CN1902270A - 聚酰胺合成泡沫塑料 - Google Patents

聚酰胺合成泡沫塑料 Download PDF

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CN1902270A
CN1902270A CNA2004800396639A CN200480039663A CN1902270A CN 1902270 A CN1902270 A CN 1902270A CN A2004800396639 A CNA2004800396639 A CN A2004800396639A CN 200480039663 A CN200480039663 A CN 200480039663A CN 1902270 A CN1902270 A CN 1902270A
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mixture
nylon
coupling agent
glass envelope
polyamide
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罗纳德·J·伊斯拉埃尔松
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3M Innovative Properties Co
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/32—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof from compositions containing microballoons, e.g. syntactic foams
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2377/00—Characterised by the use of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2377/00—Characterised by the use of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Derivatives of such polymers
    • C08J2377/02—Polyamides derived from omega-amino carboxylic acids or from lactams thereof
    • 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
    • C08K7/00—Use of ingredients characterised by shape
    • C08K7/22—Expanded, porous or hollow particles
    • C08K7/24—Expanded, porous or hollow particles inorganic
    • C08K7/28—Glass
    • 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
    • C08K9/00—Use of pretreated ingredients
    • C08K9/04—Ingredients treated with organic substances

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  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)

Abstract

一种填充热塑性树脂复合物，其包含至少一种聚酰胺，和用硅烷偶联剂或钛酸酯偶联剂中的至少一种处理过的抗碎强度至少为10000PSI的玻璃泡。

Description

聚酰胺合成泡沫塑料
交叉引用和优先权的权利要求
本申请的权利要求以2003年12月30日提出的美国临时申请号60/533320为优先权。
技术领域
本发明涉及一种填充树脂复合物。
背景技术
众所周知，在树脂组合物中加入填料可用以调节所得组合物(通常称为“复合物”或“填充复合物”)的物理性能，例如降低其密度，或者通过使用更廉价的材料降低相对昂贵的树脂比例，从而降低费用。已知填料的实例包括固体颗粒，例如二氧化钛、玻璃等。已知还可使用中空颗粒，例如中空玻璃泡。尽管玻璃泡经常已成功用于降低最终复合物的密度，但在很多情况下在处理复合物的过程中将玻璃泡压碎，因此削弱了所希望的密度降低。而且，包含玻璃泡的树脂组合物经常表现出所需物理性能所不希望的损失，例如抗张强度。已知向聚合物中加入非增强性填料会导致聚合复合物的机械强度(抗张强度、冲击强度等)的降低。非增强性填料可定义为长径比(长度对直径)小于2的颗粒。可以认为机械强度的损失主要由于填料造成聚合物链的破坏，并且由于聚合物与填料间的无效键合；其中键的强度被认为弱于聚合物链自身的拉伸强度。
美国专利3769126(Kolek)、4243575(Myers等)、4923520(Anzai等)和5695851(Watanabe等)和欧洲申请No.1142685(Akesson)中公开了填充树脂复合物的示意性实例。
发明概述
本发明提供一种填充树脂复合物。本发明的复合物提供了抗张强度和降低重量方面令人惊讶的组合。由本发明的组合物提供的这种改进性能使得可将填充树脂复合物用于一些产品应用中，而这些应用是其它技术所不能提供的。
总之简要地，在一个典型实施例中，本发明的复合物包含一种聚酰胺和玻璃泡，其中所述的聚酰胺例如尼龙，例如尼龙-6，6(例如来自Dupont的Zytel 101L)；和尼龙混合物(例如来自GE的尼龙与聚苯醚的混合物NORYL GTX)。依照本发明，所述玻璃泡在加入复合物之前经过氨基丙基三乙氧基硅烷(APS)的处理。
玻璃泡应当表现出至少10000PSI的抗碎强度，使其能够经受许多挤压操作。在一些实施方式中，它们会优选地表现出至少18000PSI的抗碎强度，使其能够经受注射模塑和挤压操作。通常使用ASTMD3102-72中的“Hydrostatic Collapse Strength of Hollow GlassMicropheres”来测量玻璃泡的强度。
本发明提供了填充的尼龙-6，6复合物，可用于形成需要标准抗张性能的轻质部件，即，未填充的尼龙-6，6。进一步地，由填充尼龙-6，6制成的模制品成型后也具有比标转尼龙-6，6更优良的低收缩量(由于替代的聚合物)和其它优点。
一些用于具有良好抗张性能的轻质部件的实例也包括体育用品，可降低其使用者的疲劳和/或提高其性能；节约燃料的运输(汽车、航空等)部件，从而提高加速性能或更高的最高速度，并降低燃料排放。
通常，为“结构”应用(承重)而制备的部件不适合选择具有非增强性填料的尼龙-6，6。作为本发明的结果，轻质结构部件可由填充尼龙-6，6制备。
本发明可使用可商购到的玻璃泡填料，用于树脂复合物中。优选地，该玻璃泡具有较高的强度变化，例如ScotchliteTM Glass BubblesS60HS，其为苏打-石灰-硼硅酸盐玻璃。这些玻璃泡表现出均衡的抗碎强度为18000psi，密度为0.60g/cc，和平均直径为约30微米。
测试方法
拉伸模量
根据ASTM Test Method D-638测试拉伸模量，报告以Mpa。
极限拉伸模量
根据ASTM Test Method D-638测试极限拉伸模量，报告以Mpa。
弯曲模量
根据ASTM Test Method D-790测试弯曲模量，报告以Mpa。
极限弯曲模量
根据ASTM Test Method D-790测试极限弯曲模量，报告以Mpa。
断裂伸长率
根据ASTM Test Method D-638测试断裂伸长率，报告以％。
密度
从Micromeritics，Norcross，Georgia获得的商品标识“ACCUPYC1330PYCNOMETER”的全自动排气比重瓶，用于依照ASTM D-2840-69中“Average True Particle Density of Hollow Microspheres”测量注射模塑复合材料的密度。
玻璃泡的硅烷处理
在Ross Mixer(可获自Charles Ross & Son Company Hauppauge，NY)中加入N-2-(氨基乙基)-3-氨基丙基三甲氧基硅烷(1500g；0.5wt.％；可获自Osi Specialties，Albany，NY，商品名为“A1120”)的溶液。在中等搅拌速度下，缓慢加入玻璃泡(可获自3M Company，St.Paul，MN，商品名为“S60HS”)，将该混合物混合15分钟。将随后的糊状物倒入铝盘中，在80℃的强迫通风炉中干燥过夜。将干燥的玻璃泡用180微米筛子过筛，从中除去块状物。
尼龙复合物的混合和成型
在双螺杆挤出机(BerstorffUltra Glide；螺杆直径为25mm；长径比为36∶1；螺杆速度范围为200-250rpm；温度设定范围为200-575(93℃-302℃)，实际范围为148-575(64℃-302℃)；通过量为10lbs/hr(4.5Kg/hr))上安装有玻璃泡的侧进料设备；造粒机附件中充满尼龙66(可获自DuPont，Wilmington，DE，商品名为“ZYTEL 101L”；在275℃下的熔融指数为60g/10m，Tg为50℃；Tm为260-262℃，密度为1.14g/cm3)。将测试样品在注射模塑机(150吨Engel InjectionMolding Machine；带有ASTM四腔铸模)中成型，螺杆直径为30mm，喷注压力保持低于18000psi(124MPa)。
表1
  实施例
  材料   1   2   3   4   5
  “A1120”处理   -   无   无   有   有
  “ZYTEL 101L”wt.％   100   90   80   88   74
  “S60HS”wt.％   0   10   20   12   26
  机械性能
  真密度(g/cc)   1.14   1.05   0.97   1.04   0.95
  拉伸模量(MPa)   2758   3153   4898   3420   4700
  极限拉伸强度(MPa)   76.3   60.8   51.9   76.5   77.0
  断裂伸长率(％)   35.4   5.9   1.8   4.3   3.1
  弯曲模量(MPa)   2723   2493   2958   3091   3713
  极限弯曲强度(MPa)   115   93   78   122   132

