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CN108948410B - Polyol composition and polyurethane rigid foam prepared from same - Google Patents

Polyol composition and polyurethane rigid foam prepared from same Download PDF

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Publication number
CN108948410B
CN108948410B CN201810658698.4A CN201810658698A CN108948410B CN 108948410 B CN108948410 B CN 108948410B CN 201810658698 A CN201810658698 A CN 201810658698A CN 108948410 B CN108948410 B CN 108948410B
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Prior art keywords
polyol
prepared
reaction
polyurethane
parts
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CN108948410A (en
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刘站站
李鹏
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Qingdao Haier Refrigerator Co Ltd
Haier Smart Home Co Ltd
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Qingdao Haier Refrigerator Co Ltd
Haier Smart Home Co Ltd
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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    • 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
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    • 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
    • C08G18/4804—Two or more polyethers of different physical or chemical nature
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    • C08G18/40—High-molecular-weight compounds
    • C08G18/48—Polyethers
    • C08G18/50—Polyethers having heteroatoms other than oxygen
    • C08G18/5021—Polyethers having heteroatoms other than oxygen having nitrogen
    • C08G18/5024—Polyethers having heteroatoms other than oxygen having nitrogen containing primary and/or secondary amino groups
    • C—CHEMISTRY; METALLURGY
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    • C08G18/40—High-molecular-weight compounds
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    • 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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    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/77—Polyisocyanates or polyisothiocyanates having heteroatoms in addition to the isocyanate or isothiocyanate nitrogen and oxygen or sulfur
    • C08G18/78—Nitrogen
    • C08G18/79—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates
    • C08G18/791—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates containing isocyanurate groups
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    • C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
    • C08G65/26—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds
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    • C08G65/2624—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing nitrogen containing amine groups containing aliphatic amine groups
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    • C08G65/2627—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing nitrogen containing amine groups containing aromatic or arylaliphatic amine groups
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Abstract

The invention discloses a polyol composition, which consists of a plurality of polyether polyols and a polyol I, wherein the polyol I is prepared by taking a reactant generated by the reaction of cardanol glycidyl ether and a plurality of amines as an initiator and carrying out addition reaction with olefin oxide; the typical characteristic viscosity of polyol I is 1500-3000 mPa.s, and the hydroxyl value is 300-450mg KOH/g. The invention also discloses the application of the polyol composition in polyurethane rigid foam plastic and a preparation method thereof. According to the invention, the polyhydric alcohol I is prepared by taking cardanol derivatives as an initiator, and has good compatibility with components taking cyclopentane or a composition as a foaming agent due to a long alkane structure; the polyurethane rigid foam prepared by the polyol has the advantages of reduced foam density difference, high closed cell rate, reduced comprehensive heat conductivity coefficient, and improved compressive strength and dimensional stability.

Description

Polyol composition and polyurethane rigid foam prepared from same
Technical Field
The invention relates to the technical field of polyurethane foam plastics, and particularly provides a polyol composition and a polyurethane rigid foam plastic prepared from the polyol composition.
Background
The polyurethane is a polymer with a main chain containing-NHCOO-repeated structural units and is mainly prepared by polymerizing isocyanate, polyester polyol, a chain extender and other raw materials. Because the polyurethane contains strongly polar urethane groups, is insoluble in nonpolar groups, has good oil resistance, toughness, wear resistance, aging resistance and adhesiveness, and can be used for preparing materials with a wide temperature range, such as elastomers, thermoplastic resins, thermosetting resins and the like. Polyurethane is used as an organic polymer material with higher cost performance, is widely applied to various fields in actual life at present, and the yield and the consumption of the polyurethane are increased year by year.
