CN104119671A - Formula of high-performance polyurethane foam for lightweight automotive interiors and process of high-performance polyurethane foam - Google Patents
Formula of high-performance polyurethane foam for lightweight automotive interiors and process of high-performance polyurethane foam Download PDFInfo
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- CN104119671A CN104119671A CN201410282720.1A CN201410282720A CN104119671A CN 104119671 A CN104119671 A CN 104119671A CN 201410282720 A CN201410282720 A CN 201410282720A CN 104119671 A CN104119671 A CN 104119671A
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Abstract
The invention discloses a formula of high-performance polyurethane foam for lightweight automotive interiors and a process of the high-performance polyurethane foam. The PU (polyurethane) foam comprises the following three raw materials (in parts by mass): 100 parts of combined polyether polyol, 140-190 parts of isocyanate and 5-15 parts of combined endothermic packing. The process of the high-performance polyurethane foam comprises the following steps: evenly stirring and mixing the polyether polyol and various additives such as a catalyst, an open-hole agent and the like in the preset proportion; adding two or more types of endothermic packing to a high-speed ball mill in the preset proportion; carrying out ball mill mixing when spraying a silane or titanate coupling agent. According to the PU foam obtained by the process, the tensile property, the compression performance and the impact resistance of the foam are differently improved, the overall holes of the foam are smaller, denser and more uniform in distribution, and the aperture ratio is also improved. Thus the sound absorption performance and the air permeability of the foam are improved, and the lightweight automotive interiors can be produced. In addition, the preparation process disclosed by the invention is simple and feasible, and low in cost, and is completely suitable for large-scale box-type foaming.
Description
Technical field
The present invention relates to a kind of formula and technique of polyurethane foam, be specifically related to formula and the technique of high performance polyurethane foam for a kind of lightweight automotive trim.
Background technology
In urethane (PU) foams, Application and Development the earliest be the foams that hardness is very high, and obtain market approval, most widely used be flex foam.As hardness between this two class A foam As body, be called semi-rigid foamed plastics, be called for short and partly hard bubble.Partly hard bubble and be that with soft bubble and the key distinction of hard bubbling it possesses higher compressive strength, after its load unloading, the speed that its foams restore is very slow, shows good energy absorption, bumper and absorbing shock characteristic.In view of these characteristics, partly hard bubble and be widely used at present upholstery material, as dashboard, interior lining panel, ceiling, skylight slip lid, head rest, hat rack etc.
PU foaming machine mainly contains two large classes at present, one class is that mechanical type is continuous foamed, easy and simple to handle, speed is fast, and foaming properties is excellent, but required equipment is various, cost is high, and be limited to the width of travelling belt, when foam specification is more, the efficiency of mechanical foaming is just had a greatly reduced quality, so the continuous foamed close foams of one or more sizes of scale operation that are applicable to of mechanical type more; Another kind of is discontinuous box foaming, although the foaming properties that this method obtains not as mechanical foaming, equipment is simple, cost is low, and applicable foam size is flexible and changeable, while being applied to produce the large foam of size difference, efficiency is high.At present, due to the multi-size of froth product, domestic and international many enterprises all adopt discontinuous box method (the box foaming of hereinafter referred) to produce PU foam.
In recent years, box foam process was constantly improved, and the higher box foaming of mechanization degree at present adopts the bottomless tempering tank of hoisting type (as shown in Figure 1) more, and after treating mixing of materials, tempering tank mentions at the bottom of case, at the bottom of mixed liquor is full of case.Yet the heat release problem of foam is a difficult problem all the time in box foam process, seriously limited the further optimization of quality product.This is mainly because in the production process of PU foam, two kinds of raw materials are that polyvalent alcohol can be emitted a large amount of heat with reacting of isocyanic ester, and the volume of foam is large and internal structure is unfavorable for heat radiation, cause temperature in foams sharply to rise in the foaming process of three limit closeds, the highest over 200 ℃.Under high temperature like this, PU molecular chain and airborne oxygen reaction produce oxidation immediately, make even blackout (being commonly called as " burning core ") of foam center color jaundice, and meeting spontaneous combustion when serious and cause fire causes the massive losses that cannot retrieve.In addition, foam inside heat radiation inequality also can affect its physicals in various degree, as mechanical property, distribution of cells homogeneity and density distribution homogeneity etc.Therefore, how can effectively solve the heat dissipation problem of PU foam in box foaming, and prepare high performance PU foam and become a generally acknowledged technical barrier in industry.
