CN101627079A - Flame retardant polycarbonate compositions - Google Patents
Flame retardant polycarbonate compositions Download PDFInfo
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- CN101627079A CN101627079A CN200880007489A CN200880007489A CN101627079A CN 101627079 A CN101627079 A CN 101627079A CN 200880007489 A CN200880007489 A CN 200880007489A CN 200880007489 A CN200880007489 A CN 200880007489A CN 101627079 A CN101627079 A CN 101627079A
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Abstract
The present invention relates to novel flame retardant polycarbonate resin compositions comprising at least one aromatic polycarbonate resin, at least one anti-drip agent, and at least one salt as defined herein. The present invention also provides methods for preparing articles comprising said flame retardant composition, and articles made therefrom.
Description
Technical field
The present invention relates to the novel flame-retardant poly carbonate resin composition.
Background of invention
Polycarbonate resin has excellent physical strength (especially shock strength), electrical characteristic and optical clarity, and is widely used in multiple fields such as business automation equipment, electric machinery and electric mechanical, motor vehicle and buildings.The polymkeric substance that uses in as business automation equipment and electric machinery and electric mechanical field need have high flame retardant.Usually prevent promptly that the fused resin from dripping from scorching hot polycarbonate resin and make polycarbonate resin have flame retardant resistance by mixing fire retardant and dripping inhibitor.
United States Patent (USP) 3,775,367 disclose an alkali metal salt that comprises perfluoro alkyl sulfonic acid or the flame retardant polycarbonate composition of tetraalkylammonium salt.United States Patent (USP) 5,449,710 disclose an alkali metal salt that comprises perfluoroalkanes sulfonic acid or the flame retardant polycarbonate composition of alkaline earth salt.
Yet, still need and can join in the polycarbonate resin so that their fire-retardant compounds by low levels.The invention provides the non-fluoridized sulfonated salts of giving the polycarbonate resin flame retardant resistance.
The invention summary
One embodiment of the invention relate to flame retardant polycarbonate composition, and described composition comprises:
(A) at least a aromatic polycarbonate resin;
(B) at least a dripping inhibitor; And
(C) at least a have a formula M
+Q
-Salt, M wherein
+And Q
-Such as hereinafter definition.In a particular, flame retardant polycarbonate composition comprise about 100 parts component (A), about 0.01 to about 5.0 parts component (B) and about 0.001 to about 2.0 parts component (C).In addition, described flame retardant polycarbonate composition also can be chosen wantonly and comprise one or more additives, filler or their combination.
In another embodiment of the invention, dripping inhibitor can be a tetrafluoroethylene.In another embodiment, dripping inhibitor provides with mixture or the test kit that comprises component (C).
Another embodiment of the invention also provides method and the goods prepared therefrom that prepare the anti-flaming polycarbonate ester articles.Described method comprises:
(a) with the component (A) of described poly carbonate resin composition, (B) and (C) and optional additive, filler and their combination mix, to form the blended composition;
(b) the blended composition is configured as particle;
(c) particle melt with step (b) is configured as the anti-flaming polycarbonate ester articles.
Detailed Description Of The Invention
The present invention relates to fire-retarded polycarbonate resin composition.
In one embodiment, the present invention relates to comprise the fire-retarded polycarbonate resin composition of following component:
(A) at least a aromatic polycarbonate resin;
(B) at least a dripping inhibitor; And
(C) at least a have a formula M
+Q
-Salt, M wherein
+Be that positively charged ion or (2) that (1) is selected from lithium, sodium, potassium and caesium are selected from following 11 kinds of cationic positively charged ions:
The pyridine pyridazine
The pyrimidine pyrazine
The imidazoles pyrazoles
Sai Zuo oxazole
Triazole
The Phosphonium ammonium
R wherein
1, R
2, R
3, R
4, R
5And R
6Be independently selected from:
(a)H
(b) halogen
(c) randomly be selected from Cl, Br, F, I, OH, NH by at least one
2With the group of SH replace-CH
3,-C
2H
5, or C
3To C
25, preferred C
3To C
20, straight chain, side chain or cyclic alkane or alkene;
(d) comprising one to three is selected from the heteroatoms of O, N, Si and S and randomly is selected from Cl, Br, F, I, OH, NH by at least one
2With the group of SH replace-CH
3,-C
2H
5, or C
3To C
25, preferred C
3To C
20, straight chain, side chain or cyclic alkane or alkene;
(e) has one to three heteroatomic C that is independently selected from O, N, Si and S
6To C
25Unsubstituted aryl or C
6To C
25Unsubstituted heteroaryl; And
(f) has one to three heteroatomic C that is independently selected from O, N, Si and S
6To C
25The aryl or the C that replace
6To C
25The heteroaryl that replaces; And the aryl of wherein said replacement or the heteroaryl of replacement have one to three substituting group, and described substituting group is independently selected from:
(1) randomly is selected from Cl, Br, F, I, OH, NH by at least one
2With the group of SH replace-CH
3,-C
2H
5, or C
3To C
25, preferred C
3To C
20, straight chain, side chain or cyclic alkane or alkene,
(2)OH，
(3) NH
2, and
(4)SH；
R
7, R
8, R
9And R
10Be independently selected from:
(g) randomly be selected from Cl, Br, F, I, OH, NH by at least one
2With the group of SH replace-CH
3,-C
2H
5, or C
3To C
25, preferred C
3To C
20, straight chain, side chain or cyclic alkane or alkene,
(h) comprising one to three is selected from the heteroatoms of O, N, Si and S and randomly is selected from Cl, Br, F, I, OH, NH by at least one
2With the group of SH replace-CH
3,-C
2H
5, or C
3To C
25, preferred C
3To C
20, straight chain, side chain or cyclic alkane or alkene;
(i) has one to three heteroatomic C that is independently selected from O, N, Si and S
6To C
25Unsubstituted aryl or C
6To C
25Unsubstituted heteroaryl; And
(j) has one to three heteroatomic C that is independently selected from O, N, Si and S
6To C
25The aryl or the C that replace
6To C
25The heteroaryl that replaces; And the aryl of wherein said replacement or the heteroaryl of replacement have one to three substituting group, and described substituting group is independently selected from:
(1) randomly is selected from Cl, Br, F, I, OH, NH by at least one
2With the group of SH replace-CH
3,-C
2H
5, or C
3To C
25, preferred C
3To C
20, straight chain, side chain or cyclic alkane or alkene,
(2)OH，
(3) NH
2, and
(4) SH; And wherein
Optional R
1, R
2, R
3, R
4, R
5, R
6, R
7, R
8, R
9And R
10In at least two can form cyclic or bicyclic alkyl or alkenyl together;
And Q wherein
-Be the negatively charged ion that is selected from formula I and formula II:
Formula I
Wherein:
R
11Be selected from:
(1) halogen;
(2) randomly be selected from Cl, Br, I, OH, NH by at least one
2With the group of SH replace-CH
3,-C
2H
5, or C
3To C
15, preferred C
3To C
6, the alkane of straight or branched or alkene;
(3) randomly be selected from C l, Br, I, OH, NH by at least one
2With the group of SH replace-OCH
3,-OC
2H
5, or C
3To C
15, preferred C
3To C
6, the alkoxyl group of straight or branched;
(4) randomly be selected from Cl, Br, I, OH, NH by at least one
2The C that replaces with the group of SH
1To C
15, preferred C
1To C
6, the fluoro-alkyl of straight or branched;
(5) randomly be selected from Cl, Br, I, OH, NH by at least one
2The C that replaces with the group of SH
1To C
15, preferred C
1To C
6, the fluoroalkyl of straight or branched;
(6) C
1To C
15, preferred C
1To C
6, the perfluoroalkyl of straight or branched; And
(7) C
1To C
15, preferred C
1To C
6, the perfluoro alkoxy of straight or branched;
And
Formula II
Wherein:
R
12Be selected from:
(1) halogen;
(2) randomly be selected from Cl, Br, I, OH, NH by at least one
2With the group of SH replace-CH
3,-C
2H
5, or C
3To C
15, preferred C
3To C
6, the alkane of straight or branched or alkene;
(3) randomly be selected from Cl, Br, I, OH, NH by at least one
2With the group of SH replace-OCH
3,-OC
2H
5, or C
3To C
15, preferred C
3To C
6, the alkoxyl group of straight or branched;
(4) randomly be selected from Cl, Br, I, OH, NH by at least one
2The C that replaces with the group of SH
1To C
15, preferred C
1To C
6, the fluoro-alkyl of straight or branched;
(5) randomly be selected from Cl, Br, I, OH, NH by at least one
2The C that replaces with the group of SH
1To C
15, preferred C
1To C
6, the fluoroalkyl of straight or branched;
(6) C
1To C
15, preferred C
1To C
6, the perfluoroalkyl of straight or branched; And
(7) C
1To C
15, preferred C
1To C
6, the perfluoro alkoxy of straight or branched.
