Method for preparing hydroxy-functionalized polybutadiene

Abstract

The present invention relates to a process for preparing hydroxy-functionalized polydienes, preferably polybutadiene or polyisoprene, by reacting a monomeric diene with hydrogen peroxide in the presence of a hydrophilic organic solvent, wherein the total amount of monomeric diene used is added to the reaction in at least two portions, the second portion being added to the reaction at a temperature of the reaction mixture differing by at least +5 K from the temperature of the reaction mixture at the time of the addition of the first portion of monomeric diene; to hydroxy-functionalized polybutadienes having a dispersion index D of less than 2.7, a viscosity at 30°C of less than 3200 mPa*s, an OH number of 50 to 90, a number average molecular weight Mn of 1.6 to 2.5 kDa, and a weight number average molecular weight Mw of 4.0 to 5.6 kDa, and comprising a specific proportion of monomer units derived from 1,3-butadiene; and to the use of the hydroxy-functionalized polybutadienes for producing polyurethane-based thermal or electrical insulators, adhesives or sealants, or polyesters.

Description

[Technical Field]

[0001] The present invention relates to a process for preparing hydroxy-functionalized polydienes, preferably polybutadiene or polyisoprene, by reacting a monomeric diene with hydrogen peroxide in the presence of a hydrophilic organic solvent, wherein the total amount of monomeric diene used is added to the reaction in at least two portions, the second portion of monomeric diene being added to the reaction at a temperature of the reaction mixture which differs by at least +5 K from the temperature of the reaction mixture at the time of the addition of the first portion of monomeric diene, a dispersion index D of less than 2.7, The present invention relates to a hydroxy-functionalized polybutadiene having a viscosity of less than 3200 mPa*s at 30°C, an OH value of 50 to 90, a number average molecular weight Mn of 1.6 to 2.5 kDa, and a weight number average molecular weight Mw of 4.0 to 5.6 kDa, and containing a specific ratio of monomer units derived from 1,3-butadiene, and to use of the hydroxy-functionalized polybutadiene for producing a polyurethane-based thermal or electrical insulator, adhesive or sealant, or polyester. [Background technology]

[0002] The production of hydroxy-functionalized polydienes is well known in the art. British Patent No. 1401144A describes the preparation of polybutadiene with terminal OH groups by polymerization of 1,3-butadiene in the presence of hydrogen peroxide in aqueous 2-propanol at 118°C for 2 hours.

[0003] US Pat. No. 5,043,484 A describes the production of OH-terminated polybutadiene by polymerization of butadiene in the presence of aqueous H2O2 solution and propylene glycol tertiary alkyl ether as solvent.

[0004] Japanese Patent No. 07068302B describes the preparation of OH-terminated liquid polyisoprene by polymerization of isoprene in BuOH in the presence of H2O2 under stirring at 120°C for 2 hours.

[0005] WO2013178293A1 discloses a method for polymerizing dienes, comprising the steps of reacting a diene with hydrogen peroxide in a hydrophilic organic solvent in the presence of water at a temperature of 50-150°C and a pressure of 0-5 MPa to form a reaction mixture, contacting the reaction mixture with water having a temperature of 20-80°C, preferably 50-65°C, separating the unreacted gaseous diene from the reaction mixture contacted with water in step b) and subsequently concentrating, distilling, and recycling the unreacted gaseous diene, separating an aqueous phase comprising a hydrophilic solvent from the reaction mixture and subsequently recycling the hydrophilic solvent in step a), and purifying the polymerization product by distillation.

[0006] All of these examples describe the free radical polymerization of 1,3-butadiene in a batch process, in which all reagents are placed in a reactor vessel and the mixture is then heated to the desired reaction temperature. If necessary, the ratio of monomer to hydrogen peroxide is adjusted to adjust the molecular weight of the final polymer; however, too much hydrogen peroxide increases the OH number and therefore decreases the molecular weight. [Prior art documents] [Patent documents]

[0007] [Patent Document 1] British Patent No. 1401144A [Patent Document 2] U.S. Patent No. 5,043,484A [Patent Document 3] Japanese Patent No. 07068302B [Patent Document 4] International Publication No. 2013178293A1 Summary of the Invention [Problem to be solved by the invention]

[0008] The processes described in the prior art could be improved, especially in the appropriate manner of carrying out the reaction and purification of the diene monomer, as well as in the process using oxygen-containing reagents, which requires the use of a minimum amount of explosive materials to reduce the risk of explosion. [Means for solving the problem]

[0009] Against this background, it was an object of the present invention to provide a method for preparing hydroxy-functionalized polydienes which meets relatively stringent safety requirements, in particular with regard to the risk of explosion.

[0010] A further object of the present invention was to provide a method for preparing hydroxy-functionalized polydienes having low viscosity and low dispersity.

[0011] Surprisingly, it has been found that these and further objects can be achieved by the subject matter of the present patent application, in particular by the subject matter of the attached independent claims, as well as by the embodiments specified in the dependent claims. DETAILED DESCRIPTION OF THE INVENTION

[0012] The present invention therefore provides a method for preparing a hydroxy-functionalized polydienes, preferably polybutadiene or polyisoprene, by reacting a monomeric diene with hydrogen peroxide in the presence of a hydrophilic organic solvent, wherein the total amount of monomeric diene used is added to the reaction in at least two portions, and the temperature of the reaction mixture at which the second portion of monomeric diene is added differs by at least +5 K from the temperature of the reaction mixture at the time of the addition of the first portion of monomeric diene.

[0013] The present invention further provides a hydroxy-functionalized polybutadiene having a dispersion index D of less than 2.7, a viscosity at 30°C of less than 3200 mPa*s, an OH number of 50 to 90, a number average molecular weight Mn of 1.6 to 2.5 kDa, and a weight number average molecular weight Mw of 4.0 to 5.6 kDa, and containing monomer units derived from 1,3-butadiene in the following specific ratios:

[0014] The present invention also relates to the use of the hydroxy-functionalized polybutadienes according to the invention for the preparation of polyurethane-based thermal or electrical insulators, adhesives or sealants, or polyesters, preferably block copolyesters.

[0015] The process according to the invention has the advantage that the reaction has a lower probability of exothermic reaction and can therefore be carried out in a much safer way, since the diene raw material is introduced in some parts which requires keeping the probability of exothermic reaction low and using less explosive hydrogen peroxide.

