Liquid monofunctional 1,3-dioxolane copolymer

Abstract

The present invention provides 1,3-dioxolane copolymers of general formula I and methods for their preparation. H-[O-CH 2 -O-CH 2 -CH 2 -] x1 [O-CH 2 -CH 2 O-CH 2 -] x2 [O-CH 2 -O-CHR 1 -CHR 2 -] y1 [O-CHR 1 -CHR 2 O-CH 2 -] y2 OR 3 (I) [In the formula, x1+x2 has a value from 10 to 2000, R 1 and R 2 is a hydrogen group or C 1 ~C 18 In both cases, the unit [O-CH 2 -O-CHR 1 -CHR 2 -] y1 and [O-CHR 1 -CHR 2 O-CH 2 -] y2 At least one group R 1 or R 2 is C 1 ~C 18 is an alkyl group, Here, y1+y2 has a value between 3*(x1+x2+y1+y2) / 100 and 50*(x1+x2+y1+y2) / 100, R 3 is an aliphatic saturated group or an unsaturated hydrocarbon group, which is unsubstituted or is substituted with a halogen atom, an amino group, 1~6 Alkyl group, C 1~6 substituted with an alkoxy group or a silyl group, having 1 to 100 carbon atoms, among which one or more -CH 2 The unit is an -O- group, an -S- group, a C=O group, an -OC(O)- group or an -NR4 - groups, in which one or more non-adjacent =CH units are optionally replaced by -N= groups; R 4 is a hydrogen group or C 1 ~C 18 is an alkyl group.

Description

[Technical Field]

[0001] The present invention relates to monofunctional 1,3-dioxolane copolymers of 1,3-dioxolane and alkyl-substituted 1,3-dioxolanes and methods for making the same. [Background technology]

[0002] The serious impact of increasing CO2 emissions on climate change is indisputable, and it has been said, not only since the signing of the Paris Agreement, that reducing CO2 emissions is a key factor in halting the rise in global average temperatures.

[0003] The production of plastics also releases a significant amount of CO2 into the atmosphere. According to projections by EIT Climate-KIC, by 2050, only 15-20% of global CO2 emissions will come from plastic production. One way to counter this trend is to utilize CO2 in plastic production and integrate it into the value chain as a starting material rather than a waste product.

[0004] In this context, polyacetals represent an attractive class of plastics, which can be produced via cyclic acetal intermediates, in particular by catalytic fixation of CO2 with green hydrogen.

[0005] However, conventional polyacetals, also known as polyoxymethylenes (POM), such as those obtainable by polymerization of formaldehyde or trioxane (POM-H) or by ring-opening polymerization of 1,3-dioxolane (POM-C), are solid at room temperature due to the presence of crystalline subsections and associated melting points, which hinder further processing in some applications. The possibility of preparing liquid representatives of this material class would significantly expand the range of applications for polyacetals.

[0006] Conventional polyoxymethylene is terminated with alkyl groups during synthesis, which stabilizes the polymer but also prevents functionalization or further reaction.

[0007] Equipping polymers with additional functional groups that allow polymer-like reactions in polyacetals would also expand the range of applications of these materials, as they can be converted into attractive hybrid materials by simple organic reactions. Monofunctional polymers in particular have proven advantageous for the preparation of these hybrid materials, as they tend not to exhibit crosslinking behavior.

[0008] Lutz et al., "One-Step Synthesis of Bis-Macromonomers of Poly(1,3-dioxolane) Catalyzed by Maghnite-H," J. Appl. Polym. Sci., Vol. 99, 3147-3152 (2006), describe the preparation of α,ω-difunctional polydioxolanes by acid-catalyzed ring-opening polymerization of 1,3-dioxolane in the presence of methacrylic anhydride. However, this method does not allow for the production of either monofunctional or liquid products.

[0009] Goethals et al., "Polymer Networks Based on α,ω-Methacrylate-Terminated Poly(1,3-dioxolane)," Polym. Int., Vol. 38, 89-94 (1995), also describe a similar synthesis, in which methylene-bis(oxyethyl methacrylate) participates in the initiation and chain termination of the acid-catalyzed ring-opening polymerization of 1,3-dioxolane, resulting in a difunctional α,ω-methacrylate-terminated solid polydioxolane.

