CN108276546A - Polyurethane rigid foam plastic and preparation method thereof - Google Patents
Polyurethane rigid foam plastic and preparation method thereof Download PDFInfo
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- CN108276546A CN108276546A CN201711465425.XA CN201711465425A CN108276546A CN 108276546 A CN108276546 A CN 108276546A CN 201711465425 A CN201711465425 A CN 201711465425A CN 108276546 A CN108276546 A CN 108276546A
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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
- C08G18/4009—Two or more macromolecular compounds not provided for in one single group of groups C08G18/42 - C08G18/64
- C08G18/4018—Mixtures of compounds of group C08G18/42 with compounds of group C08G18/48
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- 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
- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
- C08G18/4205—Polycondensates having carboxylic or carbonic ester groups in the main chain containing cyclic groups
- C08G18/4208—Polycondensates having carboxylic or carbonic ester groups in the main chain containing cyclic groups containing aromatic groups
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- 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
- C08G18/487—Polyethers containing cyclic groups
- C08G18/4883—Polyethers containing cyclic groups containing cyclic groups having at least one oxygen atom in the ring
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- 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
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- 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
- C08J9/142—Compounds containing oxygen but no halogen atom
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- 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
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- 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
- C08J9/149—Mixtures of blowing agents covered by more than one of the groups C08J9/141 - C08J9/143
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2110/00—Foam properties
- C08G2110/0025—Foam properties rigid
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- 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
- C08J2203/12—Organic compounds only containing carbon, hydrogen and oxygen atoms, e.g. ketone or alcohol
-
- 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
- C08J2203/142—Halogenated saturated hydrocarbons, e.g. H3C-CF3
-
- 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
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- 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
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- 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
- C08J2375/06—Polyurethanes from polyesters
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- 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)
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- Materials Engineering (AREA)
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Abstract
The present invention provides a kind of polyurethane rigid foam plastics and preparation method thereof, and according to the mass fraction, rigid foam is prepared by following component：100 parts of combination polyalcohol, 10 30 parts of foaming agent and 125 150 parts of isocyanates；Foaming agent therein includes the PF5056 of the methyl formate of 10 30 mass parts, the HFO of 1 10 mass parts and 15 mass parts, and HFO includes 1 chlorine 3, and 3,3, trifluoro propene, cis- 1,1, Isosorbide-5-Nitrae, one or both of 4,4 hexafluoro, 2 butylene.The polyurethane rigid foam plastic of the present invention, foaming agent is formed with methyl formate, HFO and PF5056, ODP the and GWP numerical value of foaming agent can be reduced, improve the mobility of foamed material, keep polyurethane foam density more uniform, cell diameter reduces, and the heat of radiation consumption can be greatly lowered, to which thermal coefficient be greatly lowered.
Description
Technical field
The present invention relates to thermal insulation material technical fields, more particularly to polyurethane rigid foam plastic and preparation method thereof.
Background technology
With the requirement of national energy-saving environmental protection, the important developing direction of refrigerator is exactly that low thermal conductivity and high heat preservation are imitated
Fruit.The main expanded material of refrigerator is still to be moulded by the hard polyurethane foam of primary blowing agent of pentamethylene under normal temperature and pressure at present
Expect material, foam density distribution difference is larger, thermal coefficient is higher and the asking it is easy to appear cavity in abnormity/stenosis
Topic.
Invention content
In view of the above problems, it is an object of the present invention to provide one kind to overcome the above problem or solve at least partly
The certainly polyurethane rigid foam plastic and preparation method thereof of the above problem.
A further object of the present invention is to provide a kind of more environmentally-friendly polyurethane rigid foam plastic and promoted poly-
The comprehensive performance of urethane rigid foam.