The polyol, which is one of the main components, generally includes polyether and polyester polyols, and has the characteristics of large polarity, strong hydrophilicity, and the like. Polyester polyols are typically prepared by the condensation (or transesterification) of organic dicarboxylic acids (anhydrides or esters) with polyhydric alcohols (including diols) or by the polymerization of lactones with polyhydric alcohols. The dibasic acid may be phthalic acid, phthalic anhydride or its ester, adipic acid, halogenated phthalic acid, etc. The polyhydric alcohol may be ethylene glycol, propylene glycol, diethylene glycol, trimethylolpropane, pentaerythritol, 1, 4-propylene glycol, etc. The polyurethane product obtained by the polycondensation reaction of the common polyester polyol and raw materials such as isocyanate, a chain extender and the like has defects in the aspects of heat resistance, thermal stability, demoulding performance and the like.
The foaming agent is one of important raw materials for preparing the polyurethane rigid foam, and the performance of the foaming agent has a crucial influence on the performance of the polyurethane foam. Cyclopentane is currently the most widely used blowing agent. However, cyclopentane is a non-polar substance and has poor compatibility with polyol, cyclopentane is easy to phase separate from foaming material, polyol has poor storage stability and is easy to delaminate, and the prepared rigid polyurethane foam has the defects of large cells, uneven cell size, high thermal conductivity, general comprehensive performance and the like.
Therefore, various means for modifying the polyol have been proposed, for example, patent CN105992784A discloses that a cardanol-modified epoxy polyol can be used to form a polyurethane resin system; the polyurethane resin system includes an isocyanate-reactive component having a first cardanol component and the cardanol-modified epoxy polyol, and an isocyanate component including at least one polyisocyanate; the cardanol-modified epoxy polyol is a reaction product of an epoxy component and an epoxy reactive component at a ratio of epoxy groups to epoxy reactive groups of 1: 0.95 to 1: 5, but the epoxy reaction cost is high and the process is complex.
Therefore, the method has important significance for further developing novel high-efficiency, low cost, no by-product and simple process, and can be directly applied to the preparation of polyurethane rigid foam plastic by using the multi-modified polyol.
Disclosure of Invention
The invention aims to make up the defects of the prior art and provide a polyol composition which is low in cost, simple in process and good in compatibility with a foaming agent and a preparation method thereof.
Another object of the present invention is to provide the use of the polyol composition for the preparation of rigid polyurethane foams.
One embodiment of the invention discloses a polyol composition, which consists of a plurality of polyether polyols and a polyol I, and comprises the following raw materials in parts by weight:
Figure BDA0001706137130000021
the polyhydric alcohol I is prepared by taking a reactant generated by the reaction of cardanol glycidyl ether and various amines as an initiator and carrying out addition reaction with olefin oxide;
the typical characteristic viscosity of the polyol I is 1500-3000 mPa.s, and the hydroxyl value is 300-450mg KOH/g.
As a further improvement of an embodiment of the present invention, the amine is selected from at least one of ethanolamine, diethanolamine, methylamine, ethylamine, monoamine having 3 to 12 carbon chains, aniline, ethylenediamine, hexamethylenediamine, diamine having 3 to 12 carbon chains, diethylenetriamine, triethylenetetramine, 4' -diaminodiphenylmethane, m-phenylenediamine, diaminodicyclohexylmethane, isophoronediamine, aminoethylpiperazine, 1, 3-cyclohexanediamine, xylylenediamine, and polyetheramine.
As a further improvement of the embodiment of the present invention, the polyether polyol II is prepared by an addition reaction of at least one initiator selected from the group consisting of ethylene glycol, propylene glycol, diethylene glycol, triethylene glycol, neopentyl glycol, and hexylene glycol with an alkylene oxide;
the polyether polyol II has a typical characteristic viscosity of 150-250 mPas, a hydroxyl value of 160-300mg KOH/g and an average functionality of 1-2.
As a further improvement of the embodiment of the invention, the polyether polyol III is prepared by taking at least one of glycerol and trimethylolpropane as an initiator and carrying out addition reaction with alkylene oxide;
the polyether polyol III has a typical characteristic viscosity of 400-800 mPas, a hydroxyl value of 250-500mg KOH/g and an average functionality of 2-3.
