CN109942846A - A kind of bis- (the bromo- 2- methyl-propyl of 2,3- bis-) ether fire-retardant master granules of tetrabromobisphenol A and preparation method thereof - Google Patents
A kind of bis- (the bromo- 2- methyl-propyl of 2,3- bis-) ether fire-retardant master granules of tetrabromobisphenol A and preparation method thereof Download PDFInfo
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- CN109942846A CN109942846A CN201910237970.6A CN201910237970A CN109942846A CN 109942846 A CN109942846 A CN 109942846A CN 201910237970 A CN201910237970 A CN 201910237970A CN 109942846 A CN109942846 A CN 109942846A
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- 239000003063 flame retardant Substances 0.000 title claims abstract description 149
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 title claims abstract description 106
- VEORPZCZECFIRK-UHFFFAOYSA-N 3,3',5,5'-tetrabromobisphenol A Chemical compound C=1C(Br)=C(O)C(Br)=CC=1C(C)(C)C1=CC(Br)=C(O)C(Br)=C1 VEORPZCZECFIRK-UHFFFAOYSA-N 0.000 title claims abstract description 88
- 239000008187 granular material Substances 0.000 title claims abstract description 74
- -1 bromo- 2- methyl-propyl Chemical group 0.000 title claims abstract description 62
- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- 239000011347 resin Substances 0.000 claims abstract description 66
- 229920005989 resin Polymers 0.000 claims abstract description 66
- 239000006057 Non-nutritive feed additive Substances 0.000 claims abstract description 31
- 239000004611 light stabiliser Substances 0.000 claims abstract description 29
- 230000000979 retarding effect Effects 0.000 claims abstract description 25
- 150000002170 ethers Chemical class 0.000 claims abstract description 24
- CJZGTCYPCWQAJB-UHFFFAOYSA-L calcium stearate Chemical compound [Ca+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CJZGTCYPCWQAJB-UHFFFAOYSA-L 0.000 claims abstract description 21
- 235000013539 calcium stearate Nutrition 0.000 claims abstract description 21
- 239000008116 calcium stearate Substances 0.000 claims abstract description 21
- 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 abstract description 21
- 229960001545 hydrotalcite Drugs 0.000 claims abstract description 21
- 229910001701 hydrotalcite Inorganic materials 0.000 claims abstract description 21
- OUPZKGBUJRBPGC-UHFFFAOYSA-N 1,3,5-tris(oxiran-2-ylmethyl)-1,3,5-triazinane-2,4,6-trione Chemical compound O=C1N(CC2OC2)C(=O)N(CC2OC2)C(=O)N1CC1CO1 OUPZKGBUJRBPGC-UHFFFAOYSA-N 0.000 claims abstract description 19
- 239000002994 raw material Substances 0.000 claims abstract description 11
- 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 claims abstract description 3
- 238000002844 melting Methods 0.000 claims description 33
- 230000008018 melting Effects 0.000 claims description 33
- 238000001125 extrusion Methods 0.000 claims description 30
- 239000000203 mixture Substances 0.000 claims description 29
- XUMFBUWGVLTWTH-UHFFFAOYSA-N 1,2-dibromo-3-(2,3-dibromo-2-methylpropoxy)-2-methylpropane Chemical compound BrCC(Br)(C)COCC(C)(Br)CBr XUMFBUWGVLTWTH-UHFFFAOYSA-N 0.000 claims description 20
- 238000000034 method Methods 0.000 claims description 16
- 238000005453 pelletization Methods 0.000 claims description 16
- 238000001035 drying Methods 0.000 claims description 14
- 229910000410 antimony oxide Inorganic materials 0.000 claims description 10
- VTRUBDSFZJNXHI-UHFFFAOYSA-N oxoantimony Chemical group [Sb]=O VTRUBDSFZJNXHI-UHFFFAOYSA-N 0.000 claims description 10
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 8
- 206010013786 Dry skin Diseases 0.000 claims description 8
- 239000004698 Polyethylene Substances 0.000 claims description 8
- 239000006096 absorbing agent Substances 0.000 claims description 8
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 8
- 229910052794 bromium Inorganic materials 0.000 claims description 8
- 238000007599 discharging Methods 0.000 claims description 8
- 230000004927 fusion Effects 0.000 claims description 8
- 238000002156 mixing Methods 0.000 claims description 8
- 229920000573 polyethylene Polymers 0.000 claims description 8
- 239000004594 Masterbatch (MB) Substances 0.000 claims description 6
- 150000004645 aluminates Chemical class 0.000 claims description 6
- 239000007822 coupling agent Substances 0.000 claims description 6
- 238000009775 high-speed stirring Methods 0.000 claims description 6
- 239000003963 antioxidant agent Substances 0.000 claims description 2
- 230000003078 antioxidant effect Effects 0.000 claims description 2
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 23
- 230000000694 effects Effects 0.000 abstract description 22
- 231100000693 bioaccumulation Toxicity 0.000 abstract description 3
- 239000012757 flame retardant agent Substances 0.000 abstract description 3
- 206010023126 Jaundice Diseases 0.000 abstract description 2
- 231100000331 toxic Toxicity 0.000 abstract description 2
- 230000002588 toxic effect Effects 0.000 abstract description 2
- 206010056508 Acquired epidermolysis bullosa Diseases 0.000 description 59
- 239000000047 product Substances 0.000 description 22
- 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 description 15
- 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 description 14
- ZQBAKBUEJOMQEX-UHFFFAOYSA-N phenyl salicylate Chemical compound OC1=CC=CC=C1C(=O)OC1=CC=CC=C1 ZQBAKBUEJOMQEX-UHFFFAOYSA-N 0.000 description 10
- 239000000523 sample Substances 0.000 description 9
- 239000003795 chemical substances by application Substances 0.000 description 7
- 238000004519 manufacturing process Methods 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- 239000012876 carrier material Substances 0.000 description 6
- 238000001816 cooling Methods 0.000 description 6
- 238000005469 granulation Methods 0.000 description 6
- 230000003179 granulation Effects 0.000 description 6
- 239000000843 powder Substances 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- 229960000969 phenyl salicylate Drugs 0.000 description 5
- 230000008901 benefit Effects 0.000 description 4
- 229920002521 macromolecule Polymers 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 3
- 230000007613 environmental effect Effects 0.000 description 3
- 239000012774 insulation material Substances 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 239000002957 persistent organic pollutant Substances 0.000 description 3
- 239000004033 plastic Substances 0.000 description 3
- 229920003023 plastic Polymers 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 230000002195 synergetic effect Effects 0.000 description 3
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 2
- 238000009825 accumulation Methods 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 239000012752 auxiliary agent Substances 0.000 description 2
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000011981 development test Methods 0.000 description 2
- 230000018109 developmental process Effects 0.000 description 2
- SNRUBQQJIBEYMU-UHFFFAOYSA-N dodecane Chemical compound CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 2
- 230000002124 endocrine Effects 0.000 description 2
- 230000002708 enhancing effect Effects 0.000 description 2
- 230000002349 favourable effect Effects 0.000 description 2
- 238000001746 injection moulding Methods 0.000 description 2
- 231100000252 nontoxic Toxicity 0.000 description 2
