CN108659339A - 一种具有良好光稳定性的阻燃聚丙烯材料及其制备方法 - Google Patents
一种具有良好光稳定性的阻燃聚丙烯材料及其制备方法 Download PDFInfo
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- CN108659339A CN108659339A CN201810497313.0A CN201810497313A CN108659339A CN 108659339 A CN108659339 A CN 108659339A CN 201810497313 A CN201810497313 A CN 201810497313A CN 108659339 A CN108659339 A CN 108659339A
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- polypropylene material
- retardant
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- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 32
- 239000004411 aluminium Substances 0.000 claims abstract description 22
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 22
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- 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 claims abstract description 8
- 239000003963 antioxidant agent Substances 0.000 claims abstract description 7
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- CPELXLSAUQHCOX-UHFFFAOYSA-N Hydrogen bromide Chemical compound Br CPELXLSAUQHCOX-UHFFFAOYSA-N 0.000 claims abstract description 5
- 239000006057 Non-nutritive feed additive Substances 0.000 claims abstract description 5
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 5
- 150000001875 compounds Chemical class 0.000 claims abstract description 5
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- 125000003545 alkoxy group Chemical group 0.000 claims abstract 3
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- TYFJTEPDESMEHE-UHFFFAOYSA-N 6,8-dihydroxy-3-[2-(4-methoxyphenyl)ethyl]-3,4-dihydroisochromen-1-one Chemical compound C1=CC(OC)=CC=C1CCC1OC(=O)C2=C(O)C=C(O)C=C2C1 TYFJTEPDESMEHE-UHFFFAOYSA-N 0.000 claims description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 3
- 238000005469 granulation Methods 0.000 claims description 3
- 230000003179 granulation Effects 0.000 claims description 3
- 229910052760 oxygen Inorganic materials 0.000 claims description 3
- 239000001301 oxygen Substances 0.000 claims description 3
- 239000002245 particle Substances 0.000 claims description 3
- XSAOTYCWGCRGCP-UHFFFAOYSA-K aluminum;diethylphosphinate Chemical compound [Al+3].CCP([O-])(=O)CC.CCP([O-])(=O)CC.CCP([O-])(=O)CC XSAOTYCWGCRGCP-UHFFFAOYSA-K 0.000 claims description 2
- 239000007822 coupling agent Substances 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
- 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
- 239000000314 lubricant Substances 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
