CN100358973C - Composite flame retardant in bromine series, preparation method and application - Google Patents
Composite flame retardant in bromine series, preparation method and application Download PDFInfo
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- CN100358973C CN100358973C CNB2006101440220A CN200610144022A CN100358973C CN 100358973 C CN100358973 C CN 100358973C CN B2006101440220 A CNB2006101440220 A CN B2006101440220A CN 200610144022 A CN200610144022 A CN 200610144022A CN 100358973 C CN100358973 C CN 100358973C
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- flame retardant
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- retardant
- bromine series
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- 239000003063 flame retardant Substances 0.000 title claims abstract description 109
- 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 69
- 239000002131 composite material Substances 0.000 title claims abstract description 44
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical class [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 title claims description 44
- 238000002360 preparation method Methods 0.000 title claims description 23
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Chemical group O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 claims abstract description 32
- DEIGXXQKDWULML-UHFFFAOYSA-N 1,2,5,6,9,10-hexabromocyclododecane Chemical compound BrC1CCC(Br)C(Br)CCC(Br)C(Br)CCC1Br DEIGXXQKDWULML-UHFFFAOYSA-N 0.000 claims abstract description 23
- 239000000203 mixture Substances 0.000 claims abstract description 22
- 238000002156 mixing Methods 0.000 claims abstract description 14
- 230000002195 synergetic effect Effects 0.000 claims abstract description 10
- 239000005995 Aluminium silicate Substances 0.000 claims abstract description 6
- 235000012211 aluminium silicate Nutrition 0.000 claims abstract description 6
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000004927 clay Substances 0.000 claims abstract description 3
- -1 organo montmorillonite Chemical compound 0.000 claims description 29
- 229930188012 Bromoether Natural products 0.000 claims description 23
- HJCMMOODWZOXML-UHFFFAOYSA-N bromo hypobromite Chemical compound BrOBr HJCMMOODWZOXML-UHFFFAOYSA-N 0.000 claims description 23
- 239000000463 material Substances 0.000 claims description 18
- 239000003795 chemical substances by application Substances 0.000 claims description 16
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 claims description 15
- 239000012756 surface treatment agent Substances 0.000 claims description 14
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical group [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 11
- 239000007822 coupling agent Substances 0.000 claims description 11
- 238000000354 decomposition reaction Methods 0.000 claims description 8
- 229910052901 montmorillonite Inorganic materials 0.000 claims description 7
- 238000003756 stirring Methods 0.000 claims description 5
- 239000002253 acid Substances 0.000 claims description 3
- 125000002252 acyl group Chemical group 0.000 claims description 3
- HTDKEJXHILZNPP-UHFFFAOYSA-N dioctyl hydrogen phosphate Chemical compound CCCCCCCCOP(O)(=O)OCCCCCCCC HTDKEJXHILZNPP-UHFFFAOYSA-N 0.000 claims description 3
- 229920001169 thermoplastic Polymers 0.000 claims description 2
- 239000004416 thermosoftening plastic Substances 0.000 claims description 2
- 239000004033 plastic Substances 0.000 abstract description 11
- 229920003023 plastic Polymers 0.000 abstract description 11
- 229920000098 polyolefin Polymers 0.000 abstract description 8
- 238000002844 melting Methods 0.000 abstract description 5
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 abstract description 4
- 230000008018 melting Effects 0.000 abstract description 3
- 238000000034 method Methods 0.000 abstract description 3
- 238000012986 modification Methods 0.000 abstract description 3
- 230000004048 modification Effects 0.000 abstract description 3
- BZQKBFHEWDPQHD-UHFFFAOYSA-N 1,2,3,4,5-pentabromo-6-[2-(2,3,4,5,6-pentabromophenyl)ethyl]benzene Chemical compound BrC1=C(Br)C(Br)=C(Br)C(Br)=C1CCC1=C(Br)C(Br)=C(Br)C(Br)=C1Br BZQKBFHEWDPQHD-UHFFFAOYSA-N 0.000 abstract 1
- 229910017059 organic montmorillonite Inorganic materials 0.000 abstract 1
- 239000005022 packaging material Substances 0.000 abstract 1
- 238000001746 injection moulding Methods 0.000 description 26
- 239000008188 pellet Substances 0.000 description 18
- 238000012360 testing method Methods 0.000 description 15
- 230000000052 comparative effect Effects 0.000 description 12
- 230000000694 effects Effects 0.000 description 11
- 229920001155 polypropylene Polymers 0.000 description 10
- 239000004743 Polypropylene Substances 0.000 description 9
- 230000008859 change Effects 0.000 description 9
- 229920005989 resin Polymers 0.000 description 9
