CN1980967B - Flexible polyurethane foam - Google Patents
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- CN1980967B CN1980967B CN2005800228178A CN200580022817A CN1980967B CN 1980967 B CN1980967 B CN 1980967B CN 2005800228178 A CN2005800228178 A CN 2005800228178A CN 200580022817 A CN200580022817 A CN 200580022817A CN 1980967 B CN1980967 B CN 1980967B
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Abstract
Flexible polyurethane foam is made by mixing prepolymer with foam-forming ingredients comprising isocyanate and water which react to give carbon dioxide. The prepolymer is hydroxyl-tipped, being made by reacting polyol with less than the theoretical proportion of isocyanate required to react with available hydroxyl groups of the polyol. The prepolymer is a new storage stable starting material for use in making flexible polyurethane foam, and the foam produced with the prepolymer has advantageous properties with regard to hydrolysis resistance. The prepolymer may be made with low or high viscosity by appropriate selection of the proportion of isocyanate which reacts with the polyol. At high viscosities cell structure can be advantageously controlled by appropriate gasification or degasification during foaming.
Description
The present invention relates to flexible polyurethane (PU) foam.
The method of production flexible polyurethane foam (flexible PU foam) is known in the art, and for example sees to be set forth in Plastic Manual (plastics handbook) the 7th volume; Polyurethanes (urethane), Becher/Braun, the 2nd edition; Carl Hanser Verlag publishes, the 170-235 page or leaf.
Common flexible PU foam can prepare through polyvalent alcohol and polyfunctional isocyanate reaction, makes to form amino-formate bond through addition reaction NCO and hydroxyl, and the carbonic acid gas that passes through the generation of isocyanic ester and water reaction original position subsequently is with polyurethane foam.
Can adopt so-called " single stage method " to carry out this ordinary method, polyvalent alcohol, isocyanic ester and water are mixed, make in same step, to form urethane and foaming.
But, the also known two-step approach of using, the first step, polyvalent alcohol and isocyanate reaction obtain so-called " prepolymer ", second step, produce carbonic acid gas through isocyanic ester and water reaction, foam.
GB870119 and GB929371 have all described polyvalent alcohol and tolylene diisocyanate (TDI) reaction, obtain the heavy-gravity prepolymer, subsequently with water and catalyst mix, produce foam.
But these existing publications have been described the prepolymer through enough TDI and all available hydroxyl reaction preparations of polyvalent alcohol, and resulting prepolymer is that NCO is end capped; It is so-called " isocyanate prepolymer ", does not contain available hydroxyl.The NCO base of prepolymer can react with water, thereby forms the PU foam, need not to add other isocyanic ester.
So-called " polyol prepolymer " also is known in the preparation of PU material.Like " Polyurethane Handbook (polyurethane handbook) "; Dr.G ü nter Oertel; HanserPublishers; The 76th page said, and polyol prepolymer stays the oligomeric affixture that remaining hydroxyl makes for through polyethers and polyester polyol and the insufficient isocyanate reaction conversion of stoichiometry.Of document, these prepolymers are urethane-modified polyvalent alcohol, and are higher than unmodified polyvalent alcohol viscosity, are used for lacquer, paint, coating and sealer field.For example the hard coating of thermal activation (baking-type coating) can be by polyol prepolymer and dead front type or end capped POLYMETHYLENE POLYPHENYLISOCYANATE prepared in reaction.This Application Areas is different from the flexible PU foam field that the present invention relates to.
In flexible PU foam field, known hydrolysis causes that foam is aging, particularly deliquescing.Because therefore the aging characteristic of material in application that change do not hope in various application that foam is aging.
A target of the present invention is that a kind of flexible PU foam with significantly improved hydrolytic resistance is provided.
Therefore; The invention provides and a kind ofly prepare PU foamy method by prepolymer and the mixture that forms the foamy component; Wherein said prepolymer is through at least a polyvalent alcohol and at least a polyfunctional isocyanate reaction preparation; It is characterized in that prepolymer is the not polyol prepolymer of foaming that contains available hydroxyl, said formation foamy component comprises at least a polyfunctional isocyanic ester and water.
Discovery can prepare the PU foam with surprising hydrolysis aging according to said method.
As stated, known use polyol prepolymer prepares the for example hard coating of baking-type, and finds to can be used for preparing the flexible PU foam with advantageous property surprisingly.
Describe the isocyanate-terminated prepolymer of use with above-mentioned existing publication and prepare the foamy instruction on the contrary; The present invention uses the isocyanic ester/polyol prepolymer with available hydroxyl; Therefore need to add in addition isocyanic ester and prepare the PU foam, discovery can obtain having the foam of surprising hydrolytic resistance.