Claims (6)

1.一种填充热塑性树脂复合物，包含至少一种聚酰胺，和用硅烷偶联剂或钛酸酯偶联剂中的至少一种处理过的抗碎强度至少为10000PSI的玻璃泡。
2.权利要求1的复合物，其中所述的聚酰胺选自尼龙和尼龙混合物。
3.权利要求2的复合物，其中所述的硅烷偶联剂是氨基硅烷。
4.权利要求3的复合物，其中所述的硅烷偶联剂选自氨基丙基三乙氧基硅烷和N-2-(氨基乙基)-3-氨基丙基三甲氧基硅烷。
5.权利要求1的复合物，其中所述的玻璃泡表现出的抗碎强度至少为18000PSI。
6.一种包含权利要求1的复合物的制品。
CNA2004800396639A 2003-12-30 2004-12-30 聚酰胺合成泡沫塑料 Pending CN1902270A (zh)

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US60/533,320 2003-12-30

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CN103502357A (zh) * 2011-05-02 2014-01-08 3M创新有限公司 含有中空玻璃微球的热塑性树脂复合物
CN111868158A (zh) * 2018-03-27 2020-10-30 巴斯夫欧洲公司 聚酰胺组合物、其制备方法、应用和制品
CN114729158A (zh) * 2019-09-09 2022-07-08 赢彩科技股份有限公司 轻质增强复合材料配方及其制造方法

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US8362114B2 (en) 2007-02-28 2013-01-29 Solvay Advanced Polymers, L.L.C. Thermoplastic compositions containing microspheres
RU2461589C2 (ru) * 2007-04-05 2012-09-20 Тейджин Арамид Б.В. Пена из полимеров
US8617702B2 (en) 2010-04-28 2013-12-31 Sabic Innovative Plastics Ip B.V. Thermally insulated structural members, and doors and windows incorporating them
ES2716557T3 (es) 2010-09-08 2019-06-13 3M Innovative Properties Co Burbujas de vidrio, materiales compuestos a partir de las mismas y método de fabricación de burbujas de vidrio
US9187609B2 (en) * 2013-10-02 2015-11-17 Greatario Industrial Storage Systems Ltd. System for covering hydrocarbon liquids and method of forming same
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Publication number Priority date Publication date Assignee Title
CN103502357A (zh) * 2011-05-02 2014-01-08 3M创新有限公司 含有中空玻璃微球的热塑性树脂复合物
CN103502357B (zh) * 2011-05-02 2016-02-03 3M创新有限公司 含有中空玻璃微球的热塑性树脂复合物
CN111868158A (zh) * 2018-03-27 2020-10-30 巴斯夫欧洲公司 聚酰胺组合物、其制备方法、应用和制品
CN111868158B (zh) * 2018-03-27 2023-02-17 巴斯夫欧洲公司 聚酰胺组合物、其制备方法、应用和制品
CN114729158A (zh) * 2019-09-09 2022-07-08 赢彩科技股份有限公司 轻质增强复合材料配方及其制造方法

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