- 239000011347 resin Substances 0.000 description 9
- SHRRVNVEOIKVSG-UHFFFAOYSA-N 1,1,2,2,3,3-hexabromocyclododecane Chemical class BrC1(Br)CCCCCCCCCC(Br)(Br)C1(Br)Br SHRRVNVEOIKVSG-UHFFFAOYSA-N 0.000 description 8
- 229920005672 polyolefin resin Polymers 0.000 description 7
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 6
- 229910021502 aluminium hydroxide Inorganic materials 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 5
- 229910052794 bromium Inorganic materials 0.000 description 5
- 229910052787 antimony Inorganic materials 0.000 description 4
- 235000019504 cigarettes Nutrition 0.000 description 4
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 4
- 239000000347 magnesium hydroxide Substances 0.000 description 4
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 4
- 125000000962 organic group Chemical group 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 238000002485 combustion reaction Methods 0.000 description 3
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 2
- CPELXLSAUQHCOX-UHFFFAOYSA-N Hydrogen bromide Chemical compound Br CPELXLSAUQHCOX-UHFFFAOYSA-N 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- GHPGOEFPKIHBNM-UHFFFAOYSA-N antimony(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Sb+3].[Sb+3] GHPGOEFPKIHBNM-UHFFFAOYSA-N 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- WHHGLZMJPXIBIX-UHFFFAOYSA-N decabromodiphenyl ether Chemical compound BrC1=C(Br)C(Br)=C(Br)C(Br)=C1OC1=C(Br)C(Br)=C(Br)C(Br)=C1Br WHHGLZMJPXIBIX-UHFFFAOYSA-N 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 238000012856 packing Methods 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 230000000979 retarding effect Effects 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- AQPHBYQUCKHJLT-UHFFFAOYSA-N 1,2,3,4,5-pentabromo-6-(2,3,4,5,6-pentabromophenyl)benzene Chemical group BrC1=C(Br)C(Br)=C(Br)C(Br)=C1C1=C(Br)C(Br)=C(Br)C(Br)=C1Br AQPHBYQUCKHJLT-UHFFFAOYSA-N 0.000 description 1
- OZHJEQVYCBTHJT-UHFFFAOYSA-N 1,2,3,4,5-pentabromo-6-methylbenzene Chemical compound CC1=C(Br)C(Br)=C(Br)C(Br)=C1Br OZHJEQVYCBTHJT-UHFFFAOYSA-N 0.000 description 1
- CMQUQOHNANGDOR-UHFFFAOYSA-N 2,3-dibromo-4-(2,4-dibromo-5-hydroxyphenyl)phenol Chemical compound BrC1=C(Br)C(O)=CC=C1C1=CC(O)=C(Br)C=C1Br CMQUQOHNANGDOR-UHFFFAOYSA-N 0.000 description 1
- 241000446313 Lamella Species 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 229920001617 Vinyon Polymers 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 125000001246 bromo group Chemical class Br* 0.000 description 1
- 238000012824 chemical production Methods 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000009841 combustion method Methods 0.000 description 1
- 230000000295 complement effect Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- CJBJHOAVZSMMDJ-HEXNFIEUSA-N darunavir Chemical compound C([C@@H]([C@H](O)CN(CC(C)C)S(=O)(=O)C=1C=CC(N)=CC=1)NC(=O)O[C@@H]1[C@@H]2CCO[C@@H]2OC1)C1=CC=CC=C1 CJBJHOAVZSMMDJ-HEXNFIEUSA-N 0.000 description 1
- 229960005107 darunavir Drugs 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 238000005469 granulation Methods 0.000 description 1
- 230000003179 granulation Effects 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 229910000042 hydrogen bromide Inorganic materials 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000010128 melt processing Methods 0.000 description 1
- HZVOZRGWRWCICA-UHFFFAOYSA-N methanediyl Chemical compound [CH2] HZVOZRGWRWCICA-UHFFFAOYSA-N 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000011342 resin composition Substances 0.000 description 1
- 239000013535 sea water Substances 0.000 description 1
- 230000011218 segmentation Effects 0.000 description 1
- 239000000779 smoke Substances 0.000 description 1
- 238000003892 spreading Methods 0.000 description 1
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- 238000009941 weaving Methods 0.000 description 1
Abstract
This invention provides a method for preparing brominated composite flame retardant and its application. The brominated composite flame retardant comprises: brominated flame retardant 100 parts, synergistic flame retardant 30-45 parts, and anti-melting drop 30-60 parts. The brominated flame retardant is a mixture of decabromodiphenyl ethane or octabromo ether and heat-stable hexabromocyclododecane at a weight ratio of (2:1)-(1:2). The synergistic flame retardant is antimony trioxide. The anti-melting drop is one or more of organic montmorillonite, kaolin and clay. The method comprises: adequately mixing the above components according to the formula. The brominated composite flame retardant has a flame retardant grade up to V-0 without melting drop when used in flame retardant modification of polyolefin plastics. Besides, the brominated composite flame retardant has good mechanical properties, and can be used as packaging material for military products and electronic products.
