CN102369243B - 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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- CN102369243B CN102369243B CN201080012173.5A CN201080012173A CN102369243B CN 102369243 B CN102369243 B CN 102369243B CN 201080012173 A CN201080012173 A CN 201080012173A CN 102369243 B CN102369243 B CN 102369243B
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Classifications
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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
- 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
- C08G63/06—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from hydroxycarboxylic acids
- C08G63/08—Lactones or lactides
-
- 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
- C08K5/10—Esters; Ether-esters
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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
- C08G83/00—Macromolecular compounds not provided for in groups C08G2/00 - C08G81/00
- C08G83/002—Dendritic macromolecules
- C08G83/005—Hyperbranched macromolecules
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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
- C08K5/0033—Additives activating the degradation of the macromolecular compound
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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
- C08K5/14—Peroxides
-
- 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
- C08K5/16—Nitrogen-containing compounds
- C08K5/34—Heterocyclic compounds having nitrogen in the ring
- C08K5/3467—Heterocyclic compounds having nitrogen in the ring having more than two nitrogen atoms in the ring
- C08K5/3477—Six-membered rings
- C08K5/3492—Triazines
- C08K5/34928—Salts
-
- 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
- C08K5/51—Phosphorus bound to oxygen
- C08K5/52—Phosphorus bound to oxygen only
- C08K5/5205—Salts of P-acids with N-bases
-
- 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
- C08L101/005—Dendritic macromolecules
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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Abstract
在促进可生物降解聚合物与支化剂之间自由基反应的温度下，通过将可生物降解聚合物与支化剂熔融加工来制备超支化的可生物降解聚合物。该可生物降解组合物良好地平衡了机械性能，适用于阻燃应用。
Description
相关申请的交叉参照
