JP3299803B2 - Method for producing polyether polyol - Google Patents
Method for producing polyether polyolInfo
- Publication number
- JP3299803B2 JP3299803B2 JP06285193A JP6285193A JP3299803B2 JP 3299803 B2 JP3299803 B2 JP 3299803B2 JP 06285193 A JP06285193 A JP 06285193A JP 6285193 A JP6285193 A JP 6285193A JP 3299803 B2 JP3299803 B2 JP 3299803B2
- Authority
- JP
- Japan
- Prior art keywords
- polyether polyol
- oxide
- propylene oxide
- ring
- viscosity
- 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 - Fee Related
Links
Landscapes
- Polyethers (AREA)
Description
【０００１】[0001]
【産業上の利用分野】本発明は、複合金属シアン化物錯
体触媒を用い、開始剤にアルキレンオキシドを重合させ
てポリエーテルポリオールを製造する方法に関する。The present invention relates to a method for producing a polyether polyol by polymerizing an alkylene oxide as an initiator using a double metal cyanide complex catalyst.
【０００２】[0002]
【従来の技術】従来のポリエーテルポリオールは、粘度
が高く、経時的に粘度が変化するところから、用途が限
定される欠点があった。2. Description of the Related Art Conventional polyether polyols have a drawback that their use is limited because their viscosity is high and their viscosity changes with time.
【０００３】[0003]
【発明が解決しようとする課題】本発明は、上記の欠点
を解消し、低粘度で粘度の経時変化の少ないポリエーテ
ルポリオールを製造する方法を提供する。SUMMARY OF THE INVENTION The present invention solves the above-mentioned drawbacks and provides a method for producing a polyether polyol having a low viscosity and a small change in viscosity with time.
【０００４】[0004]
【課題を解決するための手段】本発明は下記発明であ
る。 複合金属シアン化物錯体触媒を用い、開始剤にアル
キレンオキシドを重合させてポリエーテルポリオールを
製造する方法において、アルキレンオキシドとして、下
記（１）又は（２）を用いて重合させた後、さらに、下
記（３）又は（４）を用いて重合させることを特徴とす
るポリエーテルポリオールの製造方法。 （１）プロピレンオキシド及び炭素数４以上のアルキレ
ンオキシドの混合物。 （２）エチレンオキシド、プロピレンオキシド及び炭素
数４以上のアルキレンオキシドの混合物。 （３）プロピレンオキシド。 （４）エチレンオキシド及びプロピレンオキシドの混合
物。SUMMARY OF THE INVENTION The present invention is the following invention . Using double coupling metal cyanide complex catalyst, a method of an alkylene oxide is polymerized in the initiator to produce a polyether polyol, as alkylene oxides, after being polymerized using the following (1) or (2), further, A method for producing a polyether polyol, which comprises polymerizing using the following (3) or (4). (1) A mixture of propylene oxide and an alkylene oxide having 4 or more carbon atoms. (2) A mixture of ethylene oxide, propylene oxide and an alkylene oxide having 4 or more carbon atoms. (3) Propylene oxide. (4) A mixture of ethylene oxide and propylene oxide.
【０００５】[0005]
【作用】本発明は、プロピレンオキシド及び炭素数４以
上のアルキレンオキシドをポリエーテルポリオールの主
鎖中に導入することにより、ポリエーテルポリオールの
結晶性を低め、粘度値の低減と、結晶化度の変化にとも
なう粘度経時変化を低減させたポリエーテルポリオール
の製造に成功したことに基づく。より低粘度で粘度の経
時変化のより少ないポリエーテルポリオールを製造する
ためには、得られたポリエーテルポリオールにおける炭
素数４以上のアルキレンオキシドの開環した単位の含量
が０．１〜５０重量％となるように原料を配合すること
が特に好ましい。The present invention reduces the crystallinity of a polyether polyol by introducing propylene oxide and an alkylene oxide having 4 or more carbon atoms into the main chain of the polyether polyol, thereby reducing the viscosity value and the crystallinity. It is based on the success of producing a polyether polyol in which the change with time in viscosity due to the change is reduced. In order to produce a polyether polyol having a lower viscosity and less change in viscosity with time, the content of the ring-opened unit of the alkylene oxide having 4 or more carbon atoms in the obtained polyether polyol is 0.1 to 50% by weight. It is particularly preferable to mix the raw materials such that
【０００６】本発明で用いる炭素数４以上のモノエポキ
シドとしては、１，２−ブチレンオキシド、２，３−ブ
チレンオキシド、１，２−ヘキシレンオキシド等のアル
キレンオキシドが好ましい。上記ポリエーテルポリオー
ルの分子量は、特に限定されないが、水酸基価で約８０
以下のものが望ましい。The monoepoxide having 4 or more carbon atoms used in the present invention is preferably an alkylene oxide such as 1,2-butylene oxide, 2,3-butylene oxide, and 1,2-hexylene oxide. Although the molecular weight of the polyether polyol is not particularly limited, it is about 80 in hydroxyl value.