As a further improvement of the embodiment of the invention, the polyether polyol IV is prepared by addition reaction of at least one of toluene diamine and pentaerythritol and an alkylene oxide, and has a typical characteristic viscosity of 1000-2000mPa & s, a hydroxyl value of 350-500mg KOH/g and an average functionality of 3-4;
the alkylene oxide comprises at least one of ethylene oxide, propylene oxide and butylene oxide.
As a further improvement of the embodiment of the present invention, the raw material composition of the polyurethane foamed rigid plastic includes the polyol composition as described above;
the raw material composition of the polyurethane foaming rigid plastic comprises the following components in parts by weight:
Figure BDA0001706137130000031
as a further improvement of an embodiment of the present invention, the blowing agent is selected from any one of cyclopentane, isopentane, pentafluoropropene, 1-chloro-3, 3, 3-trifluoropropene, and hexafluorobutene.
As a further refinement of an embodiment of the present invention, the isocyanate is polymethylene polyphenyl isocyanate;
the isocyanate content is 30.5-32.0%, and the viscosity is 150-250 mPas.
The embodiment of the invention also discloses a method for preparing the polyurethane foaming rigid plastic,
s1, mixing the polyol I, the polyether polyol, the catalyst and the surfactant according to the proportion at the temperature of 20-30 ℃ and under the pressure of 1-2MPa to prepare a first mixture;
s2, mixing the foaming agent with the first mixture prepared in the S1 according to a preset proportion at the temperature of 20-30 ℃ and under the pressure of 2-3MPa to prepare a second mixture;
s3, mixing the preheated isocyanate at the temperature of 20-30 ℃ with the second mixture obtained in the step S2, injecting the mixture into a preheated 40-45 ℃ mould at the pressure of 120-140MPa for foaming and curing to obtain polyurethane rigid foam;
and S4, cooling and demolding the foamed polyurethane rigid foam, and performing performance test.
As a further refinement of an embodiment of the present invention, the method further comprises preparing polyol I in the polyol composition, specifically comprising the steps of:
adding amine into a reaction kettle, raising the reaction temperature to 70-80 ℃, then dropwise adding cardanol glycidyl ether, after dropwise adding is completed within 0.5-1 hour, after heat preservation reaction is performed for 1-2 hours, replacing gas in the reaction kettle with nitrogen, then adding a catalyst and at least one of ethylene oxide, propylene oxide and butylene oxide, raising the reaction temperature to 120-150 ℃, preserving heat for 4-8 hours, cooling and discharging.
In another aspect, another embodiment of the present invention discloses the use of the rigid polyurethane foam or the rigid polyurethane foam prepared by the method in an interior thermal insulation material for home appliances, and in a specific implementation, the rigid polyurethane foam composite disclosed by the present invention can be used for the interior thermal insulation of home appliances such as refrigerators, freezers, solar energy, gas water heaters, and disinfection cabinets.
The embodiment of the invention has the following beneficial effects:
1) the polyol I provided by the embodiment of the invention is prepared by taking a cardanol derivative as an initiator and reacting with other substances to prepare the polyol, and due to the hydrocarbon structure with 15 carbon atoms on the side chain, the compatibility of the polyol I and alkane foaming agents such as cyclopentane and the like can be remarkably improved, so that the compatibility of the polyol composition and the foaming agents is improved, the storage stability of the polyol and the foaming agents is improved, and the layering caused by long-time storage is avoided;
2) the reaction raw materials prepared by taking cardanol derivatives as the initiator of the polyhydric alcohol I provided by the embodiment of the invention are wide in source, easy to obtain and low in cost;
3) according to the raw material composition containing the polyurethane foamed rigid plastic provided by the embodiment of the invention, the polyol composition in the composition has good compatibility with cyclopentane due to the longer alkyl chain, so that the viscosity of the polyurethane foamed rigid plastic can be reduced, the fluidity is improved, and the polyurethane foamed rigid plastic can fill the whole die cavity conveniently;
4) the polyurethane rigid foam prepared by the polyol has the advantages that the foam pore size is reduced, and the radiation heat dissipation is reduced; the number of the foam holes in unit area is increased, the foam density difference is reduced, the closed pore rate is high, the comprehensive heat conductivity coefficient is reduced, and the compressive strength and the dimensional stability are improved.
