CN109762288A - A kind of flame-proof highly anti-flush polyphenylacetylene material and preparation method thereof with good photo and thermal stability - Google Patents
A kind of flame-proof highly anti-flush polyphenylacetylene material and preparation method thereof with good photo and thermal stability Download PDFInfo
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- CN109762288A CN109762288A CN201910110903.8A CN201910110903A CN109762288A CN 109762288 A CN109762288 A CN 109762288A CN 201910110903 A CN201910110903 A CN 201910110903A CN 109762288 A CN109762288 A CN 109762288A
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- 239000000463 material Substances 0.000 title claims abstract description 26
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- 239000003063 flame retardant Substances 0.000 claims abstract description 63
- 229920005669 high impact polystyrene Polymers 0.000 claims abstract description 45
- 239000004797 high-impact polystyrene Substances 0.000 claims abstract description 45
- 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 claims abstract description 24
- 229940116351 sebacate Drugs 0.000 claims abstract description 20
- CXMXRPHRNRROMY-UHFFFAOYSA-L sebacate(2-) Chemical compound [O-]C(=O)CCCCCCCCC([O-])=O CXMXRPHRNRROMY-UHFFFAOYSA-L 0.000 claims abstract description 20
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 claims abstract description 15
- RKMGAJGJIURJSJ-UHFFFAOYSA-N 2,2,6,6-Tetramethylpiperidine Substances CC1(C)CCCC(C)(C)N1 RKMGAJGJIURJSJ-UHFFFAOYSA-N 0.000 claims abstract description 9
- 230000006641 stabilisation Effects 0.000 claims abstract description 9
- 238000011105 stabilization Methods 0.000 claims abstract description 9
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Inorganic materials O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000003963 antioxidant agent Substances 0.000 claims abstract description 8
- 230000003078 antioxidant effect Effects 0.000 claims abstract description 8
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical class OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 claims abstract description 7
- 238000002156 mixing Methods 0.000 claims abstract description 6
- 238000002844 melting Methods 0.000 claims abstract description 5
- 230000008018 melting Effects 0.000 claims abstract description 5
- 239000006057 Non-nutritive feed additive Substances 0.000 claims abstract description 4
- 229920005989 resin Polymers 0.000 claims abstract description 4
- 239000011347 resin Substances 0.000 claims abstract description 4
- 239000000203 mixture Substances 0.000 claims description 12
- BZQKBFHEWDPQHD-UHFFFAOYSA-N 1,2,3,4,5-pentabromo-6-[2-(2,3,4,5,6-pentabromophenyl)ethyl]benzene Chemical group BrC1=C(Br)C(Br)=C(Br)C(Br)=C1CCC1=C(Br)C(Br)=C(Br)C(Br)=C1Br BZQKBFHEWDPQHD-UHFFFAOYSA-N 0.000 claims description 9
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 4
- 239000003795 chemical substances by application Substances 0.000 claims description 4
- ZITDOJMAOFWSQI-UHFFFAOYSA-N 4-(2,3,4-tribromophenoxy)triazine Chemical class BrC1=C(Br)C(Br)=CC=C1OC1=CC=NN=N1 ZITDOJMAOFWSQI-UHFFFAOYSA-N 0.000 claims description 3
- 125000000217 alkyl group Chemical group 0.000 claims description 3
- GHPGOEFPKIHBNM-UHFFFAOYSA-N antimony(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Sb+3].[Sb+3] GHPGOEFPKIHBNM-UHFFFAOYSA-N 0.000 claims description 3
- 150000001875 compounds Chemical class 0.000 claims description 3
- 239000002245 particle Substances 0.000 claims description 3
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 2
- 229910052794 bromium Inorganic materials 0.000 claims description 2
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 claims description 2
- 238000001035 drying Methods 0.000 claims description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 2
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 2
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 2
- 238000005303 weighing Methods 0.000 claims description 2