The following are desirable:
【０００７】開始剤に、アルキレンオキシド等のモノエ
ポキシドを開環重合させて得られるポリエーテル類は、
ポリウレタンなどの合成樹脂の原料、界面活性剤、機能
油、潤滑油の原料、その他の用途に広く用いられてい
る。Polyethers obtained by ring-opening polymerization of a monoepoxide such as an alkylene oxide as an initiator include:
It is widely used as a raw material for synthetic resins such as polyurethane, a surfactant, a functional oil, a raw material for lubricating oil, and other uses.
【０００８】開始剤は、Ａ−（Ｈ）ｎ（Ａ：水酸基含有
化合物の水酸基の水素原子を除いた残基、ｎ：１以上の
整数）で表される水酸基含有化合物である。開始剤とし
ては、例えば１価アルコール、多価アルコール、１価フ
ェノール、多価フェノールなどがある。また、ヒドロキ
シアルキルアミノ基を有する化合物、アルカノールアミ
ン類やアミン類−アルキレンオキシド付加物なども開始
剤として用いられる。さらに、上記開始剤には、モノエ
ポキシドを反応させて得られる、目的物であるポリエー
テルポリオールより低分子量のポリエーテルポリオール
もまた使用される。The initiator is a hydroxyl group-containing compound represented by A- (H) n (A: residue excluding the hydrogen atom of the hydroxyl group of the hydroxyl group-containing compound, n: an integer of 1 or more). Examples of the initiator include a monohydric alcohol, a polyhydric alcohol, a monohydric phenol, and a polyhydric phenol. In addition, compounds having a hydroxyalkylamino group, alkanolamines and amines-alkylene oxide adducts are also used as initiators. Further, as the initiator, a polyether polyol obtained by reacting a monoepoxide and having a lower molecular weight than the target polyether polyol is also used.
【０００９】本発明におけるポリエーテルポリオール
は、上記開始剤にモノエポキシドを多数開環付加反応さ
せて得られる下記のような化合物である。 Ａ−［（Ｒ−Ｏ）ｍ−Ｈ］ｎ （Ｒ−Ｏ）：モノエポキシドの開環した単位 ｎ，ｍ：１以上の整数The polyether polyol in the present invention is the following compound obtained by subjecting the above-mentioned initiator to multiple ring-opening addition reaction of a monoepoxide. A-[(RO) m -H] n (RO): ring-opened unit of monoepoxide n, m: an integer of 1 or more
【００１０】ポリエーテル類の製造方法として、複合金
属シアン化物錯体触媒を用いることは知られている（米
国特許第３２７８４５７号明細書、米国特許第３２７８
４５８号明細書及び米国特許第３２７８４５９号明細書
参照）が、本発明者は、この複合金属シアン化物錯体触
媒が、アルキレンオキシドのランダム共重合反応触媒と
して高いランダム性発現能を有することを見いだし、本
発明の低粘度で粘度の経時的変化の少ないポリオキシア
ルキレンポリオールの製造方法に到達した。It is known to use a double metal cyanide complex catalyst as a method for producing polyethers (US Pat. No. 3,278,457, US Pat. No. 3,278).
No. 458 and U.S. Pat. No. 3,278,459), the present inventors have found that this double metal cyanide complex catalyst has a high ability to develop randomness as a random copolymerization reaction catalyst of alkylene oxide, The process of the present invention for producing a polyoxyalkylene polyol having a low viscosity and a small change in viscosity over time has been achieved.