- 150000003009 phosphonic acids Chemical class 0.000 claims 2
- WMDPJKZHARKRQI-UHFFFAOYSA-N dipropylphosphinic acid Chemical class CCCP(O)(=O)CCC WMDPJKZHARKRQI-UHFFFAOYSA-N 0.000 claims 1
- 238000001035 drying Methods 0.000 claims 1
- 150000002989 phenols Chemical class 0.000 claims 1
- 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 abstract description 45
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- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 3
- 238000002485 combustion reaction Methods 0.000 description 3
- 239000004611 light stabiliser Substances 0.000 description 3
- 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
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- 231100000053 low toxicity Toxicity 0.000 description 2
- XYFCBTPGUUZFHI-UHFFFAOYSA-N phosphine group Chemical group P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 2
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- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 241001465382 Physalis alkekengi Species 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 238000012356 Product development Methods 0.000 description 1
- HOHPOKYCMNKQJS-UHFFFAOYSA-N [P].[Br] Chemical compound [P].[Br] HOHPOKYCMNKQJS-UHFFFAOYSA-N 0.000 description 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
- 229910021502 aluminium hydroxide Inorganic materials 0.000 description 1
- 229910000410 antimony oxide Inorganic materials 0.000 description 1
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Inorganic materials O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910000416 bismuth oxide Inorganic materials 0.000 description 1
- 239000004566 building material Substances 0.000 description 1
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- 238000009833 condensation Methods 0.000 description 1
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- 238000007334 copolymerization reaction Methods 0.000 description 1
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- 238000006731 degradation reaction Methods 0.000 description 1
- TYIXMATWDRGMPF-UHFFFAOYSA-N dibismuth;oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Bi+3].[Bi+3] TYIXMATWDRGMPF-UHFFFAOYSA-N 0.000 description 1
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 1
- QLZHNIAADXEJJP-UHFFFAOYSA-L dioxido-oxo-phenyl-$l^{5}-phosphane Chemical compound [O-]P([O-])(=O)C1=CC=CC=C1 QLZHNIAADXEJJP-UHFFFAOYSA-L 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
