CN103502361A - 生物基聚合物组合物 - Google Patents
生物基聚合物组合物 Download PDFInfo
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- CN103502361A CN103502361A CN201280022102.2A CN201280022102A CN103502361A CN 103502361 A CN103502361 A CN 103502361A CN 201280022102 A CN201280022102 A CN 201280022102A CN 103502361 A CN103502361 A CN 103502361A
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- 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 claims abstract description 23
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- RDWGLYCGVYTLAK-UHFFFAOYSA-N (2,3,4-tribromophenyl) dihydrogen phosphate Chemical compound OP(O)(=O)OC1=CC=C(Br)C(Br)=C1Br RDWGLYCGVYTLAK-UHFFFAOYSA-N 0.000 description 1
- CHLNHIVUNRZION-UHFFFAOYSA-N (2,3-dibromophenyl) dihydrogen phosphate Chemical compound OP(O)(=O)OC1=CC=CC(Br)=C1Br CHLNHIVUNRZION-UHFFFAOYSA-N 0.000 description 1
- XMNIXWIUMCBBBL-UHFFFAOYSA-N 2-(2-phenylpropan-2-ylperoxy)propan-2-ylbenzene Chemical compound C=1C=CC=CC=1C(C)(C)OOC(C)(C)C1=CC=CC=C1 XMNIXWIUMCBBBL-UHFFFAOYSA-N 0.000 description 1
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- UEESZGRNYSPHAC-UHFFFAOYSA-N 4-chlorobut-1-ene phosphoric acid Chemical compound OP(O)(O)=O.OP(O)(O)=O.ClCCC=C UEESZGRNYSPHAC-UHFFFAOYSA-N 0.000 description 1
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- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 description 1
- 150000001989 diazonium salts Chemical class 0.000 description 1
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- 229910052751 metal Inorganic materials 0.000 description 1
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- 229910000000 metal hydroxide Inorganic materials 0.000 description 1
- 150000004692 metal hydroxides Chemical class 0.000 description 1
- 229910001960 metal nitrate Inorganic materials 0.000 description 1
- CAAULPUQFIIOTL-UHFFFAOYSA-L methyl phosphate(2-) Chemical compound COP([O-])([O-])=O CAAULPUQFIIOTL-UHFFFAOYSA-L 0.000 description 1
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- PMOIAJVKYNVHQE-UHFFFAOYSA-N phosphanium;bromide Chemical compound [PH4+].[Br-] PMOIAJVKYNVHQE-UHFFFAOYSA-N 0.000 description 1
- 150000003016 phosphoric acids Chemical class 0.000 description 1
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- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
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- 150000003609 titanium compounds Chemical class 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
