CN112694596B - High-temperature-resistant creep-resistant pipeline thermal insulation material and preparation method thereof - Google Patents
High-temperature-resistant creep-resistant pipeline thermal insulation material and preparation method thereof Download PDFInfo
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Abstract
The invention relates to the technical field of polyurethane thermal insulation materials, in particular to a high-temperature-resistant and creep-resistant pipeline thermal insulation material and a preparation method thereof. The high-temperature-resistant creep-resistant pipeline heat-insulating material is prepared by mixing a component A and a component B according to the mass ratio of 1:1.4-1.6, wherein the component A is prepared from sucrose polyether polyol A, epoxy resin modified polyether polyol B, polyester polyol, a cross-linking agent, deionized water, a foam stabilizer and a catalyst; the modified isocyanate is prepared by modifying a mixture of polymethylene polyphenyl polyisocyanate and diphenylmethane diisocyanate by adopting one or two of hydroxyl-terminated fluorine-containing polyester polysiloxane and hydroxyl-terminated polysiloxane. The high-temperature-resistant creep-resistant pipeline thermal insulation material disclosed by the invention has excellent high-temperature dimensional stability, lower heat conductivity coefficient and good bonding property, also has good high-temperature resistance and creep resistance, and can meet the long-term high-temperature conveying requirement; the invention also provides a preparation method of the composition.
Description
Technical Field
The invention relates to the technical field of polyurethane thermal insulation materials, in particular to a high-temperature-resistant and creep-resistant pipeline thermal insulation material and a preparation method thereof.
Background
The polyurethane thermal insulation material is widely applied to heat pipe network transportation due to low heat conductivity coefficient and simple processing technology. Along with the heat supply demand and development of urban clean energy, the new mode of large-temperature-difference long-distance heat and power cogeneration centralized heat supply is rapidly developed, the water supply temperature of a primary pipe network reaches 120-. The heat conductivity coefficient of polyurethane foam will rise after ageing, and shear strength will descend, receives the ambient pressure effect simultaneously, produces great creep deformation, leads to polyurethane foam heat preservation heat-proof quality to obviously reduce, and great influence heat supply effect causes the wasting of resources.
Disclosure of Invention
The invention aims to provide a high-temperature-resistant creep-resistant pipeline heat-insulating material which not only has excellent high-temperature dimensional stability, lower heat conductivity coefficient and good adhesive property, but also has good high-temperature-resistant creep-resistant property and can meet the long-term high-temperature conveying requirement; the invention also provides a preparation method of the composition.
The high-temperature-resistant creep-resistant pipeline heat-insulating material is prepared by mixing a component A and a component B according to the mass ratio of 1:1.4-1.6, and comprises the following components in parts by weight,
the component A is as follows:
the component B is as follows:
50-80 parts of polymethylene polyphenyl polyisocyanate,
20-50 parts of modified isocyanate;
the epoxy resin modified polyether polyol B is prepared by taking epoxy resin and glycerol as composite initiators and propylene oxide as a polymerization monomer, and has the functionality of 2.2-2.6 and the hydroxyl value of 70-90mg KOH/g;
the modified isocyanate is prepared by modifying a mixture of polymethylene polyphenyl polyisocyanate and diphenylmethane diisocyanate by adopting one or two of hydroxyl-terminated fluorine-containing polyester polysiloxane and hydroxyl-terminated polysiloxane, and the NCO content of the modified isocyanate is 23-26%.
The epoxy resin of the epoxy resin modified polyether polyol B is one or two of bisphenol A type epoxy resin, bisphenol F type epoxy resin and bisphenol S type epoxy resin; the mass of the epoxy resin is 20-35% of the total mass of the epoxy resin and the glycerol.
The preparation method of the modified isocyanate comprises the following steps: firstly, stirring hydroxyl-terminated fluorine-containing polyester polysiloxane and hydroxyl-terminated polysiloxane at the temperature of 90-110 ℃, dehydrating for 2-4 hours in vacuum, cooling to 50-60 ℃, adding isocyanate, reacting at the temperature of 80-90 ℃ to prepare modified isocyanate, and packaging for later use; wherein the addition amount of the hydroxyl-terminated fluorine-containing polyester polysiloxane and the hydroxyl-terminated polysiloxane is 10-18%, and the mass ratio of the polymethylene polyphenyl polyisocyanate to the diphenylmethane diisocyanate is 1: 0.4-1.
