CN112384563A - 用于海底保温的热塑性硫化橡胶改性的聚丙烯 - Google Patents
用于海底保温的热塑性硫化橡胶改性的聚丙烯 Download PDFInfo
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Abstract
公开了一种聚丙烯/热塑性硫化橡胶保温涂料。所述涂料特别适合海底应用,特别是为油井管道和其它机械的接头提供保温。所述涂料表现出优于本领域已知的接头保温涂料的机械特性,尤其是与其它保温涂料组合时。
Description
交叉引用
本国际专利申请要求于2018年6月29日提交的美国临时专利申请第62/692,164号的优先权。
技术领域
本发明涉及用于管道和其它输送流体的材料的保温。确切地说,本发明涉及一种保温材料,所述保温材料可被施加到另外经保温管道的裸露端上,并将补充先前存在的保温体的机械特性。
背景技术
深海石油生产和运输机械,例如海底出油管道和油井“圣诞树(Christmastree)”,需要保温涂料,以确保机械中所容纳的热原油能够正常流动。深海机械保温体的最常见形式之一是5层聚丙烯(5LPP)保温体。顾名思义,5LPP保温体是一种多层聚丙烯保温体,包含提供粘合功能的层,以及提供保温功能的中空玻璃球,以及提供防水、机械完整性和耐冲击性的未改性聚丙烯。5LPP通常施加在长度在33′至82′之间且直径在6″至16″之间的钢管上。这样的管道通常经由“现场对接(field joint)”方法在现场焊接在一起。为了准备现场对接,应去除管道末端的保温体,并对裸露的管道进行清洗,焊接,进一步清洗并用防腐蚀涂料进行处理。最后,将现有的聚丙烯的保温涂料注射成型到裸露的管道上。在WO2007096209中公开了这种方法。
现有的聚丙烯是与5LPP保温体中使用的聚丙烯不同的材料,且因此具有不同的机械和物理特性。通常,现有的聚丙烯与5LPP的组合会导致在离岸海底应用中部署管道时发生故障(呈开裂的形式)。由于任何维修都必须在困难的情况下离岸完成,因此,此类故障成本高昂、费时且有潜在危险。美国专利第8,415,447号试图通过公开使用涂布聚烯烃的钢管来解决开裂的问题。但是,聚烯烃缺乏5LPP的层结构,且因此材料的机械特性较差。
所需要的是一种保温涂料,所述保温涂料不仅可以代替现有的聚丙烯,而且在机械特性方面相对于5LPP更为匹配,并且/或者具有较低的收缩率,从而在注射成型后具有较低的残余应力。
发明内容
所公开的发明包括将含有聚丙烯和热塑性硫化橡胶的保温涂料施加到本来用另一保温材料涂布的管道的裸露端。
所公开的发明用充当弹性体的热塑性硫化橡胶(TPV)对现有的聚丙烯(PP)进行了改性。在一个优选的实施例中,将35重量%TPV添加到现有的聚丙烯中。已经确定,TPV的添加引起聚丙烯的收缩率降低,与现有材料相比,这使残余应力基本上降低了约50%。
附图说明
图1是描绘涂布有所公开的保温PP/TPV涂料的管道的图。
图2是描绘经受推力测试的PP/TPV样本的位移与载荷的关系的图。
图3是比较现有的聚丙烯与用35重量%TPV改性的现有的聚丙烯的残余应力的图。
图4是比较现有的聚丙烯与用35重量%TPV改性的现有的聚丙烯的蠕变应变的图。
具体实施方式
所公开的发明包括将含有聚丙烯和热塑性硫化橡胶的保温涂料施加到本来用另一保温材料涂布的管道的裸露端。
除非另有说明,否则本文所述的所有百分比均为重量百分比(重量%)。
除非另有说明,否则温度以摄氏度(℃)为单位,且“环境温度”意指介于20℃与25℃之间。
“聚合物”通常是指通过聚合相同或不同类型的单体制备的聚合化合物或“树脂”。如本文所用,通用术语“聚合物”包括由一种或多种类型的单体制成的聚合化合物。
聚丙烯
聚丙烯(PP)是具有以下化学式的热塑性聚合物:
PP的特性取决于分子量和分子量分布、结晶度、共聚单体(如果使用的话)的类型和比例以及全同规整度。PP通常既坚韧又柔软,可以承受高于100℃的温度而不会熔化,并且在低于0℃的温度下会变脆。PP通常经由注射成型以及吹塑成型和注射拉伸吹塑成型而成型。
“现有的聚丙烯”是指含有通常包括在本领域已知的商业聚丙烯产品中的添加剂的聚丙烯。现有的聚丙烯含有至少约50重量%的聚丙烯。
热塑性硫化橡胶
热塑性硫化橡胶(TPV)是热塑性弹性体的一个子类。顾名思义,热塑性弹性体是由具有热塑性和弹性体两种特性的材料组成的聚合物。由于它们兼具橡胶和塑性特性,因此热塑性弹性体可用于制造应用,例如注射成型。