- 238000000034 method Methods 0.000 abstract description 5
- 238000012545 processing Methods 0.000 abstract description 5
- 238000005469 granulation Methods 0.000 abstract description 3
- 230000003179 granulation Effects 0.000 abstract description 3
- 230000008569 process Effects 0.000 abstract description 3
- 230000000052 comparative effect Effects 0.000 description 21
- 150000002148 esters Chemical class 0.000 description 10
- 238000012360 testing method Methods 0.000 description 10
- 150000001412 amines Chemical class 0.000 description 8
- ISIJQEHRDSCQIU-UHFFFAOYSA-N tert-butyl 2,7-diazaspiro[4.5]decane-7-carboxylate Chemical compound C1N(C(=O)OC(C)(C)C)CCCC11CNCC1 ISIJQEHRDSCQIU-UHFFFAOYSA-N 0.000 description 8
- 239000002131 composite material Substances 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- 239000000654 additive Substances 0.000 description 6
- 230000000996 additive effect Effects 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 230000009970 fire resistant effect Effects 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 6
- -1 polypropylene Polymers 0.000 description 6
- 230000002195 synergetic effect Effects 0.000 description 6
- 239000004793 Polystyrene Substances 0.000 description 5
- LXWPJAGZRHTAOO-UHFFFAOYSA-N [Sb].[Br] Chemical compound [Sb].[Br] LXWPJAGZRHTAOO-UHFFFAOYSA-N 0.000 description 5
- 239000004033 plastic Substances 0.000 description 5
- 229920003023 plastic Polymers 0.000 description 5
- 230000032683 aging Effects 0.000 description 4
- 230000008859 change Effects 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 239000004611 light stabiliser Substances 0.000 description 4
- 150000008301 phosphite esters Chemical class 0.000 description 4
- 230000004580 weight loss Effects 0.000 description 4
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical group C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 3
- 230000001133 acceleration Effects 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 230000018109 developmental process Effects 0.000 description 3
- 239000012757 flame retardant agent Substances 0.000 description 3
- 238000001746 injection moulding Methods 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 150000003254 radicals Chemical class 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 2
- 239000004743 Polypropylene Substances 0.000 description 2
- BGYHLZZASRKEJE-UHFFFAOYSA-N [3-[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxy]-2,2-bis[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxymethyl]propyl] 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)OCC(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 BGYHLZZASRKEJE-UHFFFAOYSA-N 0.000 description 2
- 238000005452 bending Methods 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
- 229920006351 engineering plastic Polymers 0.000 description 2
- 150000003053 piperidines Chemical class 0.000 description 2
- 229920001155 polypropylene Polymers 0.000 description 2
- 229920002223 polystyrene Polymers 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- JYEUMXHLPRZUAT-UHFFFAOYSA-N 1,2,3-triazine Chemical compound C1=CN=NN=C1 JYEUMXHLPRZUAT-UHFFFAOYSA-N 0.000 description 1
- 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 1
- ITFVVOQVJUXDHY-UHFFFAOYSA-N 1-hydroxy-2,2,6,6-tetramethylpiperidin-3-ol Chemical compound CC1(C)CCC(O)C(C)(C)N1O ITFVVOQVJUXDHY-UHFFFAOYSA-N 0.000 description 1
- BSZXAFXFTLXUFV-UHFFFAOYSA-N 1-phenylethylbenzene Chemical compound C=1C=CC=CC=1C(C)C1=CC=CC=C1 BSZXAFXFTLXUFV-UHFFFAOYSA-N 0.000 description 1
- HQWDILUMZXPFNW-UHFFFAOYSA-N 2-cyano-2-nitroacetamide Chemical class NC(=O)C(C#N)[N+]([O-])=O HQWDILUMZXPFNW-UHFFFAOYSA-N 0.000 description 1
- SGQUHMXHLSTYIH-UHFFFAOYSA-N 2-phenylbutan-2-ylbenzene Chemical compound C=1C=CC=CC=1C(C)(CC)C1=CC=CC=C1 SGQUHMXHLSTYIH-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- CPELXLSAUQHCOX-UHFFFAOYSA-N Hydrogen bromide Chemical compound Br CPELXLSAUQHCOX-UHFFFAOYSA-N 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 229910000410 antimony oxide Inorganic materials 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 230000003796 beauty Effects 0.000 description 1
