CN100554302C - The manufacture method of polyurethane foaming body - Google Patents
The manufacture method of polyurethane foaming body Download PDFInfo
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- CN100554302C CN100554302C CNB2005101040632A CN200510104063A CN100554302C CN 100554302 C CN100554302 C CN 100554302C CN B2005101040632 A CNB2005101040632 A CN B2005101040632A CN 200510104063 A CN200510104063 A CN 200510104063A CN 100554302 C CN100554302 C CN 100554302C
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Abstract
The method that can make the polyurethane foaming body with fine and uniform foam structure by mechanical foaming effectively is provided, comprise following operation: the fluid composition to the formed urethane that contains polyvalent alcohol and isocyanic ester carries out mechanical stirring in first stirring mixer and under the atmosphere of inert gases, thereby be mixed with the spumescence composition that in this fluid composition, is dispersed with rare gas element, again this spumescence delivery of composition is carried out mechanical stirring in second stirring mixer, then from second mixing and blending machine, discharge the rotor revolution number (r when in first stirring mixer, stirring
1) be 200～1500rpm, the rotor revolution number (r when in second stirring mixer, stirring
2) be 240～3000rpm, ratio of revolution (r
2/ r
1) be 1.2～5.0.
Description
Technical field
The present invention relates to the manufacture method of polyurethane foaming body, more specifically, relate to make effectively the polyurethane foaming body manufacture method of polyurethane foaming body (polyurethane foaming body) with fine and uniform foam structure.
Background technology
As the manufacture method of polyurethane foaming body, be known that by under atmosphere of inert gases, mix the composition (polyvalent alcohol and isocyanic ester) that can form urethane carry out mechanical foaming mechanical foaming (referring to, for example patent documentation 1).
Mechanical foaming has following advantage: the forming operation than chemical blowing process (water foaming) is simpler, and can not occur causing the inferior foam of rerum natura etc. because of urea groups.
In mechanical foaming, be that polyvalent alcohol, isocyanic ester and rare gas element (air) are provided in the stirring mixer (mixinghead), be mixed with the spumescence raw material by mechanical stirring polyvalent alcohol and isocyanic ester under atmosphere of inert gases, again it is discharged from stirring mixer, and inject mould etc. and be cured.
The polyurethane foaming body that is obtained by this method must form fine and uniform abscess (bubble that is formed by rare gas element).
Patent documentation 1 spy opens 2001-89547
Summary of the invention
The foam structure of polyurethane foaming body depends on the agitation condition (the particularly revolution of rotor) of stirring mixer.No matter be the revolution low excessively (stirring insufficient) of rotor, or the revolution of rotor too high (excessive agitation), all can not form and have fine and polyurethane foaming body uniform foam structure.Therefore, the inventor is carrying out wholwe-hearted research aspect the best agitation condition setting of the miniaturization of the abscess of seeking to obtain polyurethane foaming body and homogenizing repeatedly.
But only the miniaturization and the homogenizing of the abscess that is reached by the agitation condition (rotor revolution number) of optimizing stirring mixer are limited.
The present invention is based on above situation and makes, and the method that can make the polyurethane foaming body with fine and uniform foam structure effectively that provides is provided.
In order to solve problem, the inventor has carried out research intently repeatedly, found that by under certain agitation condition, the spumescence composition that is obtained by stirring mixer being carried out mechanical stirring again, can obtain with in the past known method can not obtain have fine and polyurethane foaming body uniform foam structure has been finished the present invention based on this understanding.
Manufacture method of the present invention is to make the method for polyurethane foaming body by mechanical foaming, it is characterized in that comprising following operation: the fluid composition to the formed urethane that contains polyvalent alcohol and isocyanic ester carries out mechanical stirring in first stirring mixer and under the atmosphere of inert gases, thereby be mixed with the spumescence composition that in this fluid composition, is dispersed with rare gas element, again this spumescence delivery of composition is carried out mechanical stirring in second stirring mixer, then from second mixing and blending machine, discharge the revolution (r of the rotor when in first stirring mixer, stirring
1) be 200～1500rpm, the revolution (r of the rotor when in second stirring mixer, stirring
2) be 240～3000rpm, ratio of revolution (r
2/ r
1) be 1.2～5.0.
In manufacture method of the present invention, preferred following embodiment.
(1) in second stirring mixer that the spumescence composition is transported to, imports rare gas element, in second stirring mixer He under the atmosphere of inert gases, again the spumescence composition is carried out mechanical stirring.
(2) in second stirring mixer that the spumescence composition is transported to, add the additive (for example catalyzer, suds-stabilizing agent) that is used to form polyurethane foaming body.
(3) in second stirring mixer that the spumescence composition is transported to, add chemical foaming agent.
(4) as preliminary process, under premixer neutralizes the situation that does not have rare gas element, polyvalent alcohol and isocyanic ester are mixed, thereby obtain to form the fluid composition (uniform mixing liquid) of urethane, and this fluid composition is supplied with first stirring mixer.
(5) ratio of revolution (r
2/ r
1) be 1.5～4.0.
Invention according to claim 1, by the spumescence composition that is obtained by first stirring mixer being carried out mechanical stirring once more with second stirring mixer, can obtain to have fine (for example, mean cell diameter is below 60 μ m) and the even polyurethane foaming body of the foam structure of (for example, the cell diameter deviation is in ± 20 μ m).
Invention according to claim 2, also under atmosphere of inert gases, carry out (two stages were implemented mechanical foaming) by making the mechanical stirring that adopts second stirring mixer, make the polyurethane foaming body that is obtained have finer foam structure (for example, mean cell diameter is below 40 μ m).
Invention according to claim 3, do not provide additive (for example catalyzer, suds-stabilizing agent) to first stirring mixer, therefore can in first stirring mixer, fully stir (stirring under the long-time and/or high revolution), and needn't consider influence that this additive is caused etc.Thereby, make the polyurethane foaming body that is obtained have finer foam structure (for example, mean cell diameter is below 40 μ m).
According to the invention of claim 4, obtain the spumescence composition with first stirring mixer by mechanical foaming, serve as that foaming nuclear carries out chemical foaming (using chemical foam blowing agent) in second stirring mixer with the bubble that constitutes this spumescence composition.Make thus obtained polyurethane foaming body have atomic thin and uniform foam structure by chemical blowing process.
Invention according to claim 5, owing to be provided to first stirring mixer and obtain the polyvalent alcohol that mixes and the uniform mixing liquid of isocyanic ester in the premixer, thereby the revolution of first stirring mixer and/or second stirring mixer can be set at than the revolution when first stirring mixer provides polyvalent alcohol and isocyanic ester is lower respectively.As a result, in the time of can avoiding in first stirring mixer or second stirring mixer, carrying out high revolution and stir because of the problems such as raw material curing that the polyurethane-reinforcement reaction causes take place.
Below the present invention is described in detail.
