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    • 专利摘要:
    The present invention is a tetrahydrofuran / but-2-yn-1,4- having a C-C triple bond, having an average molecular weight M n of 500 to 3,500 Daltons and having 0.5 to 3 moles of triple bonds per mole of copolymer. A diol copolymer and a combination of this copolymer with polytetrahydrofuran having an average molecular weight M n of 500 to 3,500 Daltons. The invention also relates to a process for the preparation of this copolymer or combination and to the use thereof.
    公开号:KR19980702696A
    申请号:KR1019970706103
    申请日:1996-02-21
    公开日:1998-08-05
    发明作者:크리스토프 지크바르트；롤프 피숴；라이너 벡커；클라우스-디터 프리츠코；게르트 하일렌；크리스토프 팔름；페터 그롤
    申请人:페라스타르크；바스프악티엔게젤샤프트；
    IPC主号:
    专利说明:

    Tetrahydrofuran / but-2-yne-1,4-diol copolymer with C-C triple bond
    The present invention is a tetrahydrofuran / but-2-yne-1,4- having a C-C triple bond and having an average molecular weight M n of 500 to 3,500 Daltons and a triple bond content of 0.5 to 3.0 moles per mole of copolymer. A diol copolymer and a combination of this copolymer with polytetrahydrofuran having an average molecular weight M n of 500 to 3,500 Daltons.
    The invention also relates to a process for the preparation of tetrahydrofuran / but-2-yne-1,4-diol copolymers having C-C triple bonds.
    The present invention also provides a process for preparing polyoxytetramethylene glycol (polytetrahydrofuran, PTHF) and a process for preparing polyoxytetramethylene glycol with C-C double bond, 500 to 3,500 Daltons with internal C-C double bond Average molecular weight M n and polyoxytetramethylene glycol having a double bond content of 0.1 to 3 moles per mole of polyoxytetramethylene glycol and an average of 500 to 3,500 daltons with such polyoxytetramethylene glycol having an internal C-C double bond It relates to a combination with polytetrahydrofuran having a molecular weight M n .
    It is known that tetrahydrofuran can be polymerized to provide saturated polyether polyols by using saturated α, ω-diol and hydrated heteropolyacids as catalyst. According to US Patent No. 4,658,065 (Aoshima et al.), Polyoxy as a continuous experiment for the polymerization of tetrahydrofuran using hydrated dodeca tungstate phosphoric acid as a catalyst, for example in the presence of 1,4-butanediol Tetramethylene glycol can be obtained. This method has the disadvantage that undesirable space-time yields are obtained, for example, when preparing polytetrahydrofuran with a relatively low average molecular weight from polytetrahydrofuran with an average molecular weight of 1000 Daltons. This disadvantage is particularly problematic because polytetrahydrofuran, which has a relatively low average molecular weight, is of particular commercial interest.
    According to EP 503,393, polyoxytetramethylene glycol monoethers are prepared from monohydric alcohols by the polymerization of tetrahydrofuran with anhydrous heteropolyacid catalysts in the presence of monohydric alcohols.
    According to Maksimov et al. (Polymer SCienCe, Ser.B. 36 (1994), 412), monopropargyl ethers of tetrahydrofuran can be prepared using propargyl alcohol in the presence of anhydrous tungstate phosphoric acid. Obtained by polymerizing tetrahydrofuran, but due to its chemical structure it is not practically used for industrial use.
    According to EP 126,471, hydrated heteropolyacids are used as catalyst for the polymerization of tetrahydrofuran (THF) to give polyoxytetramethylene glycol. A disadvantage of this method is that the THF conversion is as low as about 8%, especially in the production of polyoxytetramethylene glycols having a relatively low average molecular weight which is of commercial concern. Polyoxytetramethylene glycols produced by this method have room for further improvement in their color number.
    It is an object of the present invention to provide new polyoxyalkylene glycols having C-C triple bonds or C-C double bonds, wherein such unsaturated groups must be located at the ends and / or inside of the polyoxyalkylene glycol molecule. Another object of the present invention is to provide a process for producing such polyoxyalkylene derivatives. Also provided is a process for producing polyoxytetramethylene glycol, also referred to as polytetrahydrofuran (PTHF), using such unsaturated polyoxyalkylene glycol derivatives as starting materials. It is an object of the present invention to obtain polytetrahydrofuran having a particularly low color number and high uniformity.
    The inventors of the present invention have tetrahydrofuran / but-2-yn-1 having a C-C triple bond and having an average molecular weight M n of 500 to 3,500 daltons and a triple bond content of 0.5 to 3.0 moles per mole of copolymer. , 4-diol copolymers, and combinations of this copolymer with polytetrahydrofuran having an average molecular weight M n of 500 to 3,500 Daltons.
    The inventors also note that tetrahydrofuran / but- with C-C triple bonds consists of copolymerizing tetrahydrofuran with but-2-yn-1,4-diol in an essentially anhydrous reaction medium using a heteropolyacid catalyst. A process for the preparation of 2-yne-1,4-diol copolymers has been found.
    The present inventors also found a process for producing polyoxytetramethylene glycol, which consists of hydrogenating a tetrahydrofuran / but-2-yne-1,4-diol copolymer using a hydrogenation catalyst.
    We also provide a process for the preparation of polyoxytetramethylene glycols having double bonds, consisting of partially hydrogenating C-C triple bonds of tetrahydrofuran / but-2-yne-1,4-diol copolymers on a hydrogenation catalyst. Found.
    The new tetrahydrofuran / but-2-yne-1,4-diol copolymer has an average molecular weight M n of 500 to 3,500 Daltons, preferably 650 to 2900 Daltons, as determined by 1 H nuclear magnetic resonance (NMR) spectroscopy and Triple bond -CBC- 0.5 to 3 moles, preferably 0.6 to 2.5 moles, particularly preferably 0.7 to 1.25 moles C-C triple bond content per mole of copolymer.
    According to this preparation method, the copolymer contains a polymerized but-2-yn-1,4-diol unit distributed thereon, and the result of evaluation of the 1 H-NMR spectrum of the copolymer is but- 2 -yn- Units derived from 1,4-diol are mainly included as end groups in the copolymer and present in small amounts inside the copolymer molecules, and the but-2-yn-1,4-diol monomer units in the copolymer It is clearly shown that it is randomly distributed. In the NMR spectrum, the distinction between the Boot-2-yn-1,4-diol units contained within the copolymer and those contained as end groups of the copolymer and their quantification differ from those of the proton signal of the methylene group immediately adjacent to the triple bond. -CBC-CH 2 -O-CH 2 -units, ie boot-2-, which are made possible by chemical shifts and which are located inside of -CBC-CH 2 -OH units, ie end groups or copolymers Depending on the presence of the phosphorus-1,4-diol unit, a low or high field is generally seen at 4.3 or 4.2 pm based on internal standard tetramethylsilane. By synthesizing these NMR signals, it is possible to determine the ratio of the boot-2-yn-1,4-diol unit or end group in the copolymer present inside the molecule.
    The molar ratio of terminal boot-2-yn-1,4-diol units to internal boot-2-indiol units in the copolymer is generally from 1.0: 0.1 to 1.0: 1.6.
