JPS5958026A - Manufacture of polyester containing sulfonate group - Google Patents
Manufacture of polyester containing sulfonate groupInfo
- Publication number
- JPS5958026A JPS5958026A JP16908582A JP16908582A JPS5958026A JP S5958026 A JPS5958026 A JP S5958026A JP 16908582 A JP16908582 A JP 16908582A JP 16908582 A JP16908582 A JP 16908582A JP S5958026 A JPS5958026 A JP S5958026A
- Authority
- JP
- Japan
- Prior art keywords
- acid
- polyester
- polyhydric alcohol
- unsaturated
- polybasic acid
- 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
Landscapes
- Polyesters Or Polycarbonates (AREA)
Abstract
Description
【発明の詳細な説明】
ポリエステル中にスルホン酸塩基を導入する試みは、顔
料や磁性体の分散性に優れたバインダー、アニオン官能
型樹脂等への新規用途が期待されると共に、スルホン酸
塩基の導入是を比較的多くすることによりポリエステル
樹脂の水溶性化を可能ならしめ繊維糊剤、紙加二[、塗
料、接着剤等の分野への応用がより拡大されることから
古くから仙究が行われている。Detailed Description of the Invention The attempt to introduce sulfonic acid groups into polyester is expected to find new applications in binders with excellent dispersibility for pigments and magnetic materials, anionic functional resins, etc. By introducing a relatively large amount of water, it is possible to make polyester resin water-soluble, and its application to fields such as textile pastes, paper pastes, paints, and adhesives has been expanded since ancient times. It is being done.
従来ポリエステル中へスルホン[−一)゛塩基を導入す
る方法としてはスルホン酸塩基金イf化^・物を細喧合
する方法が最も周知であり該方法は例えばスルホン酸塩
基含有化合物、代表的に15−ソジクムスルホイソフタ
ル酸とイソ7クル酸等のジカルボン酸、ジエチレングリ
コール等ノ多価アルコールを縮合させるものである。得
られる水溶性ポリエステルは繊A、(シ用糊剤、絹ザイ
ジング剤等に有用である。Conventionally, the most well-known method for introducing sulfone [-1) base into polyester is the method of finely mixing the sulfonate base, for example, with a sulfonate group-containing compound. 15-Sodicumsulfoisophthalic acid is condensed with a dicarboxylic acid such as iso-7curic acid or a polyhydric alcohol such as diethylene glycol. The resulting water-soluble polyester is useful as fiber A, (sizing agent for silk, silk sizing agent, etc.).
しかしながら、5−ソジクムスルボイソフタル酸は高価
な化合物であるという問題があり、工業的方法において
t:1:より安価な原料を用いることによってポリエス
テル中にスルホン酸塩基が導入出来ればそれだけ有利で
あることけ目う°までもない。However, there is a problem that 5-sodicumsulboisophthalic acid is an expensive compound, and the more sulfonic acid groups can be introduced into polyester by using cheaper raw materials than t:1 in industrial methods, the more advantageous it becomes. I can't even tell you what happened.
しかるに本発明者等はかかる問題を解決すべく鋭意研究
を重ねた結果、不飽和多価アルコールの不飽和結合に酸
性亜硫酸塩を付加したスルホン化多価アルコールと多塩
基酸を反応させるか、不飽和多1曲アルコールと多塩基
酸を反応させて得られる不飽和ポリエステルの不飽和結
合に酸性亜硫酸塩を付加させる場合、スルホン酸塩基の
導入が幼率良く行われ、水溶性ポリエステルが容易に1
91J造出来ることを見出し本発明を完成するに到った
。However, as a result of intensive research to solve this problem, the inventors of the present invention found that either a sulfonated polyhydric alcohol in which an acidic sulfite is added to the unsaturated bonds of an unsaturated polyhydric alcohol is reacted with a polybasic acid, or an unsaturated polyhydric alcohol has a polybasic acid. When acidic sulfite is added to the unsaturated bonds of an unsaturated polyester obtained by reacting a saturated polyalcohol and a polybasic acid, the introduction of sulfonic acid groups is carried out at a high rate, and the water-soluble polyester is easily converted into 1
91J was discovered and the present invention was completed.