According to the present invention, fire-retarded polycarbonate resin composition is to satisfy the poly carbonate resin composition that flame retardant resistance requires after the composition compounding.In the U.S., the flame retardant resistance of the composition of compounding can be as Underwriter ' s Laboratories, and Inc. (Northbrook, measured originally by the test specimens of the preparation of compositions of described compounding by use described in testing method UL-94 IL).Preferably the composition of described compounding has the V-0 grade according to UL-94.
Component in the described poly carbonate resin composition (A), (B) and part by weight (C) be about 100 parts component (A), about 0.01 to about 5.0 parts component (B) and about 0.001 to about 2.0 parts component (C).In a more particular embodiment, component (B) is added with about 0.1 to about 3.0 parts, and in one even more particular embodiment, component (B) is added with about 0.25 to about 1.0 parts.In another embodiment, component (C) is added with about 0.01 to about 1.0 parts, and in one even more particular embodiment, component (C) is added with about 0.1 to about 0.5 part.When the aromatic polycarbonate resin of using more than one, dripping inhibitor, the combined wt of aromatic polycarbonate resin, salt or dripping inhibitor that the representative of part by weight value is independent.Annexing ingredient filler or pigment as described below can add in the described resin combination.Dripping inhibitor, salt or the amount of adding other the optional component of adding in the component (A) to will depend on many factors, and the machinery of the flame retardant resistance of the product that for example adds the cost of component, is prepared by described poly carbonate resin composition and the product that prepared by described poly carbonate resin composition and physical property be shock strength for example.
Be used for the residue of divalent that aromatic polycarbonate resin of the present invention comprises the dihydric phenol that closes by carbonic ether connection base key, and by representing with following formula:
Wherein Ar is the aryl of divalence.Ar is preferably by the divalent aryl of representing with following formula :-Ar
1-Y-Ar
2-, Ar wherein
1And Ar
2Expression independently of one another has the divalence isocyclic or the heterocyclic aryl of 5 to 30 carbon atoms, and Y represents to have the divalent alkyl of 1 to 30 carbon atom.
As used herein, term " isocyclic " is meant to have or relate to or be characterised in that the ring that is made of carbon atom.As used herein, term " heterocyclic " is meant the ring that has or relate to or be characterised in that more than one atoms; Especially comprise the carboatomic ring that at least one is not the atom of carbon." heterocyclic aryl " is the aryl with one or more theheterocyclic nitrogen atoms, Sauerstoffatom or sulphur atom.
Divalent aryl Ar
1And Ar
2Be not substituted separately or replaced by at least one substituting group, described substituting group does not influence polyreaction.The example of suitable substituent comprises halogen atom, have the alkyl of 1 to 10 carbon atom, have alkoxyl group, phenyl, phenoxy group, vinyl, cyano group, ester group, amide group and the nitro of 1 to 10 carbon atom.
Be suitable for aromatic polycarbonate resin of the present invention (as
HF1110) can from supplier (commercially available as General Electric (Waterford, MA)), perhaps can be synthetic by any method known to those skilled in the art.The general remark of the preparation of polycarbonate, processing and characteristic is found in Brunelle, " Polycarbonates " in Kirk-Othmer Encyclopedia ofChemical Technology (the 5th edition (2006), the John Wiley﹠amp of D.J.; Sons, Inc., Hoboken, NJ, the 19th volume, 797-828 page or leaf) in.This paper has described two kinds of methods of preparation aromatic polycarbonate resin; These methods are intended to usefulness and explain the method for preparing aromatic polycarbonate resin, and do not comprise all modification or modification.
According to a kind of method, can react by melt condensation and prepare aromatic polycarbonate resin, for example United States Patent (USP) 5,717, and 057 the 1st hurdle the 4th walks to the 45th hurdle the 10th row, United States Patent (USP) 5,606,007 the 2nd hurdles the 63rd walk to the 25th hurdle the 23rd row, and United States Patent (USP) 5,319,066 the 2nd hurdles the 5th walk to described in the 7th hurdle the 22nd row.Being used for suitable polycarbonate of the present invention can prepare by the base catalyzed reactions of diaryl carbonate and dihydric phenol.Use multiple diaryl carbonate and dihydric phenol to produce the polycarbonate of various character.The limiting examples of diaryl carbonate is diphenyl carbonate (DPC), carboxylol ester, carbonic acid two (chlorobenzene) ester, carbonic acid m-tolyl ester, carbonic acid dinaphthyl ester, carbonic acid two (hexichol) ester, diethyl carbonate, methylcarbonate, dibutyl carbonate and carbonic acid two cyclohexyls, carbonic acid two (cresotinic acid) ester.The limiting examples of dihydric phenol is 1,1-two (4-hydroxy phenyl) methane, 1,1-two (4-hydroxy phenyl) ethane, 2,2-two (4-hydroxy phenyl) propane (" dihydroxyphenyl propane " hereinafter or " BPA "), 2,2-two (4-hydroxy phenyl) butane, 2,2-two (4-hydroxy phenyl) octane, 1,1-two (4-hydroxy phenyl) propane, 1,1-two (4-hydroxy phenyl) normal butane, two (4-hydroxy phenyl) phenylmethane, 2,2-two (4-hydroxyl-1-aminomethyl phenyl) propane, 1,1-two (4-hydroxyl tert-butyl-phenyl) propane, two (hydroxyaryl) alkane for example 2,2-two (4-hydroxyl-3-bromophenyl) propane, 1,1-two (4-hydroxy phenyl) pentamethylene, 4,4 '-'-biphenyl diphenol, and two (hydroxyaryl) naphthenic hydrocarbon for example 1,1-two (4-hydroxy phenyl) hexanaphthene.The general combination that is used for industrial polycarbonate production is DPC and BPA.
Being suitable for aromatic polycarbonate resin of the present invention also can prepare by the phase interface method.Being used for polycarbonate synthetic phase interface method knows, and be described in for example Chemistry and Physics of Polycarbonates of H.Schnell, Polymer Reviews, the 9th volume, Interscience Publisher s, 1964, the 33 pages of New York and following etc. in; Polymer Reviews, the 10th volume, " Condensation Polymers by Interfacialand Solution Methods ", Paul W.Morgan, Interscience Publishers, New York 1965, chapter 8, the 325th page; Dres.U, " Polycarbonate " in Becker/Braun of Grigo, K.Kircher and P.R.M ü ller, Kunststoff-Handbuch, the 3/1st volume, Polycarbonate, Polyacetale, Polyester, Celluloseester, Carl Hanser Verlag Munich, Vienna 1992, the 118-145 pages or leaves; And United States Patent (USP) 5,235,026 the 2nd hurdle the 65th walks to the 8th hurdle eighth row.
According to this method, the phosgenation of the disodium salt of bis-phenol (or mixture of various bis-phenols) (it has been introduced in the alkaline aqueous solution (or suspension) at first) is in the existence of inert organic solvents or solvent mixture (it the forms second phase) enforcement of getting off.Make formed oligo-ester carbonate (it mainly is present in the organic phase) by means of appropriate catalyst (such as but not limited to tertiary amine and quaternary amine for example triethylamine and tetramethyl ammonium chloride) the further condensation of experience to obtain being dissolved in the high-molecular-weight polycarbonate in the organic phase.At last, isolate organic phase and isolate polycarbonate thus by the method described in the Morgan (supra).
Be suitable for polycarbonate of the present invention and also comprise polydimethylsiloxane-common-BPA polycarbonate.The synthetic United States Patent (USP) 3,189 that is described in of these polycarbonate, 662 the 1st hurdles the 9th walk to the 6th hurdle the 7th row and United States Patent (USP) 3,419, and 634 the 1st hurdles the 24th walk in the 15th hurdle the 22nd row.Described polydimethylsiloxane in the combined wt that adds BPA by dimethyl siloxane approximately at least 1.0% weight be present in polydimethylsiloxane-altogether-BPA polycarbonate.These polymkeric substance be different from above-described those because they have low-down second-order transition temperature, also kept excellent thermostability, and had good weathering resistance.Other preparation method is described in Brunelle, among the D.J. (supra).
Be suitable for the blend that polycarbonate of the present invention also comprises polycarbonate and one or more following materials: polyimide, polyetherimide, polymeric amide, polyketone, polyester, polyphenylene oxide, polystyrene, vinyl cyanide vinylbenzene, acronitrile-butadiene-styrene, polyethylene, polypropylene and polymethylmethacrylate.