- 125000001246 bromo group Chemical class Br* 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000007822 coupling agent Substances 0.000 description 1
- 125000000753 cycloalkyl group Chemical group 0.000 description 1
- WJTCGQSWYFHTAC-UHFFFAOYSA-N cyclooctane Chemical compound C1CCCCCCC1 WJTCGQSWYFHTAC-UHFFFAOYSA-N 0.000 description 1
- 239000004914 cyclooctane Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 238000002845 discoloration Methods 0.000 description 1
- 238000010292 electrical insulation Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 229920006248 expandable polystyrene Polymers 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 125000000623 heterocyclic group Chemical group 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 239000010985 leather Substances 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 1
- 239000000347 magnesium hydroxide Substances 0.000 description 1
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002103 nanocoating Substances 0.000 description 1
- 210000003739 neck Anatomy 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- VTRUBDSFZJNXHI-UHFFFAOYSA-N oxoantimony Chemical compound [Sb]=O VTRUBDSFZJNXHI-UHFFFAOYSA-N 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- QARVLSVVCXYDNA-UHFFFAOYSA-N phenyl bromide Natural products BrC1=CC=CC=C1 QARVLSVVCXYDNA-UHFFFAOYSA-N 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 125000005936 piperidyl group Chemical group 0.000 description 1
- 150000004291 polyenes Chemical class 0.000 description 1
- 238000012667 polymer degradation Methods 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 238000004080 punching Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 230000000979 retarding effect Effects 0.000 description 1
- 239000000779 smoke Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000012430 stability testing Methods 0.000 description 1
- 230000003335 steric effect Effects 0.000 description 1
- 238000009864 tensile test Methods 0.000 description 1
- YEAUATLBSVJFOY-UHFFFAOYSA-N tetraantimony hexaoxide Chemical compound O1[Sb](O2)O[Sb]3O[Sb]1O[Sb]2O3 YEAUATLBSVJFOY-UHFFFAOYSA-N 0.000 description 1
- 125000003698 tetramethyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
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- Compositions Of Macromolecular Compounds (AREA)
Abstract
A kind of flame-proof highly anti-flush polyphenylacetylene (HIPS) material and preparation method thereof with good photo and thermal stability of invention.The HIPS material is using bromide fire retardant as main flame retardant, Sb2O3For synergist, bis- (1- alkoxy -2,2,6,6- tetramethyl piperidine -4- bases) sebacates are the retardant synergist for having light stabilization concurrently, are made by melting mixing, granulation.It is formed and the mass fraction of each component is as follows: HIPS resin 80-90%, bromide fire retardant 9-15%, Sb2O33-5%, bis- (1- alkoxy -2,2,6,6- tetramethyl piperidine -4- bases) sebacate 0.1-1.0%, antioxidant 0.0-0.5%, other processing aid 0-1.0%.HIPS material obtained not only has good flame retardant property by the above process, and flame retardant rating can reach V-0 grades of UL94, and photo-thermal stability, processing performance and satisfactory mechanical property.
Description
Technical field
The present invention relates to a kind of flame-proof highly anti-flush polyphenylacetylene material and preparation method thereof with good photo and thermal stability,
Specifically using bromide fire retardant as main flame retardant, Sb2O3For synergist, bis- (1- alkoxy -2,2,6,6- tetramethyl piperidines -
4- yl) sebacate is the retardant synergist for having light stabilization concurrently, there is good photo-thermal as made from melting mixing, granulation
The flame-proof highly anti-flush polyphenylacetylene material of stability belongs to polymeric material field.