At present less for the report of this technical barrier, at the box free foaming technique of < < hard polyurethane foam, brief talk > > (Dai Qiansheng, polyurethane industrial, 1999, 14 (3): the discussion > > (Li Zuohua that 43～44) burns core factor in producing with < < polyurethane flexible foam, polyurethane industrial, 2007, 22 (3): 31～33), author is once to the analysis of summarizing of the burning core phenomenon of PU foam, but effective solution is not clearly proposed.In existing patent, CN102796239A mentions, by adding fire retardant, can effectively reduce burning core phenomenon, wherein fire retardant is the anti-fire retardant of feeling terribly worried, comprise the auspicious A3007B-LS of reaching of U.S.'s rising sun, FYrolA117S, FyrolHF-4, the YOKEV166 of Qingdao Rui Nuo Chemical Co., Ltd., the FR-38 of Zhejiang Province Wansheng Chemical Co., Ltd, but in industry, do not have promotion message.
Summary of the invention
For above technical barrier, the present invention has designed a kind of combination heat absorption filler, and formula and the technique of a kind of lightweight automotive trim with high performance polyurethane foam are provided, and concrete technical scheme of the present invention is as follows:
The invention discloses a kind of lightweight automotive trim high performance polyurethane foam, the starting material of PU foam comprise three kinds of materials: 100 parts of (massfraction) combined polyether glycols, 140～190 parts of isocyanic ester, the combination heat absorption filler of 5～15 parts.
As improving further, combined polyether glycol of the present invention comprises: 10～45 parts of glycerine are initiator, hydroxyl value is that propylene oxide/oxyethane polyether glycol of 25～40mgKOH/g or 15～35 parts be take sorbyl alcohol as initiator, propylene oxide/oxyethane polyether glycol of hydroxyl value 400～500mgKOH/g or 0～20 part be take quadrol as initiator, propylene oxide/oxyethane polyether glycol of hydroxyl value 380～450mgKOH/g; 0.5～3 part of water; 0.05～2 part of amines catalyst, 0.03～1.5 part of pore-creating agent, 0.1～3 part of tensio-active agent and 10～30 parts of dipropylene glycols.
As improving further, isocyanic ester of the present invention is 108～122 parts of polyphenyl polymethylene isocyanic ester, and nco value is 30%～32%.
As improving further, combination heat absorption filler of the present invention is the mixture of small-molecule substance and polymeric powder, described small-molecule substance is one or more the mixture in sodium-acetate, sodium carbonate, aluminium hydroxide, hydrated barta or calcium chloride, and polymeric powder is one or more the mixture in ethylene-vinyl acetate copolymer, ethylene-propylene acetoacetic ester, modified poly ethylene, modified polypropene, polystyrene, polyvinyl chloride, thermoplastic polyolefin elastomer, Polyurethane Thermoplastic Elastomer, copolymer nylon.
As improving further, the addition of combination heat absorption filler small molecular material of the present invention is 1～5 part, and the addition of polymeric powder is 3～15 parts.
A preparation technology according to the lightweight automotive trim described in any one in claim 1 to 5 with high performance polyurethane foam, concrete preparation process is as follows:
(1) the various additives such as polyether glycol and catalyzer, pore-creating agent are uniformly mixed to stirring velocity 1200r/min, time 1min by default proportioning; (the speed here and time, preferably a scope)
(2) two or more heat absorption fillers are added in high speed ball mill by default proportioning, when spraying silane or titanate coupling agent, carry out ball milling mixing, after the speed mixing 10～30min with 300～800r/min, obtain combination heat absorption filler;
(3) combination heat absorption filler is added in the combined polyether glycol mixing to high-speed stirring for some time;
(4) isocyanic ester is poured into rapidly in the mixed solution that step 3 obtains, high-speed stirring 15～40s, speed is 1000～2500r/min;
(5) mixed solution obtaining in step (4) is poured in foam box, and put into thermopair with the temperature at tracking and testing foam center, behind foam contacting thermopair end, every 1min, record temperature, until temperature stops record after declining, after foaming is introduced, density uniformity, percentage of open area, stretching and the bending property of cutting and testing PU foam.
