阅读说明：本技术 用于制备低粘度聚氧化烯聚醚多元醇的产物到产物法 (Product-to-product process for preparing low viscosity polyoxyalkylene polyether polyols ) 是由 J·R·里斯 Y·杨 J·F·帕索斯 E·P·布朗 于 2019-12-13 设计创作，主要内容包括：本发明涉及用于制备具有窄分子量分布的低粘度聚氧化烯聚醚多元醇(P)的半分批方法。这种方法包括使H-官能起始剂物质(S-(i))、H-官能起始剂物质(S-(x))和H-官能起始剂物质(S-(c))与一种或多种环氧烷在双金属氰化物(DMC)催化剂存在下反应。所得聚氧化烯多元醇(P)具有2至8的官能度和5至35 mg KOH/g多元醇的羟值。此外,可在低连续添加起始剂(CAOS)封端下完成聚氧烷基化。(The present invention relates to a semi-batch process for preparing low viscosity polyoxyalkylene polyether polyols (P) having a narrow molecular weight distribution. This process comprises reacting an H-functional starter substance (S) i ) H-functional initiator substances (S) x ) And H-functional initiator substances (S) c ) With one or more alkylene oxides in the presence of a Double Metal Cyanide (DMC) catalyst. The resulting polyoxyalkylene polyol (P) has a functionality of 2 to 8 and a hydroxyl number of 5 to 35 mg KOH/g polyol. In addition, polyoxyalkylation can be accomplished with low continuous addition initiator (CAOS) capping.)

1. By H-functional initiator substances (S)_i)、(S_c) And (S)_x) A process for preparing polyoxyalkylene polyols (P) having a functionality of from 2 to 8 and a hydroxyl number of from 5 to 35 mg KOH/g by reaction with one or more alkylene oxides in the presence of a double metal cyanide catalyst (DMC), which comprises

(. alpha.) formation of a substance (S) comprising said H-functional initiator_i) And (S)_x) And an initiator mixture of said double metal cyanide catalyst, and optionally, stripping said initiator mixture with nitrogen under vacuum;

(γ) continuously adding (a) alkylene oxide to the starter mixture of step (α);

and

(delta) continuous addition of the H-functional starter substance (S)_c)；

Wherein

(i) Steps (γ) and (δ) begin simultaneously or step (γ) begins before step (δ);

(ii) the H-functional initiator substance (S)_i) Is the same as the theoretical functionality of the polyoxyalkylene polyol (P), and the H-functional initiator substance (S)_i) Is within 10% of the measured hydroxyl value of the polyoxyalkylene polyol (P);

(iii) the H-functional initiator substance (S)_x) Has an equivalent weight greater than or equal to 10 Da and less than or equal to 250 Da;

(iv) the H-functional initiator substance (S)_c) Has an equivalent weight greater than or equal to 10 Da and less than or equal to 70 Da;

(v) in step (. delta.), an H-functional starter substance (S)_c) Until polyoxyalkylation with alkylene oxide is complete, wherein the H-functional starter substance (S)_c) Until 30 to 95 wt% of the total weight of alkylene oxide has been added in step (y), and then the H-functional starter substance (S)_c) With epoxyThe feed rate ratio of the alkane is reduced to the H-functional starter substance (S)_c) Ratio of final feed rate of alkylene oxide to H-functional starter substance (S)_c) The final feed rate ratio to alkylene oxide is H-functional starter substance (S)_c) 50 to 5% of the initial feed rate ratio of alkylene oxide;

and

(vi) the hydroxyl number is determined according to ASTM D4274-11.

2. The method according to claim 1, further comprising:

(β) adding an activating amount of (b) alkylene oxide to the starter mixture of step (α);

wherein alkylene oxide (a) is continuously added to the mixture formed in (β) in step (γ); and

(v) in step (. delta.), the H-functional starter substance (S)_c) Until polyoxyalkylation with alkylene oxide is complete, wherein the H-functional starter substance (S)_c) The initial feed rate ratio to alkylene oxide is continued until 30 to 95 wt.% of the total weight of alkylene oxide has been added in steps (. beta.) and (. gamma.) and then reduced to the H-functional starter substance (S)_c) The final feed rate ratio to alkylene oxide, which is the H-functional starter substance (S)_c) 50 to 5% of the initial feed rate ratio of alkylene oxide.

3. The process according to claim 1, wherein (ii) the H-functional starter substance (S)_i) Is within 5% of the measured hydroxyl value of the polyoxyalkylene polyol (P).

4. A process according to claim 1, wherein (v) in step (δ), an H-functional starter substance (S)_c) Until polyoxyalkylation with alkylene oxide is complete, wherein the H-functional starter substance (S)_c) Until 30 to 95 wt% of the total weight of alkylene oxide has been added in step (y), and then the H-functional starter substance (S)_c) The feed rate ratio to alkylene oxide is reduced to an H-functional starter substance(S_c) Ratio of final feed rate of alkylene oxide to H-functional starter substance (S)_c) The final feed rate ratio to alkylene oxide is H-functional starter substance (S)_c) 45 to 10% of the initial feed rate of alkylene oxide.

5. A process according to claim 2, wherein (v) in step (δ), the H-functional starter substance (S)_c) Until polyoxyalkylation with alkylene oxide is complete, wherein the H-functional starter substance (S)_c) The initial feed rate ratio to alkylene oxide is continued until 30 to 95 wt.% of the total weight of alkylene oxide has been added in steps (. beta.) and (. gamma.) and then reduced to the H-functional starter substance (S)_c) The final feed rate ratio to alkylene oxide, which is the H-functional starter substance (S)_c) 45 to 10% of the initial feed rate of alkylene oxide.

6. The process according to claim 1, wherein the H-functional starter substance (S)_i) Having a functionality of about 2 to about 8 and a hydroxyl number of 5 to 35.

7. The process according to claim 1, wherein the H-functional starter substance (S)_i) Comprising a polyoxyalkylene polyol containing double metal cyanide catalyst residues.

8. The method of claim 7 wherein said double metal cyanide catalyst residue has been previously exposed to alkylene oxide.

9. The process of claim 7 wherein said double metal cyanide catalyst residue comprises a pre-activated double metal cyanide catalyst previously exposed to alkylene oxide under reaction conditions.

10. The process according to claim 1, wherein the H-functional starter substance (S)_i) Comprising a polyoxyalkylene polyol containing an antioxidant and/or an acid.

11. The process according to claim 1, wherein the H-functional starter substance (S)_x) Having an equivalent weight of about 20 Da to about 70 Da.

12. The process according to claim 1, wherein the H-functional starter substance (S)_x) Comprising ethylene glycol, propylene glycol, butylene glycol, glycerin, water, trimethylolpropane, sorbitol, sucrose, or combinations thereof.

13. The process according to claim 1, wherein the H-functional starter substance (S)_c) Having an equivalent weight of about 30 Da to about 50 Da.

14. The process of claim 1 wherein the alkylene oxide of (a) that is continuously added in (γ) comprises propylene oxide, ethylene oxide, or a combination thereof.

15. The process of claim 2 wherein (b) said alkylene oxide added in (β) comprises propylene oxide, ethylene oxide or combinations thereof.

16. The process according to claim 1, wherein the H-functional starter substance (S)_x) With the H-functional starter substance (S) present in the starter mixture based on step (alpha)_i) Is present in an amount of from 0.1 to 2.0 wt%.

17. The process according to claim 1, wherein the H-functional starter substance (S)_x) And the H-functional starter substance (S)_c) Are the same substance.

18. The process according to claim 1, wherein the H-functional starter substance (S)_c) Comprising ethylene glycol, propylene glycol, butylene glycol, glycerin, water, trimethylolpropane, sorbitol, sucrose, or combinations thereof.

19. The method according to claim 1Process, wherein the H-functional starter substance (S)_c) Further comprising at least one acid.

20. The process according to claim 1, wherein the polyoxyalkylene polyol (P) formed has a functionality of from 2 to 6 and a hydroxyl number of from about 8 to 30.

21. The process according to claim 1, wherein the amount of (a) alkylene oxide added in step (γ) to activate the catalyst is the amount of H-functional starter substance (S) present in the starter mixture of step (α)_i) 1 to 12 wt%.

22. The process according to claim 2, wherein the amount of (b) alkylene oxide added in step (β) to activate the catalyst is the amount of H-functional starter substance (S) present in the starter mixture of step (α)_i) 1 to 12 wt%.

23. The process according to claim 1, wherein (δ) the H-functional starter substance (S) is added continuously_c) Starting before feeding in 4% by weight of the total weight of alkylene oxide fed in from step (. gamma.).

24. The process according to claim 2, wherein (δ) the H-functional starter substance (S) is added continuously_c) Starting before feeding 4% by weight of the total weight of alkylene oxide fed in from steps (. beta.) and (. gamma.).

25. The process according to claim 1, wherein the resulting polyoxyalkylene polyol (P) additionally comprises an antioxidant and/or an acid.

26. The process of claim 1, wherein in step (δ), an H-functional starter substance (S)_c) Final feed rate ratio to alkylene oxide< 1.0%。

27. The process of claim 1, wherein in step (δ) the H-functional starter substance (S) is fed in at a final feed rate ratio_c) Is heavyIn an amount of H-functional starter substance (S)_c) And H-functional initiator substances (S)_x) Of total combined weight of>1% by weight.

28. The process of claim 1, wherein the H-functional initiator species (S)_c) Is a H-functional starter substance (S)_c) And H-functional initiator substances (S)_x) Of total combined weight of>50% by weight.

Technical Field

The present invention relates to an improved process for preparing low viscosity polyoxyalkylene polyols (P). These polyoxyalkylene polyols (P) have a functionality of from 2 to 8 and a hydroxyl (OH) number of from about 5 mg KOH/g polyol to 35 mg KOH/g polyol. The present invention also relates to an improved semi-batch process that eliminates the need to use lower molecular weight polyether polyols to produce higher molecular weight polyether polyols by using a starter charge of the target polyether polyol product and a low equivalent weight starter material as the initial polyether polyol starter mixture.

Background

One challenge in the commercial production of DMC-catalyzed polyols is the inability to directly use low equivalent weight materials, such as propylene glycol, dipropylene glycol, and glycerol, as the major components of the starter mixture. These low equivalent weight starter substances inhibit the catalytic activity of the DMC catalyst when present as the major component of a starter mixture used to produce semi-batch DMC-catalyzed polyether polyols. Initiation of the reaction with such low equivalent weight starter materials also requires special commercial equipment because of the small amount of starter needed to make the higher equivalent weight product. For example, when making a 500 equivalent weight propylene glycol initiated polyether polyol, 7.5 weight percent propylene glycol is required as a low equivalent weight initiator. However, when making 4000 equivalent weight propylene glycol initiated polyether polyols, only 0.95% by weight propylene glycol is required as a low equivalent weight initiator. Thus, the preparation of 4000 equivalent weight propylene glycol initiated polyether polyols requires a large reaction build ratio (built ratio). The reaction growth ratio is defined as the product equivalent weight divided by the starter equivalent weight. Thus, for the propylene glycol initiated 500 EW polyether polyol, the reaction growth ratio was 500/38 or 13.2. In contrast, in the case of the 4000 EW polyether polyol, the growth ratio was 4000/38 or 105. This large reaction growth ratio requires special reaction equipment to operate the low amount of starter required at the start of the process. The minimum reactor charge depends on the mixing configuration (i.e., contacting or covering the lowermost agitator blade) and the heating requirements (i.e., covering sufficient surface area for jacketed or internal heating/cooling systems, or filling the external recirculation loop for external heating/cooling systems). The industry has overcome this challenge of commercial production of products having a wide range of equivalent weights by making and storing starter polyether polyols that can cover the entire range of products to be made. Typically, this may require the storage of more than one initiator polyether polyol. One starter polyether polyol is used to make low to medium equivalent weight products (i.e., those having hydroxyl values of 112 to 28 mg KOH/g polyol) and the other starter polyether polyol is used to make higher equivalent weight products (i.e., those having hydroxyl values of < 28 mg KOH/g polyol). Those skilled in the art will recognize that these starter polyether polyols, referred to herein as low equivalent weight starter polyether polyols, have lower equivalent weights than the target polyether polyol product, but higher equivalent weights than the initial low equivalent weight starter species (i.e., propylene glycol, dipropylene glycol, glycerin, etc.) and are initially loaded into the reactor to provide the minimum charge required for the reactor configuration. The storage of these low equivalent weight starter polyether polyols and their production in the reactor system takes away resources for the manufacture of the final product. Therefore, it is desirable to exclude these low equivalent weight starter polyether polyols.