- 230000003000 nontoxic effect Effects 0.000 description 2
- 230000002688 persistence Effects 0.000 description 2
- 229920000058 polyacrylate Polymers 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 210000004994 reproductive system Anatomy 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- ZYUVGYBAPZYKSA-UHFFFAOYSA-N 5-(3-hydroxybutan-2-yl)-4-methylbenzene-1,3-diol Chemical compound CC(O)C(C)C1=CC(O)=CC(O)=C1C ZYUVGYBAPZYKSA-UHFFFAOYSA-N 0.000 description 1
- RQHZDJUTSGQPAO-UHFFFAOYSA-N C1CCCCCCCCCCC1.[Br] Chemical compound C1CCCCCCCCCCC1.[Br] RQHZDJUTSGQPAO-UHFFFAOYSA-N 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- XXFKYQVWZOJMRR-UHFFFAOYSA-N OC1=CC=C(C=C1)C(C)(C)C1=CC=C(C=C1)O.[Br] Chemical compound OC1=CC=C(C=C1)C(C)(C)C1=CC=C(C=C1)O.[Br] XXFKYQVWZOJMRR-UHFFFAOYSA-N 0.000 description 1
- 241000219000 Populus Species 0.000 description 1
- 238000003723 Smelting Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
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- 238000005452 bending Methods 0.000 description 1
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- 229940106691 bisphenol a Drugs 0.000 description 1
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 1
- 231100000481 chemical toxicant Toxicity 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
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- NHADDZMCASKINP-HTRCEHHLSA-N decarboxydihydrocitrinin Natural products C1=C(O)C(C)=C2[C@H](C)[C@@H](C)OCC2=C1O NHADDZMCASKINP-HTRCEHHLSA-N 0.000 description 1
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- 125000000623 heterocyclic group Chemical group 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
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- 239000007769 metal material Substances 0.000 description 1
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Landscapes
- Compositions Of Macromolecular Compounds (AREA)
- Fireproofing Substances (AREA)
- Processes Of Treating Macromolecular Substances (AREA)
Abstract
The present invention relates to a kind of tetrabromobisphenol As bis- (2, the bromo- 2- methyl-propyl of 3- bis-) ether fire-retardant master granule and preparation method thereof, the flame retardant agent content solved in prior art fire retardant preparation process is low, product color jaundice, product thermal stability and poor compatibility, it is big to material itself Effect on Mechanical Properties, toxic and bioaccumulation and the big technical problem of biological magnification.The present invention provides a kind of tetrabromobisphenol A bis- (2, the bromo- 2- methyl-propyl of 3- bis-) ether fire-retardant master granule and preparation method thereof, according to parts by weight, it is made of following raw material components: bis- (2,3- bis- bromo- 2- methyl-propyl) 30-35 parts of the ethers of 40-45 parts of Gao Liudong EBA resin, fire retardant tetrabromobisphenol A, 15-20 parts of calcium stearate, 2-4 parts of hydrotalcite, 5-10 parts of fire retarding synergist, 4-5 parts of processing aid, 0.1-0.4 parts of TGIC, 0.5-1 parts of light stabilizer.The present invention is widely used in fire-retardant FRW technical field.
Description
Technical field
The present invention relates to fire-retardant FRW technical fields, and in particular to a kind of bis- (2,3- bis- bromo- 2- methyl of tetrabromobisphenol A
Propyl) ether fire-retardant master granule and preparation method thereof.
Background technique
Hexabromocyclododecane (HBCD) is the most common fire retardant of EPS/XPS, 350,000 tons of year usage amount >.In EPS/XPS
Thermal insulation material flame retardant area occupies always 70% or more the market share.It is found by the use of many years, hexabromocyclododecane
It is a kind of persistence organic pollutant (POPs), with very strong bioaccumulation and biological magnification, there is data to suggest that
There is toxic hazard to human endocrinological's system and reproductive system, control substance is asserted by European Union ROHS instruction；2013
Year the United Nations " Convention of Stockholm about persistence organic pollutant ", which votes, adopts a ban unanimously: in the world
It is inside forbidden to use hexabromocyclododecane (HBCD), which implements in the U.S., European Union and Japan.China also has been turned on hexabromo
Cyclododecane market withdrawal mechanism, on December 20th, 2017, Chinese Ministry of Environmental Protection have issued " the toxic chemical name of an article that China strictly limits
Record " (2018) bulletin, hexabromocyclododecane EPS/XPS exempt phase on December 25th, 2021.Therefore hexabromo ring is broken through
Dodecane substitute synthesizes key technology, realizes the research and development of hexabromocyclododecane substitute and industrialization is extremely urgent.In September, 2013
24, Environmental Protection Agency USA (EPA) promulgated that fire retardant hexabromocyclododecane (HBCD) is replaced according to Environment Design (DfE) project
For the draft report of object.Specifying bis- (the bromo- 2- methyl-propyl of the 2,3- bis-) ethers of tetrabromobisphenol A is that hexabromocyclododecane well substitutes
Product.
Bis- (the bromo- 2- methyl-propyl of 2,3- bis-) the ether fire-retardant master granules of tetrabromobisphenol A and its product have no domestic and international related patents
Document report, there are flame retardant agent contents low, the product color jaundice of the sample of domestic fire-retardant master granule processing enterprise trial-production, product heat are steady
The disadvantages of qualitative and poor compatibility, fire-retardant master granule dosage is big, is not able to satisfy downstream client use.
At present EPS/XPS thermal insulation material it is flame-retardant modified mostly be using directly addition fire retardant, but each based flame retardant due to
There are poor dispersion, production technologies to be not easy to control and operation for mostly powder, directly addition, is difficult to ensure flame retardant effect etc.,
These problems can be well solved using fire-retardant master granule, and are conducive to avoid wasting and reduce environmental pollution.
With the development of science and technology improvement of living standard, high molecular material especially synthesizes macromolecule, such as plastics, rubber
Status in people's lives is more and more important, and widened trend year by year is presented in application.But most high-molecular organic material
With inflammable characteristic different degrees of in air, in order to realize it in military, space flight, traffic, electric power and all multirows such as civilian
The application of industry carries out it flame-retardant modified as new project.Thermoplastic second made of ethylene and butyl acrylate copolymerization
Alkene-butyl acrylate copolymer (EBA) has good flexibility, impact resistance, bending fatigue resistance, thermal stability and processing
Performance, however EBA easily aptitude to burn hinders its application in some fields, therefore prepares fire-retardant EBA material, improves
Its safety used is highly desirable.At present it is more satisfactory to plastic flame method of modifying often by be added fire retardant
Or the product of flame-retardant master batch etc improves the fire protecting performance of plastics.
