CN1033093C - Process for the preparation of polyether polyols with reduced unsaturation - Google Patents
Process for the preparation of polyether polyols with reduced unsaturation Download PDFInfo
- Publication number
- CN1033093C CN1033093C CN 93104169 CN93104169A CN1033093C CN 1033093 C CN1033093 C CN 1033093C CN 93104169 CN93104169 CN 93104169 CN 93104169 A CN93104169 A CN 93104169A CN 1033093 C CN1033093 C CN 1033093C
- Authority
- CN
- China
- Prior art keywords
- unsaturation
- initiator
- parts
- weight
- degree
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
Landscapes
- Polyethers (AREA)
Abstract
Polyether polyols having an equivalent weight of from 200 to 4000 are prepared by the process of this invention. The process uses barium- or strontium-containing alkoxylation catalysts to provide products with reduced unsaturation in comparison to similar products produced with potassium hydroxide catalysis. In a preferred embodiment of the process, water is added during the reaction of the monoepoxy compound with the initiator. The quantity of water added is one percent or less by weight of the total weight of monoepoxy compound to be reacted with the initiator.
Description
The present invention relates to make a kind of organic polymeric polyisocyanate to contact and prepare the method for polyether polyols with reduced unsaturation with the polyhydric alcohol composition that contains 0.1 to 99.9% low-unsaturation-degree polyvalent alcohol.
The present invention relates to possess the preparation method of the polyether glycol of less degree of unsaturation.
The polyvalent alcohol that is used to the to prepare urethane initiator compounds by containing reactive hydrogen atom and alkylene oxide usually reacts in the presence of alkaline alkoxylating catalyst such as tertiary amine or sodium hydroxide and potassium hydroxide or potassium alcoholate and sodium alkoxide and prepares.Yet, though all use these catalyzer usually, they can cause producing the polyvalent alcohol of high degree of unsaturation, particularly like this when these polyvalent alcohol equivalents are higher.
Propylene oxide through base catalysis when containing the initiator addition of reactive hydrogen atom, mainly be growth by secondary hydroxyl terminated polyoxyalkylene chain.Yet, under the reaction conditions of temperature, pressure and catalyst concn and so on, before itself and initiator for reaction, form undersaturated vinyl carbinol thereby isomerization and rearrangement reaction can take place propylene oxide.
Can increase with the reactive hydrogen of propylene oxide reaction and then the molecular weight that has limited on required initiator because vinyl carbinol contains, institute is so that prepare the ability of high equivalent weight product and descend to some extent in the presence of vinyl carbinol.Along with needed polyvalent alcohol equivalent increases, the problem of degree of unsaturation becomes more serious.
When the polyvalent alcohol that adopts high equivalent weight with high degree of unsaturation prepares such as flexible foam plastic polyether polyols with reduced unsaturation, can produce the product that possesses unsaturated characteristic.So just, can run into such as foam fade, ultimate compression strength and tensile strength is low, reactive low, modulus in flexure is low with anti-moisture aging a little less than problem.So, be necessary to provide a kind of method that reduces degree of unsaturation in this class polyvalent alcohol, so that prepare improved polyether polyols with reduced unsaturation.
People such as Dege have disclosed the kind of end group degree of unsaturation and have reduced the method for degree of unsaturation by the purpose product being carried out acid treatment (1959) the 3374th pages of " JACS " the 81st volumes.The degree of unsaturation that is used for preparing the polyvalent alcohol of polyether polyols with reduced unsaturation can be reduced by product is carried out acid treatment according to content described in United States Patent (USP) 2996550 and 3271462.
United States Patent (USP) 3393243 has been introduced and has been utilized IA family metal catalyst cesium hydroxide to prepare the polyoxygenated propylidene polyether glycol that its equivalent reduces to some extent for 1500-2500, its degree of unsaturation quantity.Because the molecular weight height of caesium needs a large amount of catalyzer when operating under waiting volumetric molar concentration, so compare with alternative surrogate-basic catalyst, the cost of this catalyzer is too expensive.
Recently, EP268922-A and EP268920-A report utilizes cesium hydroxide to make alcohol that alkoxylation take place as catalyzer and can produce the less product of degree of unsaturation.
Be necessary exploitation-kind can prepare low-unsaturated polyether polyatomic alcohol and minimizing or exempt and use such as cesium hydroxide expensive catalyst and/or reaction product is carried out acid-treated method.
In the presence of promotor, use to contain the ethoxylation that titanate catalyst carries out alcohol and can make nonionogenic tenside, referring to, for example, United States Patent (USP) 4210764,4239917 and EP46647.
It is 187 or the method for lower polyether glycol that the hydrated barta preparation that Japanese Patent 55/092,733-A have been introduced the combination of use and carbonic acid gas contains oxyethane, equivalent.The product that so makes is because wherein remaining alkoxylating catalyst content is very low thereby be applicable to preparation rigidity or semi rigid urethane foam.
Have found that high equivalent weight and low-unsaturated polyether polyatomic alcohol can prepare by the catalyzer that employing contains alkaline-earth metal barium and strontium.
At first, thereby the present invention relates in the presence of catalyzer to contain at least two initiator for reaction that contain active hydrogen group in monocycle oxycompound and the per molecule and prepare the method that its equivalent is the polyvalent alcohol of 200-4000, the method is characterized in that catalyzer wherein is selected from the mixture of barium or strontium or their oxide compound, oxyhydroxide, hydroxide hydrate or single hydroxide salt or these materials by making.
