JPS623200B2 - - Google Patents
Info
- Publication number
- JPS623200B2 JPS623200B2 JP13976779A JP13976779A JPS623200B2 JP S623200 B2 JPS623200 B2 JP S623200B2 JP 13976779 A JP13976779 A JP 13976779A JP 13976779 A JP13976779 A JP 13976779A JP S623200 B2 JPS623200 B2 JP S623200B2
- Authority
- JP
- Japan
- Prior art keywords
- copolymer
- maleic anhydride
- olefin
- reaction
- alcohol
- 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.)
- Expired
Links
- 239000000203 mixture Substances 0.000 claims description 20
- 125000004432 carbon atom Chemical group C* 0.000 claims description 17
- 239000010779 crude oil Substances 0.000 claims description 17
- 239000010763 heavy fuel oil Substances 0.000 claims description 16
- 125000001931 aliphatic group Chemical group 0.000 claims description 7
- 150000001875 compounds Chemical class 0.000 claims description 5
- 229920001577 copolymer Polymers 0.000 description 36
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 35
- 150000001336 alkenes Chemical class 0.000 description 31
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 31
- 238000006243 chemical reaction Methods 0.000 description 25
- 239000004711 α-olefin Substances 0.000 description 20
- 150000005690 diesters Chemical class 0.000 description 17
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 14
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 12
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 12
- 239000003921 oil Substances 0.000 description 12
- 239000003054 catalyst Substances 0.000 description 11
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 10
- 238000000034 method Methods 0.000 description 10
- 239000008096 xylene Substances 0.000 description 10
- 230000015572 biosynthetic process Effects 0.000 description 8
- 238000003786 synthesis reaction Methods 0.000 description 8
- 239000002994 raw material Substances 0.000 description 7
- 239000001993 wax Substances 0.000 description 7
- DNIAPMSPPWPWGF-GSVOUGTGSA-N (R)-(-)-Propylene glycol Chemical class C[C@@H](O)CO DNIAPMSPPWPWGF-GSVOUGTGSA-N 0.000 description 6
- 229910052757 nitrogen Inorganic materials 0.000 description 6
- GLDOVTGHNKAZLK-UHFFFAOYSA-N octadecan-1-ol Chemical compound CCCCCCCCCCCCCCCCCCO GLDOVTGHNKAZLK-UHFFFAOYSA-N 0.000 description 6
- 238000010992 reflux Methods 0.000 description 6
- 239000002904 solvent Substances 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 5
- -1 polyethylenes Polymers 0.000 description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 230000018044 dehydration Effects 0.000 description 4
- 238000006297 dehydration reaction Methods 0.000 description 4
- 230000000881 depressing effect Effects 0.000 description 4
- BTFJIXJJCSYFAL-UHFFFAOYSA-N icosan-1-ol Chemical compound CCCCCCCCCCCCCCCCCCCCO BTFJIXJJCSYFAL-UHFFFAOYSA-N 0.000 description 4
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 239000004927 clay Substances 0.000 description 3
- 238000000354 decomposition reaction Methods 0.000 description 3
- 238000004821 distillation Methods 0.000 description 3
- NOPFSRXAKWQILS-UHFFFAOYSA-N docosan-1-ol Chemical compound CCCCCCCCCCCCCCCCCCCCCCO NOPFSRXAKWQILS-UHFFFAOYSA-N 0.000 description 3
- 229960000735 docosanol Drugs 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 239000003999 initiator Substances 0.000 description 3
- 239000011973 solid acid Substances 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 2
- 239000002841 Lewis acid Substances 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 150000001338 aliphatic hydrocarbons Chemical group 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
- LQZZUXJYWNFBMV-UHFFFAOYSA-N dodecan-1-ol Chemical compound CCCCCCCCCCCCO LQZZUXJYWNFBMV-UHFFFAOYSA-N 0.000 description 2
- IRHTZOCLLONTOC-UHFFFAOYSA-N hexacosan-1-ol Chemical compound CCCCCCCCCCCCCCCCCCCCCCCCCCO IRHTZOCLLONTOC-UHFFFAOYSA-N 0.000 description 2
- BXWNKGSJHAJOGX-UHFFFAOYSA-N hexadecan-1-ol Chemical compound CCCCCCCCCCCCCCCCO BXWNKGSJHAJOGX-UHFFFAOYSA-N 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 150000002430 hydrocarbons Chemical group 0.000 description 2
