CN117003980A - Polyol composition, polyurethane hard foam and preparation method thereof - Google Patents

Polyol composition, polyurethane hard foam and preparation method thereof Download PDF

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Publication number
CN117003980A
CN117003980A CN202311032844.XA CN202311032844A CN117003980A CN 117003980 A CN117003980 A CN 117003980A CN 202311032844 A CN202311032844 A CN 202311032844A CN 117003980 A CN117003980 A CN 117003980A
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China
Prior art keywords
polyol
polyether polyol
composite
low
polyether
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CN202311032844.XA
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Chinese (zh)
Inventor
邢益辉
吴一鸣
张蒙蒙
王金祥
芮强
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Nanjing Hongbaoli Polyurethane Co ltd
Hongbaoli Group Co ltd
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Nanjing Hongbaoli Polyurethane Co ltd
Hongbaoli Group Co ltd
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Application filed by Nanjing Hongbaoli Polyurethane Co ltd, Hongbaoli Group Co ltd filed Critical Nanjing Hongbaoli Polyurethane Co ltd
Priority to CN202311032844.XA priority Critical patent/CN117003980A/en
Publication of CN117003980A publication Critical patent/CN117003980A/en
Pending legal-status Critical Current

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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
    • C08G18/4804—Two or more polyethers of different physical or chemical nature
    • C08G18/482—Mixtures of polyethers containing at least one polyether containing nitrogen
    • 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
    • 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
    • C08G18/4833—Polyethers containing oxyethylene units
    • C08G18/4837—Polyethers containing oxyethylene units and other oxyalkylene units
    • 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
    • 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
    • C08G18/5027—Polyethers having heteroatoms other than oxygen having nitrogen containing primary and/or secondary amino groups directly linked to carbocyclic 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
    • C08G18/40—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
    • C08G18/5036—Polyethers having heteroatoms other than oxygen having nitrogen containing -N-C=O groups
    • C08G18/5039—Polyethers having heteroatoms other than oxygen having nitrogen containing -N-C=O groups containing amide 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
    • 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
    • C08J9/143—Halogen containing compounds
    • C08J9/144—Halogen containing compounds containing carbon, halogen and hydrogen only
    • C08J9/146—Halogen containing compounds containing carbon, halogen and hydrogen only only fluorine as halogen atoms
    • 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
    • C08J2203/00—Foams characterized by the expanding agent
    • C08J2203/16—Unsaturated hydrocarbons
    • C08J2203/162—Halogenated unsaturated hydrocarbons, e.g. H2C=CF2
    • 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
    • C08J2203/18—Binary blends of expanding agents
    • C08J2203/182—Binary blends of expanding agents of physical blowing agents, e.g. acetone and butane
    • 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
    • C08J2205/00—Foams characterised by their properties
    • C08J2205/10—Rigid foams
    • 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 polyol composition, a polyurethane hard foam and a preparation method thereof. The polyol composition contains a complex polyol, a catalyst, a foam stabilizer and water; the composite polyol contains at least one polyether polyol which is polyether polyol I and hydroxyl equivalent weight N Ⅰ > 350, and 2 < average functionality f Ⅰ < 6; the average hydroxyl value of the composite polyol is 330-520 mgKOH/g, and the average functionality is more than 3; at least 15g of a physical blowing agent component containing at least 50 mole percent of low boiling point materials having a boiling point of < 9 ℃ is soluble per 100g of polyol composition at room temperature. The invention can realize the equivalent transformation process without the transformation process by matching with the specific polyol compositionThe technical effect is that the operation flow is simplified. The polyurethane low-boiling foaming technology can be used in the fields of refrigerators, freezers and the like, and can obtain the rigid polyurethane foam with low density, low aperture ratio and excellent comprehensive performance.

Description

Polyol composition, polyurethane hard foam and preparation method thereof
Technical Field
The invention belongs to the technical field of polyurethane, and particularly relates to a polyol composition, a polyurethane hard foam and a preparation method thereof.
Background
Physical blowing agents are one of the important raw materials for preparing rigid polyurethane foams. The foaming agent can be classified into a gaseous foaming agent and a liquid foaming agent according to the boiling point of the foaming agent, wherein the gaseous foaming agent has the advantage of improving the dimensional stability of the low-density foam and is widely used. However, the boiling point of the gaseous blowing agent is lower than normal temperature, and the reaction for preparing polyurethane is an exothermic process, and the gaseous blowing agent escapes from the material system in the early stage of the reaction. Therefore, gaseous blowing agents are often used in applications where the reaction is rapid, such as spray polyurethane rigid foams. Meanwhile, since the premature escape of the foaming agent also causes the problem of an increase in the open cell content, as disclosed in U.S. patent application No. 20200317931A1, a two-component polyurethane or polyisocyanurate spray foam composition containing a hydrohaloolefin foaming agent, which uses low boiling trans-1, 3-tetrafluoropropene as the main foaming agent, the open cell content of the resulting rigid polyurethane foam is 15%.
And the standard requirement of the rigid polyurethane foam plastic for the refrigerator and the freezer is that the closure rate is more than or equal to 90 percent. However, when the polyurethane material of the low boiling point gaseous foaming agent system is used for filling the cavities of the refrigerator, the freezer and other cases, a relatively slow reaction speed is required due to a certain length of flowing distance in the case, which obviously increases the risk that the gaseous foaming agent escapes from the material system, and further reduces the surface performance and the closed porosity. In particular, when it is desired to prepare a mixture having a density of 30kg/m or less 3 When the polyurethane is hard-foamed, the total consumption of the foaming agent needs to be increased, but the conventional material system has limited capacity for packaging the gaseous foaming agent, so that the total quantity of the foaming agent is seriously lost, and the aperture ratio is increased. The increase of the aperture ratio brings about the problems of increased heat conductivity, poor adhesion between the foam and the substrate, and the like. Such as CN101014680ADisclosed is a composition containing fluorine-substituted olefin, wherein the polyol foam prepared by using trans-1, 3-tetrafluoropropene as a physical foaming agent has a high thermal conductivity coefficient of 0.0211W/(m.K).
In general, for blowing agent systems containing low boilers, depressurization accelerates the escape loss of the low boilers, and therefore, measures for pressurization are taken during injection to reduce vaporization of the low boilers. In the pressurizing process, the higher the pressure value is, the better the effect of reducing the escape of low-boiling-point substances is, but the larger pressure is not beneficial to the flow of materials, and the incomplete filling is caused. Therefore, a pressure reducing step is usually added after the pressurization, which requires precise control of pressure change in the whole filling process, and the operation is complicated.
Therefore, polyurethane products containing low boiling point gaseous blowing agents have limited application in the refrigerator and freezer fields.