Summary of the invention
The object of the invention is in order to overcome the above-mentioned deficiencies of the prior art, provide a kind of flame retardant agent content height, product
It being creamy white, product thermal stability is high and compatibility is good, small to material itself Effect on Mechanical Properties, nontoxic using fire-retardant master granule,
Bis- (the bromo- 2- methyl-propyl of 2,3- bis-) the ether fire-retardant master granules of tetrabromobisphenol A and its system of inanimate object accumulation property and biological magnification
Preparation Method.
The technical proposal for solving the technical problem of the invention is:
A kind of bis- (2,3- bis- bromo- 2- methyl-propyl) ether fire-retardant master granules of tetrabromobisphenol A, according to parts by weight, by following original
Material group is grouped as: bis- (the bromo- 2- methyl-propyl of 2,3- bis-) the ether 30-35 of 40-45 parts of Gao Liudong EBA resin, fire retardant tetrabromobisphenol A
Part, 15-20 parts of calcium stearate, 2-4 parts of hydrotalcite, 5-10 parts of fire retarding synergist, 4-5 parts of processing aid, TGIC0.1-0.4 parts,
0.5-1 parts of light stabilizer.
Preferably, according to parts by weight, raw material components form are as follows: 42 parts of Gao Liudong EBA resin, fire retardant tetrabromobisphenol A
Bis- (the bromo- 2- methyl-propyl of 2,3- bis-) 32 parts of ethers, 18 parts of calcium stearate, 3 parts of hydrotalcite, 8 parts of fire retarding synergist, processing aid 5
Part, TGIC0.3 parts, 0.7 part of light stabilizer.
Preferably, Gao Liudong EBA resin model is 3717AC, and Gao Liudong EBA resin is needed before use through 80 DEG C of dryings extremely
Moisture is less than 100ppm.
Preferably, bromine content >=65% in bis- (2, the 3- bis- bromo- 2- methyl-propyl) ethers of fire retardant tetrabromobisphenol A, fusing point
110-115 DEG C, 5%WLT >=250 DEG C, content >=98.5%.
Preferably, fire retarding synergist is antimony oxide, or the antimony oxide through aluminate coupling agent treatment.
Preferably, processing aid is polyethylene wax；Light stabilizer is ultraviolet absorbing agent.
A kind of preparation side of bis- (the bromo- 2- methyl-propyl of 2,3- bis-) the ether fire-retardant master granules of tetrabromobisphenol A of above-mentioned any one
Method, comprising the following steps:
1) weigh: number weighs high flowing EBA resin, bis- (the bromo- 2- of 2,3- bis- of fire retardant tetrabromobisphenol A according to the required weight
Methyl-propyl) ether, calcium stearate, hydrotalcite, fire retarding synergist, processing aid, TGIC, light stabilizer；
2) it mixes: by the processing aid of the EBA resin of half parts by weight weighed in step 1) and half parts by weight
It is added in high efficient mixer and carries out mixed at high speed stirring, add the fire retardant tetrabromo of weighed half parts by weight in step 1)
Bis- (2, the 3- bis- bromo- 2- methyl-propyl) ethers of bisphenol-A are mixed；It is separately added into the EBA tree of remaining weight number in order again
Rouge, the processing aid of remaining weight number, bis- (2, the 3- bis- bromo- 2- methyl-props of the fire retardant tetrabromobisphenol A of remaining weight number
Base) ether, after the weighed calcium stearate of step 1), hydrotalcite, fire retarding synergist, TGIC and light stabilizer, it is mixed again, until
After mixing, mixture is obtained；
3) extruding pelletization: mixture obtained in step 2) is transferred to screw extruder, by screw extruder through melting
Extruding pelletization obtains bis- (2,3- bis- bromo- 2- methyl-propyl) the ether fire-retardant master granules of tetrabromobisphenol A.
Preferably, in step 3), when screw extruder is granulated through melting extrusion, double vacuum systems are opened, first with high stream
Dynamic EBA resin carrier walks material, after linear outflow is stablized in discharging, then is replaced with mixture obtained in step 2) and is melted
Extruding pelletization.
Preferably, in step 3), the screw speed of Screw Extrusion machine host is 250r/min, fusion pressure 1.4MPa.
Preferably, melting temperature subregion is set, and subregion set temperature is followed successively by 20 DEG C, and 70 DEG C, 90 DEG C, 95 DEG C, 95 DEG C,
100 DEG C, 110 DEG C, 105 DEG C, 100 DEG C, 90 DEG C, 80 DEG C, 80 DEG C.
Beneficial effects of the present invention:
(1) bis- (the bromo- 2- methyl-propyl of 2,3- bis-) the ether fire-retardant master granules of tetrabromobisphenol A prepared by the present invention are compatible with substrate
Property it is good, small to the Effect on Mechanical Properties of resin, fire-retardant master granule dosage is few, ensure product have excellent properties while, reduce
Production cost.
Bis- (2,3- bis- bromo- 2- methyl-propyl) ether fire-retardant master granules of tetrabromobisphenol A of the invention and preparation method thereof, using four
Bis- (2, the 3- bis- bromo- 2- methyl-propyl) ethers of bromine bisphenol-A coat tetrabromobisphenol as carrier as fire-retardant main body, extraordinary model EBA
Bis- (the bromo- 2- methyl-propyl of 2,3- bis-) the ether flame retardant powder of A and it is aided with the auxiliary agents such as synergistic, enhancing and prepares good fire-retardant of compatibility
Master batch, the fire-retardant master granule dosage is low, good flame retardation effect, small to the Effect on Mechanical Properties of material, should compared with hexabromocyclododecane
Fire-retardant master granule effect on environment is small, has a wide range of application.
(2) bis- (2,3- bis- bromo- 2- methyl-propyl) ether fire-retardant master granules of tetrabromobisphenol A of the invention and preparation method thereof, work
Skill is easy to operate, implements to be easy, can be used for industrialized production and implementation.
(3) fire-retardant master granule is combination, modification and the association for passing through a variety of fire-retardant compositions on the basis of fire retardant
A kind of granular product prepared by effect effect.Different from fire retardant, flame-retardant master batch, which has, to be easy to add in resin, and cleaning is defended
Raw, flame retarding efficiency is high, and additive amount is small, small to the Effect on Mechanical Properties of resin, and layering, decorative pattern, precipitation etc. are not susceptible to after addition
Many advantages, such as bad phenomenon, saving human and material resources cost and time.So fire-retardant master granule is realized as macromolecule material product
One of optimal selection of fire protection requirement, and become effective substitute of fire retardant powder.
