CN108192065A - Polyurethane rigid foam plastic and preparation method thereof - Google Patents
Polyurethane rigid foam plastic and preparation method thereof Download PDFInfo
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- CN108192065A CN108192065A CN201711463118.8A CN201711463118A CN108192065A CN 108192065 A CN108192065 A CN 108192065A CN 201711463118 A CN201711463118 A CN 201711463118A CN 108192065 A CN108192065 A CN 108192065A
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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
-
- 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
- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
-
- 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
- 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
-
- 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
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2110/00—Foam properties
- C08G2110/0025—Foam properties rigid
-
- 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
- C08J2203/20—Ternary blends of expanding agents
-
- 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
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 120 150 parts of isocyanates；Foaming agent includes alkane, the methyl formate of 10 30 mass parts and the HFO type foaming agents of 1 10 mass parts of 10 30 mass parts, and hydrofluoroolefin foaming agent includes 1 chlorine 3,3,3 trifluoro propenes, cis- 1,1,1, one or both of 4,4,4 hexafluoro, 2 butylene.It is more environmentally-friendly with the foaming agent that said components and proportioning are formed, thus the density of the polyurethane rigid foam plastic prepared is relatively low, is evenly distributed, and thermal conductivity factor is relatively low, and its compressive strength and demoulding time are preferable, and low-temperature stability and hydrothermal stability are preferable.
Description
Technical field
The present invention relates to thermal insulation material technical field, more particularly to polyurethane rigid foam plastic and preparation method thereof.
Background technology
At present be usually used in the thermal insulators such as refrigerator, refrigerator-freezer polyurethane rigid foam plastic be all by hydrocarbon blowing agents foaming and
Into hydrocarbon blowing agents are inflammable and explosive, and the density foam formed is larger, and thermal conductivity factor is higher, and it is released into air
Put Organic volatile matter (VOC).How Cost And Performance is taken into account, be foaming agent needed for current polyurethane rigid foam plastic
Exploitation main flow direction.
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
Certainly polyurethane rigid foam plastic of the above problem and preparation method thereof.
The present invention one is further objective is that providing a kind of more environmentally-friendly polyurethane rigid foam plastic and being 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 plastic, according to the mass fraction,
Rigid foam is prepared by following component：
Combine polyalcohol：100 parts；
Foaming agent：10-30 parts；
Isocyanates：120-150 parts；
Foaming agent includes the alkane of 10-30 mass parts, the methyl formate of 10-30 mass parts and 1-10 mass parts
Hydrofluoroolefin foaming agent, hydrofluoroolefin foaming agent include 1- chloro-3,3,3 ,-trifluoropropenes, cis- -1,1, Isosorbide-5-Nitrae, 4,4- six
One or both of fluoro- 2- butylene.
Optionally, according to the mass fraction, foaming agent includes：
Alkane：10-20 parts；
Methyl formate：10-20 parts；
Hydrofluoroolefin foaming agent：1-5 parts.
Optionally, isocyanates-NCO group with combine polyalcohol hydroxyl molar ratio be 1-1.2：1；
Viscosity under isocyanates room temperature is 150-250mpa.s, and the content of-NCO group is 30.5-32%.
Optionally, combination polyalcohol includes polyether polyol A, polyether polyol B, polyether polyol C, polyether polyol D
And polyester polyol；
Polyether polyol A is using mannitol as initiator, reacts and is prepared with oxyalkylene；
Polyether polyol B is using pentaerythrite as initiator, reacts and is prepared with oxyalkylene；
Polyether polyol C is using sucrose and glycerine as initiator, reacts and is prepared with oxyalkylene；
Polyether polyol D be with triethanolamine, ethylenediamine, toluenediamine it is one or more for initiator, with oxyalkylene
Hydrocarbon reaction is prepared；
Polyester polyol is to be synthetically prepared to obtain with polyalcohol with one kind in phthalic acid, adipic acid, phthalate anhydride；
Optionally, it is 1500-3000mpa.s, hydroxyl value 350-500mgKOH/g to combine the viscosity under polyalcohol room temperature.
