JPH03275728A - Production of powdery blocked polyisocyanate - Google Patents
Production of powdery blocked polyisocyanateInfo
- Publication number
- JPH03275728A JPH03275728A JP7473690A JP7473690A JPH03275728A JP H03275728 A JPH03275728 A JP H03275728A JP 7473690 A JP7473690 A JP 7473690A JP 7473690 A JP7473690 A JP 7473690A JP H03275728 A JPH03275728 A JP H03275728A
- Authority
- JP
- Japan
- Prior art keywords
- solvent
- blocked polyisocyanate
- separation
- reaction
- blocked
- 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
- 239000005056 polyisocyanate Substances 0.000 title claims abstract description 38
- 229920001228 polyisocyanate Polymers 0.000 title claims abstract description 38
- 238000004519 manufacturing process Methods 0.000 title claims description 3
- 239000002904 solvent Substances 0.000 claims abstract description 37
- 238000000926 separation method Methods 0.000 claims abstract description 25
- 239000000654 additive Substances 0.000 claims abstract description 13
- 230000000996 additive effect Effects 0.000 claims abstract description 12
- 239000002736 nonionic surfactant Substances 0.000 claims abstract description 5
- 239000007810 chemical reaction solvent Substances 0.000 claims description 9
- 239000000843 powder Substances 0.000 claims description 4
- 238000006243 chemical reaction Methods 0.000 abstract description 8
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 abstract description 6
- 229920000642 polymer Polymers 0.000 abstract description 2
- 229920002503 polyoxyethylene-polyoxypropylene Polymers 0.000 abstract description 2
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 9
- 238000000034 method Methods 0.000 description 8
- -1 diisocyanate compound Chemical class 0.000 description 7
- 239000006185 dispersion Substances 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- 238000009835 boiling Methods 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 230000003247 decreasing effect Effects 0.000 description 2
- 238000010828 elution Methods 0.000 description 2
- 239000000839 emulsion Substances 0.000 description 2
- 239000012948 isocyanate Substances 0.000 description 2
- 150000002513 isocyanates Chemical class 0.000 description 2
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 2
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 239000004094 surface-active agent Substances 0.000 description 2
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 description 2
- VBICKXHEKHSIBG-UHFFFAOYSA-N 1-monostearoylglycerol Chemical compound CCCCCCCCCCCCCCCCCC(=O)OCC(O)CO VBICKXHEKHSIBG-UHFFFAOYSA-N 0.000 description 1
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 239000005057 Hexamethylene diisocyanate Substances 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 239000003945 anionic surfactant Substances 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000003093 cationic surfactant Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 1
- TZMQHOJDDMFGQX-UHFFFAOYSA-N hexane-1,1,1-triol Chemical compound CCCCCC(O)(O)O TZMQHOJDDMFGQX-UHFFFAOYSA-N 0.000 description 1
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 229920000126 latex Polymers 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- WHIVNJATOVLWBW-UHFFFAOYSA-N n-butan-2-ylidenehydroxylamine Chemical compound CCC(C)=NO WHIVNJATOVLWBW-UHFFFAOYSA-N 0.000 description 1
- 229920005862 polyol Polymers 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
Abstract
Description
【発明の詳細な説明】
〈産業上の利用分野〉
本発明は有機溶剤を含まない粉末ブロック化ポリイソシ
アネートの製造方法に関するものであり、本発明によっ
て得られるブロック化ポリイソシアネートは水分政体と
することによって繊維の接着剤、ゴムラテックスまたは
エマルジョンの架橋剤などに使用される。[Detailed Description of the Invention] <Industrial Application Field> The present invention relates to a method for producing a powder-blocked polyisocyanate that does not contain an organic solvent, and the blocked polyisocyanate obtained by the present invention is in a water regime. Used as fiber adhesive, rubber latex or emulsion crosslinking agent, etc.
