CN110453499A - 阻燃聚丙烯复合纱线及其制品 - Google Patents
阻燃聚丙烯复合纱线及其制品 Download PDFInfo
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- CN110453499A CN110453499A CN201910682108.6A CN201910682108A CN110453499A CN 110453499 A CN110453499 A CN 110453499A CN 201910682108 A CN201910682108 A CN 201910682108A CN 110453499 A CN110453499 A CN 110453499A
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- polypropylene
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- thermoplastic elastomer
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- -1 Polypropylene Polymers 0.000 title claims abstract description 74
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- 229920001155 polypropylene Polymers 0.000 title claims abstract description 67
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- 239000000835 fiber Substances 0.000 claims abstract description 37
- 239000000203 mixture Substances 0.000 claims abstract description 25
- DWSWCPPGLRSPIT-UHFFFAOYSA-N benzo[c][2,1]benzoxaphosphinin-6-ium 6-oxide Chemical compound C1=CC=C2[P+](=O)OC3=CC=CC=C3C2=C1 DWSWCPPGLRSPIT-UHFFFAOYSA-N 0.000 claims abstract description 24
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- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 3
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- 125000002877 alkyl aryl group Chemical group 0.000 claims description 2
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- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims description 2
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims description 2
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- 238000006467 substitution reaction Methods 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 33
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- DXZMANYCMVCPIM-UHFFFAOYSA-L zinc;diethylphosphinate Chemical compound [Zn+2].CCP([O-])(=O)CC.CCP([O-])(=O)CC DXZMANYCMVCPIM-UHFFFAOYSA-L 0.000 description 7
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- 229910019142 PO4 Inorganic materials 0.000 description 4
- 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 4
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Chemical compound BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 4
- 238000002485 combustion reaction Methods 0.000 description 4
- 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 4
