Patent Application
20100168295
The invention relates to compositions comprising fluorocarbon or siloxane terminated polycarbonates and to a process for imparting flame retardancy to a polymer substrate comprising polycarbonates and fluorocarbon terminated polycarbonates.
Polycarbonates are thermoplastic polymers of high toughness, outstanding transparency, excellent compatibility with several polymers, and high heat distortion resistance. Polycarbonates correspond to the general formula
The economically most important polycarbonate is 2,2-bis(4-hydroxyphenyl)propane polycarbonate (1), also termed bisphenol A polycarbonate [24936-68-3] (BPA-PC):
cf. Ullmann's Encyclopaedia of Industrial Chemistry, On-Line Edition, Wiley-VCH, DOI: 10.1002/14356007.a21—207, and entry Polycarbonate, Roempp On-line, www.roempp.com.
Various additives for improving the mechanical, chemical and thermal properties of polycarbonates are known. Fluorocarbon terminated poly-carbonates are useful for various technical applications, such as reducers of surface energy, “surface modifiers”, for organic materials, preferably polycarbonates, polyesters, polyacrylates or polymethacrylates or their mixtures, blends or alloys. Polymers with such a reduced surface energy possess desirable properties, such as “easy to clean”, “self-cleaning”, “antisoiling”, “soil-release”, “antigraffiti”, “oil resistance”, “solvent resistance”, “chemical resistance”, “self lubricating”, “scratch resistance”, “low moisture absorption” and “hydrophobic” surface. The preparation of particularly useful fluorocarbon terminated polycarbonates is described in the International Patent Application No. PCT/EP2004/053331.
Flame retardants are added to polymeric materials (synthetic or natural) to enhance the flame retardant properties of the polymers. Depending on their composition, flame retardants may act in the solid, liquid or gas phase either chemically, e.g. as a spumescent by liberation of nitrogen, and/or physically, e.g. by producing a foam coverage. Flame retardants interfere during a particular stage of the combustion process, e.g. during heating, decomposition, ignition or flame spread.
The addition of flame retardants to polycarbonates is known, cf. J. Troitzsch, Plastics Flammability Handbook, 3rd edition, Hanser Publishers, Munich 2004, pp. 158-172 (ISBN 3-446-21308-2).
Alkali metal, earth alkali metal or ammonium salt-based flame retardants are particularly suitable at low concentrations. Among these salts, perfluoroalkane sulphonates belong to the more efficient ones. Their use as flame retardants in polycarbonates has been known; cf. T. Ishikawa et al., Journal of Macromolecular Science, Part A-Pure and Applied Chemistry, Vol. A41, No. 5, pp. 523-535, 2004.
In applications where a sample thickness smaller or equal than 1.6 mm is required, a flame retardancy of V-0, according to UL-94 (Underwriter's Laboratories Subject 94), is only obtained by the addition of an anti-dripping agent, such as polytetrafluoroethylene (PTFE). However, these anti-dripping agents cause in flame retardants containing polycarbonates a considerable decrease or even loss of light transparency. An excellent light transparency of polycarbonates is a crucial factor in most of its technical applications, such as glazings, partition walls, lamp covers, front panels, etc.
Other co-additives for flame retardants have been proposed, such as haloarylphosphates, cf. U.S. Pat. No. 5,478,874 or guanidine salts; cf. U.S. Pat. No. 6,518,340. The addition of polysiloxanes of different structures has been proposed in various references; cf. U.S. Pat. Nos. 6,660,787, 6,727,302 or 6,730,720. A problem of these additives is seen in the fact that the concentration of the flame retardant must be increased to arrive at the V-0 classification, which is detrimental to the mechanical, chemical and thermal properties of polycarbonates.
Therefore, the present invention relates to finding suitable additives, which are applicable in polycarbonates in combination with flame retardants at low concentrations.
It has surprisingly been found that fluorocarbon or siloxane terminated polycarbonates are suitable compatibilizing and anti-dripping agents for transparent, flame-retarded polycarbonates, even at low concentrations. Like the flame retardants of first choice, such as alkali metal, earth alkali metal or ammonium salt-based flame retardants, fluorocarbon and siloxane terminated poly-carbonates are present in small quantities in the polycarbonates and, due to the low dosing levels, have no significant negative effect on polymer mechanics and other properties.
The present invention relates to a composition, particularly a flame retardant composition, which comprises
According to an alternative embodiment the present invention relates to a composition, particularly a flame retardant composition, which comprises
A further embodiment of the invention relates to a composition, particularly a flame retardant composition, which comprises
The compositions according to the invention attain the desirable V-0 rating, according to UL-94 (Underwriter's Laboratories Subject 94) and other excellent ratings in related test methods while preserving the excellent mechanical, chemical and thermal properties of polycarbonates, such as light transparency.
The composition, as defined above, comprises the following components:
A salt of an acid selected from the group consisting of aromatic carboxylic acids, aromatic sulphonic acids, perfluoroalkanesulphonic acids, phosphorus containing oxo acids, NH-acidic sulphonamides, NH-acidic sulphonimides and complex fluoro acids is preferably a metal salt, for example an alkali metal or alkaline earth metal salt, e.g. the sodium, potassium, calcium salt.
According to an alternative embodiment, the term salts comprises non-metallic salts, e.g. ammonium, (C1-C22alkyl)1-4ammonium or (2-hydroxyethyl)1-4ammonium, e.g. tetramethylammonium, tetraethylammonium or the 2-hydroxyethyltrimethylammonium salt.
The term salt of an aromatic carboxylic acid preferably comprises alkali metal salts of benzoic or terephthalic acid, such as the sodium or potassium salt of terephthalic, dichlorobenzoic or trichlorobenzoic acid.
The term salt of an aromatic sulphonic acid comprises alkali metal salts of benzene, toluene, naphthalene sulphonic acids, such as the sodium or potassium salt of benzene, toluene or naphthalene sulphonic acid.
