CN1468880A - Hard polyurethane foam material and insulator - Google Patents
Hard polyurethane foam material and insulator Download PDFInfo
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- CN1468880A CN1468880A CNA031236294A CN03123629A CN1468880A CN 1468880 A CN1468880 A CN 1468880A CN A031236294 A CNA031236294 A CN A031236294A CN 03123629 A CN03123629 A CN 03123629A CN 1468880 A CN1468880 A CN 1468880A
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Abstract
Provided is a rigid polyurethane foam that achieves combination of a low heat conductivity and a low density and has a reduced deterioration with time of heat conductivity and a high dimensional stability. The rigid polyurethane foam is formed by using a polyol, an isocyanate, a mixed foaming agent of cyclopentane and water, a catalyst and a foam stabilizer. The polyol contains a polyether polyol component in which propylene oxide is added to tolylenediamines as a first polyol component, a polyether polyol component in which propylene oxide is added to triethanolamines as a second polyol component, and an aromatic polyester polyol as a third polyol component. The polyol contains the first and the second polyol components each >=6 times of the third polyol component.
Description
Technical field
The present invention relates to rigid polyurethane foam and thermal insulator, the thermal insulator of especially using rigid polyurethane foam and the refrigerating unit that is applicable to refrigerator or freezer etc. of the mixed foaming agent of pentamethylene and water to use.
Technical background
The refrigerating unit of refrigerator and freezer etc. uses the thermal insulator of filling rigid polyurethane foam in the space of outside plate and inner panel.Rigid polyurethane foam makes by making polyhydroxy reactant, isocyanate prepolymer composition, whipping agent, catalyzer and suds-stabilizing agent reaction.Whipping agent can use fluorine Lyons and the pentamethylene that replaces fluorine Lyons.
Te Kaiping 8-193115 communique has been put down in writing and used above polyhydroxy reactant, the hydrocarbon moisture and that pentamethylene 50 weight % are above of polyester polyol 30 weight % that contains hydroxyl value 300～600 is the rigid polyurethane foam of whipping agent, catalyzer and the suds-stabilizing agent of necessary composition.
In addition, Te Kaiping 8-73553 communique has been put down in writing the polyether glycol that uses propylene oxide and sucrose addition, the rigid polyurethane foam of whipping agent, catalyzer and the suds-stabilizing agent of the pure and mild propylene oxide of polyester polyols that aromatic carboxylic acid or its acid anhydrides and polyvalent alcohol polycondensation make and polyether glycol composition, water and the hydrocarbon of propylene glycol addition.
In addition, the spy open flat 11-248344 communique put down in writing the polyhydroxy reactant of the hydroxyl value 380～480 of using oxyethane and propylene oxide and tolylene diamine addition, isocyanate prepolymer composition, as the pentamethylene of whipping agent and the rigid polyurethane foam of water, catalyzer and suds-stabilizing agent.
In addition, the spy open flat 11-29652 communique put down in writing the polyhydroxy reactant of the hydroxyl value 350～500 of using propylene oxide and tolylene diamine addition, isocyanate prepolymer composition, as the pentamethylene of whipping agent and the rigid polyurethane foam of water, catalyzer and suds-stabilizing agent.
In addition, the spy opens the 2001-158815 communique and has put down in writing and use aromatic ester polyvalent alcohol 20～50 quality % that contain hydroxyl value 405～500, contain ortho-toluene diamine 50 quality % above polyhydroxy reactant, isocyanate prepolymer composition, C
5～C
6The rigid polyurethane foam of the whipping agent of hydrocarbon compound.
In addition, the spy opens flat 2001-172359 communique and put down in writing the rigid polyurethane foam that epoxide is used with the polyester polyol of the polyether glycol of the initiator addition system of selecting and polyalcohols-polyvalent carboxylic acid condensate system as polyvalent alcohol from polyamines class, alkanol amine, phenols and polyalcohols.
In addition, the spy open flat 11-201628 communique, spy open flat 11-248344 communique with special when opening the 2001-133135 communique and having proposed foam filled rigid polyurethane foam and during running because the corresponding energy-conservation high performance that improves heat insulating ability and reduction carbamate usage quantity of pentamethylene whipping agent etc.
Yet; consider from the global warmingization and the position of global environment protection; though the pentamethylene of expectation exploitation hydro carbons is the energy-conservation polyurethane material that the rigid polyurethane foam conduct of whipping agent can improve heat insulating ability; but these hydrocarbon blowing agents are compared with existing whipping agent, the thermal conductivity height of gas, have the problem of poor insulation property.
The inventor is at first in order to realize the reduction of thermal conductivity, studied that attempting to reduce water cooperates umber.That is, remaining unreacted NCO radical reaction in water and the rigid polyurethane foam generates carbonic acid gas, the result makes carbonic acid gas ratio rising in the hole, causes the deterioration of thermal conductivity, so attempt by reducing the moisture content number, the reaction of inhibition and remaining unreacted NCO base reduces thermal conductivity.Yet, reduce water and cooperate umber to cause the increase or the mobile deterioration of premix polyvalent alcohol fluid viscosity, become the major cause that polyurethane foamed material density increases, the result causes the increase of carbamate injection rate, and cost raises.
In addition, in order to realize the reduction of thermal conductivity, also studied the hydroxyl value that increases polyvalent alcohol, the poreization of seeking rigid polyurethane foam.That is, estimate that then general thermal conductivity is also low if the aperture is little.Particularly,, try to quicken the reaction of polyvalent alcohol and isocyanic ester, that is, promote gelation reaction to suppress the growth of crafters in order to become the little state in aperture.In addition, try the independent crafters of pentamethylene to be dispersed in the foams, reduce thermal conductivity by adopting to the immiscible polyvalent alcohol of pentamethylene.
Yet, though reached the result who reduces significantly for the initial stage thermal conductivity in this way, find thermal conductivity through the time deterioration increase.Relevant its reason, estimation are because reactivity is fast, and unreacted NCO base remaining in the rigid polyurethane foam reacts with water (for example seeing through the water of ABS plane materiel from the outside), generates carbonic acid gas, and the carbonic acid gas ratio increases in the hole.In addition, poor dimensional stability under the high temperature estimates that this also is that the gas ratio in the hole increases because of fast reactivity, and the influence of gas expansion, contraction causes.