〈従来の技術〉
官能性ポリイソシアネート化合物の一種であるブロック
化ポリイソシアネート類は水やアルコールなどに対して
安定であり、一般には有機溶剤を含まない水分散体とし
て広く利用されている。<Prior Art> Blocked polyisocyanates, which are a type of functional polyisocyanate compounds, are stable in water, alcohol, etc., and are generally widely used as water dispersions that do not contain organic solvents.
ブロック化ポリイソシアネートは通常トリレンジイソシ
アネート、ジフェニルメタンジイソシアネート、ヘキサ
メチレンジイソシアネート等のジイソシアネート化合物
とトリメチロールプロパン、ヘキサントリオール等のポ
リオール化合物の反応によってまず付加生成物を作り、
次いでフェノール化合物、アルコール化合物、ラクタム
化合物、オキシム化合物等を用いて付加生成物が持って
いるイソシアネート基をブロック化することによって得
られる。Blocked polyisocyanates are usually produced by first forming an addition product by reacting a diisocyanate compound such as tolylene diisocyanate, diphenylmethane diisocyanate, or hexamethylene diisocyanate with a polyol compound such as trimethylolpropane or hexanetriol.
Next, it is obtained by blocking the isocyanate group of the addition product using a phenol compound, alcohol compound, lactam compound, oxime compound, or the like.
これら一連の反応には通常エステル、ケトン、エーテル
、芳香族炭化水素などの有機溶剤が使用されている。Organic solvents such as esters, ketones, ethers, and aromatic hydrocarbons are usually used in these series of reactions.
ブロック化ポリイソシアネートを水分散体として使用す
る場合、この溶剤は屹燥時に火災の原因となるばかりで
なく、エマルジョンの不安定化や環境悪化の原因ともな
るので除去することが必要である。When a blocked polyisocyanate is used as an aqueous dispersion, this solvent must be removed because it not only causes a fire during drying, but also destabilizes the emulsion and degrades the environment.
通常、反応終了後、反応時に用いた溶剤を減圧下に加熱
溜去してブロック化ポリイソシアネートを取り出すが、
この工程の後半には溶液の粘度は極めて高くなり、攪拌
が困難となるばかりでなく、製品が団子状となって溶剤
の除去効率は大幅に低下し、容器への付着も問題であっ
た。また溶剤を含んだブロック化ポリイソシアネートを
界面活性剤によって水中に分散し、水分散体を減圧下に
加熱するか、または水蒸気を吹き込んで溶剤を油出させ
る方法も実施されているが、溶剤を完全に除去するには
長時間の加熱が必要であり、加熱によるブロック化ポリ
イソシアネートの分解が問題であった。Usually, after the reaction is completed, the solvent used during the reaction is distilled off under reduced pressure to remove the blocked polyisocyanate.
In the latter half of this process, the viscosity of the solution not only became extremely high, making stirring difficult, but also caused the product to form lumps, significantly reducing the solvent removal efficiency and causing problems with adhesion to containers. Another method has been used in which a blocked polyisocyanate containing a solvent is dispersed in water using a surfactant and the aqueous dispersion is heated under reduced pressure or steam is blown into the water to release the solvent. Complete removal requires long-term heating, and decomposition of the blocked polyisocyanate due to heating has been a problem.
〈発明が解決しようとする問題点〉
従来技術の課題であったブロック化ポリイソシアネート
から反応時の溶剤を除去する方法に関して鋭意検討の結
果、本発明者らは製品の品質を損なうことなく、効率的
に溶剤を除去する粉末プロ道
ツク化ポリイソシアネートの製層方法を見い出した。<Problems to be Solved by the Invention> As a result of intensive studies on the method of removing the solvent during reaction from blocked polyisocyanate, which had been a problem in the prior art, the present inventors have devised an efficient method without impairing product quality. We have discovered a method for forming layers of powdered processed polyisocyanate that allows the solvent to be removed in a timely manner.