In manufacture method of the present invention, in first stirring mixer, carry out mechanical stirring (mechanical foaming) and in second stirring mixer, carry out mechanical stirring, thereby prepare uncured spumescence composition.
Fig. 1 [1]～[5] are the artworks that schematically shows the present invention's (invention of claim 1～5) manufacture method, and in the figure, 10 is first stirring mixer, and 20 is second stirring mixer, and 30 is premixer, and 40 is mould.Herein, first stirring mixer 10 and second stirring mixer 20 are made up of of the same type, unidimensional mixing and blending machine in fact.
＜the first embodiment 〉
In the manufacture method shown in Fig. 1 [1], when polyvalent alcohol (being abbreviated as " poly " among the figure), isocyanic ester (being abbreviated as " iso " among the figure) and additive (being abbreviated as " add " among the figure) are provided, import air (being abbreviated as " Air " among the figure) as rare gas element in first stirring mixer 10.
In first stirring mixer 10, by not shown rotor the liquid form mixt of the formed urethane that contains polyvalent alcohol, isocyanic ester and additive is being carried out mechanical stirring under air (rare gas element) atmosphere and under the specific agitation condition.Be formulated in the spumescence composition that is dispersed with rare gas element in this liquid form mixt thus.This spumescence composition (being designated as " F (1) " among the figure) is discharged from first stirring mixer 10, offer second stirring mixer 20 again.
Under specific agitation condition, the spumescence composition that is provided to second stirring mixer 20 is carried out mechanical stirring again by not shown rotor.Thereby make the bubble (abscess) that constitutes the spumescence composition become finer and even.
To from second stirring mixer 20, discharge through above-mentioned churned mechanically spumescence composition (being designated as " F (2) " among the figure), and injection mould 40, under the situation that keeps its foamed state (fine, uniform foam structure), in mould 40, be cured, thus the moulding product that acquisition is made of polyurethane foaming body.
Fig. 2 is the explanatory view that shows the schematic configuration of a stirring mixer example that is used as first stirring mixer 10 or second mixing and blending machine 20.
In Fig. 2,21 is cylinder-like shell, and 22 is mixing section, and 23 is rotor, and 24 is its turning axle, and 251,252 is the raw material supplying mouth, and 26 is gas supply port, and 27 is the raw material relief outlet.
Shell 21 has the double-sleeve structure of outer tube 211 and interior pipe 212, forms the zone of the stream 213 of heat-eliminating medium (water) by outer tube 211 and interior pipe 212.214 is the heat-eliminating medium influx, and 215 is the heat-eliminating medium spout.
The periphery of rotor 23 be provided with on the length direction of turning axle 24 arrange at regular intervals, be radial outward extending post 23P from turning axle 24.
On the other hand, the inner peripheral surface of shell 21 (interior pipe 212) is provided with on its length direction (with post 23P identical distance) arrange and post 21P that extend internally at regular intervals.As shown in Figure 2, by the post 23P of the rotor 23 that is crisscross arranged and the post 21P of shell 21, can carry out effective stirring operation (applying shearing force).The capacity of mixing section 22 is, for example 200～3000cm
3
If give an example to using first stirring mixer 10 (stirring mixer of structure shown in Figure 2) liquid towards composition (polyvalent alcohol, isocyanic ester and additive) under atmosphere of inert gases to carry out churned mechanically method, can be to provide polyvalent alcohol and additive from raw material supplying mouth 251 to mixing section 22 respectively, provide isocyanic ester from raw material supplying mouth 252 to mixing section 22, provide rare gas element (air) from gas supply port 26 simultaneously.Herein, the ratio of fluid composition that provides to the mixing section 22 of first stirring mixer 10 and rare gas element count by measure and be preferably 1: 9～1: 0.01.
By the rotation of rotor 23, the fluid composition (polyvalent alcohol, isocyanic ester and additive) that is provided to mixing section 22 is stirred under rare gas element (air) atmosphere.
Also have, when stirring, can make water pass through heat-eliminating medium stream 213, thereby the temperature in the mixing section 22 that suppresses to cause because of shear heat rises.
Revolution (the r of rotor when in first stirring mixer 10, stirring
1) be 200～1500rpm, be preferably 200～800rpm, more preferably 200～400rpm.
If revolution (r
1) not enough 200rpm, then polyvalent alcohol and isocyanic ester can not reach sufficient homogenizing, and rare gas element can not be disperseed fully.On the other hand, as revolution (r
1) when surpassing 1500rpm, the shear heat that produces during stirring is excessive, may solidify because of the raw material that makes of polyurethane-reinforcement reaction.
The spumescence composition that obtains is in a manner described discharged from the raw material relief outlet 27 of first stirring mixer 10, and be transported to the mechanical stirring of carrying out in second stirring mixer 20 once more.
If give an example to using second stirring mixer 20 (stirring mixer of structure shown in Figure 2) that the spumescence composition is carried out churned mechanically method, can be to provide the spumescence composition to mixing section 22 from raw material supplying mouth (251 or 252), not supplying with under the situation of rare gas element, the spumescence composition is stirred by the rotation of rotor 23 from gas supply port 26.In addition, when stirring, can make water pass through heat-eliminating medium stream 213, thereby the temperature in the mixing section 22 that suppresses to cause because of shear heat rise.
Thereby, the spumescence composition that reaches abscess miniaturization, homogenizing is discharged from raw material relief outlet 27, inject mould etc.
Revolution (the r of rotor when in second stirring mixer 20, stirring
2) be 240～3000rpm, be preferably 400～2000rpm, more preferably 500～800rpm.
If revolution (r
2) not enough 240rpm, then ratio of revolution (r
2/ r
1) do not reach more than 1.2.On the other hand, if stirring above under the revolution of 3000rpm, the destruction that will steep (over mix) makes the polyurethane foaming body that is obtained not have uniform foam structure.In addition, because the shear heat that produces is excessive, the excessive temperature in the mixing section 22 raises and the raw material generation is solidified.
In the manufacture method shown in Fig. 1 [1], the rotor revolution number (r when stirring with second stirring mixer 20
2) rotor revolution number (r when stirring with first stirring mixer 10
1) ratio (r
2/ r
1) be 1.2～5.0, be preferably 1.5～4.0.Owing to make ratio of revolution (r
2/ r
1) be limited in the above-mentioned scope, make can pass that in the past manufacture method (utilizing the manufacture method of independent stirring mixer) can not obtain, have fine and polyurethane foaming body uniform foam structure.
If this ratio of revolution (r
2/ r
1) less than 1.2, then in second stirring mixer 20, be damaged with 10 formation of first stirring mixer and steeping oneself-meeting of maintenance, can not make the polyurethane foaming body that obtains have fine foam structure.On the other hand, if ratio of revolution (r
2/ r
1) surpass 5.0, then can cause overmixing, can not make the polyurethane foaming body that obtains have fine and uniform foam structure.
