HIGH MOLECULAR WEIGHT POLYOXYALKYLENE WITH LOW GLASS TRANSITION TEMPERATURE, PRODUCED BY THE GRAFTING THROUGH METHOD

Abstract

A method for preparing polyoxyalkylene monomers, comprising the step of the reaction of one or more H-functional starter substance(s), one or more alkylene oxides and carbon dioxide in the presence of a DMC catalyst is characterized in that at least one of the H-functional starter substance(s) comprises a carbon-carbon double bond, wherein the carbon-carbon double bond is part of a cyclic structure. The macromonomers obtained can be used in a method for preparing polyoxyalkylene brush polymers, wherein this method comprises the step of the reaction with an olefin metathesis catalyst. The polyoxyalkylene brush polymers obtained may subsequently be crosslinked.

Claims

1. A process for preparing polyoxyalkylene macromers, comprising reacting one or more H-functional starter substances and one or more alkylene oxides in the presence of a catalyst, wherein at least one of the H-functional starter substances comprises a carbon-carbon double bond which is part of a cyclic structure, and wherein the starter substance and the alkylene oxide are metered continuously into the reactor during the reaction.

2. The process as claimed in claim 1, wherein the H-functional starter substance which comprises a carbon-carbon double bond corresponds to the following general formula: ##STR00011## wherein o represents a natural number from 0 to 8, R1, R2, R3, R4 and R5 each independently represent hydrogen, a C1-C22 alkyl radical, a C6-C14 aryl radical, a C7-C14 aralkyl radical, a C7-C14 alkylaryl radical, a C5-C12 cycloalkyl radical, or are an ester group COOR6, wherein R6 represents a C1-C22 alkyl radical, a C6-C14 aryl radical, a C7-C14 aralkyl radical, a C7-C14 alkylaryl radical, a C5-C12 cycloalkyl radical, or the radicals R1 and R3 together form a C1-C3 alkylene bridge or an ether bridge, p represents a natural number from 1 to 6, and X represents a carboxyl group, an OH group, a C1-C22 alkyl radical substituted by a carboxyl group or OH group, a C6-C14 aryl radical substituted by a carboxyl group or OH group, or a COOAlkOH radical, wherein AlkOH represents a C2 to C12 hydroxyalkyl radical.

3. The process as claimed in claim 1, wherein the H-functional starter substance comprises norbornenecarboxylic acid, hydroxyethyl norbornenecarboxylate, hydroxypropyl norbornenecarboxylate, hydroxybutyl norbornenecarboxylate, hydroxynorbornene, hydroxymethylnorbornene, cyclopentenecarboxylic acid, cyclooctenecarboxylic acid, cyclodecenecarboxylic acid, cyclopentenol, cyclooctenol, or a mixture thereof.

4. The process as claimed in claim 1, wherein the reaction of one or more H-functional starter substance and one or more alkylene oxide is conducted in the presence of a double metal cyanide (DMC) catalyst and of carbon dioxide.

5. The process as claimed in claim 4, comprising () optionally, initially charging a portion of the H-functional starter substance and/or a suspension medium containing no H-functional groups in a reactor, in each case optionally together with DMC catalyst, () optionally, adding a portion of alkylene oxide to the mixture from step () at temperatures of 90 to 150 C., and halting the addition of the alkylene oxide compound, and () continuously metering one or more H-functional starter substance(s) into the reactor during the reaction.

6. The process as claimed in claim 1, wherein the alkylene oxide comprises propylene oxide, ethylene oxide, 1-butylene oxide, 1-hexene oxide, 1-dodecene oxide, epichlorohydrin, methyl glycidyl ether, ethyl glycidyl ether, butyl glycidyl ether, dodecyl glycidyl ether, tetradecyl glycidyl ether, methoxyethyl glycidyl ether, methoxyethoxyethyl glycidyl ether, allyl glycidyl ether, phenyl glycidyl ether, cresyl glycidyl ether, furfuryl glycidyl ether, benzyl glycidyl ether, tetrahydrofurfuryl glycidyl ether, or mixtures thereof.

7. Polyoxyalkylene macromers comprising the reaction product of an H-functional starter substance and an alkylene oxide, in the presence of a catalyst, wherein said H-functional starter substance comprises a carbon-carbon double bond which is part of a cyclic structure, and wherein the H-functional starter substance and the alkylene oxide are continuously metered into the reactor.