- 150000007517 lewis acids Chemical class 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 238000005086 pumping Methods 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 238000007127 saponification reaction Methods 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- HLZKNKRTKFSKGZ-UHFFFAOYSA-N tetradecan-1-ol Chemical compound CCCCCCCCCCCCCCO HLZKNKRTKFSKGZ-UHFFFAOYSA-N 0.000 description 2
- FPLNRAYTBIFSFW-UHFFFAOYSA-N tricosan-1-ol Chemical compound CCCCCCCCCCCCCCCCCCCCCCCO FPLNRAYTBIFSFW-UHFFFAOYSA-N 0.000 description 2
- BZJTUOGZUKFLQT-UHFFFAOYSA-N 1,3,5,7-tetramethylcyclooctane Chemical group CC1CC(C)CC(C)CC(C)C1 BZJTUOGZUKFLQT-UHFFFAOYSA-N 0.000 description 1
- CRSBERNSMYQZNG-UHFFFAOYSA-N 1-dodecene Chemical compound CCCCCCCCCCC=C CRSBERNSMYQZNG-UHFFFAOYSA-N 0.000 description 1
- GQEZCXVZFLOKMC-UHFFFAOYSA-N 1-hexadecene Chemical compound CCCCCCCCCCCCCCC=C GQEZCXVZFLOKMC-UHFFFAOYSA-N 0.000 description 1
- URRHKOYTHDCSDA-UHFFFAOYSA-N 2,5,8,11-tetramethyldodec-2-ene Chemical group CC(C)CCC(C)CCC(C)CC=C(C)C URRHKOYTHDCSDA-UHFFFAOYSA-N 0.000 description 1
- 239000004342 Benzoyl peroxide Substances 0.000 description 1
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 238000000862 absorption spectrum Methods 0.000 description 1
- 239000003377 acid catalyst Substances 0.000 description 1
- 125000003158 alcohol group Chemical group 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 235000019400 benzoyl peroxide Nutrition 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 150000001728 carbonyl compounds Chemical class 0.000 description 1
- 239000007810 chemical reaction solvent Substances 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 150000001990 dicarboxylic acid derivatives Chemical class 0.000 description 1
- 125000005678 ethenylene group Chemical group [H]C([*:1])=C([H])[*:2] 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 150000002432 hydroperoxides Chemical class 0.000 description 1
- 239000012442 inert solvent Substances 0.000 description 1
- 238000006317 isomerization reaction Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000012188 paraffin wax Substances 0.000 description 1
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920000193 polymethacrylate Polymers 0.000 description 1
- 150000003138 primary alcohols Chemical class 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- TYWMIZZBOVGFOV-UHFFFAOYSA-N tetracosan-1-ol Chemical compound CCCCCCCCCCCCCCCCCCCCCCCCO TYWMIZZBOVGFOV-UHFFFAOYSA-N 0.000 description 1
- 238000005292 vacuum distillation Methods 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
Landscapes
- Liquid Carbonaceous Fuels (AREA)
Description
沸点が350℃より高く、且つ流動点が25℃より
も高い残留燃料油及び原油は、その流動性との関
係において多くのトラブルが発生する。即ち油が
加熱装置のないタンクに貯蔵される場合、外気で
冷却され硬くなり、油をポンピングする時に問題
が発生する。又、輸送においてパイプライン中で
強い流動抵抗を生じ、このため非常に大きなポン
プ動力を要する。
これらの問題を解決するためには、一般に低温
流動性改良剤と呼ばれる添加剤が使用される。こ
の種の添加剤は油中のワツクスと共晶したり、ワ
ツクスを吸着したりして、その結晶の大きさ、形
状、及び表面を変化させ、低温における油の流動
特性をいちじるしく改善する。
現在使用されている低温流動性向上剤には、ア
ルキルナフタレンポリマー、ポリメタアクリレー
ト、枝分れポリエチレン、エチレン酢酸ビニル共
重合体及びこれらの混合物等があり、又特に、本
発明に関連する日本特許としては特公昭50−
15005がある。その内容はα−オレフインとエチ
レン系不飽和ジカルボン酸との共重合体のエステ
ル化物を含有した改良された流動点を有する炭化
水素燃料又は炭化水素油組成物である。
本発明者等は、残留燃料油及び原油の流動性を
改善する研究を行なう中で、特に、内部オレフイ
ンと無水マレイン酸との共重合体のジエステル化
物が、α−オレフインと無水マレイン酸との共重
合体のエステル化物に比較して、よりすぐれた流
動性改良能を有する事を見い出した。又、内部オ
レフインと無水マレイン酸との共重合体のジエス
テル化物は、α−オレフインと無水マレイン酸と
の共重合体のジエステル化物と比較すると、その
流動点及び粘度の低下によりハンドリングもいち
じるしく改善される。
本発明は、大部分の残留燃料油又は原油中に一
般式
（但し、式中R1及びR2は、炭素原子数（以下炭素
数と略称す）12〜30の飽和脂肪族炭化水素基、
R3及びR4は、炭素数１〜29の飽和脂肪族炭化水
置基であり、かつ、R3及びR4は炭素数の合計が
10〜30になる様な迸ばれた飽和脂肪族炭化水素
基、ｎは２〜30の正数を示す。）にて表わされる
化合物を100〜20000ppm含有することを特徴と
する改良された流動性を有する残留燃料油及び原
油組成物に関するものである。
本発明にかかわる残留燃料油及び原油組成物
は、その流動性が大幅に改善されると共に、ワツ
クスの分散性もいちじるしく改善される。
次に、本発明において用いられる内部オレフイ
ンと無水マレイン酸との共重合体のジエステル化
物の製造方法について説明する。
まず、α−オレフインを公知の方法で異性化さ
せる。
原料α−オレフインとしては、ドデセン−１、
テトラテセン−１、ヘキサデセン−１、エイコセ
ン−１、ドコセン−１、テトラコセン−１、オク
タコセン−１、テトラプロピレン、テトライソブ
