CN112679724B - Preparation method of polyether polyol macromonomer, obtained macromonomer and application - Google Patents
Preparation method of polyether polyol macromonomer, obtained macromonomer and application Download PDFInfo
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Abstract
The invention provides a preparation method of polyether polyol macromonomer, the macromonomer and the application, wherein the preparation method comprises the following steps: under the condition that the oxygen content is less than or equal to 100ppm, raw materials including polyether polyol, solid maleic anhydride and epoxy compound are added into a reaction kettle to react to obtain polyether polyol macromonomer, wherein the polyether polyol and the solid maleic anhydride are pre-reacted firstly, and then the epoxy compound is added. By optimizing the solid maleic anhydride feeding mode and through the extension section with the radian in the kettle during adding, the solid maleic anhydride is prevented from being adhered to the top and the wall of the kettle when being sucked in vacuum, the esterification utilization rate of the maleic anhydride is improved, and production waste residues are avoided; when the catalyst is added, the contact part of the catalyst and the reaction solution is changed, so that the phenomenon that the unreacted maleic anhydride is locally overheated after meeting the alkali catalyst to cause the implosion and even explosion of the epoxy compound is avoided; the safety and stability of the epoxidation process are enhanced by optimizing the solvent used in the base catalyst.
Description
Technical Field
The invention relates to a polyether polyol macromonomer, in particular to a preparation method of a polyether polyol macromonomer, an obtained macromonomer and application.
Background
The modified polyether variety prepared by graft polymerization with polyether polyol as initiator (or called basic polyether), vinyl monomer (acrylonitrile and styrene) as grafting monomer and azo or organic peroxide as initiator has the characteristics of vinyl polymer branch chain, such as rigidity, fire resistance, etc. it has improved physical property of polyurethane product, expanded application range of polyurethane product, and may be used widely in automobile decoration, furniture, mattress, etc.
There are two common methods of synthesis of polymer polyols currently used in the industry: in situ polymerization, macromonomer.
1) In-situ polymerization: the method of graft copolymerization of polyether or polyether containing unsaturated double bond and vinyl monomer is called in-situ polymerization method. Obtaining free radicals through an initiator, transferring methine hydrogen atoms on a polyether main chain to form chain free radicals, and initiating vinyl monomer polymerization to form a graft polymer, wherein azo and peroxide are commonly used as the free radical initiator, polyether with hydroxyl functionality of 2 to 6 and average molecular weight of 300 to 5000 is used as a carrier, acrylonitrile and styrene are used as vinyl monomers, in-situ polymerization is carried out in a polyether phase within the range of an optimized ratio of 30 to 70.
2) Macromer method: in order to obtain polymer polyols having a high solids content, a process of introducing polyether polyols having double bonds, known as the macromer process, is generally employed. During polymerization, the macromer is also grafted onto the copolymer chain to form a block copolymer comprising polyether and acrylonitrile, styrene copolymer, which acts as a phase dispersion stabilizer between the continuous and dispersed phases to avoid agglomeration of the grafted polyether particles. The amount of macromer used is generally from 1 to 15% by weight of the monomers, and the macromer generally has a molecular weight of greater than 2000g/mol and comprises a linear or branched polyol having at least one reactive ethylenically unsaturated terminal group. The ethylenically unsaturated groups may be introduced into the polyether polyol by reaction with acid anhydrides (maleic anhydride, fumaric anhydride, phthalic anhydride, etc.), acrylate and methacrylate derivatives and isocyanate derivatives.
The content of the macromonomer in the polyether polyol not only affects the relative molecular mass of the macromonomer, but also directly affects the polymerization characteristics (such as the selection of the type of the vinyl unsaturated bond), thereby affecting the particle size, viscosity and the like of the grafted polyether polyol, and the research shows that according to the existing copolymerization kinetics of the vinyl monomer and the macromonomer: as the amount of the macromonomer used increases, the small particle size fraction of the synthesized polymer polyol gradually decreases and the viscosity of the system tends to increase.
Stability is an important technical indicator for grafted polyether polyol products. The stabilizer is a key factor influencing the stability of the system, and is generally considered to have amphipathy, namely, the stabilizer is compatible with the base polyether, is compatible with the dispersed phase of the copolymer, is anchored on the surface of particles, and thus has the functions of stable dispersion, particle aggregation prevention and steric stabilization.
In general, in the process of synthesizing the graft polyether polyol, a macromonomer is mostly used as a stabilizer precursor, and a graft product generated by in-situ polymerization plays a role of a stabilizer, and is a linear or branched polyol with the molecular weight of more than or equal to 2000 and containing at least one reactive ethylenically unsaturated end group. During free radical polymerization, the macromer is incorporated into the copolymer chain to form a block copolymer having polyether and polyacrylonitrile/styrene blocks, which acts as a phase mediator at the interface of the continuous and dispersed phases and inhibits agglomeration of the graft polyol particles.
The macromers therefore play a crucial role in the synthesis of the entire graft polyether polyol.
In patent CN1656139A entitled "method for preparing polymer polyols", a synthesis of macromonomers is disclosed, wherein a macromer is described, which is prepared by a process comprising reacting a polyol with a cyclic dicarboxylic acid anhydride not containing any polymerizable double bond, followed by reaction with an epoxy compound containing a polymerizable double bond, and then with an isocyanate compound. The preferred anhydride is phthalic anhydride and the polyol is initially initiated with sorbitol.