8. The polyoxyalkylene macromers as claimed in claim 7, wherein the polyoxyalkylene macromer has a CO.sub.2 content of 3% by weight to 35% by weight, wherein the CO.sub.2 content has been determined by means of .sup.1H NMR.

9. The polyoxyalkylene macromers as claimed in claim 7, wherein the polyoxyalkylene macromer wherein has a number-average molecular weight M.sub.n of 500 g/mol to 1 000 000 g/mol, which has been determined by means of GPC.

10. The polyoxyalkylene macromers as claimed in claim 7, wherein the polyoxyalkylene macromer has a glass transition temperature T.sub.g of 80 C. mol to 1 C.

11. A process for preparing polyoxyalkylene brush polymers, comprises reacting a polyoxyalkylene macromer as claimed in claim 7 with an olefin metathesis catalyst.

12. The process as claimed in claim 11, wherein the reaction is additionally conducted in the presence of a cyclic olefin.

13. The process as claimed in claim 11, wherein the olefin metathesis catalyst comprises a ruthenium carbene complex(es) which comprises dichloro[1,3-bis(2,4,6-trimethylphenyl)-2-imidazolidinylidene](benzylidene)bis(3-bromopyridine)ruthenium(II), dichloro[1,3-bis(2,4,6-trimethylphenyl)-2-imidazolidinylidene](2-isopropoxyphenylmethylene)ruthenium(II), dichloro(benzylidene)bis(tricyclohexylphosphine)ruthenium(II), dichloro[1,3-bis(2-methylphenyl)-2-imidazolidinylidene](2-isopropoxyphenylmethylene)ruthenium(II), and mixtures thereof.

14. Polyoxyalkylene brush polymers comprising the reaction product of the polyoxyalkylene macromer of claim 7 with an olefin metathesis catalyst.

15. Crosslinked polyoxyalkylene polymers comprising: (i) the reaction product of polyoxyalkylene brush polymers which contain an OH end group as claimed in claim 14 with polyisocyanates; (ii) the reaction product of polyoxyalkylene brush polymers which contain an OH end group as claimed in claim 14 with polycarboxylic acids or cyclic carboxylic anhydrides; or (iii) the free-radical of polyoxyalkylene brush polymers as claimed in claim 14.

Description

EXAMPLES

Feedstocks

H-Functional Starter Substances

[0138] NCA: 5-norbornene-2-carboxylic acid (Sigma-Aldrich, 98%)

Epoxides

[0139] propylene oxide (Chemogas NV, 99.9%)

Comonomer

[0140] norbornene (Sigma-Aldrich, 99%)

Suspension Medium

[0141] cPC: cyclic propylene carbonate (Sigma-Aldrich, 99%)

Catalyst

[0142] The DMC catalyst used in all examples was DMC catalyst prepared according to example 6 in WO 01/80994 A1.

[0143] Grubbs catalyst: dichloro[1,3-bis(2,4,6-trimethylphenyl)-2-imidazolidinylidene](benzylidene)bis(3-bromopyridine)ruthenium(II) (Sigma-Aldrich)

Methods

[0144] The polymerization reactions were conducted in a 300 ml Parr pressure reactor. The pressure reactor used in the examples had a height (internal) of 10.16 cm and an internal diameter of 6.35 cm. The reactor was equipped with an electric heating jacket (510 watts' maximum heating power). The counter-cooling consisted of an immersed tube of external diameter 6 mm which had been bent into a U shape and which projected into the reactor up to 5 mm above the base, and through which flowed cooling water of about 10 C. The water flow was switched on and off by means of a solenoid valve. In addition, the reactor was equipped with an inlet tube and a thermal sensor of diameter 1.6 mm, which both projected into the reactor up to 3 mm above the base.

[0145] The sparging stirrer used in the examples was a hollow shaft stirrer in which the gas was introduced into the reaction mixture via a hollow shaft in the stirrer. The stirrer body attached to the hollow shaft comprised four arms, had a diameter of 35 mm and a height of 14 mm. Each arm end had two gas outlets of diameter 3 mm attached to it. The rotation of the stirrer gave rise to a reduced pressure such that the gas present above the reaction mixture (CO.sub.2 and possibly alkylene oxide) was drawn off and introduced through the hollow shaft of the stirrer into the reaction mixture. The abbreviation rpm refers to the number of revolutions of the stirrer per minute.

