CN1313523C - Flame retardant compositions - Google Patents
Flame retardant compositions Download PDFInfo
- Publication number
- CN1313523C CN1313523C CNB2004100286999A CN200410028699A CN1313523C CN 1313523 C CN1313523 C CN 1313523C CN B2004100286999 A CNB2004100286999 A CN B2004100286999A CN 200410028699 A CN200410028699 A CN 200410028699A CN 1313523 C CN1313523 C CN 1313523C
- Authority
- CN
- China
- Prior art keywords
- fire retardant
- clay
- polyester
- silver
- manufacture method
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
- 239000003063 flame retardant Substances 0.000 title claims abstract description 106
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 title claims abstract description 39
- 239000000203 mixture Substances 0.000 title abstract description 16
- 239000004927 clay Substances 0.000 claims abstract description 93
- 229910052709 silver Inorganic materials 0.000 claims abstract description 68
- 239000004332 silver Substances 0.000 claims abstract description 67
- 229920000728 polyester Polymers 0.000 claims abstract description 48
- -1 silver ions Chemical class 0.000 claims abstract description 41
- 239000004033 plastic Substances 0.000 claims abstract description 22
- 229920003023 plastic Polymers 0.000 claims abstract description 22
- 238000002156 mixing Methods 0.000 claims abstract description 12
- 239000002245 particle Substances 0.000 claims abstract description 10
- 230000002829 reductive effect Effects 0.000 claims abstract description 9
- 229920001707 polybutylene terephthalate Polymers 0.000 claims description 28
- 239000000835 fiber Substances 0.000 claims description 23
- 239000004594 Masterbatch (MB) Substances 0.000 claims description 20
- 238000000034 method Methods 0.000 claims description 19
- 239000003795 chemical substances by application Substances 0.000 claims description 18
- 238000004519 manufacturing process Methods 0.000 claims description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 18
- 239000004568 cement Substances 0.000 claims description 17
- 125000000217 alkyl group Chemical group 0.000 claims description 14
- 150000003863 ammonium salts Chemical group 0.000 claims description 12
- 239000008367 deionised water Substances 0.000 claims description 12
- 229910021641 deionized water Inorganic materials 0.000 claims description 12
- 229910052760 oxygen Inorganic materials 0.000 claims description 12
- 239000001301 oxygen Substances 0.000 claims description 12
- 230000004048 modification Effects 0.000 claims description 10
- 238000012986 modification Methods 0.000 claims description 10
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 9
- 229910052799 carbon Inorganic materials 0.000 claims description 9
- 239000012802 nanoclay Substances 0.000 claims description 9
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims description 8
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims description 8
- 229920000139 polyethylene terephthalate Polymers 0.000 claims description 7
- 239000005020 polyethylene terephthalate Substances 0.000 claims description 7
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonium chloride Substances [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims description 6
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 6
- 239000012279 sodium borohydride Substances 0.000 claims description 6
- 229910000033 sodium borohydride Inorganic materials 0.000 claims description 6
- 239000004575 stone Substances 0.000 claims description 6
- 125000005211 alkyl trimethyl ammonium group Chemical group 0.000 claims description 5
- WOWHHFRSBJGXCM-UHFFFAOYSA-M cetyltrimethylammonium chloride Chemical compound [Cl-].CCCCCCCCCCCCCCCC[N+](C)(C)C WOWHHFRSBJGXCM-UHFFFAOYSA-M 0.000 claims description 5
- GGCZERPQGJTIQP-UHFFFAOYSA-N sodium;9,10-dioxoanthracene-2-sulfonic acid Chemical compound [Na+].C1=CC=C2C(=O)C3=CC(S(=O)(=O)O)=CC=C3C(=O)C2=C1 GGCZERPQGJTIQP-UHFFFAOYSA-N 0.000 claims description 5
- 235000019270 ammonium chloride Nutrition 0.000 claims description 4
- 229960000892 attapulgite Drugs 0.000 claims description 4
- 239000000440 bentonite Substances 0.000 claims description 4
- 229910000278 bentonite Inorganic materials 0.000 claims description 4
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 claims description 4
- 229910052626 biotite Inorganic materials 0.000 claims description 4
- GDVKFRBCXAPAQJ-UHFFFAOYSA-A dialuminum;hexamagnesium;carbonate;hexadecahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Al+3].[Al+3].[O-]C([O-])=O GDVKFRBCXAPAQJ-UHFFFAOYSA-A 0.000 claims description 4
- 239000004744 fabric Substances 0.000 claims description 4
- 229910000271 hectorite Inorganic materials 0.000 claims description 4
- KWLMIXQRALPRBC-UHFFFAOYSA-L hectorite Chemical compound [Li+].[OH-].[OH-].[Na+].[Mg+2].O1[Si]2([O-])O[Si]1([O-])O[Si]([O-])(O1)O[Si]1([O-])O2 KWLMIXQRALPRBC-UHFFFAOYSA-L 0.000 claims description 4
- 229910001701 hydrotalcite Inorganic materials 0.000 claims description 4
- 229960001545 hydrotalcite Drugs 0.000 claims description 4
- 229910052625 palygorskite Inorganic materials 0.000 claims description 4
- 230000009467 reduction Effects 0.000 claims description 4
- 229910000275 saponite Inorganic materials 0.000 claims description 4
- 229910001961 silver nitrate Inorganic materials 0.000 claims description 4
- 238000003756 stirring Methods 0.000 claims description 4
- 239000000454 talc Substances 0.000 claims description 4
- 229910052623 talc Inorganic materials 0.000 claims description 4
- 235000012222 talc Nutrition 0.000 claims description 4
- 235000019354 vermiculite Nutrition 0.000 claims description 4
- FOIXSVOLVBLSDH-UHFFFAOYSA-N Silver ion Chemical compound [Ag+] FOIXSVOLVBLSDH-UHFFFAOYSA-N 0.000 claims description 3
- 239000004411 aluminium Substances 0.000 claims description 3
