LIQUID MONOFUNCTIONAL 1,3-DIOXOLANE COPOLYMERS

Abstract

1,3-Dioxolane copolymers and methods of producing the same. Where the 1,3-Dioxolane copolymers have a general formula I

##STR00001##

Claims

1-11. (canceled)

12. 1,3-Dioxolane copolymers, comprising: wherein the 1,3-Dioxolane copolymers have a general formula I ##STR00005## wherein x1+x2 has values of 10 to 2000; wherein R.sup.1 and R.sup.2 are hydrogen radicals or C.sub.1 to C.sub.18 alkyl radical, wherein in each case at least one radical R.sup.1 or R.sup.2 in the units [OCH.sub.2OCHR.sup.1CHR.sup.2-].sub.y1 and [0-CHR.sup.1CHR.sup.2OCH.sub.2-].sub.y2 is a C.sub.1 to C.sub.18 alkyl radical; wherein y1+y2 has values of 3*(x1+x2+y1+y2)/100 to 50*(x1+x2+y1+y2)/100; wherein R.sup.3 is an aliphatically saturated or unsaturated hydrocarbon radical which is unsubstituted or substituted by halogen atoms, amino groups, C.sub.1-6 alkyl, C.sub.1-6 alkoxy or silyl groups and has 1 to 100 carbon atoms, in which one or more mutually non-adjacent CH.sub.2 units may be replaced by O, S, C?O, OC(O) or NR.sup.4 groups and in which one or more mutually non-adjacent ?CH units may be replaced by N? groups; and wherein R.sup.4 is a hydrogen radical or C.sub.1 to C.sub.18 alkyl radical.

13. The 1,3-dioxolane copolymers of claim 12, wherein the radicals R.sup.1 and R.sup.2 are selected from hydrogen radicals or methyl, ethyl, n-propyl or i-propyl radicals.

14. The 1,3-dioxolane copolymers of claim 12, wherein in each case only one radical R.sup.1 or R.sup.2 in the units [OCH.sub.2OCHR.sup.1CHR.sup.2-].sub.y1 and [OCHR.sup.1CHR.sup.2OCH.sub.2-].sub.y2 is a C.sub.1 to C.sub.18 alkyl radical.

15. The 1,3-dioxolane copolymers of claim 12, wherein the copolymers have a molecular weight Mw of between 750-300 000, measured against a polystyrene standard, in THF, at 35? C., flow rate 0.3 ml/min and detection with RID (refractive index detector) on an Agilent PLgel MiniMIX-C Guard column with an injection volume of 20 ?l.

16. The 1,3-dioxolane copolymers of claim 12, wherein the copolymers have a dynamic viscosity at 25? C. of between 50 mPas-500 Pas, measured on an Anton Paar MCR 320 rotational viscometer at 25? C., where the graphical evaluation is performed by plotting viscosity against shear stress.

17. The 1,3-dioxolane copolymers of claim 12, wherein R.sup.3 is an alkyl radical having 1 to 18 carbon atoms.

18. The 1,3-dioxolane copolymers of claim 12, wherein R.sup.3 is an alkenyl radical having 2 to 10 carbon atoms, in which one or more mutually non-adjacent CH.sub.2 units may be replaced by O or OC(O) groups.