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- 239000003546 flue gas Substances 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
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- 230000006872 improvement Effects 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- 239000010977 jade Substances 0.000 description 1
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 1
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 1
- 239000000347 magnesium hydroxide Substances 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
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- 230000004048 modification Effects 0.000 description 1
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical group CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 1
- 239000002103 nanocoating Substances 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
- 238000011056 performance test Methods 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 150000003007 phosphonic acid derivatives Chemical class 0.000 description 1
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical class OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 1
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- 229920000573 polyethylene Polymers 0.000 description 1
- 229920000137 polyphosphoric acid Polymers 0.000 description 1
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- 229920002223 polystyrene Polymers 0.000 description 1
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K13/00—Use of mixtures of ingredients not covered by one single of the preceding main groups, each of these compounds being essential
- C08K13/02—Organic and inorganic ingredients
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/32—Phosphorus-containing compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/13—Phenols; Phenolates
- C08K5/134—Phenols containing ester groups
- C08K5/1345—Carboxylic esters of phenolcarboxylic acids
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/34—Heterocyclic compounds having nitrogen in the ring
- C08K5/3467—Heterocyclic compounds having nitrogen in the ring having more than two nitrogen atoms in the ring
- C08K5/3477—Six-membered rings
- C08K5/3492—Triazines
- C08K5/34928—Salts
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/49—Phosphorus-containing compounds
- C08K5/51—Phosphorus bound to oxygen
- C08K5/52—Phosphorus bound to oxygen only
- C08K5/524—Esters of phosphorous acids, e.g. of H3PO3
