DE1217616B - Process for the preparation of polymers or copolymers of trioxane - Google Patents

Description

FEDERAL REPUBLIC OF GERMANY GERMAN WIW PATENT OFFICE

EDITORIAL

Int. Cl .:

Number:
File number:
Registration date:
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C08g

German class: 39 c-19

1217 616
B74274IVd / 39c
November 14, 1963
May 26, 1966

It is known that trioxane can be converted into a high molecular weight in the presence of electrophilic catalysts Polymerize polyoxymethylene, which is used to produce plastic molding compounds and films suitable. For example, British patent specification 878 163 describes the polymerization of trioxane in the presence of a electrophilic catalyst to high molecular weight polyoxymethylene. As for polymerization especially suitable catalysts are mentioned:

1. Fluorides, chlorides and bromides of metals and metalloids belonging to the general class of Include catalysts known as Friedel-Crafts catalysts;

2. Complexes of (1) with water or with organic compounds in which the donor atom is oxygen or is sulfur;

3. non-oxidizing organic acids and their complexes with boron trifluoride;

4. Complexes of boron trifluoride with very weakly basic nitrogen compounds, in which the Donor atom is nitrogen;

5. Halogens and compounds of the halogens with one another and

6. Oxonium salts.

It is also known that electrophilic catalysts, especially the aforementioned classes, can also be used for the preparation of trioxane copolymers. Examples of suitable comonomers which can be copolymerized with trioxane in the presence of electrophilic catalysts to form valuable polymeric products are: Cyclic ethers, e.g. B. ethylene oxide, propylene oxide and dioxolane; cyclic carboxylic acid esters which are much more reactive than γ-lactones when copolymerized with trioxane, e.g. B. / J-propiolactone; <5-valerolactone and ε-caprolactone; Aldehydes, e.g. B. chloral, anisaldehyde and cinnamaldehyde; Styrene and substituted styrenes, ζ. B. α-methylstyrene, anethole, 1- and 2-substituted vinylnaphthalenes, stilbene, indole and acenaphthylene; Vinyl ethers, e.g. B. Isobutyl vinyl ether and methyl vinyl ether; N-vinyl and C-vinyl substituted derivatives of aromatic heterocyclic compounds, e.g. B. N-vinyl carbazole and 2-vinyl pyridine; Ethylenically unsaturated aliphatic and aHcyclic hydrocarbons, e.g. B. isobutene, butadiene and cyclohexene; Allyl compounds, e.g. B. allyl ethers and allyl esters; Isocyanates, ζ. Β. Phenyl isocyanate; and nitriles, ζ. B. acrylonitrile, adiponitrile and benzonitrile. Copolymers can also be made from trioxane and more processes for the production of polymers
or copolymers of trioxane

Applicant:

British Industrial Plastics Limited, London

Representative:

Dr. W. Müller-Bore, Dipl.-Ing. H. Gralfs
and Dipl.-Phys. Dr. rer. nat. G. Manitz,
Patent attorneys, Braunschweig, Am Bürgerpark 8

Named as inventor:

Herbert May,

Oldbury, Birmingham (Great Britain)

Claimed priority:

Great Britain 14 November 1962 (43 094)

as one of the above-mentioned comonomers. Usually copolymerized not more than 20% of comonomers, preferably not more than 10%. A special one the preferred range is 2 to 5% based on the weight of the trioxane.

Finally, it is already known to use tetrafluoborates for polymerization or copolymerization of trioxane to use. For example, the Austrian patent specification 220 366 describes in Example 13 the Polymerization with the help of triethyloxonium tetrafluoborate.

The invention relates to a process for the production of polymers or copolymers of trioxane by polymerization of trioxane alone or with one or more with trioxane copolymerizable compounds under practically anhydrous conditions in the presence of electrophiles Catalysts, which is characterized in that the catalysts used are carbenium or halogenium tetrafluoborates used.

The tetrafluoborates used according to the invention are particularly useful for the polymerization of trioxane

609 570/546

3 4 ■

suitable and lead to polymeric products that still contain organic solvents, such as acetone, have better properties than those that can be brought about with the known.

Catalysts obtained polymers, in particular fourth, have those using the new

a higher thermal stability and a larger catalyst obtained polymers a very good Have molecular weight. 5 heat resistance.