- 229910052782 aluminium Inorganic materials 0.000 claims description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 3
- 150000001413 amino acids Chemical class 0.000 claims description 3
- 239000007864 aqueous solution Substances 0.000 claims description 3
- KDVOJISTAOBJDJ-UHFFFAOYSA-M benzyl-dimethyl-undecylazanium;chloride Chemical compound [Cl-].CCCCCCCCCCC[N+](C)(C)CC1=CC=CC=C1 KDVOJISTAOBJDJ-UHFFFAOYSA-M 0.000 claims description 3
- 239000002775 capsule Substances 0.000 claims description 3
- 238000006243 chemical reaction Methods 0.000 claims description 3
- 229910052742 iron Inorganic materials 0.000 claims description 3
- 229910052987 metal hydride Inorganic materials 0.000 claims description 3
- 150000004681 metal hydrides Chemical class 0.000 claims description 3
- 239000010445 mica Substances 0.000 claims description 3
- 229910052618 mica group Inorganic materials 0.000 claims description 3
- 239000002689 soil Substances 0.000 claims description 3
- 229910052902 vermiculite Inorganic materials 0.000 claims description 3
- 239000010455 vermiculite Substances 0.000 claims description 3
- 229910052728 basic metal Inorganic materials 0.000 claims description 2
- 150000003818 basic metals Chemical class 0.000 claims description 2
- 150000004985 diamines Chemical class 0.000 claims description 2
- CQLFBEKRDQMJLZ-UHFFFAOYSA-M silver acetate Chemical compound [Ag+].CC([O-])=O CQLFBEKRDQMJLZ-UHFFFAOYSA-M 0.000 claims description 2
- KKKDGYXNGYJJRX-UHFFFAOYSA-M silver nitrite Chemical compound [Ag+].[O-]N=O KKKDGYXNGYJJRX-UHFFFAOYSA-M 0.000 claims description 2
- YPNVIBVEFVRZPJ-UHFFFAOYSA-L silver sulfate Chemical compound [Ag+].[Ag+].[O-]S([O-])(=O)=O YPNVIBVEFVRZPJ-UHFFFAOYSA-L 0.000 claims description 2
- 239000001509 sodium citrate Substances 0.000 claims description 2
- HRXKRNGNAMMEHJ-UHFFFAOYSA-K trisodium citrate Chemical compound [Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O HRXKRNGNAMMEHJ-UHFFFAOYSA-K 0.000 claims description 2
- 229940038773 trisodium citrate Drugs 0.000 claims description 2
- HTZCNXWZYVXIMZ-UHFFFAOYSA-M benzyl(triethyl)azanium;chloride Chemical compound [Cl-].CC[N+](CC)(CC)CC1=CC=CC=C1 HTZCNXWZYVXIMZ-UHFFFAOYSA-M 0.000 claims 2
- IQDGSYLLQPDQDV-UHFFFAOYSA-N dimethylazanium;chloride Chemical compound Cl.CNC IQDGSYLLQPDQDV-UHFFFAOYSA-N 0.000 claims 2
- 125000002948 undecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims 2
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 abstract description 60
- 230000000694 effects Effects 0.000 abstract description 10
- 238000002844 melting Methods 0.000 abstract description 3
- 230000008018 melting Effects 0.000 abstract description 3
- 239000003638 chemical reducing agent Substances 0.000 abstract 1
- 239000000047 product Substances 0.000 description 17
- 238000012360 testing method Methods 0.000 description 17
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 10
- 238000002485 combustion reaction Methods 0.000 description 9
- 229910052736 halogen Inorganic materials 0.000 description 9
- 150000002367 halogens Chemical class 0.000 description 9
- 239000012467 final product Substances 0.000 description 8
- 238000001914 filtration Methods 0.000 description 7
- 238000009987 spinning Methods 0.000 description 7
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 6
- 238000009472 formulation Methods 0.000 description 6
- 229910052698 phosphorus Inorganic materials 0.000 description 6
- 239000011574 phosphorus Substances 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- 101710134784 Agnoprotein Proteins 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- 230000018044 dehydration Effects 0.000 description 4
- 238000006297 dehydration reaction Methods 0.000 description 4
- 230000007613 environmental effect Effects 0.000 description 4
- 230000006870 function Effects 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- 239000000654 additive Substances 0.000 description 3
- 230000000996 additive effect Effects 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 description 3
- 239000011347 resin Substances 0.000 description 3
- 229920005989 resin Polymers 0.000 description 3
- 239000004753 textile Substances 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 2
- 229910010082 LiAlH Inorganic materials 0.000 description 2
- 150000001649 bromium compounds Chemical class 0.000 description 2
- 235000011089 carbon dioxide Nutrition 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 239000000571 coke Substances 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 230000036541 health Effects 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- SZVJSHCCFOBDDC-UHFFFAOYSA-N iron(II,III) oxide Inorganic materials O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 description 2
- 238000002074 melt spinning Methods 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- 238000005453 pelletization Methods 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- TXEYQDLBPFQVAA-UHFFFAOYSA-N tetrafluoromethane Chemical compound FC(F)(F)F TXEYQDLBPFQVAA-UHFFFAOYSA-N 0.000 description 2
- 208000019901 Anxiety disease Diseases 0.000 description 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 230000036506 anxiety Effects 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 230000003115 biocidal effect Effects 0.000 description 1
- VNSBYDPZHCQWNB-UHFFFAOYSA-N calcium;aluminum;dioxido(oxo)silane;sodium;hydrate Chemical compound O.[Na].[Al].[Ca+2].[O-][Si]([O-])=O VNSBYDPZHCQWNB-UHFFFAOYSA-N 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 description 1
- REZZEXDLIUJMMS-UHFFFAOYSA-M dimethyldioctadecylammonium chloride Chemical compound [Cl-].CCCCCCCCCCCCCCCCCC[N+](C)(C)CCCCCCCCCCCCCCCCCC REZZEXDLIUJMMS-UHFFFAOYSA-M 0.000 description 1
- YGANSGVIUGARFR-UHFFFAOYSA-N dipotassium dioxosilane oxo(oxoalumanyloxy)alumane oxygen(2-) Chemical compound [O--].[K+].[K+].O=[Si]=O.O=[Al]O[Al]=O YGANSGVIUGARFR-UHFFFAOYSA-N 0.000 description 1