The functionality of the sucrose polyether polyol A is 5.5-6.0, the hydroxyl value is 380-460mg KOH/g, and the viscosity at 25 ℃ is 12000-16000mpa & s; the composite material is prepared by taking sucrose and one or two of glycerin, propylene glycol and ethylene glycol as a composite initiator and taking propylene oxide as a polymerization monomer.
The catalyst is one or more of trimethyl hydroxyethyl ethylenediamine, trimethyl hydroxyethyl propylenediamine, N-bis (dimethylaminopropyl) isopropanolamine and 2,4, 6-tris (dimethylaminomethyl) phenol.
The functionality of the polyester polyol is 2, the viscosity at 25 ℃ is 2500-.
The cross-linking agent is one or more of 1, 4-butanediol, 1, 3-butanediol, dodecanediol and triethanolamine.
The foam stabilizer is hydrophilic polyurethane rigid foam silicone oil, preferably B84817 (winning) or M8855 (Maillard).
The preparation method of the high-temperature-resistant creep-resistant pipeline heat-insulating material comprises the following steps:
(1) and (2) component A: uniformly stirring sucrose polyether polyol A, epoxy resin modified polyether polyol B, polyester polyol, a cross-linking agent, deionized water, a foam stabilizer and a catalyst at normal temperature to obtain a component A;
(2) and the component B comprises: uniformly stirring polymethylphenyl polyisocyanate and modified isocyanate at normal temperature to obtain a component B;
(3) mixing and curing: when in use, the component A and the component B are mixed and foamed according to the mass ratio of 1:1.4-1.6, and the high-temperature-resistant creep-resistant pipeline heat-insulating material is obtained.
Compared with the prior art, the invention has the following beneficial effects:
(1) according to the invention, the epoxy resin modified polyether polyol B is adopted, and the epoxy resin is grafted into the polyether polyol, so that on one hand, the epoxy resin contains more benzene rings and carbon-carbon bonds to improve the overall temperature resistance of the foam; on the other hand, a temperature-resistant oxazolidinone structure is generated by the reaction of the epoxy group and the isocyanurate, so that the temperature resistance of the foam is further improved;
(2) according to the invention, hydroxyl-terminated fluorine-containing polyester polysiloxane and hydroxyl-terminated polysiloxane modified isocyanate are adopted, 1, 4-butanediol, dodecanediol and the like are used as cross-linking agents, the foam cross-linking degree is improved, silicon-oxygen bonds and carbon-carbon bonds are introduced into a polyurethane macromolecular chain, the oxidation resistance of foam at high temperature is improved, and the aging resistance and creep resistance of a foam heat insulation system are realized;
(3) the invention adopts a reactive catalyst, the formula index is between 1.02 and 1.08, the reaction is promoted to produce temperature-resistant groups such as urea, carbamate and the like by optimizing the catalyst system and the formula index, the generation of allophanate and biuret with poor temperature resistance is reduced, the integral temperature resistance of foam is improved, and the catalyst participates in the reaction and is connected on a polyurethane macromolecular chain, so that the influence of the catalyst separated at high temperature on the foam structure is avoided.
Detailed Description
The parts mentioned in the following examples and comparative examples are parts by mass.
The preparation method of the epoxy resin modified polyether polyol B adopted in the embodiment comprises the following steps:
the epoxy resin is prepared by taking bisphenol A epoxy resin and glycerol as composite initiators (wherein the bisphenol A epoxy resin accounts for 30 percent) and taking propylene oxide as a polymerization monomer, and the epoxy resin has the functionality of 2.4 and the hydroxyl value of 80 mgKOH/g.
