JPH08151422A - Production of methylene-bridged polyphenylenepolyamine - Google Patents
Production of methylene-bridged polyphenylenepolyamineInfo
- Publication number
- JPH08151422A JPH08151422A JP6292772A JP29277294A JPH08151422A JP H08151422 A JPH08151422 A JP H08151422A JP 6292772 A JP6292772 A JP 6292772A JP 29277294 A JP29277294 A JP 29277294A JP H08151422 A JPH08151422 A JP H08151422A
- Authority
- JP
- Japan
- Prior art keywords
- aniline
- mda
- formaldehyde
- ratio
- mixture
- 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.)
- Granted
Links
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明はメチレン架橋ポリフェニ
レンポリアミンの製造方法に関する。更に詳しくは、特
殊な組成を有するメチレン架橋ポリフェニレンポリアミ
ン（以下ポリＭＤＡ混合物と略記）を製造する方法に関
する。本発明の目的物であるポリＭＤＡ混合物は樹脂の
硬化剤として用いられるほか、不活性溶媒の存在下、ホ
スゲンと反応させてメチレン架橋ポリフェニレンポリイ
ソシアネ−ト（以下、ポリＭＤＩ混合物と略記）を製造
する中間体として重要である。ポリＭＤＩ混合物は極め
て反応性に富む物質で、ポリウレタンフォ−ム、エラス
トマ−、接着剤および塗料等の広範囲の製品製造に利用
されている。FIELD OF THE INVENTION The present invention relates to a method for producing a methylene-bridged polyphenylene polyamine. More specifically, it relates to a method for producing a methylene-bridged polyphenylene polyamine (hereinafter abbreviated as poly MDA mixture) having a special composition. The poly MDA mixture, which is the object of the present invention, is used as a curing agent for resins, and is reacted with phosgene in the presence of an inert solvent to give methylene-bridged polyphenylene polyisocyanate (hereinafter abbreviated as poly MDI mixture). It is important as an intermediate to be produced. Poly MDI blends are extremely reactive materials and are used in the manufacture of a wide range of products such as polyurethane foams, elastomers, adhesives and paints.
【０００２】[0002]
【従来の技術及び発明が解決しようとする課題】メチレ
ン架橋ポリフェニレンポリアミンは、工業的には酸触媒
の存在下、アニリンとホルムアルデヒドとを縮合させる
ことによって製造されており、ポリＭＤＡ混合物を不活
性溶媒の存在下、ホスゲンと反応させることによってポ
リＭＤＩ混合物が製造されている。BACKGROUND OF THE INVENTION Methylene-bridged polyphenylene polyamines are industrially produced by condensing aniline with formaldehyde in the presence of an acid catalyst, and a poly MDA mixture is mixed with an inert solvent. Poly MDI mixtures have been prepared by reacting with phosgene in the presence of
【０００３】生成するポリＭＤＩ混合物の組成は原料の
ポリＭＤＡ混合物の組成によって決まり、ポリＭＤＩ混
合物の組成はウレタン形成時の反応性や分子構造を左右
する重要な因子である。The composition of the resulting poly MDI mixture is determined by the composition of the raw material poly MDA mixture, and the composition of the poly MDI mixture is an important factor that influences the reactivity and molecular structure during urethane formation.
【０００４】例えば、ポリＭＤＩ混合物中のイソシアネ
−ト基含有率の低い多核体の低減はフォ−ムの脆さを抑
える。また、３核体の含有率を高くした場合、３核体の
３つのイソシアネ−ト基のうち１つが立体障害により反
応性が低いため発泡させたときゲル化速度が遅くなり可
使時間の延長や発泡倍率の上昇がみられる。これは、Ｃ
ＡＦＥ（メ−カ−別燃料費効率基準）規制に対応するた
めの自動車の軽量化に寄与すると期待されている。For example, the reduction of polynuclear bodies having a low content of isocyanate groups in the poly MDI mixture suppresses the brittleness of the foam. In addition, when the content of the trinuclear body is increased, one of the three isocyanate groups of the trinuclear body has low reactivity due to steric hindrance, so that the gelation rate becomes slow when foamed and the pot life is extended. And the expansion ratio is increased. This is C
It is expected to contribute to weight reduction of automobiles in order to comply with AFE (fuel cost efficiency standard by manufacturer) regulations.