すなわち、反応用溶剤を含むブロック化ポリイソシアネ
ートに分離用溶剤と分離用添加剤としてノニオン系界面
活性剤を加えることにより、これら溶剤の除去工程にお
いてブロック化ポリイソシアネートが団子状となるのが
防止され、短時間にて粉末状の製品が得られることを見
い出して本発明に至った。なお本発明の方法によって得
られたブロック化ポリイソシアネートを水分散体として
用いる場合には通常の方法によって水中での粉砕分散化
が可能である。That is, by adding a separation solvent and a nonionic surfactant as a separation additive to the blocked polyisocyanate containing the reaction solvent, the blocked polyisocyanate is prevented from forming into lumps in the process of removing these solvents. They discovered that a powdered product can be obtained in a short time, leading to the present invention. When the blocked polyisocyanate obtained by the method of the present invention is used as an aqueous dispersion, it can be pulverized and dispersed in water by a conventional method.
く問題点を解決するための手段〉
本発明はブロック化ポリイソシアネートの合成に使用し
た溶剤を除去するにあたり、この溶液中に他の異なる分
離用溶剤および分離を促進する添加剤を加えることによ
りブロック化ポリイソシアネートから極めて溜去し難い
反応用溶剤を容易に取り去ることが可能となった。Means for Solving the Problems> The present invention provides a block polyisocyanate solution by adding a different separation solvent and an additive that promotes separation to this solution when removing the solvent used in the synthesis of blocked polyisocyanate. It became possible to easily remove the reaction solvent, which is extremely difficult to distill off, from the polyisocyanate.
本発明において使用する分離用溶剤は反応用溶剤と相溶
性があること、反応用溶剤の沸点より高い沸点を有する
こと、ブロック化ポリイソシアネートを溶解しないこと
などの条件が必要である。The separation solvent used in the present invention must be compatible with the reaction solvent, have a boiling point higher than the boiling point of the reaction solvent, and not dissolve the blocked polyisocyanate.
分離用溶剤の具体例としてはｎ−ヘキサン、ｎ−へブタ
ン、ｎ−オクタンなどが挙げられるが、とりわけｎ−へ
ブタンが好ましい。Specific examples of the separation solvent include n-hexane, n-hebutane, n-octane, etc., with n-hebutane being particularly preferred.
分離用添加剤は反応用溶剤に溶けること、分離用溶剤に
不溶であること、ブロック化ポリイソシアネートおよび
その使用時の熱分解によって生成する遊離イソシアネー
トに対して不活性であること、ブロック化ポリイソシア
ネートを水分散体とした場合にその分散性および安定性
に支障とならないことなどが必要である。The separating additive must be soluble in the reaction solvent, insoluble in the separating solvent, inert to blocked polyisocyanates and free isocyanates formed by thermal decomposition during their use, and blocked polyisocyanates. When made into an aqueous dispersion, it is necessary that the dispersibility and stability of the dispersion are not affected.
またこれらの条件を満たす分離用添加剤としては一般的
な界面活性剤の内、アニオンおよびカチオン系界面活性
剤は不適当であり、ノニオン系界面活性剤の中から１種
または２種を選ぶことができる。中でもポリオキシエチ
レン−ポリオキシプロピレンブロックポリマーまたはグ
リセリンモノステアレートなどが有効である。Also, among common surfactants, anionic and cationic surfactants are not suitable as separation additives that meet these conditions, so one or two types of nonionic surfactants should be selected. I can do it. Among them, polyoxyethylene-polyoxypropylene block polymers or glycerin monostearate are effective.
反応用溶剤に溶解しているブロック化ポリイソシアネー
トに常温にて分離用溶剤と分離用添加剤を加えて攪拌す
ると、一部の溶質が析出する。次イソシアネートは分離
用溶剤中に分散した粉体へとその形態が変化する。さら
に内容物を製品の品質を損わない温度に加熱し、分離用
溶剤を溜去すれば、いずれの溶剤をも含まない粉体状の
ブロック化ポリイソシアネートが得られる。When the separation solvent and the separation additive are added to the blocked polyisocyanate dissolved in the reaction solvent at room temperature and stirred, a part of the solute is precipitated. The isocyanate then changes its form into a powder dispersed in the separation solvent. Furthermore, by heating the contents to a temperature that does not impair product quality and distilling off the separation solvent, a powdered blocked polyisocyanate containing no solvent can be obtained.