The preparation method of the modified isocyanate adopted in the examples comprises the following steps:
firstly, stirring and vacuum dehydrating hydroxyl-terminated fluorine-containing polyester polysiloxane and hydroxyl-terminated polysiloxane at the temperature of 100 ℃, then cooling to 50 ℃, adding polymethylene polyphenyl polyisocyanate and diphenylmethane diisocyanate, reacting at the temperature of 85 ℃ to prepare modified isocyanate, and packaging for later use. Wherein the adding amount of the hydroxyl-terminated fluorine-containing polyester polysiloxane and the hydroxyl-terminated polysiloxane is 15 percent, the mass ratio of the polymethylene polyphenyl polyisocyanate to the diphenylmethane diisocyanate is 1:0.8, and the NCO content of the modified isocyanate is controlled to be 25 percent.
The polyester polyol PS-3152 manufacturer adopted in the examples is Nanjing Jinling Spodol chemical Co., Ltd; the manufacturer of the foam stabilizer B84817 is Germany WingChuangdeshi company; the polyether polyol C210 manufacturer is Shandong Nowey new material Co., Ltd, the functionality is 2, the hydroxyl value is 109-115mgKOH/g, and the viscosity (25 ℃) is 120-180mpa & s.
Example 1
(1) The component A comprises: weighing 44.4 parts of sucrose polyether polyol A (with the functionality of 5.7, the hydroxyl value of 410 +/-5 mgKOH/g, the viscosity of 13500 +/-100 mpa.s at 25 ℃ and sucrose and glycerol as composite initiators), 30 parts of epoxy resin modified polyether polyol B, PS-315210 parts of polyester polyol, 4 parts of 1, 4-butanediol, 3 parts of dodecanediol, 3.6 parts of deionized water, 4 parts of foam stabilizer B848173 parts, 0.2 part of trimethyl hydroxyethyl ethylenediamine, 1 part of N, N-bis (dimethylaminopropyl) isopropanolamine and 0.8 part of 2,4, 6-tris (dimethylaminomethyl) phenol, and uniformly stirring at normal temperature to obtain a component A;
(2) and the component B comprises: weighing 70 parts of polymethylene polyphenyl polyisocyanate and 30 parts of modified isocyanate, and uniformly stirring at normal temperature to obtain a component B;
(3) mixing and curing: when the high-temperature-resistant creep-resistant pipeline heat-insulating material is used, the component A and the component B are mixed and foamed according to the mass ratio of 1:1.5, and the high-temperature-resistant creep-resistant pipeline heat-insulating material is obtained.
Example 2
(1) And (2) component A: 55 parts of sucrose polyether polyol A (with the functionality of 5.6, the hydroxyl value of 400 +/-5 mg KOH/g, the viscosity of 13000 +/-100 mpa & s at 25 ℃ and sucrose and glycerol as composite initiators), 12 parts of epoxy resin modified polyether polyol B, 503L 15 parts of polyester polyol PE-B, 4 parts of 1, 3-butanediol, 5 parts of dodecanediol, 3.8 parts of deionized water, 4 parts of foam stabilizer B848173 parts, 0.4 part of trimethyl hydroxyethyl ethylenediamine, 0.9 part of N, N-bis (dimethylaminopropyl) isopropanolamine and 0.9 part of 2,4, 6-tris (dimethylaminomethyl) phenol are weighed and stirred uniformly at normal temperature to obtain a component A;
(2) and B component: weighing 80 parts of polymethylene polyphenyl polyisocyanate and 20 parts of modified isocyanate, and uniformly stirring at normal temperature to obtain a component B;
(3) mixing and curing: when the high-temperature-resistant creep-resistant pipeline heat-insulating material is used, the component A and the component B are mixed and foamed according to the mass ratio of 1:1.4, and the high-temperature-resistant creep-resistant pipeline heat-insulating material is obtained.