According to a further aspect of the present invention, a kind of preparation side of any of the above-described polyurethane rigid foam plastic is additionally provided
Method, including：
Combination polyalcohol by predetermined ratio is mixed, obtains the first mixture；
Alkane and methyl formate are added in by predetermined ratio in the first mixture, obtain the second mixture；
Hydrofluoroolefin foaming agent is added in by predetermined ratio in the second mixture and is mixed, obtains third mixture；
Isocyanates by predetermined ratio and third mixture is mixed, and inject membrane cavity, after foaming, curing, is obtained poly-
Urethane rigid foam.
Optionally, combination polyalcohol stirs 2-3 hours under conditions of temperature is 20-25 DEG C, pressure is 1-2bar；
Alkane and methyl formate and the first mixture stir 1-2 under conditions of temperature is 20-25 DEG C, pressure is 1-2bar
Hour.
Optionally, hydrofluoroolefin foaming agent and the second mixture are in the condition that temperature is 20-25 DEG C, pressure is 2-3bar
Lower stirring 2-3 hours.
Optionally, isocyanates and third mixture mix under conditions of temperature is 20-25 DEG C, pressure is 120-130bar
It closes, injection preheats 40-45 DEG C of membrane cavity.
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 present invention polyurethane rigid foam plastic, prepare the foaming agent used in it with alkane, methyl formate and
Hydrofluoroolefin foaming agent is combined according to special proportioning, avoids ozone layer destroying and the whole world that perhaloalkenes foaming agent is brought
The potential threat warmed, it is more environmentally-friendly, and the density of obtained polyurethane rigid foam plastic can be reduced, reduce foaming
The filling cost of material.
Further, polyurethane rigid foam plastic of the invention, to combine polyalcohol, foaming agent and isocyanic acid
Ester is prepared according to special ratio, and the polyurethane rigid foam plastic thus prepared has density relatively low, is evenly distributed, leads
Hot coefficient is relatively low, and compressive strength and demoulding time are preferable, low-temperature stability and the preferable advantage of hydrothermal stability.
Further, the preparation method of polyurethane rigid foam plastic of the invention utilizes special proportioning and special group
The polyurethane foam system divided prepares polyurethane rigid foam plastic with special process conditions, and the method is simple, reliable, carries
The comprehensive performance of prepared polyurethane rigid foam plastic is risen.
According to the accompanying drawings to the detailed description of the specific embodiment of the invention, 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 of detailed description of the present invention by way of example rather than 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 embodiment
The present embodiment provides firstly a kind of polyurethane rigid foam plastic, wherein, polyurethane rigid foam plastic by with
Lower component is prepared：100 parts combination polyalcohol, 10-30 parts of foaming agent, 120-150 parts of isocyanates.Its
In, foaming agent includes alkane, the methyl formate of 10-30 mass parts and the hydrogen fluorine of 1-10 mass parts of 10-30 mass parts
Olefines foaming agent (trade name：HFO types foaming agent), hydrofluoroolefin foaming agent includes 1- chloro-3,3,3 ,-trifluoropropene (commodity
Name：LBA), cis- -1,1,1,4,4,4- hexafluoros -2- butylene (trade names：One or both of FEA-1100).Alkane can be with
For one or both of pentamethylene, isopentane.
The performance parameter of each foaming agent is as shown in table 1 in above-mentioned foaming agent.
The performance parameter of 1 foaming agent of table
Wherein, ODP dives value for ozone-depleting, and GWP is global warming potential.
The polyurethane rigid foam plastic of the present embodiment avoids perhaloalkenes foaming agent using above-mentioned foaming agent
The potential threat warmed of ozone layer destroying and the whole world brought, it is more environmentally-friendly, by adding hydrofluoroolefin foaming agent, can reduce
Foam density reduces the filling cost of foamed material.Thus the density of the polyurethane rigid foam plastic prepared is relatively low, and distribution is equal
It is even, and the polyurethane rigid foam plastic prepared has relatively low thermal conductivity factor and stronger compressive strength, and when demoulding
Between preferably, low-temperature stability and hydrothermal stability are preferable.