According to an aspect of the present invention, the present invention provides a kind of polyurethane rigid foam plastics, according to the mass fraction,
Rigid foam is prepared by following component：
Combine polyalcohol：100 parts；
Foaming agent：10-30 parts；
Isocyanates：125-150 parts；
Foaming agent include the methyl formate of 10-30 mass parts, 1-10 mass parts hydrofluoroolefin foaming agent and
The fluorine class nucleating agent of 1-5 mass parts, hydrofluoroolefin foaming agent include 1- chloro- 3,3,3,-trifluoro propene, cis- -1,1, Isosorbide-5-Nitrae,
One or both of 4,4- hexafluoro -2- butylene.
Optionally, isocyanates is polyisocyanate, the viscosity under room temperature be 150-250mpa.s, isocyanates-
The content of NCO group is 30-32%.
Optionally, combination polyalcohol includes polyether polyol and polyester polyol；
Polyether polyol includes polyether glycol I, polyether glycol I I and polyether glycol I II；
The degree of functionality for combining polyalcohol is 3-5, and viscosity is 400-480mPa.s at room temperature.
Optionally, polyether glycol I is using toluenediamine and diethanol amine or triethanolamine as initiator and oxyalkylene
Under the action of catalyst prepared by addition reaction for hydrocarbon；
Polyether glycol I I is using pentaerythrite as initiator and oxyalkylene addition reaction preparation under the action of catalyst；
Polyether glycol I II is using sucrose as initiator and oxyalkylene addition reaction preparation under the action of catalyst；
Polyester polyol is benzoic anhydride polyester polyol, and benzoic anhydride polyester polyol is by aromatic anhydride, polyalcohol and O-phthalic
Acid is prepared by polycondensation reaction.
Optionally, the viscosity of polyether glycol I is 200-400mpa.s, hydroxyl value 200-300mgKOH/g；
The viscosity of polyether glycol I I is 200-400mpa.s, hydroxyl value 200-300mgKOH/g；
The viscosity of polyether glycol I II is 2000-4000mpa.s, hydroxyl value 400-550mgKOH/g；
The viscosity of polyester polyol is 800-1600mpa.s, hydroxyl value 200-300mgKOH/g.
Optionally, polyether polyol includes the polyether glycol I of 45 mass parts, the polyether glycol I I of 40 mass parts, 5 matter
Measure the polyester polyol of the polyether glycol I II and 10 mass parts of part.
According to a further aspect of the present invention, a kind of preparation method of polyurethane rigid foam plastic is additionally provided, including：
Combination polyalcohol is mixed by predetermined ratio, obtains the first mixture；
Fluorine class nucleating agent is pumped by predetermined ratio in the first mixture and is mixed, the second mixture is obtained；
Methyl formate, hydrofluoroolefin foaming agent are pumped into the second mixture by predetermined ratio and are mixed, third is obtained
Mixture；
Isocyanates is mixed by predetermined ratio with third mixture, and injects membrane cavity, after foaming, curing, is obtained poly-
Urethane rigid foam.
Optionally, combination polyalcohol stirs 1-2 hours under conditions of temperature is 20-25 DEG C；
Fluorine class nucleating agent and the first mixture are under conditions of temperature is 20-25 DEG C, pressure is 1-2bar with 1500-2000
Rev/min speed stir 2-3 hours；
Methyl formate, hydrofluoroolefin foaming agent and the second mixture are in the item that temperature is 20-25 DEG C, pressure is 1-2bar
It is stirred 2-3 hours under part.
Optionally, isocyanates is preheating to 20-25 DEG C and the mixing of third mixture, is injected under the pressure of 120-140bar
The membrane cavity of 30-40 DEG C of preheating.
According to a further aspect of the present invention, a kind of refrigerator is additionally provided, the thermal insulation material of refrigerator is using any of the above-described
Polyurethane rigid foam plastic prepared by method.
The polyurethane rigid foam plastic of the present invention, with methyl formate, hydrofluoroolefin foaming agent and fluorine-based additive group
At foaming agent, ODP the and GWP numerical value of foaming agent can be reduced, the mobility of foamed material is improved, keeps polyurethane foam close
Degree is more uniform, and cell diameter reduces, and the heat of radiation consumption can be greatly lowered, to significantly reduce heat conduction
Coefficient.