Background technique
High impact polystyrene (HIPS) is to carry out a kind of anti-impact with higher that toughening modifying obtains to polystyrene
The polymer material of hit intensity.HIPS is because having excellent processing performance, mechanical property, electrical insulation capability, dimensional stability
And the advantages that cheap and be widely used in the fields such as household electrical appliance, office equipment, instrument and meter, auto parts and components [Du Qiangguo,
Zhang Chuanxian, He Hui plastics industry handbook: Beijing phenylethylene resin series [M]: Chemical Industry Press, 2004:198].But
HIPS belongs to inflammable product, needs fire-retardant and fire-retardant rank higher, generally requires by UL94V-0 grades.HIPS resistance used at present
Firing agent is mainly bromide fire retardant, and using antimony oxide as synergist.Common bromide fire retardant has deca-BDE (DBDPO)
(development of Zhou Jian, Wang Lingling Toughening Flame Retardant Hips, engineering plastics application, 2008,36 (2): 21-24；Quan Ying,
Yang Mingshan, the development of the Flame Retarded HIPS with Low Smoke Generation such as tight celebrating, Chinese Plastics, 2003,17 (8): 39-42；Zhang Weiqin,
Yang Qi, Zheng protect equality high impact polystyrene fire-retardant and Research on Toughening, plastics industry, 2009,37 (11): 14-17), ten bromines
Diphenylethane (DBDPE) (the fire-retardant research of the high impact polystyrene such as Li Xiang, Xu Xiaonan, Yang Liang, plastics, 2004,33 (6):
54-57), three (tribromophenoxy) triazine (present Research and development prospect of Xu Hongying, Zhang Junjie, Li Hongxia fire retardant, material
Expect Leader, 2006,20 (12): 39-12) etc..It is general that the above bromine antimony composite flame-retardant agent will obtain good flame retardant effect additive amount
It is larger, thus it is fire-retardant at high cost, the physical property of material is influenced also larger.
Synergist is the flame retardant effect for improving fire retardant, reduces the important means of fire retardant additive amount.Dimethyl -2 2,3-,
3- diphenyl butane (abbreviation bicummyl) is the retardant synergist used earliest.Early in last century the fifties, Germany, Japan, beauty
The country such as state has just applied for many patents about bicummyl and its derivative as retardant synergist.Bicummyl is mainly used for polyene
The fire-resistant synergistic of hydrocarbon, especially polypropylene and polystyrene, such as a kind of flame retardant expandable styrene polymer of week good invention
Composition, mainly using non-bromine series fire retardant and bromide fire retardant as main flame retardant, non-bromine series fire retardant can choose red phosphorus, phosphoric acid
The Phosphorus bromine-free flame-retardant agent of ester, magnesium hydroxide, expansible graphite, nitrogen, bromide fire retardant mainly select hexabromocyclododecane (HBCD),
Three (2,3- dibromopropyl) fulminuric acid esters (TBC), tetrabromo cyclooctane etc..Using the C-C bond type radical initiator such as bicummyl
For mixture with peroxide as retardant synergist, antimony class compound is fire retarding synergist.Wherein the additional amount of bicummyl is only
0.2%, fire-retardant rank can reach B1, the content of bromine in fire retardant is reduced, the mechanical performance (week of composite material is improved
It is good, a kind of flame retardant expandable polystyrene polymer compositions of Chen Zhiqiang and its manufacturing method .CN105175917A, 2015-
12-23.)。
Although bicummyl has good fire-resistant synergistic effect, have a single function, unglazed heat stabilization cannot assign resistance
Fire the good photostability of PS.Therefore, in addition fire-retardant PS need to generally add light stabilizer.
Hindered amines (HALS) light stabilizer is current most outstanding one of light stabilizer.HALS from be found with
Come, rapidly developed in light stabilizer field, with efficient, resistance to extraction, high temperature resistant, low toxicity or nontoxic and not easy coloring
Equal excellent properties and be widely used in the necks such as polyolefin agricultural film, high-molecular coating, artificial carpet and leather, engineering plastics
Domain.
Hindered amine is primarily referred to as piperidine derivative.Such compound includes a nitrogenous hexa-member heterocycle, and is had relatively strong
Space steric effect, general formula of the chemical structure is as follows:
X=H, R or OR, R are alkyl or cycloalkyl, and A is the auxiliary group for connecting piperidyl.X is that the hindered amine of OR is known as
N- alkoxy hindered amine (abbreviation NORs).