Fire retardant used in the present invention is bis- (2, the 3- bis- bromo- 2- methyl-propyl) ethers of tetrabromobisphenol A, which is six
The favorable substitutes of bromine cyclododecane (HBCD).
Specific embodiment
The present invention is further explained in the light of specific embodiments, to help the contents of the present invention are understood.The present invention
Used in method unless otherwise required, be conventional production method；Used raw material is unless otherwise required
Conventional commercial product.
Embodiment 1
A kind of method for preparing bis- (2,3- bis- bromo- 2- methyl-propyl) ether fire-retardant master granules of tetrabromobisphenol A, including following step
It is rapid:
1) weigh: number according to the required weight weighs high flowing 40 parts of EBA resin, fire retardant tetrabromobisphenol A bis- (2,3- bis-
Bromo- 2- methyl-propyl) 30 parts of ether, 15 parts of calcium stearate, 2 parts of hydrotalcite, 5 parts of fire retarding synergist antimony oxide, processing aid
4 parts of polyethylene wax, TGIC0.1 parts, 0.5 part of light stabilizer；Height flowing EBA resin model is 3717AC, and Gao Liudong EBA resin exists
It needs to be less than 100ppm through 80 DEG C of dryings to moisture before use；In bis- (the bromo- 2- methyl-propyl of the 2,3- bis-) ethers of fire retardant tetrabromobisphenol A
Bromine content >=65%, 110-115 DEG C of fusing point, 5%WLT >=250 DEG C, content >=98.5%；Light stabilizer is ultraviolet absorbing agent
Phenyl salicylate.
2) it mixes: by the processing aid of the EBA resin of half parts by weight weighed in step 1) and half parts by weight
It is added in high efficient mixer and carries out mixed at high speed stirring 5min, add the fire retardant of weighed half parts by weight in step 1)
10min is mixed in bis- (2, the 3- bis- bromo- 2- methyl-propyl) ethers of tetrabromobisphenol A；It is separately added into remaining weight number in order again
EBA resin, the processing aid of remaining weight number, bis- (2, the 3- bis- bromo- 2- of the fire retardant tetrabromobisphenol A of remaining weight number
Methyl-propyl) ether, after the weighed calcium stearate of step 1), hydrotalcite, fire retarding synergist, TGIC and light stabilizer, mix again
10min is stirred, until after mixing, obtaining mixture.
3) extruding pelletization: being transferred to screw extruder for mixture obtained in step 2), opens double vacuum systems, passes through spiral shell
Bar extruder is granulated through melting extrusion, and water is cooling, air-dried, pelletizing, drying and packs, and obtains white tetrabromobisphenol A bis- (2,3- bis-
Bromo- 2- methyl-propyl) ether fire-retardant master granule.
When screw extruder is granulated through melting extrusion, double vacuum systems are opened, are walked first with height flowing EBA resin carrier
Material after linear outflow is stablized in discharging, then is replaced with mixture feeding obtained, host setting charging rate in step 2)
10KG/h carries out melting extrusion granulation.The screw speed of Screw Extrusion machine host is 250r/min, fusion pressure 1.4MPa；Melting
The setting of temperature subregion, subregion set temperature are followed successively by 20 DEG C, and 70 DEG C, 90 DEG C, 95 DEG C, 95 DEG C, 100 DEG C, 110 DEG C, 105 DEG C, 100
DEG C, 90 DEG C, 80 DEG C, 80 DEG C.
Embodiment 2
A kind of method for preparing bis- (2,3- bis- bromo- 2- methyl-propyl) ether fire-retardant master granules of tetrabromobisphenol A, including following step
It is rapid:
1) weigh: number according to the required weight weighs high flowing 45 parts of EBA resin, fire retardant tetrabromobisphenol A bis- (2,3- bis-
Bromo- 2- methyl-propyl) 35 parts of ether, 20 parts of calcium stearate, 4 parts of hydrotalcite, 10 parts of fire retarding synergist antimony oxide, processing aid
5 parts of polyethylene wax, TGIC0.4 parts, 1 part of light stabilizer；Height flowing EBA resin model is 3717AC, and Gao Liudong EBA resin makes
100ppm need to be less than through 80 DEG C of dryings to moisture before；Bromine in bis- (the bromo- 2- methyl-propyl of the 2,3- bis-) ethers of fire retardant tetrabromobisphenol A
Content >=65%, 110-115 DEG C of fusing point, 5%WLT >=250 DEG C, content >=98.5%；Light stabilizer is ultraviolet absorbing agent water
Poplar acid phenenyl ester.
2) it mixes: by the processing aid of the EBA resin of half parts by weight weighed in step 1) and half parts by weight
It is added in high efficient mixer and carries out mixed at high speed and stir 10min, add the fire-retardant of weighed half parts by weight in step 1)
10min is mixed in bis- (2, the 3- bis- bromo- 2- methyl-propyl) ethers of agent tetrabromobisphenol A；It is separately added into remaining weight part in order again
Several EBA resins, the processing aid of remaining weight number, the fire retardant tetrabromobisphenol A of remaining weight number is bis-, and (2,3- bis- is bromo-
2- methyl-propyl) ether, after the weighed calcium stearate of step 1), hydrotalcite, fire retarding synergist, TGIC and light stabilizer, is mixed again
Stirring 10min is closed, until after mixing, obtaining mixture.
3) extruding pelletization: being transferred to screw extruder for mixture obtained in step 2), opens double vacuum systems, passes through spiral shell
Bar extruder is granulated through melting extrusion, and water is cooling, air-dried, pelletizing, drying and packs, and obtains white tetrabromobisphenol A bis- (2,3- bis-
Bromo- 2- methyl-propyl) ether fire-retardant master granule.
When screw extruder is granulated through melting extrusion, double vacuum systems are opened, are walked first with height flowing EBA resin carrier
Material after linear outflow is stablized in discharging, then is replaced with mixture feeding obtained, host setting charging rate in step 2)
10KG/h carries out melting extrusion granulation.The screw speed of Screw Extrusion machine host is 250r/min, fusion pressure 1.4MPa.Melting
The setting of temperature subregion, subregion set temperature are followed successively by 20 DEG C, and 70 DEG C, 90 DEG C, 95 DEG C, 95 DEG C, 100 DEG C, 110 DEG C, 105 DEG C, 100
DEG C, 90 DEG C, 80 DEG C, 80 DEG C.