[0016] By introducing the raw materials into the reaction in multiple batches, the reaction process and the resulting products can be easily controlled.

[0017] A further advantage of the process of the present invention is that it is possible to produce hydroxy-functionalized polybutadiene with reduced viscosity and dispersibility compared to state-of-the-art batch processes.

[0018] The hydroxy-functionalized polybutadienes according to the invention have very good wetting properties, which allow them to be advantageously used as adhesives or in the formulation of adhesives, especially those used to bond or insulate very small parts.

[0019] The methods, products, and uses according to the present invention are described below by way of example, without intending that the present invention be limited to these exemplary embodiments. When ranges, general formulas, or classes of compounds are specified below, these are intended to encompass not only the corresponding ranges or groups of compounds explicitly mentioned, but also all subranges and subgroups of compounds that can be obtained by extracting individual values ​​(ranges) or compounds. When documents are cited in the context of this specification, their contents, with respect to the matters specifically mentioned, fully form part of the disclosure of the present invention. When figures are expressed hereinafter as percentages, they are weight percentages unless otherwise specified. When average values, such as molar mass average values, are specified hereinafter, they are numerical averages unless otherwise specified. When material properties, such as viscosity, are mentioned hereinafter, they are material properties at 25°C unless otherwise specified. When chemical (empirical) formulas are used in the present invention, the given indices can be either absolute numbers or average values. In the case of polymeric compounds, the indices preferably represent average values.

[0020] The process according to the present invention for preparing hydroxy-functionalized polydienes, preferably polybutadiene or polyisoprene, by reacting a monomeric diene with hydrogen peroxide in the presence of a hydrophilic organic solvent is characterized in that the total amount of monomeric diene used is added to the reaction in at least two (separate) portions, and the temperature of the reaction mixture at which the second portion of monomeric diene is added differs by at least +5 K from the temperature of the reaction mixture at the time of the addition of the first portion of monomeric diene.

[0021] Preferably, the second portion of monomeric diene is added to the reaction at least 30 minutes after the first addition of monomeric diene, preferably 30 to 90 minutes after.

[0022] It may be advantageous to add the second portion of monomeric diene to the reaction at a temperature of the reaction mixture that preferably differs by at least +15 K, more preferably by +25 to +35 K, from the temperature of the reaction mixture at the time of addition of the first portion of monomeric diene.

[0023] A first portion of the monomeric diene is preferably added to the reaction before the addition of the hydrogen peroxide, and a second portion of the monomeric diene is preferably added to the reaction after the addition of the hydrogen peroxide.

[0024] It may be advantageous to add the second portion of the monomeric diene to the reaction at least 30 minutes, preferably 30 to 90 minutes, after the addition of the first portion of the monomeric diene, and to add the second portion of the monomeric diene to the reaction at a temperature of the reaction mixture that differs by at least +5 K, preferably +15 K, more preferably +25 to +35 K from the temperature of the reaction mixture at the time of the addition of the first portion of the monomeric diene, and to add the first portion of the monomeric diene to the reaction preferably before the addition of the hydrogen peroxide and to add the second portion of the monomeric diene to the reaction preferably after the addition of the hydrogen peroxide.

[0025] The method according to the invention preferably comprises: a) heating a hydrophilic organic solvent to a temperature of 75 to 105°C under a pressure of 0.0 to 5.0 MPa, preferably 1.2 to 3.0 MPa; b) adding a first portion of the total amount of diene before, during or after the start of step a), preferably before the start of heating in step a) to create a pressure of 0.1 to 5.0 MPa, preferably 0.5 to 3.0 MPa, most preferably 0.75 to 2.0 MPa; c) adding hydrogen peroxide to the mixture; d) heating the mixture obtained in step c) to a temperature of 110 to 150°C, preferably 115 to 130°C; e) adding a second portion of the total amount of diene while heating in step d) or at the final temperature obtained in step d), maintaining the reaction mixture at a temperature equal to or differing by a maximum of + / - 10°C from the temperature obtained in step d); and f) terminating the reaction.

[0026] Preferably, the addition of the second portion of the total amount of monomeric diene in step d) is completed before the final temperature obtained in step d) is reached, which final temperature is preferably below 130°C.

[0027] Preferably, the process of the present invention is carried out in a reactor. More preferably, process steps a) to e) are carried out in a reactor. Preferably, all steps a) to e) are carried out in the same reactor. The reactor is preferably a stainless steel reactor, more preferably a stainless steel autoclave.

[0028] The hydrophilic organic solvent is preferably an alkanol that is liquid at room temperature. Preferably, the hydrophilic organic solvent is an organic solvent that is miscible with water at 25°C without forming an organic phase separate from the aqueous phase. In a preferred embodiment, the hydrophilic organic solvent is an unbranched or branched alkanol that is liquid at room temperature, more preferably an unbranched or branched 1-alkanol, most preferably isopropanol or ethanol. The proportion of the hydrophilic organic solvent, preferably ethanol, is 15 to 50% by weight, preferably 17.5 to 30% by weight, more preferably 20 to 30% or 22 to 30% by weight.

[0029] The total amount of hydrophilic organic solvents used is preferably 15 to 50% by weight, more preferably 22 to 30% by weight, the total amount of dienes is preferably 50 to 80% by weight, the total amount of water is preferably less than 15% by weight, more preferably 2 to 8% by weight, and the total amount of hydrogen peroxide is preferably 1 to 15% by weight, more preferably 1.5 to 7.5% by weight, each based on the total weight of the reaction mixture.

[0030] The hydrogen peroxide used is preferably an aqueous solution of hydrogen peroxide, more preferably an aqueous solution containing 25% to 99% by weight, preferably 33.3% to 75% by weight, and most preferably 50% by weight of hydrogen peroxide based on the total weight of the aqueous hydrogen peroxide solution.

[0031] The temperature of the reaction mixture in step c) is preferably 100° C. or higher.

[0032] The reaction time measured from the addition of the second portion of diene in step e) is at least 0.5 hours, more preferably 1 to 3 hours, most preferably 1.5 to 2.5 hours.

[0033] The weight ratio of the diene in the first portion added to the diene in the second portion added is preferably 2:1 to 1:10, more preferably 1:1 to 1:8, even more preferably 1:3 to 1:5, and most preferably 1:4.

[0034] The weight ratio of the total amount of hydrogen peroxide used to the total amount of diene used is preferably 1:10 to 1:40, more preferably 1:15 to 1:30, and most preferably 1:16 to 1:23.