    As noted above, the tetrahydrofuran / but-2-indiol copolymer has 0.5 to 3 moles of C-C triple bonds, corresponding to 0.5 to 3 moles of but-2-indiol monomer units per mole of copolymer. Can have Especially when the C-C triple bond content of the copolymer is low, for example when the triple bond content of the copolymer is less than 1, since the copolymerization occurs randomly, tetrahydrofuran / but-2-yn-1,4 Blending of the diol copolymer with polytetrahydrofuran without a C-C triple bond occurs. Since the tetrahydrofuran / but-2-yne-1,4-diol copolymer cannot be separated from the polytetrahydrofuran present therein, the triple bond content of the copolymer is only statistically, for example, It can be determined by nuclear magnetic resonance spectroscopy describing the fraction represented by the formula for triple bond content. Blends of copolymers with PTHF are used more as they are due to their poor separability. The average molecular weight M n of the polytetrahydrofuran present in these blends is between 500 and 3500 Daltons, which is approximately the same value as that of the particular copolymer produced.
    The new copolymer is produced by heteropolyacid catalyzed copolymerization of but-2-yn-1,4-diol and tetrahydrofuran, hereinafter also referred to simply as butynediol.
    Examples of heteropolyacids that can be used as catalysts in this new process are the following compounds:
    Dodecyl kamol rib Daytona acid (H 3 PMo 12 O 40 · nH 2 O),
    Dodecyl kamol rib Daytona silicate (H 4 SiMo 12 O 40 · nH 2 O),
    Dodecanoic acid kamol rib Daytona cerium (IV) (H 8 CeMo 12 O 42 · nH 2 O),
    Dodecyl kamol rib Daytona scattering (V) (H 3 AsMo 12 O 42 · nH 2 O),
    Hexamolybdatetochromic acid (III) (H 3 CrMo 6 O 24 H 6 nH 2 O),
    Hexamolybdatetonic acid (II) (H 4 NiMo 6 O 24 H 6 .5H 2 O),
    Hexahydro molybdate Daytona periodic acid (H 5 IMo 6 O 24 · nH 2 O),
    Octa decanoic molybdate day toy acid (H 6 P 2 Mo 18 O 62 · 11H 2 O),
    Octa decanoic molybdate day toy scattering (V) (H 6 As 2 Mo 18 O 62 · 25H 2 O),
    Na molybdate Daytona manganese oxide (IV) (H 6 MnMo 9 O 32 · nH 2 O),
    Undecanoic kamol rib Daytona bar Daytona acid (H 4 PMo 11 VO 40 · nH 2 O),
    Deca molybdate day Todi bar Daytona phosphoric acid (H 5 PMo 10 V 2 O 40 · nH 2 O),
    Kavanagh Daytona dodecyl phosphate (H 7 PV 12 O 36 · nH 2 O),
    Dodecyl kateong stay Sat silicate (H 4 SiW 12 O 40 · 7H 2 O),
    Dodecyl kateong stay Sat acid (H 5 BW 12 O 40 · nH 2 O),
    Octa decanoic tongue stay toy acid (H 6 P 2 W 18 O 62 · 14H 2 O),
    Octa decanoic tongue stay toy scattering (V) (H 6 As 2 W 18 O 62 · 14H 2 O), and
    Hexamolybdatetohexatungstate phosphate (H 3 PMo 6 W 6 O 40 nH 2 O).
    Of course, mixtures of heteropolyacids may be used. Because of their ease of implementation, dodeca tungstate phosphoric acid, dodeca molybdate tooic acid, nonamolybdate tooic acid, dodeca molybdate day silicic acid and dodeca tungstate silicate are preferably used in the new method.
    Free heteropolyacids are preferably used according to the invention as catalysts, but salts thereof, in particular their alkali and alkaline earth metal salts, can also be used as catalysts. Heteropolyacids and salts thereof are known compounds and known methods, for example Brauer (editor): HandbuCh der Praeparativen AnorganisChen Chemie, Vol. III, Enke, Stuttgart, 1981; Or Top. Curr. Chem. 76 (1978), 1).
    Heteropolyacids thus prepared are generally in hydrated form. Before using it in a new method, the water present in it and preferably bound by coordination bonds is removed. This dehydration reaction can be carried out thermally advantageously by the method described, for example, in Makromol. Chem. 190 (1989), 929.
    As mentioned above, heteropolyacid catalysts are preferably used in dehydrated form in new processes. The water content of the heteropolyacid catalyst of 0.1 to 15 moles of water per mole of the heteropolyacid gives an undesirable result, but the copolymerization reaction still occurs even with this water content. However, heteropolyacid catalysts having a water content of less than 0.1 mole of water per mole of heteropolyacid are particularly preferably used as anhydrous heteropolyacids.
    For the preparation of fresh THF / butynediol copolymers, a mixture of THF and butynediol is reacted on a heteropolyacid catalyst. In this reaction, tetrahydrofuran oligomers having low molecular weight may be present. Comonomers THF and butynediol are preferably used in their essentially anhydrous form, but low water contents up to about 100 ppm by weight of such reactants may be acceptable. In addition to the two reactants THF and butynediol, the butynediol content of the reaction mixture comprising a heteropolyacid catalyst and, if necessary, a solvent inert under the reaction conditions affects the average molecular weight M n of the copolymer formed. In general, the higher the content of but-2-yn-1,4-diol in the reaction mixture, the lower the average molecular weight of the copolymer formed. Therefore, as the but-2-yn-1,4-diol content of the reaction mixture decreases, the average molecular weight of the formed copolymer increases. The term average molecular weight or average molecular mass is understood to mean the number average molecular weight M n of the polymer contained in the polymerization product produced in the present invention.
    In addition, the butynediol content of the reaction mixture affects its phase change. If the butynediol content of the reaction mixture is high, the reaction mixture consists of a homogeneous phase, which may make it more difficult to subsequently treat the reaction mixture and remove the catalyst. If the butynediol content of the reaction mixture is very low, the heteropolyacid is no longer completely dissolved by the two comonomers THF and butynediol. The new process is preferably carried out using a reaction mixture having a butynediol content that forms two homogeneous liquid phases in the reaction mixture, the two phases containing most of the heteropolyacid catalyst and butynediol in addition to THF and the copolymer formed immediately. It is a light weight upper phase containing, as a main component, the THF and copolymer dissolved therein in addition to the weight lower phase and the residual amount of butynediol and catalyst.
    In a batch embodiment, in particular of the new process, the but-2-yn-1,4-diol content of the reaction mixture is from 0.1 to 15 moles, preferably of but-2-yn-1,4-diol per mole of heteropolyacid. 1 to 8 moles are advantageous.
