CN87105522A - 无定形聚x-烯烃的制备方法 - Google Patents

无定形聚x-烯烃的制备方法 Download PDF

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CN87105522A
CN87105522A CN87105522.8A CN87105522A CN87105522A CN 87105522 A CN87105522 A CN 87105522A CN 87105522 A CN87105522 A CN 87105522A CN 87105522 A CN87105522 A CN 87105522A
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alpha
olefines
poly
amorphous
amorphous poly
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CN1023808C (zh
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斯蒂文·路易斯·奥汀
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El Paso Products Co
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F6/00—Post-polymerisation treatments
    • C08F6/26—Treatment of polymers prepared in bulk also solid polymers or polymer melts
    • C08F6/28—Purification
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F6/00—Post-polymerisation treatments
    • C08F6/26—Treatment of polymers prepared in bulk also solid polymers or polymer melts
    • 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
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    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S526/00—Synthetic resins or natural rubbers -- part of the class 520 series
    • Y10S526/902—Monomer polymerized in bulk in presence of transition metal containing catalyst

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  • Medicinal Chemistry (AREA)
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  • Organic Chemistry (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Polymers With Sulfur, Phosphorus Or Metals In The Main Chain (AREA)
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Abstract

在无定形聚X-烯烃的聚合区出料口和闪蒸区之间放置一个循环回路，以便于输送脱汽的聚合物产品的熔融物料。

Description

本发明是关于在高温高压下，采用高活性载体催化剂体系，直接生产实际上为无定形的聚α-烯烃的本体聚合工艺方法，尤其是关于生产无定形丙烯均聚物或共聚物的工艺方法。无定形聚合物是本方法的唯一产物，在分离未反应的单体，去除残留在聚合物中催化剂的活性和对聚合物进行抗热、抗氧稳定化处理之后，即可从本方法得到最终产物。
此无定形聚α-烯烃是作为液体丙烯的30-60%的溶液，通常在130°F至175°F温度范围内，在大约400磅/平方吋到550磅/平方吋的表压下，离开反应器的。在生产高结晶度的全同立构丙烯聚合物的传统淤浆聚合工艺方法中，从反应器流出的物料，仅仅通过一个保持在较低压力下的汽化区域，通常为旋流袋式过滤系统（cyclone-bag    filter    combination），在该区域，未反应丙烯单体的分离或闪蒸是在上部发生的，与此同时，固体状的、实际上是干燥的自由流动聚合物以粉末状的形式在汽化区域的底部收集。
这样的装置对于无定形聚α-烯烃的制备方法是完全不适用的，这是由该聚合物产品的物理特性决定的，也就是由于该聚合物的高粘度及“粘着性”，会妨碍它在非堵塞型过滤器上，以粉状固体形式进行回收。
