CN1076933A - The preparation method of high-resiliency low-density moulded polyurethane foam - Google Patents
The preparation method of high-resiliency low-density moulded polyurethane foam Download PDFInfo
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- CN1076933A CN1076933A CN 92102234 CN92102234A CN1076933A CN 1076933 A CN1076933 A CN 1076933A CN 92102234 CN92102234 CN 92102234 CN 92102234 A CN92102234 A CN 92102234A CN 1076933 A CN1076933 A CN 1076933A
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Abstract
It is basic material and triethylene diamine, diethanolamine, two-(2-dimethyl aminoethyl) ether that the present invention adopts high activity polyether commonly used and polymer polyatomic alcohol, dibutyl tin laurate, silicone based polymkeric substance open cell type suds-stabilizing agent, TD1 (80/20) or TDI (80/20) mix with MDI in the foamed material that is made into and to add trolamine and to be dissolved with the cellulosic polyoxyethylene glycol of carboxylic first tomb, simultaneously will two-(2-dimethyl aminoethyl) ether carry out after the pre-treatment with acid solution form and other physical mixed with volatile acid such as formic acid, acetate or phosphoric acid.Utilize high resilience polyurethane foam density that the inventive method produces at 42 kilograms/meter
3Below, cream time is long during foaming, and demould time is short, and foam is opened bubble voluntarily.
Description
The present invention relates to a kind of preparation method of high resilience cold-curing molded polyurethane foam.
High resilience cold-curing molding is poly-to have more good rebound performance and other good physicalies by ester foam (HR foam) softer foam, chair cushion, the bedding of making is comfortable, handling ease, technology are simple, the goods cost is low, manual frothing mold moulding can be satisfied the production requirement of many specifications, many kinds, different amounts, thereby is widely used in top-grade furniture and the automobile making.The appearance of extensive, the new further purposes of using along with the HR foam has also proposed more and more higher requirement to HR foamy performance, quality.Not only require foam to have good rebound performance, mechanical strength properties, suitable hardness and the compression set that is fit to, to satisfy the different service requirementss of using of different purposes, try one's best low density to reduce the weight of goods but also require foam to have, reduce the production cost that raw material consumption reduces goods.For this reason, people have carried out all improvement to RH foamy preparation method, have proposed various prescription, but mostly these improvement are that raw material is carried out modification handles and adopt special catalyzer, linking agent to realize.Carry out material modification and need increase new equipment and investment, increased raw material manufacturing process simultaneously, strengthened process cost, raw materials cost is risen, and new special catalyst, linking agent price height, thereby the cost of the foam article of making rises greatly.
Making in actual production at present that the HR foam article generally adopts is to be basic material with high activity polyether and polymer polyatomic alcohol mixture, carries out with isocyanic ester in the presence of catalyzer, linking agent that polymerization crosslinking makes through the water foaming.The foamed material cream time of existing technology is short, and gelation rate is fast, the rapid multiviscosisty of foamed material in the foaming operation process, and the bridging loss is big during batch turning.Easily can not be full of the defective that mould causes product because of foamed material.Gelation rate is fast, and the rapid gel of material produces a large amount of closed pores during foaming, needs the roll extrusion perforate after the demoulding, causes foamy resilience, elongation, tension, anti-strength degradation.
The objective of the invention is the HR foam formulation and the technology of existing production application are improved, provide a kind of foam density at 42 kilograms 1 meter below 3, the goods cost is low, the foamed material cream time is long, gelation rate is moderate, demould time is short, foam has good strength property and rebound performance, the preparation method of the high-resiliency low-density moulded polyurethane foam of moderate hardness and proper compression set.
The preparation method of high-resiliency low-density moulded polyurethane foam is: adopting molecular weight is 4500-6500, proportion of primary OH groups is 60-80%, hydroxyl value is the high activity polyether of 29-35 milligram KOH/ gram and is parent with the primary hydroxyl polyethers, acrylonitrile, vinylbenzene is that monomer is polymerized through free radical reaction, hydroxyl value be the mixture formed of the polymer polyatomic alcohol of 25-29 milligram KOH/ gram as basic material and methyl vulcabond (80/20) (TDI80/20) or TDI(80/20) and diphenylmethanediisocyanate (MDI) mixture at the catalyzer triethylene diamine, dibutyl tin laurate, two-(2-dimethyl aminoethyl) ether, the linking agent diethanolamine, silicone based foam of polymers stablizer carries out polymerization under existing, crosslinkedly in the foamed material of water foaming, add trolamine, when the preparation foamed material, utilize formic acid simultaneously, any one acid earlier will two-(2-dimethyl aminoethyl) ether be carried out acidification and is made acid solution and be mixed and made into foamed material with unclassified stores again in acetate or the phosphoric acid.
