of the auxiliary alcohol; and (c) removing of the ester of the auxiliary alcohol from the product mixture obtained in process step (b); wherein the auxiliary alcohol is a primary or secondary alcohol having a boiling point of not more than 150° C., measured at a pressure of 10.sup.5 Pa.

17. The process of claim 16, wherein, in process step (c), the ester of the auxiliary alcohol is removed from the product mixture by distillation.

18. The process of claim 17, wherein, in process step (a) the epoxide of general Formula (III) is selected from the group consisting of: ethylene oxide; propylene oxide; 1-hexene oxide; cyclohexene oxide; cyclopentene oxide; 1-butene oxide; 2-butene oxide; isobutene oxide; styrene oxide; and glycidyl methacrylate.

19. The process of claim 18, wherein process step (a) is carried out in the presence of the first catalyst, the second catalyst and the co-catalyst.

20. The process of claim 19, wherein the co-catalyst is selected from the group consisting of: tetrabutylammonium chloride; tetrabutylammonium bromide; tetraethylammonium chloride; tetrabutylammonium acetate; tetramethylammonium chloride; tetrapentylammonium bromide; cetyl-trimethylammonium bromide; 1-butyl-3-methyl-imidazolyl chloride; cetylpyridinium chloride; and triethylbenzylammonium chloride; and the second catalyst is a chromium (III) carboxylate.

Description

EXAMPLES

Abbreviations

(1) AAH acrylic acid anhydride

(2) Ac.sub.2O acetic acid anhydride

(3) CHO cyclohexene oxide

(4) DMAP dimethylaminopyridine

(5) EO ethylene oxide

(6) GC gas chromatography

(7) MAAH methacrylic acid anhydride

(8) MSAA methanesulfonic acid anhydride

(9) PO propylene oxide

(10) PPG polypropylene glycol

(11) SO styrene oxide

(12) TEBAC triethylbenzylammonium chloride

(13) THE tetrahydrofurane

GENERAL REMARKS

(14) All materials were used as commercially available without further purification.

(15) All employed (meth)acrylic anhydrides were stabilized with 2000 ppm (by weight) of 2,4-dimethyl-6-tert-butylphenol.

Example 1 (Comparative): Reaction Between MAAH and PO in the Absence of any Catalyst

(16) ##STR00011##

(17) In a 15 ml pressure tube with magnetic stirrer, 3.08 g (0.02 mol) methacrylic acid anhydride (MAAH) were placed and 1.16 g (0.02 mol) propylene oxide (PO) were carefully added dropwise. No exothermic reaction could be monitored. The tube was sealed with a Teflon® plug and heated for 3 h to 70° C.

(18) Subsequently, the sample was cooled to room temperature and analyzed using gas chromatography (GC).

(19) Result (GC area-%):

(20) TABLE-US-00001 PO 27.30% MAAH 70.81% product: none

(21) No uncatalysed reaction between MAAH and PO took place.

Examples 2-7 (Comparative): Reaction Between MAAH and PO in Presence of a First Catalyst, a Second Catalyst or a Co-Catalyst

(22) A first catalyst, a second catalyst or a co-catalyst specified in Table 1 was placed in a 15 ml pressure tube with magnetic stirrer, 3.08 g (0.02 mol) MAAH was added and 1.16 g (0.02 mol) PO were carefully added dropwise. The tube was sealed with a Teflon® plug and heated afterwards for 3 h to 70° C.

(23) After the time had elapsed, the sample was cooled to room temperature and analyzed using GC.

(24) TABLE-US-00002 TABLE 1 Catalyst tested for the reaction between MAAH and PO MAAH, PO, Product, Catalyst/ GC GC GC Ex. co-catalyst Amount Color area % area % area-% 2 MgBr.sub.2*6 H.sub.2O 0.006 g colorless 69.59 26.04  1.43 (0.1 mol.-%, rel. to PO) 3 lanthanum (III) 0.012 g colorless 68.95 16.07  0.51 triflate (0.1 mol.-%, rel. to PO) 4 triethylbenzyl- 0.091 g orange 31.28 15.57 33.05 ammonium (2 mol.-%, chloride rel. to PO) (TEBAC) 5 H.sub.2SO.sub.4 0.020 g colorless 67.78 23.31  0.29 (1 mol.-%, rel. to PO) 6 Cr(III) 2-ethyl- 0.064 g green 72.50 18.52  2.14 hexanoate (1.5 wt.-% (7 wt.-%) in rel. to entire polypropylene batch) glycol 400 7 DMAP 0.049 g black 43.20 18.60 28.90 (2 mol.-% rel. to PO)

(25) DMAP and TEBAC showed some catalytic activity so that minor amounts of the desired product could be detected.

(26) Furthermore, small amounts of the desired product were detected in the presence of chromium (Ill) carboxylates and MgBr.sub.2. These results are surprising, because MgBr.sub.2 is known to be a highly active catalyst for activation of anhydrides.

Examples 8-14: Reaction Between MAAH and PO in Presence of a Catalyst/Co-Catalyst

(27) A catalyst/co-catalyst as specified in Table 2 in combination listed in Table 3 was placed in a 15 ml pressure tube with magnetic stirrer, 3.08 g (0.02 mol) MAAH was added and 1.16 g (0.02 mol) PO were carefully added dropwise. The tube was sealed with a Teflon® plug and heated afterwards for 3 h to 70° C.

(28) After the time had elapsed, the sample was cooled to room temperature and analyzed using GC.

(29) TABLE-US-00003 TABLE 2 Catalysts/co-catalysts for reaction between MAAH and PO in Table 3. Nr. Catalyst/co-catalyst Amount 1 MgBr.sub.2*6 H.sub.2O 0.006 g (0.1 mol.-%, rel. to PO)   2 TEBAC 0.091 g (2 mol.-%, rel. to PO) 3 Cr(III) 2-ethyl-hexanoate (7 wt.-%) 0.064 g in polypropylene glycol 400 (1.5 wt.-% rel. to entire batch) 4 dimethylaminopyridine (DMAP) 0.049 g (2 mol.-% rel. to PO)

(30) TABLE-US-00004 TABLE 3 Catalyst/co-catalyst combinations tested for the reaction between MAAH and PO MAAH PO Product GC GC GC Ex. Catalytic system Color Comment area-% area-% area-%  8 1 + 3 green 61.431 15.638  4.051 MgBr.sub.2*6 H.sub.2O/ Cr.sup.3+  9 1 + 2 colorless 32.735 12.604 45.705 MgBr.sub.2*6 H.sub.2O/ TEBAC 10 3 + 4 black solids  0.093  1.652 83.862 Cr.sup.3+/DMAP precipitated 11 1 + 3 + 4 black solids  0.156  1.567 87.153 MgBr.sub.2*6 H.sub.2O/ precipitated Cr.sup.3+/DMAP 12 1 + 2 + 4 brown 18.431 10.151 54.827 MgBr.sub.2*6 H.sub.2O/ TEBAC/DMAP 13 1 + 2 + 3 black solid  0.082  1.195 89.643 MgBr.sub.2*6 H.sub.2O/ precipitated TEBAC/Cr.sup.3+ 14 2 + 3 + 4 black  0.028  0.632 82.181 TEBAC/Cr.sup.3+/ DMAP

(31) Catalytic systems comprising a combination of a co-catalyst with a first catalyst and/or with the second catalyst show a good catalytic activity. In contrast, a combination of a first catalyst and a second catalyst is not catalytically active in the absence of a co-catalyst.

