CN110105537B - Polyurethane rigid foam material and preparation method thereof - Google Patents
Polyurethane rigid foam material and preparation method thereof Download PDFInfo
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- CN110105537B CN110105537B CN201910339284.XA CN201910339284A CN110105537B CN 110105537 B CN110105537 B CN 110105537B CN 201910339284 A CN201910339284 A CN 201910339284A CN 110105537 B CN110105537 B CN 110105537B
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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
- C08G18/08—Processes
- C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
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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
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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
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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
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
- C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
- C08G18/7657—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings
- C08G18/7664—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl 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
- C08G2110/00—Foam properties
- C08G2110/0025—Foam properties rigid
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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
- C08G2110/00—Foam properties
- C08G2110/0041—Foam properties having specified density
- C08G2110/0058—≥50 and <150kg/m3
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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
- C08G2110/00—Foam properties
- C08G2110/0083—Foam properties prepared using water as the sole blowing agent
Abstract
The invention provides a polyurethane rigid foam material and a preparation method thereof, belonging to the field of polyurethane foam. Firstly, mixing isocyanate and polyether polyol in proportion, and reacting at 35-90 ℃ for 0.2-3 h to prepare an isocyanate-terminated semi-prepolymer; then, fully mixing polyether polyol, water, a catalyst and a fluorine-containing surfactant according to the mass ratio of 83.5-100: 0.5-3: 0.2-2.5: 0.5-10 in a container for 0.2-2 hours, keeping the temperature at 20-50 ℃, standing and degassing to obtain a polyol mixture; and finally, fully mixing the isocyanate-terminated semi-prepolymer with a polyol mixture, pouring, foaming and demolding to obtain the polyurethane rigid foam material. The rigid polyurethane foam prepared by the method has small diameter of the foam hole, high closed-cell rate and low heat conductivity coefficient. The heat conductivity can be reduced to 0.022W/m.K, and the diameter of the cells can be reduced to 90 um.
Description
Technical Field
The invention belongs to the field of polyurethane foam, and further relates to a polyurethane rigid foam material and a preparation method thereof.
Background
The polyurethane rigid foam plastic has the excellent characteristics of low density, low thermal conductivity, high compression strength, good dimensional stability, high closed cell rate, good water resistance and the like, and is widely applied to refrigerators, freezers, factory facilities (storage tanks and pipelines), transportation of liquefied natural gas, heat insulation of ship bodies and buildings and the like.
In order to prepare the polyurethane rigid foam with high mechanical strength, high dimensional stability, low thermal conductivity and good processing and forming performance, the fluorotrichloromethane (CFC-11) is always used as the most ideal foaming agent. Scientists have found, however, that CFC-1 has problems of depleting atmospheric ozone and destroying the earth's environment, so that it must exit the history stage. Hydrofluorocarbons (HFCs), represented by 1,1,1,3, 3-pentafluoropropane and 1,1,1,3, 3-pentafluorobutane, which are third-generation blowing agents, are currently widely used in the field of polyurethane foams. But its Global Warming Potential (GWP) is high, and developed countries have begun to restrict use.
The patent CN 102498237B takes 1-chloro-3, 3, 3-trifluoropropene as a foaming agent to prepare polyurethane foam which can meet the requirements of energy conservation and environmental protection; patent CN 103881131 discloses a blowing agent composition containing 1-chloro-3, 3, 3-trifluoropropene and 1,1,1,3, 3-pentafluoropropene, and a polyurethane foam prepared therefrom has a reduced thermal conductivity when used in a refrigerator, as compared to 1,1,1,3, 3-pentafluoropropene system and cyclopentane system. However, the molecular structure of trans-1-chloro-3, 3, 3-trifluoropropene contains both Cl atoms and carbon-carbon double bonds, and thus, the compound is easy to react with a nucleophilic reagent, reduces the activity of amine catalysts, and destroys silicone oil surfactants; the storage stability of the 1-chloro-3, 3, 3-trifluoropropene-containing polyol formulation composition is obviously shortened, and the actual operability is reduced; and the fluorine-containing foaming agents are all small molecular compounds and can easily migrate to the natural world.