Any suitable dripping inhibitor component (B) can be used in the poly carbonate resin composition of the present invention.The described dripping inhibitor for example powder of fine grinding provides.Typical dripping inhibitor is ultrafine powder tetrafluoroethylene (p-TFE) (can be from E.I.du Pont de Nemours and Company, Wilmington DE is commercially available).In one embodiment, described at least a dripping inhibitor can be used as and comprises the described at least a dripping inhibitor and the mixture of described at least a salt (component (C)) or the part of test kit and provide.Powder or dispersion that described dripping inhibitor can be used as in mixture or the test kit provide.For example, ultrafine powder or dispersion that p-TFE can be used as in mixture or the test kit provide with component (C), and wherein component C is 1,1,2,2-tetrafluoro ethyl sulfonic acid or 1,1,2,3,3, the lithium of 3-hexafluoropropanesulacidc acidc, sodium, potassium or cesium salt.More particularly, component C can be 1,1,2,2-tetrafluoro ethyl sulfonic acid potassium or 1,1,2,3,3,3-hexafluoropropanesulacidc acidc potassium.
In a preferred embodiment of the invention, component (C) comprises and is selected from following negatively charged ion (Q
-): 1,1,2,2-tetrafluoro ethyl sulfonic acid root; 2-chloro-1,1,2-trifluoro ethyl sulfonic acid root; 1,1,2,3,3,3-hexafluoropropanesulacidc acidc root; 1,1,2-three fluoro-2-(trifluoromethoxy) ethyl sulfonic acid roots; 1,1,2-three fluoro-2-(five fluorine oxyethyl groups) ethyl sulfonic acid root; 2-(1,2,2,2-tetrafluoro oxyethyl group)-1,1,2,2-tetrafluoro ethyl sulfonic acid root; 2-(1,1,2,2-tetrafluoro oxyethyl group)-1,1,2,2-tetrafluoro ethyl sulfonic acid root; 2-(1,1,2,2-tetrafluoro-2-iodine oxyethyl group)-1,1,2,2-tetrafluoro ethyl sulfonic acid root; 1,1,2,2-tetrafluoro-2-(five fluorine oxyethyl groups) ethyl sulfonic acid root; N, N-two (1,1,2,2-tetrafluoro ethylsulfonyl) imines; And N, N-two (1,1,2,3,3,3-hexafluoro third alkylsulfonyl) imines.
Therefore, in one embodiment, comprise as the described at least a salt of component (C) and be selected from following positively charged ion: as lithium, sodium, potassium, caesium, pyridine, pyridazine, pyrimidine, pyrazine, imidazoles, pyrazoles, thiazole, oxazole, triazole, Phosphonium and the ammonium of defined in above all embodiments; Be selected from following negatively charged ion: 1,1,2,2-tetrafluoro ethyl sulfonic acid root; 2-chloro-1,1,2-trifluoro ethyl sulfonic acid root; 1,1,2,3,3,3-hexafluoropropanesulacidc acidc root; 1,1,2-three fluoro-2-(trifluoromethoxy) ethyl sulfonic acid roots; 1,1,2-three fluoro-2-(perfluor oxyethyl group) ethyl sulfonic acid root; 2-(1,2,2,2-tetrafluoro oxyethyl group)-1,1,2,2-tetrafluoro ethyl sulfonic acid root; 2-(1,1,2,2-tetrafluoro oxyethyl group)-1,1,2,2-tetrafluoro ethyl sulfonic acid root; 2-(1,1,2,2-tetrafluoro-2-iodine oxyethyl group)-1,1,2,2-tetrafluoro ethyl sulfonic acid root; 1,1,2,2-tetrafluoro-2-(five fluorine oxyethyl groups) ethyl sulfonic acid root; N, N-two (1,1,2,2-tetrafluoro ethylsulfonyl) imines; And N, N-two (1,1,2,3,3,3-hexafluoro third alkylsulfonyl) imines.
In another embodiment, the described at least a salt as component (C) is selected from: 1-butyl-2,3-methylimidazole 1,1,2,2-tetrafluoro esilate, 1-butyl-Methylimidazole 1,1,2,2-tetrafluoro esilate, 1-ethyl-3-Methylimidazole 1,1,2,2-tetrafluoro esilate, 1-ethyl-3-Methylimidazole 1,1,2,3,3,3-hexafluoropropanesulacidc acidc salt, 1-hexyl-3-Methylimidazole 1,1,2,2-tetrafluoro esilate, 1-dodecyl-3-Methylimidazole 1,1,2,2-tetrafluoro esilate, 1-hexadecyl-3-Methylimidazole 1,1,2,2-tetrafluoro esilate, 1-octadecyl-3-Methylimidazole 1,1,2,2-tetrafluoro esilate, N-(1,1,2,2-tetrafluoro ethyl) propyl imidazole 1,1,2,2-tetrafluoro esilate, N-(1,1,2,2-tetrafluoro ethyl) ethyl perfluoro hexyl imidazoles 1,1,2,2-tetrafluoro esilate, 1-butyl-3-Methylimidazole 1,1,2,3,3,3-hexafluoropropanesulacidc acidc salt, 1-butyl-3-Methylimidazole 1,1,2-three fluoro-2-(trifluoromethoxy) esilates, 1-butyl-3-Methylimidazole 1,1,2-three fluoro-2-(perfluor oxyethyl group) esilate, tetradecyl (three n-hexyl) Phosphonium 1,1,2-three fluoro-2-(perfluor oxyethyl group) esilate, tetradecyl (three normal-butyl) Phosphonium 1,1,2,3,3,3-hexafluoropropanesulacidc acidc salt, tetradecyl (three n-hexyl) Phosphonium 1,1,2-three fluoro-2-(trifluoromethoxy) esilates, 1-ethyl-3-Methylimidazole 1,1,2,2-tetrafluoro-2-(five fluorine oxyethyl groups) sulfonate, (3,3,4,4,5,5,6,6,7,7,8,8,8-ten trifluoro octyl groups)-San Xin Ji Phosphonium 1,1,2,2-tetrafluoro esilate, 1-methyl-3-(3,3,4,4,5,5,6,6,7,7,8,8,8-ten trifluoro octyl groups) imidazoles 1,1,2,2-tetrafluoro esilate, four positive fourth base Phosphonium 1,1,2-three fluoro-2-(perfluor oxyethyl group) esilate, 1,1,2,2-tetrafluoro ethyl sulfonic acid potassium, 1,1,2,3,3,3-hexafluoropropanesulacidc acidc potassium, and 1,1,2-three fluoro-2-(perfluor oxyethyl group) ethyl sulfonic acid potassium.
Positively charged ion (the M that is used for component (C)
+) the commercially available acquisition of originating, perhaps can be synthetic by method known to those skilled in the art.The fluoro-alkyl azochlorosulfonate acid anion sulfonate anion of formula I generally can be synthetic by perfluorination terminal olefin or perfluorinated vinyl ethers according to the method described in the 12nd section to the 88th section of the 14th section to the 65th section of U.S. Patent application 2006/0276670 and the U.S. Patent application 2006/0276671; In one embodiment, potassium sulfite and Potassium hydrogen sulfite are used as damping fluid, and in another embodiment, when no radical initiator exists, react.Preferred separation method comprises lyophilize or spraying drying with thick 1,1,2,2-tetrafluoro esilate and 1,1,2,3,3,3-hexafluoropropanesulacidc acidc salt product is isolated from aqueous reaction mixture, uses acetone to extract thick 1,1,2,2-tetrafluoro esilate and 1,1,2,3,3,3-hexafluoropropanesulacidc acidc salt, and by cooling off 1,1,2-three fluoro-2-(trifluoromethoxy) esilates and 1,1,2-three fluoro-2-(five fluorine oxyethyl groups) esilate crystallization from reaction mixture goes out.Two (fluoroalkyl alkylsulfonyl) imines of formula I I can be as two (perfluoroalkyl group sulfonyl) inferior amine salt compound as (R
fSO
2)
2The synthetic of N (-) M (+) (participated in United States Patent (USP) 5,847,616; DesMarteau, D. and Hu, L.Q. (Inorg.Chem. (1993), 32,5007-5010); United States Patent (USP) 6,252,111; Caporiccio, and people such as G. (J.Fluor.Chem. (2004), 125,243-252); And United States Patent (USP) 6,399,821) come synthetic described in.For example, at first as United States Patent (USP) 2,403,207 and European patent application EP 47946 described in, by with suitable chlorizating agent such as PCl
5Or catechol-PCl
3Reaction is with 1,1,2, and 2-tetrafluoro ethyl sulfonic acid changes into corresponding SULPHURYL CHLORIDE.Can in organic solvent such as acetonitrile, use Potassium monofluoride that chlorine is replaced to produce sulfonic acid fluoride with fluorine.