The term salt of a perfluoroalkanesulphonic acids comprises non-metallic salts, e.g. ammonium or (C1-C22alkyl)1-4ammonium salts, e. g. the tetraethylammonium salt, or alkali metal salts, e.g. the sodium or potassium salt of perfluoro-C1-C8alkanesulphonic acid (CnF2n+1SO3H), particularly perfluoro-C1-C4alkanesulphonic acid, e.g. perfluoromethanesulphonic acid or perfluoro-n-butanesulphonic acid.
According to a preferred embodiment of the invention the composition comprises as component a) the alkali metal salt, e.g. the sodium or potassium salt of perfluoro-C1-C4alkanesulphonic acid.
According to a highly preferred embodiment of the invention the composition comprises sodium or potassium perfluorobutanesulphonate (C4F9SO3−Na+, KFBS, Rimer salt).
The term salt of a phosphorus containing oxo acid comprises alkali metal or ammonium salts of a phosphorus containing oxo acid selected from the group consisting of meta-phosphoric, ortho-phosphoric or polyphosphoric acid, phosphonic acid, phosphinic acid and partial esters thereof. According to an alternative embodiment, the oxygen in the phosphorus containing oxo acid is partially or completely replaced by sulphur (thio derivatives).
Metaphosphoric acid is the condensation product derived from the monomeric meta-phosphoric acid HPO3, as represented by the formula (HPO3)p, wherein p represents a numeral of at least three, preferably 3-100. Preferred is metaphosphoric acid, wherein p represents 3 or 4 (cyclic structures).
Polyphosphoric acid is the condensation product of ortho-phosphoric acid H3PO4, as represented by the formula HO(PO3)pH, wherein p represents a numeral of at least two, preferably 3-100.
The term phosphonic acid comprises within its scope derivatives of phosphonic acid HP(═O)(OH)2, wherein the hydrogen atom which is directly attached to the phosphorus atom is substituted by an organic substituent, particularly C1-C6alkyl, aryl, e.g. phenyl, aryl-C1-C4alkyl, e.g. benzyl or 1- or 2-phenethyl, or (C1-C4alkyl)1-3aryl.
Examples of phosphonic acids are represented by the structural formula
in which
R1 represents a linear or branched C1-C6alkyl radical, or a phenyl radical; and
R2 represents hydrogen, a linear or branched C1-C6alkyl radical, or a phenyl radical.
The term phosphonic acid also comprises within its scope ester derivatives of phosphorous acid P(OH)3, which is the tautomeric form of phosphonic acid HP(═O)(OH)2. The term ester derivatives comprises the ester of phosphorous acid P(OR)3 or the partial esters P(OH)2OR and POH(OR)2, wherein R is an organic substituents, particularly C1-C6alkyl, aryl, e.g. phenyl, aryl-C1-C4alkyl, e.g. benzyl or 1- or 2-phenethyl, or (C1-C4alkyl)1-3aryl.
Examples of such phosphonic acids are represented by the formula
Wherein
One of R1, R2 and R3 represents hydrogen and two of R1, R2 and R3 represent a linear or branched C1-C6alkyl radical, or a phenyl radical; or
Two of R1, R2 and R3 represent hydrogen and one of R1, R2 and R3 represent a linear or branched C1-C6alkyl radical, or a phenyl radical; or
R1, R2 and R3 represent a linear or branched C1-C6alkyl radical, or a phenyl radical.
The term phosphinic acid comprises within its scope derivatives of phosphinic acid, H2P(═O)OH, wherein one or two hydrogen atoms, which are directly attached to the phosphorus atom, have been substituted by organic substituents, particularly C1-C6alkyl, aryl, e.g. phenyl, aryl-C1-C4alkyl, e.g. benzyl or 1- or 2-phenethyl, or (C1-C4alkyl)1-3aryl.
Examples of phosphinic acids are represented by the structural formulae
in which
R1, R2 represents a linear or branched C1-C6alkyl radical, or a phenyl radical; and
R3 represents a linear or branched C1-C10alkylene, arylene, alkylarylene, or arylalkylene radical.
The term phosphinic acid comprises within its scope the tautomeric form HP(OH)2, wherein the hydrogen atom which is directly attached to the phosphorus atom is substituted by an organic substituent, particularly C1-C6alkyl, aryl, e.g. phenyl, aryl-C1-C4alkyl, e.g. benzyl or 1- or 2-phenethyl, or (C1-C4alkyl)1-3aryl.
A phosphorus containing oxo acid, wherein the oxygen is partially or completely replaced by on or two sulphur atoms (thio derivatives) is, for example, thiophosphonic acid HP(═S)(OH)2 or dithiophosphonic acid HP(═O)(SH)2 or HP(═S)(SH)(OH). The hydrogen atoms are partially or fully substituted by the organic groups as defined above.
The term salt of NH-acidic sulphonamides and sulphonimides comprises within its scope alkali metal or ammonium salts of sulpho substituted amides of the general formula
R1SO2NHR2 and imides of the general formula R1SO2NHSO2R2, wherein R1 and R2independently of one another represent organic substituents, such as C1-C6alkyl, aryl, e.g. phenyl, aryl-C1-C4alkyl, e.g. benzyl or 1- or 2-phenethyl, (C1-C4alkyl)1-3aryl, a heterocyclic group, such as thiazolyl or pyrimidinyl, or a heterocyclic group substituted by C1-C4alkyl.
Representative examples of NH-acidic sulphonamides and sulphonimides are N-methyl-p-toluene sulphonamide, benzene sulphonamide, p-toluene sulphonamide, N-(p-toluene sulphonic)-p-toluene sulphimide, N-(N′-benzylaminocarbonyI)-sulphanilimide, N-(phenylcarboxyl)-sulphanilimide, N-(2-pyrimidinyl)sulphanilimide or N-(2-thiazolyl)sulphanilimide.