Further, polyurethane rigid foam plastic of the invention is formed with a variety of polyether polyol and polyester polyol
Polyalcohol is combined, and combination polyalcohol and foaming agent are prepared into polyurethane rigid foam plastic with specific proportioning, is improved
Polyurethane rigid foam plastic obtained it is comprehensive.
Further, the preparation method of polyurethane rigid foam plastic of the invention, in advance and group by fluorine-based additive
Polyalcohol mixing is closed, is then mixed again with methyl formate, hydrofluoroolefin foaming agent, is finally mixed with isocyanates, thus make
The mobility of the polyurethane rigid foam plastic obtained is more preferable, and molded density smaller, foam bubble hole diameter smaller, foams are more
Exquisiteness, thermal coefficient is lower, and heat insulation effect is more preferable.
According to the following detailed description of specific embodiments of the present invention in conjunction with the accompanying drawings, those skilled in the art will be brighter
The above and other objects, advantages and features of the present invention.
Description of the drawings
Some specific embodiments that the invention will be described in detail by way of example and not limitation with reference to the accompanying drawings hereinafter.
Identical reference numeral denotes same or similar component or part in attached drawing.It should be appreciated by those skilled in the art that these
What attached drawing was not necessarily drawn to scale.In attached drawing：
Fig. 1 is the preparation method flow chart of polyurethane rigid foam plastic according to an embodiment of the invention.
Specific implementation mode
The present embodiment provides firstly a kind of polyurethane rigid foam plastic, according to the mass fraction, rigid foam by
Following component is prepared：100 parts of combination polyalcohol, 10-30 parts of foaming agent and 125-150 parts of isocyanic acid
Ester.Wherein, foaming agent include the methyl formate of 10-30 mass parts, 1-10 mass parts hydrofluoroolefin foaming agent (quotient
The name of an article is HFO) and 1-5 mass parts fluorine class nucleating agent (trade name PF5056), HFO includes 1- chloro- 3,3,3 ,-trifluoro propene
One or both of (trade name LBA), cis- -1,1,1,4,4,4- hexafluoros -2- butylene (trade name FEA-1100).
In above-mentioned foaming agent, the ODP and GWP value of methyl formate are very low, and thermal coefficient is relatively low, nonflammable, safety
Coefficient is high, and can reduce usage amounts of the LBA to the corrosivity of liner and reduction HFO, to reduce cost；In addition, PF5056
Addition foaming agent can be assisted to foam, so that the abscess grain size of foaming agent is reduced, the quantity of abscess increases in unit area, from
And makes foam finer and smoother, reduce heat loss through radiation and reduce thermal coefficient.
Isocyanates is polyisocyanate, and the viscosity under room temperature is 150-250mpa.s, and-the NCO's of isocyanates contains
Amount is 30-32%.It includes polyether polyol and polyester polyol to combine polyalcohol, and the degree of functionality for combining polyalcohol is 3-5, room temperature
Lower viscosity is 400-480mPa.s.
Polyether polyol includes polyether glycol I, polyether glycol I I, polyether glycol I II.Wherein, polyether glycol I
It is using toluenediamine and diethanol amine or triethanolamine as initiator and oxyalkylene addition reaction system under the action of catalyst
It is standby；Polyether glycol I I is using pentaerythrite as initiator and oxyalkylene addition reaction preparation under the action of catalyst；Polyethers
Polyalcohol III is using sucrose as initiator and oxyalkylene addition reaction preparation under the action of catalyst；Polyester polyol is benzene
Acid anhydride polyester polyol, benzoic anhydride polyester polyol are prepared by aromatic anhydride, polyalcohol and phthalic acid by polycondensation reaction.
