SA515361032B1 - Improved continuous process for the production of low molecular weight polyethers with double metal cyanide catalyst - Google Patents

Abstract

Low molecular weight polyoxyalkylene polyether polyols having a hydroxyl content of from about 3.4 to about 12.1% by weight, and OH numbers of from about 112 to about 400 are produced by a continuous process using a DMC catalyst. In the process of the present invention, oxyalkylation conditions are established in a continuous reactor in the presence of a DMC catalyst; alkylene oxide and a low molecular weight starter are continuously introduced into the continuous reactor; a partially oxyalkylated polyether polyol is recovered from the reactor; and the recovered partially oxyalkylated polyether polyol is allowed to further reactor until the unreacted alkylene oxide content of the mixture is reduced to 0.001% or less by weight. The alkoxylation of the present invention must be carried out a pressure sufficiently high to prevent deactivation of the DMC catalyst. Pressures of from 45 to 55 psia are preferred.

Description

— \ — Improved continuous process for the production of low molecular weight ‎polyethers with double metal cyanide catalyst FULL DESCRIPTION BACKGROUND The invention relates to a continuous process Optimized for the production of low molecular weight polyether polyols. This continuous process polymerizes an alkylene oxide with a starter compound in the presence of a double metal cyanide (DMC) catalyst. Preparation of polyoxyalkylene polyols with double metal cyanide catalysts (DMC) known and described; JU in US Patent No. 7 1e Lal Alalah 5 AAA) 09 DMC-catalyzed polyoxyalkylene polyols have low unsaturation and low polydispersion (i.e. limited molecular weight range). One advantage of 0 dimetal cyanide catalysts is that they do not induce the (sale) arrangement of a propylene oxide in propenyl alcohol which acts as a monofunctional initiator in the polymerization of propylene oxide. The presence of propenyl alcohol induces the formation of monoalcohols which are impurities in the process. Another advantage of bimetallic cyanide catalysts includes the ability to leave a catalytic residue in the product. This leads to a lower production cost since no catalyst residues must be stripped or otherwise removed from the YO polyoxyalkylene polyol prior to use. Although dimetallic cyanide catalysts provide multiple advantages in the preparation of polyoxyalkylene polyols, it is; Unfortunately, there are some drawbacks to this type of motivation. See US Patents Nos. 2/9/7197 10/7998 and 791981/5. These disadvantages include the tendency of the catalyst to become inert in the presence of high concentrations of hydroxyl groups, the inability to polymerize oy \ 0

A in the presence of low molecular weight starting materials, such as glycerin, and the fact that; add to desired product; DMC catalysts produce a small amount of a very high molecular weight polymer (ie 000001 JAY molecular weight and higher). This high molecular weight polymer is often referred to as an ultra high molecular weight tail. A high molecular weight tail causes difficulties in the foaming process when a polyol© (alcohol containing many hydroxyl groups) (polyols) reacts with a WY polyisocyanate. Js foam. Polyurethane foam. There have been many efforts over the years to improve and expand the catalysis a double metal cyanide to enable effective oxyalkylation of low molecular weight starting materials Jie glycerin; and for the production of low molecular weight polyoxyalkylene polyols. particulary. US Patent No. 109779978 describes the direct alkylation of polyoxy-00 00/38110/18/a0m for glycerin with DMC lia in which the catalytic quenching is reduced by (1) the acidification of an acid-sensitive low molecular weight starting material prior to the introduction of the starting material (¥) treat the acid-sensitive low-molecular-weight starting material with an effective amount of base reactant or non-acid-base absorbent before introducing the low-molecular-weight (al) into the reactor; (5) Adding an effective amount of acid to prevent catalytic quenching to the reactor where the acid is not present in a feed stream containing an acid-sensitive low molecular weight starter. US Patent #79,195,975 describes a polyoxy alkylation process using a double metal cyanide catalyst (DMC) wherein the low molecular weight starting material is acidified with at least one protonated inorganic mineral acid and an organic acid wherein the acid is present in an amount greater than 0 . typical; The acid is present in an amount greater than 100 ppm; Depending on the weight of the starting material. This process allows a smaller amount of catalyst to be used and enables lower molecular weight starting materials to be used in the process without catalyst quenching. Another process for preparing polyethers using DMC catalysts is described in Yo's published US patent application 0071191/0001. This process uses © to 0001 oF

It is a ppm of a double metal cyanide catalyst in an oxy-alkylation reaction; and requires that the low molecular weight starting material have an average molecular weight number of less than about 700 Daltons; Containing from about 00 to about 5001 ppm cole and acidified with from about 01 to about voor ppm of at least one inorganic proto-mineral acid and an organic acid. The addition of © acid to a low molecular weight starting material having a relatively high water content reduces and/or prevents quenching of the catalyst by water. US Patent No. 1,709,190 also describes a process for the preparation of polyether polyols from dimetallic cyanide catalysts. in the process; The epoxide is polymerized in the presence of a DMC catalyst and the first primer is continuously added. Epoxide and starter 0-1 are continuously added to the reactor in a first step to produce intermediate compound. The polyol intermediate is then reacted with an additional epoxide and optionally an additional DMC catalyst and a second primer to produce a polyether polyol. Suitable starting materials include: 7069-hexanediol A1,6-06*»80600; bis-hydroxyethyl cyclohexane dimethanol (bis—hydroxyethyl chydroquinonone and bis—hydroxyethyl resorcinol Yo) in addition to this; the mole ratio for epoxide to all of the first starting material is at least about 0:7; and the first starter added in the first step shall have an impurity level (of all water; propylene glycol and neutral base residues) of less than about 100 ppm by weight. 13/578409 Registered 71 Jun 0101 Yo process for the preparation of low molecular weight polyoxyalkylene polyether polyols in a continuous process where the low molecular weight starting material is alkoxylated (to which an alkoxy is added ) is alkoxylated in the presence of a double metal cyanide catalyst in which the oxy-alkylation reaction is maintained at a sufficiently high ha level to aid the quenching of the catalyst; even in the presence of elevated levels of low molecular weight starting materials.

