The long-chain polyether polyols with a high content of primary hydroxyl groups

 

(57) Abstract:

The invention relates to polyether polyols with the content of primary hydroxyl groups of from 40 to 95 mol.% and General content oxyethylene blocks more than 25 wt.%, which are obtained in the presence of CBM - catalyst poly(oksietilenom/oxypropylene) - terminal block. The invention relates to a method for producing polyols. The invention allows to obtain long chain polyether polyols with a high content of primary hydroxyl groups at a very low concentration of catalyst. 2 S. and 6 C.p. f-crystals.

The invention concerns a long-chain polyether polyols with a high content of primary hydroxyl groups, as well as the way they are received by cyanide catalysis bimetal (CBM-catalysis).

The long-chain polyether polyols with a high content of primary hydroxyl groups are required for many applications of polyurethane. For example, they are used in hot and cold forming of foamed materials, as well as in the injection molding of the reaction liquid compositions (see, for example, Gum, Riese, Ulrich (resp. amended): "Reaction Polymers", Ed. Hanser, Munich, 1992, pp. 67-70). Dinosaurium way when first polimerizuet the propylene oxide (or a mixture of propylene oxide and ethylene oxide in the presence of the parent compounds with active hydrogen atoms and the alkaline catalyst, while having polyether polyol with predominantly secondary hydroxyl groups. Then in the second stage, the so-called ethylenoxide, alkaline polymerizate add the ethylene oxide, with the largest part of the secondary hydroxyl groups of turns in the primary. This method is usually used the same catalysts (e.g., KOH) for the reactions of propoxycarbonyl and ethoxycarbonyl.

Catalysts based on cyanide bimetal (CBM-catalysts) to obtain polyether polyols known for a long time (see, for example, U.S. patents 3404109, 3829505, 3941849 and 5158922). The application of these CBM-catalysts for production of polyether polyols, in particular, contributes to the decrease in the proportion of monofunctional polyethers with terminal double bonds, so-called Manolov, compared with the traditional receipt of polyether polyols using alkaline catalysts. Thus obtained polyether polyols can be processed into high-value polyurethanes (for example, tah ER-AND 700949, 761708, international patent applications 97/40086, 98/16310, patent applications Germany 19745120, 19757574 and 198102269, moreover, have an extremely high activity and make possible the obtaining of polyether polyols with very low concentrations of catalyst (25 ppm or less), so there is no need to separate the catalyst from the polyol.

The disadvantage of applying CBM-catalysts for production of polyol polyether is that in contrast to alkaline catalysts, these catalysts do not contribute directly to the education ethylenoxide system. If ethylene oxide is added to contain CBM catalyst poly(oxypropylene)polyol, you get a heterogeneous mixture, which consists mainly of unreacted poly(oxypropylene)-polyol (with predominantly secondary hydroxyl groups) and to a lesser extent from vysokomehanizirovannogo poly(oxypropylene)polyol and/or polyethylene oxide. Therefore, the usual way of obtaining CBM-polyols with a high content of primary hydroxyl groups is to conduct ethylenoxide stage to the second, separate step by a conventional alkaline catalysis (e.g., catalyzed by potassium hydroxide) (see, for example, patai, the fact that the obtained alkaline polymerizat need to process a very expensive way, for example, neutralization, filtration and dehydration.

From U.S. patent 5648559 follows that obtained by CBM-catalyzed poly(oxyalkylene)polyols with poly(oxypropylene/oksietilenom)-end blocks contain <50 mol.% primary hydroxyl groups. The maximum total content oxyethylene blocks in these polyols is 20 wt.%. In U.S. patent 5700847 described poly-(oxyalkylene)polyols, which contain up to 25 wt.% oxyethylene blocks, and they can be in mixed blocks or homogeneous poly(oksietilenom)-terminal blocks. Obtained without ethylenoxide stage polyols have <50 mol.% primary hydroxyl groups. In U.S. patent 5668191 also described the use of poly(oxyalkylene)polyols with a maximum of 20 wt.% oxyethylene blocks and less than 50 mol.% primary hydroxyl groups.

Currently, it is found that by CBM-catalyzed polyaddition of a mixture of ethylene oxide(EO)/propylene oxide(PO) as of the end block to the original compounds with active hydrogen atoms can be obtained long chain polyether polyols with primary content hydroc the S.%.