Although do not hope to be confined to the mechanism of any hydrolytic resistance, we think that the PU foam that uses prepolymer to obtain contains the urea key, is difficult for and the water attack.
Through addition reaction, isocyanic ester and polyol reaction obtain amino-formate bond.
I.R-NCO+HO-R′→R-NH-CO-O-R′
Isocyanic ester and water reaction obtain amine and carbonic acid gas.
II.R-NCO+H
2O→RNHCOOH→RNH
2+CO
2
Amine and isocyanate reaction obtain amino-formate bond.
III.R-NCO+RNH
2→R-NH-CO-NH-R
Amino-formate bond is hydrolysis progressively, obtains amine and carbonic acid gas.
IV.R-NH-CO-NH-R+H
2O→2RNH
2+CO
2
Because NCO, OH, H take place in above-mentioned reaction I, II, III simultaneously
2O reacts to each other, and obtains being combined with the PU chain of urea key.
Common flexible PU foam has block structure, and this block structure is made up of the flexible polyvalent alcohol chain of length that is connected with polyureas aromatics hard segment through urethane, and polar group (the for example NH and carbonyl of urea and amino-formate bond) links to each other through hydrogen bond.
Water can cause through this structure of hydrolysis urea key attack and dissociates, and promptly according to reaction IV division chain, also changes hydrogen bond through infiltration structure and causes chain slippage in structure, causes that therefore foam changes its physicals, particularly deliquescing.
Think owing to form PU chain network, have no chance basically to form the urea key, when therefore before using foaming, the prepolymer of part isocyanic ester/polyol reaction having taken place, can farthest reduce the formation of urea key through isocyanic ester/water reaction.
Also think when isocyanic ester simultaneously with water and prepolymer on during available hydroxyl reaction, those urea keys that in foaming process, form really have better " tissue " in the network of PU chain, make difficult and water attack.As stated, a kind of possible PU base that is interpreted as is as the kind that forms urea, thereby obtains more systematism or heterogeneous system, causes cracking thereby make water be difficult for infiltration with hydrolysis urea key, or changes hydrogen bond and cause slippage.In prepolymer, increase isocyanic ester and can increase the systematism level, but as mentioned below, increase the viscosity that isocyanic ester can increase prepolymer, can change foamy physics and chemical property.
In so-called " single stage method ", reacting together through isocyanic ester, polynary alcohol and water; Or through under isocyanate-terminated prepolymer and the water prepared in reaction PU foamy situation; The urea key can be combined in more in the two-phase system of " random ", makes through hydrolysis or chain slippage more responsive to " structural rearrangement " of PU chain network.This " structural rearrangement " causes softening or hardness reduces.
In the present invention, said prepolymer can be the material of stable storing, does not exist under the situation of water fully or basically, through isocyanic ester and polyol reaction preparation.Said prepolymer is a ready-formed; In step subsequently; Through being exposed to the blown with carbon dioxide that the reaction of isocyanic ester and water produces, and this step can carry out after the preparation prepolymer in identical or different device soon, perhaps under the independent fully preparation of the prepolymer of stable storing or the situation of supplying; If desired, use different devices sometimes.
Be meant urethane-modified polyvalent alcohol on term " prepolymer " ordinary meaning that this paper uses, promptly, be used to prepare the end product polyurethane material through the polymer materials that contains amino-formate bond of polyvalent alcohol and isocyanate reaction preparation.Equally, " prepolymer does not foam " as herein described is meant the prepolymer that has no foam to produce basically.In fact and since inevitably exist trace water (for example being included in the raw polyol) can with isocyanate reaction, the foaming of insignificant or slight extent can be arranged.But, preferably purpose not being arranged or specially in the preparation process of prepolymer, add entry, selective reaction condition and each component are to suppress or to make isocyanic ester/water reaction produce the degree minimum of carbonic acid gas.
Will also be understood that method of the present invention can relate to the purposes of single prepolymer (single prepolymer); Promptly plant the polymer materials that polyfunctional isocyanate reaction makes with list through single polyvalent alcohol of planting; Method perhaps of the present invention can relate to the purposes of many prepolymers (multiple prepolymer), the multiple different prepolymer of blended and/or one or more multipolymers that promptly obtain through multiple polyvalent alcohol and multiple polyfunctional isocyanate reaction.