The proportioning of foaming agent is preferably：Alkane is 10-20 mass parts, methyl formate is 10-20 mass parts, HFO
Type foaming agent is 1-5 mass parts.
Isocyanates-NCO group with combine polyalcohol hydroxyl molar ratio be 1-1.2:1, thereby ensure that-NCO bases
The appropriate excess of group, to ensure the extent of reaction of hydroxyl.Wherein, viscosity is 150-250mpa.s under the room temperature of isocyanates ,-
The content of NCO group is 30.5-32%.
Combination polyalcohol may include polyether polyol A, polyether polyol B, polyether polyol C, polyether polyol D and polyester
Polyalcohol.It is 1500-3000mpa.s, hydroxyl value 350-500mgKOH/g to combine the viscosity under polyalcohol room temperature.
Wherein, polyether polyol A is using mannitol as initiator, reacts and is prepared with oxyalkylene；Polyether polyol B
It is using pentaerythrite as initiator, reacts and be prepared with oxyalkylene；Polyether polyol C is using sucrose and glycerine as starting
Agent is reacted with oxyalkylene and is prepared；Polyether polyol D be with triethanolamine, ethylenediamine, toluenediamine it is one or more
For initiator, react and be prepared with oxyalkylene；Polyester polyol is in phthalic acid, adipic acid, phthalate anhydride
One kind is synthetically prepared to obtain with polyalcohol.Wherein, polyalcohol can be ethylene glycol, propylene glycol, season used by polyester polyol
Penta tetrol etc..
The polyurethane rigid foam plastic of the present embodiment, with said combination polyalcohol with above-mentioned foaming agent with special
Proportioning is made, and the polyurethane foam of preparation can significantly reduce polyurethane foam compared to foams prepared by more traditional foaming agent
Thermal conductivity factor, improve heat insulation effect.The molecular weight of methyl formate is relatively low, can largely reduce the usage amount of foaming agent,
Cost is reduced, simultaneously because the compatibility of methyl formate, is remarkably improved the compatibility of the other components of alkane and foaming system,
And the use of HFO foaming agents can reduce thermal conductivity factor, reduce loading.
Fig. 1 is the flow chart of the preparation method of polyurethane rigid foam plastic according to an embodiment of the invention.This hair
Bright to additionally provide a kind of preparation method for preparing polyurethane rigid foam plastic, this method specifically includes：
Combination polyalcohol by predetermined ratio is mixed, obtains the first mixture by S102；
Alkane and methyl formate are added in by predetermined ratio in the first mixture and mixed, obtains the second mixture by S104；
HFO types foaming agent is added in by predetermined ratio in the second mixture and mixed, obtains third mixture by S106；
S108 is mixed isocyanates, and inject membrane cavity by predetermined ratio and third mixture, after foaming, curing,
Obtain polyurethane rigid foam plastic.
Combination polyalcohol stirs 2-3 hours under conditions of temperature is 20-25 DEG C, pressure is 1-2bar, that is to say, combines
Polyether polyol A, polyether polyol B, polyether polyol C, polyether polyol D and polyester polyol in polyalcohol is according to predetermined
Ratio mixes 2-3 hours under conditions of 20-25 DEG C, 1-2bar, obtains the first mixture.
Alkane and methyl formate and the first mixture are 20-25 DEG C in temperature, and pressure stirs 1-2 under conditions of being 1-2bar
Hour, it that is to say, alkane and methyl formate are added in by predetermined ratio in above-mentioned first mixture, and mixing temperature is 20-25 DEG C, is mixed
Resultant pressure is 1-2bar, and incorporation time is 1-2 hours, obtains the second mixture.
It is small that HFO types foaming agent and the second mixture stir 2-3 under conditions of temperature is 20-25 DEG C, pressure is 2-3bar
When, it that is to say, HFO types foaming agent is added according to predetermined ratio in above-mentioned second mixture, is carried out under 20-25 DEG C, 2-3bar
Mixing mixes 2-3 hours, obtains third mixture.