For attempting to reduce the thermal insulator that above-mentioned thermal conductivity is studied, produce that density increases, thermal conductivity through the time deterioration increase, poor dimensional stability etc. the problem of all characteristic variation of having concurrently of original hope.
Summary of the invention
The object of the present invention is to provide have that thermal conductivity reduces concurrently and low densityization, suppress thermal conductivity through the time deterioration, the rigid polyurethane foam and the thermal insulator of dimensional stability simultaneously.
Moreover other objects and advantages of the present invention can be found out by the following stated.
The inventor is for the rigid polyurethane foam of the suitableeest lower thermal conductivity of developing that refrigerator etc. uses, the optimization of research polyvalent alcohol, thus finished the present invention.
That is,, explored the test of the polyvalent alcohol that imports many initiators with the aromatic nucleus that causes steric barrier easily in order to seek the reduction of rigid polyurethane foam thermal conductivity.In the mixed system of discovery adding aromatic polyester polyol composition (the 3rd polyhydroxy reactant) in propylene oxide and the polyether glycol composition (the 2nd polyhydroxy reactant) with the polyether glycol composition (the 1st polyhydroxy reactant) of the toluylenediamine addition of aromatic nucleus and propylene oxide and trolamine addition, it is effective to lower thermal conductivityization to increase by the 1st and the 2nd polyhydroxy reactant.
In addition, balance for acquired character, discovery contains the addition polymer (the 5th polyhydroxy reactant) of the initiator of useful sucrose and the addition polymer of propylene oxide addition (the 4th polyhydroxy reactant) and propylene oxide and glycerine addition, to improve the total content (more than the 85 weight % of for example the suitableeest precursor composition) of 1-the 5th polyhydroxy reactant simultaneously effective except the initiator that aromatic nucleus is arranged.
In addition, in order to have the reduction of poreization and thermal conductivity concurrently, isocyanate prepolymer composition is selected the composition of mixed prepolymer modification tolylene diisocyanate in normally used diphenylmethanediisocyanate polykaryon for use.Its reason is because by mixed prepolymer modification tolylene diisocyanate, realizes the gentlenessization of tackify behavior, and distance between the high densityization of amino-formate bond and urea key or shortening cross-linking set can form even minute aperture.
In addition, the most adaptive composition and division in a proportion, catalyzer, suds-stabilizing agent to pentamethylene and water, research have concurrently the reduction of thermal conductivity and thermal conductivity through the time deterioration result that reduces, the most adaptive composition and division in a proportion of finding pentamethylene and water is with respect to polyvalent alcohol 100 weight parts, the water of 0.5～2.0 weight part and the pentamethylene of 10～20 weight parts are made up, the N of Primary Catalysts and urea acid estersization, N ', N " also use; promote the minimizing and the rapid reaction of remaining NCO base, the suds-stabilizing agent of selecting low surface tension for use is effective by the active catalyst of three (3-dimethylamino-propyls), six hydrogen-S-triazine etc.
For the 1st kind of method of the present invention that reach aforementioned purpose as follows.
(1) in the rigid polyurethane foam that mixed foaming agent, catalyzer and suds-stabilizing agent with polyvalent alcohol, isocyanic ester, pentamethylene and water generate, the polyether glycol composition that aforementioned polyvalent alcohol contains propylene oxide addition tolylene diamine class as the polyether glycol composition of the 1st polyhydroxy reactant, propylene oxide addition trolamine class as the 2nd polyhydroxy reactant, and the aromatic polyester polyol composition as the 3rd polyhydroxy reactant, the aforementioned the 1st and the 2nd polyhydroxy reactant content is more than 6 times of aforementioned the 3rd polyhydroxy reactant.
In addition, the 2nd kind of method of the present invention is as follows.
(2) in aforementioned the 1st kind of method, as the 5th polyhydroxy reactant, the total content of aforementioned the 1st polyhydroxy reactant, aforementioned the 2nd polyhydroxy reactant, aforementioned the 4th polyhydroxy reactant and aforementioned the 5th polyhydroxy reactant is more than the 85 weight % of aforementioned polyvalent alcohol to the polyether glycol composition that aforementioned polyvalent alcohol contains propylene oxide and sucrose addition as the polyether glycol composition of the 4th polyhydroxy reactant, propylene oxide and glycerine addition.
In addition, the 3rd kind of method of the present invention is as follows.
(3) be in aforementioned the 2nd kind of method, generate with three polyureas acid esters (ヌ レ one ト) catalyzer.
In addition, the 4th kind of method of the present invention is as follows.
(4) in any method of the aforementioned the 1st to the 3rd kind of method, aforementioned polyvalent alcohol is the 1st polyhydroxy reactant 40～50 weight parts of the hydroxyl value 400～500 of propylene oxide and toluylenediamine addition, the 2nd polyhydroxy reactant 25～35 weight parts of the hydroxyl value 350～450 of propylene oxide and trolamine addition, the 4th polyhydroxy reactant 5～10 weight parts of the hydroxyl value 400～480 of propylene oxide and sucrose addition, the 5th polyhydroxy reactant 5～10 weight parts of the hydroxyl value 350～450 of propylene oxide and glycerine addition, mixture with the 3rd polyhydroxy reactant 5～15 weight parts of the hydroxyl value 300～360 of Tetra hydro Phthalic anhydride and ethylene glycol condensation.
In addition, the 5th kind of method of the present invention is as follows.
(5) in aforesaid the 4th kind of method, with respect to aforementioned polyvalent alcohol 100 weight parts, with the water generation of pentamethylene 10～20 weight parts and 0.5～2.0 weight part.
In addition, the 6th kind of method of the present invention is as follows.
(6) space that forms between outside plate and inner panel is filled and is used polyvalent alcohol, isocyanic ester, the mixed foaming agent of pentamethylene and water, in the thermal insulator of the rigid polyurethane foam that catalyzer and suds-stabilizing agent generate, aforementioned polyvalent alcohol contains the tolylene diamine class polyether glycol composition of propylene oxide addition as the 1st polyhydroxy reactant, the trolamine class polyether glycol composition of propylene oxide addition is as the 2nd polyhydroxy reactant, reach the aromatic polyester polyol composition as the 3rd polyhydroxy reactant, the aforementioned the 1st and the 2nd polyhydroxy reactant content is more than 6 times of aforementioned the 3rd polyhydroxy reactant.