Reclaim sulfonic acid fluoride, then can be as Lyapkalo, (Te t rahedron (2006) 62 3137-3145) describedly connects bimolecular sulfonic acid fluoride to prepare two (fluoroalkyl alkylsulfonyl) imines I.M..According to this step, for example use ammonium chloride and triethylamine (Et in the acetonitrile at organic solvent
3N) sulfonic acid fluoride is changed into the triethyl ammonium (NHEt of two (fluoroalkyl alkylsulfonyl) imines
3) salt.In aqueous methanol, obtain sylvite then by using potassium hydroxide further to handle.
Except component (A), (B) with (C), poly carbonate resin composition of the present invention also can be chosen wantonly and comprise one or more additives, filler or their combination, as long as these annexing ingredients are not reduced to worthless level with thermostability or photochemical stability, perhaps the flame retardant resistance of polycarbonate are not reduced to worthless level or no longer satisfy the flame retardant resistance requirement.The example of additive includes but not limited to antioxidant for example hindered phenol, phosphorous acid ester, phosphoric acid ester and amine; UV light absorber is benzotriazole and benzophenone for example; Photostabilizer is hindered amine for example; Internal lubricant is alphatic carboxylic acid ester, paraffin, silicone oil and polyethylene wax for example; With fire retardant or flame retardant; Releasing agent is tetramethylolmethane or glycerine for example; Static inhibitor; Tinting material; And their combination.
Can be with aromatic polycarbonate resin and at least a filler compounding known in the art.The example of filler comprises potassium titanate crystal whisker, mineral fibre is mineral wool for example, glass fibre, carbon fiber, steel fiber is Stainless Steel Fibre for example, aluminium borate whisker, silicon nitride crystal whisker, boron fibre, the ZnOw of four pin shapes, talcum, clay, mica, pearl mica, aluminium foil, aluminum oxide, glass flake, granulated glass sphere, glass sphere, carbon black, graphite, lime carbonate, calcium sulfate, Calucium Silicate powder, titanium dioxide, zinc sulphide, zinc oxide, silicon-dioxide, asbestos, silica powder, and their combination.Can filler be carried out surface treatment by physics or chemical process and merge the enhancing mechanical property to improve interface junction.The interface is in conjunction with being meant two combinations that object keeps together that the surface contacted with each other by intermolecular power.Filler can use following material to handle: for example metal-salt of silylation coupling agent, higher fatty acid, lipid acid, unsaturated organic acid, organic titanate, resinous acid, polyoxyethylene glycol or Me
3Si-O-[SiOMe
2]
m-[SiOMeH]
n-SiMe
3The polymethyl hydrogen siloxane fluid of type, wherein Me is a methyl, m can be in the scope of 0-100, and n can be in the scope of 1-50.Most preferably m is 0, and n is about 50.
Described at least a filler generally uses with about 1 part to about 70 parts (with respect to 100 parts described at least a aromatic polycarbonate resin) by weight.When using more than one filler, ratio value is by weight represented the combined wt of each single filler.In a more particular embodiment, described at least a filler uses with about 2 parts to about 40 parts (with respect to 100 parts described at least a aromatic polycarbonate resin) by weight.
The invention still further relates to the method for preparing the anti-flaming polycarbonate ester articles.According to this method, can prepare the anti-flaming polycarbonate ester articles by following process, described process comprises:
(a) as mentioned above and (C), and optional additive, filler and their combination mix with the component (A) of described poly carbonate resin composition, (B);
(b) the blended composition is configured as particle;
(c) particle melt with step (b) is configured as the anti-flaming polycarbonate ester articles.
More particularly, can use any processing operation known to those skilled in the art, by the component of described composition being carried out compounding or kneading mixes the component of poly carbonate resin composition.Handle the Brunelle that describes, " Polycarbonates " in Kirk-Othmer Encyclopedia of ChemicalTechnology (the 5th edition (2006), the John Wiley﹠amp of D.J. referring to for example being used for polycarbonate; Sons, Inc., Hoboken, NJ, the 19th volume, 797-828 page or leaf).For example can using, Banbury mixer, single screw extrusion machine, twin screw extruder, multiple screw extruder etc. carry out compounding or kneading.Usually to about 300 degrees centigrade temperature, carry out compounding at about 240 degrees centigrade.Component (B), (C) and optional additive or filler and described at least a aromatic polycarbonate resin can be added together.Alternatively, for example can the one or more point downstream in forcing machine add these components.Add component in the downstream and can reduce for example loss of filler of solid, and/or improve dispersion, and/or reduce the thermal history of relatively hot unstable components, and/or reduce the loss that causes by the volatile constituent evaporation.After blending ingredients, processing or cut into pellet or be suitable for to other particle of expecting in the melt forming machine can be shaped their.Melt forming is carried out in for example injection moulding of method that can be by being generally used for thermoplastics, blowing, extrusion molding, compression moulding, calendering molding, rotational moulding etc., to form required goods.
Expect that the formed goods that comprise poly carbonate resin composition of the present invention will find effectiveness in many application (wherein using polycarbonate at present).Example includes but not limited to: glass port and thin plate; Motor vehicle assemblies; Utensil is as household article and power tool; Packing material is as water bottle that can recharge and the feeding bottle that can recharge; Electricity assembly, electronic package and technology component; The goods that medical treatment is relevant with health care; And leisure and security article.The example of glass port and sheet applications includes but not limited to be used for the window of aircraft, train and school; And high-speed aircraft canopy.This series products can use for example softish internal layer lamination.The example of motor vehicle assemblies includes but not limited to preceding lamp part, inner dashboard, snubber and window glass of motor vehicle.The example of electricity assembly, electronic package and technology component includes but not limited to electric connector, telephone network device, outlet box, computer and business machine housings, dashboard, membrane switch and isolator.The leisure and the example of security article include but not limited to protective headgear (for example sports helmet, motorcycle helmet and be used for the firemen and builder's crash helmet) and protectiveness eyeshade (for example eye-protection glasses, safety glasses, safety guard, glasses and face shield).Described resin combination is particularly useful for those application examples that need fire retardant material such as business automation equipment and electric machinery and electric mechanical.
Can use appropriate means to measure the inflammableness of described poly carbonate resin composition.For example, spendable method is suitable for wherein will using the country of polycarbonate.In the U.S., may need fire-retardant polycarbonate of the present invention satisfy Underwriter ' s Laboratory standard, especially UL-94 (Underwriters Laboratories, Inc., Northbrook, IL).UL-94 resists the incendiary ability based on material when repeating to apply flame, and material to drippage and subsequently because the dropping that produces ignites the originate resistivity of (cotton) of inflammable substance come material is tested.Be installed in test sample book in the sample room and lighted for 10 seconds.If sample extinguishes, just note the time of residual flame, then sample was refired for 10 seconds.Then based on the residual flame time and by the cotton ignition that causes of burning dropping with the material classification.The grade of accepting extensively most is V-0, V-1 and V-2.The V-1 level allows the residual flame time longer than V-0, and V-2 has the residual flame time identical with V-1, but allows the cotton ignition.For the present invention, for V-0, then use＜10 seconds residual flame time, and, then use＜30 seconds residual flame time for V-1 and V-2.
In following examples, will describe the present invention in more detail with reference to comparing embodiment and embodiment, yet described embodiment should be interpreted as restriction the present invention.
General material and method
Used following abbreviation in the literary composition:
Degree centigrade be " C " or " ℃ "; Gram is " g "; " h " is hour; Relative humidity is " RH "; Millimeter is " mm "; Nucleus magnetic resonance is " NMR "; And dsc is " DSC ".
1,1,2,3,3,3-hexafluoropropanesulacidc acidc potassium (HFPS-K) and 1,1,2, the synthetic of 2-tetrafluoro ethyl sulfonic acid potassium (TFES-K) is described among U.S. Patent application 2006/027661, the embodiment 2,4 and 5.
Si Zheng Ding Ji Phosphonium 1,1,2,3,3,3-hexafluoropropanesulacidc acidc salt (TBP-HFPS) synthetic:
With deionized water (2800mL) and 1,1,2,3,3, (HFPS-K 551.2g) joins in the Erlenmeyer flask of 4L 3-hexafluoropropanesulacidc acidc potassium.At room temperature the content of magnetic agitation flask dissolves to produce limpid colourless solution up to HFPS-K.To this solution add 75 weight % four normal-butyl bromination Phosphonium (
443W, Cytec Canada Inc., aqueous solution 923.0g).Formed a large amount of laminar white precipitates, made this mixture at room temperature stir 8h then.Isolate the product that is settled out of white by suction filtration.Then with the saturated sodium carbonate magnetic agitation of crude product and 1000mL 30 minutes to remove any acidic impurities.Isolate product once more by suction filtration.With the further washed product of the deionized water of 3 * 1000mL part to remove the carbonate of any remnants.Isolate this material by suction filtration, (70 ℃, 100 holders 18h) are anhydrated to remove in the above vacuum-drying of its fusing point then.Make cooling and the curing in baking oven under nitrogen purging of this product.The solid product muffin is taken out from baking oven, then by #14 order (1.4mm) screen cloth to obtain free-pouring solid (893g, 89% yield).