- FPAFDBFIGPHWGO-UHFFFAOYSA-N dioxosilane;oxomagnesium;hydrate Chemical compound O.[Mg]=O.[Mg]=O.[Mg]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O FPAFDBFIGPHWGO-UHFFFAOYSA-N 0.000 description 4
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- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 3
- 229920000388 Polyphosphate Polymers 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 229910052794 bromium Inorganic materials 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 239000011159 matrix material Substances 0.000 description 3
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 3
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- YNPNZTXNASCQKK-UHFFFAOYSA-N phenanthrene Chemical compound C1=CC=C2C3=CC=CC=C3C=CC2=C1 YNPNZTXNASCQKK-UHFFFAOYSA-N 0.000 description 3
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 3
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- 239000001205 polyphosphate Substances 0.000 description 3
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- 239000004753 textile Substances 0.000 description 3
- 239000002341 toxic gas Substances 0.000 description 3
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 2
- 229920000742 Cotton Polymers 0.000 description 2
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 2
- 230000009471 action Effects 0.000 description 2
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- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Chemical compound O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 description 2
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- XZAXQWXHBDKYJI-UHFFFAOYSA-N 2-[(6-oxobenzo[c][2,1]benzoxaphosphinin-6-yl)methyl]butanedioic acid Chemical compound C1=CC=C2P(CC(CC(=O)O)C(O)=O)(=O)OC3=CC=CC=C3C2=C1 XZAXQWXHBDKYJI-UHFFFAOYSA-N 0.000 description 1
- FHVDTGUDJYJELY-UHFFFAOYSA-N 6-{[2-carboxy-4,5-dihydroxy-6-(phosphanyloxy)oxan-3-yl]oxy}-4,5-dihydroxy-3-phosphanyloxane-2-carboxylic acid Chemical compound O1C(C(O)=O)C(P)C(O)C(O)C1OC1C(C(O)=O)OC(OP)C(O)C1O FHVDTGUDJYJELY-UHFFFAOYSA-N 0.000 description 1
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- QWEXUGUTYLTMID-UHFFFAOYSA-N C1=CC=CC=2C3=CC=CC=C3C=CC12.[P] Chemical class C1=CC=CC=2C3=CC=CC=C3C=CC12.[P] QWEXUGUTYLTMID-UHFFFAOYSA-N 0.000 description 1