Examples 15-18: Reaction Between MAAH and PO in Presence of Varying Amounts of a Chromium Catalyst

(32) A catalyst/co-catalyst mixture, containing different amounts of MgBr.sub.2 with a Cr(III) salt and TEBAC selected from Table 4 was placed in a 15 ml pressure tube with magnetic stirrer, 3.08 g (0.02 mol) MAAH was added and 1.16 g (0.02 mol) PO were carefully added dropwise. The tube was sealed with a Teflon® plug and heated afterwards for 3 h to 70° C.

(33) After the time had elapsed, the sample was cooled to room temperature and analyzed using GC.

(34) TABLE-US-00005 TABLE 4 Catalytic systems for the reaction between MAAH and PO in Table 5 Nr. Catalyst/co-catalyst 1 0.0058 g MgBr.sub.2*6 H.sub.2O 0.1 mol.-% rel. to PO 0.0911 g TEBAC 2 mol.-% rel. to PO 0.0424 g Cr(III) * 1 wt.-% rel. to entire batch 2 0.0058 g MgBr.sub.2*6 H.sub.2O 0.1 mol.-% rel. to PO 0.0911 g TEBAC 2 mol.-% rel. to PO 0.0212 g Cr(III) * 0.5 wt.-% rel. to entire batch 3 0.0058 g MgBr.sub.2*6 H.sub.2O 0.1 mol.-% rel. to PO 0.0456 g TEBAC 2 mol.-% rel. to PO 0.0637 g Cr(III) * 1.5 wt.-% rel. to entire batch 4 0.0058 g MgBr.sub.2*6 H.sub.2O 0.1 mol.-% rel. to PO 0.0456 g TEBAC 2 mol.-% rel. to PO 0.0318 g Cr(III) * 0.75 wt % rel. to entire batch * Cr(III) = Cr(III) 2-ethyl-hexanoate (7 wt.-%) in polypropylene glycol 400

(35) TABLE-US-00006 TABLE 5 Catalyst combinations tested for the reaction between MAAH and PO Catalytic system MAAH PO Product from GC GC GC Ex. Table 4 Color Comment area-% area-% area-% 15 1 brown solids precipitated 0.136 1.110 91.464 16 2 grey solids precipitated 0.096 0.939 91.450 17 3 brown solids precipitated 0.104 1.197 90.395 18 4 green solids precipitated 0.100 1.241 91.346

(36) The results show that the amount of the chromium (Ill) catalyst in the catalytic system can be varied within abroad range without noticeable change in observed product yields.

Examples 19-23: Reaction Between MAAH and PO in Presence Different Catalyst Amounts

(37) A catalyst/co-catalyst mixture, containing different amounts of MgBr.sub.2 with Cr(III) salt and TEBAC selected from Table 6 was placed in a 15 ml pressure tube with magnetic stirrer, 3.08 g (0.02 mol) MAAH was added and 1.16 g (0.02 mol) PO were carefully added dropwise. The tube was sealed with a Teflon® plug and heated afterwards for 3 h to 70° C.

(38) After the time had elapsed, the sample was cooled to room temperature and analyzed using GC.

(39) TABLE-US-00007 TABLE 6 Catalytic system for the reaction between MAAH and PO in Table 7 Nr. Catalyst/co-catalyst 1 0.0058 g MgBr.sub.2*6 H.sub.2O 0.10 mol.-% rel. to PO 0.0456 g TEBAC 1.00 mol.-% rel. to PO 0.0318 g Cr(III) * 0.75 wt.-% rel. to entire batch 2 0.0117 g MgBr.sub.2*6 H.sub.2O 0.20 mol.-% rel. to PO 0.0228 g TEBAC 0.50 mol.-% rel. to PO 0.0318 g Cr(III) * 0.75 wt.-% rel. to entire batch 3 0.0117 g MgBr.sub.2*6 H.sub.2O 0.20 mol.-% rel. to PO 0.0228 g TEBAC 0.50 mol.-% rel. to PO 0.0212 g Cr(III) * 0.50 wt.-% rel. to entire batch 4 0.0117 g MgBr.sub.2*6 H.sub.2O 0.20 mol.-% rel. to PO 0.0114 g TEBAC 0.25 mol.-% rel. to PO 0.0212 g Cr(III) * 0.50 wt.-% rel. to entire batch 5 0.0117 g MgBr.sub.2*6 H.sub.2O 0.20 mol.-% rel. to PO 0.0114 g TEBAC 0.25 mol.-% rel. to PO 0.0106 g Cr(III) * 0.25 wt.-% rel. to entire batch * Cr(III) = Cr(III) 2-ethyl-hexanoate (7 wt.-%) in polypropylene glycol 400

(40) The composition of the obtained product mixtures is summarized in Table 7.

(41) TABLE-US-00008 TABLE 7 Catalyst combinations tested for the reaction between MAAH and PO Catalytic system MAAH PO Product from GC GC GC Ex. Table 6 Color Comment area-% area-% area-% 19 1 brown 0.136 0.637 88.176 20 2 grey 0.096 1.007 91.955 21 3 grey 0.104 1.136 89.036 22 4 grey 0.100 1.843 87.998 23 5 green solids 8.912 4.353 75.943 precipitated

(42) All tested catalytic systems allowed preparation of the desired product in good yields.

Examples 24-29: Reaction Between MAAH and PO at 70° C. in Presence of a Catalyst/Co-Catalyst Mixture with Different Reaction Times

(43) A catalyst/co-catalyst mixture, containing 0.0117 g MgBr.sub.2*6 H.sub.2O with 0.0318 g Cr(III) 2-ethylhexanoate (7 wt.-%) in polypropylene glycol 400 and 0.0228 g TEBAC was placed in a 15 ml pressure tube with magnetic stirrer, 3.08 g (0.02 mol) MAAH was added and 1.16 g (0.02 mol) PO were carefully added dropwise. The tube was sealed with a Teflon® plug and heated afterwards for different time (cf. Table 8) to 70° C.

(44) After the time had elapsed, the sample was cooled to room temperature and analyzed using GC.

(45) TABLE-US-00009 TABLE 8 Catalyst combinations tested for the reaction between MAAH and PO MAAH PO Product Reaction GC GC GC Ex. time Color Comment area-% area-% area-% 24 0.5 h green 15.841 8.145 64.961 25 1.0 h green solids  3.004 2.299 82.957 precipitated 26 1.5 h green  0.137 1.117 87.432 27 2.0 h green-gray  0.100 1.860 88.983 28 2.5 h dark-green  0.096 1.820 87.229 29 3.0 h dark-green  0.116 0.679 89.018

(46) All reactions were substantially complete at 70° C. after 90 min of reaction time.

Examples 30-32: Reaction Between MAAH and PO at 60° C. in Presence of a Catalyst/Co-Catalyst Mixture with Different Reaction Times

(47) A catalyst/co-catalyst mixture, containing 0.0117 g MgBr.sub.2*6 H.sub.2O with 0.0318 g Cr(III) 2-ethylhexanoate (7 wt.-%) in polypropylene glycol 400 and 0.0228 g TEBAC was placed in a 15 ml pressure tube with magnetic stirrer, 3.08 g (0.02 mol) MAAH was added and 1.16 g (0.02 mol) PO were carefully added dropwise. The tube was sealed with a Teflon® plug and heated afterwards for different time (cf. Table 9) to 60° C.

(48) After the time had elapsed, the sample was cooled to room temperature and analyzed using GC.

