JPH02237943A - Separation of 2,7-dimethylnaphthalene - Google Patents
Separation of 2,7-dimethylnaphthaleneInfo
- Publication number
- JPH02237943A JPH02237943A JP5862289A JP5862289A JPH02237943A JP H02237943 A JPH02237943 A JP H02237943A JP 5862289 A JP5862289 A JP 5862289A JP 5862289 A JP5862289 A JP 5862289A JP H02237943 A JPH02237943 A JP H02237943A
- Authority
- JP
- Japan
- Prior art keywords
- complex
- dimethylnaphthalene
- substance
- forming
- raw material
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- LRQYSMQNJLZKPS-UHFFFAOYSA-N 2,7-dimethylnaphthalene Chemical compound C1=CC(C)=CC2=CC(C)=CC=C21 LRQYSMQNJLZKPS-UHFFFAOYSA-N 0.000 title claims description 31
- 238000000926 separation method Methods 0.000 title claims description 8
- 238000000034 method Methods 0.000 claims abstract description 43
- 229930195733 hydrocarbon Natural products 0.000 claims abstract description 26
- 150000002430 hydrocarbons Chemical class 0.000 claims abstract description 25
- 239000000126 substance Substances 0.000 claims abstract description 25
- 239000004215 Carbon black (E152) Substances 0.000 claims abstract description 24
- ZKUYSJHXBFFGPU-UHFFFAOYSA-N 2516-95-2 Chemical compound OC(=O)C1=CC(Cl)=CC=C1[N+]([O-])=O ZKUYSJHXBFFGPU-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000002994 raw material Substances 0.000 abstract description 24
- 239000002904 solvent Substances 0.000 abstract description 15
- 238000000354 decomposition reaction Methods 0.000 abstract description 11
- 239000011280 coal tar Substances 0.000 abstract description 6
- 150000001875 compounds Chemical class 0.000 abstract description 5
- 239000003208 petroleum Substances 0.000 abstract description 5
- 229920001002 functional polymer Polymers 0.000 abstract description 4
- 239000002861 polymer material Substances 0.000 abstract description 3
- WPUMVKJOWWJPRK-UHFFFAOYSA-N naphthalene-2,7-dicarboxylic acid Chemical compound C1=CC(C(O)=O)=CC2=CC(C(=O)O)=CC=C21 WPUMVKJOWWJPRK-UHFFFAOYSA-N 0.000 abstract description 2
- 230000003647 oxidation Effects 0.000 abstract description 2
- 238000007254 oxidation reaction Methods 0.000 abstract description 2
- 239000002244 precipitate Substances 0.000 abstract description 2
- 239000003795 chemical substances by application Substances 0.000 abstract 1
- 238000007670 refining Methods 0.000 abstract 1
- QNLZIZAQLLYXTC-UHFFFAOYSA-N 1,2-dimethylnaphthalene Chemical compound C1=CC=CC2=C(C)C(C)=CC=C21 QNLZIZAQLLYXTC-UHFFFAOYSA-N 0.000 description 53
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 20
- 239000003921 oil Substances 0.000 description 19
- 239000000203 mixture Substances 0.000 description 15
- YGYNBBAUIYTWBF-UHFFFAOYSA-N 2,6-dimethylnaphthalene Chemical compound C1=C(C)C=CC2=CC(C)=CC=C21 YGYNBBAUIYTWBF-UHFFFAOYSA-N 0.000 description 14
- 239000007787 solid Substances 0.000 description 11
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- 238000006243 chemical reaction Methods 0.000 description 7
- 239000000047 product Substances 0.000 description 7
- 239000007789 gas Substances 0.000 description 6
- 239000007788 liquid Substances 0.000 description 6
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 5
- 239000007864 aqueous solution Substances 0.000 description 5
- -1 polyethylene naphthalate Polymers 0.000 description 5
- 239000000374 eutectic mixture Substances 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- AFPHTEQTJZKQAQ-UHFFFAOYSA-N 3-nitrobenzoic acid Chemical compound OC(=O)C1=CC=CC([N+]([O-])=O)=C1 AFPHTEQTJZKQAQ-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- 229920000106 Liquid crystal polymer Polymers 0.000 description 3
- 239000004977 Liquid-crystal polymers (LCPs) Substances 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 238000009835 boiling Methods 0.000 description 3
- 238000004587 chromatography analysis Methods 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 238000004821 distillation Methods 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 3
- 230000001590 oxidative effect Effects 0.000 description 3
- 239000012188 paraffin wax Substances 0.000 description 3
- 238000005504 petroleum refining Methods 0.000 description 3
- YGOZXWGXCINERK-UHFFFAOYSA-N 2-phenylethyl 3,5-dinitrobenzoate Chemical compound [O-][N+](=O)C1=CC([N+](=O)[O-])=CC(C(=O)OCCC=2C=CC=CC=2)=C1 YGOZXWGXCINERK-UHFFFAOYSA-N 0.000 description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- SIKJAQJRHWYJAI-UHFFFAOYSA-N Indole Chemical compound C1=CC=C2NC=CC2=C1 SIKJAQJRHWYJAI-UHFFFAOYSA-N 0.000 description 2