SUMMARY

The invention relates to the functionalization by HInitiator substance (S)_i)、(S_c) And (S)_x) A process for preparing polyoxyalkylene polyols (P) having a functionality of from 2 to 8 and a hydroxyl number of from 5 mg KOH/g polyol to 35 mg KOH/g polyol by reaction with one or more alkylene oxides in the presence of a double metal cyanide catalyst (DMC). The method comprises

(. alpha.) formation of a H-functional initiator-containing substance (S)_i) H-functional initiator substances (S)_x) And a double metal cyanide catalyst, and optionally, stripping the starter mixture with nitrogen under vacuum;

(γ) continuously adding (a) alkylene oxide to the starter mixture of step (α);

and

(delta) continuous addition of H-functional starter substance (S)_c)；

Wherein

(i) Steps (γ) and (δ) begin simultaneously or step (γ) begins before step (δ);

(ii) h-functional initiator substances (S)_i) Is the same as the theoretical functionality of the polyoxyalkylene polyol (P), and an H-functional initiator substance (S)_i) Is within 10% of the measured hydroxyl value of the polyoxyalkylene polyol (P);

(iii) h-functional initiator substances (S)_x) Has an equivalent weight greater than or equal to 10 Da and less than or equal to 250 Da;

(iv) h-functional initiator substances (S)_c) Has an equivalent weight greater than or equal to 10 Da and less than or equal to 70 Da;

(v) in step (. delta.), an H-functional starter substance (S)_c) Until polyoxyalkylation with alkylene oxide is complete, wherein the H-functional starter substance (S)_c) The initial feed rate ratio to alkylene oxide is continued until 30 to 95 wt% of the total weight of alkylene oxide added in step (. gamma.) has been added, and then the H-functional starter substance (S)_c) The feed rate ratio to alkylene oxide is reduced to the H-functional starter substance (S)_c) Ratio of final feed rate of alkylene oxide to H-functional starter substance (S)_c) The final feed rate ratio to alkylene oxide is H-functional starterTexture (S)_c) 50 to 5% (preferably 45 to 10%, more preferably 40 to 15%) of the initial feed rate ratio of alkylene oxide;

and

(vi) hydroxyl number was determined according to ASTM D4274-11.

The method of the invention may additionally comprise:

(beta) adding an activating amount of (b) one or more alkylene oxides to the starter mixture of step (alpha),

wherein in step (γ) alkylene oxide (a) is continuously added to the mixture formed in (β); and

(v) in step (. delta.), an H-functional starter substance (S)_c) Until polyoxyalkylation with alkylene oxide is complete, wherein the H-functional starter substance (S)_c) The initial feed rate ratio to alkylene oxide is continued until 30 to 95 wt.% of the total weight of alkylene oxide added in steps (. beta.) and (. gamma.) has been added and then reduced to an H-functional starter substance (S)_c) The final feed rate ratio to alkylene oxide, which is the H-functional starter substance (S)_c) From 50 to 5% (preferably from 45 to 10%, more preferably from 40 to 15%) of the initial feed rate of alkylene oxide.

The present invention also relates to a process for producing DMC-catalyzed polyoxyalkylene polyols having a narrow (i.e., symmetrical) molecular weight distribution and low viscosity, and provides an efficient process for making such polyoxyalkylene polyols by eliminating dedicated low equivalent weight starter polyether polyols and using only low equivalent weight starter substances as starter mixtures that are mixed with polyoxyalkylene polyether substances having similar hydroxyl numbers, functionalities and compositions of the product to be made. This may be referred to as a "product-to-product" process, wherein the starter mixture comprises the same product being prepared and a low equivalent weight starter material. Furthermore, the novel process is sustainable (i.e. short cycle time, low catalyst amount, reduced energy consumption, etc.) and it forms a high quality polyol product (i.e. a product with narrow molecular weight distribution and low viscosity).

It is an object of the present invention to provide a process for preparing polyoxyalkylene polyols which exhibit good viscosity and polydispersity without the need to produce and store the low equivalent weight initiator polyether polyols used in the prior art.

Brief Description of Drawings

FIG. 1 is a GPC illustrating the molecular weight distribution of a product prepared by a prior art process without pre-CAOS loading and with 5% non-CAOS capping (cap).

FIG. 2 is a GPC illustrating the molecular weight distribution of a product prepared according to the present invention under pre-CAOS loading and 50% low-CAOS capping.

FIG. 3 is S_cAnd a graphical representation of alkylene oxide feed rate profiles, wherein polyoxyalkylene polyols were made using a non-CAOS capping process. The figure shows that S_cThe alkylene oxide feed rate ratio is constant during the production of the product and once all the continuously added H-functional starter substance (S) has been fed in_c) The product was completed with non-CAOS capping. In other words, there is no continuous addition of H-functional starter substance (S) at the end of the process_c) In the case of (2) alkylene oxide is added.

FIG. 4 is S_cAnd a graphical representation of alkylene oxide feed rate profiles, where polyoxyalkylene polyols were made using a low-CAOS capping process. The figure shows that S_cFeed rate and hence S_cThe alkylene oxide feed rate ratio is decreased in the production process of a polyoxyalkylene polyol, and S_cThe feed is continued until the end of the alkylene oxide feed, thus completing the product with low-CAOS termination. In other words with the continuous addition of H-functional starter substance (S)_c) Continuously added H-functional starter substance (S) added at the beginning of the feed_c) The addition of a lower continuously added H-functional starter substance (S) at the end of the alkylene oxide feed compared to the feed rate ratio of the alkylene oxide_c) To the feed rate of alkylene oxide.

Detailed Description

The invention will now be described for purposes of illustration and not limitation. Other than in the operating examples, or where otherwise indicated, all numerical parameters should be understood as being preceded in all instances by the term "about" and as modified by the term "about," where the numerical parameter has inherent variability characteristics characteristic of the underlying measurement technique used to determine the value of the parameter. Examples of such numerical parameters include, but are not limited to, OH number, equivalent weight and/or molecular weight, functionality, amount, percentage, and the like. At the very least, and not as an attempt to limit the application of the doctrine of equivalents to the scope of the claims, each numerical parameter described in this specification should at least be construed in light of the number of reported significant digits and by applying ordinary rounding techniques.

Any numerical range recited herein is also intended to include all sub-ranges subsumed within the recited range. For example, a range of "1 to 10" is intended to include all sub-ranges between (and including) the recited minimum value of 1 and the recited maximum value of 10, i.e., having a minimum value equal to or greater than 1 and a maximum value of equal to or less than 10. Unless otherwise specified, all endpoints of any range are included. Any maximum numerical limitation recited in this specification is intended to include all lower numerical limitations subsumed therein, and any minimum numerical limitation recited in this specification is intended to include all higher numerical limitations subsumed therein. Accordingly, applicants reserve the right to modify the specification (including the claims) to specifically recite any sub-ranges subsumed within the ranges specifically recited herein. All such ranges are inherently described in this specification, such that modifications explicitly reciting any such subranges are in accordance with the requirements of 35 u.s.c. § 112 and 35 u.s.c. § 132 (a).

As used herein, the grammatical articles "a", "an" and "the" are intended to include "at least one" or "one or more", even if "at least one" or "one or more" is used in some instances, unless otherwise indicated. For example and without limitation, "a component" refers to one or more components, and thus more than one component may be considered and may be employed or used in the practice of the described embodiments. Furthermore, unless the context of such usage requires otherwise, the use of a singular noun includes the plural, and the use of a plural noun includes the singular.

Unless otherwise indicated, equivalent weights and molecular weights given herein in daltons (Da) are number average equivalent weights and number average molecular weights as determined by GPC.

As used herein, the hydroxyl number (OH number) is determined according to STM D4274-11 and is reported in mg [ KOH ]/g [ polyol ].

The viscosity was measured at 25 ℃ on an Anton-Paar SVM 3000 viscometer, which has been shown to give results equivalent to those generated with ASTM-D4878-15. The instrument was calibrated using a mineral oil reference standard of known viscosity.

The number-and weight-average (Mn and Mw, respectively) molecular weights were determined by Gel Permeation Chromatography (GPC) using a method based on DIN 55672-1 using chloroform as eluent and detection by means of a mixed-bed column (Agilent PL Gel; SDVB; 3 μm pore size: 1xMixed-E + 5 μm pore size: 2 xMixed-D), Refractive Index (RI) and calibration with polyethylene glycol as standard.

According to the invention, the process comprises (alpha) forming a starting material (S) comprising an H-function_i) H-functional initiator substances (S)_x) And a starter mixture of a double metal cyanide catalyst, wherein the starter mixture is stripped with nitrogen, optionally under vacuum. Such starter mixtures are usually formed in a reactor. Once the alkylene oxide has been introduced into the reactor, the double metal cyanide catalyst and the H-functional starter substance (S)_i) And (S)_x) Is effective to initiate polyoxyalkylation of the starter mixture.

Suitable H-functional starter substances (S) for use according to the invention_i) Including, for example, polyoxyalkylene polyols having a molecular weight approximately equal to that of the product, i.e., the polyoxyalkylene polyol (P) formed. According to the invention, H-functional starter substances (S)_i) Is the same as the theoretical functionality of the polyoxyalkylene polyol (P), and an H-functional initiator substance (S)_i) Is within 10%, preferably within 5% of the measured hydroxyl value of the polyoxyalkylene polyol (P). Thus, H-functional initiator substances (S)_i) May have a functionality of 2 to 8, or preferably 2 to 6, or more preferably 2 to 3 and an OH number of 5 to 35, or preferably about 8 to 30, or more preferably about 14 to about 28. In a preferred embodiment, the H-functional initiator substance (S)_i) Is the same product as the final target product (based on functionality)And hydroxyl number). This embodiment is achieved by using the end product from a previous production batch as H-functional starter substance (S) of the starter mixture_i) (and thus a product-to-product process) to achieve the goal of eliminating the need to produce a low equivalent weight starter polyether polyol and to store this material using a separate storage tank.