TPV的一种来源在商业上称为Santoprene,且可从埃克森美孚(ExxonMobil)获得。Santoprene通常可以通过动态硫化或交联来制备。橡胶相在高温下与热塑性材料熔融混合时发生交联。TPV优选包含乙丙二烯单体(EPDM)橡胶,其中聚丙烯作为优选的热塑性材料。适用于所公开发明的EPDM橡胶通常具有以下化学式:
适用于本发明的EPDM优选地是约60重量%至约70重量%的乙烯单体、约25重量%至约35重量%的丙烯单体和约1重量%至约10重量%的二烯,且更优选地是65重量%的乙烯、30重量%的丙烯和5重量%的二烯。优选的二烯包括二环戊二烯、5-亚乙基-2-降冰片烯和1,4-己二烯,且更优选地是5-亚乙基-2-降冰片烯。TPV的密度在0.89-0.98g/cm3之间,肖氏硬度(Shore hardness)是35A-50D,且工作温度在-60℃与135℃之间。适用于本发明的TPV的重量平均分子量优选地在约300kg/mol与400kg/mol之间,且更优选地是380kg/mol。
当将完全固化的EPDM橡胶颗粒添加到熔体混合物中时,聚丙烯用作基体材料并封装填充剂EPDM橡胶颗粒,从而形成复合材料。这样,所得的TPV表现出EPDM橡胶的弹性特性以及聚丙烯的塑性特性。
使用方法
本发明的TPV改性的PP可以经由本领域已知的任何注射成型和/或挤出成型方法来制备。在一种优选的方法中,将TPV和PP粒料的混合物进料到挤出成型机中,并加热到高于它们的熔点(约190℃),以使TPV和PP共混并形成PP/TPV混合物。然后将PP/TPV混合物经由挤出机的模头挤出,并沉积在管道或其它材料上。优选地,PP/TPV混合物的TPV在约15重量%与约40重量%之间,且更优选地TPV为35重量%。优选地,PP/TPV混合物是在大于60%与约85%之间的现有的聚丙烯。
工作实例
以下实例说明了本文公开和要求保护的本发明的各种非限制性实施例及其某些属性。
样本制备
将现有的PP和TPV聚合物在塑料袋中干混,使得混合物为35重量%TPV。将空气引入袋子中以将其吹成球形,并紧紧关闭袋子的开口以防止空气释放。然后将袋子多次搅动60秒,以获得PP和TPV的充分分散的共混物。然后通过进料器将混合的共混物重力进料到料斗中,所述料斗又与Micro-18双螺杆挤出机的机筒相连。PP/TPV混合物最初以约2.2磅/小时的速度进料,随后随着挤出机中的扭矩和压力稳定而提高到4磅/小时。
PP/TPV粒料混合物从料斗行进到进料喉,所述进料喉接着将混合物分配到卧式挤出机机筒中,所述机筒含有两个以200rpm旋转的纺丝螺杆。挤出机的机筒具有受控的加热区,这些加热区已预热到140℃、160℃、180℃、190℃和200℃。这样,当PP/TPV混合物从挤出机的进料段通过到达模头段时,将其逐渐加热至超过其熔融温度。PP/TPV混合物熔融并共混在一起,形成热聚合物树脂。随后将树脂推过筛网,然后推过挤出机的模头。
在挤出PP/TPV混合物之前,将外径为2″且壁厚为0.049″的低碳钢制成的圆管切成4″长。用二氧化硅类介质清洗所述管以从管的表面除去杂质。所述管然后用丙酮冲洗并用氮气干燥。然后用高温金属密封带将4″管同心地连接到直径为6″且高度为2″的金属平底盘上。金属管与金属平底盘之间的空间充满了挤出的PP/TPV聚合物树脂。一旦聚合物达到金属平底盘的最高高度,就停止挤出并且使聚合物随时间冷却。然后从平底盘中取出金属管/聚合物样本,得到包含被直径为6″的环形PP/TPV聚合物树脂围绕的直径为2″的金属管的样本。在图1中描绘了具有金属管2和PP/TPV涂料3的代表性样本1。
重复样本制备以产生多个样本。还制备了使用100%现有的聚丙烯的样本。
环剪测试-残余应力测量
在Instron 5581机械测试架上对PP/TPV和100%的现有的聚丙烯样本进行推力测试。推力测试试图将金属管从其聚合物涂料上移开。以0.05″/分钟的位移速率进行测试。图2中描绘了PP/TPV样本的位移与载荷的关系。如图2所示,金属管PP/TPV组合展现出一个初始峰值载荷,其随后趋于平稳,表明聚合物对金属管发生摩擦滑动。已确定,所述摩擦滑动是由于PP/TPV组合对金属管施加的压缩力造成的。100%的现有的聚丙烯样本呈现出相似的形状峰值/平台力-位移曲线。
获得了从PP/TPV和100%现有的聚丙烯样本的平台部分获取的载荷平均值。称重样本并计算其体积。尽管每个样本的直径相同(归因于平底盘的形状均匀),但每个样本的高度由于挤压的变化而略有变化。这样,测量每个样本的高度。每个样本的残余应力σ经由以下公式确定:
其中P是测量的推出(平台)力,而A是与钢管接触的聚合物的表面积。摩擦系数μ在ASTM表征实验室中进行了测量,且所有样本的平均值视为0.58。
计算每个样本的残余应力,并计算PP/TPV和100%现有的聚丙烯样本的平均残余应力。这些平均残余应力描绘在图3中示出。如图3所示,与100%的现有的聚丙烯相比,PP/TPV混合物表现出优异的残余应力。
三轴压缩测试
环剪测试完成后,从环剪样本上切出直径为1″且厚度为1/4″的圆盘。然后将样本置于可密封的三轴压缩测试仪中,并加热到150℃。施加30MPa的压缩压力,并在150℃下保持12小时,符合ISO 12736压力下海底涂料的标准。随时间测量PP/TPV和100%现有的聚丙烯样品的压缩蠕变应变,并描绘在图4中。如图4所示,与100%的现有的聚丙烯样品相比,PP/TPV表现出较小的蠕变应变。
尽管已经参考如以上说明书和附图中公开的本发明优选实施例描述了本发明,但是在不脱离本发明的情况下,本发明的更多实施例是可能的。因此,本发明的范围应仅由所附权利要求书限制。
Claims (20)
1.一种使具有第一保温涂料且第一端不具有所述第一保温涂料的管道保温的方法,所述方法包含以下步骤:
在所述管道的所述第一端上施加第二保温涂料,
其中所述第二保温涂料包含现有的聚丙烯和热塑性硫化橡胶。
2.根据权利要求1所述的方法,其中所述管道包含金属。
3.根据权利要求1所述的方法,其中所述第二保温涂料包含在约15重量%至约40重量%之间的热塑性硫化橡胶。
4.根据权利要求2所述的方法,其中所述第二保温涂料包含在大于60%至约85%之间的现有的聚丙烯。
5.根据权利要求2所述的方法,其中所述第二保温涂料包含约35重量%的热塑性硫化橡胶。
6.根据权利要求1所述的方法,其中所述热塑性硫化橡胶包含聚丙烯基体材料和乙丙二烯单体(EPDM)橡胶填充剂材料。
7.根据权利要求6所述的方法,其中所述EPDM橡胶填充剂材料包含在约60重量%至约70重量%之间的乙烯单体、在约25重量%至约35重量%之间的丙烯单体以及在约1重量%至约10重量%之间的二烯。
8.根据权利要求7所述的方法,其中所述EPDM橡胶填充剂材料包含约65重量%的乙烯、约30重量%的丙烯和约5重量%的二烯。
9.根据权利要求6所述的方法,其中所述EPDM橡胶填充剂材料包含选自由二环戊二烯、5-亚乙基-2-降冰片烯和1,4-己二烯组成的群组的二烯。
10.根据权利要求9所述的方法,其中所述EPDM橡胶填充剂材料包含5-亚乙基-2-降冰片烯。
11.根据权利要求1所述的方法,其中所述热塑性硫化橡胶的重量平均分子量在约300kg/mol与约400kg/mol之间。
12.根据权利要求11所述的方法,其中所述热塑性硫化橡胶的重量平均分子量为约380kg/mol。
13.一种用于在高压环境中提供保温的涂料,所述涂料包含现有的聚丙烯和热塑性硫化橡胶。
14.根据权利要求13所述的涂料,其中所述涂料包含在约15重量%至约40重量%之间的热塑性硫化橡胶。
15.根据权利要求13所述的涂料,其中所述涂料包含在大于60%至约85%之间的现有的聚丙烯。
16.根据权利要求13所述的涂料,其中所述涂料包含约35重量%的热塑性硫化橡胶。
17.根据权利要求13所述的涂料,其中所述热塑性硫化橡胶包含聚丙烯基体材料和乙丙二烯单体(EPDM)橡胶填充剂材料;
其中所述EPDM橡胶填充剂材料包含约65重量%的乙烯、约30重量%的丙烯和约5重量%的二烯。
18.根据权利要求17所述的涂料,其中所述二烯包含5-亚乙基-2-降冰片烯。
19.根据权利要求13所述的涂料,其中所述热塑性硫化橡胶的重量平均分子量在约300kg/mol与约400kg/mol之间。
20.一种用于在高压环境中为金属管道提供保温的涂料,所述涂料包含现有的聚丙烯和热塑性硫化橡胶;
其中所述涂料包含约35重量%的热塑性硫化橡胶;
其中所述热塑性硫化橡胶的重量平均分子量为约380kg/mol;
其中所述热塑性硫化橡胶包含聚丙烯基体材料和乙丙二烯单体(EPDM)橡胶填充剂材料;
其中所述EPDM橡胶填充剂材料包含约65重量%的乙烯、约30重量%的丙烯和约5重量%的二烯;
其中所述二烯包含5-亚乙基-2-降冰片烯;且
其中所述涂料能够结合到金属管上。
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Citations (12)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0472268A2 (en) * | 1990-08-22 | 1992-02-26 | Gencorp Inc. | Forming abrasion-resistant coatings on elastomeric substrates |
