Obtaining polyols using double metallocyanide catalyst by continuous addition of starter

 

(57) Abstract:

The invention relates to polyols, catalyzed double metallocyanide catalyst that get through improved method, in which the starter continuously added during polymerization of the epoxide. The method includes continuously added starter Scand, optionally, the source downloaded the starter Si. Continuously added starter includes at least about 2 equivalent percent of the total used amount of starter. The method allows the use of water and polylogue starters low molecular weight in the process of DMC-catalyzed synthesis of polyols. The method also allows to obtain the polyether polyols having reduced levels of paleologou tail fractions of high molecular weight, which can have a negative effect on technological properties of polyurethane foam. 3 S. and 11 C.p. f-crystals, 3 tab., 5 Il.

The technical field to which the invention relates

The present invention relates to a process for the preparation of polyether polyols suitable for the manufacture of polyurethane foams, elastomers, sealants, coating materials and adhesives. In castellanii (DMC) catalyst. A distinctive feature of this method is the use of water or polyol of low molecular weight as a starter for the polymerization and obtain polyols, which has a low content of paleologou tail fractions of high molecular weight.

Background of the invention

Double metallocyanide (DMC) complexes are highly active catalysts for the receipt of polyether polyols by polymerization of epoxides. The above-mentioned catalysts allow to obtain the polyether polyols having a narrow distribution of molecular weight and very low degree of unsaturation (low Manolov) even at high molecular masses. A consequence of recent improvements have been the DMC catalysts with exceptionally high activity. See, for example, U.S. patent 5470813.

Despite the fact that DMC catalysts known from the sixties, commercialization polyols obtained using these catalysts, is a recent event, and the majority of industrial polyether polyols and yet still receive using potassium hydroxide. One of the reasons is difficult DMC commercial availability of polio Roman etc. very poorly (if at all) initiate DMC-catalyzed polymerization of epoxides, especially in a regular periodic method of obtaining polyols. In the ordinary case, paleology starter and DMC catalyst loaded into the reactor and heated with a small amount of resin, the catalyst is activated and the rest of the epoxide continuously added to the reactor to complete the polymerization.

In a typical periodic method of obtaining polyols using KOH or DMC catalyst whole paleology starter loaded into the reactor in the beginning. In the case of using the line in as the starter motor specialists in the art will understand that the continuous addition of starter (usually polyol of low molecular weight, such as glycerin or propylene glycol) with the epoxide formed polyols having a broader distribution of molecular weights, compared with the products obtained by loading only starter from the outset. This is especially true because the speed alkoxysilane CON, essentially, does not depend on the molecular weight of the polyol. In the case of continuous injection of material of low molecular weight, distribution of molecular weight EXT is they have a relatively high viscosity, that may adversely affect the workability of polyurethane compositions, in particular, in the case when the prepolymers are derived from polyols. In addition, the polyols with a narrow distribution of molecular masses, as a rule, allow to obtain polyurethanes with the best physical properties.

Experts in the art have suggested that continuous addition of starter in the synthesis of DMC-catalyzed polyols will also lead to the formation of polyols having a relatively wide distribution of molecular masses. Therefore, in the technical field relates to the synthesis of polyols using DMC catalysts, almost exclusively used in a manner in which the whole starter is loaded into the reactor from the outset, with continuous addition of epoxide in the polymerization process.

One exception is the U.S. patent 3404109 (Milgram /Milgrom/). Milgram discloses a semi-industrial way of getting polyetherdiol using the DMC catalyst and water as a starter. According to the method of Milgrom in a bottle for beverages make a DMC catalyst, the whole subject of the use of epoxide and water, followed by heating bottles, corked cap, and maintain the STW water to obtain telomeres low molecular weight, it is preferable to add water with a gradual increase in volume, since significant quantities of water reduces the rate of telomerization". Add starter (water) with a gradual increase in volume is used to obtain the "practical" response speed. Thus, Milgram loads all of epoxide in the reactor from the start, but the starter adds with a gradual increase in volume.

Interestingly, Milgram also indicates that the gradual addition of water can also be used to obtain telomeres with a broader distribution of molecular weight compared to the possible in the case when all the water is added at the beginning of the reaction. In other words, the result expected from the DMC-catalyzed method, the same as the result obtained in the case of CON-catalyzed method: continuous or incremental addition of the starter is to provide polyols with a wide distribution of molecular masses. Thus, specialist description Milgrom understands that the incremental addition of starter process DMC-catalyzed polymerization of epoxide are obtained polyols having a wider distribution Momoko beginning.

HEUVELLAND (Heuvelsland) (U.S. patent 5114619) discloses a method of producing polyether polyols, which includes the continuous addition of water and the epoxide to the reaction mixture, which includes the catalyst oxide or hydroxide of barium or strontium. DMC-catalyzed process is not disclosed. By way of HEUVELLAND get polyols with low unsaturation. The effect of continuous addition of water in the presence of catalysts based on barium or strontium on the distribution of molecular weight polyols is not discussed. HEUVELLAND notes that, unlike water, the continuous addition of diols, triodes and polyoxyethyleneglycol low molecular weight does not reduce the degree of unsaturation of polyols. In addition, the substitution of KOH catalyst catalyst on the basis of barium or strontium does not bring improvement.

Since traditional Paleologue starters are initiated with DMC catalysts is very slow, typically use Paleologue starters higher molecular weight (for example, propoxycarbonyl glycerol with molecular weight of 400-700). Mentioned Paleologue starters with higher molecular weight, in the preferred embodiment, is removed, as their neo is m for this reactor. Along with this, the KOH catalyst must be removed from the starter polyol before it is used as initiator DMC-catalyzed process of obtaining a polyol, as even a small amount of basic substances often inactivate DMC catalysts. Thus, to obtain a starter polyol, which could productively be used with the DMC catalyst, it is necessary CON-polyol as one link with cleansing abilities. Valuable would be the way making use of the DMC catalyst with a traditional starter such as propylene glycol or glycerin.