- 239000004664 distearyldimethylammonium chloride (DHTDMAC) Substances 0.000 description 1
- 229920006351 engineering plastic Polymers 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000012764 mineral filler Substances 0.000 description 1
- 229910052901 montmorillonite Inorganic materials 0.000 description 1
- 229910052627 muscovite Inorganic materials 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 229910000273 nontronite Inorganic materials 0.000 description 1
- 230000000149 penetrating effect Effects 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 229910052903 pyrophyllite Inorganic materials 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 239000011819 refractory material Substances 0.000 description 1
- 150000004760 silicates Chemical class 0.000 description 1
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical class O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910001415 sodium ion Inorganic materials 0.000 description 1
- SFVFIFLLYFPGHH-UHFFFAOYSA-M stearalkonium chloride Chemical compound [Cl-].CCCCCCCCCCCCCCCCCC[N+](C)(C)CC1=CC=CC=C1 SFVFIFLLYFPGHH-UHFFFAOYSA-M 0.000 description 1
Images
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The present invention relates to a flame retardant composition which is suitable for polyester and plastics. In the flame retardant composition, nano silver is added to clay, and then the flame retardant composition is used for polyester and plastics in order to improve the fire retardance of the polyester and the plastics. In flame retardant composition of the present invention, silver ions and clay are thoroughly mixed first, and then the silver ions in the clay are reduced to nano silver by a reducing agent. The nano silver clay is added in a melting and mixing state when polyester mother particles are prepared in order to obtain nano polyester mother particles with a high flame retardant effect by mixing; after the nano mother particles are melted, the molten nano mother particles can be prepared into a product with high flame retardance.
Description
Technical field
The relevant a kind of fire retardant prescription that is applicable to fibre product and plastic cement of the present invention, and the fire retardant prescription of particularly relevant a kind of polyester (polyester) or polyester composite.
Background technology
The fibre product or the plastic cement of artificial polymkeric substance manufacturing apply in the human life already in a large number.Artificial polymkeric substance nearly all is an organism, and general organic characteristic to be exactly burning-point low is easier to burning, so being generally maintenance personnel and home safety or special purpose uses, have the fibre product of flame retardant resistance or the exploitation of engineering plastic and its necessity is arranged really with development, the demand that also has its market is so the flame-retardant formulations of development of new and material are constantly underway always.
Be to add phosphorous or halogen-containing flame retardant in traditional fire-retardant fibre goods or the plastic cement, prescription all can have some shortcomings unsatisfactory, as expensive, addition greatly, not environmental protection and do not conform to rules etc.Use expensive fire retardant not only not meet cost requirement, and the big regular meeting of the amount of adding change the characteristic of fibre product or plastic cement.Moreover the additive regular meeting of phosphorus system or halogen system causes the pollution of environment, not environmental protection and often cause personnel's damage.Therefore, the use of the fire retardant of phosphorus system or halogen system does not often meet the regulation of the environmental regulation of advanced country, and this represents phosphorous system or halogen is that the fire-retardant fibre goods or the plastic cement of additive can't be squeezed into this state market.Therefore for solving the above problems, need the fire retardant of development of new, to reach the requirement in market.
Clay (clay) is one of recently very popular in the field of study nano material, and it has considerable function, some clay or upgrading cross clay be verified have far infrared rays, functions such as antibiotic, uvioresistant, wear-resisting, dimensional stability and flame retardant resistance.
Clay itself has anti-flaming function and mainly contains several reasons: one, this inorganics of clay as silicates, and itself just has nonflammable characteristic; Two, the clay in plastic cement or resin, its laminate structure can stop or reduce penetrating of oxygen, can improve the burning difficulty of plastic cement or resin; Three, after clay and plastic cement or resin have burnt, can form coke layer and can protect inside not encroached on by flame.Based on above-mentioned three reasons, clay has basic flame-retarding characteristic.Therefore, some can be seen in document, for example as Study of Flame Retardant one after another with clay: denomination of invention has disclosed clay, fire retardant and polycarbonate for US4280949 number to form a fire-retardant polymkeric substance composition for the United States Patent (USP) of " having the improvement polyester composition (Modified polyester compositionscontaining mineral filler) that clay adds "; Denomination of invention has disclosed polyorganosilicate, carbon fluoride for US5773502 number as a flame-retardant formulations for the United States Patent (USP) of " fire-retardant composition (Fire retardantblends) ", polyorganosilicate is as flame retardant, and the use of polyorganosilicate can reduce the usage quantity of carbon fluoride.