[0146] Subsequently, the reaction mixture was diluted with dichloromethane (20 ml) and the solution was passed through a falling-film evaporator. The solution (0.1 kg in 3 h) ran downwards along the inner wall of a tube of diameter 70 mm and length 200 mm which had been heated externally to 120 C., in the course of which the reaction mixture was distributed homogeneously as a thin film on the inner wall of the falling-film evaporator in each case by three rollers of diameter 10 mm rotating at a speed of 250 rpm. Within the tube, a pump was used to set a pressure of 3 mbar. The reaction mixture which had been purified to free it of volatile constituents (unconverted epoxides, cyclic carbonate, solvent) was collected in a receiver at the lower end of the heated tube.

[0147] a) The copolymerization of propylene oxide and CO.sub.2 not only resulted in the cyclic propylene carbonate but also in the polyethercarbonate macromer which firstly contains polycarbonate units shown in the following formula:

##STR00009##

and secondly contains polyether units shown in the following formula:

##STR00010##

[0148] For .sup.1H NMR spectra, the sample was dissolved in deuterated chloroform and analyzed on a Bruker spectrometer (AV400, 400 MHz).

[0149] The relevant resonances in the .sup.1H NMR spectrum (based on TMS=0 ppm) which were used for integration are as follows:

[0150] I1: 1.10-1.17 ppm: CH.sub.3 group of the polyether units, area of the resonance corresponds to three hydrogen atoms,

[0151] I2: 1.25-1.34 ppm: CH.sub.3 group of the polycarbonate units, area of the resonance corresponds to three hydrogen atoms,

[0152] I3: 6.22-6.29 ppm: CH group of the double bond obtained in the polymer via the incorporation of 5-norbornene-2-carboxylic acid, area of the resonance corresponds to two hydrogen atoms.

[0153] Data reported are the molar ratio of carbonate groups to ether groups in the polyethercarbonate macromer (e/f), the proportion of carbonate groups (mol %) in the polyethercarbonate macromer, the proportion of ether groups (mol %) in the polyethercarbonate macromer, the proportion of NCA (mol %) in the polyethercarbonate macromer and also the proportion of CO.sub.2 (% by weight) in the polyethercarbonate macromer.

[0154] Molar ratio of carbonate groups to ether groups in the polyethercarbonate macromer (e/f):

e/f=I2/I1

[0155] The proportion of carbonate groups (mol %) in the polyethercarbonate macromer:

[00001]$\mathrm{carbonate}.Math..Math.\mathrm{group}.Math..Math.\mathrm{incorporation}.Math..Math.\left(\mathrm{mol}.Math.\%\right).Math.=\left[\frac{\left(\frac{l.Math..Math.2}{3}\right)}{\left(\frac{l.Math..Math.1}{3}\right)+\left(\frac{l.Math..Math.2}{3}\right)+\left(\frac{l.Math..Math.3}{2}\right)}\right]*1.Math.0.Math.0$

[0156] The proportion of ether groups (mol %) in the polyethercarbonate macromer:

[00002]$\mathrm{ether}.Math..Math.\mathrm{group}.Math..Math.\mathrm{incorporation}.Math..Math.\left(\mathrm{mol}.Math.\%\right)=\left[\frac{\left(\frac{l.Math..Math.2}{3}\right)}{\left(\frac{l.Math..Math.1}{3}\right)+\left(\frac{l.Math..Math.2}{3}\right)+\left(\frac{l.Math..Math.3}{2}\right)}\right]*100$

[0157] The proportion of NCA (mol %) in the polyethercarbonate macromer:

[00003]$\mathrm{NCA}.Math..Math.\mathrm{incorporation}.Math..Math.\left(\mathrm{mol}.Math.\%\right)=\left[\frac{\left(\frac{l.Math..Math.2}{3}\right)}{\left(\frac{l.Math..Math.1}{3}\right)+\left(\frac{l.Math..Math.2}{3}\right)+\left(\frac{l.Math..Math.3}{2}\right)}\right]*100$

[0158] The proportion of CO.sub.2 incorporation (% by weight) in the polyethercarbonate macromer:

[00004]${\mathrm{CO}}_2.Math..Math.\mathrm{incorporation}.Math..Math.\left(\%.Math..Math.\mathrm{by}.Math..Math.\mathrm{wieght}\right)=.Math.[\frac{\left(\frac{l.Math..Math.2}{3}\right)*4.Math.4}{\left(\frac{l.Math..Math.1}{3}*5.Math.8\right)+\left(\frac{l.Math..Math.2}{3}*1.Math.0.Math.2\right)+\left(\frac{l.Math..Math.3}{2}*1.Math.3.Math.8\right)}]*1.Math.0.Math.0$

OH Number (Hydroxyl Number)

[0159] The OH number (hydroxyl number) was determined on the basis of DIN 53240-2, except N-methylpyrrolidone rather than THF/dichloromethane was used as the solvent. Titration was effected with 0.5 molar ethanolic KOH solution, with endpoint recognition by means of potentiometry. The test substance used was certified castor oil. The reporting of the unit in mg KOH/g relates to mg[KOH]/g[polyethercarbonate macromer].

Gel Permeation Chromatography

[0160] The number-average M.sub.n and the weight-average M.sub.w molecular weights of the polyethercarbonate polyols obtained were determined by means of gel permeation chromatography (GPC). The procedure was that of DIN 55672-1: Gel permeation chromatography, Part 1Tetrahydrofuran as eluent (SECurity GPC system from PSS Polymer Service, flow rate 1.0 ml/min; columns: 2PSS SDV linear M, 8300 mm, 5 m; RID detector). Polystyrene samples of known molar mass were used for calibration. The polydispersity was calculated as the ratio M.sub.w/M.sub.n.

Rheology

[0161] The viscosity of the product mixture was determined using a Physica MCR 501 rheometer from Anton Paar at 25 C., using a sphere/plate configuration with a sphere diameter of 25 mm and with a distance of 0.05 mm between sphere and plate. The shear rate was increased from 0.01 to 1000 1/s within 10 minutes. A value was taken every 10 s. The result reported is the viscosity as the average of the total of 60 measurement values.

Thermal Analysis

[0162] The glass transition temperature was measured using a Mettler Toledo DSC 1. Between 4 and 10 mg of the sample to be measured were heated from 80 C. to 40 C. at a heating rate of 10 K/min. The evaluation software used was STAR.sup.e 25 SW 11.00. For the determination of the glass transition temperature, a tangential evaluation method was applied unless otherwise stated. The glass transition temperature reported is the mid-point between the point of intersection of the middle tangent with the low-temperature tangent and the point of intersection of the middle tangent with the high-temperature tangent.

Example 1: Preparation of a Polyethercarbonate Macromer by Copolymerization in the Semi-Batch CAOS Process at 15 bar of CO.SUB.2

Step

[0163] A 300 ml pressure reactor equipped with a sparging stirrer was initially charged with a mixture of DMC catalyst (21.5 mg) and cyclic propylene carbonate (30 g) and this initial charge was stirred (800 rpm) at 110 C. for 30 minutes under a partial vacuum (50 mbar), with argon being passed through the reaction mixture.

Step

[0164] The suspension was then heated up to 130 C. and CO.sub.2 was injected to 15 bar, in the course of which a slight drop in temperature was observed. On reattainment of a temperature of 130 C., 1.5 g of propylene oxide were metered in with the aid of an HPLC pump (1 ml/min). The reaction mixture was stirred (800 rpm) at 130 C. for 20 min. The addition of 1.5 g of the monomer mixture was repeated a second and third time.

Step

[0165] The temperature was readjusted to 110 C. and, during the subsequent steps, the pressure in the pressure reactor was kept at 15 bar with the aid of a mass flow regulator by metering in further CO.sub.2. While stirring, a further 15.5 g of a propylene oxide were metered in by means of an HPLC pump (1 ml/min), while continuing to stir the reaction mixture (800 rpm). Three minutes after the start of addition of propylene oxide, 2.12 g of 5-norbornene-2-carboxylic acid were metered in by means of a separate HPLC pump (0.16 ml/min) while stirring. After the addition of propylene oxide had ended, the reaction mixture was stirred at 110 C. for a further 30 min. The reaction was ended by cooling the pressure reactor in an ice bath, and the elevated pressure was released.