另外，由于减压闪蒸操作中固有的温度下降，结果从反应器流出的物料会凝结，并堵塞通向汽化区域的管道。
因此，本发明的一个目的是提供一种从未反应的单体中分离无定形聚α-烯烃的改进方法。
本发明的另一个目的的是提供一种以流体的形式收集无定形聚α-烯烃产物的方法。
本发明的其它目的可由本发明的详细说明书明显看出。
所给的附图是本发明方法的一种实施方案的示意流程图。
依照本发明，提供一种以流体形式直接生产聚α-烯烃的方法，它包括以下几个步骤：
（1）从温度约在130°F至175°F之间，表压约在400磅/平方吋至550磅/平方吋之间的本体聚合区域，经一阀门，排出含有无定形聚α-烯烃和液态未反应的单体的反应器物料;
（2）当反应器流出的物料通过上述的阀排出时，马上同由后述第（6）步得到的被加热的脱汽无定形聚α-烯烃直接接触，脱汽无定形聚α-烯烃的温度大约在350°F和425°F之间;
（3）将第（2）步得到的混合物通到闪蒸区，闪蒸区的表压维持在大约40至80磅/平方吋，其温度维持在大约300°F和375°F之间;
（4）从上述的闪蒸区排出未反应单体的汽化物料;
（5）从上述的闪蒸区排出脱汽的无定形聚α-烯烃;和
（6）通过间接的热交换，加热由第（5）步得到的部分所述的脱汽聚α-烯烃，然后将加热的部分通往上述的第（1）步。
在制备无定形聚α-烯烃的过程中，选择什么样的淤浆聚合条件和催化系统，对于本发明的成功与否是无关紧要的。无论聚合物是均聚物或是共聚物也无关紧要。虽然如此，在美国专利申请号S.N.880，456（1986年6月30日提交）中，公开了一个制备这种无定形聚α-烯烃的特别有益的方法，这里作为参考且并入本申请。
由本发明的方法制备的聚合物产品具有优良的性能，适用于各种应用领域，例如粘合剂、堵漏剂、密封剂和屋顶材料成分等等。
为了更好的理解本发明，可参考所附的示意流程图，它描绘了我们申请的方法中的一个具体实例。含有无定形共聚物的反应器流出物料由管线10供给，无定形共聚物的主要成分是丙烯，其余的是乙烯，也就是大约有85%（重量份）的丙烯和15%（重量份）的乙烯。该物料一般还含有大约从40%到70%（重量份）的未反应单体和用于调节分子量的氢，该物料通过一个周期卸料阀或布利波（nlipper）阀11，该阀是一种可连续不断地开闭的阀，因此，从聚合反应器（图中没有标出）中排出的物料近似于连续卸料操作。然后，该物料在尽可能靠近布利波阀11的出口处，通过与来自管线12的温度大约在350°F和425°F之间的熔融无定形聚合物进行混合而被加热。在管线12和管线10中的无定形聚α-烯烃的重量比（以不含单体为基准）应该控制在大约10∶1和15∶1之间。
混合物料13被引入闪蒸罐14，闪蒸罐的压力控制在表压大约为40至80磅/平方吋之间。未反应的单体蒸气气流（其中也包含少量用作分子量调节剂的氢），从闪蒸罐14经过管线16通入分离器17中，以便除去少量夹带的聚合物，然后经过纯化再循环到聚合反应器中（图中没有标出）。脱汽的聚合物排放到管线21中，纯净的聚合物产品，其温度在300°F和375°F之间，经过液面控制器19，流过管道21，通往产品贮槽（图中未标出）。被排放出的聚合物中的其余部分，由泵22输送到安装于管线23上的列管式热交换器进行循环。加热介质是高压蒸汽，例如表压大约为600磅/平方吋的蒸汽，它由管线26供给，其流量由温度控制阀27进行调节。热油也可以用作为加热介质。
本发明的方法具有种种优点，其中包括：
1）它提供了一种即简单又非常有效的方法，可以从聚合物产品中汽化和连续分离未反应的单体。
2）它使得可用泵输送的产品料流顺利地通过整个过程的设备，例如从反应器出口，通往分离设备，最后送到产品贮槽或送到用来向客户输送最终产品的加热槽车。
可以理解，本发明的方法能进行各种变动和改进。所有这些变化都被认为是在本发明的范围内，并由本说明书和所附的权利要求书加以限定。

Claims (3)

1、一种以流体形式生产聚α-烯烃的方法，它包括以下几个步骤：
(1)从温度约在130°F至175°F之间，表压约在400磅/平方吋至550磅/平方吋之间的本体聚合区域，经一阀门，排出含有无定形聚α-烯烃和液态未反应的单体的反应器物料；
(2)当反应器流出的物料通过上述的阀排出时，马上同由后述第(6)步得到的被加热的脱汽无定形聚α-烯烃直接接触，脱汽无定形聚α-烯烃的温度大约在350°F和425°F之间；
(3)将第(2)步得到的混合物通到闪蒸区，闪蒸区的表压维持在大约40至80磅/平方吋，其温度维持在大约300°F和375°F之间；
(4)从上述的闪蒸区排出未反应单体的汽化物料；
(5)从上述的闪蒸区排出脱汽的无定形聚α-烯烃；和
(6)通过间接的热交换，加热由第(5)步得到的部分所述的脱汽聚α-烯烃，然后将加热的部分通往上述的第(1)步。
2、在权利要求1的方法中，第（2）步中被加热的脱汽聚合物与第（1）步中排出的无定形聚α-烯烃之间的重量比大约控制在10∶1和15∶1之间。
3、在权利要求1的方法中，无定形聚α-烯烃是以丙烯为主的聚合物，它包括无定形的丙烯均聚物、丙烯和乙烯的无定形共聚物和丙烯、乙烯以及每个分子中含有4至8个碳原子的另一α-烯烃的无定形共聚物。
CN87105522A 1986-08-15 1987-08-11 无定型聚α-烯烃的制备方法 Expired - Fee Related CN1023808C (zh)

