CN116410577A - 耐冲阻燃聚酯材料 - Google Patents
耐冲阻燃聚酯材料 Download PDFInfo
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- 239000003063 flame retardant Substances 0.000 title claims abstract description 75
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 title claims abstract description 71
- 239000000463 material Substances 0.000 title claims abstract description 64
- 229920000728 polyester Polymers 0.000 title claims abstract description 41
- 239000003963 antioxidant agent Substances 0.000 claims abstract description 24
- 230000003078 antioxidant effect Effects 0.000 claims abstract description 21
- 229920005989 resin Polymers 0.000 claims abstract description 20
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- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 12
- 239000000945 filler Substances 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 7
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 6
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 6
- 239000003365 glass fiber Substances 0.000 claims description 6
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 claims description 6
- 229910052757 nitrogen Inorganic materials 0.000 claims description 6
- 229910052698 phosphorus Inorganic materials 0.000 claims description 6
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- 229920005648 ethylene methacrylic acid copolymer Polymers 0.000 claims description 5
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- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 4
- 239000002131 composite material Substances 0.000 claims description 4
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- 239000002530 phenolic antioxidant Substances 0.000 claims description 3
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 claims description 3
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- 229920006124 polyolefin elastomer Polymers 0.000 claims description 3
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- WXMKPNITSTVMEF-UHFFFAOYSA-M sodium benzoate Chemical compound [Na+].[O-]C(=O)C1=CC=CC=C1 WXMKPNITSTVMEF-UHFFFAOYSA-M 0.000 claims description 3
- 235000010234 sodium benzoate Nutrition 0.000 claims description 3
- 239000004299 sodium benzoate Substances 0.000 claims description 3
- 159000000000 sodium salts Chemical class 0.000 claims description 3
- YKIBJOMJPMLJTB-UHFFFAOYSA-M sodium;octacosanoate Chemical compound [Na+].CCCCCCCCCCCCCCCCCCCCCCCCCCCC([O-])=O YKIBJOMJPMLJTB-UHFFFAOYSA-M 0.000 claims description 3