19. A process for producing 1,3-dioxolane copolymers, comprising: providing 1,3-dioxolane copolymers having the general formula I ##STR00006## wherein x1+x2 has values of 10 to 2000, wherein R.sup.1 and R.sup.2 are hydrogen radicals or C.sub.1 to C.sub.18 alkyl radical, where in each case at least one radical R.sup.1 or R.sup.2 in the units [OCH.sub.2OCHR.sup.1CHR.sup.2-].sub.y1 and [OCHR.sup.1CHR.sup.2OCH.sub.2-].sub.y2 is a C.sub.1 to C.sub.18 alkyl radical, wherein y1+y2 has values of 3*(x1+x2+y1+y2)/100 to 50*(x1+x2+y1+y2)/100, wherein R.sup.3 is an aliphatically saturated or unsaturated hydrocarbon radical which is unsubstituted or substituted by halogen atoms, amino groups, C.sub.1-6 alkyl, C.sub.1-6 alkoxy or silyl groups and has 1 to 100 carbon atoms, in which one or more mutually non-adjacent CH.sub.2 units may be replaced by O, S, C?O, OC(O) or NR.sup.4 groups and in which one or more mutually non-adjacent=CH units may be replaced by N? groups, and wherein R.sup.4 is a hydrogen radical or C.sub.1 to C.sub.18 alkyl radical; and copolymerizing the 1,3-dioxolane copolymers with an alkyl-substituted 1,3-dioxolane of the general formula II ##STR00007## in the presence of a Lewis or Br?nsted acid and an alcohol of the general formula R.sup.3OH, where the molar ratio of Lewis or Br?nsted acid to alcohol of the general formula R.sup.3OH is less than 1.

20. The process of claim 19, wherein the acid is trifluoromethanesulfonic acid.

21. The process of claim 19, wherein 50 to 10 000 mol ppm of Lewis or Br?nsted acid is used per mol of the sum total of 1,3-dioxolane and alkyl-substituted 1,3-dioxolane of the general formula II.

22. The process of claim 19, wherein the temperature is between 10? C. and 60? C.

Description

EXAMPLES

Analysis for the Entire Invention:

[0067] NMR spectroscopy to determine the proportion of alkyl ethylene oxide bridges. The measurement is effected in solution in CDCl3 on a Bruker Avance 500 or Ascend 500 (500 MHz for 1H spectrum). All measurements are referenced against TMS as external standard. The relative ratios of the monomer units in the polymer are determined by integrating the respective sets of signals. In addition, the chain length and the molar mass of the polymer can be determined by integrating the end group signals.

[0068] SEC (Size-Exclusion Chromatography): to determine the number-average and mass-average molecular weights Mn, Mw and the polydispersity:

[0069] The measurement is effected against a polystyrene standard, determined in THF, at 35? C., flow rate 0.3 ml/min and detection with RID (refractive index detector) on an Agilent PLgel MiniMIX-C Guard column with an injection volume of 20 ?l.

Rheometer to Determine the Dynamic Viscosity

[0070] The measurement is effected on an Anton Paar MCR 320 rotational viscometer at 25? C. The graphical evaluation is performed by plotting viscosity against shear stress.

[0071] DSC (Differential Scanning Calorimetry/Differential Thermal Analysis) to determine the melting point and the glass transition temperature:

[0072] The measurements were effected on a Mettler Toledo DSC-1 device in a temperature range of ?150? C. to 150? C. in two runs with a heating or cooling rate of 10 K, the second run being used to determine the melting point and the glass transition temperature.

TGA Analysis to Determine the Start of Decomposition:

[0073] The start of decomposition (onset) was determined on a Mettler Toledo TGA-2 device, the sample being heated at a heating rate of 10 K/min in an oxygen atmosphere.

Example 1

[0074] Preparation of the catalyst solution: 10 ml of dry dichloromethane, 1.9 ml of allyloxyethanol and 76 ?l of trifluoromethanesulfonic acid are combined and stirred for 1 h at room temperature. 1.35 ml of the previously prepared catalyst solution is placed in a flask and adjusted to a temperature of 23? C. 10.12 g (96 mmol) of 4-ethyl-1,3-dioxolane (EDX) and 6.75 ml (96 mmol) of 1,3-dioxolane (DXL) are then added and stirred.

[0075] After 4 h, pyridine is added until the mixture loses its color. The product is washed with heptane and distilled water and then dried under reduced pressure.

Example 2

[0076] 2.7 ml of the catalyst solution prepared in Example 1 is placed in a flask and adjusted to a temperature of 23? C. 10.12 g (96 mmol) of 4-ethyl-1,3-dioxolane (EDX) and 6.75 ml (96 mmol) of 1,3-dioxolane (DXL) are then added and stirred.