[0035] It may be advantageous to terminate the reaction in step f) by contacting the reaction mixture with water, preferably deionized water, preferably at a temperature of 20 to 80°C, more preferably 30 to 70°C, most preferably 50 to 65°C.

[0036] It may be advantageous to contact the reaction mixture with water in step e) without prior cooling. Preferably, the reaction mixture from step e) has a temperature at the start of step f) that is at most 20°C, preferably at most 15°C, more preferably at most 10°C lower than the temperature in step e).

[0037] It may be advantageous if the process according to the invention further comprises a step g) of separating the unreacted gaseous diene from the reaction mixture obtained after step f), followed by condensation, distillation and recycling of the unreacted gaseous diene, and / or separation of the hydrophilic organic solvent from the reaction mixture obtained after step f) and optionally recycling of the hydrophilic organic solvent in step a), and optionally purification of the polymerization product by distillation. Suitable processes are described in Fluidverfahrenstechnik, edited by R. Goedecke, p. 637 ff, 2006 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

[0038] The separation of the hydrophilic solvent from the polymerization product can be preferably carried out using a bottom valve or a decanter. The hydrophilic organic solvent can be recovered from the aqueous phase by distillation and reused in the polymerization reaction in step a). Distillation methods are described in Fluidverfahrenstechnik, edited by R. Goedecke, p. 689 ff (Chapter 8 Rektifikation), 2006 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

[0039] It may also be advantageous if at least a portion of the unreacted gaseous diene is separated from the reaction mixture prior to step f), optionally followed by condensation, distillation and / or recycling of the unreacted gaseous diene. This can be done by releasing the pressure from the reactor immediately prior to step f).

[0040] Gas removal by means of flash devices is described in Fluidverfahrenstechnik, edited by R. Goedecke, p. 693, 2006 Wiley-VCH Verlag GmbH&Co KGaA, Weinheim.

[0041] The concentrated diene obtained by separating the unreacted gaseous diene by any of the above methods is preferably contacted with an antioxidant, preferably selected from the group consisting of dithionite, pyrogallol, ascorbic acid, and a mixture containing bisulfite and sulfite. Preferably, the antioxidant is used at a concentration of 0.1 to 1.5 wt. %, more preferably 0.2 to 1 wt. %, based on the concentrated diene. Most preferably, the antioxidant is a mixture containing iron bisulfite and iron sulfite at a final concentration of 0.1 to 1.5 wt. %, preferably 0.2 to 1 wt. %, based on the concentrated diene.

[0042] The process according to the invention is preferably carried out in an apparatus for the polymerization of dienes, the apparatus comprising: a reactor (1) for the polymerization of dienes, the reactor being suitable for reacting dienes with hydrogen peroxide in a hydrophilic organic solvent to form a reaction mixture; a flash unit (2) into which the reaction mixture from the reaction vessel (1) is discharged, and in which the unreacted gaseous diene from the flash unit is separated from the reaction mixture and transferred into a condenser (5) and then into a distillation unit (6) and finally returned to the reaction vessel (1), and in which water is first admitted therein and allowed to contact the reaction mixture from the reaction vessel (1) to form an aqueous phase comprising a hydrophilic organic solvent; a phase separator (3) arranged downstream of the flash unit, suitable for transferring therein the reaction mixture separated from the unreacted gaseous diene in the flash unit (2) and for allowing the aqueous phase containing the hydrophilic organic solvent to be separated from the reaction mixture and transferred first to the distillation unit (7) and finally back into the reactor (1); The system further includes a distillation apparatus (4) downstream of the phase separation apparatus (3), suitable for transferring the reaction mixture separated from the aqueous phase containing the hydrophilic organic solvent in the phase separation apparatus (3) thereto and for purifying the product from the reaction mixture separated from the aqueous phase containing the hydrophilic organic solvent by distillation. The reaction vessel (1) is preferably a vessel made of passivated stainless steel. The system preferably includes appropriate connecting pipes for connecting the reaction vessel (1), the flash apparatus (2), the concentration apparatus (5), the distillation apparatus (6), the phase separation apparatus (3), and the distillation apparatus (7).

[0043] The concentrator (5) preferably contains an antioxidant selected from the group consisting of dithionite, pyrogallol, ascorbic acid, and mixtures containing bisulfite and sulfite. The phase separator (3) is preferably a decanter. In a preferred apparatus used in the process according to the invention, the reactor (1) is adapted to allow the unreacted gaseous diene to be transferred from the reactor to a condensation unit (5), then to a distillation unit (6) and finally returned to the reactor (1).

[0044] The process of the present invention is particularly useful for preparing hydroxy-functionalized polydienes, preferably hydroxy-functionalized polybutadienes or polyisoprenes, more preferably hydroxy-functionalized polybutadienes, most preferably hydroxy-functionalized polybutadienes according to the present invention.

[0045] In the context of the present invention, the term "polybutadiene" should be understood to mean a product obtained by polymerization of monomer units each having at least two conjugated double bonds, at least 80, 85, 90, 95, 98, 99 or 99.9% (each successively more preferred) of the monomer units being 1,3-butadiene, preferably exclusively. Possible further compounds (impurities) can be, for example, alkanes or alkenes having 3 to 5 carbon atoms, preferably propene, 1-butene or 1,2-butadiene.

[0046] The hydroxy-functionalized polybutadiene according to the present invention is characterized in that it has a dispersion index D(Mw / Mn) of less than 2.7, preferably from 2.1 to 2.7, a viscosity at 30°C of less than 3200 mPa*s, preferably from 2100 to 3200 mPa*s, an OH number of 50 to 90, more preferably from 70 to 90, a number average molecular weight Mn of 1.6 to 2.5 kDa, preferably from 1.6 to 2.0 kDa, and a weight number average molecular weight Mw of 4.0 to 5.6 kDa, preferably from 4.0 to 5.0 kDa, and contains monomer units derived from 1,3-butadiene; [ka] The proportion of (A) in all monomer units derived from 1,3-butadiene present in the polybutadiene is 10 to 60 mol %, and the sum of the proportions of (B) and (C) in all monomer units derived from 1,3-butadiene present in the polybutadiene is 40 to 90 mol %.