Qo _ _ The present invention allows low molecular weight polyoxyalkylene polyether polyols to be prepared by a continuous process whereby the alkoxylated low molecular weight starting material is in the presence of a double metal cyanide catalyst by carefully maintaining the pressure during the oxy-alkylation reaction at 1,78? to [ala BST ATTAAS absolute poison to prevent catalyst quenching; even in the presence of high levels of low molecular weight starting materials. The benefits of the present invention include sufficient sustainable production of useful low molecular weight products in polyurethane applications. The present invention also provides ALE persistence means sufficient to produce low molecular weight polyHd products useful as starting materials for higher molecular weight polyether products. The present invention makes the production of low molecular weight polyethers possible at optimal 6/1 catalyst concentrations. 00 skilled in the art understands that a continuous process is effective (iS) for a batch or semi-batch process used Lad gal to make low molecular weight polyether products and/or polyether primers. The present invention relates to a continuous process for the production of polyoxyalkylene polyether polyols. Polyoxyalkylene polyether polyols have a hydroxyl content of about 7.4 to about 2171 by weight. In this continuous process: (1) Yo oxy-alkylation conditions are established in a continuous oxy-alkylation reactor in the presence of a double metal cyanide catalyst ¢ (DMC) and (7) alkylene oxide sales of a low molecular weight initiator (average number Molecular Weight 50 to You Preferred 50 to YY Preferred AS 00 to Yoo Preferred More than 00 to 001) to continuous oxy alkylation reactor; and AR (7) Partially oxy-alkylated alkylated polyols are recovered from Jolie continuous oxy-alkylation.In this process, the pressure in the continuous oxy-alkylation reactor is maintained during the oxy-alkylation reaction at a sufficiently high pressure (preferably at least 7.1177815 kg/kg) Yau absolute; more preferably at least 2.797497770 kg/cm absolute) To prevent quenching of DMC lia the concentration of unreacted alkylene oxide in the contents of the continuous reactor is kept at a level from 1 to 77 Ad \ 0 [+]

h —_ _ (preferably 1 to (IY) wt. The hydroxyl content of the reactor contents is kept at 3.4 to 717.1 wt. The alkylated polyether polyol is then reacted with the partially oxy recovered from the continuous oxy-alkylation reactor further until the unreacted alkylene oxide content of the mixture is reduced to 20.009 or 0 less (dat) * 0 720,00 or less) by weight.Another embodiment of the present invention also relates to a continuous process for the production of a polyoxyalkylene polyether polyol having a hydroxyl content from about 7.4 to about 777.1 by weight where: (1) AN-oxy solidifies in a continuous oxy-alkylation reactor in the presence of a double metal cyanide catalyst; Va (7) continuously introduces alkylene oxide sales A low molecular weight initiator (having at least two hydroxyl groups per molecule and an equivalent weight of up to 111) to a continuous oxy-alkylation reactor; (7) An alkylated polyether polyol with partially oxy is recovered from a continuous oxy-alkylation Jolie. In this process; Jolie oxy alkylation Continuous oxy alkylation at pressures from 2.15 to 3.8774805 kg/cmAt; preferably from about 3.7949777 to about Vo 3.1809534 kg/Yau absolute; most preferably about to 57515, ?kg/Yau absolute thus preventing quenching of the DMC catalyst The concentration of unreacted alkylene oxide in the continuous reactor contents is kept at a level of 1 to 727 wt and the hydroxyl content of the reactor contents is kept at 4 to 707.1 By weight. An alkylated polyether polyol may be further reacted with the partially recovered oxy-alkylation from a continuous oxy-alkylation reactor until the non-0 reacted alkylene oxide content of the mixture is reduced to 70.001 or less by weight. In the second embodiment described above; It is preferred that the building ratio in a continuous oxy-alkylation reactor be from ET to 11.7 and the overall building ratio is from 5.16 to 116.7 and the Sha FAI degree increases

the reaction mixture in the additional reaction step to 40070 as a result of the .exothermic shall polymerization reaction in the HAT embodiment of the present invention; It continuously produces polyoxyalkylene polyether polyols having a hydroxyl content of about 7.4 to about 797.1 by weight by: (1) Continuous polymerization for at least one alkylene oxide in the presence of a double metal cyanide catalyst ( DMC) in a continuous reactor while maintaining pressure from 2.1674815 to 7.8771488 kg/Yau absolute. (Y) feed sale A low molecular weight precursor having at least two hydroxyl groups per mol and an equivalent weight of 111 and at least one alkylene oxide to a continuous reactor Vy containing an alkylene oxide and a double metal cyanide catalyst; and (©) recovery of the partially oxy alkylated polyol mixture from the continuous reactor. The unreacted alkylene oxide concentration in the contents of the continuous reactor is kept at a level 1 to 77 (preferably 1 to (XY) by weight and the hydroxyl content of the reactor contents is kept at 3.4 to 717.1 by weight. Hence; it is permissible to mix the alkylated polyol with oxy-particulate drawn from the continuous reactor the reaction further until the unreacted alkylene oxide content of the mixture is reduced to 70.0009 or less (preferably 70.0005 or less) by weight. embodiment The build ratio in the continuous oxy alkylation reactor is preferably from ET to 16.7 and the total build ratio is from 5.7 to 11.7 and the temperature of the reaction mixture in the additional reaction step increases to 4,5010 as a result of the extrusion polymerization reaction Shall Ye in another aspect of the invention (all) is polymerized continuously for alkylene oxide in the presence of a double metal cyanide polymerization catalyst (DMC) to form a polyether polyol having a hydroxyl content of about ,? to about ,707. 1 by weight in a process where in the first step; a precursor having at least two hydroxyl groups per molecule and an equivalent weight of up to 111 and at least one alkylene oxide is fed into a continuous reactor containing a metal cyanide catalyst; and a copolymer mixture oy \ 0

