DE102008014115A1 - 6-Amino- (6H) -dibenzo [c, e] [1,2] oxaphosphorines, process for their preparation and their use as flame retardants for epoxy resins - Google Patents

Abstract

Preparation of a substituted 6-amino-(6H)-dibenz[c,e][1,2]-oxazaphosphorine compound (VI), comprises transamination of an 6-alkylamino-(6H)-dibenz[c,e][1,2]-oxazaphosphorine compound (IVa) using an amine compound (a). Preparation of a substituted 6-amino-(6H)-dibenz[c,e][1,2]-oxazaphosphorine compound of formula (VI), comprises transamination of an 6-alkylamino-(6H)-dibenz[c,e][1,2]-oxazaphosphorine compound of formula (IVa) using an amine compound of formula (R1-NH-X-N(R2)-R5) (a). X : arylene, alkylene, cycloalkylene, bisarylene, bisarylenealkylene, ketone or its derivative, imine, carbonate, O, bisaryleneoxide, sulfide, sulfoxide, sulfone, amine, phosphor derivate or silicon derivative; R1, R2 : alkyl, cycloalkyl or aryl (all optionally substituted), allyl, aryl, H, arylalkyl, heteroaryl or heterocycloalkyl; R3, R4 : H, alkyl, cycloalkyl or aryl; n : 0-5; and R5 : R2 or R3. Independent claims are included for: (1) the substituted 6-amino-(6H)-dibenz[c,e][1,2]-oxazaphosphorine compound (VI); and (2) use of 6-amino-(6H)-dibenz[c,e][1,2]-oxazaphosphorine compounds of formulae (IV) and (V), and (VI) as flame retardant. [Image] [Image].

Description

All Documents cited in the present application are by reference fully incorporated into the present disclosure (= incorporated by reference in their entirety).

The present invention relates to 6-amino- (6H) -dibenzo [c, e] [1,2] oxaphosphorines, Process for their preparation and their use as flame retardants.

State of the art:

Organophosphorus compounds are increasingly being used as environmentally friendly and efficient flame retardants for epoxy resins and epoxy resin composites. As flame retardants for these materials in particular 6H-dibenz [c, e] [1,2] -oxaphosphorin-6-oxide (DOPO), some of its derivatives and metal phosphinates and hydroxy-terminated phosphonates ( P. Jain, V. Choudhary, IK Varma, Flame Retardant Epoxies with Phosphorus, J. Makromol. Sci.-Polym. Rev. 2002, C42, 139-183 ; Brochure "Halogen-free Flame Retardants in E & E Applications", M. Döring, J. Diederichs, 2007 ). The structures of some flame retardants are listed below:

So far is the use of organophosphorus compounds as a flame retardant For epoxy resins, a deterioration of the material properties inevitable. At the same time, application-relevant parameters become important such as B. the glass transition temperature, the decomposition temperature and the impact resistance of the epoxy resins significantly reduced. This undesirable influence occurs when phosphorus-containing Additives such. As metal phosphinates are used, but also when reactive flame retardants such. DOPO, DOPO derivatives or hydroxy-terminated phosphonates used as flame retardants become.

It It is therefore desirable to use efficient phosphorus-containing flame retardants to develop that can be produced inexpensively, but almost no deterioration of valuable parameters of Cause epoxy resins.

Known preparation methods for 6-amino- (6H) -dibenz [c, e] [1,2] -oxaphosphorines IV and V (see below) are the reaction of 6-chloro- (6H) -dibenz [c, e] [ 1,2] -oxaphosphorines or 6-amino- (6H) -dibenz [c, e] [1,2] -oxaphosphorines with amines according to EP 0 005 441 A1 ,

links of the general structure VI have not been described so far.

Desirable is also an access to the compounds of structure VI.

Task:

task The present invention is novel 6-amino- (6H) -dibenz [c, e] [1,2] oxaphosphorines and to provide.

Further It is an object of the present invention, efficient synthesis for the preparation of substituted 6-amino- (6H) -dibenzo [c, e] [1,2] oxaphosphorines provide.

As well It is an object of the present invention to provide efficient flame retardants, especially for epoxy resins and epoxy resin composites, to provide.

Solution:

These Task is performed by the procedures, the substances and the uses according to the Claims solved.

Definition of terms:

in the The scope of the present invention are all amounts, if not stated otherwise, to be understood as weight data.

in the In the context of the present invention, the term "room temperature" means a Temperature of 20 ° C. Temperatures are, if not otherwise stated, in degrees Celsius (° C).

Provided unless otherwise stated, the reactions cited or process steps at normal pressure (atmospheric pressure) carried out.

in the In the context of the present invention, the term "composites" means physical and / or chemical mixtures or compounds of polymers, copolymers or mixtures of polymers or copolymers with at least 10 Wt .-% of one or more inorganic substances. inorganic Substances that may be included are preferably pigments, Fillers and / or glass fibers of various lengths and Diameter.