本申请要求于2009年3月19日提交的临时专利申请号为61/161546的美国优先权，该处全文引用其公开内容。
技术领域
本发明涉及一种超支化组合物。具体来说，本发明是一种可生物降解聚合物和支化剂的组合，其形成的超支化聚合物可具有优异的阻燃性能和机械性能。
背景技术
可生物降解聚合物广泛运用在许多应用中，包括汽车、房屋建筑、电子和消费类产品。该聚合物可由生物基(bio-based)聚合物或石油基聚合物组成。在这些材料的预期用途告终后，聚合物的生物降解是解决与处置该材料相关的环境问题的首选。然而，聚合物必须满足某些物理和化学特性，才能适合其目标应用。可生物降解聚合物在某些应用中的一个常见要求是其必须阻燃。然而，某些阻燃剂(如卤素化合物)可能会在燃烧过程中产生有害气体。
在聚合物组合物中添加传统阻燃材料可能对组合物的物理特性产生不利影响，最终使得该组合物不适宜或不满足其目标用途。由于其分子结构，高填充阻燃聚合物的物理特性与竞争性材料相比往往处于劣势。这种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，其他阻燃组合物的分子结构可能会限制后续处理。
发明内容
本发明的可生物降解聚合物组合物良好地平衡了机械性能，并使组合物在其最初混合后即可熔融加工。这些属性的组合是由于这些组合物的分子结构产生的。在一个具体实施方案中，在促进可生物降解
聚合物与支化剂之间自由基反应的温度下，通过将可生物降解聚合物与支化剂熔融加工来制备本发明的超支化可生物降解聚合物。在一个具体实施方案中，聚合物是一种可生物降解的线性聚酯，支化剂则是烯键式不饱和化合物。该组合物在不采用传统阻燃化合物的情况下就具有一定的阻燃特性。
本发明中包含的超支化组合物所具有的分子结构部分是由组合物中采用的支化剂产生的。在一个具体实施方案中，本发明的支化剂包括多官能化合物，该多官能化合物可以在熔融加工期间进行自由基均裂反应，并与可生物降解聚酯发生反应，形成超支化可生物降解聚酯。聚合物链的支化和相互作用程度具有分子量较高的材料的特性，同时仍可进行后续熔融加工。
如UL 94测试参数的通过评级(passing rating)所体现的，超支化聚合物可显示出阻燃特性。可选地，可以添加磷基化合物等阻燃剂以增强阻燃特性。这种组合物具有理想的机械性能，而且该聚合物是自熄(self extinguishing)的。
出于本发明的目的，本申请中使用的下列术语定义如下：
“可生物降解聚合物”是指能够通过化学方式降解成较低分子量的材料的聚合物材料或树脂。
“组合物”是指聚合物材料和添加剂或填料的混合物。
“超支化”是指具有三个或更多个链末端的可熔融加工聚合物。
“可熔融加工组合物”是指熔融加工的剂型，其通常在高温下，采用传统的聚合物加工技术(例如挤出或注塑)熔融加工。
“熔融加工技术”是指挤出、注塑、吹塑、滚塑或分批混合。
本发明的上述概述并不用于描述预设发明的各个公开的具体实施方案或每一个实施。后续的详细说明更加具体地举例说明了它的具体实施方案。
具体实施方式
本发明的聚合物是通过将可生物降解聚合物和支化剂熔融加工而制备的。可生物降解聚合物可包括本领域技术人员普遍认为分解成分子量较低的化合物的那些聚合物。适合实践本发明的可生物降解聚合 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。
一方面，可生物降解聚合物是线性聚酯。线性聚酯的非限定性例子包括聚氨基酸、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、聚丁二酸亚丁酯(polybutylene succinate)、聚己二酸亚丁酯、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)。
在一个具体实施方案中，本发明的支化剂包含多官能化合物，该多官能化合物可以在熔融加工期间进行自由基均裂反应，并与可生物降解聚酯发生反应，形成超支化可生物降解聚酯。适用于本发明的支化剂包括包含多个烯键式不饱和部位的有机化合物，该烯键式不饱和部位能够在熔融加工过程中与存在的自由基物种发生反应。有用的烯键式不饱和支化剂的具体例子可包括多官能丙烯酸酯和甲基丙烯酸酯化合物。多官能化合物的非限定性例子包括：1，6-己二醇二甲基丙烯酸酯、1，6-己二醇二丙烯酸酯、乙二醇二甲基丙烯酸酯、乙二醇二丙烯酸酯、三羟甲基丙烷三丙烯酸酯、三羟甲基丙烷三甲基丙烯酸酯、甘油三甲基丙烯酸酯、甘油三丙烯酸酯、甘油二甲基丙烯酸酯、甘油二丙烯酸酯、季戊四醇三丙烯酸酯、季戊四醇三甲基丙烯酸酯、季戊四醇四丙烯酸酯、季戊四醇四甲基丙烯酸酯。本发明的支化剂包括每分子至少具有三个不饱和丙烯酸或甲基丙烯酸部分的多官能丙烯酸酯或甲基丙烯酸酯。
在一个可选的具体实施方案中，用于衍生超支化聚合物的材料可任选地包含自由基引发剂与支化剂。自由基引发剂是在熔融加工时会形成活性自由基部分的物种。本发明中使用的自由基引发剂包括有机过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二异丁腈。可熔融加工组合物中可包含的自由基引发剂的量小于0.25重量％。
