DE1520750C - Process for the polymerization of olefin oxides - Google Patents

Description

As for the catalysts to be used for the polymerization of olefin oxides, there have been hitherto Friedel-Crafts compounds such as boron trifluoride, tin tetrachloride and zinc chloride as well as acids and alkalis and alkaline earth carbonates are used. Recently, metal halides, such as ferric, metal alkoxides and metal alkyl compounds have been reported.

Among these catalysts, those known to be more excellent in olefin oxide polymers Properties and which are currently in commercial use, various Disadvantages, which include the fact that their preparation is complicated that they are difficult to handle and that they have a higher purity of the monomer and other reactants require.

From British Patent 646 292 is the use of alkali metal phosphates as catalysts for the olefin oxide polymerization is known.

However, alkali phosphates have only a low catalytic effectiveness. Runs in her presence the polymerization is not only very slow, but also only relatively low molecular weight Polymers that also have very different molecular weights. The course of the polymerization is therefore not reproducible, which is why one encounters greater difficulties when Polymer products with constant properties are to be produced.

The process of the invention for the polymerization of olefin oxides can be used run a catalyst which is easy to manufacture and handle and compared to the conventional catalysts do not so carefully purify the monomer and others Respondent required. The process according to the invention can be carried out continuously. the Physical properties of the polymer product can be largely determined by changing the manufacturing conditions of the catalysts present.

The process according to the invention for the polymerization of olefin oxides is characterized in that ethylene oxide, propylene oxide, epichlorohydrin, styrene oxide or other olefin oxides having up to 9 carbon atoms in the molecule are brought into contact with a catalyst which is composed of a metal salt of oxyacids of phosphorus of the general composition formula H _w M _x POj, is composed, where M is selected from the metals of Group IV to VIII of the Periodic Table and their metal oxide groupings (oxygen-containing metal radicals), w is a number lower than 3, χ a number higher than 0, but not higher than 3, and y -a number not lower than 2.0 but not higher than 4.

The catalyst to be used in the process of the invention, composed essentially of a metal phosphate or a metal phosphite, can be any of the metal salts of the oxyacids of phosphorus, e.g. B. the metal salts of ortho-, meta-, hypo-, pyro-, polymeta- and other phosphates and phosphites. M can be a metal or one of the metal oxide groups such as vanadyl (VO), chromyl (CrO ₂ ), neptunyl (NpO,) · plutonyl (PuO ₂ ), titanyl (TiO), zirconyl (ZrO) or hafnyl - (HfO) be.

In addition to the phosphates and phosphites, the chemical composition of which is known, other compounds produced by the reaction of phosphoric acid, phosphorous acid, a phosphate or a phosphite with a metallic compound (such as halide, oxyhalide, oxide, nitrate or sulfate) can be used, even if their chemical composition or crystalline structure is not obviously known. Such phosphates often have w, x and y values which are not exactly integers in the general composition formula defined above.

For example, a compound formed as it is precipitated by the reaction of the halide or oxyhalide of a metal from Group IV to VIII with a water-soluble phosphate or phosphite salt in an aqueous medium, separated off, washed well with water, dried, if desired, calcined and in the invention Method used. Typical examples of such compounds include the phosphate of titanium (composition and structure not clear) or zirconium pyrophosphate (ZrP ₂ O ₇ ). Or a compound is used which is formed by the reaction of a metal oxide with phosphoric acid, vanadyl orthophosphate (VO · PO ₄ ), zirconyl pyrophosphate ((ZrO) ₂ P ₂ O ₇ ), chromium metaphosphate (CrPO ₃ ) being typical examples. Examples of compounds that are formed by the reaction of a metal nitrate with phosphoric acid or a phosphate are phosphates of manganese (Mn ₂ P ₂ O ₇ ), thorium (ThP ₂ O ₇ ) and uranium ((UO ₂ ) ₂ P ₂ Ö ₇ ) . An example of compounds which are formed by the reaction of a metal sulfate with a phosphate is chromium phosphate (Cr (PO ₃ ) ₃ ). In the metal phosphates and phosphites used in the invention, M in the formula may be one or more than one kind of the metals and metal oxide moieties.

Therefore, the composition of the catalyst used in the process according to the invention .according to the kind and type of phosphate and according to the manufacturing conditions, as well as according to the proportions of the reactants vary. In addition, the crystal properties vary according to the firing conditions. Accordingly, the rate of polymerization is as well as the Properties of the polymer product depending on

depending on the variation of the catalyst used.