Secondly, the present invention relates to prepare the method that its equivalent is the polyvalent alcohol of 200-4000, this method is included in to make under the catalyzer existence and contains at least two initiator for reaction that contain active hydrogen group in monocycle oxycompound and each molecule, it is characterized in that catalyzer wherein is selected from the mixture of barium or strontium or their oxide compound, oxyhydroxide, hydroxide hydrate or single hydroxide salt or these materials, its feature also was between the above-mentioned reaction period, gross weight in the monocycle oxycompound is a benchmark, is added with the nearly water of 1% (weight).
The 3rd, the present invention relates to polyvalent alcohol by the inventive method preparation.
The 4th, the present invention relates to contain the polyhydric alcohol composition of 0.1-99.9% (weight) by the polyvalent alcohol of the inventive method preparation.
The 5th, the present invention relates to by making organic polymeric polyisocyanate and the polyvalent alcohol made polyether polyols with reduced unsaturation that is in contact with one another and then reacts by the inventive method preparation.
Surprisingly the invention provides a kind of method for preparing high equivalent weight, low-unsaturation-degree polyvalent alcohol.In addition, compare with the normal conditions of using potassium hydroxide catalyst, the present invention allows product to exist under higher temperature of reaction and catalyst concn and can improve degree of unsaturation quantity seasonably.
As mentioned above, can have at least two initiator generation alkoxylations that contain active hydrogen group in each molecule and prepare the low saturation polyvalent alcohol that equivalent is 200-4000 by making.Be used for of the present invention contain active hydrogen group be defined to famous Zerewitinoff test can take place positive reaction those contain hydrogen group.Referring to Kohler, " JACS " the 49th volume (1927), the 3181st page.Representationally contain active hydrogen group and comprise-OH ,-COOH ,-SH and wherein R be hydrogen, alkyl, cycloalkyl and aryl-NHR.Be good wherein with hydroxyl.
The hydroxyl of initiator can be primary hydroxyl or secondary hydroxyl.In order to make catalyzer possess resolvability, suitable employing contains the initiator or the initiator mixture of primary hydroxyl.
As being applicable to the initiator for preparing polyvalent alcohol by the inventive method, containing 2-8 in each molecule individual, individual with 2-4 is the good active hydrogen group that contains, and its equivalent is 5-1500, is good with 9-750, for better, is best with 80-300 with 50-550.
The example of suitable initiator comprises water, glycerine, TriMethylolPropane(TMP), tetramethylolmethane, hexanetriol and various isomer, such as lactose, the Alpha-Methyl glucoside, α-hydroxyethyl glucoside, hexitol, heptitols, sorbyl alcohol, dextrose, mannitol, the carbohydrate of sucrose and so on, such as ammonia, quadrol, Diethylenetriamine, aminoethyl piperazine, aniline, the amine compound of diaminotoluene and so on, aromatic substance such as the condensation product of the condenses of phenol and acetone or formaldehyde or phenol and formaldehyde and alkanolamine, and their mixture.Other suitable initiator also comprises polyoxyalkylene glycol and other polyoxyalkylene polyols.United States Patent (USP) 4269945 and 4394431 has disclosed the initiator that contains active hydrogen group of having that other is suitable for.
Preferred initiator comprises water, ethylene glycol, 1,2-propylene glycol, 1, ammediol, the various isomer of butyleneglycol, pentanediol and hexylene glycol, glycerine, TriMethylolPropane(TMP), tetramethylolmethane, quadrol and their polyoxyalkylene adducts, and composition thereof.
Be applicable to monocycle oxycompound of the present invention comprise α-and β-alkylene oxide and halo and Fang Dai derivative, contain the glycidyl ether of 3-20 carbon atom, the cyclic ethers such as tetrahydrofuran (THF), and composition thereof.
The example of suitable alkylene oxide comprises oxyethane, 1,2 epoxy prapane, 1,2-butylene oxide ring, 2,3-butylene oxide ring, Styrene oxide 98min., Racemic glycidol and Epicholorohydrin.The example of suitable glycidyl ether comprises glycidyl allyl ether, phenyl glycidyl ether and butylglycidyl ether.
The preferred monocycle oxycompound that is applicable to the inventive method comprises oxyethane, 1,2 epoxy prapane, 1,2-butylene oxide ring, 2,3-butylene oxide ring and composition thereof.When the monocycle oxycompound with initiator for reaction comprised propylene oxide or butylene oxide ring, the inventive method was particularly useful for preparing polyvalent alcohol.Wherein thereby propylene oxide is easier to take place isomerization reaction than other oxide compound and produces degree of unsaturation.
The kind of oxide compound and quantity and charging sequence (random or block) depend on the purpose application of the final equivalent and the urethane of product to be prepared.For instance, when needing the polyvalent alcohol of hyperergy, the charging sequence can stop so that obtain containing the product of primary hydroxyl with oxyethane.
Equivalent according to the polyvalent alcohol of the inventive method preparation is 200-4000, is good with 500-3500, with 1000-2500 for better.Aptly, when making this class polyvalent alcohol, with the gross weight of the monocycle oxycompound of initiator for reaction 45, with 60 be good, with 70 for better, to 100% (weight) nearly be propylene oxide and/or butylene oxide ring.In addition, resulting polyvalent alcohol be characterised in that their degree of unsaturation sum be lower than aptly 0.100 milliequivalent/gram polyvalent alcohol, be lower than 0.080 for good, be lower than 0.050 for good, be lower than 0.040 for better, be the best to be lower than 0.020.
