CN1997698B - 用不含卤素的添加剂阻燃的聚酯组合物 - Google Patents
用不含卤素的添加剂阻燃的聚酯组合物 Download PDFInfo
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- CN1997698B CN1997698B CN2004800437535A CN200480043753A CN1997698B CN 1997698 B CN1997698 B CN 1997698B CN 2004800437535 A CN2004800437535 A CN 2004800437535A CN 200480043753 A CN200480043753 A CN 200480043753A CN 1997698 B CN1997698 B CN 1997698B
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- 229910001379 sodium hypophosphite Inorganic materials 0.000 description 1
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- C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
- C08L67/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
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- 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
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- C08K5/49—Phosphorus-containing compounds
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- C08K5/52—Phosphorus bound to oxygen only
- C08K5/521—Esters of phosphoric acids, e.g. of H3PO4
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Abstract
本发明涉及基于聚酯树脂的无卤素阻燃热塑性模压组合物,其制备方法和相应的无卤素阻燃制品。本发明的组合物包含0,1-30重量%的至少一种次磷酸铝作为无卤素阻燃添加剂(除其它无卤素阻燃添加剂混合物之外)及5-95重量%的至少一种基于聚酯特别是线型聚酯树脂的聚合物。
Description
发明主题
本发明涉及基于聚酯树脂的无卤素阻燃热塑性模压组合物,其制备方法和相应的无卤素阻燃制品。
发明背景
市场对无卤素阻燃添加剂的兴趣日益增加。对这些产品的大量需求在于:增强或不增强制品的高阻燃效应、本色淡、热稳定性好、机械和电性能好、成本低。
除了含卤素系统外,用于热塑性聚合物的无卤素阻燃(FR)添加剂有以下这些物质:
-无机阻燃剂,例如属于金属氢氧化物一类(氢氧化镁和氢氧化铝)。这些产品必须大量使用才有效,因此相关产品的机械性能受到极大的损害。
-三聚氰胺衍生物,如氰脲酸三聚氰胺、(多)磷酸三聚氰胺或焦磷酸三聚氰胺。这些产品没有克服某些热塑性聚合物加工条件的足够热稳定性,对于聚酯来说也不是完全令人满意的。
-磷酸的有机衍生物,如磷酸酯(P的化合价=+5),也是人们熟知的无卤素阻燃添加剂。这些产品不是十分有效的,而且它们具有一些缺点:遇热有渗出倾向,一般为液体状态因而难以操作,水解稳定性不足,可能影响终产品的机械和热性能。虽然新的高分子量产品带来了很多进步,例如具有来自双酚A(JP No.6-228426)的结构的磷酸酯缩合物,但是,有关的聚合物制品因可燃性与抗冲击、热稳定性和耐候性的结合不平衡而不具有能完全令人满意的性能。