(49) TABLE-US-00010 TABLE 9 Catalyst combinations tested for the reaction between MAAH and PO Reaction MAAH PO Product Ex. time Color GC area-% GC area-% GC area-% 30 2.0 h green 5.766 3.490 79.281 31 4.0 h green 0.121 0.859 89.837 32 6.0 h green 0.073 2.644 89.261

(50) The reaction rate follows the Arrhenius equation and the reaction can be carried out within a broad temperature range.

Examples 33-37 (Comparative): Reaction Between MAAH and PO in Presence of a Co-Catalyst

(51) A catalytic system from Table 10 was placed in a 15 ml pressure tube with magnetic stirrer, 3.08 g (0.02 mol) MAAH was added and 1.16 g (0.02 mol) PO were carefully added dropwise. The tube was sealed with a Teflon® plug and heated afterwards for 3 h to 70° C.

(52) After the time had elapsed, the sample was cooled to room temperature and analyzed using GC.

(53) TABLE-US-00011 TABLE 10 Co-catalysts tested for the reaction between MAAH and PO MAAH PO Product GC GC GC Ex. Catalyst Amount Color area-% area-% area-% 33 Tributyl- 0.0817 g clear, 64.989 11.327 10.322 phosphine (2.0 mol.-%, red- rel. to PO) brown 34 Tetrabutylphos- 0.1180 g clear, 39.217 16.600 31.315 phonium (2.0 mol.-%, color- chloride rel. to PO) less 35 Triethylamine 0.0202 g clear, 63.161 25.711  2.651 (1.0 mol.-%, color- rel. to PO) less 36 Triphenyl- 0.0525 g clear, 60.711 24.228  3.660 phosphine (1.0 mol.-%, red- rel. to PO) orange 37 Triethyl- 0.1598 g clear, 64.691 26.435  0.027 sulfonium (2.0 wt.-% color- bis(trifluoro- rel. to entire less methyl- batch) sulfonyl)imide

(54) In all tests only minor amounts of the desired product were detected. This indicates that co-catalysts of the present invention (tertiary amines and phosphines) have an insufficiently low catalytic activity in the absence of a first catalyst or a second catalyst.

Examples 38-39: Reaction Between MAAH and PO

(55) Catalytic systems of Table 11 were placed in a 15 ml pressure tube with magnetic stirrer, 3.08 g (0.02 mol) MAAH was added and 1.16 g (0.02 mol) PO were carefully added dropwise. The tube was sealed with a Teflon® plug and heated afterwards for 3 h to 70° C.

(56) After the time had elapsed, the sample was cooled to room temperature and analyzed using GC.

(57) TABLE-US-00012 TABLE 11 Catalytic system for the reaction between MAAH and PO in Table 12 Nr. Catalyst/co-catalyst 1 MgBr.sub.2*6 H.sub.2O 0.20 mol.-% rel. to PO tributylphosphine 2.00 mol.-% rel. to PO Cr(III) * 0.22 mol.-% rel. to PO 2 MgBr.sub.2*6 H.sub.2O 0.20 mol.-% rel. to PO tetrabutylphosphonium 2.00 mol.-% rel. to PO chloride Cr(III) * 0.22 mol.-% rel. to PO * Cr(III) = Cr(III) 2-ethyl-hexanoate (7 wt.-%) in polypropylene glycol 400

(58) The composition of the obtained product mixtures is summarized in Table 12.

(59) TABLE-US-00013 TABLE 12 Catalyst combinations tested for the reaction between MAAH and PO Catalytic system MAAH PO Product Ex. from Table 11 Color GC area-% GC area-% GC area-% 38 1 clear, light 1.7 1.3 82.0 brown 39 2 clear, green 1.1 0.6 83.0

(60) Use of the catalytic system of the present invention allowed preparation of the desired products in good yields.

Examples 40-41 (Comparative): Reaction Between MAAH and THF in Presence of a Co-Catalyst

(61) A catalyst/co-catalyst from Table 13 was placed in a 15 ml pressure tube with magnetic stirrer, 3.08 g (0.02 mol) MAAH was added and 1.4422 g (0.02 mol)tetra hydrofurane (THE) were added. The tube was sealed with a Teflon® plug and heated afterwards for 3 h to 70° C.

(62) After the time had elapsed, the sample was cooled to room temperature and analyzed using GC.

(63) TABLE-US-00014 TABLE 13 Catalyst tested for the reaction between MAAH and THF MAAH THF Product Catalyst/ GC GC GC Ex. co-catalyst Amount Color area-% area-% area-% 40 TEBAC 0.0911 g clear, 63.856 34.177 none (2.0 mol.-%, colorless, rel. to THF) with solids 41 H.sub.2SO.sub.4, 0.0144 g clear, 63.367 33.908 none conc. (1.0 wt.-%, colorless rel. to THF)

(64) MAAH did not react with THE under employed conditions and no reaction products were obtained.

Examples 42-47: Reaction Between Various Acid Anhydrides and Different Epoxides

(65) A mixture of 0.0911 g TEBAC (2 mol.-%), MgBr.sub.2*6H.sub.2O (0.2 mol.-%) and Cr(III) 2-ethylhexanoate (7 wt.-%) (0.22 mol.-%) was placed in a 15 ml pressure tube with magnetic stirrer and an epoxide and an acid anhydride selected from Table 13 was added. The tube was sealed with a Teflon® plug and heated afterwards for 3 h to 70° C. After the time had elapsed, the sample was cooled to room temperature and analyzed using GC.

(66) TABLE-US-00015 TABLE 14 Epoxide and acid anhydride used in test reactions of Table 13 Nr. Starting material 1 1.161 g PO = 0.02 mol 2 2.403 g styrene oxide (SO) = 0.02 mol 3 1.963 g cyclohexene oxide (CHO) = 0.02 mol 4 3.0832 g MAAH = 0.02 mol 5 2.5222 g acrylic acid anhydride = 0.02 mol 6 2.0418 g acetic acid anhydride = 0.02 mol

(67) TABLE-US-00016 TABLE 15 reaction of various epoxides with various anhydrides. Epoxide and anhydride Anhydride Epoxide Product Ex. from Table 13 Color GC area-% GC area-% GC area-% 42 1 + 4 cloudy, green 1.4 0.9 83.0 43 2 + 4 clear, green 2.29 2.29 83.0 44 1 + 5 clear, green 0.0 1.2 53 45 1 + 6 cloudy, green 7.3 8.7 68 46 2 + 6 clear, green 6.8 25.2 58 47 3 + 6 clear, green 34.4 13.6 41

(68) The performed tests confirm that the process of the present invention is applicable to a broad range of starting materials.

Example 48: Reaction of MAAH with PO on 1 L Scale

(69) Equipment: 1 L reactor equipped with a porcelain stirrer with motor and a Teflon® sleeve, NiCr—Ni thermocouple, reflux cooler, dropping funnel (coolable) with cryostat (−10° C.), thermostat for heating of the reactor.

(70) Chemicals:

(71) TABLE-US-00017 770.8 g MAAH = 5 mol 290.4 g PO = 5 mol, ratio = 1:1 2.92 g MgBr.sub.2*6 H.sub.2O = 0.20 mol.-% rel. to PO 5.69 g TEBAC = 0.50 mol.-% rel. to PO 7.96 g Cr(III) 2-ethylhexanoate 0.75 wt.-% rel. to entire batch 7 wt.-% in PPG 400 =

(72) Procedure:

(73) The catalysts and co-catalyst were placed in the reactor with MAAH and heated. PO was slowly added at first at 30° C. (exothermic reaction) continued at 40 to 50° C. and finally at 60° C. whereby previously unreacted PO was consumed. Subsequently the temperature was lowered to 55° C. until all remaining PO was added.