When needing the polyvalent alcohol of hyperergy, this polyvalent alcohol can be determined on a case-by-case basis and contain terminal primary hydroxyl by making oxyethane (EO) suitably react and form in the final stage of alkoxylation.This class polyvalent alcohol is defined as the EO capped polyols.The quantity that is used as the end capped oxyethane of polyoxyalkylene polyols depends on the required whole polyol reaction and the equivalent of purpose product.-as under the situation, the quantity that increases oxyethane can improve reactivity.Aptly, adopt the EO of capacity can obtain containing to account for polyvalent alcohol total hydroxy at least 25% primary hydroxyl, with at least 45% for good, be better product with at least 65%.
Be used for the inventive method so that promote the catalyzer of alkoxylation to comprise the mixture of barium, strontium and their oxide compound, oxyhydroxide, hydroxide hydrate, single hydroxide salt or these materials, preferred catalyzer is hydrated barta, hydronium(ion) oxidation barium and single oxyhydroxide barium salt or their mixture and the strontium compound that is equal to.Particularly preferably hydrated barta-hydrate.
When preparing polyvalent alcohol by the inventive method, catalyst concentration makes product form in acceptable time.Aptly, be benchmark in the initiator gross weight that exists, at least 100ppm, be that good metallic cation is fit to katalysis is played in reaction with 500ppm at least.Preferably, be benchmark in the initiator weight of question response, catalyst consumption be 0.01-50% (weight), with 0.01-30% (weight) for better, be the best with 0.01-15% (weight).
The catalyst levels that is used for catalyzed reaction must make in neutralization or before removing the treating processes of remainder catalyst formed crude product contain in existing purpose product weight be benchmark be less than the 20000ppm metal, so that to be less than 10000ppm be good and be the best to be less than 5000ppm.If the catalyst content in the resulting crude product is excessive, just can't effectively neutralize and/or filter so that remove catalyzer.
In the preferred embodiment of the inventive method, during in the presence of the above-mentioned catalyzer alkoxylation taking place, can add the water of controlling the size at initiator and alkylene oxide.
The water yield that adds between the reaction period must be enough to further reduce the degree of unsaturation quantity of final alkoxylation product, realizes that the required water yield of this purpose can change with selected initiator, monocycle oxycompound kind and reaction conditions.Generally speaking, be benchmark in gross weight with the monocycle oxycompound of initiator for reaction, the water yield can reach 1% (weight), is good with 0.1% (weight) nearly.Aptly, be benchmark in the gross weight that remains with the monocycle oxycompound of initiator for reaction, the water yield be about the 1/1000-1/20000 weight part, with the 1/1000-1/7000 weight part be good, with the 1/3000-1/5000 weight part for better.
The addition manner of water is not most important, and it depends primarily on selected equipment and device.The interpolation of water can be added into to increase progressively between the reaction period to add or be added into the substep process that reaction hockets with the monocycle oxycompound and finishes by being included in the monocycle oxycompound.In addition, can select the adding mode that comprises that water and monocycle oxycompound are added simultaneously continuously for use.Under latter event, depend on selected equipment, water and monocycle oxycompound can be used as a kind of mixture flow or two kinds of independent logistics are added into.Whenever possible, based on the consideration of economy and equipment capacity aspect, be necessary to add water by continuation method." continuously " speech can be understood that water and the charging of monocycle oxycompound begin and termination simultaneously.
When adding entry, aptly, the monocycle oxycompound of initial number and initiator were reacted before adding first water with the method for fractional steps.The monocycle oxycompound of the initial number that is added only need lack to accounting for produces 5% of the required single epoxy group(ing) charging total amount of necessary equivalent product, but is good with at least 15%, with at least 25% for better.
According to the inventive method, this reaction suits to carry out under 60-180 ℃, is good with 75-130 ℃, with 80-125 ℃ for better.This reaction is carried out under the pressure that is no more than 150 pounds of/square inch (1034Kpa) (gauge pressures) usually in closed system usually, to be no more than 120 pounds/square inch (827kpa) for good, is the best to be no more than 75 pounds/square inch (520kpa).These pressure values keep by the quantity of oxide compound in the gas phase under control feeding rate of alkylene oxide and then the control reaction temperature.What exceed bring usefulness and can form the product with high chroma or degree of unsaturation can not for usually the quality of formed product with the temperature and pressure that is higher than these spans.
Can and/or remove by any those skilled in the art currently known methods neutralization by catalyzer remaining in the polyvalent alcohol of the inventive method preparation, for example, according to United States Patent (USP) 3000963 described employing such as phosphoric acid, sulfuric acid, acetate and solid organic acid catalyst neutralisation.Catalyzer can also be removed or be removed on the activated earth by being attracted to such as Magnesium Silicate q-agent by the described CO 2 refining step of Japanese Patent 55/092733-A.Remove and/or catalyst neutralisation after, the metallic cation content of polyvalent alcohol is lower than 500ppm aptly, is good to be lower than 100ppm, to be lower than 50ppm for better.The catalyst concn that exceeds and be higher than these spans can not help using this product usually and prepare urethane.