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- SMWDFEZZVXVKRB-UHFFFAOYSA-N Quinoline Chemical compound N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 description 2
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical compound C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 235000011114 ammonium hydroxide Nutrition 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 230000009918 complex formation Effects 0.000 description 2
- DIOQZVSQGTUSAI-UHFFFAOYSA-N decane Chemical compound CCCCCCCCCC DIOQZVSQGTUSAI-UHFFFAOYSA-N 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- RXOHFPCZGPKIRD-UHFFFAOYSA-N naphthalene-2,6-dicarboxylic acid Chemical compound C1=C(C(O)=O)C=CC2=CC(C(=O)O)=CC=C21 RXOHFPCZGPKIRD-UHFFFAOYSA-N 0.000 description 2
- 229920003207 poly(ethylene-2,6-naphthalate) Polymers 0.000 description 2
- 229920000728 polyester Polymers 0.000 description 2
- 239000011112 polyethylene naphthalate Substances 0.000 description 2
- FCEHBMOGCRZNNI-UHFFFAOYSA-N 1-benzothiophene Chemical compound C1=CC=C2SC=CC2=C1 FCEHBMOGCRZNNI-UHFFFAOYSA-N 0.000 description 1
- AMOYMEBHYUTMKJ-UHFFFAOYSA-N 2-(2-phenylethoxy)ethylbenzene Chemical compound C=1C=CC=CC=1CCOCCC1=CC=CC=C1 AMOYMEBHYUTMKJ-UHFFFAOYSA-N 0.000 description 1
- SLAMLWHELXOEJZ-UHFFFAOYSA-N 2-nitrobenzoic acid Chemical compound OC(=O)C1=CC=CC=C1[N+]([O-])=O SLAMLWHELXOEJZ-UHFFFAOYSA-N 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 125000002619 bicyclic group Chemical group 0.000 description 1
- 229910002056 binary alloy Inorganic materials 0.000 description 1
- 239000001273 butane Substances 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 238000004523 catalytic cracking Methods 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000008030 elimination Effects 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- 229920006351 engineering plastic Polymers 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000005755 formation reaction Methods 0.000 description 1
- 238000007710 freezing Methods 0.000 description 1
- 230000008014 freezing Effects 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 1
- PZOUSPYUWWUPPK-UHFFFAOYSA-N indole Natural products CC1=CC=CC2=C1C=CN2 PZOUSPYUWWUPPK-UHFFFAOYSA-N 0.000 description 1
- RKJUIXBNRJVNHR-UHFFFAOYSA-N indolenine Natural products C1=CC=C2CC=NC2=C1 RKJUIXBNRJVNHR-UHFFFAOYSA-N 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 239000008204 material by function Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 1
- KYTZHLUVELPASH-UHFFFAOYSA-N naphthalene-1,2-dicarboxylic acid Chemical compound C1=CC=CC2=C(C(O)=O)C(C(=O)O)=CC=C21 KYTZHLUVELPASH-UHFFFAOYSA-N 0.000 description 1
- 150000005338 nitrobenzoic acids Chemical class 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 125000003367 polycyclic group Chemical group 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 229930195734 saturated hydrocarbon Natural products 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- KKEYFWRCBNTPAC-UHFFFAOYSA-L terephthalate(2-) Chemical compound [O-]C(=O)C1=CC=C(C([O-])=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-L 0.000 description 1
- 229930192474 thiophene Natural products 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明は、電荷移動錯体形成により炭化水素油中の２，
７−ジメチルナフタレンを分離回収する方法に関するも
のである。さらＫ詳しくは電荷移動錯体形成物質として
、５−クロロ−２−ニトロ安息香酸を用いて、原料炭化
水素油中のジメチルナフタレン組成と異なり、組成とし
て２，７−ジメチルナフタレンを主とするジメチルナフ
タレンを得ることを特徴とする２，７−ジメチルナフタ
レンの分離方法に関するものである。DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention provides a method for reducing 2,
The present invention relates to a method for separating and recovering 7-dimethylnaphthalene. In detail, 5-chloro-2-nitrobenzoic acid is used as a charge transfer complex-forming substance to produce dimethylnaphthalene whose composition is mainly 2,7-dimethylnaphthalene, which is different from the dimethylnaphthalene composition in the raw hydrocarbon oil. The present invention relates to a method for separating 2,7-dimethylnaphthalene, which is characterized in that it obtains 2,7-dimethylnaphthalene.
ジメチルナフタレンは石油の減圧軽油を接触分解して得
られる軽質分解軽油（ Ｌｉｇｈｔ ＣｙｃｌｅＱｉｌ
以下、ＬＣＯと略記する）や石炭タール中に含まれてお
り、酸化によりナフタレンジカルボン酸となり、染料、
顔料やエンジニアリングプラスチック、液晶ボリマー等
の機能性高分子の原料として利用できる重要な物質であ
る。Dimethylnaphthalene is a light cracked gas oil (Light Cycle Qil) obtained by catalytic cracking of petroleum vacuum gas oil.
(hereinafter abbreviated as LCO) and coal tar, it becomes naphthalene dicarboxylic acid by oxidation, and dyes,
It is an important substance that can be used as a raw material for functional polymers such as pigments, engineering plastics, and liquid crystal polymers.