19F?NMR(CD
2Cl
2)δ-74.9(m，3F)；-115.3，-122.8(ABq，J＝264Hz，2F)；-210.1(dm，1F)。
1H?NMR(CD
2C?l?
2)δ1.0(t，J＝7.3Hz，12H)；1.5(m，16H)；2.2(m，8H)；5.4(dm，J
FH＝54Hz，1H)。
Water per-cent by the Karl-Fisher titration measuring: 671ppm.
Fusing point (DSC): 74 ℃.
C
19H
37F
6O
3The ultimate analysis of PS: calculated value: %C, 46.5:H, 7.6:N, 0.0.
Experimental result: %C, 46.9:H, 8.0:N,＜0.1.
1,1,2-three fluoro-2-(perfluor oxyethyl group) ethyl sulfonic acid potassium (TPES-K) synthetic:
The synthetic of TFES-K has been described in the U.S. Patent application 2006/0276671.To 1 gallon
Pack in the C276 reaction vessel hydration potassium sulfite (88g, 0.56mol), the solution of Potassium hydrogen sulfite (340g, 1.53mo l) and deionized water (2000ml) partially.Container is cooled to 7 ℃, empties to 0.05MPa, and use nitrogen purging.Repeating emptying/purging again circulates twice.(PEVE, 600g 2.78mol), are heated to 125 ℃ then, and this moment, internal pressure was 2.31MPa to add perfluor (ethyl vinyl ether) then in this container.Temperature of reaction is remained on 125 ℃ of 10h.Pressure drops to 0.26MPa, and this moment is with container emptying and be cooled to 25 ℃.Thick reaction product is the white crystals throw out, and colourless waterbearing stratum (pH=7) is arranged on it.
This white solid
19It is pure desired product that F NMR spectrum shows, but and the spectrum in waterbearing stratum shows the impurity of fluoridizing of small but detection limit.Desired isomer is less dissolving in water, so it is with the pure form precipitation of isomery.
By the sintered glass funnel suction filtration, (60 ℃, 0.01MPa) middle drying is 48 hours at vacuum oven with wet filter cake then with the product slurries.Obtain canescence crystalline product (904g, 97% yield).
19F NMR (D
2O) δ-86.5 (s, 3F);-89.2 ,-91.3 (son splits branch ABq, J
FF=147Hz, 2F);
-119.3 ,-121.2 (son splits branch ABq, J
FF=258Hz, 2F);-144.3 (dm, J
FH=53Hz, 1F).
1H?NMR(D
2O)δ6.7(dm，J
FH＝53Hz，1H)。
Mp(DSC)263℃。
C
4HO
4F
8The ultimate analysis calculated value of SK: C, 14.3:H, 0.3.Experimental result: C, 14.1:H, 0.3.
TGA (air): at 359 ℃, 10 weight % loss; At 367 ℃, 50 weight % loss.
TGA (N
2): at 362 ℃, 10 weight % loss; At 374 ℃, 50 weight % loss.
Similarly method can be used for the synthetic of TFES-Na, uses the above-described molar weight that equals to be used for potassium.
1-butyl-3-Methylimidazole 1,1,2,2-tetrafluoro esilate (BMIM-TFES) synthetic:
With 1-butyl-3-methyl imidazolitm chloride (60.0g) and highly purified dry acetone (＞99.5%, 300ml) be incorporated in 1 liter the flask, and under magnetic agitation, be heated to backflow, dissolve fully until solid.At room temperature, in 1 liter of independent flask, with 1,1,2, (TFES-K 75.6g) is dissolved in the highly purified dry acetone (500ml) 2-tetrafluoro ethyl sulfonic acid potassium.At room temperature these two kinds of solution are merged, and under positive nitrogen pressure with its magnetic agitation 2 hours.Stop to stir, thereby make KCl avale, carry out suction filtration by passing sintered glass funnel then, so that it is removed with celite pad.Vacuum is removed acetone to obtain xanchromatic oil.By using high purity acetone (100ml) dilution and being further purified this oil with decolorizing carbon (5g) stirring.Once more mixture suction filtration and vacuum are removed acetone to obtain colourless oil.Should the further dry 6h of oil under 4Pa and 25 ℃, to obtain the product of 83.6g.
19F?NMR(DMSO-d?
6)δ-124.7(d?t，J＝6Hz，J＝8Hz，2F)；-136.8(dt，J＝53Hz，2F)。
1H?NMR(DMSO-d
6)δ0.9(t，J＝7.4Hz，3H)；1.3(m，2H)；1.8(m，2H)；3.9(s，3H)；4.2(t，J＝7Hz，2H)；6.3(d?t，J＝53Hz，J＝6Hz，1H)；7.4(s，1H)；7.5(s，1H)；8.7(s，1H)。
Water per-cent by the Karl-Fisher titration measuring: 0.14%.
C
9H
12F
6N
2O
3The ultimate analysis calculated value of S: C, 37.6:H, 4.7:N, 8.8.
Experimental result: C, 37.6:H, 4.6:N, 8.7.
TGA (air): at 380 ℃, 10 weight % loss; At 420 ℃, 50 weight % loss.
TGA (nitrogen): at 375 ℃, 10 weight % loss; At 422 ℃, 50 weight % loss.
Synthesizing of the lithium salts of fluorinated alkyl sulfonic acid and cesium salt:
Can be as proposing in the U.S. Patent application 2006/0276671, the sylvite of fluorinated alkyl sulfonic acid and sodium salt (purifying reaction mixture that cross or that cross as thick drying) are changed into their anhydrous acid.Can make these acid and Quilonum Retard or cesium carbonate in organic solvent such as methyl alcohol, react lithium salts or the cesium salt that obtains corresponding fluorinated alkyl sulfonic acid with high yield then.Can remove organic solvent and isolate described lithium salts or cesium salt product with vacuum distilling then by at first with removing by filter any excessive undissolved carbonate.For the lithium salts care should be used to, to keep this system anhydrous, because lithium salts very easily moisture absorption usually.
By 1,1,2,2-tetrafluoro ethyl sulfonic acid (TFESA) synthesizes 1,1,2,2-tetrafluoro ethyl sulfonic acid lithium (TFES- Li):
With 1,1,2, (10.05g is 0.055mol) with exsiccant methyl alcohol (10mL for 2-tetrafluoro ethyl sulfonic acid; EMD Chemicals Inc., Gibbstown NJ) joins in the bottle of 20mL.This solution is being cooled to 0 ℃ under the nitrogen atmosphere under the magnetic agitation in ice bath.In an independent flask, with Quilonum Retard (0.95g, 0.026mol; Aldrich, St.Louis MO) mixes with exsiccant methyl alcohol (10mL), and under nitrogen atmosphere in ice bath magnetic agitation also be 0 ℃ until it.Then TFESA solution is slowly joined in the carbonate mixture, produce a large amount of gas CO
2After interpolation was finished, gas release stopped, and vacuum is removed methyl alcohol on rotatory evaporator.Then flask is heated to 80 ℃ of 3h to remove anhydrate (it during reaction forms) under vacuum.Isolate white powdered product (TFES-Li, 8.7g, 84% yield) and sign.
Water per-cent by the Karl-Fisher titration measuring: 0.27 weight %
C
2H
1F
4LiO
3The ultimate analysis of S: calculated value: %C, 12.78:H, 0.54.
Experimental result: %C, 12.53:H, 0.74.
1-butyl-3-Methylimidazole Synthesizing of nine fluorine fourth sulfonate (BMIM-NONA):
Can described in people Tet rahedron (2006) 62:3137-3145 such as S.K.Quek, synthesize BMIM-NONA.
Tetradecyl (three normal-butyls)Phosphonium
1,1,2,2-tetrafluoro esilate ([4.4.4.14] P-TFES) Synthetic:
In the 1000mL flask, stir 1,1,2 at 25 ℃ of lower magnetic forces, 2-tetrafluoro ethyl sulfonic acid potassium (TFESK, 85.2g, 0.39mol) and deionized water (150mL) dissolve until solid.In an independent 500mL flask, at first make tetradecyl (three normal-butyl) phosphonium chloride (168g, 0.39mol by being heated to 50 ℃
IL 167; Cytec (West Paterson, NJ)) fusion is added in the TFESK solution then to produce the oily precipitation.Under 25 ℃ with flask restir 19h so that product precipitate fully.
