CN1271106C - Catalytic complex for preparing isocyanurate foam from bagasse ployol - Google Patents
Catalytic complex for preparing isocyanurate foam from bagasse ployol Download PDFInfo
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- CN1271106C CN1271106C CN 200510034637 CN200510034637A CN1271106C CN 1271106 C CN1271106 C CN 1271106C CN 200510034637 CN200510034637 CN 200510034637 CN 200510034637 A CN200510034637 A CN 200510034637A CN 1271106 C CN1271106 C CN 1271106C
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- bagasse
- ployol
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Abstract
The present invention relates to a catalytic compound used for preparing polyurethane foams from bagasse ploylol. The present invention is characterized in that catalytic compound is prepared from 100 parts of solvent, 0 to 20 parts of foaming catalyst, 1 to 15 parts of chain growth catalyst and 15 to 60 parts of foam stabilizing agent according to parts by quality. The catalytic compound of the present invention is suitable for water foaming systems of bagasse polylol; the catalytic compound can regulate reactive speeds and can also make each auxiliary agent uniformly perform functions. Therefore, the present invention provides the same catalytic function and the same supporting function for each part to avoid the frequent phenomenon of non-uniformity of each part of products in a forming reaction, and also provides favorable elasticity, strength and density for foams. Moreover, the present invention can has the advantages of making production precise, easily controlling the dosage of auxiliary agents, decreasing weighing errors and ensuring the quality of products.
Description
Technical field
The present invention relates to a kind of catalytic complex, relate in particular to a kind of catalytic complex that is used for preparing isocyanurate foam from bagasse ployol.
Background technology
Mainly contain the reaction of three classes in the building-up process of urethane foam, promptly transfer reaction, interlinkage reaction and gas react.The molecular chain that transfer reaction generates forms cancellated superpolymer by the interlinkage reaction, become the channels and collaterals and the skeleton of foams, the abscess that foamable reaction produces then distributes therebetween, the reaction of three classes is harmonious, then can provide good elasticity, intensity and density for foams, otherwise hollow can take place in foams, and even the bubble that collapses.Do not having under the catalyzer situation, dominant in foaming process is transfer reaction and foamable reaction, and interlinkage speed of response and the two differ bigger, the speed of conditioned reaction, then need to depend on the effect of catalyzer.Therefore in the prescription of preparation urethane foam, of paramount importance auxiliary agent is catalyzer and suds-stabilizing agent, and they can promote the carrying out of all kinds of reactions in the foaming process effectively, and guarantees the foamy stable growth.
The catalyzer of synthesis of polyurethane porous plastics commonly used is amines catalyst and organotin catalysts, amines catalyst mainly acts on the foamable reaction, it can accelerate foamable reaction speed, we are called kicker, organotin catalysts mainly acts on the transfer reaction, we are called the chainpropagation catalyzer with it, it has great katalysis for isocyanic ester and hydroxyl reaction, katalysis for isocyanic ester and water reaction is then relative weak many, this characteristic is extremely important, can be used for regulating in foaming process the speed of two kinds of reactions.
Suds-stabilizing agent mainly plays emulsification and the capillary effect of reduction system in foamable reaction.Emulsifying effect is that the hydrophilic radical by the molecular chain two ends contacts each component thorough mixing with hydrophobic grouping to become homogeneous system, help various successful reaction and carry out; The surface tension of reduction system can make pore fine and closely woven evenly, and hole wall is stable, helps the growth of pore, and this point is particularly important when the initial reaction stage system viscosity is low.
In sum, in the production process of polyurethane foam, though catalyzer and suds-stabilizing agent consumption are few, effect but is critical, for an individual system, find the proportioning and the consumption of its only catalyzer and suds-stabilizing agent, be very important work in the urethane research process.