In the case of the catalysts used according to the invention, suitable conditions under which the polymer

it concerns the following tetrafluoborates, and sation of trioxane in the presence of an electrophile Although the catalyst can be effected, are in the

British Patent 878163. These

a) Carbenium tetrafluoborates, e.g. B. Triphenylmethyl- ₁₀ conditions are also suitable for the tetrafluoborate C + (C ₆ H ₆ ) ₃ BF ₄ , diphenylmethyl process according to the invention.

tetrafluoborate, tropylium tetrafluoborate and di- Preferably one works with a saturated one

oxoHnium tetrafluoborate aliphatic or alicyclic hydrocarbon

as an inert liquid medium, a dry inert

CH ₂ -O. 15 atmosphere, such as nitrogen and / or carbon dioxide,

CH ⁺ BF ~ ^unc ^ ^ ^euier temperature above 50 ⁰ C and one

/ * Water content less than 0.01 percent by weight.

CH ₂ O The catalysts used according to the invention

also show towards those from the Austrian

b) halogenium tetrafluoborates, e.g. B. Jodoniumtetra- ^ao patent specification 220 366 known catalysts überfluoborat J ⁺ BFr, bromoniumtetrafluoborat surprising technical advantages. This results when Br ⁺ BF ₄ T and diphenyl iodonium tetrafluoborate are used in example 13 of the Austrian patent J + (C _e H ₆ ) _{2 BFr.} ^'Instead of Triäthyloxoniumtetrafluoborat tri-

phenylmethyltetrafluoborate in the same molar ratio

The nits can be used as comonomers in this process.

Example 13 of the Austrian patent cited above as a compound mentioned in the prior art

gen can be used. for the thermal stability of the product

It should be noted that the catalysts used in the value of 0.29 ° / ₀ / min. at 202 ⁰ C and a relatively inventive method are used, not low viscosity of 0.93, in butyrolactone only the free ionic appearance as measured by 30.

the above formulas is reproduced, but the product made using the triphenyl

can also have the solvated ionic form. methyl salt is obtained, however, has a vis-

A particular advantage of using this viscosity of 1.58, under the same conditions, new electrophilic catalysts is that they lead to measured and thermal stability at 202 ^° C. polymers with high molecular weight. 35 is 0.08% / min. in the first 10 minutes, for example, it is possible to use a polymer at 0.14% / min. for the next 20 minutes and 0.13% / to generate a viscosity number of more than 2 min. in the 30th to 60th minute. This results in an average heat stability of 0.125% / min. Measured with 2% -pinene (measured at 60 ° C in ^{a 0.5% solution in p-chlorophenol).} over the entire time of 60 minutes. One sees

Another great advantage of many of the Carboni- 40 from the fact that the verum tetrafluoborate according to the invention is that they are very stable crystalline drive obtained product a much better one Are compounds that have thermal stability even in moist air than that according to the Austrian Storage does not disintegrate. The Halogenium Tetrafluo Patent. Also is the molecular weight Borates are not as stable in the unsolvated form of the polymer obtained according to the invention as from however, gain great stability when it emerges from the higher viscosity, for example, much higher than that be solvated wisely with nitroethane. according to the Austrian patent specification.

Another advantage is that this new catalyst The invention is described below with reference to the

Sators are particularly useful when the poly examples are explained in more detail. In these examples, the values of the thermal decomposition rate liquid medium of a saturated alicyclic carbon 50 (K ₂₂₂ ) according to the by Schweitzer and coworkers ICnWaSSCrStOfTeS ₅ ZB ₁ CyClOhBXaH, or a saturated hydrocarbon described in the above-mentioned reference, were merized in these examples, eg η-hexane, carried out method determined and the viscosity numbers at 6O ⁰ C is. The carbenium and halogenium tetrafluoborates in 0.5 percent by weight solutions in p-chlorophenol are expediently measured in a solution of nitroethane with 2 percent by weight of pinene,
produced and used and are in this form 55 Examples 14 to 17, which use the in a saturated aliphatic hydrocarbon, electrophilic catalysts according to the British such as η-hexane, soluble. These properties of the new patent specification 878 163 show, were added to comparison catalysts enable improved homo purposes,
genicity and distribution of the catalyst in the as

Medium used saturated aliphatic carbon 60 for example

Hydrogen, which in turn leads to an improvement

the physical form and properties of the sun. A reaction vessel was filled with 20 g of trioxane and

obtained polymer leads. 14 g of cyclohexane charged. The water content of the

A third advantage is that the new catalysts, the reaction mixture was less than 0.01 weight light from the polymer may be removed percent 65, determined by the Karl-Fischer method, and its separation by a simple washing with The mixture was in at 6O ⁰ C one atmosphere of water or with an aqueous washing liquid, ζ. B. kept dry nitrogen, and 0.05 g of an aqueous ammonia solution, or with a 25% solution of bromonium tetrafluoborate in

5 6

Nitroethane was added with vigorous stirring. Example 10
The polymerization took place quickly.