例えば、２，６−ジメチルナフタレンを酸化して得られ
るナフタレン−２，６−ジカルボン酸とエチレングリコ
ールとのポリエステル体であるポリエチレンナフタレー
トは、繊維、フィルム、ボトルなどとしての用途が広く
知られるポリエチレンテレフタレート（ＰＥＴ）の酸部
分を、このナフタレン−２，６−ジカルボン酸に置換し
たもので、その利用が有望視されている。ポリエチレン
ナフタレートは弾性率が高く、耐熱性もＰＥＴより優れ
ているため、例えばビデオテープ等のフィルムヲ薄くす
ることができ、それによって、テーブケースを小型化し
たり長時間記録を可能にする等の効果が期待できる。ま
た、ボリアミドやボリチオエステル体等も知られている
。さらに、液晶ボリマーの原料としても注目されている
。液晶ボリマーは、溶融状態で結晶のように高度圧配向
する性質をもち、高強度・高弾性率をもつ機能性高分子
材料となり得る。２，７−ジメチルナフタレンも酸化に
より、繊維やフイルムとして有用なポリエステル、ある
いは可塑剤等に用いられるナフタレンー２．７ージカル
ボン酸を製造でき、２．６−ジメチルナフタレンと同様
の用途が期待でき、いずれも有機機能性材料の基礎原料
として、今後重要な位置を占めると考えられる。これら
の機能性高分子材料の原料としての２，７−ジメチルナ
フタレンは、約９５重量％穆度以上の高純度のものが要
求される。For example, polyethylene naphthalate, which is a polyester of naphthalene-2,6-dicarboxylic acid obtained by oxidizing 2,6-dimethylnaphthalene and ethylene glycol, is a polyethylene that is widely known for its uses as fibers, films, bottles, etc. This naphthalene-2,6-dicarboxylic acid replaces the acid moiety of terephthalate (PET), and its use is considered promising. Polyethylene naphthalate has a high modulus of elasticity and better heat resistance than PET, so it can be used to make films such as video tapes thinner, which has benefits such as downsizing tape cases and making long-term recording possible. can be expected. Furthermore, polyamides, polythioesters, and the like are also known. Furthermore, it is attracting attention as a raw material for liquid crystal polymers. Liquid crystal polymers have the property of being oriented under high pressure like crystals in a molten state, and can be used as functional polymer materials with high strength and high elastic modulus. By oxidizing 2,7-dimethylnaphthalene, it is possible to produce polyester, which is useful for fibers and films, and naphthalene-2,7-dicarboxylic acid, which is used as a plasticizer, etc., and it is expected that it will be used in the same way as 2,6-dimethylnaphthalene. It is thought that it will occupy an important position in the future as a basic raw material for organic functional materials. The 2,7-dimethylnaphthalene used as a raw material for these functional polymer materials is required to have a high purity of about 95% by weight or higher.
２，７−ジメチルナフタレンは、２，６−ジメチルナフ
タレン等他の異性体と共にＬＣＯ留分、あるいは石炭タ
ール中に含まれているが、分離回収することは極めて困
難である。2,7-dimethylnaphthalene is contained in LCO fractions or coal tar together with other isomers such as 2,6-dimethylnaphthalene, but it is extremely difficult to separate and recover it.
ＬＣＯ留分には約７０〜８０妬の芳香族が含まれ、との
うち約２０〜４０係が二環芳香族であることが知られて
いる。しかしながら、ジメチルナフタレンは全体の約５
〜１０％で、ジメチルナフタレンの沸点範囲である約２
６０〜２７０Ｃ留分を蒸留によって得ることができても
他の種々の多環芳香族が存在するため約４０〜５０係程
度までしか濃縮できない。It is known that the LCO fraction contains about 70 to 80 aromatics, of which about 20 to 40 are bicyclic aromatics. However, dimethylnaphthalene is about 5
~10%, which is the boiling range of dimethylnaphthalene, about 2
Even if a 60-270C fraction can be obtained by distillation, it can only be concentrated to about 40-50C because of the presence of various other polycyclic aromatics.
この濃縮されたジメチルナフタレン混合物中には、２，
７−ジメチルナフタレンをはじめ数種のジメチルナフタ
レンが存在するが、その異性体の沸点範囲が約２６０〜
２７０Ｃ内で近接しているため、２，７−ジメチルナフ
タレンを蒸留にて分離することは困難である。さらに凝
固点の違いを利用して冷却による分離を試みても共融混
合物を作るため、この共融混合物から再結晶法や部分溶
融法で、２，７−ジメチルナフタレンを分離することは
できない。共融混合物の例としては、二成分系の場合２
，７−ジメチルナフタレンは、２，６−ジメチルナフタ
レンと約３：２のモル比で二成分系共融混合物を形成す
ることが知られており、この分離は極めて困難である。This concentrated dimethylnaphthalene mixture contains 2,
There are several types of dimethylnaphthalene including 7-dimethylnaphthalene, but the boiling point range of its isomers is about 260~
Due to their close proximity within 270C, it is difficult to separate 2,7-dimethylnaphthalene by distillation. Furthermore, even if separation by cooling is attempted by taking advantage of the difference in freezing point, a eutectic mixture is produced, so 2,7-dimethylnaphthalene cannot be separated from this eutectic mixture by recrystallization or partial melting. An example of a eutectic mixture is 2 in the case of a binary system.
, 7-dimethylnaphthalene is known to form a binary eutectic mixture with 2,6-dimethylnaphthalene in a molar ratio of approximately 3:2, making this separation extremely difficult.