The viscosity of polyether glycol I is 200-400mpa.s, hydroxyl value 200-300mgKOH/g；Polyether glycol I I's is viscous
Degree is 200-400mpa.s, hydroxyl value 200-300mgKOH/g；The viscosity of polyether glycol I II is 2000-4000mpa.s, hydroxyl
Value is 400-550mgKOH/g；The viscosity of polyester polyol is 800-1600mpa.s, hydroxyl value 200-300mgKOH/g.Combination
The mass fraction of each component can be in polyalcohol：Polyether glycol I is 45 parts, polyether glycol I I is 40 parts, polyether polyol
III is 5 parts, polyester polyol is 10 parts.
It is polynary to form combination with a variety of polyether polyol and polyester polyol for the polyurethane rigid foam plastic of the present embodiment
Alcohol, and be prepared with specific proportioning using combination polyalcohol and foaming agent, improve rigid poly urethanes bubble obtained
The comprehensive performance of foam plastics.
Fig. 1 is the preparation method flow chart of polyurethane rigid foam plastic according to an embodiment of the invention.The present invention
A kind of preparation method of polyurethane rigid foam plastic is additionally provided, this method specifically includes：
Combination polyalcohol is mixed by predetermined ratio, obtains the first mixture by S102；
PF5056 is pumped by predetermined ratio in the first mixture and is mixed by S104, obtains the second mixture；
Methyl formate, HFO are pumped by predetermined ratio in the second mixture and are mixed, obtain third mixture by S106；
Isocyanates is mixed by predetermined ratio with third mixture, and injects membrane cavity by S108, after foaming, curing,
Obtain polyurethane rigid foam plastic.
Wherein, combination polyalcohol stirs 1-2 hours under conditions of temperature is 20-25 DEG C, that is to say, polyether glycol I,
Polyether glycol I I, polyether glycol I II and polyester polyol are pre-mixed 1- according to predetermined ratio at a temperature of 20-25 DEG C
2 hours, to be uniformly mixed, obtain the first mixture.
PF5056 and the first mixture turn under conditions of temperature is 20-30 DEG C, pressure is 1-2bar with 1500-2000/
Point speed stir 2-3 hour, that is to say, PF5056 is fluorinated liquid pump and enters in the first mixture, at 20-25 DEG C, the pressure of 1-2bar
It is stirred 2-3 hours with 1500-2000 revs/min of speed under power, obtains the second mixture.
It is small that methyl formate, HFO stir under conditions of temperature is 20-25 DEG C, pressure is 1-2bar 2-3 with the second mixture
When, it that is to say, methyl formate, HFO are pumped into the second mixture, are mixed 2-3 hours under 20-25 DEG C, the pressure of 1-2bar,
Obtain third mixture.
Isocyanates is preheating to 20-25 DEG C, is then mixed with third mixture, bets in the pressure of 120-140bar
Enter to preheat 30-40 DEG C of membrane cavity, after foaming, curing, obtains polyurethane rigid foam plastic.It is prepared using above-mentioned raw materials for verification
Polyurethane rigid foam plastic performance, after polyurethane rigid foam plastic foaming curing after, the foams cooled down are taken off
Mould carries out the test of correlated performance.
The preparation method of the present embodiment polyurethane rigid foam plastic, by PF5056 in advance with combine polyalcohol mix,
In mixed process, by apply high shear, so that PF5056 is sufficiently mixed uniformly with polyalcohol is combined, then again with formic acid first
Ester, HFO mixing, finally mix with isocyanates, so that the mobility of foaming system is more preferable so that rigid polyurethane obtained
The molded density smaller of matter foamed plastics, the cell diameter smaller of foams, foams are finer and smoother, and thermal coefficient is lower, heat preservation
Effect is more preferable.
The present invention also provides a kind of refrigerator, the thermal insulation material of refrigerator using above-mentioned polyurethane rigid foam plastic or on
The polyurethane rigid foam plastic of method preparation is stated, it is possible thereby to greatly improve the heat-insulating property and the feature of environmental protection of refrigerator, is promoted
The overall quality of refrigerator.
It is following to be compared with multiple embodiments to verify the performance of polyurethane rigid foam plastic, test multiple implementations
The performance of polyurethane rigid foam plastic obtained by example.