By add trolamine in foamed material the foaming original speed is slowed down, prolong cream time, making foamed material have good flowability has time enough to be full of mould.Under tin catalyst and tertiary amine catalyst synergy, carry out chainpropagation and foaming simultaneously.When the trolamine that foams to a certain degree crosslinked action takes place simultaneously and late phase reaction speed is quickened, make foaming promptly certain intensity be arranged and make a large amount of steam bubbles perforate voluntarily that the reaction later stage produces at the gelation of the triethylene diamine phase abscess that also do not peak.Along with not breaking out of the carrying out of polyreaction, reaction heat, the foamed material temperature constantly raises, and acid is constantly volatilized, two-(2-dimethyl aminoethyl) ether constantly discharges the participation foamable reaction accelerates crosslinking reaction, gelation rate rises rapidly, and the curing time shortens, thereby has shortened demould time.
The proportion scale that is added with the foamed material of trolamine is:
Molecular weight is 4500-6500, proportion of primary OH groups is 60-85%, hydroxyl value is that the high activity polyether of 29-35 milligram KOH/ gram is a 45-65%(weight) and the primary hydroxyl polyethers be parent, vinyl cyanide, vinylbenzene is that monomer is polymerized through free radical reaction, hydroxyl value is that the polymer polyatomic alcohol of 25-29 milligram KOH/ gram is a 35-55%(weight) mixture be basic material, adding is 100 with basic material weight, triethylene diamine is 0.1-0.6, silicone based foam of polymers stablizer commercially available product DC5043 or L5307 are 0.8-2.0, dibutyl tin laurate is 0.012-0.06, two-(2-dimethyl aminoethyl) ether is 0.3-1.0,85%(weight) the diethanolamine aqueous solution is 0.5-1.2, trolamine is 1.0-0.8, fluoro trichloromethane (F11) is 0-6, isocyanate index is 105-108, TDI(80/20) single using or TDI(80/20) mix use, formic acid with MDI, acetate, any one is 0.1-0.5 in the phosphoric acid, and total water is 2.6-3.2.
For the perforate that helps foaming, become nuclear volume when improving foaming naturally, improve the foamy feel, add polyoxyethylene glycol and carboxymethyl cellulose in the batching.
The foamed material mixing ratio that is added with polyoxyethylene glycol and carboxymethyl cellulose is:
High activity polyether and polymer polyatomic alcohol mixture are basic material, and high activity polyether accounts for 45-65%(weight in the basic material), polymer polyatomic alcohol accounts for 35-55%(weight).
With basic material heavily is 100, triethylene diamine is 0.1-0.6, silicone based foam of polymers stablizer commercially available product DC5043 or DL5307 are 0.8-2.0, dibutyl tin laurate is 0.012-0.05, two (2-dimethyl aminoethyl) ether is 0.3-1.0, formic acid, any one is 0.1-0.5 for acetate or phosphoric acid, 85%(weight) the diethanolamine aqueous solution is 0.5-1.2, trolamine is 0.1-0.8, total water is 2.6-3.2, be dissolved with 15%(weight) water, 10%(weight) polyoxyethylene glycol of carboxymethyl cellulose is 0.5-2.0, fluoro trichloromethane (F11) is 0-6, and isocyanate index is 105-108TDI(80/20) single with or TDI(80/20) mix use with MDI.
When pressing proportion scale preparation foamed material, will two-(2-dimethyl aminoethyl) ether mix to be incorporated in to mix under the high-speed stirring to pour into and foam in the mould with sour mixed dissolution and then with unclassified stores in preparing burden,-(2-dimethyl aminoethyl) ether two for making is dissolved in the acid rapidly and forms stable homogeneous system, mixes can add an amount of ethylene glycol when molten.Be 1 with sour weight generally, ethylene glycol is 2.5-3.