Below, reference table and figure explanation are as the rigid polyurethane foam and the thermal insulator of embodiment of the present invention.
Rigid polyurethane foam of the present invention prepares by the following method: in the mixed foaming agent of pentamethylene and water, in the presence of polyether glycol and polyester polyol and catalyzer, suds-stabilizing agent, react with aromatic isocyanate.
For the thermal conductivity in the mixed foaming agent of seeking to be reduced in pentamethylene and water, this polyhydroxy reactant with toluylenediamine and trolamine as the addition polymer of initiator as mother metal.The addition polymer of this polyether glycol since the difference of various oxirane affixtures and different with the intermiscibility of pentamethylene whipping agent, propylene oxide adduct is better than the intermiscibility of ethylene oxide adduct.Stability during from premix is considered, preferably high to pentamethylene intermiscibility system.
In addition, aromatic isocyanate is by using the mixture of diphenylmethanediisocyanate polykaryon and prepolymer modification tolylene diisocyanate, and the differences in viscosity when dwindling the polyvalent alcohol premix also improves the intermiscibility with polyether glycol simultaneously.That is, the application's polyurethane material is owing to form minute aperture, thus can by after quickening initial reaction, acceleration gelation or curing makes.
In addition, the crowd knows that the thermal conductivity of rigid polyurethane foam influences the heat transfer of solid part or the heat transfer and the radiative transfer of gas part.With regard to the solid thermal conductance of this resin part, the tolylene diisocyanate mixed system shows low value.This estimation is that owing to the carbodiimide formation reaction produces carbonic acid gas, partial pressure of carbon dioxide raises, so thermal conductivity increases in foaming process when the coenocytic single foams of diphenylmethanediisocyanate.
And find, because radiative transfer influences aperture and separated foam rate, so the tolylene diisocyanate mixed system of the prepolymer modification that the bubble aperture evenly diminishes easily also can reduce thermal conductivity.Reason estimates it is because 4 of tolylene diisocyanates active high, and behind foaming initial stage and polyol reaction, so tackify behavior gentlenessization when amino-formate bond forms hole count nuclear control and foaming is the junction of crafters minimizing.
Find out that by above-mentioned result of study when the tolylene diisocyanate mixed system ratio of prepolymer modification used diphenylmethanediisocyanate separately, the homogeneity of its crafters or all rerum naturas such as reduction of thermal conductivity were improved.Therefore, the preferred composition of mixed prepolymer modification tolylene diisocyanate 5～20 weight parts in the diphenylmethanediisocyanate polykaryon.
Obtain as the object of the invention can performance and the polyurethane material deposited, the use level of pentamethylene whipping agent and blowing promotor water also has a significant impact.When increasing the water use level, because the dividing potential drop of the carbon dioxide gas in the crafters increases, so the tendency that increases also appears in thermal conductivity.Therefore, the most adaptive composition and division in a proportion of pentamethylene and water with respect to polyvalent alcohol 100 weight parts, preferably makes up the water of 0.5～2.0 weight part (more preferably 0.8～1.2 weight part) and the pentamethylene of 10～20 weight parts (more preferably 14～18 weight parts).
In addition, as catalysts, though must be the N of urea acid estersization, N ', N " three (3-dimethylamino-propyls), six hydrogen-s-triazine, but also can use for example N in addition; N '-dimethylcyclohexylamine, N, N; N ', N ', N " five methyl diethylentriamine, N, N, N ', N ', N " tetramethyl-hexamethylene-diamine, trimethylammonium aminoethylpiperazine etc.The use level of catalysts, preferred 2～5 weight parts of per 100 weight part polyhydroxy reactants.
In addition, suds-stabilizing agent is B-8462, the F-392 of SHIN-ETSU HANTOTAI's chemistry system etc. of go one Le De シ ユ ミ Star ト system for example, consider from the stability of premix intermiscibility, preferably with the material that be suitable for low emulsifying effect of Si molecular weight 1800～3000 with Si containing ratio 25～30.The use level of suds-stabilizing agent, per 100 weight part polyhydroxy reactants are 1.5～4 weight parts.
In addition, as isocyanic ester, mainly use the polykaryon and the prepolymer modification tolylene diisocyanate of diphenylmethanediisocyanate.Tolylene diisocyanate can use mixture of isomers, promptly 2,4-body 100%, 2,4-body/2,6-body=80/20,65/35 (weight ratio) can certainly make the urethane-modified tolylene diisocyanate of trade(brand)name ケ ネ one ト 4040 prepolymers such as grade of the field medicine system of useing force, allophanate-modified tolylene diisocyanate, biuret modified tolylene diisocyanate, isocyanurate-modified tolylene diisocyanate etc.
Rigid polyurethane foam of the present invention forms with common foaming machine (for example プ ロ マ one ト corporate system PU-30 type foaming machine).Foaming condition is difference according to the difference of foaming machine kind and more or less, but 18～30 ℃ of preferred liquid temperature, outlet pressure 80～150kg/cm
2, 35～45 ℃ of output 15～30kg/min, molding box temperature.More preferably 20 ℃ of liquid temperature, outlet pressure 100kg/cm
2, about 45 ℃ of output 25kg/min, molding box temperature.
Like this, fill heat insulating member formation thermal insulator in the space that the inner panel of the outside plate of outer container surface iron plate etc. and interior case resin wall etc. constitutes, the bubble that absolute construction is arranged, the rigid polyurethane foam of mixed foaming agent that uses pentamethylene and water simultaneously is as described heat insulating member, as this rigid polyurethane foam, can have the reduction and the low densityization of thermal conductivity concurrently, can suppress thermal conductivity through the time deterioration, use the good material of dimensional stability simultaneously, so reduced refrigerator and freezer etc. refrigerating unit thermal insulator the heat leak amount and realize energy-conservation, simultaneously inexpensive, become the good thermal insulator of outward appearance grade.
Description of drawings
Fig. 1 is the longitudinal diagram of refrigerator of filling the rigid polyurethane foam of a kind of embodiment of the present invention.