-红磷,已被证明是有效的阻燃添加剂(WO:98/30632,WO:99/27016,JPA:11-335531,US 2003/0018108),但不幸的是,其固有的深红色使相应的聚合物产品难以用作天然或浅色应用。
-有机亚膦酸盐,特别是关于铝和锌的亚膦酸盐,近来被描述为新的一族聚酯的无卤素阻燃添加剂(US 5,281,637;EP 0699708;EP0899296;WO 09739053),特别是与含氮化合物合用。从成本/性能的角度来看,这些产品并非完全能令人满意。
-次磷酸金属盐,或者称作次磷酸盐或无机亚膦酸盐,也被报告作为无卤素阻燃添加剂,用于阻燃的含苯乙烯聚合物(US.4,618,633)。其中,次磷酸钙在与含氮化合物如焦磷酸三聚氰胺、磷酸脲或多磷酸三聚氰胺合用时,在PBT上制得的填充玻璃的聚酯树脂组分中特别有效(US:6,503,969,WO:098117720;DE:10137930,EP:0919591)。但是,次磷酸钙作为单独的添加剂使用时及与氰脲酸三聚氰胺合用时并不显示作用。
发明目的
本发明的一个目的是提供无卤素阻燃热塑性模压组合物及基于聚酯树脂特别是线型聚酯树脂的制品,它们有或无玻璃纤维加固而保持良好的机械性能、良好的耐候性,以及良好的阻燃剂等级。
本发明的另一个目的是提供无卤素阻燃模塑组合物及相应的基于聚酯树脂特别是线型聚酯树脂的模塑制品,它们特别是玻璃纤维加固的聚酯,表现明显的阻燃性能和良好的电性能。
本发明的还有一个目的是提供无卤素阻燃模塑组合物及基于聚酯树脂特别是线型聚酯树脂的制品,它们特别是玻璃纤维加固的,按照UL 94分类标准归为VO,按照IEC 61335-1,通过了775℃下的GWIT试验。
本发明的再一个目的是提供无卤素阻燃模塑组合物及基于聚酯树脂特别是线型聚酯树脂的制品的制备方法。
发明的描述
本发明涉及一种热塑性组合物,包含至少一种次磷酸铝(亚膦酸铝(aluminium phosphinate))作为无卤素阻燃剂及至少一种基于聚酯特别是线型聚酯树脂的聚合物。
按照本发明,热塑性组合物包含:
A)5-95重量%的至少一种聚酯树脂;
B)0,1-30重量%的至少一种次磷酸铝作为无卤素阻燃添加剂,除其它无卤素阻燃添加剂混合物之外;
C)0,5-10重量%的至少一种添加剂,选自:加工助剂、热和加工稳定剂、紫外稳定剂、抗滴下剂(PTFE-聚四氟乙烯)、色素、脱模剂、橡胶弹性聚合物、成核剂或它们的混合物;
D)0%-50重量%无机填充剂。
A-D组分的总重量百分比为100%。
令人惊讶地发现,用包含至少一种次磷酸铝(亚膦酸铝)作为无卤素阻燃添加剂及至少一种基于线型聚酯树脂的聚合物的热塑性模塑组合物和模塑制品,满意地达到了本发明的目的。
下面详细地描述本发明,特别关注包含在本发明的阻燃热塑性树脂组合物中的组分。
组分A):
组合物包含作为组分A)的5-95%(较佳为20-70%,更佳为35-60%)的至少一种热塑性聚酯树脂。
在本发明的意义上,热塑性聚酯树脂是基于至少一种芳族二羧酸和至少一种脂族或芳族二羟基化合物的任何聚对苯二酸亚烷基酯。
这样的聚对苯二酸亚烷基酯本身是已知的,在文献中有描述。它们由芳族二羧酸或其酯与脂族或芳族二羟基化合物反应而制得。优选的芳族二羧酸包括对苯二甲酸和间苯二酸或其混合物。优选不多于10摩尔%芳族二羧酸可被脂族或环脂族二羧酸如己二酸、壬二酸、癸二酸或环己二羧酸替代。
特别优选的聚酯A)为由2-6个碳原子的链烷二醇衍生而来的聚对苯二酸亚烷基酯,特别优选聚对苯二酸乙二酯和聚对苯二酸丁二酯和/或它们的混合物。
聚酯A)的粘数为50-220,较佳为80-150,按照ISO 1628,以苯酚/o-二氯苯混合物(1∶1)中浓度为0.5%wt的溶液所测得值。
这样的聚酯还可包含≤100mval/kg(更佳为≤40mval/kg)的羧基端基,如电位滴定法所测值。
例如,本发明的一种模塑组合物包含聚对苯二酸乙二酯(PET)和聚对苯二酸丁二酯(PBT)混合物作为组分A),其中PET聚合物为聚合物总重量的10%-30重量%。
还有一个有利的方面是在与新鲜PBT聚合物组成的混合物中使用回收再利用的PET(也称作PET废料)。
再循环的材料通常为:
-后工业产品,如从注模而来的熔渣,从注模和挤压而来的起始料,或从挤压机压片或压膜而来的边角料;
-后消费者再循环材料,如吹塑制成的PET瓶,在终端消费者使用后经收集和处理而得到。
再循环的材料可以小丸状或再研磨后使用。
聚酯可能在加工过程中并由于水分的存在而发生水解,因此宜将再循环和新鲜的材料预干燥至残留的水分含量低于0.6%。
从芳族二羧酸和芳族二羟基化合物而来的完全芳香性聚酯也可作为组分A)。
合适的芳族二羧酸为例如上述聚对苯二酸亚烷基酯。作为芳族二羟基化合物,下表所列产品或其混合物是特别优选的:
4,4′-二羟基联苯;
2,4-二(4′-羟基苯基)-2-甲基丁烷;
αα′-二(4-羟基苯基)-p-二异丙基苯;
2,2-二(3′-氯-4′-羟基苯基)丙烷;
2,2′-二(4′-羟基苯基)丙烷;
1,1-二(4′-羟基苯基)环己烷;
3,4′-二羟基苯甲酮;
4,4′-二羟基二苯砜;
2,2-二(3′5′-二甲基-4′-羟基苯基)丙烷。
按照本发明,也可使用聚对苯二酸亚烷基酯和完全芳族聚酯的混合物。
为本发明的目的,组分A)还包括前述聚酯与聚碳酸酯的混合物,后者可由芳族二羟基化合物如双酚A(Bisphenol A)与光气聚合而成。聚碳酸酯的量可为≤50%wt(以组分A)为100%wt)。
还可以使用如文献US 3,651,014报告所得到的聚酯嵌段共聚物或共聚酯。
组分B):
新型模塑组合物包含作为组分B)的化学式Al(H2PO2)3对应的无机亚膦酸铝,占模塑组合物重量的0.1-30重量%,较佳为2%-20重量%。
亚膦酸铝,也称作次磷酸铝,可单独使用,或与其它无卤素阻燃添加剂合用。
如文献(J.Chem.Soc.1952,2945)报道,次磷酸铝可由次磷酸钠与氯化铝在约100℃的水溶液中反应而得到。
次磷酸铝是热稳定性的,加工时不产生聚合物的分解,它不影响模塑组合物的塑模及聚合物制品的机械和美学性能。
产品略溶于水,它不影响聚合物制品的电学性能,特别是CTI值;此外,它几乎不被水提出,使聚合物制品在寿命期内即使暴露于严峻的条件下(高温和高湿度)也具有阻燃效应。
包含次磷酸铝的聚合物组合物显示:
·按照UL94标准,在厚度为0.8mm时具有V0良好阻燃等级;
·按照IEC 61335-1标准进行试验,大于1mm厚度的任何厚度均具有通过960℃ GWFI(白炽金属丝可燃指数)和775℃ GWIT(白炽金属丝着火温度)的对白炽金属丝的抗力;
·按照IEC 112用标准溶液A测试,具有CTI值(相比起痕指数)约600V的良好电学性能。
为了达到上述性能,可取的是,亚膦酸铝粉末的平均粒度(D50%)低于40μm,最高粒度低于100μm。更可取的是,D50%应低于15μm,最高粒度低于30μm。
本发明与次磷酸铝合用的不含卤素阻燃添加剂较佳为:
·有机磷酯类,包括如磷酸三苯酯(TPP)、磷酸三甲苯酯、磷酸三(二甲苯)酯(trixylilenphosphate)、磷酸三甲酯、磷酸三丁酯、磷酸三辛酯或类似的产品。最优选的产品为:双酚A二(联苯基)磷酸酯和间苯二酚二(联苯基)磷酸酯。这两个产品均有市售品,例如,AkzoNobel phosphorus chemicals制造的商品名为Fyroflex RDP和Fyroflex BDP的产品。
·含氮产品。在本发明的范围内,三聚氰胺焦磷酸盐、三聚氰胺多磷酸盐、三聚氰胺硼酸盐、氰尿酸胍、氰尿酸脲、苯并胍胺及其与磷酸和焦磷酸、三羟基乙基异氰酸酯的加合物是合适的产品。最佳的产品是氰尿酸三聚氰胺,它可由等摩尔量三聚氰胺和氰尿酸在90-100℃水溶液中反应制得。市售产品是平均粒度1.5μm-7μm的白色粉末。
为了减少混合和模塑时产品的流出,且不影响聚合物终产品的机械和热性能,上述活性助剂(co-agent)的量相应于次磷酸铝的1/1-1/3。
组分C):加工助剂、稳定剂等。
新型模塑组合物还可包含作为组分C)的一种或几种下列常规加工助剂,如热稳定剂、紫外稳定剂、润滑剂、脱模剂、着色剂、增塑剂、抗冲改性树脂、抗滴下剂、成核剂、抗酸成分等。更特别的是,所述添加剂,直接使用或以混合物形式使用,其量可为0.5-10重量%。
热稳定剂的例子:有空间位阻的酚类和/或芳族亚磷酸盐或亚膦酸盐类、氢醌类及其混合物,其用量为例如聚合物组合物重量的1%重量。