    However, new THF / butyndiol copolymers are preferably prepared by a continuous procedure. When the new method is carried out by a continuous procedure, a portion of the but-2-yn-1,4-diol, mainly product- and monomer-containing phases dissolved at the top is continuously discharged from the reactor with the product but is present at the bottom. But-2-in-1,4-diol, mainly the catalyst containing phase, is consumed in the formation of the copolymer, so that the concentration ratio of but-2-in-1,4-diol consumed and released to form on the catalyst It is advantageous to adjust the supply of but-2-yn-1,4-diol to the reaction mixture for replenishment. Under these conditions, a reaction system consisting of the two homogeneous liquid phases is formed, wherein the THF / butyndiol-based copolymer has in fact a predetermined average molecular weight, in particular an average molecular weight of 500 to 3500 Daltons, particularly preferably 650 to 2900 Daltons Copolymers having can be prepared with good selectivity in a controlled manner.
    Boot-on catalysts for the production by a particularly continuous process of a new THF / butynediol copolymer having a C-C triple bond, having an average molecular weight of 500-3,500 Daltons and a narrow molecular weight distribution. It has been found that if 2-in-1,4-diol content is required for the preparation of such polymers, it is advantageous to remain as constant as possible. Thus, in a continuous process, the reaction is provided by supplying fresh or recycled butynediol such that the boot-2-yn-1,4-diol content on the catalyst remains substantially constant, taking into account the diols released with the product-containing upper phase. It is advantageous to apply a procedure in which the but-2-yn-1,4-diol in the mixture is continuously replenished at a rate that is consumed in the reaction.
    In the procedure according to EP 503 392, the but-2-yn-1,4-diol content on a heteropolyacid containing catalyst can be measured by measuring conductivity. The supply of fresh but-2-yn-1,4-diol can be controlled by this measuring method according to the needs of the continuous industrial method through the associated continuous regulation. Measurement of conductivity is a new method, for example, in T. and L. Shedlovski in A. Weissberger, BW Rossiter (Ed.) TeChniques of Chemistry, Volume I, pages 163-204, Wiley-IntersCienCe, New York, 1971 Can be performed using the technique, circulation and measurement device described in Suitable concentrations of but-2-yn-1,4-diol in the catalyst phase can be readily determined using measured conductivity values obtained based on previously prepared calibration curves. Since the conductivity measurement is an electrical measurement method, the measuring device can be very easily coupled to the boot-2-yne-1,4-diol metering device for the purpose of continuous control of the boot-2-yn-1,4-diol addition. . This combined measurement and metering method has a very beneficial effect on the quality of the product, especially in the continuous embodiment of the new method.
    The average molecular weight M n of the new THF / butynediol copolymer with C-C triple bonds formed by the new method is not dependent only on the amount of heteropolyacid catalyst and but-2-yn-1,4-diol added, It is also influenced by the type of heteropolyacid used.
    By varying the amount and type of heteropolyacids used or the Boot-2-yn-1,4-diol content on the catalyst, new copolymers with C-C triple bonds having a narrow average molecular weight and a narrow average molecular weight distribution It can manufacture. Such process parameters can generally be determined by several routine experiments.
    In both continuous and batch embodiments of the new method, heteropolyacids are advantageously used in amounts of 10 to 300, preferably 50 to 150 parts by weight, based on 100 parts by weight of tetrahydrofuran. It is also possible to use large amounts of heteropolyacid catalysts.
    Heteropolyacids can be added to the reaction in the form of a solid and then solvated gradually upon formation of the liquid catalyst phase as a result of contact with further reactants. In addition, the catalyst solution slurried together with but-2-yn-1,4-diol and / or tetrahydrofuran to be used may be passed through the reactor in the form of a liquid catalyst phase. Both the catalyst phase and the monomer starting material can be obtained initially in the reactor. However, both components may be passed into the reactor at the same time.
    The polymerization is generally carried out at 0 to 100 ° C, preferably at 30 to 80 ° C. Atmospheric pressure is advantageously used, but under overpressure, the reaction mainly under the magnetic pressure of the reaction system can also prove advantageous.
    Since the polymerization is preferably carried out in the above system, it is necessary to thoroughly mix the two phases. For this purpose, the reactor should be equipped with efficient mixing means, for example agitators, in both batch and continuous procedures. In a batch process, stirred kettles are generally used for this purpose, and the two liquid phases are separated from one another after the end of the reaction.
    However, continuous procedures are preferably used. Here, the reaction can be carried out in a reactor apparatus suitable for a conventional reactor or continuous process, for example in a tube reactor or stirred kettle cascade equipped with an internal baffle to thoroughly mix the ideal system, followed by monomer- and product-containing The catalyst phase is removed continuously from the top phase. The apparatus as schematically shown in the figures is advantageously used in a new method.
    This device is a stirring kettle 1 connected with a phase separator 2, which is different from the conventional design and can be equipped with an internal or external heater and is generally a star for passing gaseous individual reactants and supplying gas with an inert gas. A personal inlet connection 5 is provided. In the figure, the heating device is not shown for the sake of clarity of the kettle and only one inlet connection 5 representing everything else is shown. In addition, a pressure equalizer 6 and a discharge connection 7 are provided above the reactor. All such devices are provided with separate adjusting devices 8, 9, 10, for example slide valves or valves, which enable the opening and closing of these connections and the adjustment of the feed. The reactor is provided with an agitator 12 connected to the outside by a passage 11 enclosed by a bush 13. The stirring kettle 1 is connected to the phase separator 2 by roughly mounted feeds 3 and 4 at the third height of the top and bottom, respectively. The product solution obtained in the reaction is removed from the apparatus via an outlet connection 18 advantageously mounted above the feed 3. The outflow of the product solution is regulated by a regulating device 19 which can be, for example, a slide valve or a valve.
    For the operation of the continuous apparatus, the reactants are initially placed in a reactor and mixed thoroughly with stirrer 12 at the desired reaction temperature at which an emulsion phase mixture is formed on the catalyst and on the top. The stirrer flows into the reaction mixture such that the emulsion phase mixture passes through the feed 3 to the phase separator 2 where the catalyst phase and the monomer- and product-containing upper phases are separated due to their density differences. The clear, colorless product-containing top phase and the clear catalyst phase, depending on the heteropolyacid used, are separated approximately above line 16 and below line 17 from the turbid emulsion phase reaction mixture, respectively. The product phase is removed by the outlet 18, while the aspiration is effected by the stirrer 12 so that the catalyst phase is flowed back through the feed 4 into the stirring kettle where it is thoroughly mixed with the monomer- and product-containing upper phase again. do. Lines 14 and 15 represent the approximate liquid meniscus and liquid height in the stirring kettle and phase separator, respectively, during operation. Fresh THF and fresh But-2-yn-1,4-diol are introduced into the stirring kettle through the filling connection 5. The diol feed is controlled by the conductive cell 20 immersed on the liquid catalyst so that the desired diol content in the catalyst phase remains constant within the accuracy of regulation.
    Fresh THF is usually metered into the reactor and controlled by height adjustment. Fresh THF is advantageously added at the rate at which product and unconverted THF are released from the reactor. In this method, the residence time and polymerization time can be controlled, which provides an additional means of influencing and obtaining the average molecular weight M n of the copolymer formed. In general, depending on the catalytic amount and the reaction temperature, the polymerization is carried out in a batch process for 0.5 to 50, preferably 1 to 10, particularly preferably 1 to 8 hours. At the start of the continuous reaction, the described reaction system requires some time for the steady state equilibrium to be formed, during which the outlet 18 is kept closed with the control device 19, ie from the reaction device. It may be advantageous not to release the product solution.