When the H-functional starter substance (S) of the starter mixture_i) When a polyoxyalkylene polyol is included, such polyoxyalkylene polyol may be a known residual amount of product remaining in the reactor from a previous batch of the same product. Such polyoxyalkylene polyols may be prepared from the same reactants as the final product prepared by the process of the present invention, have the same functionality, molecular weight and hydroxyl number as the final product obtained from the process of the present invention, and are therefore substantially the same as the final product prepared by the process as claimed. However, the skilled person will recognize that it is not actually the same product as the final product, as it is prepared in a different batch or reactor batch. As an example, after production of a batch of polyoxyalkylene polyol by DMC catalysis in the reactor is complete, 90% of the product is removed from the reactor. The remaining 10% of the polyoxyalkylene polyol product may remain in the reactor and be used as the H-functional starter substance (S) of the starter mixture of the present invention_i). It is also possible for the H-functional starter substance (S) of the starter mixture to be_i) May comprise the final polyoxyalkylene polyol product from a previous production run (previous campaign) stored in a finished storage vessel, which may serve as the H-functional starter material (S) for the starter mixture_i) And is returned to the reactor. H-functional starter substance (S) of the starter mixture_i) It may also comprise a final polyoxyalkylene polyol product of similar molecular weight to the target product made using basic catalysis (KOH or equivalent) and refined to remove or neutralize the basic catalyst. For example, when such a product is used as an H-functional initiator material (S) for the initial or first production of a polyoxyalkylene polyol (P) product_i) When this is the case, it is necessary to use a polyoxyalkylene product which is catalyzed by bases and subsequently neutralized. Those skilled in the art will recognize that even trace amounts of base or alkalinity will resultDeactivating or suppressing the DMC catalyst present in the starter mixture is required from use as an H-functional starter substance (S)_i) The basic catalyst is removed or neutralized in the final polyoxyalkylene polyol product. In all cases, when polyoxyalkylene polyols are used as H-functional starter substances (S)_i) When used, the polyoxyalkylene polyol serves as the reaction medium to provide the minimum starter charge required for the reactor configuration (e.g., covering the agitator blades, filling the recirculation loop, covering the internal heating/cooling coils, etc.). In one embodiment, H-functional starter substances (S) are used as starter mixtures_i) The polyoxyalkylene polyol of (b) has the same molecular weight and alkylene oxide composition as the target final polyoxyalkylene polyol product (P). In one embodiment, H-functional starter substances (S) are used as starter mixtures_i) The polyoxyalkylene polyol of (a) does not substantially participate in the reaction. H-functional starter substance (S) of starter mixture comprising polyoxyalkylene polyol_i) Provides an opportunity to produce a final polyoxyalkylene polyol product (P) having a narrow molecular weight distribution and a low viscosity. In one embodiment, this H-functional starter substance (S) comprises a starter mixture of polyoxyalkylene polyols_i) Containing double metal cyanide catalyst residues. In one embodiment, the double metal cyanide catalyst residue was previously exposed to alkylene oxide. In one embodiment, H-functional starter substances (S) are used as starter mixtures_i) The double metal cyanide catalyst residue of the polyoxyalkylene polyol of (a) was previously exposed to alkylene oxide under reaction conditions ("pre-activated" catalyst).

H-functional starter substance (S) comprising polyoxyalkylene polyols_i) Antioxidants and/or acids known to those skilled in the art may be included. For example, suitable antioxidants for polyoxyalkylene polyols include hindered phenolic compounds such as BHT (i.e., butylated hydroxytoluene), octadecyl 3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate (i.e., Irganox 1076), 3, 4-dihydro-2, 5,7, 8-tetramethyl-2- (4,8, 12-trimethyltridecyl) -2H-1-benzopyran-6-ol (i.e., Irganox E-201), and the like. Examples of suitable acids include, for exampleAny inorganic protic inorganic or organic acid known to be suitable in the art. Phosphoric acid is one example of a suitable acid.

H-functional starter substances (S) possibly comprising polyoxyalkylene polyols_i) Steam and/or nitrogen vacuum stripping may be used to remove any residual compounds introduced by the reaction or starting materials. H-functional initiator substances (S)_i) Can be carried out with addition of H-functional starter substance (S)_x) Before or after. H-functional initiator substances (S)_i) The stripping of (2) can also be carried out before or after the addition of the double metal cyanide catalyst.

Use as low equivalent weight H-functional starter substance (S)_x) Have an equivalent weight of less than or equal to 250 Da, or preferably less than or equal to 70 Da, or more preferably less than or equal to 50 Da. Use as low equivalent weight H-functional starter substance (S)_x) Suitable compounds of (a) may also have an equivalent weight of greater than or equal to 10 Da, preferably greater than or equal to 20 Da, more preferably greater than or equal to 30 Da. Thus, H-functional initiator substances (S)_x) There may be an equivalent weight between any combination of these upper and lower values, for example, greater than or equal to 10 Da to less than or equal to 250 Da, or preferably greater than or equal to 20 Da to less than or equal to 70 Da, or more preferably greater than or equal to 30 Da to less than or equal to 50 Da. Suitable compounds include, for example, compounds having a functionality of 2 to 8 or preferably 2 to 3. As H-functional initiator substances (S)_x) Some examples of suitable compounds of (a) include diols and triols, such as ethylene glycol, propylene glycol, butylene glycol, glycerol, water, Trimethylolpropane (TMP), sorbitol, sucrose, and other low equivalent weight polyoxyalkylene polyols having equivalent weights within the above ranges. In one embodiment, the low equivalent weight H-functional starter substance (S) of the starter mixture_x) Can be fed continuously with H-functional starter substance (S)_c) The same substance.

Low equivalent weight H-functional initiator material (S)_x) With a polyoxyalkylene polyol H-functional starter substance (S) based on the starter mixture of step (. alpha.)_i) 0.1 to 2.0% by weight (c)Or 0.25 to 1.75 wt.%, or 0.5 to 1.5 wt.%). Low equivalent weight H-functional initiator material (S)_x) Polyoxyalkylene polyol H-functional initiator materials (S) which can be in the above initiator mixtures_i) Before, after or simultaneously to the reaction vessel. Low equivalent weight H-functional initiator material (S)_x) The DMC catalyst may be added to the reaction vessel before, after, or simultaneously with the DMC catalyst. Low equivalent weight H-functional initiator material (S)_x) Polyoxyalkylene polyol H-functional initiator materials (S) which can be in initiator mixtures_i) And the DMC catalyst is added before or after bubbling with nitrogen under vacuum. Low equivalent weight H-functional initiator material (S)_x) It is necessary to add the polyoxyalkylene polyol H-functional initiator material (S) prior to adding the alkylene oxide to the reaction vessel_i) And DMC catalysts. The presence of a low equivalent weight H-functional starter substance (S) in the starter mixture formed in (. alpha.)_x) Known as "pre-CAOS" ((pre-CAOS))Continuous Addition of Starter) (continuous addition of starter) charge.

Low equivalent weight H-functional initiator species (S) may be used_x) Addition of acid to the Low equivalent weight H-functional Starter substance (S) before or after addition to the reaction vessel_x) In (1). The acid may be any inorganic protic inorganic or organic acid known to be suitable as described in the art. Typically, to a low equivalent weight H-functional initiator material (S)_x) The amount of acid in (A) is based on the low equivalent weight of the H-functional starter substance (S)_x) 30 to 250 ppm by weight. Phosphoric acid is one example of a suitable acid.

Suitable double metal cyanide catalysts for use in the present invention include any DMC catalyst known in the art. Well known DMC catalysts are typically the reaction product of a water soluble metal salt (e.g., zinc chloride) and a water soluble metal cyanide salt (e.g., potassium hexacyanocobaltate). The preparation of DMC catalysts is described in various references, including, for example, U.S. Pat. nos. 5,158,922, 4,477,589, 3,427,334, 3,941,849, 5,470,813, and 5,482,908, the disclosures of which are incorporated herein by reference. A particular DMC catalyst that is preferred in some embodiments of the invention is zinc hexacyanocobaltate. In one embodiment, the DMC catalyst is non-crystalline.

The DMC catalyst comprises an organic complexing agent. As taught in the aforementioned references, complexing agents are required for the active catalyst. Preferably, the complexing agent comprises a water-soluble heteroatom-containing organic compound that is capable of complexing with the DMC compound. In one embodiment, it is preferred that the complexing agent is a water-soluble aliphatic alcohol. Tert-butanol is a preferred complexing agent for some embodiments. In addition to the organic complexing agent, the DMC catalyst may also include a polyether as described in U.S. patent 5,482,908, the disclosure of which is incorporated herein by reference.

Preferred DMC catalysts for use in accordance with one or more embodiments of the present process are high activity DMC catalysts as described in U.S. Pat. nos. 5,482,908 and 5,470,813. The high activity allows the use of very low concentrations of catalyst. More specifically, the desired catalyst concentration is generally low enough to overcome or eliminate any need to remove the catalyst from the final polyoxyalkylene polyol product (P) formed in the process. In particular, the catalyst concentration is generally in the range of 10 ppm to 300 ppm, or 20 ppm to 200 ppm, or 30 ppm to 100 ppm based on the weight of the final polyoxyalkylene polyol (P).

The DMC catalyst can be added directly to the starter mixture as a dry powder or dispersed in the H-functional starter substance (S described above)_iOr S_x) And added to the starter mixture. DMC catalyst added to the starter mixture with H-functional starter substance (S) used as starter mixture_i) The DMC catalyst residues contained in the polyoxyalkylene polyol of (1) were the same. The DMC catalyst added to the starter mixture may be an unactivated or fresh catalyst, i.e., a catalyst that has not been previously exposed to an alkylene oxide, that has been under non-reactive conditions (i.e., temperature)<90 ℃) catalyst exposed to alkylene oxide; or "preactivated" catalysts, i.e., catalysts that have been previously exposed to alkylene oxide under reaction conditions (i.e., temperatures ≧ 90 ℃). Polyoxyalkylene polyol H-functional initiator materials (S) of initiator mixtures_i) The DMC catalyst residue in (A) is considered to be a "pre-activated" catalyst because such a catalyst is initiatedPolyoxyalkylene polyol H-functional initiator materials (S) of the agent mixture_i) Is exposed to alkylene oxide under reaction conditions. Polyoxyalkylene polyol H-functional initiator materials (S) of initiator mixtures_i) The "preactivated" catalysts in (A) are advantageous for the present invention, so that the starter mixture is rapidly activated on addition of alkylene oxide and counteracts the low equivalent weight of H-functional starter substance (S) present in the starter mixture_x) Known inhibitory effects of (a). Polyoxyalkylene polyol H-functional initiator material (S) from initiator mixture_i) The combination of the "preactivated" catalyst and the fresh or "preactivated" catalyst added to the starter mixture also ensures that the H-functional starter substance (S) added continuously is added_c) Good reaction (i.e. no rapid pressure increase or temperature fluctuations). The DMC catalyst added to the starter mixture can be reacted with the polyoxyalkylene polyol H-functional starter substance (S) of the starter mixture_i) The residual catalyst or "pre-activated" catalyst in (a) is the same or different.

The DMC catalyst, which may be fresh catalyst or preactivated catalyst, is typically added to the starter mixture. However, it can also be divided between the starter mixture and the continuously added H-functional starter substance (S)_c) In the meantime. Splitting the DMC catalyst and reacting with an H-functional starter substance (S)_c) The continuous feeding of DMC catalyst provides a lower initial catalyst concentration in the starter mixture and a more uniform catalyst concentration during the production of the polyoxyalkylene polyol product (P).

In the process of the present invention, the DMC catalyst present in the starter mixture is activated in the presence of alkylene oxide. Activation of the DMC catalyst present in the starter mixture is effected by optionally (β) adding an activating amount of (b) alkylene oxide to the starter mixture formed in (α). The activated alkylene oxide used for the starter mixture can be added in one portion to the starter (S) of step (. alpha.)_i、S_xAnd DMC catalyst) in a reactor system, wherein the pressure in the reactor system will increase rapidly, or the alkylene oxide may be added slowly during an initial ramp-up (initial ramp-up) of the alkylene oxide feed, wherein the reaction is reversedThe pressure in the reactor system will slowly increase. Activation of the DMC catalyst present in the starter mixture is detected when a drop in pressure to half the peak pressure amount is detected in the case of rapid addition of alkylene oxide or when the pressure begins to drop and the reactor system begins to cool the reaction (indicating that a reaction is present) in the case of slow addition of alkylene oxide. The amount of alkylene oxide added for activation is based on the H-functional starter substance (S) present in the starter mixture_i) In an amount of 1 to 12 wt%. As used herein, the amount of alkylene oxide necessary to activate the DMC catalyst present in the starter mixture of step (a) may be referred to as "initial" or "activated" alkylene oxide.

