CN106029706A - 用于制备导热性定向uhmwpe产品以及从中获得产品的工艺 - Google Patents

用于制备导热性定向uhmwpe产品以及从中获得产品的工艺 Download PDF

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CN106029706A
CN106029706A CN201580009350.7A CN201580009350A CN106029706A CN 106029706 A CN106029706 A CN 106029706A CN 201580009350 A CN201580009350 A CN 201580009350A CN 106029706 A CN106029706 A CN 106029706A
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uhmwpe
technique
product
orientation
conductivity
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A·B·马图尔
S·V·卡达姆
S·S·R·甘达姆
U·S·萨特帕蒂
K·R·萨尔马
N·F·帕特尔
G·M·梅赫塔
Y·M·阿明
A·K·P·沙阿
V·K·帕特尔
R·V·扎斯拉
D·K·舒克拉
A·I·帕瑞卡
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Reliance Industries Ltd
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Reliance Industries Ltd
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Priority claimed from IN701MU2014 external-priority patent/IN2014MU00701A/en
Publication of CN106029706A publication Critical patent/CN106029706A/zh
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C43/00—Compression moulding, i.e. applying external pressure to flow the moulding material; Apparatus therefor
    • B29C43/003—Compression moulding, i.e. applying external pressure to flow the moulding material; Apparatus therefor characterised by the choice of material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C43/00—Compression moulding, i.e. applying external pressure to flow the moulding material; Apparatus therefor
    • B29C43/02—Compression moulding, i.e. applying external pressure to flow the moulding material; Apparatus therefor of articles of definite length, i.e. discrete articles
    • B29C43/14—Compression moulding, i.e. applying external pressure to flow the moulding material; Apparatus therefor of articles of definite length, i.e. discrete articles in several steps
    • B29C43/146—Compression moulding, i.e. applying external pressure to flow the moulding material; Apparatus therefor of articles of definite length, i.e. discrete articles in several steps for making multilayered articles
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B29C43/00—Compression moulding, i.e. applying external pressure to flow the moulding material; Apparatus therefor
    • B29C43/22—Compression moulding, i.e. applying external pressure to flow the moulding material; Apparatus therefor of articles of indefinite length
