DE1233841B - Process for the production of tertiary polypropylene phosphites - Google Patents

Description

FEDERAL REPUBLIC OF GERMANY

GERMAN

PATENT OFFICE

EDITORIAL

Int. CL:

German class: 12 ο -5/04

Number: 1233 841

File number: P 29266IV b / 12 ο

Filing date: April 27, 1962

Opened on: January 26, 1967

The invention relates to the production of tertiary phosphite esters of polypropylene glycol.

The phosphates to be produced according to the invention are new substances in which the Phosphorus atom ester groups of the following general Formula are bound:

HIGH ₂ / OCH ₂ CH - O \

CH ₃

CHn

In this formula, * means an integer of at least 1. Although the majority, namely about 90 percent by weight, of these groups in the specified In the form of a secondary alcohol, part of the product also has groups of the following general formula:

HOCH ₂ CH / OCHCH _a O \

' III so

CH ₃ V CH ₃ /.

and another part contains the group: HOCH ₈ CH / OCH ₂ CHOX

CH,

CH _a

It has been known for over a decade that phosphite esters of higher alcohols can be produced by transesterification of triaryl phosphites with high-boiling alcohols with replacement of the aryl radicals by alkyl radicals. Such displacement reactions by simple monohydric alcohols are z. B. in the German Auslegeschrift 1 075 584 and in the book by Kosolapoff, "Organophosphorus Compounds", 1950, pp 191 to 192, has been described. In this section of Kosolapoff's book, the replacement of an ethyl group in ethylo-phenylene phosphite by a hydroxyphenyl group is mentioned, but it is expressly pointed out that the result of the transesterification with alcohols cannot be foreseen without further ado; For example, when propanol acts on the phenyl phosphites, the expected phosphite esters are not obtained, but isomerization takes place. It was all the less to be expected that this uresterification reaction would be suitable for the solution of the problem according to the invention, in which it is important to prepare esters of phosphorous acid with dihydric alcohols in such a way that the end products each have a free one for further reactions available hydroxyl group process for the preparation of tertiary
Polypropylene phosphites

Applicant:

Pure Chemicals Limited, Liverpool, Lancashire

(Great Britain)

Representative:

Dr.-Ing. V. Hartmann, patent attorney,

Berlin 12, Weimarer Str. 2

Named as inventor:

Lester Friedman, New York, N.Y. (V. St. A.)

Claimed priority:

V. St. v. America May 15, 1961 (109 842)

on the ester groups. In the transesterification of aryl phosphites with dihydric alcohols was expect the formation of polymeric phosphates.

It has now been found that, surprisingly, in the implementation of triaryl or trialkyl phosphites with polypropylene glycol almost completely the expected formation of polymeric phosphites does not occur while the reaction gives the corresponding trishydroxyalkylphosphites in excellent yield leads.

On the basis of this knowledge, the subject matter of the invention consists in a method for production of tertiary polypropylene glycol phosphites by transesterification in the presence of a catalyst, which is characterized in that at least 3 moles of polypropylene glycol with 1 mole of a triaryl or Trialkyl phosphites are implemented.

The new phosphite esters can be used in many ways. So z. B. They prove to be stabilizers for polyether-polyurethanes against oxidation and degradation phenomena (evident from the retardation of yellow or brown discolouration, as in the case of such urethanes under the action of light) and serve as \ ^ someone for polyurethanes. '23 ^k

The tripolypropylene glycol phosphites in particular are extremely useful. You stand out because of her reactive hydroxyl groups as an additive to urethane systems, in which they interact with the isocyanate

709 508/321

3 4

end groups in the growing polymer chains in As reaction catalysts, alkaline cata-

React and become fixated in this way. lysers are used, e.g. B. 0.1 to 10% sodium phenolate,

Due to their reactivity, they also serve the sodium cresylate, potassium phenolate, sodium methylate,

Cross-linking and reinforcement of the polymer chains. Sodium decylate, sodium dipropylene glycolate or the like.