Hindered amine shows different alkalinity according to the difference of X.Traditional hindered amine is the tetramethyl that X is H or R mostly
The derivative of piperidines, since it is with very strong alkalinity, the acid that can be generated with fire retardant of the addition in high molecular material
Matter (such as HBr) reacts, and generates similar NH4 +Br-Ammonium salt and so that HALS is lost activity (Antos K, Sedlar
J.Influence of brominated flame retardant thermal decomposition products on
HALS.Polymer Degradation and Stability,2005,90(1):188-194).NORs alkalinity is most weak, is not easy
It reacts with the acidic components in high molecular material, maintains the stability of material, and alkoxy is introduced into hindered amine matrix
In, the cloud density around the activated nitrogen atom in NORs is not only reduced, and it just participates in capturing following for free radical
The ability that NO free radical (NO) captures active group is improved in ring, thus improves its light stabilization.Exactly by
In the reason, the lower NORs of alkalinity obtains fast development gradually by the attention of researcher.
In recent years, people were surprised to find that N- alkoxy hindered amine (NORs) also had fire-retardant and heat stabilization, but mesh concurrently
Preceding industrialized NORs only Flamestab NOR 116, it is only effective to polypropylene thin article, to thick product (injection mould
Plate etc.) flame retardant effect is limited, and it is worse to the effect of other polymer, also have not seen its PS fire-retardant to bromine antimony compound and HIPS tool
The report for thering is fire-resistant synergistic to act on.In addition, the chemical structure of Flamestab NOR 116 is (as follows) complicated, synthesis technology
Troublesome, atom utilization is low, and the three wastes discharge amount in synthesis process is very big.
The dosage of fire retardant is significantly reduced to the flame retardant effect of HIPS in order to improve bromine antimony composite flame-retardant agent, and assigns it
Good photostability, Tang Linsheng etc. develop serial phosphorous acid three (1- alkoxy -2,2,6,6- tetramethylpiperidinols) ester, and
It was found that it not only has significant synergies to bromine antimony composite flame-proof HIPS, but also the good light of flame-retarding HIPS can be assigned and stablized
Property ((1- alkoxy -4- hydroxyl -2,2,6, the 6- tetramethylpiperidinols) ester of the such as Tang Linsheng, Wu Hongzhi, Yang Jingwei phosphorous acid three and
Preparation method, CN 106916183 A, 2017-07-04；The one kind such as Wu Hongzhi, Guo Xiuan, Yang Xisheng has good light steady
Qualitative flame-proof highly anti-flush polyphenylacetylene material and preparation method thereof, Chinese Patent Application No.: 201910058806.9,2019-
01-22)。
Nevertheless, but phosphorous acid three (1- alkoxy -4- hydroxyl -2,2,6,6- tetramethylpiperidinols) ester thermal stability
Less desirable, thermal weight loss 2%, 5%, 10% and maximum heat weight loss rate temperature only respectively may be about 240 DEG C, 255 DEG C, 257 DEG C
With 270 DEG C (nitrogen environment, 10 DEG C/min of heating rate).When processing temperature is excessively high or heated time is too long, three (1- of phosphorous acid
Alkoxy -4- hydroxyl -2,2,6,6- tetramethylpiperidinol) ester can generate decomposition and drop its fire-resistant synergistic and light stabilization
It is low, or even failure, and the 2,2,6,6-tetramethylpiperidine nitroxide for decomposing generation makes fire-retardant material because itself being pale red
Material discoloration.
Summary of the invention
The shortcomings that for phosphorous acid three (1- alkoxy -4- hydroxyl -2,2,6,6- tetramethylpiperidinols) ester, the hair of the application
The many new structural NORs of bright person's design and synthesis pass through further investigation and find bis- (1- alkoxy -2,2,6,6- tetramethyls
Piperidin-4-yl) sebacate (abbreviation sebacate) have good thermal stability, thermal weight loss 2%, 5%, 10% and maximum heat
Weight loss rate temperature respectively may be about 270 DEG C, 285 DEG C, 295 DEG C and 310 DEG C (nitrogen environment, 10 DEG C/min of heating rate), remote high
In phosphorous acid three (1- alkoxy -4- hydroxyl -2,2,6,6- tetramethylpiperidinols) ester, it is able to satisfy the requirement of plastic processing temperature.
