Increasing the molecular weight of low molecular weight a,w-polysiloxanediols

Abstract

A process can be used for increasing the molecular weight of low molecular weight α,ω-polysiloxanediols. The process involves heating the low molecular weight α,ω-polysiloxanediols in the presence of acetic anhydride at temperatures of 80° C. to 220° C., preferably at temperatures of 100 to 200° C., and particularly preferably at temperatures of 120-180° C., for 1 h to 24 h, preferably for 2 h to 16 h, and particularly preferably for 3 h to 12 h. The molar amount of the silanol groups used is greater than that of the acetic anhydride used.

Claims

1. A process for increasing the molecular weight of at least one low molecular weight α,ω-polysiloxanediol, the process comprising: heating the at least one low molecular weight α,ω-polysiloxanediol in the presence of acetic anhydride in a reaction mixture, at a temperature of 80° C. to 220° C. for 1 h to 24 h, to obtain an end product comprising at least one linear α,ω-polysiloxanediol, wherein a molar amount of silanol groups used is greater than that of the acetic anhydride used.

2. The process according to claim 1, wherein a molar ratio of the silanol groups to the acetic anhydride is 2.00 to 1.00.

3. The process according to claim 1, wherein the process is conducted under inert conditions.

4. The process according to claim 1, wherein the reaction mixture is neutralized after the heating.

5. The process according to claim 1, wherein the at least one linear α,ω-polysiloxanediol satisfies at least formula (I): ##STR00003## wherein R.sup.1 is an alkyl radical and/or aromatic radical, comprising 1 to 10 carbon atoms, and wherein 10≤n≤10,000.

6. The process according to claim 1, wherein the end product is cooled and filtered.

7. The process according to claim 1, wherein an increase in the number-average molecular weight of the end product is determined by a Si-NMR spectroscopy.

8. A method of production, comprising: producing a composition with the end product produced by the process according to claim 1, as a raw material, wherein the composition is at least one selected from the group consisting of a rubber composition, a lubricating oil composition, a defoamer composition, a thermal oil composition, a sealing compound composition, and an adhesive composition.

9. A method of functionalizing, comprising: functionalizing a surface or a particle with the end product produced by the process according to claim 1.

10. The process according to claim 1, wherein the heating is at a temperature of 120° C. to 180° C.

11. The process according to claim 1, wherein the heating is for 3 h to 12 h.

12. The process according to claim 2, wherein the molar ratio of the silanol groups to the acetic anhydride is 2.00 to <1.00.

13. The process according to claim 3, wherein the process is conducted under anhydrous conditions.

14. The process according to claim 3, wherein the process is conducted under a gas blanket.

15. The process according to claim 5, wherein R.sup.1 is a methyl radical.

16. The process according to claim 5, wherein n is between 100 and 1,000.

Description

BRIEF DESCRIPTION OF THE DRAWING

[0024] The FIGURE shows the .sup.29Si-NMR spectrum according to Example 1.

DETAILED DESCRIPTION OF THE INVENTION

[0025] In the context of this invention, “essentially cycle-free” means that the cumulative proportion, determinable by gas chromatography, consisting of octamethylcyclotetrasiloxane (D.sub.4), decamethylcyclopentasiloxane (D.sub.5) and dodecamethylcyclohexasiloxane (D.sub.6) amounts to ≤0.15% by weight, preferably ≤0.10% by weight, based on the content proportion of the α,ω-siloxanediol.

[0026] The process according to the invention surprisingly makes it possible to produce higher molecular weight, essentially cycle-free α,ω-polysiloxanediols, without adding amines or a catalyst. The simplified process regime, in the sense of a reduction in process steps, is also a further advantage according to the invention.

[0027] In the context of this invention, “higher molecular weight α,ω-polysiloxanediols” means that the end product has a higher number-average molecular weight than that of the reactant used.

[0028] The preferred acetic anhydride has a purity of greater than 99%, particularly preferably of greater than 99.5%. However, use may also be made of any acetic anhydride known to those skilled in the art.

[0029] It is preferable according to the invention that the molar ratio of silanol groups used to acetic anhydride is 2.00 to 1.00 or preferably 2.00 to <1.00.

[0030] To ensure the stoichiometric ratio which is the aim of the invention, use is made of .sup.29Si-NMR spectroscopy, which allows the number-average molecular weight of the respective α,ω-polydimethylsiloxanediol to be determined. The characteristic signal for a silanol group (D-OH unit) is at a chemical shift of −10.7 ppm. The group of signals for the unmodified D units is in the shift region at −20 to −23 ppm. The number-average molecular weight Mn can be determined on the basis of the following formula:

[00001]$M_n=2M_{D-\mathrm{OH}}+2\frac{I_D}{I_{D-\mathrm{OH}}}{M}_D$

where I represents the integral value of the respective signal. The molecular weight of a D unit is M.sub.D=74.1 g.Math.mol.sup.−1 and the molecular weight of a D-OH unit is M.sub.D-OH=83.1 g.Math.mol.sup.−1, it being assumed in the latter case in purely mathematical terms that half the atomic mass of an oxygen atom should be counted towards the molecular weight of a D-OH unit.