The tripolypropylene glycol phosphites can also 5 The reaction can also be carried out with a diaryl or di-

are added to the epoxy resin systems. Thus, alkylphospb.it can be catalyzed, e.g. B. with 0.1 to 1%

z. B. the tridipropylene glycol phosphite directly in a diphenyl phosphite, di-o-cresyl phosphite, di-p-cresyl

Epoxysysteni, which is preferably formed by an alkyl phosphite, dimethylphosphite, diethylphosphite, di-

aminate is catalyzed, enter into reaction. Tripolydecyl phosphite, dioctadecyl phosphite and others. m.

propylene glycol phosphite can be treated with malein- io when using alkaline catalysts it is

anhydride or other polybasic acids or an advantageous if they have a pH of in a 0.1 η solution

hydrides are reacted, namely with formation of at least 11 possess.

of the corresponding acid ester phosphite ester, thanks to the fact that the alcohol groups in

on the other hand, in many epoxy systems without additional catalytic dipropylene glycol (and the other polypropylene

can react. 15 glycols) are secondary and accordingly

The tripolypropylene glycol phosphites can also react relatively slowly, it is possible that

Used to make polyesters are tripolypropylene glycols, although the three are functional

z. B. by reaction - for example in Molver- have hydroxyl groups, with a minimum of

ratio 1: 1 - with maleic anhydride, phthalic acid cross-linking or polymerization. the

anhydride, dimethyl terephthalate, fumaric acid, succinic 20 tripolypropylene glycol products are insoluble and

stinic acid, oxalic acid, itaconic acid, etc. τη. are not subject to hydrolytic attack

The novel phosphites are also valuable to water.

as lubricants, heat transfer fluids, the higher polypropylene glycol phosphites can

hydraulic fluids and fluids for by reaction of tridipropylene glycol phosphite with

Pump. They have good flow properties and are made of 25 propylene oxide. The reaction takes place

insoluble in water and practically embody at the same time in the places of the free hydroxyl groups, and

a stabilizer and a sauce acceptor. A tripolypropylene glycol phosphite is also formed as a result.

Plasticizers in polyester systems are they are useful, all parts and percentages mean if nothing

as well as for systems formed from free radicals, other information is given, parts by weight and weight

z. B. Polynierized Methyl Methacrylate. You can get 30 percent.

in the already existing lubricants and example 1
Glycol-type liquids can be used.

The preparation of the polypropylene glycol phosphites 3100 g (10 mol) of triphenyl phosphite, 15 g of diphenyl is carried out by transesterification of triaryl phosphites or phosphite (catalyst) and 4422 g of dipropylene glycol trialkyl phosphites with a polypropylene glycol. It is 35 (33 mol, ie 10% excess) are heated ^{in vacuo to produce a tripolypropylene (10 mm) at 120 ° C.} The resulting phenol glykolphosphits least 3 moles of polypropylene glycol was collected (Kp. = 10 mm 85 to 90 ⁰ C). The reaction temperature was allowed to act on 1 mole of triaryl or trialkyl phosphite for the course of the reaction. It is preferable to use a slight increase to 155 ± 5 ° C. During this time there was an excess of polypropylene glycol. For preparation 40 the distillate was initially available, namely until about 80% of bis-polypropylene glycol monoaryl or mono of the theoretical amount had been collected; only 2MoI of polypropylene are alkyl phosphites from pure phenol. It then distilled with tensile glycol to 1 mole of triaryl or trialkyl phosphite mixed with increasing amounts of dipropylene glycol. For the production of mono over. The reaction was complete when 3250 g of the polypropylene glycol-bis-aryl-or-bis-alkyl phosphite 45 mixed distillate were present. The residue of the reused if only 1 mole of polypropylene glycol was added to the action vessel after filtration through 1 mole of triaryl or trialkyl phosphite. If one uses Filterzel) (a diatomaceous earth) as tridipropylene less than 3 moles of polypropylene glycol per mole of triglycol phosphite, a viscous colorless aryl or trialkyl phosphite, shows a liquid with an n'i = 14,610, specific tendency towards the formation of polymers as 50 weight "= 1097.
By-product. Such by-products can be seen in the example) 2
can be used in the same way as the monomers
Products. In the same way as in Example 1 were