Detailed Description
In order to make the objects, technical solutions and advantages of the present application more apparent, the technical solutions of the present application will be described in detail and completely with reference to the detailed description of the present application. It should be apparent that the described embodiments are only some embodiments of the present application, and not all embodiments. All other embodiments obtained by a person of ordinary skill in the art without any inventive work based on the embodiments in the present application are within the scope of protection of the present application.
The following detailed description of embodiments of the invention is intended to be illustrative, but not limiting, of the invention.
One embodiment of the invention discloses a polyol composition, which consists of a plurality of polyether polyols and a polyol I, and comprises the following raw materials in parts by weight:
Figure BDA0001706137130000051
the polyhydric alcohol I is prepared by taking a reactant generated by the reaction of cardanol glycidyl ether and various amines as an initiator and carrying out addition reaction with olefin oxide;
the typical characteristic viscosity of the polyol I is 1500-3000 mPa.s, and the hydroxyl value is 300-450mg KOH/g.
As a further improvement of an embodiment of the present invention, the amine is selected from at least one of ethanolamine, diethanolamine, methylamine, ethylamine, monoamine having 3 to 12 carbon chains, aniline, ethylenediamine, hexamethylenediamine, diamine having 3 to 12 carbon chains, diethylenetriamine, triethylenetetramine, 4' -diaminodiphenylmethane, m-phenylenediamine, diaminodicyclohexylmethane, isophoronediamine, aminoethylpiperazine, 1, 3-cyclohexanediamine, xylylenediamine, and polyetheramine.
As a further improvement of the embodiment of the present invention, the polyether polyol II is prepared by an addition reaction of at least one initiator selected from the group consisting of ethylene glycol, propylene glycol, diethylene glycol, triethylene glycol, neopentyl glycol, and hexylene glycol with an alkylene oxide;
the polyether polyol II has a typical characteristic viscosity of 150-250 mPas, a hydroxyl value of 160-300mg KOH/g and an average functionality of 1-2.
As a further improvement of the embodiment of the invention, the polyether polyol III is prepared by taking at least one of glycerol and trimethylolpropane as an initiator and carrying out addition reaction with alkylene oxide;
the polyether polyol III has a typical characteristic viscosity of 400-800 mPas, a hydroxyl value of 250-500mg KOH/g and an average functionality of 2-3.
As a further improvement of the embodiment of the invention, the polyether polyol IV is prepared by addition reaction of at least one of toluene diamine and pentaerythritol and an alkylene oxide, and has a typical characteristic viscosity of 1000-2000mPa & s, a hydroxyl value of 350-500mg KOH/g and an average functionality of 3-4;
the alkylene oxide comprises at least one of ethylene oxide, propylene oxide and butylene oxide.
As a further improvement of the embodiment of the present invention, the raw material composition of the polyurethane foamed rigid plastic includes the polyol composition as described above;
the raw material composition of the polyurethane foaming rigid plastic comprises the following components in parts by weight:
Figure BDA0001706137130000061
as a further improvement of an embodiment of the present invention, the blowing agent selected is any one selected from the group consisting of cyclopentane, isopentane, pentafluoropropene (245fa), 1-chloro-3, 3, 3-trifluoropropene (LBA), and hexafluorobutene (FEA-1100).
As a further refinement of an embodiment of the present invention, the isocyanate is polymethylene polyphenyl isocyanate;
the isocyanate content is 30.5-32.0%, and the viscosity is 150-250 mPas.
The embodiment of the invention also discloses a method for preparing the polyurethane foaming rigid plastic,
s1, mixing the polyol I, the polyether polyol, the catalyst and the surfactant according to the proportion at the temperature of 20-30 ℃ and under the pressure of 1-2MPa to prepare a first mixture;
s2, mixing the foaming agent with the first mixture prepared in the S1 according to a preset proportion at the temperature of 20-30 ℃ and under the pressure of 2-3MPa to prepare a second mixture;
s3, mixing the preheated isocyanate at the temperature of 20-30 ℃ with the second mixture obtained in the step S2, injecting the mixture into a preheated 40-45 ℃ mould at the pressure of 120-140MPa for foaming and curing to obtain polyurethane rigid foam;
and S4, cooling and demolding the foamed polyurethane rigid foam, and performing performance test.