[0077] After 4 h, pyridine is added until the mixture loses its color. The product is washed with heptane and distilled water and then dried under reduced pressure.

Example 3

[0078] 5.4 ml of the catalyst solution prepared in Example 1 is placed in a flask and adjusted to a temperature of 23? C. 10.12 g (96 mmol) of 4-ethyl-1,3-dioxolane (EDX) and 6.75 ml (96 mmol) of 1,3-dioxolane (DXL) are then added and stirred.

[0079] After 4 h, pyridine is added until the mixture loses its color. The product is washed with heptane and distilled water and then dried under reduced pressure.

Example 4

[0080] Preparation of the catalyst solution: 10 ml of dry dichloromethane, 5.15 g of hydroxypropyl methacrylate and 152 ?l of trifluoromethanesulfonic acid are combined and stirred for 1 h at room temperature. 4.05 ml of the previously prepared catalyst solution is placed in a flask and adjusted to a temperature of 23? C. 15.18 g (144 mmol) of 4-ethyl-1,3-dioxolane (EDX) and 10.12 ml (144 mmol) of 1,3-dioxolane (DXL) are then added and stirred.

[0081] After 4 h, pyridine is added until the mixture loses its color. The product is washed with heptane and distilled water and then dried under reduced pressure.

Example 5

[0082] Preparation of the catalyst solution: 10 ml of dry dichloromethane, 3.34 g of 1-dodecanol and 76 ?l of trifluoromethanesulfonic acid are combined and stirred for 1 h at room temperature. 1.35 ml of the previously prepared catalyst solution is placed in a flask and adjusted to a temperature of 23? C. 10.12 g (96 mmol) of 4-ethyl-1,3-dioxolane (EDX) and 6.75 ml (96 mmol) of 1,3-dioxolane (DXL) are then added and stirred.

[0083] After 4 h, pyridine is added until the mixture loses its color. The product is washed with heptane and distilled water and then dried under reduced pressure.

Example 6

[0084] Preparation of the catalyst solution: 10 ml of dry dichloromethane, 1.05 ml of ethanol and 76 ?l of trifluoromethanesulfonic acid are combined and stirred for 1 h at room temperature. 1.35 ml of the previously prepared catalyst solution is placed in a flask and adjusted to a temperature of 23? C. 10.12 g (96 mmol) of 4-ethyl-1,3-dioxolane (EDX) and 6.75 ml (96 mmol) of 1,3-dioxolane (DXL) are then added and stirred. After 4 h, pyridine is added until the mixture loses its color. The product is washed with heptane and distilled water and then dried under reduced pressure.

Example 7 (Non-Inventive)

[0085] 1.35 ml of the catalyst solution prepared in Example 1 is placed in a flask and adjusted to a temperature of 23? C. 13.5 ml (193 mmol) of 1,3-dioxolane (DXL) is then added and stirred. It is no longer possible to stir the reaction mixture after 10 min. 1 ml of pyridine and 10 ml of dichloromethane are added to the reaction solution. The solids are then precipitated in heptane, washed with distilled water and dried under reduced pressure.

[0086] The results of the examples are detailed in Table 1:

TABLE-US-00001 TABLE 1 Amount of M in Mn in Mw in initiator in g/mol g/mol g/mol Viscosity Tg in Example Initiator mol % (NMR) (SEC) (SEC) PDI in Pas ? C. 1 Allyloxyethanol 1.25 4120 2750 6560 2.47 5.4 ?64 2 Allyloxyethanol 2.5 2810 3860 6340 1.64 2.7 ?65 3 Allyloxyethanol 5.0 1600 1610 2700 1.67 0.87 ?67 4 Hydroxybutyl 5.6 1800 2010 3520 1.75 1.7 ?62 methacrylate 5 Dodecanol 1.26 4980 3510 6470 1.85 4.6 ?64 6 Ethanol 1.26 4020 4020 7300 1.82 7.3 ?63 7* Allyloxyethanol 1.24 4800 3720 9420 2.53 n.d. ?62 (product is solid) *non-inventive