[0047] Preferably, the proportion of units of formula (A) in all monomer units derived from 1,3-butadiene present in the polybutadiene is 15 to 30 mol %, the proportion of units of formula (B) in all monomer units derived from 1,3-butadiene present in the polybutadiene is 50 to 70 mol %, and the proportion of units of formula (C) in all monomer units derived from 1,3-butadiene present in the polybutadiene is 15 to 30 mol %, with the proviso that the total of all monomer units (A), (B) and (C) is a maximum of 100 mol %.

[0048] In the monomer units represented by formulas (A), (B), and (C), where the brackets in the formula representations selected in this application indicate the monomer units (A), (B), and (C) derived from 1,3-butadiene present in the polybutadiene, the bond marked by each bracket does not terminate, for example, in a methyl group; instead, the related monomer unit is bonded to another monomer unit via this bond. In this case, the monomer units (A), (B), and (C) can be arranged in the polymer in any desired order. A random arrangement is preferred.

[0049] The proportion of monomer units not conforming to any of formulas (A), (B), or (C) in the polybutadiene according to the present invention is preferably less than 20 mole percent, preferably less than 5 mole percent, particularly preferably less than 1 mole percent, and particularly preferably less than 0.1 mole percent, based on the total monomer units. The proportion of monomer units not conforming to any of formulas (A), (B), or (C) in the polybutadiene according to the present invention can be controlled in the production process by using 1,3-butadiene containing impurities, in particular dienes that are not 1,3-butadiene, preferably less than 20 mole percent, preferably less than 5 mole percent, particularly preferably less than 1 mole percent, and particularly preferably less than 0.1 mole percent. Determination of the proportion of monomer units in the polybutadiene can be carried out as described in the Experimental Section (Test Methods).

[0050] The hydroxy-terminated polybutadiene according to the present invention preferably has an average functionality of 0.1 to 4, more preferably 0.7 to 3, and particularly preferably 1.2 to 2.8, which means that the polybutadiene molecule, regardless of its length, has, on average, preferably 0.1 to 4, more preferably 0.7 to 3, and particularly preferably 1.2 to 2.8 OH groups.

[0051] The hydroxy-functionalized polybutadiene according to the invention is preferably obtainable by the process according to the invention.

[0052] The hydroxy-functionalized polybutadienes according to the present invention are preferably used in polyurethane-based thermal or electrical insulation, adhesives or sealants or for the preparation of polyesters, preferably block copolyesters.

[0053] The present invention is further illustrated by the following non-limiting examples that illustrate additional features, embodiments, aspects and advantages of the present invention.

[0054] (Example) Test Method: a) Determination of OH number (OHN): The concentration of OH groups is determined in milligrams of KOH per gram of polymer by titration according to DIN 53240-2.

[0055] b) Determination of viscosity: The viscosity of the polymers produced was determined in Pa.s according to DIN EN ISO 3219 using a rotational viscometer at the temperature specified in each case.

[0056] c) Determination of molecular weight and dispersity: The number-average and weight-average molecular weights (Mn and Mw, respectively) of the polymers used in the context of this invention are determined by gel permeation chromatography in accordance with DIN 55672-1 using tetrahydrofuran as eluent and polystyrene as calibration. Measurements were carried out at 40°C in tetrahydrofuran (THF) at a concentration of 1 g / l and a flow rate of 0.3 ml / min. Chromatographic separation was achieved using a PSS SDV Micro 5μ / 4.6 x 30 mm precolumn and a PSS SDV Micro linear S 5μ / 4.6 x 250 mm (2x) separation column. Detection was performed using an RI detector. Calibration was performed using polybutadiene standards (PSS-Kit polybutadiene-1,4, Mp 831-106000, product number: PSS-bdfkit, Mn: 1830 / 4330 / 9300 / 18000 / 33500). Dispersity D = Mw / Mn.

[0057] d) Determination of the molar ratio of monomer units The molar ratio of the monomer units according to formulas (A), (B), and (C) is determined by IR spectroscopy relative to a polybutadiene standard. For this purpose, the sample (approximately 80-250 mg) is dissolved in 10 ml of carbon disulfide (CS2). For high vinyl contents, lower concentrations are used, and for high cis contents, higher concentrations are used. Measurements are carried out in an IR cuvette with a NaCl window and a path length of 0.5 mm. The solvent is subtracted and the spectrum is evaluated in the range 1100-600 cm. -1 For absorbances above 1, repeat the measurement at a lower concentration. Determine the absorbance above baseline for the following signals: Trans-1,4-polybutadiene: 968 cm -1 1,2-Polybutadiene: 911 cm -1 cis-1,4-polybutadiene: 730 cm -1 The molar ratio of the monomer components is given by: %comp(i)=Ext(i)*100% / (E(i)*c*d*) During the ceremony, Ext(i) = absorbance above baseline E(i) = extinction coefficient (substance specific, determined by calibration) [E] = L / (g*cm) d = cuvette path length (cm) c = concentration of sample (g / L) Example 1: Comparative Example

[0058] 520 ml of toluene-denatured ethanol (ethanol concentration: 97 wt%) was initially placed in a 5 L passivated stainless steel autoclave (Model 4; stainless steel: 1.4571; pressure rating: -0.1 to 4.0 MPa) manufactured by Buchi. Subsequently, 1,086 g of 1,3-butadiene (m BD(a) in Table 1) was introduced into the reactor, and the contents of the reactor were heated. After the temperature reached at least 90 °C, 148 mL of hydrogen peroxide (aqueous solution, hydrogen peroxide concentration: 50 wt%) was introduced through the lock. The contents of the reactor were then further heated to 124 °C. The reaction mixture was brought to 124 °C within 1 hour of the hydrogen peroxide introduction and then maintained at this temperature for 1 hour.

[0059] After the reaction time had elapsed, the reactor contents were cooled to below 100°C. During this cooling process, the reactor pressure was slowly reduced from 2.0-4.0 MPa to 0.3 MPa within 30 minutes. After the temperature reached 100°C and the pressure reached 0.3 MPa, the reactor contents were transferred to a specially prepared vessel (a flash apparatus) filled with 650 g of water at 60°C. To separate the excess butadiene, the contents of the flash vessel were stirred at 60°C for 1 hour under a pressure of 0.02-0.04 MPa below atmospheric pressure to remove residual butadiene monomer. After a settling period of approximately 1 hour, two phases were obtained. The upper organic phase contained the desired polymer, and the lower aqueous phase contained unreacted hydrogen peroxide.