[0010] WO14095971 A2 describes the polymerization of trioxane and cyclic acetals starting from difunctional polyols, the terminal OH groups of which are then terminated with glutaric anhydride to form carboxylic acid-terminated polymers, and a solid product is obtained. [Prior art documents] [Patent documents]

[0011] [Patent Document 1] International Publication No. 2014 / 095971 [Non-patent literature]

[0012] [Non-Patent Document 1] Lutz et al., One-Step Synthesis of Bis-Macromonomers of Poly(1,3-dioxolane) Catalyzed by Maghnite-H, J. Appl. Polym. Sci., Vol. 99,3147-3152(2006) [Non-patent document 2] Goethals et al., Polymer Networks Based on α,ω-Methacrylate-Terminated Poly(1,3-dioxolane), Polym. Int., Vol. 38,89-94(1995) Summary of the Invention [Problem to be solved by the invention]

[0013] It was therefore an object of the present invention to obtain monofunctional polyacetals which are liquid over a wide temperature range and which can be prepared from cyclic acetals. [Means for solving the problem]

[0014] The present invention provides 1,3-dioxolane copolymers of general formula I: H-[O-CH2-O-CH2-CH2-] x1 [O-CH2-CH2O-CH2-] x2 [O-CH2-O-CHR 1 -CHR 2 -] y1 [O-CHR 1 -CHR2 O-CH2-] y2 OR 3 (I) During the ceremony, x1+x2 has a value between 10 and 2000, R 1 and R 2 is a hydrogen group or a C1-C 18 alkyl group, in both cases the unit [O-CH2-O-CHR 1 -CHR 2 -] y1 and [O-CHR 1 -CHR 2 O-CH2-] y2 At least one group R 1 or R 2 is C1~C 18 is an alkyl group, where y1+y2 has a value between 3*(x1+x2+y1+y2) / 100 and 50*(x1+x2+y1+y2) / 100, R 3 is an aliphatic saturated group or an unsaturated hydrocarbon group, which is unsubstituted or contains a halogen atom, an amino group, C 1~6 Alkyl group, C 1~6 and is substituted by an alkoxy group or a silyl group, and has 1 to 100 carbon atoms, in which one or more non-adjacent —CH2 units are an —O— group, an —S— group, a C═O group, an —OC(O)— group, or an —NR 4 - groups, in which one or more non-adjacent =CH units may be replaced by -N= groups; R 4 is a hydrogen group or a C1-C 18 It is an alkyl group. DETAILED DESCRIPTION OF THE INVENTION

[0015] The 1,3-dioxolane copolymers of general formula I are polyacetals.

[0016] The controlled incorporation of defects in the form of alkyl groups pendant from the polymer backbone of the 1,3-dioxolane copolymers of general formula I means that the crystallinity of the polyacetal is eliminated, not merely reduced. Such amorphous behavior can be detected by differential scanning calorimetry, where only a glass transition point is present but no melting point is present.

[0017] The copolymers are formed from 1,3-dioxolanes and 1,3-dioxolanes substituted at the 4- and / or 5-positions. They are liquid over a wide temperature range and are therefore very suitable for further processing.

[0018] They preferably have a glass transition between -50°C and -70°C and particularly preferably no melting point. The copolymers start to decompose above 100°C, especially above 110°C.

[0019] 1,3-dioxolane copolymers consist of the units [O-CH2-O-CH2-CH2-] x1 , [O-CH2-CH2O-CH2-] x2 , [O-CH2-O-CHR 1 -CHR 2 -] y1 , [O-CHR 1 -CHR 2 O-CH2-] y2 Randomly or in blocks.

[0020] Preferably, x1+x2 has a value of 20-1000, particularly preferably 30-500, in particular 50-300.

[0021] Alkyl group R 1 , R 2 and R 4 Examples of R are straight-chain and branched-chain alkyl groups such as methyl, ethyl, i-octyl and n-octyl groups, and cycloalkyl groups such as cyclohexyl groups. 1 , R 2 and R 4is independently in each occurrence a hydrogen group or a C1-C6 alkyl group, particularly preferably a hydrogen group or a methyl group, an ethyl group, an n-propyl group or an i-propyl group.

[0022] Preferably, in each case the unit [O-CH2-O-CHR 1 -CHR 2 -] y1 and [O-CHR 1 -CHR 2 O-CH2-] y2 One group R in 1 or R 2 Only C1~C 18 It is an alkyl group.

[0023] R 3 has preferably 1 to 30, especially 1 to 18 carbon atoms.