Disclosure of Invention
The invention aims to: the invention aims at overcoming the defects of the prior art and provides a polyol composition, a polyurethane hard foam and a preparation method thereof. The invention can realize the technical effect equivalent to the transformation process without the transformation process by matching with the specific polyol composition, and simplifies the operation flow. The polyurethane low-boiling foaming technology provided by the invention can be used in the fields of refrigerators, freezers and the like, and can obtain the rigid polyurethane foam with low density, low aperture ratio and excellent comprehensive performance.
The technical scheme is as follows: the aim of the invention is achieved by the following technical scheme:
the invention provides a polyol composition, which comprises a composite polyol, a catalyst, a foam stabilizer and water, wherein the composite polyol comprises at least one polyether polyol, the polyether polyol is polyether polyol I, and the hydroxyl equivalent N of the polyether polyol I Ⅰ > 350, and 2 < average functionality f Ⅰ The average hydroxyl value of the composite polyol is 330-520 mgKOH/g, and the average functionality is more than 3;
and at least 15g of a physical blowing agent component per 100g of the polyol composition is soluble at room temperature, said physical blowing agent component comprising a molar ratio of at least 50% of low boilers having a boiling point of < 9 ℃.
The polyol composition of the present invention is a mixture capable of reacting with isocyanate to form polyurethane, and generally contains a composite polyol, a catalyst, a foam stabilizer, water, and the like. The physical blowing agent may be added to the polyol composition in advance or may be added at the time of use. Thus, polyol compositions generally comprise two types, one containing a physical blowing agent and consisting essentially of a composite polyol, a catalyst, a foam stabilizer, water, a physical blowing agent and other adjuvants, and the other containing no physical blowing agent and consisting essentially of a composite polyol, a catalyst, a foam stabilizer, water and other adjuvants. For polyol compositions that do not contain a physical blowing agent, it is generally meant that the physical blowing agent is not contained during storage and shipping, and when it is desired to prepare a rigid polyurethane foam, the physical blowing agent is premixed with the polyol composition to a premix and then mixed with the isocyanate to react. Wherein the composite polyol generally comprises at least one of a polyether polyol, a polyester polyol, a bio-based polyol. The other auxiliary agent can be selected from compatilizer, flame retardant, fluoroether compound, perfluoroalkane and the like.
Whether the polyol composition contains a physical blowing agent during the production, storage, and transportation stages, etc., the physical blowing agent enters the polyol composition and cooperates with each other during the final stage of the preparation of the rigid polyurethane foam. Therefore, the specific composition of the polyol composition is affected by the type of blowing agent and needs to be matched with the characteristics of the physical blowing agent used in order to give a compromise between a good foaming process and excellent polyurethane rigid foam properties. In particular, when the physical blowing agent component contains low boiling substances, the solubility of the physical blowing agent component in the polyol composition determines the residence time and nucleation effect of the low boiling substances in the interior of the material at the initial stage of the reaction, thereby affecting the shape and distribution of the cells. The inventors have found that, since the temperature of the polyol composition is generally higher than the boiling point of the low boiling point substance, when the low boiling point substance having a boiling point of < 9 ℃ is contained in the physical blowing agent component, the low boiling point substance is extremely liable to escape from the material system, resulting in an increase in the open cell content. When the molar ratio of the low-boiling-point substance is higher, the larger the escape effect is, the larger the aperture ratio is. It was found that when the polyether polyol I was contained in the composite polyol and the average hydroxyl value of the composite polyol was 332 to 417mgKOH/g and the average functionality was > 3, it was advantageous to increase the solubility of the physical blowing agent to 17 to 45g/100g. When the high-solubility polyol composition is mixed with low-boiling substances, the closed pore ratio of the hard foam can be effectively improved. Particularly, when the boiling point of the low-boiling-point substances is less than or equal to 0 ℃ and/or the mole ratio of the low-boiling-point substances in the physical foaming agent is more than or equal to 50%, the compound polyol with the average hydroxyl value of 332-417 mgKOH/g and the average functionality of 3.4-5.7 is used, and at least 15g (15-35 g) of the low-boiling-point substances can be dissolved in every 100g of the polyol composition under the room temperature condition, the escape loss of the physical foaming agent can be obviously reduced, and the closed cell rate of the polyurethane hard foam can be improved.
The polyether polyol I is prepared by ring-opening polymerization of an active hydrogen-containing initiator component I and an alkylene oxide component I, wherein the initiator component I can be selected from common initiators in the field, such as sucrose, glycerol, sorbitol, dihydric alcohols, polyamines and the like. The alkylene oxide component I may be selected from epoxides commonly used in the art, such as propylene oxide and/or ethylene oxide, and the like. The polyether polyol I is further preferably 359 < hydroxyl equivalent weight N Ⅰ Less than 1300, and an average functionality f of 2.3.ltoreq. Ⅰ Less than or equal to 5.5; the mass ratio M of the polyether polyol I in the composite polyol based on the total weight of the composite polyol 1 8.0 to 43wt%.
The physical foaming agent component of the invention can be composed of low-boiling-point substances only, and can also contain low-boiling-point substances and non-low-boiling-point substances at the same time. The low-boiling-point substances can be selected from fluoroolefins and/or alkanes. Wherein, the fluoroolefins may be selected from 3, 3-trifluoropropene, trans-1, 3-tetrafluoropropene, 2, 3-tetrafluoropropene 1, 3-pentafluoropropene, 1,2, 3-pentafluoropropene, 1,2, 3-pentafluoropropene, 1, 3-pentafluoropropene 1, 3-pentafluoropropene, 1,2, 3-pentafluoropropene 1,2, 3-pentafluoropropene, 1, 3-pentafluoropropene. The alkane may be selected from n-butane and/or isobutane. As one scheme, the boiling point of the low-boiling-point substance is less than 0 ℃, the boiling point of the low-boiling-point substance is less than-12 ℃ in the other scheme, and the boiling point of the low-boiling-point substance in the other scheme is between-15 ℃ and-30 ℃.
The low-boiling-point substances are preferably selected from fluoroolefins in combination with environmental protection.
The non-low boiling substance, i.e. a compound having a boiling point higher than that of the low boiling substance, may be selected from at least one of pentane, such as cyclopentane, n-pentane, isopentane, neopentane, cis-1, 4-hexafluoro-2-butene or 1-chloro-3, 3-trifluoropropene.
When fluoroolefins and/or butanes are used as the low boiling point substance, in order to increase the solubility of the low boiling point substance in the polyol composition, improve the inclusion of the material in the polyurethane foaming reaction process for gas-phase fluoroolefins and butanes, reduce the number of surface cells, and the composite polyol preferably uses polyether polyol with strong inclusion, wherein the polyether polyol can be polyether polyol I. In addition, other polyether polyols having a similar effect, such as at least one of polyether polyol II or polyether polyol III, are also possible.