Example 3
(1) The component A comprises: weighing 39 parts of sucrose polyether polyol A (with the functionality of 5.8, the hydroxyl value of 420 +/-5 mg KOH/g, the viscosity of 14000 +/-100 mpa.s at 25 ℃ and sucrose and glycerol as composite initiators), 16.4 parts of epoxy resin modified polyether polyol B, 503L 20 parts of polyester polyol PE-B, 4 parts of 1, 4-butanediol, 5 parts of dodecanediol, 6 parts of triethanolamine, 4 parts of deionized water, 4 parts of foam stabilizer B848174, 0.2 part of trimethyl hydroxyethyl ethylene diamine, 0.3 part of trimethyl hydroxyethyl propylene diamine, 0.6 part of N, N-bis (dimethylaminopropyl) isopropanolamine and 0.5 part of 2,4, 6-tris (dimethylaminomethyl) phenol, and uniformly stirring at normal temperature to obtain a component A;
(2) and B component: weighing 50 parts of polymethylene polyphenyl polyisocyanate and 50 parts of modified isocyanate, and uniformly stirring at normal temperature to obtain a component B;
(3) mixing and curing: when the high-temperature-resistant creep-resistant pipeline heat-insulating material is used, the component A and the component B are mixed and foamed according to the mass ratio of 1:1.6, and the high-temperature-resistant creep-resistant pipeline heat-insulating material is obtained.
Example 4
(1) And (2) component A: weighing 49 parts of sucrose polyether polyol A (with the functionality of 5.9, the hydroxyl value of 430 +/-5 mg KOH/g, the viscosity of 15000 +/-100 mpa.s at 25 ℃ and sucrose and glycerol as composite initiators), 22 parts of epoxy resin modified polyether polyol B, PS-315212 parts of polyester polyol, 4 parts of 1, 4-butanediol, 4.9 parts of dodecanediol, 3.9 parts of deionized water, 4 parts of foam stabilizer B848173 parts, 0.4 part of trimethyl hydroxyethyl ethylenediamine, 0.5 part of N, N-bis (dimethylaminopropyl) isopropanolamine and 0.3 part of 2,4, 6-tris (dimethylaminomethyl) phenol, and uniformly stirring at normal temperature to obtain a component A;
(2) and B component: weighing 60 parts of polymethylene polyphenyl polyisocyanate and 40 parts of modified isocyanate, and uniformly stirring at normal temperature to obtain a component B;
(3) mixing and curing: when the high-temperature-resistant creep-resistant pipeline heat-insulating material is used, the component A and the component B are mixed and foamed according to the mass ratio of 1:1.5, and the high-temperature-resistant creep-resistant pipeline heat-insulating material is obtained.
Comparative example 1
Compared with the example 1, the preparation method of the comparative example, which adopts the conventional polyether polyol C210 to replace the epoxy resin modified polyether polyol B, comprises the following steps:
(1) the component A comprises: weighing 44.4 parts of sucrose polyether polyol A (with the functionality of 5.7, the hydroxyl value of 410 +/-5 mgKOH/g, the viscosity of 13500 +/-100 mpa.s at 25 ℃ and sucrose and glycerol as composite initiators), 44.4 parts of polyether polyol C21030 parts, PS-315210 parts of polyester polyol, 4 parts of 1, 4-butanediol, 3 parts of dodecanediol, 3.6 parts of deionized water, 4 parts of foam stabilizer B848173 parts, 0.2 part of trimethyl hydroxyethyl ethylenediamine, 1 part of N, N-bis (dimethylaminopropyl) isopropanolamine and 0.8 part of 2,4, 6-tris (dimethylaminomethyl) phenol, and uniformly stirring at normal temperature to obtain a component A;
(2) and B component: weighing 70 parts of polymethylene polyphenyl polyisocyanate and 30 parts of modified isocyanate, and uniformly stirring at normal temperature to obtain a component B;
(3) mixing and curing: when the high-temperature-resistant creep-resistant pipeline heat-insulating material is used, the component A and the component B are mixed and foamed according to the mass ratio of 1:1.5, and the high-temperature-resistant creep-resistant pipeline heat-insulating material is obtained.