Description
Technical field:
The present invention relates to a kind of novel halogen containing flame-retardant composition that can be applicable to polyolefin plastics, say further, relate to a kind of composite flame retardant in bromine series and preparation method thereof and its application flame-retardant modified in polyolefin plastics.
Background technology:
In the actual use of resin material, aspect its flame retardant properties, all require material to reach degree fire-retardant, difficult combustion under a lot of situations.As everyone knows, polyolefin plastics is present most widely used in the world general-purpose plastics, and their light weights, nontoxic have excellent electric insulation performance and resistance to chemical corrosion and physical strength, and forming process is convenient, less expensive.Therefore be widely used in electrical equipment, chemical industry, machinery, weaving, building, furniture, food product pack, industries such as military affairs.Yet resins such as polypropylene and vinyon have very easily incendiary characteristics, and when burning produce a large amount of smog, and the molten drop phenomenon is arranged, other objects that very easily ignite, so its application has been subjected to very big restriction.At present, having carried out a lot of research at resin aspect fire-retardant, mainly is by adding organic and inorganic or phosphorus flame retardant improves flame retardant properties.In existing technology, the additive capacity of fire retardant is bigger, and mechanical property descends, and especially impact property descends, and flame retardant effect is not really desirable, and the cost height.As: there are decabromodiphynly oxide and eight bromo ether (chemistry is by name 1.1 '-(methyl oneself fork)-two [(3.5-dibromo)-4 (2.3-dibromo propoxy benzene)]), decabromodiphenyl and 12 chloro-, ten dihydro methylene radical dibenzocyclooctanes, hexabromocyclododecane and fire retardants such as tetrabromo-bisphenol, decabromodiphynly oxide or pentabromotoluene to prepare anti-flaming polypropylene material both at home and abroad in disclosed patent application or the document.Though all have certain flame retardant properties, the additive capacity of fire retardant is bigger, and the molten drop phenomenon of material is serious, and the cigarette amount is bigger, and flame retardant effect is not really desirable, the cost height.For example adopt the special-purpose flame-proof mother granule of ten bromines connection (two) phenylate and making such as hexabromo ether, antimonous oxide, aluminium hydroxide or magnesium hydroxide described in the Chinese patent application CN1049366, described according to it, in its addition scope, the combustibility of its material＜30 millimeter/minute, it is flammable to be that material still belongs to, and flame retardant effect is unsatisfactory.And in use all there are some problems in existing these fire retardants, and for example eight bromo ether is easily separated out, and secular flame retardant effect of material and outward appearance are relatively poor; Thermal stability of hexabromocyclododecane is poor, easily decomposes under higher processing temperature; Decabromodiphynly oxide easily generates many bromos dibenzodioxin alkane and PBDF when burning, environment is polluted.
Summary of the invention:
The present invention according to different flame retardant under differing temps, it suppresses the effect difference of flame, adopt the compound prescription of several bromide fire retardants to carry out fire-retardant to resin base material, thereby provide a kind of composite flame retardant in bromine series, make under the less situation of fire retardant addition, can reach that polyolefin resin (polypropylene or polyethylene etc.) is well fire-retardant, the effect of anti-molten drop.
The objective of the invention is in order to overcome that polyolefin resines such as existing polyethylene, acrylic plastering very easily burn and shortcoming such as the big molten drop phenomenon of amount of smoke is serious, and provide a kind of efficient composite flame retardant in bromine series that can be applicable to polyolefin resin, thereby make resin material reach fire-retardant, press down cigarette, the requirement of anti-molten drop, normally use and prevent spreading of fire with what guarantee the extranal packing box interior items.
Another object of the present invention provides the preparation method of described composite flame retardant in bromine series.
A further object of the present invention provides the application of this kind composite flame retardant in bromine series in polyolefin resin.
Composite flame retardant in bromine series of the present invention, the following component that includes blend: a. bromide fire retardant, b. synergistic fire retardant, the anti-molten drop agent of c., be 100 parts by weight in component a bromide fire retardant wherein, the components b synergistic fire retardant is 30～45 weight parts, is preferably 33～40 weight parts; The anti-molten drop agent of amount of component b is 30～60 weight parts, is preferably 35～56 weight parts.