With chloroform (500mL; Alrich) join in the mixture, its restir 30 minutes.The chloroform layer that will comprise product is isolated and is placed on one side.Extract water layer with chloroform (5 * 20mL washing), and with these aliquots containigs and original chloroform layer merging.(5 * 20mL washs with saturated aqueous sodium carbonate with the chloroformic solution after merging; Aldrich) deionized water (5 * 20mL) washings, the pH=8 that has until final washing water are used in washing subsequently.
This solution is gone up drying at anhydrous magnesium sulfate (Aldrich), and add the 10g decolorizing carbon to remove foreign pigment this moment.Filter with before removing carbon elimination at pillar (celite/alkali alumina post is housed), with this solution restir 30 minutes by the 6-inch.This solution is gone up dry at anhydrous magnesium sulfate (Aldrich) again, and on rotatory evaporator, is concentrated, further dry then (60 millitorrs, 25 ℃, 8h) with obtain limpid light yellow oil [
4.4.4.14] P-TFES product (173g, 77% yield).
19F?NMR(CDCl
3)δ-124.3(dt，
3J
FH＝6Hz，
3J
FF＝8Hz，2F)；-136.0(dt，
2J
FH＝53Hz，2F)。
1H?NMR(CDCl
3)δ0.8(t，J＝7.0Hz，3H)；1.0(t，J＝7.0Hz，9H)；1.3(br??s，20H)；1.5(m，16H)；2.2(m，8H)；6.2(tt，
2J
FH＝53Hz，
3J
FH＝6Hz，1H)。
Water per-cent by the Karl-Fisher titration measuring: 594ppm.
Embodiment 1: the flame retardant resistance of polycarbonate resin (comparing embodiment)
With polycarbonate resin (1484.5g; With trade(brand)name
HF-1110 (GeneralElectric Co., Pittsfield MA) sell) place be equipped with the V-pyramid type stirrer that strengthens bar (Patterson Kelly, East Stroudsburg, PA) in.Described resin the is coated polydimethylsiloxane DC-200-60M of 4g (Dow Corning, Midland, MI).Make coating adhere to resin after last 5 minute, with the polycarbonate pellet that applies be encased in 275 ℃ the 30mm twin screw extruder (Werner-Pfleiderer, Coperion, Ramsey, NJ) in.(PA) (Newington CT) goes up injection mouldings to 1.5 of simple gate flexural bars mould ounces of Arburg injection molding machines for ASTM International, West Conshohocken at the ASTM that is equipped with 1/16 inch (approximately 1.59mm) with the polycarbonate of institute's compounding.Before tested flame retardant resistance, with sample storage in 22 ℃ and 50% relative humidity room minimum 1 day.
(Northbrook IL) tests all samples for Underwriters Laboratories, Inc. according to standard flame retardant resistance test procedure UL-94.On vertical position, test sample book is tested.The flame that regulates is placed 10 seconds on the test sample book, and the time record that flame oneself is extinguished is t1 then.Placed on the test sample book piece remove then for 10 seconds again flame, will be recorded as t2 second combustion time.Also to write down the existence of burning dropping.When flame is removed, do not find the residual flame on any test sample book.The standard that is used for sample is classified as V-0, V-1 or V-2 is shown in Table 1, and wherein t1 and t2 are to report second.The results are shown in the table 2.
Table 1: the standard that is used for sample is classified as V-0, V-1 or V-2
The time of V-0, V-1 and V-2 is in second.
| Standard | ??V-0 | ??V-1 | ??V-2 |
| The residual flame time t1 or the t 2 of each independent sample | ??＜10 | ??＜30 | ??＜30 |
| Total residual flame time of set any condition (t 1 of 5 samples adds t 2) | ??＜50 | ??＜250 | ??＜250 |
| The cotton indicator that burned particle or dropping ignite | Not | Not | Be |
Embodiment 2: polycarbonate resin adds the flame retardant resistance (comparing embodiment) of dripping inhibitor
Repeat the step of embodiment 1, yet add tetrafluoroethylene (p-TFE) dripping inhibitor (7g; MP1400, E.I.DuPont, Wilmington DE).The results are shown in the table 2.
Embodiment 3-6: polycarbonate resin is with the flame retardant resistance of salt
Repeat the step of embodiment 2, different is except p-TFE, has also added as directed 4.5g salt.The results are shown in the table 2.
Table 2: the flame retardant resistance test that has or do not have the polycarbonate of dripping inhibitor and/or salt
All values are the mean value of 5 measurements in the table 2.
Abbreviation: TBP-HFPS, Zheng Ding Ji Phosphonium 1,1,2,3,3,3-hexafluoropropanesulacidc acidc salt; HFPS-K, 1,1,2,3,3,3-hexafluoropropanesulacidc acidc potassium; TPES-K, 1,1,2-three fluoro-2-(perfluor oxyethyl group) ethyl sulfonic acid potassium; BMIM-TFES, 1-butyl-3-Methylimidazole 1,1,2,2-tetrafluoro esilate.
| The embodiment numbering | Sample | ??t1 | ??t2 | The burning drippage | Grade |
| ??1 | Resin | ??9.5 | ??3.2 | Be | ??V-2 |
| ??2 | ??p-TFE | ??7.5 | ??2.4 | Be | ??V-2 |
| ??3 | ??TBP-HFPS | ??1.0 | ??2.4 | Not | ??V-0 |
| ??4 | ??HFPS-K | ??2.4 | ??9.0 | Not | ??V-0 |
| ??5 | ??TPES-K | ??4.3 | ??2.4 | Not | ??V-0 |
| ??6 | ??BMIM-TFES | ??0.9 | ??0.8 | Not | ??V-0 |
Embodiment 7-14: polycarbonate resin is with the flame retardant resistance of salt
Use 3000ppm salt and 5000ppm p-TFE ultrafine powder as shown in following table 3, come compounding polycarbonate sample (sample) as described in example 1 above.The polycarbonate of institute's compounding further is molded as described in example 1 above piece.Come test sample is tested according to foregoing UL-94.The results are shown in the table 3.
Table 3: the flame retardant resistance test of polycarbonate
| The embodiment numbering | Sample | ??t1 | ??t2 |
| ??7 | Resin+p-TFE only | ??13.5 | ??23.0 |
| ??8 | ??TFES-K | ??1.1 | ??2.0 |
| ??9 | ??BM?IM-TFES | ??1.5 | ??1.5 |
| ??10 | ??BMIM-NONA | ??1.0 | ??1.0 |
| ??11 | ??TBP-TFES | ??4.3 | ??1.0 |
| ??12 | ??BMIM-TFES | ??4.0 | ??1.5 |
| ??13 | ??[4.4.4.14]P-TFES | ??3.0 | ??1.0 |
| ??14 | ??BMIM-NONA | ??2.0 | ??1.0 |
Embodiment 15-20: salt concn is to the influence of polycarbonate sample flame retardant resistance
Measure the influence of salt concn to flame retardant resistance.Concentration shown in the following table 4 uses BMIM-TFES or TFES-K as salt, and polycarbonate sample (sample) and the p-TFE ultrafine powder of the 5000ppm described in the embodiment 7-14 are carried out compounding.The polycarbonate of institute's compounding further is molded as described in example 1 above piece.Come test sample is tested according to foregoing UL-94.The results are shown in the table 4.