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- NEAPKZHDYMQZCB-UHFFFAOYSA-N N-[2-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperazin-1-yl]ethyl]-2-oxo-3H-1,3-benzoxazole-6-carboxamide Chemical compound C1CN(CCN1CCNC(=O)C2=CC3=C(C=C2)NC(=O)O3)C4=CN=C(N=C4)NC5CC6=CC=CC=C6C5 NEAPKZHDYMQZCB-UHFFFAOYSA-N 0.000 description 1
- NIPNSKYNPDTRPC-UHFFFAOYSA-N N-[2-oxo-2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 NIPNSKYNPDTRPC-UHFFFAOYSA-N 0.000 description 1
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- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 125000001820 oxy group Chemical group [*:1]O[*:2] 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- 150000003014 phosphoric acid esters Chemical class 0.000 description 1
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 230000007096 poisonous effect Effects 0.000 description 1
- 239000005020 polyethylene terephthalate Substances 0.000 description 1
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- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 229920006124 polyolefin elastomer Polymers 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 239000003340 retarding agent Substances 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 239000004759 spandex Substances 0.000 description 1
- 150000003440 styrenes Chemical class 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 229920000576 tactic polymer Polymers 0.000 description 1
- 238000009965 tatting Methods 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 229920005992 thermoplastic resin Polymers 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
- DLGPQXZJGXTJHC-UHFFFAOYSA-N tribromo phosphate Chemical compound BrOP(=O)(OBr)OBr DLGPQXZJGXTJHC-UHFFFAOYSA-N 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 238000004804 winding Methods 0.000 description 1
- 210000002268 wool Anatomy 0.000 description 1
Classifications
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
- D06M11/32—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with oxygen, ozone, ozonides, oxides, hydroxides or percompounds; Salts derived from anions with an amphoteric element-oxygen bond
- D06M11/36—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with oxygen, ozone, ozonides, oxides, hydroxides or percompounds; Salts derived from anions with an amphoteric element-oxygen bond with oxides, hydroxides or mixed oxides; with salts derived from anions with an amphoteric element-oxygen bond
