CN115232281A - Polyurethane rigid foam based on bio-based polyol and preparation method thereof - Google Patents
Polyurethane rigid foam based on bio-based polyol and preparation method thereof Download PDFInfo
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- CN115232281A CN115232281A CN202210863332.7A CN202210863332A CN115232281A CN 115232281 A CN115232281 A CN 115232281A CN 202210863332 A CN202210863332 A CN 202210863332A CN 115232281 A CN115232281 A CN 115232281A
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- foam
- polyurethane
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- 229920002635 polyurethane Polymers 0.000 title claims abstract description 68
- 239000004814 polyurethane Substances 0.000 title claims abstract description 68
- 239000006260 foam Substances 0.000 title claims abstract description 61
- 229920005862 polyol Polymers 0.000 title claims abstract description 61
- 150000003077 polyols Chemical class 0.000 title claims abstract description 61
- 238000002360 preparation method Methods 0.000 title abstract description 9
- 238000004917 polyol method Methods 0.000 title description 2
- 239000000463 material Substances 0.000 claims abstract description 58
- 239000012948 isocyanate Substances 0.000 claims abstract description 31
- 150000002513 isocyanates Chemical class 0.000 claims abstract description 31
- 238000002156 mixing Methods 0.000 claims abstract description 21
- 239000004088 foaming agent Substances 0.000 claims abstract description 20
- 239000004359 castor oil Substances 0.000 claims abstract description 17
- 235000019438 castor oil Nutrition 0.000 claims abstract description 17
- ZEMPKEQAKRGZGQ-XOQCFJPHSA-N glycerol triricinoleate Natural products CCCCCC[C@@H](O)CC=CCCCCCCCC(=O)OC[C@@H](COC(=O)CCCCCCCC=CC[C@@H](O)CCCCCC)OC(=O)CCCCCCCC=CC[C@H](O)CCCCCC ZEMPKEQAKRGZGQ-XOQCFJPHSA-N 0.000 claims abstract description 17
- 239000003377 acid catalyst Substances 0.000 claims abstract description 13
- 239000012970 tertiary amine catalyst Substances 0.000 claims abstract description 12
- 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 claims abstract description 6
- 229930006000 Sucrose Natural products 0.000 claims abstract description 6
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 claims abstract description 6
- TVXBFESIOXBWNM-UHFFFAOYSA-N Xylitol Natural products OCCC(O)C(O)C(O)CCO TVXBFESIOXBWNM-UHFFFAOYSA-N 0.000 claims abstract description 6
- HEBKCHPVOIAQTA-UHFFFAOYSA-N meso ribitol Natural products OCC(O)C(O)C(O)CO HEBKCHPVOIAQTA-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000005720 sucrose Substances 0.000 claims abstract description 6
- HEBKCHPVOIAQTA-SCDXWVJYSA-N xylitol Chemical compound OC[C@H](O)[C@@H](O)[C@H](O)CO HEBKCHPVOIAQTA-SCDXWVJYSA-N 0.000 claims abstract description 6
- 235000010447 xylitol Nutrition 0.000 claims abstract description 6
- 239000000811 xylitol Substances 0.000 claims abstract description 6
- 229960002675 xylitol Drugs 0.000 claims abstract description 6
- 230000000379 polymerizing effect Effects 0.000 claims abstract description 3
- 238000003756 stirring Methods 0.000 claims description 35
- 229920005830 Polyurethane Foam Polymers 0.000 claims description 29
- 239000011496 polyurethane foam Substances 0.000 claims description 29
- 238000006243 chemical reaction Methods 0.000 claims description 21
- 239000002994 raw material Substances 0.000 claims description 14
- 238000000034 method Methods 0.000 claims description 12
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 claims description 10
- 238000010438 heat treatment Methods 0.000 claims description 9
- 238000006116 polymerization reaction Methods 0.000 claims description 8
- 230000035484 reaction time Effects 0.000 claims description 6
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 claims description 5
- 238000000137 annealing Methods 0.000 claims description 5
- 238000001816 cooling Methods 0.000 claims description 5
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 4
- IMNIMPAHZVJRPE-UHFFFAOYSA-N triethylenediamine Chemical compound C1CN2CCN1CC2 IMNIMPAHZVJRPE-UHFFFAOYSA-N 0.000 claims description 4
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims description 2