The object of the present invention are long chain polyether polyols with the content of primary hydroxyl groups of from 40 to 95 mol.%, preferably 50 to 90 mol.%, and General content oxyethylene blocks more than 25 wt.%, preferably more than 30 wt.%, especially preferably more than 35 wt.%, which have a poly(oxypropylene/oksietilenom)-terminal block obtained in the presence of CBM-catalyst.

In addition, the object of the invention is a method of producing polyols according to the invention by polyprionidae mixture ethylene oxide/propylene oxide with a mass ratio of EC:from 40:60 to 95:5, preferably from 50:50 to 90:10, particularly preferably from 60:40 to 90:10, in the presence of CBM-catalysts, as of the end block to the original compounds with active hydrogen atoms.

Suitable for the method according to the invention CBM-catalysts, in principle, are known and described in the above prior art. Preferably use advanced, high-level CBM-catalysts are described, for example, in European patents EP-A 700949, 761708, international patent applications WO 97/40086, 98/16310, patent applications Germany 19745120, 19757574 and 198102269. A typical example of I the metal (for example, cinchocaine-cobaltate(III)) and the organic complex ligand (e.g. tert.-butanol) contain a simple polyester with srednetsenovoj molecular weight of more than 500 g/mol.

As a source of compounds with active hydrogen atoms are preferably used compounds with molecular weights from 18 to 2000 g/mol, preferably from 200 to 2000 g/mol and from 1 to 8, preferably from 2 to 6 hydroxyl groups. For example, should be called butanol, ethylene glycol, diethylene glycol, triethylene glycol, 1,2-propylene glycol, 1,4-butanediol, 1,6-hexanediol, bisphenol a, trimethylolpropane, glycerin, pentaerythritol, sorbitol, sucrose is cleaved starch or water.

Advantageous to apply such a source of compounds with active hydrogen atoms, which are obtained, for example, conventional alkaline catalysis of the previously mentioned low molecular weight starting compounds and represent oligomeric products alkoxysilane with srednekislye molecular mass of from 200 to 2000 g/mol.

Preferably used oligomeric propoxycarbonyl parent compound with 1 to 8 hydroxyl groups, especially preferably from 2 to 6 hydroxyl groups, and srednekislye molecular mosammat in a long chain polyether polyol with a high content of primary hydroxyl groups and content oxyethylene blocks >25 wt.%, preferably >30 wt.%, particularly preferably >35 wt.%, CBM-catalyzed polyprionidae to a mixture of ethylene oxide/propylene oxide with a mass ratio of EC:from 40:60 to 95:5, preferably from 50:50 to 90:10, particularly preferably from 60:40 to 90:10, as the end of the block.

However, it is preferable to first extend the original connection CBM-catalyzed propoxycarbonyl, preferably up to srednetsenovoj molecular weight between 500 and 15000 g/mol, and then elongated propoxyethanol intermediate product CBM-catalyzed polyprionidae to a mixture of ethylene oxide/propylene oxide with a mass ratio of EC: from 40:60 to 95:5, preferably from 50:50 to 90:10, particularly preferably from 60:40 to 90:10, as the end of the block to get a long chain polyether polyol with a high content of primary hydroxyl groups and content oxyethylene blocks >25 wt.%, preferably >30 wt.%, particularly preferably >35 wt.%.

In this case, the method according to the invention is particularly preferably carried out in a so-called "reaction in one device, wherein after CBM-catalyzed propoxycarbonyl, without intermediate processing aderrasi ethylene oxide/propylene oxide as the end of the block.

CBM-Catalyzed, polyprionidae mixture ethylene oxide/propylene oxide as the terminal block to the original compounds (or elongated propoxycarbonyl intermediate products), in General, takes place at temperatures from 20 to 200°C, preferably in the range from 40 to 180°C, particularly preferably at temperatures from 50 to 150°C. the Reaction can be carried out at total pressures of from 0.001 to 20 bar. Polyprionidae can be performed in bulk or in an inert organic solvent such as toluene or tetrahydrofuran. The amount of solvent is usually from 10 to 30 wt.%, counting on the amount of polyether polyol.

Polyprionidae can be performed continuously or periodically, for example periodic or properities way.

The mass ratio is subject to transformation mixture ethylene oxide/propylene oxide is from 40:60 to 95:5, preferably from 50:50 to 90:10, particularly preferably from 60:40 to 90:10.