Unusually high reactivity of DMC catalysts is for manufacturers polyols another problem: contamination of the reactor. In reactors that use DMC catalysts can be formed sticky Paleologue gels, which tend to accumulate over time, contaminating the reactor and causing, in the end, it forced shut-down. Gels, are not seen with conventional KOHN-catalyzed synthesis of polyols, should, in the preferred case eliminated.

One of the consequences of downloading the entire volume of the I inefficient use of reactors. For example, to obtain polyoxypropylene having a molecular weight of 4000 (4K diol) from Polyoxypropylenediamine "starter", having a molecular weight of 2000 (2K diol), a reactor at the beginning of the reaction fill nearly half; to get 50 gallons (189,266 l) product, you must start with 25 gallons (94,633 l) 2K delovogo starter. A valuable way possible to overcome such limitations "factor accumulation" and would ensure the efficient use of the reactor, regardless of molecular weight starter or desired product. For example, it would be nice to be able to download the 50 gallon reactor only 5 gallons 2K delovogo starter and, nevertheless, to get 50 gallons 4K delovogo product.

In addition to the issues arising in the case of methods using DMC catalysis, industrial application of DMC-catalyzed polyols delayed variability of processing parameters polyols and their characteristics, especially when receiving elastic and molded foams. DMC-catalyzed polyols, as a rule, cannot sbrasyvatsya in polyurethane compositions, designed to CON-catalyzed polyols, because the process of polyols is neost foam. The variability of polyols from batch to batch causes of unpredictability polyurethane compositions. Because the causes of such neprognoziruemoe polyurethane compositions with the DMC-catalyzed polyols are not well understood, get permanent results is not possible.

Needed an improved method of obtaining a DMC-catalyzed polyols. Especially, you need a method that eliminates the need for separate synthesis Paleologo starter by KOH catalysis and allowing the use of simple starters, such as water, propylene glycol and glycerin. The best way should eliminate the problem of contamination of the reactor polyolefine gels, to ensure the effective use of reactors and the possibility of overcoming the limitations of factor accumulation. In a preferred embodiment, the method should provide polyether polyols having a relatively narrow distribution of molecular weight, as these polyols are much easier handled and provide polyurethanes with good physical properties. Also needed polyols, which are composed of polyurethane compositions, in particular elastic and molded foam is the shadow

The present invention represents an improved method of producing polyols, which uses dual metallocyanide catalyst. The method includes receiving polyetherpolyols by polymerization of epoxide in the presence of double metallocyanide (DMC) catalyst, continuously added starter (Swith), and, optionally, the source is loaded starter (Si). Continuously added starter includes at least about 2 equivalent percent of the total volume used starter (shared starter = Swith+Si). At that time, as in traditional methods of obtaining DMC-catalyzed polyols entire volume of starter designed for use in a reactor is loaded before the beginning of polymerization, the method corresponding to the present invention, which is its distinguishing feature, as epoxide, and Swithcontinuously added to the reaction mixture during the polymerization.

The method corresponding to the present invention, is causing surprise and valuable advantages. First, unlike other DMC-catalyzed methods for producing polyols, in the process corresponding nastoiashiaia starters usually avoided due to their inherent properties very slow initiation. Secondly, because as a starter may be used water or polyol of low molecular weight, the method eliminates the need for synthesizing expensive Paleologo starter higher molecular weight by means of KOH catalysis in separate, specially designed for this reactor. Thirdly, the method eliminates the problem of contamination of the reactor due to the formation Paleologo gel, which accompanies the use of DMC catalysts. Fourthly, a method that meets the present invention provides efficient use of reactors and overcomes a large number of limitations associated with factor accumulation. Fifthly, the method corresponding to the present invention unexpectedly allows to obtain the polyether polyols which have a narrow distribution of molecular weight, provides good physical properties of the polyurethane. Although previous methods in the art prevention continuous addition of starter, us, surprisingly, it was found that the continuous addition of starter in the case of DMC-catalyzed synthesis of polyols does not lead to obtaining polyols with a wide resposta continuous addition of epoxide and at least about 2 equiv.% Swithin the process of DMC-catalyzed synthesis of polyols. These polyols provide polyurethane compositions causing surprise and valuable benefits. In particular, in the composition of the above-mentioned polyols is smaller, compared with the previous DMC-catalyzed polyols, the share of the tail fraction of high molecular weight (i.e., polyol, having srednekamennogo molecular weight in excess of approximately 100,000).

The inventor, to his own surprise, found that polyols having reduced the number of tail fraction of high molecular weight, it is much easier are introduced in the composition of polyurethane systems, especially elastic and molded polyurethane foam, and provide more predictable characteristics and technological properties. The results obtained by the inventor show that changes in the properties of polyurethane foams, often observed in the case of DMC-catalyzed polyols, caused mainly by the presence of even small amounts of tail fraction polyols of high molecular weight. The polyols corresponding to the present invention, which include a reduced number of hosteter, provide improved technological properties, cause fewer problems associated with the rigidity of the foam or its destruction, and provide flexible and molded polyurethane foam with excellent physical properties.

Polyurethane can be obtained by interaction of polyetherpolyols with isocyanate, which can be used any of known isocyanates suitable for the production of polyurethanes, under the conditions usually used in the preparation of polyurethanes.

Brief description of drawings

In Fig. 1-5 presents the results of the gel permeation chromatographic (GPC) analysis of samples of polyetherpolyols obtained by DMC-catalyzed methods of the present invention, using a continuous addition of starter (Fig.1-3) or comparative methods (Fig.4-5). Figures and more are explained in the following Example 5, Comparative Example 6 and Example 18.

Detailed description of the invention

The method corresponding to the present invention, includes receiving polyetherpolyols by polymerization of epoxide in the presence of double metallocyanide (DMC) ASS="ptx2">

In General, the method can be used any epoxide, the polymerized using a DMC catalyst. Among the preferred epoxides include ethylene oxide, propylene oxide, butylenes (for example, 1,2-butylenes, isobutylene), styrene oxide, etc., and mixtures thereof. In the art it is well known that in the polymerization of epoxides using DMC catalysts and starters, which include a hydroxyl group, get the polyether polyols.