Isocyanates and third mixture mix under conditions of temperature is 20-25 DEG C, pressure is 120-130bar, injection
The membrane cavity of 40-45 DEG C of preheating, is foamed and is cured.To verify the polyurethane rigid foam plastic prepared using above-mentioned raw materials
Performance after polyurethane rigid foam plastic foaming curing, the foams cooled down is demoulded, carry out the test of correlated performance.
The preparation method of the polyurethane rigid foam plastic of the present embodiment utilizes the polyurethane of special proportioning and special component
Foaming system prepares polyurethane rigid foam plastic with special process conditions, and the method is simple, reliable, improves polyurethane
The comprehensive performance of rigid foam.
The present invention also provides a kind of refrigerator, the thermal insulation material of refrigerator using above-mentioned polyurethane rigid foam plastic or on
Polyurethane rigid foam plastic prepared by the preparation method stated, it is possible thereby to greatly improve heat-insulating property and the environmental protection of refrigerator
Property improves the overall quality of refrigerator.
It is following to be carried out with multiple embodiments to verify the performance of the polyurethane rigid foam plastic prepared using above-mentioned raw materials
Comparison, tests the performance of the polyurethane rigid foam plastic obtained by multiple embodiments, and test table is as shown in table 2.
Embodiment 1
The composition number of each raw material in embodiment 1：Polyalcohol：100 parts, pentamethylene：10 parts, methyl formate：20 parts, LBA：
5 parts, isocyanates：140 parts.
Polyurethane rigid foam plastic preparation method is specially：
(1) polyalcohol will be combined and mixes 2-3H under 20-25 DEG C, the pressure of 1-2bar, obtain (the first mixing of pre- white material
Object)；
(2) pentamethylene and methyl formate are added in upper pre- white material, mixing temperature is 20-25 DEG C, blend pressure 1-
2bar, incorporation time 1-2h obtain the second mixture；
(3) LBA is added in the second mixture, is mixed under 20-25 DEG C, 2-3bar, incorporation time 2-3h,
Obtain third mixture；
(4) third mixture and isocyanates are mixed under 20-25 DEG C, 120-130bar pressure, injection preheating 40-45
DEG C die cavity die cavity, foaming and curing；
(5) foams cooled down are demoulded, carries out the test of correlated performance.
Embodiment 2
The composition number of each raw material in embodiment 2：Polyalcohol：100 parts, pentamethylene：13 parts, methyl formate：15 parts, LBA：
5 parts, isocyanates：130 parts.The preparation method reference implementation example 1 of polyurethane rigid foam plastic.
Embodiment 3
The composition number of each raw material in embodiment 3：Polyalcohol：100 parts, pentamethylene：10 parts, isopentane 10：Part, formic acid first
Ester：10 parts, LBA：5 parts, isocyanates：150 parts.The preparation method of polyurethane rigid foam plastic is roughly the same with embodiment 1.
Embodiment 4
The composition number of each raw material in embodiment 3：Polyalcohol：100 parts, pentamethylene：13 parts, methyl formate：15 parts, FEA-
1100 are：5 parts, isocyanates：140 parts.The preparation method reference implementation example 1 of polyurethane rigid foam plastic.
Embodiment 5
The composition number of each raw material in embodiment 5：Polyalcohol：100 parts, pentamethylene：13 parts, methyl formate：10 parts, FEA-
1100 are：5 parts, isocyanates：120 parts.Polyurethane rigid foam plastic preparation method reference implementation example 1.
Embodiment 6
The composition number of each raw material in embodiment 6：Polyalcohol：100 parts, pentamethylene：13 parts, methyl formate：13 parts, FEA-
1100：1 part, isocyanates：140 parts.Polyurethane rigid foam plastic preparation method reference implementation example 1.
Comparative example 1
The composition number of each raw material in comparative example 1：Polyalcohol：100 parts, pentamethylene：20 parts, isocyanates：140 parts.