- DXZMANYCMVCPIM-UHFFFAOYSA-L zinc;diethylphosphinate Chemical group [Zn+2].CCP([O-])(=O)CC.CCP([O-])(=O)CC DXZMANYCMVCPIM-UHFFFAOYSA-L 0.000 claims description 3
- 239000000454 talc Substances 0.000 claims description 2
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- 238000002425 crystallisation Methods 0.000 description 7
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- ZQKXQUJXLSSJCH-UHFFFAOYSA-N melamine cyanurate Chemical compound NC1=NC(N)=NC(N)=N1.O=C1NC(=O)NC(=O)N1 ZQKXQUJXLSSJCH-UHFFFAOYSA-N 0.000 description 6
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- 238000004064 recycling Methods 0.000 description 3
- 239000004114 Ammonium polyphosphate Substances 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 235000019826 ammonium polyphosphate Nutrition 0.000 description 2
- 229920001276 ammonium polyphosphate Polymers 0.000 description 2
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- 238000003763 carbonization Methods 0.000 description 2
- 238000002485 combustion reaction Methods 0.000 description 2
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- 231100000252 nontoxic Toxicity 0.000 description 2
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- 229920000877 Melamine resin Polymers 0.000 description 1
- PYLQXBCYFPDGBI-UHFFFAOYSA-N Nc1nc(N)nc(N)n1.OCC(CO)(CO)COP(O)(=O)OP(O)(O)=O Chemical compound Nc1nc(N)nc(N)n1.OCC(CO)(CO)COP(O)(=O)OP(O)(O)=O PYLQXBCYFPDGBI-UHFFFAOYSA-N 0.000 description 1
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- 239000000654 additive Substances 0.000 description 1
- 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 1
- 238000004134 energy conservation Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000011010 flushing procedure Methods 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 230000003014 reinforcing effect Effects 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 235000012222 talc Nutrition 0.000 description 1
- 239000001038 titanium pigment Substances 0.000 description 1
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
- C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
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- C08G63/18—Dicarboxylic acids and dihydroxy compounds the acids or hydroxy compounds containing carbocyclic rings
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Abstract
本发明提供一种耐冲阻燃聚酯材料,包括PET树脂、晶核剂、阻燃剂、抗氧化剂、棒状填充补强材以及兼容剂。PET树脂包括原生粒或环保回收粒,可实现回收材料导入的需求。
Description