不発りjで使用する酸性亜硫酸塩は工業的に容易に入手
し得る安価な化合物であるので、かかる原料を用いてポ
リエステル中ヘスルボン酸塩基を導入する零発り1の方
法は産業上極めて有用である。Since the acidic sulfite used in Fudanri is an inexpensive compound that can be easily obtained industrially, the method from scratch 1 of introducing hesulfonic acid groups into polyester using such raw materials is extremely useful industrially. be.
本発明においては、不飽和多価アルコールに酸性亜硫酸
塩を反応させて、該アルコール中の不飽和結合に酸性亜
硫酸塩を付加させたスルホン化多価アルコールと多塩基
酸を重縮合する方法、不飽和多価アルコールと多塩基酸
とを重縮合して得られる不飽和ポリエステルに酸性亜硫
酸塩を反応させて不飽和結合に酸性亜硫酸塩を付加させ
る方法のいずれも実施出来るが、前者の方法がポリエス
テルの安定性の面で実用的である0
前者の方法においては−まず不飽和多価アルコールと酸
性亜硫酸塩を付加反応させてスルホン化多価アルコール
を調製する。両者の反応は例えば2−ブテン−1,4−
ジオールと亜(iAt酸水索す) IJクムを酸化鉄の
存在下に70°C程度に加熱することによって行われる
。In the present invention, an unsaturated polyhydric alcohol is reacted with an acidic sulfite, and a polybasic acid is polycondensed with a sulfonated polyhydric alcohol in which the acidic sulfite is added to the unsaturated bonds in the alcohol. Although it is possible to carry out either method of reacting an acidic sulfite with an unsaturated polyester obtained by polycondensation of a saturated polyhydric alcohol and a polybasic acid and adding the acidic sulfite to the unsaturated bond, the former method is suitable for polyester. In the former method, an unsaturated polyhydric alcohol and an acidic sulfite are first subjected to an addition reaction to prepare a sulfonated polyhydric alcohol. The reaction between the two is, for example, 2-butene-1,4-
This is done by heating IJ cum to about 70°C in the presence of iron oxide.
次に該スルホン化多価アルコールと多塩基酸を縮合させ
てポリエステルを得る。この反応は通常のポリエステル
の反応と同様な条件で行われるので特別の操作は必要で
ない。すなわち多価アルコールと多塩基酸をジブチルチ
ンオキシド、三酸化アンチモン、酢酸亜鉛等のエステル
化触媒の存在下、170〜280℃の温度でエステル化
反応したのち、縮合触媒の存在下に0.5〜1.0 m
HHの真空下で温度240〜280°(:で縮合反応を
する。縮合触媒としては酸化ゲルマニクム、三酸化アン
チモン、テトラブチルチタネート、ジブチルチンオキシ
ド等が挙げられる。Next, the sulfonated polyhydric alcohol and polybasic acid are condensed to obtain a polyester. This reaction is carried out under the same conditions as for ordinary polyester reactions, so no special operations are required. That is, after esterifying a polyhydric alcohol and a polybasic acid at a temperature of 170 to 280°C in the presence of an esterification catalyst such as dibutyltin oxide, antimony trioxide, or zinc acetate, 0.5 ~1.0 m
The condensation reaction is carried out under the vacuum of HH at a temperature of 240 to 280°. Examples of the condensation catalyst include germanicum oxide, antimony trioxide, tetrabutyl titanate, dibutyltin oxide, and the like.