- 238000009413 insulation Methods 0.000 abstract description 4
- 239000000203 mixture Substances 0.000 description 6
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 4
- 239000004721 Polyphenylene oxide Substances 0.000 description 4
- 229920000570 polyether Polymers 0.000 description 4
- 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 description 3
- 235000014113 dietary fatty acids Nutrition 0.000 description 3
- 229930195729 fatty acid Natural products 0.000 description 3
- 239000000194 fatty acid Substances 0.000 description 3
- 150000004665 fatty acids Chemical class 0.000 description 3
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- 238000004321 preservation Methods 0.000 description 3
- 239000002699 waste material Substances 0.000 description 3
- 239000004604 Blowing Agent Substances 0.000 description 2
- RGSFGYAAUTVSQA-UHFFFAOYSA-N Cyclopentane Chemical compound C1CCCC1 RGSFGYAAUTVSQA-UHFFFAOYSA-N 0.000 description 2
- 239000005057 Hexamethylene diisocyanate Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000004231 fluid catalytic cracking Methods 0.000 description 2
- 238000005187 foaming Methods 0.000 description 2
- 238000009472 formulation Methods 0.000 description 2
- 235000011187 glycerol Nutrition 0.000 description 2
- 239000004519 grease Substances 0.000 description 2
- 239000012774 insulation material Substances 0.000 description 2
- AYLRODJJLADBOB-QMMMGPOBSA-N methyl (2s)-2,6-diisocyanatohexanoate Chemical compound COC(=O)[C@@H](N=C=O)CCCCN=C=O AYLRODJJLADBOB-QMMMGPOBSA-N 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 description 2
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 description 1
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 description 1
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 description 1
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 1
- OYHQOLUKZRVURQ-HZJYTTRNSA-N Linoleic acid Chemical compound CCCCC\C=C/C\C=C/CCCCCCCC(O)=O OYHQOLUKZRVURQ-HZJYTTRNSA-N 0.000 description 1
- 239000005642 Oleic acid Substances 0.000 description 1
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 description 1
- 241001464837 Viridiplantae Species 0.000 description 1
- KXBFLNPZHXDQLV-UHFFFAOYSA-N [cyclohexyl(diisocyanato)methyl]cyclohexane Chemical compound C1CCCCC1C(N=C=O)(N=C=O)C1CCCCC1 KXBFLNPZHXDQLV-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- -1 etc. Chemical compound 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000006261 foam material Substances 0.000 description 1
- DMEGYFMYUHOHGS-UHFFFAOYSA-N heptamethylene Natural products C1CCCCCC1 DMEGYFMYUHOHGS-UHFFFAOYSA-N 0.000 description 1
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 1
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 description 1
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 description 1
- 235000020778 linoleic acid Nutrition 0.000 description 1
- OYHQOLUKZRVURQ-IXWMQOLASA-N linoleic acid Natural products CCCCC\C=C/C\C=C\CCCCCCCC(O)=O OYHQOLUKZRVURQ-IXWMQOLASA-N 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003225 polyurethane elastomer Polymers 0.000 description 1
- WBHHMMIMDMUBKC-XLNAKTSKSA-N ricinelaidic acid Chemical compound CCCCCC[C@@H](O)C\C=C\CCCCCCCC(O)=O WBHHMMIMDMUBKC-XLNAKTSKSA-N 0.000 description 1
- 229960003656 ricinoleic acid Drugs 0.000 description 1
- FEUQNCSVHBHROZ-UHFFFAOYSA-N ricinoleic acid Natural products CCCCCCC(O[Si](C)(C)C)CC=CCCCCCCCC(=O)OC FEUQNCSVHBHROZ-UHFFFAOYSA-N 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000005809 transesterification reaction Methods 0.000 description 1
- UFTFJSFQGQCHQW-UHFFFAOYSA-N triformin Chemical compound O=COCC(OC=O)COC=O UFTFJSFQGQCHQW-UHFFFAOYSA-N 0.000 description 1
- 235000015112 vegetable and seed oil Nutrition 0.000 description 1
- 239000008158 vegetable oil Substances 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
- 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
- C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
- C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
- C08G18/6666—Compounds of group C08G18/48 or C08G18/52
- C08G18/667—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38
- C08G18/6674—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3203