The bagasse polyvalent alcohol is the mixture that is rich in hydroxyl that generates after baggasse fiber is degraded in organic solvent, and it can substitute traditional polyethers and polyester polyol, prepares polyurethane foamed material with isocyanate reaction.Yet the bagasse polyvalent alcohol is a very complicated system, and to compare difference very big with traditional polymerized polyalcohol, and hydroxyl wherein is not the two ends that are distributed in molecular chain, but uneven distribution, and its distribution can't accurately characterize so far.Therefore, use the preparing isocyanurate foam from bagasse ployol material, can not only use single catalyzer, and multiple catalyzer will be used altogether, and selected catalyzer also should have than conventional system and contain ability widely except will having higher activity, and because bagasse polyvalent alcohol system complicated component, during foaming again mainly with water as whipping agent, therefore it is just extremely important to seek suitable water-resisting type wide spectrum suds-stabilizing agent.
We find in real work in addition, adopt method in the past, each catalyzer and suds-stabilizing agent are added two shortcomings of existence in the reaction system respectively: the one, weighing is inaccurate, because the consumption of catalyzer and suds-stabilizing agent is all fewer, be easy to generate error when weighing, this brings restriction also for the adjustment of prescription; The 2nd, be difficult to mix, catalyzer and suds-stabilizing agent mix evenly more with the bagasse polyvalent alcohol in the reaction process, and be favourable more to reaction, but because consumption is few, bagasse polyhydroxy reactant complexity in addition, and with the structural difference of auxiliary agent, make to mix to be not easy to reach even.
Summary of the invention
The object of the present invention is to provide the accurate weighing of a kind of energy and be easy to follow the bagasse polyvalent alcohol to mix and can fully promote the catalyst complex of urethane building-up reactions.
The present invention will be applicable to that kicker, chainpropagation catalyzer and the suds-stabilizing agent of bagasse polyvalent alcohol are dissolved in certain solvent, obtained the catalytic complex that is easy to accurate weighing and mixes with the bagasse polyvalent alcohol, catalyzer wherein is controls reaction speed well, coordinate the balance between foamable reaction and the transfer reaction, suds-stabilizing agent wherein can provide enough supports for the growth of pore in the foamable reaction, thereby has realized purpose of the present invention.
A kind of catalytic complex that is used for preparing isocyanurate foam from bagasse ployol of the present invention is characterized in that according to the mass fraction, by 100 parts of solvents, and 0～20 part of kicker, 1～15 part of chainpropagation catalyzer and 15～60 parts of compositions of suds-stabilizing agent.
Described solvent can be a polyvalent alcohol, the mixture of one or more in ethylene glycol, polyoxyethylene glycol, the glycerol for example, and polyoxyethylene glycol can be poly(oxyethylene glycol) 400, Polyethylene Glycol-600 or cetomacrogol 1000 etc.; Described kicker can be an amine, for example triethylenediamine, triethylamine or trolamine etc.; Described chainpropagation catalyzer can be an organotin, for example dibutyltin dilaurate or stannous octoate etc., described suds-stabilizing agent can be a polydimethylsiloxane, dimethyl-silicon wet goods for example, it also can be polysiloxane-polyether copolymer, for example AK-8805, AK-8806, TEGOSTAB B 8404 and TEGOSTAB B8408 etc. can also be the olefin oxide modified dimethyl polysiloxanes, for example F-502 etc.
The preparation method who is used for the catalytic complex of preparing isocyanurate foam from bagasse ployol of the present invention, comprise the steps: according to the mass fraction, in 100 parts of solvents, 0～20 part of kicker, 1～15 part of chainpropagation catalyzer and 15～60 parts of adding Glass Containerss of suds-stabilizing agent, magnetic agitation 5～10min, promptly get catalytic complex, seal that to put into moisture eliminator standby, stir 2～5min before each the use, each component is mixed.