In a way corresponding to the present invention can include other monomers, copolymerizes with the epoxide in the presence of a DMC catalyst, to obtain an epoxy polymers of other types. For example, epoxides copolymerized with oxetane (which is disclosed in U.S. patent 3404109) with the formation of polyesters or with anhydrides to form polyesters or polyether and polyester (which is disclosed in the U.S. patents 5145883 and 3538043).

A catalyst is a dual metallocyanide (DMC) catalyst. For use in this way is suitable for any DMC catalyst known in the art. To these well-known catalysts are the reaction products of water-soluble metal salt (for example, PI is DMC catalysts described in many sources, including, for example, in U.S. patents 5158922, 4477589, 3427334, 3941849, 5470813 and 5482908, which is incorporated into this description by reference. Particularly preferred DMC catalysts are hexacyanocobaltate zinc.

The composition of the DMC catalyst is an organic complexing agents. As disclosed in the foregoing sources, the complexing agents required for an active catalyst. Preferred complexing agents are water-soluble organic compounds, which include heteroatom, can form complex compounds with the DMC compound. Particularly preferred complexing agents are water-soluble aliphatic alcohols. Most preferred is tributyl alcohol. The composition of the DMC catalyst as described in U.S. patent 5482908, along with organic complexing agents may include polyester.

Preferred DMC catalysts for use in the above-mentioned method are highly active catalysts, for example, described in U.S. patent 5482908 and 5470813. High activity allows the use of catalysts in very low concentrations, preferably in concentrations sufficiently low to Jesse, the corresponding present invention, is used continuously added starter (Swith). In the traditional processes of production of polyols, including CON-catalyzed and DMC-catalyzed processes, the catalyst and the entire volume of the starter, intended for use, is loaded into the reactor at the beginning of the polymerization, followed by continuous addition of the epoxide. In contrast, in the process corresponding to the present invention, adding epoxide continuously added at least about 2 equiv.% total starter. Swithcan be mixed with the epoxide or added as a separate stream.

Swithin the preferred embodiment, is a water or polyol of low molecular weight. The polyols of low molecular weight, as defined in this description, have 1 or more hydroxyl groups and srednekamennogo molecular weight of about less than 300. Among the suitable polyols of low molecular weight include, for example, glycerol, propylene glycol, dipropyleneglycol, ethylene glycol, trimethylolpropane, sucrose, sorbitol, tripropyleneglycol, etc. and mixtures thereof. Preferred continuously added starter assurednever molecular weight approximately, more than 300 and less srednekamennogo molecular weight of the target Paleologo product. The composition of the Sc can enter all of the volume of the starter; thus, the method corresponding to the present invention may be used to obtain a DMC-catalyzed polyol only from the main starter, for example propylene glycol or glycerin.

Starter Swithcan be other active compounds, including hydrogen, known as the initiators of the DMC-catalyzed polymerization of epoxides, including, for example, alcohols, thiols, aldehydes and ketones, which include analiziruem hydrogens, malonic esters, fooly, carboxylic acids and anhydrides, aromatic amines, acetylene, etc. and mixtures thereof. Examples of suitable active compounds, including hydrogen, are presented in U.S. patent 3900518, 3941849 and 4472560, which is incorporated into this description by reference.

The number of Swithis at least about 2 equiv.% of the total used amount of starter. The total number of starter (St) is continuously added starter (Swithplus the amount of original loaded starter (Si). Thus. St+Si)]100. The number of Swithused in a particular case depends on many factors, including the size of the reactor, the target molecular weight, nature Swith, reasons for the use of Swithand other factors. For example, if Swithuse only for the elimination of paleologou tail fractions of high molecular weight in the traditional in all other respects, the method of DMC-catalyzed obtain polyol, the required number of Swithmay be small; the number of Swithused for this purpose, in the preferred case, is approximately from 2 to 10 EQ.%. Conversely, you may need to add more parts or the entire amount of starter in the form of Swithin particular, when you want to remove Paleologo starter based on the CON.

Swithcan be added continuously at any desired point in the polymerization process. For example, at the beginning may be added pure epoxide, followed by continuous addition of epoxide and Swith. In another variant, Swithadded with the epoxide in the initial stages of polymerization and then adding pure epoxide. The last-mentioned variant is illustrated by the Example of the Tarter (Si), which may be the same or different from the continuously added starter. The original downloaded the starter could be the "rest" of the preceding process of obtaining a polyol. For example, using DMC catalysis can get polyoxypropylene having a molecular weight of 2000 (2K diol), then remove 90% of the product. 10% of "the rest" 2K diol can be used as S; to get the other party 2K diol (diol or higher molecular weight). "Residual" process illustrates the Example below 7.

In General, Siis a polyol having srednekamennogo molecular weight of less than or equal to srednekamennogo molecular weight Paleologo product obtained from Si. In addition, Siin General, has a hydroxyl number of superior or equal to the hydroxyl number of the target Paleologo product.imay be a polyol of low molecular weight, such as glycerin or propylene glycol, provided that the amount used as Siless amount sufficient to deactivation of the DMC catalyst. In a more preferred embodiment, however, Siin the case of its use, can be a polyol more easigo. Preferred Siare polyether polyols having an average number of functional hydroxyl Pupp from 1 to 8, srednekislye molecular weight in the range of about 400-30000 and a hydroxyl number in the range, approximately, from 560 to 5 mg KOH/g

When enabled, Siin a way corresponding to the present invention, the amount used depends on many factors, including, for example, the size of the reactor, the nature of Si, the molecular weight of Siand the target product, the reasons for the use of Siand other factors. In a preferred embodiment, the number of Siin the case of its use is in the range of approximately from 1 to 98 EQ. % of the total volume used starter. Up to 98 EQ.% Sican be used, for example, in the case of applying it to eliminate paleologou tail fractions of high molecular weight upon receipt of polyols with conventional in all other respects DMC-catalyzed method. On the other hand, Sican be completely eliminated or used in small quantities, when the goal is getting Paleologo product, mainly from the continuously added starter.

the. Preferred inert solvents are aliphatic and aromatic hydrocarbons (e.g. toluene, hexane) and ethers (e.g. tetrahydrofuran). It is often necessary to obtain initial batch of polyol using an inert solvent, in particular, when the starter is mainly continuously added starter. Subsequent party polyol can be obtained using the "residual" method.