- C08G18/6677—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3203 having at least three hydroxy 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
- C08G18/30—Low-molecular-weight compounds
- C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
- C08G18/3203—Polyhydroxy compounds
- C08G18/3206—Polyhydroxy compounds aliphatic
-
- 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
- C08G18/30—Low-molecular-weight compounds
- C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
- C08G18/3203—Polyhydroxy compounds
- C08G18/3218—Polyhydroxy compounds containing cyclic groups having at least one oxygen 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
- 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
- C08G18/4829—Polyethers containing at least three hydroxy groups
-
- 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
- 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
- C08J9/141—Hydrocarbons
-
- 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
- C08G2110/0041—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
- 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
- C08J2203/14—Saturated hydrocarbons, e.g. butane; Unspecified hydrocarbons
-
- 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)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Polyurethanes Or Polyureas (AREA)
Abstract
The invention discloses a polyurethane rigid foam based on bio-based polyol, which comprises the following components in parts by weight: 100 parts of polyurethane hard foam white material; 15 parts of a foaming agent; 135-144 parts of isocyanate; the polyurethane hard foam white material comprises the following components in parts by weight: 10-20 parts of bio-based polyol; 15-45 parts of trimethylolpropane; 15-45 parts of xylitol; 10-20 parts of sucrose; the bio-based polyol is obtained by polymerizing castor oil under the action of an acid catalyst and a tertiary amine catalyst. The invention also discloses a preparation method of the polyurethane rigid foam, which comprises the following steps: uniformly mixing bio-based polyol, trimethylolpropane, xylitol and sucrose in proportion; mixing with foaming agent in proportion; and quickly injecting the isocyanate and the isocyanate into a mold at the same time, and standing to obtain the product. The polyurethane rigid foam provided by the invention adopts bio-based polyol, so that non-renewable resources are saved, and the prepared polyurethane rigid foam has good toughness and heat insulation performance.
Description
Technical Field
The invention belongs to the field of organic materials, and particularly relates to a polyurethane rigid foam based on bio-based polyol and a preparation method thereof.
Background
The rigid polyurethane foam plastic, polyurethane rigid foam for short, is used in the polyurethane product in an amount which is second to that of the polyurethane flexible foam. The polyurethane hard foam is mostly of a closed-cell structure, has the excellent characteristics of good heat insulation effect, light weight, high specific strength, convenient construction and the like, has the characteristics of sound insulation, shock resistance, electric insulation, heat resistance, cold resistance, solvent resistance and the like, and is widely used for heat insulation materials of refrigerator bodies of refrigerators and freezer cases, refrigerator houses, refrigerated trucks and the like, and heat insulation materials of buildings, storage tanks and pipelines. In general, the lower density rigid polyurethane foam is mainly used as a heat insulating (heat preserving) material.
Polyols and isocyanates are the two main components of polyurethane foaming systems. At present, the annual demand of polyol for polyurethane rigid foam in China is about 55 ten thousand tons, and the polyol rapidly increases in a two-digit ratio every year. The traditional polyol for hard foam polyurethane is obtained by taking non-renewable petroleum resources as main raw materials through an FCC (fluid catalytic cracking) preparation method, so that how to reduce the use of the petroleum resources and search for alternative energy sources to synthesize the polyol is one of the hot subjects in recent years.