Detailed description:

worin die Variablen die folgenden Bedeutungen haben:
X Arylen, Alkylen, Cycloalkylen, Bisarylen, Bisarylenalkylen, -keton und derivate, -imin, -carbonat, Sauerstoff, Bisarylenoxid, -sulfid, -sulfoxid, -sulfon, -amin, -phosphorderivate, -siliciumderivate
R₁-R₂ H, Alkyl, Cycloalkyl, Allyl, Aryl, Arylalkyl, substituierte Alkyl, Cycloalkyl und Aryl, Heteroaryl, Heterocycloalkyl).
R₃-R₄ H, Alkyl, Cycloalkyl, Aryl
R₅ wie R₂ und R₃.The invention relates to 6-amino- (6H) -dibenz [c, e] [1,2] oxaphosphorines of the general formula VI

wherein the variables have the following meanings:
X is arylene, alkylene, cycloalkylene, bisarylene, bisarylenealkylene, ketone and derivatives, iminine, carbonate, oxygen, bisarylene oxide, sulfide, sulfoxide, sulfone, amine, phosphorus derivatives, silicon derivatives
R ₁ -R ₂ H, alkyl, cycloalkyl, allyl, aryl, arylalkyl, substituted alkyl, cycloalkyl and aryl, heteroaryl, heterocycloalkyl).
R ₃ -R ₄ H, alkyl, cycloalkyl, aryl
R ₅ such as R ₂ and R ₃ .

durch Transaminierung von Stoffen der allgemeinen Formel IVa.

gemäß Gleichung (C3)

worin die Variablen die oben angegebenen Bedeutungen haben.The invention also provides a process for the preparation of 6-amino- (6H) -dibenz [c, e] [1,2] oxaphosphorines of the general formula VI

by transamination of substances of general formula IVa.

according to equation (C3)

wherein the variables have the meanings given above.

worin die Variablen die oben angegebenen Bedeutungen haben, als Flammschutzmittel, insbesondere für bzw. in Epoxidharzen oder epoxidharzhaltigen Mischungen, Epoxidharz-Verbundmaterialien und/oder Kompositen.Further, the use of 6-amino- (6H) -dibenz [c, e] [1,2] oxaphosphorines of the general formulas IV, V, VI

wherein the variables have the meanings given above, as flame retardants, in particular for or in epoxy resins or epoxy resin-containing mixtures, epoxy resin composite materials and / or composites.

Another The present invention relates to epoxy resins or epoxy resin-containing Containing mixtures, epoxy resin composites and / or composites Compounds of the general formulas IV, V, VI.

in the Within the scope of the present invention, 6-chloro (6H) -dibenzo [c, e] [1,2] oxaphosphorines first with low-boiling alkylamines into the 6-alkylamino- (6H) -dibenzo [c, e] [1,2] oxaphosphorines IVa are converted (equation B4).

The Compounds of the general formula IVa can then subsequently with less volatile amines or diamines to the compounds VI are implemented (equation C3).

These Transaminations according to equation C3 are new reactions; the synthesis of VI by transamination of IVa was so far unknown.

The Suitability of compounds IV, V, VI as flame retardants for Epoxy resins and epoxy resin composites which optionally fiber reinforced, was so far unknown. These substances have a structural similarity to the DOPO system, however, differ from this by the Binding of nitrogen to the phosphorus atom.

The Compounds of the general formulas IV, V, VI can accordingly be described as Flame retardants, in particular for epoxy resins and epoxy resin composite materials, be used.

These Substances show even at relatively low concentrations very good flame retardant effect as well as a very extreme little influence on the mechanical properties of the materials.

6-amino- (6H) -dibenz [c, e] [1,2] oxaphosphorins general structure VI have not been previously described and are new.

The reaction according to the invention (C3) proceeds with nearly quantitative yields.

The Compounds of general formulas IV, V, VI are efficient flame retardants for high performance epoxy resins and for these based composites.

you particular advantage is that they are important parameters of this Materials do not influence or only minimal influence, z. For example, they have little influence on the glass transition and decomposition temperatures.

The various embodiments of the present invention, for. B. those of the various dependent claims, can be combined with each other in any way become.

QUOTES INCLUDE IN THE DESCRIPTION

This list The documents listed by the applicant have been automated generated and is solely for better information recorded by the reader. The list is not part of the German Patent or utility model application. The DPMA takes over no liability for any errors or omissions.

Cited patent literature

• - EP 0005441 A1 [0006]

Cited non-patent literature

• P.Jain, V. Choudhary, IK Varma, Flame Retardant Epoxies with Phosphorus, J. Makromol. Sci.-Polym. Rev. 2002, C42, 139-183 [0003]
• - Brochure "Halogen-free Flame Retardants in E & E Applications", M. Döring, J. Diederichs, 2007 [0003]

Claims (6)

Process for the preparation of 6-amino- (6H) -dibenz [c, e] [1,2] oxaphosphorines of the general formulas VI

from substances of the general formula IVa

by transamination according to equation (C3);

where X = arylene, alkylene, cycloalkylene, bisarylene, bisarylenealkylene, ketone and derivatives, iminine, carbonate, oxygen, bisarylene oxide, sulfide, sulfoxide, sulfone, amine, phosphorus derivatives, -silicon derivatives R ₁ -R ₂ = H, alkyl, cycloalkyl, allyl, aryl, arylalkyl, substituted alkyl, cycloalkyl and aryl, heteroaryl, heterocycloalkyl). R ₃ -R ₄ = H, alkyl, cycloalkyl, aryl R ₅ such as R ₂ and R ₃ . Process according to Claim 1, characterized in that the compound of the general formula IVa is obtained by reacting 6-chloro (6H) -dibenz [c, e] [1,2] oxaphosphorines according to equation (B4)

will be produced. Compounds of the general formula VI. Use of the substances of the general formulas IV, V, VI

as a flame retardant. Use according to claim 4, as a flame retardant for or in epoxy resins or epoxy resin-containing mixtures and / or composites. Epoxy resins or epoxy resin-containing mixtures and / or Composites comprising compounds of the general formulas IV, V, VI.