Fig. 2 is the mode chart of filling rigid polyurethane foam in the refrigerator of Fig. 1.
Nomenclature
1 ... body of thermal insulating box, 1a ... outer container (outside plate), 1b ... interior case (inner panel),
1c ... rigid polyurethane foam, 3 ... refrigerating chamber, 4 ... vegetable compartment,
5 ... refrigeration chamber, 6 ... refrigerating-chamber door, 7 ... vegetable compartment door, 8 ... the epimere refrigerating chamber door,
9 ... hypomere refrigerating chamber door, 11 ... carbamate injector head, 12 ... the carbamate materials flow,
13 ... carbamate inlet, 21 ... vaporizer, 22 ... cooling fan, 23 ... compressor.
Embodiment
Below, specifically describe embodiments of the invention and comparative example with reference to table 1, Fig. 1 and Fig. 2.Among the following embodiment and comparative example, " part " or " % " represents " weight part ", " weight % " respectively.
Table 1
| Comparative example | Embodiment | Appendix | ||||||
| ????1 | ????2 | ????3 | ???1 | ????2 | ????3 | ????4 | ||
| Polyvalent alcohol A | ????30 | ????30 | ????40 | ???40 | ????50 | ????50 | ????48 | The 1st kind of composition: toluylenediamine class |
| Polyvalent alcohol B | ????10 | ????- | ????10 | ???35 | ????25 | ????30 | ????25 | The 2nd kind of composition: trolamine class |
| Polyvalent alcohol C | ????10 | ????10 | ????5 | ???10 | ????7.5 | ????5 | ????10 | The 4th kind of composition: sucrose |
| Polyvalent alcohol D | ????30 | ????10 | ????5 | ???5 | ????7.5 | ????5 | ????5 | The 5th kind of composition: glycerols |
| Polyol E | ????20 | ????30 | ????40 | ???10 | ????10 | ????10 | ????12 | The 3rd kind of composition: polyester |
| Polyvalent alcohol F | ????- | ????20 | ????- | ???- | ????- | ????- | ????- | The 6th kind of composition: ortho-toluene diamine class |
| Pentamethylene | ????20 | ????15 | ????10 | ???15 | ????18 | ????14 | ????17 | |
| Water | ????0.6 | ????1.2 | ????1.5 | ???1.2 | ????0.8 | ????1.2 | ????1.0 | |
| Sandwich layer density (Kg/m 3) | ????35.2 | ????34.0 | ????33.5 | ???29.8 | ????30.9 | ????29.8 | ????31.2 | |
| Thermal conductivity (mW/mK) | ????17.5 | ????18.2 | ????18.5 | ???16.8 | ????17.0 | ????16.8 | ????17.0 | |
| Compressive strength (MPa) | ????0.09 | ????0.10 | ????0.10 | ???0.13 | ????0.11 | ????0.13 | ????0.11 | |
| Low temperature size changing rate (%) | ????-0.85 | ????-0.65 | ????-0.55 | ???-0.34 | ????-0.45 | ????-0.54 | ????-0.42 | |
| High temperature size changing rate (%) | ????2.35 | ????2.12 | ????1.72 | ???0.51 | ????1.37 | ????0.95 | ????1.15 | |
| Thermal conductivity through the time deterioration (%) | ????6.3 | ????5.8 | ????6.8 | ???1.8 | ????2.3 | ????1.9 | ????2.2 | |
(comparative example 1)
Comparative example 1, as polyhydroxy reactant, as shown on Table 1 Comparative Example 1, by the toluylenediamine class polyether glycol with the propylene oxide addition of average hydroxyl value 450 (is the 1st polyhydroxy reactant, title polyvalent alcohol A) 30 part, trolamine class polyether glycol with the propylene oxide addition of average hydroxyl value 400 (is the 2nd polyhydroxy reactant, title polyvalent alcohol B) 10 part, sucrose polyether glycol with the propylene oxide addition of average hydroxyl value 440 (is the 4th polyhydroxy reactant, title polyvalent alcohol C) 10 part, glycerols polyether glycol with the propylene oxide addition of average hydroxyl value 400 (is the 5th polyhydroxy reactant, title polyvalent alcohol D) 30 part, 20 parts of blended polyol blend compositions of the polyester polyol of average hydroxyl value 330 (be the 3rd polyhydroxy reactant, claim polyol E) constitute.
And, in 100 parts of this polyol blend compositions, cooperate 0.6 part of 20 parts of pentamethylene whipping agent, water and N as catalysts, 1.5 parts of N '-dimethylcyclohexylamine (KAO. Corp. SA's system), N, N, N ', N ', 2 parts of tetramethyl-hexamethylene-diamines (KAO. Corp. SA's system) of N " 1 part of five methyl diethylentriamine (KAO. Corp. SA's system), N, N; N '; N ', N " are as 2 parts of the organo-siloxane B-8462 (go-Le De シ ユ ミ Star ト corporate system) of suds-stabilizing agent.
In addition, as isocyanic ester, foam for 133 parts with the diphenylmethanediisocyanate polykaryon.The polyvalent alcohol of this moment and the liquid temperature of isocyanic ester are adjusted to 20 ℃.At first, stir polyvalent alcohol and isocyanic ester, inject in the aluminium-making mould of 540 * 320 * 35mmt that is adjusted to 45 ℃, filling ratio is 110% to foam.After 5 minutes,, measure with the 35mmt heat-insulating shield of rigid polyurethane foam its moulding product demoulding from mould.
As this assay method, density for the sample size and weight of measuring 200mm * 200mm * 35mmt after, remove the value of weight with volume, thermal conductivity is expanded smart machine corporate system HC-073 type (heat flowmeter method, 10 ℃ of medial temperatures) with English and is estimated.The compressive strength foam sample distortion that makes 50mm * 50mm * 35mmt by input speed 4mm/min, the value of the stress when removing 10% distortion with original load area is estimated.Low temperature size changing rate and high temperature size changing rate adopt to be placed the foams of 150mm * 300mm * 35mmt 24 hours or estimates at the velocity of variation of 70 ℃ of placements thickness in the time of 24 hours at-20 ℃.
It is the results are shown in the comparative example 1 of table 1.
