DD288828A5 - METHOD FOR MODIFYING POLYETHERAL COCOOLS - Google Patents

Abstract

The invention relates to a process for the modification of polyether alcohols which are used in particular for the preparation of polymer polyols and / or flame-resistant polyurethane flexible foams. According to the invention, melamine and a melamine polyether are added to the reaction mixture before and / or during the alkylene oxide addition. {Polyurethane; polyether; Method; fireproofing; Modification; Melamine}

Description

Field of application of the invention

The invention relates to a process for the modification of polyether alcohols, which are used in particular for the preparation of polymer polyols and / or flame-resistant flexible polyurethane foam.

Characteristic of the known state of the art

The preparation of polyether alcohols by addition of alkylene oxides, in particular of propylene and / or ethylene oxide at temperatures of 80 to 13O ⁰ C, pressures of 0.1 to 1.0 MPa, use of basic catalysts such as potassium hydroxide and using OH-functional starter substances such as polyvalent Alcohols, in particular of glycerol and / or ethylene glycol and addition of the alkylene oxides in the form of alkylene oxide blocks and / or in random arrangement with the starting substances for the preparation of high molecular weight polyethers, have long been known and frequently described prior art.

The production of certain starting substances and of a specific type and amount of n-alkylene oxide, as well as possible modifications by end-group conversion or, in particular, by certain additive and / or reactive additives, are always geared to a very specific application. Thus, in the preparation of Welchschaumpolyetheralkoholen particular glycerol and / or Ethylonr,! Ykol used as a starting substance and reacted to high molecular weights with propylene and ethylene oxide.

In the preparation or modification of foamed polyether alcohols having flame retardancy for polyurethane foams, additive additives such as e.g. Phosphorus compounds and / or halogen compounds, in particular phosphoric acid, phosphorus chloride and / or bromine compounds used.

Such compounds are also used additively or reactively after reactions to give polyesters or with alkylene oxides to give polyethers. These substances with flame retardant effect, with which, inter alia, high molecular weight polyethers are modified for flame retardancy, z. B. in DD-WP 125035 .. DD-WP 264118 or DE-OS 1518747 described. These additive flame retardants have only limited effects in the field of flexible polyurethane foams and bring considerable disadvantages as a result of their susceptibility to hydrolysis. Another possibility, bypassing the disadvantages mentioned above, is the additive addition of melamine to the polyether or to the system component and to the conversion to the polyurethane foam. Polyether alcohol are modified by the addition of melamine to control the curing of polyurothane, stabilizing or flame retardant. DE-AS 2200752 describes such melamine additives. A major disadvantage is the insolubility of melamine in the polyurethane system, in addition to dosing problems, it also leads to significant settling and thus concentration differences. An improvement in miscibility is, as set out in DE-OS 2118868, achieved by reaction with alkylene oxides in the presence of basic catalysts and Ν, Ν-dialkylamides as solvent. Because of the poor efficiency of the solvents, a proportion of greater than 20% of N, N-dialkylamide must be present in the solvent mixture, and this mixture is added to the reaction mixture at an excess of 50 to 95%.

Dorartigo procedures work very unrontabol, the solvent must have been elaborately entfornt, the Roaction with dom Alkoxylic oxide is incomplete and residual traces of solvents interfere with use in the polyurethane system. Dor in

DE-OS 3412082 way, melamine umzusotzon in the presence of alcohols without catalysts with alkoxide is

Although passable, but only with a Uborschuß of alcoholic substances ontsprechondo Umsotzungsproduktonergostollt be.

Thus, the character of the reaction products is predominantly goprflgt from the coinitiator substance, and olno Polyethormodifizlorung with respect to Flammfostmachung by Verbossorung dor Homogenisierung of Polyothor / Melamine blending is not achieved. Completely disregarded remains the preparation or modification of Polyether alcohols for use in the preparation of polymorpolyols boi simultaneous molamine use. By dio reaction without addition of catalyst is only olno tollwolse Alkoxyllorung up to OH-Zahlon 210 to 640mg KOH / g

possible. For use in the production of polyurothane foam polyethor or polymorpolyl ionlon insbosondorehigh molecular weight polyethers with OH number less than 60 mg KOH / g used, these are with the above mentioned

Process variant can not be produced. Also boi use of glycol-Polyethoralkoholo with Molgowlcht to 500 are weighed from it horgostollton polyothoric alcohols

the high diolantoil only limited use in the field of flexible polyurethane foam.