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/49—Phosphorus-containing compounds
- C08K5/51—Phosphorus bound to oxygen
- C08K5/53—Phosphorus bound to oxygen bound to oxygen and to carbon only
- C08K5/5313—Phosphinic compounds, e.g. R2=P(:O)OR'
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/02—Flame or fire retardant/resistant
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
本发明公开了一种具有良好光稳定性的阻燃聚丙烯材料及其制备方法。该聚丙烯材料以三聚氰胺氢溴酸盐(MHB)与次膦酸铝(包括无机次磷酸铝和烷基次膦酸铝)的复合物为阻燃剂,亚磷酸三(1‑烷氧基‑2,2,6,6‑四甲基哌啶基)酯为多功能阻燃增效剂,通过熔融混炼、造粒制得。其组成和各组分的质量分数如下:聚丙烯树脂90‑99%,MHB0.4‑4%,次膦酸铝0.4‑4%,亚磷酸三(1‑烷氧基‑2,2,6,6‑四甲基哌啶基)酯0.05‑0.5%,抗氧剂0.0‑0.5%,其它加工助剂0‑1.0%。按以上方法制得的PP材料不仅具有良好的阻燃性能,阻燃等级可达到UL94 V‑1级,而且光稳定性能良好,加工性能和机械性能基本接近于纯PP。
Description
技术领域
本发明涉及一种具有良好光稳定性的阻燃聚丙烯材料及其制备方法,具体地说是以三聚氰胺氢溴酸盐与次膦酸铝(包括无机次磷酸铝和烷基次膦酸铝)的复合物为阻燃剂,亚磷酸三(1-烷氧基-2,2,6,6-四甲基哌啶基)酯为多功能阻燃增效剂,通过熔融混炼、造粒制得的具有良好光稳定性的阻燃聚丙烯材料,属高分子材料领域。
背景技术
聚丙烯(PP)因具有高刚性、高强度、耐热性好、容易加工等优良性能而广泛用于机械、汽车、电器等行业,是目前通用塑料中增长速度最快、新产品开发最为活跃的品种之一。但是PP易燃,且燃烧速率快,放热量高,并且产生大量熔滴而很容易传播火焰。因此,阻燃PP的研究一直受到国内外的重视。
添加阻燃剂是提高PP阻燃性能的主要措施。用于PP的阻燃剂主要有卤系阻燃剂、金属氢氧化物阻燃剂、膨胀型阻燃剂(IFR)等。尽管卤系阻燃剂对PP具有良好的阻燃效果,但由于其使用存在严重的环境及安全问题,并严重降低了PP的光稳定性,因此,卤系阻燃剂的应用愈来愈受到限制(张雨山,高春娟,蔡荣华.溴系阻燃剂的应用研究及发展趋势.化学工业与工程,2009,26(5):460-466)。氢氧化铝和氢氧化镁等金属氢氧化物被誉为“无公害阻燃剂”,具有不挥发、稳定性好、烟气无毒、成本低和资源丰富等优点,但金属氢氧化物阻燃效率低,要获得良好的阻燃效果,所需添加量很大,加上与PP的相容性差,因而对PP的加工性能和机械性能影响很大(王丽丽,邱桂学,潘炯玺等.氢氧化物阻燃剂在聚乙烯中的应用技术和研究进展.塑料助剂,2005,(1):12-16;田雪梅.金属氢氧化物阻燃剂研究进展.塑料助剂,2011,(6):13-17)。IFR具有阻燃效率高、低烟、低毒、添加量少等优点,尤其是在解决阻燃聚烯烃类滴落的难题上具有其它阻燃剂不可比拟的优势,符合当前阻燃材料抑烟、低毒的要求,而被公认为是实现阻燃剂无卤化的有效途径之一,但IFR也存在添加量大,对PP的加工性能和机械性能影响大等问题,且目前主要使用的聚磷酸铵基IFR耐水性差(何庆东,曹有名,岑兰等.环保高效膨胀型阻燃剂研究进展.塑料科技,2008,36(2):104-108;黄琰,张翔宇,游歌云等.聚丙烯膨胀型阻燃剂研究进展.精细化工中间体,2011,41(6):1-7;张金凯,马丽,葛维娟等.膨胀型阻燃剂阻燃聚丙烯的研究进展.材料导报,2015,29(5):68-72)。因此,寻找高效绿色的阻燃方案一直是阻燃PP领域面临的而又迫切需要解决的重大难题。此外,高分子材料中往往需要添加多种助剂来实现多种功能,但这些助剂有时会相互之间产生影响,如卤系阻燃剂的使用会严重降低光稳定剂的稳定作用。因此,开发多功能助剂已成为高分子材料领域研究的热点。
增效剂是提高阻燃剂的阻燃效果,降低阻燃剂添加量的重要手段。2,3-二甲基-2,3-二苯基丁烷(DMDPB,简称联枯)是最早使用的阻燃增效剂。早在上世纪五十年代,德国、日本、美国等国家就申请了许多关于联枯及其衍生物作为阻燃增效剂的专利。近期仍有不少研究报道。联枯主要用于聚烯烃,特别是PP和聚苯乙烯,可作为各种溴系阻燃剂、磷系阻燃剂和溴磷复合阻燃体系等的增效剂。例如,王良民等采用3-(三溴新戊基)磷酸酯与次磷酸铝为阻燃剂,联枯为增效剂,当复合阻燃剂的质量添加分数为2.5%时,共聚聚丙烯(1.6毫米)燃烧等级可达FV-2(王良民,李建业,王德强等.低卤阻燃增强共聚聚丙烯的制备.广东化工,2015,42(18):43-44)。李艳复合使用溴系阻燃剂[如三聚氰胺氢溴酸盐(MHB)]、苯基次磷酸铝和联枯,制备出一种低卤阻燃聚丙烯材料,当阻燃剂用量为2%时,阻燃等级达到V-2级(李艳.一种低卤聚丙烯阻燃材料及其制备方法.CN 104004270A,2014-08-27)。彭维礼以MHB、各种次磷酸盐或烷基次膦酸盐为阻燃剂,联枯及其衍生物等为增效剂,氧化锑(或氧化铋)等为协效剂,制备出一种无表面析出的阻燃聚丙烯复合材料。当阻燃剂总用量约为2%,材料的阻燃等级就可达FV-2(彭维礼.一种阻燃PP/ABS复合材料及其制备方法.CN101880420A,2010-11-10)。以MHB和次磷酸铝复合物为阻燃剂,联枯为增效剂的阻燃体系目前已较广泛地用于PP阻燃,制备V-2或V-1的阻燃PP。对均聚PP,阻燃剂的添加量一般为2%左右,对共聚PP,阻燃剂的添加量一般为5%左右。尽管联枯具有很好的阻燃增效作用,但其功能单一,无光热稳定作用,不能解决阻燃PP光稳定性差的问题。