m _ part of the continuous reactor. In this first step; The continuous reactor is kept at a pressure of 2,178 to 7,8778858 kg/Yau absolute and the degree of polymerization sha is greater than or equal to Yo 0 (preferably greater than or equal to aI) the concentration of unreacted alkylene oxide is kept in The contents of the continuous reactor at a level of 1 to 77 (preferably 1 to IY©) by weight; the hydroxyl content of the reactor contents is kept at 7.4 to 797.1 by weight. In a subsequent second step, the mixture is allowed to polymerize Partially withdrawn from the reactor in the first step by further reaction until the unreacted alkylene oxide content of the mixture is reduced to 70,0009 or less (preferably 0 * 720.00 or less) by weight.In this embodiment of the present invention, the building ratio in the first step is preferably of ET 0 to VY and the total building ratio is from −1 to OY and the temperature of the reaction mixture in the second step is increased to ©?” as a result of an exothermic polymerization reaction. The present invention also relates to a continuous process for the production of a polyoxyalkylene polyol An ether having a hydroxyl number (OH) from 11 to 6 (Yeo is preferred to 0 dL where: (1) The conditions for oxy-alkylation in Jolie establish a continuous oxy-alkylation while maintaining At pressure 0 from 2.1317815 to 7.8174485 kg/Yau absolute in the presence of a double metal cyanide catalyst ¢ (DMC) (Y) continuously introduces alkylene oxide and low molecular weight starting materials having at least two hydroxyl groups per mol and average molecular weight number from 0 to You (preferably from to YY preferably from Ov to AK and preferably from Orv to 10 ) to the reactor; AR (7) A partially oxy-alkylated polyether polyol is recovered from a continuous oxy-alkylation reactor; and oy \ 0

_q —_

(2) An alkylated polyether polyol reacts additionally with a partially recovered oxy from Jeli for continuous oxy alkylation, thus forming a polyoxyalkylene polyether polyol having an OH number from 11 to 6 (Yeo is preferred to (Yve)

In a preferred embodiment of this continuous process; The building ratio in Jolie is oxy-alkylation

© continues from ELT to 11.7 and the total building ratio from 4.76 to 11.7 The temperature of the reaction mixture in the step (the reaction step Alay) is increased to 5 °C as a result of the exothermic polymerization reaction .

A particularly favored embodiment of the present invention relates to a process for producing a polyoxypolyol

alkylene polyethers by continuous polymerization to an alkylene oxide in the presence of a double-0 metal cyanide polymerization (DMC) catalyst to form a polyether polyol having a hydroxyl content of about 7.4 to about 21 by weight where:

(1) A precursor having at least two hydroxyl groups per molecule and an equivalent weight of up to 111 and at least one alkylene oxide is fed into a continuous reactor while maintaining pressure from 2.15 to 1485 7.87 kg/Yau An absolute containing a double metal cyanide catalyst

YO Withdraw the partially polymerized mixture from the continuous reactor. wherein the concentration of unreacted alkylene oxide in the contents of the continuous reactor is maintained at a level of 1 to 77 (preferably 1 to IY) by weight and the hydroxyl content of the reactor contents is kept at 3.4 to Seal 79.1 (7 ) in a later step; the partially polymerized mixture withdrawn from the reactor at (1) 0 is allowed to react further until the unreacted alkylene oxide content of the mixture is reduced to 70.009 or less (preferably 0.0005 7 or less) by weight where the building ratio is in Step (a) is from 1.1 to 16.7 and the total building ratio is from 1.1 to OLY and as the temperature of the reaction mixture in step (b) is raised to about 4 4507 C as a result of the extrusive polymerization reaction Shall Detailed description: oy \ 0

=« \ _ The invention (Jad) is now described for illustrative purposes. Except in running examples; or where otherwise indicated; It is understood that all numbers expressing quantities; percentages; OH numbers are functions; Thus in the specification as modified by the term “about” as used here all gram molecular weights shall be the mean number of the molecular weights unless otherwise specified. The continuous process described herein is suitable for the production of polyoxyalkylene polyether polyols. These polyoxyalkylene polyether polyols have a hydroxyl content of about YE to about 797.1 by weight; Based on 77001 by weight of polyoxyalkylene polyether polyols. Polyoxyalkylene polyether polyols produced by this process are also described as having a 0 OH number typically of at least around ONY and preferably at least around Yee These polyoxyalkylene polyether polyols typically also have an OH number less than or equal to about ctor and preferably less than or equal to 375. Polyoxyalkylene polyether polyols also have an OH number between any combination of these higher and lower values; Sie lea) for example at least about 01 to less than or equal to about ctor and preferably at least about 00010 to less than or equal to 0 to about Yve as defined by a person skilled in the art; OH numbers from about 11" to about 400 correspond to equivalent weights from about 00 to about Vee respectively; OH numbers from about 0010 to about FYE correspond to equivalent weights from about 780 to about about von respectively.In addition to this the conversion of an OH number to a hydroxyl content and of a 0 hydroxyl content to an OH number is easily calculated and determined by the average person skilled in the art.The polyol is an alkylated polyether with a polyoxy which has An OH number of about 111 has a hydroxyl content of about 77.4 by weight; an alkylated polyether polyol with a polyoxy which has an OH number of about 400 has a hydroxyl content of about 717.1 by weight.