As a further refinement of an embodiment of the present invention, the method further comprises preparing polyol I in the polyol composition, specifically comprising the steps of:
adding amine into a reaction kettle, raising the reaction temperature to 70-80 ℃, then dropwise adding cardanol glycidyl ether, after dropwise adding is completed within 0.5-1 hour, after heat preservation reaction is performed for 1-2 hours, replacing gas in the reaction kettle with nitrogen, then adding a catalyst and at least one of ethylene oxide, propylene oxide and butylene oxide, raising the reaction temperature to 120-150 ℃, preserving heat for 4-8 hours, cooling and discharging.
In another aspect, another embodiment of the present invention discloses the use of the rigid polyurethane foam or the rigid polyurethane foam prepared by the method in an interior thermal insulation material for home appliances, and in a specific implementation, the rigid polyurethane foam composite disclosed by the present invention can be used for the interior thermal insulation of home appliances such as refrigerators, freezers, solar energy, gas water heaters, and disinfection cabinets.
Example 1
The embodiment discloses a polyhydric alcohol I and a preparation method thereof, wherein the polyhydric alcohol I is prepared by reacting cardanol glycidyl ether, diethanolamine and olefin oxide, and the preparation method specifically comprises the following steps:
adding 120g of diethanolamine into a reaction kettle, raising the temperature to 70 ℃, then dropwise adding 360g of cardanol glycidyl ether, after finishing dropwise adding and carrying out heat preservation reaction for 3 hours, replacing gas in the reaction kettle with nitrogen, then adding 2000g of butylene oxide, adding 2g of KOH catalyst, raising the temperature to 130 ℃, carrying out heat preservation reaction for 5 hours, then cooling to 50 ℃ and discharging;
the polyol I prepared has a typical characteristic viscosity of 1600-2100 mPa.s and a hydroxyl value of 320-360mg KOH/g.
In order to verify the compatibility of the polyol and cyclopentane, 100g of the polyol is added into a glass bottle at room temperature of 20 ℃, 20g of cyclopentane is added, high-speed stirring is carried out, large bubbles are formed after standing, the large bubbles disappear slowly, and no layering phenomenon appears after sealing and standing overnight, which indicates that the polyol and cyclopentane have good compatibility.
Example 2
The embodiment discloses a polyhydric alcohol I and a preparation method thereof, wherein the polyhydric alcohol I is prepared by reacting cardanol glycidyl ether, butylamine and olefin oxide, and the preparation method specifically comprises the following steps:
adding 80g of butylamine into a reaction kettle, raising the temperature to 80 ℃, then dropwise adding 800g of cardanol glycidyl ether, after the dropwise adding is finished, carrying out heat preservation reaction for 2 hours, replacing gas in the reaction kettle with nitrogen, then adding 800g of ethylene oxide, adding 1g of KOH catalyst, heating to 130 ℃, carrying out heat preservation reaction for 6 hours, then cooling to 40 ℃, and discharging.
The typical characteristic viscosity of the prepared polyol I is 1500-1800 mPa.s, and the hydroxyl value is 300-340mg KOH/g.
In order to verify the compatibility of the polyol and cyclopentane, 100g of the polyol is added into a glass bottle at room temperature of 25 ℃, 20g of cyclopentane is added, high-speed stirring is carried out, large bubbles are formed after standing, the large bubbles disappear slowly, and no layering phenomenon appears after sealing and standing overnight, which indicates that the polyol and cyclopentane have good compatibility.