The Polyurethane (PU) foam production was statistically $ 541.9 billion in 2018, and PU foam production was predicted to reach $ 797.7 billion by 2023. Based on such a large yield, a novel process for preparing polyurethanes is of great importance. Because the dispersion forces of the fluorine element and the carbon dioxide are matched, the fluorine-containing auxiliary agent has good compatibility with the carbon dioxide and is beneficial to the formation of uniform and stable closed cell pores, so that the discovery of the green, harmless and non-migratory fluorine-containing auxiliary agent is very important for polyurethane foaming.
The structure of the perfluoropolyether surfactant adopted by the invention is as follows: RfCH2CH2O (CH 2O) xH, where Rf ═ F (CF2CF2) y, x ═ 0 to 25, y ═ 1 to 12, and one end is a hydroxyl group and one end is a perfluoro segment. Wherein, the hydroxyl end of the perfluoropolyether reacts with the isocyanate chain segment, so that the compatibility of the surfactant and a system can be effectively enhanced, and the surfactant is not easy to separate out. The perfluorinated chain segment at the other end is matched with the dispersion force of carbon dioxide, so that carbon dioxide gas is locked and is not easy to resolve, and the foam stabilizing effect is achieved. The external perfluoropolyether has very high LD56 value in an oral acute toxicity test on mice, has no accumulation in organisms, is almost nontoxic and has higher practical application value.
Disclosure of Invention
In order to solve the problems in the prior art, the invention provides a preparation method of rigid polyurethane foam, and the foam prepared by using the composition has the characteristics of excellent density distribution performance, low heat conductivity coefficient, short demoulding time and uniform cell size.
In order to achieve the purpose, the technical scheme of the invention is as follows:
a preparation method of a polyurethane rigid foam material comprises the following steps:
(1) preparation of isocyanate-terminated semi-prepolymer
Mixing isocyanate and polyether polyol in proportion, and reacting at 35-90 ℃ for 0.2-3 h, wherein the molar ratio of isocyanic acid radical of the isocyanate to hydroxyl of the polyether polyol is 8-12: 1;
(2) preparation of polyol mixtures
Mixing polyether polyol, water, a catalyst and a fluorine-containing surfactant according to a mass ratio of 83.5-100: 0.5-3: 0.2-2.5: 0.5-10 in a container for 0.2-2 hours, keeping the temperature at 20-50 ℃, standing and degassing to obtain the catalyst;
(3) and (2) fully mixing the isocyanate-terminated semi-prepolymer and a polyol mixture at the temperature of 40-90 ℃ with the control index of 90-110, pouring, foaming and demolding to obtain the polyurethane rigid foam material.
Further, the molar ratio of isocyanate in the step (1) to hydroxyl in the polyether polyol is 9-10: 1; in the step (2), the mass ratio of the polyether polyol, the water, the catalyst and the fluorine-containing surfactant is 85.3-86.8: 1-2: 0.3-1: 1.5-3;
a preparation method of a polyurethane rigid foam material comprises the following steps:
(1) preparation of isocyanate-terminated semi-prepolymer
Mixing isocyanate and polyether polyol in proportion, and reacting at 35-90 ℃ for 0.2-3 h, wherein the molar ratio of isocyanic acid radical of the isocyanate to hydroxyl of the polyether polyol is 8-12: 1;
(2) preparation of polyol mixtures
The preparation method comprises the following steps of (1) fully mixing polyether polyol, water, a catalyst, a fluorine-containing surfactant and an organic silicon surfactant according to a mass ratio of 83.5-100: 0.5-3: 0.2-2.5: 0.5-10: 0.1-3 in a container for 0.2-2 hours, keeping the temperature at 20-50 ℃, standing and degassing to obtain the polyether polyol;
(3) and (2) fully mixing the isocyanate-terminated semi-prepolymer and a polyol mixture at the temperature of 40-90 ℃ with the control index of 90-110, pouring, foaming and demolding to obtain the polyurethane rigid foam material.
Further, the molar ratio of isocyanate in the step (1) to hydroxyl in the polyether polyol is 9-10: 1; in the step (2), the mass ratio of the polyether polyol, the water, the catalyst and the fluorine-containing surfactant is 85.3-86.8: 1-2: 0.3-1: 1.5-3: 1-1.5;
further, the fluorine-containing surfactant is perfluoropolyether.