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    • B29C55/00—Shaping by stretching, e.g. drawing through a die; Apparatus therefor
    • B29C55/005—Shaping by stretching, e.g. drawing through a die; Apparatus therefor characterised by the choice of materials
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
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    • B29C55/04—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets uniaxial, e.g. oblique
    • B29C55/06—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets uniaxial, e.g. oblique parallel with the direction of feed
    • B29C55/065—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets uniaxial, e.g. oblique parallel with the direction of feed in several stretching steps
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2023/00—Use of polyalkenes or derivatives thereof as moulding material
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    • B29K2105/00—Condition, form or state of moulded material or of the material to be shaped
    • B29K2105/0005—Condition, form or state of moulded material or of the material to be shaped containing compounding ingredients
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
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    • B29K2105/00—Condition, form or state of moulded material or of the material to be shaped
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    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B29K2105/00—Condition, form or state of moulded material or of the material to be shaped
    • B29K2105/06—Condition, form or state of moulded material or of the material to be shaped containing reinforcements, fillers or inserts
    • B29K2105/16—Fillers
    • B29K2105/165—Hollow fillers, e.g. microballoons or expanded particles
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2105/00—Condition, form or state of moulded material or of the material to be shaped
    • B29K2105/06—Condition, form or state of moulded material or of the material to be shaped containing reinforcements, fillers or inserts
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    • B29K2105/165—Hollow fillers, e.g. microballoons or expanded particles