Find out that by table 1 comparative example 1 density is big, be 35.2kg/m
3, thermal conductivity 17.5mW/mK, big slightly, compressive strength 0.09MPa, slightly little, low temperature size changing rate-0.85%, big slightly, high temperature size changing rate 2.35% is big especially.In addition, paste aluminium strip at the truncation surface of the heat-insulating shield of comparative example 1, be determined at the process when leaving standstill under the condition of 30 ℃ of temperature, humidity 50% fate thermal conductivity through the time impairment grade the result, the deterioration through 2 weeks is 6.3%, and is bigger.
Following with reference to the evaluation of Fig. 1 and Fig. 2 explanation to carrying out with the real machine thermal insulator of the rigid polyurethane foam of comparative example 1.
The body of thermal insulating box 1 of refrigerator as shown in Figure 1, forms refrigerating chamber 3, vegetable compartment 4, refrigeration chamber 5 in inside.And, at the former configuration refrigerating-chamber door 6 of refrigerating chamber 3,, epimere refrigerating chamber door 8 and hypomere refrigerating chamber door 9 are set in the front of refrigeration chamber 5 at the former configuration vegetable compartment door 7 of vegetable compartment 4.In addition, the back portion configuration vaporizer 21 at refrigeration chamber 5 disposes cooling fan 22 above it.By making cooling fan 22 runnings, cold air direction is as shown by arrows circulated by vaporizer 21, makes the case internal cooling to design temperature.In addition, at the mechanical(superphosphate)den of the lower backside of body of thermal insulating box 1 configuration compressor 23, constitute the part of freeze cycle with vaporizer 21.Above-mentioned body of thermal insulating box 1, be the outer container 1a of the iron plate system that constitutes outside plate with constitute the space filling rigid polyurethane foam 1c formation that forms between the case 1b in inner panel plastic.In addition, each 6～9 also is that the space that forms between the outside plate of iron plate system and synthetic resins system inner panel is filled rigid polyurethane foam and constituted.
Fill the method for rigid polyurethane foam to body of thermal insulating box 1, as shown in Figure 2, body of thermal insulating box 1 was fallen, be fixed on foaming with on the anchor clamps, in the liquid temperature of polyvalent alcohol and isocyanic ester is that 20 ℃, anchor clamps temperature are under 40 ℃ the state, and 4 places are filled rigid polyurethane foam simultaneously and foamed from the back side.Particularly, at the tip that 4 the local carbamate inlets that form 13 in the back side of body of thermal insulating box 1 insert carbamate injector head 11, fill rigid polyurethane foam (polyol blends, water and pentamethylene, catalyzer, the premixed blend compositions of suds-stabilizing agent and isocyanic ester) in the space of outer container 1a and interior case 1b formation.The polyvalent alcohol and the isocyanic ester generation chemical reaction of polyurethane foamed material because blow(ing) pressure pressurizes, in the polyurathamc foam injection space, form body of thermal insulating box at this moment.The injection of this moment, 200 liters the casing of for example having an appointment, set the zero padding (real machine is filled essential minimum injection rate) of polyurethane material after, inject by 110% filling ratio of excessive filling.
Measure the result of the thermoacoustic refrigerator spillage of this comparative example 1, with use special open the rigid polyurethane foam shown in described the 7th embodiment of 2001-133135 communique (below, the conventional example that claims table 1 explanation) conventional example compares, and the heat leakage amount does not reduce basically.
(comparative example 2)
Comparative example 2, as polyhydroxy reactant, shown in the comparative example 2 of table 1, constitute by 20 parts of blended polyol blend compositions of the ortho-toluene diamine class polyether glycol of the propylene oxide addition of polyvalent alcohol A30 part and polyvalent alcohol C10 part and polyvalent alcohol D10 part and 30 parts of polyol Es and average hydroxyl value 500 (be the 6th polyhydroxy reactant, claim polyvalent alcohol F).
And, in 100 parts of this polyol blend compositions, cooperate 15 parts of pentamethylene whipping agents, 1.2 parts in water, with N as catalysts, N ', N " three (3-dimethylamino-propyl) six 0.5 part of hydrogen s-triazine (KAO. Corp. SA's system), N; 1 part of N '-dimethylcyclohexylamine (KAO. Corp. SA's system); N; N, N ', N '; N " 1 part of-five methyl diethylentriamine (KAO. Corp. SA's system), 1.5 parts of trimethylammonium aminoethylpiperazine are as 2 parts of the organo-siloxanes (trade(brand)name: F-392, chemical company of SHIN-ETSU HANTOTAI system) of suds-stabilizing agent.
In addition, as isocyanic ester, foam for 133 parts with diphenylmethanediisocyanate.The polyvalent alcohol of this moment and the liquid temperature of isocyanic ester are adjusted to 20 ℃.At first, stir polyvalent alcohol and isocyanic ester, inject in the aluminium-making mould of 540 * 320 * 35mmt that is adjusted to 45 ℃, filling ratio is 110% to foam.After 5 minutes, with its moulding product demoulding, similarly measure with the 35mmt heat-insulating shield and the comparative example 1 of rigid polyurethane foam from mould.It is the results are shown in the comparative example 2 of table 1.
As can be seen from Table 1, comparative example 2 density 34kg/m
3(greatly), thermal conductivity 18.2mW/mK (greatly), compressive strength 0.1MPa (slightly little), low temperature size changing rate-0.65% (little), high temperature size changing rate 2.12% (big especially).In addition, paste aluminium strip at the cutting surface of the heat-insulating shield of comparative example 2, be determined at when leaving standstill under the condition of 30 ℃ of temperature, humidity 50% through the thermal conductivity of number of days through the time impairment grade the result, the deterioration through 2 weeks is 5.8% (bigger).
In addition,, measure the result of heat leak amount, compare, do not reduce the heat leak amount basically with conventional example with the thermal insulator that comparative example 1 is similarly made the real machine of the rigid polyurethane foam that uses comparative example 2.
(comparative example 3)
Comparative example 3 as polyhydroxy reactant, shown in the comparative example 3 of table 1, carries out blended polyol blend composition for 40 parts by polyvalent alcohol A40 part, polyvalent alcohol B10 part, polyvalent alcohol C5 part, polyvalent alcohol D5 part and polyol E and constitutes.