技术领域
本发明涉及一种聚酯材料,且特别涉及一种耐冲阻燃聚酯材料。
背景技术
未来市场逐渐导向循环经济与节能减碳的趋势,在此市场潮流下,以低碳排放的回收再生材料导入产品为未来产业发展重要目标。回收材料导入系在机械性能与加工性不受影响的前提下,导入环保再生材料,将有助于达到全球减塑节能的目标。
PET聚酯材料为塑料材料中回收产业链最健全的材料,其回收来源包括:宝特瓶、离型膜、工业膜材等。透过固态聚合、扩链改质,能使回收PET的机械物性与原生料(VirginPET)相当。然而,其耐冲击性、结晶速度、刚性(弯曲模数)、阻燃性均无法达到计算机部件、事务机壳、电池电器外壳等高阶电子电器产品需求。
基于上述,开发出一种耐冲阻燃聚酯材料,可有效地改善耐冲击性、结晶速度、刚性(弯曲模数)、阻燃性,为本领域技术人员亟欲发展的目标。
发明内容
本发明提供一种耐冲阻燃聚酯材料,透过磷系与氮系阻燃剂偕同提升PET材料的阻燃性,实现无卤无毒阻燃的产品,并透过混练改质技术改善PET材料结晶速度慢、耐冲击强度及刚性不足的问题,使其可射出成形应用于计算机部件、事务机壳、电池电器外壳、链接器等电子电器产品。
本发明的耐冲阻燃聚酯材料包括PET树脂、晶核剂、阻燃剂、抗氧化剂、棒状填充补强材以及兼容剂。
在本发明的一实施例中,以耐冲阻燃聚酯材料的总重量计,PET树脂的添加量为58wt%至72wt%,晶核剂的添加量为0.5wt%至2wt%,阻燃剂的添加量为10wt%至18wt%,抗氧化剂的添加量为0.1wt%至1wt%,棒状填充补强材的添加量为10wt%至15wt%,相容剂的添加量为3wt%至6wt%。
在本发明的一实施例中,PET树脂包括原生粒或环保回收粒。环保回收粒的来源可包括瓶用回收粒、膜材回收粒、织物回收粒或工业回收环保再生聚酯粒(离型膜等)。
在本发明的一实施例中,PET树脂的相对黏度为0.55至1.0。
在本发明的一实施例中,晶核剂包括有机晶核剂、无机晶核剂或其共混物。
在本发明的一实施例中,有机晶核剂包括有机钠盐类,所述有机钠盐类包括苯甲酸钠、褐煤酸钠或乙烯-甲基丙烯酸共聚物(EMAA)。
在本发明的一实施例中,无机晶核剂包括无机微奈米粉体,无机微奈米粉体包括滑石粉、钛白粉、二氧化硅或碳酸钙。
在本发明的一实施例中,阻燃剂为无卤阻燃剂,无卤阻燃剂包括氮系阻燃剂、磷系阻燃剂或其复合共混物。
在本发明的一实施例中,抗氧化剂包括受阻酚系抗氧化剂、酚类抗氧化剂、混合型抗氧化剂、亚磷酸酯系抗氧化剂、复合型抗氧化剂或其组合。
在本发明的一实施例中,棒状填充补强材包括经硅氧烷改质的玻璃纤维。
在本发明的一实施例中,相容剂包括乙烯-丙烯酸甲酯-甲基丙烯酸缩水甘油酯共聚物(E-MA-GMA)、聚烯烃弹性体接枝甲基丙烯酸缩水甘油酯(POE-g-GMA)、聚乙烯接枝甲基丙烯酸缩水甘油酯(PE-g-GMA)或其组合。
基于上述,本发明提供一种耐冲阻燃聚酯材料,透过磷系与氮系阻燃剂偕同提升PET材料的阻燃性,实现无卤无毒阻燃的产品,并透过混练改质技术改善PET材料结晶速度慢、耐冲击强度及刚性不足的问题,使其可射出成形应用于计算机部件、事务机壳、电池电器外壳、链接器等电子电器产品。此外,本发明所使用的PET原料,除了PET原生粒(Virginresin)之外,更可以环保回收PET(PCR-PET)导入,其机械性能、阻燃特性及加工性与原生粒相当,因此,可实现回收材料导入的需求。
附图说明
无
具体实施方式
以下,将详细描述本发明的实施例。然而,这些实施例为例示性,且本发明揭露不限于此。
在本文中,由“一数值至另一数值”表示的范围,是一种避免在说明书中一一列举该范围中的所有数值的概要性表示方式。因此,某一特定数值范围的记载,涵盖该数值范围内的任意数值以及由该数值范围内的任意数值界定出的较小数值范围,如同在说明书中说明文写出该任意数值和该较小数值范围一样。
本发明的耐冲阻燃聚酯材料包括PET树脂、晶核剂、阻燃剂、抗氧化剂、棒状填充补强材以及兼容剂。以下,将对上述各种组分进行详细说明。
PET树脂
在本实施例中,PET树脂可包括原生粒或环保回收粒,其中环保回收粒的来源可包括瓶用回收粒、膜材回收粒、织物回收粒或工业回收环保再生聚酯粒(离型膜等),以实现回收材料导入的需求,但本发明并不以此为限。PET树脂的相对黏度例如是0.55至1.0。以耐冲阻燃聚酯材料的总重量计,PET树脂的添加量例如是58wt%至72wt%。
晶核剂
在本实施例中,晶核剂可包括有机晶核剂、无机晶核剂或其共混物。有机晶核剂可包括有机钠盐类,有机钠盐类可包括苯甲酸钠、褐煤酸钠或乙烯-甲基丙烯酸共聚物(EMAA)。无机晶核剂可包括无机微奈米粉体,无机微奈米粉体可包括滑石粉、钛白粉、二氧化硅或碳酸钙。以耐冲阻燃聚酯材料的总重量计,晶核剂的添加量例如是0.5wt%至2wt%,较佳例如是1wt%至1.5wt%。加入晶核剂可提升PET材料的结晶固化速度,进而提升其加工性。
阻燃剂
在本实施例中,为符合产品的RoHS及无卤素需求,阻燃剂为无卤阻燃剂,所述无卤阻燃剂可包括氮系阻燃剂、磷系阻燃剂或其复合共混物。磷系阻燃剂可包括双磷酸季戊四醇酯蜜胺盐(MPP)、聚磷酸铵(APP)、磷酸甲苯二甲苯酯或次磷酸盐类。氮系阻燃剂可包括三聚氰胺氰尿酸盐(MCA)、三聚氰胺等。更详细而言,以次磷酸盐类与三聚氰胺氰尿酸盐(MCA)复配效果较佳,次磷酸盐类与三聚氰胺氰尿酸盐(MCA)比例例如是4:1至1:1,最佳比例例如是2:1。以耐冲阻燃聚酯材料的总重量计,阻燃剂的添加量例如是10wt%至18wt%。阻燃剂可透过表面成碳性来抑制PET的燃烧,提升阻燃特性。
抗氧化剂
在本实施例中,抗氧化剂可包括受阻酚系抗氧化剂、酚类抗氧化剂、混合型抗氧化剂、亚磷酸酯系抗氧化剂、复合型抗氧化剂或其组合。以耐冲阻燃聚酯材料的总重量计,抗氧化剂的添加量例如是0.1wt%至1wt%。抗氧化剂可提升材料的耐热与加工性。