    The catalyst phase remains in the reaction apparatus, which is continuously replenished by adding fresh catalyst and / or by recycling the released catalyst as needed, depending on the catalyst loss resulting from releasing a small amount of catalyst with the product containing upper phase. do.
    The new process for preparing new THF / butynediol copolymers with C-C triple bonds is advantageously carried out in an inert gas atmosphere, and any inert gas such as nitrogen or argon may be used. Before using the reactants, any water and peroxides present therein are removed.
    Inert organic solvents, for example aliphatic and aromatic hydrocarbons or halohydrocarbons, can be added under the reaction conditions, thereby having the advantageous effect of facilitating phase separation of the catalyst and upper phases. In general, THF acts as both reactant and solvent in new methods.
    Copolymer-containing upper phases may contain, for example, trace amounts of heteropolyacids present in bases, such as alkali metal or alkaline earth metal hydroxide solutions, ammonia, alkali metal or alkaline earth metal carbonate solutions or alkali metal or alkaline earth metal bicarbonate solutions. It can be treated by adding to neutralize, distilling off the monomers present therein and separating the precipitated salts by filtration of the fresh THF / butynediol copolymer having a C-C triple bond and remaining in the distillation residue. The monomer and low molecular weight THF / butyndiol cooligomer recovered from the distillation can of course be recycled to the reaction system.
    Preferably, however, the residual amount of heteropolyacid is removed by subjecting the copolymer containing upper phase to the addition of hydrocarbons, for example n-heptane or n-octane, followed by treatment with activated carbon by the method described in US Pat. No. 4,677,231.
    Surprisingly, it has been found that the polymerization of but-2-yn-1,4-diol and THF in the presence of heteropolyacids takes place in spite of the C-C triple bond present in the butynediol. For example, when cis-but-2-ene-1,4-diol is used in place of but-2-yn-1,4-diol in a continuous polymerization experiment, the catalyst phase becomes black and the C-C double bond It was found that THF / but-2-ene-1,4-diol copolymer having a low THF conversion had a dark dark color.
    Surprisingly, in the copolymerization of tetrahydrofuran with but-2-yn-1,4-diol, especially in the preparation of copolymers having a relatively low average molecular weight M n of commercial interest, saturated 1,4-butanediol It has been found that significantly higher space-time yields can be obtained than when used in place of this butynediol.
    The new THF / butyndiol copolymer serves as the diol component for the production of thermoplastic polyurethanes and polyesters.
    In addition, the new THF / butyndiol copolymer can be converted to polytetrahydrofuran by complete hydrogenation of C-C triple bonds, and the polytetrahydrofuran formed has very high purity, especially low color number and dispersion degree D. Have The C-C triple bond of the new THF / butyndiol copolymer is converted to a C-C double bond by partial hydrogenation, corresponding to a THF / but-2-ene-1,4-diol copolymer in terms of its chemical structure. Is formed. Such THF / but-2-ene-1,4-diol copolymers are provided as diol components for the production of, for example, radiation curable polyurethanes and polyester finishes. Such THF / but-2-ene-1,4-diol copolymers can not be obtained with satisfactory quality by copolymerization of Uetrahydrofuran with but-2-ene-1,4-diol in a similar manner to the new method. none.
    For the preparation of polytetrahydrofuran from a new THF / butynediol copolymer, the THF / butynediol copolymer is carried out by a procedure in which all C-C triple bonds present in the copolymer are converted to C-C single bonds. Catalytic hydrogenation reaction. For this purpose, the new THF / butynediol copolymers are generally at 1 to 300 bar, preferably at 20 to 250 bar, particularly preferably at 40 to 200 bar, and generally at 20 to 250 ° C., preferably at 60 to Conversion to polyoxytetramethylene glycol in the presence of hydrogen and a hydrogenation catalyst at 200 ° C., particularly preferably from 100 to 160 ° C. The obtained polyoxytetramethylene glycol is according to the average molecular weight M n of THF / butyne diol copolymer used for the hydrogenation, it is generally from 500 to 3500 Daltons, preferably have an average molecular weight M n of 650 to 2900 Daltons.
    The new method of hydrogenating the THF / butyndiol copolymer with polytetrahydrofuran can be carried out in the absence of solvent or advantageously in the presence of an inert solvent, under reaction conditions. Examples of such solvents are ethers such as dioxane, dimethoxyethane, tetrahydrofuran, methyl tert-butyl ether and di-n-butyl ether, methanol, ethanol, propanol, isopropanol, butanol, isobutanol and tert-butanol Alcohols, hydrocarbons such as n-hexane, n-heptane and n-octane, and N-alkyllactams such as N-methylpyrrolidone and N-octylpyrrolidone. Preferred solvents are tetrahydrofuran and / or hydrocarbons. The THF- and hydrocarbon containing reaction mixtures obtained after the residual amount of heteropolyacid catalyst have been separated off are particularly preferably used for hydrogenation.
    In general, all catalysts suitable for hydrogenation of C-C triple bonds can be used as hydrogenation catalysts in new processes. Hydrogenation catalysts may also be used that dissolve in the reaction medium to provide a homogeneous solution, as described in Houben-Weyl, Methoden der Organis Chen Chemie, Volume IV / 1C, pages 16-26.
    However, the new process is preferably carried out using heterogeneous hydrogenation catalysts, ie hydrogenation catalysts which are almost insoluble in the reaction medium. In principle, virtually all heterogeneous hydrogenation catalysts can be used to hydrogenate a C-C triple bond of a copolymer to a C-C single bond. Among these hydrogenation catalysts, preference is given to containing at least one element of the Groups Ib, VIIb and / or VIIIb of the Periodic Table of Elements, in particular nickel, copper and / or palladium. Such catalysts may contain one or more other elements, such as chromium, tungsten, molybdenum, manganese and / or rhenium, in addition to the above components and a carrier added on demand. As a result of the preparation, oxidized phosphorus compounds, for example phosphates, may be present in the catalyst.
    Heterogeneous hydrogenation catalysts containing metals in the form of activated fine powder with large surface areas, for example laney nickel, laney copper or palladium sponges, can be used in the new process.
    For example, the precipitated catalyst may be used in new methods. Such catalysts precipitate their catalytically active components from their salt solutions, in particular from their solutions of nitrates and / or acetates, for example alkali metals and / or alkalis as poorly soluble hydroxides, hydrated oxides, basic salts or carbonates. The earth metal hydroxide and / or carbonate solution is added and the resulting precipitates are dried and subsequently calcined at generally from 300 to 700 ° C., in particular from 400 to 600 ° C., generally at 100 to 700 ° C., especially from 150 to 400 ° C. By treating with hydrogen or a hydrogen containing gas to reduce the related metals and / or oxide compounds in a low oxidation state and converting them into a substantially catalytically active form, the related oxides, mixed oxides and / or mixed-bonds are converted into oxides. Can be. In general, the reduction continues until no more water is formed.