As will be clear to experts in the field of technology, there are many acceptable ways to use the method corresponding to the present invention, and each of them has its own advantages. A common feature for all modifications of this method is permanent add at least 2 equiv.% starter during polymerization of the epoxide. The following illustrates a few variations on this theme.

The first one uses the method corresponding to the present invention, is the traditional way to get Paleologo starter. For example, glycerin propoxylated to get propoxyethanol glicerynowego starter with a molecular weight of several hundred, and prod DMC catalyst and activate certain amount of propylene oxide. The additional amount of propylene oxide, which includes a small amount of water, propylene glycol or glycerin (Swith) add to get polyetherpolyols product molecular weight of several thousands. Swithincludes approximately from 2 to 10 equivalents. % of the total volume used starter. In the resulting politicheskogo product is a reduced amount paleologou tail fractions of high molecular weight (i.e., polyol, having srednekamennogo molecular weight of approximately more than 100,000, according to the results of measurements made by gel permeation chromatography using light scattering detector) compared with polyols obtained without continuous addition of starter. Such a scenario is illustrated below examples 8-10 and 12-15.

Previously described methods can be used to obtain a product, which includes a mixture of polyetherdiol and polyetherdiol. Such mixtures are often required as part polyurethane products with improved physical properties. In this embodiment, the continuously added starter is a diol such as propylene glycol or a mixture of the triol/diol (on olifirovich and triology components. Examples 12-15 illustrate the application of the method to obtain tzolova/dolovich mixtures.

In another method corresponding to the present invention, a large portion or the entire volume of the starter as a whole continuously add together with the epoxide to the reaction mixture, which includes active DMC catalyst. This method eliminates the need for Paleologo starter from COHN, illustrated in Examples 1-5. Initially in the reaction mixture composition is only DMC catalyst and a solvent (e.g. toluene) without Si. After activation of the catalyst to the reaction mixture continuously add epoxide, which includes a small amount of water or Paleologo starter (Swithsmall molecular weight. After this part of the reaction product is used as a starter (Sifor further polymerization. Thus, the DMC-catalyzed polyols successfully get using traditional polianovich starters low molecular weight, for example propylene glycol or glycerol, continuously adding them to the reaction mixture; in contrast, these starters are not used in the traditional ways (in which the entire starter download from the very beginning is Alenia almost any number of starter has important implications for the efficiency of the process. The dimensions of the reactor and raw materials, as a rule, limiting "factor accumulation", which can be used to obtain a specific product. Such restrictions on factor accumulation largely eliminated in a manner consistent with the present invention.

Suppose, for example, that we want to get 100 gallons (388,533 l) polyoxypropylene with molecular weight of 4000 (4K diol) from delovogo starter with a molecular weight of 2000 (2K diol). According to the traditional method, was charged to the reactor to about 50 gallons (189,266 l) 2K diol and DMC catalyst and add the propylene oxide to obtain 100 gallons 4K diol. The efficiency of the process is limited by the accumulation factor 2 (100 Gal/50 Gal.); half the volume of the reactor is only required for starter.

Consider how the method can be improved by using continuous addition of starter; in one of the methods of the present invention, in our reactor is loaded only 10 gallons (37,853 l) 2K delovogo starter to get 100 gallons 4K delovogo product (factor accumulation 10/1). Twenty percent (20 gallons (75,707 l)) end 4K delovogo of 1.6 percent (wt.) propylene glycol in the feed propylene oxide. Thus, 80 gallons (302,826 l) of the final product is 4K diol derived from propylene glycol, is added in the form of Swith. In General, the method corresponding to the present invention, provides the best use of the reactor and reduces the required number of relatively expensive 2K delovogo starter. Liquidated inherent in obtaining 4K diol from 2K diol restrictions on factor accumulation: we take the traditional factor accumulation and diology starter (molecular weight up to 4K) and continuously adding the calculated amount of starter (Swith) with the epoxide to obtain 4K delovogo product.

The method corresponding to the present invention, together with advantages in efficiency described in the above example, has a number of advantages. First, the present invention allows the use of water and polylogue starters low molecular weight for the DMC-catalyzed synthesis of polyols. In contrast, in the traditional DMC-catalyzed method for obtaining polyols are integrated starters (for example, propoxycarbonyl glycerin), to avoid problems due to slow initiation in the case ispolzovat be used water or polyol small molecular weight, the method eliminates the need for synthesizing expensive Paleologo starter higher molecular weight by means of KOH catalysis in separate, specially designed for this reactor. Such Paleologue starters require the removal of residues CON before using them to run DMC-catalyzed synthesis, because the Foundation inactivate DMC catalysts. Thus, to obtain a starter polyol, which could productively be used with the DMC catalyst, it is necessary traditional CON-polyol as one link with cleansing abilities. In General, a method that meets the present invention overcomes the aforementioned main limitation of the traditional DMC-catalyzed synthesis of polyols.

Thirdly, the method corresponding to the present invention, unexpectedly, allows to obtain the polyether polyols having a narrow distribution of molecular weight, is necessary to ensure good physical properties of polyurethanes. The methods used in the art, in General, indicated that the continuous addition of starter CON-catalyzed method will produce polyols having a very wide spread is a, in the case of DMC-catalyzed synthesis of polyols, allows to obtain polyols with a narrow distribution of molecular masses (see Example 5 and Comparative example 6).