The bromide fire retardant of the above component a is the mixture of any one and thermostability hexabromocyclododecane in TDE or the eight bromo ether, wherein the part by weight of any one in TDE or the eight bromo ether and thermostable type hexabromocyclododecane is 2: 1～1: 2, is preferably 2: 1～1: 1.
The inventor finds that in experiment common hexabromocyclododecane decomposes easily under the temperature of resin treatment, thereby cause effect to descend, so be heat decomposition temperature more than or equal to 200 ℃ thermostable type hexabromocyclododecane at the hexabromocyclododecane described in the composite flame retardant in bromine series of the present invention.Decabrominated dipheny base ethane not only has the plurality of advantages of decabromodiphynly oxide, and aspect such as thermostability, light stability, anti-transport property is all good than decabromodiphynly oxide.Decabrominated dipheny base ethane quite stable in the use system, exudative low than other fire retardants can recycle with its fire-retardant thermoplastics.The more important thing is owing to do not have ehter bond in its molecule,, environment is not worked the mischief so do not generate the danger of many bromos dibenzodioxin alkane and PBDF.In order to reach good resin flame retardant effect, its key should be complementary by the decomposition temperature of the decomposition temperature of fire-retardant thing and fire retardant.Adopt the mixture of two kinds of fire retardants can obtain better flame retardant effect.The hexabromocyclododecane mixing use of selecting TDE or eight bromo ether and thermostable type for use is that flame retarding efficiency is higher because TDE or eight bromo ether and hexabromocyclododecane play the fire-retardant flame-retardant system of fire retardation formation segmentation in high-temperature zone and cold zone respectively.In addition, eight bromo ether and hexabromocyclododecane mix use can reduce the consumption of eight bromo ether, thereby avoids separating out phenomenon because of a large amount of eight bromo ethers that use eight bromo ethers to cause.
The synergistic fire retardant of the above components b is an antimonous oxide.Bromide fire retardant is synergist with the antimonous oxide, can with its formation halogen-antimony collaboration system, when the composite use of hydrogeneous bromide fire retardant in antimonous oxide and the halogenated flame retardant, antimonous oxide can generate antimony tribro-or bromine weisspiessglanz with reaction of hydrogen bromide in combustion processes.And the bromine weisspiessglanz can continue to be decomposed into antimony tribro-in very wide temperature range, and the antimony tribro-of formation can effectively stop the carrying out of combustion reactions, improves flame retarding efficiency.
The anti-molten drop agent of the above amount of component b can be played significant feature and is anti-molten drop, press down cigarette in fire-retardant, reduce the content of halogenated flame retardant, reaches environmental requirement.Described anti-molten drop agent is for comprising at least a following material: organo montmorillonite, kaolin, clay.The median size of described anti-molten drop agent is smaller or equal to 1000nm.
In order to improve the blended avidity of composite flame retardant in bromine series and macromolecule resin system, improve the mechanical property of its flame-retardant modified back material.Composite flame retardant in bromine series of the present invention also can include surface treatment agent.Surface treatment agent is a titanate coupling agent, and titanate coupling agent is preferably at least a in the following material; Sec.-propyl three (different perester radical) titanic acid ester, sec.-propyl three (dioctyl phosphoric acid ester acyl group) titanic acid ester, sec.-propyl three (dioctylphyrophosphoric acid ester acyl group) titanic acid ester.The content of surface treatment agent is 3～5%wt of the anti-molten drop agent three component gross weights of described component a bromide fire retardant, components b synergistic fire retardant and amount of component b.
The preparation method of composite flame retardant in bromine series of the present invention comprises the above each component is carried out blend, thorough mixing by described amount.In order to obtain the better mixing effect, the mixing of each component can be divided into some steps, promptly the preparation method of composite flame retardant in bromine series of the present invention preferably includes following steps:
1. described each component except that surface treatment agent is mixed;
2. surface treatment agent is added said mixture while stirring, carry out thorough mixing.
Composite flame retardant in bromine series of the present invention can be applicable to the flame-retardant modified of polyolefin plastics.Composite flame retardant in bromine series of the present invention and polyolefin plastics are carried out melt blending by the general-purpose plastics processing units, make the resin material modification reach fire-retardant, press down the requirement of cigarette, anti-molten drop, thereby have good flame-retardant effect.Generally speaking, be 100 parts by weight in polyolefin resin, add-on 10～40 parts by weight of composite flame retardant in bromine series.