Example 3
The embodiment discloses a polyhydric alcohol I and a preparation method thereof, wherein the polyhydric alcohol I is prepared by reacting cardanol glycidyl ether, dodecylamine and olefin oxide, and the preparation method specifically comprises the following steps:
adding 200g of dodecylamine into a reaction kettle, raising the temperature to 75 ℃, then dropwise adding 800g of cardanol glycidyl ether, after finishing dropwise adding and carrying out heat preservation reaction for 3 hours, replacing gas in the reaction kettle with nitrogen, then adding 800g of ethylene oxide, adding 2g of KOH catalyst, raising the temperature to 130 ℃, carrying out heat preservation reaction for 6 hours, then cooling to 40 ℃ and discharging.
The typical characteristic viscosity of the prepared polyol I is 1700-1900 mPas, and the hydroxyl value is 310-340mg KOH/g.
In order to verify the compatibility of the polyol and cyclopentane, 100g of the polyol is added into a glass bottle at room temperature of 25 ℃, 20g of cyclopentane is added, high-speed stirring is carried out, large bubbles are formed after standing, the large bubbles disappear slowly, and no layering phenomenon appears after sealing and standing overnight, which indicates that the polyol and cyclopentane have good compatibility.
Example 4
The embodiment discloses a polyhydric alcohol I and a preparation method thereof, wherein the polyhydric alcohol I is prepared by reacting cardanol glycidyl ether, diethylenetriamine and olefin oxide, and the preparation method specifically comprises the following steps:
adding 100g of diethylenetriamine in a reaction kettle, raising the temperature to 80 ℃, then dropwise adding 800g of cardanol glycidyl ether, after finishing dropwise adding and carrying out heat preservation reaction for 3 hours, replacing gas in the reaction kettle with nitrogen, then adding 600g of ethylene oxide, adding 1g of KOH catalyst, raising the temperature to 130 ℃, carrying out heat preservation reaction for 8 hours, then cooling to 40 ℃ and discharging. The polyol I prepared has a typical characteristic viscosity of 2500-.
In order to verify the compatibility of the polyol and cyclopentane, 100g of the polyol is added into a glass bottle at room temperature of 25 ℃, 20g of cyclopentane is added, high-speed stirring is carried out, large bubbles are formed after standing, the large bubbles disappear slowly, and no layering phenomenon appears after sealing and standing overnight, which indicates that the polyol and cyclopentane have good compatibility.
Example 5
The embodiment discloses a polyhydric alcohol I and a preparation method thereof, wherein the polyhydric alcohol I is prepared by reacting cardanol glycidyl ether, m-phenylenediamine and olefin oxide, and the preparation method specifically comprises the following steps:
adding 100g of m-phenylenediamine into a reaction kettle, raising the temperature to 75 ℃, then dropwise adding 900g of cardanol glycidyl ether, after finishing dropwise adding, carrying out heat preservation reaction for 2.5 hours, replacing gas in the reaction kettle with nitrogen, then adding 800g of ethylene oxide, adding 1-2g of KOH catalyst, raising the temperature to 150 ℃, carrying out heat preservation reaction for 8 hours, then cooling to 45 ℃ and discharging. The polyol prepared has typical characteristic viscosity of 2200-2500 mPa.s and hydroxyl value of 360-390mg KOH/g.
In order to verify the compatibility of the polyol and cyclopentane, 100g of the polyol is added into a glass bottle at room temperature of 25 ℃, 20g of cyclopentane is added, high-speed stirring is carried out, large bubbles are formed after standing, the large bubbles disappear slowly, and no layering phenomenon appears after sealing and standing overnight, which indicates that the polyol and cyclopentane have good compatibility.
Example 6
The embodiment discloses a polyol I and a preparation method thereof, wherein the polyol I is prepared by reacting cardanol glycidyl ether, polyetheramine and olefin oxide, and the preparation method specifically comprises the following steps:
230g of commercial polyetheramine D230 is added into a reaction kettle, the temperature is raised to 80 ℃, 900g of cardanol glycidyl ether is added dropwise, after the completion of dropwise addition and heat preservation reaction is carried out for 3 hours, gas in the reaction kettle is replaced by nitrogen, 5000g of ethylene oxide is added, 1.5g of KOH catalyst is added, the temperature is raised to 150 ℃, after the heat preservation reaction is carried out for 8 hours, the temperature is lowered to 50 ℃ and discharging is carried out. The polyol prepared has an intrinsic viscosity of 2500-.
