Synthetic resins or natural rubbers -- part of the class 520 ser – Synthetic resins – From phosphorus-containing reactant
Reexamination Certificate
2001-09-13
2003-10-07
Truong, Duc (Department: 1711)
Synthetic resins or natural rubbers -- part of the class 520 ser
Synthetic resins
From phosphorus-containing reactant
C528S398000, C528S403000, C528S421000, C528S487000
Reexamination Certificate
active
06630565
ABSTRACT:
The present invention relates to a phosphorus-comprising polyol. The invention also relates to an oligomer derived from this phosphorus-comprising polyol and to the composition comprising this phosphorus-comprising polyol and to the composition comprising this oligomer. The invention also relates to a polymer derived from this oligomer.
The invention also relates to processes for the preparation of this phosphorus-comprising polyol, of this oligomer, of this polymer and of this composition. The invention also relates to the uses of this phosphorus-comprising polyol, of this oligomer, of this polymer and of these compositions.
The composition which comprises the phosphorus-comprising polyol as constituent exhibits flame-retardant properties. The composition which comprises the oligomer can be cross-linked by irradiation and also exhibits flame-retardant properties.
The coatings industry is continually on the lookout for materials exhibiting an improved resistance to attacks and in particular an improved flame resistance.
Furthermore, this same industry is also on the lookout for materials which, while possessing the above improved resistance, are polymerisable in the form of a coating, as a thin or thick layer, while having recourse either to thermal curing or to one of the irradiation techniques, such as ultraviolet radiation or ionising radiation, such as gamma rays, X-rays or an electron beam.
Coatings having flame-retardant properties have already been obtained by polymerisation of compositions comprising phosphorus-comprising oligomers. Thus, U.S. Pat. No. 5,456,984 discloses a composition which can be polymerised by irradiation comprising an oligomer terminated by functional groups which can be copolymerised by irradiation, this oligomer being prepared from a polyisocyanate and a polyol comprising phosphorus in the phosphonate form, the oligomer reacting with a hydroxylated acrylate. The process for the preparation of the described composition is not easy, owing to the fact that the preparation of the polyol takes place in the presence of a solvent and a catalyst and that it is necessary to remove the water (abstract of Romanian Patent Application 88-134852 and abstract of Japanese Patent Application 81-48905) or the ethanol produced by azeotropic distillation and the solvent by vacuum distillation and the catalyst over a prolonged time.
Likewise, the preparation of another polyol (U.S. Pat. No. 5,456,984) comprising phosphorus in the phosphate and phosphonate form involves the use of alkylene oxides, the commonest of which are gases at atmospheric pressure, such as ethylene oxide, and therefore requires a specific industrial plant comprising appropriate reactors.
Furthermore, a phosphorus-comprising resin has already been described [D. Derouet, F. Morvan and J. C. Brosse, Journal of Applied Polymer Science, Vol. 62, 1855-1868 (1996)]; this resin has flame-retardant properties. The process for the preparation of this resin comprises the partial reaction between an epoxide compound, bisphenol A 4,4′-diglycidyl ether, and a dialkyl phosphate. The phosphorus-comprising epoxy resin which is thus prepared can be polymerised by heating in the presence of a cross-linking agent, such as a diamine (4,4′-diaminodiphenyl sulphone), and results in a composition having flame-retardant properties. However, this resin cannot be polymerised by irradiation and cannot therefore be applied to heat-sensitive substrates, such as fabrics, wood or paper. Furthermore, this polymerisation technique is expensive, on the one hand, in energy because of the heating and, on the other hand, in time, as the kinetics of polymerisation by heating are much slower than those by irradiation. Finally, a major disadvantage is the low content of phosphorus in the resin; the introduction of phosphorus into the epoxy resin takes place by opening the epoxide functional group and thus decreases the concentration of epoxide functional groups necessary for the polymerisation.
A demand therefore exists for a simple and economical process for the preparation of compounds of polyol type which comprise phosphorus atoms which can be used as starting material in the preparation of more complex compounds exhibiting flame-retardant properties.
To this end, the invention provides a process which does not require the presence of any solvent and of any catalyst. The separation of the final product from the solvent and catalyst is therefore unnecessary. It is not necessary to provide any separation and/or distillation stage. This simple process can therefore be employed at atmospheric pressure in a standard industrial plant. It is therefore particularly economical.
The invention provides a composition which has flame-retardant properties which are appreciably increased because of its phosphorus content. This composition can be cross-linked by irradiation and has flame-retardant properties. The composition of the invention can be applied to any type of substrate, such as, in particular, wood, textiles, paper and plastics, such as polyethylene and polypropylene.
The gases given off during the combustion of the composition according to the invention are less corrosive than those given off during the combustion of the known compositions which comprise halogens and consequently generate corrosive gases during the combustion. These corrosive gases, in addition to their toxic properties, cause significant damage to electronic components, present in particular in computers, which very often results in the loss of essential data and irreparable damage.
The invention provides a composition which makes it possible to obtain a coating which exhibits flame-retardant properties and good resistance to external conditions.
Furthermore, the invention provides a composition comprising one (or more) oligomer(s) having pendant phosphorus-comprising groups on the chain of this oligomer. This exhibits the advantage of avoiding cleavage of the chain during possible hydrolysis of this phosphorus-comprising group and of thus minimising the impact on the physicochemical and mechanical properties of the polymer obtained after cross-linking this composition by irradiation.
The present invention therefore overcomes the disadvantages of the known techniques.
To this end, the present invention provides a novel phosphorus-comprising polyol comprising at least two terminal phosphate ester groups or at least two terminal phosphonate ester groups or at least one terminal phosphate ester group and one terminal phosphonate ester group.
The term “polyol” is understood to mean a compound comprising at least two hydroxyl functional groups not bonded to the same carbon.
The term “terminal phosphate ester group” is understood to mean a group of general formula
in which R
1
and R
2
independently represent a substituted or unsubstituted, aliphatic, cycloaliphatic or aromatic radical having from 1 to 16 carbon atoms.
The phosphate ester groups can be identical or different and they are preferably identical. The R
1
and R
2
radicals can be identical or different and they are preferably identical.
The term “terminal phosphonate ester group” is understood to mean a group of general formula
in which R
1b
represents a hydroxyl radical, a substituted or unsubstituted oxyalkyl or oxyaryl radical having from 1 to 16 carbon atoms, or a hydrogen atom; and R
2b
represents a substituted or unsubstituted, aliphatic, cycloaliphatic or aromatic radical having from 1 to 16 carbon atoms.
The phosphonate groups can be identical or different and they are preferably identical. The R
1b
and R
2b
radicals are preferably identical.
The phosphorus-comprising polyol of the invention usually comprises from 2 to 10 terminal phosphate or phosphonate groups. It preferably comprises 2 or 8 terminal phosphate or phosphonate groups. Good results have been obtained when it comprises 2 terminal phosphate or phosphonate groups.
The phosphorus-comprising polyol of the invention is usually the reaction product of at least one polyoxirane and of at least one phosphorus-comprisi
Van Den Bergen Hugues
Vanovervelt Jean-Claude
Truong Duc
UCB S.A.
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