- D06M11/46—Oxides or hydroxides of elements of Groups 4 or 14 of the Periodic Table; Titanates; Zirconates; Stannates; Plumbates
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
- D06M11/77—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with silicon or compounds thereof
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
- D06M13/244—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing sulfur or phosphorus
- D06M13/282—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing sulfur or phosphorus with compounds containing phosphorus
- D06M13/292—Mono-, di- or triesters of phosphoric or phosphorous acids; Salts thereof
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- D—TEXTILES; PAPER
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- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
- D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
- D06M15/21—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- D06M15/227—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of hydrocarbons, or reaction products thereof, e.g. afterhalogenated or sulfochlorinated
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- D—TEXTILES; PAPER
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- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
- D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
- D06M15/37—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
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- D06M2101/00—Chemical constitution of the fibres, threads, yarns, fabrics or fibrous goods made from such materials, to be treated
- D06M2101/16—Synthetic fibres, other than mineral fibres
- D06M2101/18—Synthetic fibres consisting of macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- D06M2101/20—Polyalkenes, polymers or copolymers of compounds with alkenyl groups bonded to aromatic groups
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- D—TEXTILES; PAPER
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- D06M2200/00—Functionality of the treatment composition and/or properties imparted to the textile material
- D06M2200/30—Flame or heat resistance, fire retardancy properties
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- Engineering & Computer Science (AREA)