【００１１】本発明における複合金属シアン化物錯体触
媒としては、ハロゲン化金属塩の金属としてＺｎ（Ｉ
Ｉ），Ｆｅ（ＩＩ），Ｆｅ（ＩＩＩ），Ｃｏ（ＩＩ），
Ｎｉ（ＩＩ），Ｍｏ（ＩＶ），Ｍｏ（ＶＩ），Ａｌ（Ｉ
ＩＩ），Ｖ（Ｖ），Ｓｒ（ＩＩ），Ｗ（ＩＶ），Ｗ（Ｖ
Ｉ），Ｍｎ（ＩＩ），Ｃｒ（ＩＩＩ）の群より１種類又
は２種類以上を選び、アルカリ金属シアノメタレートの
アルカリ金属としてＦｅ（ＩＩ），Ｆｅ（ＩＩＩ），Ｃ
ｏ（ＩＩ），Ｃｏ（ＩＩＩ），Ｃｒ（ＩＩＩ），Ｍｎ
（ＩＩ），Ｍｎ（ＩＩＩ），Ｖ（ＩＶ），Ｖ（ＶＩ）の
群より１種類又は２種類以上を選び、有機配位子として
アルコール、アミドの中より１種類又は２種類以上の混
合配位子を選んで合成した複合金属シアン化物錯体触媒
を用いることができる。The double metal cyanide complex catalyst used in the present invention includes Zn (I) as a metal of a metal halide salt.
I), Fe (II), Fe (III), Co (II),
Ni (II), Mo (IV), Mo (VI), Al (I
II), V (V), Sr (II), W (IV), W (V
I), Mn (II), Cr (III), one or more kinds are selected, and Fe (II), Fe (III), C
o (II), Co (III), Cr (III), Mn
(II), Mn (III), V (IV), V (VI), one or more kinds are selected, and one or more kinds of alcohols and amides are used as organic ligands. A double metal cyanide complex catalyst synthesized by selecting a ligand can be used.
【００１２】[0012]
【実施例】以下に本発明を実施例及び比較例にて具体的
に説明するが、本発明は、これらの実施例のみに限定さ
れない。EXAMPLES The present invention will be specifically described below with reference to Examples and Comparative Examples, but the present invention is not limited to only these Examples.
【００１３】（実施例１） プロピレンオキシド単独開環重合で得られた数平均分子
量５０００の３官能ポリエーテルポリオール５０００ｇ
に、プロピレンオキシド１００重量部及び１，２−ブチ
レンオキシド２０重量部からなる混合物５０００ｇを混
合し、亜鉛ヘキサシアノコバルテート錯体触媒を用い、
数平均分子量が１００００になるまで開環付加重合さ
せ、さらに、プロピレンオキシド６０００ｇを混合して
数平均分子量が１６０００になるまで開環重合させた。
得られたポリエーテルポリオールには、１，２−ブチレ
ンオキシドの開環した単位が５．２２重量％導入され
た。(Example 1) 5000 g of a trifunctional polyether polyol having a number average molecular weight of 5,000 obtained by propylene oxide homo-ring-opening polymerization
Was mixed with 5000 g of a mixture consisting of 100 parts by weight of propylene oxide and 20 parts by weight of 1,2-butylene oxide, and a zinc hexacyanocobaltate complex catalyst was used.
Ring-opening addition polymerization was carried out until the number average molecular weight became 10,000, and 6000 g of propylene oxide was further mixed to carry out ring opening polymerization until the number average molecular weight became 16,000.
5.22% by weight of a ring-opened unit of 1,2-butylene oxide was introduced into the obtained polyether polyol.
【００１４】（参考例１） プロピレンオキシド単独開環重合で得られた数平均分子
量１５００の２官能ポリエーテルポリオール１５００ｇ
に、プロピレンオキシド１００重量部及び１，２−ブチ
レンオキシド０．５重量部からなる混合物１４５００ｇ
を混合し、亜鉛ヘキサシアノコバルテート錯体触媒を用
い、数平均分子量が１６０００になるまで開環付加重合
させた。得られたポリエーテルポリオールには、１，２
−ブチレンオキシドの開環した単位が０．４５重量％導
入された。 Reference Example 1 1500 g of a bifunctional polyether polyol having a number average molecular weight of 1500 and obtained by ring-opening polymerization of propylene oxide alone.
A mixture of 100 parts by weight of propylene oxide and 0.5 part by weight of 1,2-butylene oxide in an amount of 14500 g
And a ring-opening addition polymerization was carried out using a zinc hexacyanocobaltate complex catalyst until the number average molecular weight reached 16,000. The resulting polyether polyol contains 1,2
0.45% by weight of ring-opened units of butylene oxide were introduced.
【００１５】（参考例２） プロピレンオキシド単独開環重合で得られた数平均分子
量１０００の３官能ポリエーテルポリオール１０００ｇ
に、プロピレンオキシド９０重量部、エチレンオキシド
１０重量部及び１，２−ブチレンオキシド５重量部から
なる混合物４０００ｇを混合し、亜鉛ヘキサシアノコバ
ルテート錯体触媒を用い、数平均分子量が５０００にな
るまで開環付加重合させた。得られたポリエーテルポリ
オールには、１，２−ブチレンオキシドの開環した単位
が３．８４重量％導入された。 Reference Example 2 1000 g of a trifunctional polyether polyol having a number average molecular weight of 1,000 and obtained by homocyclic ring-opening polymerization of propylene oxide.