In the manufacture method shown in Fig. 1 [1], the time (residence time of raw material) of using first stirring mixer 10 and second stirring mixer 20 to stir during manufacturing respectively is, for example 30～90 seconds.
In addition, the amount of the spumescence composition of being discharged by raw material relief outlet 27 is 400～5000cm
3/ minute.
In addition, have no particular limits the set time in the mould, from the angle of preparation efficiency, is preferably in 30 minutes.
According to the manufacture method (first embodiment) shown in Fig. 1 [1], owing to the mechanical stirring of the spumescence composition that obtains in first stirring mixer 10 being carried out in second stirring mixer 20 once more, thereby can obtain can not obtain by in the past manufacture method (adopting the manufacture method of single stirring mixer), have fine (for example, mean cell diameter is that 60 μ m are following) and the even polyurethane foaming body of the foam structure of (for example, the deviation of cell diameter is in ± 20 μ m).
＜the second embodiment 〉
Manufacture method shown in Fig. 1 [2] is the air that also imports in second stirring mixer 20 that the spumescence composition is transported to as rare gas element, under the atmosphere in second stirring mixer 20 and at rare gas element foam composition is carried out once more mechanical stirring.
According to this manufacture method (second embodiment), mechanical stirring in second stirring mixer 20 also is to implement under the atmosphere at rare gas element, the result is: two stages have been experienced in the enforcement of mechanical foaming, make the polyurethane foaming body that obtains have finer foam structure (for example, mean cell diameter is that 40 μ m are following).
＜the three embodiment 〉
Manufacture method shown in Fig. 1 [3] is to supply with the method for additive (for example catalyzer, suds-stabilizing agent) in second stirring mixer 20 that the spumescence composition is transported to.
According to this manufacture method (the 3rd embodiment), can in first stirring mixer 10, not supply with additive, thereby can be in not considering first stirring mixer 10 additive (be for example impacted etc., quicken curing reaction because of catalyzer exists) situation under, carry out the abundant stirring under the long-time and/or high revolution.Therefore, the polyurethane foaming body that is formed by the spumescence composition that obtains through fully stirring just has finer foam structure (for example, mean cell diameter is that 40 μ m are following).
＜the four embodiment 〉
Manufacture method shown in Fig. 1 [4] is the method for providing chemical whipping agent in second stirring mixer 20 that the spumescence composition is transported to (being designated as " forming agent " among the figure).
In this manufacture method (the 4th embodiment), in first stirring mixer 10, obtain the spumescence composition by mechanical foaming, the bubble that will constitute this spumescence composition again carries out chemical foaming (passing through chemical foam blowing agent) as foaming nuclear in second stirring mixer 20.
Owing to adopted chemical blowing process, make thus obtained polyurethane foaming body have very fine (for example, mean cell diameter is that 30 μ m are following) and foam structure uniformly.
＜the five embodiment 〉
The feature of the manufacture method shown in Fig. 1 [5] is under premixer 30 neutralizes the situation that does not have rare gas element polyvalent alcohol, isocyanic ester and additive to be mixed, thereby be mixed with fluid composition (uniform mixing liquid), this fluid composition is supplied with first stirring mixer 10, other technology is identical with content shown in Fig. 1 [1] again.
That is to say, in this manufacturing process (the 5th embodiment), the married operation (adopt premixer 30 carry out mix) of preparation fluid composition (the uniform mixing liquid of polyvalent alcohol, isocyanic ester and additive) and rare gas element dispersive in fluid composition is operated (mechanical stirring of carrying out with first stirring mixer 10) and is implemented respectively.
Fig. 3 is the explanatory view of schematic configuration that shows the example of a premixer 30.
In the figure, 31 is shell, and 32 is cushion block (head block), and 33 is mixing section, and 34 is rotor, and 35 is its turning axle, and 36 is first nozzle, and 37 is second nozzle, and 38 is the raw material relief outlet.
Be formed with spiral groove 39 on the periphery of rotor 34.Also have, the periphery shape of rotor 34 has no particular limits, as long as can improve stirring efficiency, for example can form concavo-convex on whole peripherys.
The capacity of the mixing section 33 of premixer 30 is, for example 10～450cm
3
The married operation of polyvalent alcohol, isocyanic ester and additive is to carry out in the mixing section 33 that is surrounded by shell 31 and cushion block 32.Particularly,, supply with isocyanic ester, both are mixed by the rotation of rotor 34 from second nozzle 37 when first nozzle 36 is supplied with polyvalent alcohol and additive.
This married operation is to carry out under the situation that inert-free gas exists.By this operation, even under lower revolution, (for example 200～1000rpm) also can make both reach homogenizing effectively.
Herein, the revolution of rotor 34 is preferably more than the 200rpm, more preferably 200～900rpm.
In addition, the time (residence time of raw material) of using premixer 30 to mix is, for example 0.5～10 second.
By mixing of premixer 30, can obtain the fluid composition that is uniformly mixed to form by polyvalent alcohol, isocyanic ester and additive.This fluid composition is discharged from raw material relief outlet 38, be delivered to first stirring mixer 10, the raw material supplying mouth (raw material supplying mouth 251 shown in Figure 2 or any one of 252) from first stirring mixer 10 supplies to the mixing section again.
According to this manufacture method (the 5th embodiment), uniform mixing liquid (liquid form mixt) after mixing in premixer 30 is fed in first stirring mixer 10, thereby the revolution of first stirring mixer 10 and/or second stirring mixer 20 can be set at revolution lower (even slow speed also can make rare gas element obtain differential and loose) when polyvalent alcohol and isocyanic ester are supplied with first stirring mixer 10 respectively.Under this slow speed, implement mechanical stirring, reduce the shear heat that is produced, consequently in first mixing and blending machine 10 or second stirring mixer 20, can not produce the raw material curing (phenomenon that occurs when under high revolution, stirring) that the polyurethane-reinforcement reaction is caused.
＜other embodiment 〉
More than the embodiment of manufacture method of the present invention is illustrated, but the present invention is not limited thereto, can carry out various variations.For example, can be to carrying out appropriate combination more than 2 kinds or 3 kinds in above-mentioned 5 kinds of embodiments.
In addition,, the part (for example suds-stabilizing agent) of additive can also be supplied to first stirring mixer 10, the remainder (for example catalyzer) of additive is supplied to second stirring mixer 20 as the variation example of the third embodiment.
And, can also on second stirring mixer 20, connect one or more other stirring mixers, use the stirring mixer (the 3rd stirring mixer, the 4th stirring mixer ... n stirring mixer) that is connected that the spumescence composition of discharging from second stirring mixer 20 is implemented mechanical stirring once more.