チレン、ヘキサプロピレン等が用いられる。また
一般的には共重合体の油への溶解性を良くするた
め、使用するα−オレフインは、上記のもののう
ちいくつかの混合物が使用される。α−オレフイ
ンの異性化反応は、アルカリ金属、固体酸等を用
いて、100〜300℃の反応温度において行なう。
次に、内部オレフインと無水マレインとを公知
の方法で共重合させる。共重合反応は、ルイス
酸、固体酸及びラジカル開始剤等を用いて反応さ
せるのが一般的であるが、反応条件によつては無
触媒でも進行させることが可能である。反応温度
は50〜250℃において行なう。ルイス酸として
は、活性白土、酸性白土及び塩化アルミニウム
等、固体酸としては、シリカ、アルミナ系触媒及
びラジカル開始剤としては、アゾ化合物、ハイド
ロパーオキサイド等の内から共重合体反応温度に
適した分解速度をもつものが迸ばれる。反応溶媒
は特に使用しなくても良いが、ベンゼン、トルエ
ンン、キシレン或はクロルベンゼン等を使用する
ことができる。
溶媒を用いる場合その使用量は反応にあずかる
内部オレフインと無水マレイン酸の合計量に対し
て20〜80重量％が適当である。
内部オレフインと無水マレイン酸の反応モル比
は、一般に0.5〜1.0：1.0〜0.5であるが、好まし
くは、1.0：0.5〜1.0である。触媒濃度は、内部オ
レフインに対し、0.1〜0.005モルが適当である。
反応時間は、１〜20時間である。
上記反応により得られる共重合体は、次の如き
一般式で表わされる。
（但し、式中R3及びR4は炭素数１〜29の飽和脂肪
族炭化水素でかつR3及びR4の炭素数の合計が10
〜30になる様な迸ばれた飽和脂肪族炭化水素基、
ｎは２−30の正数を示す。）
次にこの共重合体を炭素数12〜30の飽和脂肪族
アルコールとモル比１：1.8〜１：２で無溶媒又
は不活性溶媒の存在下で酸、アルカリ触媒を用い
て反応温度100〜220℃で脱水させることによつて
内部オレフインと無水マレイン酸との共重合体の
ジエステル化物が容易に得られる。酸触媒として
は硫酸、Ｐ−トルエンスルホン酸等が、アルカリ
触媒としては、水酸化ナトリウム、水酸化カリウ
ム等が使用される。
反応時間は、４〜12時間である。
ここで使用される原料飽和脂肪族アルコールと
しては、ドデシルアルコール、テトラデシルアル
コール、ヘキサデシルアルコール、オクタデシル
アルコール、エイコシルアルコール、ドコシルア
ルコール、トリコシルアルコール、テトラコシル
アルコール、ヘキサコシルアルコール、オクタコ
シルアルコール、トルアコンチルアルコール等の
如き直鎖ノルマル第一級アルコールが挙げられる
が、所要の鎖長を持つ飽和脂肪族アルコールより
なる市販アルコール混合物を用いる事もできる。
この様な混合物の一例としては、新日本理化社製
の「コノール40N」があつて、オクタデシルアル
コール、エイコシルアルコール、ドコシルアルコ
ールよりなる。又、他のものとしてはコンチネン
タル・オイル・カンパニー社製の「アルフオール
ス22＋」があつて、主として、ドコシルアルコー
ルよりなるが、炭素数20〜28個のアルコールも含
有する。
本発明の残留燃料油又は原油組成物には他の添
加剤も併用する事が出来る。
次に代表的な実施例をもつて本発明を説明す
る。
実施例 １
（内部オレフインの合成）
コンデンサー付きフラスコにα−オレフインを
規定量、シリカ、アルミナ系触媒（アエロ・キヤ
クト）を、α−オレフインに対して1.0重量％仕
込み180〜200℃の反応温度において窒素気流中で
５時間反応させた。
反応終了後、過で触媒を除き、内部オレフイ
ンを得た。
この内部オレフインの赤外吸収スペクトルを測
定した所、ビニル基の吸収帯（910cm-1）は消失し
て、ビニレン基の吸収帯（970cm-1）に変化した。
実施例 ２
（内部オレフインと無水マレイン酸との共重合
体の合成）
ワツクス分解法により得られた炭素数15〜20の
α−オレフインを実施例１と同様な方法で異性化
した内部オレフインを245ｇ（1.0モル）無水マレ
イン酸を98ｇ（1.0モル）さらに溶媒としてベン
ゼンを350ｇ、リフラツクスコンデンサー付きフ
ラスコに仕込み、次いで内容物に窒素を導入しな
がらフラスコ内の温度を60℃迄上げ、反応開始剤
としてベンゾイルパーオキシド9.7ｇ（0.04モ
ル）を加え反応温度85〜90℃でベンゼンを還流さ
せながら12時間反応させた。反応終了後、減圧蒸
留によりベンゼン、未反応内部オレフイン及び未
反応無水マレイン酸を除き、内部オレフインと無
水マレイン酸との共重合体305ｇを得た。この共
重合体のケン化価は305重量平均分子量は4000
（ケルパーミエーシヨン法）であつた。尚、原料
とした炭素数15〜20のワツクス分解α−オレフイ
ンの組成は次に示す如くであつた。
Residual fuel oils and crude oils with boiling points higher than 350°C and pour points higher than 25°C cause many problems in relation to their fluidity. That is, if oil is stored in a tank without a heating device, it will cool and become hard in the outside air, causing problems when pumping the oil. Also, during transportation, strong flow resistance occurs in the pipeline, which requires a very large pumping power. To solve these problems, additives commonly called cold flow improvers are used. Additives of this type co-crystallize with or adsorb the wax in the oil, changing the size, shape and surface of its crystals, and significantly improving the flow properties of the oil at low temperatures. Currently used cold flow improvers include alkylnaphthalene polymers, polymethacrylates, branched polyethylenes, ethylene-vinyl acetate copolymers and mixtures thereof, and are particularly described in Japanese patents related to the present invention. As for the special public service in 1970-
There is 15005. The content is a hydrocarbon fuel or hydrocarbon oil composition with an improved pour point containing an esterified copolymer of an alpha-olefin and an ethylenically unsaturated dicarboxylic acid. While conducting research to improve the fluidity of residual fuel oil and crude oil, the present inventors found that a diester product of a copolymer of internal olefin and maleic anhydride was developed as a copolymer of α-olefin and maleic anhydride. It has been found that it has a superior ability to improve fluidity compared to esterified copolymers. In addition, the diester product of a copolymer of internal olefin and maleic anhydride has significantly improved handling due to its lower pour point and viscosity compared to the diester product of a copolymer of α-olefin and maleic anhydride. Ru. The present invention provides that most residual fuel oil or crude oil contains the general formula (However, in the formula, R 1 and R 2 are saturated aliphatic hydrocarbon groups having 12 to 30 carbon atoms (hereinafter abbreviated as carbon number),