Usable polypropylene glycols are: dipropylene 3100 g triphenyl phosphite (10 mol), 15 g diphenyl

glycol, polypropylene glycol-425 (i.e. a polypropylene phosphite (catalyst) and 12,750 g of polypropylene glycol

Pylene glycol reacted with one another with an average molecular weight of 425 (30.3 mol). Which he-

weight of 425), polypropylene glycol-1025 (polyheating continued until 2780 g phenol

propylene glycol with an average mole (97% of theory) recovered. The im

kular weight of 1025), polypropylene glycol 2025 reaction vessel remaining tripolypropylene glycol (poly) propylene glycol with an average of 60,425 phosphite was a colorless viscous liquid molecular weight 2025) and polypropylene glycol and had an n ¹ = 14 535 and a D ^! f = 1028. an average molecular weight of 3000 or their

Geroic. Example 3

Examples of useful triaryl or trialkyl

phosphites are: triphenyl phosphite, tri-o-cresylphos- 65 polypropylene glycol-1025 (9235 g, 9.09 mol), triphite, Tri-p-cresyl phosphite, tri-m-cresyl phosphite, triphenyl phosphite (930 g, 3 moles) and diphenyl phosphite xylenyl phosphite, tridecyl phosphite, diphenyldecyl · (20 g, catalyst) were mixed together in vacuo

phosphite and tri-ethyl phosphite. with stirring at a temperature of 210 ° C and

heated to a pressure of 5 mm. Phenol with a melting point of 40 ^° C. was collected (816 g). The mixture was then driven with stick push "for 2 hours at 210 to 22O ⁰ C and 10 mm pressure to complete the phenol distillation. The total yield were further collected g 34th of phenol was 850 g (the theoretical yield was 846 g, and 18 g from the catalyst, ie a total of 864 g).

The residue in the reaction vessel at 150 ⁰ C was allowed to cool, it treated with bleaching earth and received after filtration Tripolypropylenglykol-1025-phosphite in a nearly theoretical yield as a liquid with the following properties: ni - _s f 14 515 specific gravity = 1 022nd

Example 4

Similarly, polypropylene glycol-2025 (18,216 g, 9.09 mol), triphenylphosphite (930 g, 3 mol) ao and diphenylphosphite (50 g, catalyst) were reacted with each other to give tripolypropylene glycol-2025-phosphite in almost theoretical Yield as a liquid with the following properties: n ^? § = 14 501, specific weight Y ₅ = 1006.

Example 5

Dipropylene glycol (884 g, 6.16 moles, 10% excess), triphenyl phosphite (610 g, 2 moles) and sodium (0.5 g, dissolved in a little dipropylene glycol) were, as described in Example 1, reacted with one another. Approximately 90% of the phenol was distilled out of the reaction mixture free of the co-distilling dipropylene glycol. Towards the end of the reaction, a mixture of the phenol and glycol was obtained. The residue in After treatment with bleaching earth and subsequent filtration, the reaction vessel consisted of a product, which in every respect resembled the material produced according to Example 1.

To produce the phosphite esters, the Use of alkaline catalysts together with high polymers !!! Polypropylene glycol used will.

Claims (3)

Patent claims: 1. Process for the precipitation of tertiary polypropylene glycol phosphites by transesterification in the presence of a catalyst, thereby characterized in that at least 3 moles of polypropylene glycol with 1 mole of a triaryl or ao trialkyl phosphites are implemented. 2. The method according to claim 1, characterized in that a diaryl or a catalyst Dialkyl phosphite or an alkaline catalyst is used. 3. The method according to claim 1 and 2, characterized in that a metal alcoholate is used as the catalyst or a metal phenate is used .. Considered publications:
German Auslegeschrift No. 1 075 584;
Kosolapoff, Organophosphorus Compounds, 1950, pp. 191 to 192;
Chemisches Zentralblatt, 1957, p. 9060 (A rbus ο w). 709 $ 08/321 1.67 © Biindesdiuckeiei Berlin