The concrete preparation method and the application of composite flame retardant in bromine series of the present invention are summarized as follows:
Composite flame retardant in bromine series of the present invention preparation: with in TDE or the eight bromo ether any one respectively with the thermostable type hexabromocyclododecane according to the formula rate weighing, and add in the high-speed mixer by consumption with (can comprise surface treatment agent) such as anti-molten drop agent, antimonous oxides.Usually carrying out high-speed mixing under the high-speed mixing condition, for example: under 70～100 ℃, blender blend rotating speed is to mix stirring 5～10 minutes under the condition of 800～1000 commentariess on classics/min, promptly gets described composite flame retardant in bromine series; Above-mentioned each component that perhaps will be except surface treatment agent is preliminary mix after, add described surface treatment agent in the high-speed mixer while stirring again, carry out above-mentioned high-speed mixing then, make above each component carry out sufficient surface modification, promptly get described composite flame retardant in bromine series.
The application of bromide fire retardant of the present invention: will be through composite flame retardant in bromine series and polyolefin plastics blend in high-speed mixer of above-mentioned preparation, perhaps with in described TDE or the eight bromo ether any one respectively with the thermostable type hexabromocyclododecane according to the formula rate weighing, and same polyolefin plastics, anti-molten drop agent, antimonous oxide etc. add blend in the high-speed mixer to by consumption.Blend composition by twin screw extruder, under the common melt processing temperature of plastics, through the conveying and the shear stress of screw rod, is fully melted, blend, again through head extrude, cooling, gas blower, dicing machine make flame-proof polyolefin resin composition.
It is flame-retardant modified that composite flame retardant in bromine series of the present invention is applied to polyolefin resin, and fire-retardant rank can reach the V-0 level, and no molten drop has good stretching and impact property, compliance with environmental protection requirements.Be applicable to extranal packing box materials such as military products and electronic product.
Embodiment:
Below in conjunction with embodiment, further specify the present invention.
Raw material:
Polypropylene: copolymerized type propene polymer, the Beijing Yanshan Petrochemical Company chemical plant produces, and the trade mark is K8303, and melt flow rate (MFR) is 1～2.5g/10min.
The thermostable type hexabromocyclododecane: Lianyun Harbour legend fire retardant company limited produces, fusing point 175-190 ℃ bromine content 74.7%, and heat decomposition temperature surpasses 200 ℃, and its decomposition temperature is 220 ℃.
TDE: the refined precious chemical production of the U.S., brominated amount 82.27%.
Eight bromo ether: Lianyungang Sea Water Chemical Co., Ltd. produces, and molecular weight is 801.4, and molecular formula is C
12H
2Br
8, melting temperature is 70～150 ℃, bromine content is not less than 78%., its decomposition temperature is higher than 250 ℃.
Decabromodiphenyl oxide: U.S. big lake company produces, and molecular weight is 959.12, and melting temperature is 300～310 ℃, and bromine content is not less than 83.3%, and decomposition temperature is higher than 357 ℃.
Organo montmorillonite: Zhejiang Feng Hong responsibility company limited produces, trade mark DK4, and median size is smaller or equal to 1000 nanometers, and average wafer thickness is smaller or equal to 25nm, and interlamellar spacing is below the 2.5nm.
Nano lamellar kaolin: the new new high-tech material company limiteds in Zaozhuang, Shandong three produce, and the trade mark is SK-80, is the nanometer lamella, and interlamellar spacing is 1.8nm, below the 3.8nm, and median size is smaller or equal to 500nm.
Antimonous oxide: rainbow fire retardant company limited in Hunan, Tianjin produces, and crystalline form is full cubic-crystal.
Magnesium hydroxide, aluminium hydroxide: commercially available.
Titanate coupling agent: NanJing Shuguang Chemical Group Co., Ltd. produces,
Trade mark NDZ-101, chemical name are sec.-propyl three (different perester radical) titanic acid ester;
Trade mark DZ-102, chemical name are sec.-propyl three (dioctyl phosphoric acid ester acyl group) titanic acid ester;
Trade mark TMC-114, chemical name are sec.-propyl three (dioctylphyrophosphoric acid ester acyl group) titanic acid ester.
Mechanics and combustionproperty test:
According to GB/T 1040-92, the test of mechanical properties such as GB/T9343-2000, GB/T1043-93 stretch respectively, bending, impact; Combustionproperty is measured according to the limiting oxygen index determination standard of GB/T2406-93 and the vertical combustion method of GB/T4609-93.