Patent CN1354764A entitled "macromer stabilizer precursor for polymer polyol" discloses the synthesis of a macromer, wherein a macromer is described, which is prepared by reacting a polyol with a cyclic dicarboxylic acid anhydride not containing any polymerizable double bond, followed by reaction with an epoxy compound containing a polymerizable double bond, and then with an isocyanate compound. The ratio of polyol to cyclic anhydride was 0.2:1 to 4:1, the ratio of epoxy compound to initiator is 0.2:1 to 4:1, the ratio of the amount of the multifunctional epoxy compound to the amount of the isocyanate is 1: 10-1: 1.
in patent CN101311203A entitled Process for the preparation of Polymer polyol stabilizers Using maleic anhydride and Polymer polyol stabilizers prepared therefrom, it is mentioned that a stabilizer having a molecular weight of 5000 to 30000, a functionality of 6 to 10 and a viscosity of 3000 to 15000CPS (25 ℃) is prepared by reacting maleic anhydride with a polyether polyol having a functionality of 3 to 8 and a molecular weight of 3000 to 15000 at an oxygen concentration of 30 to 80PPM and then with ethylene oxide. Wherein in the reaction with ethylene oxide < 200ppm of potassium hydroxide is used as catalyst.
In patent CN101657485A entitled "method for preparing polymer polyol", a method for preparing macromonomers is mentioned: the polyol is reacted with a cyclic dicarboxylic anhydride having no polymerizable double bond, followed by reaction with an epoxy compound having a polymerizable double bond to prepare a macromonomer.
However, in the prior art, either solid maleic anhydride is used, but productive waste residues are generated; or the occurrence of productive waste residue can be avoided by adopting liquid maleic anhydride, but in the actual generation process, the cost of enterprises is increased, and the operation conditions are harsh: firstly, the liquid maleic anhydride provided by a supplier is directly used, and high requirements are put on storage and transportation; and secondly, purchased solid maleic anhydride is dissolved automatically, so that the risk in the dissolving process is increased, and particularly, the maleic anhydride has higher requirements on temperature, material pressure grade of a used metal container and the like.
Disclosure of Invention
In order to overcome the problems in the prior art, the solid maleic anhydride feeding mode is optimized, and the extension section with the radian in the kettle is used during feeding, so that the solid maleic anhydride is prevented from being adhered to the top and the wall of the kettle during vacuum suction, the esterification utilization rate of the maleic anhydride is improved, and the production waste residue is avoided; when the catalyst is added, the contact part of the catalyst and the reaction solution is changed, so that the phenomenon that the unreacted maleic anhydride is locally overheated after meeting the alkali catalyst to cause the implosion and even explosion of the epoxy compound is avoided; the safety and stability of the epoxidation process are enhanced by optimizing the solvent used by the base catalyst.
The invention provides a preparation method of polyether polyol macromonomer, which comprises the following steps: under the condition that the oxygen content is less than or equal to 100ppm, raw materials including polyether polyol, solid maleic anhydride and an epoxy compound are reacted to obtain the polyether polyol macromonomer; wherein, the polyether glycol and solid maleic anhydride are pre-reacted, and then the epoxy compound is added.
In a preferred embodiment, the polyether polyol has a functionality of 3 to 6 and a molecular weight of 2000 to 20000g/mol, preferably 4000 to 15000g/mol.
In a preferred embodiment, the polyether polyol is obtained by reacting a polyol with an epoxy compound.
The polyhydroxy compound refers to a compound containing a plurality of hydroxyl groups, and the epoxy compound refers to a compound containing an epoxy group.
In a further preferred embodiment, the polyol is selected from at least one of propylene glycol, glycerol, pentaerythritol, sorbitol, and the epoxide is selected from ethylene oxide and/or propylene oxide.
The synthesis method adopted by the polyether polyol in the invention can be any one of the following methods:
the method comprises the following steps: the polyether polyol is synthesized by traditional alkali metal catalyzed ring-opening polymerization, wherein the alkali metal comprises alkaline hydroxide compounds or mixtures such as potassium hydroxide, sodium hydroxide and the like, or potassium alkoxide, sodium alkoxide or organic alkaline substances.
The method 2 comprises the following steps: polyether polyol synthesized by coordination polymerization of a bimetallic complex catalyst DMC or MMC.
The method 3 comprises the following steps: the initial polyether polyol is first synthesized in any one of the processes 1-2, and the polyether polyol is then subjected to one of two other processes to synthesize the desired polyether polyol.
In a preferred embodiment, the preparation is carried out batchwise, preferably by initially charging the polyether polyol, with subsequent addition of the maleic anhydride in solid form, and after a pre-reaction period, addition of the epoxide compound.
Wherein the reaction vessel is equipped with a stirrer, optionally with temperature and pressure regulation. The autoclave is preferably a 316L stainless steel autoclave. The temperature of the reaction kettle is controlled before and after adding the polyether polyol.
In a preferred embodiment, the solid maleic anhydride is added into the reaction kettle through a feeding pipe, and an extension section is arranged on the feeding pipe and extends into the reaction kettle.
Wherein, after the reaction kettle is subjected to vacuum operation to ensure that all equipment of the reaction kettle is in a closed state and a static state, solid maleic anhydride is added into the reaction kettle through a feeding pipe.
In a further preferred embodiment, the ratio of the length of the extension section to the inner diameter of the reaction vessel is 1 (3-4).
In a further preferred embodiment, the extension is bent 30 to 90 ° toward the center of the reaction vessel.
Specifically, as shown in fig. 1, the feeding inlet of the feeding tube is vertical outside the reaction kettle, and the extension section extending into the kettle bends toward the center of the reaction kettle at an arc of 30-90 degrees, so that the material enters the kettle, and the wall adhesion phenomenon is avoided.
Therefore, the solid maleic anhydride can be prevented from being adhered to the top and the wall of the kettle when being sucked in vacuum, and the reaction utilization rate of the maleic anhydride is improved.