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    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2995/00—Properties of moulding materials, reinforcements, fillers, preformed parts or moulds
    • B29K2995/0012—Properties of moulding materials, reinforcements, fillers, preformed parts or moulds having particular thermal properties
    • B29K2995/0013—Conductive
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
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    • C—CHEMISTRY; METALLURGY
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    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F10/00—Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
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Abstract

本发明涉及一种高导热性高热容量定向超高分子量聚乙烯(UHMWPE)产品的制备工艺。工艺将UHMWPE送入辊获得预层压，然后进一步热拉伸以获得具有高导热性高热容量定向UHMWPE产品。整个流程中，拉伸温度保持低于UHMWPE的熔融温度。还提供一种通过本发明工艺制备的高导热性高热容量定向UHMWPE产品。定向UHMWPE产品具有以下特性，轴向导热性在70到200W/mK之间，横向导热性在0.022到0.045W/mK之间，热容量在6到25MJ/m3K之间。

Description

用于制备导热性定向UHMWPE产品以及从中获得产品的工艺
技术领域
本发明涉及高导热性定向超高分子量聚乙烯产品及其制备。
定义
本发明中使用的下列术语通常具有如下规定的含义，除非在使用它们的上下文中另有说明。
解缠结：“解缠结”指超高分子量聚乙烯-乙烯的均聚物或共聚物，该聚合物具有以下特点：摩尔量在30万至2000万之间；结晶度高于75％；融解热高于200J/g，体积密度在0.01至0.3g/cc之间，其中,聚乙烯链具有低缠结或完全解缠结。
定向产品：“定向产品”指纤维丝、板、膜、带或其他具有定向聚合物链的聚合物产品。
拉伸比：“拉伸比”指热拉伸膜和砑光机辊轧板材相对单位重量和体积的比率。
预层压：“预层压”指将UHMWPE通过辊后获得的板材，该板材进一步进行热拉伸获得定向UHMWPE产品。
背景技术
聚合物具有许多优势，如低质量密度、化学稳定性、高强度质量比等。聚合物材料通常导热性差，使用非晶态聚合物制备的聚合物(如泡沫)广泛用于隔热。但用于热交换器和热量控制的材料需要高导热性，常见导体通常具有高导热性，如铜、铝、钛等。
最近关于聚乙烯纳米纤维和天然生物聚合物高导热性的报道重新引发研究人员对导热聚合物的兴趣。众所周知，具有高结晶度和链对齐趋势的聚合物具有更高导热性。聚合物中的热量沿共价分子链传导，对于定向产品，导热性取决于结晶度、方向、晶体大小、分子链长度、化学桥接点、结晶态或非晶态边界、缺陷、分子链末端和缠结以及结晶态和非晶态结构。折叠超高分子量聚乙烯(UHMWPE)链组成的随机定向结晶区域变为扩展链组成的高定向结晶区域。扩展链在结晶区域中沿共价链轴方向导热可提高导热性。
用于制备带或UHMWPE板材的UHMWPE纤维传统制备方法需要制备凝胶，使用大量合适溶剂解缠结聚合物链以实现扩展链组成的高定向结晶区域。此外，目前报道的工艺能量密集且麻烦，从而限制其用于商业应用。
因此本发明设计一种可消除传统工艺缺点的高导热UHMWPE制备工艺。
发明目的
下面将在此讨论本发明的一些目的：
本发明的一个目的是提供一种具备高轴向导热性和高热容量的定向UHMWPE产品制备工艺。
本发明的另一个目的是提供一种具备高轴向导热性和高热容量的定向UHMWPE产品制备工艺，该工艺简单、商业可行并且环保。
本发明的另一个目的是提供具备高轴向导热性和高热容量的定向UHMWPE产品。
本发明的另一个目的是改善现有技术的一个或多个问题或至少提供一种有用的选择方案。
以下说明将进一步揭示本发明的其他目的和优势。
发明内容
本发明的一个方面涉及一种高导热性和高热容量定向超高分子量聚乙烯(UHMWPE)产品的制备工艺。工艺将UHMWPE送入具有预先确定线性辊速度和第一次预先确定温度的至少一对辊的辊隙中，获得预层压。获得预层压在预先确定的线性辊速度和第二次预先确定温度下热拉伸，获得具有高导热性和热容量的定向UHMWPE产品。本发明使用的UHMWPE基本解缠结。用于制备预层压和热拉伸的温度可以低于UHMWPE熔融温度。
在另一个方面中，提供一种通过本发明工艺制备的高导热性高热容量定向UHMWPE产品。本发明的高导热性高热容量定向UHMWPE产品的轴向导热性在70到200W/mK之间，横向导热性在0.022到0.045W/mK之间，热容量在6到25MJ/m3K之间。
详细描述