Utilize the inventive method to prepare the HR foam, do not adopt special catalyzer and linking agent and expensive basic material to prepare the HR foam of high-resiliency low-density.Foam density is below 42 kilograms/meter.Cream time is long during foaming, material fluidity good, has time enough to be full of mould, has eliminated because of the short disadvantageous effect of bringing for the foam article quality of cream time.Foam is perforate voluntarily, and foamy rebound performance, strength property and other physicalies are good, is the lower raw material of normally used price owing to what prepare the foam use, so the foam article cost is low.
Comparative example
Proportion scale
Molecular weight is 4500-6500, proportion of primary OH groups is that high activity polyether and the primary hydroxyl polyethers that 29-35 milligram KOH/ restrains is parent for the 60-85% hydroxyl value, vinyl cyanide, vinylbenzene are that hydroxyl value that monomer is polymerized through free radical reaction is that the mixture that the polymer polyatomic alcohol of 25-29 milligram KOH/ gram is formed is that basic material takes by weighing 100 grams, polyethers is a 45-65%(weight in the basic material), polymer polyatomic alcohol is a 35-55%(weight).With basic material weight is 100, triethylene diamine adds 0.1-0.6, silicone based foam of polymers stablizer DC5043 or L5307(commercially available product) adding 0.8-2.0, dibutyl tin laurate adds 0.012-0.05, two-(2-dimethyl aminoethyl) ether adds 0.3-1.0,85%(weight) the diethanolamine aqueous solution adds 0.5-1.2, and total water adds 2.6-3.2, isocyanate index 105-108TDI(80/20) single with or TDI(80/20) and MDI use with.Fluoro trichloromethane adds 0-6
(2) operation
Take by weighing each material by above-mentioned proportion scale, each material is mixed at normal temperatures and carry out high-speed stirring, pour in the mould immediately after mixing and foam.
Three, result
(1) foamed material foaming cream time is 5-8 second, and curing temperature is 45-55 ℃, and demould time is 10-12 minute, needs the roll extrusion perforate after the demoulding.
(2) foam physics, mechanical property measured result (pressing the national standard method test)
1, foam hardness: softer, deflection is bad.
2, density: 42-45 kilogram/rice
3
3, falling-rebounding ball rate (%) 45-50%
4, elongation (%) 90-110
5, tensile strength: 110-14.0 newton/centimetre
2
6, compression set 75%:9-11
Embodiment 2:
One, proportion scale
Adopt the proportion scale of comparative example to take by weighing basic material 100 gram and other materials, the while is added trolamine in batching, the trolamine add-on is: with basic material weight is 100, and trolamine adds 0.1-0.8.
Two, operation
Identical with comparative example 1, be the single stage method operation.
Three, result
(1) foamed material foaming cream time is 8-12 second, and curing temperature is 25-35 ℃, and demould time is the 5-8 branch, and foam is perforate voluntarily, need not the roll extrusion perforate after the demoulding.
(2) foamy physics, mechanical property measured result, (pressing the national standard method test)
1, foam hardness is moderate, and deflection is good.
2, foam density: 35-40 kilogram/rice
3
3, falling-rebounding ball rate (%) 50-60
4, elongation (%): 125-145
5, tensile strength: 14.0-17.0 newton/centimetre
2
6, compression set 24-75%:5-9
Embodiment 3:
Adopt the proportion scale of comparative example, add in trolamine, formic acid, acetate or the phosphoric acid any one simultaneously, be dissolved with the poly-oxalic acid of carboxymethyl cellulose.Taking by weighing basic material 100 gram, is 100 with basic material weight, adds trolamine 0.5-0.8, and any one adds 0.1-0.5 in formic acid, acetate or the phosphoric acid, is dissolved with 15%(weight) water, 10%(weight) the polyoxyethylene glycol 0.5-2.0 of carboxymethyl cellulose.
Two, operation
(1) with dosage two-(2-dimethyl aminoethyl) ether and proper amount of glycol add to heat in the acid of dosage to be dissolved it to form the homogeneous phase body fully, general ethylene glycol add-on is 1 for the sour weight with dosage, ethylene glycol is incorporated as 2.5-3.
(2) take by weighing batching 1/3rd the basic material and the TDI(80/20 of dosage) or TDI(80/20) and the MDI mixture at normal temperatures high-speed stirring mix.
(3) remaining 2/3rds basic material and the unclassified stores in the batching are stirred to tremble mix.
(4) acid solution of at normal temperatures step () being made and mixture that step (three) is made mix the mixture of again step (two) being made add high-speed stirring tremble mix after, foamed material poured in the mould immediately foams.