[0060] The aqueous phase was separated from the organic phase by a bottom valve. Volatile organic components were removed from the organic phase using a rotary evaporator and reduced pressure, leaving 760 g of the desired product, corresponding to a 70.0% yield based on the amount of butadiene used. The raw materials used are listed in Table 1. Some properties of the resulting product are listed in Table 2.

[0061] Example 2: Addition of butadiene in two separate batches according to the present invention 520 ml of toluene-denatured ethanol (97 wt % ethanol) was initially placed in a 5 L Buchi passivated stainless steel autoclave (Model 4; stainless steel: 1.4571; pressure rating: -1 to 40 bar) as a reactor. 537 g of 1,3-butadiene (m BD(a) in Table 1) was then introduced, and the reactor contents were heated. After the temperature reached at least 90 °C, 148 mL of hydrogen peroxide (aqueous solution, hydrogen peroxide concentration 50 wt %) was introduced through the lock. The reactor contents were then further heated to 124 °C. Once the reaction temperature of 124 °C was reached, an additional 537 g of 1,3-butadiene (m BD(b) in Table 1) was introduced. The reaction mixture was brought to 124 °C within 1 hour of the hydrogen peroxide introduction and then maintained at this temperature for 1 hour. After the reaction time had elapsed, the reactor contents were cooled to below 100°C. During this cooling process, the reactor pressure was slowly reduced from 2.0-4.0 MPa to 0.3 MPa within 30 minutes. After the temperature reached 100°C and the pressure reached 0.3 MPa, the reactor contents were transferred to a specially prepared vessel (a flash apparatus) filled with 650 g of water at 60°C. To separate the excess butadiene, the contents of the flash vessel were stirred at 60°C for 1 hour under a pressure of 0.02-0.04 MPa below atmospheric pressure to remove residual butadiene monomer. After a settling period of approximately 1 hour, two phases were obtained. The upper organic phase contained the desired polymer, and the lower aqueous phase contained unreacted hydrogen peroxide.

[0062] The aqueous phase was separated from the organic phase by a bottom valve. Volatile organic components were removed from the organic phase using a rotary evaporator and reduced pressure, leaving 680 g of the desired product, corresponding to a 62.4% yield based on the amount of butadiene used. The raw materials used are listed in Table 1. Some properties of the resulting product are listed in Table 2.

[0063] Example 3: Addition of butadiene in two separate batches according to the present invention 520 ml of toluene-denatured ethanol (ethanol concentration: 97 wt%) was initially placed in a 5 L Buchi passivated stainless steel autoclave (Model 4; stainless steel: 1.4571; pressure rating: -1 to 40 bar) as a reactor. Subsequently, 537 g of 1,3-butadiene (m BD(a) in Table 1) was introduced, and the contents of the reactor were heated. After the temperature reached at least 90 °C, 134 mL of hydrogen peroxide (aqueous solution, hydrogen peroxide concentration: 50 wt%) was introduced through the lock. The contents of the reactor were then further heated to 124 °C. Once the reaction temperature of 124 °C was reached, an additional 537 g of 1,3-butadiene (m BD(b) in Table 1) was introduced within 30 min. The reaction mixture was brought to 124 °C within 1 h of the hydrogen peroxide introduction and then maintained at this temperature for 1 h. The pressure in the reactor varied from 1.4 to 2.8 MPa during the reaction.

[0064] After the reaction time had elapsed, the reactor contents were cooled to below 100°C. During this cooling process, the reactor pressure was slowly reduced from 2.0-4.0 MPa to 0.3 MPa within 30 minutes. After the temperature reached 100°C and the pressure reached 0.3 MPa, the reactor contents were transferred to a specially prepared vessel (a flash apparatus) filled with 650 g of water at 60°C. To separate the excess butadiene, the contents of the flash vessel were stirred at 60°C for 1 hour under a pressure of 0.02-0.04 MPa below atmospheric pressure to remove residual butadiene monomer. After a settling period of approximately 1 hour, two phases were obtained. The upper organic phase contained the desired polymer, and the lower aqueous phase contained unreacted hydrogen peroxide.

[0065] The aqueous phase was separated from the organic phase by a bottom valve. Volatile organic components were removed from the organic phase using a rotary evaporator and reduced pressure, leaving 656 g of the desired product, corresponding to a 61.0% yield based on the amount of butadiene used. The raw materials used are listed in Table 1. Some properties of the resulting product are listed in Table 2.

[0066] Example 4: Dosing of Butadiene During Heating According to the Invention 520 ml of toluene-denatured ethanol (97 wt % ethanol) was initially placed in a 5 L Buchi passivated stainless steel autoclave (Model 4; stainless steel: 1.4571; pressure rating: -1 to 40 bar). 537 g of 1,3-butadiene (m BD(a) in Table 1) was then introduced, and the contents of the reactor were heated. After the temperature reached at least 90 °C, 134 mL of hydrogen peroxide (aqueous solution, 50 wt % hydrogen peroxide) was introduced through the lock. The contents of the reactor were then further heated to 124 °C, and within 30 minutes of initiating heating, 537 g of 1,3-butadiene (m BD(b) in Table 1) was introduced. The reaction mixture was brought to 124 °C within 1 hour of the hydrogen peroxide introduction and then maintained at this temperature for 1 hour.

[0067] After the reaction time had elapsed, the reactor contents were cooled to below 100°C. During this cooling process, the reactor pressure was slowly reduced from 2.0-4.0 MPa to 0.3 MPa within 30 minutes. After the temperature reached 100°C and the pressure reached 0.3 MPa, the reactor contents were transferred to a specially prepared vessel (a flash apparatus) filled with 650 g of water at 60°C. To separate the excess butadiene, the contents of the flash vessel were stirred at 60°C for 1 hour under a pressure of 0.02-0.04 MPa below atmospheric pressure to remove residual butadiene monomer. After a settling period of approximately 1 hour, two phases were obtained. The upper organic phase contained the desired polymer, and the lower aqueous phase contained unreacted hydrogen peroxide.

[0068] The aqueous phase was separated from the organic phase by a bottom valve. Volatile organic components were removed from the organic phase using a rotary evaporator and reduced pressure, leaving 741 g of the desired product, corresponding to a 67.5% yield based on the amount of butadiene used. The raw materials used are listed in Table 1. Some properties of the resulting product are listed in Table 2.