本発明の方法は分離用溶剤と分離用添加剤の併用によっ
て始めて可能となるものであり、分離用添加剤を使用し
ない場合には粉体状の製品が得られず、装置内壁への内
容物の付着などの問題が認められた。The method of the present invention can only be made possible by using a separation solvent and a separation additive in combination; if the separation additive is not used, a powdered product cannot be obtained, and the contents may not reach the inner wall of the device. Problems such as adhesion were observed.
以下に実施例と比較例を挙げて本発明を具体的に説明す
るが、本発明はこれらの実施例によって何ら限定される
ものではない。EXAMPLES The present invention will be specifically described below with reference to Examples and Comparative Examples, but the present invention is not limited to these Examples in any way.
実施例１
攪拌機および温度調節装置の付いたステンレス製小型反
応機に５２２ｙ（１モル〉のトリレンジイソシアネート
と１８４５’ （１モル）のトリメチロールプロパンを
仕込み、８８（ｌの酢酸エチル（沸点７７．１９Ｃ）中
にて少量の有機錫化合物を触媒として用いて反応させて
付加生成物を得た。さらにこのものに２８７９ＣＢ、８
モル）のメチルエチルケトオキシムを加えて反応を行い
、ブロック化ポリイソシアネートを合成した。Example 1 A small stainless steel reactor equipped with a stirrer and a temperature control device was charged with 522y (1 mol) of tolylene diisocyanate and 1845' (1 mol) of trimethylolpropane, and 88 (l) of ethyl acetate (boiling point 77. 19C) using a small amount of an organotin compound as a catalyst to obtain an addition product.
mol) of methyl ethyl ketoxime was added to react, and a blocked polyisocyanate was synthesized.
得られた反応終了品の固形分濃度は５２％であった。次
いで容器内を減圧することにより酢酸エチルを油出させ
て固形分濃度を６５％にまで濃縮した。The solid content concentration of the obtained reaction-completed product was 52%. Next, the pressure inside the container was reduced to cause ethyl acetate to come out as an oil, and the solid content was concentrated to 65%.
この中に分離用添加剤として１５ノのレオドールＭＳ−
５Ｑ１）を加えて３０分攪拌した後、７６０りのｎ−ヘ
プタン（Ｓ点９８．４℃）を２０分かけて添加した。添
加終了時の内容物はブロック化ポリイソシアネートの析
出によってシャーベット状を呈した。この後、系内を約
２５℃に保ちつつ２００〜２５０ｍＨ５’まで減圧し、
酢酸エチルを系外へ油出させた。やがて油出量が低下し
たところで容器を６５℃まで加温し、ｎ−へブタンの溶
去を行った。In this, 15 pieces of Rheodol MS- were added as a separation additive.
After adding 5Q1) and stirring for 30 minutes, 760 grams of n-heptane (S point 98.4°C) was added over 20 minutes. At the end of the addition, the contents had a sherbet-like appearance due to precipitation of blocked polyisocyanate. After that, while keeping the inside of the system at about 25°C, reduce the pressure to 200 to 250mH5',
Ethyl acetate was allowed to drain out of the system. When the amount of oil coming out eventually decreased, the container was heated to 65° C., and n-hebutane was eluted.
得られたブロック化ポリイソシアネートは粉末状であり
、溶剤の含有量は０．８％であった。またこの操作中で
溶剤溶去に要した時間は８０分であった。The obtained blocked polyisocyanate was in powder form, and the solvent content was 0.8%. Further, during this operation, the time required to dissolve the solvent was 80 minutes.