(74) The reaction was finally continued at an inner temperature of ca. 70° C. for 2 hours, before the reaction was cooled to RT and analyzed by GC.

(75) The reaction product contained 31 ppm inhibitor and had a purity of 84.7 GC-area-%.

Example 49: Reaction of MAAH with Isobutenoxide

(76) ##STR00012##

(77) Equipment: 1 L 4-necked flask with a porcelain stirrer with motor and a Teflon® sleeve, thermometer, reflux condenser.

(78) Chemicals:

(79) TABLE-US-00018 Isobutenoxide 216.33 g = 3.00 mol MAAH 462.48 g = 3.00 mol Phenothazine 1.51 g = 2000 ppm MgBr.sub.2*6 H.sub.2O 1.75 g = 0.20 mol % TEBAC 3.42 g = 0.50 mol % Cr(III) * 4.40 g = 0.22 mol %

(80) Procedure:

(81) The catalysts and co-catalyst were placed in the flask with MAAH and heated. The epoxide was slowly added at 80° C.

(82) The reaction was finally continued at an inner temperature of ca. 80° C. for 15 hours, before the reaction was cooled to RT and analyzed by GC.

(83) The reaction product had a purity of 56.3 GC-area-%.

Example 50 (Comparative): Reaction of MAAH with Isobutenoxide

(84) ##STR00013##

(85) Equipment: 500 mL 4-necked flask with a porcelain stirrer with motor and Teflon sleeve, thermometer, reflux condenser.

(86) Chemicals:

(87) TABLE-US-00019 Isobutenoxide 108.17 g = 1.50 mol MAAH 231.24 g = 1.50 mol Phenothazine 0.76 g = 2000 ppm DMAP 3.67 g = 2.00 mol %

(88) Procedure:

(89) The co-catalyst was placed in the flask with MAAH and heated. The epoxide was slowly added to the reaction mixture at 80° C.

(90) The reaction was finally continued at an inner temperature of ca. 80° C. for 5 hours, before the reaction mixture was cooled to RT and analyzed by GC.

(91) No desired product was detected.

Example 51: Reaction of MAAH with PO on 2 L Scale

(92) Equipment: 2 L autoclave with an inner glass beaker (1.6 L), autoclave rack, stirring motor, oil bath, glass piston pump, coolable dropping funnel, cryostat (5° C.)

(93) Chemicals:

(94) TABLE-US-00020 925 g MAAH = 6 mol 348.5 g PO = 6 mol ratio = 1:1 3.51 g MgBr.sub.2*6 H.sub.2O = 0.20 mol.-% rel. to PO 6.83 g TEBAC = 0.50 mol.-% rel. to PO 9.55 g Cr(III) 2-ethylhexanoate 0.75 wt.-% rel. to entire batch 7 wt.-% in PPG 400 =

(95) Procedure:

(96) The catalysts/co-catalyst (MgBr.sub.2, TEBAC and Cr(III)) were fed with MAAH into the glass beaker of the autoclave. The autoclave was sealed and heated to 60° C. Then PO (precooled to 5° C. in a dropping funnel) was fed with a glass piston pump into the reactor. The resulting pressure was kept below 1.5 bar and the temperature around 70° C.

(97) After the end of dosing, stirring was continued at 70° C. for 2 hours. The oil bath is then removed and the autoclave was ventilated.

(98) Temperature Control:

(99) The oil bath was removed at an internal temperature of 60° C. Reaction temperature of 70° C. was controlled by dosing without medium. Over temperature was counter-cooled with water bath, in case of insufficient temperature, heating with oil bath.

(100) Protocol:

(101) TABLE-US-00021 Bath- Inner- local Temp Temp. Pressure Time [° C.] [° C.] [bar] remark 11:45 23 22 — heating 12:15 64 43 0 data loggers starts 13:10 70 62 0.1 heating removed, pump 150 ml/h PO 13:25 34 66 0.5 pump 200 ml/h PO 13:40 33 67 0.7 — 13:55 27 75 0.9 cooling, pump stoped 14:15 14 74 0.5 cooling removed, pump 200 ml/h PO 15:13 25 63 1 pump 150 ml/h PO 15:22 1 min. cooling, pump 200 ml/h PO 15:47 27 64 1.1 — 16:08 15 70 1.4 1 minute cooling 16:22 27 66 1.3 End of dosing, sample A 16:38 43 65 1.1 heat 16:56 65 70 1.2 Heating removed 17:23 33 69 0.8 Sample B 17:37 62 66 0.8 heat 18:20 70 62 — Sample C, ventilated & cool down

(102) Result:

(103) 1251.3 g of a clear dark green liquid which fills the container to ¾ was obtained.

(104) TABLE-US-00022 Epoxide MAAH Product Sample GC area-% GC area-% GC area-% Sample A End of dosing 1.800 18.750 68.353 Sample B 1 h post-reaction 0.260 1.277 87.678 Sample C 2 h post-reaction 0.150 0.197 89.010

(105) An excellent reaction conversion upon formation of the desired product was observed.

Example 52: Reaction of MAAH with PO on 24 L Scale

(106) Equipment:

(107) 24 L autoclave with double jacket reactor, temperature control unit (single), agitator motor, scale, glass piston lifting pump, Paravisc agitator

(108) Chemicals

(109) TABLE-US-00023 9.25 kg MAAH = 60 mol 3.48 kg PO = 60 mol, ratio = 1:1 35.1 g MgBr.sub.2*6 H.sub.2O = 0.20 mol.-% rel. to PO 68.3 g TEBAC = 0.50 mol.-% rel. to PO 95.5 g Cr(III) 2-ethylhexanoate 0.75 wt.-% rel. to entire batch 7 wt.-% in PPG 400 =

(110) Procedure:

(111) The catalytic system (MgBr.sub.2, TEBAC and Cr(III)) was placed into the autoclave and MAAH was fed with a pump. (The solid catalysts must be placed in the open autoclave, as they do not dissolve and therefore cannot be fed via pipes).

(112) The autoclave was sealed and heated to 60° C. Then PO was fed with a glass piston pump into the reactor. The resulting pressure was kept below 1.5 bar (no pressure build up was noticed) and the temperature was between 65 and 75° C. After the end of dosing, stirring was continued at 70° C. for 2 hours. The autoclave was then cooled to RT and finally ventilated.

(113) Temperature Control:

(114) The oil bath was removed at an internal temperature of 60° C. Reaction temperature of 70° C. was controlled by dosing without applying cooling or heating medium.

(115) Protocol:

(116) TABLE-US-00024 Oil Oil Re- @- @- Inner- Pres- action entry exit Temp. sure Time [° C.] [° C.] [° C.] [bar] Pump remark 00:00 15 15 17 0/— — heating to 65° C. 00:12 64 61 28 0/— — heating to 75° C. 00:50 68 65 59 0/0 on heating to 60° C. 01:00 58 57 59 0/0 ~12.5 g/min  heating to 63° C., addition of 126 g PO 01:18 61 60 60 0/0 ~12.5 g/min  addition of 348 g PO ~1/10 of total amount 01:42 61 61 65 0/0 ~12.5 g/min. heating stopped, cooling 03:00 54 54 69 0/0 ~12.5 g/min. — 04:00 51 52 70 0/0 ~12.5 g/min. — 05:00 53 54 70 0/0 ~12.5 g/min. — 05:20 53 54 70 0/0 off end of dosing 05:25 53 54 69 0/— — heating 07:00 70 69 69 0/— — — 07:40 70 69 69 0/— — cooling 08:00 27 33 49 0/— — — 08:20 20 23 32 0/— — Ventilated, switched off 09:00 15 15 17 0/— — heating to 65° C. 09:12 64 61 28 0/— — heating to 75° C.