In the presence of a low equivalent weight H-functional starter substance (S)_x) With the addition of the H-functional starter substance (S) continuously at the beginning (delta)_c) Is reacted with an activating amount of (b) alkylene oxide added to the starter mixture of step (alpha) in step (beta) during activation of the DMC catalyst or (a) alkylene oxide during an initial ramp of the continuous addition of alkylene oxide in step (gamma). Starting in step (. delta.) with an H-functional starter substance (S)_c) Before the continuous addition of a low equivalent weight H-functional starter substance (S)_x) Reaction with an activating or initial amount of alkylene oxide prevents the H-functional starter substance (S) used as starter mixture_i) With such an activated or initial amount of alkylene oxide and the polydispersity of the final polyoxyalkylene polyol product (P) is increased. Low equivalent weight H-functional initiator material (S)_x) Must be added to the starter mixture in an amount sufficient to react with the activated and/or initial alkylene oxide (i.e., at the start (. delta.) of the H-functional starter species (S)_c) Prior to continuous addition) and limiting the amount of polyoxyalkylene polyol H-functional starter material (S) consisting of an activated and/or initial amount of alkylene oxide in admixture with the starter_i) The reaction of (a) results in an increase in the polydispersity and viscosity of the final polyoxyalkylene polyol (P) product. However, too much of the low equivalent weight H-functional starter substance (S) is added_x) Will result in no or slow reaction of the activated and/or initial amount of alkylene oxide and possibly inhibit the DMC catalyst toResulting in the production of low quality products (i.e., products having high polydispersity and high viscosity). It is known and understood by the skilled artisan that the lowest equivalent weight species is preferably reacted with alkylene oxide in the presence of DMC catalyst, and thus a low equivalent weight H-functional starter species (S)_x) Will preferentially react with the activating amount and/or the initial amount of alkylene oxide present. This is well known to those of ordinary skill in the art and is known as "catch-up kinetics". The catch-up kinetics are described in "Chemistry and Technology of Polyols for Polyurethanes", 2 nd edition, volume 1, 2016, M. Ionescu, page 189-.

The process of the present invention additionally comprises a step (γ) of continuously adding (a) alkylene oxide to the mixture of step (β) when step (β) is present or to the mixture of step (α) when step (β) is absent. Such continuous addition includes starting and increasing the addition of alkylene oxide in a steady state manner until the final target feed rate of alkylene oxide is reached. The ramping up of the alkylene oxide feed(s) typically takes 5 to 35 minutes before the final target feed rate(s) is reached.

Suitable alkylene oxides for use as alkylene oxide (a) and/or (b) according to the present invention include, but are not limited to, compounds such as ethylene oxide, propylene oxide, 1, 2-and 2, 3-butylene oxide, isobutylene oxide, epichlorohydrin, cyclohexene oxide and styrene oxide. In addition to the alkylene oxide block(s), carbon dioxide can be added in combination with the alkylene oxide(s) to form the polyether carbonate polyol. The alkylene oxide(s) used as component (a) and/or (b) in the present invention may be the same or different.

According to the invention, the process additionally comprises (delta) continuous addition of H-functional starter substance (S)_c)。

Used as a continuously added H-functional starter substance (S)_c) Suitable compounds of (b) include, for example, compounds having a (nominal) hydroxyl functionality of at least about 2 to about 8, or preferably about 2 to about 3, and having an equivalent weight of greater than or equal to 10 Da, or at least 30 Da, and less than or equal to70 Da, or preferably less than or equal to about 50 Da. Thus, H-functional initiator substances (S)_c) There may be an equivalent weight between any combination of these upper and lower values, for example, greater than or equal to 10 Da to less than or equal to 70 Da, or preferably about 30 Da to about 50 Da. As H-functional starter substance (S) continuously added in this context_c) Suitable compounds of (a) include, for example, but are not limited to, compounds such as ethylene glycol, propylene glycol, butylene glycol, water, glycerol, trimethylolpropane, sorbitol, sucrose, and the like. Mixtures of monomeric initiators or their oxyalkylated oligomers may also be used. Continuously added H-functional initiator substance (S)_c) A low equivalent weight H-functional starter substance (S) which can be mixed with the starter mixture formed in step (alpha)_x) The same or different.

In one embodiment of the invention, a continuously added H-functional starter substance (S)_c) Selected from propylene glycol and/or glycerol. In one embodiment, a continuously added H-functional starter substance (S)_c) With low equivalent weight H-functional starter substance (S) in the starter mixture_x) The same is true. In one embodiment, a continuously added H-functional starter substance (S)_c) Is a continuously added H-functional starter substance (S)_c) And a low equivalent weight H-functional initiator material (S)_x) Greater than 50 wt% of the total combined weight of (a), which can be expressed as: (S)_c / (S_c + S_x) >50%). This embodiment provides sufficient continuous addition of H-functional starter substance (S)_c) To provide good exchange on the catalyst surface, which is essential for good product quality (i.e. viscosity and molecular weight distribution).

Continuously added H-functional initiator substance (S)_c) Acidification with small amounts of a suitable acid may be achieved as described, for example, in U.S. patent 6,077,978 and U.S. patent 7,919,575. The acid may be any inorganic protic inorganic or organic acid known to be suitable as described in the art. Usually, to a continuously added H-functional starter substance (S)_c) The amount of acid in (A) is based on the continuously added H-functional starter substance (S)_c) 30 to250 ppm. In one embodiment, a continuously added H-functional starter substance (S)_c) Containing 120 to 240 ppm of acid. Phosphoric acid is one example of a suitable acid.

In the process of the invention, the H-functional starter substance (S) is started in step (. delta.)_c) And may be ramped up simultaneously with the continuous addition of alkylene oxide in step (γ). Before 4% by weight (preferably 2% by weight) of the total weight of alkylene oxide fed in from step (. gamma.) or from steps (. beta.) and (. gamma.), including the weight of alkylene oxide fed in order to activate the DMC catalyst present in the starter mixture, has been fed in, the continuous addition of H-functional starter substance (S) is started_c)。

According to the invention, an H-functional starter substance (S) is achieved_i、S_xAnd S_c) Polyoxyalkylation with alkylene oxide from step (. gamma.) and optionally from step (. beta.) to form polyoxyalkylene polyol (P) having a functionality of 2 to 8 and an OH number of about 5 to 35. The polyoxyalkylene polyol (P) formed by the process of the present invention typically has a functionality of from 2 to 8, or preferably from 2 to 6, or more preferably from 2 to 3 and an OH number of from about 5 to 35, or preferably from about 8 to 30, or more preferably from about 14 to about 28.

In the process of the invention, (i) steps (γ) and (δ) are started simultaneously or step (γ) is started before step (δ); (ii) h-functional initiator substances (S)_i) Is the same as the theoretical functionality of the polyoxyalkylene polyol (P), and an H-functional initiator substance (S)_i) Is within 10%, or preferably within 5% of the measured hydroxyl value of the polyoxyalkylene polyol (P); (iii) h-functional initiator substances (S)_x) Has an equivalent weight greater than or equal to 10 Da and less than or equal to 250 Da, or preferably greater than or equal to 20 Da and less than or equal to 70 Da, or more preferably greater than or equal to 30 Da to less than or equal to 50 Da; (iv) h-functional initiator substances (S)_c) Has an equivalent weight greater than or equal to 10 Da and less than or equal to 70 Da; (v) in step (. delta.) an H-functional starter substance (S)_c) Until polyoxyalkylation with alkylene oxide is complete, with a continuously added H-functional starter substance (S)_c) With alkylene oxidesUntil from 30 to 95% by weight of the total weight of the alkylene oxide is added to the reactor, and then a continuous addition of H-functional starter substance (S)_c) The feed rate ratio to alkylene oxide is reduced to a continuously added H-functional starter substance (S)_c) A final feed rate ratio to alkylene oxide, wherein the final feed rate ratio is a continuously added H-functional starter substance (S)_c) 50 to 5% (preferably 45 to 10%, more preferably 40 to 15%) of the initial feed rate ratio of alkylene oxide(s); and (vi) determining the hydroxyl number according to ASTM D4274-11.

In the process of the invention, (v) an H-functional starter substance (S) added continuously in step (. delta.) (S)_c) Until polyoxyalkylation with the alkylene oxide is complete. At the end of step (. delta.) by reducing the continuously added H-functional starter substance (S)_c) Ratio to feed rate of alkylene oxide to complete the continuous addition of H-functional starter material (S)_c) Or (2) is added. Continuously added H-functional initiator substance (S)_c) The final feed rate ratio to alkylene oxide is continuously added H-functional starter substance (S)_c) 50 to 5% of the initial feed rate ratio of alkylene oxide. Continuously added H-functional initiator substance (S)_c) The instantaneous feed rate ratio to alkylene oxide (referred to herein as the feed rate ratio) is defined as the continuously added H-functional starter substance (S) fed in_c) Feed rate of (a)/feed rate of alkylene oxide. Continuously added H-functional initiator substance (S)_c) The initial feed rate ratio to alkylene oxide is defined as the ratio of the H-functional starter substance (S) added continuously at a reduced level_c) Is fed in at a feed rate of_c) Feed rate of (a)/feed rate of alkylene oxide. Continuously added H-functional initiator substance (S)_c) The final feed rate ratio to alkylene oxide is defined as the ratio of the H-functional starter substance (S) added continuously_c) With a reduced feed rate of a continuously added H-functional starter substance (S)_c) Feed rate of (a)/feed rate of alkylene oxide. Such a decrease in the initial feed rate ratio to the final feed rate ratio results in the production of a polyoxyalkylene polyol (P) as shown in FIG. 4low-CAOS termination formed above. More specifically, FIG. 4 illustrates alkylene oxide and H-functional initiator species (S)_c) How the feed rate profile of (c) varies during the process to form a low CAOS cap on the polyoxyalkylene polyol product (P). In FIG. 4, 1 represents the feed rate (in g/min) distribution of the alkylene oxide and 2 represents the H-functional starter substance (S)_c) Distribution of the feed rates in g/min, 3 represents the added H-functional starter substance (S)_c) To the initial feed rate of alkylene oxide until a specified amount (i.e., 30 to 95 weight percent) of alkylene oxide is added to the reactor, 5 representing the specified amount (i.e., 50 to 5 percent) of H-functional starter material (S) reduced to the initial feed rate ratio_c) To alkylene oxide, thereby forming a low-CAOS end-cap on the final polyoxyalkylene polyol product (P), 6 represents a reduced H-functional starter species (S) by addition at the end of the process_c) low-CAOS cap formation compared to the feed rate of alkylene oxide.

Determination of the continuously added H-functional initiator substance (S)_c) Another method of ratio to alkylene oxide is to use a continuously added H-functional starter substance (S) fed in at a constant ratio_c) Weight of (c)/weight of alkylene oxide. Continuously added H-functional initiator substance (S)_c) The initial weight ratio to alkylene oxide is defined as the ratio of the H-functional starter substance (S) added continuously_c) Until the continuous addition of H-functional starter substance (S)_c) Is reduced, is fed with H-functional starter substance (S)_c) Weight of (c)/weight of alkylene oxide. Continuously added H-functional initiator substance (S)_c) The final weight ratio to alkylene oxide is defined as the weight ratio of the H-functional starter substance (S) added continuously_c) Until a continuous addition of H-functional starter substance (S)_c) At the end of this time, H-functional starter substance (S) is fed in_c) Weight of (c)/weight of alkylene oxide.