【０００５】また、特開昭６３−３０９５１２に示され
るように、３核体，４核体及び５核体の含有率を増大し
たポリＭＤＡ混合物から得られたポリＭＤＩ混合物を用
いて耐炎性および低い表面脆性を有するポリウレタン発
泡体が製造されている。このように近年高性能のポリイ
ソシアネ−トとして特殊な核体比を有するポリイソシア
ネ−ト、特に３核体含有率の多いポリイソシアネ−トが
望まれている。Further, as shown in JP-A-63-309512, the flame resistance and the poly-MDI mixture obtained from the poly-MDA mixture having the increased content of the trinuclear, tetranuclear and pentanuclear bodies are used. Polyurethane foams with low surface brittleness have been produced. As described above, in recent years, a polyisocyanate having a special nucleus ratio as a high-performance polyisocyanate, particularly a polyisocyanate having a high trinuclear content, has been desired.
【０００６】ポリアミン混合物の核体比を制御する方法
としては、特開昭５０−３８０９５に示されるようにポ
リアミン混合時のアニリン／塩酸／ホルムアルデヒド
比、縮合温度などを変える方法が知られている。具体的
には、アニリン／ホルムアルデヒド比を上げれば３核体
／４核体以上の比、４核体／５核体以上の比を上げるこ
とが出来るが、２核体アミンの生成量が増加し、それに
伴い３核体，４核体の生成量は減少する。３核体、４核
体の多い組成物を得るためには、蒸留または晶析により
多量の２核体を除去する必要がある。As a method for controlling the nuclei ratio of the polyamine mixture, there is known a method of changing the aniline / hydrochloric acid / formaldehyde ratio at the time of mixing the polyamine, the condensation temperature, etc., as shown in JP-A-50-38095. Specifically, if the aniline / formaldehyde ratio is increased, the ratio of three-nuclear body / four-nuclear body or more can be increased, but the ratio of four-nuclear body / five-nuclear body or more can be increased, but the production amount of binuclear amine increases. The amount of trinuclear and tetranuclear production decreases accordingly. In order to obtain a composition containing a large amount of trinuclear bodies, it is necessary to remove a large amount of dinuclear bodies by distillation or crystallization.
【０００７】また、２核体はポリイソシアネ−ト混合物
から蒸留あるいは晶析によって単離することができるの
で比較的容易に得られることは知られているが、３核体
以上のポリイソシアネ−トは通常の蒸留法で単離するこ
とは困難であり組成比を自由にコントロ−ルできない。It is known that the binuclear compound can be obtained relatively easily because it can be isolated from the polyisocyanate mixture by distillation or crystallization. However, the trinuclear or more polyisocyanate is usually obtained. It is difficult to isolate by the distillation method and the composition ratio cannot be freely controlled.
【０００８】特開平５−３１０６７６には特定の組成を
有するポリイソシアネ−ト混合物から、抽出法により３
核体／４核体以上の比が１．５以上という特殊なイソシ
アネ−トを分離する方法が述べられているが、溶媒抽出
法は、溶媒ロスによる原単位向上などの問題を内存して
おり、多量にかつ連続的に製造するプロセスには望まし
くない。従って、目的組成を有するポリＭＤＡ混合物を
調整し、これをホスゲン化することにより、目的組成を
有するポリＭＤＩ混合物を得る技術が望まれている。Japanese Unexamined Patent Publication (Kokai) No. 5-310676 discloses a method of extracting a polyisocyanate mixture having a specific composition by an extraction method.
A method for separating a special isocyanate having a ratio of nuclides / four nuclides of 1.5 or more is described, but the solvent extraction method has problems such as improvement of the unit consumption due to solvent loss. , Not desirable for high volume and continuous manufacturing processes. Therefore, a technique for preparing a poly MDA mixture having a target composition and phosgenating the mixture to obtain a poly MDI mixture having a target composition is desired.
【０００９】[0009]
【発明を解決するための手段】本発明者らは、上記課題
を解決する為、特定の核体比を有する高性能のポリアミ
ンの製造方法を鋭意検討した結果、アニリンとホルマリ
ンによる２核ＭＤＡ生成の反応機構は、ｐ−アミノベン
ジルカチオンとアニリンの反応によることを見いだし
た。これらの知見をもとに３核ＭＤＡを製造する方法を
検討した。その結果、ｐ−アミノベンジルカチオンの反
応性は２核ＭＤＡよりアニリンとの方が高く、さらに、
２核ＭＤＡのメチレン基に対してｏ位よりｐ位の方への
反応性が高いことがわかった。そこで、ｐ−アミノベン
ジルカチオンとメチレン基に対しＰ位の位置の空いた
２，４’−ジアミノジフェニルメタンを反応させること
により３核ＭＤＡが生成しやすいことを見いだし本発明
に至った。In order to solve the above problems, the inventors of the present invention have earnestly studied a method for producing a high-performance polyamine having a specific nuclide ratio. As a result, the aniline and formalin produce binuclear MDA. It has been found that the reaction mechanism of (1) is due to the reaction of p-aminobenzyl cation and aniline. Based on these findings, a method for producing trinuclear MDA was examined. As a result, the reactivity of p-aminobenzyl cation was higher with aniline than with binuclear MDA, and
It was found that the p-position is more reactive than the o-position with respect to the methylene group of binuclear MDA. Then, it was found that trinuclear MDA is easily produced by reacting a p-aminobenzyl cation with 2,4′-diaminodiphenylmethane having a vacant position at the P-position with respect to a methylene group, and the present invention was completed.