An alternative embodiment of the invention is: the polyether polyol I can be replaced by polyether polyol II, the alkylene oxide component of the polyether polyol II contains epoxide of C4-C6 alkene, and the epoxide of the C4-C6 alkene is at least one of butylene oxide, pentene oxide, hexene oxide, cyclopentene oxide or cyclohexene oxide.
Specifically, the polyether polyol II is prepared by ring-opening polymerization of an active hydrogen-containing initiator component II and an alkylene oxide component II, wherein the initiator component II is at least one of conventional initiators such as sucrose, glycerol, sorbitol, ethylene glycol and polyamine. The alkylene oxide component II contains epoxide of C4-C6 alkene, preferably the alkylene oxide component II is at least one of butylene oxide, pentylene oxide, hexylene oxide, cyclopentene oxide or cyclohexene oxide, wherein the alkylene oxide component II is epoxide and propylene oxide of C4-C6 alkene, or epoxide and ethylene oxide and propylene oxide of C4-C6 alkene. The butylene oxide can be selected from at least one of 1, 2-epoxybutane or 2, 3-epoxybutane or methyl epoxypropane; the oxidized pentene may be at least one selected from 1, 2-pentaoxide, 2, 3-pentaoxide, 1, 2-epoxy-3-methylbutane, 2, 3-epoxy-2-methylbutane or 1, 2-epoxy-2-methylbutane; the hexene oxide may be selected from at least one of 1, 2-epoxyhexane, 2-methyl-2-propyl-oxirane, or 2, 3-dimethyl-2, 3-epoxybutane and isomers thereof.
The epoxide component of the C4-C6-olefin is preferably present in a proportion M, based on the mass of the polyether polyol II 0 > 4wt%. Preferably M 0 4 to 51wt%. Average functionality f of the polyether polyol II Ⅱ > 2.5 hydroxyl equivalent N Ⅱ > 70. Further preferably, the average functionality f is 2.6.ltoreq. Ⅱ Less than or equal to 6.5, 73 is less than hydroxyl equivalent N Ⅱ < 340. Wherein, the epoxide component of the C4-C6 olefin refers to the part of the epoxide of the C4-C6 olefin bonded in the molecular structure of the polyether polyol after ring opening, and the hydroxyl equivalent is the value of dividing the molecular weight of the polyether polyol by the average functionality. The mass ratio M of the polyether polyol II in the composite polyol based on the total weight of the composite polyol 2 9 to 100 weight percent.
Another alternative embodiment of the invention is: the polyether polyol I can be replaced by polyether polyol III, the polyether polyol III is a bio-based polyol with molecular weight less than or equal to 3000, and can be selected from castor oil, castor oil derivative polyol, soybean oil polyol, palm oil polyol or cashew nut shell oil polyol, preferably the hydroxyl equivalent weight of the polyether polyol III is less than or equal to 250N Ⅲ And 863 is less than or equal to. The mass ratio M of the polyether polyol III in the composite polyol based on the total weight of the composite polyol 3 8 to 41 weight percent.
Since the polyol composition and its dissolved physical blowing agent component are eventually mixed with the isocyanate component, the inclusion effect of the isocyanate component on the polyol molecular segments further affects the solubility of the physical blowing agent component in the isocyanate component and thus also affects the formation and distribution of cells and ultimately affects the properties of the polyurethane rigid foam. In order to further optimize the uniformity of cell distribution in order to increase the inclusion of the isocyanate component in the physical blowing agent component, in particular the low boilers, it is preferred according to the invention that the composite polyol contains aromatic rings which are introduced into the polyether polyol IV and/or the polyester polyol V by aromatic ring compounds and/or alicyclic rings which are introduced into the polyether polyol IV and/or the polyester polyol V by alicyclic ring compounds.
The polyether polyol IV is prepared by ring-opening polymerization of at least one initiator component which is aromatic ring compound and/or alicyclic ring compound and alkylene oxide under the action of a catalyst. The polyester polyol V is formed by polycondensation of at least one carboxylic acid component or anhydride component of aromatic ring compound and/or alicyclic compound and small molecule polyol (including dihydric alcohol), wherein the small molecule polyol is commonly used in the polyester field, and ethylene glycol, propylene glycol, butanediol, diethylene glycol, dipropylene glycol and the like can be selected. Wherein, the total proportion Q of the initiator component, the carboxylic acid component and the anhydride component in the composite polyol Total (S) The sum of the masses of aromatic and alicyclic compounds used in the preparation of the polyether polyol IV and/or the polyester polyol V is taken as a basis and the ratio M 4 More than or equal to 20 weight percent, and even more preferably, the weight percent is more than or equal to 20 weight percent and less than or equal to M 4 Less than or equal to 70 weight percent. Wherein the total share Q Total (S) I.e., the sum of the masses of the starter component, carboxylic acid component and anhydride component used for all kinds of polyether polyols and polyester polyols in the composite polyol.
For ease of understanding, an example will now be described, in which the composite polyol consists of 40g of sucrose polyether polyol (30 wt% sucrose based on the mass of the sucrose polyether polyol), 30g of glycerol polyether polyol (10 wt% glycerol based on the mass of the glycerol polyether polyol) and 30g of phenylenediamine polyether polyol (25 wt% phenylenediamine based on the mass of the phenylenediamine polyether polyol), then Q Total (S) ＝40×30％+30×10％+30×25％＝22.5g，M 4 ＝(30×25％)/Q Total (S) ＝33.3wt%. Further preferably, the hydroxyl equivalent weight of the polyether polyol IV is 90 to 160, and the hydroxyl equivalent weight of the polyester polyol V is 125 to 185.
The aromatic ring compound is selected from at least one of aromatic polyamine (such as toluenediamine, diaminodiphenylmethane, phenylenediamine, 2-bis (4-aminophenyl) propane, etc.), aromatic polyol (such as bisphenol A), aromatic amide (such as phthalic acid amide, N-bis (2-hydroxypropyl) phthalic acid amide, N-bis (2-hydroxyethyl) phthalic acid amide, etc.), mannich base containing benzene ring (such as 2- (N, N-bis (2-hydroxyethyl) aminomethyl) phenol), vegetable oil containing benzene ring (such as cashew oil), aromatic anhydride (including benzoic anhydride, diphenyl anhydride, phthalic anhydride, halogenated phthalic anhydride), aromatic dicarboxylic acid (terephthalic acid, phthalic acid, isophthalic acid).