後者の方法では゛まず不飽和ポリエステルの調製に当っ
ては多塩基酸1モルに対して不飽和多価アルコール及び
飽和アルコールを1.5〜2モル程度の割合で触媒、安
定剤と共に撹拌機、全細器、分縮器及びトルクメーター
のイ・]設された反応缶に仕込み温度230〜270°
ににて粕U反応を行なう。In the latter method, first, to prepare an unsaturated polyester, unsaturated polyhydric alcohol and saturated alcohol are mixed in a ratio of about 1.5 to 2 moles per mole of polybasic acid, together with a catalyst and a stabilizer, using a stirrer, The temperature is 230 to 270° when charged into a reaction vessel equipped with a finer, a partial condenser, and a torque meter.
Carry out the lees U reaction.
次に該不飽和ポリニスデルと酸性亜硫酸塩を反応させて
、ポリエステル中の不飽和結合に酸性亜硝、酸塩を付加
させる。Next, the unsaturated polynisder and acidic sulfite are reacted to add acidic nitrite and acid salt to the unsaturated bonds in the polyester.
反応Ll不飽和ポリエステルをベンゼンに溶解し酸化鉄
の存在下、酸性亜硫酸す) IJクムを不飽和基の10
モル%〜200モル%の割合で混合し、60℃〜沸点下
で加熱する。約60分〜6時間後、過剰の酸性亜硫、酸
ナトリクムを水酸化ナトリウムで中和して反応を終了す
る。Reaction: Dissolve the unsaturated polyester in benzene and add acidic sulfite in the presence of iron oxide.
They are mixed in a proportion of mol % to 200 mol % and heated at 60° C. to the boiling point. After about 60 minutes to 6 hours, excess acidic sulfur and acid sodium are neutralized with sodium hydroxide to complete the reaction.
前記のいずれの方法においても、ポリエステル中の不飽
和結合を構成する成分として不飽和多1111アルコー
ルを要件とすることが必須であり、これに代えて不飽和
多塩基酸を用いると重合時にゲル化の恐れがある。In any of the above methods, it is essential to require an unsaturated poly-1111 alcohol as a component constituting the unsaturated bonds in the polyester, and if an unsaturated polybasic acid is used instead, gelation occurs during polymerization. There is a risk of
本発明で使用する不飽和多価アルコールとしては6−プ
テンート2−ジオール、2−プテンート4−ジオール、
2・5−ジメチル−6−ヘキセン−2・5−ジオール等
のオレフィン系グリコール、1・5−ヘキツ゛ジエン−
6・4−ジオール2・6−オクタジニンー4・5−ジオ
ール崎のジオレフィン糸グリコールが挙げらhる。The unsaturated polyhydric alcohols used in the present invention include 6-ptento-2-diol, 2-ptento-4-diol,
Olefinic glycols such as 2,5-dimethyl-6-hexene-2,5-diol, 1,5-hexene-
Examples include diolefin thread glycols such as 6,4-diol 2,6-octazine-4,5-diol.
上記以外に併用されるアルコールとしてはエチレングリ
コール、ジエチレングリコール、フロピレンゲリコール
、ジプロピレングリコール、ネオペンチルグリコール、
シクロヘキサンジメタツール、ペンタエリスリトール等
が例示される。Examples of alcohols used in combination with other than the above include ethylene glycol, diethylene glycol, fluoropylene glycol, dipropylene glycol, neopentyl glycol,
Examples include cyclohexane dimetatool and pentaerythritol.