Three, result
(1) foamed material foaming cream time is 12-18 second, and curing temperature is 25-35 ℃, and demould time is the 2-7 branch, and foam is perforate voluntarily, need not the roll extrusion perforate after the demoulding.
(2) foam physics, mechanical property measured result (pressing the national standard method test)
1, foam hardness: moderate deflection is good;
2, foam density: 35-40 kilogram/rice
3
3, falling-rebounding ball rate (%): 50-65
4, elongation (%) 145-170;
5, tensile strength: 160-180 newton/centimetre
2
6, compressive strength: 24 ℃ of 75%:5-9.
Claims (3)
1, a kind of preparation method of high-resiliency low-density moulded polyurethane foam, the employing molecular weight is 4500-6500, proportion of primary OH groups is 60-85%, hydroxyl value is that the high activity polyether of 29-35 milligram KOH/ gram is that 45-65% (weight) and its polyethers of uncle's hydroxyl are parent, vinyl cyanide, vinylbenzene is that monomer polymerization forms, hydroxyl value is that the polymer polyatomic alcohol of 25-29 milligram KOH/ gram is that the mixture that 35-55% (weight) forms is a basic material, with basic material weight is 100, add triethylene diamine 0.1-0.6, silicone based foam of polymers stablizer DC5043 or L53070.8-2.0, dibutyl tin laurate 0.012-0.06, two-(2-dimethyl aminoethyl) ether 0.3-1.085% (weight) diethanolamine aqueous solution 0.5-1.2, total water 2.6-3.1,-fluoro trichloromethane 0-6, isocyanate index 105-108TDI (80/20) single with or TDI (80/20) and MDI mix and use the composition foamed material through the moulding of water frothing mold, it is characterized in that adding in basic material weight in the foamed material is 100,0.1-0.8 trolamine, the formic acid of 0.1-0.5, any one acid in acetate or the phosphoric acid.
2, press the preparation method of the described polyurethane foam of claim 1, it is characterized in that earlier two-(2-dimethyl aminoethyl) ether being mixed and made into foamed material with the miscible back of acid with unclassified stores, add proper amount of glycol during the preparation acid solution, its add-on is for being 1 with sour weight, and ethylene glycol is 2.5-3.
3, press the preparation method of the described polyurethane foam of claim 1, it is characterized in that in foamed material adding and be dissolved with 15%(weight) water, 10%(weight) polyoxyethylene glycol of carboxymethyl cellulose, its add-on for count 100 with basic material weight, polyoxyethylene glycol is 0.5-2.0.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 92102234 CN1076933A (en) | 1992-03-31 | 1992-03-31 | The preparation method of high-resiliency low-density moulded polyurethane foam |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 92102234 CN1076933A (en) | 1992-03-31 | 1992-03-31 | The preparation method of high-resiliency low-density moulded polyurethane foam |
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| CN1076933A true CN1076933A (en) | 1993-10-06 |
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| CN 92102234 Pending CN1076933A (en) | 1992-03-31 | 1992-03-31 | The preparation method of high-resiliency low-density moulded polyurethane foam |
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| CN1112392C (en) * | 1995-12-22 | 2003-06-25 | 阿克奥化学技术有限公司 | Elastomeric polyurethanes with improved properties based on crystallizable polyols in combination with low monol polyoxypropylene polyols |
| CN101885956A (en) * | 2010-07-02 | 2010-11-17 | 上海汇宇精细化工有限公司 | Composite cloth adhesive bridging agent and preparation method thereof |
| CN102414233A (en) * | 2009-02-13 | 2012-04-11 | 拜尔材料科学股份公司 | Aqueous coating systems based on physically drying urethane acrylates |
| CN102492109A (en) * | 2011-11-28 | 2012-06-13 | 西安科技大学 | Biodegradable high-resilience flexible polyurethane foam plastics and its preparation method |
| CN104193939A (en) * | 2014-08-05 | 2014-12-10 | 滁州宝瑞橡胶制品有限公司 | High-resilience polyurethane foam |
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-
1992
- 1992-03-31 CN CN 92102234 patent/CN1076933A/en active Pending
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| CN102492109A (en) * | 2011-11-28 | 2012-06-13 | 西安科技大学 | Biodegradable high-resilience flexible polyurethane foam plastics and its preparation method |
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