Polyvalent alcohol by the inventive method preparation can be produced polyether polyols with reduced unsaturation or form composition with other compound that contains reactive hydrogen with the polymeric polyisocyanate reaction.This based composition possesses and comprises the many purposes that prepare polyether polyols with reduced unsaturation.Polyhydric alcohol composition contains one or more polyvalent alcohols by the inventive method preparation of 0.1-99.9% (weight).
When making by the polyvalent alcohol of the inventive method preparation and polymeric polyisocyanate prepared in reaction polyether polyols with reduced unsaturation, the visual particular case of reaction system contains other active hydrogen compounds, catalyzer, tensio-active agent, stablizer, filler, dyestuff, fire retardant, whipping agent and other additive.United States Patent (USP) RE24514,3821130 and English Patent 1534258 introduced the proper method of preparation polyether polyols with reduced unsaturation.J.H.Saunders and K.G.Frisch roll up at " polyurethane chemistry and technology " I, II, R.E.Krieger publishing company, and Ine has further discussed the suitable apparatus and method for for preparing polyether polyols with reduced unsaturation among the ISBN 0-89874-561-6.
The polyvalent alcohol of the inventive method preparation is applicable to the required polyether polyols with reduced unsaturation of the many Application Areass of preparation.These fields comprise that magma material and molded foam plastics, carpet use and the insulation rigid foam with lining and lamination.Can also prepare and comprise the suitable non-microvoid polyurethane polymkeric substance of making coating, sole and molding application and so on elastomerics.
In addition, the polyvalent alcohol of the present invention's preparation can also be used in preparation isocyanate end prepolymer process polymeric polyisocyanate be carried out modification.
The following example supplies to describe the present invention's usefulness but is not the formation limitation of the scope of the invention.Except as otherwise noted, all umbers are weight part.Except as otherwise noted, the input speed of monocycle oxycompound must make reactor pressure constant till about 40-60psig (275-415kpa gauge pressure) is when the charging that drops into reaction reaches desired number.
According to the equivalent of the viewed hydroxy number calculating of ASTME326-69 method product, determine total degree of unsaturation by ASTMD2849-69.Show " carrying out quantitative organic analysis by functional group " the 4th edition by Siggia, the described method of ISBN0-471-03273-5 is determined propenyl degree of unsaturation (vinyl ether).
All degree of unsaturation values relate to all wherein that catalyzer has been neutralized and/or by the product of filtering.
Embodiment 1
With 203 parts of equivalents is that the initiator mixture of 200 polyoxygenated trimethylene glycol and 47 parts of hydrated barta eight hydrates is heated to 135 ℃ and carry out flash distillation till all oxyhydroxide are all dissolved." flash distillation " speech is meant by being lower than an atmospheric pressure and removes water.But the reduced pressure that is adopted is enough to remove water but can remove other volatile products.Flash distillation proceeds to that free water content is reduced to till about 2500ppm in the mixture.
With 444 parts of propylene oxide under 100 ℃ temperature of reaction to be enough to the keeping speed of this constant voltage of about 45-60psig (275-415kpa gauge pressure) to be added in 61 parts of initiators.The equivalent of resulting product is 1575, degree of unsaturation is 0.020 milliequivalent/gram.Subsequently with 140 parts of oxyethane under identical temperature and pressure to this product carry out that thereby termination process obtains that its equivalent is 1975, its proportion of primary OH groups is 91.4% final product.
Embodiment 2
With 431 parts of propylene oxide under 95 ℃ temperature of reaction to be enough to the keeping speed of this constant voltage of about 45-60psig (275-415kpa gauge pressure) to add in the initiator of 42 parts of embodiment 1.The equivalent of resulting product is 2425, degree of unsaturation is 0.035 milliequivalent/gram.Subsequently with 117 parts of oxyethane to this product carry out that thereby termination process obtains that equivalent is 3000, proportion of primary OH groups be 93.0% and degree of unsaturation be the purpose product of 0.028 milliequivalent/gram.
Embodiment 3
75 parts of hydrated barta-hydrates are added in 140 parts of single trimethylene glycols (MPG).With this mixture heating up to 90 ℃ and carry out flash distillation till all catalyzer are all dissolved.To form equivalent be 210 and contain the midbody product of 10% (weight) hydrated barta catalyzer of having an appointment to add propylene oxide subsequently.300 parts of propylene oxide are added under 95 ℃ in 43 parts of these midbody products, add 90 parts of oxyethane subsequently.The equivalent of purpose product is 2000, proportion of primary OH groups is 90%, degree of unsaturation is 0.017 milliequivalent/gram.
Embodiment 4
Prepare initiator mixtures and hold it in 105 ℃ by 128 parts of MPG, 28.5 parts of hydrated barta-hydrates and 67 parts of hydrated barta eight hydrates, carry out flash distillation simultaneously till all catalyzer are dissolved.Cool the temperature to 95 ℃ and add 350 parts of propylene oxide and form its hydroxyl equivalent and be about 225 intermediate product subsequently.
In temperature of reaction is 445 parts of propylene oxide to be added under 90 ℃ among 38 parts of above-mentioned intermediate products again, adds 98 parts of oxyethane subsequently.The equivalent of resulting product is 2735, proportion of primary OH groups is 88%, degree of unsaturation is 0.022 milliequivalent/gram.