紫外稳定剂,其常用量为≤聚合物组合物重量的2%重量,为各种水杨酸盐(酯)类、间苯二酚类、苯并三唑类、苯甲酮类及位阻胺类衍生物。
润滑剂和脱模剂宜选自如下化合物:长链脂肪酸如硬脂酸,或脂肪酸盐如硬脂酸钠、硬脂酸钙或硬脂酸锌,或褐煤蜡,或具有10-40个碳原子(优选16-22个碳原子)的饱和脂族羧酸与具有2-40个碳原子(优选2-6个碳原子)的饱和脂肪醇或胺反应所得的酯或酰胺。优选的酯和酰胺的例子是:季戊四醇四硬脂酸酯、三月桂酸甘油酯、去水山梨糖醇二油酸酯、乙二胺二硬脂酸酯、硬脂酸甘油酯。
在着色剂中,优选的产品是:无机色素,如二氧化钛、三氧化二铁、碳黑,但是也可使用有机色素,如酞青类、喹吖啶酮类、苝、苯胺黑、蒽醌类。
新型的模塑组合物还可包含0-1%重量的含氟乙烯聚合物,当组合物着火使起到防树脂熔化物滴下的效应。
这些含氟乙烯聚合物是:聚四氟乙烯(PTFE)或四氟乙烯-六氟丙烯共聚物,有以Algoflon TM为商标名的市售品。
特别优选的是颗粒大小为0,1μm to 10μm的含氟聚合物。
本发明的阻燃模塑组合物可进一步包含所用的增塑剂,例如,其量最多到重量%热塑性组合物的2重量%。这些产品通常促使无机材料分散在聚合物基质中。所用增塑剂的例子包括带来官能团如羟基、羰基、氨基或环氧基的邻苯二甲酸酯、烃油和有机硅氧烷。本发明的阻燃模塑组合物还可进一步包含选自水滑石、水菱镁矿、氧化锌、硼酸锌、碳酸镁、锡酸锌或类似产品的一种或几种抗酸组分。
抗冲改性剂树脂通常是包含至少二种以下单体的共聚物,这些单体是:乙烯、丙烯、丁二烯、异丁烯、异戊二烯、醋酸乙烯酯、苯乙烯、丙烯腈、丙烯酸酯和/或甲基丙烯酸酯。
某些优选的抗冲改性剂是称作乙烯-丙烯(EPM)和乙烯-丙烯-二烯(EPDM)橡胶的物质。
EPM和EPDM橡胶可用活性羧酸或其衍生物如丙烯酸、甲基丙烯酸、马来酸酐加以接枝。另一组优选的橡胶包含乙烯与丙烯酸和/或甲基丙烯酸的共聚物,它可包含二羧酸,如马来酸和延胡索酸或这些酸的衍生物,和/或包含环氧基的单体。
这种类型的聚合物本身是已知的,在文献中有描述。它们优选在高压和升高的温度下进行无规共聚合或用乳液聚合或悬浮聚合法加以制备。
本发明方法中可用的成核剂是:亚膦酸钠、苯基亚膦酸钠、氧化铝、二氧化硅,较佳为滑石和硬脂酸钡。
组分D):本发明的热塑性模压组合物还可任选地包含填充剂。
在本发明的方法中,填充剂可以是本领域中已知的起增强剂作用的纤维或微粒状物质。优选的纤维状填充剂的例子是碳纤维、芳族聚酰胺纤维,较佳为以商业上可购得的呈短切玻璃形式使用的玻璃纤维。
为了改善与热塑性树脂的相容性,可用硅烷化合物对纤维状填充剂作表面处理。
当使用纤维状填充剂时,其量应为树脂重量的10%-50%,较佳为20%-35%。如果其量低于10%,在机械性能上观察不到有益效应。如果其量高于50%,组合物的粘度会太高。
微粒状物质的例子是玻璃珠、无定形二氧化硅、白垩、云母、经锻烧的高岭土、钙硅石、滑石、碳酸镁或类似的产品,它们可用脂肪酸等作表面处理或在脂肪酸等存在下进行研磨。
只要颗粒平均大小在2μm至20μm,任何有效进入市场作为热塑性树脂添加剂的颗粒状物质均适用于本发明的组合物。使用时,加到树脂组合物中的颗粒物质的量为树脂组合物重量的40%以下,较佳为30%以下。如果颗粒物质的量高于40%,组合物的熔融粘度会太高,树脂组合物的模塑性会很差。
上述产品也可以混合物的形式使用。
制备本发明的树脂组合物的方法本身是已知的,即以上述预定比例混合和捏和起始组分A)至C),可任选地,D)。
混合和捏和操作可在任何熟知的设备中进行,如密闭式混炼器(Banbury mixers)、单螺杆挤压机或双螺杆挤压机,然后将其挤压出来。
还可将起始组分与热塑性树脂预先混合以制备可包含预定比例的各种组分或全部添加剂的母体混合物,然后在制丸用的挤压设备中用添加的聚合物将其稀释。
组分被捏和的温度一般为240℃至300℃。
将挤出物冷却和制丸。
通过注射模塑、吹塑或注射压缩模塑可将所得丸状物模塑成各种模塑物。
本发明的新型热塑性模压组合物被赋予如下性能:
·阻燃性好,特别是在厚度为1.6mm和0.8mm时抗775℃白炽金属线和具有UL 94等级标准;