The term salt of a complex fluoro acid comprises within its scope alkali metal salts of complex fluoro acids of aluminum, boron or antimony. Representative examples are sodium hexafluoroaluminate or sodium tetrafluroboranate.
According to a preferred embodiment the composition comprises as component a) at least one alkali metal, earth alkali metal or ammonium salt of an acid selected from the group consisting of aromatic carboxylic acids, aromatic sulphonic acids, perfluoroalkanesulphonic acids, phosphorus containing oxo acids or partial esters thereof, NH-acidic sulphonamides, NH-acidic sulphonimides and complex fluoro acids.
According to a particularly preferred embodiment the composition comprises as component a) at least one alkali metal, earth alkali metal or ammonium salt of a perfluoroalkanesulphonic acid or an alkali metal, earth alkali metal or ammonium salt of a phosphorus containing oxo acid selected from the group consisting of meta-phosphoric, ortho-phosphoric or polyphosphoric acid, phosphonic acid, phosphinic acid and partial esters thereof.
The acids and their salts, as defined above, are known compounds.
Component b1)
In the compound (I), as defined above, the substituents are defined as follows:
R1 and R2 independently of one another represent an aliphatic group substituted by fluorine;
X1 and X2 independently of one another represent the direct bond or C1-C12alkylene;
m represents a numeral from 1 to 1000;
R5, R6, R7 and R8 independently of one another represent hydrogen, C1-C12alkyl or C3-C12alkenyl; and
Y represents the direct bond or a bivalent group selected from the group consisting of
Both Ra and Rb represent hydrogen or halogen; or
One of Ra, and Rb represents hydrogen and the other one represents halogen;
R3 and R4, together with the carbon atom to which they are bonded, form a C5-C8-cycloalkylidene group with 1 to 3 C1-C4alkyl groups as optional substituents; or
R3 and R4 independently of one another represent hydrogen, an aliphatic group substituted by fluorine, C1-C12alkyl, C1-C12alkyl substituted by carboxy, C2-C12alkenyl, aryl, or the group (A), as defined above, wherein n represents a numeral from 0-10 000 and X2, Y, R2, R5, R6, R7 and R8 are as defined above.
R1 and R2 defined as an aliphatic group substituted by fluorine is preferably a straight chain or branched or hydrocarbon group, which contains at least one fluoro atom with at least one hydrogen atom remaining, for example C1-C25fluoroalkyl, or is a perfluoroalkyl group of the partial formula
—(CF2)pF (B),
wherein p is a numeral from 1 to 100.
C1-C25Fluoroalkyl is for example, mono- or difluoromethyl, 2-fluoroethyl, 3-fluoropropyl, 4-fluorobutyl, 5-fluoropentyl, 6-fluorohexyl, 7-fluoroheptyl or pentafluorobutyl.
Perfluoroalkyl is a group (B) derived from the perfluoro alcohol F(CF2)p—OH wherein p is 1 to 50, for example trifluoromethyl (p=1) or pentafluoroethyl (p=2). Preferred perfluoroalkyl groups are derived form perfluoro alcohols wherein p is 5, 8, 9 or 11.
X1 and X2 defined as C1-C12alkylene is a branched or unbranched bivalent group, for example methylene, ethylene, propylene, trimethylene, tetramethylene, pentamethylene, hexamethylene, heptamethylene, octamethylene, decamethylene or dodecamethylene. One of the preferred definitions for X1 and X2 is C1-C8alkylene, for example C2-C8alkylene. An especially preferred definition for X1 and X2 is C2-C4alkylene, for example ethylene.
R5, R6, R7 and R8 defined as C1-C12alkyl is a straight chain or, where possible, branched radical, for example methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, 2-ethylbutyl, n-pentyl, isopentyl, 1-methyl pentyl, 1,3-dimethylbutyl, n-hexyl, 1-methylhexyl, n-heptyl, isoheptyl, 1,1,3,3-tetramethylbutyl, 1-methylheptyl, 3-methyiheptyl, n-octyl, 2-ethylhexyl, 1,1,3-trimethylhexyl, 1,1,3,3-tetramethylpentyl, n-nonyl, n-decyl, n-undecyl, 1-methylundecyl or n-dodecyl. One of the preferred definitions is, for example, C1-C8alkyl, for example C1-C4alkyl, such as methyl.
R5, R6, R7 and R8 defined as C3-C12alkenyl is a straight chain or, where possible, branched radical, for example allyl, 2-butenyl, 3-butenyl, isobutenyl, n-2,4-pentadienyl, 3-methyl-2-butenyl, n-2-octenyl, n-2-dodecenyl or iso-dodecenyl.
Y defined as a bivalent group of the partial formula
is preferably methylene (CH2═, Ra and Rb═H). According to alternative embodiments, both Ra, and Rb represent hydrogen or halogen, for example chlorine or bromine, or one of Ra and Rb represents hydrogen and the other one represents halogen.
R3 and R4 defined as a C5-C8-cycloalkylidene group with 1 to 3 C1-C4alkyl groups as optional substituents is, for example, cydopentylidene, methylcyclopentylidene, dimethylcyclopentylidene, cyclohexylidene, methylcyclohexylidene, dimethylcydohexylidene, trimethylcyclohexylidene, tert-butylcyclohexylidene, cycloheptylidene or cydooctylidene. Preference is given to cyclohexylidene.
R3 and R4 defined as an aliphatic group substituted by fluorine is for example C1-C25fluoroalkyl, as defined above, or is the above-mentioned perfluoroalkyl group (B), wherein p is 1 to 50.
R3 and R4 defined as C1-C12alkyl is as defined above with regard to R5, R6, R7 and R8.
R3 and R4 defined as C1-C12alkyl substituted by carboxy is, for example, carboxymethyl or 1- or 2-carboxyethyl.
R3 and R4 defined as aryl is preferably phenyl or 1- or 2-naphthyl.
In the group (A) the index n represents a numeral from 0-10 000 and X2, Y, R2, R5, R6, R7 and R8 are as defined above.