R 3 and R 4 are saturated aliphatic hydrocarbon substituents having 1 to 29 carbon atoms, and R 3 and R 4 have a total number of carbon atoms of
10 to 30 saturated aliphatic hydrocarbon groups, n is a positive number of 2 to 30. ) The present invention relates to residual fuel oil and crude oil compositions having improved fluidity, characterized in that they contain 100 to 20,000 ppm of the compound represented by (a). The residual fuel oil and crude oil compositions according to the present invention have significantly improved fluidity and also markedly improved wax dispersibility. Next, a method for producing a diester of a copolymer of internal olefin and maleic anhydride used in the present invention will be described. First, α-olefin is isomerized by a known method. As the raw material α-olefin, dodecene-1,
Tetrathecene-1, hexadecene-1, eicosene-1, docosene-1, tetracosene-1, octacosene-1, tetrapropylene, tetraisobutylene, hexapropylene, etc. are used. Generally, in order to improve the solubility of the copolymer in oil, a mixture of some of the above α-olefins is used. The isomerization reaction of α-olefin is carried out using an alkali metal, a solid acid, etc. at a reaction temperature of 100 to 300°C. Next, the internal olefin and maleic anhydride are copolymerized by a known method. Although the copolymerization reaction is generally carried out using a Lewis acid, a solid acid, a radical initiator, etc., it is possible to proceed without a catalyst depending on the reaction conditions. The reaction temperature is 50 to 250°C. Lewis acids include activated clay, acid clay, aluminum chloride, etc. Solid acids include silica and alumina catalysts, and radical initiators include azo compounds, hydroperoxides, etc. suitable for the copolymer reaction temperature. Things with a decomposition rate are ejected. Although there is no particular need to use a reaction solvent, benzene, toluene, xylene, chlorobenzene, etc. can be used. When a solvent is used, the appropriate amount is 20 to 80% by weight based on the total amount of internal olefin and maleic anhydride participating in the reaction. The reaction molar ratio of internal olefin and maleic anhydride is generally 0.5-1.0:1.0-0.5, preferably 1.0:0.5-1.0. The appropriate catalyst concentration is 0.1 to 0.005 mol based on the internal olefin.
Reaction time is 1 to 20 hours. The copolymer obtained by the above reaction is represented by the following general formula. (However, in the formula, R 3 and R 4 are saturated aliphatic hydrocarbons having 1 to 29 carbon atoms, and the total number of carbon atoms of R 3 and R 4 is 10
~30 exposed saturated aliphatic hydrocarbon groups,
n represents a positive number from 2 to 30. ) Next, this copolymer is reacted with a saturated aliphatic alcohol having 12 to 30 carbon atoms at a molar ratio of 1:1.8 to 1:2 using an acid or alkali catalyst in the absence of a solvent or in the presence of an inert solvent at a temperature of 100 to 100°C. A diester product of a copolymer of internal olefin and maleic anhydride can be easily obtained by dehydration at 220°C. As the acid catalyst, sulfuric acid, P-toluenesulfonic acid, etc. are used, and as the alkali catalyst, sodium hydroxide, potassium hydroxide, etc. are used. Reaction time is 4-12 hours. The raw material saturated aliphatic alcohols used here include dodecyl alcohol, tetradecyl alcohol, hexadecyl alcohol, octadecyl alcohol, eicosyl alcohol, docosyl alcohol, tricosyl alcohol, tetracosyl alcohol, hexacosyl alcohol, octadecyl alcohol, Straight chain normal primary alcohols such as cosyl alcohol, toluacontyl alcohol and the like can be used, but commercially available alcohol mixtures consisting of saturated aliphatic alcohols having the required chain length can also be used.