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- 150000003755 zirconium compounds Chemical class 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G64/00—Macromolecular compounds obtained by reactions forming a carbonic ester link in the main chain of the macromolecule
- C08G64/42—Chemical after-treatment
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G81/00—Macromolecular compounds obtained by interreacting polymers in the absence of monomers, e.g. block 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
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/005—Processes for mixing polymers
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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
- C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
- C08K5/0025—Crosslinking or vulcanising agents; including accelerators
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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
- C08K5/49—Phosphorus-containing 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
- C08K5/00—Use of organic ingredients
- C08K5/54—Silicon-containing compounds
- C08K5/541—Silicon-containing compounds containing oxygen
- C08K5/5425—Silicon-containing compounds containing oxygen containing at least one C=C bond
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L101/00—Compositions of unspecified macromolecular compounds
- C08L101/16—Compositions of unspecified macromolecular compounds the macromolecular compounds being biodegradable
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K21/00—Fireproofing materials
- C09K21/06—Organic materials
- C09K21/12—Organic materials containing phosphorus
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
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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
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- C08J2367/04—Polyesters derived from hydroxy carboxylic acids, e.g. lactones
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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- C08J2483/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen, or carbon only; Derivatives of such polymers
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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- C08K5/34—Heterocyclic compounds having nitrogen in the ring
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- General Chemical & Material Sciences (AREA)