【００１０】すなわち、本発明は酸触媒の存在下、アニ
リンとホルムアルデヒドとの縮合によりメチレン架橋ポ
リフェニレンポリアミンを製造する方法において、２，
４’−ジアミノジフェニルメタン（以下、ｏ−ｐ’ＭＤ
Ａと略記）を添加することを特徴とするメチレン架橋ポ
リフェニレンポリアミンの製造方法である。That is, the present invention provides a method for producing a methylene-bridged polyphenylene polyamine by condensation of aniline and formaldehyde in the presence of an acid catalyst.
4'-diaminodiphenylmethane (hereinafter referred to as op-MD
A) is added thereto, which is a method for producing a methylene-bridged polyphenylene polyamine.
【００１１】以下に本発明を詳細に説明する。酸触媒の
存在下、アニリンとホルムアルデヒドとの縮合を１０〜
４０℃以下で行う。ホルムアルデヒドに対するアニリン
のモル比は１〜３，また、アニリンに対する酸触媒のモ
ル比は０．１〜１とするのが適切である。特に好ましく
は、アニリン／ホルムアルデヒド＝２．２〜２．６，酸
／アニリン＝０．３〜０．５である。The present invention will be described in detail below. In the presence of an acid catalyst, the condensation of aniline and formaldehyde is performed for 10
It is performed at 40 ° C or lower. It is appropriate that the molar ratio of aniline to formaldehyde is 1 to 3, and the molar ratio of the acid catalyst to aniline is 0.1 to 1. Particularly preferably, aniline / formaldehyde = 2.2 to 2.6, acid / aniline = 0.3 to 0.5.
【００１２】酸触媒としては、例えば塩酸，硫酸，燐酸
などを使用することが出来る。縮合反応は転位反応をで
きるだけ抑制するために、４０℃を越える温度に上げる
のは好ましくない。また、１０℃未満になると撹拌が困
難となる。ホルムアルデヒドに対するアニリンのモル比
が３以上になると、製造したポリＭＤＡ混合物中の２核
ＭＤＡの含有量が多くなり、目的組成物を得るために、
蒸留または晶析により２核ＭＤＡを多量に除去する必要
がある。As the acid catalyst, for example, hydrochloric acid, sulfuric acid, phosphoric acid or the like can be used. In order to suppress the rearrangement reaction as much as possible in the condensation reaction, it is not preferable to raise the temperature to more than 40 ° C. Further, if the temperature is lower than 10 ° C, stirring becomes difficult. When the molar ratio of aniline to formaldehyde is 3 or more, the content of binuclear MDA in the produced poly MDA mixture increases, and in order to obtain the target composition,
It is necessary to remove a large amount of binuclear MDA by distillation or crystallization.
【００１３】本発明では縮合反応液にｏ−ｐ’ＭＤＡを
添加する。ｏ−ｐ’ＭＤＡの添加は、アニリンとホルム
アルデヒドとｏ−ｐ’ＭＤＡを一括挿入して縮合反応を
行うか、またはアニリンとホルムアルデヒドの縮合反応
が終了した反応液へｏ−ｐ’ＭＤＡを添加するかのどち
らの方法でもよい。ｏ−ｐ’ＭＤＡの添加量はホルムア
ルデヒドに対して０．５〜１．５倍モルである。特に好
ましくは、１倍モルである。ｏ−ｐ’ＭＤＡの添加量が
多すぎると、未反応のｏ−ｐ’ＭＤＡが大量に残るので
好ましくない。ｏ−ｐ’ＭＤＡはポリＭＤＡ混合物か
ら、２核ＭＤＡを蒸留で抜き出すときの初留中に多く含
まれている。初留からｏ−ｐ’ＭＤＡを蒸留により単離
することが可能であり、これを反応に使用することがで
きる。また、ｏ−ｐ’ＭＤＡは完全に単離する必要はな
く、４，４’−ジアミノジフェニルメタンとの混合物で
も問題はない。In the present invention, op'MDA is added to the condensation reaction liquid. The addition of op-MDA is carried out by inserting aniline, formaldehyde and op-MDA all at once to carry out the condensation reaction, or adding op-MDA to the reaction solution after the condensation reaction of aniline and formaldehyde is completed. Either method may be used. The addition amount of op-MDA is 0.5 to 1.5 times the mole of formaldehyde. Particularly preferably, the molar ratio is 1 time. If the amount of addition of op-MDA is too large, a large amount of unreacted op-MDA remains, which is not preferable. Op-MDA is abundantly contained in the initial distillate when dinuclear MDA is extracted from the poly MDA mixture. It is possible to isolate op-MDA from the initial distillation by distillation, which can be used in the reaction. Further, it is not necessary to completely isolate op'MDA, and a mixture with 4,4'-diaminodiphenylmethane causes no problem.