多塩基酸としては例えばシュク酸、マロン酸、ジメチル
マロン酸 コハク酸、ゲルタールへ夕、アジピン酸、ト
リメチルアジピン酸、ピメリン酸、2・2−ジメチルゲ
ルタール酸、アゼライン酸、セバシン酸、1・6−シク
口ヘキサンジヵルボン酸、1・6−シクロペンクンジカ
ルボン酸、1・4−シクロヘキサンジカルボン酸、フタ
ル1゛1焚゛、テレフタル酸、イソフタル酸、2・5−
ノルボルナンジカルボン酸、1・4−ナフタール酸、シ
フエニン酸、4・4′−オギシ安息査酸、ジグリコール
酸、チオジプロピオン、4・4′−スルホニルジ安息査
酸、2・5−ナフタレンジカルボン酸等の飽和カルボン
酸が挙げられる。Examples of polybasic acids include succinic acid, malonic acid, dimethylmalonic acid, succinic acid, geltal acid, adipic acid, trimethyladipic acid, pimelic acid, 2,2-dimethylgeltaric acid, azelaic acid, sebacic acid, 1,6 -Cyclohexanedicarboxylic acid, 1,6-cyclopencunedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, phthalic acid, terephthalic acid, isophthalic acid, 2,5-
Norbornane dicarboxylic acid, 1,4-naphthalic acid, siphenic acid, 4,4'-ogishibenzoic acid, diglycolic acid, thiodipropion, 4,4'-sulfonyl dibenzoic acid, 2,5-naphthalene dicarboxylic acid Examples include saturated carboxylic acids such as.
必要であればマレイン酸、ノllξ水マレイン酸、フマ
ル酸、イタコン酸、シトラコン酸等の不飽和カルボン酸
を併用しても良い。If necessary, an unsaturated carboxylic acid such as maleic acid, hydromaleic acid, fumaric acid, itaconic acid, or citraconic acid may be used in combination.
前記したカルボン酸は低級アルキルエステルあるいけ酸
クロライド等の形状であっても良い。The above carboxylic acid may be in the form of lower alkyl ester, silicic acid chloride, or the like.
酸性並値1酸塩としてV」酸性亜硝、酸す) IJクム
、酸性亜硫酸カリタム等が実用的に用いられる。As the acidic average monoacid, acidic nitrite, acidic nitrite, acidic potassium sulfite, etc. are practically used.
かくして得られるポリエステル−1繊維用糊剤、紙加工
剤、繊維加工剤、接着剤、塗料、水溶性フィルム、繊維
、顔料や磁性体の分散性に浸れたノ匂fンダー、アニオ
ン官能ヘリ樹脂等とt、てイ]゛用である。The thus obtained polyester-1 fiber paste, paper processing agent, fiber processing agent, adhesive, paint, water-soluble film, fiber, pigment and magnetic substance dispersibility, anionic functional resin, etc. It is for t, te].
次に実例を拳げて木兄E’lJの方法を更に具体的に説
明する。Next, I will explain E'lJ's method in more detail using an example.
実施例1
撹拌機、精留堵、窒素堺入管、真空装置を付した5 j
l Ome容I!、応化にテレフタル酸0.5モル、イ
ソフタル酸0.4モル、アジピン酸0.1モル、エチレ
ングリコール0.45モル、ジエチレングリコール1.
0モル、2−ラジオスルホ−1,4−ブタンジオール0
.15モル及びジブチルチンオキサイド0.1部を仕込
み撹拌下に14.0〜220°Cでエステル化を行った
後、リン酸0.05部、三酸化アンチモン0.1部を添
加し0 、5〜l 、 Om+++IIgの真空下25
0°Cで重縮りを行って極限粘度0.58のポリエステ
ルを製造した。該ポリエステル20ノを撹拌下K 80
me (D温水(80’C)K[加したところ、6分
後に1士透す1な水溶液が得られた。Example 1 5j equipped with a stirrer, rectification, nitrogen sakai inlet tube, and vacuum device
l Ome Yong I! , terephthalic acid 0.5 mol, isophthalic acid 0.4 mol, adipic acid 0.1 mol, ethylene glycol 0.45 mol, diethylene glycol 1.
0 mol, 2-radiosulfo-1,4-butanediol 0
.. After charging 15 mol and 0.1 part of dibutyltin oxide and carrying out esterification at 14.0 to 220°C with stirring, 0.05 part of phosphoric acid and 0.1 part of antimony trioxide were added. ~l, under vacuum of Om+++IIg25
A polyester having an intrinsic viscosity of 0.58 was produced by performing polyfoaming at 0°C. K 80 while stirring 20 kg of the polyester
When K was added to warm water (80'C), an aqueous solution that was 100% permeable was obtained after 6 minutes.