[0166] The reaction mixture diluted with dichloromethane (20 ml), the solution passed through a falling-film evaporator and the resulting product analyzed. The proportion of carbonate groups (mol %), ether groups (mol %), NCA groups (mol %) and CO.sub.2 (% by weight) incorporated in the polyethercarbonate macromer obtained, the ratio of carbonate units to ether units, the molecular weight obtained, the polydispersity index (PDI), the glass transition temperature (T.sub.g) and the decomposition temperature (T.sub.D) are reported in table 1.

Example 2: Preparation of a Polyethercarbonate Macromer by Copolymerization in the Semi-Batch CAOS Process at 15 Bar of CO.SUB.2

Step

[0167] A 300 ml pressure reactor equipped with a sparging stirrer was initially charged with a mixture of DMC catalyst (21.5 mg) and cyclic propylene carbonate (30 g) and this initial charge was stirred (800 rpm) at 110 C. for 30 minutes under a partial vacuum (50 mbar), with argon being passed through the reaction mixture.

Step

[0168] The suspension was then heated up to 130 C. and CO.sub.2 was injected to 15 bar, in the course of which a slight drop in temperature was observed. On reattainment of a temperature of 130 C., 2.0 g of propylene oxide were metered in with the aid of an HPLC pump (1 ml/min). The reaction mixture was stirred (800 rpm) at 130 C. for 20 min. The addition of 2.0 g of the monomer mixture was repeated a second and third time.

Step

[0169] The temperature was readjusted to 110 C. and, during the subsequent steps, the pressure in the pressure reactor was kept at 15 bar with the aid of a mass flow regulator by metering in further CO.sub.2. While stirring, a further 41.2 g of a propylene oxide were metered in by means of an HPLC pump (1 ml/min), while continuing to stir the reaction mixture (800 rpm). Three minutes after the start of addition of propylene oxide, 2.74 g of 5-norbornene-2-carboxylic acid were metered in by means of a separate HPLC pump (0.08 ml/min) while stirring. After the addition of propylene oxide had ended, the reaction mixture was stirred at 110 C. for a further 30 min. The reaction was ended by cooling the pressure reactor in an ice bath, and the elevated pressure was released.

[0170] The reaction mixture diluted with dichloromethane (20 ml), the solution passed through a falling-film evaporator and the resulting product analyzed. The proportion of carbonate groups (mol %), ether groups (mol %), NCA groups (mol %) and CO.sub.2 (% by weight) incorporated in the polyethercarbonate macromer obtained, the ratio of carbonate units to ether units, the molecular weight obtained, the polydispersity index (PDI), the glass transition temperature (T.sub.g) and the decomposition temperature (T.sub.D) are reported in table 1.

Comparative Example 3: Preparation of a Polyethercarbonate Macromer by Copolymerization in the Semi-Batch Process at 15 Bar of CO.SUB.2

[0171] The procedure was as described in example 1, with 5-norbornene-2-carboxylic acid (2.74 g) being initially charged in step . No polyethercarbonate macromer was obtained.

Comparison

[0172] Table 1 below shows a comparison of the results obtained for continuous metering of the starter (Continuous Addition Of Starter, CAOS, examples 1 to 3) compared to metering of the starter in batch mode (comparative example 4).

TABLE-US-00001 TABLE 1 Carbonate Ether NCA CO.sub.2 Metering groups groups groups content e/f M.sub.n PDI T.sub.g T.sub.D Example of starter [mol %] [mol %] [mol %] [% by wt.] [] [g/mol] [] [ C.] [ C.] 1 CAOS 15.6 81.9 2.6 10.4 0.19 1488 1.3 60.3 320.5 2 CAOS 15.9 81.9 2.3 10.6 0.19 2693 2.9 55.6 322.8 3 (comp.) Batch No polymer formation (comp.): Comparative example

[0173] Table 1 shows that no polymer formation takes place in the case where the starter is initially charged at the start of the reaction (comparative example 4). The metering of the starter in the CAOS process is therefore essential for the preparation of polyethercarbonate macromers when using acid-functional starters.

Example 4: Preparation of a Polyethercarbonate Macromer by Copolymerization in the Semi-Batch CAOS Process at 50 Bar of CO.SUB.2

Step

[0174] A 300 ml pressure reactor equipped with a sparging stirrer was initially charged with a mixture of DMC catalyst (21.5 mg) and cyclic propylene carbonate (30 g) and this initial charge was stirred (800 rpm) at 110 C. for 30 minutes under a partial vacuum (50 mbar), with argon being passed through the reaction mixture.