Can be for example in the presence of the catalyzer in one or more other components, mix to form prepolymer with the mixture of isocyanic ester or multiple isocyanic ester through mixture with polyvalent alcohol or multiple polyvalent alcohol.Said mixing can batch process (for example under agitation) or is carried out through mixing first-class reinforced continuous processing.Mixing can at room temperature be carried out, and can keep any suitable time (for example 24 hours), still according to the character of each reactant and any other component, can be other temperature and times.
Polyvalent alcohol can be any suitable kind.Usually polyethers and polyester polyol are used to prepare the PU foam, and preferred polyol of the present invention is mainly polyether glycol fully or at least.The PU foam of polyether glycol preparation is more insensitive to hydrolysis than the PU foam that uses the polyester polyol preparation.When using polyether glycol, fully preferred or be mainly propylene oxide (PO) deutero-polyether glycol, but also can use oxyethane (EO) to replace PO, perhaps use EO and PO.EO deutero-polyvalent alcohol is than PO facile hydrolysis more.But also can use the mixture of polyester polyol or polyethers and polyester polyol.The OH functionality of suitable polyvalent alcohol can be 2-6,2-4 particularly, and molecular weight (MW) can be about 400-10,000.
Known in this field; Use the active of blended polyvalent alcohol change system or give resulting PU foam required performance, for the present invention, though usually preferred PO deutero-polyether glycol; But can use if desired, the mixture of other polyvalent alcohols or multiple polyvalent alcohol.
The embodiment of the spendable polyether glycol of the present invention is as being described in Plastic Manual (plastics handbook), the 7th volume, Polyurethanes (urethane), Becher/Braun, the 2nd edition, CarlHanser Verlag publication, 44-54 page or leaf and 75-78 page or leaf.
Therefore, polyvalent alcohol can be for example following:
I. derived from the polyvalent alcohol of PO and Ucar 35, viscosity (25 ℃) is 250-350mPas, and hydroxyl value is 56 ± 3.
II. derived from the polyvalent alcohol of EO, PO and TriMethylolPropane(TMP), viscosity (25 ℃) is 750-900mPas, and hydroxyl value is 35 ± 2.
III. derived from the polyvalent alcohol of PO and TriMethylolPropane(TMP), viscosity is 600-700mPas, and hydroxyl value is 380 ± 25.
IV. derived from PO and glycerine, viscosity is 450-550mPas, and hydroxyl value is 56 ± 3.
Use brookfield's viscometer to carry out all viscosimetric analysis (mPas of unit).Unless otherwise indicated, otherwise measure down viscosity at 25 ℃.Hydroxyl value is conventional parameter, is the concentration of per unit weight NCO-activity hydroxy, and unit is mg KOH/g.
Hydroxyl value (OH)=[molecular weight of (56.1 * functionality)/polyvalent alcohol] * 1000
Also can use those polyether glycols that comprised the catalyzer that includes, for example described those materials of WO03/016373A1.Also can use the mixture of above-mentioned polyether glycol.
Preferred polyhydric alcohols is such triol, and it is the propylene oxide adduct of glycerine, and molecular weight is 3,000 orders of magnitude.Product examples Voranol
3008 (Dow? ChemicalCompany) or DESMOPHEN
20WB56 (Bayer).
As for polyfunctional isocyanic ester, preferred vulcabond, particularly TDI (tolylene diisocyanate).But can use the polyfunctional isocyanic ester of the preferred functionality of independent or any appropriate combination as 2-5.Identical isocyanic ester can be used for preparing prepolymer and prepares foam subsequently, perhaps can use different isocyanic ester.
Therefore, said polyfunctional isocyanic ester can be the material below any one or more:
TDI (all isomer blends of tolylene diisocyanate)
MDI (ditan-4,4 '-vulcabond),
Can be pure substance or polymkeric substance variant (therefore being called aromatic isocyanate).
More particularly, polyfunctional isocyanic ester is the POLYMETHYLENE POLYPHENYLISOCYANATE that comprises two or more isocyanos, uses standard merchandise vulcabond and/or triisocyanate usually.The instance of suitable POLYMETHYLENE POLYPHENYLISOCYANATE have aliphatic series, alicyclic, aryl is aliphatic and/or aromatic isocyanate; For example 2 of commercial toluene diisocyanate (TDI); 4-and 2; The 6-mixture of isomers, institute's commodity of selling Caradate
T80 (Shell) by name or Voranate
T80 and T65 (DowChemicals).Also can use 4,4 '-ditan-vulcabond (=4,4 '-methylene-bis (phenyl isocyanate); MDI) and the mixture of TDI and MDI.But also can use isocyanate prepolymer based on TDI or MDI and polyvalent alcohol.Also can use modification or blended isocyanic ester (for example Desmodur
MT58, available from Bayer).The instance of aliphatic isocyanate has 1; 6-hexamethylene diisocyanate or triisocyanate; Desmodur
N1000 or N3300 for example is available from Bayer.