Though but clay has fire-retardant characteristic, it's a pity that its flame retardant resistance is not enough, so in the prior art only with clay as the supporting role in the flame-retardant formulations, the leading role in the flame-retardant formulations still is the fire retardant of traditional phosphorus system or halogen system.Like this, though because of the seriousness of the problem that use produced of the fire retardant of traditional phosphorus system or halogen system can be slowed down, but still can't avoid, because the interpolation of clay only is the fire-retardant addition that has reduced traditional phosphorus system or halogen system at most, and this place of can not at all dealing with problems.
Summary of the invention
Therefore, the present invention promptly studies at the basic flame-retarding characteristic that clay had, and is modified into more highly effective flame-retardant, and becomes the new flame-retardant formulations of a uniqueness.
The prescription that the purpose of this invention is to provide a kind of fire retardant is applicable on fibre product and the plastic cement, is the mixture with nanometer silver and clay, replaces traditional fire retardant prescription.
Another object of the present invention provides a kind of prescription of fire retardant, is applicable on fibre product and the plastic cement, need not to use the fire retardant of traditional phosphorus system or halogen system fully.
Another purpose of the present invention provides the prescription of a kind of group of combustion agent, be applicable on fibre product and the plastic cement, and its addition is little, to fibre product and the plastic cement influence of physical properties originally little a lot of than traditional flame-retardant formulations.
A further object of the present invention provides a kind of prescription of fire retardant, is applicable on fibre product and the plastic cement, and its employed material can not cause the pollution of environment.
Therefore, for realizing above-mentioned purpose of the present invention, a kind of prescription of fire retardant is proposed, on fibre product and plastic cement.The present invention mainly utilizes the mixture of nanometer silver and clay to strengthen the flame retardant resistance of polyester or polyester composite, this clay can comprise one or more laminar silicic acid salt, comprises polynite (montmorillonite), bentonite (bentonite), the lubricious stone of aluminium (beidellite), lubricious stone of iron or capsule take off soil (nontronite), saponite (saponite), vermiculite (vermiculites), hectorite (hectorite), hydrotalcite (volknerite or hydrotalcite), white mica (muscovite), biotite (biotite), attapulgite (attapulgite), talcum (talc) and agalmatolite (pyrophyllite).At first, with argentiferous ionic silver salt, for example: Silver Nitrate (AgNO
3), silver nitrite (AgNO
2), Silver monoacetate (CH
3COOAg), Sulfuric acid disilver salt (Ag
2SO
4) or wherein optional two or more combination, place a certain amount of deionized water with clay jointly with a specific ratio, stir a set time down in a fixed temperature, wherein, this fixed temperature is approximately between room temperature is spent to Celsius 95, be preferably between 40 degree Celsius are spent to Celsius 90, this set time is preferably between 5～24 hours approximately between 3～48 hours.Then, water removed and with centrifugal in addition again behind the deionized water rinsing throw out, get final product argentiferous ionic clay.
Then can use a reductive agent, for example sodium borohydride (NaBH
4), Trisodium Citrate (Na
3C
6H
5O
7), aluminium lithium hydride (LiAlH
4), hydrogen-oxygen aluminium lithium hydride (LiAlH (OH)
3), diamine (N
2H
4), metal hydride (MetalHydride), basic metal or other similar reductive agents, silver ion reduction in the clay is become argent, because silver ions is fully disperseed by clay, so can obtain containing the clay of nanometer silver, wherein, the size of nanometer silver approximately between 5 nanometers between 500 nanometers.The prepared nanometer silver clay that contains can be directly and standby behind polyester powder uniform mixing after drying or the convection drying.Contain the nanometer silver clay and can handle with modification agent more in addition,, and use the conforming to property that increases between nanometer silver clay and polyester with the hydrophobicity of increase nanometer silver clay.Modification agent can be ammonium salt, the one-level ammonium salt and the quarternary ammonium salt that particularly have straight chained alkyl, the one-level ammonium salt and the amino acid that for example have 3 carbon to 17 carbon straight chained alkyl, cetyl trimethylammonium bromide (Cetyltrimethylammonium bromide, CTAB), palmityl trimethyl ammonium chloride (Cetyltrimethylammonium chloride, CTAC), two undecyl alkyl dimethyl ammonium chlorides (Distearyldimethylammonium Chloride), undecyl benzyl dimethyl ammonium chloride (Stearylbenzyldimethylammonium chloride), positive alkyl triethyl brometo de amonio and ammonium chloride (n-Alkyltriethylammonium bromides, chloride), positive alkyl trimethyl ammonium bromide and ammonium chloride (n-Alkyltriethylammonium bromides, chloride) or the like, wherein the carbon number of positive alkyl can be 13,15,17,21 or 23.
The prepared nanometer silver clay that contains is taken out, with in addition dry behind the polyester powder uniform mixing, wherein polyester can be polyethylene terephthalate (Polyethylene Terephthalate, PET), polybutylene terephthalate (Polybutylene Terephthalate, PBT), the mixing or other polyester of the arbitrary proportion of polybutylene terephthalate (PBT) and polyethylene terephthalate (PET).Be mixed with the master batch that the polyester powder that contains the nanometer silver clay can continue to carry out with list or twin screw extruder machine melting mixing and make, with polyester and the pelletizing that the cooling tank cooling is extruded, get final product a polyester master particle that contains nanometer silver and nano clay.