When the preparing isocyanurate foam from bagasse ployol material, according to the mass fraction, add 1～10 part of catalytic complex of the present invention, with 100 parts of bagasse polyvalent alcohols, after 0～10 part of whipping agent mixes, add 30～300 parts of isocyanic ester again, pour free foaming in the mould into after on homogenizer, stirring 15～30s fast, be allowed to condition under the room temperature and solidify, also can put into 60～80 ℃ of baking ovens to accelerate its curing, the demoulding behind the completion of cure just obtains polyurethane foamed material.Bagasse polyvalent alcohol wherein can adopt existing preparation method to make, the method that provides of Chinese patent application 200310117508.1 and 03146953.1 etc. for example, and its hydroxyl value is 80～450mg KOH/g, viscosity is between 100～400mPas; Whipping agent is selected from fluorohydrocarbon class, methylene dichloride, pentane class or water, and the fluorohydrocarbon class can be fluoro trichloromethane, a fluorine ethylene dichloride (HCFC-141b) etc., and the pentane class can be pentamethylene, iso-pentane or Skellysolve A, preferably water and HCFC-141b; Isocyanic ester can be diphenylmethanediisocyanate, polymerization diphenylmethanediisocyanate, tolylene diisocyanate and rough tolylene diisocyanate, wherein preferred polymeric diphenylmethanediisocyanate.
Catalytic complex of the present invention is compared with suds-stabilizing agent with the catalyzer that uses separately in the past, following advantage is arranged: (1) is compared with amines catalyst, this mixture is the speed of conditioned reaction well, amines catalyst is little for the katalysis difference of the reaction of the reaction of isocyanic ester and hydroxyl and isocyanic ester and water, and usually need the speed of two kinds of reactions different in the practical application, so that adjust the foamy performance, ratio by chainpropagation catalyzer and kicker in the adjustment composite formulations, just can regulate the speed of two classes reaction easily, make it satisfy our needs; (2) compare with organotin catalysts, this mixture is more suitable for the water foaming system in the bagasse polyvalent alcohol, a little less than the katalysis of organotin catalysts for isocyanic ester and water reaction, this is for the not influence of conventional polyurethanes that with the fluorochlorohydrocarbon is whipping agent, and the bagasse polyvalent alcohol is because self, and the consideration of environmental protection adopts water as whipping agent more, include the kicker that can promote water and isocyanate reaction in the catalytic complex, can well address this problem; (3) suds-stabilizing agent in the mixture is selected at the system of bagasse polyvalent alcohol complexity, is the suds-stabilizing agent of hydrolysis, broad spectrum type, is fit to multiple foaming system; (4) this mixture can make each auxiliary agent play a role more equably, because catalyzer and suds-stabilizing agent are dissolved in the appropriate solvent, when reaction, can make their faster, more uniform being distributed in the system like this, for each several part provides identical catalysis and support effect, avoided the inhomogenous phenomenon of recurrent goods each several part in the foamable reaction; (5) consumption that this mixture can more accurate, easier control auxiliary agent, in the prescription of preparation polyurethane foam, the consumption of auxiliary agent is seldom, this has brought very big difficulty for accurate weighing, especially when adjusting prescription, the consumption of raw material is all smaller, wants just accurately to control difficulty more.Owing in catalytic complex, added appropriate solvent, played the effect of secondary dilution, be equivalent to increase sample weighting amount like this, thereby reduced the error of weighing, make that also weighing is more prone to.
Embodiment
Following embodiment further specifies of the present invention, but the invention is not restricted to following embodiment.Triethylenediamine, dibutyltin dilaurate, stannous octoate and dimethyl silicone oil used among the embodiment are buied by market, suds-stabilizing agent F-502 is produced by chemical company of Japanese SHIN-ETSU HANTOTAI, suds-stabilizing agent AK-8805 and AK-8806 produce by Nanjing dolantin generation wound company, suds-stabilizing agent TEGOSTAB B 8408 is produced by German Goldschmidt company, the polymerization diphenylmethanediisocyanate is produced by Yantai Wanhua Polyurethane Co., Ltd, and the trade mark is PM-200.
Embodiment 1:
100g ethylene glycol, 1g triethylenediamine, 6g dibutyltin dilaurate and 50gF-502 are added in the Glass Containers, and magnetic agitation 5～10min seals then, and it is standby to put into moisture eliminator.