At the end of the reaction without continuous addition of H-functional starter substance (S)_c) The feeding of alkylene oxide in this case is referred to as "non-CAOS" capping. Feeding a continuously added H-functional starter substance at a constant ratio: (S_c) Until 100% of the target alkylene oxide is added means that 0% of the "non-CAOS" end-capping of the product is present. The term "non-CAOS" end-capping is defined as the end of a batch without the continuous addition of H-functional initiator species (S)_c) In the case of (2) the amount of alkylene oxide fed is divided by the total batch weight. FIG. 3 illustrates a non-CAOS capping method. More specifically, FIG. 3 illustrates alkylene oxide and H-functional initiator species (S)_c) How the feed rate profile of (c) varies during the process to form a non-CAOS end-capping on the polyoxyalkylene polyol product (P). In FIG. 3, 1 represents the feed rate (in g/min) distribution of the alkylene oxide and 2 represents the H-functional starter substance (S)_c) Distribution of the feed rates in g/min, 3 represents the added H-functional starter substance (S)_c) With alkylene oxide until all H-functional starter substance (S) has been added_c) And 4 represents the H-functional starter substance (S) at the end of the process by adding it without succession_c) In the case of (2) a non-CAOS cap formed by the addition of alkylene oxide. In other words, when at the end of the process there is no continuous addition of H-functional starter substance (S)_c) When an alkylene oxide is added in the case of (B), a non-CAOS cap is formed on the polyoxyalkylene polyol product (P).

At the end of the batch, a continuously added H-functional starter substance (S) is used_c) The process with the final reduced feed rate ratio of alkylene oxide is referred to as "low-CAOS" capping (see fig. 4). The "low-CAOS" capping ratio or percentage is defined as the amount of alkylene oxide fed at the final reduced feed rate ratio divided by the total batch weight. In this aspect of the invention, a continuously added H-functional starter substance (S)_c) The ratio of initial feed rate to alkylene oxide is higher than that of the continuously added H-functional starter substance (S)_c) To the final feed rate of alkylene oxide. Continuously added H-functional initiator species (S) in a "Low-CAOS" capping process_c) The change or reduction in the feed rate ratio to alkylene oxide is carried out when from 30 to 95% by weight of the total weight of alkylene oxide which has been added in step (. gamma.) or, when present (. beta.) in steps (. beta.) and (. gamma.). Continuously added H-functional initiator substance (S)_c) Andthe final feed rate ratio of the alkylene oxide is less than the continuously added H-functional starter substance (S)_c) To the initial feed rate of alkylene oxide. H-functional starter substance (S) added continuously at the end of the batch_c) The low ratio feed with alkylene oxide promotes the exchange on the catalyst surface at the end of the batch when the hydroxyl concentration is low and produces a product with a narrow molecular weight distribution and low viscosity. The "low-CAOS" end-capping helps to prevent the molecular weight distribution from shifting towards higher molecular weights and helps to maintain a symmetrical distribution. A reduced rate or reduced amount of a continuously added H-functional starter substance (S) added near the end of the alkylene oxide feed_c) It also surprisingly does not shift the molecular weight distribution towards lower molecular weights as would be expected for a 0% "non-CAOS" end-capping, provided that the H-functional starter species (S) is continuously added_c) The final feed rate ratio to alkylene oxide is continuously added H-functional starter substance (S)_c) 50 to 5% of the initial feed rate ratio of alkylene oxide. Such "low CAOS" end-capping is particularly beneficial in the preparation of polyoxyalkylene polyol products (P) having equivalent weights equal to or greater than 4000, because of the continuously added H-functional starter species (S) required for the production of these products_c) Low amounts and an increased tendency to produce higher viscosity products.

In one embodiment of the invention, a continuously added H-functional starter substance (S)_c) The final feed rate ratio to alkylene oxide is less than 1.0% ((H-functional starter substance (S) fed in the course of the final feed rate ratio)_c) Feed rate of (c)/feed rate of alkylene oxide fed during the final feed rate ratio) × 100). In another embodiment of the invention, the continuously added H-functional starter substance (S) is added at the final feed rate ratio_c) Is a continuously added H-functional starter substance (S)_c) And H-functional initiator substances (S)_x) Of total combined weight of>1.0% (i.e. (S added at the final feed rate ratio)_cWeight of (1)/S_cWeight of + S_xTotal weight of (d) × 100). These embodiments ensure that there is a sufficient amount of H-functional starter substance (S) added continuously_c) To promote exchange on the catalyst surface but limit the final feed rate ratio to prevent shifts in molecular weight distribution.

According to one embodiment of the invention, a "low-CAOS" termination may be followed by a "non-CAOS" termination.

According to the invention, in step (. delta.) an H-functional starter substance (S) is added continuously_c) When added to the reaction mixture, must be reacted with a continuously added H-functional starter substance (S)_c) At the same time, alkylene oxide is added. In the presence of a continuously added H-functional starter substance (S)_c) If for any reason, the addition of the H-functional starter substance (S) is continued_c) Or the feed of alkylene oxide is interrupted and stopped and the other feed must also be stopped. When restarting after a feed interruption, both feeds must start and ramp up simultaneously. Without the continuous addition of H-functional initiator species (S) prior to non-CAOS capping_c) The feeding of alkylene oxide feed can significantly change the molecular weight distribution and increase the product viscosity even if the correct amount of continuously added H-functional starter substance (S) is added later in the batch_c) (thus achieving the correct hydroxyl number or equivalent weight). The continuously added H-functional starter substance (S) is fed in without alkylene oxide_c) DMC catalyst reactivity problems can result when the alkylene oxide feed is restarted, including DMC catalyst deactivation and/or temperature drift, which results in undesirable changes in molecular weight distribution and viscosity.

According to the invention, the process is typically carried out in a stainless steel reaction vessel (e.g., 35 liters or more) equipped with an electrically heated jacket and internal coils that can be used to heat or cool the reaction mixture. Steam, water, or a combination of both, may be passed through the cooling coil to control the reaction temperature. Temperature regulated water (tempered water) or hot oil systems may also be used to control temperature. The reactor system comprises a mechanical stirrer which may be equipped with a single stirring device, such as a gate mixer or anchor mixer or other such devices known to those skilled in the art. The agitator may also be equipped with one or more mixers, such as a pitched blade impeller, Rushton-type impeller, flat blades, curved blades, pitched blades, or other such devices known to those skilled in the art. These vanes may be used independently or in combination. The stirrer speed may be constant or variable during the batch. The reactor internals may include baffles. The reactor may also be equipped with a recirculation pump loop which takes the reaction mixture from the bottom of the reactor and pumps it back to the reactor via a dip tube or spray nozzle in the upper part of the reactor or via a dip tube or spray ring in the bottom of the reactor. The recirculation loop may include a heat exchanger for temperature control or may include a static mixing device. The reactor and associated metering and monitoring equipment are connected to a digital process control system.

The reactor system includes an alkylene oxide metering system for one or more alkylene oxide feeds (e.g., propylene oxide and/or ethylene oxide). When more than one alkylene oxide is used, these alkylene oxides may be introduced together or separately into the reactor. They may be mixed and fed together, or they may be stored separately and mixed using static mixing means prior to introduction into the reactor. The alkylene oxide can be introduced into the headspace of the reactor via a dip tube or spray nozzle, or into the liquid phase in the reactor via a dip tube or spray ring. The mixing impeller can be optimized to match the alkylene oxide addition location to provide a high shear/mixing zone near the alkylene oxide injection location. The alkylene oxide can also be introduced into the recirculation line directly or by means of a static mixing device.

The reactor system comprises an H-functional starter substance (S) for continuous addition_c) The metering system of (1). When more than one successively added H-functional starter substance (S) is used_c) When this is the case, these may be introduced into the reactor together or separately. They may be mixed and fed together, or they may be stored separately and mixed using static mixing means prior to introduction into the reactor. Continuously added H-functional initiator substance (S)_c) Can be introduced into the headspace of the reactor via a dip tube or spray nozzle, or into the liquid phase in the reactor via a dip tube or spray ring. The mixing impeller can be optimized to match the continuously added H-functional starter substance (S)_c) The position of the addition point, so as to add the H-functional initiator substance (S) continuously_c) A high shear/mixing zone is provided near the injection location. Continuously added H-functional initiator substance (S)_c) Or can also be usedThe recirculation line is introduced directly or by means of a static mixing device. Continuously added H-functional initiator substance (S)_c) It is also possible to premix with the alkylene oxide and introduce it directly into the reactor via a dip tube or a spray ring or via a static mixing device. The alkylene oxide feed may be metered in the range of 0.25 hours to 20 hours, depending on the reactor configuration (mixing) and heat removal capacity.

The final polyoxyalkylene polyol product (P) of the present invention containing residual DMC catalyst may be vacuum stripped with steam and/or nitrogen to remove any residual compounds introduced by the reaction or starting materials. The final polyoxyalkylene polyol product (P) is also typically inhibited with antioxidants as known to the skilled person. Examples of suitable antioxidants for the polyether polyols include hindered phenolic compounds such as BHT (i.e., butylated hydroxytoluene), octadecyl 3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate (i.e., Irganox 1076), 3, 4-dihydro-2, 5,7, 8-tetramethyl-2- (4,8, 12-trimethyltridecyl) -2H-1-benzopyran-6-ol (i.e., Irganox E-201), or other equivalent antioxidants or inhibitors. The final polyoxyalkylene polyol product (P) may also be acidified with any inorganic protic inorganic or organic acid as is known to be suitable as described in the art. The final polyoxyalkylene polyol product (P) is preferably inhibited with an antioxidant in advance of steam and/or nitrogen vapor. The additional inhibitor may be added after stripping (with or without steam and/or nitrogen present), and any acid additive is preferably added after stripping (with or without steam and/or nitrogen present), if desired. The final inhibitor and/or acid may be added directly to the stripping vessel, or to the storage vessel, or may be added continuously to the product in a transfer line between the stripping vessel and the storage vessel. Alternatively, the polyoxyalkylene polyol product (P) may be stored with the antioxidant alone, and any desired acid may be added to the storage vessel or to the shipping vessel prior to shipping — either directly to the vessel or continuously to the transfer line between the storage vessel and the shipping vessel or prior to use of the final product.

In a first embodiment, the present invention relates to the synthesis of a compound via an H-functional initiator species (S)_i)、(S_c) And (S)_x) With alkylene oxidesA process for preparing polyoxyalkylene polyols (P) having a functionality of from 2 to 8 and a hydroxyl number of from 5 to 35 mg KOH/g by reaction in the presence of a double metal cyanide catalyst (DMC), which comprises (. alpha.) forming a polyoxyalkylene polyol comprising the H-functional starter substance (S)_i) And (S)_x) And an initiator mixture of said double metal cyanide catalyst, and optionally, stripping said initiator mixture with nitrogen under vacuum; (γ) continuously adding (a) alkylene oxide to the starter mixture of step (α); and (delta) continuously adding the H-functional starter substance (S)_c) (ii) a Wherein (i) steps (γ) and (δ) begin simultaneously or step (γ) begins before step (δ); (ii) the H-functional initiator substance (S)_i) Is the same as the theoretical functionality of the polyoxyalkylene polyol (P), and the H-functional initiator substance (S)_i) Is within 10% of the measured hydroxyl value of the polyoxyalkylene polyol (P); (iii) the H-functional initiator substance (S)_x) Has an equivalent weight greater than or equal to 10 Da and less than or equal to 250 Da; (iv) the H-functional initiator substance (S)_c) Has an equivalent weight greater than or equal to 10 Da and less than or equal to 70 Da; (v) in (. delta.), an H-functional starter substance (S)_c) Until polyoxyalkylation with alkylene oxide is complete, wherein the H-functional starter substance (S)_c) The initial feed rate ratio to alkylene oxide is continued until 30 to 95 wt.% of the total weight of alkylene oxide has been added in step (. gamma.) and then the H-functional starter substance (S)_c) The feed rate ratio to alkylene oxide is reduced to the H-functional starter substance (S)_c) Ratio of final feed rate of alkylene oxide to H-functional starter substance (S)_c) The final feed rate ratio to alkylene oxide is H-functional starter substance (S)_c) 50 to 5% of the initial feed rate ratio of alkylene oxide; and (vi) determining the hydroxyl number according to ASTM D4274-11.