従って、ＬＣＯ留分等の石油精製工業の各過程で得られ
る油や石炭タール等の原料から２，７−ジメチルナフタ
レンを濃縮、分離するためκは蒸留、冷却分離以外の方
法を用いる必要がある。Therefore, in order to concentrate and separate 2,7-dimethylnaphthalene from raw materials such as oil and coal tar obtained in each process of the petroleum refining industry such as LCO fraction, it is necessary to use methods other than distillation and cooling separation. .
上記以外の方法として電荷移動錯体を形成して分離する
方法があり、ジメチルナフタレンを含む炭化水素油から
電荷移動錯体を形成させることによってジメチルナフタ
レンを分離する方法としてはｍ−ニトロ安息香酸を用い
る方法（特公昭４７〜２９８９３他）、３，５−ジニト
ロ安息香酸フェネチルエステルを用いる方法（特開昭４
９−３５３６８）、ポリニトロ＝β−ナフトエ酸（特開
昭５０−１０１ ３ ４７）を用いる方法等が知られて
いる。In addition to the above methods, there is a method of separating dimethylnaphthalene by forming a charge transfer complex, and a method of separating dimethylnaphthalene by forming a charge transfer complex from a hydrocarbon oil containing dimethylnaphthalene is a method using m-nitrobenzoic acid. (Japanese Patent Publication No. 47-29893, etc.), a method using 3,5-dinitrobenzoic acid phenethyl ester (Japanese Patent Publication No. 47-29893),
9-35368), a method using polynitro-β-naphthoic acid (Japanese Patent Application Laid-open No. 1983-1013-47), and the like are known.
電荷移動錯体は、電子供与体の物質から電子受容体の物
質に電子が部分的に移動して結合が生じることにより形
成された分子化合物であり、これらの方法の特徴を要約
すると、いずれの方法も、ジメチルナフタレンを含む炭
化水素油とこれらの錯体形成物質を接触させることを特
徴とする方法で、ｍ−ニトロ安息香酸を用いる方法は、
特Ｋ２，６−ジメチルナフタレンと選択的に、また、３
，５−シニトロ安息香酸フエネチルエステルを用いる方
法は、特に２．７−ジメチルナフタレンと選択的Ｋ錯体
な形成する物質を用いる方法として知られている。また
、ポリニトロ−β−ナフトエ酸を用いる方法は全ジメチ
ルナフタレンと錯体な形成する物質を用いる方法であり
、原料炭化水素油中のジメチルナフタレン以外の芳香族
成分および脂肪族、脂環族炭化水素等の含有率が低下さ
せられている、原料とは異なる組成のジメチルナフタレ
ンを得る分離方法として知られている。A charge transfer complex is a molecular compound formed by the partial transfer of electrons from an electron donor substance to an electron acceptor substance to form a bond.To summarize the characteristics of these methods, both methods Also, a method using m-nitrobenzoic acid is characterized in that these complex-forming substances are brought into contact with a hydrocarbon oil containing dimethylnaphthalene.
Selectively with K2,6-dimethylnaphthalene, also with 3
, 5-cinitrobenzoic acid phenethyl ester is particularly known as a method using a substance that forms a selective K complex with 2,7-dimethylnaphthalene. In addition, the method using polynitro-β-naphthoic acid is a method using a substance that forms a complex with all dimethylnaphthalene, and aromatic components other than dimethylnaphthalene in the raw hydrocarbon oil, aliphatic, alicyclic hydrocarbons, etc. It is known as a separation method for obtaining dimethylnaphthalene with a lower content of dimethylnaphthalene and a composition different from that of the raw material.
ｍ−ニトロ安息香酸は２，６−ジメチルナフタレンと選
択的に、ポリニトロ−β−ナフトエ酸はジメチルナフタ
レン各異性体と反応するので、２．７−ジメチルナフタ
レンの分離には利用できない。Since m-nitrobenzoic acid reacts selectively with 2,6-dimethylnaphthalene, and polynitro-β-naphthoic acid reacts with each isomer of dimethylnaphthalene, it cannot be used to separate 2,7-dimethylnaphthalene.
また３，５−ジニトロ安息香酸フェネチルエステルは２
，７−ジメチルナフタレンと選択的に反応するが、原料
炭化水素中にパラフィン、ナフテン等を含み、ジメチル
ナフタレン濃度が低濃度であると、錯体形成そのものが
進行しない場合があり、２，７−ジメチルナフタレンを
充分に分離できない難点がある。In addition, 3,5-dinitrobenzoic acid phenethyl ester is 2
,7-dimethylnaphthalene, but if the raw material hydrocarbon contains paraffin, naphthene, etc. and the dimethylnaphthalene concentration is low, the complex formation itself may not proceed. There is a drawback that naphthalene cannot be separated sufficiently.
本発明者らは、このような従来法の課題を解決すべく鋭
意検討を行なった結果、２，７−ジメチルナ７タレンと
選択的〈電荷移動錯体を形成する物質を用いて、ジメチ
ルナフタレンを含む炭化水素油から効率よ＜２，７−ジ
メチルナフタレンを分離する方法を見い出し、本発明を
完成させたものである。The present inventors conducted intensive studies to solve the problems of the conventional method, and as a result, the inventors of the present invention discovered that using a substance that forms a selective charge transfer complex with 2,7-dimethylnaphthalene, The present invention was completed by discovering a method for efficiently separating <2,7-dimethylnaphthalene from hydrocarbon oil.