尚、対照例として2−ラジオスルホ−1,4−ブタンジ
オールの使用を省略した以外は実施例1と同一の方法で
得たポリエステルについて同様のテストを行ったところ
膨潤すらおこらながっだ。As a control example, a similar test was conducted on a polyester obtained in the same manner as in Example 1, except that the use of 2-radiosulfo-1,4-butanediol was omitted, and no swelling occurred.
実施例2
撹拌機、精栢塔、窒素導入管、真空装置を付した5 0
0 me容反応出にテ1/フタル酸o、42モル、イソ
フタル酸0.46モル、アジピン酸0.15モル、エチ
レンクリコール0.76モル、ネオベンザルクリコール
0.75モル、2−ラジオスルホ−14−ブタンジオー
ルO,[]22モルびジグチルチンオキーゾ゛イド0.
1部を仕込み撹拌下に140〜220℃でニスデルを行
った後、リン酸0.05部、三酸化アンチモン[1,1
部を添加し肌5〜1 、0 rn=tIIKの真空下で
屯細6を行って極限粘度0.68のポリエステルを製造
した、。Example 2 50 equipped with a stirrer, refinement tower, nitrogen introduction pipe, and vacuum device
0 me volume reacted with Te1/phthalic acid, 42 mol, isophthalic acid 0.46 mol, adipic acid 0.15 mol, ethylene glycol 0.76 mol, neobenzal glycol 0.75 mol, 2-radio Sulfo-14-butanediol O, [ ] 22 mol and digityltin ochizoid 0.
After charging 1 part and carrying out Nisdel treatment at 140 to 220°C with stirring, 0.05 part of phosphoric acid, antimony trioxide [1,1
A polyester having an intrinsic viscosity of 0.68 was produced by adding 5 to 1 parts of the polyester and performing grading under a vacuum of 0 rn = tIIK.
該ポリエステル20yを撹拌下に80 meの温水(8
0℃)に添加したところ、6り、)後に#[透E)1な
水溶液が得られた。The polyester 20y was heated with 80 me warm water (80 me) while stirring.
When the solution was added at 0° C., an aqueous solution of #[transparency E]1 was obtained after 60 minutes.
尚、対照例と17で2−ラジオスルホ−1,4−ブタン
ジオールの使用を省11+、14 した以外は実施例2
と同一の方法で得たポリエステルについてし1様のテス
トを行ったとζろ膨潤ずらおこらなかった。In addition, Example 2 except that the use of 2-radiosulfo-1,4-butanediol in Control Example and 17 was omitted in 11+ and 14.
When the same test was conducted on polyester obtained by the same method as above, no zeta-swelling shift occurred.
実施例6
実施例1における2−ソジオスルホ−1・4−ブタンジ
オールに代えて3−ソジオスルホ−1・2−ブタンジオ
ールを用いた以外は該例と同一の方法を行ったところ、
舷側と同一の結果が得られた。Example 6 The same method as in Example 1 was carried out except that 3-sodiosulfo-1,2-butanediol was used instead of 2-sodiosulfo-1,4-butanediol.
The same results as for the side were obtained.
特許出願人 日本合成化学工粟株式会社手続補正群
(帥白)
昭和58年4!12JI1
1、Y許庁長官若杉相大殿
1、す1件の表示
昭和57年特許願第169085シJ゛2、発明の名称
スルホン酸塩基を含伯するポリエステルの製造法3、補
正をする者
111件との関係 特許出願人
任 所 火阪市北区野崎町9番6号
4、補正の対象
明細書の発1−11.−Jの詳細なH(l明の榴5、内
容
1月細書第10頁実施例乙の後に次の文を追加−)−る
。Patent Applicant: Nippon Gosei Kagaku Kosou Co., Ltd. Procedural Amendment Group (Hakuhaku) 1981 4!12 JI1 1, Director General of the Y License Office Wakasugi Sodaidono 1, Displaying 1 Patent Application No. 169085 J゛2 , Name of the invention: Process for producing polyester containing sulfonic acid groups 3, Relationship with the person making the amendment (111 cases) Patent applicant: 9-6-4, Nozaki-cho, Kita-ku, Hiaka-shi, Patent specification subject to amendment Issue 1-11. -Detailed H of J (1 Ming no Kana 5, Contents January Specification, Page 10, Add the following sentence after Example B) -.