Table 4: the flame retardant resistance test of polycarbonate
| The embodiment numbering | Sample | Salt concn (ppm) | ??t1 | ??t2 |
| ??15 | ??BMIM-TFES | ?3000 | ??1.0 | ??0.6 |
| ??16 | ??BM?IM-TFES | ?1500 | ??0.8 | ??0.0 |
| ??17 | ??BM?IM-TFES | ?750 | ??0.4 | ??0.2 |
| ??18 | ??TFES-K | ?3000 | ??0.8 | ??2.4 |
| ??19 | ??TFES-K | ?1500 | ??1.0 | ??3.0 |
| ??20 | ??TFES-K | ?750 | ??1.0 | ??1.3 |
Claims (23)
1. fire-retarded polycarbonate resin composition, described composition comprises:
(A) at least a aromatic polycarbonate resin;
(B) at least a dripping inhibitor; And
(C) at least a have a formula M
+Q
-Salt, M wherein
+Be that (1) is selected from lithium, sodium, potassium
Be selected from following 11 kinds of cationic positively charged ions with positively charged ion or (2) of caesium:
The pyridine pyridazine
The pyrimidine pyrazine
The imidazoles pyrazoles
Sai Zuo oxazole
Triazole
The Phosphonium ammonium
R wherein
1, R
2, R
3, R
4, R
5And R
6Be independently selected from:
(a)H
(b) halogen
(c) randomly be selected from Cl, Br, F, I, OH, NH by at least one
2With the group of SH replace-CH
3,-C
2H
5Or C
3To C
25Straight chain, side chain or cyclic alkane or alkene;
(d) comprising one to three is selected from the heteroatoms of O, N, Si and S and randomly is selected from Cl, Br, F, I, OH, NH by at least one
2With the group of SH replace-CH
3,-C
2H
5, or C
3To C
25Straight chain, side chain or cyclic alkane or alkene;
(e) has one to three heteroatomic C that is independently selected from O, N, Si and S
6To C
25Unsubstituted aryl or C
6To C
25Unsubstituted heteroaryl; And
(f) has one to three heteroatomic C that is independently selected from O, N, Si and S
6To C
25The aryl or the C that replace
6To C
25The heteroaryl that replaces; And the aryl of wherein said replacement or the heteroaryl of replacement have one to three substituting group, and described substituting group is independently selected from:
(1) randomly is selected from Cl, Br, F, I, OH, NH by at least one
2With the group of SH replace-CH
3,-C
2H
5Or C
3To C
25Straight chain, side chain or cyclic alkane or alkene,
(2)OH，
(3) NH
2, and
(4)SH；
R
7, R
8, R
9And R
10Be independently selected from:
(g) randomly be selected from Cl, Br, F, I, OH, NH by at least one
2With the group of SH replace-CH
3,-C
2H
5, or C
3To C
25Preferred straight chain, side chain or cyclic alkane or alkene;
(h) comprising one to three is selected from the heteroatoms of O, N, Si and S and randomly is selected from Cl, Br, F, I, OH, NH by at least one
2With the group of SH replace-CH
3,-C
2H
5, or C
3To C
25Straight chain, side chain or cyclic alkane or alkene;
(i) has one to three heteroatomic C that is independently selected from O, N, Si and S
6To C
25Unsubstituted aryl or C
6To C
25Unsubstituted heteroaryl; And
(j) has one to three heteroatomic C that is independently selected from O, N, Si and S
6To C
25The aryl or the C that replace
6To C
25The heteroaryl that replaces; And the aryl of wherein said replacement or the heteroaryl of replacement have one to three substituting group, and described substituting group is independently selected from:
(1) randomly is selected from Cl, Br, F, I, OH, NH by at least one
2With the group of SH replace-CH
3,-C
2H
5Or C
3To C
25Straight chain, side chain or cyclic alkane or alkene,
(2)OH，
(3) NH
2, and
(4) SH; And wherein
Optional R
1, R
2, R
3, R
4, R
5, R
6, R
7, R
8, R
9And R
10In at least two can form cyclic or bicyclic alkyl or alkenyl together;
And Q wherein
-Be the negatively charged ion that is selected from formula I and formula II:
Formula I
Wherein:
R
11Be selected from:
(1) halogen;
(2) randomly be selected from Cl, Br, I, OH, NH by at least one
2With the group of SH replace-CH
3,-C
2H
5Or C
3To C
15The alkane of straight or branched or alkene;
(3) randomly be selected from Cl, Br, I, OH, NH by at least one
2With the group of SH replace-OCH
3,-OC
2H
5Or C
3To C
15The alkoxyl group of straight or branched;
(4) randomly be selected from Cl, Br, I, OH, NH by at least one
2The C that replaces with the group of SH
1To C
15The fluoro-alkyl of straight or branched;
(5) randomly be selected from Cl, Br, I, OH, NH by at least one
2The C that replaces with the group of SH
1To C
15The fluoroalkyl of straight or branched;
(6) C
1To C
15The perfluoroalkyl of preferred straight or branched; And
(7) C
1To C
15The perfluoro alkoxy of straight or branched;
And
Formula II
Wherein:
R
12Be selected from:
(1) halogen;
(2) randomly be selected from Cl, Br, I, OH, NH by at least one
2With the group of SH replace-CH
3,-C
2H
5Or C
3To C
15The alkane of straight or branched or alkene;
(3) randomly be selected from Cl, Br, I, OH, NH by at least one
2With the group of SH replace-OCH
3,-OC
2H
5Or C
3To C
15The alkoxyl group of straight or branched;
(4) randomly be selected from Cl, Br, I, OH, NH by at least one
2The C that replaces with the group of SH
1To C
15The fluoro-alkyl of straight or branched;
(5) randomly be selected from Cl, Br, I, OH, NH by at least one
2The C that replaces with the group of SH
1To C
15The fluoroalkyl of straight or branched;
(6) C
1To C
15The perfluoroalkyl of straight or branched; And
(7) C
1To C
15The perfluoro alkoxy of straight or branched.
2. the composition of claim 1, described composition have about 100 parts component (A), about 0.01 to about 5.0 parts component (B) and about 0.001 to about 2.0 parts component (C).
3. the composition of claim 2, described composition has about 100 parts component (A) and about 0.1 to about 3.0 parts component (B).
4. the composition of claim 2, described composition has about 100 parts component (A) and about 0.01 to about 1.0 parts component (C).
5. the composition of claim 1, wherein said at least a aromatic polycarbonate resin is by diphenyl carbonate and 2, and the reaction of 2-two (4-hydroxy phenyl) propane prepares.
6. the composition of claim 1, wherein dripping inhibitor is a tetrafluoroethylene.
7. the composition of claim 1, wherein Q-is selected from: 1,1,2,2-tetrafluoro ethyl sulfonic acid root; 2-chloro-1,1,2-trifluoro ethyl sulfonic acid root; 1,1,2,3,3,3-hexafluoropropanesulacidc acidc root; 1,1,2-three fluoro-2-(trifluoromethoxy) ethyl sulfonic acid roots; 1,1,2-three fluoro-2-(perfluor oxyethyl group) ethyl sulfonic acid root; 2-(1,2,2,2-tetrafluoro oxyethyl group)-1,1,2,2-tetrafluoro ethyl sulfonic acid root; 2-(1,1,2,2-tetrafluoro oxyethyl group)-1,1,2,2-tetrafluoro ethyl sulfonic acid root; 2-(1,1,2,2-tetrafluoro-2-iodine oxyethyl group)-1,1,2,2-tetrafluoro ethyl sulfonic acid root; 1,1,2,2-tetrafluoro-2-(five fluorine oxyethyl groups) ethyl sulfonic acid root; N, N-two (1,1,2,2-tetrafluoro ethylsulfonyl) imines; And N, N-two (1,1,2,3,3,3-hexafluoro third alkylsulfonyl) imines.
8. the composition of claim 1, wherein component (C) is selected from: 1-butyl-2,3-methylimidazole 1,1,2,2-tetrafluoro esilate, 1-butyl-Methylimidazole 1,1,2,2-tetrafluoro esilate, 1-ethyl-3-Methylimidazole 1,1,2,2-tetrafluoro esilate, 1-ethyl-3-Methylimidazole 1,1,2,3,3,3-hexafluoropropanesulacidc acidc salt, 1-hexyl-3-Methylimidazole 1,1,2,2-tetrafluoro esilate, 1-dodecyl-3-Methylimidazole 1,1,2,2-tetrafluoro esilate, 1-hexadecyl-3-Methylimidazole 1,1,2,2-tetrafluoro esilate, 1-octadecyl-3-Methylimidazole 1,1,2,2-tetrafluoro esilate, N-(1,1,2,2-tetrafluoro ethyl) propyl imidazole 1,1,2,2-tetrafluoro esilate, N-(1,1,2,2-tetrafluoro ethyl) ethyl perfluoro hexyl imidazoles 1,1,2,2-tetrafluoro esilate, 1-butyl-3-Methylimidazole 1,1,2,3,3,3-hexafluoropropanesulacidc acidc salt, 1-butyl-3-Methylimidazole 1,1,2-three fluoro-2-(trifluoromethoxy) esilates, 1-butyl-3-Methylimidazole 1,1,2-three fluoro-2-(perfluor oxyethyl group) esilate, tetradecyl (three n-hexyl) Phosphonium 1,1,2-three fluoro-2-(perfluor oxyethyl group) esilate, tetradecyl (three normal-butyl) Phosphonium 1,1,2,3,3,3-hexafluoropropanesulacidc acidc salt, tetradecyl (three n-hexyl) Phosphonium 1,1,2-three fluoro-2-(trifluoromethoxy) esilates, 1-ethyl-3-Methylimidazole 1,1,2,2-tetrafluoro-2-(five fluorine oxyethyl groups) sulfonate, (3,3,4,4,5,5,6,6,7,7,8,8,8-ten trifluoro octyl groups)-San Xin Ji Phosphonium 1,1,2,2-tetrafluoro esilate, 1-methyl-3-(3,3,4,4,5,5,6,6,7,7,8,8,8-ten trifluoro octyl groups) imidazoles 1,1,2,2-tetrafluoro esilate, four positive fourth base Phosphonium 1,1,2-three fluoro-2-(perfluor oxyethyl group) esilate, 1,1,2,2-tetrafluoro ethyl sulfonic acid potassium, 1,1,2,3,3,3-hexafluoropropanesulacidc acidc potassium, and 1,1,2-three fluoro-2-(perfluor oxyethyl group) ethyl sulfonic acid potassium.