    In the preparation of precipitated catalysts containing a carrier, precipitation of the catalytically active component can be carried out in the presence of a suitable carrier. However, the catalytically active component may be precipitated simultaneously with the carrier from a suitable salt solution.
    Supported catalysts prepared by conventional methods and containing at least one of said catalytically active elements may be used as heterogeneous hydrogenation catalysts in new processes. Such supported catalysts are advantageously prepared by impregnating the carrier with a metal salt solution of a suitable element, followed by drying and calcining generally at 300 to 700 ° C., preferably 400 to 600 ° C. and reducing in a hydrogen containing gas stream. Drying of the impregnated carrier is generally carried out at 20 to 200 ° C., preferably at 50 to 50 ° C., under atmospheric or reduced pressure. It can also be dried at higher temperatures. Catalytically active catalyst components are generally reduced under the conditions described above for the precipitated catalyst.
    In general, oxides of alkaline earth metals, aluminum and titanium, zirconium dioxide, silica, diatomaceous earth, silica gel, alumina, silicates such as magnesium silicate or aluminum, barium sulfate or activated carbon can be used as the carrier. Preferred carriers are zirconium dioxide, alumina, silica and activated carbon. Mixtures of other carriers can of course also be used as carriers for catalysts which can be used in new processes.
    Hydrogenation catalysts which are preferably used in the new process are laney nickel, laney copper, palladium sponges, impregnated supported catalysts such as palladium on activated carbon, palladium on alumina, palladium on silica, palladium on calcium oxide, palladium on barium sulfate, Nickel on alumina, nickel on silica, nickel on zirconium dioxide, nickel on titanium dioxide, nickel on activated carbon, copper on alumina, copper on silica, copper on zirconium dioxide, copper on titanium dioxide, copper or silica on activated carbon, and carriers Nickel and copper on the containing precipitation catalyst, for example Ni / Cu on zirconium dioxide, Ni / Cu on alumina, or Ni / Cu on titanium dioxide.
    Preparation of New Hydrogenation of Polytetrahydrofuran with Raney Nickel, Nickel and Copper on Palladium Supported Catalysts, Particularly on Palladium on Carriers of Palladium or Alumina and Calcium Oxide, and Nickel and Copper on Carrier-Containing Precipitation Catalysts It is preferably used for the method.
    The palladium supported catalyst generally contains 0.2 to 10% by weight, preferably 0.5 to 5% by weight, of palladium, calculated as Pd, based on the total weight of the catalyst. The alumina / calcium oxide carrier for the palladium supported catalyst may generally contain up to 50% by weight, preferably up to 30% by weight, based on the weight of the carrier.
    Other preferred supported catalysts generally contain 5-40% by weight, preferably 10-30% by weight of nickel, calculated as NiO, based on the total weight of the non-reduced oxide catalyst in each case, calculated as CuO Nickel and copper on silica catalysts which generally contain 1 to 15% by weight, preferably 5 to 10% by weight, and generally 10 to 90% by weight, preferably 30 to 80% by weight, of SiO 2 . . The catalyst further contains in each case 0.1 to 5% by weight manganese calculated as Mn 3 O 4 and 0.1 to 5% by weight phosphorus calculated as H 3 PO 4 , based on the total weight of the non-reduced oxide catalyst. can do. Of course, the content of the catalyst components is the amount added until the total content of these components in the catalyst is 100% by weight. Advantageously, this catalyst impregnates the silica molding with a salt solution of the catalytically active component, for example a solution of its nitrate, acetate or sulphate, and then the impregnated carrier is subjected to 20 to 200 ° C., preferably in air or under reduced pressure. Is prepared by drying at 100 to 150 ° C., calcining at 400 to 600 ° C., preferably 500 to 600 ° C. and reducing with hydrogen containing gas. Such catalysts are described, for example, in European Patent Publication No. 295 435.
    Nickel and copper on zirconium dioxide precipitation catalysts generally contain 20 to 70% by weight, preferably 40 to 60% by weight of nickel, calculated as NiO, based on the total weight of the non-reduced oxide catalyst in each case, It may contain 5 to 40% by weight, preferably 10 to 35% by weight, and generally 25 to 45% by weight of zirconium dioxide, calculated as CuO. This catalyst may further contain 0.1 to 5% by weight of molybdenum, calculated as MoO 3 , based on the total weight of the non-reduced oxide catalyst. Such catalysts and methods for their preparation are described in US Pat. No. 5,037,793, which is incorporated herein by reference.
    The new method can be carried out continuously and batchwise. In a continuous procedure, for example, it is possible to use tube reactors which are advantageously arranged in the form of a stationary phase in which the reaction mixture can be passed by the liquid phase up to the triCkle-bed method. In a batch procedure, either a simple stirred reactor or advantageously a loop reactor can be used. This catalyst is advantageously arranged in the form of a fixed bed when a loop reactor is used and this heterogeneous catalyst is preferably used as a suspension when a stirred reactor is used. The new method is preferably carried out in the liquid phase.
    The hydrogenation product polytetrahydrofuran (PTHF) is generally separated from the released hydrogenation mixture by conventional methods, for example by distilling off the solvent present in the released hydrogenation mixture and any other low molecular weight compounds present.
    Polytetrahydrofuran is produced worldwide and serves as an intermediate for the preparation of polyurethanes, polyesters and polyamide elastomers, where it is used as the diol component. PTHF incorporated in such polymers makes the polymer soft and flexible, and therefore PTHF is also referred to as the soft segment of this polymer.
    In the new hydrogenation process, the tetrahydrofuran / but-2-yne-1,4-diol copolymer is converted to polytetrahydrofuran with a narrow molecular weight distribution and very low color number.
    The present invention also relates to a process for preparing tetrahydrofuran / but-2-yn-1,4-diol copolymers by partially hydrogenating the in-phase bonds of the new THF / butynediol copolymer to double bonds.
    The new polyoxytetramethylene glycols containing but-2-ene-1,4-diyl groups and which also form the subject of the present invention generally have an average molecular weight and polyoxytetra of 500 to 3,500 Daltons, preferably 650 to 2700 Daltons. Corresponding to the but-2-ene-1,4-diyl content of methylene glycol, DeutsChes ArzneibuCh; 10th edition 1991 with 2nd Supplement 1993; offiCial edition; V. 3.4.4 Jodzahl; DeutsCher Apotheker Verlag, Stuttgart 0.1 to 3 moles, preferably 0.2 to 2 moles, preferably 0.2 to 2 moles, double bond -CH = CH- per mole of polyoxytetramethylene glycol, as determined by determining the iodine number by the method of Kaufmann described To C-C double bond content of from 1.5 mol. But-2-ene-, referred to below as THF / but-2-ene-1,4-diol copolymer according to its preparation from a novel tetrahydrofuran / but-2-yne-1,4-diol copolymer 1,4-diyl containing polyoxytetramethylene glycol is a but-2-ene-1,4-diyl unit distributed on a polymer like the starting material tetrahydrofuran / but-2-yn-1,4-diol copolymer It contains. Thus, but-2-ene-1,4-diyl units are mostly present as end groups bound to terminal OH groups in THF / but-2-ene-1,4-diol copolymers.