CN1255511A (zh) * | 1998-07-01 | 2000-06-07 | 高级弹性体系统两合公司 | 用无规丙烯共聚物对热塑性硫化橡胶改性 |
US6121383A (en) * | 1993-01-19 | 2000-09-19 | Advanced Elastomer Systems, L.P. | Thermosplastic vulcanizates from blends of a polypropylene and elastic α-olefin/cyclic olefin copolymers |
CN1373791A (zh) * | 1999-09-10 | 2002-10-09 | 高级弹性体系统两合公司 | 用于汽车挡风雨密封件的烯烃润滑涂料 |
US20070299160A1 (en) * | 2004-09-21 | 2007-12-27 | Jean-Luc Delanaye | Insulating Extrudates from Polyolefin Blends |
US20080015313A1 (en) * | 2006-07-11 | 2008-01-17 | Oansuk Chung | Method for improving extrusion surface smoothness in thermoplastic vulcanizates |
CN101432346A (zh) * | 2006-05-01 | 2009-05-13 | 利安德巴塞尔高级聚烯烃美国有限责任公司 | 可发泡的热塑性硫化橡胶共混物、方法及其制品 |
CN102134350A (zh) * | 2010-12-31 | 2011-07-27 | 广州鹿山新材料股份有限公司 | 油气输送3pp管道外防腐防滑粉末及其制备方法 |
CN104087211A (zh) * | 2014-07-29 | 2014-10-08 | 南京航空航天大学 | 深海油气输送钢管外壁的防腐涂料所用胶黏剂及制备方法 |
CN105037954A (zh) * | 2015-07-02 | 2015-11-11 | 金发科技股份有限公司 | 一种耐压聚丙烯保温材料及其制备方法和应用 |
US20160340480A1 (en) * | 2015-05-22 | 2016-11-24 | Exxonmobil Chemical Patents Inc. | Thermoplastic Vulcanizates Comprising Propylene-Based Elastomers and Methods for Making the Same |
CN107810232A (zh) * | 2015-06-19 | 2018-03-16 | 埃克森美孚化学专利公司 | 含有超高分子量聚乙烯的热塑性弹性体组合物及其制备方法 |
Family Cites Families (18)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4132698A (en) * | 1974-03-20 | 1979-01-02 | Exxon Research & Engineering Co. | Elastomeric thermoplastics |
DE3012804C2 (de) * | 1980-04-02 | 1982-05-27 | Dynamit Nobel Ag, 5210 Troisdorf | Ternäre thermoplastische Formmasse enthaltend Polypropylen-Copolymere |
US4666989A (en) * | 1980-07-22 | 1987-05-19 | Shell Oil Company | Polybutylene modified masterbatches for impact resistant polypropylene |
US4407998A (en) * | 1981-01-05 | 1983-10-04 | Exxon Research And Engineering Co. | High impact polypropylene resin |