【００１４】ｏ−ｐ’ＭＤＡ添加後約１時間で９０〜１
００℃まで昇温する。９０〜１００℃で熟成を１時間以
上行い、転位反応を完全に終了させる。転位反応終了
後、苛性ソ−ダで中和し油層と水層に分液する。油層を
８０〜１００℃の温水で湯洗を２回以上行う。90 to 1 in about 1 hour after the addition of op-MDA
Raise the temperature to 00 ° C. The rearrangement reaction is completed by aging at 90 to 100 ° C. for 1 hour or more. After the rearrangement reaction is completed, it is neutralized with caustic soda and separated into an oil layer and an aqueous layer. The oil layer is washed with hot water at 80 to 100 ° C twice or more.
【００１５】湯洗終了後の反応液を釜温６０〜１８０
℃，真空度３００〜１Ｔｏｒｒで未反応のアニリンを蒸
留により除去することによりメチレン架橋ポリフェニレ
ンポリアミンを得る。必要な場合は２核ＭＤＡを添加し
たり、蒸留、晶析により除去を行えば、目的組成物質を
得ることが出来る。After completion of the hot water washing, the reaction liquid is heated to a kettle temperature of 60 to 180.
Unreacted aniline is removed by distillation at a temperature of 300 to 1 Torr and a methylene bridged polyphenylene polyamine is obtained. If necessary, binuclear MDA may be added, or the dinuclear MDA may be removed by distillation or crystallization to obtain the target compositional substance.
【００１６】本発明の製造方法の具体的態様としては、
連続法、バッチ法いずれも可能であるが、工業的に実施
する場合の設備面、省力面から連続法の方が好ましい。As a concrete embodiment of the production method of the present invention,
Both a continuous method and a batch method are possible, but the continuous method is preferable from the viewpoint of equipment and labor saving in industrial implementation.
【００１７】[0017]
【実施例】以下、実施例により本発明を更に詳細に説明
する。 実施例１ 反応器に９５重量％のアニリンを４９．１ｇを仕込、３
６％塩酸を２．８８ｇ／ｍｉｎで１０分間滴下した。温
度が室温から約６０℃まで上昇したので、一度３０℃ま
で冷却して３７％ホルムアルデヒドを０．２８ｇ／ｍｉ
ｎで１時間滴下した。そして、ｏ−ｐ’ＭＤＡを１９．
８ｇ添加し、３０℃で３０分間熟成した。７０℃／ｈｒ
の昇温速度で１００℃まで昇温し、１００℃で１．５時
間転位反応を行った。転位反応終了後、３２％苛性ソ−
ダ３３．５ｇで中和し、油層と水層に分液した。温水２
８．７ｇで湯洗を２回行った。最後に、釜温６０〜１８
０℃，真空度３００〜１Ｔｏｒｒで脱アニリンを行い粗
製品ＭＤＡを５２．４ｇ得た。得られたポリＭＤＡ混合
物の分析値を表１に示す。The present invention will be described in more detail with reference to the following examples. Example 1 49.1 g of 95% by weight aniline was charged into a reactor, and 3
6% hydrochloric acid was added dropwise at 2.88 g / min for 10 minutes. Since the temperature rose from room temperature to about 60 ° C, once cooled to 30 ° C, 0.2% g / mi of 37% formaldehyde was added.
It was dripped at n for 1 hour. Then, the op-MDA is set to 19.