Selective reaction forms polyvalent alcohol and the relative proportion of isocyanic ester and the MW (molecular weight) of polyvalent alcohol of prepolymer as required.The ratio of isocyanic ester can be and all available hydroxyl reactions 0.1-99% of aequum in theory, is preferably 0.1-50%.Along with the increase of isocyanic ester ratio, viscosity increases, and the upper limit depends on the needs of processing.In fact, the hydroxyl value of prepolymer can be confirmed by following relation:
OH (prepolymer)=OH (polyvalent alcohol)-(php (NCO) * 561/EW (NCO))
OH (polyvalent alcohol) is the hydroxyl value of raw polyol, can be 56 usually.Php (NCO) is the weight part ratio of per hundred parts of polyvalent alcohol NCO, and EW (NCO) is the equivalent of isocyanic ester, is 87 (being that molecular weight is divided by theoretical functionality) for TDI.
The ratio of isocyanic ester can be high, and if desired, polyvalent alcohol MW can be high, so the unusual thickness of prepolymer, and viscosity is about 30,000mPas or higher.Perhaps can use the isocyanic ester than small proportion, if desired, polyvalent alcohol MW can be lower, so less hydroxyl reaction, and thickness can be lower.More low viscous prepolymer is more suitable for preparing continuously the PU foam.Therefore, viscosity can be less than 20, and 000mPas can be less than 7,000mPas, be low to moderate approximately 700mPas and/or near or equal the viscosity of basic polyvalent alcohol basically.The MW of polyvalent alcohol can be 400-10, and 000.
Find that favourable foam of the present invention (being the good foam of hydrolytic resistance) both can also can be prepared by viscosity higher prepolymer (hydroxyl of larger proportion and isocyanate reaction) by low viscosity prepolymer (only small amount of hydroxyl groups and isocyanate reaction).As mentioned below, if desired, the foam that is prepared by the viscosity higher prepolymer also can have favourable performance, for example controls foam structure.
The viscosity of viscosity higher prepolymer can be greater than 5, and 000mPas is preferably greater than 7,000mPas, and it is about 50 that the upper limit can be, and 000mPas is preferably 35,000mPas.More particularly, favourable viscosity is 9,000-35,000mPas, particularly 15,000-35,000mPas.
Than low viscosity prepolymer can with viscosity less than 20,000mPas, particularly less than 7, the viscosity higher scope of 000mPas is overlapping, although preferred range is less than 5,000mPas is to being low to moderate viscosity near the viscosity of basic polyvalent alcohol, can be 600 or 700mPas.
Accounted for the ratio of the theoretical weight of the required isocyanic ester of all available hydroxyl reactions of polyvalent alcohol by used isocyanic ester and to confirm viscosity, the initial viscosity of the polyvalent alcohol that also can be through being used to form prepolymer or the mixture of multiple polyvalent alcohol is confirmed viscosity.Generally speaking, as stated, this ratio can be 0.1-99%.For low viscosity prepolymer, this ratio can be 0.1-30% or 0.1-23% or 25%, particularly 0.1-12%, 3-12% for example, and for the HV prepolymer, this ratio can be 30-99%, particularly 30-50%.
Can use any appropriate catalyst to carry out the isocyanic ester addition reaction.These catalyzer can be tin compound, for example two stannous octoates, dibutyl tin dilaurate or tertiary amine, and for example 1,4-diaza [2,2,2] bicyclooctane perhaps is used for other materials of this area, for example zinc octoate etc.If desired, also can use two or more different catalyst simultaneously.But, also can under the condition that does not have catalyzer, prepare prepolymer, if desired, depend on heating or other reaction initiation conditions.
Usually on a small quantity use any catalyzer that adds, 0.004% pink salt (for example dibutyl tin dilaurate, stannous octoate or higher homologue) for example, but also can use said amine and other catalyzer.Catalyzer mixes with polyvalent alcohol usually, slowly adds isocyanic ester subsequently, subsequently resulting mixture is fully reacted, with post-foaming.Therefore initial mixing can be carried out about 15 minutes, and further reaction can be carried out about 24 hours.
When forming prepolymer, also can mix other components as auxiliary agent or additive.
More particularly, these components comprise various auxiliary agents, for example chainextender, linking agent and chain terminator.