The method corresponding to the present invention, can be used to obtain a variety polyetherpolyols products. These polyols, in the preferred embodiment, have srednekamennogo molecular weight in the range of about from 400 to 30,000, in the preferred embodiment, approximately from 500 to 10000. These polyols have an average number of functional hydroxyl groups in the range approximately from 1 to 8, in the preferred embodiment, approximately from 2 to 3. In addition, the above-mentioned polyols, in the preferred embodiment, have a hydroxyl number in the range, approximately, from 560 to 5 mg KOH/g, in the preferred embodiment, approximately from 280 to 15 mg KOH/g the above-Mentioned polyols having a low degree of unsaturation compared with polyols obtained using the CON. In a preferred embodiment, the above-mentioned polyols have a degree of unsaturation of about less than 0.02 IEC/g, in the preferred embodiment, approximately, less than 0,008 IEC/,

The present invention vlachopoulos continuous addition of epoxide and at least about 2 equiv.% Swithin the process of DMC-catalyzed synthesis of polyols. These polyols provide polyurethane compositions advantage of causing surprise and valuable. In particular, the composition of these polyols include reduced amount of paleologou tail fractions of high molecular weight, compared with previous DM-catalyzed and polyols.

The number paleologou tail fractions of high molecular weight can be determined quantitatively through analysis by means of gel permeation chromatography (GPC) using a light scattering detector (see Example A). Due to this, in the samples obtained by using a method corresponding to the present invention, we observed reduced levels paleologou tail fractions of high molecular weight. "Palilula tail fraction of high molecular weight" is part of Paleologo product having srednekamennogo molecular weight of approximately more than 100,000, according to the results of measurement using GPC as described in Example A. the Best is continuously added to the polymerization process even 2 equiv.% mentioned starter.

In General, the completion method, relevant to the present invention, depends on the molecular weight of the product; a proportionately greater amount of tail fraction of high molecular weight present in the polyols having a higher srednekislye molecular weight. In the case of polymerization at 130oWith a typical duration add epoxide component 6 hours, the correlation between the number paleologou tail fractions of high molecular weight and srednekamennogo molecular weight Paleologo product, expressed, approximately, as follows:

y=Pzx2< / BR>
where: y is the number of paleologou tail fractions of high molecular weight in parts per million (ppm), x - srednekislye molecular weight Paleologo product, divided by 1000, and a value of Pzis within approximately 30 to 40. Approximate number of tail fraction computed for polyoxypropylene with molecular weight of 8000, for example, would be 35(8000/1000)2=(35)(64)=2240. This value correlates well with the experimentally measured value, amounting to approximately 2000 ppm. As shown in Table 3, when the accelerated addition of epoxide (more stringent conditions) to image the molecular mass in Palilula the sample can be measured directly using GPC, as described previously. Another way of determining the number of tail fraction is the study Paleologo sample using critical tests foaming". While conducting the above tests, polyurethane receive by making sensitive composition, which ensures the destruction of the foam in the case, when the level paleologou tail fractions of high molecular weight in the sample, with srednekamennogo molecular weight of about 3000 to exceed approximately 300 ppm. More testing on the foam described in Example C. the Test foaming provides important information about the likelihood of a successful and predictable characteristics in industrial compositions of polyurethanes.

The inventor, to his own surprise, found that polyols having reduced the number of tail fraction of high molecular weight, it is much easier are introduced in the composition of polyurethane systems, especially elastic and molded foams, as they provide a more predictable characteristics and technological properties. The results obtained by the inventor show that changes in the characteristics of panopolis even small amounts of tail fraction polyols of high molecular weight. The polyols corresponding to the present invention, in particular, those which have a hydroxyl number in the range of approximately 50-60 mg KOH/g and comprised of, approximately, less than 300 ppm tail fractions of high molecular weight, according to measurements made using gel permeation chromatography, provide improved technological properties, cause fewer problems associated with the rigidity of the foam or its destruction, and provide flexible and molded polyurethane foam with excellent physical properties.

The following examples merely illustrate the present invention; specialists in the art will be apparent, numerous variations that can be made within the spirit of the present invention and the amount of points attached claims.

Examples 1-2

Receipt of polyether polyols by means of DMC catalysis and continuous addition of starter

A complex catalyst based on zinc hexacyanocobaltate/butyl alcohol (30 mg), prepared as described in Examples 8-11 EP-A-0743093, suspended in toluene (200 ml), sufficient to ensure the work was hampered by the which consisted of 1.9% (wt.) propylene glycol (20 g), and the mixture was heated to 130oFor activation of the catalyst. In this example, propylene glycol is continuously added starter" or "Swith".

The pressure in the reactor drops 2-3 minutes, indicating activation of the catalyst. In the reactor for 2.5 hours at 130oWith continuously add an additional amount of a mixture of propylene oxide/propylene glycol (280 g; 1.9 percent (wt.) propylene glycol). The toluene is removed by deformirovaniya under vacuum. In the reactor over the next 2.5 hours at 130oWith continuously add an additional amount of a mixture of propylene oxide/propylene glycol (300 g). The result is a 4K diol (hydroxyl number = 28 mg KOH/g), the DMC catalyst in which 50 ppm. Half of this product (300 g) is removed from the reactor and analyzed (see Example 1, table 1).

The remaining 300 g 4K diol (which includes 50 ppm active DMC catalyst) for 5 hours at 130oWith continuously add an additional amount of a mixture of propylene oxide/propylene glycol (300 g; 1.9 percent (wt.) propylene glycol). (In this example, propylene glycol is "Swith"at that time, as 4K diol obtained in Example 1 and left in the reactor, is what HE/g), the level of DMC catalyst which is 25 ppm. Diology product is removed and analyzed (see Example 2, table 1).

Examples 3-5

Receipt of polyether polyols by means of DMC catalysis and continuous addition of starter

A common way of Examples 1-2 is used to get 8K diol (from the water), 6K triode (from glycerol) or 2K diol (propylene glycol).

300 g 8K diol (hydroxyl number = 14 mg KOH/g), which includes 50 ppm of active catalyst based on zinc hexacyanocobaltate, used as S (source present starter) to get the next 8K diol as follows. For 2 hours at 130oTo a mixture of Paleologo starter/catalyst (Si) is continuously added propylene oxide (300 g), which includes 0,20% (wt.) water. (In this case, "Swith"water). The obtained product is 8K diol (hydroxyl number = 13.5 mg KOH/g), the DMC catalyst which is 25 ppm. The product is removed and analyzed (Example 3, table 1).