[0069] Example 5: Dosing of Butadiene During Heating According to the Invention 520 ml of toluene-denatured ethanol (97 wt. % ethanol) was initially placed in a 5 L Buchi passivated stainless steel autoclave (Model 4; stainless steel: 1.4571; pressure rating: -1 to 40 bar). 220 g of 1,3-butadiene (m BD(a) in Table 1) was then introduced, and the contents of the reactor were heated. After the temperature reached at least 90 °C, 134 mL of hydrogen peroxide (aqueous solution, 50 wt. % hydrogen peroxide) was introduced through the lock. The contents of the reactor were then further heated to 124 °C, and within 30 min of initiating heating, 880 g of 1,3-butadiene (m BD(b) in Table 1) was introduced. The reaction mixture was brought to 124 °C within 1 h of the hydrogen peroxide introduction and then maintained at this temperature for 1 h.

[0070] After the reaction time had elapsed, the reactor contents were cooled to below 100°C. During this cooling process, the reactor pressure was slowly reduced from 2.0-4.0 MPa to 0.3 MPa within 30 minutes. After the temperature reached 100°C and the pressure reached 0.3 MPa, the reactor contents were transferred to a specially prepared vessel (a flash apparatus) filled with 650 g of water at 60°C. To separate the excess butadiene, the contents of the flash vessel were stirred at 60°C for 1 hour under a pressure of 0.02-0.04 MPa below atmospheric pressure to remove residual butadiene monomer. After a settling time of up to 1 hour, two phases were obtained. The upper organic phase contained the desired polymer, and the lower aqueous phase contained unreacted hydrogen peroxide.

[0071] The aqueous phase was separated from the organic phase by a bottom valve. Volatile organic components were removed from the organic phase using a rotary evaporator and reduced pressure, leaving 702 g of the desired product, corresponding to a 64.1% yield based on the amount of butadiene used. The raw materials used are listed in Table 1. Some properties of the resulting product are listed in Table 2.

[0072] Example 6: Dosing of Butadiene During Heating According to the Invention 520 ml of toluene-denatured ethanol (97 wt % ethanol) was initially placed in a 5 L Buchi passivated stainless steel autoclave (Model 4; stainless steel: 1.4571; pressure rating: -1 to 40 bar). 220 g of 1,3-butadiene (m BD(a) in Table 1) was then introduced, and the contents of the reactor were heated. After the temperature reached at least 90 °C, 134 mL of hydrogen peroxide (aqueous solution, 50 wt % hydrogen peroxide) was introduced through the lock. The contents of the reactor were then further heated to 124 °C, and 880 g of 1,3-butadiene (m BD(b) in Table 1) was introduced within 60 min of the start of heating. The reaction mixture was brought to 124 °C within 1 h of the hydrogen peroxide introduction and then maintained at this temperature for 1 h.

[0073] After the reaction time had elapsed, the reactor contents were cooled to below 100°C. During this cooling process, the reactor pressure was slowly reduced from 2.0-4.0 MPa to 0.3 MPa within 30 minutes. After the temperature reached 100°C and the pressure reached 0.3 MPa, the reactor contents were transferred to a specially prepared vessel (a flash apparatus) filled with 650 g of water at 60°C. To separate the excess butadiene, the contents of the flash vessel were stirred at 60°C for 1 hour under a pressure of 0.02-0.04 MPa below atmospheric pressure to remove residual butadiene monomer. After a settling period of approximately 1 hour, two phases were obtained. The upper organic phase contained the desired polymer, and the lower aqueous phase contained unreacted hydrogen peroxide.

[0074] The aqueous phase was separated from the organic phase by a bottom valve. Volatile organic components were removed from the organic phase using a rotary evaporator and reduced pressure, leaving 677 g of the desired product, corresponding to a 62.0% yield based on the amount of butadiene used. The raw materials used are listed in Table 1. Some properties of the resulting product are listed in Table 2.

[0075] Example 7: Addition of butadiene in two separate portions according to the present invention 520 ml of toluene-denatured ethanol (97 wt%) was placed in a passivation tank manufactured by Buchi as the reactor. A 5 L stainless steel autoclave (Model 4; stainless steel: 1.4571; pressure rating: 1-40 bar) was initially charged. Subsequently, 537 g of 1,3-butadiene (m BD(a) in Table 1) was introduced, and the contents of the reactor were heated. After the temperature reached at least 90 °C, 119 mL of hydrogen peroxide (50 wt%) was introduced through the lock. The contents of the reactor were then further heated to 124 °C. Once the reaction temperature of 124 °C was reached, an additional 537 g of 1,3-butadiene (m BD(b) in Table 1) was introduced within 30 min. The reaction mixture was brought to 124 °C within 1 h from the time of hydrogen peroxide introduction and then maintained at this temperature for 1 h. The pressure in the reactor during the reaction varied from 1.4 to 2.8 MPa.

[0076] After the reaction time had elapsed, the reactor contents were cooled to below 100°C. During this cooling process, the reactor pressure was slowly reduced from 2.0-4.0 MPa to 0.3 MPa within 30 minutes. After the temperature reached 100°C and the pressure reached 0.3 MPa, the reactor contents were transferred to a specially prepared vessel (a flash apparatus) filled with 650 g of water at 60°C. To separate the excess butadiene, the contents of the flash vessel were stirred at 60°C for 1 hour under a pressure of 0.02-0.04 MPa below atmospheric pressure to remove residual butadiene monomer. After a settling period of approximately 1 hour, two phases were obtained. The upper organic phase contained the desired polymer, and the lower aqueous phase contained unreacted hydrogen peroxide.

[0077] The aqueous phase was separated from the organic phase by a bottom valve. Volatile organic components were removed from the organic phase using a rotary evaporator and reduced pressure, leaving 606 g of the desired product, corresponding to a 55.7% yield based on the amount of butadiene used. The raw materials used are listed in Table 1. Some properties of the resulting product are listed in Table 2.

[0078] Example 8: Butadiene added in two portions, shortened reaction time, according to the present invention 520 ml (97 wt%) of toluene-denatured ethanol was initially placed in a 5 L Buchi passivated stainless steel autoclave (Model 4; stainless steel: 1.4571; pressure rating: 1-40 bar) as a reactor. Subsequently, 537 g of 1,3-butadiene (m BD(a) in Table 1) was introduced, and the reactor contents were heated. After the temperature reached at least 90 °C, 119 mL of hydrogen peroxide (50 wt%) was introduced through the lock. The reactor contents were then further heated to 124 °C. Once the reaction temperature of 124 °C was reached, an additional 537 g of 1,3-butadiene (m BD(b) in Table 1) was introduced within 30 min. The reaction mixture was brought to 124 °C within 1 h of the hydrogen peroxide introduction and then maintained at this temperature for 45 min. The pressure in the reactor varied from 1.4 to 2.8 MPa during the reaction.