Get the catalytic complex 2.8g that makes, stir 2～5min, add bagasse polyvalent alcohol 100g, stir, add polymerization diphenylmethanediisocyanate 300g, on 2000 rev/mins homogenizer, stirred 30 seconds, pour free foaming in the mould into.Solidify 25 ℃ of die temperatures under the room temperature.The foam density that makes is 59kgm
-3, compressive strength 470KPa.
Embodiment 2:
100g poly(oxyethylene glycol) 400,5g stannous octoate and 60gAK-8805 are added in the Glass Containers, and magnetic agitation 5～10min seals then, and it is standby to put into moisture eliminator.
Get the catalytic complex 3.10g that makes, stir 2～5min, add bagasse polyvalent alcohol 100g, water 6g stirs, and adds polymerization diphenylmethanediisocyanate 224g.On 2000 rev/mins homogenizer, stirred 20 seconds, pour free foaming in the mould into.Solidify 35 ℃ of die temperatures under the room temperature.The foam density that makes is 34kgm
-3, compressive strength 220KPa.
Embodiment 3:
100g poly(oxyethylene glycol) 400,15g triethylenediamine, 10g stannous octoate and 30gAK-8805 are added in the Glass Containers, and magnetic agitation 5～10min seals then, and it is standby to put into moisture eliminator.
Get the catalytic complex 3.5g that makes, stir 2～5min, add bagasse polyvalent alcohol 100g, water 1.5g stirs, and adds polymerization diphenylmethanediisocyanate 160g.On 2000 rev/mins homogenizer, stirred 15 seconds, pour free foaming in the mould into.Curing 20min is placed under the room temperature and solidifies 40 ℃ of die temperatures in 80 ℃ of baking ovens.The foam density that makes is 30kgm
-3, compressive strength 200KPa.
Embodiment 4:
100g Polyethylene Glycol-600,10g triethylenediamine, 6g stannous octoate and 15gTEGOSTAB B 8408 are added in the Glass Containers, and magnetic agitation 5～10min seals then, and it is standby to put into moisture eliminator.
Get the catalytic complex 6.0g that makes, stir 2～5min, add bagasse polyvalent alcohol 100g, water 3g stirs, and adds polymerization diphenylmethanediisocyanate 180g.On 2000 rev/mins homogenizer, stirred 15 seconds, pour free foaming in the mould into.Curing 20min is placed under the room temperature and solidifies 40 ℃ of die temperatures in 80 ℃ of baking ovens.The foam density that makes is 33kgm
-3, compressive strength 210KPa.
Embodiment 5:
100g Polyethylene Glycol-600,20g triethylenediamine, 15g stannous octoate and 60gAK-8806 are added in the Glass Containers, and magnetic agitation 5～10min seals then, and it is standby to put into moisture eliminator.
Get the catalytic complex 1.5g that makes, stir 2～5min, add bagasse polyvalent alcohol 100g, water 2g stirs, and adds polymerization diphenylmethanediisocyanate 170g.On 2000 rev/mins homogenizer, stirred 15 seconds, pour free foaming in the mould into.Curing 20min is placed under the room temperature and solidifies 40 ℃ of die temperatures in 80 ℃ of baking ovens.The foam density that makes is 49kgm
-3, compressive strength 153KPa.
Embodiment 6:
100g poly(oxyethylene glycol) 400,2g triethylenediamine, 1g stannous octoate and 20gAK-8805 are added in the Glass Containers, and magnetic agitation 5～10min seals then, and it is standby to put into moisture eliminator.
Get the catalytic complex 10g that makes, stir 2～5min, add bagasse polyvalent alcohol 100g, blowing agent H CFC-141b 6g stirs, and adds polymerization diphenylmethanediisocyanate 150g.On 2000 rev/mins homogenizer, stirred 30 seconds, pour free foaming in the mould into.Solidify 25 ℃ of die temperatures under the room temperature.The foam density that makes is 56kgm
-3, compressive strength 174KPa.
Embodiment 7:
Get bagasse polyvalent alcohol 100g, add 2gAK-8805, methylene dichloride 6g stirs, and adds polymerization diphenylmethanediisocyanate 300g.Stirred 30 seconds on 2000 rev/mins homogenizer, pour in the mould, foamable reaction does not take place.