(117) 13.6 kg of a liquid with suspended particles was obtained. Product yield: 93.30% (GC area-%), Remaining Inhibitor=47 ppm

Example 53: Reaction of MAAH with EO on 1 L Scale

(118) ##STR00014##

(119) Equipment: 5 L-pressure reactor with oil circulation, temperature regulator, anchor stirrer, manhole, storage tank for epoxy on scale, acid scrubber (H.sub.3PO.sub.4)

(120) Chemicals:

(121) TABLE-US-00025 308.32 g MAAH = 2.00 mol 88.10 g EO = 2.00 mol ratio = 1:1 1.1688 g MgBr.sub.2*6 H.sub.2O = 0.20 mol.-% rel. to EO 2.2777 g TEBAC = 0.50 mol.-% rel. to EO 3.1836 g Cr(III) 2-ethylhexanoate 0.39 mol.-% rel. to EO in PPG 400 [~7.8% Cr] = 0.3964 g phenothiazine = 1000 ppm rel. to MAAH

(122) Procedure:

(123) The catalytic system (MgBr.sub.2, TEBAC and Cr(III)) was placed into the pressure reactor and MAAH was fed with a pump. The pressure reactor was sealed and flushed three times with nitrogen. Subsequently, the pressure reactor was evacuated (0.1 bar) and filled with nitrogen to atmospheric pressure. The pressure reactor was heated to 60° C. inner temperature. Then EO (16 g) was fed into the pressure reactor. The resulting pressure was kept below 1.5 bar and reached 0.8 bar overpressure after addition of 29 g EO were fed.

(124) The temperature was increased first to 65° C. and then to 70° C. At this temperature the pressure dropped and the overpressure was kept constant at about 0.5 bar by adding portions of EO. At the end of dosing, stirring was continued at 75° C. for 2 hours. Since the overpressure (0.2 bar) did not completely disappeared, the temperature was elevated to 80° C. for 30 min.

(125) The pressure reactor was then cooled to RT and finally ventilated.

(126) Protocol:

(127) TABLE-US-00026 Reaction- Oil- Over- Time temp. temp. pressure hh:mm ° C. ° C. bar Remarks RT — 0/−0.9 Reactor rinsed 3 times with nitrogen. 1 time evacuated and relaxed to standard pressure with nitrogen 00:00 24 — 0 heating to 60° C. 00:05 61 65 0.1 dosage of 16 g EO 00:15 60 64 0.3 dosage of 29 g EO 00:20 60 62 0.8 00:35 60 62 0.8 heating to 65° C. 00:52 65 69 0.8 heating to 70° C. 00:55 73 78 0.8 01:02 70 73 0.75 01:10 70 72 0.6 01:20 70 72 0.45 dosage of 20 g EO 01:45 70 71 0.55 01:50 70 71 0.5 dosage of 20 g EO 02:05 70 72 0.75 heating to 75° C. 02:10 77 79 0.7 02:15 75 77 0.6 02:45 75 79 0.2 03:48 75 78 0.2 heating to 80° C. 03:53 80 84 0.2 04:07 80 84 0.2 cooling to 40° C. 04:20 50 — 0.1 04:35 40 — −0.9 relaxation with nitrogen

(128) 385 g of a dark green liquid without solids was obtained.

(129) Purity of the isolated ethylene glycol dimethacrylate was 89.71% (GC)

Example 54: Reaction of MAAH with EO on 2 L Scale

(130) ##STR00015##

(131) Equipment: 5 L-pressure reactor with oil circulation, Juchheim temperature regulator, anchor stirrer, manhole, storage tank for epoxy on scale, acid scrubber (H.sub.3PO.sub.4)

(132) Chemicals:

(133) TABLE-US-00027 1.23 kg MAAH = 8.00 mol 352.4 g EO = 8.00 mol ratio = 1:1 4.68 g MgBr.sub.2*6 H.sub.2O = 0.20 mol.-% rel. to EO 9.11 g TEBAC = 0.50 mol.-% rel. to EO 11.73 g Cr(III) 2-ethylhexanoate in 0.39 mol.-% rel. to EO PPG 400 [~7.8% Cr] = 1.59 g phenothiazine = 1000 ppm rel. to MAAH

(134) Procedure:

(135) The catalytic system (MgBr.sub.2, TEBAC and Cr(III)) were placed into the pressure reactor and MAAH was fed with a pump. The pressure reactor was sealed and flushed three times with nitrogen. The pressure reactor was evacuated (0.1 bar) and filled with nitrogen to atmospheric pressure and heated to 70° C.

(136) Then EO was fed (˜6 g/min) into the pressure reactor. The resulting overpressure was kept below 1 bar. At the end of dosing, stirring was continued at 75° C. for about 2 hours. The pressure reactor was then cooled to RT and finally ventilated.

(137) Protocol:

(138) TABLE-US-00028 Reaction Oil Over- Time temp. temp. pressure hh:mm ° C. ° C. bar Remarks 00:00 RT — 0/−0.9 reactor was rinsed 3 times with nitrogen, evacuated 1 time and expanded to standard pressure with nitrogen. Heating to 70°C. 00:09 71 75 0.2 dosing approx. 6 g/min EO up to max. 1 bar overpressure 00:19 70 75 0.5 dosing 60 g EO 00:29 70 70 0.8 dosing 100 g EO 00:39 70 70 1   dosing 145 g EO 00:49 70 68  1.05 dosing 183 g EO 00:59 70 67  1.05 dosing 218 g EO 01:09 70 66  0.95 dosing 253 g EO 01:19 70 66  0.85 dosing 289 g EO 01:29 70 66 0.8 dosing 331 g EO 01:38 70 67 0.8 dosing 361 g EO 01:49 70 70 0.5 01:59 70 71  0.35 02:09 70 72 0.3 02:19 70 72  0.25 02:29 70 72  0.25 02:39 70 73  0.25 02:49 70 73  0.225 02:59 70 73  0.225 03:59 70 73 0.2 cooling to 40° C. 04:09 51 — −0.9   deodorization 04:24 40 — 0   pressure relief to normal pressure under nitrogen

(139) 1601 g of a dark green liquid with solid was obtained. Purity of the obtained ethylene glycol dimethacrylate was 93.60% (GO).

Example 55 (Comparative): Reaction of MAAH with Hexene Oxide in the Presence of an Erbium(III) Catalyst

(140) The protocol follows the literature procedure described in R. Dalpozoet a (ARKIVOC (Gainesville, Fla., United States) (2006), (6), 67-73.

(141) Chemicals:

(142) TABLE-US-00029 1.00 g hexene oxide = 0.01 mol 3.08 g MAAH = 0.02 mol 6.1 mg erbium (III) triflate = 0.10 mol.-%

(143) Procedure:

(144) All chemicals were filled into a 15 ml pressure tube with magnetic stirrer. The tube was sealed with a Teflon® plug and stirred for 1 h at room temperature. After the time had elapsed, the sample was analyzed using GC.