    As a result of this preparation, the new tetrahydrofuran / but-2-ene-1,4-diol copolymers are generally partly tetrahydrofuran / but-2-ene-1,4-diol copolymers / for their preparation. Due to the use of the polytetrahydrofuran mixture it is also present as a mixture with polytetrahydrofuran due in part to the complete hydrogenation of the C-C triple bond to the C-C single bond.
    The catalyst for hydrogenation of C-C triple bonds to C-C single bonds can be used for hydrogenation of C-C triple bonds to C-C double bonds, but in general the amount of hydrogen used for partial hydrogenation is C It should not exceed the stoichiometric amount of hydrogen required for partial hydrogenation of the -C triple bond to the C-C double bond.
    A carrier such as calcium carbonate was impregnated with a water-soluble palladium compound such as Pd (NO 3 ) 2 , the palladium compound used was reduced to palladium metal, for example with hydrogen, and the formed palladium supported catalyst was then reacted with lead (II) acetate. Partially poisoned hydrogenation catalysts, such as Lindlar palladium, which can be prepared by partial poisoning with the same lead compound, are preferably for partial hydrogenation of C-C triple bonds to C-C double bonds. Used. Such Lindler catalysts are commercially available.
    Other preferred, partially poisoned palladium catalysts are described in German patent application No. P43 33 293.5, which may be prepared by gradual gas phase deposition of palladium first and then lead and / or cadmium onto gold or metal foils. It is a catalyst.
    Partial hydrogenation of C-C triple bonds to C-C double bonds of tetrahydrofuran / but-2-yne-1,4-diol copolymers is generally from 0 to 100 ° C, preferably from 0 to 50 ° C, in particular Preferably at 10 to 30 ° C. and at 1 to 50 bar, preferably at 1 to 5 bar, particularly preferably at 2 to 3 bar. Hydrogen is preferably used in stoichiometric amounts required for partial hydrogenation of C-C triple bonds. Hydrogen may be introduced in less than stoichiometric amounts, unless all C-C triple bonds are intended to hydrogenate into double bonds. Hydrogenation can be carried out batchwise, for example in a stirred kettle using suspended catalysts, or continuously, for example in a tube reactor using a fixed bed arrangement of catalysts.
    The starting materials tetrahydrofuran and butynediol used in the preparation of the new copolymers are the main products of the chemical industry and are described, for example, in Ullmanns EnCyklopaedie der teChnisChen Chemie, 4th edition, Volume 12, pages 20-22, Verlag Chemie, Weinheim 1976 , or Ullmann's EnCyClopedia of Industrial Chemistry, 5th Ed., Vol. A4, pages 455-457 and 462, VCH VerlagsgesellsChaft, Weinheim 1985).
    The average molecular weight (M n ) of the polymer prepared according to the example was determined by measuring the OH number. The hydroxyl groups were esterified with excess acetic anhydride / pyridine mixture to determine the OH number. After the reaction, excess acetic anhydride was hydrolyzed with acetic acid using water, and the acetic acid thus isolated was titrated back with sodium hydroxide solution. Blank samples containing no polymer were treated in the same manner.
    The OH number of the sample is the amount (mg) of potassium hydroxide equivalent to acetic acid bound in the esterification of 1 g of material. M n was calculated from the determined OH number using the following equation.
    M n = 56 · 100 · 2 / OH water [g / mol]
    The molecular weight distribution, referred to below as dispersion degree D, was calculated from the ratio of weight average molecular weight (M w ) to number average molecular weight (M n ) using the following formula.
    M w / M n = D
    M w and M n were determined by gel permeation chromatography using standardized polystyrene for calibration. From the obtained chromatography, the number average molecular weight M n is calculated according to the following formula,
    M n = Σ Ci / Σ (Ci / Mi)
    The weight average molecular weight M w was calculated according to the following equation.
    M w = Σ CiMi / Σ Ci
    Wherein Ci is the concentration of the individual polymer species i in the polymer mixture obtained and Mi is the molecular weight of the individual polymer species i.
    All reactants used in the preparation of unsaturated polyoxytetramethylene glycols were free of peroxides.
    1 H-NMR spectrum of the obtained product was recorded in the solvent CDCl 3 (internal standard tetramethylsilane).
    Example 1
    1100 g of THF containing 4% by weight of but-2-yn-1,4-diol was subjected to dodeca tungstate phosphate anhydride for 60 hours at 60 ° C. under an argon atmosphere using an apparatus as shown in the figure. Stir thoroughly with 550 g. Thereafter, 275 g / h of THF containing 4% by weight of but-2-yn-1,4-diol was fed to the reactor at 60 ° C with stirring, and the same amount of the upper phase was discharged from the reactor. The reaction mixture was mixed with an equal volume of n-heptane to separate the liquid catalyst containing phase. After separating the two phases, the organic phase was passed over activated carbon and easily volatile components such as THF and n-heptane were distilled off under reduced pressure. THF conversion over a 96 hour working period was 30%. The resulting polymer was molecularly distilled at 150 ° C. and 0.4 mbar. The distillation residue (85% of the crude polymer used) had an average molecular weight of 1200 and a degree of dispersion of 1.6.
    The designation of the triple bond content and the individual NMR signals for any group of copolymer molecules based on the evaluation of the 1 H-NMR spectrum is shown in Table 1.
    Example 2
    1100 g of THF containing 2 wt% butynediol was thoroughly stirred in the presence of 550 g of dodeca tungstate phosphoric anhydride at 60 ° C. for a 6-hour initiation period as described in Example 1. Thereafter, 275 g / h of THF containing 2 wt% but-2-yn-1,4-diol was fed to the reactor at 60 ° C with stirring, and the same amount of the upper phase was discharged from the reactor. The reaction mixture was treated as described in Example 1. THF conversion over 30 hours of operation was 30%. The molecular distillation was then carried out as described in Example 1 to give a colorless viscous polymer having an average molecular weight of 2390 as the distillation residue (89% of the crude polymer used). The degree of dispersion was 1.8.
    The evaluation results of the 1 H-NMR spectrum are shown in Table 1.
    Example 3
    1100 g of THF containing 8 wt% but-2-yn-1,4-diol was present in 550 g of dodeca tungstate phosphoric anhydride for a 6-hour initiation period at 60 ° C. as described in Example 1. Under thorough stirring. Thereafter, 275 g / h of THF containing 8 wt% but-2-yn-1,4-diol was fed to the reactor at 60 ° C with stirring, and the same amount of the upper phase was discharged from the reactor. The reaction mixture was treated as described in Example 1. The THF conversion rate over the 100-hour working period averaged 21%. The molecular distillation was then carried out as described in Example 1 to give a colorless polymer having an average molecular weight of 1060 as the distillation residue (84% of the crude polymer used). The degree of dispersion was 1.5.
    The evaluation results of the 1 H-NMR spectrum are shown in Table 1.