Embodiment 1
The mass fraction of each raw material in embodiment 1：Combine 100 parts of polyalcohol, 10 parts of methyl formate, LBA be 3.5 parts,
PF5056 is 2 parts, isocyanates is 145 parts.
HFO used in embodiment 1 is LBA, and polyurethane rigid foam plastic preparation method is specially：
(1) combination polyalcohol is pre-mixed 1-2 hours at 20-25 DEG C, the first mixture is made；
(2) PF5056 fluorination liquid is added in the first mixture, with 1500-2000 under 20-25 DEG C, 1-2bar pressure
Rev/min speed be stirred 2-3H, the second mixture is made；
(3) methyl formate, HFO are pumped into the second mixture, mix 2-3H under 20-25 DEG C, 1-2bar pressure, is made
Third mixture；
(4) isocyanates is preheating to 20-25 DEG C, is then mixed with third mixture, betted in 120-140bar pressure
Enter to preheat in 30-40 DEG C of die cavity and is foamed and cured；
(5) it waits after the completion of curing, foam is demoulded, carry out the test of correlated performance.
Embodiment 2
The mass fraction of each raw material in embodiment 2：Combine 100 parts of polyalcohol, 10 parts of methyl formate, LBA be 3.5 parts,
PF5056 is 5 parts, isocyanates is 145 parts.Polyurethane rigid foam plastic preparation method reference implementation example 1 makes in embodiment 2
HFO is LBA.
Embodiment 3
The mass fraction of each raw material in embodiment 3：Combine 100 parts of polyalcohol, 10 parts of methyl formate, LBA be 7 parts,
PF5056 is 2 parts, isocyanates is 145 parts.Polyurethane rigid foam plastic preparation method reference implementation example 1 makes in embodiment 3
HFO is LBA.
Embodiment 4
The mass fraction of each raw material in embodiment 4：Combine 100 parts of polyalcohol, 11 parts of methyl formate, FEA-1100 3.5
Part, PF5056 are 5 parts, isocyanates is 145 parts.Polyurethane rigid foam plastic preparation method reference implementation example 1, embodiment 4
The middle HFO used is FEA-1100.
Embodiment 5
The mass fraction of each raw material in embodiment 5：Combine 100 parts of polyalcohol, 10 parts of methyl formate, LBA be 1 part,
PF5056 is 1 part, isocyanates is 125 parts.Polyurethane rigid foam plastic preparation method reference implementation example 1 makes in embodiment 5
HFO is LBA.
Embodiment 6
The mass fraction of each raw material in embodiment 6：Combine 100 parts of polyalcohol, 15 parts of methyl formate, LBA be 10 parts,
PF5056 is 5 parts, isocyanates is 150 parts.Polyurethane rigid foam plastic preparation method reference implementation example 1 makes in embodiment 6
HFO is LBA.
Embodiment 7
The mass fraction of each raw material in embodiment 7：Combine 100 parts of polyalcohol, 20 parts of methyl formate, LBA be 3.5 parts,
PF5056 is 2 parts, isocyanates is 125 parts.Polyurethane rigid foam plastic preparation method reference implementation example 1 makes in embodiment 7
HFO is LBA.
Embodiment 8
The mass fraction of each raw material in embodiment 8：It is 3 parts, FEA- to combine 100 parts of polyalcohol, 15 parts of methyl formate, LBA
1100 be 3 parts, PF5056 is 2 parts, isocyanates is 150 parts.Polyurethane rigid foam plastic preparation method reference implementation example 1,
The HFO used in embodiment 8 is LBA and FEA-1100.
Comparative example 1
The mass fraction of each raw material in comparative example：Combine 100 parts of polyalcohol, 10 parts of methyl formate, FEA-1100 be 7 parts,
Isocyanates is 145 parts.