They not only have significant synergies to bromine antimony composite flame-proof HIPS, but also can assign the good photo-thermal of flame-retarding HIPS and stablize
It is bad and with the (1- alkoxy -4- hydroxyl of phosphorous acid three as flame-retarding HIPS photostability made from synergist to overcome bicummyl for property
Base -2,2,6,6- tetramethylpiperidinol) the ester disadvantage bad as flame-retarding HIPS thermal stability made from synergist.
The mass fraction of flame-retarding HIPS material with good photo and thermal stability of the invention, composition and each component is such as
Under:
HIPS resin 80-90%, bromide fire retardant 9-15%, Sb2O33-5%, bis- (1- alkoxy -2,2,6,6- tetramethyls
Phenylpiperidines -4- base) sebacate (abbreviation sebacate) 0.1-1.0%, antioxidant 0.0-0.5%, other processing aid 0-
1.0%；
The bromide fire retardant is decabromodiphenylethane (DBDPE), three (tribromophenoxy) triazines (abbreviation FR-245)
Deng；
Bis- (1- alkoxy -2,2,6,6- tetramethyl piperidine -4- base) sebacates, which refer to, to be had the following structure
Compound:
R is methyl, ethyl, propyl, isopropyl and cyclohexyl (- 1~sebacate of abbreviation sebacate -5 respectively) in formula,
It can also be other alkyl, naphthenic base and aromatic radical；
The antioxidant is various hindered phenol antioxygens, such as antioxidant 1010；
Other processing aids are lubricant, coupling agent etc..
The present invention also provides the preparation method of the above HIPS composite, detailed process is: first by bromide fire retardant,
Sb2O3, sebacate, the auxiliary agents such as antioxidant be uniformly mixed after weighing proportionally, HIPS particle is then added and is uniformly mixed, finally
By the above mixture melting mixing, granulation, dry the flame-retarding HIPS composite material with good photo and thermal stability.
HIPS material of the invention not only has good flame retardant property, and flame retardant rating can reach UL94V-0 grades, Er Qieguang
Thermal stability, processing performance and satisfactory mechanical property can be used for preparing household electrical appliance, office equipment, instrument and meter, automobile zero
The components such as component, household utensils, Medical Devices.
Specific embodiment
Hereinafter, preferred embodiments of the present invention will be described, it should be understood that preferred embodiment described herein is only used
In the description and interpretation present invention, it is not intended to limit the present invention.
Unless otherwise indicated, percentage employed in the present invention is mass percent.
HIPS used herein is the HIPS4241 (AS) of company, Total France production, and antioxidant is Linyi
The antioxidant 1010 of three rich Chemical Co., Ltd.'s productions, decabromodiphenylethane are that Hai Wang Chemical Co., Ltd. in Shandong produces, three (three
Bromobenzene oxygroup) triazine be Shouguang WeiDong Chemical Co., Ltd. production, Sb2O3It is provided by Jinan Taixing Fine Chemicals Co., ltd, respectively
Kind bis- (1- alkoxy -2,2,6,6- tetramethyl piperidine -4- base) sebacates and phosphorous acid three (hydroxyl -2,2 1- methoxyl group -4-,
6,6- tetramethylpiperidinol) ester (abbreviation phosphite ester) self-control.
Testing vertical flammability: it is tested using CZF-3 type horizontal vertical burning analyzer with reference to GB/T2408-1996, sample
Having a size of 100mm × 13mm × 1.6mm.
Measuring mechanical property: tensile property is tested according to GB/T1040-2006, sample standard size: 150mm × 20mm ×
4mm；Bending property is tested according to GB/T 9341-2008, sample standard size: 80mm × 10mm × 4mm；The punching of cantilever beam notch
Hit intensity is tested according to GB/T 1843-2008, sample standard size: 80mm × 10mm × 4mm.Impact strength uses RXJ-5.5
Type radial-boom impact tester (Jinan new ensaying testing machine Co., Ltd) measurement, stretches and bending property is using SANS-20 electricity
Sub- universal tensile testing machine (newly thinking carefully Instrument Ltd. in Shenzhen) test.The test sample of mechanical performance is using injection molding system
Standby, injection molding machine used is the 128T injection molding machine of the towering like a mountain peak plasticizing Co., Ltd production of Changzhou person of outstanding talent.