·机械性能好,尤其是抗冲击强度、弹性模量和屈服强度;
·电性能好,通过约600 V的CTI值。
本发明的模塑组合物适合在电和电子部门的应用,如办公室自动控制器具、灯的部件、插座和多极接插件、线圈成形器、继电器罩等。
下面参照实施例对本发明作更详细的描述,但是,这并不意味着对本发明范围的限制。
实施例
在温度置于250-270℃之间的双螺杆挤压机中,将下表列出的组分进行混合。制粒和干燥后,将颗粒注塑成试验样本,用于:
-UL 94可燃性试验方法,描述如下:
·在23℃和50%相对湿度下将5个样本(每个配方和厚度)调湿24小时;
·将每个调湿的样本置于离下面的绵绒约20cm垂直位置处;
·每个样本应用2次火焰(第2次应用在第1次用火点燃样本被熄灭后立即开始)。
按照下面的方法及说明书的规定报告UL 94结果如下:
·V0:当5个试验样本总的复燃时间不长于50秒钟,每次用火少于10秒钟,且没有燃烧物滴下时。
·V1:当5个试验样本总的复燃时间少于150秒钟,每次用火少于30秒钟,且没有燃烧物滴下时。
·V2:当5个试验样本总的复燃时间少于150秒钟,每次用火少于30秒钟,且有燃烧物滴下时。
·当试验结果不符合上述V0、V1和V2标准时,下面的表中不加以分级。
-LOI:按照ISO 4589-1984测得
-GWIT:按照IEC 61335-1执行
-CTI:按照IEC 112用标准溶液A执行。
在下面的实施例中,用如下材料作为起始组分:
组分A):树脂
聚对苯二甲酸丁二酯(Ultradur B 4500,BASF制造)
组分B):阻燃添加剂
次磷酸铝,白色粉末状,平均颗粒大小(d50%)为5μm,d98%为15μm以下,Italmatch Chemicals Spa制造,商标名为PhosliteIP-A。
间苯二酚二(联苯基)磷酸酯(Fyroflex RDP),粘稠液体产品,Akzo Nobel Phosphorus Chemicals制造。
氰脲酸三聚氰胺,白色固体粉末,平均颗粒大小为约3μm,Italmatch Chemicals Spa unde制造,商标名为Melagard 25。
组分C):稳定剂和加工助剂
实施例中使用如下产品:
位阻苯酚热稳定剂Irganox1010,Ciba specialty chemicals制造。
润滑剂:褐煤蜡(E wax),Hoechst制造;
单硬脂酸甘油酯(Loxiol MG),Cognis制造。
抗酸剂:硬脂酸锌,Sogis制造。
成核剂:硬脂酸钡。
组分D):填充剂和/或增强剂
钙硅石,针状,L/D(长度/直径)之比约为10/1;
短切玻璃纤维,厚度10μm(表面硅烷化(epoxysilanized))。
结果
表1显示未填充的PBT制品,在单独使用次磷酸铝(Phoslite IP-A)或与无卤素阻燃剂合用下,在厚度为1.6mm时可被阻燃,分级为V0。
表1:次磷酸铝在未填充的PBT制品上的阻燃效应
组成 | 1 | 2 | 3 | 4 | 5 | 6 | 7 |
PBT(%) | 89,5 | 87,5 | 84,5 | 74,7 | 84,5 | 84,7 | 79,7 |
Phoslite IP-A(%) | 10 | 12 | 15 | 10 | 10 | 10 | |
Melagard 25(%) | 10 | 5 | |||||
RDP(%) | 15 | 5 | 10 |
Loxiol MG | 0,2 | 0,2 | 0,2 | 0,2 | |||
Irg 1010(%) | 0,3 | 0,3 | 0,3 | 0,3 | 0,3 | 0,3 | 0,3 |
LOI(%) | na | 27 | 28 | na | na | na | na |
UL 94(3,2mm) | V1 | V0 | V0 | V2 | V0 | V1 | V0 |
UL 94(1,6mm) | V2 | V0 | V0 | V2 | V0 | V2 | V0 |
注:na=未得到数据
表2的结果显示玻璃纤维增强的PBT制品,在单独使用次磷酸铝(Phoslite IP-A)或与氰脲酸三聚氰胺合用下,在厚度为1.6mm时可被阻燃,分级为V0。
