CN1902276A - 填充复合物 - Google Patents

填充复合物 Download PDF

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Publication number
CN1902276A
CN1902276A CNA2004800396681A CN200480039668A CN1902276A CN 1902276 A CN1902276 A CN 1902276A CN A2004800396681 A CNA2004800396681 A CN A2004800396681A CN 200480039668 A CN200480039668 A CN 200480039668A CN 1902276 A CN1902276 A CN 1902276A
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mixture
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strength
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glass
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安德鲁·S·D'苏扎
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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
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/15—Heterocyclic compounds having oxygen in the ring
    • C08K5/151—Heterocyclic compounds having oxygen in the ring having one oxygen atom in the ring
    • C08K5/1535—Five-membered rings
    • C08K5/1539—Cyclic anhydrides
    • 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
    • C08K9/06—Ingredients treated with organic substances with silicon-containing compounds
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/249921—Web or sheet containing structurally defined element or component
    • Y10T428/249953—Composite having voids in a component [e.g., porous, cellular, etc.]
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/249921—Web or sheet containing structurally defined element or component
    • Y10T428/249953—Composite having voids in a component [e.g., porous, cellular, etc.]
    • Y10T428/249971—Preformed hollow element-containing

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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)
  • Glass Compositions (AREA)
  • Laminated Bodies (AREA)

Abstract

一种填充热塑性树脂复合物，其包括至少一种热塑性烯烃、马来酸酐和玻璃泡。

Description

填充复合物
优先权和交叉引用权利要求
本申请的权利要求以2003年12月30日提出的美国临时申请No.60/533348为优先权。
技术领域
本发明涉及一种填充热塑性树脂复合物。
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热塑性树脂复合物。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，本发明的组合物包含一种热塑性烯烃，例如聚丙烯、聚乙烯、聚丁烯、聚苯乙烯及其共聚物，包含马来酸酐和玻璃泡。优选地，该玻璃泡在加入到复合物中之前经硅烷偶联剂或钛酸酯偶联剂中的一种处理，例如氨基硅烷，例如氨基丙基三乙氧基硅烷(APS)或N-2-(氨基乙基)-3-氨基丙基三甲氧基硅烷。
通常地，玻璃泡应当表现出至少3000PSI的抗碎强度，使其能够经受很多挤压操作。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ASTM D3102-72中的“Hydrostatic Collapse Strength of Hollow GlassMicropheres”来测量玻璃泡的强度。
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，平均直径为约30微米。
可通过注射模塑法、挤压法和其它由热塑性聚合物形成制品的已知方法，用本发明的组合物制备制品。
实施例
本发明将进一步地通过下面意为非限定性的示例性实施例进行解释。除非特别指出，所有的含量均为以重量表示的份数。
除非特别指出，使用下面的制备和测试方法。
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％。
锯齿状缺口冲击强度(Notched Izod Impact Strength)
根据ASTM Test Method D-256测试锯齿状缺口冲击强度(NotchedIzod Impact Strength)，报告以J/cm。
密度
从Micromeritics，Norcross，Georgia获得、商品名为“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。
聚丙烯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；造粒机附件中充满聚丙烯(可获自AtoFina，商品名为“FINA 3825”；在230℃下的熔融指数为30g/10m；Tm为165℃，密度为0.905g/cm3)和马来酸酐(购自Crompton Corporation，Middlebury，CT，商品名为“POLYBOND3200”)。将测试样品在注射模塑机(150吨Engel Injection MoldingMachine；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机械性能
  实施例
  1   2   3   4
  “A1120”处理   无   无   无   有
  “FINA 3825”wt.％   100   80   78   78
  “POLYBOND 3200”wt.％   ---   ---   2   2
  “S60HS”wt.％   ---   20   20   20
  机械性能
  密度(g/cc)   0.9   0.8   0.8   0.8
  极限拉伸强度(MPa)   29.2   15.6   24.3   29.5
  弯曲模量(MPa)   1581   2264   2381   2444
  极限弯曲强度(MPa)   47.7   34.8   54.5   58.5
  断裂伸长率(％)   ---   4.7   4.0   5.9
  锯齿状缺口冲击强度(J/cm)   7.8   1.4   2.6   2.7
---意为未添加或未测量

Claims (8)

1.一种填充热塑性树脂复合物，包含至少一种热塑性烯烃、马来酸酐和玻璃泡。
2.权利要求1的复合物，其中所述的玻璃泡经硅烷偶联剂或钛酸酯偶联剂中的至少一种处理过。
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3000PSI。
6.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。
7.权利要求1的复合物，其中所述的热塑性烯烃选自聚丙烯、聚乙烯、聚丁烯、聚苯乙烯及其共聚物。
8.一种包含权利要求1的复合物的制品。
CNA2004800396681A 2003-12-30 2004-12-30 填充复合物 Pending CN1902276A (zh)

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US53334803P 2003-12-30 2003-12-30
US60/533,348 2003-12-30

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EP (1) EP1709115B1 (zh)
JP (1) JP2007517128A (zh)
CN (1) CN1902276A (zh)
AT (1) ATE360662T1 (zh)
DE (1) DE602004006170T2 (zh)
WO (1) WO2005066262A1 (zh)

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CN104884520B (zh) 2012-12-20 2017-07-04 3M创新有限公司 包含含氟聚合物的复合颗粒、其制备方法及包含其的制品
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JP2022532353A (ja) 2019-05-15 2022-07-14 スリーエム イノベイティブ プロパティズ カンパニー 粒子を相互接続するポリマー要素を含むフィルム

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WO2005066262A1 (en) 2005-07-21
DE602004006170D1 (de) 2007-06-06
US20070116942A1 (en) 2007-05-24
JP2007517128A (ja) 2007-06-28
EP1709115A1 (en) 2006-10-11
EP1709115B1 (en) 2007-04-25
ATE360662T1 (de) 2007-05-15

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