The metal phosphate and phosphite catalyst used in the process according to the invention is preferably in the dry state. If desired, the catalyst is burned at a temperature of 100 to 1500 ^° C., preferably 100 to 1000 ^{° C.} The temperature at which the catalyst is fired appears to be related to the degree of polymerization of the product. For example, a higher firing temperature results in a higher degree of polymerization of polyethylene oxide when ethylene oxide is polymerized using a zirconium phosphate. In this way, polyolefin oxides in various states from liquid, fatty, waxy, horny to resinous can be produced only by selecting the firing temperature. This fact is a remarkable advantage or feature of the invention compared to the conventional catalyst, e.g. B. strontium carbonate, in which the permissible firing temperature range is very narrow and the control of the properties of the product by the catalyst is difficult.

If desired, the catalyst used in the process of the invention can be supported such as silica, alumina, silica-alumina, and various kinds of clay.

The catalysts used in the process according to the invention are comparatively longer Effective time because it initiates the polymerization reaction as a result of the orienting adsorption of the monomer catalyze on the solid surface. In addition, if desired, the catalysts can be regenerated and reused simply by separating from the product and firing. These too Facts are advantages and features of the present invention.

Olefin oxides which are polymerized according to the invention include ethylene oxide, propylene oxide, Epichlorohydrin, styrene oxide and others with up to 9 carbon atoms in the molecule. Of these, show ethylene oxide and propylene oxide have the most remarkable properties of the invention and give excellent results.

The polymerization according to the invention can advantageously be carried out as a block polymerization without a solvent are executed. However, the polymerization can also be carried out in solution, suspension or dispersion will. Any solvent or liquid medium can be used in the latter method will,. as far as it is inert to the reaction. Examples of this are liquid hydrocarbons and halogenated hydrocarbons, ethers, ketones or esters. Selection of the type and amount of solvent or liquid medium are used to vary the properties of the polymer product.

The bringing into contact of an olefin oxide with the catalyst according to the process of the invention can be carried out batchwise, semicontinuously or continuously. In the latter case, the catalyst can be fixed in a fixed, moving or liquefied bed. The reaction conditions can be chosen within a wide range. The polymerization temperature may be within the range from 0 to 170 ⁰ C, preferably, selected within the range of 20 to 100 ⁰ C. Since lower olefin oxides have lower boiling points, their polymerization is preferably conducted in a pressure vessel or a pressure zone.

The reaction product can be appropriately recovered from the mixture. For example the product is separated from the solid catalyst by centrifugation or filtration by, if required using a suitable solvent for the product (such as chloroform) or by using centrifuged or filtered in the molten state. The solution of the separated from the solid catalyst Product is poured into a solvent to form the product precipitate, which the product cannot dissolve.

The polyolefin oxides produced have different molecular weights, for example 200 to 1,000,000. Depending on the molecular weight, the state of the product is liquid, fatty, waxy, horny or resinous. Some of the higher molecular weight products are crystalline and make stretchable films. . . ,.
example 1

A solution of titanium tetrachloride in dilute hydrochloric acid becomes aqueous with an equimolar amount Phosphoric acid solution mixed- The resulting precipitate is filtered after standing overnight and washed well with water and then for 3 days 100 ° C dried.

In a stainless steel autoclave with an internal volume of 100 cm ³ , which is equipped with an electromagnetically driven stirrer moving up and down, 0.67 g of the catalyst prepared as mentioned above are placed and the air in the autoclave is replaced by nitrogen ; While cooling the autoclave, 19 g of purified ethylene oxide are introduced under nitrogen. The reaction was allowed for 5 hours under stirring and heating at 8O ⁰ C to proceed; then the autoclave is cooled, the contents removed and dried under subatmospheric pressure. The product is dissolved in chloroform, centrifuged to separate from the catalyst and poured into ethyl ether, whereby the polymer product is precipitated. The separated product is fatty and weighs 2.5 g.

Example 2

A titanium phosphate prepared in a manner similar to Example 1 is fired in an electric furnace at 500 ° C. for 5 hours in the presence of air. Using 0.67 g of catalyst according to the same procedure as in Example 1, 15 g of ethylene oxide polymerised for 3 hours at 8O ⁰ C. Purification of the product by precipitation gives 2.3 g of a soft waxy polyethylene oxide.

Likewise, 48 g of ethylene oxide are sealed by using 0.1 g of the same catalyst in one Polymerized glass tube at room temperature for 1 month. Similarly, 1.0 g becomes one obtained waxy polymers.

Example 3.

Commercially available iron (II) phosphate is ^{burned at 500 °} C. for 5 hours. Using 0.1 g of the calcined catalyst, 6.0 g of ethylene oxide are polymerized in a closed glass tube at room temperature for 1 month. 1.1 g of a hard, waxy polymer are obtained.