[0024] R is an aliphatic saturated hydrocarbon group 3 Examples of are alkyl groups such as methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, n-pentyl, sec-pentyl, isopentyl, neopentyl and tert-pentyl groups, hexyl groups such as n-hexyl, heptyl groups such as n-heptyl, octyl groups such as n-octyl and isooctyl groups, for example 2,4,4-trimethylpentyl, nonyl groups such as n-nonyl, decyl groups such as n-decyl, dodecyl groups such as n-dodecyl, hexadecyl, e.g., n-hexadecyl, octadecyl, e.g., n-octadecyl, cycloalkyl, e.g., cyclopentyl, cyclohexyl, cycloheptyl, and methylcyclohexyl, aryl, e.g., phenyl, naphthyl, anthryl, and phenanthryl, alkaryl, e.g., o-, m-, and p-tolyl, xylyl, mesitylenyl, and o-, m-, and p-ethylphenyl, and alkaryl, e.g., benzyl, α-, and β-phenylethyl. In one preferred embodiment, R 3 includes alkyl groups having 1 to 18 carbon atoms.

[0025] R is an aliphatic unsaturated hydrocarbon group 3 Examples of preferred alkenyl groups R are alkenyl and alkynyl groups in which one or more non-adjacent -CH units may be replaced by -O- or -O-C(O)- groups. 3 has 2 to 10 carbon atoms and is, for example, vinyl, allyloxyethyl, propyl methacrylate, butyl methacrylate, methallyl, 1-propenyl, 5-hexenyl, ethynyl, butadienyl, hexadienyl, cyclopentenyl, cyclopentadienyl, cyclohexenyl, acrylate, and methacrylate, and particularly preferred are vinyl, allyl, acrylate, methacrylate, allyloxyethyl, propyl methacrylate, and butyl methacrylate.

[0026] Preferred alkenyl groups R 3 is also a polyethylene glycol having a terminal alkenyl group.

[0027] Preferably, y1+y2 has a value of 5*(x1+x2+y1+y2) / 100 to 40*(x1+x2+y1+y2) / 100, particularly preferably a value of 10*(x1+x2+y1+y2) / 100 to 30*(x1+x2+y1+y2) / 100, in particular a value of 14*(x1+x2+y1+y2) / 100 to 25*(x1+x2+y1+y2) / 100.

[0028] The 1,3-dioxolane copolymers preferably have molecular weights Mw between 750 and 300,000, particularly preferably between 1,500 and 125,000, very particularly preferably between 2,200 and 63,000, in particular between 4,000 and 25,000.

[0029] The 1,3-dioxolane copolymer preferably has a dynamic viscosity at 25° C. between 50 mPas and 500 Pas, particularly preferably between 500 mPas and 200 Pas, in particular between 700 mPas and 50 Pas.

[0030] The 1,3-dioxolane copolymers of the general formula (I) above can be prepared by a simple method and in a short reaction time. As a result of the preparation, the 1,3-dioxolane copolymers of the general formula (I) above also contain the group R 3 is replaced by a hydrogen atom, or the hydrogen atom at the other end of the 1,3-dioxolane copolymer is replaced by a group R 3 Preferably, the copolymer of general formula (I) contains at most 5 mol %, particularly preferably at most 1 mol %, in particular at most 0.1 mol % of the group R in general formula (I). 3 is replaced by a hydrogen atom, or the hydrogen atom at the other end of the 1,3-dioxolane copolymer is replaced by a group R 3 is mixed with a copolymer in which the copolymer is replaced by