- Textile Engineering (AREA)
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Multicomponent Fibers (AREA)
Abstract
阻燃聚丙烯复合纱线,具有皮芯结构,以聚丙烯长丝为内芯,弹性体包覆层材料为外皮,所述弹性体包覆层材料由包括聚丙烯树脂、热塑性弹性体、DOPO基阻燃剂的包覆层组合物制成。阻燃聚丙烯复合纱线力学性能好,并具有良好的阻燃性能,且在燃烧时发烟量低。该纱线可单独制成织物和面料,或者与其他纤维或纱线混纺制成混纺线、织物和面料。
Description
技术领域
本发明涉及一种阻燃聚丙烯纱线以及由该纱线制成的织物,属于纺织用品领域。
背景技术
聚丙烯纤维具有强度高、质量轻、易加工、成本低等优良特性,已被广泛用于服装、室内装饰、地毯、卫生医疗、土工布、汽车产业、汽车用纺织品、各种家用纺织品以及墙布等。然而其极易燃烧,燃烧释放大量热,火焰传播速度快,并伴有发烟、滴落现象,易引起大面积火灾;同时在燃烧过程中将释放大量的烟尘和有毒气体,造成窒息性气氛,对人生命安全造成巨大的威胁,从而限制了聚丙烯纤维的广泛应用。根据相关的法律法规,这些织物必须具备一定的阻燃性,为了适应这些需求,必须对聚丙烯纤维进行阻燃改性。阻燃技术能够抑制、消除燃烧,延缓、抑制燃烧的传播,同时减少热引燃出现的概率。经过阻燃处理的聚丙烯纤维与未经过阻燃处理的聚丙烯纤维相比,前者难于燃烧,且火焰传播速度明显降低,有助于阻止火灾形成,提高聚丙烯纤维制品的使用安全性。一般通过在熔纺过程中加入阻燃剂来实现聚丙烯纤维的阻燃性。用于聚丙烯纤维阻燃的阻燃剂一般应满足以下几点要求:(1)在聚丙烯加工过程中具有良好的热稳定性(>260℃);(2)与聚丙烯具有良好的相容性且不会浸出或迁移;(3)应将有毒气体的释放量降低到可接受的水平;(4)应具有高效性,添加量应尽可能少(一般应小于10%重量),以降低生产成本并减小其对纤维力学性能的影响。
目前用于聚丙烯纤维阻燃的主要有含卤阻燃剂和无卤阻燃剂。奥地利的ASTOA公司于上世纪90年代开始使用含卤阻燃剂制备阻燃聚丙烯纤维。所制备的阻燃聚丙烯纤维含卤量只有1.5%wt,尽管如此,越来越多针对含卤阻燃剂的禁令开始实施。这是因为含卤阻燃剂不仅在燃烧时会放出有毒气体,它的存在会进一步降低聚丙烯纤维的紫外稳定性和热稳定性,从而减短聚丙烯纤维制品的使用寿命。因此,从应用的角度考虑,含卤阻燃剂的阻燃性和这些缺点相矛盾。美国DEAD SEA BROMINE公司研发了一种聚丙烯纤维用卤-磷阻燃剂,其主要成分为三溴磷酸盐,其分子中溴含量高达70%wt,再加上3%wt的磷含量使得其成为一种高效阻燃剂,其熔点为181℃,在聚丙烯挤出温度下能够和聚丙烯形成熔融共混物,它的添加基本不影响聚丙烯的挤出性能。当用量为3~5%wt时,便可获得具有良好阻燃性的聚丙烯纤维。其主要优点是用量少效果好而且无需添加协效剂如三氧化锑。但是,卤系阻燃剂虽然阻燃效果很好,但在阻燃过程中会放出大量含有毒气体的黑烟,据统计,火灾中烧灼致死的人数仅占15%,而85%的人是死于毒烟导致的窒息。对此,很多国家对含卤阻燃产品提出了越来越多的限制条件。而无卤阻燃剂有低烟、无毒的优点,因此,不管是从发展经济上考虑,还是从安全方面考虑,高效的无卤阻燃剂是阻燃工业发展的方向。全球一些阻燃剂及阻燃材料生产和供应商对阻燃无卤化一直表现出相当大的热情。
奥地利的ASTOA公司于2002年开发了一种用于聚丙烯阻燃改性的无卤阻燃剂。采用该阻燃剂制备的聚丙烯纤维不仅表现出优良的阻燃性能,同时还能保持聚丙烯纤维原有的力学性能及光稳定性能,最大的优点是在燃烧时不会产生有毒或腐蚀性气体。CALP公司利用被称为FR600的无卤素阻燃剂生产的阻燃聚丙烯纤维,该纤维在火焰下不燃烧,只是熔融,而且即使在焚烧过程中也不会产生多氯乙苯(即二噁英)。这种阻燃改性不影响纤维强度、抗紫外线性能,而且健康安全,并具有良好的可纺性和加捻性,已经在产业用纺织品方面得到广泛应用。日本三菱人造丝公司开发了非卤系阻燃聚丙烯纤维,可以保持聚丙烯的耐光性和机械性能、环境适应性,同时赋予阻燃性能。
皮芯型长丝是由两种组分以皮芯结构的形式沿纤维轴向连续排列而成。这种结构的复合长丝对两组分间粘合力的要求并不严格,即使各聚合物组分之间不具有良好的粘合作用,也能形成稳定的复合纱线,所以为达到改性目的而选择组分时比较灵活。聚丙烯具有密度低、强度高、价格低等优点而得到了广泛应用,但其突出的缺点是韧性较差,尤其在低温下表现为脆性。热塑性弹性体所具有的优异弹性正好弥补了聚丙烯的不足,同时通过控制弹性体的加入比例,可以将成本控制在合理的水平。CN102230247A披露了包覆纱线,内芯为聚丙烯复丝,外皮为热塑性弹性体TPE,但未进行阻燃处理,属于易燃产品,实际应用受到很大限制。CN103710980A和CN103710981A披露了一种以丙纶丝为内芯,热塑性弹性体为外皮的包覆材料,其使用磷酸酯作为阻燃剂,该文献仅披露了阻燃性能达到UL94标准,但未具体给出UL94测试所达到的级别,也没有给出关于发烟性能的测试数据,而所用的磷酸酯类阻燃剂所能达到的阻燃性能有限,且用量过高时还会降低材料的力学性能。US2013052900A1披露了含有阻燃剂的聚丙烯/弹性体芯皮复合纱线,其分别采用三聚氰胺多磷酸盐(MPP)、有机膦、PMP、溴系化合物作为阻燃剂,极限氧指数(LOI)最高可达35%,但其未披露材料的发烟性能,且使用无卤阻燃剂时阻燃剂用量较大,不利于获得力学性能良好的产品。东华大学的彭莹莹等制备一种聚丙烯/聚烯烃弹性体皮芯型复合纤维(《合成纤维》,2009年第2期,第17-20页),但也未涉及纤维的阻燃处理。