Meanwhile, the material of the feeding tube and the extension section thereof is strictly limited, such as Hastelloy C or 316L stainless steel material.
In the case of using liquid maleic anhydride in the comparative example, the liquid maleic anhydride was transferred to the reaction tank through a line (the same or different transfer line as in the case of solid maleic anhydride) in such a manner that a vacuum operation was not required.
In a preferred embodiment, the weight ratio of the solid maleic anhydride to the polyether polyol is (0.1-50): 100, preferably (0.1-10): 100.
In a preferred embodiment, the temperature of the pre-reaction is 40 to 70 ℃.
In a further preferred embodiment, the pre-reaction is carried out in a gradual temperature rise process, preferably, the initial reaction temperature of the pre-reaction is 40 to 55 ℃, and then the temperature is raised to 55 to 70 ℃ at a speed of 3 to 6 ℃/h and is kept for 1.5 to 3h.
In the pre-reaction process, solid maleic anhydride is gradually dissolved by adopting a gradual temperature rise process, so that the utilization rate of the maleic anhydride is improved, and the reaction is complete.
As is well known, in the production of polyether polyol macromonomers, the biggest problem of adopting solid maleic anhydride as a raw material is that: the solid maleic anhydride has the defects of incomplete reaction, generation of waste residues, easy pipeline blockage or safety problem. Therefore, in the prior art, there is a document that liquid maleic anhydride is used to replace solid maleic anhydride, and the liquid maleic anhydride can avoid the occurrence of productive waste residues, but in the actual production process, the cost of enterprises is increased, and the operation conditions are harsh: firstly, the liquid maleic anhydride provided by a supplier is directly used, and high requirements are put forward on storage and transportation; secondly, the purchased solid maleic anhydride is dissolved by itself, so that the risk in the dissolving process is increased, and particularly, the maleic anhydride has higher requirements on temperature, material pressure grade of a used metal container and the like.
After a great deal of research on the problems of using solid maleic anhydride, the inventor finds that the technical means of gradually increasing the temperature in the pre-reaction process of the maleic anhydride perfectly solves the problems of insufficient reaction and massive sublimation of the maleic anhydride, and finds that under the method of the invention, no maleic anhydride crystal is found at a feeding port and no waste residue is generated during specific experiments or application.
In a preferred embodiment, the temperature of the reaction vessel after the addition of the polyether polyol until before, during or after the addition of the solid maleic anhydride is controlled to not lower than 0 ℃, preferably not lower than 20 ℃, more preferably not lower than 35 ℃ and not higher than 100 ℃.
In a further preferred embodiment, the temperature of the reaction vessel is controlled to 35 to 95 ℃ after the addition of the polyether polyol and before or during or after the addition of the solid maleic anhydride, preferably to the initial reaction temperature of the pre-reaction.
In the present invention, in order to reduce the acid value of the system, after the preliminary reaction of polyether polyol with solid maleic anhydride is substantially completed, an epoxy compound such as ethylene oxide or propylene oxide is continuously added to the reaction vessel. The basic completion of the reaction of polyether polyol and maleic anhydride is judged by measuring the acid value, and the acid value is less than or equal to 0.5mgKOH/g which is one of effective indexes for judging the macromonomer in the invention.
Due to the physicochemical property of the epoxy compound, after the pre-reaction and when the epoxy compound is added, the oxygen content is controlled to be less than or equal to 100ppm so as to avoid the severe increase of the system viscosity and the color and ensure the safe operation of the reaction.
In a preferred embodiment, a catalyst is added after the pre-reaction and before the epoxy compound is added, and the catalyst is preferably a basic substance, such as at least one of the common basic catalysts of potassium hydroxide, imidazole, sodium hydroxide, cesium hydroxide, and the like.
Wherein, the catalyst is a catalyst which can be used for epoxy polymerization and is disclosed in the prior art.
In a further preferred embodiment, the catalyst is used in an amount of less than 250ppm, preferably from 10 to 160ppm, more preferably from 30 to 160ppm, for example from 50 to 160ppm, based on 100 wt.% of the total amount of polyether polyol, solid maleic anhydride and epoxy compound.
In a further preferred embodiment, the epoxy compound is used in an amount of 1 to 10 wt.%, preferably 1.5 to 8.5 wt.%, more preferably 2 to 7.5 wt.%, based on 100 wt.% of the total amount of polyether polyol, solid maleic anhydride and epoxy compound.
Wherein, in the reaction process, the viscosity of the system is controlled not to be excessively high, and is basically 3000 to 9000MPa.S (25 ℃), and preferably, the viscosity is lower than 8000MPa.S (25 ℃) is one of effective indexes.
In a preferred embodiment, the catalyst is added to the reaction vessel in the liquid state.
In a further preferred embodiment, the polyether polyol is used to dissolve the catalyst to obtain a polyether solution of the catalyst, and then the polyether solution of the catalyst is introduced into the reaction kettle.
In a further preferred embodiment, the catalyst is present in the polyether solution in a weight concentration of 0.1 to 10 wt.%, preferably 0.5 to 2 wt.%.
Since the amount of epoxy compound used in the reaction of the esterification product with the epoxy compound is in a large excess, it is imperative to improve the safety of the process. In the stability studies of known epoxy compounds, it was found that: after adding an alkali catalyst such as potassium hydroxide, the initial exothermic temperature of the epoxy compound is greatly reduced compared with that of a pure epoxy compound under the same conditions, and a catalyst system containing a water body is more sensitive to the initial exothermic temperature of the epoxy compound, wherein the epoxy compound can be in a gas phase or a liquid phase. Therefore, in the present invention, it is preferable to replace the conventional aqueous solution with the basic catalyst dissolved in the polyether polyol as the starting material in order to improve the safety in the epoxidation process.