Of particular interest are compounds (I), wherein
R1 and R2 independently of one another represent an aliphatic group substituted by fluorine;
X1 and X2 independently of one another represent C1-C12alkylene;
m represents a numeral from 1 to 1 000;
R5, R6, R7 and R8 represent hydrogen;
Y represents the bivalent group
wherein independently of one another R3 and R4 represent hydrogen, —CF3, C1-C12alkyl, phenyl or the group (A), wherein n represents a numeral from 0 to 10 000 and X2, Y, R2, R5, R6, R7 and R8 are as defined above or R3 and R4, together with the carbon atom to which they are bonded, form the cyclohexylidene group with 1 to 3 C1-C4alkyl groups as optional substituents.
Of particular interest are also compounds (I), wherein R1 and R2 independently of one another represent groups (B), wherein p is a numeral from 1 to 50.
Of special interest are compounds (I) wherein p is a numeral from 4 to 15.
Of very special interest are compounds (I), wherein
R1 and R2 independently of one another represent groups (B), wherein p is a numeral from 1 to 50;
X1 and X2 independently of one another represent C2-C8alkylene;
m represents a numeral from 1 to 1 000;
R5, R6, R7 and R8 represent hydrogen; and
Y represents the bivalent group
R3 represents hydrogen, —CF3, C1-C12alkyl, phenyl or the group (A), wherein the numeral n represents a numeral from 0 to 10 000 and X2, Y, R2, R5, R6, R7 and R8 are as defined above or R3 and R4, together with the carbon atom to which they are bonded, form the cyclohexylidene group with 1 to 3 C1-C4alkyl groups as optional substituents.
Of high interest are compounds (I), wherein R3 and R4 independently of one another represent hydrogen or C1-C4alkyl; or R3 and R4, together with the carbon atom to which they are bonded, form the cyclohexylidene group.
Particularly preferred are also compounds (I), wherein m is a numeral from 1 to 50, and n is a numeral from 0 to 50.
The compounds (I) are prepared by known methods. A fluoro alcohol is treated with bis(2,4-dinitrophenyl)carbonate (DNPC) to give the 2,4-dinitrophenyl carbonate of the fluoro alcohol in situ. This derivative can be isolated and treated separately, for example by hydroxy terminated bisphenol A oligomers of various molecular weights.
Brunelle et al., Macromolecules 1991, 24 3035-3044, discloses the use of bis(2,4-dinitrophenyl)carbonate for preparation of dimer and cyclic oligomers of bisphenol A. The coupling reactions can also be carried out by carbonate linkage forming reagents, such as phosgene or carbonyl diimidazole (CDI).
Preferred fluoro alcohols are, for example, so-called fluorotelomer alcohols. These are, for example, commercially available from DuPont or Aldrich as Zonyl® BA-L.
Preferred bisphenol starting materials are, for example, bisphenol A and the compounds of the formulae 1, 2 and 3.
According to a particularly preferred embodiment of the invention the composition comprises as component b1) at least one compound
Wherein
R1 and R2 represent an aliphatic group substituted by fluorine;
X1 and X2 independently of one another represent the direct bond or C1-C12alkylene;
m represents a numeral from 1 to 1 000; and
R3 and R4 together with the carbon atom to which they are bonded, form a C5-C8-cydoalkylidene group with 1 to 3 C1-C4alkyl groups as optional substituents;
Or R3 and R4 independently of one another represent hydrogen, an aliphatic group substituted by fluorine, C1-C12alkyl, C2-C12alkenyl, phenyl or the group of the partial formula
Wherein n represents a numeral from 0-1 000; and
R3, R4, X2, and R2 are as defined above.
According to a highly preferred embodiment the composition comprises as component b1) at least one compound (I′), wherein
X1 and X2 represent ethylene;
R1 and R2 represent groups (B);
wherein p represents a numeral from 1 to 50;
m represents a numeral from 2 to 50; and
R3 and R4 independently of one another represent hydrogen or C1-C4alkyl or together with the carbon atom to which they are bonded form the cyclohexylidene group.
An additional embodiment of the invention relates to the mixture which comprises
In the compound (II), as defined above, the substituents are defined as follows:
R0 represents the direct bond or a bivalent prow) selected from the group consisting of
R1 and R2 independently of one another represent a silicon containing group;
R3 and R4 independently of one another represent hydrogen, an aliphatic group substituted by fluorine, a silicon containing group, C1-C12alkyl, C1-C12alkyl substituted by carboxy, C2-C12alkenyl, aryl, or a group of the partial formula
or R3 and R4, together with the carbon atom to which they are bonded represent C5-C8-cycloalkylidene or C5-C8-cycloalkylidene that is substituted by 1 to 3 C1-C4alkyl groups;
R5, R6, R7 and R8 independently of one another represent hydrogen, C1-C12alkyl or C3-C12alkenyl;
X1 and X2 independently of one another represent the direct bond, C1-C12alkylene or C4-C25alkylene interrupted by —O—;
Y1 and Y2 independently of one another represent the direct bond or a bivalent group selected from the group consisting of
R9 and R10 independently of one another represent the direct bond or C1-C4alkylene;
R11, R12 and R13 independently of one another represent hydrogen, C1-C12alkyl or C3-C12alkenyl;
R14 represents hydrogen, C1-C12alkyl or a silicon containing group;
m represents a numeral from 0 to 10 000; and
n represents a numeral from 0 to 10 000.
A silicon containing group preferably represents a group of the partial formula
wherein
R17, R18, R19 and R20 independently of one another represent C1-C12alkyl, C1-C12alkyl substituted with hydroxy or amino; C4-C12hydroxyalkyl interrupted with —O—; or represents a group of the partial formula
wherein
R21 represents C1-C12alkyl or a group of the partial formula
R22, R23, R24, R25, R26, R27, R28 and R29 independently of one another represent C1-C12alkyl or C1-C12-alkyl substituted with hydroxy or amino;
p represents 0 to 200; and
q represent 0 to 200.