8 g was added and the mixture was aged at 30 ° C. for 30 minutes. 70 ° C / hr
The temperature was raised to 100 ° C. at the heating rate of 1, and the rearrangement reaction was carried out at 100 ° C. for 1.5 hours. After the rearrangement reaction, 32% caustic
It was neutralized with 33.5 g of water and separated into an oil layer and an aqueous layer. Hot water 2
Washing with hot water was performed twice with 8.7 g. Finally, the pot temperature is 60-18
Aniline was removed at 0 ° C. and a vacuum degree of 300 to 1 Torr to obtain 52.4 g of a crude product MDA. The analytical values of the obtained poly MDA mixture are shown in Table 1.
【００１８】実施例２ ｏ−ｐ’ＭＤＡの添加量を５９．４ｇにする以外は実施
例１と同じ操作を行った。得られたポリＭＤＡ混合物の
分析値を表１に示す。Example 2 The same operation as in Example 1 was carried out except that the amount of op-MDA added was 59.4 g. The analytical values of the obtained poly MDA mixture are shown in Table 1.
【００１９】実施例３ アニリンとホルムアルデヒドとｏ−ｐ’ＭＤＡを一括挿
入して縮合反応を行う以外は実施例１と同じ操作を行っ
た。得られたポリＭＤＡ混合物の分析値を表１に示す。Example 3 The same operation as in Example 1 was carried out except that aniline, formaldehyde and op'MDA were inserted all at once to carry out the condensation reaction. The analytical values of the obtained poly MDA mixture are shown in Table 1.
【００２０】比較例１ ｏ−ｐ’ＭＤＡを添加しない以外は実施例１と同じ操作
を行った。得られたポリＭＤＡ混合物の分析値を表１に
示す。Comparative Example 1 The same operation as in Example 1 was carried out except that op-MDA was not added. The analytical values of the obtained poly MDA mixture are shown in Table 1.
【００２１】[0021]
【表１】 [Table 1]
【００２２】[0022]
【発明の効果】本発明によれば、ｏ−ｐ’ＭＤＡの添加
量を変更するだけで、３核ＭＤＡの生成量を増やし、同
時に、３核体／４核体以上の比、４核体／５核体以上の
比を上げる等の核体組成の制御が可能となり、工業的に
大量に製造されるメチレン架橋ポリフェニレンポリアミ
ンの製造方法として有効な方法である。According to the present invention, the amount of trinuclear MDA produced can be increased by simply changing the amount of op-p'MDA added, and at the same time, the ratio of trinuclear to tetranuclear is 4 tetranuclear. This is an effective method as a method for producing methylene-bridged polyphenylene polyamine which is industrially produced in a large amount, since the composition of the nucleus can be controlled by increasing the ratio of / 5 nucleus or more.
フロントページの続き (72)発明者 島松 光徳 福岡県大牟田市浅牟田町30番地 三井東圧 化学株式会社内 (72)発明者 黒田 一元 福岡県大牟田市浅牟田町30番地 三井東圧 化学株式会社内 (72)発明者 宮田 勝治 福岡県大牟田市浅牟田町30番地 三井東圧 化学株式会社内Front page continuation (72) Inventor Mitsunori Shimamatsu 30 Asamu-cho, Omuta City, Fukuoka Prefecture Mitsui Toatsu Chemical Co., Ltd. (72) Inventor Katsuji Miyata 30 Asamu-cho, Omuta-shi, Fukuoka Mitsui Toatsu Chemical Co., Ltd.
Claims (1)
ルデヒドとの縮合によりメチレン架橋ポリフェニレンポ
リアミンを製造する方法において、２，４’−ジアミノ
ジフェニルメタンを添加することを特徴とするメチレン
架橋ポリフェニレンポリアミンの製造方法。1. A process for producing a methylene-bridged polyphenylene polyamine by condensation of aniline and formaldehyde in the presence of an acid catalyst, which comprises adding 2,4′-diaminodiphenylmethane. .