Comparative example 2
Compared with the example 1, the preparation method of the comparative example adopts the conventional isocyanate to replace the modified isocyanate and comprises the following steps:
(1) the component A comprises: weighing 44.4 parts of sucrose polyether polyol A (with the functionality of 5.7, the hydroxyl value of 410 +/-5 mgKOH/g, the viscosity of 13500 +/-100 mpa.s at 25 ℃ and sucrose and glycerol as composite initiators), 30 parts of epoxy resin modified polyether polyol B, PS-315210 parts of polyester polyol, 4 parts of 1, 4-butanediol, 3 parts of dodecanediol, 3.6 parts of deionized water, 4 parts of foam stabilizer B848173 parts, 0.2 part of trimethyl hydroxyethyl ethylenediamine, 1 part of N, N-bis (dimethylaminopropyl) isopropanolamine and 0.8 part of 2,4, 6-tris (dimethylaminomethyl) phenol, and uniformly stirring at normal temperature to obtain a component A;
(2) and B component: weighing 100 parts of polymethylene polyphenyl polyisocyanate to obtain a component B;
(3) mixing and curing: when the high-temperature-resistant creep-resistant pipeline heat-insulating material is used, the component A and the component B are mixed and foamed according to the mass ratio of 1:1.5, and the high-temperature-resistant creep-resistant pipeline heat-insulating material is obtained.
Comparative example 3
Compared with the example 1, the preparation method of the comparative example adopts the conventional polyether polyol C210 to replace the epoxy resin modified polyether polyol B and adopts the conventional isocyanate to replace the modified isocyanate, and comprises the following steps:
(1) and (2) component A: weighing 44.4 parts of sucrose polyether polyol A (with the functionality of 5.7, the hydroxyl value of 410 +/-5 mgKOH/g, the viscosity of 13500 +/-100 mpa & s at 25 ℃ and sucrose and glycerol as composite initiators), 44.4 parts of polyether polyol C21030 parts, PS-315210 parts of polyester polyol, 4 parts of 1, 4-butanediol, 3 parts of dodecanediol, 3.6 parts of deionized water, a foam stabilizer B848173 parts, 0.2 part of trimethyl hydroxyethyl ethylenediamine, 1 part of N, N-bis (dimethylaminopropyl) isopropanolamine and 0.8 part of 2,4, 6-tris (dimethylaminomethyl) phenol, and uniformly stirring at normal temperature to obtain a component A;
(2) and B component: weighing 100 parts of polymethylene polyphenyl polyisocyanate to obtain a component B;
(3) mixing and curing: when the high-temperature-resistant creep-resistant pipeline heat-insulating material is used, the component A and the component B are mixed and foamed according to the mass ratio of 1:1.5, and the high-temperature-resistant creep-resistant pipeline heat-insulating material is obtained.
The polyurethane thermal insulation materials prepared in examples 1-4 and comparative examples 1-3 are subjected to performance tests according to the national standard GB/T29047-.
TABLE 1 results of performance tests of polyurethane insulation materials prepared in examples 1 to 4 and comparative examples 1 to 3
As can be seen from Table 1, the rigid polyurethane foams prepared in examples 1-4 of the present invention have the characteristics of high temperature resistance, creep resistance, high strength and high closed cell ratio, and the high temperature resistance can reach 142 ℃ and the strength can reach 0.51 MPa. When the polyether polyol modified by epoxy resin or the modified isocyanate is not added to the combined polyether, the high temperature resistance and the creep resistance of the foam are reduced to a certain extent, the high temperature resistance can not meet the CCOT requirement, and the creep resistance is deteriorated as can be seen by combining examples 1-3 and comparative examples 1-3. The multi-benzene ring and carbon-carbon bond contained in the epoxy modified polyether polyol can improve the integral temperature resistance of the foam, and the silicon-oxygen bond contained in the modified isocyanate contributes to the temperature resistance of the foam.