Step

[0175] The suspension was then heated up to 130 C. and CO.sub.2 was injected to 15 bar, in the course of which a slight drop in temperature was observed. On reattainment of a temperature of 130 C., 2.0 g of propylene oxide were metered in with the aid of an HPLC pump (1 ml/min). The reaction mixture was stirred (800 rpm) at 130 C. for 20 min. The addition of 2.0 g of the monomer mixture was repeated a second and third time.

Step

[0176] The temperature was readjusted to 110 C. and, during the subsequent steps, the pressure in the pressure reactor was kept at 15 bar with the aid of a mass flow regulator by metering in further CO.sub.2. While stirring, a further 21.0 g of a propylene oxide were metered in by means of an HPLC pump (1 ml/min), while continuing to stir the reaction mixture (800 rpm). Three minutes after the start of addition of propylene oxide, 2.74 g of 5-norbornene-2-carboxylic acid were metered in by means of a separate HPLC pump (0.11 ml/min) while stirring. After the addition of propylene oxide had ended, the reaction mixture was stirred at 110 C. for a further 30 min. The reaction was ended by cooling the pressure reactor in an ice bath, and the elevated pressure was released.

[0177] The reaction mixture diluted with dichloromethane (20 ml), the solution passed through a falling-film evaporator and the resulting product analyzed. The proportion of carbonate groups (mol %), ether groups (mol %), NCA groups (mol %) and CO.sub.2 (% by weight) incorporated in the polyethercarbonate macromer obtained, the ratio of carbonate units to ether units, the molecular weight obtained, the polydispersity index (PDI), the glass transition temperature (T.sub.g) and the decomposition temperature (T.sub.D) are reported in table 2.

Example 5: Preparation of a Polyethercarbonate Macromer by Copolymerization in the Semi-Batch CAOS Process at 50 Bar of CO.SUB.2

Step

[0178] A 300 ml pressure reactor equipped with a sparging stirrer was initially charged with a mixture of DMC catalyst (21.5 mg) and cyclic propylene carbonate (30 g) and this initial charge was stirred (800 rpm) at 110 C. for 30 minutes under a partial vacuum (50 mbar), with argon being passed through the reaction mixture.

Step

[0179] The suspension was then heated up to 130 C. and CO.sub.2 was injected to 15 bar, in the course of which a slight drop in temperature was observed. On reattainment of a temperature of 130 C., 2.0 g of propylene oxide were metered in with the aid of an HPLC pump (1 ml/min). The reaction mixture was stirred (800 rpm) at 130 C. for 20 min. The addition of 2.0 g of the monomer mixture was repeated a second and third time.

Step

[0180] The temperature was readjusted to 110 C. and, during the subsequent steps, the pressure in the pressure reactor was kept at 15 bar with the aid of a mass flow regulator by metering in further CO.sub.2. While stirring, a further 28.2 g of a propylene oxide were metered in by means of an HPLC pump (1 ml/min), while continuing to stir the reaction mixture (800 rpm). Three minutes after the start of addition of propylene oxide, 2.0 g of 5-norbornene-2-carboxylic acid were metered in by means of a separate HPLC pump (0.08 ml/min) while stirring. After the addition of propylene oxide had ended, the reaction mixture was stirred at 110 C. for a further 30 min. The reaction was ended by cooling the pressure reactor in an ice bath, and the elevated pressure was released.

[0181] The reaction mixture diluted with dichloromethane (20 ml), the solution passed through a falling-film evaporator and the resulting product analyzed. The proportion of carbonate groups (mol %), ether groups (mol %), NCA groups (mol %) and CO.sub.2 (% by weight) incorporated in the polyethercarbonate macromer obtained, the ratio of carbonate units to ether units, the molecular weight obtained, the polydispersity index (PDI), the glass transition temperature (T.sub.g) and the decomposition temperature (T.sub.D) are reported in table 2.

Comparative Example 6: Preparation of a Polyethercarbonate Macromer by Copolymerization in the Semi-Batch Process at 50 Bar of CO.SUB.2

[0182] The procedure was as described in example 5, with 5-norbornene-2-carboxylic acid (2.74 g) being initially charged in step . No polyoxyalkylene polyol macromer was obtained.