Embodiment 3
A kind of method for preparing bis- (2,3- bis- bromo- 2- methyl-propyl) ether fire-retardant master granules of tetrabromobisphenol A, including following step
It is rapid:
1) weigh: number according to the required weight weighs high flowing 42 parts of EBA resin, fire retardant tetrabromobisphenol A bis- (2,3- bis-
Bromo- 2- methyl-propyl) 32 parts of ether, 17 parts of calcium stearate, 3 parts of hydrotalcite, fire retarding synergist is through aluminate coupling agent treatment
6 parts of antimony oxide, 5 parts of processing aid polyethylene wax, TGIC0.3 parts, 0.7 part of light stabilizer；Height flows EBA resin model
3717AC, Gao Liudong EBA resin need to be less than 100ppm through 80 DEG C of dryings to moisture before use；Fire retardant tetrabromobisphenol A it is bis- (2,
The bromo- 2- methyl-propyl of 3- bis-) bromine content >=65% in ether, 110-115 DEG C of fusing point, 5%WLT >=250 DEG C, content >=98.5%；
Light stabilizer is ultraviolet absorbing agent phenyl salicylate.
2) it mixes: by the processing aid of the EBA resin of half parts by weight weighed in step 1) and half parts by weight
It is added in high efficient mixer and carries out mixed at high speed and stir 10min, add the fire-retardant of weighed half parts by weight in step 1)
10min is mixed in bis- (2, the 3- bis- bromo- 2- methyl-propyl) ethers of agent tetrabromobisphenol A；It is separately added into remaining weight part in order again
Several EBA resins, the processing aid of remaining weight number, the fire retardant tetrabromobisphenol A of remaining weight number is bis-, and (2,3- bis- is bromo-
2- methyl-propyl) ether, after the weighed calcium stearate of step 1), hydrotalcite, fire retarding synergist, TGIC and light stabilizer, is mixed again
Stirring 10min is closed, until after mixing, obtaining mixture.
3) extruding pelletization: being transferred to screw extruder for mixture obtained in step 2), opens double vacuum systems, passes through spiral shell
Bar extruder is granulated through melting extrusion, and water is cooling, air-dried, pelletizing, drying and packs, and obtains white tetrabromobisphenol A bis- (2,3- bis-
Bromo- 2- methyl-propyl) ether fire-retardant master granule.
When screw extruder is granulated through melting extrusion, double vacuum systems are opened, are walked first with height flowing EBA resin carrier
Material after linear outflow is stablized in discharging, then is replaced with mixture feeding obtained, host setting charging rate in step 2)
10KG/h carries out melting extrusion granulation.The screw speed of Screw Extrusion machine host is 250r/min, fusion pressure 1.4MPa.Melting
The setting of temperature subregion, subregion set temperature are followed successively by 20 DEG C, and 70 DEG C, 90 DEG C, 95 DEG C, 95 DEG C, 100 DEG C, 110 DEG C, 105 DEG C, 100
DEG C, 90 DEG C, 80 DEG C, 80 DEG C.
Embodiment 4
A kind of method for preparing bis- (2,3- bis- bromo- 2- methyl-propyl) ether fire-retardant master granules of tetrabromobisphenol A, including following step
It is rapid:
1) weigh: number weighs high flowing 44 parts of EBA resin, the bis- (2,3- bis- of fire retardant tetrabromobisphenol A according to the required weight
Bromo- 2- methyl-propyl) 34 parts of ether, 18 parts of calcium stearate, 4 parts of hydrotalcite, fire retarding synergist is through aluminate coupling agent treatment
8 parts of antimony oxide, 5 parts of processing aid polyethylene wax, TGIC0.3 parts, 0.9 part of light stabilizer；Height flows EBA resin model
3717AC, Gao Liudong EBA resin need to be less than 100ppm through 80 DEG C of dryings to moisture before use；Fire retardant tetrabromobisphenol A it is bis- (2,
The bromo- 2- methyl-propyl of 3- bis-) bromine content >=65% in ether, 110-115 DEG C of fusing point, 5%WLT >=250 DEG C, content >=98.5%；
Light stabilizer is ultraviolet absorbing agent phenyl salicylate.
2) it mixes: by the processing aid of the EBA resin of half parts by weight weighed in step 1) and half parts by weight
It is added in high efficient mixer and carries out mixed at high speed stirring 5-10min, add the resistance of weighed half parts by weight in step 1)
Bis- (2, the 3- bis- bromo- 2- methyl-propyl) ethers of agent tetrabromobisphenol A are fired, 10min is mixed；It is separately added into remaining weight in order again
The EBA resin of number, the processing aid of remaining weight number, the fire retardant tetrabromobisphenol A of remaining weight number bis- (2,3- bis-
Bromo- 2- methyl-propyl) ether, after the weighed calcium stearate of step 1), hydrotalcite, fire retarding synergist, TGIC and light stabilizer, again
10min is mixed, until after mixing, obtaining mixture.
3) extruding pelletization: being transferred to screw extruder for mixture obtained in step 2), opens double vacuum systems, passes through spiral shell
Bar extruder is granulated through melting extrusion, and water is cooling, air-dried, pelletizing, drying and packs, and obtains white tetrabromobisphenol A bis- (2,3- bis-
Bromo- 2- methyl-propyl) ether fire-retardant master granule.
When screw extruder is granulated through melting extrusion, double vacuum systems are opened, are walked first with height flowing EBA resin carrier
Material after linear outflow is stablized in discharging, then is replaced with mixture feeding obtained, host setting charging rate in step 2)
10KG/h carries out melting extrusion granulation.The screw speed of Screw Extrusion machine host is 250r/min, fusion pressure 1.4MPa.Melting
The setting of temperature subregion, subregion set temperature are followed successively by 20 DEG C, and 70 DEG C, 90 DEG C, 95 DEG C, 95 DEG C, 100 DEG C, 110 DEG C, 105 DEG C, 100
DEG C, 90 DEG C, 80 DEG C, 80 DEG C.
Embodiment 5
A kind of method for preparing bis- (2,3- bis- bromo- 2- methyl-propyl) ether fire-retardant master granules of tetrabromobisphenol A, including following step
It is rapid:
1) weigh: number weighs high flowing 42 parts of EBA resin, the bis- (2,3- bis- of fire retardant tetrabromobisphenol A according to the required weight
Bromo- 2- methyl-propyl) 32 parts of ether, 18 parts of calcium stearate, 3 parts of hydrotalcite, fire retarding synergist is through aluminate coupling agent treatment
8 parts of antimony oxide, 5 parts of processing aid polyethylene wax, TGIC0.3 parts, 0.7 part of light stabilizer；Height flows EBA resin model
3717AC, Gao Liudong EBA resin need to be less than 100ppm through 80 DEG C of dryings to moisture before use；Fire retardant tetrabromobisphenol A it is bis- (2,
The bromo- 2- methyl-propyl of 3- bis-) bromine content >=65% in ether, 110-115 DEG C of fusing point, 5%WLT >=250 DEG C, content >=98.5%；
Light stabilizer is ultraviolet absorbing agent phenyl salicylate.