Object of the invention

The aim of the invention is to develop a simple process for the modification of polyether alcohols by melamine addition, which can be used for the production of flame retardant polyurethane flexible foams.

Explanation of the essence of invention The invention is based on the object, an ancestor for the modification of polyether alcohols by melamine addition

develop, which takes place at the customary to Polyetherherstellung Reaktlonsbodingungen and without solvent.

According to the invention, the object is achieved in that before and / or during the basal-catalysed addition of Alkylene oxide in addition to the melamine as a special Koinitlator a Melaminpolyethor with a functionality of 3 to 6 in one Amount ratio of melamine: Melaminpolyether of 10: 1 to 1:10 is added. For modification, polyether alcohols are used which are obtained by addition of alkylene oxides, in particular propylene

and / or ethylene oxide at temperatures of 80 to 130 ° C pressures of 0.1 to 1.0 MPa of OH-functional starter substance, in particular of glycerol and / or ethylene glycol are prepared using melamine, wherein the alkylene oxides in

Form of a blockwise addition and / or addition are implemented as a statistical mixture. The modification of the polyether production by adding a Melaminpolyethers next to melamine may optionally with the addition

a further polyether in the form of a prepolymer or a Fertigpolyethors based on a triol such as glycerol or a

Triol / diol mixture such as a glycerol / ethylene glycol mixture or höhorfunktionoller alcohols »and alkylene oxide combined

become. The melamine polyether used as a special Kolnitiator is a Umsotzungsprodukt of melamine optionally in the presence of

OH-functional Koinitiatoren with alkylene oxides and is in particular as a basic reaction product of melamine Alkylene oxide used. Üio addition of alkylene oxide for the preparation of the modified polyether is particularly by the addition of Potassium hydroxide in the usual amount of 0.1 to 0.5% potassium hydroxide performed in finished polyether. The implementation

in particular for the production of high molecular weights is carried out over one or more prepolymers, wherein the

Vorpolymcrisatstufen if necessary, a monomer between propylene oxide and ethylene oxide and / or between blockweiscr

and statistical attachment can take place.

With addition of the melamine polyether next to the melamine during the Alkylenoxidanlagerung this addition is particular

take place at Vorpolymorisatstufen.

With addition of the melamine polyether next to the melamine during the Alkylenoxidanlagerung this addition is particular

take place at the Vorpolymerisatstufen.

After the end of the Alkylenoxiddosierung a post-reaction phase is connected at 120 ° C and finally the Crude polyether when using potassium hydroxide as a catalyst by acid neutralization, vacuum distillation and filtration

cleaned.

The method according to the invention has several advantages. This makes it possible for the first time, polyethers for a flameproof equipment

to modify with melamine, without the added melamine settles by gravity. This partially reactive

Einlassung or partial redemption of melamine in high molecular weight polyethers allows their immediate further processing,

e.g. to polymer polyols and / or polyurethane systems.

The usual intensive mixing of the modifier melamine is eliminated, it can also completely without inert or

functionally solvent or Koinitiatoren be worked.

Embodiment 1

In a 1.5-liter autoclave with stirrer, temperature and pressure measurement and a metering device for alkylene oxides are successively 100g melamine, 3g solid potassium hydroxide and 100g of a basic melamine polyether based on melamine, glycerol and propylene oxide with an alkalinity of 0.3% potassium hydroxide filled, purged with nitrogen and heated to 115 ° C.