In a preferred embodiment, the catalyst is fed in liquid state into the reactor by means of a device provided with a flexible line that can be bent at will.
In a further preferred embodiment, the catalyst is conveyed through the flexible line below the reaction liquid level.
Wherein, the catalyst is directly conveyed to the position below the liquid level of the reaction, thus avoiding the risks of explosion and the like caused by uncontrolled epoxidation process due to local violent heat release after the maleic anhydride monomer which is adhered to the reaction kettle and does not participate in esterification is contacted with the alkaline catalyst. On the other hand, the alkaline catalyst can be smoothly added into the reaction liquid or is close to the liquid surface to be reacted to the maximum extent, so that the effect of isolating oxygen is achieved, the safety of the epoxidation process is guaranteed to the maximum extent, and the phenomenon that oxygen exceeds the standard and the quality of the macromonomer is influenced can be avoided.
Because of the reaction characteristics, a part of epoxy compound remains in the system and does not participate in the reaction, after the acid value is measured, the excess part needs to be removed, the pressure is controlled between about-0.1 and about 0.6MPa, and the unreacted part of epoxy compound in the system is gradually removed by using a removal valve so as to ensure that the removal of the epoxy compound is carried out at a lower safe flow rate, and the removal time is generally about 0.5 to about 10 hours.
The second object of the present invention is to provide polyether polyol macromers obtainable by the process according to the first object of the present invention.
It is a further object of the present invention to provide the use of said polyether polyol macromers of the second object of the present invention in the preparation of polymer polyols.
Compared with the prior art, the invention has the following beneficial effects:
(1) According to the invention, by optimizing the solid maleic anhydride feeding mode and through the extension section with the radian in the kettle during adding, the solid maleic anhydride is prevented from being adhered to the kettle top and the kettle wall during vacuum suction, the esterification utilization rate of the maleic anhydride is improved, and the production waste residue is avoided;
(2) In order to further improve the utilization rate of the solid maleic anhydride, gradual temperature rise is adopted in the pre-reaction stage;
(3) When the catalyst is added, the contact part of the catalyst and the reaction solution is changed, so that the phenomenon that the unreacted maleic anhydride is locally overheated after meeting the alkali catalyst to cause the implosion and even explosion of the epoxy compound is avoided;
(4) The safety and stability of the epoxidation process are enhanced by optimizing the solvent used in the base catalyst.
Drawings
FIG. 1 shows a schematic view of a reaction vessel and a feed tube.
In FIG. 1, 1 denotes a feed tube, 11 denotes an extension, and 2 denotes a reaction vessel.
Detailed Description
While the present invention will be described in detail with reference to the following examples, it should be understood that the following examples are illustrative of the present invention and are not to be construed as limiting the scope of the present invention.
Materials and test methods:
in the present invention, the test methods involved are as follows:
determination of the hydroxyl number of the polyether polyols using the analytical standard method: GB/T12008.3;
analytical standard method for determining viscosity: GB/T12008.7;
analytical standard method for determination of potassium ions: GB/T12008.4-2009;
standard method for analysis of macromer viscosity: GB/T12008.7;
standard method for analysis of macromer acid number: GB/T12008.5-2010;
standard method for analyzing oxygen content: GB/T6285.
In the present invention, the polyether polyol used for the synthesis of the macromonomer may be the following:
1) Polyether polyol JM-A; according to the general steps in the field, glycerol is reacted with propylene oxide and ethylene oxide in sequence by taking potassium hydroxide as a catalyst, and the polyether polyol JM-A with the hydroxyl value of 36mgKOH/g, the viscosity of 800mPa.S (25 ℃) and the potassium ion of 2.8mg/kg is prepared by refining.
2) Polyether polyol JM-B: according to the general procedure in the art, glycerol is first reacted with propylene oxide using potassium hydroxide as a catalyst to obtain a crude polyether polyol, which is then refined to obtain an initial polyether polyol of polyether polyol having a hydroxyl value of 400mgKOH/g and a potassium ion of 4.6mg/kg, and this initial polyether polyol is then reacted with propylene oxide and ethylene oxide using a bimetallic catalyst in a blending manner to obtain polyether polyol JM-B having a hydroxyl value of 55mgKOH/g, a viscosity of 500mPa.S (25 ℃ C.) and a potassium ion of 1.9 mg/kg.
3) Polyether polyol JM-C: according to the general procedure in the art, sorbitol is reacted with propylene oxide to obtain an initial polyether polyol having a hydroxyl value of 200mgKOH/g using potassium hydroxide as a catalyst, the initial polyether polyol is reacted with ethylene oxide and propylene oxide using potassium hydroxide as a catalyst, and the initial polyether polyol is refined to obtain polyether polyol JM-C having a hydroxyl value of 28mgKOH/g, a viscosity of 1000mPa.S (25 ℃) and a potassium ion of 3.6 mg/kg.
4) In order to improve the thermal stability of the base polyether obtained above and reduce the occurrence of by-products in the preparation of the macromonomer, the base polyether is added with a suitable antioxidant which is commercially available and widely used in the industry.
In the present invention, the case of maleic anhydride used for the synthesis of the macromonomer is as follows:
1) Maleic anhydride MA1: tablets or pellets, commercially available products,
2) Maleic anhydride MA2: the maleic anhydride MA1 is a self-prepared product after being melted and is in a liquid state.
In the present invention, the epoxy compound used for the synthesis of the macromonomer is commercially available ethylene oxide and propylene oxide.
The liquid maleic anhydride used was self-melt processed by commercially available solid maleic anhydride.