Comparison

[0183] Table 2 below shows a comparison of the results obtained for continuous metering of the starter (Continuous Addition Of Starter, CAOS, examples 5 and 6) compared to metering of the starter in batch mode (comparative example 6).

TABLE-US-00002 TABLE 2 Carbonate Ether NCA CO.sub.2 Metering groups groups groups content e/f M.sub.n PDI T.sub.g T.sub.D Example of starter [mol %] [mol %] [mol %] [% by wt.] [] [g/mol] [] [ C.] [ C.] 4 CAOS 28.2 68.5 3.3 17.3 0.41 1879 2.3 45.8 309.7 5 CAOS 29.0 69.5 1.5 17.9 0.42 4072 2.1 44.2 309.7 6 (comp.) Batch No polymer formation (comp.): Comparative example

[0184] Table 2 shows that no polymer formation takes place in the case where the starter is initially charged at the start of the reaction. The metering of the starter in the CAOS process is therefore essential for the preparation of polyethercarbonate macromers when using acid-functional starters.

[0185] The comparison of the results from table 1 with the results from table 2 shows that at a higher CO.sub.2 partial pressure more CO.sub.2 is incorporated into the polyoxyalkylene polyol macromer.

Example 7: Preparation of a Polyethercarbonate Brush Polymer

[0186] In a 50 ml flask, the polyethercarbonate macromer from example 1 (404.5 mg, 172.2 mol, 1.0 eq.) was dissolved in dichloromethane (1 ml) and stirred for 15 minutes. Subsequently, a solution of third-generation Grubbs catalyst (3.8 mg, 4.3 mol, 2.3 mol %) in dichloromethane (1 ml) was added. The reaction mixture was stirred at room temperature for 60 min. The reaction was then ended by adding ethyl vinyl ether (0.5 ml, 5.3 mol). Next, the solvent was removed under reduced pressure and the product was analyzed. The molecular weight obtained, the polydispersity index (PDI), glass transition temperature (T.sub.g) are reported in table 3.

Example 8: Preparation of a Polyethercarbonate Brush Polymer

[0187] In a 50 ml flask, the polyethercarbonate macromer from example 2 (397.5 mg, 175.3 mol, 1.0 eq.) was dissolved in dichloromethane (1 ml) and stirred for 15 minutes. Subsequently, a solution of third-generation Grubbs catalyst (3.6 mg, 4.1 mol, 2.3 mol %) in dichloromethane (1 ml) was transferred. The reaction mixture was stirred at room temperature for 60 min. The reaction was then ended with the addition of ethyl vinyl ether (0.5 ml, 5.3 mol). Next, the solvent was removed under reduced pressure and the product was analyzed. The molecular weight obtained, the polydispersity index (PDI), glass transition temperature (T.sub.g) are reported in table 3.

Example 9: Preparation of a Polyethercarbonate Brush Polymer

[0188] In a 50 ml flask, the polyethercarbonate macromer from example 5 (401.1 mg, 213.5 mol, 1.0 eq.) was dissolved in dichloromethane (1 ml) and stirred for 15 minutes. Subsequently, a solution of third-generation Grubbs catalyst (3.7 mg, 4.2 mol, 2.3 mol %) in dichloromethane (1 ml) was added. The reaction mixture was stirred at room temperature for 60 min. The reaction was then ended by adding ethyl vinyl ether (0.5 ml, 5.3 mol). Next, the solvent was removed under reduced pressure and the product was analyzed. The molecular weight obtained, the polydispersity index (PDI), glass transition temperature (T.sub.g) are reported in table 4.

Example 10: Preparation of a Polyethercarbonate Brush Polymer

[0189] In a 50 ml flask, the polyethercarbonate macromer from example 6 (401.2 mg, 98.5 mol, 1.0 eq.) was dissolved in dichloromethane (1 ml) and stirred for 15 minutes. Subsequently, a solution of third-generation Grubbs catalyst (3.7 mg, 4.2 mol, 2.3 mol %) in dichloromethane (1 ml) was added. The reaction mixture was stirred at room temperature for 60 min. The reaction was then ended by adding ethyl vinyl ether (0.5 ml, 5.3 mol). Next, the solvent was removed under reduced pressure and the product was analyzed. The molecular weight obtained, the polydispersity index (PDI), glass transition temperature (T.sub.g) are reported in table 4.