The alicyclic compound is at least one selected from 2-aminocyclohexanol, 2-aminocyclopentanol, 1, 5-decalin diol or hexahydrophthalic anhydride. The aromatic ring compound and the alicyclic compound may further have release properties.
In order to increase the viscoelasticity of the cell walls and prevent cell breakage, when the composite polyol contains at least one of polyether polyol I, polyether polyol II, polyether polyol III, polyether polyol IV or polyester polyol V, or other substances which promote low-boiling-point substance solubility, it is preferable that the polyol composition further contains polyether polyol VI having an equivalent weight of < 250 and an average functionality f of 3.ltoreq. Ⅵ < 6.5. The polyether polyol vi is prepared by ring-opening polymerization of an active hydrogen-containing starter component vi selected from the group consisting of common starter in the art, such as sucrose, glycerin, sorbitol, glycols, polyamines, and the like, and an alkylene oxide component vi. The alkylene oxide component VI may be selected from epoxides commonly used in the art, such as propylene oxide and/or ethylene oxide, and the like.
In order to achieve better synergistic effect and give consideration to the solubility and the cell strength of the foaming agent, the total mass M of polyether polyol I, polyether polyol II, polyether polyol III, polyether polyol IV and polyester polyol V in the composite polyol is preferably selected Total (S) The mass ratio of the polyether polyol VI to the polyether polyol VI is (0.1-3.1): 1.
further preferred embodiments are: the polyether polyol I is used in combination with at least one of polyether polyol VI, polyether polyol IV or polyester polyol V; yet another alternative embodiment is: the polyether polyol II is used in combination with at least one of polyether polyol VI, polyether polyol IV or polyester polyol V; yet another alternative embodiment is: the polyether polyol III is used in combination with at least one of the polyether polyols VI, IV or V.
In order to achieve the comprehensive physical and chemical properties of the polyurethane hard foam, the polyol composition preferably comprises the following substances in percentage by mass: 88 to 94 weight percent of composite polyol, 2.0 to 5.9 weight percent of catalyst, 1.9 to 4.6 weight percent of foam stabilizer and 0.8 to 2.9 weight percent of water.
The invention also provides a polyurethane hard foam, which is prepared by reacting the polyol composition, a physical foaming agent component and an isocyanate component, wherein the physical foaming agent component contains low-boiling-point substances with the mol ratio of more than or equal to 50%, and the boiling point of the low-boiling-point substances is less than 9 ℃; the closed pore rate of the hard foam is more than or equal to 94%.
The polyol composition can reduce the escape loss of low-boiling-point substances, further improve the closed cell rate of hard foam and obtain better foam performance, and can be suitable for a foaming agent system with higher low-boiling-point substance content. In order to obtain polyurethane hard foam with low density and excellent performance, the polyurethane hard foam is prepared from the following components in parts by weight, wherein the polyol composition comprises a physical foaming agent component, an isocyanate component=100, (16-40) and (127-148).
The isocyanate component used in the present invention may be any of polymethylene polyphenyl polyisocyanates (abbreviated as polymeric MDI), toluene diisocyanate (abbreviated as TDI), modified isocyanates, and the like, as known in the art. When two or more isocyanates are selected, a mixture of them in any ratio may be employed. Among these, polymeric MDI preferably has an average functionality of 2.7 to 2.9 to give consideration to the thermal conductivity of polyurethane rigid foam. The polymeric MDI having an average functionality of 2.7 may be selected fromPM200、44V20L、M20s、The polymeric MDI having an average functionality of 2.9 may be selected from the group consisting of PM2010>M50、PM400、44V40L、2085. The industrial TDI is usually a mixture of 2, 4-toluene diisocyanate and 2, 6-toluene diisocyanate, and TDI-65, TDI-80, TDI-100, etc. can be used in the present invention depending on the mass ratio of 2, 4-toluene diisocyanate in the mixture. The modified isocyanate is a substance prepared by reacting polyol with isocyanate, wherein the polyol can be polyether polyol taking glycerol, glycol, diethylene glycol, pentaerythritol and the like as an initiator, or phthalic anhydride polyester polyol, or bio-based polyol. The bio-based polyol is a polyol compound prepared from soybean oil, castor oil, rapeseed oil, jatropha curcas oil, olive oil, palm oil or derivatives thereof, such as castor oil polyol, olive oil polyol, palm oil polyol, castor oil derivative polyol, etc.
The invention also provides a preparation method of the polyurethane hard foam, which comprises the following steps: the polyol composition, the physical foaming agent component and the isocyanate component are mixed and then injected into a cavity, and the absolute pressure in the cavity is more than or equal to 0.8bar during injection.
In general, for blowing agent systems containing low boilers, depressurization accelerates the loss of low boilers from escaping. Therefore, pressurizing measures are adopted during material injection so as to reduce vaporization of low-boiling-point substances. In the pressurizing process, the higher the pressure value is, the better the effect of reducing the escape of low-boiling-point substances is, but the larger pressure is not beneficial to the flow of materials, and the incomplete filling is caused. Therefore, a pressure reducing step is usually added after the pressurization, which requires precise control of pressure change in the whole filling process, and the operation is complicated. The inventors have found that when the polyol composition of the present invention is used, escape loss of low boiling substances can be effectively prevented even under relatively low pressure, even under slightly negative pressure conditions. Therefore, the absolute pressure in the cavity is more preferably 0.8 to 1.3bar, so that fluidity is considered and better uniformity of density distribution is obtained. After the material injection is completed, the pressure in the cavity can be kept unchanged, the material can be naturally released, and a decompression measure can be adopted for the material, and from the aspect of convenience in operation, the pressure in the cavity is still preferably kept at 0.8-1.0 bar.
The beneficial effects are that:
(1) The polyol composition provided by the invention is suitable for a foaming agent system with a high content of low-boiling substances, and the prepared polyurethane hard foam has the characteristics of few surface pores and high closed pore rate.
(2) The polyurethane hard foam provided by the invention has excellent heat conductivity coefficient, dimensional stability and density distribution uniformity, and has excellent comprehensive performance.
(3) The invention can realize the technical effect equivalent to the transformation process without the transformation process by matching with the specific polyol composition, and simplifies the operation flow. The low-boiling foaming technology can be used in the fields of refrigerators and freezers, and is beneficial to further reducing the core density of polyurethane hard foam.
Detailed Description
The technical scheme of the present invention is described in detail below through specific examples, but the scope of the present invention is not limited to the examples.