受阻胺类光稳定剂是当今性能最优异的光稳定剂之一,其广泛应用于聚烯烃农膜、高分子涂料等领域。近些年,人们意外地发现N-烷氧基受阻胺(NORs)还兼有阻燃和热稳定作用,广泛的研究和工业应用结果表明,NORs主要具有下列特点(曹堃,吴水良,李彦等.N-取代烷氧基受阻胺类阻燃剂及其在聚烯烃中的应用.化学进展,2011,23(6):1189-1195):
对特定的PP产品(如纤维、薄膜等)具有良好的阻燃功效,添加0.5%左右即能达到满意的阻燃性能,因而对基材的加工性能、机械性能等影响小;
与卤系、磷系及金属氢氧化物等传统阻燃剂具有良好的阻燃协效作用,使得PP材料能够通过更严格的阻燃标准,能显著减少传统阻燃剂的用量,从而降低传统阻燃剂对聚合物材料加工性能、机械性能等的影响(ROTH M.Flame retardant compositioncomprising sterically hindered amines.WO 2009080554A1,2009-07-02;KAPRINIDISN,LELLI N.Flame retardant polymer electrical parts.WO 2004035673A1,2004-04-29;BUTZ V.Flame retardant composition comprising a phosphonic acidderivative.WO 2010026230A1,2010-03-11;XALTER R,WEISS T,ROTH M,etal.Phenylphosphonate flame retardant composition.WO 2011003773 A1,2011-01-13;XIE HUALI,LAI XUEJUN,ZHOU RIMIN,et al.Effect and mechanism of N-alkoxyhindered amine on the flame retardancy,UV aging resistance and thermaldegradation of intumescent flame retardant polypropylene.Poly Degr Stab,2015,118:167-177;KAPRINIDIS N,LELLI N,KIERKELS RHM.Flame retardant composition.WO2004041919 A2,2004-05-21);
不含卤素、用量低,因而对环境的影响小,使用安全,代替昂贵的Sb2O3作为卤系阻燃剂的协效剂,可以显著降低卤系阻燃剂的阻燃成本及阻燃材料燃烧时的发烟量等(TROUTMAN MV,RAVICHANDRAN R,SRINIVASAN R,et al.Flame retardant composition.US2006084731 A1,2006-04-20);
具有良好的长效热稳定性和紫外光稳定性,成功解决了传统阻燃剂,特别是卤系阻燃剂的使用严重降低了材料的光稳定性的难题。
由于以上优点,NORs的出现被认为是阻燃领域的一次革命性进展,为发展绿色高效多功能阻燃剂开辟了一条崭新的途径,因而引起了国内外的高度重视。
尽管如此,但目前已工业化的NORs仅Flamestab NOR 116,它仅仅对聚丙烯薄制品有效,对厚制品(注塑模板等)阻燃效果有限,对其它聚合物的效果更差,也未见到它对MHB和次磷酸盐复合物阻燃PP具有阻燃增效作用的报道。此外,Flamestab NOR 116化学结构(如下所示)复杂,合成工艺很繁琐,原子利用率低,合成过程中的三废量排放大。
发明内容
为了克服Flamestab NOR 116存在的缺点,本专利申请人开发了系列亚磷酸三(1-烷氧基-4-羟基-2,2,6,6-四甲基哌啶基)酯(简称亚磷酸酯),并发现它对MHB和次磷酸铝(或二烷基次膦酸铝)复合阻燃PP不仅具有显著的增效作用,而且可赋予阻燃PP良好的光稳定性和抗氧作用,克服了用MHB/次磷酸铝(或二烷基次膦酸铝)阻燃剂,联枯作为增效剂制得的阻燃PP光稳定性不好的缺点。
本发明的具有良好光稳定性的阻燃聚丙烯材料,其组成和各组分的质量分数如下:
聚丙烯树脂90-99%,MHB 0.4-4%,次膦酸铝0.4-4%,亚磷酸酯0.05-0.5%,抗氧剂0.0-0.5%,其它加工助剂0-1.0%;
所述的聚丙烯树脂为均聚PP和共聚PP;
所述的次膦酸铝为无机次磷酸铝和各种烷基次膦酸铝,如二乙基次膦酸铝、二丙基次膦酸铝,乙基次膦酸铝等,或它们的混合物;
所述的亚磷酸酯是指具有如下结构的化合物:
式中R为甲基、乙基、丙基、异丙基和环己基(分别简称亚磷酸酯-1~亚磷酸酯-5),也可是其它烷基、环烷基和芳香基;
所述的抗氧剂为各种受阻酚抗氧剂,如抗氧剂1010,由于亚磷酸三(1-烷氧基-4-羟基-2,2,6,6-四甲基哌啶基)酯兼有辅助抗氧作用,因而不需添加其它的亚磷酸酯类抗氧剂。
所述的其它加工助剂为润滑剂、偶联剂等。
本发明还提供了以上聚丙烯复合材料的制备方法,具体过程是:首先将MHB、次膦酸铝、亚磷酸酯、抗氧剂等助剂按比例称量后混合均匀,然后加入PP颗粒混合均匀,最后将以上混合物熔融混炼、造粒、干燥得具有良好光稳定性的阻燃PP复合材料。
本发明的PP材料不仅具有良好的阻燃性能,阻燃等级可达到UL94V-1级,而且光稳定性能良好,加工性能和机械性能基本接近于纯PP,可用于制备建材、插座、波纹管及灯饰灯具等部件。
具体实施方式
以下对本发明的优选实施例进行说明,应当理解,此处所描述的优选实施例仅用于说明和解释本发明,并不用于限定本发明。
除非另有说明,本发明中所采用的百分数均为质量百分数。