As improving further, in step of the present invention (2), coupling agent is silane coupling agent or titante coupling agent.
As improving further, in step of the present invention (3), churning time is 30～90s, and speed is 500～1500r/min.
Adopt beneficial effect of the present invention as follows:
According to the present invention, can effectively solve heat dissipation problem in box foaming process, avoid burning core problem, both can reduce the uneven impact that foaming properties is caused of heat radiation, density uniformity and percentage of open area be improved significantly, also can stop the potential safety hazard in production process completely.And have benefited from adding of macromolecule resin component in combination heat absorption filler, the PU foam obtaining according to the present invention program, its tensile property, compression performance and erosion-resisting characteristics all have the hole of raising in various degree and foam integral body less, finer and close, be more evenly distributed, percentage of open area also improves, thereby is conducive to improve sound-absorbing and the permeability of foam and produces light-weighted automotive upholstery.In addition, the preparation technology in the present invention program is simple and feasible, cost is low, is applicable to extensive box foaming completely.
Accompanying drawing explanation
Fig. 1 mixes the box foam device schematic diagram of bottomless bucket with hoisting type;
The internal temperature change curve of Fig. 2 embodiment 1, comparative example 1 and comparative example 2 gained foams.
Embodiment
Below in conjunction with specific embodiment, technical scheme of the present invention is described further:
Embodiment 1
1. in reaction raw materials, combined polyether glycol comprises: 15 parts of glycerine are initiator, propylene oxide/oxyethane polyether glycol that hydroxyl value is 40mgKOH/g; Take sorbyl alcohol as initiator for 35 parts, propylene oxide/oxyethane polyether glycol of hydroxyl value 400mgKOH/g; Take quadrol as initiator for 15 parts, propylene oxide/oxyethane polyether glycol of hydroxyl value 395mgKOH/g; 1.5 parts of water; 2 parts of amines catalysts, 0.5 part of pore-creating agent, 1 part of tensio-active agent and 25 parts of dipropylene glycols.By homogenizer, stir, stirring velocity 1200r/min, time 1min, obtains combined polyether glycol.
2. 2 parts of sodium carbonate and 6 parts of modified copolymer nylon powders are added in high speed ball mill, when spraying Silane coupling agent KH550, carry out ball milling mixing, rotating speed is 300r/min, and the time is 30min, obtains combination heat absorption filler.
3. the combination heat absorption filler obtaining in step 2 is added in the combined polyether glycol that step 1 obtains, stir 30s, speed is 1500r/min.
4. 111 parts of isocyanic ester are poured into rapidly in the mixed solution that step 3 obtains, high-speed stirring 15s, speed is 2500r/min.
5. mixed solution step 4 being obtained is poured in foam box, and puts into thermopair with the temperature at tracking and testing foam center, behind foam contacting thermopair end, every 1min, records temperature, until temperature stops record after declining.After foaming is introduced, density uniformity, percentage of open area, stretching and the bending property of cutting and testing PU foam.Wherein, after foam is cut, get respectively three bubble pieces of upper, middle and lower and carry out above-mentioned test, corresponding data is in Table 1.