9. composition, described composition comprises at least a dripping inhibitor and at least a salt according to claim 1.
10. the composition of claim 1 or claim 9, described composition comprises superfine powder of polytetrafluoroethylene.
11. the composition of claim 1 or claim 9, described composition comprises polytetrafluoroethyldispersions dispersions.
12. the composition of claim 1, claim 9, claim 10 or claim 11, described composition comprises 1,1,2,2-tetrafluoro ethyl sulfonic acid or 1,1,2,3,3, the lithium of 3-hexafluoropropanesulacidc acidc, sodium, potassium or cesium salt.
13. the composition of claim 12, described composition comprises 1,1,2,2-tetrafluoro ethyl sulfonic acid potassium or 1,1,2,3,3,3-hexafluoropropanesulacidc acidc potassium.
14. the composition of claim 1, described composition also comprises at least a following component that is selected from: (1) at least a additive, described additive are selected from antioxidant, UV light absorber, photostabilizer, internal lubricant and fire retardant or flame retardant, releasing agent, static inhibitor, tinting material and their combination; (2) at least a filler; And (3) their combination.
15. the composition of claim 14, wherein antioxidant comprises hindered phenol, phosphorous acid ester, phosphoric acid ester or amine; UV light absorber comprises benzotriazole or benzophenone; Photostabilizer comprises hindered amine; Internal lubricant comprises alphatic carboxylic acid ester, paraffin, silicone oil or polyethylene wax; Releasing agent comprises tetramethylolmethane or glycerine; And filler is selected from: ZnOw, talcum, clay, mica, pearl mica, aluminium foil, aluminum oxide, glass flake, granulated glass sphere, glass sphere, carbon black, graphite, lime carbonate, calcium sulfate, Calucium Silicate powder, titanium dioxide, zinc sulphide, zinc oxide, silicon-dioxide, asbestos and the silica powder of potassium titanate crystal whisker, mineral fibre, glass fibre, carbon fiber, steel fiber, aluminium borate whisker, silicon nitride crystal whisker, boron fibre, four pin shapes.
16. the composition of claim 14, wherein filler exists with about 1 part to about 70 parts by weight.
17. the composition of claim 1, wherein component (B) comprises tetrafluoroethylene, and component (C) comprises 1,1,2,2-tetrafluoro ethyl sulfonic acid or 1,1,2,3,3, the sodium salt of 3-hexafluoropropanesulacidc acidc or sylvite.
18. the composition of claim 1, wherein component (A) is by diphenyl carbonate and 2, and the reaction of 2-two (4-hydroxy phenyl) propane prepares, and component (B) comprises tetrafluoroethylene, and component (C) comprises 1,1,2,2-tetrafluoro ethyl sulfonic acid or 1,1,2,3,3, the sodium salt of 3-hexafluoropropanesulacidc acidc or sylvite.
19. prepare the method for anti-flaming polycarbonate ester articles, described method comprises:
(a) will mix to form the blended composition as the component of defined poly carbonate resin composition in claim 1, claim 13 or the claim 14;
(b) the blended composition is configured as particle;
(c) particle melt with step (b) is configured as the anti-flaming polycarbonate ester articles.
20. the method for claim 19, wherein said mixing use Banbury mixer, single screw extrusion machine, twin screw extruder or multiple screw extruder to implement.
21. the method for claim 19, wherein said melt forming use injection moulding, blowing, extrusion molding, compression moulding, calendering molding or rotational moulding to implement.
22. comprise the anti-flaming polycarbonate ester articles according to the fire-retarded polycarbonate resin composition of claim 1, described goods are selected from glass port or thin plate; Motor vehicle assemblies; Home appliances; Packing material; Electricity assembly, electronic package or technology component; Medical treatment or the relevant goods of health care; And leisure or security article.
23. according to the anti-flaming polycarbonate ester articles of claim 22, described goods are selected from following assembly: aircraft, train, the window of school, the high-speed aircraft canopy, the motor vehicle headlamp parts, the interior of motor vehicles dashboard, the automobile buffer device, window glass of motor vehicle, household article, the family expenses power tool, the water bottle that can recharge, the feeding bottle that can recharge, electric connector, the telephone network device, outlet box, counter body, business machine housings, dashboard, membrane switch, isolator, eye-protection glasses, safety glasses, safety guard, glasses, face shield, sports helmet, motorcycle helmet, and the crash helmet that is used for firemen or builder.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US90555507P | 2007-03-07 | 2007-03-07 | |
| US60/905,555 | 2007-03-07 | ||
| US60/958,194 | 2007-07-03 |
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| CN101627079A true CN101627079A (en) | 2010-01-13 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN200880007489A Pending CN101627079A (en) | 2007-03-07 | 2008-02-29 | Flame retardant polycarbonate compositions |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102321357A (en) * | 2011-07-25 | 2012-01-18 | 琨诘电子（昆山）有限公司 | Environment-friendly heat-resistant antistatic insulating material |
| CN103013081A (en) * | 2012-12-17 | 2013-04-03 | 上海冠旗电子新材料股份有限公司 | Heat-resistant scratch-resistant halogen-free anti-flaming polycarbonate thin film |
| CN107001690A (en) * | 2014-08-29 | 2017-08-01 | 内华达高等教育系统董事会代表拉斯维加斯内华达大学 | Fire proofing and the device comprising it |
| CN108003591A (en) * | 2017-12-25 | 2018-05-08 | 桐城市祥泰塑业有限公司 | A kind of high printing opacity whisker mirror plastic material and preparation method thereof |
| US10240090B2 (en) | 2014-08-29 | 2019-03-26 | The Board Of Regents Of The Nevada System Of Higher Education On Behalf Of The University Of Nevada, Las Vegas | Fire retardant materials and devices including same |
| CN111454558A (en) * | 2020-04-09 | 2020-07-28 | 泰力（安徽）电器股份有限公司 | Preparation method of flame-retardant smoke-suppression type socket material |
| CN112500691A (en) * | 2020-12-08 | 2021-03-16 | 万华化学(四川)有限公司 | High-impact-resistance and heat and humidity aging resistant polycarbonate material and preparation method thereof |
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- 2008-02-29 CN CN200880007489A patent/CN101627079A/en active Pending
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102321357A (en) * | 2011-07-25 | 2012-01-18 | 琨诘电子（昆山）有限公司 | Environment-friendly heat-resistant antistatic insulating material |
| CN103013081A (en) * | 2012-12-17 | 2013-04-03 | 上海冠旗电子新材料股份有限公司 | Heat-resistant scratch-resistant halogen-free anti-flaming polycarbonate thin film |
| CN103013081B (en) * | 2012-12-17 | 2015-12-09 | 上海冠旗电子新材料股份有限公司 | High temperature resistant scratch resistant halogen-free flame retardant polycarbonate film |
| CN107001690A (en) * | 2014-08-29 | 2017-08-01 | 内华达高等教育系统董事会代表拉斯维加斯内华达大学 | Fire proofing and the device comprising it |
| US10240090B2 (en) | 2014-08-29 | 2019-03-26 | The Board Of Regents Of The Nevada System Of Higher Education On Behalf Of The University Of Nevada, Las Vegas | Fire retardant materials and devices including same |
| CN108003591A (en) * | 2017-12-25 | 2018-05-08 | 桐城市祥泰塑业有限公司 | A kind of high printing opacity whisker mirror plastic material and preparation method thereof |
| CN111454558A (en) * | 2020-04-09 | 2020-07-28 | 泰力（安徽）电器股份有限公司 | Preparation method of flame-retardant smoke-suppression type socket material |
| CN111454558B (en) * | 2020-04-09 | 2022-04-29 | 泰力（安徽）电器股份有限公司 | Preparation method of flame-retardant smoke-suppression type socket material |
| CN112500691A (en) * | 2020-12-08 | 2021-03-16 | 万华化学(四川)有限公司 | High-impact-resistance and heat and humidity aging resistant polycarbonate material and preparation method thereof |
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