Embodiment 8:
Get bagasse polyvalent alcohol 100g, add dibutyltin dilaurate 1g, dimethyl silicone oil 2g, water 3g stirs, and adds polymerization diphenylmethanediisocyanate 180g.Stirred 30 seconds on 2000 rev/mins homogenizer, pour in the mould and react, system expands rapidly and emits a large amount of gases, and bubble collapses behind about 90s.
Embodiment 9:
Get bagasse polyvalent alcohol 100g, add dibutyltin dilaurate 1.3g, 3 parts of dimethyl silicone oils, whipping agent pentamethylene 6g stirs, and adds polymerization diphenylmethanediisocyanate 150g.Stirred 30 seconds on 2000 rev/mins homogenizer, pour in the mould and react, system expands rapidly and emits a large amount of gases, and bubble subsequently collapses.
Claims (6)
1. catalytic complex that is used for preparing isocyanurate foam from bagasse ployol, it is characterized in that according to the mass fraction, by 100 parts of solvents, 0～20 part of kicker, 1～15 part of chainpropagation catalyzer and 15～60 parts of compositions of suds-stabilizing agent, described solvent is one or more the mixture in the polyvalent alcohol, described kicker is an amine, described chainpropagation catalyzer is an organotin, and described suds-stabilizing agent is polydimethylsiloxane or polysiloxane-polyether copolymer or olefin oxide modified dimethyl polysiloxane.
2. according to a kind of catalytic complex that is used for preparing isocyanurate foam from bagasse ployol of claim 1, it is characterized in that described solvent is one or more a mixture in ethylene glycol, polyoxyethylene glycol, the glycerol.
3. according to a kind of catalytic complex that is used for preparing isocyanurate foam from bagasse ployol of claim 2, it is characterized in that described polyoxyethylene glycol is poly(oxyethylene glycol) 400, Polyethylene Glycol-600 or cetomacrogol 1000.
4. according to a kind of catalytic complex that is used for preparing isocyanurate foam from bagasse ployol of claim 1 or 2, it is characterized in that described kicker is triethylenediamine or triethylamine or trolamine.
5. according to a kind of catalytic complex that is used for preparing isocyanurate foam from bagasse ployol of claim 1 or 2, it is characterized in that described chainpropagation catalyzer is dibutyltin dilaurate or stannous octoate.
6. according to a kind of catalytic complex that is used for preparing isocyanurate foam from bagasse ployol of claim 1 or 2, it is characterized in that described suds-stabilizing agent is dimethyl silicone oil, polysiloxane-polyether copolymer AK-8805, polysiloxane-polyether copolymer AK-8806, polysiloxane-polyether copolymer TEGOSTAB B 8404, polysiloxane-polyether copolymer TEGOSTAB B 8408 or olefin oxide modified dimethyl polysiloxane F-502.
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| Application Number | Priority Date | Filing Date | Title |
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| CN 200510034637 CN1271106C (en) | 2005-05-19 | 2005-05-19 | Catalytic complex for preparing isocyanurate foam from bagasse ployol |
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| CN 200510034637 CN1271106C (en) | 2005-05-19 | 2005-05-19 | Catalytic complex for preparing isocyanurate foam from bagasse ployol |
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| CN1271106C true CN1271106C (en) | 2006-08-23 |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US10308062B2 (en) | 2015-12-01 | 2019-06-04 | Zhongchao Special Security Technology Co., Ltd. | Optical anti-counterfeiting element and optical anti-counterfeiting product utilizing the same |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101265401B (en) * | 2008-04-23 | 2011-06-08 | 中国科学院广州化学研究所 | Method for preparing biomass polyurethane adhesive |
| CN105601871A (en) * | 2016-01-21 | 2016-05-25 | 苏州市景荣科技有限公司 | Preparation method of polyurethane combination for shoe material |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US10308062B2 (en) | 2015-12-01 | 2019-06-04 | Zhongchao Special Security Technology Co., Ltd. | Optical anti-counterfeiting element and optical anti-counterfeiting product utilizing the same |
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