[0031] Preferably, the process according to the invention is conducted under inert conditions, preferably anhydrous conditions and particularly preferably under a protective gas blanket. Suitable examples for this purpose are dry nitrogen or argon.

[0032] The reaction mixture is preferably neutralized after the reaction.

[0033] When the desired molecular weight has been reached, the end product can preferably be neutralized with a weak base to remove traces of acetic anhydride or convert any terminal acetoxy groups. Common bases are known to those skilled in the art. Examples here include the ammonium, sodium, potassium, calcium and magnesium salts of the hydrogencarbonate ion, of the carbonate ion, of the hydrogenphosphate ion and of the phosphate ion. Gaseous ammonia may also be used for neutralization.

[0034] The linear α,ω-polysiloxanediols preferably satisfy at least formula (I):

##STR00002##

[0035] where R.sup.1 is an alkyl radical and/or aromatic radical, comprising 1 to 10 carbon atoms, preferably a methyl radical, and where 10≤n≤10 000, preferably n is between 30 and 3000, particularly preferably n is between 100 and 1000.

[0036] Particularly preferably, the low molecular weight α,ω-polysiloxanediols are α,ω-polydimethylsiloxanediols.

[0037] The end product is preferably cooled and filtered.

[0038] The increase in the number-average molecular weight of the end product is preferably determined by means of .sup.29Si-NMR spectroscopy.

[0039] The invention further provides the use of the end product obtainable by the process according to the invention as raw material for further chemical syntheses, such as for the production of rubber, lubricating oil, defoamers, thermal oil, sealing compounds and adhesives and for the functionalization of surfaces and particles.

[0040] The examples which follow are provided merely to elucidate this invention to those skilled in the art and do not constitute any limitation of the described subject matter or of the described process whatsoever.

Methods

Nuclear Magnetic Resonance (NMR)

[0041] NMR spectra were recorded on a Bruker Avance III 400 spectrometer. The .sup.29Si-NMR spectra were measured at a frequency of 79.495 MHz on a Bruker PA BBO 400Si BB-H-D-10 z probe. The measurement time was 2.569 seconds per scan, with a total of 512 scans per spectrum. The .sup.29Si-NMR spectrum was used to determine the number-average molecular weight of the respective α,ω-polydimethylsiloxanediol. The characteristic signal for a silanol group (D-OH unit) is at −10.7 ppm. The group of signals for the unmodified D units is in the shift region at −20 to −23 ppm. The number-average molecular weight M.sub.n can be determined on the basis of the following formula:

[00002]$M_n=2M_{D-\mathrm{OH}}+2\frac{I_D}{I_{D-\mathrm{OH}}}{M}_D$

[0042] where I represents the integral value of the respective signal. The molecular weight of a D unit is M.sub.D=74.1 g.Math.mol.sup.−1 and the molecular weight of a D-OH unit is M.sub.D-OH=83.1 g.Math.mol.sup.−1.

Gas Chromatography (GC)

[0043] The gas chromatograms are recorded on an Agilent Technologies GC 7890B GC instrument equipped with an HP-1 column; 30 m×0.32 mm ID×0.25 μm FT (Agilent Technologies No. 19091Z-413E) and hydrogen as carrier gas with the following parameters: [0044] Detector: FID; 310° C. [0045] Injector: split; 290° C. [0046] Mode: constant flow, 2 ml/min [0047] Temperature programme: 60° C. at 8° C./min-150° C. at 40° C./min-300° C. 10 min.

[0048] To ensure the molar ratio of the reactants which is the aim of the invention, use is made of .sup.29Si-NMR spectroscopy, which allows the number-average molecular weight of the respective α,ω-polydimethylsiloxanediol to be reliably determined. The characteristic signal for a silanol group (D-OH unit) is at a chemical shift of −10.7 ppm. The group of signals for the unmodified D units is in the shift region at −20 to −23 ppm. The number-average molecular weight Mn can be determined on the basis of the following formula:

[00003]$M_n=2M_{D-\mathrm{OH}}+2\frac{I_D}{I_{D-\mathrm{OH}}}{M}_D$

[0049] where I represents the integral value of the respective signal. The molecular weight of a D unit is M.sub.D=74.1 g.Math.mol.sup.−1 and the molecular weight of a D-OH unit is M.sub.D-OH=83.1 g.Math.mol.sup.−1, it being assumed in the latter case in purely mathematical terms that half the atomic mass of an oxygen atom should be counted towards the molecular weight of a D-OH unit. The molecular weight thus ascertained represents the reference parameter according to the invention for the amount of acetic anhydride to be used.

Further Conditions

[0050] Where values are reported in % in the context of the present invention, these are % by weight values, unless stated otherwise. In the case of compositions, the values reported in % are based on the total composition, unless stated otherwise. Where averages are reported in the examples which follow, these are number averages, unless stated otherwise. Where measurement values are reported below, these measurement values, unless stated otherwise, were determined at a pressure of 101 325 Pa, a temperature of 23° C. and the ambient relative humidity of approximately 40%.