The molecular weight obtained by the method according to the invention the polyether polyols with a high content of primary hydroxyl groups lie in the region between 1000 and 100000 g/mol, preferably in the region from 1500 to 500 which can be determined from the data1H-NMR spectra peracetylated of polyether polyols in accordance with the recommendations of the American society for testing materials D 4273-83. The proportion of primary hydroxyl groups in the polyether polyols is from 40 to 95 mol.%, preferably from 50 to 90 mol.%. The proportion of primary hydroxyl groups of the polyether polyols are dependent on the reaction conditions, such as pressure, temperature and solvent, and the composition applied a mixture of ethylene oxide/propylene oxide. In General, the increase in the concentration of ethylene oxide in a mixture of ethylene oxide/propylene oxide leads to an increase of the proportion of primary hydroxyl groups in the polyol simple ether.

The concentration CBM-catalyst is chosen so that in the above reaction conditions, it was possible easy control of reaction of polyaddition. In General, the concentration of catalyst is from 0.0005 wt.% up to 1 wt.%, preferably in the region of from 0.001 wt.% to 0.1 wt.%, particularly preferably in the region of from 0.001 wt.% to 0.01 wt.%, considering the number poluchaemogo polyol polyether.

Due to the high level CBM-catalysts may receive long-chain polyether polyols with a high content of primary g is aemula polyol polyether). If obtained in this way, the polyether polyols used to produce polyurethanes, it is possible to refuse removal of the catalyst from the polyether polyol, and it does not worsen the quality of the obtained polyurethane.

Examples

Receiving highly active CBM-catalyst (synthesis according to European patent EP-A 700949)

A solution of 12.5 g (91,5 mmole) of zinc chloride in 20 ml of distilled water was added under vigorous stirring (24000 rpm) to a solution of 4 g (12 mmol) of collegexperience.net in 70 ml of distilled water. Immediately thereafter, to the resulting suspension was added a mixture of 50 g of tert.-butanol and 50 g of distilled water, and then intensively stirred (24000 rpm) for 10 minutes Then add a mixture of 1 g of polypropyleneglycol with srednetsenovoj molar mass of 2000 g/mol, 1 g of tert.-butanol and 100 g of distilled water and stirred for 3 minutes (1000 rpm). The solid is separated by filtration, then stirred for 10 minutes (10,000 rpm) with a mixture of 70 g of tert.-butanol, 30 g of distilled water and 1 g of the above-mentioned polypropylenglycol and again filtered. Then again stirred for 10 minutes (10,000 rpm) with a mixture of 100 g of tert.-butanol and 0.5 g this is th weight.

The yield of dried, powdered catalyst: 6,23,

Example 1

A 10-liter glass flask to work under pressure put 873 g of starting compound is poly(oxypropylene)Tirol (Brednikova molecular weight of 440 g/mol) and 0.30 g CBM-catalyst (50 ppm, considering the number of long-chain polyol polyether) in a protective gas atmosphere (nitrogen) and heated with stirring to 105°C. Then add a mixture of ethylene oxide/propylene oxide with a mass ratio of 70:30 (about 100 g) to increase the total pressure up to 1.5 bar. The remainder of the mixture ethylene oxide/propylene oxide again adds only then, when we celebrate the accelerated pressure drop. This rapid pressure drop indicates that the catalyst is activated. Then continuously, at a constant total pressure of 1.5 bar add the remaining mixture ethylene oxide/propylene oxide with a mass ratio of 70:30 (g 5027). After adding the total number of accelerated and endurance 5 hours at 105°With distilled volatile components at 105°C (1 mbar) and then cooled to room temperature.

Received long-chain polyol polyether HE has the number, sootvetstvuetopredelennyj blocks - to 59.8 wt.%.

Example 2

A 10-liter glass flask to work under pressure put 873 g of starting compound is poly(oxypropylene)Tirol (Brednikova molecular weight of 440 g/mol) and 0.30 g CBM-catalyst (50 ppm, considering the number of long-chain polyol polyether) in a protective gas atmosphere (nitrogen) and heated with stirring to 105°C. Then add a mixture of ethylene oxide/propylene oxide with a mass ratio 89,4:10,6 (about 100 g) to increase the total pressure up to 1.5 bar. The rest of the mixture ethylene oxide/propylene oxide again add only when you see the rapid pressure drop. This rapid pressure drop indicates that the catalyst is activated. Then continuously, at a constant total pressure of 1.5 bar add the remaining mixture ethylene oxide/propylene oxide with a mass ratio 89,4:10,6 (g 5027). After adding the total number of accelerated and endurance 5 hours at 105°With distilled volatile components at 105°C (1 mbar) and then cooled to room temperature.

