LIQUID 1,3-DIOXOLANE COPOLYMERS

Abstract

Copolymers and methods of making the same. The copolymers are 1,3-Dioxolane copolymers of the general formula I where x1+x2 has values of 10 to 2000. Where R.sup.1 and R.sup.2 are hydrogen radicals or C.sub.1 to C.sub.18 alkyl radical. 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 Cis alkyl radical. Where y1+y2 has values of 3*(x1+x2+y1+y2)/100 to 50*(x1+x2+y1+y2)/100.

Claims

1-8. (canceled)

9. Copolymers, comprising: wherein the copolymers are 1,3-Dioxolane copolymers of the general formula I
H[OCH.sub.2OCH.sub.2CH.sub.2-].sub.x1[OCH.sub.2CH.sub.2OCH.sub.2-].sub.x2
[OCH.sub.2OCHR.sup.1CHR.sup.2-].sub.y1[OCHR.sup.1CHR.sup.2OCH.sub.2-].sub.y2 OH(I), wherein x1+?2 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; and wherein y1+y2 has values of 3*(x1+x2+y1+y2)/100 to 50*(x1+x2+y1+y2)/100.

10. The copolymers of claim 9, wherein the radicals R.sup.1 and R.sup.2 are selected from hydrogen radicals or methyl, ethyl, n-propyl or i-propyl radicals.

11. The copolymers of claim 9, 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.

12. The copolymers of claim 9, wherein the 1,3-Dioxolane 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.

13. The copolymers of claim 9, wherein the 1,3-Dioxolane 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.

14. A process for producing copolymers, comprising: providing copolymers, wherein the copolymers are 1,3-Dioxolane copolymers of the general formula I
H[OCH.sub.2OCH.sub.2CH.sub.2-].sub.x1[OCH.sub.2CH.sub.2OCH.sub.2-].sub.x2
[OCH.sub.2OCHR.sup.1CHR.sup.2-].sub.y1[OCHR.sup.1CHR.sup.2OCH.sub.2-].sub.y2 OH(I), wherein x1+?2 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, copolymerizing the 1,3-dioxolane copolymers with alkyl-substituted 1,3-dioxolane of the general formula II ##STR00002## wherein the copolymerization process occurs in the presence of a Lewis or Br?nsted acid.

15. The process of claim 14, wherein the acid is selected from boron trifluoride etherate and trifluoromethanesulfonic acid.

16. The process of claim 14, wherein the temperature is between 10? C. and 60? C.

Description

EXAMPLES

Analysis for the Entire Invention:

[0049] NMR Spectroscopy to Determine the Proportion of Alkyl Ethylene Oxide Bridges y1+y2:

[0050] The measurement is effected in solution in CDCl.sub.3 on a Bruker Avance 500 or Ascend 500 (500 MHz for .sup.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.

SEC (Size-Exclusion Chromatography) to Determine the Number-Average and Mass-Average Molecular Weights Mn, Mw and the Polydispersity:

[0051] The measurement is effected 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.

Rheometer to Determine the Dynamic Viscosity:

[0052] 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.

DSC (Differential Scanning Calorimetry/Differential Thermal Analysis) to Determine the Melting Point and the Glass Transition Temperature:

[0053] The measurement is 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/min, the second run being used to determine the melting point and the glass transition temperature.

TGA Analysis to Determine the Start of Decomposition:

[0054] The start of decomposition (onset) is 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, Non-Inventive

[0055] 8.0 ml (114 mmol) of 1,3-dioxolane (DXL) is placed in a flask and 14 ?l of boron trifluoride etherate is added while stirring. An increase in viscosity can be observed, after 10 min the reaction solution is solid. 5 ml of a 5% by weight sodium carbonate solution is added. The mixture is dissolved in dichloromethane, and the product is precipitated in heptane and filtered. The white solid is dried under reduced pressure.

Example 2

[0056] 3.6 ml (50 mmol) of 1,3-dioxolane (DXL) and 5.1 g (50 mmol) of 4-ethyl-1,3-dioxolane (EDX) are placed in a flask and 14 ?l of boron trifluoride etherate is added while stirring. An increase in viscosity can be observed. After 4 h, 5 ml of a 5% by weight sodium carbonate solution is added and the product is washed with heptane. The viscous residue is dried under reduced pressure.

Example 3

[0057] 5.2 ml (75 mmol) of 1,3-dioxolane (DXL) and 2.55 g (25 mmol) of 4-ethyl-1,3-dioxolane (EDX) are placed in a flask and 14 ?l of boron trifluoride etherate is added while stirring. An increase in viscosity can be observed. After 2 h, it is no longer possible to stir the reaction mixture. 5 ml of a 5% by weight sodium carbonate solution and dichloromethane are added and the product is precipitated in heptane. The highly viscous, white residue is dried under reduced pressure.