The effect that nanometer silver is widely known by the people is its germ resistance, but nanometer silver then is to have brought into play important effect on flame retardant resistance in the present invention.The silver of bulk is a kind of quite stabile material, is to be not easy to have reactivity, and this also is the reason that silver and mercury, platinum and gold or the like metal are listed in noble metal (Noble Metal) together.But the silver of nanometer size and the silver of bulk have distinct function, are exactly its catalysis characteristics.Nanometer silver is considered as a catalyst or catalyzer in the present invention, and it can change into the carbon monoxide that aflame plastic product produced carbonic acid gas, and the not flammable carbonic acid gas that is produced surrounds plastic product, stops its further burning.Simultaneously, infer that also nanometer silver and clay can form complicated coke layer and can protect inside to prevent to burn away.
Generally speaking, can have some metal ions in the clay, sodium ion for example, when clay and the aqueous solution that contains silver ions stirred together, silver ions can replace these metal ions and be incorporated in the clay.Therefore, the upper limit that contains silver content in the nanometer silver clay that is provided among the present invention need be decided on the tradable position that clay itself is provided, generally not being higher than 20wt%, roughly is between about 0.1wt% to 15wt%, and preferable ratio is between about 2wt% to 12wt%.And the addition that contains the nanometer silver clay in polyester is many more, the flame retardant resistance of polyester is good more certainly, but contain the addition of nanometer silver clay in the polyester as long as surpass 0.01wt%, compare with polyester and can find out fire-retardant effect, if will reach required critical combustion oxygen index (the Limited Oxygen Index in commercial goods, LOI), 0.25% addition is enough.Generally speaking, in polyester or plastic cement the consumption of nanometer silver clay fire retardant approximately between between the 0.01wt% to 20wt%, but the refractory materials that requires for some high flame retardants, the addition of nanometer silver clay fire retardant can reach 30wt%.By showing in the experiment, be lower than 1% the interpolation that contains the nanometer silver clay, can reach goodish flame retardant effect, and preferable addition is approximately between between the 0.2wt% to 2wt%.Generally speaking, in the polyester with nanometer silver clay, the content of nanometer silver is about 10/1000000ths (10ppm) of weight polyester between the 1wt%, and the content of clay is about between the 0.01wt% to 2wt% of weight polyester.
Because the present invention is the basic flame retardant resistance of interpolation collocation clay with nanometer silver, can significantly promote the flame retardant effect of clay, therefore, need not fully in the present invention to add any traditional fire retardant in addition, the product that can solve in the market uses the problem that conventional flame retardant produced.One of characteristic of the present invention is can need not add any tradition fire retardant commonly used fully, can reach the desired flame retardant resistance in market, can cause environmental pollution problems and solve existing fire retardant.Another characteristic of the present invention is suitable low of the ratio that contains the nanometer silver clay of required interpolation, and is little to the reel off raw silk from cocoons rerum natura influence of back fiber of polyester, and the low addition that contains the nanometer silver clay also can significantly reduce manufacturing cost.
In addition, though disclosed nanometer silver clay is made an addition in polymkeric substance and the fabric, can not add any traditional fire retardant fully, can reach and make polymkeric substance and the fire-retardant effect of fabric, but this to be not the disclosed nanometer silver clay of expression can not use with traditional fire retardant.Disclosed nanometer silver clay traditional fire retardant of can also arranging in pairs or groups uses in the lump, can reduce the usage quantity of traditional fire retardant in the case.
For further specifying above-mentioned purpose of the present invention, constructional feature and effect, the present invention is described in detail below with reference to accompanying drawing.
Description of drawings
Fig. 1 is the filtration test result who illustrates the polybutylene terephthalate master batch that is mixed with the 0.5wt% clay: and
Fig. 2 illustrates that manufacturing is mixed with the filtration test result that 0.5wt% contains the polybutylene terephthalate master batch of nanometer silver clay according to present embodiment.
Embodiment
For allow the fire retardant prescription of fibre product provided by the present invention clear more for the purpose of, in the embodiment of the invention 1 and embodiment 2, describe in detail how to form and contain the nanometer silver clay.In addition, further describe the manufacture method that makes the female ingot of the polyester that contains the nanometer silver clay that is used to form fire-retardant polyester fibre in the embodiment of the invention 3.The embodiment of the invention 4 is the operations of carrying out spinning with the female ingot of the polyester that contains the nanometer silver clay of embodiment 3 gained, and the flame retardant resistance of test obtained flame-retardant fiber.
Embodiment 1
Silver Nitrate (AgNO with 1.7 g (0.01mole)
3) placing 500 ml deionized water jointly with PK805 clay 1 gram of hundred health potteries company, heating was stirred 24 hours as for after 90 ℃.Staticly settle after the back removes water in the mode of decant, again with behind the deionized water rinsing throw out and with centrifuge dehydration get final product argentiferous ionic clay.
Aforementioned resulting argentiferous ionic clay is placed 100 milliliters deionized water, and add that magnetite stirs.At room temperature slowly add about 0.1 g sodium borohydride as the silver ions of reductive agent to reduce in the above-mentioned clay, reaction at room temperature if be necessary to drink again add 0.05 g sodium borohydride can reduce silver ions fully.Again with the deionized water rinsing throw out, and get final product to such an extent that contain the clay of nanometer silver with centrifuge dehydration.