2) it mixes: by the processing aid of the EBA resin of half parts by weight weighed in step 1) and half parts by weight
It is added in high efficient mixer and carries out mixed at high speed stirring 5-10min, add the resistance of weighed half parts by weight in step 1)
Bis- (2, the 3- bis- bromo- 2- methyl-propyl) ethers of agent tetrabromobisphenol A are fired, 10min is mixed；It is separately added into remaining weight in order again
The EBA resin of number, the processing aid of remaining weight number, the fire retardant tetrabromobisphenol A of remaining weight number bis- (2,3- bis-
Bromo- 2- methyl-propyl) ether, after the weighed calcium stearate of step 1), hydrotalcite, fire retarding synergist, TGIC and light stabilizer, again
10min is mixed, until after mixing, obtaining mixture.
3) extruding pelletization: being transferred to screw extruder for mixture obtained in step 2), opens double vacuum systems, passes through spiral shell
Bar extruder is granulated through melting extrusion, and water is cooling, air-dried, pelletizing, drying and packs, and obtains white tetrabromobisphenol A bis- (2,3- bis-
Bromo- 2- methyl-propyl) ether fire-retardant master granule.
When screw extruder is granulated through melting extrusion, double vacuum systems are opened, are walked first with height flowing EBA resin carrier
Material after linear outflow is stablized in discharging, then is replaced with mixture feeding obtained, host setting charging rate in step 2)
10KG/h carries out melting extrusion granulation.The screw speed of Screw Extrusion machine host is 250r/min, fusion pressure 1.4MPa.Melting
The setting of temperature subregion, subregion set temperature are followed successively by 20 DEG C, and 70 DEG C, 90 DEG C, 95 DEG C, 95 DEG C, 100 DEG C, 110 DEG C, 105 DEG C, 100
DEG C, 90 DEG C, 80 DEG C, 80 DEG C.
Control group 1
A kind of method for preparing bis- (2,3- bis- bromo- 2- methyl-propyl) ether fire-retardant master granules of tetrabromobisphenol A, including following step
It is rapid:
1) weigh: number weighs high flowing 42 parts of EBA resin, the bis- (2,3- bis- of fire retardant tetrabromobisphenol A according to the required weight
Bromo- 2- methyl-propyl) 32 parts of ether, 18 parts of calcium stearate, 3 parts of hydrotalcite, fire retarding synergist is through aluminate coupling agent treatment
8 parts of antimony oxide, 5 parts of processing aid polyethylene wax, 0.7 part of light stabilizer；Height flowing EBA resin model is 3717AC, high
Flowing EBA resin needs to be less than 100ppm through 80 DEG C of dryings to moisture before use；Bis- (the bromo- 2- of 2,3- bis- of fire retardant tetrabromobisphenol A
Methyl-propyl) bromine content >=65% in ether, 110-115 DEG C of fusing point, 5%WLT >=250 DEG C, content >=98.5%；Light stabilizer is
Ultraviolet absorbing agent phenyl salicylate.
2) it mixes: by the processing aid of the EBA resin of half parts by weight weighed in step 1) and half parts by weight
It is added in high efficient mixer and carries out mixed at high speed stirring 5-10min, add the resistance of weighed half parts by weight in step 1)
Bis- (2, the 3- bis- bromo- 2- methyl-propyl) ethers of agent tetrabromobisphenol A are fired, 10min is mixed；It is separately added into remaining weight in order again
The EBA resin of number, the processing aid of remaining weight number, the fire retardant tetrabromobisphenol A of remaining weight number bis- (2,3- bis-
Bromo- 2- methyl-propyl) ether, after the weighed calcium stearate of step 1), hydrotalcite, fire retarding synergist and light stabilizer, mix again
10min is stirred, until after mixing, obtaining mixture.
3) extruding pelletization: being transferred to screw extruder for mixture obtained in step 2), opens double vacuum systems, passes through spiral shell
Bar extruder is granulated through melting extrusion, and water is cooling, air-dried, pelletizing, drying and packs, and obtains bis- (2, the 3- bis- bromo- 2- of tetrabromobisphenol A
Methyl-propyl) ether fire-retardant master granule.
When screw extruder is granulated through melting extrusion, double vacuum systems are opened, are walked first with height flowing EBA resin carrier
Material after linear outflow is stablized in discharging, then is replaced with mixture feeding obtained, host setting charging rate in step 2)
10KG/h carries out melting extrusion granulation.The screw speed of Screw Extrusion machine host is 250r/min, fusion pressure 1.4MPa.Melting
The setting of temperature subregion, subregion set temperature are followed successively by 20 DEG C, and 70 DEG C, 90 DEG C, 95 DEG C, 95 DEG C, 100 DEG C, 110 DEG C, 105 DEG C, 100
DEG C, 90 DEG C, 80 DEG C, 80 DEG C.
Further illustrate that tetrabromobisphenol A of the invention is bis- (the bromo- 2- methyl-propyl of 2,3- bis-) below by test report
The performance of ether fire-retardant master granule.
1. object and method
(1) tested material: by 1~embodiment of the embodiment of the present invention 5 the tetrabromobisphenol A produced to preparation method it is bis- (2,
The bromo- 2- methyl-propyl of 3- bis-) ether fire-retardant master granule as sample to be tested, control group 1 the tetrabromo produced to preparation method it is double
Bis- (2,3- bis- bromo- 2- methyl-propyl) the ether fire-retardant master granules of phenol A are used as to control sample, wherein the preparation method technique of control group 1
Parameter is identical as 5 preparation method technological parameter of embodiment, only different from the raw material components of embodiment 5, the raw material components of control group 1
In be not added with TGIC；Control group 2 is commercially available hexabromocyclododecane fire-retardant master granule.
Bis- (the bromo- 2- methyl-propyl of 2,3- bis-) the fire-retardant mothers of ether of the tetrabromobisphenol A that 1~embodiment of inventive embodiments 5 is produced
The fire-retardant master granule of particle test sample and control group 1, control group 2 adds EBA resin base according to 7% parts by weight fire-retardant master granule respectively
Material mixes in batch mixer, obtains fire-retardant EBA development test sample 1-5 and EBA product control group 1, EBA system through injection molding
Product control group 2；Control group 3 is the EBA resin base material for being not added with fire-retardant master granule.
(2) test method
The mechanical property and combustibility of EBA product are detected.
2. test result and conclusion
The mechanical property comparing result of material is shown in Table 1.