在另一个具体实施方案中，可在组合物中添加或引入冲击改性剂 来实现可熔融加工组合物所需的物理特性。本发明中所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存在的油。弹性体聚酯的例子包括但不仅限于以Neostar(Eastman Chemical Co.，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)销售的聚乙二醇。官能化的天然存在的油的非限定性例子包括：Cargill Inc.市售的苹果酸化(malinated)或环氧化的大豆油、亚麻籽或向日葵油。
本发明产生超支化聚合物。超支化区别于且不同于某些形式的交联聚合物，因为它允许对聚合物进行后续熔融加工。组合使用传统的多官能单体与自由基引发剂物种(如本领域技术人员所知的那些)生成高度交联的可生物降解聚酯。然而，即使并非不可能，由此产生的材料也将难以用二次熔融加工操作形成一个物品。
本发明的超支化聚合物组合物良好地平衡了机械性能，并且可熔融加工。这些属性的组合是由于本文公开的组合物的分子结构产生的。在一个具体实施方案中，在促进线性可生物降解聚酯与多官能单体之间自由基反应的温度下，通过将线性可生物降解聚酯与多官能单体熔融加工来制备本发明的超支化可生物降解聚酯。
可熔融加工的超支化组合物中的组分的量可随所需的最终用途而有所不同。在最终组合物中，聚合物可占约20重量％至约99重量％。所含支化剂最高可为10重量％的水平。
另一方面，可通过将聚合物(如线性可生物降解聚酯)与支化剂和一种或多种阻燃添加剂熔融加工来制备阻燃超支化可生物降解聚合物组合物。本发明可采用任何传统的卤化或非卤化阻燃添加剂。与线性可生物降解聚酯相比，本发明的超支化可生物降解聚酯具有改进的阻燃性能。在一个具体实施方案中，包含阻燃添加剂的阻燃超支化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，但与很多这类添加剂相关的环境危害、生物残留性和毒性使其不太适合于可生物降解聚合物组合物。非卤化阻燃剂是较优选的，因为它们不会受到这些问题的影响。可用于本发明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)、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。可熔融加工组合物中包含的阻燃添加剂可占直至80％的重量。
可取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。一方面，多磷酸铵被用作阻燃添加剂。
在本发明的另一方面，可熔融加工组合物可包含其他添加剂。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、生物杀灭剂、相容剂、增粘剂、着色剂、耦联剂和颜料。添加剂可作为粉末、丸剂、颗粒的形式或其他任何可挤出形式引入可熔融加工组合物。可熔融加工组合物中常规添加剂的数量和类型可有所不同，取决于聚合物基体和制成的组合物所需的物理性质。熟悉熔融加工的人员能够选择适当数量和类型的添加剂以匹配特定的聚合物基体，以达到制成的材料所需的物理性质。
本发明的可熔融加工的超支化组合物可通过任意的多种方式制备。例如，可生物降解聚合物、支化剂、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，例如复合磨(compounding mill)、班伯里(Banbury)密炼机或混合挤出机。材料可以使用例如粉末、丸剂或颗粒产品的形式。混合操作最方便地在聚合物的熔点或软化点以上的温度下进行。可将由此得到的经熔融共混的混合物直接挤出成最终产品形状的形式，或者将其制粒或用其他方法粉碎成所需的微粒尺寸或尺寸分布并将其送入挤出机(通常为双螺杆挤出机)，该挤出机将经共混的混合物熔融加工以形成最终产品的 形状。此外，组合物还可注塑成所需的形式。如用此方案制备超支化聚合物，所得到的组合物表现出优异的性能。
在另一个具体实施方案中，阻燃添加剂与可生物降解聚合物一起熔融加工，从而形成母料。该母料可任选地包含支化剂。在随后的熔融加工步骤中，随后放下母料至所需的阻燃添加剂水平。这两个加工步骤可具有改进阻燃添加剂的分散和最终化合物的化学和机械性能的效果。在一个可选的具体实施方案中，阻燃母粒在支化剂的存在下制备，并在随后的加工步骤中添加自由基引发剂。这两个加工步骤会生成特别有用的可生物降解的超支化阻燃聚合物组合物。熟悉熔融加工聚合物组合物的人员能够选择加工步骤以使组分达到所需的混合水平。