[0079] After the reaction time had elapsed, the reactor contents were cooled to below 100°C. During this cooling process, the reactor pressure was slowly reduced from 2.0-4.0 MPa to 0.3 MPa within 30 minutes. After the temperature reached 100°C and the pressure reached 0.3 MPa, the reactor contents were transferred to a specially prepared vessel (a flash apparatus) filled with 650 g of water at 60°C. To separate the excess butadiene, the contents of the flash vessel were stirred at 60°C for 1 hour under a pressure of 0.02-0.04 MPa below atmospheric pressure to remove residual butadiene monomer. After a settling period of approximately 1 hour, two phases were obtained. The upper organic phase contained the desired polymer, and the lower aqueous phase contained unreacted hydrogen peroxide.

[0080] The aqueous phase was separated from the organic phase by a bottom valve. Volatile organic components were removed from the organic phase using a rotary evaporator and reduced pressure, leaving 585 g of the desired product, corresponding to a 53.8% yield based on the amount of butadiene used. The raw materials used are listed in Table 1. Some properties of the resulting product are listed in Table 2.

[0081] Example 9: Addition of butadiene in two separate portions according to the present invention 520 ml of toluene-denatured ethanol (97 wt%) was placed in a passivation tank manufactured by Buchi as the reactor. A 5 L stainless steel autoclave (Model 4; stainless steel: 1.4571; pressure rating: 1-40 bar) was initially charged. 271 g of 1,3-butadiene (m BD(a) in Table 1) was then introduced, and the contents of the reactor were heated. After the temperature reached at least 90 °C, 105 mL of hydrogen peroxide (50 wt%) was introduced through the lock. The contents of the reactor were then further heated to 124 °C. Once the reaction temperature of 124 °C was reached, an additional 815 g of 1,3-butadiene (m BD(b) in Table 1) was introduced within 30 min. The reaction mixture was brought to 124 °C within 1 h from the time of hydrogen peroxide introduction and then maintained at this temperature for 1 h. The pressure in the reactor during the reaction varied between 1.4 and 2.8 MPa. After the reaction time had elapsed, the reactor contents were cooled to below 100°C. During this cooling process, the reactor pressure was slowly reduced from 2.0-4.0 MPa to 0.3 MPa within 30 minutes. After the temperature reached 100°C and the pressure reached 0.3 MPa, the reactor contents were transferred to a specially prepared vessel (a flash apparatus) filled with 650 g of water at 60°C. To separate the excess butadiene, the contents of the flash vessel were stirred at 60°C for 1 hour under a pressure of 0.02-0.04 MPa below atmospheric pressure to remove residual butadiene monomer. After a settling period of approximately 1 hour, two phases were obtained. The upper organic phase contained the desired polymer, and the lower aqueous phase contained unreacted hydrogen peroxide.

[0082] The aqueous phase was separated from the organic phase by a bottom valve. Volatile organic components were removed from the organic phase using a rotary evaporator and reduced pressure, leaving 512 g of the desired product, corresponding to a 47.1% yield based on the amount of butadiene used. The raw materials used are listed in Table 1. Some properties of the resulting product are listed in Table 2.

[0083] Example 10: Comparative Example 520 ml of toluene-denatured ethanol (ethanol concentration: 97 wt%) was initially placed in a 5 L passivated stainless steel autoclave (Model 4; stainless steel: 1.4571; pressure rating: -0.1 to 4.0 MPa) manufactured by Buchi. Subsequently, 1094 g of 1,3-butadiene (m BD(a) in Table 1) was introduced into the reactor, and the contents of the reactor were heated. After the temperature reached at least 90 °C, 104 mL of hydrogen peroxide (aqueous solution, hydrogen peroxide concentration: 50 wt%) was introduced through the lock. The contents of the reactor were then further heated to 124 °C. The reaction mixture was brought to 124 °C within 1 hour of the hydrogen peroxide introduction and then maintained at this temperature for 1 hour.

[0084] After the reaction time had elapsed, the reactor contents were cooled to below 100°C. During this cooling process, the reactor pressure was slowly reduced from 2.0-4.0 MPa to 0.3 MPa within 30 minutes. After the temperature reached 100°C and the pressure reached 0.3 MPa, the reactor contents were transferred to a specially prepared vessel (a flash apparatus) filled with 650 g of water at 60°C. To separate the excess butadiene, the contents of the flash vessel were stirred at 60°C for 1 hour under a pressure of 0.02-0.04 MPa below atmospheric pressure to remove residual butadiene monomer. After a settling period of approximately 1 hour, two phases were obtained. The upper organic phase contained the desired polymer, and the lower aqueous phase contained unreacted hydrogen peroxide.

[0085] The aqueous phase was separated from the organic phase by a bottom valve. Volatile organic components were removed from the organic phase using a rotary evaporator and reduced pressure, leaving 435 g of the desired product, corresponding to a 39.8% yield based on the amount of butadiene used. The raw materials used are listed in Table 1. Some properties of the resulting product are listed in Table 2.

[0086] Example 11: Addition of butadiene in two separate portions according to the present invention 520 ml (97 wt%) of toluene-denatured ethanol was initially placed in a 5 L Buchi passivated stainless steel autoclave (Model 4; stainless steel: 1.4571; pressure rating: 1-40 bar). Subsequently, 545 g of 1,3-butadiene (m BD(a) in Table 1) was introduced, and the contents of the reactor were heated. After the temperature reached at least 90 °C, 65 mL of hydrogen peroxide (50 wt%) was introduced through the lock. The contents of the reactor were then further heated to 124 °C. Once the reaction temperature of 124 °C was reached, another 545 g of 1,3-butadiene (m BD(b) in Table 1) was introduced within 30 min. The reaction mixture was brought to 124 °C within 1 h of the hydrogen peroxide introduction and then maintained at this temperature for 1 h. The pressure in the reactor varied from 1.4 to 2.8 MPa during the reaction.