Of special interest as a silicon containing group is a group of the partial formula (D), wherein
R17, R18, R19 and R20 independently of one another represent methyl or a group of the partial formula
R21 represents methyl or a group of the partial formula
R22, R23, R24, R25, R26, R27, R28 and R29 are methyl; and
p and q independently of one another represent 0 to 100.
Of particular interest are compounds (II), wherein
R0 represents the bivalent group
R1 and R2 independently of one another represent a silicon containing group;
R3 and R4 independently of one another represent hydrogen, trifluoromethyl, a silicon containing group, C1-C12alkyl, phenyl or the group (C); or
R3 and R4, together with the carbon atom to which they are bonded represent C5-C8-cycloalkylidene or C5-C8-cycloalkylidene that is substituted by 1 to 3 C1-C4alkyl groups;
R5, R6, R7 and R8 are hydrogen;
X1 and X2 independently of one another represent C1-C12alkylene or C4-C25alkylene interrupted by —O—;
Y1 and Y2 independently of one another represent the direct bond or a bivalent group selected from the group consisting of
R9 and R10 independently of one another represent the direct bond or methylene;
R11, R12 and R13 independently of one another represent hydrogen, C1-C4alkyl or C3-C4alkenyl;
R14 represents hydrogen or C1-C12alkyl;
m represents 0 to 10 000; and
n represents 0 to 10 000.
Of very special interest are compounds (II), wherein
R0 represents the bivalent group
R3 represents hydrogen, —CF3, C1-C12alkyl, phenyl or the group (C);
R4 represents —CF3, C1-C12alkyl or phenyl; or
R3 and R4, together with the carbon atom to which they are bonded, form a C5-C8-cydoalkylidene group or C5-C8-cycloalkylidene that is substituted by 1 to 3 C1-C4alkyl groups;
R5, R6, R7 and R8 represent hydrogen;
X1 and X2 are each independently of the one another represent C1-C12alkylene or C4-C25alkylene interrupted by —O—;
Y1 and Y2 independently of one another represent the direct bond or a bivalent group selected from the group consisting of
R9 and R10 independently of one another represent the direct bond or methylene;
R14 represents hydrogen or C1-C12alkyl;
m represents 0 to 10 000; and
n represents 0 to 10 000.
Of interest are also compounds (II), wherein
R3 and R4 independently of one another represent hydrogen or C1-C4alkyl; or
R3 and R4, together with the carbon atom to which they are bonded, form the cyclohexylidene group.
Preferred are compounds (II), wherein X1 and X2 independently of one another represent C2-C8alkylene or C4-C25alkylene interrupted with —O—.
Also preferred are compounds (II), wherein m represents 0 to 100, and n represents 0 to 100.
Of very special interest are compounds (II), wherein
R0 represents the bivalent group
R3 and R4 independently of one another represent C1-C4alkyl; or
R3 and R4, together with the carbon atom to which they are bonded, form the cyclohexylidene group;
R5, R6, R7 and R8 represent hydrogen;
X1 and X2 independently of one another represent C2-C4alkylene or C4-C25alkylene interrupted with —O—;
Y1 and Y2 independently of one another represent the direct bond or a bivalent group selected from the group consisting of
R9 and R10 independently of one another represent the direct bond or methylene;
m represents 0 to 100, and
n represents 0 to 100.
In a compound (II) C1-C12alkyl is a straight chain or, where possible, branched alkyl group, which is the same one as defined above with regard to compounds (I).
R3 and R4 defined as C1-C12alkyl substituted by carboxy is preferably carboxymethyl or 1- or 2-carboxyethyl.
R3 and R4 defined as aryl preferably represent phenyl or phenyl substituted by 1-3 C1-C4alkyl groups, e.g. methyl.
R3, R4, R5, R6, R7 and R8 defined as C2-C12alkenyl represent a straight chain or, where possible, branched alkenyl group, which is the same one as defined above with regard to compounds (I).
R3 and R4 defined as C5-C8-cycloalkylidene or C5-C8-cydoalkylidene that is substituted with 1 to 3 C1-C4alkyl groups are as defined above with regard to compounds (I).
X1, and X2, defined as C1-C12alkylene and R9 and R10 defined as C1-C4alkylene represent straight chain or, where possible, branched alkylene groups as defined above with regard to compounds (I).
X1, and X2, defined as C4-C25alkylene interrupted with —O— is straight chain or, where possible, branched, for example —CH2CH2—O—CH2CH2—, —CH2CH2CH2—O—CH2CH2—, —CH2CH2CH2—O—CH2CH2CH2— or —CH2CH2—O—CH2CH2—O—CH2CH2—.
C1-C12Alkyl substituted with hydroxy or amino is, for example, hydroxymethyl, 1- or 2-hydroxyethyl, aminomethyl, or 1- or 2-aminoethyl.
C4-C12Hydroxyalkyl interrupted with —O— is for example —CH2CH2—O—CH2CH2OH or —CH2CH2—O—CH2CH2—O—CH2CH2OH.
A fluorine containing group is a branched or unbranched radical, which contains at least one fluoro atom, for example C1-C25fluoroalkyl; or is the group (B), wherein p is 1 to 50, e.g. trifluoromethyl or pentafluoromethyl.
C1-C25Fluoroalkyl is for example fluoromethyl, 2-fluoroethyl, 3-fluoropropyl, 4-fluorobutyl, 5-fluoropentyl, 6-fluorohexyl, 7-fluoroheptyl, difluoromethyl or pentafluorobutyl.
The compounds (II) are obtainable by known methods. A silicon alcohol is treated with bis(2,4-dinitrophenyl)carbonate (DNPC) to give the 2,4-dinitrophenyl carbonate of the silicon alcohol in situ. This derivative can be isolated and treated separately, for example by hydroxy terminated bisphenol A oligomers of various molecular weights. Brunelle et al., Macromole cules 1991, 24, 3035-3044, discloses the use of bis(2,4-dinitrophenyl)carbonate for preparation of dimer and cyclic oligomers of bisphenol A. The coupling reactions can also be carried out by carbonate linkage forming reagents, such as phosgene or carbonyl diimidazole (CDI).