Photo-stability testing: the photostability of material is evaluated by artificial accelerated aging test.Device therefor is ultraviolet light
Senile experiment case (Nanjing Huan Ke testing equipment Co., Ltd), light source used are UVA-340nm, luminous intensity 0.76w/m2.nm,
Marking black temperature is 50 ± 3 DEG C, and exposure cycles are dry for 8h, 4h condensation, light application time 120h.
Heat stabilization test: test bars are placed in thermostatic drying chamber in 175 ± 5 DEG C of heating 48h, are subsequently placed into interior certainly
Test sample performance and color change is observed after so cooling.
Embodiment 1
A kind of flame-retarding HIPS material and preparation method thereof with good photo and thermal stability, the quality of composition and each component
It is listed in table 1.
Preparation method is as follows: each component quality is accurately weighed, first by bromide fire retardant, Sb2O3, sebacate, antioxygen
Agent etc. is added putty-chaser-type mixer (Tianjin Stettlen Co., Ltd) and mixes 3min, is then poured into 5L mechanical mixer, and
HIPS particle mixing 3min is added, finally (Yantai leads to the mechanical limited public affairs of powder together by double screw extruder by the above mixture
Take charge of the JS30A type double screw extruder of production, L/D=42.5cm/2cm, 20~30rpm of revolving speed, 200~210 DEG C of extrusion temperature)
Melting mixing squeezes out, is granulated, dry the flame-retarding HIPS material with good photo and thermal stability.
Table 2 is listed in by the main Mechanical and flame retardant property of flame-retarding HIPS made from composition described above and preparation method.
It is in table 2 statistics indicate that, the fire-retardant rank of HIPS obtained can reach V-0 grades according to the above method, and mechanical performance is slightly
It is worse than pure HIPS, significant change does not also occur for mechanical performance after artificial acceleration light aging, shows that it stablizes with good light
Property, significant change does not occur yet, shows it with good thermal stability for flame retardant property and color after heated test.
2~embodiment of embodiment 8
The composition of 2~embodiment of embodiment 8 and the quality of each component are listed in table 1.Preparation method is same as Example 1,
Main Mechanical and flame retardant property are listed in table 2.It is in table 2 statistics indicate that, by fire-retardant made from 2~embodiment of embodiment 8
HIPS has the characteristic almost the same with embodiment 1.
1~comparative example of comparative example 6
The composition of 1~comparative example of comparative example 6 and the quality of each component are listed in table 1.Preparation method is same as Example 1, main
Mechanical performance and flame retardant property is wanted to be listed in table 2.It is in table 2 statistics indicate that: flame-retarding HIPS made from comparative example 1 and comparative example 2 with
Almost flame retardant property having the same made from 1~embodiment of embodiment 8, but the additive amount of its fire retardant (the total inventory of Zhan
Mass fraction) than 1~embodiment of embodiment 8 high 30% or more.Although the fire retardant additive amount of comparative example 3 and comparative example 4 is than real
Apply that 1~embodiment of example 8 is still high by 20% or more, but by the flame retardant property of flame-retarding HIPS made from them be significantly worse than embodiment 1~
Embodiment 8, this shows that several sebacates that embodiment uses all have significant fire-resistant synergistic to HIPS and act on；And embodiment
It compares, the mechanical performance of 1~comparative example of comparative example 4 is slightly worse than embodiment, this is because the fire retardant additive amount of comparative example is greater than
Embodiment；The mechanical performance after artificial acceleration light aging of flame-retarding HIPS made from 1~comparative example of comparative example 4 is decreased obviously, and is shown
Its photostability is bad.Flame-retarding HIPS made from comparative example 5 and comparative example 6 almost has with made from 1~embodiment of embodiment 8
Identical flame retardant property, significant change, and the additive amount phase of fire retardant also do not occur for mechanical performance after artificial acceleration light aging
Together, but after prolonged heating flame retardant property is substantially reduced, and color is also changed, and illustrates (1- methoxyl group-the 4- of phosphorous acid three
Hydroxyl -2,2,6,6- tetramethylpiperidinol) ester (abbreviation phosphite ester) and bis- (1- alkoxy -2,2,6,6- tetramethyl piperidine -4-
Base) sebacate has same fire-resistant synergistic and light stabilization to HIPS, but thermal stability is bad.