Similarly, 300 g 6K triol (hydroxyl number = 28 mg KOH/g) is used as S, to get the next 6K Tirol. For 2 hours at 130oWith K Sicontinuously EXT the received product is 6K triol (hydroxyl number = 27.7 mg KOH/g), the level of DMC catalyst which is 25 ppm. (Example 4, Table 1).

2K diol receive, as described previously, from 300 g 2K diol, which includes 50 ppm of active catalyst based on zinc hexacyanocobaltate (Si). Continuously added starter, Sc, is propylene glycol. The propylene oxide (300 g), which includes 3.8% (wt.) propylene glycol, is continuously added, as described earlier. The product is 2K diol (hydroxyl number = 56,2 mg KOH/g), the DMC catalyst which is 25 ppm. (Example 5, Table 1).

In Fig. 2 shows the gel permeation chromatogram of the original loaded 2K starter (Si). In Fig. 3, which is virtually identical to Fig. 2, presents a gel permeation chromatogram 2K Paleologo product obtained from 2K Si.

Comparative example 6

The effect of continuous addition of starter: KOH catalysis

This example describes the attempt to obtain 2K diol from 300 grams To 1,4 diol, which includes 2500 ppm of catalyst based on potassium hydroxide. First of 1.4 To the starter was obtained in the traditional way by adding propylene oxide to polyoxypropylene (molecular weight 425) via CON cat is 4 shows a gel permeation chromatogram of 1.4 To delovogo starter.

As in Example 5, the continuously added starter, Swithis propylene glycol. Within 4 hours to a mixture of KOH/1,4 TO polyol was continuously added propylene oxide (300 g), which includes 3.8% (wt.) propylene glycol. The product is 2K diol (hydroxyl number = 64,2 mg KOH/g). Cm. Comparative example 6, table 1. In Fig. 5 shows a gel permeation chromatogram 2K delovogo product.

As clearly shown in Fig. 4 and 5, the continuous addition of starter in the case of CON-catalyzed process is formed multidimarray product having a wide distribution of molecular weight. The specialist would expect similar results in the case of DMC-catalyzed process in which the continuous addition of starter. Surprisingly, however, the continuous addition of propylene glycol to the Siin the process of DMC-catalyzed polymerization leads to the formation of monodisperse product. (Compare Fig. 4 and 5 from Fig. 2 and 3).

Example 7

The "residual" method of obtaining polyetherdiol using a continuous addition of starter

4K polyoxypropylene receive the traditional way of a complex catalyst based on zinc hexanitrostilbene number = 155 mg KOH/g). Politicially starter is a purified product obtained from propylene glycol and propylene oxide by means of KOH catalysis. By adding propylene oxide in a period of 3.3 hours at 130oTo diolo (molecular weight 725) and the DMC catalyst was obtained 4K diol, composed of 125 ppm of DMC catalyst. The product had a hydroxyl number = 30 mg KOH/g; degree of unsaturation = 0,0049 IEC/g; Mw=3960; Mn=3700; and Mw/Mn=1,07.

From the reactor was removed about 80% of the product. The rest of the 4K diol ("balance", about 150 g) were used as starter (Sifor the next cycle of polymerization. For 5 hours at 130oWith the "balance" 4K diol is continuously added propylene oxide (600 g), which includes a 1.8% (wt.) propylene glycol. In this case, Sc - propylene glycol. The obtained product is 4K diol, the level of DMC catalyst which is 25 ppm. The product has a hydroxyl number = 29 mg KOH/g; degree of unsaturation = 0,0049 IEC/g; Mw=4600; Mn=3930; and Mw/Mn=1,17.

Examples 8-10

The effect of continuous addition of 5-22% starter (water)

8K polyoxypropylene get from the original downloaded 2K polyoxypropylene (Siand of propylene oxide, which consists of various amounts, the NCA of hexacyanocobaltate/butyl alcohol (0.015 g, 25 ppm in the finished polyol) and 2K polyoxypropylene (Si) (PPG-2025 diol, the quantity used are listed in Table 2). In the reactor add the propylene oxide (Sc) containing various amounts of water (from 125 to 500 ppm, see Table 2) (20 g), and the mixture is heated at 130oFor activation of the catalyst. After the pressure drop (5-10 minutes) into the reactor for 1 hour, add the remaining amount of the mixture of propylene oxide/water. (This is a very fast addition of propylene oxide, compared with the conventional industrial process, which is believed to are obtaining products having a relatively wide distribution of molecular weight). The water in the propylene oxide is from 5.5 to 22% of the total used amount of starter. The product in each case is the 8K polyoxypropylene (see Examples 8-10, table 2).

Comparative example 11

Without the continuous addition of starter

We use the technique of Examples 8-10, except that propylene oxide is used, do not contain additional water. Thus, the only audience starter is 2K polyoxypropylene downloaded from the outset (Si). Within 1 hour, as described earlier, add 2">

The results of Examples 8-10 and Comparative example 11 demonstrate causing surprise and valuable advantages of continuous addition of from 5.5 to 22% starter in the form of water. Continuous addition of water has provided 8K Polyoxypropylenediamine product, having a much more narrow distribution of molecular weight and significantly reduced viscosity (see Table 2).

Examples 12-15

The effect of continuous addition of 2-9% starter

The method of Examples 8-10, in General, has been used for volume 38 l (10 gallons) to obtain polyols suitable for the production of flexible polyurethane plates (trioli, all secondary hydroxyl end groups, hydroxyl number = 52 mg KOH/g).

The original audience starter, Siis LHT-240 triol (adduct of glycerin/propylene oxide, hydroxyl number = 240 mg KOH/g). The catalyst is a complex of zinc hexacyanocobaltate/butyl alcohol used in the amount of 25 ppm in the finished polyol. After activation of the catalyst at 130oC for about 4 hours at 130oWith the added mixture of propylene oxide and ethylene oxide (about 20% (wt.) of ethylene oxide) to achieve a hydroxyl number of about 69 mg is the reamers 12 and 13 as in the mixture of propylene oxide/ethylene oxide, and in closing 25% portion of propylene oxide activated water (200-500 ppm). In Examples 14 and 15, simultaneously with a mixture of propylene oxide/ethylene oxide (PO/EO) and the trailing portion of propylene oxide (PO), but by a separate thread is added to propylene glycol (2000 ppm). Added water or propylene glycol is present from 2 to 9% of the total used amount of starter. The total time of the filing of epoxides is 3-6 hours. Hydroxyl number formed of polyetherdiols approximately 52 mg KOH/g (see Table 3). These products are mixtures of triol/diol as adding propylene oxide to water or propylene glycol causes an increase in the content of the diol in these materials.