After completion of the polymerization, about A 2-1 reaction flask was filled with 600 g of trioxane,

50 ml of acetone are added and the resulting sludge is charged with 12 g of dioxolane, 3 g of styrene and 400 g of hexane,

was filtered off and in the presence of about 250 ml 5 The water content of the reaction mixture was below

an approximately 2 percent by weight aqueous Am-0.01 percent by weight, according to the Karl Fischer method

monia solution homogenized. The polymer was determined. This mixture became under rapid

filtered off, with about 250 ml of approximately 0.3 weight stirring in an atmosphere of dry nitrogen

concentrated aqueous ammonia solution and then 1 ml of a 25 ° / _o solution of Jodoniumtetrafluo-

washed with about 250 ml of acetone and finally added io borate in nitroethane. The polymerization

dried in a vacuum oven at 60 ° C. took place quickly.

Details of the polymerization time, the yield After the completion of the polymerization, about

at the bottom of the polymer and its viscosity are added 200 ml of acetone with vigorous stirring,

Given in the table. A film was press-molded and the resulting sludge was filtered off and

a sample of the polymer at 190 ⁰ C produced. 15 about 16 hours with about 21 one approximating

For more information on the properties of the film, 2 weight percent aqueous ammonia solution in

are also included in the table. ground in the ball mill. The polymer was

. . filtered off, with about 21 of an approximately 3 weight

Example 2 percent aqueous ammonia solution and other

A similar reaction as in Example 1 was finally washed with about 21% acetone and carried out, but 0.05 g of triphenylmethyl were finally dried in a vacuum oven at 60 ° C., tetrafluoborate as catalyst in the polymerization. The results are shown in the table , used. The results of this example and the results of this example are shown in the table. soffit of 1 ° / ₀ malonamide and 0.5% 2,2-methylene. 25 bis (4-methyl-6-tert-butyl-phenol) stabilized in Example 3 in a known manner. The properties of this stabilized

Again, in a manner similar to that in the polymer are also shown in the table.

Example 1 followed, but 0.5 g of dioxolane.

as comonomer and 0.05 g of triphenylmethyltetra- Example 11

fluoborate used as a catalyst. 30 A reaction vessel was filled with 702 g of trioxane, 585 g

_. ■ \ λ Cyclohexane and 21 g of styrene charged. The water-

Example 4 content was less than 0.01 percent by weight, according to the

This example was also determined in the manner of Karl Fischer method. The mix was

Example 1 was carried out, but 0.4 g of styrene was added at 60 ° C. in an atmosphere of dry nitrogen

added as a comonomer and kept as a catalyst 35 and with vigorous stirring with 0.4 g of a

0.05 g triphenylmethyl tetrafluoborate used. 50 ° / _o solution of Dioxoliniumtetrafluoborat in

. . Nitromethane added. The polymerization soon began

^{ß e l s} P ^{l e} * ⁵ and was continued at 6O ⁰ C for _{3V 2 hours.}

The procedure was as in Example 1, but after completion of the polymerization were about

0.4 g of dioxolane and 0.4 g of styrene as comonomers 40 200 ml of acetone are added with vigorous stirring,

added and as a catalyst 0.05 g of a 25 ^O / _O igen and the resulting sludge was filtered off and

Solution of iodonium tetrafluoborate in nitroethane for about 16 hours with about 21

used. weight percent aqueous ammonia solution in the

Example 6 ground ball mill. The polymer was removed

45 nitrided, with about 21 an approximately 0.3 weight

The example was carried out in the percent aqueous ammonia solution described in Example 1 and other

Carried out well, however, 0.4 g / J-Propio- was finally washed with about 21 acetone and

lactone is added as a comonomer, and finally dried as a catalyst in a vacuum oven at 6O ⁰ C.