该表还显示,这些制品在775℃时通过GWIT试验,并具有良好的电性能(600V,CTI)。
表2:次磷酸铝在PBT玻璃纤维增强制品上的阻燃效应
组成 | 1 | 2 | 3 | 4 | 5 | 6 | 7 | 8 | 9 | 10 |
PBT(%) | 54,1 | 49,1 | 54,1 | 52,1 | 49,1 | 51,1 | 54,1 | 54,1 | 57,1 | 57,1 |
Phoslite IP-A(%) | 15 | 20 | 7,5 | 8,5 | 10 | 7,5 | 20 | 10 | 17 | 8,5 |
Melagard 25(%) | 7,5 | 8,5 | 10 | 7,5 | 10 | 8,5 | ||||
钙硅石(%) | 3 | |||||||||
玻璃纤维(%) | 30 | 30 | 30 | 30 | 30 | 30 | 25 | 25 | 25 | 25 |
Irg 1010(%) | 0,3 | 0,3 | 0,3 | 0,3 | 0,3 | 0,3 | 0,3 | 0,3 | 0,3 | 0,3 |
硬脂酸钡(%) | 0,3 | 0,3 | 0,3 | 0,3 | 0,3 | 0,3 | 0,3 | 0,3 | 0,3 | 0,3 |
Wax E(%) | 0,3 | 0,3 | 0,3 | 0,3 | 0,3 | 0,3 | 0,3 | 0,3 | 0,3 | 0,3 |
UL 94(3,2mm) | V0 | V0 | V0 | V0 | V0 | V0 | V0 | V0 | V0 | V0 |
UL 94(1,6mm) | V2 | V0 | V1 | V0 | V0 | V0 | V0 | V0 | nc | V0 |
UL 94(0,8mm) | na | na | na | na | na | na | na | V0 | nc | V0 |
GWFI(960℃) | 通过 | 通过 | 通过 | 通过 | 通过 | 通过 | 通过 | 通过 | 通过 | 通过 |
GWIT(775℃)(2mm) | na | 通过 | 失败 | 通过 | 通过 | 通过 | na | na | na | na |
GWIT(775℃)(3mm) | na | 通过 | 通过 | 通过 | 通过 | 通过 | 通过 | 通过 | 通过 | 通过 |
LOI(%) | na | 29 | 28 | 29 | 32 | 28 | 28 | 28 | na | 28 |
CTI(V) | na | na | 600 | 600 | 600 | 600 | na | 600 | na | 550 |
注:na=未得到数据;nc=未按UL 94试验分类。
Claims (24)
1.一种无卤素阻燃热塑性模压组合物,它包含次磷酸铝(化学式为Al(H2PO2)3的无机亚膦酸铝)作为无卤素阻燃剂及至少一种基于聚酯的聚合物;所述组合物按照以下组成:
A)5-95重量%的所述聚酯;
B)0.1-30重量%的所述次磷酸铝;
C)0.5-10重量%的至少一种添加剂,选自:加工助剂、紫外稳定剂、色素、橡胶弹性聚合物、成核剂或其混合物;
D)0%-50重量%的无机填充剂,
其中A)-D)组分的总重量百分比为100%。
2.如权利要求1所述的热塑性模压组合物,其特征在于所述加工助剂是热和加工稳定剂、抗滴下剂或脱模剂。
3.如权利要求1所述的热塑性模压组合物,其特征在于:所述聚酯是线型聚酯。
4.如权利要求2所述的热塑性模压组合物,其特征在于所述抗滴下剂选自聚四氟乙烯。
5.如权利要求1所述的热塑性模压组合物,其特征在于包含20%-70重量%所述聚酯。
6.如权利要求1所述的热塑性模压组合物,其特征在于包含35%-60重量%所述聚酯。
7.如权利要求1所述的热塑性模压组合物,其特征在于所述聚酯选自:由2-6个碳原子的链烷二醇衍生而来的聚对苯二酸亚烷基酯。
8.如权利要求7所述的热塑性模压组合物,其特征在于所述聚对苯二酸亚烷基酯是聚对苯二酸乙二酯、聚对苯二酸丁二酯和/或它们的混合物。
9.如权利要求8所述的热塑性模压组合物,其特征在于包含以混合物形式存在的所述聚对苯二酸乙二酯和聚对苯二酸丁二酯,其中聚对苯二酸乙二酯聚合物的量为聚合物总量的10%-30重量%。