The method for detecting the solubility comprises the following steps: 100g of the polyol composition was placed in a container and sealed, and the pressure in the container at this time was recorded as P 1 Introducing physical foaming agent into the container under sealed condition, and recording the pressure in the container as P 2 The mixture in the vessel was stirred until the pressure drop was P 1 And observing whether the mixture in the container is transparent, if the mixture is transparent and is not layered by standing, recording the maximum mass of the physical foaming agent which can be added under the condition, wherein the maximum mass is the solubility of the physical foaming agent in the polyol composition.
A process for the preparation of molded foams: and (3) mixing the raw materials and injecting the mixture into a mould cavity with the size of 2000mm multiplied by 200mm multiplied by 50mm by adopting a conventional mould for evaluating the performance of the polyurethane hard foam in the fields of refrigerators and freezers, wherein the absolute pressure in the mould cavity is 0.8-1.3 bar when the absolute pressure in the mould cavity exceeds 1bar, the process of increasing the natural release pressure after the material injection is completed, the overfilling coefficient is 1.13, the mould temperature is 40-42 ℃, and the polyurethane hard foam is obtained after curing and forming.
The detection method of the polyurethane rigid foam performance such as core density, closed pore ratio, heat conductivity coefficient, dimensional stability and the like is carried out according to the specification of GB/T26689-2011 rigid polyurethane foam plastic for refrigerators and freezers.
Uniformity of density distribution: the core density range is expressed as the difference between the maximum core density and the minimum core density measured at different sampling points on the same sample.
Surface air hole condition: the number of surface cells of the rigid polyurethane foam obtained by the comparison method was designated as "general" based on the number of surface cells of comparative example 6, and the other samples were designated as "better" with a smaller number and "worse" with a larger number than the number of cells of comparative example 6.
The raw materials used in the invention are as follows:
polyether polyol i:
polyether polyol I-1, average functionality f Ⅰ 3.5 hydroxyl equivalent N Ⅰ 407.7, self-made, taking sucrose and glycerol as starting agents, wherein the alkylene oxide component is ethylene oxide and propylene oxide with a molar ratio of 10:15;
polyether polyol I-2, average functionality f Ⅰ 5.0 hydroxyl equivalent N Ⅰ 448.4, self-made, taking sucrose and ethylene glycol as starting agents, wherein the alkylene oxide component is ethylene oxide and propylene oxide with a molar ratio of 1:1;
3245 (from Kochia), average functionality f Ⅰ 2.3 hydroxyl equivalent N Ⅰ 837.3;
3601 (from Kochia), average functionality f Ⅰ 4.6 hydroxyl equivalent N Ⅰ 1168.8;
4030M (from Kogyo), average functionality f Ⅰ 5.5 hydroxyl equivalent N Ⅰ 1298.6;
TEP-455s (from Mitsubishi), average functionality f Ⅰ 4.0 hydroxyl equivalent N Ⅰ 1206.5;
1135I (from Basoff), average functionality f Ⅰ 3.0 hydroxyl equivalent N Ⅰ 500.9;
CP1055 (available from Dow), average functionality f Ⅰ 2.78 hydroxyl equivalent N Ⅰ 359.6;
polyether polyol II:
polyether polyol II-1, average functionality f Ⅱ 5.0 hydroxyl equivalent N Ⅱ 166.0, self-made, taking sucrose and glycerol as composite initiator, wherein the alkylene oxide component is ethylene oxide, propylene oxide and 1, 2-butylene oxide, the mass ratio of the 1, 2-butylene oxide component in the polyether polyol II-1 is 4.3wt%, and the mass ratio of the composite initiator in the polyether polyol II-1 is 23.1wt%;
Polyether polyol II-2, average functionality f Ⅱ 3.9 hydroxyl equivalent N Ⅱ 134.5, self-made, wherein sorbitol and glycerin are taken as a composite initiator, and the alkylene oxide component is propylene oxide and cyclohexene oxide, wherein the mass ratio of the cyclohexene oxide component in the polyether polyol II-2 is 18.7wt%, and the mass ratio of the composite initiator in the polyether polyol II-2 is 22.7wt%;
polyether polyol II-3, average functionality f Ⅱ 6.0 hydroxyl equivalent N Ⅱ 187.7, self-made, taking sucrose and glycerol as composite initiator, wherein the alkylene oxide component is ethylene oxide, propylene oxide and methyl propylene oxide, the mass ratio of the methyl propylene oxide component in the polyether polyol II-3 is 12.8wt%, and the mass ratio of the composite initiator in the polyether polyol II-3 is 21.5wt%;
polyether polyol II-4, average functionality f Ⅱ 6.5 hydroxyl equivalent N Ⅱ 157.5, self-made, taking sucrose and glycerol as composite initiator, wherein the alkylene oxide component is propylene oxide and 1, 2-epoxypentane, the mass ratio of the 1, 2-epoxypentane component in the polyether polyol II-4 is 25.2wt%, and the mass ratio of the composite initiator in the polyether polyol II-4 is 26.1wt%;
Polyether polyol II-5, average functionality f Ⅱ 6.0 hydroxyl equivalent N Ⅱ 153.0 parts of self-made sorbitol is taken as an initiator, the alkylene oxide components are ethylene oxide, propylene oxide and 1, 2-epoxyhexane, wherein the mass ratio of the 1, 2-epoxyhexane component in the polyether polyol II-5 is 32.7wt%, and the mass ratio of the composite initiator in the polyether polyol II-5 is 19.8wt%;
polyether polyol II-6, average functionality f Ⅱ 5.5 hydroxyl equivalent N Ⅱ 102.4, selfPreparing, namely taking sucrose and glycerol as a composite initiator, wherein an alkylene oxide component is propylene oxide and 1, 2-epoxy-3-methylbutane, wherein the mass ratio of the 1, 2-epoxy-3-methylbutane component in the polyether polyol II-6 is 30.5wt%, and the mass ratio of the composite initiator in the polyether polyol II-6 is 38.6wt%;
polyether polyol II-7, average functionality f Ⅱ 2.6 hydroxyl equivalent N Ⅱ 73.5, self-made, wherein sucrose and ethylene glycol are used as a composite initiator, the alkylene oxide component is propylene oxide and 2, 3-epoxy-2-methylbutane, the mass ratio of the 2, 3-epoxy-2-methylbutane component in the polyether polyol II-7 is 22.5wt%, and the mass ratio of the composite initiator in the polyether polyol II-7 is 47.2wt%;