众所周知，有机聚合物是隔热材料，室温下的导热性通常<1W/mK。但是，沿聚合物链对齐方向测量的定向聚乙烯聚合物轴向导热性通过定向增加。结晶度和结晶之间的连接进一步增加聚乙烯的导热性。传统使用UHMWPE通过凝胶纺丝纤维制备的聚乙烯定向产品具有高导热性，约为聚合物树脂的30-100倍。但是，通过挤压制备高导热性UHMWPE产品的工艺需要大量溶剂。
本发明设计一种使用免溶剂流程制备聚乙烯定向产品的工艺，以及高导热性定向UHMWPE产品。
按照本发明的一个方面，提供一种高导热性高热容量定向UHMWPE产品的制备工艺。工艺包括但不局限于以下介绍的步骤。
在本发明的第一个步骤中，将UHMWPE粉末或压缩模压UHMWPE预成型送入具有预先确定线性辊速度和第一次预先确定温度的至少一对辊的辊隙中，获得预层压。在一个具体实施方式中，压缩模压UHMWPE预成型的厚度在1到3mm之间。按照本发明的辊可以是一对或多对。如果使用多对辊，可以串联或并联排列辊。
辊温度保持在聚合物熔融温度以下或接近熔融温度。在本发明的一个典型实施方式中，温度维持在125℃。
在本发明的另一个具体实施方式中，预先确定的线性辊速度在20到200cm/min之间，辊直径150mm，辊速度比在0.80到3.0之间。辊速度比指辊对中的线性辊速度的比率。
通过设置与辊平行的所需间隙，调节预层压宽度。在一个具体实施方式中，预层压的宽度和厚度分别维持在50到55mm和0.05到0.20mm。通过修改垫块间隙进一步调节预层压宽度，按照要求切开预层压获得所需宽度的带/条。
在下一个步骤中，在预先确定的温度和预先确定的线性辊速度下对获得的预层压进行热拉伸，获得定向UHMWPE产品。在特定温度和速度下拉伸可使聚合物链沿拉伸方向对齐；从而在形成的产品中引入各向异性，使其具有高导热性。在一个具体实施方式中，辊温度在130到155℃之间。请注意，UHMWPE温度不得超过熔融温度。温度高于UHMWPE熔融温度时(约140℃)，辊速度增加。辊速度增加会缩短UHMWPE与辊的接触时间，从而使UHMWPE不会接触到更高温度。拉伸速度维持在10到80mm/min之间。不同拉伸比下可以获得具有薄横截面的层压。
本工艺中使用的UHMWPE具有某些预先确定的特性。UHMWPE基本解缠结，分子量在0.3到2000万g/mole之间，使用文档WO2013076733、PCT/IN2013/000016和1440/MUM/2013介绍的合适催化剂制备。粉末还具有各种参数特性，如通过ASTM-D4020-1a测量的增比比浓黏度(RSV)；通过Mark-Houwink方法使用以下公式计算的分子量：M＝K[η]α，其中K和α为常量，K＝53700，α＝1.37，η–固有黏度；通过ASTM D-1895测量的体积密度(BD)；分子量分布，借助采用Orchestrator软件的T.A.Instruments的RDA-III熔融流变仪测量；借助ASTM D 792使用Mettler Toledo测量单位测量的密度；熔融温度(Tm)和熔融热量(ΔHTm)，通过差分扫描热量计测量。通过操纵工艺条件调节聚合物粉末的分子量分布，包括但不局限于温度和压力，以及其他数量如RSV>17dl/g，ΔH>200J/g，体积密度<0.3g/cc。上述工艺形成的UHMWPE粉末具有高结晶，并充分解缠结。
本发明的工艺还包括加入添加剂的步骤。按照本发明使用的添加剂包括但不局限于碳纳米管、石墨烯、炭黑、铝粉和氮化硼。添加剂可以采用粉末或细颗粒物形式。可以采用混合或分散方法将添加剂加入聚合物，然后将聚合物送入辊。添加剂可以进一步提高形成产品的导热性，扩大纯UHMWPE的导热极限。
在本发明的另一个方面中，提供一种通过本上述工艺制备的高导热性高热容量定向UHMWPE产品。在一个具体实施方式中，制备产品的轴向导热性在70到200W/mK之间，横向导热性在0.022到0.045W/mK之间，热容量在6到25MJ/m3K之间。产品的轴向导热性取决于板材拉伸比。按照本发明工艺制备的产品具有高导热性和高热容量。这形成本工艺与传统工艺的差别。此外，按照本工艺制备的产品还具有可透过视线的透明度。
本发明提供一种简单环保免溶剂工艺，处理具有高解缠结大分子链的高结晶UHMWPE聚合物，获得具有最高导热性的产品。因此，形成的产品在热量控制系统中具有大量应用，如印刷电路板和电子设备的换热器/散热片、计算机、打印机、汽车内部和外部、设备、电池、超导线圈、制冷系统、建筑物结构、房屋内部温度控制、化学工程设备、热太阳能设备等。本发明的产品包括但不局限于带、条、纤维丝和膜。UHMWPE膜/带/条/纤维丝制造的导热产品可以采用单层或多层(带或不带添加剂)复合形式，根据膜/带/条/纤维丝的对齐，可以定义导热路径。
下面将通过以下非限定性实施例进一步说明本发明，这些实施例仅用于说明，不解释为以任何方式限制本发明范围。
实施例1：
使用三个具有以下特性(表1)的聚合物样本，维持不同拉伸比，制备薄膜。虽然样本1和2的RSV和分子量(MW)接近，但样本2的分子量分布高于样本1。样本3的RSV、MW和MWD高于样本1和2。
表1
表2显示拉伸膜样本制备条件及其拉伸和热特性。最高拉伸比指超过该限值，薄膜将断裂。
从样本1可以看出，制备的拉伸膜轴向导热性随着拉伸模量的增加而增加，而拉伸模量与拉伸比有关(表2)。结果表明，聚合物样本2可以拉伸128.6倍，导热性为128.2W/mK，而拉伸模量比聚合物样本1较低拉伸比的拉伸膜低。这可能是因为样本2的分子量分布(MWD)比聚合物样本1宽，导致样本2的聚合物链高度对齐，并具有高拉伸性。同样，具有宽MWD的聚合物样本3可以拉伸100倍，导热性为77W/mK。样本3的拉伸模量较低，类似样本2中观测的结果。因此，增加拉伸比而不是增加拉伸模量和加宽MWD，可以实现更高轴向导热性。