本発明の要旨は、電荷移動錯体形成により炭化水素油中
の２，７−ジメチルナ７タレンを分離回収する方法にお
いて、錯体形成物質として５−クロロ−２−ニトロ安息
香酸を用いることを特徴とする２．７−ジメチルナフタ
レンの分離方法に存する。The gist of the present invention is a method for separating and recovering 2,7-dimethylna-7talene in hydrocarbon oil by forming a charge transfer complex, characterized in that 5-chloro-2-nitrobenzoic acid is used as a complex-forming substance. 2. A method for separating 7-dimethylnaphthalene.
本発明は、また原料として２．６−ジメチルナフタレン
と２．７−ジメチルナフタレンの混合物を用いる場合に
は、２，７−ジメチルナフタレンを分離することにより
２，６−ジメチルナフタレンを濃縮する技術としても利
用できる。The present invention also provides a technique for concentrating 2,6-dimethylnaphthalene by separating 2,7-dimethylnaphthalene when a mixture of 2,6-dimethylnaphthalene and 2,7-dimethylnaphthalene is used as a raw material. Also available.
本発明の方法において、原料は２，７−ジメチルナフタ
レンを含む炭化水素油であれば用いることができ、キノ
リン、インドール等の含窒素化合物及びチオフエン、チ
オナフテン等の含硫黄化合物を含んでいても特に支障は
ない。また原料炭化水素中のジメチルナフタレン濃度が
約３０重量係程度と低い原料でも用いることができる。In the method of the present invention, any hydrocarbon oil containing 2,7-dimethylnaphthalene can be used as the raw material, and even if it contains nitrogen-containing compounds such as quinoline and indole, and sulfur-containing compounds such as thiophene and thionaphthene, There is no problem. Further, it is also possible to use a raw material in which the dimethylnaphthalene concentration in the raw material hydrocarbon is as low as about 30% by weight.
原料の具体例としては、ＬＣＯ留分等の石油精製工業の
各過程で得られる油や石炭タールをあげることができ、
これらの原料をジメチルナフタレンの沸点範囲である約
２６０〜２７０ｒ留分に予備蒸留したものはより好まし
く、ジメチルナ７タレン混金物自体も使用しうろことけ
勿論である。Specific examples of raw materials include oil and coal tar obtained in each process of the petroleum refining industry, such as LCO fraction,
It is more preferable to pre-distill these raw materials into a fraction of about 260 to 270 r, which is the boiling point range of dimethylnaphthalene, and it goes without saying that the dimethylnaphthalene mixture itself can also be used.
原料炭化水素油と錯体形成物質である５−クロロ−２−
ニトロ安息香酸との混合率に特（制限はないが、錯体形
成物質は、原料炭化水素油中の２，７−ジメチルナフタ
レンＫ対して約０．３〜６のモル比、特に約１〜３のモ
ル比で反応させることが好ましい。こｔ′Ｌは、原料炭
化水素油の組成にもよるが次の理由による。すなわち一
般に錯体形成物質の添加量を増すと、錯体生成物の収量
が増加するので、原料中の２．７−ジメチルナフタレン
が錯体生成物中忙分離される割合（回収率）は大きくな
るが、得られる２，７−ジメチルナフタレンの濃度が低
下するためである。5-chloro-2- which is a complex forming substance with raw hydrocarbon oil
There are no particular restrictions on the mixing ratio with nitrobenzoic acid, but the complex-forming substance may be present in a molar ratio of about 0.3 to 6, particularly about 1 to 3, to 2,7-dimethylnaphthalene K in the feed hydrocarbon oil. It is preferable to carry out the reaction at a molar ratio of t'L, which depends on the composition of the raw hydrocarbon oil, but is due to the following reason: In general, as the amount of the complex-forming substance added increases, the yield of the complex product increases. Therefore, although the ratio (recovery rate) of 2,7-dimethylnaphthalene in the raw material being separated in the complex product increases, the concentration of the obtained 2,7-dimethylnaphthalene decreases.
反応は、原料に錯体形成物質である５−クロロ−２−ニ
トロ安息香酸を接触せしめることにより直ちに錯体が形
成するが、反応をより効率的にするためには約１０分〜
１時間程度接触させることが好ましい。反応温度は室温
でも行ない得るが、錯体形成物質の原料への溶解度をあ
げるために約４０〜１５０ Ｃ，好まし，くは約５０〜
１００Ｃに加熱し、冷却して錯体を析出させる方法が効
率がよい。In the reaction, a complex is formed immediately by bringing the raw material into contact with 5-chloro-2-nitrobenzoic acid, which is a complex-forming substance, but in order to make the reaction more efficient, the reaction time is about 10 minutes or more.
It is preferable to contact for about 1 hour. The reaction temperature can be carried out at room temperature, but in order to increase the solubility of the complex-forming substance in the raw materials, the reaction temperature is about 40 to 150 C, preferably about 50 to 150 C.
A method of heating to 100C and cooling to precipitate the complex is efficient.