Finally, it should be noted that the foregoing is only a preferred embodiment of the present invention, it is not intended to restrict the invention,
Although the present invention is described in detail referring to the foregoing embodiments, for those skilled in the art, still may be used
To modify the technical solutions described in the foregoing embodiments or equivalent replacement of some of the technical features.
All within the spirits and principles of the present invention, any modification, equivalent replacement, improvement and so on should be included in of the invention
Within protection scope.
The material of each embodiment of table 1 forms
| Embodiment | HIPS | Bromide fire retardant | Sb2O3 | Synergist | Antioxidant |
| Embodiment 1 | 4241,2000g | FR-245,265g | 88g | Sebacate -1,6g | 3g |
| Embodiment 2 | Ibid | Ibid | Ibid | Sebacate -1,8g | 2g |
| Embodiment 3 | Ibid | Ibid | Ibid | Sebacate -1,10g | 2g |
| Embodiment 4 | Ibid | Ibid | Ibid | Sebacate -2,6g | 3g |
| Embodiment 5 | Ibid | Ibid | Ibid | Sebacate -3,6g | Ibid |
| Embodiment 6 | Ibid | Ibid | Ibid | Sebacate -4,6g | Ibid |
| Embodiment 7 | Ibid | Ibid | Ibid | Sebacate -5,6g | Ibid |
| Embodiment 8 | Ibid | DBDPE, 285g | 95g | Sebacate -1,6g | Ibid |
| Comparative example 1 | Ibid | FR-245,375g | 125g | Nothing | Ibid |
| Comparative example 2 | Ibid | DBDPE, 400g | 133g | Nothing | Ibid |
| Comparative example 3 | Ibid | FR-245,338g | 112g | Nothing | Ibid |
| Comparative example 4 | Ibid | DBDPE, 360g | 120g | Nothing | Ibid |
| Comparative example 5 | Ibid | FR-245,265g | 88g | Phosphite ester, 6g | Ibid |
| Comparative example 6 | Ibid | DBDPE, 285g | 95g | Phosphite ester, 6g | Ibid |
The main performance of 2 HIPS of table and flame-retarding HIPS
Claims (4)
1. a kind of flame-proof highly anti-flush polyphenylacetylene material with good photo and thermal stability, which is characterized in that it is fire-retardant with bromine system
Agent is main flame retardant, Sb2O3For synergist, bis- (1- alkoxy -2,2,6,6- tetramethyl piperidine -4- bases) sebacates are to have concurrently
The mass fraction of the retardant synergist of light stabilization, composition and each component is as follows: high-impact polystyrene resin 80-
90%, bromide fire retardant 9-15%, Sb2O33-5%, bis- (1- alkoxy -2,2,6,6- tetramethyl piperidine -4- bases) sebacates
0.1-1.0%, antioxidant 0.0-0.5%, other processing aid 0-1.0%.
2. flame-proof highly anti-flush polyphenylacetylene material according to claim 1, which is characterized in that the bromide fire retardant is
Decabromodiphenylethane and three (tribromophenoxy) triazines.
3. flame-proof highly anti-flush polyphenylacetylene material according to claim 1, which is characterized in that bis- (1- alkoxies-
2,2,6,6- tetramethyl piperidine -4- base) sebacate refers to the compound having the following structure:
R is methyl, ethyl, propyl, isopropyl and cyclohexyl in formula, can also be other alkyl, naphthenic base and aromatic radical.
4. flame-proof highly anti-flush polyphenylacetylene material according to claim 1, which is characterized in that preparation method is: first
By bromide fire retardant, Sb2O3, bis- (1- alkoxy -2,2,6,6- tetramethyl piperidine -4- base) sebacates, antioxidant and other help
Agent is uniformly mixed after weighing proportionally, then be added HIPS particle be uniformly mixed, finally by the above mixture melting mixing, make
Grain, drying are made.
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Cited By (1)
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| EP4006125A1 (en) * | 2019-07-30 | 2022-06-01 | Adeka Corporation | Additive composition |
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