Silver Nitrate (AgNO with 1.7 g (0.01mole)
3) placing 500 ml deionized water jointly with PK805 clay 1 gram of hundred health potteries company, heating was stirred 24 hours as for after 90 ℃.Staticly settle after the back removes water in the mode of decant, again with behind the deionized water rinsing throw out and with centrifuge dehydration get final product argentiferous ionic clay.
Aforementioned resulting argentiferous ionic clay is placed 100 milliliters deionized water, and add that magnetite stirs.At room temperature slowly add about 0.1 g sodium borohydride as the silver ions of reductive agent to reduce in the above-mentioned clay, reaction at room temperature if be necessary to drink again add 0.05 g sodium borohydride can reduce silver ions fully.Again with the deionized water rinsing throw out, and get final product to such an extent that contain the clay of nanometer silver with centrifuge dehydration.
The clay that will contain nanometer silver place cetyl trimethylammonium bromide (CetyltrimethylammoniumBromide, CTAB) in 100 milliliters of 0.01M (volume molarity) aqueous solution, be heated to 60 ℃ after, stirred 3 hours.Throw out removes water in the centrifugal mode, and simultaneously with the deionized water rinsing throw out.
Embodiment 3
The prepared nanometer silver clay that contains among the embodiment 2 is taken out, with at least three kilograms polybutylene terephthalate (Polybutylene Terephthalate, PBT) in addition dry behind the powder uniform mixing.Carry out the master batch of melting mixing with list or twin screw extruder machine (Single or Twin Screw Extruder) and make, with polyester and the pelletizing that the cooling tank cooling is extruded, get final product a polyester master particle that contains nanometer silver and nano clay.
Before spinning, can carry out filtration test (Filter Test), could enter melt-spinning to assess made master batch.If the height that pressure rises very in filtering test, the particle that expression is mixed can clog the hole of filter screen, then also can cause the puzzlement on the operation in the process of spinning.It still is suitable big that general clay is made voltage rise in its pressure test of master batch, and Fig. 1 is the filtration test result who illustrates the polybutylene terephthalate master batch that is mixed with the 0.5wt% clay, by finding out among Fig. 1 that pressure rises to 175 crust (bar) in test process.But the polybutylene terephthalate master batch that contains the nanometer silver clay according to the present embodiment manufacturing then can significantly reduce voltage rise, as shown in Figure 2.Fig. 2 illustrates that manufacturing is mixed with the filtration test result that 0.5wt% contains the polybutylene terephthalate master batch of nanometer silver clay according to present embodiment, as seen from Figure 2 pressure only risen 12 the crust (bar), that is the clay that is mixed with nanometer silver distributes quite in polyester master particle evenly, there is no cohesion (aggregation) phenomenon together, the prepared polybutylene terephthalate master batch that contains the nanometer silver clay can enter spinning process really according to the present invention in this expression, and can be utilized by industrial community.In addition, be mixed with the polybutylene terephthalate master batch that 0.25wt% contains the nanometer silver clay according to making again, for the usefulness of spinning process among next embodiment with method.Because being mixed with the polybutylene terephthalate master batch that 0.5wt% contains the nanometer silver clay can be by having filtered test, do not do and filter test though make and contain polybutylene terephthalate master batch that nanometer silver clay doping reduces by half in the same way, should can not have anxiety yet by filtering test.
The embodiment 3 prepared polybutylene terephthalate master batches (0.25wt%) that contain the nanometer silver clay are spent under 295 degree Celsius Celsius 250, carry out spinning with melt spinning method.The spinning mode can for directly spin, core sheath and island mode carry out, get final product fire-retardant fibre, carry out again can be made into the fire-retardant fibre goods after the back segment processing.The same polybutylene terephthalate master batch that will only be mixed with the 0.25wt% clay promptly is not mixed with the polybutylene terephthalate master batch of nanometer silver clay, manufactures fibre product according to same mode respectively.
Resultant fibre product in the present embodiment is carried out fire retardancy test, and fire retardancy test is to detect in ASTM D2863-95 standard testing mode, test the results are shown in table one.
The critical combustion oxygen index (LOI) of table one, various polyester
| Sample | PBT without clay | 0.25wt％Clay in PBT | 0.25wt％Ag/Clay in PBT |
| Critical combustion oxygen index (LOI) | 22 | 25 | 31 |
As shown in Table 1, critical combustion oxygen index (LOI) value of not mixing the polybutylene terephthalate textiles of clay is 22, and critical combustion oxygen index (LOI) value that is mixed with the polybutylene terephthalate textiles of 0.25wt% clay is 25, is mixed with 0.25wt% and contains critical combustion oxygen index (LOI) value of polybutylene terephthalate textiles of nanometer silver clay then up to 31.Has sizable effect by the interpolation of the visible nanometer silver of variation of critical combustion oxygen index (LOI) value for the lifting of clay flame retardant resistance.
Generally speaking, the critical combustion oxygen index of fibre product (LOI) of clothing usefulness if value can reach 28 can claim be the flame retardant resistance clothing, this also is the minimum requirements of commercially available fire-retardant clothing for flame retardant resistance.The present invention quite specifically reaches the desired standard in market and surmounts it.By the invention described above preferred embodiment as can be known, use the present invention and have following advantage: fire retardant prescription provided by the present invention need not to add the fire retardant of any traditional phosphorous or Halogen etc., thus there is not environmental issue, so also meet the laws and regulations requirement of various countries; Secondly, because it is very low to contain the addition of nanometer silver clay, so the cost of fire-retardant fibre goods is also followed reduction, and contain the also obvious rerum natura of polyester originally that do not influence of few additive of nanometer silver clay, for example its pliability.Thereby the present invention also has considerable influence to flame retardant polyester market except having quite significant technique effect.