目前,尚待开发一种在保证力学性能的同时阻燃性能良好,燃烧时烟气释放量低的聚丙烯复合纱线及其制品。
发明内容
本发明提供了一种阻燃聚丙烯复合纱线及其制品,其在保证力学性能能够满足使用要求的同时,具有良好的阻燃性能且燃烧时发烟量低。
本发明的阻燃聚丙烯复合纱线,具有皮芯结构,以聚丙烯长丝为内芯,弹性体包覆层材料为外皮,所述弹性体包覆层材料由包括聚丙烯树脂、热塑性弹性体、DOPO基阻燃剂的包覆层组合物制成。
聚丙烯树脂是由丙烯聚合而制得的一种热塑性树脂,是第一个实现工业化的合成立体规整聚合物。等规聚丙烯最早由意大利齐格勒教授催化合成问世,于1957年由意大利的蒙特卡蒂尼公司开始工业化生产。用于包覆层组合物的聚丙烯树脂要求具有良好的流动性,以便于涂覆并加工成所需规格的纱线。优选地,聚丙烯树脂的熔体流动速率为1~30g/10min,进一步优选8~25g/10min,更优选10-23g/10min。
热塑性弹性体主要为嵌段或接枝聚合物,其中一相为橡胶相,贡献弹性,另一相为树脂,使热塑性弹性体具有强度,同时凭借链间作用力形成物理交联点,物理交联随温度的变化呈可逆变化,显示了热塑性弹性体的塑料加工特性。可用于所述包覆层组合物中的热塑性弹性体包括:苯乙烯类热塑性弹性体,例如SBS、氢化SBS、SEBS、氢化SEBS、SIS、氢化SIS;聚氨酯类热塑性弹性体;聚烯烃类热塑性弹性体,例如乙烯-辛烯共聚物(POE),三元乙丙橡胶(EPDM),丙烯-乙烯共聚物。从加工流动性和与聚丙烯的粘合性能考虑,优选采用聚烯烃类热塑性弹性体,特别优选丙烯-乙烯共聚物热塑性弹性体。
所述DOPO基阻燃剂是由DOPO衍生而得,包括含有DOPO结构的化合物和低聚物或聚合物。DOPO(9,10-二氢-9-氧杂-10-磷杂菲-10-氧化物)是一种磷菲类环状磷酸酯。DOPO中的联苯环和菲环,特别是侧面含磷基团以环状O=P-O键的方式接入使得其较一般未成环磷酸酯具有更好的热稳定性及化学稳定性;DOPO中的P-H键反应活性强,易与双键、羰基、环氧键等缺电子化合物发生加成反应,制备DOPO基的反应型及添加型阻燃剂。DOPO基阻燃剂P含量较高,无烟无毒、不迁移、阻燃性持久,在提高基材阻燃性、热稳定性、耐氧化性和耐水性的同时,能保持基材的机械及其他性能。DOPO可由以下反应路线合成:
所述DOPO基阻燃剂优选为下述通式(A)结构的化合物:
其中R1和R2是相同的或不同的和各自独立地表示烷基、烷氧基、芳基、芳氧基或芳烷基;n和m是0-4的整数;和R3表示衍生自不饱和二元羧酸或其酸酐的残基。
优选地,通式(A)化合物为以下结构的化合物:
从抑制阻燃剂迁移的角度看,优选使用具有长链结构的DOPO基阻燃剂。这是因为阻燃剂分子中的长链容易与聚合物基体的高分子链产生缠绕或由于氢键、反应基团等物理、化学作用使得阻燃剂分子与聚合物基体具有更强的结合力,从而使得阻燃剂被固定在聚合物基体中,相比于小分子阻燃剂化合物更不易发生迁移,使得阻燃效果更加稳定、持久,并有利于提高纱线的表观品质。
具有长链结构的DOPO基阻燃剂优选为具有下述通式(B)结构:
其中R1表示氢、甲基或乙基;R2表示残基-(CH2)m-O-R1;A是具有2-6个碳原子的支化的或未支化的亚烷基或任选经取代的芳族桥连基;和n是55-110的整数;芳香族桥连基上的取代基优选是烷基、烷氧基、芳基、芳氧基、芳烷基和烷芳基。
优选地,通式(B)化合物为以下结构的化合物:
其中n是55-110的整数。所述包覆层组合物中优选包括聚丙烯树脂30~80重量份、热塑性弹性体15~50重量份、DOPO基阻燃剂1~10重量份。其中,聚丙烯树脂的用量优选40~70重量份,更优选45~60重量份;热塑性弹性体的用量优选20~45重量份,更优选25~40重量份;DOPO基阻燃剂的用量优选1.5~7重量份,更优选2~6重量份。
所述包覆层组合物中还可任选地包括常规的助剂,例如抗氧剂、光稳定剂、紫外线光稳剂、填料、爽滑剂、抗菌剂、颜料、耐老化剂、抗静电剂等。所述助剂的用量为1~50重量份,优选5~40重量份,更优选10~35重量份。
本发明还提供了一种阻燃聚丙烯复合纱线的制备方法,包括以下步骤:
1)包覆层组合物粒料的制备
将聚丙烯树脂、热塑性弹性体、DOPO基阻燃剂、任选的助剂混合均匀得到共混物,将上述共混物进行熔融加工,得到粒料。
2)聚丙烯复合纱线的制备
将步骤1)得到的粒料熔融包覆于聚丙烯长丝表面,得到皮芯结构的复合纱线。
所述制备方法中,步骤1)中熔融加工设备为螺杆挤出机,优选双螺杆挤出机;挤出机加工温度为120~180℃,优选130~170℃;螺杆转速100~500r/min,优选200~400r/min。
步骤2)中熔融加工温度为130~200℃,优选140~190℃。
本发明的聚丙烯复合纱线可以单独使用制成各种织物和面料,也可以与其他纤维或纱线按各种比例混纺,制成功能不同的混合纱线、织物和面料。所述其他纤维包括粘胶纤维、棉纤维、莫代尔纤维、天丝、羊毛、羊绒、芳纶、芳砜纶、聚酰亚胺纤维、丙纶、氨纶、涤纶、尼龙纤维、海藻纤维、玻璃纤维等。所述其他纱线为上述其他纤维的纯纺线或2种以上的混纺线。
本发明的阻燃聚丙烯复合纱线及其制品力学性能好,并具有良好的阻燃性能,且在燃烧时发烟量低。
具体实施方式