Table 1 is for pressing the various performance parameters contrast of the prepared PU bubble piece of embodiment 1, comparative example 1 and comparative example 2 schemes.In embodiment 1, due to adding of heat absorption material sodium-acetate and copolymer nylon, the a large amount of reaction heat that generate in foaming process make these two kinds of material heat absorptions occur to change mutually, there is decomposition in the former, the latter's fusion plastification that absorbs heat, all can consumption of calorie, thereby effectively alleviated the heat dissipation problem of PU foam, as can be seen from Figure 2, combination heat absorption makes PU foam inside temperature reduce by 13～17 ℃ than pure PU (comparative example 1) adding of filler, effect is remarkable, and the density distribution homogeneity of embodiment 1 gained foam and density are obviously better than comparative example 1 gained foam (in Table 1).In addition, when the temperature in foam surpasses the fusing point of copolymer nylon, copolymer nylon powder heat absorption melting also starts to assemble, and after foaming in body temperature decline gradually, copolymer nylon is also cooling immediately becomes solid again from melt.As can be seen from Table 1, copolymer nylon add the strength and toughness that has significantly improved foam, compare with comparative example 1 gained bubble, tensile strength and the compressive strength of embodiment 1 gained bubble have increased respectively 19.6% and 22.4%, elongation at break has increased by 35.2%.Can obtain thus, combination heat absorption filler not only can effectively solve the heat dissipation problem of PU foam inside, also can significantly improve the over-all properties of foam.
In comparative example 2, change the combination heat absorption filler in embodiment 1 into magnesium hydroxide and silicon carbide powder, the former minimum dehydration temperaturre is 340 ℃, far above the top temperature in PU foaming process, and approximately 800 ℃ of the decomposition temperatures of silicon carbide, therefore, in foaming process, these two kinds of fillers all cannot improve heat dissipation problem by heat absorption.As can be seen from Figure 2, two kinds of fillers add reducing the interior temperature of PU bubble without obvious effect.In addition, as can be seen from Table 1, no matter two kinds of fillers is to density uniformity, percentage of open area if adding, or mechanical property, is all not improved effect, decrease to some degree on the contrary, especially elongation at break.This is mainly because two kinds of fillers are inorganic substance, though through surface treatment, still not good with the consistency of PU, causing part filler to occur to reunite becomes focal point of stress, and the mechanical property of material is decreased.Therefore, polymeric powder is indispensable as the main body in combination heat absorption filler.
Comparative example 1
1. in reaction raw materials, combined polyether glycol comprises: 15 parts of glycerine are initiator, propylene oxide/oxyethane polyether glycol that hydroxyl value is 40mgKOH/g; Take sorbyl alcohol as initiator for 40 parts, propylene oxide/oxyethane polyether glycol of hydroxyl value 400mgKOH/g; Take quadrol as initiator for 15 parts, propylene oxide/oxyethane polyether glycol of hydroxyl value 395mgKOH/g; 1.5 parts of water; 2 parts of amines catalysts, 0.5 part of pore-creating agent, 1 part of tensio-active agent and 25 parts of dipropylene glycols.By homogenizer, stir, stirring velocity 1200r/min, time 1min, obtains combined polyether glycol.
2. 111 parts of isocyanic ester are poured into rapidly in the polyether glycol that step 1 obtains, high-speed stirring 15s, speed is 2500r/min.
3. mixed solution step 2 being obtained is poured in foam box, and puts into thermopair with the temperature at tracking and testing foam center, behind foam contacting thermopair end, every 1min, records temperature, until temperature stops record after declining.After foaming is introduced, density uniformity, percentage of open area, stretching and the bending property of cutting and testing PU foam.Wherein, after foam is cut, get respectively three bubble pieces of upper, middle and lower and carry out above-mentioned test, corresponding data is in Table 1.
Comparative example 2
1. in reaction raw materials, combined polyether glycol comprises: 15 parts of glycerine are initiator, propylene oxide/oxyethane polyether glycol that hydroxyl value is 40mgKOH/g; Take sorbyl alcohol as initiator for 40 parts, propylene oxide/oxyethane polyether glycol of hydroxyl value 400mgKOH/g; Take quadrol as initiator for 15 parts, propylene oxide/oxyethane polyether glycol of hydroxyl value 395mgKOH/g; 1.5 parts of water; 2 parts of amines catalysts, 0.5 part of pore-creating agent, 1 part of tensio-active agent and 25 parts of dipropylene glycols.By homogenizer, stir, stirring velocity 1200r/min, time 1min, obtains combined polyether glycol.