-11- Polyoxyalkylene polyether polyols prepared by the aforementioned process typically have at least about 771 preferred; It is more preferred over TE hydroxyl content of at least about, at least about 77 by weight. These polyoxyalkylene polyether polyols typically also have a more preferable TYE less than or equal to 717.1 hydroxyl content less than or equal by weight. Polyols 79.1 more preferably also less than or equal to 7016 less than or equal to oxyalkylene polyethers have a hydroxyl content between any combination of these higher values 797 preferable more than JY, 8 the lowest; Total examples from 77.4 to 1,717; preferably from 77 wt to from 7001 wt; Depending on 745.1 and more preferably also from 77 to 790056 to polyoxyalkylene polyols. Used in the process of the present invention (DMC) suitable double metal cyanide catalysts IK

DMC is known. This includes all of the DMC catalysts including; For example; Any known and described crystalline catalyst; DMC is both crystalline and intrinsically amorphous (ie, intrinsically amorphous). Exemplary 77774 catalysts (0Y0AAYY in US patents (JU) for example exhibiting properties of a non-(DMC) dimetal cyanide) and 4970817E.4 catalysts in Jal patents are intrinsically crystalline (i.e. being essentially amorphous) known and described; eg 10

LOVATO 5 8487460 US PATENT The catalysts described in US Patents 5474960 and 59,787817 differ from others in that these catalysts exhibit a substantially amorphous form. In addition to this, DMC catalysts, the ana-] and the alcohol compound, these catalysts depend on the union of bonding compounds; As 4-butyl alcohol (polypropylene oxide) Js (polydentate bonded polyol oxide) 0

DMC catalysts (zinc hexacyanocobaltates) are preferred (zinc hexacyanocobaltate) are intrinsically amorphous catalysts. DMC is preferred. Poly A catalysts in the innovative process To ensure good control of the DMC reaction a catalyst concentration is selected under the described reaction conditions. The catalyst concentration for polyoxyalkylation is preferably 10 ppm; Most preferred in the range from Yoo ppm to Vo in the range from YO ory.

— \ \ —

ppm to 151 ppm; It is also more preferred in the range of 980 to 181 ppm; Depending on the weight of the resulting polyether polyol. DMC catalysts are both crystalline and intrinsically amorphous

by an amount ranging from any union of these values to the sum of the said values. Suitable low molecular weight starting compounds include compounds having a functionalization of at least © of about ¥ up to about oA preferably of about ? to about 1 and have an equivalent weight of up to about ml and preferably up to about Den Suitable starting compounds include; but without Caan monols (monols 03-05); J Sula (ethylene glycol propylene glycol —Y) “glycol propanediol 401 ¢ 1,3-propanediol -1,4-butanediol” 10 -butanediol ¢1,2-butanediol 1”?-butanediol 1,3-butanediol 7′?-butane

0 diol 12,3-51806010; water; glycerin cglycerin sorbitol etc. can also

The use of mixtures of monomeric raw materials or oligomers 0119007615 alkylated with oxy of them. Preferred starting compounds are propylene glycol and glycerin. Glycerin is the most preferred starting compound. Compounds starting with starting materials may also be referred to.

E Suitable low molecular weight starting compounds may also be described as compounds having the functionality described Sed and an average molecular weight number less than or equal to about You preferably less than or equal to about 177; more preferably less than or equal to 107; preferably More also less than or equal to 5. Typically, the starting compound has an average molecular weight number of at least about 0 5.

include alkylene oxides useful in the present invention » but without limitation; Ethylene oxide

1,2-butylene-71 propylene oxide cethylene oxide 0 isobutylene ©2,3-5017/160; Isobutylene oxide and 707-butylene oxide “cyclohexene oxide” cyclohexene oxide cepichlorohydrin epichlorohydrin oxide It is preferable to use propylene oxide alone or in mixtures of styrene oxide and styrene oxide in the invention 00:90 preferably More in the proportion of 15:85 propylene with ethylene oxide, preferably in a proportion

oy \ 0

Q1 current. Other alkylene oxides mixed with propylene oxide have also proven useful in innovative processes. Propylene oxide alone is the most preferred alkylene oxide. in the process of invention; The oxy-alkylation conditions are established in the continuous reactor by packing a polyether polyol containing a double metal cyanide catalyst (DMC) into the continuous reactor; Preferably a continuous stirred tank reactor. Polyether polyols shall contain from about 0 to about VY ppm of DMC catalyst. Once a polyether polyol containing DMC catalyst is packed into the reactor “the contents of the reactor are slowly heated to a temperature of psi”). VO preferably at least £0. Once the reactor and its contents are heated up; An initial charge of “pli” oxide is filled, preferably propylene oxide; to the reactor over a period of time from © to 10 minutes. within a short period of time” i.e. 0 from about © to about 10 minutes; Once the DMC lin is activated a feed stream of at least one alkylene oxide (preferably propylene oxide) is started and the feed continues to the reactor. In addition to this a separate feed stream is initiated from a low weight starting material (iad) having an Aria weight of 0 to You (or one of the described 1 possible ranges (Ls) and the feed continues to the reactor. The feed stream is The sale feed low molecular weight starter also typically contains DMC catalyst in an amount of 111 to ia 0001 ppm, depending on the hydroxyl number of the final product and the final desired catalyst concentration.An alternative method of adding the catalyst is to have a third stream containing contains a catalyst charge of 1 to ?7 wt in either the low molecular weight starting material or the low molecular weight polyether.In this alternative method the second stream 0 contains the sale low molecular weight initiator and is free of DMC catalyst The first stream comprises alkylene oxide.Oxy alkylation takes place in the reactor which is maintained at a pressure sufficient to prevent quenching of the DMC catalyst Preferably; this pressure is at least 7.1174815 kgf/cm; more preferably at least 3.7749777 kg / cm absolute. The maximum pressure in the Yo reactor is preferably about 7.8717888 kg/ (Glas Yau but more preferably about 3.1584734 To add yee kg/cm¥ absolute and more preferably also about 5 7.557 kg/cm¥ absolute. Oxy-alkylation may take place in the reactor at a pressure between any combination of these higher and lower values” in all. One or more retention times while 1 the oxy-alkylation reaction lasts for ; one or more retention times; It preferably maintains a different positive temperature between the reaction temperature and the cooling/heating loop temperature. This indicates an exothermic reaction requiring cooling. during oxy alkylation; The concentration of alkylene oxide other than © to 727 wt;1 AY to 1 reactant is preferably kept in the contents of the continuous reactor at a level of depending on the total weight of the contents in the reactor; The hydroxyl content is retained from the contents by weight (or any of the other appropriate ranges for 797.1 reactor contents in the range from 7.4 to 7.4 wt contents. 7000 hydroxyl content); Depending on the temperature at which the oxy-alkylation reaction takes place, it is generally from 0.00 to 11 to 100*V aap Va. From Te from an oxy-alkylation reactor Wiha an alkylated polyether polyol with continuous oxy is preferably recovered but can be discontinuous in some embodiments Temperature and pressure can be increased when the reaction of an alkylated polyether polyol with oxy Additional molecules are added during this step due to the residual exothermic alkylene oxide reaction at the end of the polymer chains. A lower Vo or non-external quenching is typically applied at this point in the process. In addition to this it is not typically necessary for the exothermic that occurs here. As sald the heating of this part of the process due to the general nature of the reaction, the temperature of the reaction mixture entering in this step of the process shall be at least approx. about 7"C. 71 The reaction involved in this step is also typically less than or equal to about 0. In addition to this, the temperature of the reaction mixture may be increased at this step or Part of the process to 05? in general; With this, the temperature of this reaction mixture increases