Polyurethane rigid foam plastic preparation method is specially：
(1) polyalcohol will be combined and mixes 2-3H under 20-25 DEG C, the pressure of 1-2bar, obtain (the first mixing of pre- white material
Object)；
(2) pentamethylene is added in upper pre- white material, mixing temperature is 20-25 DEG C, blend pressure 1-2bar, incorporation time
For 1-2h, the second mixture is obtained；
(3) the second mixture and isocyanates are mixed under 20-25 DEG C, 120-130bar pressure, injection preheating 40-45
DEG C die cavity die cavity, foaming and curing；
(4) foams cooled down are demoulded, carries 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
Averag density, compressive strength, thermal conductivity factor, Low-Temperature Size stability, hydrothermal stability and rate of closed hole of rigid foam etc.
Performance.The performance of embodiment 1 to the polyurethane rigid foam plastic of the preparation of embodiment 6 and comparative example 1 is specific such as 2 institute of table
Show.
Table 2
Pass through the pentamethylene foaming agent more simple compared with the result of comparative example 1 can be seen that of embodiment 1 to 6, this implementation
The blowing agent system of example can reduce the usage amount of pentamethylene, while the averag density of polyurethane rigid foam plastic obtained,
Thermal conductivity factor etc. has and significantly reduces, so as to be remarkably improved the heat-insulating property of foam.
By the comparison of embodiment 1 and embodiment 2, embodiment 4 and embodiment 5 as can be seen that the additive amount of methyl formate
All have an impact to the thermal conductivity factor of foam, compressive strength and averag density, with the increase of methyl formate additive amount, foam
Thermal conductivity factor and averag density reduce, and compressive strength decreases.
It is obtained by comparative example 1 and embodiment 4, embodiment 2 and 5 result of embodiment, adds foam plastic made of LBA
The thermal conductivity factor of material, by increasing the dosage of LBA, can be promoted less than the thermal conductivity factor of foamed plastics made of addition FEA-1100
The heat-insulating property of foamed plastics.And the averag density for adding foamed plastics made of LBA, which is substantially less than, adds FEA-1100 systems
Into foamed plastics averag density, by increasing the dosage of LBA, the averag density of foamed plastics can be reduced, so as to reduce hair
The loading of foam material, reduces cost.
Show that isopentane can improve the compressive strength of foam, but can lead to other performances with 3 by comparing implementation 1
It reduces, such as the raising of thermal conductivity factor and the increase of averag density.
The polyurethane rigid foam plastic of the present embodiment reduces the usage amount of hydrocarbon blowing agents, reduces VOC releases,
It is more environmentally friendly, and GWP (the potential value that warms in the whole world) is lower.Also, since methyl formate molecular weight is smaller, foaming agent can be reduced
Usage amount, while decrease HFO foaming agent usage amounts, play cost-effective purpose, the rigid poly urethanes thus prepared
The density of foamed plastics is relatively low, is evenly distributed, and thermal conductivity factor is relatively low, and its compressive strength and demoulding time are preferable, low
Temperature stability and hydrothermal stability are preferable.
So far, although those skilled in the art will appreciate that detailed herein have shown and described multiple showing for the present invention
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：120-150 parts；
The foaming agent includes the alkane of 10-30 mass parts, the methyl formate of 10-30 mass parts and 1-10 mass parts
Hydrofluoroolefin foaming agent, the hydrofluoroolefin foaming agent include 1- chloro-3,3,3 ,-trifluoropropenes, cis- -1,1, Isosorbide-5-Nitrae, 4,
One or both of 4- hexafluoro -2- butylene.
2. foamed plastics according to claim 1, wherein
According to the mass fraction, the foaming agent includes：
Alkane：10-20 parts；
Methyl formate：10-20 parts；
Hydrofluoroolefin foaming agent：1-5 parts.
3. foamed plastics according to claim 1, wherein
The isocyanates-NCO group and the hydroxyl molar ratio for combining polyalcohol be 1-1.2：1；
Viscosity under the isocyanates room temperature is 150-250mpa.s, and the content of described-NCO group is 30.5-32%.