10.如权利要求9所述的热塑性模压组合物,其特征在于所述聚对苯二酸乙二酯是回收再利用的聚对苯二酸乙二酯。
11.如权利要求1所述的热塑性模压组合物,其特征在于所述聚酯选自经至少一种芳族二羧酸或酯与至少一种脂族或芳族二羟基化合物反应所制得的聚合物。
12.如权利要求11所述的热塑性模压组合物,其特征在于所述芳族二羧酸或酯部分被选自己二酸、壬二酸、癸二酸或环己二羧酸的脂族或脂环族二羧酸替代。
13.如权利要求11所述的热塑性模压组合物,其特征在于所述芳族二羧酸选自对苯二甲酸、间苯二酸或其混合物。
14.如权利要求11所述的热塑性模压组合物,其特征在于所述脂族或芳族二羟基化合物选自:
4,4′-二羟基联苯;
2,4-二(4′-羟基苯基)-2-甲基丁烷;
αα′-二(4-羟基苯基)-p-二异丙基苯;
1,1-二(4′-羟基苯基)环己烷;
4,4′-二羟基二苯砜;
2,2-二(3′5′-二甲基-4′-羟基苯基)丙烷。
15.如权利要求1所述的热塑性模压组合物,其特征在于包含以组合物重量计2%-20重量%的所述次磷酸铝。
16.如权利要求1所述的热塑性模压组合物,其特征在于所述次磷酸铝的平均粒度D50%低于15μm,最高粒度低于3.0μm。
17.如权利要求1所述的热塑性模压组合物,其特征在于包含填充剂,其量为热塑性模压组合物重量的10%-50%。
18.如权利要求17所述的热塑性模压组合物,其特征在于所述填充剂的量为热塑性模压组合物重量的20%-35重量%。
19.如权利要求17或18所述的热塑性模压组合物,其特征在于所述填充剂是纤维状填充剂。
20.如权利要求19所述的热塑性模压组合物,其特征在于所述纤维状填充剂选自碳纤维、芳族聚酰胺纤维和玻璃纤维。
21.制备权利要求1所述的热塑性模压组合物的方法,其特征在于以预定的比例混合和捏和所有组分,将其挤出并制丸。
22.如权利要求21所述的方法,其特征在于捏和的温度为240℃至300℃。
23.权利要求1所述的热塑性模压组合物在制备模塑制品上的应用。
24.从权利要求1所述热塑性模压组合物得到的模塑制品。
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PCT/IB2004/001891 WO2005121232A1 (en) | 2004-06-10 | 2004-06-10 | Polyester compositions flame retarded with halogen-free additives |
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CN1997698B true CN1997698B (zh) | 2013-01-09 |
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US (1) | US7700680B2 (zh) |
EP (1) | EP1756210A1 (zh) |
KR (1) | KR101106365B1 (zh) |
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WO (1) | WO2005121232A1 (zh) |
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CN1997698A (zh) | 2007-07-11 |
KR20070034044A (ko) | 2007-03-27 |
US7700680B2 (en) | 2010-04-20 |
KR101106365B1 (ko) | 2012-01-18 |
EP1756210A1 (en) | 2007-02-28 |
US20080090950A1 (en) | 2008-04-17 |
WO2005121232A1 (en) | 2005-12-22 |
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