The mechanical property and combustibility testing result of 1 EBA product of table
Burning time in table 1: flame vertical lights sample, leaves flame after 10s, if self-extinguishment, rekindles, gradually contracts
The time of short sample flame from lighting to leaving until not extinguishing after sample leaves flame, and records time used, sample
Burning time is longer, and flame retardant effect is better.Thus illustrate, by adding tetrabromobisphenol A of the invention in EBA resin base material
Bis- (2,3- bis- bromo- 2- methyl-propyl) ether fire-retardant master granules improve the flame retardant property of EBA resin base material, common compared with control group 2
Hexabromocyclododecane fire-retardant master granule, bis- (2,3- bis- bromo- 2- methyl-propyl) the fire-retardant effects of ether fire-retardant master granule of tetrabromobisphenol A of the invention
Fruit is more preferable.
By mechanical property and the combustibility testing result of EBA product in table 1 it is found that according to 7% parts by weight fire-retardant master granule
Add EBA resin base material to mix in batch mixer, obtains fire-retardant EBA development test sample 1-5 and EBA product pair through injection molding
According to group 1, EBA product control group 2；Control group 3 is to be not added with the mechanical property of the EBA resin base material of fire-retardant master granule to compare, EBA system
The mechanical property of product test specimen 1-5 is compared compared with the mechanical property for the EBA resin base material for being not added with fire-retardant master granule, almost without drop
It is low, however its mechanical property decrease to some degree when control group 2 adds commercially available hexabromocyclododecane fire-retardant master granule, so
Mechanical property of the addition of bis- (the bromo- 2- methyl-propyl of 2,3- bis-) the ether fire-retardant master granules of tetrabromobisphenol A of the invention to EBA resin base material
It can have little effect, and significantly improve its flame retardant property, burning time improves significantly to 39.2s-45.2s from 24.8s, into
One step illustrates that the compatibility of bis- (the bromo- 2- methyl-propyl of 2,3- bis-) the ether fire-retardant master granules of tetrabromobisphenol A of the invention is good.
Bis- (the bromo- 2- methyl-propyl of 2,3- bis-) the ether fire-retardant master granules of tetrabromobisphenol A made from 1- of embodiment of the present invention embodiment 5
Appearance is presented: even particle size, without particle adhesion phenomenon, white, and applicable range is wide.
Fire-retardant master granule is to make on the basis of fire retardant by the combination of a variety of fire-retardant compositions, modification and synergistic
A kind of granular product prepared by.Different from fire retardant, flame-retardant master batch, which has, to be easy to add in resin, sanitation and hygiene,
Flame retarding efficiency is high, and additive amount is small, small to the Effect on Mechanical Properties of resin, and it is bad that layering, decorative pattern, precipitation etc. are not susceptible to after addition
Many advantages, such as phenomenon, saving human and material resources cost and time.So fire-retardant master granule becomes macromolecule material product and realizes fire prevention
It is required that one of optimal selection, and become effective substitute of fire retardant powder.
Compared with prior art, bis- (2,3- bis- bromo- 2- methyl-propyl) the ether fire-retardant master granules of tetrabromobisphenol A produced by the present invention
Have many advantages, such as good flame retardation effect, dispersed good, wide adaptability and convenient to use, and is used in EPS/XPS thermal insulation material
Halogen-free flame-proof environmental protection may be implemented efficiently and reach UL94V-0 grades of flame retardant property requirements, thus there is significant social economy effect
Benefit.Especially traditional hexabromocyclododecane, hexabromo ring ten are replaced with bis- (2, the 3- bis- bromo- 2- methyl-propyl) ethers of tetrabromobisphenol A
Dioxane its with very strong bioaccumulation and biological magnification, endanger to human endocrinological's system and reproductive system with toxicity
Evil, and bis- (2, the 3- bis- bromo- 2- methyl-propyl) ethers of the tetrabromobisphenol A that the present invention uses are nontoxic as fire retardant, inanimate object accumulation
Property and biological magnification, meet today's society pursuit energy-saving and environment friendly theory, be conducive to sustainable development.Institute of the present invention
The fire retardant used is bis- (2, the 3- bis- bromo- 2- methyl-propyl) ethers of tetrabromobisphenol A, which is hexabromocyclododecane (HBCD)
Favorable substitutes.
Bis- (the bromo- 2- methyl-propyl of 2,3- bis-) the ether fire-retardant master granules of tetrabromobisphenol A of the present invention are prepared in raw material components and are used
TGIC (1,3,5- three-glycidyl-S- triazinetrione；Triglycidyl isocyanurate) it is white particle or powder, it is a kind of
Heterocyclic epoxy compounds, with good heat-resisting weatherability, cementability and excellent high-temperature behavior, 88-98 DEG C of fusing point.Existing skill
Main application in art: the crosslinking and curing agent as pure polyesters powdery paints, as carboxylic polyacrylate (PA)
Crosslinking and curing agent.And TGIC is double by the tetrabromobisphenol A of embodiment 1- embodiment 5 in table 1 as antioxidant in formula of the invention
Bis- (the bromo- 2- methyl-propyl of the 2,3- bis-) ethers of the tetrabromobisphenol A of (the bromo- 2- methyl-propyl of 2,3- bis-) ether fire-retardant master granule and control group 1
The performance of fire-retardant master granule is compared, and the preparation method technological parameter of control group 1 is identical as 5 preparation method technological parameter of embodiment, only
It is different from the raw material components of embodiment 5, TGIC is not added in the raw material components of control group 1, embodiment 1- embodiment 5 is only a small amount of
In the presence of TGIC, so that it may delay or inhibit the progress of polymer oxidation process, to prevent the aging of polymer and extend it to make
With the service life, and the Effect on Mechanical Properties of EBA product is significantly improved, while its combustibility also significantly improves.
In the preparation method of bis- (2,3- bis- bromo- 2- methyl-propyl) the ether fire-retardant master granules of tetrabromobisphenol A of the invention, according to mother
The characteristic requirements of material smelting process accurately control the temperature in each region of screw extruder, ensure that masterbatch produces raw material
Sufficiently melting and molecule aggregation effect；Then the alternating magnetic field that high speed variation is generated with high-frequency pulse current, makes metal melting
Cylinder, which generates vortex, makes metal material itself fast heating, improves the diffusion activation that macromolecule is kneaded polymer melt strand
Can, using bis- (2, the 3- bis- bromo- 2- methyl-propyl) ethers of tetrabromobisphenol A as fire-retardant main body, extraordinary model EBA is as carrier, packet
Cover bis- (the bromo- 2- methyl-propyl of 2,3- bis-) the ether flame retardant powder of tetrabromobisphenol A and be aided with the auxiliary agents such as synergistic, enhancing prepare it is compatible
The good fire-retardant master granule of property, the fire-retardant master granule dosage is low, good flame retardation effect, small to the Effect on Mechanical Properties of material, with hexabromo ring ten
Dioxane is small compared to the fire-retardant master granule effect on environment, has a wide range of application.