0.05 g of a 25 ° / _o solution of Jodoniumtetra- had The in 60% yield product obtained

fluoborate used in nitroethane. 50 has a viscosity number of 0.95 and a K ₂₂₂ value

_. . . _ Of O, 6 _^0/0 / min.

Example 7.

",. . ". ·, ■! «Ι. -Ji-I example 12
The procedure was as in Example 1, but as

Catalyst 0.05 g of a 25% solution of Jo- Man worked as described in Example 11,

donium tetrafluoborate used in nitroethane. However, 55 used in place of those listed there

. ₁₀ starting materials 737 g trioxane, 614 g cyclohexane,

Example 8 _{22 g of styrene and 2 g of a 5 o} / o i _gen solution of

The procedure was as in Example 1, but DioxoUniumtetrafluoborat were in nitromethane. The "pro-

0.25 g of styrene and 0.5 g of dioxolane as comonomers product had a viscosity number of 0.93 and one

was added, and 0.05 g of a 25 ° / _o solution of 60 K ₂₂₂ value of 0.55 ° / o / min.

Jodoniumtetrafluoborat in nitroethane were used as.

Catalyst used. 13 e 1 s ρ 1 e 1 Ii

. -in this example was made with the same catalyst

Example 9 _UQ j. _under the same, j _en conditions as Example 12

The procedure was as in Example 1, but 65 was carried out, but 824 g of trioxane and 687 g were used

0.5 g of dioxolane as comonomer and 0.05 g of a cyclohexane are used and the reaction takes 4 hours

^E continued 25% strength solution of n in Jodoniumtetrafluoborat. The product had a viscosity number

Nitroethane as a catalyst. of 1.25 and a K ₂₂₂ value of 0.6 ° / ₀ / min.

Example 14 (for comparison)

This example was carried out as in Example 1, but 0.05 g of boron trifluoride diethyl etherate were used as Catalyst used in the polymerization.

Example 16 (for comparison)

The procedure was as in Example 1, but were

0.5 g of dioxolane was added as a comonomer, and the catalyst was 0.05 g of boron trifluoride diethyl etherate.

Example 15 (for comparison)

Example 17 (for comparison)

This example was performed as Example 10 Also, this example was as Example 1, however, throughput 1 ml of a 25 ° / _o solution of Borgeführt, however, as a catalyst 0.05 g of boron trifluoride io-di-n-butyl etherate used in nitroethane as catalytrifluoride di-n-butyl etherate. used for polymerization.

At-
game Comonomer - reaction time Approximate
yield K ₂₂₂ Viscosity
number Film properties ° / o of trioxane Dioxolane (2 ¹ I ₂ ⁰ I ₀ ) hours % % per minute 1 Styrene (2%) 1 60 flexible 2 Dioxolane (2%); Styrene (2%) IV ₂ 80 0.8 1.3 flexible 3 /? - propiolactone (2%) 1 80 0.15 - brittle 4th - 1 85 0.35 - partly flexible 5 Styrene (IV / a); Dioxolane (2V ₂ ⁰ Zo) 1 80 0.10 1.3. flexible 6th Dioxolane (2 ¹ Z ₂ ⁰ Z ₀ ) 6th 60 0.20 - flexible 7th Styrene (e / ₂ %); Dioxolane (2 ° / ₀ ) - - 0.45 2.8 flexible 8th Styrene (V / o) - - 0.16 flexible 9 Styrene (V / o) 0.15 2.2 flexible 10 - - 0.22; 0.04 * 1.4 flexible 11 : 60 0.60 0.95 12th - - 0.55 0.93 13th Dioxolane (2 ¹ I ₂ ⁰ I ₀ ) - 0.60 1.25 14 ** Styrene ( ¹ I ₂ ⁰ I ₀ ); Dioxolane (2 ° / ₀ ) 0.85 1.1 flexible 15th - 0.65 1.4 flexible 16 0.20 1.1 flexible 17th - 0.33 1.3 flexible

*) After stabilization.
* ♦) Examples 14 to 17 are comparative examples with known catalysts.

Claims (1)

Claim: Process for the preparation of polymers or copolymers of trioxane by polymerization of trioxane alone or copolymerizable with one or more with trioxane Compounds under practically anhydrous Conditions in the presence of electrophilic catalysts, characterized in that that carbenium or halogenium tetrafluoborates are used as catalysts. Considered publications: Austrian patent specification No. 220 366. 609 570/546 5.66 © Bundesdruckerei Berlin