Sha is a preferred embodiment; The degree of BAT typically increases from about 10 μm to about the reaction mixture to about 4 7 μm due to exothermic polymerization.

“yoo

The partially complete polyether polyol (ie, alkylated with oxy) is continuously removed from the fully liquid reactor through the back pressure regulator. The alkylated polyether polyol with Wha-oxy is left to react further until the unreacted alkylene oxide content of the reaction mixture is reduced to 20.00 or less; 70.0005 or less is preferred; by weight. The final product typically contains small amounts of residue (liad) less than or equal to about eda 1001 per million; more preferably less than or equal to 5 0 ppm; small amounts of the initial compound or the low molecular weight alkoxylates thereof; and small amounts of other organic impurities and water. It is also known in the production of alkylated polyether polyols with polyoxy; The volatile compounds may be flashing or dissociated from polyols; Catalyst residues may remain in the product or may be removed. can be removed

0 moisture by stripping polyols. Preferably alkylated polyether polyols react with an oxy-molecule further in a Jolie tube. This typically occurs by passing a partially oxy-alkylated polyether polyol through a steam-heated Jolie tube to maintain a high temperature of about L to react the remaining alkylene oxide. The further reaction preferably takes place for an alkylated polyether polyol with

Shall Partially Oxy Evenly 0 8.7 Minimum building ratios for a continuous oxy alkylation reactor are typically at least about, preferably at least about 4,9; more preferably at least about 5.7 and more preferably also at least Maximum build ratios for a continuous oxyalkylation reactor are typically less than or equal to about 1.1 VA preferably less than or equal to about 1.5; Preferably more Less than or equal to about VY About Build ratios for a continuous oxy-alkylation reactor may range from any combination of these higher and lower values; 0 VY is preferred Overall eg; For example; at least about 7,; to less than or equal to 5.7 at least about 4; to less than or equal to about 1.9; Preferably more at least about to less than or equal to about 4,. These same building proportions are also suitable for the overall process. It is preferable to 7,4 when glycerin is the starting compound 5,1 in particular using building ratios of yr

Low molecular weight. Other preferred building ratios for the invention range at least about TY

to about less than or equal to about ALY according to the present invention; The low-molecular-weight starting compound is preferably acidified with a small amount of a suitable acid as described; For example; per US Patent 7/17/9978 and US Patent 7,919,815. The acid may be any inorganic protonated mineral acid or an organic acid known to be suitable as described in Art. typical; The amount of acid added to the low molecular weight initiator ranges from 010 to Yoo ppm; Depending on the weight of the low molecular weight starting compound. Preferably, the starting CO should contain from 0? to 0.100 ppm of acid. Phosphoric acid is phosphoric acid

Vo is the preferred acid.

It is also possible though not preferred; that when propylene glycol is used as a carrier for a catalyst (DMC) Fie phosphoric acid can be added to propylene glycol in an amount sufficient to lower the pH for propylene glycol Sle by an amount from 60 to Vo ppm without adversely affecting on the catalytic activity of DMC

Yo When a third stream containing a low molecular weight starting compound acid or a polyol is used as the catalyst carrier (see alternative embodiment described above) the acid level in the mixture of carrier and catalyst is JA of eda 15001 ppm. Preferably, the mixture of the low molecular weight starting compound or sale of a polyol and catalyst carrier should contain less than en 1500 ppm of acid.

Y. The term “partially” is understood with respect to oxy-alkylated polyether polyols formed in the processes of the present invention to mean the oxy-alkylation of the starting compound to form a substantially complete polyether polyol. In another way; after recovery or A) polyol An oxy-alkylated ether from a continuous oxy-alkylation reactor shows a small amount of reaction outside the reactor, more particularly at the recovery point of an oxy-alkylated polyol from a continuous oxy-alkylation reactor

Add

l \ _ preferably complete the reaction by at least 7948; Most preferably complete with at least 797.5%; It is also more preferred that it be completed by at least 7949. The following examples further detail the process of this invention. These examples are not intended to limit the cp lay mentioned in the previous explanation; Whether for its spirit or scope. Those skilled in the art easily understand that © known changes to terms can be used for the following actions. unless specified otherwise; All temperatures are degrees Celsius and all reproductive parts and proportions are weight parts and percentages by weight; Respectively. Examples Example 1 (Comparative) AD sls Each glycerin-based polonium (PO) polyether has a hydroxyl number of 0 (about AAAS grams) containing Te ppm DMC catalyst prepared according to procedure in US Patent 558,749,578 in a 1-gallon stainless steel reactor fitted with a mechanical stirrer and heated slowly. during heating; Continuous suction is drawn into an overhead vacuum and nitrogen is introduced to the JL phase via a dip tube. As soon as the temperature of the reaction reaches 11 6 9 Pree the suction and nitrogen for an additional 10 minutes; The nitrogen then stops and the reactor shuts down at a pressure of 1.0054705 kg/cm? absolute. An initial charge of PO is loaded into the reactor within several minutes. after 10 minutes; The pressure drop in the reactor indicates that the DMC catalyst is active. PO feed is restarted and set at fan YY min rate (equivalent to 2 1/2 hours retention time 0 6 after oxide feed solidification ¢ glycerin-containing feed starts with 0 ey 601 ppm of 0 1/6 catalyst and 75 ppm pM phosphoric acid at a rate of [an 0 7.5 min. DMC catalyst is added to glycerin by constant stirring of the glycerin/©/01 catalyst feed vessel The catalyst/glycerin feed line may have constant recirculation between the reactor feed point and the catalyst feed vessel Glycerin/01/6 to destabilize the catalyst in the call line however no static recycle is used in the current examples unless otherwise specified ADMC concentration of glycerin is sufficient to provide sia 610 FAI