[0031] The present invention also provides a method for producing a 1,3-dioxolane copolymer of general formula (I), comprising: H-[O-CH2-O-CH2-CH2-] x1 [O-CH2-CH2O-CH2-] x2 [O-CH2-O-CHR 1 -CHR 2 -] y1 [O-CHR 1 -CHR 2 O-CH2-] y2 OR 3 (I) [In the formula, x1+x2 has a value between 10 and 2000, R 1 and R 2 is a hydrogen group or a C1-C 18 alkyl group, in both cases the unit [O-CH2-O-CHR 1 -CHR 2 -] y1 and [O-CHR 1 -CHR 2 O-CH2-] y2 At least one group R 1 or R 2 is C1~C 18 is an alkyl group, where y1+y2 has a value between 3*(x1+x2+y1+y2) / 100 and 50*(x1+x2+y1+y2) / 100, R 3 is an aliphatic saturated group or an unsaturated hydrocarbon group, which is unsubstituted or contains a halogen atom, an amino group, C 1~6 Alkyl group, C 1~6 and is substituted by an alkoxy group or a silyl group, and has 1 to 100 carbon atoms, in which one or more non-adjacent —CH2 units are an —O— group, an —S— group, a C═O group, an —OC(O)— group, or an —NR 4 - groups, in which one or more non-adjacent =CH units may be replaced by -N= groups; R 4 is a hydrogen group or a C1-C 18 is an alkyl group. 1,3-Dioxolanes are Lewis or Bronsted acids and have the general formula R 3 OH is copolymerized with alkyl-substituted 1,3-dioxolanes of general formula II in the presence of alcohols of general formula R and Lewis or Bronsted acids. 3 The molar ratio of OH to alcohol is less than 1.

[0032] [ka]

[0033] In general formula II, alkyl groups R 1 and R 2 exists.

[0034] This method is a cationic induced catalyzed ring-opening polymerization of dioxolane monomers.

[0035] The catalyst is a Lewis acid or a Bronsted acid. 3 OH functions as an initiator.

[0036] In contrast to conventional methods, this method makes it possible to dispense with subsequent functionalization of the α,ω-hydroxy terminated polymer.

[0037] In this process, preferably at least 10 mol %, particularly preferably at least 20 mol %, in particular at least 30 mol % of alkyl-substituted 1,3-dioxolanes of the general formula II are used, based on the total amount of 1,3-dioxolanes and alkyl-substituted 1,3-dioxolanes of the general formula II.

[0038] Because the alkyl-substituted 1,3-dioxolanes of general formula II have lower reactivity than 1,3-dioxolane, it is necessary in this process to use more alkyl-substituted 1,3-dioxolanes than arithmetically necessary to achieve a certain ratio value of y1 + y2.

[0039] Examples of the acid include Lewis acids such as BF3, AlCl3, TiCl3, SnCl4, SO3, PCl5, POCl3, FeCl3 and their hydrates, and ZnCl2, Bronsted acids such as boric acid, tetrafluoroboric acid, nitric acid, nitrous acid, phosphoric acid, phosphorous acid, hypophosphorous acid, sulfuric acid, sulfurous acid, peroxysulfuric acid, hydrochloric acid, hydrofluoric acid, hydroiodic acid, hydrobromic acid, perchloric acid, hexafluorophosphoric acid, aluminum chloride, zinc chloride, benzenesulfonate, and the like. Examples of suitable acid-activating agents include carboxylic acids such as chloroacetic acid, trichloroacetic acid, acetic acid, acrylic acid, benzoic acid, trifluoroacetic acid, citric acid, crotonic acid, formic acid, fumaric acid, maleic acid, malonic acid, gallic acid, itaconic acid, lactic acid, tartaric acid, oxalic acid, phthalic acid and succinic acid, acidic ion exchangers, acidic zeolites, acid-activated bleaching earth and acid-activated carbon black.

[0040] Particularly preferred is trifluoromethanesulfonic acid.

[0041] This method is preferably carried out in the absence of water, whereby in general formula (I), R 3 The formation of copolymers in which the groups are replaced by hydrogen atoms is suppressed.

[0042] This process can be carried out in the presence or absence of an aprotic solvent. When an aprotic solvent is used, a solvent or solvent mixture having a boiling point or boiling range of up to 120°C at 0.1 MPa is preferred. Examples of such solvents include ethers such as dioxane, tetrahydrofuran, diethyl ether, methyl tert-butyl ether, diisopropyl ether, diethylene glycol dimethyl ether, chlorinated hydrocarbons such as dichloromethane, trichloromethane, tetrachloromethane, 1,2-dichloroethane, trichloroethylene, hydrocarbons such as pentane, n-hexane, hexane isomer mixtures, heptane, octane, benzine, petroleum ether, benzene, toluene, xylene, siloxanes, in particular trimethylsiloxanes having preferably 0 to 6 dimethylsiloxane units. Linear dimethylpolysiloxanes having silyl end groups or cyclic dimethylpolysiloxanes preferably having 4 to 7 dimethylsiloxane units, such as hexamethyldisiloxane, octamethyltrisiloxane, octamethylcyclotetrasiloxane and decamethylcyclopentasiloxane, ketones such as acetone, methyl ethyl ketone, diisopropyl ketone, methyl isobutyl ketone (MIBK), esters such as ethyl acetate, butyl acetate, propyl propionate, ethyl butyrate, ethyl isobutyrate, carbon disulfide and nitrobenzene, or mixtures of these solvents.