In a second embodiment, the present invention relates to a process according to the first embodiment, which additionally comprises (β) adding an activating amount of (b) alkylene oxide to the starter mixture of step (α), wherein in step (γ) the (a) alkylene oxide is continuously added to the mixture formed in (β); and (v) in step (iv)In step (. delta.), the H-functional initiator substance (S)_c) Until polyoxyalkylation with alkylene oxide is complete, wherein the H-functional starter substance (S)_c) The initial feed rate ratio to alkylene oxide is continued until 30 to 95 wt.% of the total weight of alkylene oxide has been added in steps (. beta.) and (. gamma.) and then the H-functional starter substance (S)_c) The feed rate ratio to alkylene oxide is reduced to the H-functional starter substance (S)_c) Ratio of final feed rate of alkylene oxide to H-functional starter substance (S)_c) The final feed rate ratio to alkylene oxide is H-functional starter substance (S)_c) 50 to 5% of the initial feed rate ratio of alkylene oxide.

In a third embodiment, the present invention relates to a process according to any one of the first or second embodiments, wherein (ii) an H-functional starter substance (S)_i) Is the same as the theoretical functionality of the polyoxyalkylene polyol (P), and an H-functional initiator substance (S)_i) Is within 5% of the measured hydroxyl value of the polyoxyalkylene polyol (P).

In a fourth embodiment, the present invention relates to a process according to any one of the first or third embodiments, wherein (v) in step (δ), an H-functional starter substance (S)_c) Until polyoxyalkylation with alkylene oxide is complete, wherein the H-functional starter substance (S)_c) The initial feed rate ratio to alkylene oxide is continued until 30 to 95 wt.% of the total weight of alkylene oxide has been added in step (. gamma.) and then the H-functional starter substance (S)_c) The feed rate ratio to alkylene oxide is reduced to the H-functional starter substance (S)_c) Ratio of final feed rate of alkylene oxide to H-functional starter substance (S)_c) The final feed rate ratio to alkylene oxide is H-functional starter substance (S)_c) From 45 to 10%, preferably from 40 to 15%, of the initial feed rate of alkylene oxide.

In a fifth embodiment, the present invention relates to a process according to any one of the second or third embodiments, wherein (v) in step (δ), an H-functional starter substance (S)_c) Until polyoxyalkylation with the alkylene oxide is complete, wherein H-Functional initiator substance (S)_c) The initial feed rate ratio to alkylene oxide is continued until 30 to 95 wt.% of the total weight of alkylene oxide has been added in steps (. beta.) and (. gamma.) and then the H-functional starter substance (S)_c) The feed rate ratio to alkylene oxide is reduced to the H-functional starter substance (S)_c) Ratio of final feed rate of alkylene oxide to H-functional starter substance (S)_c) The final feed rate ratio to alkylene oxide is H-functional starter substance (S)_c) From 45 to 10%, preferably from 40 to 15%, of the initial feed rate of alkylene oxide.

In a sixth embodiment, the present invention is directed to the method according to any one of the first to fifth embodiments, wherein the H-functional starter substance (S)_i) Having a functionality of about 2 to about 8 and a hydroxyl number of 5 to 35, preferably a functionality of 2 to 6 and a hydroxyl number of 8 to 30, more preferably a functionality of 2 to 3 and a hydroxyl number of 14 to 28.

In a seventh embodiment, the present invention is directed to the method according to any one of the first to sixth embodiments, wherein the H-functional starter substance (S)_i) Comprising a polyoxyalkylene polyol containing double metal cyanide catalyst residues.

In an eighth embodiment, the present invention is directed to the method according to any one of the first to seventh embodiments, wherein the H-functional initiator species (S)_i) Comprising a polyoxyalkylene polyol containing double metal cyanide catalyst residue, wherein said double metal cyanide catalyst residue was previously exposed to alkylene oxide.

In a ninth embodiment, the present invention relates to a process according to any one of the first to eighth embodiments, wherein the H-functional starter substance (S)_i) Comprising a polyoxyalkylene polyol containing double metal cyanide catalyst residue, wherein said double metal cyanide catalyst residue comprises a pre-activated double metal cyanide catalyst that was previously exposed to alkylene oxide under reaction conditions.

In a tenth embodiment, the present invention is directed to the method according to any one of the first to ninth embodiments, wherein the H-functional initiator species (S)_i) Comprises an antioxidantAnd/or acid polyoxyalkylene polyols.

In an eleventh embodiment, the present invention is directed to the method according to any one of the first to tenth embodiments, wherein the H-functional initiator species (S)_x) Having an equivalent weight of from about 20 Da to about 70 Da, preferably from 30 Da to 50 Da.

In a twelfth embodiment, the present invention relates to the method according to any one of the first to eleventh embodiments, wherein the H-functional starter substance (S)_x) Comprising ethylene glycol, propylene glycol, butylene glycol, glycerin, water, trimethylolpropane, sorbitol, sucrose, or combinations thereof.

In a thirteenth embodiment, the present invention is directed to the method according to any one of the first to twelfth embodiments, wherein the H-functional initiator species (S)_c) Having an equivalent weight of about 30 Da to about 50 Da.

In a fourteenth embodiment, the present invention is directed to the process according to any one of the first to thirteenth embodiments, wherein the (a) alkylene oxide continuously added in (γ) comprises propylene oxide, ethylene oxide, or a combination thereof.

In a fifteenth embodiment, the present invention relates to the process according to any one of the first to fourteenth embodiments, wherein the (b) alkylene oxide added in (β) comprises propylene oxide, ethylene oxide or a combination thereof.

In a sixteenth embodiment, the present invention relates to a process according to any one of the first to fifteenth embodiments, wherein the H-functional starter substance (S)_x) With the H-functional starter substance (S) present in the starter mixture based on step (alpha)_i) Is present in an amount of from 0.1 to 2.0 wt%, preferably from 0.25 to 1.75 wt%, more preferably from 0.5 to 1.5 wt%.

In a seventeenth embodiment, the present invention is directed to a method according to any one of the first to sixteenth embodiments, wherein the H-functional initiator species (S)_x) And H-functional initiator substances (S)_c) Are the same substance.

In an eighteenth embodiment, the present invention is directed to the methods according to the first to seventeenth embodimentsThe process of any one of, wherein the H-functional initiator species (S)_c) Comprising ethylene glycol, propylene glycol, butylene glycol, glycerin, water, trimethylolpropane, sorbitol, sucrose, or combinations thereof.

In a nineteenth embodiment, the present invention is directed to the method according to any one of the first to eighteenth embodiments, wherein the H-functional starter substance (S)_c) Further comprising at least one acid.

In a twentieth embodiment, the present invention relates to the method according to any one of the first to nineteenth embodiments, wherein the polyoxyalkylene polyol (P) formed has a functionality of from 2 to 6 and a hydroxyl number of from about 8 to 30, preferably a functionality of from 2 to 3 and a hydroxyl number of from 14 to 28.

In a twenty-first embodiment, the present invention relates to a process according to any one of the first to twentieth embodiments, wherein the amount of (a) alkylene oxide added in step (γ) to activate the catalyst is the H-functional starter substance (S) present in the starter mixture of step (α)_i) 1 to 12 wt%.

In a twenty-second embodiment, the present invention relates to a process according to any one of the first to twentieth embodiments, wherein the amount of (b) alkylene oxide added in (β) to activate the catalyst is the H-functional starter substance (S) present in the starter mixture of step (α)_i) 1 to 12 wt%.

In a twenty-third embodiment, the present invention relates to a process according to any one of the first to twenty-second embodiments, wherein step (δ) is performed by continuously adding the H-functional starter substance (S)_c) Before the feed of 4% by weight, preferably 2% by weight, of the total weight of alkylene oxide added in step (. gamma.).

In a twenty-fourth embodiment, the present invention relates to the method according to any one of the second to twenty-third embodiments, wherein step (δ) is performed by continuously adding the H-functional starter substance (S)_c) Before the feed is started 4% by weight, preferably 2% by weight, based on the total weight of alkylene oxide fed in from steps (. beta.) and (. gamma.).

In a twenty-fifth embodiment, the present invention relates to a process according to any one of the first to twenty-fourth embodiments, wherein the resulting polyoxyalkylene polyol (P) additionally comprises an antioxidant and/or an acid.

In a twenty-sixth embodiment, the present invention relates to a method according to any one of the first to twenty-fifth embodiments, wherein in step (δ), the H-functional initiator species (S)_c) Final feed rate ratio to alkylene oxide< 1.0%。

In a twenty-seventh embodiment, the present invention relates to the method according to any one of the first to twenty-sixth embodiments, wherein in step (δ) the H-functional starter substance (S) is fed in a final feed rate ratio_c) Is a H-functional starter substance (S)_c) And H-functional initiator substances (S)_x) Of total combined weight of>1% by weight.

In a twenty-eighth embodiment, the present invention is directed to the method according to any one of the first to twenty-seventh embodiments, wherein the H-functional initiator species (S)_c) Is a H-functional starter substance (S)_c) And H-functional initiator substances (S)_x) Of total combined weight of>50% by weight.

The following examples further illustrate details of the process of the present invention. The invention, which is set forth in the foregoing disclosure, is not to be limited either in spirit or scope by these examples. Those skilled in the art will readily appreciate that known variations of the conditions of the following procedures may be used. Unless otherwise indicated, all temperatures are degrees Celsius and all parts and percentages are parts by weight and percentages by weight, respectively.

Examples

In the examples, OH (hydroxyl number) was determined as described above according to ASTM D-4274-11 and reported as mg [ KOH ]/g polyol.

Viscosity was determined as described above according to ASTM-D4878-15.

Gel Permeation Chromatography (GPC) was used to determine the molecular weights (weight and number average) according to DIN 55672-1 as described above. All molecular weights are number average molecular weights unless otherwise specified.

The examples herein are inside a reactor equipped with an electric heating jacket and water-coolable reaction mixtureCoiled tubing in a 35 liter stainless steel reaction vessel. The reactor is equipped with baffles and a stirrer, which contains a Ruston-type stirrer at the bottom and inclined blades at the top. Alkylene oxide and continuously added H-functional initiator substance (S) using a submerged tube_c) The feed is introduced into the liquid phase.

The following compounds or materials were used in the examples.