In order to verify the compatibility of the polyol and cyclopentane, 100g of the polyol is added into a glass bottle at room temperature of 25 ℃, 20g of cyclopentane is added, high-speed stirring is carried out, large bubbles are formed after standing, the large bubbles disappear slowly, and no layering phenomenon appears after sealing and standing overnight, which indicates that the polyol and cyclopentane have good compatibility.
The polyol prepared in example 1, example 2, example 4 and example 6 is mixed with polyether polyol I, polyether polyol II, polyether polyol III and polyether polyol IV respectively to prepare a polyol composition, and then the above method is adopted to further prepare the polyurethane foamed rigid plastic, in detail, see examples 7-14, the composition and weight parts of the specifically selected other raw materials are shown in the following table, and compared with comparative example 1 and comparative example 2 in the prior art:
Figure BDA0001706137130000101
Figure BDA0001706137130000111
the polyurethane rigid foam plastics prepared in the above examples 7 to 14 and comparative examples 1 and 2 were subjected to performance tests of compressive strength, average density, thermal conductivity, low-temperature stability, closed cell ratio and pore size; and testing the compatibility of the polyol composition for preparing the polyurethane rigid foam plastic and a foaming agent; the experimental result shows that compared with the prior art, the polyol prepared by taking cardanol glycidyl ether as a starting point in the embodiment of the invention improves the compatibility with a foaming agent cyclopentane by introducing a structure with long-chain alkane, has a smaller pore size and a higher closed-cell rate, and has no adverse effect on mechanical properties such as compression strength, low-temperature stability and the like.
Specifically, the embodiment of the invention has the following beneficial effects:
1) the polyol I provided by the embodiment of the invention is prepared by taking a cardanol derivative as an initiator and reacting with other substances to prepare the polyol, and due to the hydrocarbon structure with 15 carbon atoms on the side chain, the compatibility of the polyol I and alkane foaming agents such as cyclopentane and the like can be remarkably improved, so that the compatibility of the polyol composition and the foaming agents is improved, the storage stability of the polyol and the foaming agents is improved, and the layering caused by long-time storage is avoided;
2) the reaction raw materials prepared by taking cardanol derivatives as the initiator of the polyhydric alcohol I provided by the embodiment of the invention are wide in source, easy to obtain and low in cost;
3) according to the raw material composition containing the polyurethane foamed rigid plastic provided by the embodiment of the invention, the polyol composition in the composition has good compatibility with cyclopentane due to the longer alkyl chain, so that the viscosity of the polyurethane foamed rigid plastic can be reduced, the fluidity is improved, and the polyurethane foamed rigid plastic can fill the whole die cavity conveniently;
4) the polyurethane rigid foam prepared by the polyol has the advantages that the foam pore size is reduced, and the radiation heat dissipation is reduced; the number of the foam holes in unit area is increased, the foam density difference is reduced, the closed pore rate is high, the comprehensive heat conductivity coefficient is reduced, and the compressive strength and the dimensional stability are improved.
It should be understood that although the present description refers to embodiments, not every embodiment contains only a single technical solution, and such description is for clarity only, and those skilled in the art should make the description as a whole, and the technical solutions in the embodiments can also be combined appropriately to form other embodiments understood by those skilled in the art.
The above-listed detailed description is only a specific description of a possible embodiment of the present invention and is not intended to limit the scope of the present invention, and equivalent embodiments or modifications made without departing from the technical spirit of the present invention are included in the scope of the present invention.