Further, the isocyanate is polymethylene polyphenyl isocyanate.
Further, the polyether polyol has a viscosity of 2000-7000 mPa.s, a hydroxyl value of 250-650 mgKOH/g and a functionality of 2-6. The preferred viscosity is 3500 to 7000 mPas, and the preferred hydroxyl value is 400 to 500 mgKOH/g.
The catalyst is a mixture of one or more of tertiary amines and tin-based organic substances, preferably triethanolamine, triethylenediamine, tetramethyldiethylenetriamine, stannous octoate, and dibutyltin dilaurate.
Further, the organosilicon surfactant is one or more of L6912, L6989, AK8815, AK8485, B8461 and B8465 which are mixed.
The polymethylene polyphenyl isocyanate is known in the art as "PAPI", colloquially referred to as "crude MDI", and may be selected from commercially available materials such as 44V-10L, 44V-20L, 44V-40L from Bayer, SUPRASEC 5005, SUPRASEC2085, SUPRASEC 5000 from Huntsman, M20S from BASF, MR200, MR100 from Mitsui corporation, PM2010, PM200 from Nitida, PAPI27 from Dow corporation, PAPI135 and the like.
One skilled in the art can add other optional additives selected from the group consisting of anti-aging agents, plasticizers, preservatives, bactericides, antistatic agents, flame retardants, smoke suppressants, crosslinking agents, pigments, fillers, perfumes, and the like, either simultaneously or separately, as needed to achieve better performance.
Compared with the prior art, the invention has the beneficial effects that:
1. the rigid polyurethane foam of the present invention has a low thermal conductivity.
2. The rigid polyurethane foam of the present invention has high hydrophobicity.
3. The foam of the invention has uniform foam pores, high closed pore rate and excellent mechanical properties.
4. The foaming is carried out by full water, the environment is friendly, and the terminal hydroxyl in the used perfluoropolyether surfactant can react with PAPI and is not easy to separate out.
5. The preparation method is simple and convenient, is easy to operate, does not need to modify equipment in the production process, has no three-waste pollution, and is safe and environment-friendly.
Drawings
FIG. 1 is a scanning electron micrograph of cells of rigid polyurethane foam of example 2.
FIG. 2 is a contact angle of rigid polyurethane foam of example 3.
Detailed Description
The present invention will be further illustrated below with reference to specific embodiments, which are to be understood as merely illustrative and not limitative of the scope of the present invention.
The raw materials in the examples are first explained:
polyether polyol: the polyether polyol used in the embodiment of the invention is HK4110A of Huaka resin, the hydroxyl value is 430 +/-30 mgKOH/g, the functionality is 4-4.5, and the viscosity is 3400 +/-400 mPa.s.
Surfactant (b): according to an embodiment of the present invention, the surfactant is perfluoropolyether Le-180 of Chunttin industries, Inc., Guangzhou.
The catalyst comprises:
foaming type catalyst: triethanolamine;
gel type catalyst: dibutyltin dilaurate;
polymethylene polyphenyl polyisocyanate: the polymethylene polyphenyl polyisocyanate used in the examples of the present invention was M20S from BASF corporation, and had an NCO content of 30% to 32%.
Examples 1-3 and comparative example 1
TABLE 1
Isocyanate and polyether polyol are uniformly mixed according to the proportion in the table 1 to form an isocyanate-terminated semi-prepolymer, and the isocyanate-terminated semi-prepolymer is reacted for 0.5h at the temperature of 40 ℃; adding water, a catalyst and a surfactant into polyether polyol according to the proportion shown in the table 1, fully mixing for 15min in a container to form a polyol mixture, keeping the temperature at 30 ℃, and standing for foaming; and finally, controlling the index of the isocyanate-terminated semi-prepolymer and a polyol mixture to be 105, fully mixing at the temperature of 80 ℃, pouring, foaming and demolding. The prepared rigid polyurethane foam is used for measuring apparent density, thermal conductivity, cell size and the like
TABLE 2 Performance parameters of examples and comparative examples
Example 2 scanning electron micrographs of cells of rigid polyurethane foam the results are shown in FIG. 1. Example 3 contact angles of rigid polyurethane foams are shown in FIG. 2.