Claims (4)
1. The utility model provides a high temperature resistant creep deformation pipeline insulation material which characterized in that: is formed by mixing a component A and a component B according to the mass ratio of 1:1.4-1.6, and comprises the following components in parts by weight,
the component A is as follows:
39-55 parts of cane sugar polyether polyol A,
12-30 parts of epoxy resin modified polyether polyol B,
10-20 parts of polyester polyol,
7-15 parts of a cross-linking agent,
3.6 to 4 portions of deionized water,
3-4 parts of a foam stabilizer,
1.6-2.2 parts of a catalyst;
the component B is as follows:
50-80 parts of polymethylphenyl polyisocyanate,
20-50 parts of modified isocyanate;
the functionality of the sucrose polyether polyol A is 5.5-6.0, the hydroxyl value is 380-460mg KOH/g, and the viscosity at 25 ℃ is 12000-16000mpa & s; the composite material is prepared by taking sucrose and one or two of glycerol, propylene glycol and ethylene glycol as a composite initiator and taking propylene oxide as a polymerization monomer;
the epoxy resin modified polyether polyol B is prepared by taking epoxy resin and glycerol as composite initiators and propylene oxide as a polymerization monomer, and has the functionality of 2.2-2.6 and the hydroxyl value of 70-90mg KOH/g;
the functionality of the polyester polyol is 2, the viscosity at 25 ℃ is 2500-;
the modified isocyanate is prepared by modifying a mixture of polymethylene polyphenyl polyisocyanate and diphenylmethane diisocyanate by adopting one or two of hydroxyl-terminated fluorine-containing polyester polysiloxane and hydroxyl-terminated polysiloxane, and the NCO content of the modified isocyanate is 23-26%; the preparation method comprises the following steps: firstly, stirring hydroxyl-terminated fluorine-containing polyester polysiloxane and hydroxyl-terminated polysiloxane at the temperature of 90-110 ℃, dehydrating for 2-4 hours in vacuum, cooling to 50-60 ℃, adding isocyanate, reacting at the temperature of 80-90 ℃ to prepare modified isocyanate, and packaging for later use; wherein the adding amount of the hydroxyl-terminated fluorine-containing polyester polysiloxane and the hydroxyl-terminated polysiloxane is 10-18%, and the mass ratio of the polymethylene polyphenyl polyisocyanate to the diphenylmethane diisocyanate is 1: 0.4-1;
the catalyst is one or more of trimethylhydroxyethylethylene diamine, trimethylhydroxyethylpropylene diamine, N-bis (dimethylaminopropyl) isopropanolamine and 2,4, 6-tris (dimethylaminomethyl) phenol;
the cross-linking agent is one or more of 1, 4-butanediol, 1, 3-butanediol, dodecanediol and triethanolamine.
2. The high temperature and creep resistant pipe insulation of claim 1, wherein: the epoxy resin of the epoxy resin modified polyether polyol B is one or two of bisphenol A type epoxy resin, bisphenol F type epoxy resin and bisphenol S type epoxy resin; the mass of the epoxy resin is 20-35% of the total mass of the epoxy resin and the glycerol.
3. The high temperature and creep resistant pipe insulation of claim 1, wherein: the foam stabilizer is hydrophilic polyurethane rigid foam silicone oil.
4. A method for preparing the high temperature and creep resistant pipe thermal insulation material according to any one of claims 1 to 3, which is characterized in that: the method comprises the following steps:
(1) the component A comprises: uniformly stirring sucrose polyether polyol A, epoxy resin modified polyether polyol B, polyester polyol, a cross-linking agent, deionized water, a foam stabilizer and a catalyst at normal temperature to obtain a component A;
(2) and B component: uniformly stirring polymethylphenyl polyisocyanate and modified isocyanate at normal temperature to obtain a component B;
(3) mixing and curing: when in use, the component A and the component B are mixed and foamed according to the mass ratio of 1:1.4-1.6, and the high-temperature-resistant creep-resistant pipeline heat-insulating material is obtained.
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| JP2018197301A (en) * | 2017-05-24 | 2018-12-13 | 東ソー株式会社 | Composition for rigid polyurethane foam and method for manufacturing rigid polyurethane foam |
| CN110964164A (en) * | 2019-12-16 | 2020-04-07 | 山东一诺威新材料有限公司 | Full-water one-step flexible heat-insulating pipe material and preparation method thereof |
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| JP2018197301A (en) * | 2017-05-24 | 2018-12-13 | 東ソー株式会社 | Composition for rigid polyurethane foam and method for manufacturing rigid polyurethane foam |
| CN110964164A (en) * | 2019-12-16 | 2020-04-07 | 山东一诺威新材料有限公司 | Full-water one-step flexible heat-insulating pipe material and preparation method thereof |
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