＜polyurethane foaming body 〉
The polyurethane foaming body that obtains by manufacture method of the present invention can form littler (for example than the cell diameter of the polyurethane foaming body that uses known in the past mechanical foaming (adopting the manufacture method of single stirring mixer) to be obtained, mean cell diameter is below the 60 μ m, particularly 40 μ m are following), the cell diameter deviation is littler (for example, deviation is in ± 20 μ m, particularly in ± 10 μ m) foam structure.
Therefore, have this finely and polyurethane foaming body uniform foam structure has high mechanical strength, and the deviation of the physical strength of different sites is little.
＜polyvalent alcohol 〉
As " polyvalent alcohol " that use in the manufacture method of the present invention, can enumerate polyether glycol, polyester polyol, polycarbonate polyol, polyolefin polyhydric alcohol, acryl polyvalent alcohol, low molecular polylol (chainextender) etc.
Particularly preferably be, use at least a polyvalent alcohol be selected from following (1) and (2) simultaneously, be selected from least a low molecular polylol in following (3).
(1) average functional group number is 2.0～4.0, number-average molecular weight is 600～10,000 polyether glycol.
(2) average functional group number is 2.0～4.0, number-average molecular weight is 600～10,000 polyester polyol.
(3) functional group's number is 2～4, molecular weight is the low molecular polylol below 600.
Polyether glycol as above-mentioned (1), can enumerate by use and have 2～4 compound bearing active hydrogen as initiator, be that poly-(ethylene oxide) polyvalent alcohol of 2.0～4.0, poly-(propylene oxide) polyvalent alcohol, poly-(tetrahydrofuran (THF)) polyvalent alcohol carry out the material that addition prepares with cyclic ethers to the average functional group of nominal number.
As " having 2～4 compound bearing active hydrogen " of being used to make polyether glycol, can enumerate ethylene glycol, 1,2-propylene glycol, 1, ammediol, 2,2-dimethyl-1, ammediol (neopentyl glycol), 1,3 butylene glycol, 1,4-butyleneglycol, 1,5-pentanediol, 1,6-hexylene glycol, glycol ether, dipropylene glycol, triglycol, decamethylene-glycol, 3-methyl isophthalic acid, low molecular weight diols such as 5-pentanediol, dihydroxyphenyl propane; Lower molecular weight triols such as glycerine, hexanetriol, TriMethylolPropane(TMP); Low molecular weight polyols such as tetramethylolmethane; Aliphatie diamine such as quadrol, propylene diamine; Aromatic diamines such as phenylenediamine, tolylene diamine, dimethylphenylene diamine, ditan diamines; Aromatic amines such as aniline; Low molecule amino alcohols such as monoethanolamine, diethanolamine, trolamine; The tetra methylol hexanaphthene; Methyl glucosides etc., they may be used singly or in combination of two or more.
As " cyclic ethers " that be used to make polyether glycol, can enumerate oxyethane, propylene oxide, butylene oxide ring, trimethylene oxide, tetrahydrofuran (THF) etc.
As the polyester polyol of above-mentioned (2), can enumerate the compound (polyvalent alcohol) that contains two above hydroxyls and utilize known method to react with the compound (polyprotonic acid) that contains two above carboxyls and the material for preparing.
As " compound (polyvalent alcohol) that contains two above hydroxyls " that be used to make polyester polyol, can enumerate above-mentioned low molecular weight diols and lower molecular weight trivalent alcohol, they may be used singly or in combination of two or more.
As " compound (polyprotonic acid) that contains two above carboxyls " that be used to make polyester polyol, can enumerate hexanodioic acid, propanedioic acid, succsinic acid, tartrate, pimelic acid, sebacic acid, oxalic acid, phthalic acid, terephthalic acid, m-phthalic acid, Tetra hydro Phthalic anhydride, nonane diacid, trimellitic acid, propene dicarboxylic acid, α-hydrogen muconic acid, β-hydrogen muconic acid, α-butyl-α-Yi Jiwuersuan, α, β-diethyl succsinic acid, benzene-1,2,3-tricarboxylic acid, 1, the 4-cyclohexane dicarboxylic acid, 2, the 6-naphthalene dicarboxylic acids, 4,4 '-diphenyl dicarboxylic acid, 4,4 '-diphenyl ether dicarboxylic acid, 4,4 '-ditan dicarboxylic acid, 4,4 '-sulfobenzide dicarboxylic acid, 4,4 '-phenylbenzene isopropylidene dicarboxylic acid, 1,2-biphenoxyl ethane-4 '; 4 "-dicarboxylic acid, the anthracene dicarboxylic acid, 2, the 5-pyridine dicarboxylic acid, benzophenone dicarboxylic acid etc., they may be used singly or in combination of two or more.
The average functional group number of the polyvalent alcohol of above-mentioned (1) and above-mentioned (2) is 2.0～4.0, is preferably 2.0～3.0.
When the average functional group number of polyvalent alcohol less than 2.0 the time, resulting polyurethane foaming body does not have high mechanical strength (tensile strength, tear strength).On the other hand, the average functional group number of polyvalent alcohol was greater than 4.0 o'clock, and resulting polyurethane foaming body does not have snappiness (elongation), shows fragility.
The number-average molecular weight of the polyvalent alcohol of above-mentioned (1) and above-mentioned (2) is 600～10,000, is preferably 1,000～5,000.
When the number-average molecular weight less than 600 of polyvalent alcohol, resulting polyurethane foaming body does not have snappiness power (tensile strength, elongation).On the other hand, when the number-average molecular weight of polyvalent alcohol surpasses at 10,000 o'clock, resulting polyurethane foaming body does not have high mechanical strength (tensile strength, tear strength) and good compression performance (for example, low compression set).
Low molecular weight polyols as above-mentioned (3), can illustration ethylene glycol, glycol ether, triglycol, propylene glycol, dipropylene glycol, 1,4-butyleneglycol, 1, low molecular weight diols such as 6-hexylene glycol, neopentyl glycol, lower molecular weight triols such as glycerine, TriMethylolPropane(TMP), trimethylolethane, hexanetriol, lower molecular weight tetrols such as Glycerol dimer etc.
By also using low molecular polylol, can give resulting polyurethane foaming body with high mechanical strength.
＜isocyanic ester 〉
As " isocyanic ester " that use in the manufacture method of the present invention, can enumerate diphenylmethanediisocyanate (MDI), phenylene diisocyanate, 2,4-tolylene diisocyanate (2,4-TDI), 2,6-tolylene diisocyanate (2,6-TDI) wait the aromatic isocyanate class, the tetramethylene vulcabond, HDI aliphatic diisocyanates such as (HDI), isophorone diisocyanate, hydrogenation TDI, alicyclic diisocyanates such as hydrogenation MDI, the terminal prepolymers of NCO base that obtained by isocyanic ester and polyol reaction etc., they may be used singly or in combination of two or more.
Wherein, the preferred terminal prepolymer of NCO base that obtains with polyol reaction by the MDI kind isocyanate (below be also referred to as " the basic terminal prepolymer of MDI class NCO ") that uses.