And, in 100 parts of this polyol blend compositions, cooperate 1.5 parts of 10 parts of pentamethylene whipping agents, water and N as catalysts, 1.5 parts of N '-dimethylcyclohexylamine (KAO. Corp. SA's system), N, N, N ', N ', N " 1.2 parts of tetramethyl-hexamethylene-diamines (KAO. Corp. SA's system), 1.2 parts of trimethylammonium aminoethylpiperazine (KAO. Corp. SA's system), as 2 parts of the organo-siloxane B-8462 (go-Le De シ ユ ミ Star ト corporate system) of suds-stabilizing agent.
In addition, as isocyanic ester, foam for 133 parts with the diphenylmethanediisocyanate polykaryon.The polyvalent alcohol of regulating this moment and the liquid temperature of isocyanic ester are 20 ℃.At first, stir polyvalent alcohol and isocyanic ester, inject in the aluminium-making mould of 540 * 320 * 35mmt that is adjusted to 45 ℃.Filling ratio is 110% to foam.After 5 minutes in the mould with its moulding product demoulding, similarly measure with the 35mmt heat-insulating shield and the comparative example 1 of rigid polyurethane foam.It is the results are shown in the comparative example 3 of table 1.
Find out comparative example 3 density 33.5kg/m by table 1
3(greatly), thermal conductivity 18.5mW/mK (greatly), compressive strength 0.1MPa (slightly little), low temperature size changing rate-0.55% (little), high temperature size changing rate 1.72% (greatly).In addition, paste aluminium strip at the cutting surface of the heat-insulating shield of comparative example 3, be determined at when leaving standstill under the condition of 30 ℃ of temperature, humidity 50% through the thermal conductivity of fate through the time change degree the result, be about 6.8% (bigger) through 2 time-of-weeks.
In addition,, measure the result of heat leak amount, compare, do not reduce the heat leakage amount basically with conventional example with the thermal insulator that comparative example 1 is similarly made the real machine of the rigid polyurethane foam of using comparative example 3.
(embodiment 1)
Embodiments of the invention 1 as polyhydroxy reactant, shown in the embodiment 1 of table 1, are made of the polyol blend composition of 10 parts of polyvalent alcohol A40 parts, polyvalent alcohol B35 part, polyvalent alcohol C10 part, polyvalent alcohol D5 part, polyol E.
And, in 100 parts of this polyol blend compositions, cooperate 1.2 parts of 15 parts of pentamethylene whipping agents, water and N, N ' as catalysts, N " 1 part of three (3-dimethylamino-propyls), six hydrogen-s-triazine (KAO. Corp. SA's system); " 1 part of five methyl diethylentriamine (KAO. Corp. SA's system) is as organosilicone compounds (2 parts of trade(brand)name: the B-8462 (go-Le De シ ユ ミ Star ト corporate system) of suds-stabilizing agent for N, 2 parts of N '-dimethylcyclohexylamine (KAO. Corp. SA's system), N; N; N ', N ', N.
In addition, as isocyanate prepolymer composition, foam for 135 parts with the mixture of diphenylmethanediisocyanate polykaryon and prepolymer modification tolylene diisocyanate.At first, stir polyvalent alcohol and isocyanic ester, inject in the aluminium-making mould of 540 * 320 * 35mmt that is adjusted to 45 ℃, filling ratio is 110% to foam.After 5 minutes in the mould with its moulding product demoulding, similarly measure with the 35mmt heat-insulating shield and the comparative example 1 of rigid polyurethane foam, it be the results are shown in the embodiment 1 of table 1.
Find out that by table 1 embodiment 1, density 29.8kg/m
3(low), thermal conductivity 16.8mW/mK (10 ℃), little, compressive strength 0.13MPa, good, low temperature size changing rate-0.34%, high temperature size changing rate 0.51%, both all can meet the demands.In addition, paste aluminium strip at the cutting surface of the heat-insulating shield of embodiment 1, be determined at when leaving standstill under the condition of 30 ℃ of temperature, humidity 50% through the thermal conductivity of number of days through the time change degree the result, be about 1.8% deterioration through 2 time-of-weeks.
In addition, with the thermal insulator that comparative example 1 is similarly made the real machine of the rigid polyurethane foam of using embodiment 1, measure the result of heat leak amount, compare with conventional example, the heat leakage amount can reduce by 3.2%.
(embodiment 2)
Embodiments of the invention 2 as polyhydroxy reactant, shown in the embodiment 2 of table 1, are made of 7.5 parts of 7.5 parts of 25 parts of 50 parts of polyvalent alcohol A, polyvalent alcohol B, polyvalent alcohol C, polyvalent alcohol D and 10 parts of blended polyol blends of polyol E composition.
And, in 100 parts of this polyol blend compositions, cooperate 0.8 part of 18 parts of pentamethylene whipping agent, water and N as catalysts, N ', N " 0.5 part of three (3-dimethylamino-propyls), six hydrogen-s-triazine (KAO. Corp. SA's system), N; 2.2 parts of N '-dimethylcyclohexylamine (KAO. Corp. SA's system); N, N, N '; N '; N " 1.5 parts of-five methyl diethylentriamines (KAO. Corp. SA's system) are as 2 parts of the organo-siloxanes (trade(brand)name: F-392, chemical company of SHIN-ETSU HANTOTAI system) of suds-stabilizing agent.
In addition, as isocyanic ester, foam for 133 parts with the diphenylmethanediisocyanate polykaryon.The polyvalent alcohol of this moment and the liquid temperature of isocyanic ester are adjusted to 20 ℃.At first, stir polyvalent alcohol and isocyanic ester, inject in the aluminium-making mould of 540 * 320 * 35mmt that is adjusted to 45 ℃, filling ratio 110% foams.After 5 minutes in the mould with its moulding product demoulding, similarly measure with the 35mmt heat-insulating shield and the comparative example 1 of rigid polyurethane foam.It is the results are shown in the embodiment 2 of table 1.
Find out that by table 1 embodiment 2, density 30.9kg/m
3, low, thermal conductivity 17.0mW/mK, little, compressive strength 0.11MPa, good, low temperature size changing rate-0.45%, high temperature size changing rate 1.37%, both all can meet the demands.In addition, paste aluminium strip at the cutting surface of the heat-insulating shield of embodiment 2, be determined at when leaving standstill under the condition of 30 ℃ of temperature, humidity 50% through the thermal conductivity of number of days through the time impairment grade the result, the deterioration about 2 weeks were 2.3%.