Patent CN107522832A discloses a bio-based polyurethane polyol, which is prepared by mixing raw materials of crude glycerin, waste grease, fatty acid and polyol and adding an acid catalyst, and also discloses a preparation method of the bio-based polyurethane polyol, and a polyurethane rigid foam prepared by using the bio-based polyurethane polyol and a preparation method thereof. The invention takes crude glycerine and waste grease as main raw materials, realizes the utilization of waste resources, but has unsatisfactory heat preservation performance and physical strength.
How to use green raw materials to synthesize the polyol for the rigid polyurethane foam and ensure that the final rigid polyurethane foam product has excellent performance is a technical problem to be solved at present.
Disclosure of Invention
In order to solve the problems in the background art, the invention provides a polyurethane rigid foam material synthesized by using green plant raw materials, and provides a preparation method of the polyurethane rigid foam based on the bio-based polyol.
The invention is realized by the following technical means:
in one aspect, the invention provides a polyurethane rigid foam based on bio-based polyol, which comprises the following components by weight:
polyurethane hard foam white material: 100 parts of (A);
foaming agent: 15 parts of a mixture;
isocyanate: 135-144 parts;
the polyurethane hard foam white material comprises the following components in parts by weight:
bio-based polyol: 10-20 parts;
trimethylolpropane: 15-45 parts of;
xylitol: 15-45 parts of;
sucrose: 10-20 parts;
the bio-based polyol is obtained by polymerizing castor oil under the action of an acid catalyst and a tertiary amine catalyst.
The castor oil is prepared by squeezing and extracting plant castor oil, is natural fatty acid triglyceride, is 90 percent of ricinoleic acid (9-alkenyl-12-transoctonic acid) which is contained in the castor oil fatty acid and 10 percent of oleic acid and linoleic acid without hydroxyl, is the only vegetable oil containing hydroxyl in nature, and belongs to renewable resources.
The bio-based polyol prepared from castor oil is further reacted with isocyanate, which has high activity due to the unsaturated bond contained in the isocyanate structure, and the bio-based polyol and the isocyanate react to generate the polyurethane elastomer.
The isocyanate is also called black material, and comprises Toluene Diisocyanate (TDI), isophorone diisocyanate (IPDI), diphenylmethane diisocyanate (MDI), dicyclohexylmethane diisocyanate (HMDI), hexamethylene Diisocyanate (HDI), lysine Diisocyanate (LDI), etc., and MDI is preferably used as a raw material for producing rigid polyurethane foam for a refrigerator in the examples of the present application.
Preferably, the weight of the acid catalyst is 0.06% -0.1% of the total mass of the raw materials; the weight of the tertiary amine catalyst is 0.05-0.2% of the total mass of the raw materials.
Preferably, the acid catalyst is any one of sulfuric acid or p-toluenesulfonic acid.
Preferably, the tertiary amine catalyst is any one of diethylenetriamine, triethanolamine, or triethylenediamine.
The castor oil is subjected to transesterification and esterification under the combined action of an acid catalyst and a tertiary amine catalyst to form corresponding polyol, and the castor oil-based polyol has high molecular weight and good compatibility with foaming agents such as cyclopentane and the like, so that the formed polyurethane foam has good toughness.
In another aspect, the present invention further provides a method for preparing a rigid polyurethane foam based on bio-based polyol, which is used for preparing the rigid polyurethane foam based on bio-based polyol, and comprises the following steps:
uniformly mixing bio-based polyol, trimethylolpropane, xylitol and sucrose in proportion to obtain a polyurethane hard foam white material;
mixing the polyurethane hard foam white material and a foaming agent in proportion to obtain a mixed white material;
and simultaneously and quickly injecting the mixed white material and isocyanate into a mold, and standing for a period of time to obtain the polyurethane rigid foam.
Further, the bio-based polyol is prepared by the steps of:
uniformly mixing castor oil and an acid catalyst in proportion, stirring and heating for reaction;
adding a tertiary amine catalyst, stirring and heating for reaction;
increasing the reaction temperature, reducing the stirring speed, and carrying out polymerization reaction;
annealing and cooling to obtain the bio-based polyol.