Embodiment 5
Making 39 parts of embodiment, 4 described initiator mixtures and 36 parts of hydroxyl equivalents be about 225 polyoxygenated trimethylene glycol mixes.22 parts of propylene oxide are added under 90 ℃ temperature of reaction in the mixture of 41 parts of above-mentioned gained, add 53 parts of oxyethane subsequently.The equivalent of resulting product is 1000, proportion of primary OH groups is 72.5%, degree of unsaturation is 0.009 milliequivalent/gram.
Embodiment 6
20 parts of propylene oxide are added under 95 ℃ temperature of reaction in 5 parts of embodiment, the 4 described initiator mixtures.The equivalent of resulting polyoxygenated trimethylene glycol is 1150, degree of unsaturation is 0.017 milliequivalent/gram.
Embodiment 7
25 parts of propylene oxide are added under 95 ℃ temperature of reaction in 3.15 parts of embodiment, the 4 described initiator mixtures.The equivalent of resulting polyoxygenated trimethylene glycol is 1725, degree of unsaturation is 0.024 milliequivalent/gram.
Embodiment 8
By 25 parts of strontium hydroxide eight hydrates are being dissolved among 75 parts of MPG and are making a mixture behind vaccum dewaterings under 95 ℃.Under 95 ℃ temperature of reaction, propylene oxide (380 parts) added in this mixture and be about 230 midbody product so that obtain equivalent.Subsequently 20 parts of propylene oxide are added in 5 parts of these midbody products.The equivalent of resulting polyoxygenated trimethylene glycol is 1150, saturation ratio is 0.018 milliequivalent/gram.
Embodiment 9
5 parts of embodiment, 8 described intermediates and 32.5 parts of its equivalents of propylene oxide are 1585 by making, degree of unsaturation is the polyoxygenated trimethylene glycol of 0.026 milliequivalent/gram.
Embodiment 10
By being to prepare initiator among 150 the polyether triol under 120 ℃ hydrated barta-hydrate being dissolved in equivalent.It is applied negative pressure till all catalyzer are all dissolved, form the solution that contains 0.075 mol catalyst/every mole of OH this moment.350 parts of propylene oxide are added under 110 ℃ temperature in 30 parts of these initiators, add 62 parts of oxyethane subsequently and form the end-blocking product that contains 14% (weight) oxyethane.The equivalent of resulting product is 2150, proportion of primary OH groups is 84.1%, degree of unsaturation is 0.035 milliequivalent/gram.
Embodiment 11
According to embodiment 10 preparation initiators, different is that wherein catalyst concn is 0.067 mol catalyst/mole OH.400 parts of propylene oxide are added under 130 ℃ temperature of reaction in 34 parts of these initiators, form the end-blocking product that contains 14% (weight) oxyethane thereby add 71 parts of oxyethane subsequently.The equivalent of product is 1975, proportion of primary OH groups is 81.8%, degree of unsaturation is 0.073 milliequivalent/gram.
Embodiment 12
According to embodiment 10 preparation initiators, different is that wherein catalyst concn is 0.106 mol catalyst/mole OH.493 parts of propylene oxide are added under 100 ℃ temperature of reaction in 35 parts of initiators, add 93 parts of oxyethane subsequently.The equivalent of products therefrom is 2390, proportion of primary OH groups is 87.6%, degree of unsaturation is 0.032 milliequivalent/gram.
Embodiment 13
According to embodiment 10 preparation initiators, different is that wherein catalyst concn is 0.106 mol catalyst/mole OH.700 parts of propylene oxide are added under 100 ℃ temperature of reaction in 35 parts of initiators, add 130 parts of oxyethane subsequently.The equivalent of products therefrom is 2740, proportion of primary OH groups is 89.8%, degree of unsaturation is 0.034 milliequivalent/gram.
Embodiment 14
According to embodiment 10 preparation initiators, different is that wherein catalyst concn is 0.106 mol catalyst/mole OH.950 parts of propylene oxide are added under 100 ℃ temperature of reaction in 35 parts of initiators, add 174 parts of oxyethane subsequently.The equivalent of products therefrom is 3400, proportion of primary OH groups is 88.8%, degree of unsaturation is 0.039 milliequivalent/gram.
Embodiment 15
By the inventive method, to adopt the used initiator of hydrated barta catalyzer and embodiment device to prepare equivalent respectively be 1350 and 1650, contain the polyether glycol of 12% and 15% oxyethane (end-blocking).Adopt the potassium hydroxide catalyst preparation similarly with reference to polyvalent alcohol.Table I provides the total concn of these products and their degree of unsaturation and the degree of unsaturation of propylidene characteristic.
By these data as can be seen, with Preparation of Catalyst polyether glycol of the present invention degree of unsaturation in the purpose product is obviously descended.In addition, as can be seen, minimizing obviously falls in propylidene part in the degree of unsaturation, and the temperature according to the equivalent and the alkoxylation of product has reduced about 30-80%.When being exposed to acid or moist condition following time, the polyether polyols with reduced unsaturation that the polyvalent alcohol that is descended to some extent by propylidene degree of unsaturation is wherein made presents the stability that is improved and is difficult for incipient scorch in porous plastics.
Table 1
| Product equivalent (% oxyethane) | Catalyst concn m/mOH ① | Temperature of reaction (℃) | Total degree of unsaturation meq/g | Propylidene degree of unsaturation meq/g | Primary hydroxyl % |
| 1350(12％) 1650(15％) 1350 ④(12％) 1650 ④(15％) | (Ba)0.085 (Ba)0.085 (K)0.085 (K)0.085 | 120 115， 120 115 | 0.033 0.030 0.061 0.061 | 0.001 0.005 0.005 0.008 | 75 83 70 80 |
1. catalyzer mole number/initiator OH mole number.(Ba)-hydrated barta; (K)-potassium hydroxide.