Example 4

Precipitations formed by the reaction of an aqueous zirconium oxychloride solution with an aqueous phosphate solution (such as NaH ₂ PO ₄ or (NHI ₂ HPO ₄ ) are dried for 3 days at 100 ° C. The product is dried for 5 hours at various temperatures, namely at 300, 500, 700, 900 and 1000 ° C. Using in each case 1.17 g of the catalyst, ethylene oxide is polymerized in an autoclave at 80 ° C. for 3 hours, similar to the method described above.

The results are given below:

Firing temperature
⁰ C Monomeric
feed
G yield
G Manifestation Intrinsic viscosity
η Softening point
⁰ C Not burned 15.5 12.6 soft wax 0.15 - 300 16 10.3 hard wax 0.49 57 to 58 500 14th 6.0 hard wax 0.49 56 to 58 700 14th 3.6 ' hard wax 0.56 57 to 59 900 22nd 2.4 resinous 0.96 60 to 62 1000 26th 2.1 resinous 0.88 59 to 60

(The inherent viscosity η in this and the following examples were determined using an Ubbelohde viscometer in water at 35 ° C.). . .

Example 5

Zirconium phosphate produced according to Example 4 is fired at 500 ° C. for 5 hours. Under use 0.1 g of 3es burned catalyst are 4.5 g of ethylene oxide in a sealed glass tube polymerized at room temperature. After 7 days, 0.8 g of pure polyethylene oxide are obtained, of which a part is resinous and film-forming. Its infrared analysis shows that it is a polyether with a high degree of crystallinity is.

Example 6

35

Commercially available vanadium pentoxide is mixed with orthophosphoric acid and the mixture for 5 days left to stand with occasional stirring.

The precipitated product is washed with methanol to remove the excess phosphoric acid and dried, followed by baking in air at 500 ° C for 5 hours.

Using 1.42 g of the calcined catalyst, 15 g of ethylene oxide are heated at 70 ° C. for 8 hours polymerized. 1.0 g of a finished polymer are obtained.

Example 7

Zirconium phosphate produced according to Example 5 is fired at 900 ° C. for 5 hours. Using 1.17 g of the catalyst, some ethylene oxide polymerization batches are carried out at 100 ° C. with changing the reaction time. The polymerizations are conducted in a 100 cm ³ autoclave which is equipped with an electromagnetically driven stirrer. The amount of monomers in each batch is 15 g. The results are shown in the following table:

Examples

Using catalysts prepared as in the examples above, the ethylene oxide polymerization batches in glass tubes at 100 ° C accomplished. The amount of each catalyst is 0.1 g and the amount of monomer fed 1 g. The polymerizations are conducted in a water bath, which is kept under constant rotating motion Temperature is maintained. The polymerization time is 6 hours in each case. The results are given below:

Polymerization time Polymer yield Intrinsic viscosity Hours. G Ί 1 1.3 1.34 3 2.7 1.16 6th 3.6 1.21 12th 4.9 1.15 24 6.9 0.96

60

65

Brenn Polymers Own catalyst temperature yield viscosity ⁰ C G V Ti phosphate 500 0.43 0.44 Phosphate of Fe 500 0.16 0.18 Zr 100 0.58 0.10 500 0.41 0.56 900 0.54 0.10

Example 9

A solution of manganese (III) nitrate in nitric acid is added hot to dilute phosphoric acid. After standing for several hours with heating, the resulting precipitates are separated off, washed with water and dried, whereby manganese (III) phosphate is obtained, which is then burned for 5 hours at 500 ° C in a stream of hydrogen to convert it to manganese (II) phosphate. Using 0.25 g of calcined catalyst, 15 g of ethylene oxide are ^{polymerized in a 100 cm 3} autoclave at the reaction temperature of 80 ° C. for 7 hours. Treatment of the reaction mixture according to the preceding examples gives 1.3 g of a soft, waxy polymer.

Example 10

A zirconium phosphate produced according to Example 5 is fired at 500 ° C. for 5 hours. 15 g of propylene oxide and 1.0 g of the calcined catalyst are placed in a 100 cm ³ autoclave, and the mixture is allowed to react at the reaction temperature of 100 ° C. for 6 hours. The catalyst is then

centrifuge separated from the reaction mixture and the monomer recovered by evaporation. It 3.7 g of a viscous, oily polymer are obtained.

Example 11

A zirconium phosphate prepared according to Example 5 is fired 5 hours at 1000 ⁰ C. Polymerizations are carried out in an autoclave by using 1.0 g of the calcined catalyst, an amount of ethylene oxide and 50 cm ^{3 of} a solvent for 3 hours at the reaction temperature of 80 ° C. The results are shown below:

solvent mono-
mer-
crowd
G Poly
meren
yield
G Manifestation Lake one
Heptane
benzene
Methylene chloride 26th
21
17th
21 3.3
3.2
2.3
2.2 fixed
fixed
waxy
waxy

20th

In cases where a solvent is used, the catalyst becomes from the reaction mixture after the reaction easily separated by mere centrifugation or filtration.