Embodiment 1
Getting in polypropylene is 23 parts of the composite flame retardant in bromine series of 100 parts by weight, and wherein 8 parts of eight bromo ethers, 4 parts of thermostable type hexabromocyclododecanes, 6 parts of organo montmorillonites, 5 parts of antimonous oxides dry by the fire 5h in air dry oven, and temperature is controlled to be 80 ℃.Dry to such an extent that material joins in the high-speed mixer with above-mentioned, get titanate coupling agent (NDZ-101) simultaneously with the 4%wt of bromide fire retardant, antimonous oxide and anti-molten drop agent gross weight, join in the high-speed mixer while stirring, at 1000 rev/mins, high-speed mixing is 10 minutes under 70 ℃ the condition, obtains described composite flame retardant in bromine series.100 parts by weight polypropylene are joined in the high-speed mixer carry out high-speed mixing with composite flame retardant in bromine series.The pellet that mixes joins in the main spout of twin screw extruder, and wherein one to seven district's temperature is 170 ℃, 175 ℃, 190 ℃, 190 ℃, 185 ℃, 175 ℃, 170 ℃ (head) on the forcing machine, and pressure is that 1.1～1.4MPa melt extrudes granulation.After making pellet by above-mentioned preparation method, pellet injection moulding in injection moulding machine is made the standard batten, carry out every Mechanics Performance Testing, its result is as shown in table 1.
Embodiment 2
Change eight bromo ether among the embodiment 1 into TDE, all the other conditions are identical with embodiment 1.After making pellet by the preparation method of embodiment 1, injection moulding makes the standard batten in injection moulding machine, carries out every Mechanics Performance Testing, and its result is as shown in table 1.
Embodiment 3
Change composite flame retardant in bromine series among the embodiment 1 into 28 parts, wherein 9 parts of TDE, 7 parts of thermostable type hexabromocyclododecanes, 6 parts of organo montmorillonites, 6 parts of antimonous oxides, all the other conditions are identical with embodiment 1.After making pellet by the preparation method of embodiment 1, injection moulding makes the standard batten in injection moulding machine, carries out every Mechanics Performance Testing, and its result is as shown in table 1.
Embodiment 4
Change composite flame retardant in bromine series among the embodiment 1 into 18 parts, wherein 5 parts of TDE, 4 parts of thermostable type hexabromocyclododecanes, 5 parts of organo montmorillonites, 4 parts of antimonous oxides, all the other conditions are identical with embodiment 1.After making pellet by the preparation method of embodiment 1, injection moulding makes the standard batten in injection moulding machine, carries out every Mechanics Performance Testing, and its result is as shown in table 1.
Embodiment 5
Change composite flame retardant in bromine series among the embodiment 1 into 30 parts, wherein 11 parts of TDE, 6 parts of thermostable type hexabromocyclododecanes, 7 parts of organo montmorillonites, 6 parts of antimonous oxides; Get the titanate coupling agent (NDZ-101) with the 5%wt of bromide fire retardant, antimonous oxide and anti-molten drop agent gross weight, all the other conditions are identical with embodiment 1.After making pellet by the preparation method of embodiment 1, injection moulding makes the standard batten in injection moulding machine, carries out every Mechanics Performance Testing, and its result is as shown in table 1.
Embodiment 6
Change composite flame retardant in bromine series among the embodiment 1 into 25 parts, wherein TDE is 9 parts, 5 parts of thermostable type hexabromocyclododecanes, and 6 parts of nano lamellar kaolin, 5 parts of antimonous oxides, all the other conditions are identical with embodiment 1.After making pellet by the preparation method of embodiment 1, injection moulding makes the standard batten in injection moulding machine, carries out every Mechanics Performance Testing, and its result is as shown in table 1.
Embodiment 7
Change composite flame retardant in bromine series among the embodiment 1 into 33 parts, wherein TDE is 10 parts, 7 parts of thermostable type hexabromocyclododecanes, 10 parts of nano lamellar kaolin, 6 parts of antimonous oxides; Get the titanate coupling agent (NDZ-101) with the 4.5%wt of bromide fire retardant, antimonous oxide and anti-molten drop agent gross weight, all the other conditions are identical with embodiment 1.After making pellet by the preparation method of embodiment 1, injection moulding makes the standard batten in injection moulding machine, carries out every Mechanics Performance Testing, and its result is as shown in table 1.
Comparative example 1
Change eight bromo ether among the embodiment 1 into decabromodiphenyl oxide, all the other conditions are identical with embodiment 1.After making pellet by the preparation method of embodiment 1, injection moulding makes the standard batten in injection moulding machine, carries out every Mechanics Performance Testing, and its result is as shown in table 1.