2. total degree of unsaturation.
3. propylidene degree of unsaturation.
4. correlation data, the non-embodiment of the invention.
Embodiment 16
This embodiment describes by substep and adds the method that entry prepares polyvalent alcohol.
To be the initiator mixture heating formed of 163 polyoxygenated propylidene triol and 8.5 parts of hydrated barta-hydrates and carry out flash distillation till all oxyhydroxide dissolvings by 100 parts of equivalents.Resulting initiator mixture contains 7.9% (weight) with-hydrated barta that hydrate is represented.
It is in 120 ℃ the initiator mixture that 50 parts of propylene oxide are added to 20 parts of temperature with the speed that keeps constant voltage to be about 45-60psig (275-415kpa).Add 0.037 part of water subsequently, meanwhile keep temperature and pressure constant.
Add 50 parts of propylene oxide and 0.037 part of water subsequently again, add 52 parts of propylene oxide at last for the third time and add 0.037 part of water for the third time.Like this, in 20 parts of initiator mixtures, add 152 parts of propylene oxide and 0.111 part of water altogether.
The weight ratio of water and propylene oxide is 1: 1370.
After the fill process of finishing propylene oxide and water, reaction mixture remained under 120 ℃ the temperature till constant reaction pressure.
When reaching constant voltage, by with Magnesium Silicate q-agent processing reaction product crude product and filter and remove remaining alkoxylating catalyst.After this, in 1 hour, the pressure in the reactor is reduced to about 0.10 and clings to and remove all volatility products.
The molecular weight of reaction products resulting is 4350, and equivalent is 1450, and total degree of unsaturation is 0.036 milliequivalent/gram.
Embodiment 17
This embodiment describes the preparation method of the polyvalent alcohol that water wherein is imported into by continuous processing.
To amount to 152 parts of propylene oxide and 0.149 part of water adds in the initiator mixture of 20 parts of embodiment 16 under 120 ℃ temperature of reaction with the speed that keeps constant voltage to be about 45-60psig (275-415kpa).Propylene oxide and water begin simultaneously with these two kinds of chargings as logistics independently and simultaneously terminated speed be added into.The weight ratio of water and propylene oxide is 1: 1016.
After the fill process of propylene oxide and water is finished, according to embodiment 16 described mode processing reaction products.
The molecular weight of reaction products resulting is 4400, equivalent is 1467, total degree of unsaturation is 0.036 milliequivalent/gram.
Embodiment 18
This embodiment carries out according to the step of embodiment 16.
Add in the initiator mixture of 20 parts of embodiment 16 amounting to 152 parts of propylene oxide and 0.037 part of water.
Water is 1: 4031 with the ratio of the parts by weight of propylene oxide.
The molecular weight of resulting product is 4350, equivalent is 1450, and total degree of unsaturation is 0.036 milliequivalent/gram.
Embodiment 19
This embodiment carries out according to the step of embodiment 17.
Add in the initiator mixture of 20 parts of embodiment 16 amounting to 152 parts of propylene oxide and 0.089 part of water.
Water is 1: 17000 with the ratio of the parts by weight of propylene oxide.
The molecular weight of resulting product is 4450, equivalent is 1483, and total degree of unsaturation is 0.041 milliequivalent/gram.
Embodiment 20
This embodiment 17-19 in conjunction with the embodiments is described under the similar method condition and can reducing degree of unsaturation further during the alkoxylation when adding entry.In this embodiment, the method condition is identical with embodiment 17-19, but does not add entry.
Add in 20 parts of embodiment, the 16 resulting initiator mixtures with the speed that keeps constant voltage in the reactor to be about 45-60psig (275-415kpa) under 120 ℃ temperature of reaction amounting to 152 parts of propylene oxide.
Treating that propylene oxide is added finishes, according to embodiment 16 described processing reaction products.
The molecular weight of resulting product is 4400, equivalent is 1467, and total degree of unsaturation is 0.048 milliequivalent/gram.
Embodiment 21
This embodiment describes the production method of glycol, and wherein water is imported into by continuous processing.
To be the initiator mixture heating formed of 200 polyoxygenated trimethylene glycol and 11 parts of hydrated barta-hydrates and carry out flash distillation till all oxyhydroxide dissolvings by 100 parts of hydroxyl equivalents.Resulting initiator mixture contains 10.1% (weight) hydrated barta-hydrate.
190 parts of propylene oxide of total and 0.051 part of water are added in 20 parts of resulting initiator mixtures with the speed that keeps constant voltage to be about 45-60psig (275-415kpa) under 120 ℃ temperature of reaction.Propylene oxide and water are imported into while charging and while terminated speed as independent flow.The weight ratio of water and propylene oxide is 1: 3725.
Treat that propylene oxide and water add when finishing, according to embodiment 16 described processing reaction products.
The molecular weight of reaction products resulting is 3300, equivalent is 1650, total degree of unsaturation is 0.042 milliequivalent/gram.
Adopt low molecular weight diols, three pure and mild other polyoxyalkylene glycols to replace water can't make degree of unsaturation occur similarly reducing.Similarly, adopt other traditional alkoxylating catalyst such as potassium hydroxide to replace the above-mentioned alkoxylating catalyst of present method can't make the degree of unsaturation of products therefrom occur similarly descending.