After reaching the temperature successively 800ml of propyl oxide cindoelort and reacted and then 100ml ethylene oxide angolagort. After completion of the alkyoxylation, olefin post-lactation is completed, and the homogrown crude polyether is gorelled as usual by acid extraction, vacuum distillation, and filtration

Hydroxyl number = 62 Water content = 0.1%

, Viscosity at 25 ⁰ C = 57OmPa-S

and can be encapsulated in the base poly-homopolymer for the preparation of polypolyol,

Implementation Guide 2

In a 1.5-liter autoclave according to Ausführungsbolspiol 1 100g melamine, 100g of a basic prepolymer of glycine, ethylene glycol and propylene oxide having a molecular weight of 900.60g of a Molamlnpolyotheraus melamine and propyl oxide and 2g solid potassium hydroxide are charged, purged with nitrogen and warmed to 12O ⁰ C. After reaching the temperature, a mixture of 800 ml of propylene oxide and 200 ml of ethylene oxide was metered in successively and reacted. After a usual cleaning the Fortigpolyether has the following characteristics:

Hydroxyl number - 48 Water content = 0.1% Viscosity at 25 ° C = 68OmPa-S

and is directly useable for the preparation of polymorphol.

Implementation Bills 3 In a 1.5 liter autoclave are successively 20 g of melamine, 60 g of glycerol, 10 g of ethylene glycol, 50 g of basic melamine polyether

from melamine, glyzorol, ethylene glycol and propylene oxide with an alkalinity of 0.25% potassium hydroxide and 2g solid

Filled with potassium hydroxide, purged with nitrogen and heated. After reaching a temperature of 12O ⁰ C successively 900 ml Prcpylonoxid be metered. The resulting A prepolymer having a molecular weight of about 1000 is filled in and 100 g of it are orneut filled and with 800 ml Propylene oxide and finally reacted 200 ml of ethylene oxide. After a usual cleaning, the finished polyethor the following Key figures:

hydroxyl , .. mg KOH = Jo g water content = 0.1% Viscosity at 25 ° C = 49OmPa -s

and can be used directly for the production of flame-retardant flexible foam systems.

Embodiment 4 In a 1.5-liter autoclave successively 100g melamine, 200g o Alkaline Fertigpolyethers based on glycerol, Ethylene glycol, propylene oxide and ethylene oxide having a total alkalinity of 0.3% potassium hydroxide and 50 g of an alkaline Melamine polyethers based on melamine, glycerol and propylene oxide with a gas katte alkalinity of 0.2% potassium hydroxide

filled, purged with nitrogen and heated to 12O ⁰ C.

At this temperature, a mixture of 800 ml of propylene oxide and 200 ml of ethylene oxide is metered in and reacted

brought. After a standard cleaning, the finished polyether has following Konnzahlen:

Hydroxyl number = 38 Water content = 0.1% Viscosity at 25 ⁰ C = 52OmPa-S

and is useful for the preparation of polymer polyol.

Claims (5)

1. A process for the modification of polyether alcohols by addition of alkylene oxides, in particular of propylene and / or ethylene oxide at temperatures of CO to 13O ⁰ C and pressures of 0.1 to 1.0 MPa to OH-funktlonelle Startsubstanzon, in particular glyzorol and / or Ethylene glycol with addition of the alkylene oxides in the form of a blockwise addition and / or addition as a random mixture using melamine and the addition of special Koinitiatoren, characterized in that before and / or during the basic catalyzed addition of alkyne oxides in addition to the melamine as a special Koinitiator a Molaminpolyether with a functionality of 3 to 6 in (linear ratio of melamine: Molaminpolyether of 10: 1 to 1:10 is added. 2. The method according to claim 1, characterized in that as melamine polyether a reaction product of melamine is optionally used in the presence of OH-functional Koinitiatoren with alkoxide oxides. 3. The method according to claim 1, characterized in that is used as the melamine polyether, in particular a basic reaction product of melamine with alkylene oxide. 4. The method according to claim 1, characterized in that further Polye.ner be used in the form of prepolymers or ready polyethers based on a triol such as glycerol or a triol / diol mixture such as a glycerol / Eihylenglykolgemisches or higher alcohols and alkylene oxides together with the melamine polyether can. 5. The method according to claim 1, characterized in that on addition of the melamine polyether during the Alkylenoxidanlagerung this addition is carried out in particular to Vorpolymerisationstufen.