4. foamed plastics according to claim 1, wherein
It is more that the combination polyalcohol includes polyether polyol A, polyether polyol B, polyether polyol C, polyether polyol D and polyester
First alcohol；
The polyether polyol A is using mannitol as initiator, reacts and is prepared with oxyalkylene；
The polyether polyol B is using pentaerythrite as initiator, reacts and is prepared with oxyalkylene；
The polyether polyol C is using sucrose and glycerine as initiator, reacts and is prepared with oxyalkylene；
The polyether polyol D be with triethanolamine, ethylenediamine, toluenediamine it is one or more for initiator, with oxyalkylene
Hydrocarbon reaction is prepared；
The polyester polyol is to be synthetically prepared to obtain with polyalcohol with one kind in phthalic acid, adipic acid, phthalate anhydride.
5. foamed plastics according to claim 4, wherein
Viscosity under the combination polyalcohol room temperature is 1500-3000mpa.s, hydroxyl value 350-500mgKOH/g.
6. a kind of preparation method of any one of claim 1 to 5 polyurethane rigid foam plastic, including：
Combination polyalcohol by predetermined ratio is mixed, obtains the first mixture；
Alkane and methyl formate are added in by predetermined ratio in first mixture and mixed, obtains the second mixture；
Hydrofluoroolefin foaming agent is added in by predetermined ratio in second mixture and is mixed, obtains third mixture；
Isocyanates by predetermined ratio and the third mixture is mixed, and inject membrane cavity, after foaming, curing, obtains institute
State polyurethane rigid foam plastic.
7. according to the method described in claim 6, wherein
The combination polyalcohol stirs 2-3 hours under conditions of temperature is 20-25 DEG C, pressure is 1-2bar；
The alkane and the methyl formate and first mixture are in the condition that temperature is 20-25 DEG C, pressure is 1-2bar
Lower stirring 1-2 hours.
8. according to the method described in claim 6, wherein
The hydrofluoroolefin foaming agent and second mixture are under conditions of temperature is 20-25 DEG C, pressure is 2-3bar
Stirring 2-3 hours.
9. according to the method described in claim 6, wherein
The isocyanates and the third mixture mix under conditions of temperature is 20-25 DEG C, pressure is 120-130bar,
Injection preheats 40-45 DEG C of the membrane cavity.
10. a kind of refrigerator, the thermal insulation material of the refrigerator is using the method preparation of any one of the claims 6 to 9
Polyurethane rigid foam plastic.
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| CN109294218A (en) * | 2018-09-28 | 2019-02-01 | 上海东大聚氨酯有限公司 | Combined polyether, polyurethane foam feedstock composition, from its polyurethane foam and its preparation method and application |
| WO2021196862A1 (en) * | 2020-03-30 | 2021-10-07 | 青岛海尔电冰箱有限公司 | Foamed material, heat-preservation box body, and preparation methods therefor |
| CN115181240A (en) * | 2022-08-03 | 2022-10-14 | 福建冠翔日用塑料制品有限公司 | Wear-resistant heat-insulating polyurethane rigid foam plastic and preparation method thereof |
| US11753516B2 (en) | 2021-10-08 | 2023-09-12 | Covestro Llc | HFO-containing compositions and methods of producing foams |
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| CN109294218A (en) * | 2018-09-28 | 2019-02-01 | 上海东大聚氨酯有限公司 | Combined polyether, polyurethane foam feedstock composition, from its polyurethane foam and its preparation method and application |
| WO2021196862A1 (en) * | 2020-03-30 | 2021-10-07 | 青岛海尔电冰箱有限公司 | Foamed material, heat-preservation box body, and preparation methods therefor |
| US11753516B2 (en) | 2021-10-08 | 2023-09-12 | Covestro Llc | HFO-containing compositions and methods of producing foams |
| CN115181240A (en) * | 2022-08-03 | 2022-10-14 | 福建冠翔日用塑料制品有限公司 | Wear-resistant heat-insulating polyurethane rigid foam plastic and preparation method thereof |
| CN115181240B (en) * | 2022-08-03 | 2023-08-18 | 福建冠翔日用塑料制品有限公司 | Wear-resistant heat-insulating polyurethane rigid foam plastic and preparation method thereof |
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