In addition, with the thermal insulator that comparative example 1 is similarly made the real machine of the rigid polyurethane foam of using embodiment 2, measure the result of heat leak amount, compare with conventional example, the heat leakage amount can reduce by 3.1%.
(embodiment 3)
Embodiments of the invention 3 as polyhydroxy reactant, shown in the embodiment 3 of table 1, are made of polyvalent alcohol A50 part, polyvalent alcohol B30 part, polyvalent alcohol C5 part, polyvalent alcohol D5 part and 10 parts of blended polyol blends of polyol E composition.
And, in 100 parts of this polyol blend compositions, cooperate 1.2 parts of 14 parts of pentamethylene whipping agents, water and N, N ' as catalysts, 1.4 parts of five methyl diethylentriamines (KAO. Corp. SA's system) of N " 1 part of three (3-dimethylamino-propyls), six hydrogen-s-triazine (KAO. Corp. SA's system); N, 1.8 parts of N '-dimethylcyclohexylamine (KAO. Corp. SA's system), N, N; N '; N ', N " are as 2 parts of the organo-siloxane B-8462 (go-Le De シ ユ ミ Star ト corporate system) of suds-stabilizing agent.
In addition, as isocyanic ester, foam for 133 parts with the diphenylmethanediisocyanate polykaryon.The polyvalent alcohol of this moment and the liquid temperature of isocyanic ester are adjusted to 20 ℃.At first, stir polyvalent alcohol and isocyanic ester, inject in the aluminium-making mould of 540 * 320 * 35mmt that is adjusted to 45 ℃, filling ratio 110% foams.After 5 minutes in the mould with its moulding product demoulding, similarly measure with the 35mmt heat-insulating shield and the comparative example 1 of rigid polyurethane foam, it be the results are shown in table 1
Embodiment 3.
Found out that by table 1 embodiment 3, density is 29.8kg/m
3, low, thermal conductivity is 16.8mW/mK, and is little, compressive strength 0.13MPa is good, and low temperature size changing rate-0.54%, high temperature size changing rate 0.95%, both all can meet the demands.In addition, paste aluminium strip at the cutting surface of the heat-insulating shield of embodiment 3, be determined at when leaving standstill under the condition of 30 ℃ of temperature, humidity 50% through the thermal conductivity of number of days through the time impairment grade the result, the deterioration about 2 time-of-weeks are 1.9%.
In addition, with the thermal insulator that comparative example 1 is similarly made the real machine of the rigid polyurethane foam of using embodiment 3, measure the result of heat leak amount, compare with conventional example, the heat leakage amount can reduce by 3.3%.
(embodiment 4)
Embodiments of the invention 4 as polyhydroxy reactant, shown in the embodiment 4 of table 1, are made of polyvalent alcohol A48 part, polyvalent alcohol B25 part, polyvalent alcohol C10 part, polyvalent alcohol D5 part and 12 parts of blended polyol blends of polyol E composition.
And, in 100 parts of this polyol blend compositions, cooperate 1 part of 17 parts of pentamethylene whipping agent, water and N as catalysts, N ', N " 0.5 part of three (3-dimethylamino-propyls), six hydrogen-s-triazine (KAO. Corp. SA's system), N; 2 parts of N '-dimethylcyclohexylamine (KAO. Corp. SA's system); N, N, N '; N '; N " 1 part of-five methyl diethylentriamine (KAO. Corp. SA's system) is as 2 parts of the organo-siloxanes (trade(brand)name: F-392, chemical company of SHIN-ETSU HANTOTAI system) of suds-stabilizing agent.
In addition, as isocyanic ester, foam for 133 parts with diphenylmethanediisocyanate.The polyvalent alcohol of this moment and the liquid temperature of isocyanic ester are adjusted to 20 ℃.At first, stir polyvalent alcohol and isocyanic ester, inject in the aluminium-making mould of 540 * 320 * 35mmt that is adjusted to 45 ℃, filling ratio 110% foams.After 5 minutes in the mould with its moulding product demoulding, similarly measure with the 35mmt heat-insulating shield and the comparative example 1 of rigid polyurethane foam.It is the results are shown in the embodiment 4 of table 1.
Find out that by table 1 embodiment 4, density 31.2kg/m
3(low), thermal conductivity 17.0mW/mK (little), compressive strength 0.11MPa (well), low temperature size changing rate-0.42%, high temperature size changing rate 1.15%, both all can meet the demands.In addition, paste aluminium strip at the cutting surface of the heat-insulating shield of embodiment 4, be determined at when leaving standstill under the condition of 30 ℃ of temperature, humidity 50% through the thermal conductivity of number of days through the time impairment grade the result, the deterioration about 2 weeks were 2.2%.
In addition, with the thermal insulator that comparative example 1 is similarly made the real machine of the rigid polyurethane foam of using embodiment 4, measure the result of heat leak amount, compare with conventional example, the heat leakage amount can reduce by 3.0%.
Adopt the present invention, can obtain to have concurrently thermal conductivity reduces and low densityization, suppress thermal conductivity through the time rigid polyurethane foam and the thermal insulator of dimensional stability deterioration the time.
Claims (6)
1. rigid polyurethane foam, it is the rigid polyurethane foam that generates with the mixed foaming agent of polyvalent alcohol, isocyanic ester, pentamethylene and water, catalyzer and suds-stabilizing agent, aforementioned polyvalent alcohol contain with the tolylene diamine class polyether glycol composition of propylene oxide addition as the 1st polyhydroxy reactant, with the trolamine class polyether glycol composition of propylene oxide addition as the 2nd polyhydroxy reactant, with the aromatic polyester polyol composition as the 3rd polyhydroxy reactant, the aforementioned the 1st and the 2nd polyhydroxy reactant content is more than 6 times of aforementioned the 3rd polyhydroxy reactant.