Each of these samples polyols subjected to a critical test on the foam described in example a (below). "Passing" the tests on the foaming means that paleology the sample includes approximately less than 300 ppm paleologou tail fractions of high molecular weight, i.e., polyol, having srednekamennogo molecular weight of approximately over 100,000, according to the results of measurement by gel permeation chromatography (GPC). Content paleologou tail fraction high molecule chromatography.

Comparative examples 16 and 17

Without the continuous addition of starter

We use the technique of Examples 12-15, except that 25% of propylene oxide, added as a trailing portions, do not contain any water or propylene glycol. The product is polyetherdiol, hydroxyl number which is about 52 mg KOH/g

Both of the above sample is not passed a critical test for foaming" of Example A. This result suggests that the composition of polyols include, approximately, more than 300 ppm paleologou tail fractions of high molecular weight. The results of gel permeation chromatography confirmed the presence of more than 200 ppm paleologou tail fractions of high molecular weight (see Table 3).

Example 18

Getting 4K diol by continuous addition of water

In this example, the 4K polyoxypropylene get, using water as the Swithand PPG-725 diol as Si. Water makes up 33% of the total used amount of the starter.

Charged to the reactor PPG-725 diol (150 g) and a complex of zinc hexacyanocobaltate/butyl alcohol (0,030 g, prepared as described in Examples 8-11 EP-A-0743093. The catalyst of the act (21 lbs/sq. inch to 12 pounds per square inch), indicating activation of the catalyst. After that add the propylene oxide containing water (1500 ppm to 0.15% (wt.), 3 g/min) up until added will not, in General, 450,

Half Paleologo product (about 300 g) from the reactor is removed and optionally add 300 g of propylene oxide, which includes 1500 ppm of water. The resulting polyetherpolyols has a hydroxyl number = 26 mg KOH/g; degree of unsaturation = 0,047 IEC/g; MP=4272; Mw=4478; Mmax=4278 and Mw/Mn= 1,048. In Fig. 1 shows the gel permeation chromatogram of the mentioned product.

Example 19

Obtaining PPG-725 through continuous add

This example shows how to get PPG-725 diol by continuous addition of propylene oxide, which comprises 10% (wt.) propylene glycol.

Charged to the reactor PPG-425 diol (polyoxypropylene, molecular weight 425, 150 g) and a catalyst based on zinc hexacyanocobaltate/butyl alcohol (0.075 g, prepared as described in Examples 8-11 EP-A-0743093). The catalyst activates the pure propylene oxide (23 g). The pressure in the reactor within 26 minutes decreases and add a further quantity of propylene oxide (105 g). noxide begin to apply a mixture of propylene glycol (10% (wt.)) in the propylene oxide. This mixture (495 g) is added at a speed of 4 g/min, the Total time of addition of the epoxide is about 2 hours. The mentioned product is polyoxypropylene, a molecular weight of 725, which includes about 100 ppm active DMC catalyst.

After that, PPG-725 diol is used as a starter to get polyoxypropylene, a molecular weight of 2900, "the traditional way", adding pure propylene oxide (450 g) to 150 g of PPG-725 diol with a speed of 4 g/min

An example of a

Method gel-penetrating chromatography was carried out (GPC)

Polyetherpolyols samples analyzed by gel permeation chromatography using unstabilized tetrahydrofuran (available from Burdick and Jackson) as eluent (flow rate = 1 ml/min). The device includes an isocratic high-pressure pump Hitachi, automatic dispenser for input samples Hitachi (or manual valve dispenser), single column PLgel 5 μm MIXED-D 3007,5 mm (available from Polymer Laboratories) and evaporative light scattering detector Sedex (Richard Scientific). To limit the amount of the sample to the detector, use Electromechanical switching valve Valco.

The device calibre (available from Polymer Laboratories). Paleologue samples get by dissolving 1% (mass ratio) of the polyol in tetrahydrofuran. Samples filtered using a 0.2 μm syringe filter and the chromatographic column is injected sample volume of 250 μl. In the process of chromatographic effluent is passed to a detector on a minute longer elution of standard polystyrene sample, a molecular weight of 100,000 (about 6 minutes). By this time the rest of the sample (most of the material is low molecular weight) away from the detector in the discharge stream. The flow of the sample to the detector resume by the end of the run to restore the zero line.

Square paleologou tail fractions of high molecular weight (i.e., polyol, suirvey to the elution volume of standard polystyrene sample, a molecular weight of 100000) in the sample is determined by electronic integration. The concentration of the tail fraction of high molecular weight is calculated using the area of the tail fraction of high molecular weight, square polystyrene standards of known concentration and the correlation between the maximum log area and log concentrations of the calibration curve. The values presented are the average of the two is animania

Traditional one-stage elastic polyurethane foams are mixed by hand and poured using below "intense" compositions. Composition is defined as "tense" because it deliberately given the sensitivity to the presence of paleologou tail fractions of high molecular weight. If the level of the tail fraction exceeds about 200 ppm, as a rule, there is destruction of the foam.

Side To receive from Paleologo sample subject to analysis (100 parts, usually, polyetherdiol, molecular weight 3000), water (6.5 parts), dichloromethane (15 parts), catalyst a-1 (a product of Air Products, 0.1 part), catalyst (T-9 (a product of Air Products, and 0.25 part) and surfactant L-550 (product of Dow Corning, 0.5 parts). Toluylenediisocyanate (78,01 part index NCO/OH 110) just add to the components side, the ingredients mix well and pour into the box. The foam rises and cures; register % deposition (or destruction).

The preceding examples are given only as illustrations; following claims define the scope of the present invention.