The HFO used in comparative example 1 is FEA-1100, and polyurethane rigid foam plastic preparation method is specially：
(1) combination polyalcohol is pre-mixed 1-2H at 20-25 DEG C, the first mixture is made；
(2) methyl formate, HFO are pumped into the second mixture, mix 2-3H under 20-25 DEG C, 1-2bar pressure, is made
Second mixture；
(3) isocyanates is preheating to 20-25 DEG C, is then mixed with the second mixture, betted in 120-140bar pressure
Enter to preheat in 30-40 DEG C of die cavity and is foamed and cured；
(4) it waits after the completion of curing, foam is demoulded, carry out the test of correlated performance.
Polyurethane foam is foamed in membrane cavity after curing, and the foams cooled down are demoulded, the polyurethane after test demoulding
The performances such as averag density, compressive strength, heat-conducting system, low-temperature stability, rate of closed hole, the aperture size of rigid foam.It is real
The performance for applying the polyurethane rigid foam plastic of preparation of the example 1 to embodiment 8 and comparative example 1 is specifically as shown in table 1.
Table 1
By the comparison of embodiment 1 and comparative example 1, the addition of PF5056 can be substantially reduced the diameter of abscess, increase single
Abscess quantity in plane product, reduces heat loss through radiation, to reduce thermal coefficient, improves the comprehensive of prepared hard polyurethane foam
Close performance.
By the comparison of embodiment 1 and embodiment 2, with increasing for PF5056 additive amounts, the bubble of hard polyurethane foam
Pore size is substantially reduced, and abscess quantity increases in unit area, and heat loss through radiation reduces so that the thermal coefficient of foams is apparent
Decline.
By implementing the comparison of 1 and embodiment 3, with increasing for LBA additive amounts, averag density reduces, and reduces foaming
The loading of system reduces cost so as to save raw material；Meanwhile the heat conduction system of prepared polyurethane rigid foam plastic
Number also reduces, and improves the heat-insulating property of foam.
By the comparison of embodiment and comparative example, the raising of the addition of methyl formate can significantly reduce expansion density,
But since methyl formate has foam the dissolubility of part, the dimensional stability of hard polyurethane foam is caused to can decrease；
The addition of LBA or FEA-1100 can reduce thermal coefficient, while reduce foam density；On this basis, PF5056 is added
Foam nucleating agent can reduce the diameter of abscess, increase the abscess number to foam in unit area, heat loss through radiation be reduced, to drop
Low thermal conductivity improves heat-insulating property, while can also reduce the usage amount of methyl formate, avoids methyl formate to the molten of foam
Solution avoids being greatly lowered for foam size stability and intensity.
The polyurethane rigid foam plastic of the present embodiment forms foaming agent with methyl formate, HFO and PF5056,
ODP the and GWP numerical value that foaming agent can be reduced, improves the mobility of foamed material, keeps polyurethane foam density more uniform, abscess
Diameter reduces, and the heat of radiation consumption can be greatly lowered, to significantly reduce thermal coefficient.
Further, the polyurethane rigid foam plastic of the present embodiment, with a variety of polyether polyol and polyester polyol group
Polyurethane rigid foam plastic is prepared with specific proportioning at combination polyalcohol, and by combination polyalcohol and foaming agent, is carried
The high comprehensive performance of polyurethane rigid foam plastic obtained.
Further, the method for preparing polyurethane rigid foam plastic of the present embodiment, by PF5056 in advance with combine
Polyalcohol mixes, and then mixes with methyl formate, HFO, is finally mixed with isocyanates again, thus obtained rigid poly urethanes bubble
The mobility of foam plastics is more preferable, molded density smaller, and foam bubble hole diameter smaller, foams are finer and smoother, and thermal coefficient is more
Low, heat insulation effect is more preferable.
So far, although those skilled in the art will appreciate that present invention has been shown and described in detail herein multiple shows
Example property embodiment still without departing from the spirit and scope of the present invention, still can according to the present disclosure directly
Determine or derive many other variations or modifications consistent with the principles of the invention.Therefore, the scope of the present invention is understood that and recognizes
It is set to and covers other all these variations or modifications.