The hydroxyl value of the bio-based polyether polyol is about 160mgKOH/g and the average functionality is about 3.2.
Preferably, the mixing temperature of the polyurethane hard foam white material, the foaming agent and the isocyanate is 16-22 ℃; the standing time is 120-180s. Through standing, the rigid polyurethane foam white material, the foaming agent and the isocyanate are fully reacted and then hardened, and the formed rigid polyurethane foam has good strength.
Preferably, the castor oil and the acid catalyst are uniformly mixed according to the proportion, the reaction temperature for stirring and heating for reaction is 100-200 ℃, the stirring speed is 50-80rpm, and the reaction time is 4-8h.
Preferably, the tertiary amine catalyst is added, the reaction temperature for stirring and heating to carry out the reaction is 100-200 ℃, the stirring speed is 50-80rpm, and the reaction time is 2-4h.
Preferably, the reaction temperature of the polymerization reaction is 200-300 ℃, the stirring speed is 10-50rpm, and the reaction time is 2-5h.
Through stirring and heating, the castor oil raw material can fully react to generate polymerization, and polyether polyol is generated to perform the next reaction with isocyanate.
The polyurethane rigid foam based on the bio-based polyol disclosed by the invention can be used for foaming of refrigerators and freezers, and is particularly applied to the aspects of heat preservation treatment of refrigerators, pipelines, plates and the like. Due to the adoption of the bio-based polyol, the consumption of the common polyol synthesized by petrochemical raw materials can be reduced, non-renewable resources are saved, and the method is more environment-friendly. The preparation method of the polyurethane rigid foam based on the bio-based polyol disclosed by the invention is simple and convenient in process and easy to operate, and the prepared polyurethane rigid foam has good toughness and heat-insulating property and is suitable for large-scale industrial popularization.
Detailed Description
The present invention will be described in further detail with reference to the following examples, which are provided for illustration only and are not intended to limit the scope of the present invention.
Example 1
The method comprises the following steps:
1) Mixing castor oil and p-toluenesulfonic acid according to a weight ratio of 100:0.06, uniformly mixing, stirring at 150 ℃ for reaction, wherein the stirring speed is 75rpm, and the reaction lasts for 6 hours;
2) According to the weight ratio of 100:0.05 adding diethylenetriamine into the mixture material, stirring and reacting at the temperature of 200 ℃, wherein the stirring speed is 75rpm and lasts for 4 hours;
3) Raising the temperature to 300 ℃, adjusting the stirring speed to 30rpm, and continuing stirring for 5 hours to perform polymerization reaction;
4) Annealing and cooling, and obtaining the bio-based polyol after the temperature is reduced to be below 100 ℃.
Step two:
the formula of the polyurethane hard foam white material prepared from the bio-based polyol comprises the following components in parts by weight:
after being uniformly mixed, the polyurethane hard foam white material is mixed with a foaming agent and isocyanate according to the following weight ratio:
polyurethane hard foam white material 100
Foaming agent 15
Isocyanate 138
The steps for preparing the polyurethane rigid foam are as follows:
1) Uniformly mixing the polyurethane hard foam white material and the foaming agent according to the proportion under the condition that the material temperature is 20 ℃ to obtain a mixed white material;
2) Preparing isocyanate according to the proportion at the material temperature of 20 ℃;
3) Simultaneously and quickly injecting the mixed white material and isocyanate into a mold;
4) After standing for 300s, rigid polyurethane foam was formed.
Example 2
The method comprises the following steps:
1) Mixing castor oil and p-toluenesulfonic acid according to a weight ratio of 100:0.1, mixing evenly, stirring and reacting at 100 ℃, wherein the stirring speed is 80rpm, and keeping for 4 hours;
2) According to the weight ratio of 100:0.2 adding diethylenetriamine into the mixture material, stirring and reacting at the temperature of 100 ℃, wherein the stirring speed is 75rpm and lasts for 2 hours;
3) Raising the temperature to 300 ℃, adjusting the stirring speed to 45rpm, and continuing stirring for reaction for 3 hours to perform polymerization reaction;
4) Annealing and cooling, and obtaining the bio-based polyol after the temperature is reduced to be below 100 ℃.