1. The method includes receiving Polief is b) is continuously added starter Swith(c) optionally, a source loaded starter Siwhere Scincludes at least about 2 equiv.% of the total volume used starter and where epoxide and Sccontinuously added to the reactor during polymerization.

2. The method according to p. 1, characterized in that the epoxide selected from the number of ethylene oxide, propylene oxide, butyleneglycol and mixtures thereof.

3. The method according to p. 1 or 2, wherein the DMC catalyst is a catalyst based on zinc hexacyanocobaltate.

4. The method according to p. 3, wherein the DMC catalyst is a complex catalyst based on zinc hexacyanocobaltate/butyl alcohol.

5. The method according to any of the preceding paragraphs.1-4, characterized in that the composition of polyetherpolyols includes a reduced number paleologou tail fractions of high molecular weight in comparison with polyetherpolyols obtained without the continuous addition of starter.

6. The method according to p. 5, characterized in that the composition of Scapproximately 2-10% of the total volume of the starter.

7. The method according to any of the preceding paragraphs, characterized in that the Scchoose from water and polyols low molekulalarni mass, selected from glycerol, trimethylolpropane, propylene glycol, dipropyleneglycol and dipropyleneglycol.

9. The method according to any of the preceding paragraphs, characterized in that the Siincludes paleology intermediate product having the average number of hydroxyl functional groups of approximately 2 to 8, a hydroxyl number in the range of approximately 28-560 mg KOH/g and srednekamennogo molecular weight in the range of about 400-4000.

10. The method according to any of the preceding paragraphs, characterized in that the composition of Sipart of polyetherpolyols obtained during the preceding polymerization.

11. Polyetherpolyols obtained by means of DMC catalysis, which includes the number of tail fraction of high molecular weight less than that calculated according to the formula y = PzX2where y is the number of paleologou tail fractions of high molecular weight in parts per million (ppm), X - srednekislye molecular weight of polyetherpolyols, divided by 1000, Pzhas a value in the range of about 30-40, where the tail fraction is srednekamennogo molecular weight of approximately more than 100,000, according to the results of measurements made srednoy standards.

12. Polyetherpolyols on p. 11, having a hydroxyl number in the range of approximately 50-60 mg KOH/g and comprising approximately less than 300 ppm paleologou tail fractions of high molecular weight.

13. Polyurethane-based polyetherpolyols according to any one of paragraphs.11 and 12.

14. Polyurethane on p. 13 in the form of a foam.

 

Same patents:

The invention relates to methods of producing double metallocyanide (DМС) catalysts for the polymerization of epoxy compounds

The invention relates to a double metallocyanide catalysts suitable for the polymerization of epoxy compounds

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The invention relates to an improved dual metallocyanide (DMC) catalysts and methods for their preparation

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The invention relates to a technology for production of polyurethane foams

The invention relates to polyurethane chemistry and relates to hydroxyl-containing composition to obtain a flexible polyurethane foam (PUF) cold forming and can be used in the furniture, automotive and aviation industries

FIELD: organic chemistry, polymer materials.

SUBSTANCE: polyester-polyols are obtained by double metalcyanide catalyzed polyaddition of alkylenoxide to starting material containing active hydrogen atoms. Alkylenoxide is continuously fed into reactor during induction period while maintaining constant pressure in reactor.

EFFECT: method for polyester-polyol production with decreased induction time.

2 ex, 1 dwg

FIELD: organic chemistry, in particular polyol composition for cold-cured polyurethane production.

SUBSTANCE: claimed composition contains (pts mass): polyethertriol or mixture of polyethertriol with molecular weight of 4500-6500 and average hydroxyl functionality of 3 - 100; ethylene glycol - 3.5-6.2; 1-4-butandiol - 3,5-8,0; triethylene diamine - 0.53-0.65; water - 0.25-0.50; organosilicate foam regulator - 0.002-0.004; and high boiling by-product from isoprene production based on alkyl- and oxyalkyl-substituted dioxacyclanes (e.g., 1,3-dioxane containing 1-4 mass % of hydroxyl groups) as organic filler - 2-100. Said filler may be used in mixture with oil plasticizer. Polyurethane obtained according to present method has Shore A hardness of 20-50, and is useful in automobile industry, and as material for gasket and sealing.

EFFECT: composition for production of polyurethane with increased hardness.

2 cl, 1 tbl, 3 ex

FIELD: polymer materials.

SUBSTANCE: polyurethane resin is a product of reaction of at least one diisocyanate component and isocyanate-reactive components having first group of at least one polyol, second group of at least one polyol, and third group of at least one polyol, at least one amine, and, additionally, reaction-stopping agent, all polyols of the first group having average molecular mass between 1000 and 10000 g/mole, those of second group having average molecular mass between above 10000 and 20000 g/mole, and those of third group having average molecular mass equal to or higher than 800 g/mole. Ratio of diisocyanate component to isocyanate-reactive components is selected such that all isocyanate groups are present as products of reaction with isocyanate-reactive functional groups. Resin is used as film-forming binder in coating compositions, in particular in printing inks for printing on polyolefin substrates. Printing ink is preferably used for manufacturing printed layered articles.

EFFECT: increased gluing ability and heat resistance of ink laid on plastic substrate.

41 cl, 2 tbl, 12 ex

FIELD: polymer production.

SUBSTANCE: polyol polyethers are prepared by cycle-cleaving polymerization of ethylene oxide and at least one alkylene oxide having at least three carbon atoms in molecule and attachable to H-functional initiator in presence of catalyst. H-functional initiator binds up to 40% (based on the weight of final polyol polyether) of ethylene oxide or mixture thereof with aforesaid alkylene oxide with at least 98 wt % ethylene oxide in presence of catalyst, which is at least one basic compound. To thus obtained polyol polyether, at least one alkylene oxide as defined above or mixture of ethylene oxide with the latter containing up to 20 wt % ethylene oxide is chemically added using as catalyst at least one metal cyanide-based compound.

EFFECT: enabled preparation of polyol polyethers with high level of ethylene oxide and low hydroxyl number.

3 cl, 3 tbl, 6 ex

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