(145) No product formation was observed.

Example 56 (Comparative) Reaction of MAAH with PO in the Presence of an Erbium(II) Catalyst

(146) The protocol follows the literature procedure described in R. Dalpozo et al. (ARKIVOC (Gainesville, Fla., United States) (2006), (6), 67-73.

(147) Chemicals:

(148) TABLE-US-00030 1.16 g PO = 0.02 mol 3.08 g MAAH = 0.02 mol 12.3 mg erbium (III) triflate = 0.10 mol.-%

(149) Procedure:

(150) All chemicals were filled into a 15 ml pressure tube with magnetic stirrer. The tube was sealed with a Teflon® plug and stirred for 1 h at room temperature. After the time had elapsed, the sample was analyzed using GC.

(151) No product formation was observed.

Example 57 (Comparative) Reaction of MAAH with PO in the Presence of an Erbium(III) Catalyst

(152) The protocol follows the literature procedure described in R. Dalpozo et al. (ARKIVOC (Gainesville, Fla., United States) (2006), (6), 67-73.

(153) Chemicals:

(154) TABLE-US-00031 1.16 g PO = 0.02 mol 3.08 g MAAH = 0.02 mol 12.3 mg erbium (III) triflate = 0.10 mol.-%

(155) Procedure:

(156) All chemicals were filled into a 15 ml pressure tube with magnetic stirrer. The tube was sealed with a Teflon® plug and stirred for 1 h at 80° C. After the time had elapsed, the sample was cooled to room temperature and analyzed using GC.

(157) Only 0.6 GC-area-% product could be obtained

Example 58 (Comparative): Reaction of Acetic Anhydride with Hexene Oxide in the Presence of Tributylphophine

(158) The protocol follows the literature procedure described in Ren-Hua et al. (Tetrahedron Letters (2003), 44(23).

(159) Chemicals:

(160) TABLE-US-00032 2.00 g 1-hexene oxide = 0.02 mol 2.04 g acetic anhydride = 0.02 mol 0.41 g tributylphosphine = 10 mol.-%.

(161) Procedure:

(162) All chemicals were filled into a 15 ml pressure tube equipped with a magnetic stirrer. The tube was sealed with a Teflon® plug and stirred for 24 h at 110° C. After the time had elapsed, the sample was cooled to room temperature and analyzed using GC.

(163) 83.01 GC-area-% product could be obtained.

Example 59 (Comparative): Reaction of MAAH with Hexene Oxide in the Presence of Tributylphophine

(164) The protocol follows the literature procedure described in Ren-Hua et al. (Tetrahedron Letters (2003), 44(23).

(165) Chemicals:

(166) TABLE-US-00033 2.00 g 1-hexene oxide = 0.02 mol 3.08 g MAAH = 0.02 mol 408 mg tributylphosphine = 10 mol.-%.

(167) Procedure:

(168) All chemicals were filled into a 15 ml pressure tube with magnetic stirrer. The tube was sealed with a Teflon® plug and stirred for 24 h at 110° C. After the time had elapsed, the sample was polymerized.

(169) No desired product could be obtained.

Example 60 (Comparative): Reaction of MAAH with PO in the Presence of Zeolith CP 814E at Room Temperature

(170) The protocol follows the literature procedure described in P. Ramesh et al., Synthetic Communications (2001), 31(17), 2599-2604.

(171) Chemicals:

(172) TABLE-US-00034 1.16 g PO = 0.02 mol 3.08 g MAAH = 0.02 mol 690 mg Zeolith CP 814E = 59.4 wt.-%

(173) Procedure:

(174) All chemicals were filled into a 15 ml pressure tube with magnetic stirrer. The tube was sealed with a Teflon® plug and stirred for 9.5 h at room temperature. After the time had elapsed, the sample was cooled to room temperature and analyzed using GC.

(175) No product could be obtained.

Comparative Example 61: Reaction of MAAH with PO in the Presence of Zeolith CP 814E at 80° C.

(176) The protocol follows the literature procedure described in P. Ramesh et al., Synthetic Communications (2001), 31(17), 2599-2604.

(177) Chemicals:

(178) TABLE-US-00035 1.16 g PO = 0.02 mol 3.08 g MAAH = 0.02 mol 690 mg Zeolith CP 814E = 59.4 wt.-%

(179) Procedure:

(180) All chemicals were filled into a 15 ml pressure tube with magnetic stirrer. The tube was sealed with a Teflon® plug and stirred for 9.5 h at 80° C. After the time had elapsed, the sample was cooled to room temperature and analyzed using GC.

(181) Only 1.08 GC-area-% product was formed.

Example 62 (Comparative): Reaction of MAAH and SO in the Presence of Na.SUB.2.HPO.SUB.4

(182) The protocol follows the literature procedure described in M. Gilanizadeh et al., Journal of Chemical Research (2016), 40(5), 296-298.

(183) Chemicals:

(184) TABLE-US-00036 0.60 g Styrene oxide (SO) = 5 mmol 8.09 g MAAH = 53 mmol 895 mg Na.sub.2HPO.sub.4*10 H.sub.2O = 50 mol.-% rel. to SO

(185) Procedure:

(186) All chemicals were filled into a 15 ml pressure tube with magnetic stirrer. The tube was sealed with a Teflon® plug and stirred for 2 h at 110° C. After the time had elapsed, the sample was polymerized

(187) No product could be obtained.

Example 63 (Comparative): Reaction of MAAH and SO in the Presence of NaHSO.SUB.4

(188) The protocol follows the literature procedure described in M. Gilanizadeh et al., Journal of Chemical Research (2016), 40(5), 296-298.

(189) Chemicals:

(190) TABLE-US-00037 0.60 g SO = 5 mmol 8.09 g MAAH = 53 mmol 345 mg NaHSO.sub.4*H.sub.2O = 50 mol.-%. rel. to SO

(191) Procedure:

(192) All chemicals were filled into a 15 ml pressure tube with magnetic stirrer. The tube was sealed with a Teflon® plug and stirred for 2 h at 110° C. After the time had elapsed, the sample was polymerized.

(193) No product could be obtained.

Example 64 (Comparative): Reaction of Acetic Anhydride and PO in the Presence of Tetrabutyl Ammonium Acetate

(194) The protocol follows the literature procedure described in Md. A. Rahman et al., J. Am. Chem. Soc. 1985, 107, 5576-5578.

(195) Chemicals:

(196) TABLE-US-00038 1.16 g PO = 0.02 mol 2.04 g acetic anhydride = 0.02 mol 302 mg tetrabutyl ammonium acetate = 5 mol.-%.

(197) Procedure:

(198) All chemicals were filled into a 15 ml pressure tube with magnetic stirrer. The tube was sealed with a Teflon® plug and stirred for 6 h at 80° C. After the time had elapsed, the sample was cooled to room temperature and analyzed using GC.

(199) 77.27 GC-area-% product was formed at nearly complete conversion.

Example 65 (Comparative): Reaction of MAAH and PO in the Presence of Tetrabutyl Ammonium Acetate

(200) The protocol follows the literature procedure described in Md. A. Rahman et al., J. Am. Chem. Soc. 1985, 107, 5576-5578.

(201) Chemicals:

(202) TABLE-US-00039 1.16 g PO = 0.02 mol 2.04 g MAAH = 0.02 mol 302 mg tetrabutyl ammonium acetate = 5 mol.-%.