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US896,793 1986-08-15
US06/896,793 US4710563A (en) 1986-08-15 1986-08-15 Process for the recovery of amorphous devaporized polyalphaolefin
US896793 1986-08-15

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EP (1) EP0256716B1 (zh)
JP (1) JPH0832741B2 (zh)
KR (1) KR950006123B1 (zh)
CN (1) CN1023808C (zh)
AT (1) ATE68506T1 (zh)
AU (1) AU604709B2 (zh)
CA (1) CA1285097C (zh)
DE (1) DE3773795D1 (zh)
ES (1) ES2026542T3 (zh)

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US4868006A (en) * 1987-03-16 1989-09-19 Minnesota Mining And Manufacturing Company Polymeric film with reduced surface friction
US5028292A (en) * 1987-03-16 1991-07-02 Minnesota Mining And Manufacturing Company Adhesive bonding to quasi-amorphous polymer surfaces
US5032209A (en) * 1987-03-16 1991-07-16 Minnesota Mining And Manufacturing Company Heat sealing of semicrystalline quasi-amorphous polymers
US4824699A (en) * 1987-08-21 1989-04-25 Minnesota Mining And Manufacturing Company Process for improved adhesion to semicrystalline polymer film
US4902378A (en) * 1988-04-27 1990-02-20 Minnesota Mining And Manufacturing Company Polymer with reduced internal migration
US4822451A (en) * 1988-04-27 1989-04-18 Minnesota Mining And Manufacturing Company Process for the surface modification of semicrystalline polymers
CA2058992C (en) * 1990-04-10 1996-10-22 Eigo Miura Method for the pyrolysis of polymers
JP3722858B2 (ja) * 1993-11-25 2005-11-30 ビーエーエスエフ アクチェンゲゼルシャフト ポリアクリレート溶融体から残留揮発分を除去する方法
US5521263A (en) * 1994-10-18 1996-05-28 Eastman Chemical Company Catalysts and synthesis of high molecular weight amorphous polyolefins and recovery thereof
AT405284B (de) * 1996-10-31 1999-06-25 Danubia Petrochem Polymere Verfahren zur kontinuierlichen herstellung von elastischen polypropylenen
US20170292047A1 (en) * 2016-04-12 2017-10-12 Rextac Llc Hexene-1 Containing Amorphous Polyalphaolefins For Improved Hot Melt Adhesives

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US4184027A (en) * 1971-10-26 1980-01-15 Monsanto Company Recycle control system for continuous polymerization
GB1548203A (en) * 1975-08-05 1979-07-04 Stamicarbon Process and apparatus for the preparation of polyolefins with a widge molecular-weight distribution
JPS5267928U (zh) * 1975-11-17 1977-05-19
NL7700412A (nl) * 1977-01-15 1978-07-18 Synres Internationaal Nv Continu bereiding van polymeren in de massa.
GB2011429B (en) * 1977-12-28 1982-03-31 Sumitomo Chemical Co Process for the rcovery of atactic polymers
DE3068098D1 (en) * 1980-04-17 1984-07-12 Exxon Research Engineering Co Polymerization process
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JPS5928836A (ja) * 1982-08-05 1984-02-15 日本電信電話株式会社 縦サ−ジ防護用筐体接地回路

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EP0256716A2 (en) 1988-02-24
EP0256716A3 (en) 1989-05-24
KR880002899A (ko) 1988-05-12
KR950006123B1 (ko) 1995-06-09
ATE68506T1 (de) 1991-11-15
AU604709B2 (en) 1991-01-03
DE3773795D1 (de) 1991-11-21
ES2026542T3 (es) 1992-05-01
JPS6348306A (ja) 1988-03-01
CN1023808C (zh) 1994-02-16
JPH0832741B2 (ja) 1996-03-29
CA1285097C (en) 1991-06-18
EP0256716B1 (en) 1991-10-16
AU7426587A (en) 1988-02-18
US4710563A (en) 1987-12-01

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