用聚合物样本2制备的膜轴向导热性在49.4℃下高达130.1W/mK，这是文献报道的最高值(表5)。可以看到，聚合物膜的导热性不依赖研究的温度范围，即-21.5℃到约50℃(表3到5)。
聚合物膜横向导热性在0.022到0.045W/mK之间。
热容量(Cp)也随着膜拉伸比增加从约7.0MJ/m3K增加至24MJ/m3K(温度范围约-20℃到约50℃)，样本1的拉伸比从31增加到85，样本2约128(表3到5)。这使得拉伸聚合物膜具有独特固态热特性，极高导热性与Cp的组合。
适当调节两个辊轧的线性速度和温度，可以控制板材的处理速度。此外还发现，板材拉伸比取决于拉伸设备的设定温度。
还可以确定，根据单位形态在复合层上的方向，并施加压力压缩实现产品，UHMWPE单轴向导热膜/条/带/纤维丝的复合形态可以具有多轴向控制导热性。
表2
拉伸比指热拉伸膜和砑光机辊轧板材相对单位重量和体积的比率。
表3：样本5 PE 31
表4：样本5 PE 85
温度(℃) 导热性(W/mK) Cp(MJ/m3K)
24.2 112.3 15.38
11.5 112.9 15.06
1.7 113.4 14.76
-12.2 114.5 13.39
-21.3 113.4 13.40
25.4 115.8 15.33
48.7 117.3 17.69
表5：样本5 PE 128
温度(℃) 导热性(W/mK) Cp(MJ/m3K)
23.5 123.5 21.22
11.4 123.5 19.75
1.9 130.5 19.03
-12.1 124.3 18.82
-21.4 124.6 18.27
25.6 128.2 20.85
49.4 130.1 24.19
技术优势和经济意义：
-本发明流程简单，不含溶剂，需要的加工工具方便获取且经济。
-本发明的UHMWPE产品具有单轴向和多轴向导热性。
-UHMWPE膜/带/条/纤维丝的高单轴向导热性带来应用设计的灵活性，如印刷电路板和电子设备的换热器/散热片、计算机、打印机、汽车内部和外部、设备、电池、超导线圈、制冷系统、建筑物结构、房屋内部温度控制、化学工程设备、热太阳能设备等。
-产品具备高轴向导热性和高电绝缘性的独特组合，可用于开发高效电气产品，包括电缆、电气接线等。
贯穿本说明书中的单词“包括”，或其变形都被理解为意指包含一种所述要素、整数或步骤、或一组要素、整数或步骤，但不排除任何其他要素、整数或步骤，或要素、整数或步骤组。
本说明书中包括的所有文件、行为、材料、设备、物品等的讨论是专为本发明提供一个上下文环境。这并不意味着承认了这些资料的部分或全部就构成了在此项专利申请之前就已存在于任何国家相关领域的常识。
上述具体实施方式的描述将充分披露本发明中实施方式的一般性，在没有脱离一般概念的前提下，其他人可以很容易地运用现有知识修改和/或调整此类具体实施方式的各种应用。因此，这些调整和修改应被确定为包含在与所披露的实施方式相当的含义和范围内。需要了解的是，文中所使用的措辞或用辞是为了描述而非限制。因此，虽然文中的具体实施方式描述的是首选具体实施方式，熟知本领域的技术人员认识到在所描述的具体实施方式的精神与范围内，可以对文中的具体实施方式进行修改。

Claims (13)

1.一种高导热性高热容量定向超高分子量聚乙烯(UHMWPE)产品的制备工艺；上述工艺包括以下步骤：
a.将UHMWPE送入具有预先确定线性辊速度和第一次预先确定温度的至少一对辊的辊隙中，获得预层压；
b.在预先确定的线性辊速度和第二次预先确定温度下热拉伸上述预层压，获得具有高导热性和热容量的定向UHMWPE产品。
2.如权利要求1所述的工艺，其中定向UHMWPE产品的导热性在70到200W/mK之间。
3.如权利要求1所述的工艺，其中定向UHMWPE产品的热容量在6到25MJ/m3K之间。
4.如权利要求1所述的工艺，其中UHMWPE解缠结。
5.如权利要求1所述的工艺，其中UHMWPE采用UHMWPE粉末和压缩UHMWPE预成型的形式。
6.如权利要求1所述的工艺，其中所述预先确定的线性辊速度在2到200cm/min之间。
7.如权利要求1所述的工艺，其中所述第一次预先确定温度和所述第二次预先确定温度低于UHMWPE的熔融温度。
8.如权利要求1所述的工艺，其中所述预层压热拉伸在10到80mm/minute之间。
9.如权利要求1所述的工艺，还包括在UHMWPE聚合物中加入至少一种添加剂，送入至少一对辊的辊隙。
10.如权利要求9所述的工艺，其中所述添加剂是从以下组选择的至少一种，该组包括碳纳米管、石墨烯、炭黑、铝粉和氮化硼。
11.如权利要求1所述的工艺，其中热拉伸产品和预层压的拉伸比在30到250之间。
12.一种如权利要求1所述工艺制备的高导热性高热容量定向UHMWPE产品，具有以下特性：
a.轴向导热性在70到200W/mK之间；
b.横向导热性在0.022到0.045W/mK之间；
c.热容量在6到25MJ/m3K之间；
d.结晶度在85到95％之间。
13.如权利要求12所述的高导热性高热容量定向UHMWPE产品，其中所述产品通过以下组选择的形态获得，该组包括板、带、纤维丝和膜。
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