2. 2 parts of magnesium hydroxides and 6 parts of silicon carbide powders are added in high speed ball mill, when spraying Silane coupling agent KH550, carry out ball milling mixing, rotating speed is 300r/min, and the time is 30min, obtains combination heat absorption filler.
3. the combination heat absorption filler obtaining in step 2 is added in the combined polyether glycol that step 1 obtains, stir 30s, speed is 1500r/min.
4. 111 parts of isocyanic ester are poured into rapidly in the mixed solution that step 3 obtains, high-speed stirring 15s, speed is 2500r/min.
5. mixed solution step 4 being obtained is poured in foam box, and puts into thermopair with the temperature at tracking and testing foam center, behind foam contacting thermopair end, every 1min, records temperature, until temperature stops record after declining.After foaming is introduced, density uniformity, percentage of open area, stretching and the bending property of cutting and testing PU foam.Wherein, after foam is cut, get respectively three bubble pieces of upper, middle and lower and carry out above-mentioned test, corresponding data is in Table 1.
Embodiment 2
1. in reaction raw materials, combined polyether glycol comprises: 40 parts of glycerine are initiator, propylene oxide/oxyethane polyether glycol that hydroxyl value is 25mgKOH/g; Take sorbyl alcohol as initiator for 20 parts, propylene oxide/oxyethane polyether glycol of hydroxyl value 480mgKOH/g; Take quadrol as initiator for 20 parts, propylene oxide/oxyethane polyether glycol of hydroxyl value 395mgKOH/g; 1 part of water; 1.5 parts of amines catalysts, 1 part of pore-creating agent, 2 parts of tensio-active agents and 15 parts of dipropylene glycols.By homogenizer, stir, stirring velocity 1200r/min, time 1min, obtains combined polyether glycol.
2. 2 parts of calcium chloride and 4 parts of ethene-vinyl acetate powder are added in high speed ball mill, when spraying Silane coupling agent KH550, carry out ball milling mixing, rotating speed is 800r/min, and the time is 10min, obtains combination heat absorption filler.
3. the combination heat absorption filler obtaining in step 2 is added in the combined polyether glycol that step 1 obtains, stir 55s, speed is 800r/min.。
4. 115 parts of isocyanic ester are poured into rapidly in the mixed solution that step 3 obtains, high-speed stirring 25s, speed is 1000r/min.
5. mixed solution step 4 being obtained is poured in foam box, waits for its foaming.
Finally, it is also to be noted that, what more than enumerate is only several specific embodiment of the present invention and comparative example.Obviously, the invention is not restricted to above embodiment, can also have many distortion.All distortion that those of ordinary skill in the art can directly derive or associate from content disclosed by the invention, all should think protection scope of the present invention.
Claims (8)
1. a lightweight automotive trim high performance polyurethane foam, is characterized in that, the starting material of PU foam comprise three kinds of materials: 100 parts of (massfraction) combined polyether glycols, 140～190 parts of isocyanic ester, the combination heat absorption filler of 5～15 parts.
2. lightweight automotive trim high performance polyurethane foam according to claim 1, it is characterized in that, described combined polyether glycol comprises: 10～45 parts of glycerine are initiator, hydroxyl value is that propylene oxide/oxyethane polyether glycol of 25～40mgKOH/g or 15～35 parts be take sorbyl alcohol as initiator, propylene oxide/oxyethane polyether glycol of hydroxyl value 400～500mgKOH/g or 0～20 part be take quadrol as initiator, propylene oxide/oxyethane polyether glycol of hydroxyl value 380～450mgKOH/g; 0.5～3 part of water; 0.05～2 part of amines catalyst, 0.03～1.5 part of pore-creating agent, 0.1～3 part of tensio-active agent and 10～30 parts of dipropylene glycols.
3. lightweight automotive trim high performance polyurethane foam according to claim 1, is characterized in that, described isocyanic ester is 108～122 parts of polyphenyl polymethylene isocyanic ester, and nco value is 30%～32%.