TABLE-US-00003 TABLE 3 M.sub.n PDI T.sub.g T.sub.D Example [g/mol] [] [ C.] [ C.] 7 92 904 1.2 59.3 317.3 8 99 231 1.2 56.8 327.2 9 105 500 1.2 40.4 313.1 10 98 530 1.1 42.9 311.5

[0190] The results from table 4 show that the glass transition temperature T.sub.g of the polyethercarbonate brush polymers (examples 7, 8, 9 and 10) is only insignificantly increased compared to the corresponding polyethercarbonate macromers (examples 1, 2, 4 and 5), although the molar mass has been increased by more than a power of ten. As a result, the high molecular weight polyethercarbonate brush polymers according to the invention can be used particularly effectively for rubber applications.

Example 11: Preparation of a Polyethercarbonate Brush Polymer at a Ratio of Polyethercarbonate Macromer to Cyclic Olefin of 95:5

[0191] In a 50 ml flask, the polyethercarbonate macromer from example 5 (401.2 mg, 213.5 mol, 1.0 eq.) and norbornene (20.4 mg, 216.7 mol, 1.0 eq.) were dissolved in dichloromethane (1 ml) and stirred for 15 minutes. Subsequently, a solution of third-generation Grubbs catalyst (3.8 mg, 4.2 mol, 2.0 mol %) in dichloromethane (1 ml) was transferred. The reaction mixture was stirred at room temperature for 60 min. The reaction was then ended with the addition of ethyl vinyl ether (1 ml, 10.4 mol). Next, the solvent was removed under reduced pressure and the product was analyzed. The molecular weight obtained, the polydispersity index (PDI), glass transition temperature (T.sub.g) are reported in table 5.

Example 12: Preparation of a Polyethercarbonate Brush Polymer at a Ratio of Polyethercarbonate Macromer to Cyclic Olefin of 80:20

[0192] In a 50 ml flask, the polyethercarbonate macromer from example 5 (388.6 mg, 214.5 mol, 1.0 eq.) and norbornene (96.9 mg, 1029.2 mol, 5 eq.) were dissolved in dichloromethane (1 ml) and stirred for 15 minutes. Subsequently, a solution of third-generation Grubbs catalyst (4.2 mg, 4.6 mol, 2.0 mol %) in dichloromethane (1 ml) was transferred. The reaction mixture was stirred at room temperature for 60 min. The reaction was then ended with the addition of ethyl vinyl ether (1 ml, 10.4 mol). Next, the solvent was removed under reduced pressure and the product was analyzed. The molecular weight obtained, the polydispersity index (PDI), glass transition temperature (T.sub.g) are reported in table 5.

Example 13: Preparation of a Polyethercarbonate Brush Polymer at a Ratio of Polyethercarbonate Macromer to Cyclic Olefin of 67:33

[0193] In a 50 ml flask, the polyethercarbonate macromer from example 5 (403.1 mg, 214.5 mol, 1.0 eq.) and norbornene (202.0 mg, 2145.5 mol, 10 eq.) were dissolved in dichloromethane (1 ml) and stirred for 15 minutes. Subsequently, a solution of third-generation Grubbs catalyst (5.5 mg, 6.02 mol, 2.0 mol %) in dichloromethane (1 ml) was transferred. The reaction mixture was stirred at room temperature for 60 min. The reaction was then ended with the addition of ethyl vinyl ether (1 ml, 10.4 mol). Next, the solvent was removed under reduced pressure and the product was analyzed. The molecular weight obtained, the polydispersity index (PDI), glass transition temperature (T.sub.g) are reported in table 5.

TABLE-US-00004 TABLE 4 Monomers used PEC-M Norbornene M.sub.n PDI T.sub.g T.sub.D Example [% by wt.] [% by wt.] [g/mol] [] [ C.] [ C.] 10 100 0 105 500 1.2 40.4 313.1 11 95 5 91 352 1.2 40.0 314.0 12 80 20 101 140 1.2 37.0 311.0 13 67 33 123 070 1.2 35.0 312.0 PEC-M: Polyethercarbonate macromer Comp.: Comparative example