実施例２〜４
実施例１と同一量の原料を使用し、同様の操作にてブロ
ック化ポリイソシアネートを合成した。Examples 2 to 4 Blocked polyisocyanates were synthesized using the same amounts of raw materials as in Example 1 and in the same manner.
表−１に掲げた分離用溶剤および分離用添加剤を用いて
実施例１と同様の脱溶剤操作を実施した。Solvent removal operation similar to Example 1 was carried out using the separation solvent and separation additive listed in Table-1.
結果を実施例２〜４として表−１に示した。The results are shown in Table 1 as Examples 2 to 4.
但し実施例４は反応用溶剤にメチルエチルケトンを用い
ている。However, in Example 4, methyl ethyl ketone was used as the reaction solvent.
以１’ ／ＳＳ自
比較例１
実施例１と同様の方法にてブロック化ポリイソシアネー
トを合成し、分離用溶剤および分離用添加剤を使用せず
に反応用溶剤の溶去を行った。1'/SS Self-Comparative Example 1 A blocked polyisocyanate was synthesized in the same manner as in Example 1, and the reaction solvent was eluted without using a separation solvent or separation additive.
溶剤溶去時間を３時間以上まで延長しても製品は樹脂状
の塊となり、攪拌が不能となるばかりでなく、溶剤含有
率も１０％以下には到達しなかった。Even if the solvent elution time was extended to 3 hours or more, the product not only became a resinous lump that could not be stirred, but also the solvent content did not reach 10% or less.
比較例２
実施例１と同様の方法にてブロック化ポリイソシアネー
トを合成し、分離用溶剤として７６０ノのｎ−へブタン
を使用したが、分離用添加剤は使用せずに溶剤の溶去を
行った。溶剤溶去時間３時間にて製品中の溶剤含有率は
８．５％まで低下したが、製品は樹脂状の塊を含み、完
全な粉体とはならなかった。Comparative Example 2 A blocked polyisocyanate was synthesized in the same manner as in Example 1, and 760 g of n-hebutane was used as a separation solvent, but no separation additive was used and the solvent was eluted. went. Although the solvent content in the product decreased to 8.5% after 3 hours of solvent elution time, the product contained resinous lumps and was not a complete powder.
またこの場合、反応容器と攪拌機への製品の付着が極め
て多いことを認めた。In this case, it was also observed that there was an extremely large amount of product adhering to the reaction vessel and the stirrer.
Claims (1)
ネートに分離用溶剤と分離用添加剤としてノニオン系界
面活性剤を加えた後、溶剤を溜去してブロック化ポリイ
ソシアネートを粉体状にて取り出すことを特徴とする粉
末ブロック化ポリイソシアネートの製造方法。1. After adding a separation solvent and a nonionic surfactant as a separation additive to the blocked polyisocyanate dissolved in the reaction solvent, the solvent is distilled off and the blocked polyisocyanate is made into a powder. A method for producing a powder-blocked polyisocyanate, which comprises taking out a powder-blocked polyisocyanate.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP7473690A JPH03275728A (en) | 1990-03-23 | 1990-03-23 | Production of powdery blocked polyisocyanate |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP7473690A JPH03275728A (en) | 1990-03-23 | 1990-03-23 | Production of powdery blocked polyisocyanate |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH03275728A true JPH03275728A (en) | 1991-12-06 |
Family
ID=13555821
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP7473690A Pending JPH03275728A (en) | 1990-03-23 | 1990-03-23 | Production of powdery blocked polyisocyanate |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH03275728A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB2457995A (en) * | 2007-11-08 | 2009-09-09 | Halliburton Energy Serv Inc | Methods of preparing degradable materials and methods of use in subterranean formations |
-
1990
- 1990-03-23 JP JP7473690A patent/JPH03275728A/en active Pending
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB2457995A (en) * | 2007-11-08 | 2009-09-09 | Halliburton Energy Serv Inc | Methods of preparing degradable materials and methods of use in subterranean formations |
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