Was mixed with 4000 g of a mixture comprising 90 parts by weight of propylene oxide, 10 parts by weight of ethylene oxide and 5 parts by weight of 1,2-butylene oxide, and ring-opening addition was carried out using a zinc hexacyanocobaltate complex catalyst until the number average molecular weight became 5000. Polymerized. 3.84% by weight of a ring-opened unit of 1,2-butylene oxide was introduced into the obtained polyether polyol.
【００１６】（比較例１） プロピレンオキシド単独開環重合で得られた数平均分子
量５０００の３官能ポリエーテルポリオールに、亜鉛ヘ
キサシアノコバルテート錯体触媒を用い、さらに数平均
分子量が１６０００になるまでプロピレンオキシドを開
環付加重合させた。Comparative Example 1 To a trifunctional polyether polyol having a number average molecular weight of 5,000 obtained by propylene oxide homocyclic ring-opening polymerization, a zinc hexacyanocobaltate complex catalyst was used, and propylene oxide was further added until the number average molecular weight reached 16,000. Was subjected to ring-opening addition polymerization.
【００１７】（比較例２） プロピレンオキシド単独開環重合で得られた数平均分子
量１５００の２官能ポリエーテルポリオールに、亜鉛ヘ
キサシアノコバルテート錯体触媒を用い、さらに数平均
分子量が１６０００になるまでプロピレンオキシドを開
環付加重合させた。Comparative Example 2 A bifunctional polyether polyol having a number average molecular weight of 1500 obtained by ring-opening polymerization of propylene oxide was used, and a zinc hexacyanocobaltate complex catalyst was used. Further, propylene oxide was added until the number average molecular weight reached 16,000. Was subjected to ring-opening addition polymerization.
【００１８】（比較例３） プロピレンオキシド単独開環重合で得られた数平均分子
量１０００の３官能ポリエーテルポリオール１０００ｇ
に、プロピレンオキシド９０重量部及びエチレンオキシ
ド１０重量部からなる混合物４０００ｇを混合し、亜鉛
ヘキサシアノコバルテート錯体触媒を用い、数平均分子
量が５０００になるまで開環付加重合させた。Comparative Example 3 1000 g of a trifunctional polyether polyol having a number average molecular weight of 1000 and obtained by homocyclic ring-opening polymerization of propylene oxide
Was mixed with 4000 g of a mixture consisting of 90 parts by weight of propylene oxide and 10 parts by weight of ethylene oxide, and subjected to ring-opening addition polymerization using a zinc hexacyanocobaltate complex catalyst until the number average molecular weight became 5000.
【００１９】（評価） 以上、実施例１〜３及び比較例１〜３について合成直後
の２５℃における粘度（直後粘度）と、３０日後の２５
℃の粘度（３０日後粘度）を計測した結果を表１に示
す。(Evaluation) As described above, in Examples 1 to 3 and Comparative Examples 1 to 3, the viscosities at 25 ° C. immediately after the synthesis (immediate viscosity) and the viscosities after 30 days
Table 1 shows the results of measuring the viscosity at 30 ° C. (viscosity after 30 days).
【００２０】[0020]
【表１】 [Table 1]
【００２１】以上のように同じ数平均分子量のポリエー
テルポリオールを比べた場合、比較例に比べ実施例の方
が粘度が低いことが認められる。また、３０日経過後の
測定粘度と合成直後の粘度との差は、明らかに実施例の
方が小さく経時変化が少ないことが認められた。As described above, when polyether polyols having the same number average molecular weight are compared, it is recognized that the viscosity is lower in the examples than in the comparative examples. Further, it was confirmed that the difference between the measured viscosity after 30 days and the viscosity immediately after the synthesis was clearly smaller in the example and less changed with time.
【００２２】[0022]
【発明の効果】本発明により１，２−ブチレンオキシド
等の炭素数４以上のアルキレンオキシドとプロピレンオ
キシドをポリエーテルポリオールの主鎖中に導入するこ
とにより、ポリエーテルポリオールの結晶性を低め、粘
度値を低減し、結晶化度の変化にともなう粘度経時変化
を低減させたポリエーテルポリオールの製造を可能にし
た。According to the present invention, by introducing an alkylene oxide having 4 or more carbon atoms such as 1,2-butylene oxide and propylene oxide into the main chain of the polyether polyol, the crystallinity of the polyether polyol is reduced, and the viscosity of the polyether polyol is reduced. This has enabled the production of a polyether polyol having a reduced value and a change in viscosity with time due to a change in crystallinity.