-M1- In million of DMC catalyst in the final product. when the pressure in the reactor reaches YAAYOAY kg/Yau absolute; A valve is opened at the top of the reactor for the back pressure regulator and the liquid contents of the stirred tank reactor flow completely continuously out of the reactor. The polyether is passed through a steam preheater from the tube prior to collection in a covered, stirred and heated vessel. about 1 hour after feeding the oxide into the covered stirred vessel; The reactor cooling system switches to heating, indicating a loss of reaction. Vo after an additional minute of heating with no sign of reaction; Oxide feeds and glycerin trims stop/01/6. Example ? (comparative) using same reactor contents as described at end of example 1 and similar starting procedure 0 as in example)¢ reaction pressure set at 0.1547605 kgf cm and temperature set at 0 (455° Before beginning .DMC/py pumila s PO feeds the PO is fed at a constant rate fan YY min (equivalent to 2 ½ hours retention time). A DMC/ela feed is fed containing 5006 ppm DMC catalyst and 5/1 ppm phosphoric acid; at a constant fan rate of 7.5 0 min. When the pressure in the reactor reaches Vary (Vo kg/Yau absolute); A valve is opened at the top of the reactor for a back pressure regulator and for the contents BL from the continuously stirred tank reactor to flow completely out of the reactor. The polyether passes through a steam-heated glad from the tube before collecting in a covered, stirred and heated vessel. Approximately one hour after feeding the oxide into the covered stirred vessel; The reactor cooling system switches to heating, indicating a loss of reaction. After up to an additional minute of heating with no Je ll signal the 0 oxide feeds and glycerin feeds stop/©/01. The reaction mixture is reduced to a pressure of 0.4 0714 kg/Vou absolute. example? Using the final reactor contents as described in the example ? as a starting material; Temperature is kept at 1*450; PO feed restarts at fan rate 7 1.7 min and feed feed restarts to add

-14- ppm acid Vo DMC ppm catalyst ha 5076 containing DMC penal

Vou g/min. When the reaction pressure reaches 7.7749777 kg / 7.5 0 phosphoric at a rate of

Jolie Reactor for Backpressure Regulator and Liquid Content Flow from Ad Absolute; A valve in the stirred tank is continuously opened completely outside the reactor. The polyether passes through a steam heated section at times A) hr YY sad and heated. The reaction continues lie from the tube before collection in a covered vessel (retention) with good heating of the reaction (static reactor cooling). The bulk product has a hydroxyl number measured cST YAY g and a viscosity /(KOH) Hydroxide potassiume /mg potassium hydroxide 1/7 gram/average weight number Sia (wt. 0.0848) and polydispersion A PY 5 (Senestock) at -((Mn) number average molecular weight) Example ¢ (comparative) Ve using the final reactance constants as described in Example ¥ and following the same rates as used in Example 7; Decrease the DMC feed as used in the example ?and the same concentration per minute of 71 absolute. After approximately you pressure in the back pressure regulator to 77408, ?kg/oxide feed into the stirred capped vessel; the cooling system switches Reactor to heating indicating loss of an additional minute of heating with no sign of reaction; 10 feeds stop reaction. After 1 oxide and glycerol feeds/01/6. reaction mixture is left to stop. o Example Approved On glycerin having a hydroxyl number of 770 (approximately PO) each polyether prepared according to the procedure in the DMC patent is packaged ppm catalyst 01g) contains 4 gallons supplied with tipper 1 USA 54879078 to a reactor Stainless steel, capacity 0, mechanical, and heats up slowly. during heating; Continuous suction is drawn into an overhead vacuum and nitrogen is introduced to the liquid phase via a dip tube. Once the reaction temperature reaches the Jams close for an additional minutes; nitrogen stops 10 seconds; Suction continues and nitrogen for 6 to reactor PO kg/cm ¥ absolute. Filling an initial charge of 00159476605 reactor at ory pressure.

vy.

DMC minutes; The pressure drops in the reactor indicating that the catalyst 01 will collapse within several minutes. After g/min (equivalent to 2 1/2 hours Yo, TY time and set at active PO rate. Restart ppm of 4517 retention). after the oxide feeding solidification; Glycerin-containing feed starts with g/min. The catalyst 7.1" and 5 ppm phosphoric acid at a rate of DMC catalyst is added to glycerin by constant stirring of the glycerin/©/01 catalytic feed vessel. The DMC© feed line may have a constant circulation between the reactor feed point and the feed vessel catalyst glycerin / 01/16 sale) catalyst / glycerin recycled stationary in current examples unless (sale) with this call is not used to destabilize the catalyst in the ppm line of catalyst 1 glycerin is sufficient to provide ADMC specifies otherwise. be focus

Yau in the final product. when the pressure in the reactor reaches 3.5159758 kg/mc absolute; A valve at the reactor top of the back pressure regulator is opened and the liquid contents of the 0 continuously stirred tank reactor flow completely out of the reactor. Polyether is passed through a strip