用于生产本发明所述聚丙烯复合纱线的原料可从市场上获得。以下示例性列出主要原料:
聚丙烯树脂,牌号K8003,中国石化广州分公司生产。
热塑性弹性体,牌号威达美6202,埃克森美孚(ExxonMobil)生产。
DOPO基阻燃剂,聚[氧基-1,2-乙二基氧基[[(6-氧化-6H-二苯并[c,e][1,2]氧杂磷杂环己-6-基)甲基]-1,4-二氧代-1,4-丁二基]],UKANOL FR50/1,Schill&Seilacher。
三聚氰胺多磷酸盐,Melapur 200,巴斯夫生产。
次膦酸金属盐,Exolit OP 930,科莱恩生产。
三(1-氧代-1-磷杂-2,6,7-三氧杂双环辛烷-4-亚甲基)磷酸酯,Trimer,市售。
十溴二苯醚,山东海王化工有限公司生产。
EVA树脂,Elvax 40w,杜邦生产。
抗氧剂1010,上海汽巴精化公司生产。
光稳定剂944,巴斯夫生产。
紫外线稳定剂UV-326,巴斯夫生产。
二氧化钛,R105,杜邦生产。
爽滑剂EBO,禾大生产。
滑石粉,上海锦俊化学生产。
实施例1
1)包覆层组合物粒料的制备
将聚丙烯树脂55重量份、热塑性弹性体35重量份、DOPO基阻燃剂4重量份、EVA 3重量份加入搅拌机,高速运转5分钟(频率50HZ,温度达到45℃),加入抗氧剂1010 0.11重量份、光稳定剂944 0.09重量份、紫外线稳定剂UV-326 0.2重量份,搅拌2分钟,加入二氧化钛5重量份、爽滑剂EBO 0.13重量份、滑石粉8重量份搅拌5分钟。将搅拌均匀的原料放入待挤出仓经过喂料器(30r/min)加入双螺杆挤出机,调节双螺杆挤出机温度(12个温度段):140℃—145℃—145℃—150℃—155℃—160℃—160℃—160℃—158℃—158℃—155℃—155℃,挤出机螺杆转速300r/min。料条经过水槽冷却,风机吹干,切粒,然后在90℃下烘干,得到弹性体包覆层组合物粒料。
2)聚丙烯复合纱线的制备
将步骤1)得到的弹性体包覆层组合物粒料与聚丙烯长丝在包覆丝螺杆挤出机中进行熔融纺丝,得到皮芯结构的复合长丝,通过张力控制卷绕成卷。其中聚丙烯长丝构成内芯,外皮为步骤1)所得组合物制成的弹性体包覆层。主机转速为30r/min,牵引转速为90r/min,各区加工温度为168℃-176℃-180℃-182℃-180℃,烘干温度为70℃,烘干时间为1小时。所得复合纱线的线径为0.50mm。
实施例2
1)包覆层组合物粒料的制备
将聚丙烯树脂50重量份、热塑性弹性体35重量份、DOPO基阻燃剂3重量份、EVA 3重量份加入搅拌机,高速运转5分钟(频率50HZ,温度达到45℃),加入抗氧剂1010 0.1重量份、光稳定剂944 0.09重量份、紫外线稳定剂UV-326 0.12重量份,搅拌2分钟,加入二氧化钛6重量份、爽滑剂EBO 0.13重量份、滑石粉9重量份搅拌5分钟。将搅拌均匀的原料放入待挤出仓经过喂料器(30r/min)加入双螺杆挤出机,调节双螺杆挤出机温度(12个温度段):140℃—145℃—145℃—150℃—155℃—160℃—160℃—160℃—158℃—158℃—155℃—155℃,挤出机螺杆转速300r/min。料条经过水槽冷却,风机吹干,切粒,然后在90℃下烘干,得到弹性体包覆层组合物粒料。
2)聚丙烯复合纱线的制备
将步骤1)得到的弹性体包覆层组合物粒料与聚丙烯长丝在包覆丝螺杆挤出机中进行熔融纺丝,得到皮芯结构的复合长丝,通过张力控制卷绕成卷。其中聚丙烯长丝构成内芯,外皮为步骤1)所得组合物制成的弹性体包覆层。主机转速为30r/min,牵引转速为90r/min,各区加工温度为168℃-176℃-180℃-182℃-180℃,烘干温度为70℃,烘干时间为1小时。所得复合纱线的线径为0.50mm。
实施例3
1)包覆层组合物粒料的制备
将聚丙烯树脂50重量份、热塑性弹性体30重量份、DOPO基阻燃剂5重量份、EVA 3重量份加入搅拌机,高速运转5分钟(频率50HZ,温度达到45℃),加入抗氧剂1010 0.1重量份、光稳定剂944 0.09重量份、紫外线稳定剂UV-326 0.12重量份,搅拌2分钟,加入二氧化钛6重量份、爽滑剂EBO 0.13重量份、滑石粉9重量份搅拌5分钟。将搅拌均匀的原料放入待挤出仓经过喂料器(30r/min)加入双螺杆挤出机,调节双螺杆挤出机温度(12个温度段):140℃—145℃—145℃—150℃—155℃—160℃—160℃—160℃—158℃—158℃—155℃—155℃,挤出机螺杆转速300r/min。料条经过水槽冷却,风机吹干,切粒,然后在90℃下烘干,得到弹性体包覆层组合物粒料。
2)聚丙烯复合纱线的制备
将步骤1)得到的弹性体包覆层组合物粒料与聚丙烯长丝在包覆丝螺杆挤出机中进行熔融纺丝,得到皮芯结构的复合长丝,通过张力控制卷绕成卷。其中聚丙烯长丝构成内芯,外皮为步骤1)所得组合物制成的弹性体包覆层。主机转速为30r/min,牵引转速为90r/min,各区加工温度为168℃-176℃-180℃-182℃-180℃,烘干温度为70℃,烘干时间为1小时。所得复合纱线的线径为0.50mm。
比较例1
根据实施例1的技术方案,将其中的阻燃剂替换为相同用量的三聚氰胺多磷酸盐MPP。
比较例2
根据实施例1的技术方案,将其中的阻燃剂替换为相同用量的次膦酸金属盐Exolit OP 930。
比较例3
根据实施例1的技术方案,将其中的阻燃剂替换为相同用量的三(1-氧代-1-磷杂-2,6,7-三氧杂双环辛烷-4-亚甲基)磷酸酯(Trimer)。