Catalyst ADouble metal cyanide catalysts prepared according to the procedure in U.S. Pat. No. 5,482,908

Irganox E-201Primary (phenolic) antioxidants containing vitamin E and available from BASF

Comparative example 1The 35 liter reactor was charged with 2500 g of all PO, 8000 MW diol (S) prepared by a semi-batch process using catalyst A_i) (-. 14 OH #) and 0.6 g of catalyst A. This mixture was heated to 130 ℃. Vacuum was applied to a level of 0.1 psia and nitrogen was introduced to the liquid phase via a dip tube or for 30 minutes. Propylene oxide (100 g) was loaded to activate the catalyst. The pressure increased to 10 psia and then steadily decreased, indicating that the catalyst was active. When the pressure reached 2 psia, the PO feed was restarted and ramped up to 74.9 g/min over 20 minutes. At the same time, start-up as continuous addition of initiator (S)_c) And ramped up to a feed rate of 0.77 g/min. Starting as S after feeding 100 g of PO or 0.6% by weight of the total PO to be fed (100 g/17334 g)_cPG of (1). PG was fed at a feed rate ratio of 1.02 wt% (0.77 g/min PG/74.9 g/min PO) based on the PO feed rate. The PG and PO feeds were continued until the PG feed met the target weight of 166.2 grams. At the target PG/PO feed rate ratio of 1.02 wt%, the target was achieved after 16334 grams of PO or 94% of the total PO was fed in. The PG/PO ratio on a weight basis was 1.02 wt% (166.2 g PG/16234 g PO). The remaining 1000 grams of PO were continued at a feed rate of 74.9 g/min until a final PO target of 17334 grams was reached. Feeding 1000 g PO without PG feed corresponds to 5 wt% of "non-CAOS" end-caps based on the total batch weight (1000 g/20000 g batch). The final product (P) was inhibited with 160 ppm Irganox E-201. The final product (P) had a hydroxyl number of 14 mg KOH/g andviscosity of 3726 cst (adjusted viscosity of 3726 cst, adjusted to hydroxyl number of 14.0 mg KOH/g polyol, adjusted viscosity to given hydroxyl number is important for comparison to high equivalent weight products, as viscosity can vary significantly with equivalent weight) and polydispersity index (Mw/Mn) of 1.137. No "Pre-CAOS" charge (No S) in the starter mixture_x) The comparison was carried out with 5 wt% "non-CAOS" capping. FIG. 1 shows that the molecular weight distribution produced using this product-to-product process has shoulders or inhomogeneities on the higher molecular weight side, which result from the H-functional starter substance (S) used as starter mixture_i) Is produced by reaction of a polyoxyalkylene polyol with an activated alkylene oxide, since no PG or low equivalent weight H-functional starter material (S) is present in the starter mixture_x)。

Example 2:the 35 liter reactor was loaded with 2491 grams of a full PO, 8000 MW diol (S) made by a semi-batch process using catalyst A_i) (-. 14 OH #) and 0.673 g of catalyst A. This mixture was heated to 130 ℃. Vacuum was applied to a level of 0.1 psia and nitrogen was introduced to the liquid phase via a dip tube or for 30 minutes. After nitrogen cessation, 12.5 grams of propylene glycol (S) was added_x) (polyoxyalkylene polyol materials based on initiator mixtures (S)_i) 0.5 weight% PG) was loaded to the polyoxyalkylene polyol starter substance (S)_i) And in the catalyst mixture. 12.5 grams PG represents a 0.5 wt% "Pre-CAOS" charge (12.5 g PG/2491 g S_i). Propylene oxide (100 g) was loaded to activate the catalyst. The pressure increased to 15 psia and then steadily decreased, indicating that the catalyst was active. When the pressure reached 7 psia, the PO feed was restarted and ramped up to 85.4 g/min over 20 minutes. At the same time, start-up as continuous addition of initiator (S)_c) And ramped up to a feed rate of 0.79 g/min. Started as S after feeding 100 g of PO or 0.5% by weight (100 g/19739 g) of the total PO to be fed_cPG of (1). PG was fed at an initial feed rate ratio (0.79 g/min PG/85.4 g/min PO) of 0.94 wt% based on the PO feed rate. The PG and PO feeds were continued until the PO feed reached 18618 grams or 94% of the total PO to be fed, and the PG totaled 173.4 grams. At this time, PG is put inThe feed rate was reduced to 0.26 g/min and PO continued to be fed at 85.4 g/min to give a final PG/PO feed rate ratio of 0.3 wt%. PO and PG continue at these rates until PO reaches the target of 19739 grams and PG reaches as S_cA 176.8 gram target was fed. 176.8 g as S_cPG fed is total S_c+S_x93.4 wt.% (S)_c / (S_c+S_x) Or (176.8/189.3)). The final feed of 1121 g PO and 3.4 g PG in the batch corresponded to 5% of "low-CAOS" end capping based on the total batch weight (1121 g/22419 g batch). The 0.3 wt% final PG/PO feed rate ratio was 32% of the 0.94% initial PG/PO feed rate ratio (0.3/0.94 x 100 = 32%), and 3.4 grams of PG fed at the final feed rate ratio was 1.8% of the total PG fed (3.4/(176.8 + 12.5)). The initial PG/PO ratio, based on the weight of PG and PO fed, was 0.94 wt% (173.4 g PG/18518 g PO). The final PG/PO ratio based on the weight of PG and PO fed was 0.3 wt% (3.4 g PG/1121 g PO). The final product (P) was inhibited with 160 ppm Irganox E-201. The final product (P) had a hydroxyl number of 13.7 mg KOH/g polyol, a viscosity of 3133 cSt (adjusted viscosity of 2935 cSt, adjusted to a hydroxyl number of 14.0 mg KOH/g polyol) and a polydispersity index (Mw/Mn) of 1.075. In the presence of a "pre-CAOS" or H-functional initiator substance (S)_x) Polyoxyalkylene polyol H-functional initiator material (S) charged to initiator mixture_i) And at 5 wt% "low-CAOS" end-capping the product (P) of this example was made. The viscosity (and the viscosity regulation) and the polydispersity of the product (P) are improved by means of the "low-CAOS" end-capping compared to example 1.

Example 3:the 35 liter reactor was charged with 2500 g of all PO, 8000 MW diol (S) prepared by a semi-batch process using catalyst A_i) (-. 14 OH #) and 0.675 g of catalyst A. This mixture was heated to 130 ℃. Vacuum was applied to a level of 0.1 psia and nitrogen was introduced to the liquid phase via a dip tube or for 30 minutes. After nitrogen cessation, 12.5 grams of propylene glycol (S) was added_x) (polyoxyalkylene polyol materials based on initiator mixtures (S)_i) 0.5 weight% PG) was loaded to the polyoxyalkylene polyol starter substance (S)_i) Andin the catalyst mixture. 12.5 grams PG represents a 0.5 wt% "Pre-CAOS" charge (12.5 g PG/2500 g S)_i). Propylene oxide (100 g) was loaded to activate the catalyst. The pressure increased to 15 psia and then steadily decreased, indicating that the catalyst was active. When the pressure reached 7 psia, the PO feed was restarted and ramped up to 85.7 g/min over 20 minutes. At the same time, start-up as continuous addition of initiator (S)_c) And ramped up to a feed rate of 0.92 g/min. Started as S after feeding 100 g of PO or 0.5% by weight (100 g/19810 g) of the total PO to be fed_cPG of (1). PG was fed at an initial feed rate ratio of 1.08 wt% (0.92 g/min PG/85.7 g/min PO) based on the PO feed rate. The PG and PO feeds were continued until the PO feed reached 15310 grams or 77% of the total PO to be fed, and the PG totaled 163.9 grams. At this point the PG feed rate was reduced to 0.26 g/min and PO continued to be fed at 85.7 g/min to give a final PG/PO feed rate ratio of 0.3 wt%. PO and PG continue at these rates until PO reaches the target of 19810 grams and PG reaches as S_cA 177.4 gram target was fed. 177.4 g as S_cPG fed is total S_c+S_x93.4 wt.% (S)_c / (S_c+S_x) Or (177.4/189.9)). The feeding of 4500 grams PO and 13.5 grams PG at the end of the batch corresponded to 20% of "low-CAOS" termination based on total batch weight (4500 g/22500 g batch). The 0.3 wt% final PG/PO feed rate ratio was 28% of the 1.08% initial PG/PO feed rate ratio (0.3/1.08 x 100 = 28%), and 13.5 grams of PG fed at the final feed rate ratio was 7.1% (13.5/(177.4 + 12.5)) of the total PG fed. The initial PG/PO ratio, based on the weight of PG and PO fed, was 1.08 wt% (163.9 g PG/15210 g PO). The final PG/PO ratio based on the weight of PG and PO fed was 0.3 wt% (13.5 g PG/4500 g PO). The final product (P) was inhibited with 160 ppm Irganox E-201. The final product (P) had a hydroxyl number of 13.6 mg KOH/g polyol, a viscosity of 3136 cSt (adjusted viscosity of 2872 cSt, adjusted to a hydroxyl number of 14.0 mg KOH/g polyol) and a polydispersity index (Mw/Mn) of 1.058. In the presence of a "pre-CAOS" or H-functional initiator substance (S)_x) Polyoxyalkylene polyol material (S) charged to initiator mixture_i) In the case ofAnd the product (P) of this example was made at 20 wt% low-CAOS end-capping.

Example 4:the 35 liter reactor was loaded with 2495 grams of all PO, 8000 MW diol (S) prepared by a semi-batch process using catalyst A_i) (-. 14 OH #) and 0.674 g of catalyst A. This mixture was heated to 130 ℃. Vacuum was applied to a level of 0.1 psia and nitrogen was introduced to the liquid phase via a dip tube or for 30 minutes. After nitrogen cessation, 12.5 grams of propylene glycol (S) was added_x) (polyoxyalkylene polyol materials based on initiator mixtures (S)_i) 0.5 weight% PG) was loaded to the polyoxyalkylene polyol starter substance (S)_i) And in the catalyst mixture. 12.5 grams PG represents a 0.5 wt% "Pre-CAOS" charge (12.5 g PG/2495 g S_i). Propylene oxide (100 g) was loaded to activate the catalyst. The pressure increased to 13 psia and then steadily decreased, indicating that the catalyst was active. When the pressure reached 3 psia, the PO feed was restarted and ramped up to 85.5 g/min over 20 minutes. At the same time, start-up as continuous addition of initiator (S)_c) And ramped up to a feed rate of 1.44 g/min. Started as S after feeding 100 g of PO or 0.5% by weight (100 g/19771 g) of the total PO to be fed_cPG of (1). PG was fed at an initial feed rate ratio of 1.70 wt% (1.44 g/min PG/85.5 g/min PO) based on the PO feed rate. The PG and PO feeds were continued until the PO feed reached 8543 grams or 43% of the total PO to be fed, and PG amounted to 143.4 grams. At this point the PG feed rate was reduced to 0.26 g/min and PO continued to be fed at 85.5 g/min to give a final PG/PO feed rate ratio of 0.3 wt%. PO and PG continue at these rates until PO reaches the 19771 g target and PG reaches as S_cA 177.1 gram target was fed. 177.1 g as S_cPG fed is total S_c+S_x93.4 wt.% (S)_c / (S_c+S_x) Or (177.1/189.6)). The final feed of 11228 grams PO and 33.7 grams PG at the end of the batch corresponded to 50% low-CAOS termination based on total batch weight (11228 g/22455 g batch). 0.3 wt% of the final PG/PO feed rate ratio was 18% (0.3/1.70 x 100 = 18%) of the initial PG/PO feed rate ratio of 1.70%, and at the final feed rate ratio33.7 grams of PG fed was 17.8% (33.7/(177.1 + 12.5)) of the total PG fed. The initial PG/PO ratio based on the weight of PG and PO fed was 1.70 wt% (143.4 g PG/8443 g PO). The final PG/PO ratio, based on the weight of PG and PO fed, was 0.3 wt% (33.7 g PG/11228 g PO). The final product (P) was inhibited with 160 ppm Irganox E-201. The final product (P) had a hydroxyl number of 14 mg KOH/g polyol, a viscosity of 2842 cSt (viscosity adjusted to 2842 cSt, hydroxyl number adjusted to 14.0 mg KOH/g polyol) and a polydispersity index (Mw/Mn) of 1.054. In the presence of a "pre-CAOS" or H-functional initiator substance (S)_x) Polyoxyalkylene polyol material (S) charged to initiator mixture_i) And at 50 wt% "low-CAOS" end-capping the product (P) of this example was made. FIG. 2 shows the synthesis of DMC catalysts by activating PG (S) with PO before activating the DMC catalyst_x) Or "pre-CAOS" charging a polyoxyalkylene polyol material (S) added to the starter mixture_i) In (d), the high molecular weight shoulder is eliminated. The viscosity (and adjusted viscosity) of example 4 is lower than that of comparative example 1 due to the narrow molecular weight distribution of the product in example 4.