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Abstract
在促进生物基聚合物与丙烯酰化的硅酮聚醚之间自由基反应的温度下,通过将生物基聚合物与丙烯酰化的硅酮聚醚进行熔融加工来制备聚合物复合材料。所述生物基组合物具有极好的机械性能平衡,并适于阻燃应用。
Description
相关申请的交叉引用
本申请要求于2011年3月23日提交的美国临时专利申请No.61/466,516的优先权,其公开内容以全文引用方式并入本文。
技术领域
本发明涉及生物基(bio-based)聚合物和丙烯酰化的硅酮聚醚(acrylated silicone polyether),其组合形成可熔融加工的聚合物,该聚合物具有极好且预料不到的机械性能。
背景技术
与石油基聚合物材料相比,聚乳酸聚合物(PLA)和其他生物基聚合物具有某些物理局限性。这些局限性可包括在加工和再加工过程中它们易于降解以及失去性能。将传统材料掺入生物基聚合物组合物中可对组合物的物理特性产生不利影响,最终导致组合物不适合或不能满足其预期目的。此外,与竞争性材料相比,高度填充的生物基聚合物由于其分子结构,往往具有较劣的物理特性。这些材料往往无法达到所需的强度和冲击特性。一旦形成多组分组合物,其他生物基组合物的分子结构可能会限制后续加工。
发明内容
在此公开的生物基聚合物组合物具有优异的机械性能平衡,且该组合物一经初始掺和即能进行熔融加工。这些属性的结合随着组合物分子结构而变化。在一个实施方案中,在促进生物基聚合物和丙烯酰化的硅酮聚醚之间共价反应的温度下,通过对生物基聚合物与丙烯酰化的硅酮聚醚进行熔融加工来制备本发明的生物基聚合物。在一个实施方案中,该聚合物是生物基线性聚酯。
该组合物具有这样的分子结构,该分子结构通过在组合物中使用的丙烯酰化的硅酮聚醚部分生成。在一个实施方案中,在熔融加工以形成聚合物复合材料的过程中,丙烯酰化的硅酮聚醚经历自由基均裂反应,并与生物基聚酯发生反应。聚合物链的相互作用程度具有较高分子量材料的特性,同时后续仍可熔融加工。
如由相对较高的冲击强度(无缺口)所示的,与传统复合的生物基聚合物相比,成品聚合物可显示出改进的机械特性。
出于本发明的目的,本申请中使用的下列术语定义如下:
“生物基聚合物”是指源自可再生资源的聚合物材料或树脂。
“聚合物复合材料”是指聚合物材料和添加剂或填料的混合物。
“可熔融加工的组合物”是指例如采用常规的聚合物加工技术如挤出或注塑,通常在高温下,经熔融加工得到的制剂。
“熔融加工技术”是指挤出、注塑、吹塑、滚塑或分批混合。
“丙烯酰化的硅酮聚醚”是指具有一个或多个自硅氧烷或聚醚延伸的丙烯酸酯侧基部分(pendant acrylate moieties)的硅氧烷聚醚共聚物。
上述概述并不旨在描述该组合物的各个公开的实施方案或每一个实施方式。后续的详细说明更加具体地举例说明了示例实施方案。
具体实施方式
新的聚合物复合材料通过将生物基聚合物和丙烯酰化的硅酮聚醚进行熔融加工而制得。适于实施本发明的生物基聚合物的非限定性例子包括多糖、多肽、脂肪族聚酯、多氨基酸、聚乙烯醇、聚酰胺、聚亚烷基乙二醇及其共聚物。生物基聚合物还可以包括本领域技术人员通常认为的那些分解或降解为具有较低分子量的化合物的聚合物。所得复合材料显示出改进的机械性能,并且未显示出对弯曲性能具有任何不利影响。
在一方面,生物基聚合物是线性聚酯。线性聚酯的非限定性例子包括聚乳酸、L-聚乳酸(PLLA)以及L-乳酸和D-乳酸的无规共聚物及其衍生物。聚酯的其他非限定性例子包括聚己酸内酯、聚羟基丁酸(polyhydroxybutyric acid)、聚羟基戊酸(polyhydroxyvaleric acid)、聚丁二酸亚乙酯(polybutylene succinate)、聚丁二酸亚丁酯(polybutylene succinate)、聚己二酸亚丁酯(polybutylene adipate)、聚苹果酸、聚乙醇酸、聚丁二酸酯(polysuccinate)、聚乙二酸酯(polyoxalate)、聚丁烯基二甘醇酯(polybutylene diglycolate)和聚二氧环己酮(polydioxanone)。
将丙烯酰化的硅酮聚醚与生物基聚合物进行熔融加工,以形成聚合物组合物。聚醚组份可有助于丙烯酰化的硅酮聚醚在生物基聚合物中的分散性和相容性。具有丙烯酸酯侧基部分的两亲聚合物很适用于某些实施方案。在另一实施方案中,本发明所使用的丙烯酰化的硅酮聚醚剂包括那些可自Evonik Inc.(Parsippany,New Jersey)市购得到的通常以TEGO RAD2250(丙烯酰化的聚醚硅氧烷)出售的材料。丙烯酰化的硅酮聚醚包含在聚合物基体中的量通常至多约20%。在一些实施方案中,丙烯酰化的硅酮聚醚可占1%至5%。
自由基引发剂可用于辅助生物基聚合物和丙烯酰化的硅酮聚醚之间的熔融加工和内在反应。自由基引发剂是一种在熔融加工时形成活性自由基部分的物质。本发明中所用的自由基引发剂包括有机超氧化物和重氮化合物。特定自由基引发剂的非限定性例子包括:过氧化苯甲酰、过氧化二异丙苯、二叔丁基过氧化物和偶氮异丁腈。自由基引发剂包含在可熔融加工的组合物中的量可在0.25重量%以下。
在另一实施方案中,可在组合物中添加或引入冲击改性添加剂,以解决可熔融加工的组合物所需的物理特性。本发明中使用的冲击改性剂的非限定性例子包括弹性体共聚酯、聚亚烷基二醇和官能化的天然油脂。弹性体聚酯的例子包括但不限于以Neostar(Eastman ChemicalCo.,Kingsport,TN)、Biomax(DuPont,Wilmington,DE)和Hytrel(DuPont)商标出售的那些。聚亚烷基乙二醇的非限定性例子包括以Carbowax商标(Dow Chemical Co.,Midland,MI)出售的聚乙二醇。官能化的天然油脂的非限定性例子包括:可自Cargill Inc.市购得到的苹果酸化(malinated)的大豆油或环氧化的大豆油、亚麻籽油或向日葵油。