[ example 1 ] Synthesis of macromonomer
630g of polyether polyol JM-A are put into a reaction kettle, the temperature is reduced to 50 ℃, and then the reaction kettle is subjected to vacuum operation. After the reaction kettle is ensured to be in a closed state, 12.5g of solid maleic anhydride MA1 is sucked into the reaction kettle through a special stainless steel pipeline, and the pipeline is provided with an extension section and a certain radian in the kettle. After the material suction is finished, standing for 30-60 minutes, completely replacing air in the reaction kettle by using nitrogen flow of 0.1Mpa, measuring the oxygen content to be 91ppm, and carrying out pre-esterification reaction under the protection of the nitrogen flow of 0.1 Mpa: keeping stirring on, heating the reaction kettle to 60 ℃ at the speed of 5 ℃ per hour at the initial reaction kettle temperature of 50 ℃, and keeping the reaction kettle at 60 ℃ for 2 hours. After the pre-reaction is finished, opening a feed inlet and a vacuum pipe opening of the reaction kettle, wherein no maleic anhydride crystal is found, and no maleic anhydride is found in the part of the upper part of the reaction kettle which is not immersed in the solution. The reaction vessel was subjected to gas exchange in the presence of a nitrogen stream at 0.1MPa, the measured oxygen content was 92ppm, and the temperature was raised to 125 ℃. Subsequently, a vacuum operation was carried out by turning off a driving device, and 0.24g of 45% potassium hydroxide pure aqueous solution was fed into the reaction vessel, the line was inserted below the liquid level in the vessel, and then the reaction vessel was subjected to gas exchange in the presence of a nitrogen stream of 0.1MPa to measure an oxygen content of 94ppm, followed by raising the temperature to 125 ℃ and dropping 30g of ethylene oxide into the reaction vessel. After the dropwise addition, nitrogen is filled to 0.4MPa for pressure stabilization, the acid value of the product is analyzed after the grafting reaction is carried out for 8 hours, the acid value of the product is 0.169mgKOH/g, unreacted ethylene oxide is removed at the temperature of 115-125 ℃ and the vacuum degree of-0.095-0.085 MPa after the grafting reaction is finished, the system is cooled to 80 ℃ finally, the viscosity is measured to be 4390MPa.S (25 ℃), and the macromonomer is removed from the reaction kettle by nitrogen flow.
Wherein, the potassium hydroxide aqueous solution has very obvious promotion effect on the decomposition of the maleic anhydride, and the temperature and the pressure are rapidly gathered. In this experimental system, this situation would reduce the safety of the ethylene oxide reaction.
[ example 2 ] Synthesis of macromonomer
0.108g of potassium hydroxide was dissolved in 10g of polyether polyol JM-A heated to 60 ℃ and the temperature was maintained for further use. Adding 620g of polyether polyol JM-A into a reaction kettle, cooling to 50 ℃, and then carrying out vacuum operation on the reaction kettle. After the reactor was kept in a closed state, 12.5g of solid maleic anhydride MA1 was sucked into the reactor through a specially made stainless steel line with an extension section in the reactor. After the material suction is finished, standing for 30-60 minutes, completely replacing air in the reaction kettle by nitrogen flow of 0.1Mpa, measuring the oxygen content to be 90ppm, and carrying out pre-esterification reaction operation under the protection of the nitrogen flow of 0.1 Mpa: under the condition of keeping stirring open, the temperature of the reaction kettle is increased to 60 ℃ at the speed of increasing the temperature by 5 ℃ per hour under the initial reaction kettle temperature of 50 ℃, and is kept at 60 ℃ for 2 hours. After the pre-reaction is finished, opening a feed inlet and a vacuum pipe opening of the reaction kettle, wherein no maleic anhydride crystal is found, and no maleic anhydride is found in the part of the upper part of the reaction kettle which is not immersed in the solution. The reaction vessel was subjected to gas exchange in the presence of a nitrogen stream at 0.1MPa, the measured oxygen content was 92ppm, and the temperature was raised to 125 ℃. Subsequently, a cutting device was turned off for vacuum operation, 10.108g of potassium hydroxide polyether JM-A solution was charged into the reaction vessel, the line was inserted below the liquid level in the vessel, the reaction vessel was then subjected to gas exchange in the presence of a nitrogen stream of 0.1MPa to determine an oxygen content of 96ppm, the temperature was then raised to 125 ℃ and 30g of ethylene oxide was added dropwise to the reaction vessel. After the dropwise addition, nitrogen is filled to 0.4MPa for pressure stabilization, the acid value of the product is analyzed after the grafting reaction is carried out for 8 hours, the acid value of the product is 0.199mgKOH/g, unreacted ethylene oxide is removed at the temperature of 115-125 ℃ and the vacuum degree of-0.095-0.085 MPa after the grafting reaction is finished, the system is cooled to 80 ℃ finally, the viscosity is measured to be 4417MPa.S (25 ℃), and the macromonomer is removed from the reaction kettle by nitrogen flow.
In example 2, the change of the solvent of the basic catalyst to polyether polyol has no influence on the index of the macromonomer product, and the product is in the viscosity range recognized in the field and has feasibility.
[ example 3 ] Synthesis of macromonomer
The procedure of example 2 was repeated except that polyether polyol JM-B was used instead of polyether polyol JM-A.
Example 4 Synthesis of macromonomer
The procedure of example 2 was repeated except that polyether polyol JM-C was used instead of polyether polyol JM-A.
[ example 5 ] Synthesis of macromonomer
0.11g of potassium hydroxide was dissolved in 5.5g of polyether polyol JM-A heated to 60 ℃ and the temperature was maintained for further use. 594.5g of polyether polyol JM-A was charged into a reaction vessel, and the temperature was reduced to 55 ℃ and then the reaction vessel was subjected to vacuum operation. After the reactor was kept in a closed state, 30g of solid maleic anhydride MA1 was sucked into the reactor through a specially made stainless steel line with an extension section in the reactor. After the material suction is finished, standing for 30-60 minutes, completely replacing air in the reaction kettle by nitrogen flow of 0.1Mpa, measuring the oxygen content to be 90ppm, and carrying out pre-esterification reaction operation under the protection of the nitrogen flow of 0.1 Mpa: while stirring is kept on, the temperature of the reaction kettle is raised to 70 ℃ at the speed of raising the temperature to 3 ℃ per hour at the initial reaction kettle temperature of 55 ℃, and the temperature is kept at 70 ℃ for 1.5 hours. After the pre-reaction is finished, opening a feed inlet and a vacuum pipe opening of the reaction kettle, and ensuring that no maleic anhydride crystal is found and no maleic anhydride is found in the part of the non-immersed solution at the upper part of the reaction kettle. The reaction vessel was subjected to gas exchange in the presence of a nitrogen stream at 0.1MPa, the measured oxygen content was 92ppm, and the temperature was raised to 125 ℃. Subsequently, a cutting device was turned off to conduct a vacuum operation, 5.61g of a potassium hydroxide polyether JM-A solution was charged into a reaction vessel, the line was inserted below the liquid level in the vessel, the reaction vessel was then subjected to gas exchange in the presence of a nitrogen stream of 0.1MPa to measure an oxygen content of 96ppm, the temperature was then raised to 125 ℃ and 51g of ethylene oxide was added dropwise to the reaction vessel. After the dropwise addition, nitrogen is filled to 0.4MPa for pressure stabilization, the acid value is analyzed after the grafting reaction is carried out for 8 hours, unreacted ethylene oxide is removed for 2 to 3 hours at the temperature of between 115 and 125 ℃ and the vacuum degree of between-0.095 and-0.085 MPa after the grafting reaction is finished, finally the system is cooled to 80 ℃, and the macromonomer is removed from the reaction kettle by nitrogen flow.
[ example 6 ] Synthesis of macromonomer
0.062g of potassium hydroxide was dissolved in 12g of polyether polyol JM-A heated to 60 ℃ and the temperature was maintained for further use. 588g of polyether polyol JM-A are put into a reaction kettle, the temperature is reduced to 40 ℃, and then the reaction kettle is subjected to vacuum operation. After the reactor was kept in a closed state, 6g of solid maleic anhydride MA1 was sucked into the reactor through a specially made stainless steel line with an extension section in the reactor. After the material suction is finished, standing for 30-60 minutes, completely replacing air in the reaction kettle by using nitrogen flow of 0.1Mpa, measuring the oxygen content to be 90ppm, and carrying out pre-esterification reaction under the protection of the nitrogen flow of 0.1 Mpa: while keeping the stirring on, the temperature of the reaction kettle is raised to 56 ℃ at the speed of raising the temperature to 6 ℃ per hour at the initial reaction kettle temperature of 40 ℃, and the temperature is kept at 56 ℃ for 3 hours. After the pre-reaction is finished, opening a feed inlet and a vacuum pipe opening of the reaction kettle, wherein no maleic anhydride crystal is found, and no maleic anhydride is found in the part of the upper part of the reaction kettle which is not immersed in the solution. The reaction vessel was subjected to gas exchange in the presence of a nitrogen stream at 0.1MPa, the measured oxygen content was 92ppm, and the temperature was raised to 125 ℃. Subsequently, a shut-off device was turned off for vacuum operation, 12.062g of potassium hydroxide polyether JM-A solution was charged into the reaction vessel, the line was inserted below the liquid level in the vessel, the reaction vessel was then gas-exchanged in the presence of a nitrogen stream at 0.1MPa to determine an oxygen content of 96ppm, the temperature was then raised to 125 ℃ and 12g of ethylene oxide was added dropwise to the reaction vessel. After the dropwise addition, filling nitrogen to 0.4MPa for pressure stabilization, analyzing the acid value after 8 hours of grafting reaction, removing unreacted ethylene oxide for 2 to 3 hours at the temperature of between 115 and 125 ℃ and under the vacuum degree of between-0.095 and-0.085 MPa, cooling the system to 80 ℃, and removing the macromonomer out of the reaction kettle by using nitrogen flow.
[ Experimental example ]
Using the macromers prepared in examples 2 to 4 as starting materials, polymer polyols were prepared as follows:
1) Adding 900g of base polyether JM-B into a mixing kettle, and cooling to 25 ℃ under the protection of 0.1MPa of nitrogen flow;
2) 400g of styrene, 300g of acrylonitrile, 70g of one of the macromonomers prepared in examples 2 to 4 and 30g of chain transfer agent dodecanethiol were added;
3) Adding 1g of azobisisobutyronitrile, mixing and stirring;
4) Gradually dripping the mixed solution prepared in the mixing kettle into the reaction kettle, and controlling the temperature to be in
Reacting for 6 hours at 100-150 ℃ and 0.3-0.6 Mpa;
5) After the reaction is finished, degassing for 8 hours at the temperature of between 130 and 170 ℃ and under the pressure of between-0.088 and-0.1 Mpa;
6) Filtering the solution by a 700-mesh sample sieve to obtain polymer polyol GPOP-2045;
7) The resulting polymer polyol GPOP-2045, hydroxyl number 27.6mgKOH/g, moisture 0.047% (wt), pH:5.3, viscosity of 5127mPa.s (25 ℃), yellowish viscous liquid in appearance, and accordance with the index range approved by the industry.
[ COMPARATIVE EXAMPLE 1 ] Synthesis of macromonomer
630g of polyether polyol JM-A are put into a reaction kettle, the temperature is reduced to 50 ℃, and then the reaction kettle is subjected to vacuum operation. After the reaction kettle is ensured to be in a closed state, 12.5g of maleic anhydride MA1 is sucked into the reaction kettle, nitrogen flow of 0.1Mpa is used for multiple times to finish air replacement in the reaction kettle, the oxygen content is measured to be 95PPM, stirring is started under the protection of the nitrogen flow of 0.1Mpa, the temperature is directly raised to 115 ℃, the temperature is kept for reaction for 2 hours by timing, after the esterification reaction is finished, the temperature is lowered to 50 ℃, a feeding port and a vacuum pipe orifice of the reaction kettle are opened, and maleic anhydride crystals are found; the part of the reaction kettle, which is not immersed in the solution, has white crystals, and the Fourier transform infrared spectrum analysis shows that the positions of the crystals and the maleic anhydride peak are similar, and the components are judged to contain the maleic anhydride. The reaction vessel was subjected to gas exchange in the presence of a nitrogen stream at 0.1MPa, the measured oxygen content was 96ppm, and the temperature was raised to 125 ℃. Subsequently, a vacuum operation was carried out by turning off a cutting device, and 0.24g of a 45% aqueous potassium hydroxide solution was fed into the reaction vessel through a vessel-side line which did not extend through the vessel. The reactor was then gas exchanged in the presence of a nitrogen stream at 0.1MPa, measuring an oxygen content of 90ppm, and 30g of ethylene oxide was added dropwise to the reactor, after raising the temperature to 125 ℃. After the dropwise addition, nitrogen is filled to 0.4MPa for pressure stabilization, and the acid value of the product is analyzed after the grafting reaction is carried out for 8 hours and is 0.283mgKOH/g. After the grafting reaction is finished, removing unreacted ethylene oxide at the temperature of 115-125 ℃ and the vacuum degree of-0.095-0.085 Mpa for 2-3 hours, finally cooling the system to 80 ℃, measuring the viscosity of 4532MPa.S (25 ℃), and removing the macromonomer from the reaction kettle by using nitrogen flow.
In comparative example 1, no stepwise temperature rise was employed in the preliminary reaction, and no elongated feed tube was employed, and a crystalline product of maleic anhydride was found at the feed port and the mouth of the vacuum tube. The part of the reaction kettle, which is not immersed in the solution, has white crystals, and the Fourier transform infrared spectrum analysis shows that the position of the crystals is similar to the position of the peak of the maleic anhydride, and the components are judged to contain the maleic anhydride.
[ COMPARATIVE EXAMPLE 2 ] Synthesis of macromonomer
The procedure of example 2 was repeated except that no stepwise temperature increase was employed in the pre-reaction procedure, but a direct temperature increase to 60 ℃. During the experiment, the maleic anhydride undergoes a remarkable sublimation phenomenon.
Comparative example 3 Synthesis of macromonomer
The procedure of example 2 was repeated except that solid maleic anhydride was used in the form of a feed tube without an extension.
During the process of material suction, a large amount of maleic anhydride is adhered to the wall of the kettle and is not immersed in the polyether solution to participate in the reaction, and the maleic anhydride is sublimated to the top of the kettle, an addition port and the like during subsequent temperature rise, so that the danger of ethylene oxide reaction is increased.
[ COMPARATIVE EXAMPLE 4 ] Synthesis of macromonomer
The procedure of example 2 was repeated except that no line inserted under liquid was used for the transfer of the catalyst.
It was found that, since the catalyst (potassium hydroxide polyether solution) was not inserted below the liquid surface, the catalyst solution flowed along the wall of the vessel when sucked in by vacuum, and since the catalyst had a certain viscosity, a part of the catalyst did not participate, the reaction pressure was high when ethylene oxide was reacted.
[ COMPARATIVE EXAMPLE 5 ] Synthesis of macromonomer
630g of polyether polyol JM-A are placed in a reaction kettle and cooled to 50 ℃. Adding 12.5g of liquid maleic anhydride MA2, repeatedly replacing air in the reaction kettle with nitrogen flow of 0.1Mpa, measuring the oxygen content to be 98PPM, directly heating to 115 ℃ under the protection of nitrogen flow of 0.1Mpa, and keeping the temperature for reaction for 2 hours. Opening the feed inlet and the vacuum pipe orifice of the reaction kettle, and no maleic anhydride crystal is found. The gas exchange in the reactor was carried out in the presence of a nitrogen stream at 0.1MPa, after which a shut-off device was switched off for vacuum operation, and 0.24g of 45% aqueous potassium hydroxide solution was added to the reactor, the line being inserted below the liquid level in the reactor. The autoclave was subsequently gas-exchanged in the presence of a nitrogen stream at 0.1MPa, the oxygen content was determined to be 97ppm, and 30g of ethylene oxide were added dropwise to the autoclave at an elevated temperature of 125 ℃. After the dropwise addition, nitrogen is filled to 0.4MPa for pressure stabilization, and the acid value of the product is analyzed after 8 hours of grafting reaction, wherein the acid value of the product is 0.158mgKOH/g. After the grafting reaction is finished, removing unreacted ethylene oxide at the temperature of 115-125 ℃ and the vacuum degree of-0.095-0.085 Mpa for 2-3 hours, finally cooling the system to 80 ℃, measuring the viscosity of 4418Mpa.S (25 ℃), and removing the macromonomer from the reaction kettle by using nitrogen flow.