Example 5:the 35 liter reactor described above was loaded with 2472 grams of all PO, 11500 MW diol (S) made by a semi-batch process using catalyst A_i) (-. 9.8 OH #) and 0.678 g of catalyst A. This mixture was heated to 130 ℃. Vacuum was applied to a level of 0.1 psia and nitrogen was introduced to the liquid phase via a dip tube or for 30 minutes. After nitrogen cessation, 12.4 grams of propylene glycol (S) was added_x) (polyoxyalkylene polyol materials based on initiator mixtures (S)_i) 0.5 weight% PG) was loaded to the polyoxyalkylene polyol starter substance (S)_i) And in the catalyst mixture. 12.4 grams PG represents a 0.5 wt% "Pre-CAOS" charge (12.4 g PG/2472 g S_i). Propylene oxide (99 g) was loaded to activate the catalyst. The pressure increased to 13 psia and then steadily decreased, indicating that the catalyst was active. When the pressure reached 3 psia, the PO feed was restarted and ramped up to 55.9 g/min over 20 minutes. At the same time, the initiator (S) is started as a continuous addition_c) And ramped up to a feed rate of 0.38 g/min. At a feed of 99 g PO or total to be fed0.5 wt% PO (99 g/19648 g) was started as S_cPG of (1). PG was fed at an initial feed rate ratio (0.38 g/min PG/55.9 g/min PO) of 0.71 wt% based on the PO feed rate. The PG and PO feeds were continued until the PO feed reached 15198 grams or 77% of the total PO to be fed, and the PG amounted to 107.1 grams. At this point the PG feed rate was reduced to 0.15 g/min and PO continued to be fed at 55.9 g/min to give a final PG/PO feed rate ratio of 0.27 wt%. PO and PG continue at these rates until PO reaches the 19648 gram target and PG reaches as S_cA 118.7 gram target was fed. 118.7 g as S_cPG fed is total S_c+S_x90.5 wt.% (((S)_c / (S_c+S_x) Or (118.7/131.1)). The feeding of 4450 g PO and 11.6 g PG at the end of the batch corresponded to 20% low-CAOS termination based on total batch weight (4450 g/22251 g batch). The 0.27 wt% final PG/PO feed rate ratio was 38% (0.27/0.71 x 100 = 38%) of the 0.71 wt% initial PG/PO feed rate ratio, and 11.6 grams of PG fed at the final feed rate ratio was 8.8% (11.6/(118.7 + 12.4)) of the total PG fed. The initial PG/PO ratio, based on the weight of PG and PO fed, was 0.71 wt% (107.1 g PG/15099 g PO). The final PG/PO ratio based on the weight of PG and PO fed was 0.26 wt% (11.6 g PG/4450 g PO). The final product (P) was inhibited with 160 ppm Irganox E-201. The final product (P) had a hydroxyl number of 9.77 mg KOH/g polyol, a viscosity of 6948 cSt (adjusted viscosity of 6915 cSt, adjusted to a hydroxyl number of 9.8 mg KOH/g polyol) and a polydispersity index (Mw/Mn) of 1.066. In the presence of a "pre-CAOS" or H-functional initiator substance (S)_x) Polyoxyalkylene polyol material (S) charged to initiator mixture_i) And at 20 wt% "low-CAOS" end-capping the product (P) of this example was made.

Example 6:the 35 liter reactor described above was loaded with 2494 grams of an all PO, 11500 MW diol (S) made by a semi-batch process using catalyst A_i) (-. 9.8 OH #) and 0.68 g of catalyst A. This mixture was heated to 130 ℃. Vacuum was applied to a level of 0.1 psia and nitrogen was introduced to the liquid phase via a dip tube or for 30 minutes. After nitrogen cessation, 12.5 grams of propylene glycol was added(S_x) (polyoxyalkylene polyol materials based on initiator mixtures (S)_i) 0.5 weight% PG) was loaded to the polyoxyalkylene polyol starter substance (S)_i) And in the catalyst mixture. 12.5 grams PG represents a 0.5 wt% "Pre-CAOS" charge (12.5 g PG/2494 g S_i). Propylene oxide (100 g) was loaded to activate the catalyst. The pressure increased to 15 psia and then steadily decreased, indicating that the catalyst was active. When the pressure reached 5 psia, the PO feed was restarted and ramped up to 56.4 g/min over 20 minutes. At the same time, the initiator (S) is started as a continuous addition_c) And ramped up to a feed rate of 0.57 g/min. Started as S after feeding 100 g of PO or 0.5% by weight (100 g/19819 g) of the total PO to be fed_cPG of (1). PG was fed at an initial feed rate ratio of 1.06 wt% (0.57 g/min PG/56.4 g/min PO) based on the PO feed rate. The PG and PO feeds were continued until the PO feed reached 8600 grams or 43% of the total PO to be fed, and the PG amounted to 89.8 grams. At this point the PG feed rate was reduced to 0.15 g/min and PO continued to be fed at 56.4 g/min to give a final PG/PO feed rate ratio of 0.27 wt%. PO and PG continue at these rates until PO reaches the target of 19819 grams and PG reaches as S_cA target of 120.1 grams was fed. 120.1 g as S_cPG fed is total S_c+S_x90.6 wt.% (((S)_c / (S_c+S_x) Or (120.1/132.6)). The final feed of 11219 grams PO and 30.3 grams PG at the end of the batch corresponded to 50% of "low-CAOS" end-caps based on total batch weight (11219 g/22446 g batch). The 0.27 wt% final PG/PO feed rate ratio was 26% (0.27/1.06 x 100 = 26%) of the 1.06% initial PG/PO feed rate ratio, and 30.3 grams of PG fed at the final feed rate ratio was 22.8% (30.3/(120.1 + 12.5)) of the total PG fed. The initial PG/PO ratio based on the weight of PG and PO fed was 1.06 wt% (89.8 g PG/8500 g PO). The final PG/PO ratio, based on the weight of PG and PO fed, was 0.27 wt% (30.3 g PG/11219 g PO). The final product (P) was inhibited with 160 ppm Irganox E-201. The final product (P) had a hydroxyl number of 9.99 mg KOH/g, a viscosity of 6852 cSt (adjusted viscosity of 7061 cSt, adjusted to a hydroxyl number of 9.8 mg KOH/g polyol) and 1.057 polydispersity index (Mw/Mn). In the presence of a "pre-CAOS" or H-functional initiator substance (S)_x) Polyoxyalkylene polyol H-functional initiator material (S) charged to initiator mixture_i) And at 50 wt% "low-CAOS" end-capping the product (P) of this example was made.

Table 1.

	Composition example 1	Example 2	Example 3	Example 4	Example 5	Example 6
							Initial initiator, SiWeight, g	2500	2491	2500	2495	2472	2494
Initial initiator, SiOH #, mg KOH/g polyol	14	14	14	14	9.8	9.8
							Growth ratio	8	9	9	9	9	9
Product weight, g	20000	22419	22500	22455	22251	22446
							The target product OH #, mg KOH/g polyalcohol	14	14	14	14	9.8	9.8
Propylene glycol OH #, mg KOH/g polyol	1474.4	1474.4	1474.4	1474.4	1474.4	1474.4
							Total PG (S)c + Sx), g	166.2	189.3	189.9	189.6	131.1	132.6
Total PO, g	17334	19739	19810	19771	19648	19819
							Activation of PO, SiIn percentage by weight	4%	4%	4%	4%	4%	4%
Activated PO, g	100	100	100	100	99	100

Table 2.

	Composition example 1	Example 2	Example 3	Example 4	Example 5	Example 6
							SxOr pre-CAOS charging, SiIn percentage by weight	0.0%	0.5%	0.5%	0.5%	0.5%	0.5%
SxOr pre-CAOS charging, g	0	12.5	12.5	12.5	12.4	12.5
							Total Sc, g	166.2	176.8	177.4	177.1	118.7	120.1
Low-CAOS end capping, wt.%	0%	5%	20%	50%	20%	50%
							low-CAOS end capping, g	0	1121	4500	11228	4450	11219
non-CAOS end-capping, wt.%	5%	0%	0%	0%	0%	0%
							non-CAOS end capping, g	1000	0	0	0	0	0
S fed at initial feed rate ratioc, g	166.2	173.4	163.9	143.4	107.1	89.8
							Initial ScAlkylene oxide feed Rate ratio, (feed Rate S)cFeed rate alkylene oxide)%	1.02%	0.94%	1.08%	1.70%	0.71%	1.06%
Final ScAlkylene oxide feed Rate ratio, (feed Rate S)cFeed rate alkylene oxide)%	0.0%	0.3%	0.3%	0.3%	0.27%	0.27%
							S feeding at final feed rate ratio or in low-CAOS cappingc, g	0.0	3.4	13.5	33.7	11.6	30.3
Final ScAlkylene oxide feed Rate ratio/initial Sc/alkylene oxide feed rate ratio,%	0%	32%	28%	18%	38%	26%
							Weight% alkylene oxide when the feed rate ratio is changed,%	94%	94%	77%	43%	77%	43%
Total Sc + SxTo last ScFeed rate of alkylene oxide to weight% S of feedc, %	0.0%	1.8%	7.1%	17.8%	8.8%	22.8%
							Total Sc + SxWeight% of S inc, %	100.0%	93.4%	93.4%	93.4%	90.5%	90.6%

Table 3.

	Composition example 1	Example 2	Example 3	Example 4	Example 5	Example 6
							Actually measured OH # of the product1Mg KOH/g polyol	14	13.7	13.6	14	9.77	9.99
Viscosity of the product2, cst @ 25℃	3726	3133	3136	2842	6948	6852
							Hydroxyl number of the product to adjust viscosity3, cst @25℃	3726	2935	2872	2842	6915	7061
Polydispersity index of the product4 (Mw/Mn)	1.137	1.075	1.058	1.054	1.066	1.057

¹Measured according to ASTM-D4274-11

²Measured according to ASTM D-4878-15

³By using measured OH # and measured viscosity adjusted to the target value (14.0 mg KOH/g for examples 1,2, 3 and 4; 9.8 mg KOH/g for examples 5 and 6) and linearly increased viscosity when measured OH # is greater than the target (MW or EQ is less than target, therefore MW or EQ must be increased to reach target, therefore viscosity is increased) and linearly decreased viscosity when measured OH # is less than target (MW or EQ is greater than target, therefore MW or EQ must be decreased to reach target, therefore viscosity is decreased)

⁴Measured according to DIN 5567201.

Although the invention has been described in detail in the foregoing for the purpose of illustration, it is to be understood that such detail is solely for that purpose and that variations can be made therein by those skilled in the art without departing from the spirit and scope of the invention except as it may be limited by the claims.