Materials and Equipment

[0051] α,ω-Polydimethylsiloxanediol (PDM siloxane), from Dow [0052] Acetic anhydride, from Merck [0053] Sodium hydrogencarbonate, from Sigma-Aldrich [0054] Anhydrous sodium carbonate, from Sigma-Aldrich [0055] Trifluoromethanesulfonic acid, from Sigma-Aldrich [0056] Aluminium acetate, basic, from Sigma-Aldrich

EXAMPLES

Example 1 (Inventive)

[0057] 200.00 g of α,ω-polydimethylsiloxanediol from Batch A (corresponding to 0.157 mol of silanol groups) and 8.03 g of acetic anhydride (0.079 mol) were mixed in a 500 ml four-necked flask with stirring, corresponding to a molar ratio of silanol to anhydride of 1.99 to 1.00. The reaction mixture was heated to 100° C. with further stirring under nitrogen inertization for a duration of 12 hours. The reaction mixture was subsequently cooled to 80° C. and neutralized with 4.16 g of sodium hydrogencarbonate. After stirring for a further 2 hours, the product was left to cool to room temperature and the solids were removed by filtration through a fluted filter. The isolated end product is clear and colourless. The number-average molecular weight was determined on the basis of the .sup.29Si-NMR spectrum (see the FIGURE) and the content of D.sub.4, D.sub.5 and D.sub.6 was determined by GC. The results are collated in Table 1. As apparent from the data in Table 1, the molecular weight of the original PDM siloxane was virtually quadrupled. The cumulative proportion of D.sub.4, D.sub.5 and D.sub.6 was <0.15%.

Example 2 (Inventive)

[0058] 300.00 g of α,ω-polydimethylsiloxanediol from Batch B (corresponding to 0.2007 mol of silanol groups) and 10.25 g of acetic anhydride (0.1004 mol) were mixed in a 500 ml four-necked flask with stirring, with the result that a molar ratio of silanol to anhydride of 2.00 to 1.00 was selected. The reaction mixture was heated to 150° C. under a nitrogen atmosphere and with further stirring for a total of 6 hours. Subsequently the temperature was lowered to 80° C. and neutralization was performed with 4.16 g of sodium hydrogencarbonate. After continuing to stir for a further 2 hours, the product was cooled to room temperature and filtered. The end product is clear and colourless. The number-average molecular weight was determined with the aid of .sup.29Si-NMR spectroscopy and the content of D.sub.4, D.sub.5 and D.sub.6 was determined by GC. The results are collated in Table 1. As apparent from the data in Table 1, the molecular weight of the original PDM siloxane was increased virtually six-fold. The cumulative proportion of D.sub.4, D.sub.5 and D.sub.6 was <0.10%.

Example 3 (Non-Inventive)

[0059] 300.00 g of α,ω-polydimethylsiloxanediol from Batch B and 0.36 g of trifluoromethanesulfonic acid as catalyst were mixed in a 500 ml four-necked flask with stirring and heated to 150° C. at a pressure of 50 mbar for a duration of 12 hours. The reaction mixture was subsequently cooled to 80° C. and neutralized with 8.8 g of anhydrous sodium carbonate. After continuing to stir for a further 2 hours, the reaction mixture was cooled to room temperature and filtered through a fluted filter. The filtrate obtained is clear and colourless. The number-average molecular weight thereof was determined with the aid of .sup.29Si-NMR spectroscopy and the content of D.sub.4, D.sub.5 and D.sub.6 was determined by GC. The results are collated in Table 1. It was found that substantial amounts of cyclic siloxanes were formed.

Example 4 (Non-Inventive)

[0060] 300.00 g of α,ω-polydimethylsiloxanediol from Batch B and 0.020 g of basic aluminium acetate as catalyst were mixed in a 500 ml four-necked flask with stirring and heated to 150° C. at a reduced pressure of 60 mbar for a total of 15 hours. The reaction mixture was subsequently cooled and filtered. The filtrate obtained is clear and colourless. The number-average molecular weight of the end product was determined with the aid of .sup.29Si-NMR spectroscopy and the content of D.sub.4, D.sub.5 and D.sub.6 was determined by GC. The results are collated in Table 1. It was found that substantial amounts of cyclic siloxanes were formed.

TABLE-US-00001 TABLE 1 Molecular weights and cyclic siloxanes Mn/g .Math. Σ (D4 + Sample mol.sup.−1 D4 D5 D6 D5 + D6) PDM Batch A   2543 <0.02 <0.02 0.02 <0.06 PDM Batch B   2990 <0.02 <0.02 0.02 <0.06 Example 1 10 681 0.02 0.02 0.07 0.11 Example 2 17 823 0.02 0.03 0.04 0.09 Example 3 12 483 0.27 0.06 0.05 0.38 (non-inventive) Example 4 18 334 0.32 0.07 0.08 0.47 (non-inventive)

[0061] All figures for the cyclic siloxanes D4, D5 and D6 are in % by weight.