The terminal prepolymer of MDI class NCO base that formation can form the composition of urethane is that the reaction by MDI kind isocyanate and polyvalent alcohol obtains.
Comprise MDI (two nucleomes) and polymeric MDI (polykaryon that three nucleomes are above) in " MDI kind isocyanate " herein.
Be used to form the MDI of the terminal prepolymer of MDI class NCO base and the ratio of polymeric MDI and be preferably 30～100: 70～0, more preferably 40～100: 60～0.
In addition, have 4 among the employed MDI, 4 '-MDI, 2,4 '-MDI and 2, the isomer of 2 '-MDI, preferred 4, the ratio of 4 '-MDI is more than 70%.
As the polyvalent alcohol that is used to form the terminal prepolymer of MDI class NCO base, can enumerate dibasic alcohol such as polyether glycol, polyester glycol, polycarbonate diol.
As " polyether glycol " that be used to form the terminal prepolymer of MDI class NCO base, can illustration polyoxyethylene glycol (PEG), polypropylene glycol (PPG), polytetramethylene glycol (PTMG); With aliphatic dihydroxy alcohol (ethylene glycol, 1 for example, 3-butyleneglycol, 1,4-butyleneglycol, glycol ether, dipropylene glycol, 1,2-propylene glycol, 1, ammediol) make cyclic ethers (for example for initiator, oxyethane, propylene oxide, trimethylene oxide, tetrahydrofuran (THF)) carry out ring-opening polymerization and the polyether glycol made, they may be used singly or in combination of two or more.
As " polyester glycol " that be used to form the terminal prepolymer of MDI class NCO base, can illustration gather (ethylene glycol adipate(EGA)) glycol, poly-(hexanodioic acid propylene glycol ester) glycol, poly-(adipate glycol-propylene glycol ester) glycol, poly-(tetramethylene adipate) glycol, poly-(hexanodioic acid 1,6-hexylene glycol ester) glycol; By ethylene glycol, propylene glycol, hexanodioic acid carry out polycondensation and the copolyesters glycol made [for example, poly-(hexanodioic acid 1,4-butyleneglycol-glycol ester) glycol, poly-(hexanodioic acid 1,4-butyleneglycol-propylene glycol ester) glycol and poly-(hexanodioic acid 1,4-butyleneglycol-ethylene glycol and 1,2-propylene glycol ester) glycol]; Carry out polycondensation and the polyester glycol made by caprolactone and/or dicarboxylic acid (for example succsinic acid wherein, propanedioic acid, pimelic acid, sebacic acid and suberic acid) and low molecular weight diols, they may be used singly or in combination of two or more.
As " polycarbonate diol " that be used to form the terminal prepolymer of MDI class NCO base, lower molecular weight carbonic ether and low molecular weight diols be can enumerate and (dealcoholysis polycondensation) and the material of formation reacted, they may be used singly or in combination of two or more.
As " the lower molecular weight carbonic ether " that be used to form polycarbonate diol, can enumerate dialkyl carbonate (for example, diethyl carbonate), carbonic acid two alkylene esters (for example, carbonic acid two ethyls), diphenyl carbonate etc.
The terminal prepolymer of MDI class NCO base can mix with polyvalent alcohol by the MDI kind isocyanate, this mixture of reheat carries out the polyurethane-reinforcement reaction and is prepared.
The NCO content of the terminal prepolymer of MDI class NCO base is preferably 3～34 quality %, more preferably 4～16 quality %.
When NCO contained quantity not sufficient 3 quality %, the viscosity of this prepolymer is too high, and was poor with the Combination of polyvalent alcohol, causes preparation efficiency low.
On the other hand, when NCO content surpasses 34 quality %, this prepolymer package stability may worsen.
In addition, the average functional group number of the terminal prepolymer of MDI class NCO base is preferably 2.0～3.5, and more preferably 2.0～2.5.
When less than 2.0 was counted by average functional group, the polyurethane foaming body that is obtained did not have good compression characteristic, high mechanical strength.
On the other hand, when average functional group number surpasses 3.5, be easy to take place gelation, bad stability.
As " additive " that use in the manufacture method of the present invention, can enumerate catalyzer, suds-stabilizing agent, tinting material (pigment, dyestuff), antioxidant and UV light absorber etc.
As " catalyzer " as additive, can enumerate triethylenediamine (TEDA), tetramethyl-hexamethylene-diamine (TMHMDA), five methyl diethylentriamine (PMDETA), dimethylcyclohexylam,ne (DMCHA), two dimethylaminoethyl ethers (BDMAEA), the N-Methylimidazole, the front three aminoethylpiperazine, tripropyl amine, triethylamine, amine catalysts such as N-methylmorpholine, oxalic acid two fourth tin, dibutyl tin dilaurate (DBTDL), two lauric acid, two hot tin tin compounds such as (DOTDL), metal complexes such as acetyl acetone salt, the response type amine catalyst [for example, dimethylethanolamine (DMEA), N, N, N '-front three amino ethyl ethanolamine, N, N-dimethylamino ethoxy ethanol] etc.
Description of drawings
Fig. 1 [1]～[5] are for schematically showing the artwork of manufacture method of the present invention.
Fig. 2 is the explanatory view of demonstration as the schematic configuration of an example of the stirring mixer of first stirring mixer or second mixing and blending machine.
Fig. 3 is the explanatory view of schematic configuration that shows an example of premixer.
Nomenclature
10 first stirring mixers
20 second stirring mixers
21 shells
211 outer tubes
Pipe in 212
213 heat-eliminating medium streams
214 heat-eliminating medium influxs
215 heat-eliminating medium spouts
The 21P post
22 mixing sections
23 rotors
The 23P post
24 turning axles
251,252 raw material supplying mouths
26 gas supply ports
27 raw material relief outlets
30 premixers
31 shells
32 cushion blocks
33 mixing sections
34 rotors
35 turning axles
36 first nozzles
37 second nozzles
38 raw material relief outlets
39 spiral grooves
40 moulds
Embodiment
Below, embodiments of the invention are described, but the present invention is not limited thereto.
＜formulation example 1 〉
With the average functional group of nominal number=2, number-average molecular weight=2,000 poly-(oxygen tetramethylene) polyvalent alcohol 85.0 mass parts, the average functional group of nominal number=3, number-average molecular weight=3, poly-(oxygen propylidene) polyvalent alcohol 10.0 mass parts, 1 of 000,4-butyleneglycol 5.0 mass parts, modified organic silicon class A foam A stablizer 1.0 mass parts and tin class catalyzer (DOTDL) 0.02 mass parts are mixed, thereby obtain polyol blends.
＜formulation example 2 〉
Except not sneaking into tin class catalyzer (DOTDL), obtain polyol blends by the mode identical with formulation example 1.