Polyether polyol II-8, average functionality f Ⅱ 3.0 hydroxyl equivalent N Ⅱ 334.3, self-made, taking glycerin as an initiator, wherein the alkylene oxide component is propylene oxide and cyclopentene oxide, the mass ratio of the cyclopentene oxide component in the polyether polyol II-8 is 50.3wt%, and the mass ratio of the composite initiator in the polyether polyol II-8 is 9.2wt%;
polyether polyol II-9, average functionality f Ⅱ 4.5 hydroxyl equivalent N Ⅱ 226.3, self-made, taking sucrose and glycerin as starting agents, wherein the alkylene oxide component is propylene oxide and 2, 3-dimethyl-2, 3-butylene oxide, the mass ratio of the 2, 3-dimethyl-2, 3-butylene oxide component in the polyether polyol II-9 is 29.5wt%, and the mass ratio of the composite starting agent in the polyether polyol II-9 is 16.4wt%;
polyether polyol III:
castor oil (from Jin Haiwei), molecular weight 931.5, hydroxyl equivalent N Ⅲ 345 (shown as 345);
castor oil derivative polyolsGR-160 (from Van. Teruss), molecular weight 923.6, hydroxyl equivalent N Ⅲ 342;
castor oil derivative polyolsGR-80 (from Van. Teruss), molecular weight 1770, hydroxyl equivalent N Ⅲ 716 of the formula (I);
castor oil derivative polyolsGR-110 (from Van. Teruss), molecular weight 1330, hydroxyl equivalent N Ⅲ 515;
soybean oil polyol X-0210 (available from Gekko Swinhonis), molecular weight 1100, hydroxyl equivalent N Ⅲ 250;
palm oil polyol PKF-3000 (available from Maleimia Maskimi), molecular weight 3000, hydroxyl equivalent N Ⅲ 863;
cashew nutshell oil polyol NX-9004 (from Cardlan), molecular weight 1243.3, hydroxyl equivalent weight N Ⅲ 516;
polyether polyol IV:
polyether polyol IV-1, hydroxyl equivalent N Ⅳ 132.7, self-making, taking 2-aminocyclohexanol and 2-aminocyclopentanol as composite initiator, and taking propylene oxide as an alkylene oxide component, wherein the mass ratio of the composite initiator in polyether polyol IV-1 is 27.2wt%;
polyether polyol IV-2, hydroxyl equivalent N Ⅳ 143.1, self-making, namely taking 1, 5-decalin diol as an initiator, and taking propylene oxide as an alkylene oxide component, wherein the mass ratio of the initiator in the polyether polyol IV-2 is 59.5wt%;
polyether polyol IV-3, hydroxyl equivalent N Ⅳ The self-made catalyst is 100.1, 2-bis (4-aminophenyl) propane is taken as an initiator, and the alkylene oxide component is propylene oxide, wherein the mass ratio of the initiator in the polyether polyol IV-3 is 56.5wt%;
polyether polyol IV-4, hydroxyl equivalent N Ⅳ 143.2, self-making, taking bisphenol A as an initiator, and taking an alkylene oxide component as propylene oxide, wherein the mass ratio of the initiator in the polyether polyol IV-4 is 79.7wt%;
Polyether polyol IV-5, hydroxyl equivalent N Ⅳ 136.6, self-made, taking 4,4' -diaminodiphenylmethane as an initiator and propylene oxide as an alkylene oxide component, wherein the mass ratio of the initiator in the polyether polyol IV-5 is 36.3wt%;
polyether polyol IV-6, hydroxyl equivalent N Ⅳ 157.5, self-making, taking p-phenylenediamine as an initiator, and taking an alkylene oxide component as propylene oxide, wherein the mass ratio of the initiator in the polyether polyol IV-6 is 17.2wt%;
polyether polyol IV-7, hydroxyl equivalent N Ⅳ 120.8, self-making, namely taking phthalic acid amide as an initiator and propylene oxide as an alkylene oxide component, wherein the mass ratio of the initiator in the polyether polyol IV-7 is 34.0wt%;
polyether polyol IV-8, hydroxyl equivalent N Ⅳ 109.1, self-made, taking 2- (N, N-bis (2-hydroxyethyl) aminomethyl) phenol as an initiator, and taking propylene oxide as an alkylene oxide component, wherein the mass ratio of the initiator in polyether polyol IV-8 is 64.6wt%;
polyether polyol IV-9, hydroxyl equivalent N Ⅳ 92.1, self-making, taking N, N-bis (2-hydroxyethyl) phthalic diamide as an initiator, and taking propylene oxide as an alkylene oxide component, wherein the mass ratio of the initiator in polyether polyol IV-9 is 68.5wt%;
Polyester polyol v:
polyester polyol V-1, hydroxyl equivalent N Ⅴ 127.6, is prepared by polycondensation of biphenyl anhydride and ethylene glycol, wherein the mass ratio of biphenyl anhydride in the polyester polyol V-1 is 70.3wt%;
polyester polyol V-2, hydroxyl equivalent N Ⅴ 181.3, is prepared by polycondensation of hexahydrophthalic anhydride and propylene glycol, wherein the mass ratio of the hexahydrophthalic anhydride in the polyester polyol V-2 is 59.5wt%;
polyester polyol V-3, hydroxyl equivalent N Ⅴ 162.2, prepared by polycondensation of phthalic anhydride and diethylene glycol, wherein the mass ratio of phthalic anhydride in the polyester polyol V-3 is 45.7wt%;
polyester polyol V-4, hydroxyl equivalent N Ⅴ 141.2, self-making, namely, polycondensing terephthalic acid and propylene glycol, wherein the mass ratio of the terephthalic acid in the polyester polyol V-4 is 58.8wt%;
polyether polyol vi:
polyether polyol VI-1, average functionality f Ⅵ 6.2 hydroxyl equivalent N Ⅵ 122, self-making, namely taking sucrose and ethylene glycol as a composite initiator, wherein an alkylene oxide component is propylene oxide, and the mass ratio of the composite initiator in the polyether polyol VI-1 is 34.4wt%;
polyether polyol VI-2, average functionality f Ⅵ 5.5 hydroxyl equivalent N Ⅵ 143.8, self-making, namely taking sucrose and glycerol as a composite initiator, and taking an alkylene oxide component as propylene oxide, wherein the mass ratio of the composite initiator in the polyether polyol VI-2 is 27.2wt%;
polyether polyol VI-3, average functionality f Ⅵ 3.1 hydroxyl equivalent N Ⅵ 102.9, self-made, taking glycerin as an initiator, and taking an alkylene oxide component as propylene oxide, wherein the mass ratio of the initiator in the polyether polyol VI-3 is 30.0wt%;
polyether polyol VI-4, average functionality f Ⅵ 3.1 hydroxyl equivalent N Ⅵ 247.1, self-made, glycerin is taken as an initiator, and an alkylene oxide component is propylene oxide, wherein the mass ratio of the initiator in the polyether polyol VI-4 is 12.6wt%;
polyether polyol VI-5, average functionality f Ⅵ 4.5 hydroxyl equivalent N Ⅵ 160.3, self-made, taking sorbitol and glycerol as a composite initiator, and taking propylene oxide as an alkylene oxide component, wherein the mass ratio of the composite initiator in polyether polyol VI-5 is 19.1wt%;
polyether polyol VI-6, average functionality f Ⅵ 4.8 hydroxyl equivalent N Ⅵ 114.5, self-made, sorbitol and glycerin are taken as composite initiator, and the alkylene oxide component is propylene oxide, wherein the mass ratio of the composite initiator in polyether polyol VI-6 is 26.5wt%.