[0043] The term "solvent" does not imply that all reaction components must be dissolved therein. The reaction may also be carried out in a suspension or emulsion of one or more reactants. The reaction may also be carried out in a solvent mixture with a solubility gap, where at least one reactant is soluble in each of the mixed phases in each case.

[0044] Particularly preferably, a solution of trifluoromethanesulfonic acid and initiator is used, with methylene chloride being the preferred solvent.

[0045] The amount of catalyst and initiator used determines the achievable molecular weight of the 1,3-dioxolane copolymer of general formula I.

[0046] Alcohol R used as initiator 3 The OH controls the desired chain length of the 1,3-dioxolane copolymer of general formula (I).

[0047] Lewis acids or Bronsted acids are used in catalytic amounts to activate the initiator.

[0048] Lewis acids or Bronsted acids with general formula R 3 The molar ratio of OH to alcohol is preferably between 0.5 and 0.001, in particular between 0.1 and 0.01.

[0049] Preferably, 50 to 10,000 molar ppm, particularly preferably 100 to 5,000 molar ppm, in particular 200 to 4,000 molar ppm of Lewis acid or Bronsted acid are used per mole of the total of 1,3-dioxolane and alkyl-substituted 1,3-dioxolane of general formula II.

[0050] The Lewis or Bronsted acid is preferably added to a mixture of 1,3-dioxolane and alkyl-substituted 1,3-dioxolane of general formula R 3 It is mixed with alcohols of OH.

[0051] The process is preferably carried out at temperatures between 10° C. and 60° C., particularly preferably between 15° C. and 40° C., in particular between 21° C. and 30° C. A reaction temperature of 23° C. is very particularly preferred.

[0052] The reaction is preferably carried out by deactivating the catalyst with a suitable base, washing with a hydrocarbon such as heptane, and drying under reduced pressure.

[0053] Suitable bases are preferably pyridine, triethylamine or aqueous sodium hydroxide.

[0054] Polyacetals can be used as emulsifiers or as reactants for the preparation of functional silicone oils or for similar purposes.

[0055] In the following examples, all figures relating to amounts and percentages are by weight, all pressures are 0.10 MPa (absolute) and all temperatures are 20°C, unless otherwise stated in each case. [Example]

[0056] <Analysis of the entire invention>

[0057] NMR spectroscopy to measure the percentage of alkylethylene oxide crosslinks.

[0058] Measurements are performed in CDCl3 solution on a Bruker Avance 500 or Ascend 500 (500 MHz for 1H spectra). All measurements are referenced to TMS as an external standard. The relative ratio of monomer units in the polymer is determined by integrating each set of signals. Furthermore, the chain length and molar mass of the polymer can be determined by integrating the end group signals.

[0059] SEC (size exclusion chromatography) to determine number-average and weight-average molecular weights Mn, Mw and polydispersity

[0060] Measurements are performed against polystyrene standards measured in THF at 35° C. at a flow rate of 0.3 ml / min and detected by RID (refractive index detector) on an Agilent PLgel MiniMIX-C Guard column with an injection volume of 20 μl.

[0061] Rheometer for measuring dynamic viscosity

[0062] Measurements are carried out on an Anton Paar MCR 320 rotational viscometer at 25° C. Graphical evaluation is carried out by plotting viscosity against shear stress.

[0063] DSC (Differential Scanning Calorimetry / Differential Thermal Analysis) for Measuring Melting Points and Glass Transition Temperatures

[0064] The measurements are carried out twice on a METTLER TOLEDO DSC-1 instrument in the temperature range of -150°C to 150°C with a heating or cooling rate of 10 K, and the second run is used to measure the melting point and glass transition temperature.

[0065] TGA analysis to determine the onset of decomposition

[0066] The onset (onset) of decomposition is measured on a METTLER TOLEDO TGA-2 apparatus, heating the sample in an oxygen atmosphere at a heating rate of 10 K / min.