The invention of the embodiment 1-3 uses the solid maleic anhydride to achieve the same effect as the comparison 5 using the liquid maleic anhydride, and overcomes the technical prejudice.
Claims (18)
1. A method of preparing a polyether polyol macromer, comprising: under the condition that the oxygen content is less than or equal to 100ppm, raw materials including polyether polyol, solid maleic anhydride and an epoxy compound are reacted to obtain the polyether polyol macromonomer; firstly, carrying out pre-reaction on the polyether polyol and solid maleic anhydride, and then adding the epoxy compound;
the solid maleic anhydride is added into the reaction kettle through a feeding pipe, and an extension section is arranged on the feeding pipe and extends into the reaction kettle;
the temperature of the pre-reaction is 40 to 70 ℃, and the pre-reaction is carried out in the process of gradually increasing the temperature; the initial reaction temperature of the pre-reaction is 40 to 55 ℃, then the temperature is raised to 55 to 70 ℃ at the speed of 3 to 6 ℃/h, and the temperature is kept for 1.5 to 3h;
adding a catalyst after the pre-reaction and before adding the epoxy compound; the catalyst is added into the reaction kettle in a liquid state, the catalyst in the liquid state is conveyed into the reaction kettle by adopting equipment provided with a flexible pipeline which can be bent at will, and the catalyst is conveyed below the reaction liquid level through the flexible pipeline.
2. The method according to claim 1, wherein the polyether polyol is obtained by reacting a polyol with an epoxy compound.
3. The method according to claim 2, wherein the polyether polyol has a functionality of 3 to 6 and a molecular weight of 2000 to 20000g/mol.
4. The method according to claim 3, wherein the polyether polyol has a functionality of 3 to 6 and a molecular weight of 4000 to 15000g/mol.
5. The preparation method of the epoxy resin composition as claimed in claim 1, wherein the ratio of the length of the extension to the inner diameter of the reaction kettle is 1 (3-4).
6. The method for preparing a polyurethane foam material according to claim 1, wherein the extension is bent towards the center of the reaction kettle by 30 to 90 degrees.
7. The production method according to claim 4, wherein the temperature of the reaction vessel after the polyether polyol is added until before, during or after the solid maleic anhydride is added is controlled to not lower than 0 ℃ and not higher than 100 ℃.
8. The production method according to claim 7, wherein the temperature of the reaction vessel is controlled to not lower than 20 ℃ and not higher than 100 ℃ after the polyether polyol is added until before, during or after the solid maleic anhydride is added.
9. The production method according to claim 7, wherein the temperature of the reaction vessel after the polyether polyol is added until before, during or after the solid maleic anhydride is added is controlled to not lower than 35 ℃ and not higher than 100 ℃.
10. The preparation method according to claim 7, wherein the temperature of the reaction kettle is controlled to be 35 to 95 ℃ after the polyether polyol is added until the solid maleic anhydride is added or before or during or after the solid maleic anhydride is added.
11. The process according to claim 10, wherein the temperature of the reaction vessel is controlled to the initial reaction temperature of the preliminary reaction after the polyether polyol is added until before or during or after the solid maleic anhydride is added.
12. The method according to claim 1, wherein the catalyst is a basic substance.
13. The method according to claim 12, wherein the catalyst is at least one selected from the group consisting of potassium hydroxide, imidazole, sodium hydroxide, and cesium hydroxide.
14. The preparation method according to claim 1, characterized in that the polyether polyol is used to dissolve the catalyst to obtain a polyether solution of the catalyst, and then the polyether solution of the catalyst is introduced into the reaction kettle.
15. The method as claimed in claim 14, wherein the concentration of the catalyst in the polyether solution is 0.1 to 10wt%.
16. The method as claimed in claim 15, wherein the concentration of the catalyst in the polyether solution is 0.5 to 2wt%.
17. The production method according to any one of claims 1 to 16,
the weight ratio of the solid maleic anhydride to the polyether polyol is (0.1 to 50) 100; and/or
The catalyst is used in an amount of less than 250ppm, based on 100wt% of the total amount of polyether polyol, solid maleic anhydride and epoxy compound; and/or
The dosage of the epoxy compound is 1-10wt% calculated by the total dosage of 100wt% of polyether polyol, solid maleic anhydride and the epoxy compound.
18. The method of claim 17, wherein,
the weight ratio of the solid maleic anhydride to the polyether polyol is (0.1 to 10) 100; and/or
The dosage of the catalyst is 10 to 160ppm by taking the total dosage of the polyether polyol, the solid maleic anhydride and the epoxy compound as 100 wt%; and/or
The dosage of the epoxy compound is 1.5 to 8.5wt percent calculated by the total dosage of 100wt percent of polyether polyol, solid maleic anhydride and the epoxy compound.
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| US4997857A (en) * | 1986-09-30 | 1991-03-05 | Arco Chemical Technology, Inc. | Stabilizers for polymer/polyols |
| CN105622920A (en) * | 2014-11-05 | 2016-06-01 | 中国石油化工集团公司 | Macromolecule monomer preparation method |
| CN109796588A (en) * | 2018-12-26 | 2019-05-24 | 万华化学集团股份有限公司 | Modified polyether polylol and its application in polyurethane foamed material |
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| US4997857A (en) * | 1986-09-30 | 1991-03-05 | Arco Chemical Technology, Inc. | Stabilizers for polymer/polyols |
| CN105622920A (en) * | 2014-11-05 | 2016-06-01 | 中国石油化工集团公司 | Macromolecule monomer preparation method |
| CN109796588A (en) * | 2018-12-26 | 2019-05-24 | 万华化学集团股份有限公司 | Modified polyether polylol and its application in polyurethane foamed material |
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