また、原料炭化水素油の組成によっては、ベンゼン、ト
ルエン、キシレン等の単環芳香族化合物を添加して錯体
形成物質の溶解度をあげ、反応をより効率的に行なうこ
ともできる。反応で生成する錯体は室温で析出するので
、錯体と未反応の液体はｒ過、遠心分離などの方法で容
易に分離することができる。Furthermore, depending on the composition of the raw hydrocarbon oil, a monocyclic aromatic compound such as benzene, toluene, or xylene may be added to increase the solubility of the complex-forming substance, thereby making the reaction more efficient. Since the complex produced in the reaction precipitates at room temperature, the complex and unreacted liquid can be easily separated by filtration, centrifugation, or the like.
この錯体を分解する方法は、（１） ２ ． ７−ジメ
チルナフタレンは溶解しにくいが、５−クロロ−２−ニ
トロ安息香酸け溶解しやすい溶媒に接触させる方法、（
２）５−クロロ−２−ニトロ安息香酸は溶解しにくいが
、２，７−ジメチルナフタレンは溶解しやすい溶媒に接
触させる方法、（３）互いに非混和性の前記（１）、（
２）の２つの溶媒に錯体を同時または交互に接触させる
方法、（４）錯体を室温以上、かつ好ましくは５−クロ
ロ−２−ニトロ安息香酸の分解温度未満の温度に加熱す
る方法等が採用できる。The method for decomposing this complex is (1) 2. 7-Dimethylnaphthalene is difficult to dissolve, but 5-chloro-2-nitrobenzoic acid is easily dissolved in a solvent (
2) A method in which 5-chloro-2-nitrobenzoic acid is difficult to dissolve, but 2,7-dimethylnaphthalene is easily dissolved in a solvent, (3) mutually immiscible methods (1), (
Methods such as (2) bringing the complex into contact with the two solvents simultaneously or alternately, and (4) heating the complex to a temperature above room temperature and preferably below the decomposition temperature of 5-chloro-2-nitrobenzoic acid are employed. can.
以下、これらの分解方法について説明する。These decomposition methods will be explained below.
分解方法（１）は、２，７−ジメチルナフタレンは溶解
しにくく、５−クロロ−２−ニトロ安息香酸を溶解しや
すい溶媒と接触させることによりこの錯体を分解する方
法である。このような溶媒は水（熱水）、アルカリ性水
溶液等が好ましい。アルカリ性水溶液としては、例えば
、水溶性のアルカリ金属及びアルカリ士類金属の水酸化
物、酸化物、炭酸塩やアンモニア水、水溶性アミン等の
水溶液があげられ、水酸化ナトリウム、水酸化カリウム
、アンモニア水等が好適に使用される。溶媒として水を
用いる場合は、錯体形成物質の溶解度をあげるために約
５０Ｃ以上に加熱することが好ましい。Decomposition method (1) is a method in which 2,7-dimethylnaphthalene is difficult to dissolve, and this complex is decomposed by bringing it into contact with a solvent in which 5-chloro-2-nitrobenzoic acid is easily dissolved. Preferably, such a solvent is water (hot water), alkaline aqueous solution, or the like. Examples of alkaline aqueous solutions include aqueous solutions of water-soluble alkali metals and alkali metal hydroxides, oxides, and carbonates, aqueous ammonia, and water-soluble amines, including sodium hydroxide, potassium hydroxide, ammonia Water and the like are preferably used. When water is used as a solvent, it is preferably heated to about 50C or higher to increase the solubility of the complex-forming substance.
分解方法（２）は、５−クロロ−２−ニトロ安息香酸は
溶解しに〈〈、２，７−ジメチルナフタレンを溶解しや
すい溶媒と接触させることによりこの錯体を分解する方
法である。この方法に適する溶媒としては、例えば、プ
ロパン、ブタン、石油エーテル、ペンタン、ヘキサン、
ヘプタン、オクタン、デカン、リクロイン、シクロベン
タン、シクロヘキサン等の炭素数３〜１０、特に５〜８
の脂肪族炭化水素、特にこれらの飽和炭化水素が好適で
ある。またエチルエーテル等のエーテル類も利用できる
。Decomposition method (2) is a method of decomposing this complex by bringing it into contact with a solvent in which 5-chloro-2-nitrobenzoic acid is dissolved and 2,7-dimethylnaphthalene is easily dissolved. Solvents suitable for this method include, for example, propane, butane, petroleum ether, pentane, hexane,
Heptane, octane, decane, licroin, cyclobentane, cyclohexane, etc. with 3 to 10 carbon atoms, especially 5 to 8 carbon atoms
Aliphatic hydrocarbons, especially these saturated hydrocarbons, are preferred. Ethers such as ethyl ether can also be used.
分解方法（３）は、互いに非混和性の前記（１）、（２
）の２つの溶媒に錯体を同時または交互に接触させる方
法である。この場合、錯体分解後の２，７−ジメチルナ
フタレンは（２）の溶媒層中に溶解しているので、（２
）の溶媒層を分離した後、溶媒の一部を留去し冷却する
か、全部を留去すれば原料炭化水素と異なる組成の２，
７−ジメチルナフタレン浪合物が分離される。Decomposition method (3) involves using the above-mentioned (1) and (2) which are immiscible with each other.
) is a method in which the complex is brought into contact with two solvents simultaneously or alternately. In this case, since the 2,7-dimethylnaphthalene after complex decomposition is dissolved in the solvent layer of (2),
) After separating the solvent layer, either part of the solvent is distilled off and cooled, or if all of the solvent is distilled off, 2.