＜synthesis example 1 (synthesizing of the terminal prepolymer of NCO base) 〉
Disposing stirrer, cooling tube, the capacity of nitrogen ingress pipe and thermometer be add in the reaction vessel of 1000mL MDI (contain 1 quality % following by 2,2 '-MDI and 2, more than isomer mixture that 4 '-MDI forms and the 99 quality % 4, the diphenylmethanediisocyanate of 4 '-MDI) the average functional group of 100.0 mass parts and nominal number=2, number-average molecular weight=2, poly-(oxygen tetramethylene) polyvalent alcohol 166.2 mass parts of 000, stir down 4 hours carrying out the polyurethane-reinforcement reaction at 80 ℃, thereby obtain the terminal prepolymer of NCO base that NCO content is 10.0 quality %.
＜embodiment 1 〉
(1) mixes by premixer
Is the premixer 30 (capacity=15cm of mixing section that 1.05 ratio supply to shown in Figure 3 structure in the latter's isocyanate group with respect to the mol ratio ([NCO]/[OH]) of the former hydroxyl with the terminal prepolymer of NCO base that obtains in the polyol blends that obtains in the formulation example 1 and the synthesis example 1
3) in, under the situation that does not have rare gas element, make rotor carry out the rotation of 600rpm and both are mixed, thereby preparation is as the fluid composition of the formed urethane of uniform mixing liquid, the fluid composition that obtains discharged from premixer continuously (residence time of raw material in the mixing section (measured value)=3 second).
(2) carry out mechanical stirring by first stirring mixer
The fluid composition that to discharge from premixer is transported to continuously has mixing section (capacity=450cm structure shown in Figure 2 and first stirring mixer 10 that link to each other with premixer 30
3) in, the continuous simultaneously rare gas element (dry air) that is 0.7 capacity part ratio with respect to this fluid composition 1 capacity part to the mixing section supply, cool off with cold water on one side, make the rotor of first stirring mixer 10 carry out the rotation of 300rpm on one side, under atmosphere of inert gases, this fluid composition is carried out mechanical stirring, thereby be formulated in little spumescence composition that is dispersed with rare gas element in the fluid composition, resulting spumescence composition discharged from first stirring mixer 10 continuously (residence time of raw material in the mixing section (measured value)=60 second).
(3) carry out mechanical stirring by second stirring mixer
The spumescence composition that to discharge from first stirring mixer 10 is transported to continuously has mixing section (capacity=450cm structure shown in Figure 2 and second stirring mixer 20 that link to each other with first stirring mixer 10
3) in, cool off with cold water on one side, make the rotor of second stirring mixer 20 carry out the rotation of 600rpm on one side, thereby this spumescence composition is carried out mechanical stirring (miniaturization of abscess, homogenizing are handled), then this spumescence composition is discharged continuously (residence time of raw material in the mixing section (measured value)=60 second, output=833cm from second stirring mixer 20
3/ min).
(4) casting, solidification treatment
Under normal pressure, will from second stirring mixer 20, discharge the spumescence composition and inject mould (260mm * 220mm * 30mm) continuously, after mould is airtight, this mould was placed 30 minutes in 110 ℃ baking oven, thereby the spumescence composition that makes injection solidifies and makes polyurethane foaming body, it is taken out from mould again.
＜embodiment 2 〉
(1) mixes by premixer
By preparing the fluid composition that can form urethane, the fluid composition that obtains is discharged from premixer continuously (residence time of raw material in the mixing section (measured value)=3 second) with the same mode of embodiment 1 (1).
(2) carry out mechanical stirring by first stirring mixer
The fluid composition that use is discharged from premixer, except the rotor revolution number with first stirring mixer 10 becomes 400rpm, prepare the spumescence composition by the mode identical, resulting spumescence composition is discharged from first stirring mixer 10 continuously (residence time of raw material in the mixing section (measured value)=60 second) with embodiment 1 (2).
(3) carry out mechanical stirring by second stirring mixer
The spumescence composition that to discharge from first stirring mixer 10 is transported to continuously has mixing section (capacity=450cm structure shown in Figure 2 and second stirring mixer 20 that link to each other with first stirring mixer 10
3) in, supplying with respect to the fluid composition 1 capacity part that constitutes this spumescence composition to mixing section continuously simultaneously is the rare gas element (dry air) of 0.5 capacity part ratio, cool off with cold water on one side, make the rotor of second stirring mixer 20 carry out the rotation of 600rpm on one side, thereby under the atmosphere of rare gas element, this spumescence composition is carried out mechanical stirring, then it is discharged continuously (residence time of raw material in the mixing section (measured value)=60 second, output=833cm from second stirring mixer 20
3/ min).
(4) casting, solidification treatment
The spumescence composition that use is discharged from second stirring mixer 20 is made polyurethane foaming body by the mode identical with embodiment 1 (4).
＜embodiment 3 〉
(1) mixes by premixer
Except the polyol blends that replaces obtaining in the formulation example 1 with the polyol blends that obtains in the formulation example 2 (mixture that does not contain DOTDL) ([NCO]/[OH]=1.05), by preparing the fluid composition that can form urethane, the fluid composition that obtains is discharged from premixer continuously (residence time of raw material in the mixing section (measured value)=3 second) with the same mode of embodiment 1 (1).
(2) carry out mechanical stirring by first stirring mixer
The fluid composition that use is discharged from premixer, except the rotor revolution number with first stirring mixer 10 becomes 200rpm, prepare the spumescence composition by the mode identical, resulting spumescence composition is discharged from first stirring mixer 10 continuously (residence time of raw material in the mixing section (measured value)=60 second) with embodiment 1 (2).
(3) carry out mechanical stirring by second stirring mixer
The spumescence composition that to discharge from first stirring mixer 10 is transported to continuously has mixing section (capacity=450cm structure shown in Figure 2 and second stirring mixer 20 that link to each other with first stirring mixer 10
3) in, supplying with respect to fluid composition 100 mass parts that constitute this spumescence composition to mixing section continuously simultaneously is the tin class catalyzer (DOTDL) of 0.02 mass parts ratio, cool off with cold water on one side, make the rotor of second stirring mixer 20 carry out the rotation of 800rpm on one side, this spumescence composition is carried out mechanical stirring, then it is discharged continuously (residence time of raw material in the mixing section (measured value)=60 second, output=833cm from second stirring mixer 20
3/ min).
(4) casting, solidification treatment
The spumescence composition that use is discharged from second stirring mixer 20 is made polyurethane foaming body by the mode identical with embodiment 1 (4).
＜embodiment 4 〉
(1) mixes by premixer
Prepare the fluid composition that can form urethane by the mode identical, the fluid composition that obtains is discharged from premixer continuously (residence time of raw material in the mixing section (measured value)=3 second) with embodiment 1 (1).
(2) carry out mechanical stirring by first stirring mixer
Prepare the spumescence composition by the mode identical, resulting spumescence composition is discharged from first stirring mixer 10 continuously (residence time of raw material in the mixing section (measured value)=60 second) with embodiment 1 (2).