Though the present invention discloses as above with the preferred embodiment of fabric; yet it is not in order to limit the present invention; any person skilled in the art person without departing from the spirit and scope of the present invention; various equivalences changes or equivalence is replaced when making; for example; utilize disclosed fire retardant to add among any plastic cement or the polymkeric substance increasing the flame retardant resistance of this material, so protection scope of the present invention is when looking being as the criterion that accompanying Claim defines.
Claims (26)
1. a fire retardant is applicable on polyester and the plastic cement, comprises at least:
5 nanometers are to the nano-Ag particles and the nano clay of 500 nanometers;
Wherein this nano clay and this nano-Ag particles uniform mixing.
2. fire retardant as claimed in claim 1 is characterized in that this nano clay is selected from polynite, bentonite, the lubricious stone of aluminium, the lubricious stone of iron or capsule and takes off one of soil, saponite, vermiculite, hectorite, hydrotalcite, white mica, biotite, attapulgite, talcum and agalmatolite and arbitrary combination thereof.
3. fire retardant as claimed in claim 1, the weight ratio that it is characterized in that this nanometer silver and nano clay is between between the 0.1wt% to 15wt%.
4. fire retardant as claimed in claim 1, the weight ratio that it is characterized in that this nanometer silver and nano clay is between between the 2wt% to 12wt%.
5. fire retardant as claimed in claim 1 is characterized in that also comprising a modification agent.
6. fire retardant as claimed in claim 5 is characterized in that this modification agent is an ammonium salt.
7. fire retardant as claimed in claim 5 is characterized in that this modification agent is one-level ammonium salt or the quarternary ammonium salt with straight chained alkyl.
8. fire retardant as claimed in claim 5 is characterized in that this modification agent is to be selected from one-level ammonium salt and one of amino acid, cetyl trimethylammonium bromide, palmityl trimethyl ammonium chloride, two undecyl alkyl dimethyl ammonium chloride, undecyl benzyl dimethyl ammonium chloride, positive alkyl triethyl brometo de amonio, nalka TEBA, positive alkyl trimethyl ammonium bromide, positive alkyl trimethyl ammonium chloride and the arbitrary combination thereof with 3 carbon to 17 carbon straight chained alkyl.
9. fire retardant as claimed in claim 8 is formed, and it is characterized in that the carbon number of this positive alkyl can be 13,15,17,21 or 23.
10. a flame retardant polyester master batch is characterized in that it is to adopt each a described fire retardant and a polyester uniform mixing as claim 1 to 9 to form.
11. flame retardant polyester master batch as claimed in claim 10, the consumption that it is characterized in that this fire retardant in this polyester is between between the 0.01wt% to 30wt%.
12. flame retardant polyester master batch as claimed in claim 10, the consumption that it is characterized in that this fire retardant in this polyester is between between the 0.2wt% to 2wt%.
13. flame retardant polyester master batch as claimed in claim 10 is characterized in that this polyester is polybutylene terephthalate, polyethylene terephthalate, polybutylene terephthalate and the mixing of the arbitrary proportion of polyethylene terephthalate.
14. a fire-retardant fabric fiber is characterized in that it is to adopt each described flame retardant polyester master batch of claim 10 to 13 to form.
15. the manufacture method of a fire retardant comprises at least:
Place deionized water between 95 degree Celsius, to stir 3～48 hours silver salt, nano clay in room temperature;
Remove water; And
With reductive agent with the silver ion reduction Cheng Yin in this silver salt.
16. the manufacture method of fire retardant as claimed in claim 15 is characterized in that temperature of reaction is between 90 degree Celsius between 40 degree Celsius.
17. the manufacture method of fire retardant as claimed in claim 15 is characterized in that churning time is between 5～24 hours.
18. the manufacture method of fire retardant as claimed in claim 15 is characterized in that this silver salt is to be selected from one of Silver Nitrate, silver nitrite, Silver monoacetate, Sulfuric acid disilver salt and arbitrary combination thereof.
19. the manufacture method of fire retardant as claimed in claim 15, the method that it is characterized in that removing water is a centrifuging.
20. the manufacture method of fire retardant as claimed in claim 15 is characterized in that this reductive agent is to be selected from one of sodium borohydride, Trisodium Citrate, aluminium lithium hydride, hydrogen-oxygen aluminium lithium hydride, metal hydride, basic metal, diamine.
21. the manufacture method of fire retardant as claimed in claim 15 is characterized in that this nano clay is selected from polynite, bentonite, the lubricious stone of aluminium, the lubricious stone of iron or capsule and takes off one of soil, saponite, vermiculite, hectorite, hydrotalcite, white mica, biotite, attapulgite, talcum, agalmatolite and arbitrary combination thereof.
22. the manufacture method of fire retardant as claimed in claim 15, it is characterized in that with this reductive agent with the silver ion reduction Cheng Yin in this silver salt after, also comprise:
The aqueous solution with a modification agent carries out upgrading to this clay.
23. the manufacture method of fire retardant as claimed in claim 22 is characterized in that this modification agent is an ammonium salt.
24. the manufacture method of fire retardant as claimed in claim 22 is characterized in that this modification agent is one-level ammonium salt or the quarternary ammonium salt with straight chained alkyl.