2. the rigid polyurethane foam of claim 1, aforementioned polyvalent alcohol contains the sucrose polyether glycol composition of propylene oxide addition as the 4th polyhydroxy reactant, the glycerin polyether polyhydroxy reactant of propylene oxide addition is as the 5th polyhydroxy reactant, and the total content of aforementioned the 1st polyhydroxy reactant, aforementioned the 2nd polyhydroxy reactant, aforementioned the 4th polyhydroxy reactant and aforementioned the 5th polyhydroxy reactant is more than the 85 weight % of aforementioned polyvalent alcohol.
3. the rigid polyurethane foam of claim 2 generates with three polyureas acid esters catalyzer.
4. each rigid polyurethane foam among the claim 1-3, it is characterized in that aforementioned polyvalent alcohol is the 1st polyhydroxy reactant 40～50 weight parts of the hydroxyl value 400～500 of propylene oxide and toluylenediamine addition, the 2nd polyhydroxy reactant 25～35 weight parts of the hydroxyl value 350～450 of propylene oxide and trolamine addition, the 4th polyhydroxy reactant 5～10 weight parts of the hydroxyl value 400～480 of propylene oxide and sucrose addition, the mixture of the 3rd polyhydroxy reactant 5～15 weight parts of the 5th polyhydroxy reactant 5～10 weight parts of the hydroxyl value 350～450 of propylene oxide and glycerine addition and the hydroxyl value 300～360 of Tetra hydro Phthalic anhydride and ethylene glycol condensation.
5. the rigid polyurethane foam of claim 4 with respect to aforementioned polyvalent alcohol 100 weight parts, uses the water of pentamethylene 10～20 weight parts and 0.5～2.0 weight part to generate.
6. thermal insulator, it is the space filling polyvalent alcohol that forms between outside plate and inner panel, isocyanic ester, the mixed foaming agent of pentamethylene and water, the thermal insulator of the rigid polyurethane foam that catalyzer and suds-stabilizing agent generate, aforementioned polyvalent alcohol contains the tolylene diamine class polyether glycol composition of propylene oxide addition as the 1st polyhydroxy reactant, the trolamine class polyether glycol composition of propylene oxide addition is as the 2nd polyhydroxy reactant, with the aromatic polyester polyol composition as the 3rd polyhydroxy reactant, the aforementioned the 1st and the 2nd polyhydroxy reactant content is more than 6 times of aforementioned the 3rd polyhydroxy reactant.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2002187250A JP4054615B2 (en) | 2002-06-27 | 2002-06-27 | Rigid polyurethane foam and insulation |
| JP187250/2002 | 2002-06-27 |
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| Publication Number | Publication Date |
|---|---|
| CN1468880A true CN1468880A (en) | 2004-01-21 |
| CN1213089C CN1213089C (en) | 2005-08-03 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 03123629 Expired - Fee Related CN1213089C (en) | 2002-06-27 | 2003-05-09 | Hard polyurethane foam material and insulator |
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| Country | Link |
|---|---|
| JP (1) | JP4054615B2 (en) |
| CN (1) | CN1213089C (en) |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101831045A (en) * | 2010-04-30 | 2010-09-15 | 北京化工大学 | High-performance rigid polyurethane foam material containing epoxide group |
| CN101260181B (en) * | 2008-04-09 | 2010-10-13 | 南通华盛高聚物科技发展有限公司 | Melt spinning spandex interlinkage agent and producing method thereof |
| CN102432794A (en) * | 2011-09-14 | 2012-05-02 | 可利亚多元醇（南京）有限公司 | Hard polyurethane composition with low thermal conductivity and rapid demoulding property as well as its preparation method |
| CN103374113A (en) * | 2012-04-23 | 2013-10-30 | 日立空调·家用电器株式会社 | Hard polyurethane foam and premixed dolichol for manufacturing the same |
| CN102203158B (en) * | 2008-11-06 | 2013-11-27 | 旭有机材工业株式会社 | Expandable composition for polyurethane foam, and polyurethane foam |
| CN107245137A (en) * | 2017-04-14 | 2017-10-13 | 合肥华凌股份有限公司 | Refrigerator combined polyether and its production and use |
| CN114057981A (en) * | 2021-11-09 | 2022-02-18 | 红宝丽集团股份有限公司 | Polyurethane rigid foam and combined polyether used by same |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN106832248B (en) * | 2017-01-23 | 2019-01-29 | 山东一诺威新材料有限公司 | The preparation method of fast demoulding rigid-foam polyether polyol |
-
2002
- 2002-06-27 JP JP2002187250A patent/JP4054615B2/en not_active Expired - Fee Related
-
2003
- 2003-05-09 CN CN 03123629 patent/CN1213089C/en not_active Expired - Fee Related
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101260181B (en) * | 2008-04-09 | 2010-10-13 | 南通华盛高聚物科技发展有限公司 | Melt spinning spandex interlinkage agent and producing method thereof |
| CN102203158B (en) * | 2008-11-06 | 2013-11-27 | 旭有机材工业株式会社 | Expandable composition for polyurethane foam, and polyurethane foam |
| CN101831045A (en) * | 2010-04-30 | 2010-09-15 | 北京化工大学 | High-performance rigid polyurethane foam material containing epoxide group |
| CN101831045B (en) * | 2010-04-30 | 2012-10-17 | 北京化工大学 | High-performance rigid polyurethane foam material containing epoxide group |
| CN102432794A (en) * | 2011-09-14 | 2012-05-02 | 可利亚多元醇（南京）有限公司 | Hard polyurethane composition with low thermal conductivity and rapid demoulding property as well as its preparation method |
| CN103374113A (en) * | 2012-04-23 | 2013-10-30 | 日立空调·家用电器株式会社 | Hard polyurethane foam and premixed dolichol for manufacturing the same |
| CN103374113B (en) * | 2012-04-23 | 2015-10-07 | 日立空调·家用电器株式会社 | Hard polyurethane foam and the many alcohol of hard polyurethane foam manufacture pre-mixing |
| CN107245137A (en) * | 2017-04-14 | 2017-10-13 | 合肥华凌股份有限公司 | Refrigerator combined polyether and its production and use |
| CN114057981A (en) * | 2021-11-09 | 2022-02-18 | 红宝丽集团股份有限公司 | Polyurethane rigid foam and combined polyether used by same |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2004027074A (en) | 2004-01-29 |
| JP4054615B2 (en) | 2008-02-27 |
| CN1213089C (en) | 2005-08-03 |
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