Comparative Examples A
Prepare initiator by potassium hydroxide is dissolved in equivalent under 120 ℃ in the polyoxygenated trimethylene glycol of OO.Dissolving sufficient hydrogen potassium oxide forms the solution that contains 0.041 mol catalyst/mole OH.330 parts of propylene oxide are added under 90 ℃ temperature of reaction in 50 parts of initiators.The equivalent of resulting product is 1575, degree of unsaturation is 0.044 milliequivalent/gram.Degree of unsaturation 0.020 milliequivalent/gram among this and the embodiment 1 contrasts, although embodiment 1 finishes test under comparatively high temps, this can improve degree of unsaturation usually.
Comparative example B
200 parts of propylene oxide are added in the initiator of 34 parts of Comparative Examples A 90 ℃ of reactions down.Subsequently with 32 parts of reacting ethylene oxides.The equivalent of resulting product is 1000, degree of unsaturation is 0.024 milliequivalent/gram.This with under the identical process temperature among the embodiment 5 degree of unsaturation 0.009 milliequivalent/gram contrast.
Comparative example C
By potassium hydroxide is dissolved in hydroxyl equivalent under 120 ℃ is to prepare initiator in 67 the polyoxygenated trimethylene glycol.Dissolving sufficient hydrogen potassium oxide forms and contains the solution that 0.016 mol catalyst/mole OH and wherein whole water all are removed.660 parts of propylene oxide are added under 95 ℃ temperature in 26.6 parts of initiators, add 164 parts of oxyethane subsequently.The equivalent of products therefrom is 2100, degree of unsaturation is 0.048 milliequivalent/gram.This with contrast by the degree of unsaturation 0.017 milliequivalent/gram among the embodiment 3 of single trimethylene glycol preparation.
Comparative example D
By potassium hydroxide is dissolved in hydroxyl equivalent under 120 ℃ is to prepare initiator in 150 the polyoxygenated propylidene triol.Form vacuum and produce the solution that contains 0.085 mol catalyst/mole OH until all catalyst dissolution.625 parts of propylene oxide are added under 110 ℃ in 45 parts of initiators, add 105 parts of oxyethane subsequently, form the end-blocking product that contains 13.5% (weight) oxyethane.The equivalent of resulting product is 2025, proportion of primary OH groups is 78%, degree of unsaturation is 0.084 milliequivalent/gram.Proportion of primary OH groups 84.1%, degree of unsaturation 0.035 milliequivalent/gram contrast among these numerical value and the embodiment 10.
Comparative example E
690 parts of propylene oxide are added in the initiator of 45 parts of comparative example D, under 130 ℃, react, add 130 parts of oxyethane subsequently, obtain containing the end-blocking product of 15% (weight) oxyethane.The equivalent of resulting product is 1955, proportion of primary OH groups is 80%, degree of unsaturation is 0.143 milliequivalent/gram.Hydroxy radical content 81.8% among these numerical value and the embodiment 11, degree of unsaturation 0.073 milliequivalent/gram contrast.
Comparative example F
625 parts of propylene oxide are added in the initiator of 31 parts of comparative example D and under 95 ℃, react, add 62 parts of oxyethane subsequently, obtain the end-blocking product.The equivalent of products therefrom is 2430, proportion of primary OH groups is 80.51%, degree of unsaturation is 0.065 milliequivalent/gram.The proportion of primary OH groups 87.6% of these numerical value and embodiment 12, degree of unsaturation 0.032 milliequivalent/gram contrast.Embodiment 12 tests under comparatively high temps, and the common like this degree of unsaturation that makes increases.
By these embodiment as can be seen, prepare by the inventive method that the high equivalent weight polyether glycol can obtain that total degree of unsaturation reduces greatly and the product that obviously reduced of propylidene degree of unsaturation wherein.In addition, the present invention allows to prepare product comparing under higher temperature of reaction and the catalyst concn with the normal conditions that adopt potassium hydroxide catalyst, and can increase degree of unsaturation sharply.
By embodiment 10,11 and 12 and comparative example D, E and F as can be seen, compare with the situation that is prepared according to the inventive method, it is higher with primary hydroxyl (as the end-blocking) content of the polyvalent alcohol of total ethylene oxide content to possess similar equivalent.
Claims (11)
1. method for preparing polyether polyols with reduced unsaturation, this method comprises to be made a kind of organic polymeric polyisocyanate and contains the polyhydric alcohol composition of polyvalent alcohol that 0.1 to 99.9% (weight) has the 200-4000 equivalent and be lower than the degree of unsaturation of 0.05 milliequivalent/gram polyvalent alcohol and contact, it is characterized in that described polyvalent alcohol is to be selected from barium, strontium and their oxide compound, oxyhydroxide, a hydroxide hydrate or a hydroxide salts, or a kind of catalyzer of their mixture makes under existing and comprises propylene oxide, 1,2-butylene oxide ring or 2 contains two or more initiator for reaction that contain active hydrogen group in the monocycle oxycompound of 3-butylene oxide ring and a kind of each molecule and makes.
2. in accordance with the method for claim 1, the polyether polyols with reduced unsaturation that wherein obtains is a kind of isocyanate end polymkeric substance.
3. in accordance with the method for claim 1, wherein further comprise a kind of whipping agent so that the polyether polyols with reduced unsaturation foams to be provided.
