CN112759755A - Preparation method of polyether polyol for super-soft slow-rebound foam - Google Patents
Preparation method of polyether polyol for super-soft slow-rebound foam Download PDFInfo
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- CN112759755A CN112759755A CN202011581713.3A CN202011581713A CN112759755A CN 112759755 A CN112759755 A CN 112759755A CN 202011581713 A CN202011581713 A CN 202011581713A CN 112759755 A CN112759755 A CN 112759755A
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- 239000004721 Polyphenylene oxide Substances 0.000 title claims abstract description 77
- 229920000570 polyether Polymers 0.000 title claims abstract description 77
- 229920005862 polyol Polymers 0.000 title claims abstract description 73
- 150000003077 polyols Chemical class 0.000 title claims abstract description 73
- 239000006260 foam Substances 0.000 title claims abstract description 41
- 238000002360 preparation method Methods 0.000 title claims abstract description 8
- 239000003054 catalyst Substances 0.000 claims abstract description 17
- 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 10
- 229910052783 alkali metal Inorganic materials 0.000 claims abstract description 9
- 150000001340 alkali metals Chemical class 0.000 claims abstract description 9
- 238000000034 method Methods 0.000 claims abstract description 8
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 36
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 claims description 29
- 238000006243 chemical reaction Methods 0.000 claims description 29
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 24
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 21
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 claims description 21
- 238000006116 polymerization reaction Methods 0.000 claims description 20
- 229910052757 nitrogen Inorganic materials 0.000 claims description 18
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 13
- 239000001301 oxygen Substances 0.000 claims description 13
- 229910052760 oxygen Inorganic materials 0.000 claims description 13
- 239000000178 monomer Substances 0.000 claims description 9
- 230000005587 bubbling Effects 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 6
- 238000001914 filtration Methods 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- FBPFZTCFMRRESA-FSIIMWSLSA-N D-Glucitol Natural products OC[C@H](O)[C@H](O)[C@@H](O)[C@H](O)CO FBPFZTCFMRRESA-FSIIMWSLSA-N 0.000 claims description 5
- 239000000600 sorbitol Substances 0.000 claims description 5
- 150000001335 aliphatic alkanes Chemical class 0.000 claims description 4
- 239000003999 initiator Substances 0.000 claims description 4
- 239000003795 chemical substances by application Substances 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- 230000003472 neutralizing effect Effects 0.000 claims description 3
- 239000006227 byproduct Substances 0.000 claims description 2
- 238000010438 heat treatment Methods 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims description 2
- 238000006386 neutralization reaction Methods 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 9
- 238000011084 recovery Methods 0.000 claims 9
- FBPFZTCFMRRESA-JGWLITMVSA-N D-glucitol Chemical compound OC[C@H](O)[C@@H](O)[C@H](O)[C@H](O)CO FBPFZTCFMRRESA-JGWLITMVSA-N 0.000 claims 1
- 230000006835 compression Effects 0.000 abstract description 8
- 238000007906 compression Methods 0.000 abstract description 8
- 238000006555 catalytic reaction Methods 0.000 abstract description 5
- 230000000704 physical effect Effects 0.000 abstract description 5
- 238000013461 design Methods 0.000 abstract description 4
- 229920002635 polyurethane Polymers 0.000 abstract description 4
- 239000004814 polyurethane Substances 0.000 abstract description 4
- 230000015572 biosynthetic process Effects 0.000 abstract description 2
- 230000008569 process Effects 0.000 abstract description 2
- 238000003786 synthesis reaction Methods 0.000 abstract description 2
- 230000003197 catalytic effect Effects 0.000 abstract 1
- 239000006261 foam material Substances 0.000 abstract 1
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 15
- 239000003463 adsorbent Substances 0.000 description 4
- 238000010521 absorption reaction Methods 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 230000006872 improvement Effects 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000007086 side reaction Methods 0.000 description 2
- 229920000079 Memory foam Polymers 0.000 description 1
- 229920005830 Polyurethane Foam Polymers 0.000 description 1
- 239000001361 adipic acid Substances 0.000 description 1
- 235000011037 adipic acid Nutrition 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000006870 function Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000008210 memory foam Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000011496 polyurethane foam Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
Classifications
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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
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
- C08G18/4833—Polyethers containing oxyethylene units
- C08G18/4837—Polyethers containing oxyethylene units and other oxyalkylene units
- C08G18/4841—Polyethers containing oxyethylene units and other oxyalkylene units containing oxyethylene end 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