An example of such a mixture is "Conol 40N" manufactured by Shin Nippon Chemical Co., Ltd., which consists of octadecyl alcohol, eicosyl alcohol, and docosyl alcohol. Another example is "Alphorus 22+" manufactured by Continental Oil Company, which mainly consists of docosyl alcohol, but also contains alcohols having 20 to 28 carbon atoms. Other additives may also be used in the residual fuel oil or crude oil composition of the present invention. Next, the present invention will be explained using representative examples. Example 1 (Synthesis of internal olefin) A flask with a condenser was charged with a specified amount of α-olefin, silica and alumina-based catalyst (Aero-Kyakto) at 1.0% by weight based on α-olefin, and the reaction temperature was 180 to 200°C. The reaction was carried out for 5 hours in a nitrogen stream. After the reaction was completed, the catalyst was removed by filtration to obtain an internal olefin. When the infrared absorption spectrum of this internal olefin was measured, the vinyl group absorption band (910 cm -1 ) disappeared and changed to the vinylene group absorption band (970 cm -1 ). Example 2 (Synthesis of copolymer of internal olefin and maleic anhydride) 245 g of internal olefin was obtained by isomerizing α-olefin having 15 to 20 carbon atoms obtained by wax decomposition method in the same manner as in Example 1. (1.0 mol) 98 g (1.0 mol) of maleic anhydride and 350 g of benzene as a solvent were charged into a flask equipped with a reflux condenser, and then the temperature inside the flask was raised to 60°C while nitrogen was introduced into the contents, and a reaction initiator was added. 9.7 g (0.04 mol) of benzoyl peroxide was added thereto, and the mixture was reacted for 12 hours at a reaction temperature of 85 to 90° C. while refluxing benzene. After the reaction was completed, benzene, unreacted internal olefin and unreacted maleic anhydride were removed by vacuum distillation to obtain 305 g of a copolymer of internal olefin and maleic anhydride. The saponification value of this copolymer is 305, and the weight average molecular weight is 4000.
(Kölpermeation method). The composition of the wax-decomposed α-olefin having 15 to 20 carbon atoms as a raw material was as shown below.
【表】
実施例 ３
（内部オレフインと無水マレイン酸との共重合
体の合成）
チーグラー法による炭素数16〜18のα−オレフ
インを実施例１と同様な方法で異性化した内部オ
レフインを462ｇ（2.0モル）、無水マレイン酸を
98ｇ（1.0モル）及び触媒として活性白土4.6ｇを
リフラツクスコンデンサー付きフラスコに仕込み
窒素気流中で190℃１時間反応させた後、無水マ
レイン酸の消費に従つつて反応温度を徐々に220
℃迄上げ、更に５時間反応させた。反応液が完全
に透明になつた点を反応の終点とし減圧下で過剰
のオレフインを取除き内部オレフインと無水マレ
イン酸との共重体282ｇを得た。この共重合体の
ケン化価は288重量平均分子量は3000（ゲルパー
ミエーシヨン法）であつた。尚、原料とした炭素
数16〜18のα−オレフインの組成は次に示す如く
であつた。[Table] Example 3 (Synthesis of copolymer of internal olefin and maleic anhydride) 462 g of internal olefin was prepared by isomerizing α-olefin having 16 to 18 carbon atoms by the Ziegler method in the same manner as in Example 1 ( 2.0 mol), maleic anhydride
98 g (1.0 mol) and 4.6 g of activated clay as a catalyst were placed in a flask equipped with a reflux condenser and reacted in a nitrogen stream at 190°C for 1 hour, then the reaction temperature was gradually increased to 220°C as maleic anhydride was consumed.
The temperature was raised to 0.degree. C., and the reaction was continued for an additional 5 hours. The reaction was terminated when the reaction solution became completely transparent, and excess olefin was removed under reduced pressure to obtain 282 g of a copolymer of internal olefin and maleic anhydride. The saponification value of this copolymer was 288, and the weight average molecular weight was 3000 (gel permeation method). The composition of the α-olefin having 16 to 18 carbon atoms used as a raw material was as shown below.
【表】
実施例 ４
（内部オレフインと無水マレイン酸との共重合
体のジエステル化物の合成）
コンデンサー及び検水管付きのフラスコ内に、
実施例２で得られた内部オレフインと無水マレイ
ン酸との共重合体を185ｇ（0.5モル）、脂肪族ア
ルコールとして、新日本理化社製の「コノコール
40N」を296ｇ（1.0モル）溶媒としてキシレンを
150ｇさらに触媒としてＰ−トルエンスルホン酸
を９ｇを込む。次いで、フラスコ内容物に窒素を
導入しながら反応温度140〜145℃にてキシレンを
還流させながら５時間反応させた。規定量の水が
留出した点を終点とした。
反応終了後、減圧蒸留により、キシレンを除
き、さらに水洗によりＰ−トルエンスルホン酸を
除いた後脱水乾燥して流動点降下能を有する内部
オレフインと無水マレイン酸との共重合体のジエ
ステル化物405ｇを得た。尚、原料とした「コノ
ール40N」の組成は、次に示す如くの飽和脂肪族
アルコールであつた。[Table] Example 4 (Synthesis of diester product of copolymer of internal olefin and maleic anhydride) In a flask equipped with a condenser and a sample tube,
185 g (0.5 mol) of the copolymer of internal olefin and maleic anhydride obtained in Example 2 and an aliphatic alcohol were added to "Conocol" manufactured by Shin Nippon Chemical Co., Ltd.