YY sad Steam heated from the tube before assembling in a covered container stirred and heated. Reaction proceeds (retention times) with good heating of the reaction (cooling of the static reactor). Combined product has number A) h ALY (Senestock) at 051 YAY g viscosity [KOH mg YY hydroxyl measured (Mn / (molecular weight 0.088 g) and polydispersion Vo Example 6 (Comparative) Using the final reactor constants as described in Example © and following the same 1/16 rates and concentration as used in Example © slowly decreasing © Jie feed as used in Absolute through 2 hours after Yau the pressure in the pressure regulator back to 7.1711775 kg/min from feeding the oxide into the stirred capped vessel; the reactor cooling system switches to Te Ye approximately an additional minute of heating with no signal 0 Heating indicating loss of reaction. After the reaction, the oxide feeds and glycerol trimmings are stopped/©/01 and the reaction mixture is left to stand still. Steady state. 1 and © 7 1 dd

Although the invention has been described in detail in the above Ua ya Explanation; It is understood that these particulars are for this purpose only and changes may be made by those skilled in the art without deviating from the spirit and scope of the invention except as specified in the claims. Ad \ 0 [+]

Claims (1)

And Hama elements 1- A continuous process for the production of polyoxyalkylene polyether polyol with a hydroxyl content from 5.4 to 797.1 by weight, including: (a) oxyalkylation in a reactor Continuous oxyalkylation in the presence of a tdouble metal cyanide catalyst (b) Continuously introduces alkylene oxide and a low molecular weight starting material into a continuous oxyalkylation reactor where the starting material has an average molecular weight number 0 to You (=) an alkylated polyether polyol with 0 oxyalkylated polyether polyol is partly recovered from the continuous oxyalkylation reactor, where (1) the oxyalkylation appears in A continuous oxyalkylation reactor at sufficiently high pressure aids the quenching of a double metal cyanide catalyst; (i) the concentration of unreacted alkylene oxide in the contents of the continuous reactor is kept at a level of 1 to 77 by weight; and) ) the hydroxyl content of the reactor contents is kept at 797.1 (VLE by weight; s Ve (9) reaction is allowed Additional L for an alkylated polyether polyol with an oxyalkylated polyether polyol molecule recovered from the oxyalkylation reactor continued to appear until the unreacted alkylated oxide content of the mixture was reduced to 70.009 or less by weight. "-The process from claim 0; where the resulting polyol polyoxyalkylene polyether has 0 hydroxyl number from 11" to Een? 4,1 to AY ?-Operation from protection 0 where the overall construction ratio is 4,6 to AY S5 - Process of claim 0 wherein alkylene oxide is propylene oxide or a mixture of propylene oxide and ethylene oxide containing at least 785 by weight of propylene oxide. 1-Process from claim 1, whereby the hydroxyl content of the reactor contents is kept at 1 to 711.4 by weight. '-Process from claim 0 wherein the unreacted alkylene oxide is retained in the contents of the continuous oxy-alkylation reactor at a level of 1 to 77 wt. -Process from claim 1 where the substance Low Molecular Weight Lal includes glycerine 0 4-Process from claim 1; the continuous oxy-alkylation reactor is a continuously stirred tank reactor and the further reaction is conducted for a polyether polyol Partially alkylated with oxy in Jolie tube. 0-Process from claim 0, wherein the concentration of a double metal cyanide catalyst in Jolie continuous oxyalkylation is from 0 to 171 ppm; Depending on the weight of the product. 11-Operation of claim 1; wherein the pressure in the continuous oxy-alkylation reactor is at least 10 3.1178158 kg/You absolute. 1- The process from claim 1 where the pressure in the continuous oxy alkylation reactor is from 2.1173815 to 1/485 7.87 kg/You absolute. 1- The process from claim 11 where the double metal cyanide catalyst is a zinc hexacyanocobaltate catalyst complex. Hydroxyl content from 7 to 720076 by weight. -Process from claim 11 where the low molecular weight prefix sald) includes glycerin and the overall building ratio is oY to NA 7 -Process from claim 0; where the alkylated polyether polyol passes with oxy Lida Yo recovered from Jolie undergoes continuous oxy alkylation through a steam heated tube reactor to maintain No elevated temperature 0 12ºC for reaction of the remaining oxide until the unreacted alkylene oxide content of the mixture is reduced to 70.0005 or less by weight. 11-The process of claim 1, wherein the further reaction of an alkylated polyether polyol with a partially oxy is exothermic. 0 81-Continuous process for the production of polyoxyalkylene polyether polyols having a hydroxyl content of VE to 717.1 by weight comprising: (a) oxy-alkylation in a continuous oxy-ASH reactor in the presence of a double metal cyanide catalyst; (b) A low-molecular-weight initiator sales alkylene oxide is continuously introduced into the continuous oxy-alkylation reactor; where the starting material has at least two hydroxyl groups per molecule and an equivalent weight of 0 up to Yo (c) the partially oxy-alkylated polyether is recovered from the continuous oxy-alkylation reactor; where (1) the oxy-alkylation occurs in the continuous oxy-alkylation reactor at a pressure high enough to prevent quenching of a double metal cyanide catalyst; (1) the concentration of unreacted alkylene oxide in the contents of the continuous reactor remains at a level of 1 to 77 by weight; and (vii) the hydroxyl content VO of the reactor contents is kept at 7.4 to 797.1 by weight; and (ix) a further reaction is allowed for an alkylated polyether polyol with an oxy-molecule recovered from the continuous oxy-alkylation reactor until The unreacted alkylene oxide content of the mixture decreases to 70.009 or less by weight 0 where the build-up ratio in the continuous oxy-alkylation reactor is from ,7 to 16.7 and the total build-up ratio is from 4.7 to VT, and where it is higher The temperature of the reaction mixture in the further reaction step (d) to ©"C as a result of the exotherimc polymerization reaction 80-continuous process to produce a polyether polyol having a hydroxyl content of 7.4 to 797.1 by weight; includes : Yo (a) continuous polymerization of at least one alkylene oxide in the presence of a double metal cyanide catalyst in a continuous reactor; —vo- (b) Feed a low molecular weight starting material having at least two hydroxyl groups each and at least one alkylene oxide to the continuous reactor containing 111 molecules and an equivalent weight of up to an alkylene oxide and a double metal cyanide catalyst; Partially oxy-alkylated polyol mixture recovered from the continuous reactor VATTAAS maintains a continuous reactor at a pressure of 174,819,? to (1) where o is absolute; (1) the concentration of unreacted alkylene oxide in the reactor contents is kept at Yau kg/wt to 77 kg; and (3) the hydroxyl content of the continuous 1 contents is kept at a level of of wt. 1.1 reactor at 4,?to And 01 (c) (Ga) an alkylated polyol mixture is further reacted with the partially oxy drawn from the continuous reactor until the unreacted alkylene oxide content in the mixture is reduced to 70.009 or SE by weight Where the build ratio in the continuous oxy alkylation reactor is from ET to 16.7 and the total build ratio is from 4.6 to OY and as the temperature of the reaction mixture rises in the reaction step The additional Shall to 5 ″ as a result of the reaction of repellent polymerization 1 where the polyol of the resulting polyether has a hydroxyl number of 109 from the protection element YL-001 ee to 01 continuous polymerization for alkylene oxide in the presence of a catalyst Polymetallic cyanide polymerized to form shimmer-171 by weight, where: 797.1 polyether polyols having a hydroxyl content of 7.4 to 01 (a) in the first step; A protocomplex having at least two hydroxyl groups per molecule and an equivalent weight of up to 111 and at least one alkylene oxide is fed into a continuous reactor containing a double metal cyanide catalyst; A partially polymerized mixture is withdrawn from the continuous reactor; Where (1) the continuous reactor is maintained at a pressure of 3.1137815 to YATIAAS kg/Yau absolute; (7) the concentration of unreacted alkylene oxide is maintained in the reactor contents continuous YO at a level of 1 to 77 wt; and (vii) the hydroxyl content of the reaction contents is retained at YE to 797.1 wt; And to add yi (1) (b) in a second step; The partially polymerized mixture withdrawn from the reactor in step SE reacts further until the content of unreacted alkylene oxide in the mixture decreases to 70.009 or by weight and the total build-up ratio is from 176.7 where the build-up percentage in step (a) is 4,7 to and where the temperature of the reaction mixture in step (b) is raised to 5?”C as a result of the VY reaction to 4,1 0 exothermic polymerization. where the resulting polyether polyol has a hydroxyl number of oF) “?-Process from Claim Aan to 1111 is continuous for the production of a hydroxylated polyoxyalkylene polyether polyol of Aleem YY comprising: 5060 to 0 oxy continuous in the presence of a metal cyanide catalyst Double; ASH oxy alkylation in reactor (1) Continuously introduces alkylene oxide and a low molecular weight starting material into the reactor” be (7) to 256 ?; 0 SI of the starting material average weight number and The partially oxy-alkylated polyether polyol is recovered from the (Y)Yo continuous oxyalkylation reactor; the oxy-alkylation in the continuous reactor is at pressure high enough to prevent quenching of pad (1) wherein the double metal cyanide catalyst is; and Alkylation Jolie Win Reacts In addition, an alkylated polyether polyol with oxy (2) 111 continuous oxy, thus forming a polyoxyalkylene polyether polyol with a hydroxyl number of 0 SO, where the building ratio in the continuous oxy alkylation reactor is YY from the protective element Alea Y Sha And where the degree of OY rises, the total building ratio is from 4.16 to 16.7 from 5.6 to the reaction for an alkylated polyether polyol with partially oxy in step (4) to 2270 as a result of a repellent polymerization reaction To heat. Yo to add yy >- the process from the claim YY where the oxy alkylation occurs in the continuous reactor at a temperature of at least 5 712 C. 7- the process from the claim YF where the alkylated polyether polyol reacts with oxy Win recovered from continuous oxy-A reactor in a centrifugal manner Shall 0 77-process from safeguard YY where the alkylated polyether polyol reacts with oxy-Win recovered from the continuous oxy-alkylation reactor until the alkylene oxide content is reduced Unreacted in the mixture to 70,000 or less by weight. Lee YA continuous polymerization of an alkylene oxide in the presence of a metal cyanide polymerization catalyst to form a polyether polyol having a hydroxyl content of 9.4 to 795.1 wt; where: 1 (a) in the first step; A protocomplex having at least two hydroxyl groups per molecule and an equivalent weight of up to 111 and at least one alkylene oxide is fed into a continuous reactor containing a double metal cyanide catalyst; A partially polymerized mixture is withdrawn from the continuous reactor where (1) the continuous reactor is retained at a pressure of 1,178,150 ? to YATIAAS kg/Yau absolute; (7) the unreacted alkylene oxide concentration is retained in the contents of the reactor 1 continuous at a level from 1 to 77 wt; and (vii) the hydroxyl content of the reaction contents is retained at 795.1 Ye wt” and (b) in a later step; the partially polymerized mixture withdrawn from the reactor in step (a) reacts ) additionally until the unreacted alkylene oxide content of the mixture is reduced to 50.001 or less by weight Y. where the building ratio in step (a) is from 1.1 to 16.7 and the total building ratio is from 1 to OLY and where the temperature of the reaction mixture in step (b) is raised to ; M as a result of an exothermic polymerization reaction. Add The validity period of this patent is twenty years from the date of filing the application, provided that the annual financial fee is paid for the patent and that it is not invalid or forfeited for violating any of the provisions of the patent system, layout designs of integrated circuits, plant varieties, and industrial designs, or its executive regulations issued by King Abdulaziz City for Science and Technology; Saudi Patent Office P.O. Box TAT Riyadh 57??11 ¢ Kingdom of Saudi Arabia Email: Patents @kacst.edu.sa