Received long-chain polyol polyether HE has is a number corresponding 58.5 mg KOH/g, the content of double bonds - 2 mmol/kg, the proportion of pervi the 10-liter glass flask to work under pressure placed 840 g of starting compound - poly(oxypropylene)Tirol (Brednikova molecular weight of 446 g/mol) and 0.30 g CBM-catalyst (50 ppm, considering the number of long-chain polyol polyether) in a protective gas atmosphere (nitrogen) and heated with stirring to 105°C. Then added propylene oxide (about 100 g) to increase the total pressure up to 1.5 bar. The rest of the propylene oxide again adds only then, when we celebrate the accelerated pressure drop. This rapid pressure drop indicates that the catalyst is activated. Then continuously, at a constant total pressure of 1.5 bar add the remaining propylene oxide (2152 g). Then gradually, at a constant pressure of 1.5 bar was added a mixture of ethylene oxide/propylene oxide with a mass sootnosheniem 80:20 (2908 g). After adding the total number of accelerated and endurance 5 hours at 105°With distilled volatile components at 105°C (1 mbar) and then cooled to room temperature.

Received long-chain polyol polyether HE has is a number corresponding 53,9 mg KOH/g, the content of double bonds - 5 mmol/kg, the proportion of primary hydroxyl groups is 52 mol.% and content oxyethylene blocks to 38.8 wt.%.

Example 4

A 10-liter is non-numeric molecular weight of 446 g/mol) and 0.30 g CBM-catalyst (50 ppm, considering the number of long-chain polyol polyether) in a protective gas atmosphere (nitrogen) and heated with stirring to 105°C. Then added propylene oxide (about 100 g) to increase the total pressure up to 1.5 bar. The remaining propylene oxide again added only when you see the rapid pressure drop. This rapid pressure drop indicates that the catalyst is activated. Then continuously, at a constant total pressure of 1.5 bar add the remaining propylene oxide (989 g). Then gradually, at a constant pressure of 1.5 bar was added a mixture of ethylene oxide/propylene oxide with a mass ratio of 80:20 (4071 g). After adding the total number of accelerated and endurance 5 hours at 105°With distilled volatile components at 105°C (1 mbar) and then cooled to room temperature.

Received long-chain polyol polyether HE has is a number corresponding 54,0 mg KOH/g, the content of double bonds - 2 mmol/kg, the proportion of primary hydroxyl groups is 67 mol.% and content oxyethylene blocks or 54.3 wt.%.

1. The polyether polyols with the content of primary hydroxyl groups of 40 to 95 mol.% and the total content of anxietyproducing)-end block.

2. The polyether polyols under item 1 with srednetsenovoj molecular weight of 1000 to 100000 g/mol.

3. The method of producing polyols under item 1 or 2, in which the starting compound with active hydrogen atoms are subjected to transformation by CBM-catalyzed polyaddition to a mixture of ethylene oxide/propylene oxide with a mass ratio of EC:40:60 - 95:5.

4. The method according to p. 3, which use the original connection 1-8 hydroxyl groups and a molecular mass of 18 - 2000 g/mol.

5. The method according to p. 3 or 4, in which as a source of compounds with active hydrogen atoms using oligomeric propoxycarbonyl source connection 1-8 hydroxyl groups and srednekislye molecular mass of 200 to 2000 g/mol.

6. The method according to one of paragraphs.3-5, in which the original connection with the active hydrogen atoms first lengthened by CBM-catalyzed propoxycarbonyl and then elongated propoxyethanol intermediate product CBM-catalyzed polyprionidae to a mixture of ethylene oxide/propylene oxide with a mass ratio of EC: = 40:60 = 95:5 as of the end block receive long-chain polyol polyether content primary hydroxilase of PP.3-6, when CBM-catalyzed, polyprionidae mixture ethylene oxide/propylene oxide as the terminal block to the original compounds with active hydrogen atoms is carried out at temperatures of 20 to 200°C, the total pressure of 0.001 to 20 bar and in the absence or in the presence of an inert organic solvent.

8. The method according to one of paragraphs.3-7, which are used CBM catalyst in concentrations of 0.001 - 0.1 wt.%, counting on the amount of polyether polyol.



 

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