Comparative example 2
Change the eight bromo ether among the embodiment 1 into 13 parts, the thermostable type hexabromocyclododecane changes 0 part into, and all the other conditions are identical with embodiment 1.After making pellet by the preparation method of embodiment 1, injection moulding makes the standard batten in injection moulding machine, carries out every Mechanics Performance Testing, and its result is as shown in table 1.
Comparative example 3
Change the eight bromo ether among the embodiment 1 into TDE, 13 parts of TDE, the thermostable type hexabromocyclododecane changes 0 part into, and all the other conditions are identical with embodiment 1.After making pellet by the preparation method of embodiment 1, injection moulding makes the standard batten in injection moulding machine, carries out every Mechanics Performance Testing, and its result is as shown in table 1.
Comparative example 4
It is 100 parts by weight, 7 parts of TDE, 6 parts of eight bromo ethers, 5 parts of antimonous oxides, 6 parts of titanate coupling agents (NDZ-101) that reach with the 4%wt of TDE, eight bromo ether, antimonous oxide and aluminium hydroxide gross weight of aluminium hydroxide that raw material is got polypropylene; After making pellet by the preparation condition of the foregoing description 1, pellet injection moulding in injection moulding machine is made the standard batten, carry out every Mechanics Performance Testing, its result is as shown in table 1.
Comparative example 5
Raw material is got polypropylene 100 parts by weight, 8 parts of TDE, 4 parts of thermostable type hexabromocyclododecanes, 5 parts of titanate coupling agents (NDZ-101) that reach with the 4%wt of TDE, thermostable type hexabromocyclododecane, antimonous oxide gross weight of antimonous oxide do not add anti-molten drop agent; After making pellet by the preparation condition of the foregoing description 1, pellet injection moulding in injection moulding machine is made the standard batten, carry out every Mechanics Performance Testing, its result is as shown in table 1.
Comparative example 6
Raw material is got polypropylene 100 parts by weight, 8 parts of TDE, 4 parts of thermostable type hexabromocyclododecanes, 5 parts of antimonous oxides, aluminium hydroxide and 6 parts of titanate coupling agents (NDZ-101) that reach with the 4%wt of TDE, thermostable type hexabromocyclododecane, antimonous oxide, aluminium hydroxide and magnesium hydroxide gross weight of 1: 1 mixture of magnesium hydroxide weight ratio; After making pellet by the preparation condition of the foregoing description 1, pellet injection moulding in injection moulding machine is made the standard batten, carry out every Mechanics Performance Testing, its result is as shown in table 1.
Table 1
| Tensile strength | The simply supported beam notched Izod impact strength | Flexural strength | Elongation | Oxygen index | The UL94 standard | |
| Unit | MPa | kJ/m 2 | MPa | ％ | ％ | |
| Embodiment 1 | 26.69 | 23.49 | 32.18 | 428.3 | 29.1 | V-0 does not have molten drop |
| Embodiment 2 | 26.70 | 26.12 | 31.47 | 539.4 | 30.1 | V-0 does not have molten drop |
| Embodiment 3 | 27.67 | 38.45 | 35.12 | 621 | 30.8 | V-0 does not have molten drop |
| Embodiment 4 | 27.5 | 32 | 27 | 411.2 | 28.6 | V-0 does not have molten drop |
| Embodiment 5 | 26.1 | 30 | 25.6 | 429.8 | 31.6 | V-0 does not have molten drop |
| Embodiment 6 | 26.8 | 31.3 | 26 | 438.4 | 27.2 | V-0 does not have molten drop |
| Embodiment 7 | 27.2 | 31 | 26.8 | 432.3 | 31.1 | V-0 does not have molten drop |
| Comparative example 1 | 24.05 | 23.26 | 31.22 | 431.0 | 26.9 | V-1 has molten drop |
| Comparative example 2 | 26.44 | 22.74 | 30.43 | 449.9 | 24.2 | V-2 is from putting out |
| Comparative example 3 | 25.84 | 21.83 | 29.71 | 433.2 | 25.4 | V-2 is from putting out |
| Comparative example 4 | Do not survey | Do not survey | Do not survey | Do not survey | 25 | V-1 has molten drop |
| Comparative example 5 | 19.8 | 20.5 | 19.1 | 304.6 | 20.1 | V-2 is from putting out |
| Comparative example 6 | 20.2 | 22 | 21 | 348.7 | 23.1 | V-1 has molten drop |
| Reference standard | GB1040 | GB1043 | GB9341 | GB9341 | GB2406 | GB2408 |
Claims (8)
1. composite flame retardant in bromine series includes the following component of blend:
A. bromide fire retardant 100 weight parts
B. synergistic fire retardant 30～45 weight parts
C. anti-molten drop agent 30～60 weight parts
The bromide fire retardant of above component a is the mixture of any one and thermostable type hexabromocyclododecane in TDE or the eight bromo ether, and described thermostable type hexabromocyclododecane is a heat decomposition temperature more than or equal to 200 ℃ hexabromocyclododecane; Wherein the part by weight of any one in TDE or the eight bromo ether and thermostable type hexabromocyclododecane is 2: 1～1: 2; The synergistic fire retardant of above components b is an antimonous oxide; The median size of the anti-molten drop agent of above amount of component b is smaller or equal to 1000nm, and it is selected from least a in the following material: organo montmorillonite, kaolin, clay.