Especially preferred silicon containing groups are derived from mono hydroxypolysiloxanes, wherein p=10; polysiloxanes, wherein p=64; polyalkylene oxides modified heptamethyltrisiloxanes; or 3-(polyoxyethylene)propylheptamethyltrisiloxane. Representative structural formulae are shown below:
Preferred bisphenol starting materials are the same ones as the ones mentioned above with regard to the preparation of the compounds (I).
An additional embodiment of the invention also relates to the mixture which comprises
A further embodiment of the invention also relates to the mixture which comprises
Components a) and b1), components a) and b2), as well as components a) and b), are present in the mixture in a weight percentage of a) 0.001-5.0%, preferably 0.01-2.0%, most preferably 0.04-0.5%: b) of 0.01-5.0%, preferably 0.25-1.0%.
A further embodiment of the invention relates to a process for imparting flame retardancy to a polymer substrate comprising polycarbonates or polycarbonate blends, which process comprises adding to said polymer substrate the mixtures as defined above.
Another preferred embodiment of the invention relates to a process for imparting flame retardancy and light transparency to a polymer substrate comprising polycarbonates or polycarbonate blends, which process comprises adding to said polymer substrate the mixture as defined above.
A particularly preferred embodiment relates to a process for imparting flame retardancy and transparency to a polycarbonate which process comprises adding to said polymer substrate the mixture as defined above.
The polymer substrate comprising polycarbonates or polycarbonate blends may be of any grade and prepared by any known method. The term polymer substrate comprises within its scope any polycarbonate homopolymers or copolymers thereof, such as copolymers with polyesters.
Polycarbonates are thermoplastic polymers that correspond to the general formula
Polycarbonates are obtainable by interfacial processes or by melt processes (catalytic transesterification). The polycarbonate may be either branched or linear in structure and may include any functional substituents. Polycarbonate copolymers and polycarbonate blends are also within the scope of the invention. The term polycarbonate should be interpreted as inclusive of copolymers and blends with other thermoplastics. Methods for the manufacture of polycarbonates are known, for example, from U.S. Pat. Nos. 3,030,331; 3,169,121; 4,130,458; 4,263,201; 4,286,083; 4,552,704; 5,210,268; and 5,606,007. A combination of two or more polycarbonates of different molecular weights may be used.
Preferred are polycarbonates obtainable by reaction of a diphenol, such as bisphenol A, with a carbonate source. Examples of suitable diphenols are:
The carbonate source may be either a carbonyl halide, a carbonate ester or a haloformate. Suitable carbonate halides are phosgene or carbonylbromide. Suitable carbonate esters are dialkylcarbonates, such as dimethyl- or diethylcarbonate, diphenyl carbonate, phenyl-alkyl-phenylcarbonate, such as phenyl-tolylcarbonate, dialkylcarbonates, such as dimethyl- or di-ethylcarbonate, di-(halophenyl)carbonates, such as di-(chlorophenyl)carbonate, di-(bromophenyl)carbonate, di-(trichlorophenyl)carbonate or di-(trichlorophenyl)carbonate, di-(alkylphenyl)carbonates, such as di-tolylcarbonate, naphthylcarbonate, dichloronaphthylcarbonate and others.
Other process details, such as the addition of molecular weight regulators, acid acceptors, catalysts are disclosed in the references mentioned above.
According to an additional embodiment, the polymer substrate comprising polycarbonates or polycarbonate blends is a polycarbonate-copolymer, wherein isophthalate/terephthalate-resorcinol segments are present. Such polycarbonates are commercially available, e.g. Lexan®SLX (General Electrics Co. USA). Other polymeric substrates of component c) may additionally contain in the form as admixtures or as copolymers a wide variety of synthetic polymers including polyolefins, polystyrenes, polyesters, polyethers, polyamides, poly(meth)acrylates, thermoplastic polyurethanes, polysulphones, polyacetals and PVC, including suitable compatibilizing agents. For example, the polymer substrate may additionally contain thermoplastic polymers selected from the group of resins consisting of polyolefins, thermoplastic polyurethanes, styrene polymers and copolymers thereof. Specific embodiments include polypropylene (PP), polyethylene (PE), polyamide (PA), polybutylene terephthalate (PBT), polyethylene terephthalate (PET), glycol-modified polycyclohexylenemethylene terephthalate (PCTG), polysulphone (PSU), polymethylmethacrylate (PMMA), thermoplastic polyurethane (TPU), acrylonitrile-butadiene-styrene (ABS), acrylonitrile-styrene-acrylic ester (ASA), acrylonitrile-ethylene-propylene-styrene (AES), styrene-maleic anhydride (SMA) or high impact polystyrene (HIPS).
A list of suitable synthetic polymers is given below:
Component a) is added to the substrate of component c) in an amount of about 0.001 to 5.0 weight %, preferably 0.01 to 2.0 weight % and most preferably 0.04 to 0.5 weight %.
Component b) is added to the substrate of component c) in an amount of about 0.01 to 5.0 weight % and preferably 0.25 to 1.0 weight %.
A particularly preferred embodiment of the invention relates to a composition, which comprises
—(CF2)p—F (B),
Another particularly preferred embodiment of the invention relates to a composition, which comprises
The instant invention further pertains to a composition, which comprises, in addition to the components a), b) and c), as defined above, d) further additives selected from the group consisting of polymer stabilizers and additional flame-retardants, such as phosphorus containing flame-retardants, nitrogen containing flame-retardants, halogenated flame-retardants and inorganic flame-retardants.
Stabilizers are preferably halogen-free and selected from nitroxyl stabilizers, nitrone stabilizers, amine oxide stabilizers, benzofuranone stabilizers, phosphite and phosphonite stabilizers, quinone methide stabilizers and monoacrylate esters of 2,2′-alkylidenebisphenol stabilizers.