25. the manufacture method of fire retardant as claimed in claim 22 is characterized in that this modification agent is to be selected from one-level ammonium salt and one of amino acid, cetyl trimethylammonium bromide, palmityl trimethyl ammonium chloride, two undecyl alkyl dimethyl ammonium chloride, undecyl benzyl dimethyl ammonium chloride, positive alkyl triethyl brometo de amonio, nalka TEBA, positive alkyl trimethyl ammonium bromide, positive alkyl trimethyl ammonium chloride and the arbitrary combination thereof with 3 carbon to 17 carbon straight chained alkyl.
26. the manufacture method of fire retardant as claimed in claim 25, the carbon number that it is characterized in that this positive alkyl is 13,15,17,21 or 23.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2004100286999A CN1313523C (en) | 2004-03-12 | 2004-03-12 | Flame retardant compositions |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2004100286999A CN1313523C (en) | 2004-03-12 | 2004-03-12 | Flame retardant compositions |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1667030A CN1667030A (en) | 2005-09-14 |
| CN1313523C true CN1313523C (en) | 2007-05-02 |
Family
ID=35038323
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB2004100286999A Expired - Lifetime CN1313523C (en) | 2004-03-12 | 2004-03-12 | Flame retardant compositions |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1313523C (en) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102534860B (en) * | 2011-12-19 | 2013-09-18 | 中国人民解放军总后勤部军需装备研究所 | Antibacterial conductive polymer composite fiber and preparation method thereof |
| TW201328732A (en) * | 2012-01-04 | 2013-07-16 | A T P Co Ltd | Hydrophilic antimicrobial film |
| CN103102635B (en) * | 2013-02-20 | 2018-01-09 | 合肥杰事杰新材料股份有限公司 | A kind of efficient halogen-free anti-inflaming unsaturated polyester die plastic and preparation method thereof |
| CN105297180A (en) * | 2015-11-13 | 2016-02-03 | 昆山华阳新材料股份有限公司 | Manufacturing process of PET/PTT composite fiber |
| CN109371685B (en) * | 2018-06-25 | 2021-05-04 | 太极石股份有限公司 | Antibacterial far-infrared health-care down-like short fiber and preparation method and application thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1064097A (en) * | 1992-02-27 | 1992-09-02 | 郭子辉 | Fire retarding material for cable |
| CN1261005A (en) * | 1999-11-26 | 2000-07-26 | 孟庆福 | High-speed efficient fire-extinguishing chemical |
-
2004
- 2004-03-12 CN CNB2004100286999A patent/CN1313523C/en not_active Expired - Lifetime
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1064097A (en) * | 1992-02-27 | 1992-09-02 | 郭子辉 | Fire retarding material for cable |
| CN1261005A (en) * | 1999-11-26 | 2000-07-26 | 孟庆福 | High-speed efficient fire-extinguishing chemical |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1667030A (en) | 2005-09-14 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Gong et al. | Organic-inorganic hybrid engineering MXene derivatives for fire resistant epoxy resins with superior smoke suppression | |
| CN101928448A (en) | Nano composite flame-retardant reinforced polyester engineering plastic and preparation method thereof | |
| CN102174247A (en) | Halogen-free flame retardant glass fiber reinforced polyester composite and preparation method thereof | |
| CN1313523C (en) | Flame retardant compositions | |
| CN109082093B (en) | Wear-resistant transparent flame-retardant polycarbonate material and preparation method thereof | |
| CN104744865A (en) | Environment-friendly cable shield material with high flame resistance and preparation method of environment-friendly cable shield material | |
| CN106700271A (en) | Hydrotalcite-intercalated flame-retarding-enhanced polypropylene material and preparing method thereof | |
| TW200530310A (en) | Flame retarded composition | |
| CN111269408B (en) | In-situ polymerization-based flame-retardant anti-dripping negative ion health-care polyester and preparation method thereof | |
| CN104877169B (en) | Preparation method and application of inorganic hybrid flame retardant with high thermal stability | |
| CN100417691C (en) | Preparation method of nylon/montmorillonoid fire retarding composite material | |
| CN106496920B (en) | low smoke density ABS resin and preparation method thereof | |
| CN102382439B (en) | Modified polycarbonate and preparation method thereof | |
| CN106398192A (en) | Low-separation red phosphorus flame-retardant polyamide material and preparation method thereof | |
| CN102942750B (en) | Environment-friendly type flame retardant additive used for soft PVC product, and preparation method and application thereof | |
| CN101519509A (en) | Magnesium hydrate powder coated by inorganic compound as well as preparation method and application of same | |
| CN104292525B (en) | A kind of flame retardant rubber and preparation method thereof | |
| CN114656731B (en) | High-rigidity PVC (polyvinyl chloride) power conduit and preparation method thereof | |
| CN107641318B (en) | A kind of phosphate glass synergistic halogen-free flame-retardant nylon 6 composition and preparation method thereof | |
| Xu et al. | A novel coal gangue thermal stabilizer and its effect on thermal stability and mechanical properties of poly (vinyl chloride) | |
| CN105585855B (en) | A kind of organic montmorillonite flame-retardant pitch and preparation method thereof | |
| CN107304300B (en) | A kind of organic montmorillonite flame-retardant pitch and preparation method thereof | |
| CN113248848A (en) | Flame-retardant high-temperature-resistant cable and preparation method thereof | |
| CN107236287A (en) | A kind of new aeroge enhancing nylon heat-insulation composite material and preparation method thereof | |
| CN1244674C (en) | Method for fabricating thermal stablilizer made from wool ester, rare earth in use for PVC |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CX01 | Expiry of patent term | ||
| CX01 | Expiry of patent term |
Granted publication date: 20070502 |