    Evaluation of the 1 H-NMR Spectrum:
    As mentioned above, the new THF / butynediol copolymers are but-2-yn-1,4-yloxy and terminal 1-hydroxybut-2-yne- derived from the butynediol monomer present inside the copolymer. And tetramethylene-1,4-yloxy and terminal 1-hydroxytetramethylene-4-yloxy groups derived from tetraylfuran monomers present inside of 4-yloxy groups and copolymers. Formula I, shown below, which serves only as a model for the new THF / butyndiol copolymer, represents all methylene groups that can be distinguished for their chemical shifts in the 1 H-NMR spectrum. Thus, Formula I was only prepared to represent all possible methylene groups of the THF / butyndiol copolymer that can be distinguished by their chemical shifts in the 1 H-NMR spectrum. The relevant chemical shift of the signal of this methylene group in the 1 H-NMR spectrum is also shown. Since the incorporation of butindiol monomers in THF copolymers is almost random, of course, it is not possible to provide accurate chemical structures for the individual copolymers obtainable according to the present invention. Structural characterization of such copolymers, ie the determination of the proportion of structural units present inside the molecule or functioning as end groups and derived from but-2-yn-1,4-diol monomers, is shown in the 1 H-NMR spectrum shown in Table 1. It is based on the evaluation and it relates to the theoretical relationship of signal strength, where the designation and strength of individual NMR signals for any methylene group in the copolymer is obtained by incorporating the relevant 1 H-NMR signals. Since the individual copolymer molecules cannot be characterized in the 1 H-NMR spectrum, the evaluation of the spectra is based on But-2-yn-1, which is present inside the copolymer among the copolymers prepared according to the individual examples, Only the relative frequencies of the triple unsaturated structural units derived from functioning as 4-diol monomers and end groups are provided.
    Chemical shifts of the 1 H-NMR signals a to f, shown for individual methylene groups based on their chemical shifts, were determined in each case for the maximum signal.
    Chemical shifts of individual signals a-f:
    a: 4.3 ppm d: 3.5 ppm
    b: 4.2 ppm e: 1.6 ppm
    C: 3.6 ppm f: 3.4 ppm
    Evaluation of the 1 H-NMR spectra of the copolymers obtained according to Examples 1 to 3 (areas of signals b and C are based on area of signal a, normalized to area 1) ExampleM n abcF (TB / copolymer) One1200One1.91.51.16 22390One4.23.51.16 31060One1.21.70.82 M n = average molecular weight F = relative triple bond content of the copolymer = (a + b) / (a + c) TB = triple bond
    Comparative Example 1 (Comparison to Example 1)
    This example shows that the copolymerization of THF with 1,4-butanediol shows much worse space-time yield than with the new copolymerization of THF with but-2-yn-1,4-diol.
    1100 g of THF was thoroughly stirred with 3.5% by weight of 1,4-butanediol in the presence of 550 g of dodeca tungstate phosphoric anhydride at 60 ° C. for a 6 hour initiation period. Thereafter, 275 g / h of THF containing 3.5% by weight of 1,4-butanediol was fed to the reactor at 60 ° C with stirring, and an equal amount of the upper phase was discharged from the reactor. The reaction mixture was treated as described in Example 1.
    The THF conversion over an 96-hour working period averaged 5.3%. Subsequently, the molecular distillation was carried out as described in Example 1 to obtain a polymer having an average molecular weight of 1090 as the distillation residue. The color number of the product was 70-80 APHA.
    Comparative Example 2 (Comparison to Example 1)
    This example shows that the copolymerization of THF with but-2-ene-1,4-diol shows a much poorer space-time yield than the copolymerization of THF with but-2-yn-1,4-diol and thus produced THF / But-1-ene-1,4-diol copolymer shows a completely unsatisfactory color number.
    1100 g THF, as described in Example 1, with 4% by weight of cis-2-butene-1,4-diol in the presence of 550 g of dodeca tungstate phosphate anhydride at 60 ° C. for a 6 hour start-up Stir thoroughly. Thereafter, 275 g / h of THF containing 4% by weight of cis-2-butene-1,4-diol was fed to the reactor at 60 ° C with stirring, and the same amount of the upper phase was discharged from the reactor. The reaction mixture was treated as described in Example 1. The THF conversion over the 72 hour working period averaged 5.4%.
    The molecular distillation was then carried out as described in Example 1 to give a dark brown polymer as distillation residue (88 wt%).
    Analytical data of the product:
    Average molecular weight: M n = 905
    Polydispersity: D = 1.5
    Chromaticity APHA〉 150
    The double bond content of the THF / but-2-ene-1,4-diol copolymer thus prepared was determined by the literature (Iodine number determination according to Kaufmann: DeutsChes ArzneibuCh; 10th edition 1991 with 2nd Supplement 1993; offiCial edition; V 3.4.4 Jodzahl; Deutscher Apotheker Verlag, Stuttgart) was determined by measuring the iodine number.
    Method for determination of iodine number (IN) according to Kafman: 1 g of material was dissolved in 15 ml of chloroform in a 250 ml dry flask for determination of iodine number. Thereafter, 25.0 ml of iodine monobromide solution was added slowly. The flask was sealed and shaken frequently and kept in the dark for 30 minutes. After addition of 10 ml of potassium iodide 10% (m / V) solution and 100 ml of water, the solution was titrated vigorously with 0.1 N sodium thiosulfate solution until the yellow disappeared substantially completely. After 5 ml of starch solution was added, titration was continued by dropwise addition until the blue disappeared (0.1 N sodium thiosulfate solution n 1 ml). Blank measurements were carried out under the same conditions (0.1 N sodium thiosulfate solution n 2 ml). The iodine number was calculated using the following formula (m = weight in g of material).
    IN = 1.269 · (n 2 -n 1 ) / m
    25 g of iodine was consumed per 100 g of copolymer corresponding to a 0.0985 mole double bond content or 0.10 F value per mole of 0.11 copolymer.
    Example 4
    Hydrogenation of THF / butynediol Copolymer to PTHF
    In a 300 ml metal autoclave, 50 g of THF / butyndiol copolymer (crude which had not been molecularly distilled) obtained according to Example 1 in 100 g of tetrahydrofuran was nickel- and copper-containing at 100 ° C. and 40 bar. Catalyst (prepared according to US Pat. No. 5,037,793; 50 wt% Ni content as NiO; 17 wt% Cu content as CuO; 2 wt% molybdenum content as MoO 3 ; Carrier: ZrO 2 content 31 wt% %; 6x3 mm tablets) was hydrogenated with hydrogen for 6 hours. The catalyst was previously activated in a hydrogen stream at 200 ° C. for 2 hours. After the catalyst was separated and the solvent was distilled off under reduced pressure, 44 g of residue was obtained. This residue was further distilled at 150 ° C./0.3 mbar. The distillation residue obtained was colorless polytetrahydrofuran which no longer has triple bonds according to the 1 H-NMR spectrum. According to the 1 H-NMR spectrum, the double bond content was less than 0.5%. The PTHF thus obtained had an average molecular weight M n of 1070 and a dispersion degree of 1.7. His color number was 30 APHA.