2. composite flame retardant in bromine series according to claim 1 includes the following component of blend:
A. bromide fire retardant 100 weight parts
B. synergistic fire retardant 33～40 weight parts
C. anti-molten drop agent 35～56 weight parts.
3. composite flame retardant in bromine series according to claim 1, the part by weight of any one among its component a in TDE or the eight bromo ether and thermostable type hexabromocyclododecane is 2: 1～1: 1.
4. according to each described composite flame retardant in bromine series of claim 1～3, wherein include surface treatment agent, surface treatment agent is a titanate coupling agent, and the content of surface treatment agent is 3～5%wt of the anti-molten drop agent three component gross weights of described component a bromide fire retardant, components b synergistic fire retardant and amount of component b.
5. composite flame retardant in bromine series according to claim 4, the titanate coupling agent of wherein said surface treatment agent are at least a in the following material; Sec.-propyl three (different perester radical) titanic acid ester, sec.-propyl three (dioctyl phosphoric acid ester acyl group) titanic acid ester, sec.-propyl three (dioctylphyrophosphoric acid ester acyl group) titanic acid ester.
6. the preparation method according to each described composite flame retardant in bromine series of claim 1～5 comprises described each component is carried out blend, thorough mixing by described amount.
7. according to the preparation method of the described composite flame retardant in bromine series of claim 6, may further comprise the steps:
1. described each component except that surface treatment agent is mixed;
2. surface treatment agent is added said mixture while stirring, carry out thorough mixing.
8. application according to each described composite flame retardant in bromine series of claim 1～5, it comprises described composite flame retardant in bromine series and thermoplastic molten blend.
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| CN105295274A (en) * | 2015-11-24 | 2016-02-03 | 宁夏润龙包装新材料股份有限公司 | Bromine-series composite flame retardant and preparation method thereof |
| CN106784527A (en) * | 2016-12-22 | 2017-05-31 | 陈申申 | A kind of lead-acid accumulator dividing plate and preparation method thereof |
| CN107641247B (en) * | 2017-11-08 | 2020-04-14 | 深圳市绿泰环保科技有限公司 | Method for preparing flame-retardant material from modified antimony oxide |
| CN109111932A (en) * | 2018-08-16 | 2019-01-01 | 浙江蓝盾电工新材料科技有限公司 | A kind of pre-dispersed composite flame-retardant agent filler of clay and preparation method |
| CN109722179A (en) * | 2019-01-04 | 2019-05-07 | 东莞市宏泰基阻燃材料有限公司 | A kind of new flame retardant and preparation method thereof |
| CN110093089A (en) * | 2019-05-21 | 2019-08-06 | 湖北来斯化工新材料有限公司 | A kind of warping resistance type fire-proof powdery paint and preparation method thereof |
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| CN1175267A (en) * | 1995-02-16 | 1998-03-04 | 智索公司 | Crystalline polyolefin resin composition and electrical insulation parts made from said composition |
| EP1170116A1 (en) * | 2000-07-05 | 2002-01-09 | REHAU AG + Co | Moisture curable polyolefine elastomer profiles |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1079494A (en) * | 1993-06-25 | 1993-12-15 | 生寿斋 | Anti-electrostatic fire retardant composition and preparation method thereof |
| CN1175267A (en) * | 1995-02-16 | 1998-03-04 | 智索公司 | Crystalline polyolefin resin composition and electrical insulation parts made from said composition |
| EP1170116A1 (en) * | 2000-07-05 | 2002-01-09 | REHAU AG + Co | Moisture curable polyolefine elastomer profiles |
| CN1358790A (en) * | 2000-12-12 | 2002-07-17 | 西巴特殊化学品控股有限公司 | Antiweatherability improved flame-retarded polyolefine |
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