US4769283A (en) * | 1986-01-31 | 1988-09-06 | Minnesota Mining And Manufacturing Company | Pressure-sensitive adhesive tape |
US5247007A (en) * | 1990-03-16 | 1993-09-21 | Mitsui Toatsu Chemicals, Inc. | Polypropylene resin composition and method for coating molded products of the resin composition |
US5508318A (en) * | 1993-07-15 | 1996-04-16 | Montell North America Inc. | Compositions of irradiated and non-irradiated olefin polymer materials with reduced gloss |
US5409992A (en) * | 1994-02-28 | 1995-04-25 | Himont Incorporated | Calenderable blends containing broad molecular weight distribution propylene polymer material |
US6245856B1 (en) * | 1996-12-17 | 2001-06-12 | Exxon Chemical Patents, Inc. | Thermoplastic olefin compositions |
US6100334A (en) * | 1999-01-05 | 2000-08-08 | Advanced Elastomer Systems, L.P. | Thermoplastic vulcanizates from a cyclic olefin rubber, a polyolefin, and a compatiblizer |
DE19955726C1 (de) * | 1999-11-15 | 2001-06-28 | Eupec Pipecoatings Gmbh | Vorrichtung zur Kunststoffummantelung einer Rohrleitung an Rohrverbindungen |
EP1260547A1 (en) | 2001-05-21 | 2002-11-27 | Borealis Technology OY | Polyolefin coated steel pipes |
JP5216182B2 (ja) * | 2002-01-15 | 2013-06-19 | アドバンスド エラストマー システムズ,エル.ピー. | 熱可塑性エラストマーの製造方法 |
WO2004035681A2 (en) * | 2002-10-17 | 2004-04-29 | Exxonmobil Chemical Patents Inc. | Hetero phase polymer compositions |
KR100632603B1 (ko) * | 2003-08-20 | 2006-10-09 | 에스케이 주식회사 | 열가소성 에라스토머 조성물 및 이의 제조방법 |
KR20080106524A (ko) | 2006-02-23 | 2008-12-08 | 바셀 폴리올레핀 이탈리아 에스.알.엘 | 사출 성형품을 위한 프로필렌 중합체 |
JP5764669B2 (ja) * | 2010-12-30 | 2015-08-19 | ダウ グローバル テクノロジーズ エルエルシー | 熱可塑性加硫組成物、その製造方法、及びそれから製造される物品 |
WO2016052029A1 (ja) * | 2014-09-30 | 2016-04-07 | 豊田合成株式会社 | ウエザストリップ用摺動材の製造方法 |
-
2019
- 2019-05-29 US US17/253,009 patent/US12018166B2/en active Active
- 2019-05-29 EP EP19731449.5A patent/EP3814420A1/en active Pending
- 2019-05-29 WO PCT/US2019/034333 patent/WO2020005442A1/en active Application Filing
- 2019-05-29 CN CN201980045693.7A patent/CN112384563B/zh active Active
- 2019-05-29 MX MX2021000078A patent/MX2021000078A/es unknown
- 2019-05-29 CA CA3104619A patent/CA3104619A1/en active Pending
Patent Citations (12)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0472268A2 (en) * | 1990-08-22 | 1992-02-26 | Gencorp Inc. | Forming abrasion-resistant coatings on elastomeric substrates |
US6121383A (en) * | 1993-01-19 | 2000-09-19 | Advanced Elastomer Systems, L.P. | Thermosplastic vulcanizates from blends of a polypropylene and elastic α-olefin/cyclic olefin copolymers |
CN1255511A (zh) * | 1998-07-01 | 2000-06-07 | 高级弹性体系统两合公司 | 用无规丙烯共聚物对热塑性硫化橡胶改性 |
CN1373791A (zh) * | 1999-09-10 | 2002-10-09 | 高级弹性体系统两合公司 | 用于汽车挡风雨密封件的烯烃润滑涂料 |
US20070299160A1 (en) * | 2004-09-21 | 2007-12-27 | Jean-Luc Delanaye | Insulating Extrudates from Polyolefin Blends |
CN101432346A (zh) * | 2006-05-01 | 2009-05-13 | 利安德巴塞尔高级聚烯烃美国有限责任公司 | 可发泡的热塑性硫化橡胶共混物、方法及其制品 |
US20080015313A1 (en) * | 2006-07-11 | 2008-01-17 | Oansuk Chung | Method for improving extrusion surface smoothness in thermoplastic vulcanizates |
CN102134350A (zh) * | 2010-12-31 | 2011-07-27 | 广州鹿山新材料股份有限公司 | 油气输送3pp管道外防腐防滑粉末及其制备方法 |
CN104087211A (zh) * | 2014-07-29 | 2014-10-08 | 南京航空航天大学 | 深海油气输送钢管外壁的防腐涂料所用胶黏剂及制备方法 |
US20160340480A1 (en) * | 2015-05-22 | 2016-11-24 | Exxonmobil Chemical Patents Inc. | Thermoplastic Vulcanizates Comprising Propylene-Based Elastomers and Methods for Making the Same |
CN107810232A (zh) * | 2015-06-19 | 2018-03-16 | 埃克森美孚化学专利公司 | 含有超高分子量聚乙烯的热塑性弹性体组合物及其制备方法 |
CN105037954A (zh) * | 2015-07-02 | 2015-11-11 | 金发科技股份有限公司 | 一种耐压聚丙烯保温材料及其制备方法和应用 |
Non-Patent Citations (2)
Title |
---|
沈军等: "三元乙丙橡胶/聚丙烯动态硫化热塑性弹性体的相态结构", 《合成橡胶工业》 * |
沈军等: "三元乙丙橡胶/聚丙烯动态硫化热塑性弹性体的相态结构", 《合成橡胶工业》, vol. 29, no. 05, 25 September 2006 (2006-09-25), pages 356 - 359 * |
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