To sum up, bis- (2,3- bis- bromo- 2- methyl-propyl) ether fire-retardant master granules of tetrabromobisphenol A of the invention and preparation method thereof,
Technological operation is simple, implements to be easy, can be used for industrialized production and implementation；Fire-retardant master granule is good with substrate compatibility, to resin
Effect on Mechanical Properties is small, and fire-retardant master granule dosage is few, while ensureing that product has excellent properties, reduces production cost.
Only as described above, only specific embodiments of the present invention, when the model that cannot be limited the present invention with this and implement
It encloses, it is all according to equivalent changes and modifications within the scope of the patent application of the present invention, it is all covered by the present invention.
Claims (10)
1. a kind of bis- (2,3- bis- bromo- 2- methyl-propyl) ether fire-retardant master granules of tetrabromobisphenol A, which is characterized in that according to parts by weight,
It is made of following raw material components: bis- (the bromo- 2- methyl-props of 2,3- bis- of 40-45 parts of Gao Liudong EBA resin, fire retardant tetrabromobisphenol A
Base) 30-35 parts of ether, 15-20 parts of calcium stearate, 2-4 parts of hydrotalcite, 5-10 parts of fire retarding synergist, 4-5 parts of processing aid, TGIC
0.1-0.4 parts, 0.5-1 parts of light stabilizer.
2. bis- (2,3- bis- bromo- 2- methyl-propyl) the ether fire-retardant master granules of a kind of tetrabromobisphenol A according to claim 1, special
Sign is, according to parts by weight, the raw material components composition are as follows: 42 parts of Gao Liudong EBA resin, fire retardant tetrabromobisphenol A it is bis- (2,
The bromo- 2- methyl-propyl of 3- bis-) 32 parts of ether, 18 parts of calcium stearate, 3 parts of hydrotalcite, 8 parts of fire retarding synergist, 5 parts of processing aid,
0.3 part of TGIC, 0.7 part of light stabilizer.
3. bis- (2,3- bis- bromo- 2- methyl-propyl) the ether fire-retardant master granules of a kind of tetrabromobisphenol A according to claim 1, special
Sign is that the height flowing EBA resin model is 3717AC, and the high flowing EBA resin is needed before use through 80 DEG C of dryings extremely
Moisture is less than 100ppm.
4. bis- (2,3- bis- bromo- 2- methyl-propyl) the ether fire-retardant master granules of a kind of tetrabromobisphenol A according to claim 1, special
Sign is, bromine content >=65% in bis- (2, the 3- bis- bromo- 2- methyl-propyl) ethers of fire retardant tetrabromobisphenol A, fusing point 110-115
DEG C, 5%WLT >=250 DEG C, content >=98.5%.
5. bis- (2,3- bis- bromo- 2- methyl-propyl) the ether fire-retardant master granules of a kind of tetrabromobisphenol A according to claim 1, special
Sign is that the fire retarding synergist is antimony oxide, or the antimony oxide through aluminate coupling agent treatment.
6. bis- (2,3- bis- bromo- 2- methyl-propyl) the ether fire-retardant master granules of a kind of tetrabromobisphenol A according to claim 1, special
Sign is that the processing aid is polyethylene wax；The antioxidant is TGIC；The light stabilizer is ultraviolet absorbing agent.
7. a kind of bis- (the bromo- 2- methyl-propyl of 2,3- bis-) ethers of tetrabromobisphenol A described in -6 any one are fire-retardant according to claim 1
The preparation method of master batch, which comprises the following steps:
1) weigh: number weighs high flowing EBA resin, bis- (the bromo- 2- methyl of 2,3- bis- of fire retardant tetrabromobisphenol A according to the required weight
Propyl) ether, calcium stearate, hydrotalcite, fire retarding synergist, processing aid, TGIC, light stabilizer；
2) it mixes: the EBA resin of half parts by weight weighed in step 1) and the processing aid of half parts by weight is added
Mixed at high speed stirring is carried out in high efficient mixer, adds the fire retardant tetrabromobisphenol of weighed half parts by weight in step 1)
Bis- (2, the 3- bis- bromo- 2- methyl-propyl) ethers of A are mixed；It is separately added into the EBA resin of remaining weight number in order again, remains
The processing aid of remaining parts by weight, bis- (2, the 3- bis- bromo- 2- methyl-propyl) ethers of the fire retardant tetrabromobisphenol A of remaining weight number,
It after the weighed calcium stearate of step 1), hydrotalcite, fire retarding synergist, TGIC and light stabilizer, is mixed again, until mixing is equal
After even, mixture is obtained；
3) extruding pelletization: mixture obtained in step 2) is transferred to screw extruder, by screw extruder through melting extrusion
It is granulated, obtains bis- (2,3- bis- bromo- 2- methyl-propyl) the ether fire-retardant master granules of tetrabromobisphenol A.
8. a kind of preparation of bis- (the bromo- 2- methyl-propyl of 2,3- bis-) the ether fire-retardant master granules of tetrabromobisphenol A according to claim 7
Method, which is characterized in that in step 3), when the screw extruder is granulated through melting extrusion, opens double vacuum systems, use first
Height flowing EBA resin carrier is walked to expect, after linear outflow is stablized in discharging, then is replaced with mixture progress obtained in step 2)
Melting extrusion is granulated.
9. a kind of preparation of bis- (the bromo- 2- methyl-propyl of 2,3- bis-) the ether fire-retardant master granules of tetrabromobisphenol A according to claim 7
Method, which is characterized in that in step 3), the screw speed of the Screw Extrusion machine host is 250r/min, fusion pressure 1.4MPa.
10. a kind of system of bis- (the bromo- 2- methyl-propyl of 2,3- bis-) the ether fire-retardant master granules of tetrabromobisphenol A according to claim 7
Preparation Method, which is characterized in that melting temperature subregion setting, subregion set temperature are followed successively by 20 DEG C, and 70 DEG C, 90 DEG C, 95 DEG C,
95 DEG C, 100 DEG C, 110 DEG C, 105 DEG C, 100 DEG C, 90 DEG C, 80 DEG C, 80 DEG C.
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Effective date of registration: 20240612 Address after: 261108 East of Lingang Road and north of Liaohe West Street, Binhai Economic and Technological Development Zone, Weifang City, Shandong Province Patentee after: Weifang Runpu Chemical Co.,Ltd. Country or region after: China Address before: 262737 South expansion of Lingang Industrial Park, Binhai Economic and Technological Development Zone, Weifang City, Shandong Province Patentee before: SHANDONG RUNKE CHEMICAL Co.,Ltd. Country or region before: China |