(3) carry out mechanical stirring by second stirring mixer
The spumescence composition that to discharge from first stirring mixer 10 is transported to continuously has mixing section (capacity=450cm structure shown in Figure 2 and second stirring mixer 20 that link to each other with first stirring mixer 10
3) in, supplying with respect to fluid composition 100 mass parts that constitute this spumescence composition to mixing section continuously simultaneously is the chemical foaming agent (methylene dichloride) of 1.0 mass parts ratios, cool off with cold water on one side, make the rotor of second stirring mixer 20 carry out the rotation of 500rpm on one side, this spumescence composition is carried out mechanical stirring, then it is discharged continuously (residence time of raw material in the mixing section (measured value)=60 second, output=833cm from second stirring mixer 20
3/ min).
(4) casting, solidification treatment
The spumescence composition that use is discharged from second stirring mixer 20 is made polyurethane foaming body by the mode identical with embodiment 1 (4).
＜comparative example 1 〉
(1) mixes by premixer
Prepare the fluid composition that can form urethane by the mode identical, the fluid composition that obtains is discharged from premixer continuously (residence time of raw material in the mixing section (measured value)=3 second) with embodiment 1 (1).
(2) carry out mechanical stirring by stirring mixer
The fluid composition that to discharge from premixer is transported to continuously has mixing section (capacity=450cm structure shown in Figure 2 and stirring mixer that link to each other with premixer
3) in, the continuous simultaneously rare gas element (dry air) that is 0.67 capacity part ratio with respect to this fluid composition 1 capacity part to the mixing section supply, cool off with cold water on one side, make the rotor of stirring mixer carry out the rotation of 500rpm on one side, thereby under the atmosphere of rare gas element, this fluid composition is carried out mechanical stirring, be formulated in little spumescence composition that is dispersed with rare gas element in the fluid composition thus, resulting spumescence composition is discharged continuously (residence time of raw material in the mixing section (measured value)=60 second, output=833cm from stirring mixer
3/ min).
(3) casting, solidification treatment
The spumescence composition that use is discharged from stirring mixer is made polyurethane foaming body by the mode identical with embodiment 1 (4).
＜comparative example 2 〉
(1) mixes by premixer
Prepare the fluid composition that can form urethane by the mode identical, the fluid composition that obtains is discharged from premixer continuously (residence time of raw material in the mixing section (measured value)=3 second) with embodiment 1 (1).
(2) carry out mechanical stirring by first stirring mixer
The fluid composition that use is discharged from premixer, except the rotor revolution number with first stirring mixer 10 becomes 800rpm, prepare the spumescence composition by the mode identical, resulting spumescence composition is discharged from first stirring mixer 10 continuously (residence time of raw material in the mixing section (measured value)=60 second) with embodiment 1 (2).
(3) carry out mechanical stirring by second stirring mixer
The spumescence composition that use is discharged from first stirring mixer 10, except the rotor revolution number with second stirring mixer 20 becomes 200rpm, by the mode identical this spumescence composition is carried out mechanical stirring with embodiment 1 (3), and it is discharged continuously (residence time of raw material in the mixing section (measured value)=60 second, output=833cm from second stirring mixer 20
3/ min).
(4) casting, solidification treatment
The spumescence composition that use is discharged from second stirring mixer 20 is made polyurethane foaming body by the mode identical with embodiment 1 (4).
Respectively resulting polyurethane foaming body in embodiment 1～4 and the comparative example 1～2 is measured, estimated according to following project.The results are shown in the following table 1.
(1) mean cell diameter (mean value (D
Av)):
At an arbitrary position polyurethane foaming body is cut off, on 5 cut surfaces that balance is selected, measure area=2cm respectively
2The sampling scope in the diameter of the abscess that exists, obtain the mean cell diameter (D on each cut surface
1, D
2, D
3, D
4, D
5), calculate their mean value (D again
Av) [D
Av=(D
1+ D
2+ D
3+ D
4+ D
5)/5].
(2) cell diameter deviation:
Whole cell diameter (measurement range=2cm by above-mentioned (1) mensuration
2* 5=10cm
2) maximum value (D
Max) and minimum value (D
Min) obtain and above-mentioned mean value (D
Av) difference (D
Max-D
Av) and (D
Min-D
Av).
(3) density:
Measure according to JIS Z 8807.
(4) hardness:
According to JIS K 6253, use sclerometer (A type) to measure hardness (JIS-A hardness).
(5) tensile strength and elongation (mean value and deviation)
According to JIS K 6251, the test film (No. 3, dumbbell) that is made into taking a sample from 5 positions of balance selection under the condition that draw speed=500mm/ divides carries out tension test, based on the determination data (n=5) of tensile strength and elongation, obtain separately mean value and deviation [(maximum value-mean value)/mean value and (minimum value-mean value)/mean value].
(5) tear strength (mean value and deviation)
According to JIS K 6252, the test film (Type B dumbbell) that is made into taking a sample from 5 positions of balance selection under the condition that draw speed=200mm/ divides carries out tear test, obtains the mean value and the deviation [(maximum value-mean value)/mean value and (minimum value-mean value)/mean value] of tear strength.
Above the results are shown in the following table 1.
Table 1
Manufacturing method according to the invention can be manufactured on when having fine and uniform foam structure, the little polyurethane foaming body of deviation of the physical strength of physical strength height and different sites effectively.
The polyurethane foaming body that obtains by manufacture method of the present invention can be applied to building materials field (packing, exempt from blanket, filler etc.), railway material field (packing, impact absorbing material etc.), vehicular field (impact absorbing material etc.), various rubber surrogate (light elastomerics etc.), cosmetic field (powder puff etc.), coiled material (OA coiled material etc.), hygienic articles fields such as (toilets etc.).
Claims (9)
1, the manufacture method of polyurethane foaming body, this method is to utilize the method for mechanical foaming manufactured polyurethane foaming body, it comprises following operation: the fluid composition to the formed urethane that contains polyvalent alcohol and isocyanic ester carries out mechanical stirring in first stirring mixer and under the atmosphere of inert gases, thereby be mixed with the spumescence composition that in this fluid composition, is dispersed with rare gas element, again this spumescence delivery of composition is carried out mechanical stirring in second stirring mixer, then from second stirring mixer, discharge;
Rotor revolution number r when in first stirring mixer, stirring
1Be 200～1500rpm, the rotor revolution number r when in second stirring mixer, stirring
2Be 240～3000rpm, ratio of revolution r
2/ r
1Be 1.2～5.0.
2, the manufacture method of the described polyurethane foaming body of claim 1, wherein in second stirring mixer that the spumescence composition is transported to, import rare gas element, in second stirring mixer He under the atmosphere of inert gases, once more the spumescence composition is carried out mechanical stirring.