棒状填充补强材
在本实施例中,棒状填充补强材可包括经硅氧烷改质的玻璃纤维,表面经硅氧烷改质可提升兼容性,玻纤直径例如是10μm至13μm,切股长度例如是3mm至4mm。以耐冲阻燃聚酯材料的总重量计,棒状填充补强材的添加量例如是10wt%至15wt%。棒状填充补强材可有效提升材料冲击强度与刚性,其中物性提升效果与棒状补强材的分散程度直接相关,因此,需同步导入-GMA接枝的兼容剂,以提升棒状填充补强材于PET中的分散性。
相容剂
在本实施例中,相容剂包括乙烯-丙烯酸甲酯-甲基丙烯酸缩水甘油酯共聚物(E-MA-GMA)、聚烯烃弹性体接枝甲基丙烯酸缩水甘油酯(POE-g-GMA)、聚乙烯接枝甲基丙烯酸缩水甘油酯(PE-g-GMA)或其组合。以耐冲阻燃聚酯材料的总重量计,兼容剂的添加量例如是3wt%至6wt%。兼容剂可提升棒状填充补强材与PET树脂之间的兼容性,以提升材料补强效果。
本发明耐冲阻燃聚酯材料的改质过程,包括以下步骤。首先,先将PET树脂、晶核剂、抗氧化剂及相容剂在主进料温度230℃至250℃加入押出机。之后,在进料温度250℃至270℃将阻燃剂加入押出机。接下来,在进料温度255℃至275℃,将棒状填充补强材加入押出机。最后,在真空温度245℃至265℃,即可制成本发明的耐冲阻燃聚酯材料。
以下,藉由实验例来详细说明上述本发明的耐冲阻燃聚酯材料。然而,下述实验例并非用以限制本发明。
实验例
为了证明本发明所提出的聚酯组成物具有优异的机械物性,更可进一步具有良好的阻燃性能,以下特别作此实验例。
测试方法
比重:ASTM D792
拉伸强度、延伸率:ASTM D638
弯曲强度、弯曲模数:ASTM D790
阻燃:UL94
材料性质评估
将计算机部件用PC+ABS、未改质PET、未经阻燃改质的15%玻纤补强PET(PET+15%GF)以及本发明的耐冲阻燃聚酯材料以上述测试方法进行测试,测试结果列于以下表1中。在表1中,本发明的耐冲阻燃聚酯材料包括63.7wt%PET树脂、1wt%晶核剂、15wt%阻燃剂、0.3wt%抗氧化剂、15wt%棒状填充补强材以及5wt%兼容剂。
由以下表1可得知,相较于未改质PET以及未经阻燃改质的15%玻纤补强PET(PET+15%GF),本发明的耐冲阻燃聚酯材料与计算机部件用PC+ABS同样具有阻燃特性,同时具有良好的机械物性。
表1
综上所述,本发明的耐冲阻燃聚酯材料加入阻燃剂、晶核剂及棒状填充补强材等添加剂以进行改质。加入晶核剂可提升PET材料的结晶固化速度,进而提升其加工性。阻燃剂可透过表面成碳性来抑制PET的燃烧,提升阻燃特性。棒状填充补强材则能有效提升材料冲击强度与刚性,其中物性提升效果与棒状补强材的分散程度直接相关,因此,需同步导入-GMA接枝的兼容剂以提升棒状补强材于PET的分散性。抗氧化剂可提升材料的耐热与加工性。如此一来,能够有效地改善PET材料结晶速度慢、耐冲击强度及刚性不足的问题,使其可射出成形应用于计算机部件、事务机壳、电池电器外壳、链接器等电子电器产品。此外,本发明所使用的PET原料,除了PET原生粒(Virgin resin)之外,更可以环保回收PET(PCR-PET)导入,其机械性能、阻燃特性及加工性与原生粒相当,因此,可实现回收材料导入的需求,更符合循环经济的趋势。
最后应说明的是:以上各实施例仅用以说明本发明的技术方案,而非对其限制;尽管参照前述各实施例对本发明进行了详细的说明,本领域的普通技术人员应当理解:其依然可以对前述各实施例所记载的技术方案进行修改,或者对其中部分或者全部技术特征进行等同替换;而这些修改或者替换,并不使相应技术方案的本质脱离本发明各实施例技术方案的范围。
Claims (11)
1.一种耐冲阻燃聚酯材料,其特征在于,包括:
PET树脂;
晶核剂;
阻燃剂;
抗氧化剂;
棒状填充补强材;以及
相容剂。
2.根据权利要求1所述的耐冲阻燃聚酯材料,其特征在于,以所述耐冲阻燃聚酯材料的总重量计,所述PET树脂的添加量为58wt%至72wt%,所述晶核剂的添加量为0.5wt%至2wt%,所述阻燃剂的添加量为10wt%至18wt%,所述抗氧化剂的添加量为0.1wt%至1wt%,所述棒状填充补强材的添加量为10wt%至15wt%,所述相容剂的添加量为3wt%至6wt%。
3.根据权利要求1所述的耐冲阻燃聚酯材料,其特征在于,所述PET树脂包括原生粒或环保回收粒。
4.根据权利要求1所述的耐冲阻燃聚酯材料,其特征在于,所述PET树脂的相对黏度为0.55至1.0。
5.根据权利要求1所述的耐冲阻燃聚酯材料,其特征在于,所述晶核剂包括有机晶核剂、无机晶核剂或其共混物。
6.根据权利要求5所述的耐冲阻燃聚酯材料,其特征在于,所述有机晶核剂包括有机钠盐类,所述有机钠盐类包括苯甲酸钠、褐煤酸钠或乙烯-甲基丙烯酸共聚物。
7.根据权利要求5所述的耐冲阻燃聚酯材料,其特征在于,所述无机晶核剂包括无机微奈米粉体,所述无机微奈米粉体包括滑石粉、钛白粉、二氧化硅或碳酸钙。
8.根据权利要求1所述的耐冲阻燃聚酯材料,其特征在于,所述阻燃剂为无卤阻燃剂,所述无卤阻燃剂包括氮系阻燃剂、磷系阻燃剂或其复合共混物。
9.根据权利要求1所述的耐冲阻燃聚酯材料,其特征在于,所述抗氧化剂包括受阻酚系抗氧化剂、酚类抗氧化剂、混合型抗氧化剂、亚磷酸酯系抗氧化剂、复合型抗氧化剂或其组合。
10.根据权利要求1所述的耐冲阻燃聚酯材料,其特征在于,所述棒状填充补强材包括经硅氧烷改质的玻璃纤维。
11.根据权利要求1所述的耐冲阻燃聚酯材料,其特征在于,所述相容剂包括乙烯-丙烯酸甲酯-甲基丙烯酸缩水甘油酯共聚物、聚烯烃弹性体接枝甲基丙烯酸缩水甘油酯、聚乙烯接枝甲基丙烯酸缩水甘油酯或其组合。
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