Additional flame-retardants as of present component d) are known components, items of commerce or can be obtained by known methods.
Representative phosphorus containing flame-retardants, in addition to the ones defined above with regard to component b), are for example:
Tetraphenyl resorcinol diphosphite (FYROLFLEX® RDP, Akzo Nobel), tetrakis(hydroxymethyl)phosphonium sulphide, triphenyl phosphate, diethyl-N,N-bis(2-hydroxyethyl)-amino-methyl phosphonate, hydroxyalkyl esters of phosphorus acids, ammonium polyphosphate (APP) or (HOSTAFLAM® AP750), resorcinol diphosphate oligomer (RDP), phosphazene flame-retardants and ethylenediamine diphosphate (EDAP).
Nitrogen containing flame-retardants are, for example, isocyanurate flame-retardants, such as polyisocyanurate, esters of isocyanuric acid or isocyanurates. Representative examples are hydroxyalkyl isocyanurates, such as tris-(2-hydroxyethyl)isocyanurate, tris(hydroxymethyl)isocyanurate, tris(3-hydroxy-n-proyl)isocyanurate or triglycidyl isocyanurate.
Nitrogen containing flame-retardants include melamine-based flame-retardants. Representative examples are: melamine cyanurate, melamine borate, melamine phosphates, melamine polyphosphate, melamine pyrophosphate, melamine ammonium polyphosphate and melamine ammonium pyrophosphate.
Further examples are: benzoguanamine, tris(hydroxyethyl) isocyanurate, allantoin, glycoluril, melamine cyanurate, melamine phosphate, dimelamine phosphate, melamine pyrophosphate, urea cyanurate, melamine polyphosphate, melamine borate, ammonium polyphosphate, melamine ammonium polyphosphate or melamine ammonium pyrophosphate, a condensation product of melamine from the series melem, melam, melon and/or a higher condensed compound or a reaction product of melamine with phosphoric acid and/or a reaction product of condensation products of melamine with phosphoric acid or a mixture thereof.
Special emphasis should be given to: dimelamine pyrophosphate, melamine polyphosphate, melem polyphosphate, melam polyphosphate, and/or a mixed polysalt of such a type, more especially melamine polyphosphate.
Representative organohalogen flame-retardants are, for example:
Polybrominated diphenyl oxide (DE-60F, Great Lakes Corp.), decabromodiphenyl oxide (DBDPO; SAYTEX® 102E), tris[3-bromo-2,2-bis(bromomethyl)propyl]phosphate (PB 370®, FMC Corp.), tris(2,3-dibromopropyl)phosphate, tris(2,3-dichloropropyl)phosphate, chlorendic acid, tetrachlorophthalic acid, tetrabromophthalic acid, poly-β-chloroethyl triphosponate mixture, tetrabromobisphenol A bis(2,3-dibromopropyl ether) (PE68), brominated epoxy resin, ethylene-bis(tetrabromophthalimide) (SAYTEX® BT-93), bis(hexachlorocydopentadieno)-cyclooctane (DECLORANE PLUS®), chlorinated paraffins, octabromodiphenyl ether, hexachlorocydopentadiene derivatives, 1,2-bis(tribromophenoxy)ethane (FF680), tetrabromo-bisphenol A (SAYTEX® RB100), ethylene bis-(dibromo-norbornanedicarboximide) (SAYTEX® BN-451), bis-(hexachlorocycloentadeno) cyclooctane, PTFE, tris-(2,3-dibromopropyl)-isocyanurate, and ethylene-bis-tetrabromophthalimide.
The flame-retardant mentioned above routinely combined with an inorganic oxide synergist. Most common for this use are zinc or antimony oxides, e.g. Sb2O3 or Sb2O5. Boron compounds are suitable, too.
The above-mentioned flame-retardant classes are advantageously contained in the composition of the invention in an amount from about 0.5% to about 45.0% by weight of the organic polymer substrate; for instance about 3.0% to about 40.0%; for example about 5.0% to about 35.0% by weight of the polymer. For example, the flame-retardant of component b), which includes components b1 and b2), is employed from about 0.5% to about 10.0% by weight, from about 1.0% to about 10.0%, from about 3.0% to about 10.0% or from about 5.0% to about 10.0% by weight, based on the weight of the polymer substrate. For example, component b) is employed from about 0.5% to about 8.0%, from about 0.5% to about 6.0%, from about 0.5% to about 5.0%, or from about 0.5% to about 3.0% by weight, based on the weight of the polymer substrate.
As mentioned above, the composition according to the invention may additionally contain one or more conventional additives, for example selected from pigments, dyes, plasticizers, antioxidants, thixotropic agents, levelling assistants, basic co-stabilizers, metal passivators, metal oxides, organophosphorus compounds, further light stabilizers and mixtures thereof, especially pigments, phenolic antioxidants, calcium stearate, zinc stearate, UV absorbers of the 2-hydroxy-benzophenone, 2-(2′-hydroxyphenyl)benzotriazole and/or 2-(2-hydroxyphenyl)-1,3,5-triazine groups. More specific examples are the following components:
where R=3′-tert-butyl-4′-hydroxy-5′-2H-benzotriazol-2-ylphenyl, 2-[2′-hydroxy-3′-(α,α-dimethylbenzyl)-5′-(1,1,3,3-tetramethylbutyl)phenyl]benzotriazole; 2-[2′-hydroxy-3′-(1,1,3,3-tetramethylbutyl)-5′-(α,α-dimethylbenzyl)phenyl]benzotriazole, such as commercially available light stabilisers from the Tinuvin® series, such as TINUVIN 234, 326, 329, 350, 360 or TINUVIN 1577.