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP29277294A JP3154631B2 (en) | 1994-11-28 | 1994-11-28 | Method for producing methylene-crosslinked polyphenylenepolyamine |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP29277294A JP3154631B2 (en) | 1994-11-28 | 1994-11-28 | Method for producing methylene-crosslinked polyphenylenepolyamine |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH08151422A true JPH08151422A (en) | 1996-06-11 |
| JP3154631B2 JP3154631B2 (en) | 2001-04-09 |
Family
ID=17786147
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP29277294A Expired - Lifetime JP3154631B2 (en) | 1994-11-28 | 1994-11-28 | Method for producing methylene-crosslinked polyphenylenepolyamine |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3154631B2 (en) |
Cited By (26)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB2409202A (en) * | 2003-12-12 | 2005-06-22 | Clearwater Int Llc | Diamine terminated primary amine-aldehyde adducts for use in scavenging or converting noxious sulphur species, such as hydrogen sulphide and thiols |
| US7517447B2 (en) | 2004-01-09 | 2009-04-14 | Clearwater International, Llc | Sterically hindered N-methylsecondary and tertiary amine sulfur scavengers and methods for making and using same |
| US20120097893A1 (en) * | 2007-02-21 | 2012-04-26 | Clearwater International, Llc | Compositions for reducing hydrogen sulfide in water treatment systems or other systems that collect and transmit bi-phasic fluids |
| US8835364B2 (en) | 2010-04-12 | 2014-09-16 | Clearwater International, Llc | Compositions and method for breaking hydraulic fracturing fluids |
| US8846585B2 (en) | 2010-09-17 | 2014-09-30 | Clearwater International, Llc | Defoamer formulation and methods for making and using same |
| US8871694B2 (en) | 2005-12-09 | 2014-10-28 | Sarkis R. Kakadjian | Use of zeta potential modifiers to decrease the residual oil saturation |
| US8899328B2 (en) | 2010-05-20 | 2014-12-02 | Clearwater International Llc | Resin sealant for zonal isolation and methods for making and using same |
| US8946130B2 (en) | 2005-12-09 | 2015-02-03 | Clearwater International Llc | Methods for increase gas production and load recovery |
| US8950493B2 (en) | 2005-12-09 | 2015-02-10 | Weatherford Technology Holding LLC | Method and system using zeta potential altering compositions as aggregating reagents for sand control |
| US9012378B2 (en) | 2007-05-11 | 2015-04-21 | Barry Ekstrand | Apparatus, compositions, and methods of breaking fracturing fluids |
| US9062241B2 (en) | 2010-09-28 | 2015-06-23 | Clearwater International Llc | Weight materials for use in cement, spacer and drilling fluids |
| US9085724B2 (en) | 2010-09-17 | 2015-07-21 | Lubri3ol Oilfield Chemistry LLC | Environmentally friendly base fluids and methods for making and using same |
| US9090809B2 (en) | 2010-09-17 | 2015-07-28 | Lubrizol Oilfield Chemistry LLC | Methods for using complementary surfactant compositions |
| US9234125B2 (en) | 2005-02-25 | 2016-01-12 | Weatherford/Lamb, Inc. | Corrosion inhibitor systems for low, moderate and high temperature fluids and methods for making and using same |
| US9328285B2 (en) | 2009-04-02 | 2016-05-03 | Weatherford Technology Holdings, Llc | Methods using low concentrations of gas bubbles to hinder proppant settling |
| US9334713B2 (en) | 2005-12-09 | 2016-05-10 | Ronald van Petegem | Produced sand gravel pack process |
| US9447657B2 (en) | 2010-03-30 | 2016-09-20 | The Lubrizol Corporation | System and method for scale inhibition |
| US9605195B2 (en) | 2007-06-19 | 2017-03-28 | Lubrizol Oilfield Solutions, Inc. | Oil based concentrated slurries and methods for making and using same |
| US9909404B2 (en) | 2008-10-08 | 2018-03-06 | The Lubrizol Corporation | Method to consolidate solid materials during subterranean treatment operations |
| US9945220B2 (en) | 2008-10-08 | 2018-04-17 | The Lubrizol Corporation | Methods and system for creating high conductivity fractures |
| US10001769B2 (en) | 2014-11-18 | 2018-06-19 | Weatherford Technology Holdings, Llc | Systems and methods for optimizing formation fracturing operations |
| US10202828B2 (en) | 2014-04-21 | 2019-02-12 | Weatherford Technology Holdings, Llc | Self-degradable hydraulic diversion systems and methods for making and using same |
| US10202836B2 (en) | 2011-09-28 | 2019-02-12 | The Lubrizol Corporation | Methods for fracturing formations using aggregating compositions |
| US10309172B2 (en) | 2013-04-19 | 2019-06-04 | Weatherford Technology Holdings, Llc | Hydraulic diversion systems to enhance matrix treatments and methods for using same |
