CN114479048B - Preparation method of polymer-based rigid foam polyether polyol - Google Patents
Preparation method of polymer-based rigid foam polyether polyol Download PDFInfo
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- CN114479048B CN114479048B CN202111578465.1A CN202111578465A CN114479048B CN 114479048 B CN114479048 B CN 114479048B CN 202111578465 A CN202111578465 A CN 202111578465A CN 114479048 B CN114479048 B CN 114479048B
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- polyether polyol
- kettle
- propylene oxide
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- 229920005862 polyol Polymers 0.000 title claims abstract description 63
- 150000003077 polyols Chemical class 0.000 title claims abstract description 63
- 239000004721 Polyphenylene oxide Substances 0.000 title claims abstract description 41
- 229920000570 polyether Polymers 0.000 title claims abstract description 41
- 229920000642 polymer Polymers 0.000 title claims abstract description 40
- 239000006260 foam Substances 0.000 title claims abstract description 24
- 238000002360 preparation method Methods 0.000 title abstract description 9
- 238000006243 chemical reaction Methods 0.000 claims abstract description 43
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 claims abstract description 38
- 238000000034 method Methods 0.000 claims abstract description 30
- 238000010438 heat treatment Methods 0.000 claims abstract description 21
- 238000003756 stirring Methods 0.000 claims abstract description 21
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 15
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000003999 initiator Substances 0.000 claims abstract description 11
- 150000001412 amines Chemical class 0.000 claims abstract description 9
- 239000000178 monomer Substances 0.000 claims abstract description 9
- 229910052783 alkali metal Inorganic materials 0.000 claims abstract description 7
- 150000001340 alkali metals Chemical class 0.000 claims abstract description 7
- 239000003054 catalyst Substances 0.000 claims abstract description 7
- 238000007789 sealing Methods 0.000 claims abstract description 7
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 6
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 16
- 239000000463 material Substances 0.000 claims description 14
- 239000007787 solid Substances 0.000 claims description 11
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 9
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 8
- 238000007599 discharging Methods 0.000 claims description 8
- HCWCAKKEBCNQJP-UHFFFAOYSA-N magnesium orthosilicate Chemical compound [Mg+2].[Mg+2].[O-][Si]([O-])([O-])[O-] HCWCAKKEBCNQJP-UHFFFAOYSA-N 0.000 claims description 8
- 229910052919 magnesium silicate Inorganic materials 0.000 claims description 8
- 235000019792 magnesium silicate Nutrition 0.000 claims description 8
- 239000000391 magnesium silicate Substances 0.000 claims description 8
- 238000000967 suction filtration Methods 0.000 claims description 6
- ZETYUTMSJWMKNQ-UHFFFAOYSA-N n,n',n'-trimethylhexane-1,6-diamine Chemical compound CNCCCCCCN(C)C ZETYUTMSJWMKNQ-UHFFFAOYSA-N 0.000 claims description 4
- 239000002994 raw material Substances 0.000 claims description 4
- DJDBATHKYZGQBJ-UHFFFAOYSA-N 2-[hydroxy(propan-2-yl)amino]phenol Chemical compound OC1=C(N(C(C)C)O)C=CC=C1 DJDBATHKYZGQBJ-UHFFFAOYSA-N 0.000 claims description 3
- RNLHGQLZWXBQNY-UHFFFAOYSA-N 3-(aminomethyl)-3,5,5-trimethylcyclohexan-1-amine Chemical compound CC1(C)CC(N)CC(C)(CN)C1 RNLHGQLZWXBQNY-UHFFFAOYSA-N 0.000 claims description 3
- -1 o-toluylene diamine Chemical compound 0.000 claims description 3
- 239000000314 lubricant Substances 0.000 claims description 2
- FSWDLYNGJBGFJH-UHFFFAOYSA-N n,n'-di-2-butyl-1,4-phenylenediamine Chemical compound CCC(C)NC1=CC=C(NC(C)CC)C=C1 FSWDLYNGJBGFJH-UHFFFAOYSA-N 0.000 claims description 2
- TZIHFWKZFHZASV-UHFFFAOYSA-N methyl formate Chemical compound COC=O TZIHFWKZFHZASV-UHFFFAOYSA-N 0.000 abstract description 22
- 239000004088 foaming agent Substances 0.000 abstract description 11
- 229920005830 Polyurethane Foam Polymers 0.000 abstract description 10
- 229920003023 plastic Polymers 0.000 abstract description 10
- 239000004033 plastic Substances 0.000 abstract description 10
- 239000011496 polyurethane foam Substances 0.000 abstract description 10
- 238000004519 manufacturing process Methods 0.000 abstract description 3
- 230000000052 comparative effect Effects 0.000 description 5
- 239000002131 composite material Substances 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 238000005187 foaming Methods 0.000 description 5
- FRCHKSNAZZFGCA-UHFFFAOYSA-N 1,1-dichloro-1-fluoroethane Chemical compound CC(F)(Cl)Cl FRCHKSNAZZFGCA-UHFFFAOYSA-N 0.000 description 3
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 3
- RGSFGYAAUTVSQA-UHFFFAOYSA-N Cyclopentane Chemical compound C1CCCC1 RGSFGYAAUTVSQA-UHFFFAOYSA-N 0.000 description 2
- WGQKYBSKWIADBV-UHFFFAOYSA-N benzylamine Chemical compound NCC1=CC=CC=C1 WGQKYBSKWIADBV-UHFFFAOYSA-N 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- PAFZNILMFXTMIY-UHFFFAOYSA-N cyclohexylamine Chemical compound NC1CCCCC1 PAFZNILMFXTMIY-UHFFFAOYSA-N 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 238000009413 insulation Methods 0.000 description 2
- WZLFPVPRZGTCKP-UHFFFAOYSA-N 1,1,1,3,3-pentafluorobutane Chemical compound CC(F)(F)CC(F)(F)F WZLFPVPRZGTCKP-UHFFFAOYSA-N 0.000 description 1
- NDKGUMMLYBINOC-UHFFFAOYSA-N 1,2-dichloro-1-fluoroethane Chemical compound FC(Cl)CCl NDKGUMMLYBINOC-UHFFFAOYSA-N 0.000 description 1
- RLYCRLGLCUXUPO-UHFFFAOYSA-N 2,6-diaminotoluene Chemical compound CC1=C(N)C=CC=C1N RLYCRLGLCUXUPO-UHFFFAOYSA-N 0.000 description 1
- 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 description 1
- CZMRCDWAGMRECN-UGDNZRGBSA-N Sucrose Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 CZMRCDWAGMRECN-UGDNZRGBSA-N 0.000 description 1
- 229930006000 Sucrose Natural products 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 230000008030 elimination Effects 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- DMEGYFMYUHOHGS-UHFFFAOYSA-N heptamethylene Natural products C1CCCCCC1 DMEGYFMYUHOHGS-UHFFFAOYSA-N 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- MSSNHSVIGIHOJA-UHFFFAOYSA-N pentafluoropropane Chemical compound FC(F)CC(F)(F)F MSSNHSVIGIHOJA-UHFFFAOYSA-N 0.000 description 1
- 229920001228 polyisocyanate Polymers 0.000 description 1
- 239000005056 polyisocyanate Substances 0.000 description 1
- 229920006389 polyphenyl polymer Polymers 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 238000011417 postcuring Methods 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 229920002545 silicone oil Polymers 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000000600 sorbitol Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000005720 sucrose Substances 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 229920002994 synthetic fiber Polymers 0.000 description 1
- 238000010792 warming 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
- C08G65/2618—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 nitrogen
- C08G65/2621—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 nitrogen containing amine groups
- C08G65/2627—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 nitrogen containing amine groups containing aromatic or arylaliphatic amine 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
- C08G18/50—Polyethers having heteroatoms other than oxygen
- C08G18/5021—Polyethers having heteroatoms other than oxygen having nitrogen
- C08G18/5024—Polyethers having heteroatoms other than oxygen having nitrogen containing primary and/or secondary amino groups
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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
- 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
- C08G18/50—Polyethers having heteroatoms other than oxygen
- C08G18/5021—Polyethers having heteroatoms other than oxygen having nitrogen
- C08G18/5024—Polyethers having heteroatoms other than oxygen having nitrogen containing primary and/or secondary amino groups
- C08G18/5027—Polyethers having heteroatoms other than oxygen having nitrogen containing primary and/or secondary amino groups directly linked to carbocyclic groups
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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
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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
- C08G65/2618—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 nitrogen
- C08G65/2621—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 nitrogen containing amine groups
- C08G65/2624—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 nitrogen containing amine groups containing aliphatic amine groups
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
- C08J9/12—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a physical blowing agent
- C08J9/14—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a physical blowing agent organic
- C08J9/142—Compounds containing oxygen but no halogen atom
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2110/00—Foam properties
- C08G2110/0025—Foam properties rigid
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2203/00—Foams characterized by the expanding agent
- C08J2203/12—Organic compounds only containing carbon, hydrogen and oxygen atoms, e.g. ketone or alcohol
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2205/00—Foams characterised by their properties
- C08J2205/10—Rigid foams
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2375/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
- C08J2375/04—Polyurethanes
- C08J2375/08—Polyurethanes from polyethers
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
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- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Polyethers (AREA)
- Polyurethanes Or Polyureas (AREA)
Abstract
The invention relates to a preparation method of polyether polyol, in particular to a preparation method of polymer-based hard foam polyether polyol. The method comprises the following steps: and (3) putting the polymer polyol, the amine initiator and the alkali metal catalyst into a reaction kettle, sealing the reaction kettle, carrying out nitrogen replacement and deoxidization, heating and stirring, controlling the temperature in the reaction kettle, continuously dropwise adding propylene oxide for the first time to carry out a first-stage polymerization reaction, continuously dropwise adding the rest propylene oxide for the second time to carry out a second-stage polymerization reaction after the reaction is finished, removing unreacted monomers, and carrying out aftertreatment to obtain a polyether polyol product. The rigid polyurethane foam plastic prepared by the polymer-based rigid foam polyether polyol and taking methyl formate as a foaming agent can effectively improve the dimensional stability of foam and reduce the heat conductivity coefficient of the foam plastic, and meanwhile, the invention has the advantages of simple process, high production efficiency and stable performance of the obtained product.
Description
Technical Field
The invention relates to a preparation method of polyether polyol, in particular to a preparation method of polymer-based hard foam polyether polyol.
Background
The rigid polyurethane foam plastic is one of main varieties of polyurethane synthetic materials, has good heat insulation effect, light weight, large specific strength and other excellent performances, and is widely used in the fields of refrigerator and freezer, refrigerated transportation, industrial storage tank and pipeline heat insulation, furniture manufacturing and the like.
According to the regulations of Montreal protocol, the foaming agent replaces a schedule, and the elimination of HCFC-141b is more and more close, and as the environmental protection requirement is more and more strict, the foaming agent replaces the urgent need, wherein methyl formate belongs to a green environment-friendly foaming agent, is the only foaming agent which simultaneously satisfies ODP=0, GWP (global warming potential) approximately 0 and VOC-free conditions in the foaming agents which are put into use at present, and particularly accords with the development trend of the foaming agent. The relative molecular mass of methyl formate is only half of HCFC-141b, which is far lower than HFC-245fa and HFC-365mfc, so that the same foaming efficiency as the traditional foaming agent can be achieved under the condition of obviously reducing the dosage, thereby greatly improving the economy of the foaming process. The boiling point and solubility of methyl formate are very close to those of HCFC-141b, making it an ideal substitute for HCFC-141 b.
Because methyl formate has a certain solvent effect, the foam size stability is poor and the heat conductivity coefficient is high when the methyl formate is singly used as a foaming agent. Therefore, it is important to effectively make up for and improve the modification of the performance defect of the methyl formate type composite material in the composite material application, so that the development of a modified polymer polyol can effectively improve the dimensional stability of the rigid polyurethane foam plastic manufactured by the methyl formate type composite material and reduce the heat conductivity coefficient. Therefore, the development of the rigid foam system by using the modified polymer polyol is urgent, and the market prospect is expected to be quite broad.
Disclosure of Invention
The invention aims to solve the technical problems that: the preparation method of the polymer-based rigid foam polyether polyol overcomes the defects of the prior art, and the rigid polyurethane foam plastic prepared by adopting the polymer-based rigid foam polyether polyol and taking methyl formate as a foaming agent can effectively improve the dimensional stability of foam and reduce the heat conductivity coefficient of the foam plastic.
The preparation method of the polymer-based hard foam polyether polyol comprises the following steps:
and (3) putting the polymer polyol, the amine initiator and the alkali metal catalyst into a reaction kettle, sealing the reaction kettle, carrying out nitrogen replacement and deoxidization, heating and stirring, controlling the temperature in the reaction kettle, continuously dropwise adding propylene oxide for the first time to carry out a first-stage polymerization reaction, continuously dropwise adding the rest propylene oxide for the second time to carry out a second-stage polymerization reaction after the reaction is finished, removing unreacted monomers, and carrying out aftertreatment to obtain a polyether polyol product.
In the preparation method, the mass ratio of each raw material is calculated according to the mass parts,
polymer polyol: 20-30 parts of a lubricant;
amine initiator: 5-10 parts;
alkali metal catalyst: 0.1-0.3 part;
propylene oxide: 59.7-74.9 parts.
Wherein:
the polymer polyol is one or more of CHP-2150 type polymer polyol, CHP-2045 type polymer polyol, CHP-H50 type polymer polyol, CHP-H45 type polymer polyol and CHP-H30 type polymer polyol.
The amine initiator is one or more of isophorone diamine, o-toluylene diamine, dihydroxyisopropyl aniline, 1, 4-di-sec-butylamino benzene or trimethyl hexamethylene diamine.
The alkali metal catalyst is solid KOH.
The conditions of heating and stirring are as follows: heating to 100-130 deg.c and stirring for 1-5 hr.
The first stage polymerization reaction specifically comprises the following steps: continuously dripping propylene oxide for the first time at 90-130 ℃ in the reaction kettle, controlling the material temperature at 90-130 ℃ in the process, controlling the pressure in the kettle to be 0.1-0.4MPa, and curing for 2-3h after the dripping is finished.
The second-stage polymerization reaction specifically comprises the following steps: vacuumizing and heating to 120-150 ℃, continuously dripping the rest propylene oxide for the second time, controlling the temperature to 120-150 ℃ in the process, controlling the pressure in the kettle to be 0.1-0.4MPa, and curing for 2-3h after the dripping is finished.
The post-treatment is as follows: reducing the temperature in the reaction kettle to 70-80 ℃, adding phosphoric acid and pure water, stirring, adding magnesium silicate, heating to 110-120 ℃, vacuumizing and dehydrating, controlling the pressure in the kettle to be minus 0.08-minus 0.09MPa, detecting that the water content is lower than 0.1%, discharging, and carrying out suction filtration to obtain the polyether polyol product.
The hydroxyl value of the polyether polyol product is 430-480mg/KOH, and the viscosity is 20000-30000 mPa.s.
Compared with the prior art, the invention has the following beneficial effects:
1. the invention adopts polymer polyol and amine initiator as composite initiator raw materials, and can obtain basic indexes: the product with the hydroxyl value of 430-480mg/KOH and the viscosity of 20000-30000 mPa.s adopts the collocation of the polymer polyol and the composite initiator of the special amine initiator to play the role of synergistic high-activity catalytic polymerization, improves the crosslinking degree of the polyol product, and has post-curing effect and fine cells.
2. The high-hydroxyl-value high-viscosity system of the polyether effectively increases the crosslinking degree of the product in the foaming process, and the high reactivity effectively improves the dimensional stability of the product.
3. The polyether polyol prepared by the method is used for preparing the rigid polyurethane foam plastic by taking methyl formate as a foaming agent, and can effectively improve the dimensional stability of the foam plastic and reduce the heat conductivity coefficient of the foam plastic.
4. The invention has simple process and high production efficiency, and the performance of the obtained product is stable.
Detailed Description
The invention is further illustrated below with reference to examples, which are not intended to limit the practice of the invention.
All materials used in the examples are commercially available without any particular explanation.
Example 1
750g of CHP-H30 polymer polyol, 200g of dihydroxyisopropyl aniline and 7.5g of solid KOH are put into a reaction kettle, the sealing kettle is operated, the temperature is raised to 100 ℃, and the stirring rotation speed is 500 revolutions for 2 hours. Controlling the temperature in the polymerization kettle to be 102.5+/-2.5 ℃, continuously dropwise adding propylene oxide, controlling the actual temperature of materials in the process to be 104.5+/-2.5 ℃ for reaction, controlling the feeding speed to be less than 0.4MPa, controlling the pressure in the kettle, and curing for 3 hours after the completion of dropwise adding 801g of propylene oxide. And (3) vacuumizing and heating to 107.5+/-2.5 ℃, continuously dropwise adding 1201.5g of propylene oxide, controlling the temperature to 127.5+/-2.5 ℃ and the pressure to be less than 0.4MPa in the process, and curing for 3 hours until the propylene oxide is completely dropwise added. Controlling the temperature in the kettle to be 115.5+/-2.5 ℃, vacuumizing to control the pressure in the kettle to be-0.08 to-0.09 MPa, and removing unreacted propylene oxide monomer for 1h. Reducing the temperature in the reaction kettle to 80+/-5 ℃, adding 32.5g of phosphoric acid and 155g of water, stirring for 1h, adding 3.85g of magnesium silicate, heating to 105+/-5 ℃, vacuumizing and dehydrating, controlling the pressure in the kettle to be-0.08 to-0.09 MPa, timing for 4h, detecting that the water content is lower than 0.1%, discharging, and performing suction filtration to obtain a qualified polyether polyol finished product. A polyether polyol having a hydroxyl number of 435mg/KOH and a viscosity of 25700 mPas was obtained.
Example 2
875g of CHP-H50 polymer polyol, 280g of trimethyl hexamethylenediamine and 8.75g of solid KOH are put into a reaction kettle, the reaction kettle is sealed, the temperature is raised to 100 ℃, and the stirring rotation speed is 500 revolutions for 2 hours. Continuously dropwise adding propylene oxide at the temperature of 102.5+/-2.5 ℃ in the polymerization kettle, controlling the actual temperature of materials to react at the temperature of 102.5+/-2.5 ℃ in the process, controlling the pressure in the kettle to be less than 0.4MPa at the feeding speed, and curing for 3 hours after all the dropwise adding of 935g of propylene oxide. Vacuumizing and heating to 107.5+/-2.5 ℃, continuously dripping 1402g of propylene oxide, controlling the temperature to 127.5+/-2.5 ℃ and the pressure to be less than 0.4MPa in the process, and curing for 3 hours until the propylene oxide is completely dripped. Controlling the temperature in the kettle at 122.5+/-2.5 ℃, vacuumizing, controlling the pressure in the kettle at-0.08 to-0.09 MPa, and removing unreacted propylene oxide monomer for 1h. Reducing the temperature in the reaction kettle to 80+/-5 ℃, adding 32.5g of phosphoric acid and 155g of water, stirring for 1h, adding 3.85g of magnesium silicate, heating to 105+/-5 ℃, vacuumizing and dehydrating, controlling the pressure in the kettle to be-0.08 to-0.09 MPa, timing for 4h, detecting that the water content is lower than 0.1%, discharging, and performing suction filtration to obtain a qualified polyether polyol finished product. A polyether polyol having a hydroxyl number of 446mg/KOH and a viscosity of 28700 mPa.s was obtained.
Example 3
Put 48 g of CHP-H50 polymer polyol, 493g of CHP-H30 polymer polyol, 280g of trimethyl hexamethylenediamine and 8.75g of solid KOH into a reaction vessel, and then the reaction vessel was sealed, and the temperature was raised to 100℃and the stirring rotation speed was 500 rpm for 2 hours. Continuously dropwise adding propylene oxide at the temperature of 102.5+/-2.5 ℃ in a polymerization kettle, controlling the actual temperature of materials to react at 123+/-2.5 ℃ in the process, controlling the pressure in the kettle to be less than 0.4MPa at a feeding speed, completely dropwise adding 935g of propylene oxide, curing for 3 hours, vacuumizing and heating to the temperature of 107.5+/-2.5 ℃, continuously dropwise adding 1402g of propylene oxide, ensuring the temperature to be 127.5+/-2.5 ℃ in the process, and controlling the pressure to be less than 0.4MPa until the whole propylene oxide is completely dropwise added, and curing for 3 hours. Controlling the temperature in the kettle at 102.5+/-2.5 ℃, vacuumizing, controlling the pressure in the kettle at-0.08 to-0.09 MPa, and removing unreacted propylene oxide monomer for 1h. Reducing the temperature in the reaction kettle to 80+/-5 ℃, adding 32.5g of phosphoric acid and 155g of water, stirring for 1h, adding 3.85g of magnesium silicate, heating to 105+/-5 ℃, vacuumizing and dehydrating, controlling the pressure in the kettle to be-0.08 to-0.09 MPa, timing for 4h, detecting that the water content is lower than 0.1%, discharging, and performing suction filtration to obtain a qualified polyether polyol finished product. A polyether polyol having a hydroxyl number of 452mg/KOH and a viscosity of 22700 mPa.s was obtained.
Comparative example 1
500g of sorbitol solid, 140g of glycerol and 5g of solid KOH are put into a reaction kettle, the sealing kettle operation is carried out, the nitrogen deoxidization operation is carried out, the temperature in the reaction kettle is raised to 120 ℃, the stirring rotation speed is 500 revolutions and continuously carried out for 2 hours, propylene oxide is continuously added dropwise, the actual reaction temperature of materials is controlled to be 122.5+/-2.5 ℃ in the process for reaction, the feeding speed is controlled in the feeding process to enable the pressure in the kettle to be lower than 0.4MPa, and 1200g of propylene oxide is continuously added dropwise until all the propylene oxide is completely added dropwise, and the reaction is cured for 4 hours. And (3) vacuumizing to control the pressure in the reaction kettle to be lower than-0.09 MPa, and removing unreacted monomers for about 1h. Then reducing the temperature in the reaction kettle to 72.5+/-2.5 ℃, adding 12g of phosphoric acid and 92g of water, stirring for 1.5 hours, adding 3.6g of magnesium silicate, heating to 125.5+/-2.5 ℃, vacuumizing and dehydrating, controlling the pressure in the kettle to be-0.08 to-0.09 MPa, timing for 4 hours, detecting that the water content is less than 0.1%, discharging and filtering to obtain qualified polyether polyol, and obtaining a polyether product with the hydroxyl value of 440mg/KOH and the viscosity of 26000 mPa.s.
Comparative example 2
100g of isophorone diamine, 400g of sucrose solid and 5g of solid KOH are put into a reaction kettle, the sealing kettle is operated, the nitrogen deoxidization operation is carried out, the temperature in the reaction kettle is raised to 120 ℃, the stirring speed is 500 revolutions and continuously carried out for 2 hours, propylene oxide is continuously added dropwise, the actual reaction temperature of materials is controlled to be 122.5+/-2.5 ℃ in the process for reaction, the feeding speed is controlled in the feeding process to enable the pressure in the kettle to be lower than 0.4MPa, and 1200g of propylene oxide is continuously added dropwise until all the propylene oxide is completely added dropwise, and the reaction is cured for 4 hours. And (3) vacuumizing to control the pressure in the reaction kettle to be lower than-0.09 MPa, and removing unreacted monomers for about 1h. Then reducing the temperature in the reaction kettle to 72.5+/-2.5 ℃, adding 12g of phosphoric acid and 80g of water, stirring for 1.5 hours, adding 3.2g of magnesium silicate, heating to 112.5+/-2.5 ℃, vacuumizing and dehydrating, controlling the pressure in the kettle to be-0.08 to-0.09 MPa, timing for 4 hours, detecting that the water content is less than 0.1%, discharging and filtering to obtain qualified polyether polyol, and obtaining a polyether product with the hydroxyl value of 445mg/KOH and the viscosity of 26500 mPa.s.
Comparative example 3
400g of o-toluenediamine and 8g of solid KOH are put into a reaction kettle, the operation of the reaction kettle is carried out, the temperature is raised to 100 ℃, and the stirring rotation speed is 500 revolutions for 2 hours. Controlling the temperature in the polymerization kettle to be 102.5+/-2.5 ℃, continuously dropwise adding propylene oxide, controlling the actual temperature of materials in the process to be 102.5+/-2.5 ℃ for reaction, controlling the feeding speed to be less than 0.4MPa, controlling the pressure in the kettle, and curing for 3 hours after the dropwise adding of 1400g of propylene oxide is completed. And (3) opening the kettle, adding 5.5g of solid KOH, then performing sealing kettle operation, replacing nitrogen for three times, vacuumizing and heating to 107.5+/-2.5 ℃, continuously dropwise adding 2050g of propylene oxide, ensuring that the temperature is controlled to be 107.5+/-2.5 ℃ and the pressure is less than 0.4MPa in the process, and curing for 3 hours until the propylene oxide is completely dropwise added. Controlling the temperature in the kettle at 127.5+/-2.5 ℃, vacuumizing, controlling the pressure in the kettle at-0.08 to-0.09 MPa, and removing unreacted propylene oxide monomer for 1h. Reducing the temperature in the reaction kettle to 80+/-5 ℃, adding 32.5g of phosphoric acid and 155g of water, stirring for 1h, adding 3.85g of magnesium silicate, heating to 105+/-5 ℃, vacuumizing and dehydrating, controlling the pressure in the kettle to be-0.08 to-0.09 MPa, timing for 4h, detecting that the water content is lower than 0.1%, discharging, and performing suction filtration to obtain a qualified polyether polyol finished product. A polyether polyol having a hydroxyl number of 445mg/KOH and a viscosity of 28200 mPas was obtained.
The polyether polyol prepared in the above examples and comparative examples is used as a raw material to prepare a rigid polyurethane foam material, wherein the rigid polyurethane foam material comprises a component A and a component B in a mass ratio of 1:1, and the components are calculated according to parts by weight:
and (3) a component A: 40 parts of polyether polyol INOVOL R5118G, 20 parts of INOVOL R6205, 40 parts of polyether, 0.8 part of cyclohexylamine, 1.5 parts of benzylamine, 2 parts of silicone oil, 1.8 parts of methyl formate and 15 parts of cyclopentane are weighed, and the weighed materials are uniformly mixed to obtain a product with qualified component A.
The component B is polyphenyl polymethylene polyisocyanate.
A, B components were prepared according to a: b=100:100 weight ratio, and the materials are mixed to prepare a rigid polyurethane foam material, the foaming index of the product is detected, the foaming activity is controlled to be consistent with the density of the final foam finished product by adjusting the small-size formula, and the detection result is shown in table 1.
Table 1 analysis of experimental data for examples and comparative examples
As can be seen from the table, the invention can obviously improve the dimensional stability of the rigid polyurethane foam, reduce the heat conductivity coefficient and obtain the rigid polyurethane foam plastic with good dimensional stability and low heat conductivity coefficient.
Of course, the foregoing is merely preferred embodiments of the present invention and is not to be construed as limiting the scope of the embodiments of the present invention. The present invention is not limited to the above examples, and those skilled in the art will appreciate that the present invention is capable of equally varying and improving within the spirit and scope of the present invention.
Claims (7)
1. A method for preparing polymer-based rigid foam polyether polyol, which is characterized in that: the method comprises the following steps:
putting polymer polyol, amine initiator and alkali metal catalyst into a reaction kettle, sealing the reaction kettle, carrying out nitrogen replacement and deoxidization, heating and stirring, controlling the temperature in the reaction kettle, continuously dripping propylene oxide for the first time to carry out first-stage polymerization reaction, continuously dripping the rest propylene oxide for the second time to carry out second-stage polymerization reaction after the reaction is finished, removing unreacted monomers, and carrying out aftertreatment to obtain a polyether polyol product;
the mass ratio of each raw material, calculated by mass parts,
polymer polyol: 20-30 parts of a lubricant;
amine initiator: 5-10 parts;
alkali metal catalyst: 0.1-0.3 part;
propylene oxide: 59.7-74.9 parts;
the polymer polyol is one or more of CHP-2150 type polymer polyol, CHP-2045 type polymer polyol, CHP-H50 type polymer polyol, CHP-H45 type polymer polyol or CHP-H30 type polymer polyol;
the amine initiator is one or more of isophorone diamine, o-toluylene diamine, dihydroxyisopropyl aniline, 1, 4-di-sec-butylamino benzene or trimethyl hexamethylene diamine.
2. The method of preparing a polymer-based rigid foam polyether polyol according to claim 1, wherein: the alkali metal catalyst is solid KOH.
3. The method of preparing a polymer-based rigid foam polyether polyol according to claim 1, wherein: the conditions of heating and stirring are as follows: heating to 100-130 deg.c and stirring for 1-5 hr.
4. The method of preparing a polymer-based rigid foam polyether polyol according to claim 1, wherein: the first stage polymerization reaction is specifically: continuously dripping propylene oxide for the first time at 90-130 ℃ in the reaction kettle, controlling the material temperature at 90-130 ℃ in the process, controlling the pressure in the kettle to be 0.1-0.4MPa, and curing for 2-3h after the dripping is finished.
5. The method of preparing a polymer-based rigid foam polyether polyol according to claim 1, wherein: the second stage polymerization reaction is specifically: vacuumizing and heating to 120-150 ℃, continuously dripping the rest propylene oxide for the second time, controlling the temperature to 120-150 ℃ in the process, controlling the pressure in the kettle to be 0.1-0.4MPa, and curing for 2-3h after the dripping is finished.
6. The method of preparing a polymer-based rigid foam polyether polyol according to claim 1, wherein: the post-treatment is as follows: reducing the temperature in the reaction kettle to 70-80 ℃, adding phosphoric acid and pure water, stirring, adding magnesium silicate, heating to 110-120 ℃, vacuumizing and dehydrating, controlling the pressure in the kettle to be minus 0.08-minus 0.09MPa, detecting that the water content is lower than 0.1%, discharging, and carrying out suction filtration to obtain the polyether polyol product.
7. The method for preparing a polymer-based rigid foam polyether polyol according to claim 1 or 6, wherein: the polyether polyol product has hydroxyl value of 430-480mg/KOH and viscosity of 20000-30000 mPa.s.
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