本申请所用均聚聚丙烯树脂为兰州石化公司生产的PPH8020,共聚聚丙烯树脂为中国石化齐鲁石化分公司生产的PPSP179,抗氧剂为山东省临沂市三丰化工有限公司生产的抗氧剂1010,MHB和无机次磷酸铝(简称次磷酸铝)由济南泰星精细化工有限公司提供,二乙基次膦酸铝为青岛欧普瑞新材料有限公司生产。
燃性能测试:极限氧指数(LOI)采用JF-3型氧指数测定仪(南京市江宁区分析仪器厂)根据GB/T2046-1993测定,测试样品尺寸为100mm×6.5mm×1.6mm;垂直燃烧试验采用CZF-3型水平垂直燃烧测定仪参考GB/T2408-1996试验,试样尺寸为100mm×13mm×1.6mm。
机械性能测试:拉伸性能按照GB/T1040-2006测试,试样标准尺寸:150mm×20mm×4mm;弯曲性能按照GB/T 9341-2008测试,试样标准尺寸:80mm×10mm×4mm;悬臂梁缺口冲击强度按照GB/T 1843-2008测试,试样标准尺寸:80mm×10mm×4mm。冲击强度采用RXJ-5.5型悬臂梁冲击试验机(济南新试金试验机有限公司)测定,拉伸和弯曲性能采用SANS-20电子万能拉力试验机(深圳市新三思仪器有限公司)测试。机械性能的测试样品采用注塑制备,所用注塑机为常州豪屹塑化有限公司生产的128T注塑机。
光稳定性试验:通过人工加速老化试验评价材料的光稳定性。所用设备为紫外光老化实验箱(南京环科试验设备有限公司),所用光源为UVA-340nm,光强度为0.76w/m2.nm,标黑温度为50±3℃,暴露周期为8h干燥,4h凝露,光照时间为120h。
实施例1
一种具有良好光稳定性的阻燃聚丙烯材料及其制备方法,其组成和各组分的质量列于表1:
其制备方法如下:准确称取各组分质量,首先将MHB、无机次磷酸铝、亚磷酸酯-1、抗氧剂加入研磨混合机(天津泰斯特有限公司)混合3min,然后将其倒入5L机械混合机中,并加入PP颗粒混合3min,最后将以上混合物通过双螺杆挤出机(烟台齐通粉末机械有限公司生产的JS30A型双螺杆挤出机,L/D=42.5cm/2cm,转速20-30rpm,挤出温度190-200℃)熔融混炼挤出、造粒、干燥得具有良好光稳定性的阻燃PP材料。
按以上组成及制备方法制得的阻燃PP的主要机械性能和阻燃性能列于表2。
表2中的数据表明,按上述方法制得的PP的阻燃级别可达到V-1级,机械性能与纯PP几乎无明显差异,经人工加速光老化后机械性能也未发生明显变化,表明其具有良好的光稳定性。
实施例2~实施例20
实施例2~实施例20的组成及各组分的质量均列于表1。制备方法与实施例1相同,主要机械性能和阻燃性能列于表2。表2中的数据表明,按实施例2~实施例20制得的阻燃PP具有与实施例1几乎相同的特性。
比较例1和比较例2
比较例1和比较例2的组成及各组分的质量均列于表1。制备方法与实施例1相同,主要机械性能和阻燃性能列于表2。表2中的数据表明,比较例1和比较例2制得的阻燃PP与实施例1~实施例20制得的几乎具有相同的阻燃性能和机械性能,但经人工加速光老化后机械性能明显下降,表明其光稳定性不好。
表1 各实施例的物料组成
表2 PP及阻燃PP的主要性能
最后应说明的是:以上所述仅为本发明的优选实施例而已,并不用于限制本发明,尽管参照前述实施例对本发明进行了详细的说明,对于本领域的技术人员来说,其依然可以对前述各实施例所记载的技术方案进行修改,或者对其中部分技术特征进行等同替换。凡在本发明的精神和原则之内,所作的任何修改、等同替换、改进等,均应包含在本发明的保护范围之内。
Claims (6)
1.一种具有良好光稳定性的阻燃聚丙烯材料,其特征在于它以三聚氰胺氢溴酸盐与次膦酸铝的复合物为阻燃剂,亚磷酸三(1-烷氧基-2,2,6,6-四甲基哌啶基)酯为多功能阻燃增效剂,其组成和各组分的质量分数如下:聚丙烯树脂90-99%,三聚氰胺氢溴酸盐0.4-4%,次膦酸铝0.4-4%,亚磷酸三(1-烷氧基-2,2,6,6-四甲基哌啶基)酯0.05-0.5%,抗氧剂0.0-0.5%,其它加工助剂0-1.0%。
2.根据权利要求1所述的阻燃聚丙烯材料,其特征在于,所述的次膦酸铝为无机次磷酸铝、二乙基次膦酸铝、二丙基次膦酸铝,乙基次膦酸铝或它们的混合物。
3.根据权利要求1所述的阻燃聚丙烯材料,其特征在于,所述的亚磷酸三(1-烷氧基-2,2,6,6-四甲基哌啶基)酯是指具有如下结构的化合物:
式中R为甲基、乙基、丙基、异丙基和环己基,也可是其它烷基、环烷基和芳香基。
4.根据权利要求1所述的阻燃聚丙烯材料,其特征在于,所述的抗氧剂为各种受阻酚抗氧剂。
5.根据权利要求1所述的阻燃聚丙烯材料,其特征在于,所述的其它加工助剂为润滑剂和偶联剂。
6.根据权利要求1所述的阻燃聚丙烯材料,其特征在于,其制备方法是:首先将MHB、次膦酸铝、亚磷酸三(1-烷氧基-2,2,6,6-四甲基哌啶基)酯、抗氧剂和其它助剂按比例称量后混合均匀,然后加入PP颗粒混合均匀,最后将以上混合物熔融混炼、造粒、干燥制得。
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CN109735038A (zh) * | 2019-01-22 | 2019-05-10 | 山东兄弟科技股份有限公司 | 一种具有良好光稳定性的阻燃高抗冲聚苯乙烯材料及其制备方法 |
CN113912938A (zh) * | 2021-10-12 | 2022-01-11 | 厦门稀土材料研究所 | 一种抗紫外老化阻燃聚丙烯材料及其制备方法 |
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CN114410010A (zh) * | 2021-11-23 | 2022-04-29 | 天津金发新材料有限公司 | 一种阻燃聚丙烯材料及其制备方法 |
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