| US10604693B2 (en) | 2012-09-25 | 2020-03-31 | Weatherford Technology Holdings, Llc | High water and brine swell elastomeric compositions and method for making and using same |
| US10669468B2 (en) | 2013-10-08 | 2020-06-02 | Weatherford Technology Holdings, Llc | Reusable high performance water based drilling fluids |
-
1994
- 1994-11-28 JP JP29277294A patent/JP3154631B2/en not_active Expired - Lifetime
Cited By (36)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB2409202A (en) * | 2003-12-12 | 2005-06-22 | Clearwater Int Llc | Diamine terminated primary amine-aldehyde adducts for use in scavenging or converting noxious sulphur species, such as hydrogen sulphide and thiols |
| US7140433B2 (en) | 2003-12-12 | 2006-11-28 | Clearwater International, Llc | Diamine terminated primary amine-aldehyde sulfur converting compositions and methods for making and using same |
| GB2409202B (en) * | 2003-12-12 | 2009-03-04 | Clearwater Int Llc | Diamine terminated primary amine-aldehyde adducts for use in scavenging or converting noxious sulphur species, such as hydrogen sulphide and thiols |
| US8012913B2 (en) | 2003-12-12 | 2011-09-06 | Clearwater International Llc | Diamine terminated primary amine-aldehyde sulfur converting compositions and methods for making and using same |
| US7517447B2 (en) | 2004-01-09 | 2009-04-14 | Clearwater International, Llc | Sterically hindered N-methylsecondary and tertiary amine sulfur scavengers and methods for making and using same |
| US8530394B2 (en) | 2004-01-09 | 2013-09-10 | Clearwater International Llc | Sterically hindered N-methyl secondary and tertiary amine sulfur scavengers and methods for making and using same |
| US9234125B2 (en) | 2005-02-25 | 2016-01-12 | Weatherford/Lamb, Inc. | Corrosion inhibitor systems for low, moderate and high temperature fluids and methods for making and using same |
| US8871694B2 (en) | 2005-12-09 | 2014-10-28 | Sarkis R. Kakadjian | Use of zeta potential modifiers to decrease the residual oil saturation |
| US9725634B2 (en) | 2005-12-09 | 2017-08-08 | Weatherford Technology Holdings, Llc | Weakly consolidated, semi consolidated formation, or unconsolidated formations treated with zeta potential altering compositions to form conglomerated formations |
| US9334713B2 (en) | 2005-12-09 | 2016-05-10 | Ronald van Petegem | Produced sand gravel pack process |
| US8946130B2 (en) | 2005-12-09 | 2015-02-03 | Clearwater International Llc | Methods for increase gas production and load recovery |
| US8950493B2 (en) | 2005-12-09 | 2015-02-10 | Weatherford Technology Holding LLC | Method and system using zeta potential altering compositions as aggregating reagents for sand control |
| US20120097893A1 (en) * | 2007-02-21 | 2012-04-26 | Clearwater International, Llc | Compositions for reducing hydrogen sulfide in water treatment systems or other systems that collect and transmit bi-phasic fluids |
| US9012378B2 (en) | 2007-05-11 | 2015-04-21 | Barry Ekstrand | Apparatus, compositions, and methods of breaking fracturing fluids |
| US9605195B2 (en) | 2007-06-19 | 2017-03-28 | Lubrizol Oilfield Solutions, Inc. | Oil based concentrated slurries and methods for making and using same |
| US10040991B2 (en) | 2008-03-11 | 2018-08-07 | The Lubrizol Corporation | Zeta potential modifiers to decrease the residual oil saturation |
| US9945220B2 (en) | 2008-10-08 | 2018-04-17 | The Lubrizol Corporation | Methods and system for creating high conductivity fractures |
| US9909404B2 (en) | 2008-10-08 | 2018-03-06 | The Lubrizol Corporation | Method to consolidate solid materials during subterranean treatment operations |
| US9328285B2 (en) | 2009-04-02 | 2016-05-03 | Weatherford Technology Holdings, Llc | Methods using low concentrations of gas bubbles to hinder proppant settling |
| US9447657B2 (en) | 2010-03-30 | 2016-09-20 | The Lubrizol Corporation | System and method for scale inhibition |
| US9175208B2 (en) | 2010-04-12 | 2015-11-03 | Clearwater International, Llc | Compositions and methods for breaking hydraulic fracturing fluids |
| US8835364B2 (en) | 2010-04-12 | 2014-09-16 | Clearwater International, Llc | Compositions and method for breaking hydraulic fracturing fluids |
| US10301526B2 (en) | 2010-05-20 | 2019-05-28 | Weatherford Technology Holdings, Llc | Resin sealant for zonal isolation and methods for making and using same |
| US8899328B2 (en) | 2010-05-20 | 2014-12-02 | Clearwater International Llc | Resin sealant for zonal isolation and methods for making and using same |
| US9085724B2 (en) | 2010-09-17 | 2015-07-21 | Lubri3ol Oilfield Chemistry LLC | Environmentally friendly base fluids and methods for making and using same |