The following phosphites are especially preferred:
Tris(2,4-di-tert-butylphenyl)phosphite (Irgafos®168, Ciba Specialty Chemicals), tris(nonylphenyl)phosphite,
Preferred additional additives for the compositions as defined above are processing stabilizers, such as the above-mentioned phosphites and phenolic antioxidants, and light stabilizers, such as benzotriazoles. Preferred specific antioxidants include octadecyl 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate (IRGANOX 1076). Specific processing stabilizers include tris(2,4-di-tert-butylphenyl)phosphite (IRGAFOS 168) and tetrakis(2,4-di-tert-butyl-phenyl)[1,1-biphenyl]-4,4′-diylbisphosphonite (IRGAFOS P-EPQ). Specific light stabilizers include 2-(2H-benzotriazole-2-yl)-4,6-bis(1-methyl-1-phenylethyl)phenol (TINUVIN 234), 2-(5-chloro(2H)-benzotriazole-2-yl)-4-(methyl)-6-(tert-butyl)phenol (TINUVIN 326), 2-(2H-benzotriazole-2-yl)-4-(1,1,3,3-tetramethylbutyl)phenol (TINUVIN 329), 2-(2H-benzotriazole-2-yl)-4-(tert-butyl)-6-(sec-butyl)phenol (TINUVIN 350), 2,2′-Methylenebis(6-(2H-benzotriazol-2-yl)-4-(1,1,3,3-tetramethylbutyl)phenol) (TINUVIN 360), and 2-(4,6-Diphenyl-1,3,5-triazin-2-yl)-5-[(hexy)oxy]-phenol (TINUVIN 1577).
The additives mentioned above are preferably contained in an amount of 0.01 to 10.0%, especially 0.05 to 5.0%, relative to the weight of the polymer component c).
The incorporation of the additive components a) and b) and optional further components into the polymer component c) is carried out by known methods such as dry blending in the form of a powder, or wet mixing in the form of solutions, dispersions or suspensions for example in an inert solvent, water or oil. The additive components a) and b) and optional further additives may be incorporated, for example, before or after molding or also by applying the dissolved or dispersed additive or additive mixture to the polymer material, with or without subsequent evaporation of the solvent or the suspension/dispersion agent. They may be added directly into the processing apparatus (e.g. extruders, internal mixers, etc.), e.g. as a dry mixture or powder, or as a solution or dispersion or suspension or melt.
The addition of the additive components to the polymer substrate c) can be carried out in all customary mixing machines in which the polymer is melted and mixed with the additives. Suitable machines are known to those skilled in the art. They are predominantly mixers, kneaders and extruders.
The process is preferably carried out in an extruder by introducing the additive during processing:
Particularly preferred processing machines are single-screw extruders, contra rotating and co-rotating twin-screw extruders, planetary-gear extruders, ring extruders or co kneaders. It is also possible to use processing machines provided with at least one gas removal compartment to which a vacuum can be applied.
Suitable extruders and kneaders are described, for example, in Handbuch der Kunststoffextrusion, Vol. 1 Grundlagen, Editors F. Hensen, W. Knappe, H. Potente, 1989, pp. 3-7, ISBN:3-446-14339-4 (Vol. 2 Extrusionsanlagen 1986, ISBN 3-446-14329-7).
For example, the screw length is 1-60 screw diameters, preferably 35-48 screw diameters. The rotational speed of the screw is preferably 10-600 rotations per minute (rpm), very particularly preferably 25-300 rpm.
The maximum throughput is dependent on the screw diameter, the rotational speed and the driving force. The process of the present invention can also be carried out at a level lower than maximum throughput by varying the parameters mentioned or employing weighing machines delivering dosage amounts.
If a plurality of components is added, these can be premixed or added individually.
The additives components a) and b) and optional further additives can also be sprayed onto the polymer substrate c). The additive mixture dilutes other additives, for example the conventional additives indicated above, or their melts so that they can be sprayed also together with these additives onto the polymer substrate. Addition by spraying during the deactivation of the polymerisation catalysts is particularly advantageous; in this case, the steam evolved may be used for deactivation of the catalyst. In the case of spherically polymerised polyolefins it may, for example, be advantageous to apply the additives of the invention, optionally together with other additives, by spraying.
The additive components a) and b) and optional further additives can also be added to the polymer in the form of a masterbatch (“concentrate”) which contains the components in a concentration of, for example, about 1.0% to about 40.0% and preferably 2.0% to about 20.0% by weight incorporated in a polymer. The polymer is not necessarily of identical structure than the polymer where the additives are added finally. In such operations, the polymer can be used in the form of powder, granules, solutions, and suspensions or in the form of lattices.
Incorporation can take place prior to or during the shaping operation. The materials containing the additives of the invention described herein preferably are used for the production of molded articles, for example roto-molded articles, injection molded articles, profiles and the like, and especially a fiber, spun melt non-woven, film or foam.
Thus, present invention further pertains to a molded or extruded article, a fiber, spun melt non-woven or a foam comprising the composition of the invention.
The following examples illustrate the invention:
Materials and Methods
PC 145 Resin (GE Plastics) is vacuum-dried for 8 h at 120° C. and stabilized with IRGAFOS® P-EPQ (Ciba Specialty Chemicals). As a flame retardant, RM65 (potassium perfluorobutane sulphonate, supplier Miteni/Italy) is used.
The polycarbonate compositions shown in Tab. 1 are extruded on a Haake TW-100 at 280° C. and pelletized by strand granulation. After drying at 120° C. for 12 h, the granulated compositions are injection molded at 290° C. into plaques of 1.6 mm thickness according to Underwriter's Laboratories flame retardancy standard UL-94.
Flame retardancy is tested according to UL-94 in the vertical mode.
1)
2)
| Number | Date | Country | Kind |
|---|---|---|---|
| 05107517.4 | Aug 2005 | EP | regional |
| Filing Document | Filing Date | Country | Kind | 371c Date |
|---|---|---|---|---|
| PCT/EP2006/065126 | 8/8/2006 | WO | 00 | 2/7/2008 |