296g (1.0mol) of ``40N'' xylene as solvent
Add 150g and 9g of P-toluenesulfonic acid as a catalyst. Next, while introducing nitrogen into the contents of the flask, the reaction was carried out at a reaction temperature of 140 to 145° C. for 5 hours while refluxing xylene. The end point was the point at which a specified amount of water was distilled off. After the reaction, xylene was removed by distillation under reduced pressure, and P-toluenesulfonic acid was removed by washing with water, followed by dehydration and drying to obtain 405 g of a diester of a copolymer of internal olefin and maleic anhydride having pour point depressing ability. Obtained. The composition of "Conol 40N" used as a raw material was a saturated aliphatic alcohol as shown below.
【表】
実施例 ５
（内部オレフインと無水マレイン酸との共重合
体のジエステル化物の合成）
コンデンサー、検水管付きのフラスコ内に、実
施例３で得られたオレフインと無水マレイン酸と
の共重合体を195ｇ（0.5モル）、脂肪族アルコー
ルとして、コンチネンタル・オイル・カンパニー
社製の「アルフオールス22＋」を489ｇ（0.95モ
ル）、溶媒としてキシレンを300ｇ、さらに触媒と
してＰ−トルエンスルホン酸を10ｇ仕込む。次い
で、フラスコ内容物に窒素を導入しながら反応温
度140〜145℃にてキシレン還流させながら５時間
反応させた。規定量の水が留出した点を終点とし
た。反応終了後、減圧蒸留によりキシレンを除
き、さらに水洗によりＰ−トルエンスルホン酸を
除いた後、脱水乾燥して、流動点降下能を有する
内部オレフインと無水マレイン酸との共重合体の
ジエステル化物380ｇを得た。尚、原料とした
「アルフオールス22＋」の組成は、次に示す如く
の飽和脂肪族アルコールであつた。[Table] Example 5 (Synthesis of diester product of copolymer of internal olefin and maleic anhydride) In a flask equipped with a condenser and a sample tube, the copolymer of the olefin obtained in Example 3 and maleic anhydride was placed. 195 g (0.5 mol) of the combined substance, 489 g (0.95 mol) of "Alphorus 22+" manufactured by Continental Oil Company as the aliphatic alcohol, 300 g of xylene as the solvent, and 10 g of P-toluenesulfonic acid as the catalyst are charged. . Next, while introducing nitrogen into the contents of the flask, the reaction was carried out for 5 hours while refluxing xylene at a reaction temperature of 140 to 145°C. The end point was the point at which a specified amount of water was distilled off. After the reaction, xylene was removed by distillation under reduced pressure, and P-toluenesulfonic acid was removed by washing with water, followed by dehydration and drying to obtain 380 g of a diester of a copolymer of internal olefin and maleic anhydride that has pour point depressing ability. I got it. The composition of "Alphorus 22+" used as a raw material was a saturated aliphatic alcohol as shown below.
【表】
残りの35重量％は、パラフインとオレフイン
と、カルボニル化合物等との混合物であつた。
実施例 ６
（内部オレフインと無水マレイン酸との共重合
体のジエステル化物の合成）
コンデンサー、検水管付きのフラスコ内に実施
例３で得られた内部オレフインと無水マレイン酸
との共重合体を195ｇ（0.5モル）、炭素数12〜15
の合成アルコールを103ｇ（0.5モル）炭素数14〜
18の天然アルコールを130ｇ（0.5モル）、溶媒と
してキシレンを150ｇ、さらに触媒としてＰ−ト
ルエンスルホン酸を６ｇ仕込む。
次いで、フラスコ内容物に窒素を導入しながら
反応温度140〜145にキシレンを還流させながら５
時間反応させた。規定量の水が留出した点を終点
とする。反応終了後、減圧蒸留によりキシレンを
除き、さらに水洗によりＰ−トルエンスルホン酸
を除いた後、脱水乾燥して流動点降下能を有する
内部オレフインと無水マレイン酸との共重合体の
ジエステル化物358ｇを得た。尚、原料としたア
ルコールの組成は、次に示す如くの飽和脂肪族ア
ルコールであつた。[Table] The remaining 35% by weight was a mixture of paraffin, olefin, carbonyl compound, etc. Example 6 (Synthesis of diester product of copolymer of internal olefin and maleic anhydride) 195 g of the copolymer of internal olefin and maleic anhydride obtained in Example 3 was placed in a flask equipped with a condenser and a sample tube. (0.5 mol), carbon number 12-15
103g (0.5 mol) of synthetic alcohol with 14 to 14 carbon atoms
130 g (0.5 mol) of natural alcohol No. 18, 150 g of xylene as a solvent, and 6 g of P-toluenesulfonic acid as a catalyst were charged. The xylene was then heated to a reaction temperature of 140-145°C while refluxing it while introducing nitrogen into the flask contents.
Allowed time to react. The end point is the point at which the specified amount of water has been distilled off. After the reaction, xylene was removed by distillation under reduced pressure, and P-toluenesulfonic acid was removed by washing with water, followed by dehydration and drying to obtain 358 g of a diester of a copolymer of internal olefin and maleic anhydride having pour point depressing ability. Obtained. The composition of the alcohol used as a raw material was a saturated aliphatic alcohol as shown below.