A 7-dimethylnaphthalene compound is separated.
（４）による分解方法は、加熱によって錯体を分解する
方法である。この場合、直接に熱を加えても良いが、窒
素、炭酸ガス、水素，低級炭化水素ガス雰囲気下で加熱
する方が望ましい。酸化雰囲気中で加熱分解すると分解
脱離により得られた２，７−ジメチルナフタレン異性体
混合物が着色したり分解したりする傾向があるからであ
る。さらに上記不活性ガスの代妙に水蒸気を用いて分解
することもできる。また、（１）、（２）、（３）で用
いた溶媒の存在下、（４）の方法を組み合わせて使用す
ることもできる。加熱温度は２，７−ジメチルナフタレ
ンが分解しない温度未満であれば何度でも良いが、５一
クロロ−２−ニトロ安息香酸を回収再使用するためには
その分解温度未満が好ましい。The decomposition method (4) is a method of decomposing the complex by heating. In this case, heat may be applied directly, but it is preferable to heat in an atmosphere of nitrogen, carbon dioxide, hydrogen, or lower hydrocarbon gas. This is because when thermally decomposed in an oxidizing atmosphere, the 2,7-dimethylnaphthalene isomer mixture obtained by decomposition and elimination tends to be colored or decomposed. Furthermore, water vapor can be used instead of the above-mentioned inert gas for decomposition. Moreover, the method (4) can also be used in combination in the presence of the solvent used in (1), (2), and (3). The heating temperature may be any number of times as long as it is below a temperature at which 2,7-dimethylnaphthalene does not decompose, but in order to recover and reuse 5-chloro-2-nitrobenzoic acid, it is preferably below its decomposition temperature.
本発明は、ＬＣＯ留分等の石油精製工業の各過程で得ら
れる油や石炭タール等の炭化水素油中の２，７−ジメチ
ルナフタレンの分離（関し、簡便な手段により効率よく
分離するのでその有用性は大きい。すなわち本発明によ
ると、原料炭化水素中のジメチルナフタレン濃度が低濃
度であっても分離可能であり、工業的に有用な２，７〜
ジメチルナフタレンを効率よく分離することができるの
で、その工業的価置が大きい。The present invention relates to the separation of 2,7-dimethylnaphthalene from oils obtained in various processes of the petroleum refining industry such as LCO fractions and hydrocarbon oils such as coal tar. According to the present invention, it is possible to separate dimethylnaphthalene even if the concentration of dimethylnaphthalene in the raw material hydrocarbon is low.
Since dimethylnaphthalene can be efficiently separated, its industrial value is great.
次に本発明を実施例により具体的に説明するが、本発明
はこれらの実施例によって限定されるものではない。EXAMPLES Next, the present invention will be specifically explained with reference to Examples, but the present invention is not limited by these Examples.
実施例−１
第１表に示す組成のＬＣＯ２５５〜２６０Ｃ留分１５．
ＯＦを原料とし、これに５−クロロ−２−ニトロ安息香
酸３．５５７を加え、８０Ｃで１時間加熱、攪拌した後
、室温まで放冷した。析出した固体をＦ別した後、石油
エーテルですげやく洗浄し、未反応の炭化水素油を分離
除去して３．３８％の固体を得た。この固体３．２８％
をエチルエーテル層と５％水酸化ナ｝ ＩＪウム水溶液
層との混合液体Ｋ加えて振とうし、錯体を分解してエチ
ルエーテル層を分離、回収し、その後エチルエーテルを
留去して白色の固体と一部茶色の液体からなる炭化水素
混合物０．０２９−を得た。分離生成物のガスクロマト
グラフ分析の結果、多環芳香族のほがＫパラフィン、ナ
フテン等をその他として約４０％含む原料を用いてもジ
メチルナフタレン以外の物質をほとんど取り込むことが
なく、２．７−ジメチルナフタレン含有量が５０重量％
以上の分離生成物が得られた。Example-1 LCO255-260C fraction 15. with the composition shown in Table 1.
Using OF as a raw material, 3.557 g of 5-chloro-2-nitrobenzoic acid was added thereto, heated and stirred at 80C for 1 hour, and then allowed to cool to room temperature. After separating the precipitated solid with F, it was rapidly washed with petroleum ether to separate and remove unreacted hydrocarbon oil, yielding a solid of 3.38%. This solid 3.28%
A mixed liquid K of an ethyl ether layer and a 5% sodium hydroxide aqueous solution layer is added and shaken to decompose the complex and separate and collect the ethyl ether layer.Then, the ethyl ether is distilled off to form a white A hydrocarbon mixture of 0.029 mm consisting of solid and partially brown liquid was obtained. As a result of gas chromatographic analysis of the separated product, even if a raw material containing about 40% of polycyclic aromatic paraffin, naphthene, etc. was used, almost no substances other than dimethylnaphthalene were incorporated, and 2.7- Dimethylnaphthalene content is 50% by weight
The above separated products were obtained.
第１表から明らかなように本発明は、原料炭化水素中に
バラフィン、ナフテン等を含み、ジメチルナフタレン濃
度が低濃度の原料であっても有効に２，７−ジメチルナ
フタレンを回収できるものである。As is clear from Table 1, the present invention can effectively recover 2,7-dimethylnaphthalene even if the raw material hydrocarbon contains paraffin, naphthene, etc. and has a low dimethylnaphthalene concentration. .