Step two:
the formula of the polyurethane hard foam white material prepared from the bio-based polyol comprises the following components in percentage by weight:
after being uniformly mixed, the polyurethane hard foam white material is mixed with a foaming agent and isocyanate according to the following weight ratio:
polyurethane hard foam white material 100
Blowing agent 15
Isocyanate 144
The steps for preparing the polyurethane rigid foam are as follows:
1) Uniformly mixing the polyurethane hard foam white material and the foaming agent according to the proportion at the material temperature of 20 ℃ to obtain a mixed white material;
2) Preparing isocyanate according to the proportion at the material temperature of 20 ℃;
3) Simultaneously and quickly injecting the mixed white material and isocyanate into a mold;
4) After standing for 270s, rigid polyurethane foam is formed.
Example 3
The method comprises the following steps:
1) Mixing castor oil and p-toluenesulfonic acid according to a weight ratio of 100:0.1, uniformly mixing, stirring and reacting at 150 ℃, wherein the stirring speed is 60rpm, and the reaction lasts for 8 hours;
2) According to the weight ratio of 100:0.2 adding diethylenetriamine into the mixture material, stirring and reacting at the temperature of 150 ℃, wherein the stirring speed is 60rpm and lasts for 4 hours;
3) Raising the temperature to 250 ℃, adjusting the stirring speed to 50rpm, and continuously stirring for reaction for 4 hours to carry out polymerization reaction;
4) Annealing and cooling, and obtaining the bio-based polyol after the temperature is reduced to be below 100 ℃.
Step two:
the formula of the polyurethane hard foam white material prepared from the bio-based polyol comprises the following components in parts by weight:
after being uniformly mixed, the polyurethane hard foam white material is mixed with a foaming agent and isocyanate according to the following weight ratio:
polyurethane hard foam white material 100
Foaming agent 15
Isocyanate 138
The steps for preparing the polyurethane rigid foam are as follows:
1) Uniformly mixing the polyurethane hard foam white material and the foaming agent according to the proportion at the material temperature of 16 ℃ to obtain a mixed white material;
2) Preparing isocyanate according to the proportion at the material temperature of 16 ℃;
3) Simultaneously and quickly injecting the mixed white material and isocyanate into a mold;
4) After standing for 420s, rigid polyurethane foam was formed.
Comparative example
The polyurethane rigid foam is prepared from the existing polyether polyol (the initial raw material is ethylenediamine) on the market, and the polyurethane white material is prepared from the common polyether according to the following formula in percentage by mass:
the polyurethane hard foam white material is uniformly mixed with a foaming agent and a black material (isocyanate) according to a certain proportion, and then the polyurethane foam is obtained, wherein the mass ratio of the polyurethane hard foam white material to the black material is as follows:
polyurethane hard foam white material 100
Blowing agent 15
Isocyanate 138
The steps for preparing the polyurethane foam are as follows:
1) Uniformly mixing the polyurethane hard foam white material and the foaming agent according to the proportion at the material temperature of 20 ℃ to obtain a mixed white material;
2) Preparing isocyanate according to the proportion at the material temperature of 20 ℃;
3) Simultaneously and quickly injecting the mixed white material and isocyanate into a mold;
4) After standing for 300s, rigid polyurethane foam is formed.
The polyurethane rigid foams prepared in examples 1 to 3 and comparative example were subjected to a performance test and compared with polyurethane rigid foam parameter indexes in the industry, and the obtained test and comparison results are shown in table 1.
TABLE 1 polyurethane rigid foam Performance test results
As can be seen from table 1, under the same conditions, the formulation of the rigid polyurethane foam based on bio-based polyol has smaller difference in parameters compared with the formulation of the conventional rigid polyurethane foam. The filling coefficient, the average core density, the thermal conductivity, the compressive strength and other properties of the polyurethane rigid foam meet the industrial standard of the polyurethane rigid foam for manufacturing the refrigerator plate, and the polyurethane rigid foam based on the bio-based polyol has excellent performances in the aspects of heat preservation performance, physical strength, compressive strength and the like, so the polyurethane rigid foam can be used as an environment-friendly raw material to replace the polyurethane rigid foam based on the traditional petrochemical material synthetic polyol. Therefore, the formula of the bio-based polyurethane hard foam provided by the application has practical application value and is beneficial to saving non-renewable resources.
The technical means disclosed in the scheme of the invention are not limited to the technical means disclosed in the above embodiments, but also include the technical means formed by any combination of the above technical features. It should be noted that those skilled in the art can make various improvements and modifications without departing from the principle of the present invention, and such improvements and modifications are also considered to be within the scope of the present invention.
Claims (10)
1. A polyurethane rigid foam based on bio-based polyol comprises the following components by weight:
polyurethane hard foam white material: 100 parts of (A);
foaming agent: 15 parts of (1);
isocyanate: 135-144 parts;
the polyurethane hard foam white material comprises the following components in parts by weight:
bio-based polyol: 10-20 parts;
trimethylolpropane: 15-45 parts of;
xylitol: 15-45 parts;
sucrose: 10-20 parts;
the bio-based polyol is characterized by being obtained by polymerizing castor oil under the action of an acid catalyst and a tertiary amine catalyst.
2. The rigid polyurethane foam based on bio-based polyol as claimed in claim 1, wherein the weight of said acid catalyst is 0.06% -0.1% of the total mass of the raw materials; the weight of the tertiary amine catalyst is 0.05-0.2% of the total mass of the raw materials.
3. The rigid polyurethane foam according to claim 1, wherein the acid catalyst is any one of sulfuric acid and p-toluenesulfonic acid.
4. The rigid polyurethane foam according to claim 1, wherein the tertiary amine catalyst is any one of diethylenetriamine, triethanolamine or triethylenediamine.
5. A method for preparing rigid polyurethane foam based on bio-based polyol, which is used for preparing the rigid polyurethane foam based on bio-based polyol, described in any one of claims 1-4, and is characterized by comprising the following steps:
uniformly mixing bio-based polyol, trimethylolpropane, xylitol and sucrose in proportion to obtain a polyurethane hard foam white material;
mixing the polyurethane hard foam white material and a foaming agent in proportion to obtain a mixed white material;
and simultaneously and quickly injecting the mixed white material and isocyanate into a mold, and standing for a period of time to obtain the polyurethane rigid foam.
6. The method for preparing rigid polyurethane foam based on bio-based polyol according to claim 5, wherein the bio-based polyol is prepared by the following steps:
uniformly mixing castor oil and an acid catalyst in proportion, stirring and heating for reaction;
adding a tertiary amine catalyst, stirring and heating for reaction;
increasing the reaction temperature, reducing the stirring speed, and carrying out polymerization reaction;
annealing and cooling to obtain the bio-based polyol.
7. The method for preparing rigid polyurethane foam based on bio-based polyol as claimed in claim 5, wherein the mixing temperature of the rigid polyurethane foam white material, the foaming agent and the isocyanate is 16-22 ℃; the standing time is 120-180s.
8. The method for preparing rigid polyurethane foam based on bio-based polyol as claimed in claim 6, wherein the castor oil and the acid catalyst are mixed uniformly in proportion, the reaction temperature for stirring and heating for reaction is 100-200 ℃, the stirring speed is 50-80rpm, and the reaction time is 4-8h.
9. The method for preparing rigid polyurethane foam based on bio-based polyol as claimed in claim 6, wherein the tertiary amine catalyst is added, the reaction temperature for stirring and heating for reaction is 100-200 ℃, the stirring speed is 50-80rpm, and the reaction time is 2-4h.
10. The method for preparing rigid polyurethane foam based on bio-based polyol as claimed in claim 6, wherein the polymerization reaction temperature is 200-300 ℃, the stirring speed is 10-50rpm, and the reaction time is 2-5h.
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