比较例4
根据实施例1的技术方案,将其中的阻燃剂替换为相同用量的十溴二苯醚。
比较例5
根据实施例1的技术方案,将其中的阻燃剂替换为15重量份的MPP。
比较例6
根据实施例1的技术方案,将其中的阻燃剂替换为15重量份的次膦酸金属盐Exolit OP 930。
比较例7
根据实施例1的技术方案,将其中的阻燃剂替换为15重量份Trimer。
表1纱线性能测试
表1中氧指数根据GB/T 5454进行测定;拉伸强力和断裂伸长率根据GB/T 3916进行测定。
由表1可以看出,采用本发明中所述无卤阻燃剂的实施例1-3与采用卤系阻燃剂的比较例4(阻燃剂为十溴二苯醚)相比,具有基本上水平相当的LOI值,这表明本发明中的无卤阻燃剂具有卤系阻燃剂良好的阻燃效果,而由于不含卤素本发明的产品在其它方面更具优势。相比于使用同等含量无卤阻燃剂MPP、次膦酸金属盐和Trimer的比较例1-3,实施例1-3具有更高的氧指数,取得了更好的阻燃性能。而当MPP、次膦酸金属盐和Trimer的加入量增加至15份时(对应于比较例5-7),才能够达到实施例1-3近似水平的阻燃效果,但由于阻燃剂含量增大,对纱线的力学性能带来了不利影响,导致拉伸强度和断裂伸长率明显低于实施例1-3。
实施例4
将实施例1制得的纱线经梭织工艺制成358g/m2的平纹面料。
比较例8
采用与实施例4相同的工艺,将比较例4(阻燃剂为十溴二苯醚)的纱线制成同样规格的面料。
表2烟密度测试
测试样品 | 实施例4 | 比较例8 |
D<sub>s1.5</sub> | 7.5 | 97.0 |
D<sub>s4.0</sub> | 22.6 | 106.0 |
D<sub>s,max</sub> | 60.6 | 125.2 |
T(D<sub>s,max</sub>)秒 | 1176 | 502 |
D<sub>c</sub> | 4.5 | 10.1 |
D<sub>s10</sub> | 35.1 | 122.3 |
Ds1.5—测试开始1.5min时的比光密度;
Ds4.0—测试开始4.0min时的比光密度;
Ds,max—整个测试期间(20min)内最大比光密度;
T(Ds,max)秒—发生最大比光密度Ds,max时的时间,单位秒;
Dc—清晰光束校正因子;
Ds10—测试开始10min时的比光密度。
烟密度根据GB/T 8323.2进行测定(样品厚度约为0.8mm,样品尺寸75mm×75mm,辐射强度25kW/m2)。
从表2中可以看出,实施例4的比光密度明显小于比较例8,可知实施例4的发烟量更小,这表明相比于采用卤系阻燃剂的样品,本发明的无卤阻燃制品在燃烧时具有发烟量小的优点。
Claims (10)
1.一种阻燃聚丙烯复合纱线,其特征在于,具有皮芯结构,其中内芯为聚丙烯长丝,外皮为弹性体包覆层材料;
所述弹性体包覆层材料的原料包括聚丙烯树脂30~80重量份,热塑性弹性体15~50重量份,DOPO基阻燃剂1~10重量份,以及任选的助剂1~50重量份。
2.如权利要求1所述的阻燃聚丙烯复合纱线,其特征在于,所述聚丙烯树脂的熔体流动速率为1~30g/10min。
3.如权利要求1或2所述的阻燃聚丙烯复合纱线,其特征在于,所述热塑性弹性体选自SBS、氢化SBS、SEBS、氢化SEBS、SIS、氢化SIS、聚氨酯类热塑性弹性体、乙烯-辛烯共聚物(POE)热塑性弹性体、三元乙丙橡胶(EPDM)热塑性弹性体、丙烯-乙烯共聚物热塑性弹性体中的一种或几种。
4.如权利要求1-3任一项所述的阻燃聚丙烯复合纱线,其特征在于,所述DOPO基阻燃剂选择具有通式(A)和/或通式(B)表示的物质:
其中R1和R2是相同的或不同的和各自独立地表示烷基、烷氧基、芳基、芳氧基或芳烷基;n和m是0-4的整数;和R3表示衍生自不饱和二元羧酸或其酸酐的残基;
其中R1表示氢、甲基或乙基;R2表示残基-(CH2)m-O-R1;A是具有2-6个碳原子的支化的或未支化的亚烷基或任选经取代的芳族桥连基;和n是55-110的整数;芳香族桥连基上的取代基选自烷基、烷氧基、芳基、芳氧基、芳烷基和烷芳基。
5.如权利要求1-4任一项所述的阻燃聚丙烯复合纱线,其特征在于,所述助剂选自抗氧剂、光稳定剂、紫外线光稳剂、填料、爽滑剂、抗菌剂、颜料、耐老化剂、抗静电剂中的一种或几种。
6.如权利要求1所述的阻燃聚丙烯复合纱线,其特征在于,所述聚丙烯树脂40~70重量份,所述热塑性弹性体20~45重量份,所述DOPO基阻燃剂1.5~7重量份。
7.一种权利要求1-6任一项所述阻燃聚丙烯复合纱线的制备方法,包括以下步骤:
1)包覆层组合物粒料的制备
将聚丙烯树脂、热塑性弹性体、DOPO基阻燃剂、任选的助剂混合均匀得到共混物,将上述共混物进行熔融加工,得到粒料;
2)聚丙烯复合纱线的制备
将步骤1)得到的粒料熔融包覆于聚丙烯长丝表面,得到皮芯结构的复合纱线。
8.如权利要求7所述的制备方法,其特征在于,步骤1)中熔融加工设备为螺杆挤出机,挤出机加工温度为120~180℃,螺杆转速100~500r/min;步骤2)中熔融加工温度为130~200℃。
9.一种含有权利要求1-6任一项所述阻燃聚丙烯复合纱线的织物。
10.如权利要求9所述的织物,其特征在于,所述织物由权利要求1-6任一项所述阻燃聚丙烯复合纱线制成,或者由权利要求1-6任一项所述阻燃聚丙烯复合纱线与其他纤维或纱线混纺制成。
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