4. lightweight automotive trim high performance polyurethane foam according to claim 1, it is characterized in that, described combination heat absorption filler is the mixture of small-molecule substance and polymeric powder, described small-molecule substance is sodium-acetate, sodium carbonate, aluminium hydroxide, the mixture of one or more in hydrated barta or calcium chloride, polymeric powder is ethylene-vinyl acetate copolymer, ethylene-propylene acetoacetic ester, modified poly ethylene, modified polypropene, polystyrene, polyvinyl chloride, thermoplastic polyolefin elastomer, Polyurethane Thermoplastic Elastomer, the mixture of one or more in copolymer nylon.
5. lightweight automotive trim high performance polyurethane foam according to claim 4, is characterized in that, the addition of described combination heat absorption filler small molecular material is 1～5 part, and the addition of polymeric powder is 3～15 parts.
6. the preparation technology with high performance polyurethane foam according to the lightweight automotive trim described in any one in claim 1 to 5, is characterized in that, concrete preparation process is as follows:
(1) the various additives such as polyether glycol and catalyzer, pore-creating agent are uniformly mixed by default proportioning;
(2) two or more heat absorption fillers are added in high speed ball mill by default proportioning, when spraying silane or titanate coupling agent, carry out ball milling mixing, after the speed mixing 10～30min with 300～800r/min, obtain combination heat absorption filler;
(3) combination heat absorption filler is added in the combined polyether glycol mixing to high-speed stirring for some time;
(4) isocyanic ester is poured into rapidly in the mixed solution that step 3 obtains, high-speed stirring 15～40s, speed is 1000～2500r/min;
(5) mixed solution obtaining in step (4) is poured in foam box, and put into thermopair with the temperature at tracking and testing foam center, behind foam contacting thermopair end, record temperature, until temperature stops record after declining, after foaming is introduced, density uniformity, percentage of open area, stretching and the bending property of cutting and testing PU foam.
7. the preparation technology of high performance polyurethane foam for lightweight automotive trim according to claim 6, is characterized in that, in described step (2), coupling agent is silane coupling agent or titante coupling agent.
8. the preparation technology of high performance polyurethane foam for lightweight automotive trim according to claim 6, is characterized in that, in described step (3), churning time is 30～90s, and speed is 500～1500r/min.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN107400351A (en) * | 2017-07-18 | 2017-11-28 | 合肥广能新材料科技有限公司 | Polyurethane rigid foam exterior wall flame-retardant thermal insulation material and preparation method thereof |
| CN112225867A (en) * | 2020-06-02 | 2021-01-15 | 南京汇科高分子材料有限公司 | Polyurethane semi-rigid foam for preparing automobile skylight sun shield and spare tire cover plate |
| CN114957599A (en) * | 2022-06-17 | 2022-08-30 | 宋伟杰 | Environment-friendly automobile foot pad material and preparation method thereof |
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| CN103408925A (en) * | 2013-08-30 | 2013-11-27 | 深圳市柳鑫实业有限公司 | Rigid foamed plastic |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1763119A (en) * | 2004-10-22 | 2006-04-26 | 四川大学 | Preparation of engineering plastics powder filled hard polyurethane foam |
| CN101012332A (en) * | 2007-02-09 | 2007-08-08 | 李长玉 | Lignin and waste rigid foam powder fluorine-free polyurethane heat insulation material and preparing method |
| CN103408925A (en) * | 2013-08-30 | 2013-11-27 | 深圳市柳鑫实业有限公司 | Rigid foamed plastic |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN107400351A (en) * | 2017-07-18 | 2017-11-28 | 合肥广能新材料科技有限公司 | Polyurethane rigid foam exterior wall flame-retardant thermal insulation material and preparation method thereof |
| CN112225867A (en) * | 2020-06-02 | 2021-01-15 | 南京汇科高分子材料有限公司 | Polyurethane semi-rigid foam for preparing automobile skylight sun shield and spare tire cover plate |
| CN114957599A (en) * | 2022-06-17 | 2022-08-30 | 宋伟杰 | Environment-friendly automobile foot pad material and preparation method thereof |
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