[0067] [Example 1]

[0068] Preparation of catalyst solution: 10 ml of dry dichloromethane, 1.9 ml of allyloxyethanol, and 76 μl of trifluoromethanesulfonic acid are combined and stirred at room temperature for 1 hour. 1.35 ml of the previously prepared catalyst solution is placed in a flask and adjusted to a temperature of 23 ° C. Then, 10.12 g (96 mmol) of 4-ethyl-1,3-dioxolane (EDX) and 6.75 ml (96 mmol) of 1,3-dioxolane (DXL) are added and stirred.

[0069] After 4 hours, pyridine is added until the mixture loses its color. The product is washed with heptane and distilled water and then dried under reduced pressure.

[0070] [Example 2]

[0071] 2.7 ml of the catalyst solution prepared in Example 1 is placed in a flask and adjusted to a temperature of 23° C. Then, 10.12 g (96 mmol) of 4-ethyl-1,3-dioxolane (EDX) and 6.75 ml (96 mmol) of 1,3-dioxolane (DXL) are added and stirred.

[0072] After 4 hours, pyridine is added until the mixture loses its color. The product is washed with heptane and distilled water and then dried under reduced pressure.

[0073] [Example 3]

[0074] 5.4 ml of the catalyst solution prepared in Example 1 is placed in a flask and adjusted to a temperature of 23° C. Then, 10.12 g (96 mmol) of 4-ethyl-1,3-dioxolane (EDX) and 6.75 ml (96 mmol) of 1,3-dioxolane (DXL) are added and stirred.

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

[0076] [Example 4]

[0077] Preparation of catalyst solution: 10 ml of dry dichloromethane, 5.15 g of hydroxypropyl methacrylate, and 152 μl of trifluoromethanesulfonic acid are combined and stirred at room temperature for 1 hour. 4.05 ml of the previously prepared catalyst solution is placed in a flask and adjusted to a temperature of 23° C. Then, 15.18 g (144 mmol) of 4-ethyl-1,3-dioxolane (EDX) and 10.12 ml (144 mmol) of 1,3-dioxolane (DXL) are added and stirred.

[0078] After 4 hours, pyridine is added until the mixture loses its color. The product is washed with heptane and distilled water and then dried under reduced pressure.

[0079] [Example 5]

[0080] Preparation of catalyst solution: 10 ml of dry dichloromethane, 3.34 g of 1-dodecanol, and 76 μl of trifluoromethanesulfonic acid are combined and stirred at room temperature for 1 hour. 1.35 ml of the previously prepared catalyst solution is placed in a flask and adjusted to a temperature of 23° C. Then, 10.12 g (96 mmol) of 4-ethyl-1,3-dioxolane (EDX) and 6.75 ml (96 mmol) of 1,3-dioxolane (DXL) are added and stirred.

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

[0082] [Example 6]

[0083] Preparation of catalyst solution: 10 ml of dry dichloromethane, 1.05 ml of ethanol, and 76 μl of trifluoromethanesulfonic acid are combined and stirred at room temperature for 1 hour. 1.35 ml of the previously prepared catalyst solution is placed in a flask and adjusted to a temperature of 23° C. Then, 10.12 g (96 mmol) of 4-ethyl-1,3-dioxolane (EDX) and 6.75 ml (96 mmol) of 1,3-dioxolane (DXL) are added and stirred.

[0084] After 4 hours, pyridine is added until the mixture loses its color. The product is washed with heptane and distilled water and then dried under reduced pressure.

[0085] [Example 7 (Non-invention)]

[0086] 1.35 ml of the catalyst solution prepared in Example 1 is placed in a flask and adjusted to a temperature of 23 ° C. Then, 13.5 ml (193 mmol) of 1,3-dioxolane (DXL) is added and stirred. After 10 minutes, the reaction mixture is no longer agitated. 1 ml of pyridine and 10 ml of dichloromethane are added to the reaction solution. The solid is then precipitated in heptane, washed with distilled water, and dried under reduced pressure.

[0087] The results of the examples are detailed in Table 1.