| US9255220B2 (en) | 2010-09-17 | 2016-02-09 | Clearwater International, Llc | Defoamer formulation and methods for making and using same |
| US9090809B2 (en) | 2010-09-17 | 2015-07-28 | Lubrizol Oilfield Chemistry LLC | Methods for using complementary surfactant compositions |
| US8846585B2 (en) | 2010-09-17 | 2014-09-30 | Clearwater International, Llc | Defoamer formulation and methods for making and using same |
| US9062241B2 (en) | 2010-09-28 | 2015-06-23 | Clearwater International Llc | Weight materials for use in cement, spacer and drilling fluids |
| US10202836B2 (en) | 2011-09-28 | 2019-02-12 | The Lubrizol Corporation | Methods for fracturing formations using aggregating compositions |
| US10604693B2 (en) | 2012-09-25 | 2020-03-31 | Weatherford Technology Holdings, Llc | High water and brine swell elastomeric compositions and method for making and using same |
| US10309172B2 (en) | 2013-04-19 | 2019-06-04 | Weatherford Technology Holdings, Llc | Hydraulic diversion systems to enhance matrix treatments and methods for using same |
| US10669468B2 (en) | 2013-10-08 | 2020-06-02 | Weatherford Technology Holdings, Llc | Reusable high performance water based drilling fluids |
| US11015106B2 (en) | 2013-10-08 | 2021-05-25 | Weatherford Technology Holdings, Llc | Reusable high performance water based drilling fluids |
| US10202828B2 (en) | 2014-04-21 | 2019-02-12 | Weatherford Technology Holdings, Llc | Self-degradable hydraulic diversion systems and methods for making and using same |
| US10001769B2 (en) | 2014-11-18 | 2018-06-19 | Weatherford Technology Holdings, Llc | Systems and methods for optimizing formation fracturing operations |
Also Published As
| Publication number | Publication date |
|---|---|
| JP3154631B2 (en) | 2001-04-09 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JPH08151422A (en) | Production of methylene-bridged polyphenylenepolyamine | |
| CN1765875B (en) | Process for preparing di-and polyamines of the diphenylmethane series | |
| JPS6351171B2 (en) | ||
| RU2059607C1 (en) | Substituted n,n′-methylene-bis-anilines as chain lengthener or polyurethane cross-linking agent | |
| JP4114718B2 (en) | Preparation of MDI, especially 2,4'-MDI | |
| JPH0557977B2 (en) | ||
| KR960005794B1 (en) | Process for producing polyurethane foam | |
| KR100215951B1 (en) | Hydroxy-functional triamine catalyst compositions for polyurethane production | |
| JPH0641025A (en) | Production of polyamine mixture of polyamino-polyaryl- polymethylene series | |
| JPH0238583B2 (en) | ||
| US3860637A (en) | Selective manufacture of 4,4{40 -isomer of diaminodiphenyl-methane | |
| CN1840521B (en) | Process for preparing di-and polyamines of the diphenylmethane series | |
| US4597909A (en) | Process for the production of polyisocyanates | |
| US4870206A (en) | Aromatic polyisocyanates, their preparation and use as components for adhesives | |
| US8822726B2 (en) | Method for producing diaminodiphenyl alkanes | |
| EP0216273B1 (en) | Method of manufacturing diphenylmethane dicarbamic acid esters | |
| JP5936352B2 (en) | Method for producing diaminodiphenylalkane | |
| JPH07285925A (en) | Method for producing methylene-cross-linked triphenylene triisocyanate | |
| JP3091080B2 (en) | Method for producing methylene-crosslinked polyphenylene polyisocyanate | |
| JP2912494B2 (en) | Method for purifying methylene-crosslinked polyphenylene polyisocyanate | |
| EP0520377B1 (en) | A process for the selective preparation of 4,4-methylene-bis-(N-phenylalkylcarbamate) | |
| US4191836A (en) | Anthranilates of polyoxyethylated carboxylic acid | |
| JPS60243065A (en) | Novel azetidinedione compound | |
| WO1996002495A1 (en) | Di-amino compounds and their use in polyurethane compositions, in polyamide, polyimide, polyurea and epoxy resin | |
| JPS6053048B2 (en) | Manufacturing method of rigid polyurethane foam |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20090202 Year of fee payment: 8 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20100202 Year of fee payment: 9 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20110202 Year of fee payment: 10 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20120202 Year of fee payment: 11 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20120202 Year of fee payment: 11 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20130202 Year of fee payment: 12 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20130202 Year of fee payment: 12 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20140202 Year of fee payment: 13 |
|
| EXPY | Cancellation because of completion of term |