The method for foaming polyurethane hard foam based on full water introduces perfluoropolyether as a surfactant, and successfully improves the diameter of the foam hole, the closed-cell rate, the heat conductivity coefficient and the like of the material. In addition, a trace amount or a small amount of additives such as an age resister, a plasticizer, a preservative, a bactericide, an antistatic agent, a flame retardant, a smoke suppressor, a crosslinking agent, a pigment, a filler, a perfume, etc. do not affect the basic properties of the polyurethane rigid foam.
Those of ordinary skill in the art will understand that: the invention is not to be considered as limited to the specific embodiments thereof, but is to be understood as being modified in all respects, all changes and equivalents that come within the spirit and scope of the invention.
Claims (7)
1. The preparation method of the polyurethane rigid foam material is characterized by comprising the following steps:
(1) preparation of isocyanate-terminated semi-prepolymer
Mixing isocyanate and polyether polyol in proportion, and reacting at 35-90 ℃ for 0.2-3 h, wherein the molar ratio of isocyanic acid radical of the isocyanate to hydroxyl of the polyether polyol is 10: 1;
(2) preparation of polyol mixtures
The preparation method comprises the following steps of (1) fully mixing polyether polyol, water, a catalyst, a fluorine-containing surfactant and an organic silicon surfactant according to a mass ratio of 83.5-100: 0.5-3: 0.2-2.5: 0.5-10: 0-3 in a container for 0.2-2 hours, keeping the temperature at 20-50 ℃, standing and degassing to obtain the polyether polyol; the fluorosurfactant is RfCH2CH2O (CH 2O) xH, where Rf = F (CF2CF2) y, x =0 to 25, y =1 to 12, one end is hydroxyl and one end is perfluoro segment;
(3) and (2) fully mixing the isocyanate-terminated semi-prepolymer and a polyol mixture at the temperature of 40-90 ℃ with the control index of 90-110, pouring, foaming and demolding to obtain the polyurethane rigid foam material.
2. The preparation method of the polyurethane rigid foam material as claimed in claim 1, wherein the mass ratio of the polyether polyol, the water, the catalyst and the fluorine-containing surfactant in the step (2) is 85.3-86.8: 1-2: 0.3-1: 1.5-3.
3. The preparation method of the polyurethane rigid foam material as claimed in claim 1, wherein the mass ratio of the polyether polyol, the water, the catalyst, the fluorine-containing surfactant and the silicone surfactant in the step (2) is 85.3-86.8: 1-2: 0.3-1: 1.5-3: 1-1.5.
4. The method for preparing a rigid polyurethane foam material according to claim 1, 2 or 3, wherein the isocyanate is polymethylene polyphenyl isocyanate; the polyether polyol has the viscosity of 2000-7000 mPa.s, the hydroxyl value of 250-650 mgKOH/g and the functionality of 2-6; the catalyst is tertiary amine and tin organic matters; the organic silicon surfactant is one or more of L6912, L6989, AK8815, B8461 and B8465.
5. The method for preparing a rigid polyurethane foam material as claimed in claim 1, 2 or 3, wherein the polyether polyol has a viscosity of 3500 to 7000mPa.s and a hydroxyl value of 400 to 500 mgKOH/g; the catalyst is a tertiary amine and a tin organic matter, the tertiary amine organic matter is one or a mixture of more than two of triethanolamine, triethylene diamine and tetramethyl diethylene triamine, and the tin organic matter is one or a mixture of stannous octoate and dibutyltin dilaurate.
6. The method for preparing the rigid polyurethane foam material as claimed in claim 4, wherein the viscosity of the polyether polyol is 3500 to 7000mPa.s, and the hydroxyl value is 400 to 500 mgKOH/g; in the catalyst, tertiary amine organic matter is one or more of triethanolamine, triethylene diamine and tetramethyl diethylene triamine, and tin organic matter is one or more of stannous octoate and dibutyltin dilaurate.
7. A rigid polyurethane foam material, which is prepared by the preparation method of any one of claims 1 to 6.
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