    Example 5
    20 g of raney nickel was added to 40 g of the copolymer used in Example 4, dissolved in 160 g of THF, and hydrogenated with hydrogen at 120 ° C. and 40 bar with stirring. Treatment of the released hydrogenation mixture and molecular distillation were carried out as described in Example 4. According to the 1 H-NMR spectrum, 34 g of colorless polytetrahydrofuran having no triple bond and 2.5% residual double bond content were obtained. The color number was 40 APHA.
    Example 6
    40 g of the copolymer used in Example 4, dissolved in 160 g of THF, were kneaded with calcium containing palladium (wet Al 2 O 3 / CaO on alumina supported catalyst in the form of a 4 mm extrudate at 120 ° C. and 40 bar, and 120 dried at ℃ it was prepared by impregnating an Al 2 O 3 / CaO carrier obtained by calcining at 550 ℃ a palladium nitrate aqueous solution; 0.6% by weight the palladium content, calculated as Pd; a calcium content of 20% by weight, calculated as CaO; Al 2 O 3 content 79.4%) was hydrogenated with hydrogen for 8 hours. The catalyst was previously activated in a hydrogen stream at 150 ° C. for 2 hours. Treatment and distillation of the released hydrogenation mixture were carried out as described in Example 4. According to the 1 H-NMR spectrum, 33 g of colorless PTHF no longer having triple bonds were obtained. The residual double bond content was 3.0% and the color number was 40 APHA.
    Example 7
    40 g of the copolymer used in Example 4, dissolved in 160 g of tetrahydrofuran, palladium on an alumina catalyst in the form of a 4 mm extrudate at 150 ° C. and 40 bar (dried at 120 ° C. and calcined at 440 ° C. Al 2 Prepared by impregnating an O 3 extrudate with an aqueous palladium nitrate solution; 0.5 wt% palladium content calculated as Pd; 99.5% Al 2 O 3 content) was hydrogenated with hydrogen over 200 g. The catalyst was previously activated in a hydrogen stream at 150 ° C. for 2 hours. Treatment of the released hydrogenation mixture and bulb-tube distillation were carried out as in Example 4. According to the 1 H-NMR spectrum, 35 g of colorless PTHF having no C-C triple bond and having a residual double bond content of less than 1% were obtained. The color number was 50 APHA.
    Example 8
    Partial Hydrogenation of C-C Triple Bonds to C-C Double Bonds
    10 g of Lindler catalyst in powder form (5% Pd on CaCO 3 , poisoned with lead; manufactured by AldriCh) were added to 60 g of the copolymer prepared according to Example 8 and dissolved in 140 g of tetrahydrofuran, and The copolymer was hydrogenated with hydrogen for 6 hours with stirring at 20 ° C. and 2 bar. Treatment of the released hydrogenation mixture and molecular distillation were carried out as described in Example 4. 1 H-NMR spectra showed 55 g of a colorless polymer which no longer had triple bonds and had a C-C double bond content of F = 0.8. The color number was 40 APHA.
    权利要求:
    Claims (15)
    [1" claim-type="Currently amended] Tetrahydrofuran / but-2-yn-1,4-diol copolymer having a C-C triple bond and having an average molecular weight M n of 500 to 3,500 Daltons and a triple bond content of 0.5 to 3.0 moles per mole of copolymer Or a combination of this copolymer with polytetrahydrofuran having an average molecular weight M n of 500 to 3,500 daltons.
    [2" claim-type="Currently amended] Tetrahydrofuran having a C-C triple bond according to claim 1 comprising copolymerizing tetrahydrofuran with but-2-yn-1,4-diol using a heteropolyacid catalyst in virtually anhydrous reaction medium. / But-2-yn-1,4-diol copolymer production method.
    [3" claim-type="Currently amended] The process according to claim 2 wherein the polymerization is carried out at 0 to 80 ° C.
    [4" claim-type="Currently amended] The process according to claim 2 or 3, wherein the copolymerization is carried out in a liquid two-phase system.
    [5" claim-type="Currently amended] The process according to any one of claims 2 to 4, wherein the copolymerization is carried out continuously in an ideal system and the but-2-yn-1,4-diol content is 0.1 to 15 moles per mole of heteropolyacid on the catalyst.
    [6" claim-type="Currently amended] The process according to claim 2, wherein the metered addition of but-2-yn-1,4-diol to the reaction mixture of the copolymerization reaction is controlled by measuring the conductivity on the catalyst.
    [7" claim-type="Currently amended] The process according to claim 2, wherein the copolymerization is carried out batchwise and the but-2-yn-1,4-diol content is between 0.1 and 15 moles per mole of heteropolyacid.
    [8" claim-type="Currently amended] A method for producing polyoxytetramethylene glycol, comprising hydrogenating the tetrahydrofuran / but-2-yn-1,4-diol copolymer according to claim 1 using a hydrogenation catalyst.
    [9" claim-type="Currently amended] The process of claim 8, wherein the hydrogenation catalyst used is a heterogeneous hydrogenation catalyst.
    [10" claim-type="Currently amended] 10. The process according to claim 8 or 9, wherein the hydrogenation is carried out at 20 to 300 ° C and 1 to 300 bar.
    [11" claim-type="Currently amended] The process according to claim 8, wherein the hydrogenation catalyst used contains as active ingredient at least one element of groups Ib, VIIb or VIIIb of the Periodic Table of the Elements.
    [12" claim-type="Currently amended] The process according to claim 8, wherein the hydrogenation catalyst used contains nickel or copper as active ingredient.
    [13" claim-type="Currently amended] The process according to claim 8, wherein the hydrogenation catalyst used contains palladium as active ingredient.
    [14" claim-type="Currently amended] Preparation of a polyoxytetramethylene glycol having a double bond, comprising partially hydrogenating a C-C triple bond of the tetrahydrofuran / but-2-yn-1,4-diol copolymer according to claim 1 on a hydrogenation catalyst. Way.
    [15" claim-type="Currently amended] Polyoxytetramethylene glycols having internal C-C double bonds and having an average molecular weight M n of 500 to 3,500 daltons and a double bond content of 0.1 to 3 moles per mole of polyoxytetramethylene glycol, or polyoxytetramethylene glycol And a polyoxytetrahydrofuran having an average molecular weight M n of 500 to 3,500 daltons.
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    同族专利:
    公开号 | 公开日
    US5939590A|1999-08-17|
    EP0813561A1|1997-12-29|
    CN1177360A|1998-03-25|
    EP0813561B1|1999-05-12|
    TW340123B|1998-09-11|
    WO1996027626A1|1996-09-12|
    ES2133943T3|1999-09-16|
    JPH11501070A|1999-01-26|
    CN1085688C|2002-05-29|
    DE19507399A1|1996-09-05|
    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    法律状态:
    1995-03-03|Priority to DE1995107399
    1995-03-03|Priority to DE19507399.1
    1996-02-21|Application filed by 페라스타르크, 바스프악티엔게젤샤프트
    1998-08-05|Publication of KR19980702696A
    优先权:
    申请号 | 申请日 | 专利标题
    DE1995107399|DE19507399A1|1995-03-03|1995-03-03|C-C triple bond containing tetrahydrofuran / but-2-in-1,4-diol copolymers|
    DE19507399.1|1995-03-03|
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