[0088] Table 1

Claims

1. A liquid 1,3-dioxolane copolymer of general formula I having a glass transition between -50°C and -70°C. H-[O-CH ２ -O-CH ２ -CH ２ -] ｘ１ [O-CH ２ -CH ２ O-CH ２ -] ｘ２ [O-CH ２ -O-CHR １ -CHR ２ -] ｙ１ [O-CHR １ -CHR ２ O-CH ２ -] ｙ２ OR ３ (I) [In the formula, x1+x2 has a value between 10 and 2000, R １ and R ２ is selected from a hydrogen group or a methyl group, an ethyl group, an n-propyl group or an i-propyl group, and in each case the unit [O—CH ２ -O-CHR １ -CHR ２ -] ｙ１ and [O-CHR １ -CHR ２ O-CH ２ -] ｙ２ One group R １ or R ２ is selected from methyl, ethyl, n-propyl or i-propyl groups; However, y1+y2 has a value of 3*(x1+x2+y1+y2) / 100 to 50*(x1+x2+y1+y2) / 100, R ３ is an aliphatic saturated group or an unsaturated hydrocarbon group, which is unsubstituted or contains a halogen atom, an amino group, C １～６ Alkyl group, C １～６ substituted with an alkoxy group or a silyl group, and having 1 to 100 carbon atoms, among which one or more —CH ２ The unit may be an —O— group, an —S— group, a C═O group, an —O—C(O)— group, or an —NR ４ - groups, in which one or more non-adjacent =CH units may be replaced by -N= groups; R ４ is a hydrogen group or C １ ~C １８ is an alkyl group.

2. 2. The 1,3-dioxolane copolymer of claim 1, having a molecular weight Mw of between 750 and 300,000 as measured against polystyrene standards in THF at 35° C. at a flow rate of 0.3 ml / min and detected by RID (refractive index detector) on an Agilent PLgel MiniMIX-C Guard column with an injection volume of 20 μl.

3. 3. The 1,3-dioxolane copolymer of claim 1 or 2, having a dynamic viscosity at 25°C of 50 mPas to 500 Pas as measured with an Anton Paar MCR 320 rotational viscometer at 25°C, wherein the graphical evaluation is performed by plotting viscosity against shear stress.

4. R ３ The 1,3-dioxolane copolymer according to any one of claims 1 to 3, wherein is an alkyl group having 1 to 18 carbon atoms.

5. R ３ is an alkenyl group having 2 to 10 carbon atoms, and ２ 1,3-dioxolane copolymer according to any one of claims 1 to 4, wherein the units may be replaced by -O- groups or O-C(O)- groups.

6. A method for producing a liquid 1,3-dioxolane copolymer of general formula (I) having a glass transition of -50°C to -70°C, comprising: H-[O-CH ２ -O-CH ２ -CH ２ -] ｘ１ [O-CH ２ -CH ２ O-CH ２ -] ｘ２ [O-CH ２ -O-CHR １ -CHR ２ -] ｙ１ [O-CHR １ -CHR ２ O-CH ２ -] ｙ２ OR ３ (I) [In the formula, x1+x2 has a value between 10 and 2000, R １ and R ２ is selected from a hydrogen group or a methyl group, an ethyl group, an n-propyl group or an i-propyl group, and in each case the unit [O—CH ２ -O-CHR １ -CHR ２ -] ｙ１ and [O-CHR １ -CHR ２ O-CH ２ -] ｙ２ One group R １ or R ２ is selected from methyl, ethyl, n-propyl or i-propyl groups; However, y1+y2 has a value of 3*(x1+x2+y1+y2) / 100 to 50*(x1+x2+y1+y2) / 100, R ３ is an aliphatic saturated group or an unsaturated hydrocarbon group, which is unsubstituted or contains a halogen atom, an amino group, C １～６ Alkyl group, C １～６ substituted with an alkoxy group or a silyl group, and having 1 to 100 carbon atoms, among which one or more —CH ２ The unit may be an —O— group, an —S— group, a C═O group, an —O—C(O)— group, or an —NR ４ - groups, in which one or more non-adjacent =CH units may be replaced by -N= groups; R ４ is a hydrogen group or C １ ~C １８ is an alkyl group. 1,3-Dioxolane is a Lewis or Bronsted acid and a compound of the general formula R ３ OH with an alkyl-substituted 1,3-dioxolane of general formula II in the presence of an alcohol of general formula R ３ The process wherein the molar ratio of OH to alcohol is less than 1. 【Chemistry 1】

7. 7. The method of claim 6, wherein the acid is trifluoromethanesulfonic acid.

8. 8. The process according to claim 6, wherein 50 to 10,000 mole ppm of said Lewis acid or Bronsted acid is used per mole of the total of 1,3-dioxolane and alkyl-substituted 1,3-dioxolane of general formula II.

9. The method according to any one of claims 6 to 8, wherein the method is carried out at a temperature between 10°C and 60°C.

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