3, the manufacture method of claim 1 or 2 described polyurethane foaming bodies wherein adds the additive that is used to form polyurethane foaming body in second stirring mixer that the spumescence composition is transported to.
4, the manufacture method of claim 1 or 2 described polyurethane foaming bodies wherein adds chemical foaming agent in second stirring mixer that the spumescence composition is transported to.
5. the manufacture method of the described polyurethane foaming body of claim 3 wherein adds chemical foaming agent in second stirring mixer that the spumescence composition is transported to.
6, the manufacture method of claim 1 or 2 described polyurethane foaming bodies, wherein, under premixer neutralizes the situation that does not have rare gas element, polyvalent alcohol and isocyanic ester are mixed, thereby obtain to form the fluid composition of urethane, again this fluid composition is supplied with first stirring mixer.
7. the manufacture method of the described polyurethane foaming body of claim 3, wherein, under premixer neutralizes the situation that does not have rare gas element, polyvalent alcohol and isocyanic ester are mixed, thereby obtain to form the fluid composition of urethane, again this fluid composition is supplied with first stirring mixer.
8. the manufacture method of the described polyurethane foaming body of claim 4, wherein, under premixer neutralizes the situation that does not have rare gas element, polyvalent alcohol and isocyanic ester are mixed, thereby obtain to form the fluid composition of urethane, again this fluid composition is supplied with first stirring mixer.
9. the manufacture method of the described polyurethane foaming body of claim 5, wherein, under premixer neutralizes the situation that does not have rare gas element, polyvalent alcohol and isocyanic ester are mixed, thereby obtain to form the fluid composition of urethane, again this fluid composition is supplied with first stirring mixer.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2004305372 | 2004-10-20 | ||
| JP2004305372A JP4491837B2 (en) | 2004-10-20 | 2004-10-20 | Production method of urethane foam. |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1763118A CN1763118A (en) | 2006-04-26 |
| CN100554302C true CN100554302C (en) | 2009-10-28 |
Family
ID=36535941
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB2005101040632A Expired - Fee Related CN100554302C (en) | 2004-10-20 | 2005-09-15 | The manufacture method of polyurethane foaming body |
Country Status (3)
| Country | Link |
|---|---|
| JP (1) | JP4491837B2 (en) |
| CN (1) | CN100554302C (en) |
| TW (1) | TWI355392B (en) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101696280B (en) * | 2009-10-23 | 2011-07-20 | 河南科达节能环保有限公司 | Process for foam moulding of fluorine-free polyurethane |
| JP5555121B2 (en) * | 2010-10-08 | 2014-07-23 | 株式会社イノアックコーポレーション | Flame retardant polyurethane foam and method for producing the same |
| JP2020186309A (en) * | 2019-05-14 | 2020-11-19 | 日本発條株式会社 | Open cell-structured sponge and cosmetic puff |
| CN112175157A (en) * | 2020-09-29 | 2021-01-05 | 洛阳科博思新材料科技有限公司 | Polyurethane material and preparation method thereof, and polyurethane sleeper pad and preparation method thereof |
| CN112142939B (en) * | 2020-10-21 | 2022-06-10 | 惠彩材料科技(苏州)有限公司 | Mixed foaming method of polyurethane |
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|---|---|---|---|---|
| CN1117058A (en) * | 1989-07-19 | 1996-02-21 | 三井东压化学株式会社 | Hard polyaminoester foams and preparation of same |
| CN1123798A (en) * | 1990-11-05 | 1996-06-05 | 三井东压化学株式会社 | Production of hard polyamine ester foaming compound body |
| WO2003059979A1 (en) * | 2002-01-11 | 2003-07-24 | General Electric Company | Alkylamino oxamides as low odor, non-fugitive catalysts for the production of polyurethanes |
| US6660783B2 (en) * | 2001-06-15 | 2003-12-09 | Basf Aktiengesellschaft | Preparation of highly resilient polyurethane foams |
| CN1468881A (en) * | 2003-06-18 | 2004-01-21 | 清华大学 | Synthesis of amphiphilic biodegradable polyurethane elastomer |
| WO2004050734A1 (en) * | 2002-12-04 | 2004-06-17 | Johnson Matthey Plc | Organometallic catalyst composition and process for polyurethane manufacture using said catalyst |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2618804B2 (en) * | 1993-04-28 | 1997-06-11 | 三洋化成工業株式会社 | Method for producing foamed polyurethane moldings |
| JP2001294640A (en) * | 2000-04-11 | 2001-10-23 | Bridgestone Corp | Heat-accumulating mechanical froth type polyurethane foam and method for producing the same |
| JP3665608B2 (en) * | 2000-12-15 | 2005-06-29 | 三洋化成工業株式会社 | Rigid polyurethane foam-forming composition for foaming mechanical floss and foam molded article |
| JP2003211461A (en) * | 2002-01-22 | 2003-07-29 | Bridgestone Corp | Device and method for manufacturing polyurethane foam and method for manufacturing roller of polyurethane foam |
| JP2004149781A (en) * | 2002-10-07 | 2004-05-27 | Sanyo Chem Ind Ltd | Method for producing rigid polyurethane foam |
| JP4466313B2 (en) * | 2004-10-20 | 2010-05-26 | 日本ポリウレタン工業株式会社 | A method for producing a polyurethane foam. |
-
2004
- 2004-10-20 JP JP2004305372A patent/JP4491837B2/en not_active Expired - Fee Related
-
2005
- 2005-09-15 CN CNB2005101040632A patent/CN100554302C/en not_active Expired - Fee Related
- 2005-09-27 TW TW94133577A patent/TWI355392B/en not_active IP Right Cessation
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1117058A (en) * | 1989-07-19 | 1996-02-21 | 三井东压化学株式会社 | Hard polyaminoester foams and preparation of same |
| CN1123798A (en) * | 1990-11-05 | 1996-06-05 | 三井东压化学株式会社 | Production of hard polyamine ester foaming compound body |
| US6660783B2 (en) * | 2001-06-15 | 2003-12-09 | Basf Aktiengesellschaft | Preparation of highly resilient polyurethane foams |
| WO2003059979A1 (en) * | 2002-01-11 | 2003-07-24 | General Electric Company | Alkylamino oxamides as low odor, non-fugitive catalysts for the production of polyurethanes |
| WO2004050734A1 (en) * | 2002-12-04 | 2004-06-17 | Johnson Matthey Plc | Organometallic catalyst composition and process for polyurethane manufacture using said catalyst |
| CN1468881A (en) * | 2003-06-18 | 2004-01-21 | 清华大学 | Synthesis of amphiphilic biodegradable polyurethane elastomer |
Also Published As
| Publication number | Publication date |
|---|---|
| TW200615290A (en) | 2006-05-16 |
| JP4491837B2 (en) | 2010-06-30 |
| CN1763118A (en) | 2006-04-26 |
| TWI355392B (en) | 2012-01-01 |
| JP2006117751A (en) | 2006-05-11 |
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