Claims (5)

1. The polyol composition is characterized by comprising a plurality of polyether polyols and a polyol I, and the polyol composition comprises the following raw materials in parts by weight:
15-35 parts of polyol I
20-30 parts of polyether glycol II
20-30 parts of polyether polyol III
10-30 parts of polyether polyol IV;
the polyhydric alcohol I is prepared by taking a reactant generated by the reaction of cardanol glycidyl ether and amine as an initiator and carrying out addition reaction with olefin oxide;
the typical characteristic viscosity of the polyol I is 1500-3000mPa ∙ s, and the hydroxyl value is 300-450mg KOH/g;
adding the amine into a reaction kettle, raising the reaction temperature to 70-80 ℃, then dropwise adding cardanol glycidyl ether, after dropwise adding is completed within 0.5-1 hour, after heat preservation reaction is carried out for 1-2 hours, replacing gas in the reaction kettle with nitrogen, then adding a catalyst and the oxyalkylene comprising at least one of ethylene oxide, propylene oxide and butylene oxide, raising the reaction temperature to 120-150 ℃, after heat preservation is carried out for 4-8 hours, cooling and discharging to obtain the polyhydric alcohol I;
the amine is selected from at least one of ethanolamine, diethanolamine, methylamine, ethylamine, monoamine containing 3-12 carbon chains, aniline and ethylenediamine, diamine containing 3-12 carbon chains, diethylenetriamine, triethylene tetramine, 4' -diaminodiphenylmethane, m-phenylenediamine, diaminodicyclohexylmethane, isophorone diamine, aminoethyl piperazine, 1, 3-cyclohexanediamine, xylylenediamine and polyether amine;
the polyether polyol II is prepared by taking at least one of ethylene glycol, propylene glycol, diethylene glycol, triethylene glycol, neopentyl glycol and hexanediol as a starter and carrying out addition reaction with alkylene oxide; the polyether polyol II has a typical characteristic viscosity of 150-250mPa ∙ s, a hydroxyl value of 160-300mg KOH/g and an average functionality of 1-2;
the polyether polyol III is prepared by taking at least one of glycerol and trimethylolpropane as an initiator and carrying out addition reaction with alkylene oxide; the polyether polyol III has a typical characteristic viscosity of 400-800mPa ∙ s, a hydroxyl value of 250-500mg KOH/g and an average functionality of 2-3;
the polyether polyol IV is prepared by at least one of toluene diamine and pentaerythritol and an alkylene oxide through addition reaction; the polyether polyol IV has a typical characteristic viscosity of 1000-2000mPa ∙ s, a hydroxyl value of 350-500mg KOH/g and an average functionality of 3-4.
2. A polyurethane foamed rigid plastic, characterized in that a raw material composition of the polyurethane foamed rigid plastic comprises the polyol composition of claim 1;
the raw material composition of the polyurethane foaming rigid plastic comprises the following components in parts by weight:
polyol composition: 100 portions of
Surfactant (b): 1-2 parts of
Foaming agent: 10-30 parts of
Isocyanate: 140 parts of.
3. The polyurethane foamed rigid plastic according to claim 2, wherein the blowing agent is selected from any one of cyclopentane, isopentane, pentafluoropropene, 1-chloro-3, 3, 3-trifluoropropene, and hexafluorobutene.
4. The polyurethane foamed rigid plastic according to claim 3, wherein the isocyanate is polymethylene polyphenyl isocyanate;
the isocyanate content is 30.5-32.0%, and the viscosity is 150-250mPa ∙ s.
5. A process for preparing a polyurethane foamed rigid plastic comprising the polyol composition of claim 1,
s1, mixing the polyol I, the polyether polyol, the catalyst and the surfactant according to the proportion at the temperature of 20-30 ℃ and under the pressure of 1-2MPa to prepare a first mixture;
s2, mixing the foaming agent with the first mixture prepared in the S1 according to a preset proportion at the temperature of 20-30 ℃ and under the pressure of 2-3MPa to prepare a second mixture;
s3, mixing the preheated isocyanate at the temperature of 20-30 ℃ with the second mixture obtained in the step S2, injecting the mixture into a preheated 40-45 ℃ mould at the pressure of 120-140MPa for foaming and curing to obtain polyurethane rigid foam;
and S4, cooling and demolding the foamed polyurethane rigid foam, and performing performance test.
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