実施例−２
第２表に示す組成のジメチルナフタレン混合物原料１０
．ＯＬ？に５−クロロ−２−ニトロ安息香酸３．４４９
−を加え、ＳＯＣで１時間加熱、攪拌した後、室温まで
放冷した。析出した固体をｒ別した後、石油エーテルで
てばやく洗浄し、未反応の炭化水素油を分離除去して３
．５０ｐの固体を得た。この固体３．０９９−をエチル
エーテル層と５幅水酸化ナトリウム水溶液層との混合液
体に加えて振とうし、錯体を分解してエチルエーテル層
を分離、回収し、その後エチルエーテルを留去して茶色
の液体の炭化水素混合物０２７？を得た。分離生成物の
ガスクロマトグラフ分析の結果、２，７−ジメチルナフ
タレン含有量が４０重量係以上の分離生成物が得られた
。Example-2 Dimethylnaphthalene mixture raw material 10 having the composition shown in Table 2
．． Office lady? 5-chloro-2-nitrobenzoic acid 3.449
- was added, heated and stirred at SOC for 1 hour, and then allowed to cool to room temperature. After separating the precipitated solid, it was quickly washed with petroleum ether to separate and remove unreacted hydrocarbon oil.
．． 50p of solid was obtained. This solid 3.099- was added to a mixed liquid of an ethyl ether layer and a 5-width sodium hydroxide aqueous solution layer and shaken to decompose the complex and separate and collect the ethyl ether layer, after which the ethyl ether was distilled off. A brown liquid hydrocarbon mixture 027? I got it. As a result of gas chromatographic analysis of the separated product, a separated product having a 2,7-dimethylnaphthalene content of 40% by weight or more was obtained.
実施例−３
実施例２と同じ原料１０．０％に５−クロロ−２＝二ト
ロ安息香酸３．４４？を加え、室温で１時間攪拌した後
、実施例２と同様に固液を分離して３．３６？の固体を
得た。この固体１．２２ｙ−を実施例１と同様Ｋ処理し
て白色の固体の炭化水素混合物０．１０デを得た。分離
生成物のガスクロマトグラフ分析の結果、実施例２と同
様の結果が得られた。実施例３は、錯体形成反応が室温
でも良好な分離結果が得られることを示すものである。Example-3 5-chloro-2=nitrobenzoic acid 3.44% in 10.0% of the same raw material as in Example 2? After stirring at room temperature for 1 hour, solid and liquid were separated in the same manner as in Example 2 to obtain 3.36? A solid was obtained. This solid (1.22y) was treated with K in the same manner as in Example 1 to obtain 0.10y of a white solid hydrocarbon mixture. As a result of gas chromatographic analysis of the separated product, the same results as in Example 2 were obtained. Example 3 shows that the complex formation reaction can give good separation results even at room temperature.
Claims (1)
チルナフタレンを分離回収する方法において、錯体形成
物質として５−クロロ−２−ニトロ安息香酸を用いるこ
とを特徴とする２，７−ジメチルナフタレンの分離方法
。A method for separating and recovering 2,7-dimethylnaphthalene in a hydrocarbon oil by forming a charge transfer complex, characterized in that 5-chloro-2-nitrobenzoic acid is used as a complex-forming substance. Separation method.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP5862289A JPH02237943A (en) | 1989-03-10 | 1989-03-10 | Separation of 2,7-dimethylnaphthalene |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP5862289A JPH02237943A (en) | 1989-03-10 | 1989-03-10 | Separation of 2,7-dimethylnaphthalene |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH02237943A true JPH02237943A (en) | 1990-09-20 |
Family
ID=13089670
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP5862289A Pending JPH02237943A (en) | 1989-03-10 | 1989-03-10 | Separation of 2,7-dimethylnaphthalene |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH02237943A (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5668217A (en) * | 1996-05-16 | 1997-09-16 | Huntsman Petrochemical Corporation | Amidoamine modification of polypropylene |
| US5985999A (en) * | 1993-07-13 | 1999-11-16 | Huntsman, Petrochemical Corporation | Dyeable polyolefin containing polyetheramine modified functionalized polyolefin |
| US6093496A (en) * | 1998-05-12 | 2000-07-25 | Huntsman Petrochemical Corporation | Polyolefin containing polyetheramine modified functionalized polyolefin |
| US6146574A (en) * | 1993-07-13 | 2000-11-14 | Huntsman Petrochemical Corporation | Article manufacture using polyolefin containing polyetheramine modified functionalized polyolefin |
-
1989
- 1989-03-10 JP JP5862289A patent/JPH02237943A/en active Pending
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5985999A (en) * | 1993-07-13 | 1999-11-16 | Huntsman, Petrochemical Corporation | Dyeable polyolefin containing polyetheramine modified functionalized polyolefin |
| US6146574A (en) * | 1993-07-13 | 2000-11-14 | Huntsman Petrochemical Corporation | Article manufacture using polyolefin containing polyetheramine modified functionalized polyolefin |
| US5668217A (en) * | 1996-05-16 | 1997-09-16 | Huntsman Petrochemical Corporation | Amidoamine modification of polypropylene |
| US6093496A (en) * | 1998-05-12 | 2000-07-25 | Huntsman Petrochemical Corporation | Polyolefin containing polyetheramine modified functionalized polyolefin |
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