CN113150260A - Method for preparing low-viscosity low-unsaturation low-odor high-activity polyether polyol - Google Patents
Method for preparing low-viscosity low-unsaturation low-odor high-activity polyether polyol Download PDFInfo
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- 239000004721 Polyphenylene oxide Substances 0.000 title claims abstract description 79
- 229920000570 polyether Polymers 0.000 title claims abstract description 79
- 229920005862 polyol Polymers 0.000 title claims abstract description 62
- 150000003077 polyols Chemical class 0.000 title claims abstract description 62
- 230000000694 effects Effects 0.000 title claims abstract description 52
- 238000000034 method Methods 0.000 title claims abstract description 33
- 238000002156 mixing Methods 0.000 claims abstract description 31
- 239000003054 catalyst Substances 0.000 claims abstract description 29
- 238000009826 distribution Methods 0.000 claims abstract description 21
- GKTNLYAAZKKMTQ-UHFFFAOYSA-N n-[bis(dimethylamino)phosphinimyl]-n-methylmethanamine Chemical compound CN(C)P(=N)(N(C)C)N(C)C GKTNLYAAZKKMTQ-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000003999 initiator Substances 0.000 claims abstract description 14
- 238000011437 continuous method Methods 0.000 claims abstract description 5
- 238000006243 chemical reaction Methods 0.000 claims description 79
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 44
- 238000007872 degassing Methods 0.000 claims description 22
- 229910052757 nitrogen Inorganic materials 0.000 claims description 22
- 230000001276 controlling effect Effects 0.000 claims description 18
- 238000006116 polymerization reaction Methods 0.000 claims description 14
- 239000007788 liquid Substances 0.000 claims description 12
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 claims description 9
- 239000000203 mixture Substances 0.000 claims description 8
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 7
- 230000001105 regulatory effect Effects 0.000 claims description 7
- 239000000758 substrate Substances 0.000 claims description 7
- 238000006555 catalytic reaction Methods 0.000 claims description 6
- 238000010924 continuous production Methods 0.000 claims description 5
- -1 phosphazene compound Chemical class 0.000 claims description 5
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 claims description 4
- 150000001298 alcohols Chemical class 0.000 claims description 4
- 239000003513 alkali Substances 0.000 claims description 4
- 229920000642 polymer Polymers 0.000 claims description 4
- 239000000126 substance Substances 0.000 claims description 4
- 150000001875 compounds Chemical class 0.000 claims description 3
- 238000007599 discharging Methods 0.000 claims description 3
- 150000001720 carbohydrates Chemical class 0.000 claims description 2
- 125000004432 carbon atom Chemical group C* 0.000 claims description 2
- 125000000524 functional group Chemical group 0.000 claims description 2
- 150000004678 hydrides Chemical class 0.000 claims description 2
- 229910052739 hydrogen Inorganic materials 0.000 claims description 2
- 239000001257 hydrogen Substances 0.000 claims description 2
- 238000005086 pumping Methods 0.000 claims description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 2
- 229910052783 alkali metal Inorganic materials 0.000 abstract description 4
- 150000001340 alkali metals Chemical class 0.000 abstract description 4
- 229910052751 metal Inorganic materials 0.000 abstract description 3
- 239000002184 metal Substances 0.000 abstract description 3
- 125000002947 alkylene group Chemical group 0.000 abstract description 2
- 238000007036 catalytic synthesis reaction Methods 0.000 abstract description 2
- 125000005702 oxyalkylene group Chemical group 0.000 abstract description 2
- 230000000704 physical effect Effects 0.000 abstract description 2
- 230000035484 reaction time Effects 0.000 abstract description 2
- 238000007670 refining Methods 0.000 abstract description 2
- 238000009776 industrial production Methods 0.000 abstract 1
- 239000002685 polymerization catalyst Substances 0.000 abstract 1
- 238000007151 ring opening polymerisation reaction Methods 0.000 abstract 1
- 239000000047 product Substances 0.000 description 14
- 238000010438 heat treatment Methods 0.000 description 9
- 238000003756 stirring Methods 0.000 description 9
- 230000004913 activation Effects 0.000 description 5
- 238000007664 blowing Methods 0.000 description 5
- 238000011049 filling Methods 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- 238000013329 compounding Methods 0.000 description 4
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- 230000018044 dehydration Effects 0.000 description 3
- 238000006297 dehydration reaction Methods 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000012840 feeding operation Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 239000004593 Epoxy Substances 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 150000001339 alkali metal compounds Chemical class 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 239000000806 elastomer Substances 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 238000005187 foaming Methods 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 description 1
- 238000005194 fractionation Methods 0.000 description 1
- 229920001002 functional polymer Polymers 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- 238000012946 outsourcing Methods 0.000 description 1
- 229920001281 polyalkylene Polymers 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 238000007142 ring opening reaction Methods 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000006276 transfer reaction Methods 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
- C08G65/26—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds
- C08G65/2603—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing oxygen
- C08G65/2606—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing oxygen containing hydroxyl groups
- C08G65/2609—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing oxygen containing hydroxyl groups containing aliphatic hydroxyl groups
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
- C08G65/26—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds
- C08G65/2642—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds characterised by the catalyst used
- C08G65/2669—Non-metals or compounds thereof
- C08G65/2675—Phosphorus or compounds thereof
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- Chemical & Material Sciences (AREA)
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- Chemical Kinetics & Catalysis (AREA)
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- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Polyethers (AREA)
Abstract
The invention relates to a method for preparing low-viscosity low-unsaturation low-odor high-activity polyether polyol by adopting a phosphazene catalyst as an alkylene oxide ring-opening polymerization catalyst. Mainly solves the problems that the prior high-activity polyether polyol has only a discontinuous alkali metal catalytic synthesis process, the reaction time is too long, the refining process is complex, the productivity is limited, the product unsaturation degree is higher, and the physical properties and the smell of metal contained in the product are slightly poor. According to the invention, the phosphazene catalyst, the initiator and the oxyalkylene are continuously added into the continuous reactor to prepare the high-activity polyether polyol with narrow molecular weight distribution and low unsaturation degree, and the prepared polyol adopts a blending technical scheme, so that the problem of large viscosity caused by narrow molecular distribution is solved, and the possibility is provided for the industrial production of the low-viscosity low-unsaturation degree low-odor high-activity polyether polyol prepared by a semi-continuous method.
Description
Technical Field
The invention relates to a method for preparing polyether polyol, in particular to a method for preparing low-viscosity low-unsaturation-degree low-odor high-activity polyether polyol.
Background
Polyether polyol is called polyoxyalkylene polyol, structurally belongs to polyalkylene ether or polyoxyalkylene, and is synthesized by ring-opening homopolymerization or copolymerization reaction of oxyalkylene, polyhydroxy or amine compound (initiator) and various epoxy monomers.
At present, the traditional alkali metal batch method, bimetallic complex batch method or continuous catalysis method is mainly adopted to synthesize polyether polyol in China production. The reaction conditions of the polyether polyol produced by the alkali metal batch method are mild (the temperature is 100-130 ℃, and the pressure is 0.2-0.5 MPa), the reaction is easy to control, the catalyst cost is low, the viscosity of the reaction product is low, but the polyether polyol is easy to have a chain transfer reaction in the catalysis process, so that a series of defects of low relative molecular weight, wide product distribution, high unsaturation degree, high aldehyde content, high odor and the like are caused, the product performance index is influenced, and the application of the product is limited. The polymerization produced by using bimetallic catalyst has no above-mentioned problems, and its advantages include high activity of catalyst, small dosage, high polymerization degree, good appearance, low unsaturated end group content and greatly improved property made up by molecular weight distribution, and can frequently omit after-treatment process. However, the bimetallic catalyst cannot use a small molecular initiator (such as propylene glycol) and cannot directly end-cap by ethylene oxide to improve the primary hydroxyl content of the product and increase the activity of the product, and the generated polyether contains a metal component, so that the application of the polyether polyol is influenced.
The high-activity polyether polyol is polyether polyol with a high primary hydroxyl content, is obtained by capping ethylene oxide, is one of large varieties of soft foam polyether polyol, and accounts for about 30 percent. At present, the high-activity polyether polyol is prepared by adopting an alkali-catalyzed batch method in China. The alkali catalysis method has simple device, but has long polymerization time and high unsaturation degree of the obtained polymer. The intermittent method has mature process, cheap and easily available treating agent and high primary hydroxyl content of the product, but the process is complicated, small molecular byproducts need to be removed in vacuum before EO end capping, and sometimes a reactor needs to be additionally arranged, so that the energy consumption is increased, the production period is prolonged, the production cost is increased, and the properties of polyether polyol are deteriorated due to the added alkali metal compounds, oxides, acidic substances and the like.
Phosphazene-based catalysts were developed by the japan mitsui chemical company in the 90 s of the 20 th century. Compared with alkali catalysis, the nitrile catalyst has the advantages of high activity, low unsaturation degree of the obtained polymer and the like; compared with DMC catalysts, phosphazene catalysts have the advantages that small-molecule starters can be used, ethylene oxide blocking can be used, and the like.
Disclosure of Invention
The invention aims to solve the technical problems that the conventional high-activity polyether polyol has the defects of long reaction time, complex refining process and limited productivity, high product unsaturation degree and slightly poor metal physical property and odor in a product in the intermittent alkali metal catalytic synthesis process, and provides a novel method for preparing low-viscosity low-unsaturation degree low-odor high-activity polyether polyol by adopting a phosphazene catalyst semi-continuous method.
The preparation method of the low-viscosity low-unsaturation low-odor high-activity polyether polyol comprises the steps of firstly, continuously adding a phosphazene catalyst, an initiator and alkylene oxide into a continuous method reactor to prepare the low-odor high-activity polyether polyol with narrow molecular weight distribution and low unsaturation; and then the prepared high-activity polyether polyols are prepared by adopting a technical scheme of molecular weight blending, so that the problem of large viscosity of the high-activity polyether polyols caused by narrow molecular weight distribution is solved, and the low-viscosity low-unsaturation degree low-odor high-activity polyether polyols are obtained.
The preparation method of the polyether polyol with low viscosity, low unsaturation degree, low odor and high activity comprises the following steps: firstly, continuously adding a phosphazene catalyst, an initiator, propylene oxide and ethylene oxide into each reactor in turn to continuously prepare polyether polyol with narrow molecular weight distribution, low unsaturation degree, low odor and high activity; and then mixing the prepared high-activity polyether polyols with similar different average molecular weights in an intermittent kettle by adopting a technical scheme of molecular weight blending, solving the problem of large viscosity of the high-activity polyether polyols caused by narrow molecular weight distribution, and thus obtaining the low-viscosity low-unsaturation degree low-odor high-activity polyether polyols.
The preparation method for continuously preparing the polyether polyol with narrow molecular weight distribution, low unsaturation degree, low odor and high activity in the technical scheme comprises the following steps:
(1) firstly, mixing active hydride serving as an initiator and a phosphazene compound serving as a catalyst in a mixing kettle, removing water and other small molecular substances in vacuum, and then replacing with nitrogen;
(2) the polymerization substrate in the step (1) is injected into a reaction kettle 1 at a constant speed through a flowmeter, propylene oxide is stably fed according to the proportion of the target molecular weight, and the polymerization reaction is carried out under the pressure of 0.3mpa and the temperature of 80-140 ℃, so as to synthesize the high-activity polyether polyol intermediate;
(3) after the high-activity polyether polyol intermediate in the step (2) overflows from the reaction kettle 1 and enters the reaction kettle 2, continuously carrying out end-capping polymerization reaction on the high-activity polyether polyol intermediate and ethylene oxide in proportion at the pressure of 0.4mpa and the temperature of 80-125 ℃;
(4) and (3) overflowing the crude polyether in the step (3) from the reaction kettle 2 into a curing kettle, controlling the crude polyether to enter a degassing kettle by using a pressure regulating valve, pumping low-boiling-point components in a system by using a vacuum pump, and transferring the polymer into a separate container to obtain the narrow-distribution low-unsaturation-degree low-odor high-activity polyether polyol.
The method for obtaining the polyether polyol with low viscosity, low unsaturation degree, low odor and high activity in the technical scheme is based on the condition that the molecular structure is the same and the average molecular weight is the same, the wider the molecular weight distribution is, the lower the viscosity is. According to the method in (1) to (4) in the 2, the adjacent polyether polyol with low unsaturation degree, low odor and high activity with different average molecular weights is prepared, and then the mixture is compounded by adjusting the proportion, so that the polyether polyol with low unsaturation degree, low odor and high activity with low viscosity and low unsaturation degree, which is similar to the molecular weight distribution of the alkali catalysis method, can be obtained.
In the technical scheme, the phosphazene catalyst is an outsourcing catalyst PZN subjected to fractionation treatment, and the addition amount of the phosphazene catalyst is 0.1-0.5% of the quality of a target product.
In the technical scheme, the active hydrogen compound is a compound with a molecule containing hydroxyl and is selected from: alcohols with 2-20 carbon atoms, polyhydroxy alcohols with 2-8 hydroxyl groups, saccharides or derivatives thereof or mixtures thereof, or polyether polyol oligomers with functional groups of 2-8 and molecular weights of 70-800, preferably the 3-functional 500 molecular weight polyether and the 2-functional 400 molecular weight polyether which are common on the market today.
In the technical scheme, the ethylene oxide accounts for 5-20% of the feeding amount of all the materials.
The continuous method reactor in the technical scheme is in the following forms but not limited to other forms, three-stage reactors are adopted to be connected in series for continuously feeding and discharging materials, and the pressure of an overflow pipeline is used for controlling the reaction. The continuous process reactor capacity is 0.5-2 times of the maximum reactor, i.e. the liquid residence time is in the range of 0.5-2 h.
Drawings
FIG. 1 is a flow chart of the apparatus used in the synthesis of low unsaturation, low odor and high activity polyether polyols of the present invention.
Detailed Description
Example 1
(1) Firstly, replacing the whole device with nitrogen, and checking the air tightness to be qualified (the whole device comprises a 2L mixing kettle, a 10L PO dripping tank, a 2L EO dripping tank, a 1L reaction kettle 1, a 0.5L reaction kettle 2, a 1L curing kettle, a 3L degassing kettle and a 3L receiving tank);
(2) adding 300g of glycerol as an initiator and 1200g of basic polyether 305 (3 rd molecular weight: 500, produced by the factory) into a mixing kettle, heating to 100 ℃ for dehydration, performing nitrogen replacement, adding 12.6g of a phosphazene catalyst under the protection of nitrogen, and uniformly stirring;
(3) clicking a computer-controlled feeding program, feeding 250g of polymerization substrate into a reaction kettle 1 by a blending kettle, starting PO dropwise addition after stirring and heating to 100 ℃, feeding 750g of PO after reaction activation, almost filling the liquid level of the reaction kettle 1, starting a normal feeding program at the moment, feeding the PO into the reaction kettle 1 by the blending kettle at about 250g/h, dropwise adding the PO at 750g/h, opening a valve into the reaction kettle 2, namely feeding a high-activity polyether polyol intermediate of the reaction kettle 1 into the reaction kettle 2 at an overflow speed of 1000g/h, dropwise adding the EO at 56.3g/h, overflowing the liquid level of the reaction kettle 2 into a curing kettle after about 28min, automatically feeding the crude polyether in the curing kettle into a degassing kettle through a pressure regulating valve, degassing, and collecting a degassed product in a receiving tank. Controlling the pressure of the reaction kettle 1 to be 0.3mp and the temperature to be 100 ℃; controlling the pressure of the reaction kettle 2 at 0.4MP and the temperature at 100 ℃, controlling the temperature of the degassing kettle at 130 ℃, and carrying out nitrogen blowing to stabilize the pressure in the kettle at-0.09 MP. Target molecular weight 1125.
Example 2
(1) Firstly, replacing the whole device with nitrogen, and checking the air tightness to be qualified (the whole device comprises a 2L mixing kettle, a 10L PO dripping tank, a 2L EO dripping tank, a 1L reaction kettle 1, a 0.5L reaction kettle 2, a 1L curing kettle, a 3L degassing kettle and a 3L receiving tank);
(2) adding 1250g of initiator, namely 1136g of basic polyether 204 (2-functional polymer with the molecular weight of 400, produced by the factory) into a mixing kettle, heating to 100 ℃ to dehydrate to be qualified, performing nitrogen replacement, adding 25g of phosphazene catalyst under the protection of nitrogen, and stirring and uniformly mixing;
(3) clicking a computer-controlled feeding program, feeding 113.6g of polymerization substrate into a reaction kettle 1 by a mixing kettle, starting PO dropwise addition after stirring and heating to 100 ℃, feeding about 886.4g of PO after reaction activation, almost filling the liquid level of the reaction kettle 1, starting a normal feeding program at the moment, feeding the PO into the reaction kettle 1 at about 125g/h by the mixing kettle, dropwise adding the PO at 875g/h, then opening a valve of a reaction kettle 2, namely feeding a high-activity polyether polyol intermediate in the reaction kettle 1 into the reaction kettle 2 at an overflow speed of 1000g/h, dropwise adding the EO at a flow of 250g/h, after about 28min, overflowing the liquid level of the reaction kettle 2 into a curing kettle, automatically feeding the crude polyether in the curing kettle into a degassing kettle through a pressure regulating valve, degassing, and collecting a degassed product in a receiving tank. Controlling the pressure of the reaction kettle 1 to be 0.3mp and the temperature to be 100 ℃; controlling the pressure of the reaction kettle 2 at 0.4MP and the temperature at 100 ℃, controlling the temperature of the degassing kettle at 130 ℃, and carrying out nitrogen blowing to stabilize the pressure in the kettle at-0.09 MP. Target molecular weight 4000.
Example 3
(1) Firstly, replacing the whole device with nitrogen, and checking the air tightness to be qualified (the whole device comprises a 2L mixing kettle, a 10L PO dripping tank, a 2L EO dripping tank, a 1L reaction kettle 1, a 0.5L reaction kettle 2, a 1L curing kettle, a 3L degassing kettle and a 3L receiving tank);
(2) 1172g of basic polyether 305 (3 rd molecular weight 500, produced by the factory) serving as an initiator is added into the mixing kettle, nitrogen replacement is carried out after the mixture is dehydrated and qualified at 100 ℃, 23g of phosphazene catalyst is added under the protection of nitrogen, and the mixture is stirred and uniformly mixed;
(3) clicking a computer-controlled feeding program, feeding 117.2g of polymerization substrate into a reaction kettle 1 by a mixing kettle, starting PO dropwise addition after stirring and heating to 100 ℃, feeding about 882.8g of PO after reaction activation, almost filling the liquid level of the reaction kettle 1, starting a normal feeding program at the moment, feeding the PO into the reaction kettle 1 at about 117.2g/h by the mixing kettle, dropwise adding the PO at the flow rate of 882.8g/h, opening a valve into the reaction kettle 2, namely feeding a high-activity polyether polyol intermediate of the reaction kettle 1 into the reaction kettle 2 at the overflow speed of 1000g/h, dropwise adding the EO at the flow rate of 149.43g/h, after about 26min, overflowing the liquid level of the reaction kettle 2 into a curing kettle, automatically feeding crude polyether in the curing kettle into a degassing kettle through a pressure regulating valve, degassing, and collecting a degassed product in a receiving tank. Controlling the pressure of the reaction kettle 1 to be 0.3mp and the temperature to be 100 ℃; controlling the pressure of the reaction kettle 2 at 0.4MP and the temperature at 100 ℃, controlling the temperature of the degassing kettle at 130 ℃, and carrying out nitrogen blowing to stabilize the pressure in the kettle at-0.09 MP. Target molecular weight 5000 (i.e., commercial designation: 330N).
Example 4
(1) Firstly, replacing the whole device with nitrogen, and checking the air tightness to be qualified (the whole device comprises a 2L mixing kettle, a 10L PO dripping tank, a 2L EO dripping tank, a 1L reaction kettle 1, a 0.5L reaction kettle 2, a 1L curing kettle, a 3L degassing kettle and a 3L receiving tank);
(2) adding 1406.4g of base polyether 305 (3-functional polyether with a molecular weight of 500, produced by the factory) as an initiator into a mixing kettle, heating to 100 ℃ for dehydration, performing nitrogen replacement, adding 27.6g of a phosphazene catalyst under the protection of nitrogen, and uniformly stirring;
(3) clicking a computer-controlled feeding program, feeding 117.2g of polymerization substrate into a reaction kettle 1 by a mixing kettle, starting PO dropwise addition after starting stirring and heating to 100 ℃, feeding about 882.8g of PO after reaction activation, almost filling the liquid level of the reaction kettle 1, starting a normal feeding program at the moment, feeding about 175.8g/h of the mixing kettle into the reaction kettle 1, dropwise adding PO at the flow rate of 1324.2g/h, opening a valve into the reaction kettle 2, namely feeding a high-activity polyether polyol intermediate of the reaction kettle 1 into the reaction kettle 2 at the overflow speed of 1500g/h, dropwise adding EO at the flow rate of 298.9g/h, after about 16min, fully overflowing the liquid level of the reaction kettle 2 into a curing kettle, automatically feeding crude polyether in the curing kettle into a degassing kettle through a pressure regulating valve, degassing, and collecting a degassed product in a receiving tank. Controlling the pressure of the reaction kettle 1 to be 0.3mp and the temperature to be 100 ℃; controlling the pressure of the reaction kettle 2 at 0.4MP and the temperature at 100 ℃, controlling the temperature of the degassing kettle at 130 ℃, and carrying out nitrogen blowing to stabilize the pressure in the kettle at-0.09 MP. Target molecular weight 5000 (i.e., commercial designation: 330N).
Example 5
(1) Firstly, replacing the whole device with nitrogen, and checking the air tightness to be qualified (the whole device comprises a 2L mixing kettle, a 10L PO dripping tank, a 2L EO dripping tank, a 1L reaction kettle 1, a 0.5L reaction kettle 2, a 1L curing kettle, a 3L degassing kettle and a 3L receiving tank);
(2) adding 820g of base polyether 305 (3 rd molecular weight 500, produced by the factory) serving as an initiator into a mixing kettle, heating to 100 ℃ for dehydration, performing nitrogen displacement, adding 16.1g of phosphazene catalyst under the protection of nitrogen, and uniformly stirring;
(3) clicking a computer-controlled feeding program, feeding 117.2g of polymerization substrate into a reaction kettle 1 by a mixing kettle, starting PO dropwise addition after stirring and heating to 100 ℃, feeding about 882.8g of PO after reaction activation, almost filling the liquid level of the reaction kettle 1, starting a normal feeding program at the moment, feeding the PO into the reaction kettle 1 at about 82g/h by the mixing kettle, dropwise adding the PO at 706.2g/h, opening a valve into the reaction kettle 2, namely feeding a high-activity polyether polyol intermediate of the reaction kettle 1 into the reaction kettle 2 at an overflow speed of 700g/h, dropwise adding the EO at 119.5g/h, after about 36min, fully overflowing the liquid level of the reaction kettle 2 into a curing kettle, automatically feeding crude polyether in the curing kettle into a degassing kettle through a pressure regulating valve, degassing, and collecting a degassed product in a receiving tank. Controlling the pressure of the reaction kettle 1 to be 0.3mp and the temperature to be 100 ℃; controlling the pressure of the reaction kettle 2 at 0.4MP and the temperature at 100 ℃, controlling the temperature of the degassing kettle at 130 ℃, and carrying out nitrogen blowing to stabilize the pressure in the kettle at-0.09 MP. Target molecular weight 5000 (i.e., commercial designation: 330N).
Example 6
The same feeding procedure as in experimental example 3 was repeated except that the amount of the catalyst in the compounding vessel was changed from 23g to 57.4g (i.e., 0.5%). Target molecular weight 5000 (i.e., commercial designation: 330N).
Example 7
The same feeding procedure as in experimental example 3 was repeated except that the amount of the catalyst added to the compounding pot was changed from 23g to 11.5g (i.e., 0.1%). Target molecular weight 5000 (i.e., commercial designation: 330N).
Example 8
The same charging operation as in experimental example 3 was repeated except that the PO reaction temperature in reaction vessel 1 was changed to 80 ℃. Target molecular weight 5000 (i.e., commercial designation: 330N).
Example 9
The same charging operation as in experimental example 3 was repeated except that the PO reaction temperature in reaction vessel 1 was changed to 140 ℃. Target molecular weight 5000 (i.e., commercial designation: 330N).
Example 10
The same feeding operation as in experimental example 3 was repeated except that the EO reaction temperature in reaction vessel 2 was changed to 80 ℃. Target molecular weight 5000 (i.e., commercial designation: 330N).
Example 11
The same feeding operation as in experimental example 3 was repeated except that the EO reaction temperature in reaction vessel 1 was changed to 125 ℃. Target molecular weight 5000 (i.e., commercial designation: 330N).
Example 12
The same feeding procedure as in Experimental example 3 was repeated except that the amount of the initiator 305 added to the compounding kettle was changed from 1172g to 1106g (i.e., 0.5%). Target molecular weight 5300.
Example 13
The same feeding procedure as in experimental example 3 was repeated except that the amount of catalyst added to the compounding kettle was changed from 1172g to 1303g (i.e., 0.5%). Target molecular weight 4500.
Table 1 shows the results of the continuous process for the synthesis of low unsaturation, low odor and high activity polyether polyols
As can be seen from Table 1, the continuous process used in the present invention for synthesizing the highly reactive polyether has lower unsaturation degree, poorer odor and narrow molecular weight distribution, but also has a larger viscosity, compared with the production samples in all the examples.
The three examples 3, 12 and 13 were compounded in several proportions to give the results of Table 2 below.
As can be seen from Table 2, the formulation reduces the viscosity of the system but increases the molecular weight distribution. Therefore, the 2# compound scheme is more reasonable.
Foaming and elastomer application tests were compared with 2# and production. The results are shown in Table 3.
Claims (8)
1. A method for preparing low-viscosity low-unsaturation low-odor high-activity polyether polyol by a semi-continuous method is characterized by comprising the following steps: firstly, continuously adding a phosphazene catalyst, an initiator, propylene oxide and ethylene oxide into each reactor in turn to continuously prepare polyether polyol with narrow molecular weight distribution, low unsaturation degree, low odor and high activity; and then mixing the prepared high-activity polyether polyols with similar different average molecular weights in an intermittent kettle by adopting a technical scheme of molecular weight blending, solving the problem of large viscosity of the high-activity polyether polyols caused by narrow molecular weight distribution, and thus obtaining the low-viscosity low-unsaturation degree low-odor high-activity polyether polyols.
2. The method for continuously preparing the polyether polyol with narrow molecular weight distribution, low unsaturation degree, low odor and high activity according to claim 1 comprises the following steps:
(1) firstly, mixing active hydride serving as an initiator and a phosphazene compound serving as a catalyst in a mixing kettle, removing water and other small molecular substances in vacuum, and then replacing with nitrogen;
(2) the polymerization substrate in the step (1) is injected into a reaction kettle 1 at a constant speed through a flowmeter, propylene oxide is stably fed according to the proportion of the target molecular weight, and the polymerization reaction is carried out under the pressure of 0.3mpa and the temperature of 80-140 ℃, so as to synthesize the high-activity polyether polyol intermediate;
(3) after the high-activity polyether polyol intermediate in the step (2) overflows from the reaction kettle 1 and enters the reaction kettle 2, continuously carrying out end-capping polymerization reaction on the high-activity polyether polyol intermediate and ethylene oxide in proportion at the pressure of 0.4mpa and the temperature of 80-125 ℃;
(4) and (3) overflowing the crude polyether in the step (3) from the reaction kettle 2 into a curing kettle, controlling the crude polyether to enter a degassing kettle by using a pressure regulating valve, pumping low-boiling-point components in a system by using a vacuum pump, and transferring the polymer into a separate container to obtain the narrow-distribution low-unsaturation-degree low-odor high-activity polyether polyol.
3. The process according to claim 1 for obtaining low viscosity, low unsaturation, low odor and high activity polyether polyols is based on the fact that the broader the molecular weight distribution, the lower the viscosity, under the same molecular structure and average molecular weight.
4. According to the method in (1) to (4) in the 2, the low-unsaturation low-odor high-activity polyether polyol with narrow distribution of adjacent different average molecular weights is prepared, and then the mixture is compounded by adjusting the proportion, so that the low-unsaturation low-odor high-activity polyether polyol with low viscosity and low unsaturation and low odor with similar molecular weight distribution to that of the alkali catalysis method can be obtained.
5. The phosphazene catalyst according to claim 1 is a fractionated purchased catalyst PZN added in an amount of 0.1 to 0.5% by mass of the objective product.
6. The active hydrogen compound according to claim 1, which is a compound having a hydroxyl group in a molecule, is selected from the group consisting of: alcohols with 2-20 carbon atoms, alcohols with 2-8 hydroxyl groups, saccharides or derivatives thereof or mixtures thereof, or polyether polyol oligomers with functional groups of 2-8 and molecular weights of 70-800.
7. The proportion of ethylene oxide in the total mass of the composition according to claim 1 is in the range from 5 to 20%.
8. The continuous process reactor according to claim 1, which is a three-stage reactor with continuous feeding and discharging in series and pressure control discharging in an overflow line, wherein the capacity of the continuous process reactor is 0.5-2 times of the maximum reactor, i.e., the liquid residence time is in the range of 0.5-2 h.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2007204680A (en) * | 2006-02-03 | 2007-08-16 | Asahi Glass Co Ltd | Method for manufacturing polyether polyol |
| US20130131208A1 (en) * | 2010-08-06 | 2013-05-23 | Mitsui Chemicals, Inc. | Polyol, polyol composition, and flexible polyurethane foam using the same |
| CN109485844A (en) * | 2018-11-27 | 2019-03-19 | 山东蓝星东大有限公司 | The preparation method of high activity high molecular polyether polyol polyalcohol |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2007204680A (en) * | 2006-02-03 | 2007-08-16 | Asahi Glass Co Ltd | Method for manufacturing polyether polyol |
| US20130131208A1 (en) * | 2010-08-06 | 2013-05-23 | Mitsui Chemicals, Inc. | Polyol, polyol composition, and flexible polyurethane foam using the same |
| CN109485844A (en) * | 2018-11-27 | 2019-03-19 | 山东蓝星东大有限公司 | The preparation method of high activity high molecular polyether polyol polyalcohol |
Non-Patent Citations (1)
| Title |
|---|
| 何曼君等: "《高分子物理》", 31 January 2000, 复旦大学出版社 * |
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