Claims (10)
1. a kind of polyurethane rigid foam plastic, according to the mass fraction, the rigid foam are prepared by following component：
Combine polyalcohol：100 parts；
Foaming agent：10-30 parts；
Isocyanates：125-150 parts；
The foaming agent include the methyl formate of 10-30 mass parts, 1-10 mass parts hydrofluoroolefin foaming agent and
The fluorine class nucleating agent of 1-5 mass parts, the hydrofluoroolefin foaming agent include 1- chloro- 3,3,3,-trifluoro propene, cis- -1,1,
One or both of 1,4,4,4- hexafluoro -2- butylene.
2. foamed plastics according to claim 1, wherein
The isocyanates is polyisocyanate, and the viscosity under room temperature is the 150-250mpa.s ,-NCO of the isocyanates
The content of group is 30-32%.
3. foamed plastics according to claim 1, wherein
The combination polyalcohol includes polyether polyol and polyester polyol；
The polyether polyol includes polyether glycol I, polyether glycol I I and polyether glycol I II；
The degree of functionality of the combination polyalcohol is 3-5, and viscosity is 400-480mPa.s at room temperature.
4. foamed plastics according to claim 3, wherein
The polyether glycol I is being catalyzed as initiator and oxyalkylene using toluenediamine and diethanol amine or triethanolamine
It is prepared by the lower addition reaction of agent effect；
The polyether glycol I I is using pentaerythrite as initiator and oxyalkylene addition reaction preparation under the action of catalyst；
The polyether glycol I II is using sucrose as initiator and oxyalkylene addition reaction preparation under the action of catalyst；
The polyester polyol is benzoic anhydride polyester polyol, and the benzoic anhydride polyester polyol is by aromatic anhydride, polyalcohol and adjacent benzene
Dioctyl phthalate is prepared by polycondensation reaction.
5. foamed plastics according to claim 4, wherein
The viscosity of the polyether glycol I is 200-400mpa.s, hydroxyl value 200-300mgKOH/g；
The viscosity of the polyether glycol I I is 200-400mpa.s, hydroxyl value 200-300mgKOH/g；
The viscosity of the polyether glycol I II is 2000-4000mpa.s, hydroxyl value 400-550mgKOH/g；
The viscosity of the polyester polyol is 800-1600mpa.s, hydroxyl value 200-300mgKOH/g.
6. foamed plastics according to claim 4, wherein
The polyether polyol includes the polyether glycol I of 45 mass parts, the polyether glycol I I of 40 mass parts, 5 mass parts
The polyester polyol of polyether glycol I II and 10 mass parts.
7. a kind of preparation method of any one of claim 1 to 6 polyurethane rigid foam plastic, including：
Combination polyalcohol is mixed by predetermined ratio, obtains the first mixture；
Fluorine class nucleating agent is pumped by predetermined ratio in first mixture and is mixed, the second mixture is obtained；
Methyl formate, hydrofluoroolefin foaming agent are pumped into second mixture by predetermined ratio and are mixed, third is obtained
Mixture；
Isocyanates is mixed by predetermined ratio with the third mixture, and injects membrane cavity, after foaming, curing, obtains institute
State polyurethane rigid foam plastic.
8. according to the method described in claim 7, wherein
The combination polyalcohol stirs 1-2 hours under conditions of temperature is 20-25 DEG C；
The fluorine class nucleating agent and first mixture are under conditions of temperature is 20-25 DEG C, pressure is 1-2bar with 1500-
2000 revs/min of speed stirs 2-3 hours；
The methyl formate, the hydrofluoroolefin foaming agent and second mixture temperature be 20-25 DEG C, pressure 1-
It is stirred 2-3 hours under conditions of 2bar.
9. according to the method described in claim 7, wherein
The isocyanates is preheating to 20-25 DEG C and third mixture mixing, is injected under the pressure of 120-140bar pre-
Hot 30-40 DEG C of the membrane cavity.
10. the thermal insulation material of a kind of refrigerator, the refrigerator is prepared using the method described in any one of the claims 7 to 9
Hard polyurethane foam.
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