Comparative experiment

The superiority of the method according to the invention results from the following experiment:

Polymerization experiments were carried out with sodium phosphate, titanium phosphate and zirconium phosphate. The reaction time was 10 hours in each case, the reaction temperature 8O ⁰ C. The reaction vessel used was a thick-walled, consisting of glass test-tube to any side effect due to metal from the reaction vessel off.

The reagents used were obtained as follows:

Sodium phosphate: Na ₃ PO ₄ -12H ₂ O was dried at 160 ° C. for 8 hours before use. There was a weight loss of 50.3%.

Titanium phosphate: It was produced from TiCl ₄ and H ₃ PO ₄ , as described in Example 1, the product being calcined in air at 300 ° C. for 5 hours.

Zirconium phosphate: The production took place according to Example 5 from ZrOCl ₂ and (NH ₄ ) ₂ HPO ₄ ; it was then calcined in air at 500 ° C. for 5 hours.

Ethylene oxide: The product was poured from a bomb through a charged with granulated caustic potash, 50 cm long column distilled.

Test conditions:

tes ethylene oxide distilled into the reaction vessel. The reaction vessel was then flushed out with nitrogen and melted away 120 mm from the end. The exact amount of monomer added was determined by weighing the reaction vessel before and after charging the monomer. The reaction vessel was then stretched into an iron jacket (30 mm 300 mm), immersed in a bath kept constant at 80 ° C. and shaken every 30 minutes. After 10 hours of reaction time, the reaction vessel was removed and cooled with cold water and then with a dry ice-cooled methanol bath. The reaction vessel was then opened, the contents withdrawn and the unreacted monomer evaporated. To the remaining residue, 20 ml of benzene was added and mixed well to dissolve the product. The insoluble catalyst was filtered off through a glass filter, and the filtrate was evaporated and weighed. The inherent viscosity of the polymer was determined in a Ubbelohde viscometer in aqueous solution at 35 ⁰ C.

The results obtained in the tests are shown in the table below. With a sodium As can be seen from the JP table, the phosphate catalyst only became a small amount of a viscous Get liquid (see Experiment 1). With titanium phosphate as a catalyst, however, it was about 15 times as high Amount of a soft, waxy polymer obtained (see Experiment 2). With zirconium phosphate as a catalyst a further, substantial increase in the yield was achieved (experiment 3).

table

55

A reaction vessel consisting of a reagent tube with an inner diameter of 17 mm and a glass thickness of 2 mm was well dried, charged with 1.0 g of catalyst and over a with the Evacuation line connected to the reaction vessel for the purpose of pressure reduction and removal of air evacuated. After the pressure dropped below 1 mm Hg, the reaction vessel was cooled with a dry ice Cooled methanol bath and then cleaned 8 g from a separate, pressure-resistant glass tank.

catalyst feed
With Manufactured polymer M. Look ver Ethylene Out viscose sodium oxide
G prey
G liquid 1 phosphate 8.3. 0.02 0.08 soft, titanium waxy 2 phosphate 8.4 0.33 0.19 waxy Zircon 3 phosphate 7.6 0.69

The above table clearly shows the superiority of those in the process according to the invention catalysts used titanium phosphate and zirconium phosphate compared to the already known sodium phosphate.

At least under the reaction conditions described above (80 ° C, 10 hours) is formed at Using sodium phosphate as a catalyst is only a low molecular weight, liquid polymer. In the case of the catalysts used in the process according to the invention, however, one obtains among the same ones Reaction conditions a higher molecular weight polymer, which makes the better suitability of these catalysts for the production of waxy polymers proves.

It should also be pointed out that all the catalysts in the present experiment were less Activity than in the previous examples, suggesting differences in the reaction conditions is due.

209 541/533

Claims (1)

Claim: Process for the polymerization of olefin oxides, characterized in that ethylene oxide, propylene oxide, epichlorohydrin, styrene oxide or other olefin oxides with up to 9 carbon atoms in the molecule are brought into contact with a catalyst which is composed of a metal salt of oxyacids of phosphorus of the general composition formula H _w M _x PO _{y is} composed, wherein M is selected from metals of Group IV to VIII of the Periodic Table and their metal oxide groupings (oxygen-containing metal radicals), w is a number lower than 3, χ is a number higher than 0 but not higher than 3, and y a number is not lower than 2.0 but not higher than 4.