4. in accordance with the method for claim 1, the gross weight of wherein adding during monocycle oxycompound and initiator react to each other in the monocycle oxycompound is the nearly water of 1% (weight) of benchmark.
5. in accordance with the method for claim 4, wherein the water yield is 1 weight part with respect to every 100-20000 weight part monocycle oxycompound.
6. in accordance with the method for claim 5, wherein the water yield is 1 weight part with respect to every 1000-7000 weight part monocycle oxycompound.
7. in accordance with the method for claim 5, wherein the water yield is 1 weight part with respect to every 3000-5000 weight part monocycle oxycompound.
8. according to each described method among the claim 5-7, wherein catalyzer is hydrated barta, hydronium(ion) oxidation barium, a hydroxide barium salt, strontium hydroxide or their mixture.
9. in accordance with the method for claim 1, wherein initiator contains each molecule 2-8 reactive hydrogen atom, and its equivalent is 5-1500.
10. in accordance with the method for claim 1, wherein total degree of unsaturation of polyvalent alcohol is lower than 0.04 milliequivalent/gram polyvalent alcohol.
11. in accordance with the method for claim 1, wherein making each molecule contain 2-4 initiator that contains active hydrogen group is being in the presence of benchmark 0.1-50.5% (weight) hydrated barta, hydronium(ion) oxidation barium or the hydroxide barium salt in initiator weight and is comprising 1,2-propylene oxide or 1, the monocycle oxycompound of 2-butylene oxide ring 75-130 ℃ temperature with up to 1034 kPas pressure under react.
Applications Claiming Priority (5)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US07/273,375 US5010187A (en) | 1988-11-18 | 1988-11-18 | Production of polyether polyols with reduced unsaturation |
| US273,375 | 1988-11-18 | ||
| US07/381,220 US5114619A (en) | 1989-07-14 | 1989-07-14 | Production of polyether polyols with reduced unsaturation |
| US381,220 | 1989-07-14 | ||
| CN89108598A CN1024558C (en) | 1988-11-18 | 1989-11-18 | Production of polyether polyols with reduced unsaturation |
Related Parent Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN89108598A Division CN1024558C (en) | 1988-11-18 | 1989-11-18 | Production of polyether polyols with reduced unsaturation |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1077463A CN1077463A (en) | 1993-10-20 |
| CN1033093C true CN1033093C (en) | 1996-10-23 |
Family
ID=27178962
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 93104169 Expired - Fee Related CN1033093C (en) | 1988-11-18 | 1993-04-14 | Process for the preparation of polyether polyols with reduced unsaturation |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1033093C (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5605939A (en) * | 1996-01-26 | 1997-02-25 | Arco Chemical Technology, L.P. | Poly(oxypropylene/oxyethylene) random polyols useful in preparing flexible high resilience foam with reduced tendencies toward shrinkage and foam prepared therewith |
| WO2017210001A1 (en) * | 2016-05-31 | 2017-12-07 | Dow Global Technologies Llc | Low cathodic disbondment coating compositions |
-
1993
- 1993-04-14 CN CN 93104169 patent/CN1033093C/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| CN1077463A (en) | 1993-10-20 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN1024558C (en) | Production of polyether polyols with reduced unsaturation | |
| US5010187A (en) | Production of polyether polyols with reduced unsaturation | |
| CN1164644C (en) | Polyalcohol and polydispersion polyalcohol mixture of un-turbid polyoxyethylene dead-end | |
| CN1171927C (en) | Method for production of polyether alcohols | |
| CN1898289A (en) | Process for producing polyurethane products autocatalytic using tertiary amine capped polyether polyols | |
| CN1036656C (en) | Novel rear treatment of hydrocarby functional polyether | |
| CN1273591A (en) | Catalyst for ring-opening polymerization of alkylene oxide, method for preparation thereof and use thereof | |
| CN1497004A (en) | Preparation method of polylol of epoxy ethane blocking | |
| WO2018089566A1 (en) | Polycarbonate Based Polyols | |
| CN101031600A (en) | Method for producing polyurethane-soft foam materials | |
| CN1636989A (en) | Single reactors synthesis of KOH-capped polyols based on DMC-synthesized intermediates | |
| CN1662303A (en) | Preparation of a double metal cyanide catalyst | |
| US5070125A (en) | Production of polyether polyols with reduced unsaturation | |
| CN1264889C (en) | Polyurethane products produced from aluminum phosphonate catalyzed polyetherols | |
| CN1176136C (en) | Polyether alcohols | |
| CN1032218C (en) | Preparation process of polyoxyalkylene polyamine having terminal secondary amino group | |
| CN1033093C (en) | Process for the preparation of polyether polyols with reduced unsaturation | |
| WO2018005056A1 (en) | Process for making polyether diols | |
| CN1400237A (en) | Production process of hard foamed synthetic resin | |
| EP2223953A1 (en) | Continuous processes for the production of ethoxylates | |
| CN1040222C (en) | Alkylene oxide adducts and polyurethane foams prepared therefrom | |
| US3734871A (en) | Polyurethane foams produced from nitrogenous polyethers | |
| JPH10158388A (en) | Modified polyetherpolyol and production of polyurethane resin | |
| CN1276002C (en) | Method for producing polyether alcohols | |
| CN1180003C (en) | Method for producing flexible block foam polyols |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C06 | Publication | ||
| PB01 | Publication | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| C19 | Lapse of patent right due to non-payment of the annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |