CN117801273A - Hydrogenation catalyst for flexible polyurethane foam, preparation method and application thereof, polyurethane foam composition and application thereof - Google Patents
Hydrogenation catalyst for flexible polyurethane foam, preparation method and application thereof, polyurethane foam composition and application thereof Download PDFInfo
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- CN117801273A CN117801273A CN202410055545.6A CN202410055545A CN117801273A CN 117801273 A CN117801273 A CN 117801273A CN 202410055545 A CN202410055545 A CN 202410055545A CN 117801273 A CN117801273 A CN 117801273A
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- polyurethane foam
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- 229920005830 Polyurethane Foam Polymers 0.000 title claims abstract description 77
- 239000011496 polyurethane foam Substances 0.000 title claims abstract description 77
- 239000003054 catalyst Substances 0.000 title claims abstract description 61
- 238000005984 hydrogenation reaction Methods 0.000 title claims abstract description 54
- 239000000203 mixture Substances 0.000 title claims abstract description 18
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 26
- 229920005862 polyol Polymers 0.000 claims abstract description 16
- 150000003077 polyols Chemical class 0.000 claims abstract description 16
- 239000006260 foam Substances 0.000 claims abstract description 13
- 239000004721 Polyphenylene oxide Substances 0.000 claims abstract description 10
- 229920000570 polyether Polymers 0.000 claims abstract description 10
- 229920000642 polymer Polymers 0.000 claims abstract description 9
- 239000003431 cross linking reagent Substances 0.000 claims abstract description 8
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 6
- 239000003381 stabilizer Substances 0.000 claims abstract description 6
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000011148 porous material Substances 0.000 claims abstract description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 19
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 18
- -1 fatty alcohol amines Chemical class 0.000 claims description 15
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 claims description 14
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 12
- UKVIEHSSVKSQBA-UHFFFAOYSA-N methane;palladium Chemical compound C.[Pd] UKVIEHSSVKSQBA-UHFFFAOYSA-N 0.000 claims description 12
- 239000007800 oxidant agent Substances 0.000 claims description 12
- 230000001590 oxidative effect Effects 0.000 claims description 12
- 239000000376 reactant Substances 0.000 claims description 12
- 238000003756 stirring Methods 0.000 claims description 9
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 6
- 238000005119 centrifugation Methods 0.000 claims description 6
- 239000008367 deionised water Substances 0.000 claims description 6
- 229910021641 deionized water Inorganic materials 0.000 claims description 6
- 239000012153 distilled water Substances 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 6
- 238000001914 filtration Methods 0.000 claims description 6
- 229910052739 hydrogen Inorganic materials 0.000 claims description 6
- 239000001257 hydrogen Substances 0.000 claims description 6
- 239000000178 monomer Substances 0.000 claims description 6
- 125000004429 atom Chemical group 0.000 claims description 4
- 125000004122 cyclic group Chemical group 0.000 claims description 4
- 125000006841 cyclic skeleton Chemical group 0.000 claims description 4
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 claims description 4
- 229910052736 halogen Inorganic materials 0.000 claims description 4
- 150000002367 halogens Chemical class 0.000 claims description 4
- 238000000034 method Methods 0.000 claims description 3
- 238000005406 washing Methods 0.000 claims description 3
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 claims description 2
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims description 2
- 125000000217 alkyl group Chemical group 0.000 claims description 2
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 2
- 125000004432 carbon atom Chemical group C* 0.000 claims description 2
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 claims description 2
- 150000002191 fatty alcohols Chemical class 0.000 claims description 2
- 229910052731 fluorine Inorganic materials 0.000 claims description 2
- 239000011737 fluorine Substances 0.000 claims description 2
- 125000001207 fluorophenyl group Chemical group 0.000 claims description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 2
- 230000008569 process Effects 0.000 claims description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 claims 1
- 229910001385 heavy metal Inorganic materials 0.000 abstract description 7
- 229920000128 polypyrrole Polymers 0.000 abstract description 4
- 230000000052 comparative effect Effects 0.000 description 9
- 238000006243 chemical reaction Methods 0.000 description 7
- VDVPDGHMMDYSRR-UHFFFAOYSA-N 3,4-difluoro-2-methyl-1h-pyrrole Chemical compound CC=1NC=C(F)C=1F VDVPDGHMMDYSRR-UHFFFAOYSA-N 0.000 description 5
- OJFOWGWQOFZNNJ-UHFFFAOYSA-N 3,4-dimethyl-1h-pyrrole Chemical compound CC1=CNC=C1C OJFOWGWQOFZNNJ-UHFFFAOYSA-N 0.000 description 5
- 229920002635 polyurethane Polymers 0.000 description 5
- 239000004814 polyurethane Substances 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 150000001412 amines Chemical class 0.000 description 4
- 238000005187 foaming Methods 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 3
- 238000011010 flushing procedure Methods 0.000 description 3
- 239000012948 isocyanate Substances 0.000 description 3
- 150000002513 isocyanates Chemical class 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 235000019441 ethanol Nutrition 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 230000035699 permeability Effects 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 150000003512 tertiary amines Chemical class 0.000 description 2
- IMNIMPAHZVJRPE-UHFFFAOYSA-N triethylenediamine Chemical compound C1CN2CCN1CC2 IMNIMPAHZVJRPE-UHFFFAOYSA-N 0.000 description 2
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 1
- 241000282326 Felis catus Species 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 231100000739 chronic poisoning Toxicity 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- AYOHIQLKSOJJQH-UHFFFAOYSA-N dibutyltin Chemical compound CCCC[Sn]CCCC AYOHIQLKSOJJQH-UHFFFAOYSA-N 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 239000004088 foaming agent Substances 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 235000010746 mayonnaise Nutrition 0.000 description 1
- 239000008268 mayonnaise Substances 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 239000013518 molded foam Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920002545 silicone oil Polymers 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000012970 tertiary amine catalyst Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 150000003606 tin compounds Chemical class 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
Classifications
-
- 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
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/0605—Polycondensates containing five-membered rings, not condensed with other rings, with nitrogen atoms as the only ring hetero atoms
- C08G73/0611—Polycondensates containing five-membered rings, not condensed with other rings, with nitrogen atoms as the only ring hetero atoms with only one nitrogen atom in the ring, e.g. polypyrroles
-
- 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
- C08G18/08—Processes
- C08G18/16—Catalysts
- C08G18/18—Catalysts containing secondary or tertiary amines or salts thereof
- C08G18/20—Heterocyclic amines; Salts thereof
- C08G18/2009—Heterocyclic amines; Salts thereof containing one heterocyclic ring
- C08G18/2018—Heterocyclic amines; Salts thereof containing one heterocyclic ring having one nitrogen atom in the ring
-
- 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
- C08G2101/00—Manufacture of cellular products
-
- 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
- C08G2110/00—Foam properties
- C08G2110/0008—Foam properties flexible
-
- 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
- C08G2110/00—Foam properties
- C08G2110/0041—Foam properties having specified density
- C08G2110/005—< 50kg/m3
-
- 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
- C08G2110/00—Foam properties
- C08G2110/0083—Foam properties prepared using water as the sole blowing agent
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Polyurethanes Or Polyureas (AREA)
Abstract
The invention provides a hydrogenation catalyst for flexible polyurethane foam, a preparation method and application thereof, a polyurethane foam composition and application thereof. The hydrogenation catalyst for the flexible polyurethane foam obtained by hydrogenating polypyrrole has alkalinity, and accelerates the generation of the polyurethane foam. The polyurethane foam composition of the present application comprises, based on 100% by mass total: 35 to 43 percent of polyether polyol, 26 to 31 percent of polymer polyol, 1 to 1.5 percent of cross-linking agent, 0.6 to 1 percent of hydrogenation catalyst, 0.4 to 0.9 percent of foam stabilizer, 1 to 1.6 percent of pore opening agent, 14 to 18 percent of toluene diisocyanate, 9 to 13 percent of diphenylmethane diisocyanate and the balance of water. The polyurethane foam prepared by the invention has almost no odor and no heavy metal elements, and simultaneously maintains the tensile strength, the elongation at break and the lower density.
Description
Technical Field
The invention relates to the technical field of polyurethane foam, in particular to a hydrogenation catalyst for flexible polyurethane foam, a preparation method and application thereof, a polyurethane foam composition and application thereof.
Background
The polyurethane foam is a high molecular polymer which is formed by mixing isocyanate and polyether as main raw materials through special equipment under the action of a foaming agent, a catalyst, a flame retardant and other auxiliary agents and foaming in situ through high-pressure spraying. Polyurethane foams are classified into flexible polyurethane foams and rigid polyurethane foams, and in industrial and household areas, flexible polyurethane foams are used for many technical purposes, for example for sound insulation, for the production of mattresses or for upholstered furniture; the automotive industry is a particularly important market for flexible polyurethane foams of all types, for example for vehicle seat cushion materials.
In the production process of polyurethane foam, if the reaction of isocyanate and polyether or alcohol is required to be promoted, namely the reaction of polyurethane molecular chain growth and crosslinking, metal catalysts such as organotin compounds are generally selected, the chemical properties of the metal catalysts such as organotin compounds are unstable, and substances containing heavy metals such as lead, tin and mercury exist in the metal catalysts, and when the metal catalysts such as organotin compounds are used for production, toxicity problems and environmental problems caused by residual heavy metals in the produced products are worry, for example, the patent publication No. CN101397359A discloses an amine catalyst for preparing a low-emission and re-catalysis stable soft polyurethane foam, and the tin compounds are used as a component of the catalyst in the catalyst, so that the organotin catalysts contain unreacted complete dibutyltin and the like, and the byproducts easily cause biological or chronic poisoning;
if the reaction of isocyanate and water, that is, the foaming reaction is promoted, amine catalysts such as tertiary amine are usually selected, most of tertiary amine catalysts in the market are easy to emit small molecular products, amine compounds remain in a formed foam plastic in a free form and are slowly discharged in a volatile amine form, and the amine compounds have a bad amine odor, and can be continuously migrated out of a foam finished product in the construction process to cause harm to human health, for example, chinese patent application number 201710431981.9 discloses a high-air-permeability viscoelastic polyurethane foam of an MDI system and a preparation method thereof, and the obtained polyurethane foam has good air permeability, water permeability and elongation at break. However, the polyurethane foam obtained by using the tertiary amine catalyst has a large odor due to the discharge of amine compounds.
Therefore, it is an urgent need to provide a polyurethane foam containing a hydrogenation catalyst for flexible polyurethane foam, which can maintain a high tensile strength, a high elongation at break and a low density of the polyurethane foam, has no emission of amine compounds, has little odor, and contains no heavy metal elements.
Disclosure of Invention
Aiming at the defects in the prior art, the hydrogenation catalyst for preparing the flexible polyurethane foam is added into the polyurethane foam composition, so that the obtained polyurethane foam not only maintains higher tensile strength and elongation at break and lower density, but also has no discharge of amine compounds, almost has no odor and contains no heavy metal elements, and the problems in the prior art are solved.
In order to solve the technical problems, the technical scheme of the invention is as follows:
a hydrogenation catalyst for flexible polyurethane foam is characterized by having a structure shown in a formula I:
in the formula I, a: b=3: 2 to 9:1, a and b are integers;
wherein the R is 1 、R 2 、R 3 R is R 4 Each independently represents a halogen, an alkyl group having 1 to 5 carbon atoms, and a cyclic structure having 3 to 12 atoms in the cyclic skeleton;
wherein one or more H on the cyclic structure with the number of atoms of 3-12 in the cyclic skeleton can be substituted by halogen;
wherein, represent the connection point of chemical bond.
Further, the R 1 、R 2 、R 3 R is R 4 Each independently represents fluorine, methyl, ethylPropyl, butyl, cyclohexyl, phenyl, fluorophenyl.
Further, the molecular weight of the hydrogenation catalyst for the flexible polyurethane foam is 10000-50000.
The polypyrrole and the polyurethane material are generally physically blended to improve the performance of polyurethane, and the hydrogenation catalyst for the flexible polyurethane foam obtained by hydrogenating the polypyrrole shows alkalinity, so that the generation of the polyurethane foam is accelerated. The hydrogenation catalyst used in the present application hardly discharges an amine compound in the polyurethane foam produced, and therefore, can prevent odor caused by volatilization of the amine compound.
In another aspect, the present invention also provides a method for preparing a hydrogenation catalyst for flexible polyurethane foam, comprising the steps of:
step 1, pyrrole monomer of formula I-aAnd pyrrole monomer of formula I-b->Adding acetonitrile and deionized water into the system, and uniformly stirring; adjusting the pH of the system to between 5 and 6.5 by dilute sulfuric acid;
step 2, fe (NO) 3 ) 3 Adding a catalyst into ionized water to obtain an oxidant solution; maintaining the system temperature at 23-35 ℃, dropwise adding an oxidant solution, and maintaining the dropwise adding time at 2-4 hours; after the dripping is completed, preserving heat and reacting for 4-8 hours; filtering to obtain a reactant, washing for many times by using distilled water, and drying to obtain an intermediate;
step 3, adding the intermediate obtained in the step 2 into absolute ethyl alcohol, then putting the absolute ethyl alcohol into a pressurizing reactor, and putting palladium carbon into the pressurizing reactor; introducing hydrogen into the system, pressurizing to 10-30kg of atmospheric pressure, and continuously carrying out hydrogenation reaction for 20-40 hours at 50-70 ℃; after the hydrogenation reaction is completed, removing palladium carbon by centrifugation; distilling off the absolute ethyl alcohol solvent to obtain the hydrogenation catalyst for the flexible polyurethane foam.
In another aspect, the present invention also provides a polyurethane foam composition comprising a hydrogenation catalyst for flexible polyurethane foam, characterized by comprising, in mass percent of 100%: 35 to 43 percent of polyether polyol, 26 to 31 percent of polymer polyol, 1 to 1.5 percent of cross-linking agent, 0.6 to 1 percent of hydrogenation catalyst, 0.4 to 0.9 percent of foam stabilizer, 1 to 1.6 percent of pore opening agent, 14 to 18 percent of toluene diisocyanate, 9 to 13 percent of diphenylmethane diisocyanate and the balance of water.
Further, the molecular weight of the polyether polyol is 5000-15000, the functionality is 2-4, and the unsaturation degree is less than or equal to 0.03mmol/g.
Further, the polymer polyol has a hydroxyl value of 19 to 23mgKOH/g.
Further, the crosslinking agent is selected from at least one of fatty alcohols or fatty alcohol amines having a functionality of 2 to 4.
Further, the fatty alcohol amine of 2 to 4 functionalities is selected from one of diethanolamine or triethanolamine.
Further, the preparation method of the polyurethane foam composition comprises the following steps:
(1) Adding 5-43% of polyether polyol, 26-31% of polymer polyol, 1-1.5% of cross-linking agent, 0.6-1% of hydrogenation catalyst, 0.4-0.9% of foam stabilizer, 1-1.6% of pore opening agent and the balance of water into a container A according to mass percentage, and stirring to prepare a component A;
(2) Adding 14-18% of toluene diisocyanate, 9-13% of diphenylmethane diisocyanate and the balance of water into a container B according to mass percent, and stirring and mixing to obtain a component B;
(3) And pouring the component A and the component B into a mould through a high-pressure or low-pressure foaming machine, setting the temperature of the mould at 45-65 ℃, opening the mould for 180-245 seconds, and taking out the mould to obtain the polyurethane foam.
In another aspect, the invention also provides a hydrogenation catalyst for flexible polyurethane foam and application of the polyurethane foam composition in a vehicle seat.
Compared with the prior art, the invention has the beneficial effects that:
1. in general, pyrrole is weak base or acidic, so that the catalytic effect is not obvious when the polyurethane foam is prepared, and the hydrogenation catalyst for the flexible polyurethane foam obtained by hydrogenating polypyrrole in the application shows alkalinity so as to accelerate the generation of the polyurethane foam;
2. when the hydrogenation catalyst of the formula I is used, the density, the tensile strength and the elongation at break of the obtained polyurethane foam are kept in proper ranges, wherein the density is slightly reduced, the tensile strength and the elongation at break are slightly improved, no amine compound is discharged, and almost no odor is generated;
3. when the hydrogenation catalyst of formula I is used herein, when the hydrogenation catalyst for flexible polyurethane foam is of formula I: when b is not in the proper range, the density, tensile strength and elongation at break of the obtained polyurethane foam are kept in the proper ranges, but the density of the polyurethane foam is slightly improved, the tensile strength and the elongation at break are greatly reduced, and the mechanical property is reduced;
4. the polyurethane foam obtained by using the hydrogenation catalyst for the flexible polyurethane foam containing the formula I not only keeps higher tensile strength, elongation at break and lower density, but also has no discharge of amine compounds, almost has no odor and contains no heavy metal elements.
Detailed Description
The invention will be described below in connection with specific embodiments. The following examples are illustrative of the present invention and are not intended to limit the present invention. Other combinations and various modifications within the spirit of the invention may be made without departing from the spirit or scope of the invention.
The reagents and materials used in the following examples and comparative examples are commercially available unless otherwise specified.
The sources of raw materials and product names used in examples and comparative examples in the detailed description are as follows:
i-a pyrrole monomer: 3, 4-difluoro-methylpyrrole, CAS no: 120047-68-9 from Chongqing FuTENG pharmaceutical chemical Co., ltd;
i-b pyrrole monomer: 3, 4-dimethyl-1H-pyrrole, cat: y43510, available from shanghai source leaf biotechnology limited;
polyether polyol: model: CHE-822p,3 functionality, 7500 molecular weight, available from Jiangsu changhua polyurethane technologies limited;
polymer polyol: model: CHP-H45, available from Jiangsu Changhua polyurethane technologies Co., ltd;
toluene diisocyanate: model: lupranate T-80, available from basf;
diphenylmethane diisocyanate: model: lupranate MIPS, available from basf;
foam stabilizer: silicone oil, cat No.: 49, available from Guangzhou Co-win chemical industry Co., ltd;
crosslinking agent: diethanolamine: CAS number: 111-42-2, available from merck;
catalyst 5: triethylenediamine, CAS number: 111-40-0, available from merck;
a pore-forming agent; model: CHK-350D, available from Changhua chemical technologies Co., ltd.
Preparation of hydrogenation catalyst 1:
step 1, adding 9360g of 3, 4-difluoro-methylpyrrole and 1900g of 3, 4-dimethyl-1H-pyrrole into a system, adding 10000ml of acetonitrile and 90000ml of deionized water, and uniformly stirring; the pH of the system was adjusted to 6 by dilute sulfuric acid at a concentration of 0.1 mol/L;
step 2, 11.3g of Fe (NO 3 ) 3 Adding a catalyst into 5000ml of ionized water to obtain an oxidant solution; maintaining the system temperature at 35 ℃, dropwise adding the oxidant solution, and maintaining the dropwise adding time at 4 hours; after the dripping is completed, preserving heat and reacting for 5 hours; filtering to obtain a reactant, flushing the reactant by distilled water for 6 times, and drying the reactant at 80 ℃ for 5 hours to obtain an intermediate 1;
step 3, adding 100g of the intermediate 1 obtained in the step 2 into 5000ml of absolute ethyl alcohol, then adding the absolute ethyl alcohol into a pressurized reactor, and adding 0.01g of palladium carbon into the pressurized reactor; introducing hydrogen into the system, pressurizing to 30kg of atmospheric pressure, and continuously carrying out hydrogenation reaction for 40 hours at 70 ℃; hydrogenationAfter the reaction is completed, the palladium carbon is removed by centrifugation at 2000rpm for 30 min; after the absolute ethanol was distilled off, a hydrogenation catalyst 1 for flexible polyurethane foam of the formula I-A was obtained.Preparation of hydrogenation catalyst 2:
step 1, 10530g of 3, 4-difluoro-methylpyrrole and 950g of 3, 4-dimethyl-1H-pyrrole are added into a system, 11000ml of acetonitrile and 92000ml of deionized water are added, and stirring is uniform; the pH of the system was adjusted to 6 by dilute sulfuric acid at a concentration of 0.1 mol/L.
Step 2, 11.5g of Fe (NO 3 ) 3 Adding the catalyst into 5500ml of ionized water to obtain an oxidant solution; maintaining the system temperature at 35 ℃, dropwise adding an oxidant solution, and maintaining the dropwise adding time at 4 hours; after the dripping is completed, preserving heat and reacting for 8 hours; filtering to obtain a reactant, flushing the reactant with distilled water for 6 times, and drying the reactant at 80 ℃ for 5 hours to obtain an intermediate 2;
step 3, 110g of the intermediate 2 obtained in the step 2 is added into 5500ml of absolute ethyl alcohol, then the mixture is put into a pressurized reactor, and 0.012g of palladium-carbon is put into the pressurized reactor; introducing hydrogen into the system, pressurizing to 30kg of atmospheric pressure, and continuously carrying out hydrogenation reaction for 40 hours at 70 ℃; after the hydrogenation reaction is completed, the palladium carbon is removed by centrifugation at 2000rpm for 30 min; after distilling off the solvent ethanol, a hydrogenation catalyst 2 for flexible polyurethane foam of the formula I-B is obtained.Preparation of hydrogenation catalyst 3:
step 1, 7020g of 3, 4-difluoro-methylpyrrole and 3800g of 3, 4-dimethyl-1H-pyrrole are added into a system, 9000ml of acetonitrile and 8500ml of deionized water are added, and stirring is uniform; the pH of the system was adjusted to 6 by dilute sulfuric acid at a concentration of 0.1 mol/L;
step 2, 1.15g of Fe (NO 3 ) 3 Adding a catalyst into 4500ml of ionized water to obtain an oxidant solution; maintaining the system temperature at 35 ℃, dropwise adding an oxidant solution, and maintaining the dropwise adding time at 4 hours; after the dripping is finishedAfter the reaction, the reaction is carried out for 8 hours; filtering to obtain a reactant, flushing the reactant with distilled water for 6 times, and drying the reactant at 80 ℃ for 5 hours to obtain an intermediate 3;
step 3, adding 8g of the intermediate 3 obtained in the step 2 into 450ml of absolute ethyl alcohol, then adding the absolute ethyl alcohol into a pressurized reactor, and adding 0.008g of palladium carbon into the pressurized reactor; introducing hydrogen into the system, pressurizing to 30kg of atmospheric pressure, and continuously carrying out hydrogenation reaction for 40 hours at 70 ℃; after the hydrogenation reaction is completed, the palladium carbon is removed by centrifugation at 2000rpm for 30 min; the solvent absolute ethanol is distilled off to obtain a hydrogenation catalyst 3 for flexible polyurethane foam of the formula I-C.
Preparation of hydrogenation catalyst 4:
step 1, 11700g of 3, 4-difluoro-methylpyrrole and 950g of 3, 4-dimethyl-1H-pyrrole are added into a system, 12500ml of acetonitrile and 11500ml of deionized water are added, and the mixture is stirred uniformly; the pH of the system was adjusted to 6 by dilute sulfuric acid at a concentration of 0.1 mol/L;
step 2, 12.7g of Fe (NO 3 ) 3 Adding the catalyst into 6200ml of ionized water to obtain an oxidant solution; maintaining the system temperature at 35 ℃, dropwise adding an oxidant solution, and maintaining the dropwise adding time at 4 hours; after the dripping is completed, preserving heat and reacting for 8 hours; filtering to obtain a reactant, washing for a plurality of times by using distilled water, and drying to obtain an intermediate 4;
step 3, 130g of the intermediate 4 obtained in the step 2 is added into 6200ml of absolute ethyl alcohol, the materials are put into a pressurized reactor, and 0.014g of palladium-carbon is put into the pressurized reactor; introducing hydrogen into the system, pressurizing to 30kg of atmospheric pressure, and continuously carrying out hydrogenation reaction for 40 hours at 70 ℃; after the hydrogenation reaction is completed, the palladium carbon is removed by centrifugation at 2000rpm for 30 min; the solvent, absolute ethanol, was distilled off to give a hydrogenation catalyst 4 for flexible polyurethane foam of the formula I-D.
The preparation methods of examples 1-3 and comparative examples 1-2 include the following steps:
(1) Adding polyether polyol, polymer polyol, a cross-linking agent, a hydrogenation catalyst, a foam stabilizer, a pore opening agent and water into a container A according to mass percent, and stirring to prepare a component A;
(2) Adding toluene diisocyanate and diphenylmethane diisocyanate into a container B according to mass percent, and stirring and mixing to obtain a component B;
(3) And pouring the component A and the component B into a mould through a high-pressure or low-pressure foaming machine, setting the temperature of the mould at 62 ℃, opening the mould for 240 seconds, and taking out the mould to obtain the polyurethane foam.
The components and the content of each component used in examples 1-3 and comparative examples 1-2 are shown in Table 1:
TABLE 1
The test methods for examples 1-3 and comparative examples 1-2 were as follows:
density: ISO 845-2006;
tensile strength: ISO 1798-2008, when the tensile strength of the automobile main machine factory to the seat foam is more than or equal to 100kPa, the automobile main machine factory meets the requirements;
elongation at break: ISO 1798-2008, when the elongation at break of the seat foam of the automobile main engine factory is more than 100%, meets the requirements;
odor of foam by cutting foam of size 5×5×3cm from the center of the molded foam, placing it in a 900mL mayonnaise bottle and covering the bottle with a cap, heating the bottle at 80deg.C for 1 hr, returning to room temperature, letting five monitors smell the odor of the foam, and measuring the intensity of the odor;
o: almost no malodor, delta: a small amount of odor, x: has bad smell.
The product performance test data for examples 1-3 and comparative examples 1-2 are shown in Table 2:
TABLE 2
As is evident from the comparison of example 2 and comparative example 2, the density, tensile strength, elongation at break of the polyurethane foam obtained with the hydrogenation catalyst of formula I were kept within the appropriate ranges, with a slight decrease in density, a slight increase in tensile strength and elongation at break, and little odor.
As can be seen from the comparison of example 2 and comparative example 1, when a: when the value of b is not within the proper range, the density, tensile strength and elongation at break of the polyurethane foam obtained are kept within the proper ranges, but the density of the polyurethane foam is slightly increased, the tensile strength and elongation at break are much reduced, and the mechanical properties are lowered.
As is clear from examples 1 to 3 and comparative examples 1 to 2, the polyurethane foam of the present invention, which is produced using the hydrogenation catalyst for flexible polyurethane foam, maintains a low density, a high tensile strength and elongation at break, and has no discharge of amine compounds, little odor, and no heavy metal elements.
The foregoing description of the preferred embodiments of the invention is not intended to be limiting, but rather is intended to cover all modifications, equivalents, and alternatives falling within the spirit and principles of the invention.
Claims (10)
1. A hydrogenation catalyst for flexible polyurethane foam is characterized by having a structure shown in a formula I:
wherein a: b=3: 2 to 9:1, a and b are integers;
R 1 、R 2 、R 3 r is R 4 Each independently represents a halogen, an alkyl group having 1 to 5 carbon atoms, and a cyclic structure having 3 to 12 atoms in the cyclic skeleton;
one or more H on the cyclic structure with the number of atoms of 3-12 in the cyclic skeleton can be substituted by halogen;
* Representing the point of attachment of the repeating units.
2. The hydrogenation catalyst for flexible polyurethane foam according to claim 1, wherein R is 1 、R 2 、R 3 R is R 4 Each independently represents fluorine, methyl, ethyl, propyl, butyl, cyclohexyl, phenyl, fluorophenyl.
3. The hydrogenation catalyst for flexible polyurethane foam according to claim 2, wherein the molecular weight of the hydrogenation catalyst for flexible polyurethane foam is 10000 to 50000.
4. A process for the preparation of a hydrogenation catalyst for flexible polyurethane foam according to any one of claims 1 to 3, comprising the steps of:
step 1, pyrrole monomer of formula I-aAnd pyrrole monomer of formula I-b->Adding acetonitrile and deionized water into the system, and uniformly stirring; adjusting the pH of the system to between 5 and 6.5 by dilute sulfuric acid;
step 2, fe (NO) 3 ) 3 Adding a catalyst into ionized water to obtain an oxidant solution; maintaining the system temperature at 23-35 ℃, dropwise adding an oxidant solution, and maintaining the dropwise adding time at 2-4 hours; after the dripping is completed, preserving heat and reacting for 4-8 hours; filtering to obtain a reactant, washing for many times by using distilled water, and drying to obtain an intermediate;
step 3, adding the intermediate obtained in the step 2 into absolute ethyl alcohol, then putting the absolute ethyl alcohol into a pressurizing reactor, and putting palladium carbon into the pressurizing reactor; introducing hydrogen into the system, pressurizing to 10-30kg of atmospheric pressure, and continuously carrying out hydrogenation reaction for 20-40 hours at 50-70 ℃; after the hydrogenation reaction is completed, removing palladium carbon by centrifugation; and distilling off the absolute ethyl alcohol to obtain the hydrogenation catalyst for the flexible polyurethane foam.
5. A polyurethane foam composition comprising the hydrogenation catalyst for flexible polyurethane foam according to any one of claims 1 to 3, characterized by comprising, based on the mass of the polyurethane foam composition as a total of 100%: 35 to 43 percent of polyether polyol, 26 to 31 percent of polymer polyol, 1 to 1.5 percent of cross-linking agent, 0.6 to 1 percent of hydrogenation catalyst, 0.4 to 0.9 percent of foam stabilizer, 1 to 1.6 percent of pore opening agent, 14 to 18 percent of toluene diisocyanate, 9 to 13 percent of diphenylmethane diisocyanate and the balance of water.
6. The polyurethane foam composition according to claim 5, wherein the polyether polyol has a molecular weight of 5000 to 15000, a functionality of 2 to 4, and an unsaturation degree of 0.03mmol/g or less.
7. The polyurethane foam composition according to claim 6, wherein the polymer polyol has a hydroxyl value of 19 to 23mgKOH/g.
8. The polyurethane foam composition according to claim 7, wherein the crosslinking agent is selected from at least one of fatty alcohols or fatty alcohol amines having a functionality of 2 to 4.
9. The polyurethane foam composition according to claim 8, wherein the fatty alcohol amine of 2 to 4 functionality is selected from one of diethanolamine or triethanolamine.
10. Use of the hydrogenation catalyst for flexible polyurethane foam according to any one of claims 1 to 3, the polyurethane foam composition according to any one of claims 5 to 9 in a vehicle seat.
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