【表】
実施例 ７
（α−オレフインと無水マレイン酸との共重合
体のジエステル化物の合成）
ワツクス分解法による炭素数15〜20のα−オレ
フインと無水マレイン酸とを実施例２と同様な方
法で共重合させた。その共重合体を実施例４と同
様な方法で「コノール40N」とエステル化させて
α−オレフインと無水マレイン酸との共重合体の
ジエステル化物を得た。
実施例 ８
（α−オレフインと無水マレイン酸との共重合
体のジエステル化物の合成）
炭素数16〜18のα−オレフインと無水マレイン
とを実施例３と同様な方法で共重合させた。その
共重合体を実施例５と同様な方法で「アルフオー
ルス22＋」とエステル化させてα−オレフインと
無水マレイン酸との共重合体のジエステル化物を
得た。
実施例 ９
残留燃料油及び原油と本発明の化合物との組成
物の流動点降下能と試験結果）
実施例４、５、６、７、８、で得られたオレフ
インと無水マレイン酸との共重合体のジエステル
化物と表１に示す残留燃料油又は原油と配合し、
その流動点を測定した。[Table] Example 7 (Synthesis of diester product of copolymer of α-olefin and maleic anhydride) α-olefin having 15 to 20 carbon atoms and maleic anhydride obtained by the wax decomposition method were mixed in the same manner as in Example 2. Copolymerized by method. The copolymer was esterified with "Conol 40N" in the same manner as in Example 4 to obtain a diester of a copolymer of α-olefin and maleic anhydride. Example 8 (Synthesis of diester product of copolymer of α-olefin and maleic anhydride) α-olefin having 16 to 18 carbon atoms and maleic anhydride were copolymerized in the same manner as in Example 3. The copolymer was esterified with "Alphorus 22+" in the same manner as in Example 5 to obtain a diester of a copolymer of α-olefin and maleic anhydride. Example 9 Pour point depressing ability and test results of compositions of residual fuel oil and crude oil and the compound of the present invention) Blending the diesterified product of the polymer with the residual fuel oil or crude oil shown in Table 1,
Its pour point was measured.
【表】
原油を示す。
一般に、残留燃料油及び原油の流動点、JIS Ｋ
−2269に記載された方法で測定される。このJIS
法で測定された流動点は、油の熱経歴によつて異
なつた流動点を示す事がある。これは、残留燃料
油及び原油に含まれているワツクス、アスフアル
テン、レジンとが単に溶解混合しているのではな
く、コロイド構造を形式している事によつて起る
と考えられる。
そこで、次に示した試験方法で流動点を測定し
た。先ず、残留燃料油及び原油を100℃に加熱
し、油に混合しているワツクス、アスフアルデン
レジン等を溶解状態にさせる。次いで、それを０
℃迄急激に冷却し、ワツクス等を晶出させて油の
熱経歴を抹消させる。この油に流動性向上剤を添
加し50℃の温度で撹拌させながら溶解させる。流
動性向上剤を溶解させた残留燃料油及び原油組成
物を48℃まで加熱し46℃よりJIS Ｋ−2269法で測
定した流動点を最高流動点と呼び100℃まで再加
熱させて測定した流動点を最低流動点と呼ぶ。
表２に各実施例で得られた化合物を配合した残
留燃料油及び原油組成物の流動点測定結果を示
す。[Table] Shows crude oil.
Generally, the pour point of residual fuel oil and crude oil, JIS K
-2269. This JIS
Pour points measured by the method may show different pour points depending on the thermal history of the oil. This is thought to occur because the wax, asphaltene, and resin contained in the residual fuel oil and crude oil are not simply dissolved and mixed, but have a colloidal structure. Therefore, the pour point was measured using the test method shown below. First, residual fuel oil and crude oil are heated to 100°C to dissolve wax, asphaldene resin, etc. mixed in the oil. Then set it to 0
It is rapidly cooled to ℃ to cause wax etc. to crystallize and erase the thermal history of the oil. A fluidity improver is added to this oil and dissolved while stirring at a temperature of 50°C. The pour point of the residual fuel oil and crude oil composition in which the fluidity improver has been dissolved is heated to 48℃ and measured from 46℃ using the JIS K-2269 method, and is called the highest pour point. The point is called the lowest pour point. Table 2 shows the pour point measurement results of residual fuel oil and crude oil compositions blended with the compounds obtained in each example.
【表】【table】
【表】
表２から明らかな様に、本発明により得られた
化合物を配合された残留燃料油、及び原油組成物
の流動性は、α−オレフインと無水マレイン酸と
の共重合体のジエステル化物のそれと比較してよ
りすぐれたものとなる。又、内部オレフインと無
水マレイン酸との共重合体のジエステル化物はα
−オレフインと無水マレイン酸との共重合体のジ
エステル化物と比較すると、その流動点及び粘度
の低下によりハンドリングもいちじるしく改善さ
れる。[Table] As is clear from Table 2, the fluidity of the residual fuel oil and crude oil composition blended with the compound obtained according to the present invention is the same as that of the diesterified copolymer of α-olefin and maleic anhydride. It is better than that of . In addition, the diester of a copolymer of internal olefin and maleic anhydride is α
- Compared to a diester of a copolymer of olefin and maleic anhydride, handling is significantly improved due to the lower pour point and viscosity.