Example 4

[0058] 5.8 ml (83 mmol) of 1,3-dioxolane (DXL) and 1.74 g (17 mmol) of 4-ethyl-1,3-dioxolane (EDX) are placed in a flask and 14 ?l of boron trifluoride etherate is added while stirring. The reaction is highly exothermic and an increase in viscosity can be observed. After 5 min, it is no longer possible to stir the reaction mixture. 5 ml of a 5% by weight sodium carbonate solution and 5 ml of dichloromethane are added and the product is precipitated in heptane. The white solid is dried under reduced pressure.

Example 5

[0059] 5.1 g (50 mmol) of 4-ethyl-1,3-dioxolane (EDX) and 14 ?l of boron trifluoride etherate are placed in a flask. Within 15 min, while stirring 3.6 ml (50 mmol) of 1,3-dioxolane (DXL) is added dropwise while stirring. The reaction mixture is stopped after 2 h by addition of 5 ml of a 5% by weight sodium carbonate solution. After addition of dichloromethane, the product is washed with heptane and dried under reduced pressure. The result is a viscous oil.

Example 6

[0060] 2.55 g (25 mmol) of 4-ethyl-1,3-dioxolane (EDX) and 14 ?l of boron trifluoride etherate are placed in a flask. Within 30 min, 4.2 ml (60 mmol) of 1,3-dioxolane (DXL) is added dropwise while stirring. The reaction mixture is stopped after 2 h by addition of 5 ml of a 5% by weight sodium carbonate solution. After addition of dichloromethane, the product is added dropwise to heptane, the heptane phase is removed and the residue is dried under reduced pressure. The result is a viscous oil.

For Examples 7 to 10

Preparation of the Catalyst Solution:

[0061] 10 ml of dry dichloromethane, 1000 ?l of ethylene glycol and 76 ?l of trifluoromethanesulfonic acid are combined and stirred for 1 h at room temperature.

Example 7

[0062] 4.5 ml of catalyst solution and 4.5 ml of dry dichloromethane are placed in a flask and adjusted to a temperature of 23? C. 67.5 g (640 mmol) of 4-ethyl-1,3-dioxolane (EDX) and 45 ml (640 mmol) of 1,3-dioxolane (DXL) are then added and stirred. The reaction turns pink.

[0063] After 4.5 h, pyridine is added until the mixture loses its color. The product is washed with heptane and then dried under reduced pressure.

Example 8

[0064] 9.0 ml of catalyst solution is placed in a flask and adjusted to a temperature of 23? C. 67.5 g (640 mmol) of 4-ethyl-1,3-dioxolane (EDX) and 45 ml (640 mmol) of 1,3-dioxolane (DXL) are then added and the reaction mixture is stirred for 60 min at 21? C. The reaction mixture turns pink. After 5.5 h, pyridine is added until the mixture loses its color. The product is washed with heptane and then dried under reduced pressure.

Example 9

[0065] 0.25 ml of catalyst solution and 0.25 ml of dichloromethane are placed in a flask. 3.75 g (35 mmol) of 4-ethyl-1,3-dioxolane (EDX) and 2.5 ml (35 mmol) of 1,3-dioxolane (DXL) are then added and the mixture is stirred for 3 h at 23? C. 10 ml of dichloromethane is added to the reaction and then 10% sodium hydroxide solution is added dropwise until a pH of 7. The product is washed with twice with 20 ml of water and dried under reduced pressure.

Example 10

[0066] 0.25 ml of catalyst solution and 0.25 ml of dichloromethane are placed in a flask. 800 mg (8 mmol) of 4-ethyl-1,3-dioxolane (EDX) and 4.7 ml (67 mmol) of 1,3-dioxolane (DXL) are then added and the mixture is stirred at 23? C. After 4 h, 1 ml of pyridine and 5 ml of dichloromethane are added. After addition of heptane, the supernatant is decanted off and the product is dried under reduced pressure. The result is a white solid.

TABLE-US-00001 TABLE n (DXL) n (EDX) Incorporation Mn in Mw in Example in mmol in mmol of EDX in % g/mol g/mol PDI Tm Tg Catalyst: BF.sub.3Et.sub.2O 1* 114 0 0 4500 11 300 2.54 55? C. ?60? C. 2 50 50 19 7515 24 458 3.25 ?62? C. 3 75 25 9 5770 19 729 3.42 21? C. ?62? C. 4 83 17 7 12 910 54 341 4.21 26? C. ?61? C. 5 50 50 16 2040 4980 2.4 ?62? C. 6 60 25 14 4100 12 100 3.0 ?62? C. Catalyst solution: Trifluoromethanesulfonic acid/ethylene glycol in methylene chloride 7 640 640 19 7960 22 080 2.7 ?62? C. 8 640 640 17 3740 8720 2.3 ?62? C. 9 35 35 10 4200 12 695 3.0 14? C. ?62? C. 10 67 8 4 7070 31 400 4.4 33? C. ?62? C. *non-inventive