[実施例4
撹拌機、精留塔、室索醇入管、真空装置c7を(4[7
だ500 me等反応缶1/(テL/ 71 ル酸f1
.5 モル、イソフタル酸11.4モル、アジピン酸t
〕、1七ル、エナレノクリコール(1,75セル、ネオ
ペンチルグリコール0.75セル、2−7テンー1.4
−ジオール0.015モル及びジブチルチンオキ゛ティ
ド0.1部を仕込み撹拌下(こ140〜220 ℃でエ
ステルを行った後、リン14N1.05部、三酸化アン
チ七ン0.1部をt尻加L0.5〜□ 1.01111
+I ITgの真空下で爪ね合を行って極限粘度0.8
7σ)ポリエステルを製jh L ;Al O
得られた不飽和ポリニスデルをベンセン((:浴fす+
4 L−C濃度30重1i%の溶液と17、さらにこの
溶液に酸化鉄5y 酸性亜1141、酸す1リクム15
〕を加え、温度を611−8 noCに保持して6時間
撹拌し7て、2−ブテン−1,4−ジA−ル中の不飽和
結自に酸性亜硫酸ナトリウムを付加反応さ、t!た。反
応終了後過料の亜硫酸ナトリウムで中和12、芒硝をP
別づ〕離した後、ベンゼンを留出除去面、2−ゾ1ンー
1.4−ジオールの代わりに無水マレイン酸を月1いて
ポリ上ステルを製j占しようとしたが、製j:1中に1
1」粘が激しく存り、スルホン酸塩基召有ポリ゛Lステ
ルを得ることはできなかった。」
)人文[Example 4] Stirrer, rectification column, chamber infiltration tube, vacuum device c7 (4 [7
500 me etc. reaction can 1/(teL/71 acid f1
.. 5 mol, isophthalic acid 11.4 mol, adipic acid t
], 17 cells, enalenocricol (1,75 cells, neopentyl glycol 0.75 cells, 2-7 ten-1.4
- 0.015 mole of diol and 0.1 part of dibutyltin oxide were charged and stirred (after esterification was carried out at 140 to 220°C, 1.05 part of phosphorus 14N and 0.1 part of antisulfate trioxide were added to Shirika L0.5~□ 1.01111
+I The limiting viscosity is 0.8 by tightening the nails under a vacuum of ITg.
7σ) Polyester is prepared by mixing the obtained unsaturated polynisdel with benzene ((: bath f +
4 A solution with an L-C concentration of 30 wt 1i% and 17, and further added to this solution 5y of iron oxide, 1141 acid submers, 1 acid 15
] was added, the temperature was maintained at 611-8 noC and stirred for 6 hours, and acidic sodium sulfite was added to the unsaturated bonds in 2-butene-1,4-dial. Ta. After the reaction is completed, neutralize with sodium sulfite as a filter material, and P.