(203) Procedure:

(204) All chemicals were filled into a 15 ml pressure tube with magnetic stirrer. The tube was sealed with a Teflon® plug and stirred for 3 h at 70° C. After the time had elapsed, the sample was cooled to room temperature and analyzed using GC.

(205) 36 GC-area-% product was formed.

Example 66: Reaction of MAAH and PO in the Presence of Tetrabutyl Ammonium Acetate in Combination with Magnesium Bromide and a Chromium (III) Catalyst

(206) Chemicals:

(207) TABLE-US-00040 1.16 g PO = 0.02 mol 2.04 g MAAH = 0.02 mol 302 mg tetrabutyl ammonium acetate = 5 mol.-%. 0.0117 g MgBr.sub.2*6 H.sub.2O = 0.2 mol.-% 0.0318 g Cr(III) 2-ethyl-hexanoate 0.22 mol.-% (7 wt.-%) in PPG 400 =

(208) Procedure:

(209) All chemicals were filled into a 15 ml pressure tube with magnetic stirrer. The tube was sealed with a Teflon® plug and stirred for 3 h at 70° C. After the time had elapsed, the sample was cooled to room temperature and analyzed using GC.

(210) 68 GC-area-% product was formed.

Example 67 (Comparative): Reaction of Acetic Anhydride with PO in the Presence of Triethylamine

(211) The protocol follows the literature procedure described in U.S. Pat. No. 5,623,086.

(212) Chemicals:

(213) TABLE-US-00041 0.58 g PO = 0.01 mol 2.04 g acetic anhydride = 0.02 mol 36.4 mg triethylamine = 3.60 mol.-% rel. to PO

(214) Procedure:

(215) All chemicals were filled into a 15 ml pressure tube with magnetic stirrer. The tube was sealed with a Teflon® plug and stirred for 4 h at 120° C. After the time had elapsed, the sample was cooled to room temperature and analyzed using GC.

(216) 67.16 GC-area-% product was obtained.

Example 68 (Comparative): Reaction of MAAH with PO in the Presence of Triethylamine at 120° C.

(217) The protocol follows the literature procedure described in U.S. Pat. No. 5,623,086.

(218) Chemicals:

(219) TABLE-US-00042 0.58 g PO = 0.01 mol 3.08 g MAAH = 0.02 mol 36.4 mg triethylamine = 3.60 mol.-% rel. to PO

(220) Procedure:

(221) All chemicals were filled into a 15 ml pressure tube with magnetic stirrer. The tube was sealed with a Teflon® plug and stirred for 4 h at 120° C. After the time had elapsed, the sample was polymerized.

(222) No product could be obtained.

Example 69 (Comparative): Reaction of MAAH with PO in the Presence of Triethylamine at 80° C.

(223) The protocol follows the literature procedure described in U.S. Pat. No. 5,623,086.

(224) Chemicals:

(225) TABLE-US-00043 0.58 g PO = 0.01 mol 3.08 g MAAH = 0.02 mol 36.4 mg triethylamine = 3.60 mol.-% rel. to PO

(226) Procedure:

(227) All chemicals were filled into a 15 ml pressure tube with magnetic stirrer. The tube was sealed with a Teflon® plug and stirred for 3 h at 70° C. After the time had elapsed, the sample was polymerized.

(228) 6% product could be obtained.

Example 70 (Comparative): Reaction of Acetic Anhydride with SO in the Presence of Tetrabutyl Ammonium Chloride

(229) The protocol follows the literature procedure described in G. Fogassy et al., Catalysis Communications 2009, No. 10, 557-560.

(230) Chemicals:

(231) TABLE-US-00044 2.40 g SO = 0.02 mol 2.04 g acetic anhydride = 0.02 mol 278 mg tetrabutyl ammonium chloride = 5 mol.-%.

(232) Procedure:

(233) All chemicals were filled into a 15 ml pressure tube with magnetic stirrer. The tube was sealed with a Teflon® plug and stirred for 3 h at 110° C. After the time had elapsed, the sample was cooled to room temperature and analyzed using GC.

(234) 87.42 GC-area-% product could be obtained.

Example 71 (Comparative): Reaction of MAAH with SO in the Presence of Tetrabutyl Ammonium Chloride

(235) The protocol follows the literature procedure described in G. Fogassy et al., Catalysis Communications 2009, No. 10, 557-560.

(236) Chemicals:

(237) TABLE-US-00045 2.40 g SO = 0.02 mol 3.08 g MAAH = 0.02 mol 278 mg tetrabutyl ammonium chloride = 5 mol.-%.

(238) Procedure:

(239) All chemicals were filled into a 15 ml pressure tube with magnetic stirrer. The tube was sealed with a Teflon® plug and stirred for 3 h at 110° C. After the time had elapsed, the sample was polymerized.

(240) No product could be obtained.

Example 72 (Comparative): Reaction of MAAH with PO in the Presence of Tetrabutyl Ammonium Chloride

(241) The protocol follows the literature procedure described in G. Fogassy et al., Catalysis Communications 2009, No. 10, 557-560.

(242) Chemicals:

(243) TABLE-US-00046 1.16 g PO = 0.02 mol 3.08 g MAAH = 0.02 mol 278 mg tetrabutyl ammonium chloride = 5 mol.-%.

(244) Procedure:

(245) All chemicals were filled into a 15 ml pressure tube with magnetic stirrer. The tube was sealed with a Teflon® plug and stirred for 3 h at 110° C. After the time had elapsed, the sample was polymerized.

(246) No product could be obtained.

Example 73 (Comparative): Reaction of Acetic Anhydride with PO in the Presence of Pyridine

(247) The protocol follows the literature procedure described in V. F. Shveets et al. (Kinet. Katal. 1975, 16, 785.

(248) Chemicals:

(249) TABLE-US-00047 1.16 g PO = 0.02 mol 2.04 g acetic anhydride = 0.02 mol 791 mg pyridine = 5 mol %.

(250) Procedure:

(251) All chemicals were filled into a 15 ml pressure tube with magnetic stirrer. The tube is sealed with a Teflon® plug and stirred for 6 h at 105° C. After the time had elapsed, the sample was cooled to room temperature and analyzed using GC.

(252) 54.22 GC-Area % product could be obtained.

Example 74 (Comparative): Reaction of MAAH with PO in the Presence of Pyridine

(253) The protocol follows the literature procedure described in V. F. Shveets et al. (Kinet. Katal. 1975, 16, 785.

(254) Chemicals:

(255) TABLE-US-00048 1.16 g PO = 0.02 mol 3.08 g MAAH = 0.02 mol 791 mg pyridine = 5 mol %.

(256) Procedure:

(257) All chemicals were filled into a 15 ml pressure tube with magnetic stirrer. The tube is sealed with a Teflon® plug and stirred for 3 h at 70° C. After the time had elapsed, the sample was cooled to room temperature and analyzed using GC.

(258) Only 8 GC-Area % product could be obtained.

Example 75 (Comparative): Reaction of Acetic Anhydride with PO in the Presence of Disodium Phthalate

(259) The protocol follows the literature procedure described in E. Schwenk et al., Makromol. Chem. 1962, 51, 53-69.

(260) Chemicals:

(261) TABLE-US-00049 1.16 g PO = 0.02 mol 2.04 g acetic anhydride = 0.02 mol 210 mg disodium phthalate = 5 mol.-%.

(262) Procedure:

(263) All chemicals were filled into a 15 ml pressure tube with magnetic stirrer. The tube was sealed with a Teflon® plug and stirred for 6 h at 130° C. After the time had elapsed, the sample was cooled to room temperature and analyzed using GC.