- C08G65/2645—Metals or compounds thereof, e.g. salts
- C08G65/2648—Alkali metals or compounds thereof
-
- 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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- 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
- C08G65/269—Mixed catalyst systems, i.e. containing more than one reactive component or catalysts formed in-situ
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- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Polyethers (AREA)
- Polyurethanes Or Polyureas (AREA)
Abstract
The invention belongs to the technical field of polyether polyol synthesis, and particularly relates to a preparation method of polyether polyol for super-soft slow-rebound foam. According to the invention, a phosphazene catalyst and an alkali metal double-catalysis system are applied to the field of slow-rebound polyether polyol, so that the slow-rebound polyether polyol with ultrahigh molecular weight is synthesized, the hand feeling comfort of the slow-rebound foam is improved, and meanwhile, the high-functionality design is carried out on the molecular structure of the polyether polyol, so that the compression permanent deformation resistance is improved. Compared with the polyether synthesized by the traditional market KOH catalytic process, the polyether polyol product has high molecular weight, low unsaturation degree and narrow molecular weight distribution, and can be used for preparing the polyurethane slow-rebound foam material with comfortable hand feeling, excellent physical properties and low permanent compression set.
Description
Technical Field
The invention belongs to the technical field of polyether polyol synthesis, and particularly relates to a preparation method of polyether polyol for super-soft slow-rebound foam.
Background
The slow rebound memory sponge has unique functions of shape memory, energy absorption, sound absorption, shock absorption and the like, and is widely applied to the fields of home furnishing, bedding, automobile accessories, shoe materials, sports equipment, medical instruments, aerospace and the like. With the development of related industries and the improvement of the living standard of residents, the requirement of consumers on the softness and comfort of the slow-rebound foam is higher and higher, and whether the polyether polyol can meet the development requirement or not becomes a key when being used as one of main raw materials of a polyurethane slow-rebound foam product.
The improvement of the molecular weight of polyether polyol is a good method for improving the comfort level of slow rebound foam, but the conventional main slow rebound polyether in China is trifunctional polyether polyol with the molecular weight of 4000-5000 synthesized by a KOH process, so that the requirement of polyurethane super-soft slow rebound foam on polyether is difficult to meet. Traditional alkali metal catalysis system, along with the promotion of polyether polyol molecular weight, the side reaction increases, and the unsaturation degree increases, and the foam performance descends obviously, and only polyether polyol molecular weight increase can lead to the foam compression permanent deformation big simultaneously, is unfavorable for the transportation of foam, and traditional catalysis system and molecular structure design also are difficult to satisfy the development needs of super soft slow resilience foam.
Chinese patent CN201511029822.3 discloses a method for preparing zero-pressure-sensitive memory foam, which has good foam comfort and no pressure-sensitive property, but the main polyether polyol used in the method is the traditional polyether with three functionality and 5000 molecular weight, so that the further improvement of foam softness is limited. Chinese patent CN201910045058.0 discloses a method for preparing high-collapse-ratio slow-rebound foam, which improves the supporting ability by adding polymer polyol, has excellent rebound performance, but sacrifices the softness of the slow-rebound foam. Chinese patent CN201510834917.6 discloses a preparation method of slow rebound polyether polyol, which has low compression residue and good physical properties, but belongs to low molecular weight slow rebound polyether and can not improve the softness of foam. For the above reasons, there is a need for a slow rebound polyether polyol that further improves foam softness while maintaining good physical properties and compression set resistance.
Disclosure of Invention
The technical problem to be solved by the invention is as follows: the defects of the prior art are overcome, the preparation method of the polyether polyol for the super-soft slow-resilience foam is provided, the synergistic catalysis system of the phosphazene and the alkali metal catalyst is applied to the field of the slow-resilience polyether polyol, the polyether polyol for the slow-resilience foam with ultrahigh molecular weight is synthesized, the hand feeling comfort degree of the slow-resilience foam is improved, meanwhile, the high-functionality design is carried out on the molecular structure of the polyether polyol, and the compression permanent deformation resistance is improved. The polyether polyol product prepared by the invention has the advantages of low unsaturation degree, narrow molecular weight distribution, excellent foam physical properties and low permanent compression set.
The preparation method of the polyether polyol for the super-soft slow-rebound foam comprises the following steps:
(1) adding a micromolecular initiator and an alkali metal catalyst into a pressure-resistant reaction kettle for mixing, replacing nitrogen until the oxygen content in the kettle is less than 50ppm, then heating to 105-125 ℃, adding propylene oxide and ethylene oxide for polymerization reaction, continuing internal pressure reaction for 1.5-3.5h after the reaction is finished, and removing unreacted monomers to obtain an intermediate polyether polyol;
(2) adding the intermediate polyether polyol obtained in the step (1) and a phosphazene catalyst into a pressure-resistant reaction kettle, replacing nitrogen until the oxygen content in the kettle is less than 50ppm, carrying out nitrogen bubbling for 1-3h under the condition that the vacuum degree is lower than-0.09 MPa at 90-115 ℃, adding epoxypropane and epoxyethane for carrying out polymerization reaction after the timing is finished, continuing carrying out internal pressure reaction for 3.5-5.5h after the reaction is finished, removing unreacted monomers, then adding epoxyethane for carrying out end-capping polymerization reaction, removing the internal pressure for 1-3h after the reaction is finished, and removing unreacted residual monomers and micromolecule byproducts to obtain crude polyether polyol;
(3) and (3) adding water and a neutralizing agent into the crude polyether polyol prepared in the step (2) for neutralization, then adding a filter aid, and then drying and filtering to obtain the polyether polyol for the super-soft slow-resilience foam.
Wherein:
the micromolecule initiator in the step (1) is a mixture of glycerol and solid sorbitol, wherein the mass of the glycerol accounts for 30-75%.
The alkali metal catalyst in the step (1) is potassium hydroxide, and the addition amount of the alkali metal catalyst is 1-3%, preferably 1.5-2.5% of the designed mass of the intermediate polyether polyol.
The propylene oxide and the ethylene oxide which are subjected to preliminary polymerization in the step (1) are fed according to a constant proportion, and the copolymerized ethylene oxide accounts for 70-80% of the mass of the copolymerized alkane.
The adding amount of the phosphazene catalyst in the step (2) is 0.5-3.5 per mill of the designed mass of the crude polyether polyol, and preferably 1.5-2.5 per mill.
The polymerization temperature of propylene oxide and ethylene oxide in the step (2) is 105-125 ℃, preferably 110-120 ℃.
And (3) feeding propylene oxide and ethylene oxide which are subjected to polymerization reaction in the step (2) according to a constant proportion, wherein the copolymerized ethylene oxide accounts for 70-80% of the mass of the copolymerized alkane.
The temperature for the end-capping polymerization reaction of ethylene oxide in the step (2) is 105-125 ℃, preferably 110-120 ℃.
The amount of ethylene oxide subjected to the capping polymerization reaction in step (2) accounts for 2-10%, preferably 5-8% of the designed mass of the crude polyether polyol.
The neutralizing agent in the step (3) is an organic acid, preferably one or two of citric acid or adipic acid.
The polyether polyol prepared by the invention has a molecular weight of more than 8000.
Compared with the prior art, the invention has the following beneficial effects:
(1) the super-soft slow-resilience polyether polyol prepared by the invention has higher molecular weight, can prepare softer and more comfortable polyurethane slow-resilience foam, and the high-functionality molecular structure design ensures low compression permanent deformation and is beneficial to transportation.
(2) The invention adopts a double-catalysis system, takes KOH as a main catalyst and takes a phosphazene catalyst as a cocatalyst to synthesize the slow-rebound ultra-high molecular weight polyether polyol, the reaction activity is high, the side reaction products are few, the polyether polyol product has lower unsaturation degree and narrower molecular weight distribution, and the produced slow-rebound polyurethane foam has excellent physical properties.
Detailed Description
The present invention will be further illustrated with reference to the following specific examples, but the present invention is not limited to the following examples.
The method is a conventional method unless otherwise specified. The starting materials are commercially available from the open literature unless otherwise specified.
Example 1
Adding 92g of glycerol, 182g of sorbitol and 40g of potassium hydroxide into a pressure-resistant reaction kettle, replacing with nitrogen to ensure that the oxygen content in the kettle is less than 50ppm, then adding 431g of propylene oxide and 1295g of ethylene oxide to carry out primary polymerization reaction at the temperature of 108-112 ℃, and continuing internal pressure reaction for 3 hours after the reaction is finished to ensure that the added propylene oxide and the ethylene oxide fully react, and removing unreacted monomers to obtain the intermediate polyether polyol.
202g of intermediate polyether polyol and 2.0g of phosphazene catalyst are added into a pressure-resistant reaction kettle to be mixed, nitrogen is replaced to ensure that the oxygen content in the kettle is less than 50ppm, and nitrogen bubbling is carried out for 2 hours under the conditions that the temperature is 93-95 ℃ and the vacuum degree is less than-0.09 MPa. Feeding 434g of propylene oxide and 1303g of ethylene oxide according to the proportion at the temperature of 113-.
Adding 6.2g of citric acid and 80g of water into the crude polyether polyol, then adding an adsorbent, and drying and filtering to obtain the polyether polyol for the ultra-soft foam.
Example 2
Adding 110g of glycerol, 146g of sorbitol and 24g of potassium hydroxide into a pressure-resistant reaction kettle, replacing with nitrogen to ensure that the oxygen content in the kettle is less than 50ppm, then adding 436g of propylene oxide and 1308g of ethylene oxide to carry out preliminary polymerization reaction at the temperature of 108-110 ℃, and continuing internal pressure reaction for 3 hours after the reaction is finished to ensure that the added propylene oxide and ethylene oxide fully react, and removing unreacted monomers to obtain the intermediate polyether polyol.
202g of intermediate polyether polyol and 2.2g of phosphazene catalyst are added into a pressure-resistant reaction kettle to be mixed, nitrogen is replaced to ensure that the oxygen content in the kettle is less than 50ppm, and nitrogen bubbling is carried out for 2 hours under the conditions that the temperature is 93-95 ℃ and the vacuum degree is less than-0.09 MPa. Feeding 472g of propylene oxide and 1416g of ethylene oxide according to a proportion at the temperature of 113-.
Adding 3.9g of citric acid and 80g of water into the crude polyether polyol, then adding an adsorbent, and drying and filtering to obtain the polyether polyol for the ultra-soft foam.
Example 3
Adding 147g of glycerol, 73g of sorbitol and 30g of potassium hydroxide into a pressure-resistant reaction kettle, replacing with nitrogen to ensure that the oxygen content in the kettle is less than 50ppm, then adding 445g of propylene oxide and 1335g of ethylene oxide to carry out preliminary polymerization reaction at the temperature of 108-.
202g of intermediate polyether polyol and 2.4g of phosphazene catalyst are added into a pressure-resistant reaction kettle to be mixed, nitrogen is replaced to ensure that the oxygen content in the kettle is less than 50ppm, and nitrogen bubbling is carried out for 2 hours under the conditions that the temperature is 93-95 ℃ and the vacuum degree is less than-0.09 MPa. 508g of propylene oxide and 1522g of ethylene oxide are fed in proportion at the temperature of 113-.
Adding 4.9g of citric acid and 90g of water into the crude polyether polyol, then adding an adsorbent, and drying and filtering to obtain the polyether polyol for the ultra-soft foam.
Comparative example 1
202g of the intermediate polyether polyol obtained in the embodiment 1 is added into a pressure-resistant reaction kettle to be mixed, nitrogen is replaced to ensure that the oxygen content in the kettle is less than 50ppm, then 431g of propylene oxide and 1295g of ethylene oxide are added to carry out primary polymerization reaction at the temperature of 108-110 ℃, internal pressure reaction is continued for 3 hours after the reaction is finished, the added propylene oxide and ethylene oxide are fully reacted, and unreacted monomers are removed to obtain the intermediate polyether polyol.
202g of polyether polyol intermediate and 5g of KOH are added into a pressure-resistant reaction kettle for mixing, the oxygen content in the kettle is less than 50ppm by nitrogen replacement, and the nitrogen bubbling time is timed for 2 hours under the conditions that the temperature is 105-plus 110 ℃ and the vacuum degree is lower than-0.09 MPa. Feeding 434g of propylene oxide and 1303g of ethylene oxide according to the proportion at the temperature of 113-.
Adding 5.6g of citric acid and 80g of water into the crude polyether polyol, then adding an adsorbent, and drying and filtering to obtain the polyether polyol for the ultra-soft foam.
The polyether polyols prepared in examples 1 to 3 and comparative example 1 were subjected to index tests, and the results are shown in Table 1.
TABLE 1
Of course, the foregoing is only a preferred embodiment of the invention and should not be taken as limiting the scope of the embodiments of the invention. The present invention is not limited to the above examples, and equivalent changes and modifications made by those skilled in the art within the spirit and scope of the present invention should be construed as being included in the scope of the present invention.
Claims (10)
1. A preparation method of polyether polyol for super-soft slow-rebound foam is characterized by comprising the following steps: the method comprises the following steps:
(1) adding a small molecular initiator and an alkali metal catalyst into a pressure-resistant reaction kettle for mixing, replacing the oxygen content in the kettle by nitrogen until the oxygen content is less than 50ppm, then heating to 105-125 ℃, adding propylene oxide and ethylene oxide for preliminary polymerization, continuing the internal pressure reaction for 1.5-3.5h after the reaction is finished, and removing unreacted monomers to obtain an intermediate polyether polyol;
(2) adding the intermediate polyether polyol obtained in the step (1) and a phosphazene catalyst into a pressure-resistant reaction kettle, replacing nitrogen until the oxygen content in the kettle is less than 50ppm, carrying out nitrogen bubbling for 1-3h under the condition that the vacuum degree is lower than-0.09 MPa at 90-115 ℃, adding epoxypropane and epoxyethane for carrying out polymerization reaction after the timing is finished, continuing carrying out internal pressure reaction for 3.5-5.5h after the reaction is finished, removing unreacted monomers, then adding epoxyethane for carrying out end-capping polymerization reaction, removing unreacted residual monomers and micromolecule byproducts after the internal pressure is 1-3h after the reaction is finished, and thus obtaining crude polyether polyol;
(3) and (3) adding water and a neutralizing agent into the crude polyether polyol prepared in the step (2) for neutralization, then adding a filter aid, and drying and filtering to obtain the polyether polyol for the super-soft slow-rebound foam.
2. The process for preparing a polyether polyol for ultra-soft slow-recovery foams according to claim 1, wherein: the micromolecule initiator in the step (1) is a mixture of glycerol and sorbitol, wherein the mass ratio of the glycerol is 30-75%.
3. The process for preparing a polyether polyol for ultra-soft slow-recovery foams according to claim 1, wherein: the alkali metal catalyst in the step (1) is potassium hydroxide, and the addition amount of the alkali metal catalyst is 1-3% of the designed mass of the intermediate polyether polyol.
4. The process for preparing a polyether polyol for ultra-soft slow-recovery foams according to claim 1, wherein: the propylene oxide and the ethylene oxide subjected to preliminary polymerization in the step (1) account for 70-80% of the mass of the copolymerized alkane.
5. The process for preparing a polyether polyol for ultra-soft slow-recovery foams according to claim 1, wherein: the adding amount of the phosphazene catalyst in the step (2) is 0.5-3.5 per mill of the designed mass of the crude polyether polyol.
6. The process for preparing a polyether polyol for ultra-soft slow-recovery foams according to claim 1, wherein: the polymerization temperature of propylene oxide and ethylene oxide in the step (2) is 95-125 ℃.
7. The process for preparing a polyether polyol for ultra-soft slow-recovery foams according to claim 1, wherein: the propylene oxide and the ethylene oxide which are subjected to polymerization reaction in the step (2) account for 70-80% of the mass of the copolymerized alkane.
8. The process for preparing a polyether polyol for ultra-soft slow-recovery foams according to claim 1, wherein: the temperature of the end-capping polymerization reaction of ethylene oxide in the step (2) is 105-125 ℃.
9. The process for preparing a polyether polyol for ultra-soft slow-recovery foams according to claim 1, wherein: the amount of the ethylene oxide subjected to the end-capping polymerization reaction in the step (2) accounts for 2-10% of the designed mass of the crude polyether polyol.
10. The process for preparing a polyether polyol for ultra-soft slow-recovery foams according to claim 1, wherein: the polyether polyol has a molecular weight greater than 8000.
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| CN202011581713.3A CN112759755A (en) | 2020-12-28 | 2020-12-28 | Preparation method of polyether polyol for super-soft slow-rebound foam |
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