[0087] After the reaction time had elapsed, the reactor contents were cooled to below 100°C. During this cooling process, the reactor pressure was slowly reduced from 2.0-4.0 MPa to 0.3 MPa within 30 minutes. After the temperature reached 100°C and the pressure reached 0.3 MPa, the reactor contents were transferred to a specially prepared vessel (a flash apparatus) filled with 650 g of water at 60°C. To separate the excess butadiene, the contents of the flash vessel were stirred at 60°C for 1 hour under a pressure of 0.02-0.04 MPa below atmospheric pressure to remove residual butadiene monomer. After a settling period of approximately 1 hour, two phases were obtained. The upper organic phase contained the desired polymer, and the lower aqueous phase contained unreacted hydrogen peroxide.

[0088] The aqueous phase was separated from the organic phase by a bottom valve. Volatile organic components were removed from the organic phase using a rotary evaporator and reduced pressure, leaving 457 g of the desired product, corresponding to a 41.9% yield based on the amount of butadiene used. The raw materials used are listed in Table 1. Some properties of the resulting product are listed in Table 2.

[0089] [Table 1]

[0090] [Table 2]

[0091] The data for Examples 1 and 2 shown in Tables 1 and 2 reveal that if the butadiene feedstock is introduced in two portions, with the second portion being introduced when the reaction temperature is reached, the amount of feedstock used is the same, but the OH number (OHN) increases and in many cases polybutadiene with a lower molecular weight is obtained.

[0092] When Example 2 is repeated (Example 3) using a reduced amount of hydrogen peroxide, a polybutadiene with a higher OHN, a lower molecular weight and a lower viscosity is obtained compared to the polybutadiene obtained in Example 1.

[0093] Repeating Example 3 but adding the second half of the butadiene while the reaction mixture ramps up heat (Example 4) results in a polybutadiene with a similar OHN, a slightly higher molecular weight, and a slightly higher viscosity compared to the polybutadiene obtained in Example 1.

[0094] Repeating Example 4, but adding 80% of the butadiene used within 30 minutes while heating the reaction mixture (Example 5), results in a polybutadiene with a similar OHN, lower molecular weight and lower viscosity compared to the polybutadiene obtained in Example 1.

[0095] Repeating Example 5, but adding 80% of the butadiene used within 60 minutes while heating the reaction mixture (Example 6), results in polybutadiene with a higher OHN, lower molecular weight, and lower viscosity compared to the polybutadiene obtained in Example 1. In addition, Examples 5 and 6 show a decrease in dispersibility.

[0096] Examples 7-9 demonstrate that the amount of hydrogen peroxide required can be significantly reduced by practicing the method of the present invention. The examples also demonstrate that polybutadiene can be produced that has approximately the same OHN as conventionally produced polybutadiene, but with significantly reduced dispersibility and viscosity.

[0097] Although the yield is slightly lower, the process can be carried out in a safer mode, and the reduced yield can be tolerated since unused raw materials and solvents can be recycled.

[0098] Comparing Examples 10 and 11, it is clear that the observed effects of lower viscosity and narrower dispersity can be obtained along with a significantly reduced OH number.While having the same average molecular weight distribution, Example 11 shows a significantly lower viscosity than Comparative Example 10, but also a significantly lower OHN.In addition, the hydrogen peroxide used in synthesis is also significantly reduced, and surprisingly, the yield can be slightly improved compared to the method according to Comparative Example 10.

Claims

1. 1. A process for preparing a hydroxy-functionalized polydienes by reacting a monomeric diene with hydrogen peroxide in the presence of a hydrophilic organic solvent, characterized in that the total amount of monomeric diene used is added to the reaction in at least two portions, and the second portion of the monomeric diene is added to the reaction at a temperature of the reaction mixture that differs by at least +5 K from the temperature of the reaction mixture at the time of the addition of the first portion of the monomeric diene.

2. 10. The method of claim 1, wherein the second portion of the monomeric diene is added to the reaction at least 30 minutes after the first addition of the monomeric diene.

3. 10. The method of claim 1, wherein a first portion of the monomeric diene is added to the reaction before the addition of hydrogen peroxide and a second portion of the monomeric diene is added to the reaction after the addition of hydrogen peroxide.

4. a) heating a hydrophilic organic solvent to a temperature of 75-105°C; b) adding a first portion of the total amount of the monomeric diene before, during, or after the start of step a) to create a pressure of 0.1 to 5.0 MPa; c) adding hydrogen peroxide to the mixture; d) heating the mixture obtained in step c) to a temperature of 110-150°C; e) adding a second portion of the total amount of said monomeric diene during step d) or at the final temperature obtained in step d) while heating, maintaining said reaction mixture at a temperature equal to or differing by a maximum of + / - 10 K from the temperature obtained in step d); f) Terminating the reaction The method of claim 1 , comprising:

5. 5. The process of claim 4, wherein the addition of the second portion of the total amount of monomeric diene in step d) is completed before the final temperature obtained in step d) is reached.

6. 2. The method of claim 1, wherein the hydrophilic organic solvent is an alkanol that is liquid at room temperature.

7. 2. The process of claim 1, wherein the total amount of the hydrophilic organic solvents used is 15 to 30 wt %, the total amount of the monomeric dienes is 60 to 80 wt %, the total amount of water is less than 10 wt %, and the total amount of hydrogen peroxide is 1 to 5 wt %, each based on the total weight of the reaction mixture.

8. 2. The method of claim 1, wherein the temperature of the reaction mixture in step c) is 100° C. or higher.

9. 2. The method of claim 1, wherein the weight ratio of the first portion of the monomeric diene added to the second portion of the monomeric diene added is from 2:1 to 1:

10.

10. 2. The method of claim 1, wherein the weight ratio of the total amount of hydrogen peroxide used to the total amount of monomeric dienes used is from 1:10 to 1:

40.

11. a hydroxy-functionalized polybutadiene having a dispersion index D of less than 2.7, a viscosity at 30°C of less than 3200 mPa*s, an OH number of 50 to 90, a number average molecular weight Mn of 1.6 to 2.5 kDa, and a weight number average molecular weight Mw of 4.0 to 5.6 kDa, and comprising monomer units derived from 1,3-butadiene; 【Chemical 1】 a hydroxy-functionalized polybutadiene in which the proportion of (A) in the total monomer units derived from 1,3-butadiene present in the polybutadiene is 10 to 60 mol %, and the sum of the proportions of (B) and (C) in the total monomer units derived from 1,3-butadiene present in the polybutadiene is 40 to 90 mol %.

12. 12. Use of the hydroxy-functionalized polybutadiene of claim 11 in the manufacture of polyurethane-based thermal or electrical insulators, adhesives or sealants or polyesters.

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