The catalyst is a mixture comprising a foaming catalyst, a gel catalyst and a trimerization catalyst. The invention adopts the conventional catalyst required in the refrigerator and freezer fields, wherein the foaming catalyst comprises any one or more of pentamethyl diethylenetriamine, bis (dimethylaminoethyl) ether and tetramethyl hexamethylenediamine, the gel catalyst comprises any one or more of dibutyl tin dilaurate, N-ethylmorpholine, N, N-dimethyl cyclohexylamine, triethylenediamine, 1, 2-dimethyl imidazole and dimethylbenzylamine, and the trimerization catalyst comprises any one or more of 1,3, 5-tris (dimethylaminopropyl) hexahydrotriazine, 2,4, 6-tris (dimethylaminomethyl) phenol, methyl quaternary ammonium salt, potassium octoate, potassium acetate, ammonium (2-hydroxypropyl) trimethyl formate, quaternary ammonium salt, xin Ji ammonium salt and 2-hydroxy-N, N, N-trimethyl-1-propylamine. When two or more catalysts are selected, a mixture of them in an arbitrary ratio may be employed. In the embodiment of the invention, pentamethyldiethylenetriamine, N, N-dimethyl cyclohexylamine and 2-hydroxy-N, N, N-trimethyl-1-propylamine formate are selected in a mass ratio of 0.3:1.6:0.8.
The foam stabilizer is mainly an organosiloxane polyoxyalkylene graft copolymer, is stabilized by adopting conventional foam required in the fields of refrigerators and freezers, and can be selected from any one or more of commercially available grades AK8805, AK8830, AK8818, AK8815, AK8485, AK8812, AK8809, B8460, B8462, B8461, B8544, B8494, B8532, B8465, B8471, B8474, B8476, B8481, L6900, L6863, L6912 and L6988. When two or more foam stabilizers are selected, any ratio of mixing may be employed. AK8805 and B8461 are selected in the embodiment of the invention.
Examples of polyol compositions containing polyether polyol I are shown in Table 1 below, and the formulation compositions of rigid polyurethane foams prepared using the polyol compositions are shown in Table 2.
Table 1 polyol compositions and physicochemical properties of examples 1 to 9
TABLE 2 formulation composition of polyurethane hard foam of example 1 to example 9
Polyurethane rigid foams were prepared using the compositions of the materials in tables 1 and 2 and according to the preparation method of the aforementioned molded foam, and the resultant rigid foams were subjected to comprehensive property evaluation as shown in Table 3.
TABLE 3 comprehensive Properties of the polyurethane hard foam obtained in examples 1 to 9
The results show that the hard polyurethane foam obtained in examples 1 to 9 can completely fill the mold when the injection is carried out under the condition that the pressure in the mold cavity is 0.8 to 1.3bar, which indicates that the polyol composition used in examples 1 to 9 of the invention is suitable for the fields of refrigerators, freezers and the like. In particular, examples 1, 5 and 6 were carried out under conditions such that the molar ratio of the low boiling substance having a boiling point of < -12 ℃ was about 56.3%, and the filling effect and foam properties were comparable to those under pressurized conditions, regardless of whether under a slight negative pressure or under normal pressure conditions, indicating that the polyol composition used in the present invention could be carried out under normal pressure or under negative pressure conditions without requiring an additional pressure swing control flow, and had operational convenience.
Meanwhile, the polyether polyol I used in the examples 1 to 9 can play a role in improving the solubility of the physical foaming agent, and the obtained polyurethane hard foam still has better surface air hole condition and higher closed pore rate under the condition that the mole ratio of low-boiling-point substances with the boiling point less than 9 ℃ is 50-100%, and also has better hard foam performance under the condition that the mole ratio of low-boiling-point substances with the boiling point less than-12 ℃ is 40-70%.
Examples of polyol compositions containing polyether polyol II are shown in Table 4 below, and the formulation compositions of rigid polyurethane foams prepared using the polyol compositions are shown in Table 5.
Table 4 polyol compositions and physicochemical Properties of examples 10 to 19
TABLE 5 formulation composition of polyurethane hard foam of example 10 to example 19
Polyurethane rigid foams were prepared using the compositions of the materials in tables 4 and 5 and according to the preparation method of the aforementioned molded foam, and the resultant rigid foams were subjected to comprehensive property evaluation as shown in Table 6.
The results show that the hard polyurethane foam obtained in examples 10 to 19 fills the mold completely when the injection is carried out under the condition that the pressure in the mold cavity is 0.8 to 1.3bar, which means that the polyol composition used in examples 10 to 19 of the present invention is suitable for the fields of refrigerators, freezers, etc., and that the examples in this section can obtain better foam performance under the conditions of a little negative pressure and normal pressure, which means that the process is also convenient. Meanwhile, as can be seen from the data in Table 6, the polyol composition of the present invention can be also used in the case of higher content of low boiling point substances, such as low boiling point substances with boiling point less than 9 ℃ used in examples 10 to 19, and when the molar ratio of the low boiling point substances to the physical foaming agent is 42 to 100%, the polyether polyol II is used to facilitate the improvement of the compatibility of the polyol composition to the components of the physical foaming agent, thereby facilitating the reduction of escape loss of the low boiling point substances, obtaining better surface air hole condition and achieving higher closed cell rate. In addition, the low boiling point substance having a boiling point of less than-12℃used in examples 11 to 16 can give a good foam property even when the molar ratio thereof is 50 to 100%. Meanwhile, the invention uses polyether polyol II and polyether polyol VI in a matching way, which is favorable for further improving the closed porosity, and the polyether polyol II and polyether polyol IV or polyester polyol V in a matching way is favorable for further improving the density distribution uniformity, and the obtained polyurethane hard foam has a very small core density.
Table 6 comprehensive Properties of the polyurethane hard foam obtained in examples 10 to 19
Examples of polyol compositions containing polyether polyol III are shown in Table 7 below, and the formulation compositions of rigid polyurethane foams prepared using the polyol compositions are shown in Table 8.