[separately] After separation, benzene was removed by distillation, and maleic anhydride was added in place of 2-zonal-1,4-diol to prepare a polyamide ester, but the product was 1:1. Inside 1
1" It was extremely viscous, and it was not possible to obtain a sulfonic acid group-containing poly(L) stellate. ) Humanities
Claims (1)
(加したスルホン化多価アルコールと多塩基酸を反応さ
せるか、不飽和多価アルコールと多塩基酸を反応させて
得られる不飽和ポリエステルの不飽和結合に酸性亜硫酸
塩を付加させることを特徴とするスルホン酸塩基を含有
するポリエステルのIjA造法。Adding acidic sulfite to the unsaturated bonds of unsaturated polyhydric alcohol (
(It is characterized by adding an acidic sulfite to the unsaturated bonds of an unsaturated polyester obtained by reacting an added sulfonated polyhydric alcohol and a polybasic acid, or by reacting an unsaturated polyhydric alcohol and a polybasic acid.) IjA method for producing polyester containing sulfonic acid groups.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP16908582A JPS5958026A (en) | 1982-09-27 | 1982-09-27 | Manufacture of polyester containing sulfonate group |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP16908582A JPS5958026A (en) | 1982-09-27 | 1982-09-27 | Manufacture of polyester containing sulfonate group |
Publications (1)
Publication Number | Publication Date |
---|---|
JPS5958026A true JPS5958026A (en) | 1984-04-03 |
Family
ID=15880040
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP16908582A Pending JPS5958026A (en) | 1982-09-27 | 1982-09-27 | Manufacture of polyester containing sulfonate group |
Country Status (1)
Country | Link |
---|---|
JP (1) | JPS5958026A (en) |
Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS59202219A (en) * | 1983-05-02 | 1984-11-16 | Nippon Synthetic Chem Ind Co Ltd:The | Production of sulfonate group-containing polyester resin |
US7189798B2 (en) * | 2001-01-11 | 2007-03-13 | Eastman Chemical Company | Composition containing mixture of dihydroxybutane sulfonates |
JP2009214000A (en) * | 2008-03-10 | 2009-09-24 | Kobe Steel Ltd | Solid-liquid separation device, solid-liquid separation method, and method of preparing ashless coal |
JP2023510414A (en) * | 2020-01-16 | 2023-03-13 | 北京化工大学 | Butenediol-based polyester elastomer and manufacturing method |
Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS4948783A (en) * | 1972-05-18 | 1974-05-11 | ||
JPS50121395A (en) * | 1974-02-26 | 1975-09-23 | ||
JPS5139627A (en) * | 1974-08-02 | 1976-04-02 | Bayer Ag | Eeterukozoganjujihidorokishisurupponsanseiho |
JPS5335569A (en) * | 1976-09-14 | 1978-04-03 | Asahi Glass Co Ltd | Method of measuring outer diameter of transparent substance |
JPS5617369A (en) * | 1979-07-24 | 1981-02-19 | Copyer Co Ltd | Fixing device of copier |
-
1982
- 1982-09-27 JP JP16908582A patent/JPS5958026A/en active Pending
Patent Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS4948783A (en) * | 1972-05-18 | 1974-05-11 | ||
JPS50121395A (en) * | 1974-02-26 | 1975-09-23 | ||
JPS5139627A (en) * | 1974-08-02 | 1976-04-02 | Bayer Ag | Eeterukozoganjujihidorokishisurupponsanseiho |
JPS5335569A (en) * | 1976-09-14 | 1978-04-03 | Asahi Glass Co Ltd | Method of measuring outer diameter of transparent substance |
JPS5617369A (en) * | 1979-07-24 | 1981-02-19 | Copyer Co Ltd | Fixing device of copier |
Cited By (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS59202219A (en) * | 1983-05-02 | 1984-11-16 | Nippon Synthetic Chem Ind Co Ltd:The | Production of sulfonate group-containing polyester resin |
JPH0333173B2 (en) * | 1983-05-02 | 1991-05-16 | Nippon Synthetic Chem Ind | |
US7189798B2 (en) * | 2001-01-11 | 2007-03-13 | Eastman Chemical Company | Composition containing mixture of dihydroxybutane sulfonates |
JP2009214000A (en) * | 2008-03-10 | 2009-09-24 | Kobe Steel Ltd | Solid-liquid separation device, solid-liquid separation method, and method of preparing ashless coal |
JP2023510414A (en) * | 2020-01-16 | 2023-03-13 | 北京化工大学 | Butenediol-based polyester elastomer and manufacturing method |
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