───────────────────────────────────────────────────── フロントページの続き (58)調査した分野(Int.Cl.7，ＤＢ名) C08G 65/26 - 65/28 ──────────────────────────────────────────────────続 き Continued on front page (58) Field surveyed (Int. Cl. 7 , DB name) C08G 65/26-65/28
Claims (2)
剤にアルキレンオキシドを重合させてポリエーテルポリ
オールを製造する方法において、アルキレンオキシドと
して、下記（１）又は（２）を用いて重合させた後、さ
らに、下記（３）又は（４）を用いて重合させることを
特徴とするポリエーテルポリオールの製造方法。 （１）プロピレンオキシド及び炭素数４以上のアルキレ
ンオキシドの混合物。 （２）エチレンオキシド、プロピレンオキシド及び炭素
数４以上のアルキレンオキシドの混合物。 （３）プロピレンオキシド。 （４）エチレンオキシド及びプロピレンオキシドの混合
物。1. A method for producing a polyether polyol by polymerizing an alkylene oxide as an initiator using a double metal cyanide complex catalyst, wherein the polymerization is carried out using the following (1) or (2) as the alkylene oxide. Thereafter, the method is further polymerized using the following (3) or (4). (1) A mixture of propylene oxide and an alkylene oxide having 4 or more carbon atoms. (2) A mixture of ethylene oxide, propylene oxide and an alkylene oxide having 4 or more carbon atoms. (3) Propylene oxide. (4) A mixture of ethylene oxide and propylene oxide.
炭素数４以上のアルキレンオキシドの開環した単位の含
量が０．１〜５０重量％になるように原料を配合したこ
とを特徴とする請求項１に記載のポリエーテルポリオー
ルの製造方法。2. The raw material is blended so that the content of the ring-opened unit of the alkylene oxide having 4 or more carbon atoms in the obtained polyether polyol is 0.1 to 50% by weight. The method for producing a polyether polyol according to the above.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP06285193A JP3299803B2 (en) | 1993-02-26 | 1993-02-26 | Method for producing polyether polyol |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP06285193A JP3299803B2 (en) | 1993-02-26 | 1993-02-26 | Method for producing polyether polyol |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH06248069A JPH06248069A (en) | 1994-09-06 |
| JP3299803B2 true JP3299803B2 (en) | 2002-07-08 |
Family
ID=13212231
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP06285193A Expired - Fee Related JP3299803B2 (en) | 1993-02-26 | 1993-02-26 | Method for producing polyether polyol |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3299803B2 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2024143038A1 (en) | 2022-12-27 | 2024-07-04 | 旭化成株式会社 | Polyol-containing composition, and polyurethane and water-based polyurethane made therefrom |
| WO2025094559A1 (en) | 2023-10-30 | 2025-05-08 | 旭化成株式会社 | Aqueous polyurethane |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6103850A (en) * | 1995-12-29 | 2000-08-15 | Basf Corporation | Sealants made using low unsaturation polyoxyalkylene polyether polyols |
| DE19918727A1 (en) * | 1999-04-24 | 2000-10-26 | Bayer Ag | Polyether polyol useful for production of polyurethanes and/or polyureas has poly(oxyethylene/oxypropylene) endblock prepared in presence of double metal cyanide catalyst |
| BR112016006429B1 (en) | 2013-09-27 | 2021-08-17 | Dow Global Technologies Llc | PROCESS FOR PRODUCING POLY(1,2-BUTYLENE OXIDE) AND POLY(1,2-BUTYLENE OXIDE) POLYMERS |
| CN105237758B (en) * | 2015-11-09 | 2018-03-02 | 淄博德信联邦化学工业有限公司 | The method that PPG is prepared using methanol as initiator |
-
1993
- 1993-02-26 JP JP06285193A patent/JP3299803B2/en not_active Expired - Fee Related
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2024143038A1 (en) | 2022-12-27 | 2024-07-04 | 旭化成株式会社 | Polyol-containing composition, and polyurethane and water-based polyurethane made therefrom |
| EP4644447A1 (en) | 2022-12-27 | 2025-11-05 | Asahi Kasei Kabushiki Kaisha | Polyol-containing composition, and polyurethane and water-based polyurethane made therefrom |
| WO2025094559A1 (en) | 2023-10-30 | 2025-05-08 | 旭化成株式会社 | Aqueous polyurethane |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH06248069A (en) | 1994-09-06 |
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