虽然最佳操作温度的选择取决于组合物的熔点、熔融粘度和热稳定性，但熔融加工通常在80°至300℃的温度下进行。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组合物。适用于本发明的挤出机的描述例如参见Rauwendaal，C.，“Polymer Extrusion”，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物品。例如，引入了本发明组合物的物品可以包括：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得到的物品表现出优异的机械特性。例如，超支化聚合物具有大于每米265焦耳的冲击强度(无缺口)和大于2300兆帕的弯曲模量中的一种或多种。此外，组合物在UL 94测试程序下还表现出自熄性能。在某些具体实施方案中，超支化聚合物的UL 94水平阻燃测试评级达到HB。此外，含阻燃化合物的超支化聚合物还具有大于200焦耳/米的冲击强度(无缺口)和大于3000兆帕的弯曲模量中的一种或多种。具有阻燃成分的超支化聚合物在ASTM E84-08测试或同等的ANSI/UL 723测试下能够达到1/A级的评级。具有阻燃成分的超支化聚合物在UL 94垂直阻燃测试中还能够达到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：
可生物降解聚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(strand die)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200转每分钟的螺杆速度下加工，其使用以下的温度曲线：1-2区域＝130℃，3-4区域＝150℃，5-6区域＝170℃，7-8区域＝170℃，模头＝170℃。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ASTMD638(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公司)进行可生物降解聚合物制剂的注塑。随后分别按ASTM D790和D256的规定测试弯曲和冲击性能。按UL-94水平或垂直燃烧测试方法来测试阻燃性能。熔融指数根据ASTM D1238的规定测定。在所有情况下，测试都是在190℃下用2.1千克的负载进行的。
表1给出了所制备的对比例CE1-CE3和实施例1-7的可生物降解聚合物组合物的配方。表2给出了对比例CE1-CE3和实施例1-7的可生物降解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1-7的可生物降解聚合物制剂的配方
表2对比例CE1-CE3和实施例1-7的机械性能
*样品7不能注塑/熔融加工
根据上述公开的本发明一般原理和上述详细说明，本领域技术人员将容易理解本发明容许进行各种修改。因此，本发明的范围应仅限于权利要求书及其等同物。
Claims (15)
1.一种组合物，其包含源自可生物降解聚酯聚合物和支化剂的可熔融加工的超支化聚合物，其中可生物降解聚酯聚合物选自聚乳酸、L-聚乳酸和L-乳酸和D-乳酸的共聚物，以及其中所述支化剂是多官能丙烯酸酯或甲基丙烯酸酯化合物。
2.根据权利要求1所述的组合物，其中所述可熔融加工的超支化聚合物还源自于自由基引发剂。
3.根据权利要求1所述的组合物，其中的超支化聚合物的UL94水平阻燃测试等级为HB。
4.根据权利要求1所述的组合物，其还包含阻燃添加剂。
5.根据权利要求4所述的组合物，其中所述阻燃添加剂组合物是磷基化合物。
6.根据权利要求5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。
7.根据权利要求4所述的组合物，其中所述超支化聚合物的UL94垂直阻燃测试等级为V2、V1或V0。
8.根据权利要求5所述的组合物，其中所述组合物在UL94测试程序下表现出自熄性能。
9.根据权利要求1所述的组合物，其中多官能丙烯酸酯或甲基丙烯酸酯化合物选自1,6-己二醇二甲基丙烯酸酯、1,6-己二醇二丙烯酸酯、乙二醇二甲基丙烯酸酯、乙二醇二丙烯酸酯、三羟甲基丙烷三丙烯酸酯、三羟甲基丙烷三甲基丙烯酸酯、甘油三甲基丙烯酸酯、甘油三丙烯酸酯、甘油二甲基丙烯酸酯、甘油二丙烯酸酯、季戊四醇三丙烯酸酯、季戊四醇三甲基丙烯酸酯、季戊四醇四丙烯酸酯、季戊四醇四甲基丙烯酸酯。
10.根据权利要求1所述的组合物，其中所述组合物具有大于265焦耳/米的无缺口冲击强度和大于2300兆帕的弯曲模量中的一种或多种。
11.根据权利要求1所述的组合物，其中所述组合物还包括冲击改性剂。
12.一种方法，其包括熔融加工可生物降解聚酯聚合物和支化剂，以形成可熔融加工的超支化聚合物，其中可生物降解聚酯聚合物选自聚乳酸、L-聚乳酸和L-乳酸和D-乳酸的共聚物，以及其中所述支化剂是多官能丙烯酸酯或甲基丙烯酸酯化合物。
13.根据权利要求12所述的方法，其中多官能丙烯酸酯或甲基丙烯酸酯化合物选自1,6-己二醇二甲基丙烯酸酯、1,6-己二醇二丙烯酸酯、乙二醇二甲基丙烯酸酯、乙二醇二丙烯酸酯、三羟甲基丙烷三丙烯酸酯、三羟甲基丙烷三甲基丙烯酸酯、甘油三甲基丙烯酸酯、甘油三丙烯酸酯、甘油二甲基丙烯酸酯、甘油二丙烯酸酯、季戊四醇三丙烯酸酯、季戊四醇三甲基丙烯酸酯、季戊四醇四丙烯酸酯、季戊四醇四甲基丙烯酸酯。
14.根据权利要求12所述的方法，进一步包括形成包含可熔融加工的超支化聚合物和阻燃剂的组合物。
15.根据权利要求12所述的方法，进一步包括形成包含可熔融加工的超支化聚合物和冲击改性剂的组合物。
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