本发明的聚合物组合物具有极好的机械性能平衡,并且是可熔融加工的。某些组合物显示出优异的冲击强度,同时保持了相对较高的挠曲值。这些属性的结合随着此处公开的组合物的分子结构而变化。在一个实施方案中,在促进线性可生物降解聚酯与丙烯酰化的硅酮聚醚之间自由基反应的温度下,通过将线性生物基聚酯与丙烯酰化的硅酮聚醚进行熔融加工,由此制备本发明的生物基聚酯。
可熔融加工过程中各组分的量可根据预期最终使用应用而变化。在最终的组合物中,聚合物可占约20重量%至约99重量%。所含丙烯酰化的硅酮聚醚剂的水平可达20重量%。
在另一方面,通过将聚合物(如线性生物基聚酯)与丙烯酰化的硅酮聚醚以及一种或多种阻燃添加剂进行熔融加工来制备阻燃生物基聚合物组合物。本发明可采用任何传统的卤化或非卤化阻燃添加剂。与线性生物基聚酯相比,本发明的生物基聚酯具有改进的阻燃性能。在一个实施方案中,包含阻燃添加剂的阻燃聚酯显示出自熄阻燃性能。虽然本发明可以采用卤化阻燃剂,但与这些添加剂中的很多添加剂相关的环境危害、生物残留性和毒性使其不太可能用于生物基聚合物组合物。非卤化阻燃剂是更优选的,因为它们不受这些问题的影响。本发明所用的非卤化阻燃添加剂材料包括无机化合物(例如金属氢氧化物、金属硫酸盐、金属硝酸盐、碳酸盐化合物、锡化合物、钛化合物、锆化合物和钼化合物)、二氧化硅化合物、磷化合物、含有硼酸的化合物、有机化合物和氮化合物。阻燃添加剂包含在可熔融加工的组合物中的水平可达80重量%。
合意的非卤化磷基阻燃添加剂的非限定例子包括:磷酸铵、多磷酸铵、三聚氰胺磷酸盐、红磷、磷酯、三(氯乙基)磷酸酯、三(一氯丙基)磷酸酯、三(二氯丙基)磷酸酯、三烯丙基磷酸酯、三(3-羟丙基)磷酸酯、三(三溴苯基)磷酸酯、三-β-氯丙基磷酸酯、三(二溴苯基)磷酸酯、三(三溴新戊基)磷酸酯、四(2-氯乙基)乙烯二磷酸酯、甲基磷酸二甲酯、三(2-氯乙基)正磷酸酯、芳基缩聚磷酸酯、含卤素的缩聚有机磷酸盐、亚乙基二[三(2-氰乙基)]溴化鏻、多磷酸铵、β-氯乙基酸磷酸酯、焦磷酸丁酯、丁基酸磷酸酯、丁氧基乙基酸磷酸酯、2-乙基己基酸磷酸酯、三聚氰胺磷酸盐、含卤素的磷酸盐,以及苯基膦酸。在一方面,多磷酸铵被用作阻燃添加剂。
在本发明的另一方面,可熔融加工的组合物可含其他添加剂。常规添加剂的非限定性例子包括抗氧化剂、光稳定剂、纤维、起泡剂、发泡添加剂、防粘连剂、热稳定剂、冲击改性剂、杀生物剂、相容剂、增粘剂、着色剂、偶联剂和颜料。可用粉末、丸剂、颗粒的形式或以其它任何可挤出的形式,将添加剂引入到可熔融加工的组合物中。可熔融加工的组合物中的常规添加剂的量和类型可根据聚合物基体和成品组合物的所需物理性能而变化。为了获得成品材料的所需物理性能,熔融加工领域的技术人员能够选择适当量和类型的添加剂以匹配特定的聚合物基体。
可熔融加工的组合物可通过多种方式中的任何一种来制备。例如,生物基聚合物、丙烯酰化的硅酮聚醚、任选的阻燃剂和任选的添加剂可通过塑料工业中常用的任何混合手段而结合到一起,例如采用复合磨(compounding mill)、班伯里(Banbury)密炼机或混合挤出机。材料可以使用如粉末、丸剂或颗粒产品的形式。在聚合物熔点或软化点以上的温度下,最方便进行混合操作。所得熔融共混的混合物能够以最终产品的形状直接挤出成型;也可将该混合物制粒,或用其他方法将该混合物粉碎成所需的微粒尺寸或尺寸分布,再送入挤出机(典型的是双螺杆挤出机),共混的混合物由挤出机进行熔融加工,以形成最终产品的形状。或者,组合物还可注塑成所需的形状。用此方案制备超支化聚合物时,所得复合材料表现出优异的性能结果。
在另一实施方案中,阻燃添加剂与生物基聚合物一起熔融加工形成母料。该母料可任选地包含丙烯酰化的硅酮聚醚。在随后的熔融加工步骤中,放下(let down)母料至所需的阻燃添加剂水平。该两步加工可具有改进阻燃添加剂在最终化合物中的分散性,并改进最终化合物的化学和机械性能的效果。在一个可选的实施方案中,在丙烯酰化的硅酮聚醚的存在下,制备阻燃母料,并在随后的加工步骤中添加自由基引发剂。该两步加工生成特别有用的生物基阻燃聚合物组合物。熔融加工聚合物组合物领域的技术人员能够选择加工步骤,以达到混合的组份的所需水平。
虽然选择最佳操作温度取决于组合物的熔点、熔融粘度和热稳定性,但通常在80°至300℃的温度下进行熔融加工过程。不同类型的熔融加工设备(如挤出机)可用于加工本发明的可熔融加工的组合物。适用于本发明的挤出机的描述例如参见Rauwendaal,C.,“PolymerExtrusion”,Hansen Publishers,第11-33页,2001年。
本发明的组合物适用于制造建筑、电子、消费品和汽车工业的制品。例如,引入了本发明组合物的制品可以包括:模压结构产品、成形件、汽车零部件、建筑构件、家居用品或电子硬件。
通过熔融加工本发明组合物而制备的所得制品表现出优异的机械特性。例如,根据公开的实施方案制备的聚合物可具有265焦耳/米以上的冲击强度(无缺口)和2500兆帕以上的弯曲模量中的一种或多种。在某些实施方案中,弯曲模量对冲击强度的比率可在11:1以下,甚至是5:1或更少。此外,在UL94测试程序下,包含阻燃添加剂的组合物表现出自熄性能。在某些实施方案中,在UL94水平阻燃测试中,聚合物可有HB的评级。此外,包含阻燃化合物的聚合物还具有200焦耳/米以上的冲击强度(无缺口)和3000兆帕以上的弯曲模量中的一种或多种。在ASTM E84-08测试或同等的ANSI/UL723测试下,含有阻燃组分的聚合物复合材料能够达到1/A级的评级。在UL94垂直阻燃测试中,含有阻燃组分的聚合物还能够达到V2、V1或V0的评级。
实施例
生成以下实施例所使用的材料包括:
生物基聚合物组合物采用以下方案制备。PLA、支化剂和任选地阻燃剂在塑料袋内干混,并通过重力送入装有四个拉丝模头的26毫米同向旋转双螺杆挤出机(40:1,L:D)(市购自泰国Labtech Engineering,Samutprakarn)。所有样品均在300转每分钟的螺杆速度下加工,使用以下的温度曲线:1-2区域=180℃,3-4区域=180℃,5-6区域=180℃,7-8区域=180℃,模头=180℃。得到的拉丝随后在水浴中冷却,并制粒成0.64厘米的丸剂。得到的丸剂根据ASTM D638(张力)和D790(弯曲)的规格注塑成测试样品。采用桶和喷嘴温度为175℃的85吨机器(市购自Engel Corporation,York,PA)进行生物基聚合物制剂的注塑。随后分别按ASTM D790和D256的规定测试弯曲和冲击性能。
表1给出了所制备的对比例CE1和实施例1-4的生物基聚合物组合物的配方。表2给出了对比例CE1和实施例1-4的生物基聚合物组合物的机械和阻燃性能。
表1对比例CE1–CE3和实施例1-4的生物基聚合物制剂的配方
表2对比例CE1–CE3和实施例1-4的机械性能
根据上述公开的本发明的一般原理和上述详细说明,本领域技术人员将容易想到本发明易于进行的各种改变。因此,本发明的范围应仅由权利要求书及其等同方案加以限定。
Claims (19)
1.一种组合物,其包含可熔融加工的聚合物,所述聚合物源自生物基聚合物和丙烯酰化的硅酮聚醚。
2.根据权利要求1所述的组合物,其中所述丙烯酰化的硅酮聚醚是包含至少两个烯键式不饱和位的化合物。
3.根据权利要求1所述的组合物,其中所述可熔融加工的聚合物还源于自由基引发剂。
4.根据权利要求1所述的组合物,其中所述可熔融加工的聚合物的弯曲模量对冲击强度的比率在11:1以下。
5.根据权利要求1所述的组合物,其中所述可熔融加工的聚合物在UL94水平阻燃测试中具有HB的评级。
6.根据权利要求1所述的组合物,其还包含阻燃添加剂。
7.根据权利要求6所述的组合物,其中所述阻燃添加剂组合物是磷基化合物。
8.根据权利要求7所述的组合物,其中所述阻燃添加剂组合物是三聚氰胺多磷酸盐。
9.根据权利要求6所述的组合物,其中所述可熔融加工的聚合物在UL94垂直阻燃测试中具有V2、V1或V0的评级。
10.根据权利要求7所述的组合物,其中所述可熔融加工的组合物在UL94测试程序下表现出自熄性能。
11.根据权利要求1所述的组合物,其中所述生物基聚合物是聚酯。
12.根据权利要求11所述的组合物,其中所述聚酯包括聚己酸内酯、聚羟基丁酸、聚羟基戊酸、聚丁二酸亚乙酯、聚丁二酸亚丁酯、聚己二酸亚丁酯、聚苹果酸、聚乙醇酸、聚丁二酸酯、聚乙二酸酯、聚丁烯基二甘醇酯、聚二氧环己酮和聚乳酸。
13.根据权利要求1所述的组合物,其中所述生物基聚合物包括多糖、多肽、脂肪族聚酯、多氨基酸、聚乙烯醇、聚酰胺、聚亚烷基乙二醇及其共聚物。
14.根据权利要求1所述的组合物,其中所述组合物具有265焦耳/米以上的无缺口冲击强度和2500兆帕以上的弯曲模量中的一种或多种。
15.根据权利要求6所述的组合物,其中所述组合物具有200焦耳/米以上的无缺口冲击强度和3000兆帕以上的弯曲模量中的一种或多种。
16.一种方法,其包括熔融加工生物基聚合物和丙烯酰化的硅酮聚醚,以形成可熔融加工的聚合物。
17.一种方法,其包括通过对根据权利要求1所述的可熔融加工的聚合物进行熔融加工来形成制品。
18.根据权利要求17所述的方法,其中所述制品包括模压结构产品、成形件、汽车零部件、建筑构件、家居用品或电子硬件。
19.一种工艺,其包括把超支化聚合物挤出、注塑、吹塑、滚塑或分批混合。
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PCT/US2012/030237 WO2012129464A2 (en) | 2011-03-23 | 2012-03-23 | Biobased polymer compositions |
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US (1) | US20140163144A1 (zh) |
EP (1) | EP2688957B1 (zh) |
CN (1) | CN103502361B (zh) |
WO (1) | WO2012129464A2 (zh) |
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US9284414B2 (en) | 2013-11-26 | 2016-03-15 | Globalfoundries Inc. | Flame retardant polymers containing renewable content |
US9346922B2 (en) | 2013-11-26 | 2016-05-24 | International Business Machines Corporation | Flame retardant block copolymers from renewable feeds |
US9260550B1 (en) | 2015-01-27 | 2016-02-16 | International Business Machines Corporation | Lactide-based acrylate polymers |
US9670312B2 (en) | 2015-02-26 | 2017-06-06 | International Business Machines Corporation | Flame-retardant polymers derived from polyols and polyacids |
Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5919861A (en) * | 1995-03-30 | 1999-07-06 | Xerox Corporation | Processes for the preparation of branched polymers |
US6207782B1 (en) * | 1998-05-28 | 2001-03-27 | Cromption Corporation | Hydrophilic siloxane latex emulsions |
CN1662582A (zh) * | 2002-05-29 | 2005-08-31 | 海克尔有限公司 | 超支化聚合物 |
WO2010088067A1 (en) * | 2009-01-30 | 2010-08-05 | 3M Innovative Properties Company | Polylactic acid-containing resin compositions and films |
WO2010108076A2 (en) * | 2009-03-19 | 2010-09-23 | Jeffrey Jacob Cernohous | Biobased polymer compositions |
Family Cites Families (3)
Publication number | Priority date | Publication date | Assignee | Title |
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JP2986509B2 (ja) * | 1989-05-26 | 1999-12-06 | 三井化学株式会社 | 変性ポリエステル樹脂組成物、その製造方法、およびその用途 |
US7732516B2 (en) * | 2008-01-31 | 2010-06-08 | Sabic Innovative Plastics Ip B.V. | Flame retardant polyimide/polyester-polycarbonate compositions, methods of manufacture, and articles formed therefrom |
US8563103B2 (en) * | 2010-02-19 | 2013-10-22 | Smarthealth, Inc. | Polylactide hydrosol and articles made therefrom |
-
2012
- 2012-03-23 EP EP12759916.5A patent/EP2688957B1/en active Active
- 2012-03-23 CN CN201280022102.2A patent/CN103502361B/zh active Active
- 2012-03-23 WO PCT/US2012/030237 patent/WO2012129464A2/en active Application Filing
- 2012-03-23 US US13/821,860 patent/US20140163144A1/en not_active Abandoned
Patent Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5919861A (en) * | 1995-03-30 | 1999-07-06 | Xerox Corporation | Processes for the preparation of branched polymers |
US6207782B1 (en) * | 1998-05-28 | 2001-03-27 | Cromption Corporation | Hydrophilic siloxane latex emulsions |
CN1662582A (zh) * | 2002-05-29 | 2005-08-31 | 海克尔有限公司 | 超支化聚合物 |
WO2010088067A1 (en) * | 2009-01-30 | 2010-08-05 | 3M Innovative Properties Company | Polylactic acid-containing resin compositions and films |
WO2010108076A2 (en) * | 2009-03-19 | 2010-09-23 | Jeffrey Jacob Cernohous | Biobased polymer compositions |
Also Published As
Publication number | Publication date |
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WO2012129464A2 (en) | 2012-09-27 |
US20140163144A1 (en) | 2014-06-12 |
WO2012129464A3 (en) | 2013-01-03 |
EP2688957A2 (en) | 2014-01-29 |
EP2688957B1 (en) | 2019-02-27 |
EP2688957A4 (en) | 2014-10-01 |
CN103502361B (zh) | 2016-10-05 |
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