TABLE 7 polyol compositions and physicochemical Properties of examples 20 to 27
TABLE 8 formulation composition of polyurethane hard foam of examples 20-27
Polyurethane rigid foams were prepared using the compositions of the materials in tables 7 and 8 and according to the preparation method of the aforementioned molded foam, and the resultant rigid foams were subjected to comprehensive property evaluation as shown in Table 9.
TABLE 9 comprehensive Properties of the polyurethane hard foam obtained in examples 20 to 27
The results show that the hard polyurethane foam obtained in examples 20 to 27 fills the mold completely when the injection is carried out under the condition that the pressure in the mold cavity is 0.8 to 1.3bar, which means that the polyol compositions adopted in examples 20 to 27 of the present invention are also suitable for the fields of refrigerators, freezers, etc., and that the examples in this section can obtain better foam properties under the conditions of slightly negative pressure and normal pressure, which means that the process is also convenient. Meanwhile, the polyether polyol III used in examples 20 to 27 can also achieve the effect of improving the solubility of the physical foaming agent, and the obtained polyurethane hard foam still has better surface air hole condition and higher closed pore rate under the condition that the mole ratio of the low-boiling-point substances with the boiling point less than 9 ℃ is 49-100%, and also has better hard foam performance under the condition that the mole ratio of the low-boiling-point substances with the boiling point less than-12 ℃ is 39-100%.
The polyol composition of the comparative example is shown in Table 10 below, and the formulation composition of the rigid polyurethane foam prepared using the comparative polyol composition is shown in Table 11.
Table 10 polyol compositions of comparative examples 1 to 7 and physicochemical properties
Table 11 formulation composition of comparative examples 1 to 7 polyurethane hard foam
Polyurethane rigid foams were prepared using the compositions of the materials in tables 10 and 11 and according to the preparation method of the aforementioned molded foam, and the resultant rigid foams were subjected to comprehensive property evaluation as shown in Table 12.
Table 12 comprehensive Properties of the polyurethane hard foam obtained in comparative examples 1 to 7
The results show that comparative examples 1 to 4 do not use any of polyether polyol I, polyether polyol II or polyether polyol III, resulting in low solubility and difficulty in filling the mold completely. Therefore, it is not suitable for a blowing agent system containing a low boiling substance. In particular, in comparative example 4, under a slight negative pressure, the blowing agent largely escapes at the initial stage of the reaction, resulting in extremely low closed cell ratio and poor foam properties. The polyether polyol I, polyether polyol II or polyether polyol III used in comparative example 5 and comparative example 6 each had a solubility satisfying the condition of > 15g, but the composite polyol used in comparative example 5 and comparative example 6 had a hydroxyl value out of the range of the present invention, so that the polyurethane rigid foam produced therefrom had a poor combination of properties than the examples of the present invention. In addition, the aromatic ring content of comparative example 7 was only 15%, and the effect of promoting the uniformity of the density distribution was also weak. In conclusion, the polyol composition used in the invention has better application effect, and can prepare polyurethane hard foam with excellent performance.
As described above, although the present invention has been shown and described with reference to certain preferred embodiments, it is not to be construed as limiting the invention itself. Various changes in form and details may be made therein without departing from the spirit and scope of the invention as defined by the appended claims.

Claims (10)

1. Polyol composition comprising a composite polyol, a catalyst, a foam stabilizer and water, characterized in that the composite polyol comprises at least one polyether polyol which is a polyether polyol I having a hydroxyl equivalent weight N Ⅰ > 350, and 2 < >Average functionality f Ⅰ The average hydroxyl value of the composite polyol is 330-520 mgKOH/g, and the average functionality is more than 3;
and at least 15g of a physical blowing agent component per 100g of the polyol composition is soluble at room temperature, said physical blowing agent component comprising a molar ratio of at least 50% of low boilers having a boiling point of < 9 ℃.
2. The polyol composition of claim 1 wherein the low boiling point material is a fluoroolefin.
3. The polyol composition of claim 1, wherein the polyether polyol i is replaced with a polyether polyol ii, wherein the alkylene oxide component of the polyether polyol ii is prepared with an epoxide of a C4 to C6 olefin, and wherein the epoxide of the C4 to C6 olefin is at least one of butylene oxide, pentylene oxide, hexylene oxide, cyclopentene oxide, or cyclohexene oxide.
4. The polyol composition of claim 1, wherein the polyether polyol i is replaced with a polyether polyol iii which is a biobased polyol having a molecular weight of 3000 or less.
5. Polyol composition according to claim 1, wherein the composite polyol further comprises aromatic rings and/or alicyclic rings, wherein the aromatic rings are introduced into polyether polyol iv and/or polyester polyol v from aromatic ring compounds, and wherein the alicyclic rings are introduced into polyether polyol iv and/or polyester polyol v from alicyclic ring compounds; the sum of the masses of the aromatic ring compound and the alicyclic compound being taken as the ratio M based on the total mass of all starter components, carboxylic acid components and acid anhydride components used in the preparation of the polyether polyol IV and/or the polyester polyol V 4 ≥20wt％。
6. The polyol composition of claim 5, wherein the aromatic ring compound is at least one of an aromatic polyamine, an aromatic polyol, an aromatic amide, a benzene ring-containing mannich base, a benzene ring-containing vegetable oil, an aromatic anhydride, or an aromatic dicarboxylic acid; the alicyclic compound is at least one of 2-aminocyclohexanol, 2-aminocyclopentanol, 1, 5-decalin diol or hexahydrophthalic anhydride.
7. The polyol composition according to claim 1, wherein the polyol composition further comprises a polyether polyol VI having a hydroxyl equivalent weight of < 250 and an average functionality f of 3.ltoreq. Ⅵ ＜6.5。
8. The polyol composition of claim 1, comprising the following mass percent: 88 to 94 weight percent of composite polyol, 2.0 to 5.9 weight percent of catalyst, 1.9 to 4.6 weight percent of foam stabilizer and 0.8 to 2.9 weight percent of water.
9. The polyurethane hard foam is characterized by being prepared by reacting the polyol composition according to any one of claims 1-8 with a physical foaming agent component and an isocyanate component, wherein the physical foaming agent component contains a low-boiling-point substance with the molar ratio of more than or equal to 50%, and the boiling point of the low-boiling-point substance is less than 9 ℃; the closed pore rate of the hard foam is more than or equal to 94%.
10. The process for preparing rigid polyurethane foam according to claim 9, wherein the polyol composition, the physical blowing agent component and the isocyanate component according to any one of claims 1 to 8 are mixed and injected into a cavity, and the absolute pressure in the cavity is not less than 0.8bar, preferably 0.8 to 1.3bar, when injected.
CN202311032844.XA 2023-08-16 2023-08-16 Polyol composition, polyurethane hard foam and preparation method thereof Pending CN117003980A (en)

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