(264) 47.63 GC-area-% product could be obtained.

Example 76 (Comparative): Reaction of MAAH with PO in the Presence of Disodium Phthalate

(265) The protocol follows the literature procedure described in E. Schwenk et al., Makromol. Chem. 1962, 51, 53-69.

(266) Chemicals:

(267) TABLE-US-00050 1.16 g PO = 0.02 mol 3.08 g MAAH = 0.02 mol 210 mg disodium phthalate = 5 mol.-%.

(268) Procedure:

(269) All chemicals were filled into a 15 ml pressure tube with magnetic stirrer. The tube was sealed with a Teflon® plug and stirred for 6 h at 130° C. After the time had elapsed, the sample was polymerized.

(270) No product could be obtained.

Example 77 (Comparative): Reaction of Acetic Anhydride with Cyclohexene Oxide in the Presence of Tetrabutylammonium Chloride

(271) The protocol follows the literature procedure described in T. Yoshino, J. Chem. Soc., Perkin Trans. 1, 1977, 1266-1272.

(272) Chemicals:

(273) TABLE-US-00051 1.96 g cyclohexene oxide = 0.02 mol 2.24 g acetic anhydride = 0.022 mol 1.00 g tetrabutyl ammonium chloride = 18 mol.-%.

(274) Procedure:

(275) All chemicals were filled into a 15 ml pressure tube with magnetic stirrer. The tube was sealed with a Teflon® plug and stirred for 15 min at 130° C. After the time had elapsed, the sample was cooled to room temperature and analyzed using GC.

(276) 44.89 GC-area-% product could be obtained.

Example 78 (Comparative): Reaction of MAAH with Cyclohexene Oxide in the Presence of Tetrabutylammonium Chloride

(277) The protocol follows the literature procedure described in T. Yoshino, J. Chem. Soc., Perkin Trans. 1, 1977, 1266-1272.

(278) Chemicals:

(279) TABLE-US-00052 1.96 g cyclohexene oxide = 0.02 mol 3.39 g MAAH = 0.022 mol 1.00 g tetrabutyl ammonium chloride = 18 mol.-%.

(280) Procedure:

(281) All chemicals were filled into a 15 ml pressure tube with magnetic stirrer. The tube was sealed with a Teflon® plug and stirred for 15 min at 130° C. After the time had elapsed, the sample was polymerized:

(282) No product could be obtained.

Examples 79-81: Reaction Between MAAH and PO in Presence of Various Chromium (III) Catalysts

(283) A catalyst/co-catalyst mixture, containing different amounts of MgBr.sub.2 with a Cr(III) salt and TEBAC selected from Table 4 was placed in a 15 ml pressure tube with magnetic stirrer, 3.08 g (0.02 mol) MAAH was added and 1.16 g (0.02 mol) PO were carefully added dropwise. The tube was sealed with a Teflon® plug and heated afterwards for 3 h to 70° C.

(284) After the time had elapsed, the sample was cooled to room temperature and analyzed using GC.

(285) TABLE-US-00053 TABLE 16 Catalytic systems for the reaction between MAAH and PO in Table 16 Nr. Catalyst / co-catalyst 1 0.0058 g MgBr.sub.2*6 H2O 0.1 mol.-% rel. to PO 0.0911 g TEBAC   2 mol.-% rel. to PO 0.0023 g Cr(III) Perchlorate 0.25 mol.-%  rel. to PO 2 0.0058 g MgBr.sub.2*6 H.sub.2O 0.1 mol.-% rel. to PO 0.0911 g TEBAC   2 mol.-% rel. to PO 0.0212 g Cr(III) Acetylacetonate 0.25 mol.-%  rel. to PO 3 0.0058 g MgBr.sub.2*6 H.sub.2O 0.1 mol.-% rel. to PO 0.0456 g TEBAC   2 mol.-% rel. to PO 0.0637 g Cr(III) chloride × (THF).sub.3 0.25 mol.-%  rel. to PO

(286) TABLE-US-00054 TABLE 17 Catalyst combinations tested for the reaction between MAAH and PO Catalytic system MAAH PO Product Ex. from Table 4 Comment GC area-% GC area-% GC area-% 79 1 0.176 1.710 89.365 80 2 0.323 0.939 90.468 81 3 0.957 1.541 88.667

(287) The results show that the species of chromium (III) catalyst in the catalytic system can be varied within a broad range without noticeable change in observed product yields.

Examples 82-86: Reaction Between MAAH and PO in Presence of Different Rare Earth Triflates

(288) A catalyst/co-catalyst mixture, containing different rare earth triflates with Cr(III) 2-ethyl-hexanoate (7 wt.-%) in polypropylene glycol 400 and TEBAC selected from Table 4 was placed in a 15 ml pressure tube with magnetic stirrer, 3.08 g (0.02 mol) MAAH was added and 1.16 g (0.02 mol) PO were carefully added dropwise. The tube was sealed with a Teflon® plug and heated afterwards for 3 h to 70° C.

(289) After the time had elapsed, the sample was cooled to room temperature and analyzed using GC.

(290) TABLE-US-00055 TABLE 18 Catalytic systems for the reaction between MAAH and PO in Table 17 Nr. Catalyst/co-catalyst 1 0.0106 g Y(CF.sub.3SO.sub.3).sub.3 0.1 mol.-% rel. to PO 0.0911 g TEBAC 2 mol.-% rel. to PO 0.0318 g Cr(III) solution 0.75 wt % rel. to entire batch 2 0.0116 g La(CF.sub.3SO.sub.3).sub.3 0.1 mol.-% rel. to PO 0.0911 g TEBAC 2 mol.-% rel. to PO 0.0318 g Cr(III) solution 0.75 wt % rel. to entire batch 3 0.0123 g Yb(CF.sub.3SO.sub.3).sub.3 0.1 mol.-% rel. to PO 0.0456 g TEBAC 2 mol.-% rel. to PO 0.0318 g Cr(III) solution 0.75 wt % rel. to entire batch 4 0.0098 g Sc(SO.sub.3CF.sub.3).sub.3 0.1 mol.-% rel. to PO 0.0456 g TEBAC 2 mol.-% rel. to PO 0.0318 g Cr(III) solution 0.75 wt % rel. to entire batch 5 0.0121 g Dy(CF.sub.3SO.sub.3).sub.3 0.1 mol.-% rel. to PO 0.0456 g TEBAC 2 mol.-% rel. to PO 0.0318 g Cr(III) solution 0.75 wt % rel. to entire batch 6 0.0117 g Pr(CF.sub.3SO.sub.3).sub.3 0.1 mol.-% rel. to PO 0.0456 g TEBAC 2 mol.-% rel. to PO 0.0318 g Cr(III) solution 0.75 wt % rel. to entire batch

(291) TABLE-US-00056 TABLE 19 Catalyst combinations tested for the reaction between MAAH and PO Catalytic MAAH PO Product system GC GC GC Ex. from Table 4 Color Comment area-% area-% area-% 15 1 green solids precipitated 0.0772 1.112 90.97 16 2 green solids precipitated 0.0759 1.044 91.05 17 3 green solids precipitated 0.1337 1.163 89.36 18 4 green solids precipitated 0.0775 1.025 91.09 17 5 green solids precipitated 0.1404 1.131 88.07 18 6 green solids precipitated 0.1328 1.044 88.87

(292) The results show that Magnesium bromide in the catalytic system can be replaced by rare earth triflates without noticeable change in observed product yields.