Claims (1)
和脂肪族炭化水素基、R3及びR4は炭素数１〜29
の飽和脂肪族炭化水素基であり、かつR3及びR4
の炭素原子数の合計が10〜30になる様な迸ばれた
飽和脂肪族炭化水素基、ｎは２〜30の正数を示
す）にて表わされる化合物を100〜20000ppm含
有することを特徴とする改良された低温流動性を
有する残留燃料油及び原油組成物。[Claims] 1. Most residual fuel oil or crude oil contains the general formula (However, in the formula, R 1 and R 2 are saturated aliphatic hydrocarbon groups having 12 to 30 carbon atoms, and R 3 and R 4 are saturated aliphatic hydrocarbon groups having 1 to 29 carbon atoms.
a saturated aliphatic hydrocarbon group, and R 3 and R 4
characterized by containing 100 to 20,000 ppm of a compound represented by a blown-out saturated aliphatic hydrocarbon group having a total number of carbon atoms of 10 to 30, where n is a positive number of 2 to 30. Residual fuel oil and crude oil compositions with improved cold flow properties.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP13976779A JPS5665091A (en) | 1979-10-31 | 1979-10-31 | Residual fuel oil and crude oil composition with improved low-temperature fluidity |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP13976779A JPS5665091A (en) | 1979-10-31 | 1979-10-31 | Residual fuel oil and crude oil composition with improved low-temperature fluidity |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS5665091A JPS5665091A (en) | 1981-06-02 |
| JPS623200B2 true JPS623200B2 (en) | 1987-01-23 |
Family
ID=15252914
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP13976779A Granted JPS5665091A (en) | 1979-10-31 | 1979-10-31 | Residual fuel oil and crude oil composition with improved low-temperature fluidity |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS5665091A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US11193053B2 (en) | 2017-04-13 | 2021-12-07 | Bl Technologies, Inc. | Wax inhibitors for oil compositions and methods of using wax inhibitors to reduce wax deposition from oil |
Families Citing this family (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB2129012B (en) * | 1982-04-12 | 1985-09-18 | Mitsubishi Chem Ind | Agent for improving low temperature fluidity of fuel oil |
| JPS58222190A (en) * | 1982-06-17 | 1983-12-23 | Nippon Petrochem Co Ltd | Low-temperature fluidity modifier for medium fraction petroleum fuel and medium fraction petroleum fuel composition containing same |
| US4654050A (en) * | 1985-01-18 | 1987-03-31 | The Lubrizol Corporation | Esters of carboxy-containing interpolymers |
| GB8515974D0 (en) * | 1985-06-24 | 1985-07-24 | Shell Int Research | Gasoline composition |
| GB8521393D0 (en) * | 1985-08-28 | 1985-10-02 | Exxon Chemical Patents Inc | Middle distillate compositions |
| US4900331A (en) * | 1988-10-31 | 1990-02-13 | Conoco Inc. | Oil compositions containing alkyl amine or alkyl mercaptan derivatives of copolymers of an alpha olefin or an alkyl vinyl ether and an unsaturated alpha, beta-dicarboxylic copound |
| US4992080A (en) * | 1988-10-31 | 1991-02-12 | Conoco Inc. | Oil compositions containing alkyl amine derivatives of copolymers of an alpha olefin or an alkyl vinyl ether and an unsaturated alpha, beta-dicarboxylic compound |
| US5055212A (en) * | 1988-10-31 | 1991-10-08 | Conoco Inc. | Oil compositions containing alkyl mercaptan derivatives of copolymers of an alpha olefin or an alkyl vinyl ether and an unsaturated alpha, beta-dicarboxylic compound |
| US5232963A (en) * | 1992-07-09 | 1993-08-03 | Nalco Chemical Company | Dispersing gums in hydrocarbon streams with β-olefin/maleic anhydride copolymer |
| US5214224A (en) * | 1992-07-09 | 1993-05-25 | Comer David G | Dispersing asphaltenes in hydrocarbon refinery streams with α-olefin/maleic anhydride copolymer |
| US9212330B2 (en) * | 2012-10-31 | 2015-12-15 | Baker Hughes Incorporated | Process for reducing the viscosity of heavy residual crude oil during refining |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3854893A (en) * | 1972-06-14 | 1974-12-17 | Exxon Research Engineering Co | Long side chain polymeric flow improvers for waxy hydrocarbon oils |
| JPS5015005A (en) * | 1973-06-15 | 1975-02-17 | ||
| JPS5481307A (en) * | 1977-12-13 | 1979-06-28 | Toho Kagaku Kougiyou Kk | Liquid fuel composition |
| JPS5650995A (en) * | 1979-10-03 | 1981-05-08 | Nippon Petrochem Co Ltd | Low-temperature flow characteristic improver for fuel oil and fuel oil composition containing the same |
-
1979
- 1979-10-31 JP JP13976779A patent/JPS5665091A/en active Granted
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US11193053B2 (en) | 2017-04-13 | 2021-12-07 | Bl Technologies, Inc. | Wax inhibitors for oil compositions and methods of using wax inhibitors to reduce wax deposition from oil |
| US11261369B2 (en) | 2017-04-13 | 2022-03-01 | Bl Technologies, Inc. | Maleic anhydride copolymer with broadly dispersed ester side chain as wax inhibitor and wax crystallization enhancer |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS5665091A (en) | 1981-06-02 |
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