The compound (for example trolamine, glycerine or sugar alcohol (for example Sorbitol Powder)) that can use active dual functional compound (for example diethylolamine or water) of low-molecular-weight isocyanate or higher functional is as chainextender and/or linking agent.
The compound (for example monohydroxy-alcohol, primary amine and secondary amine) that can use the isocyanate-reactive simple function is as chain terminator.
Also can add other auxiliary agents known in the art, for example fire retardant, pigment or filler.
Prepolymer can mix or before foaming, mix with other materials.For example can add the unreacted polyvalent alcohol of identical or different kind, for example dilute said prepolymer, make that viscosity is lower or change the active or resulting foamy performance of system.
Can use conventional device, adopt conventional method foaming prepolymer, PlasticManual (plastics handbook) for example, the 7th volume; Polyurethanes (urethane), Becher/Braun, the 2nd edition, Carl Hanser Verlag publishes; The described method of 171-178 page or leaf, and use conventional foam formulations, for example Plastic Manual (plastics handbook); The 7th volume, Polyurethanes (urethane), Becher/Braun; The 2nd edition, Carl Hanser Verlag publishes, the described foam formulations of 187-193 page or leaf.
Usually in order to prepare foam, prepolymer can with water and/or other whipping agents, isocyanic ester, one or more catalyzer and one or more other components for example suds-stabilizing agent mix.
Foaming can be adopted interrupter method or continuous processing, and mixture can be used the nitrogen aerating.
More particularly, foaming component can comprise one or more following materials:
A) isocyanic ester, for example aliphatic, alicyclic, aryl is aliphatic and/or aromatic isocyanate.Instance has 2 of commercial toluene diisocyanate (TDI), 4-and 2,6-mixture of isomers.Tradename Caradate
T80 (purchased from Shell), Voranate
T80 and T65 (purchased from DowChemicals).Also can use 4,4 '-diphenylmethanediisocyanate (=4,4 '-methylene-bis (phenyl isocyanate); MDI) and the mixture of TDI and MDI.
Also can use other isocyanate prepolymers based on TDI or MDI and polyvalent alcohol.Also can use modification or blended isocyanic ester (for example Desmodur
MT58, available from Bayer).The instance of aliphatic isocyanate has two isocyanic acids 1; 6-hexamethylene diisocyanate or triisocyanate; Desmodur
N1000 or N3300 for example is available from Bayer.
Said isocyanic ester can be identical or different with the isocyanic ester that is used to prepare prepolymer.
B) water, preferred per 100 weight part polyvalent alcohols or prepolymer or polyvalent alcohol/pre-polymer mixture use the 0.5-10 weight parts water.
C) also can use liquid CO
2As other whipping agents.
D) also can choose other additives of use wantonly; The additive of those PU foam known particularly; Catalyzer for example; Be in particular amine; DMEA (dimethylethanolamine), DABCO
33LV (tertiary amine is available from Air Products) and/or organometallics tin catalyst KOSMOS29 (stannous octoate) or other catalyzer zinc octoate for example for example for example for example; Suds-stabilizing agent known in the art; Polysiloxane surfactant for example, for example Tegostab
type of (available from Goldschmidt) or Silbyk
type (available from BYK-Chemie); Chainextender and/or linking agent, for example diethylolamine, glycerine, Sorbitol Powder; And fire retardant; Filler.Can use known in the art those additives relevant and other materials of any combination with conventional foaming method.
E) be used for aerating and the nitrogen of controlling foam structure (aperture and pore size distribution).
About foaming, if desired, also can carry out in decompression or excessive rolling; Its processing conditions for example is disclosed in USP 5,194,453.
Can obtain very fine abscess as follows, the gas of fine dispersion added in the base mateiral (the for example liquid mixture of prepolymer or multiple basic components) of desire foaming.Said gas is preferably nitrogen, perhaps can use air.
As mentioned below, for the HV prepolymer,, for example viscosity is greater than 5, the prepolymer of 000mPas, and aerating is particularly useful for the control foam structure.
Except prepolymer, also can use the mixture of prepolymer and polyether glycol and/or polyester polyol or other polyvalent alcohols.Can use glycol to the hexavalent alcohol (hexol) of the oxyethane that contains any amount.
Find that subsidiary characteristic of the present invention is the may command parameter relevant with the viscosity of abscess number and prepolymer, obtain having the PU foam of advantageous property, this point is for using other special advantages of said prepolymer.
Therefore, in one embodiment, preparation has the flexible PU foam that also has irregular foam structure under foam structure or the suitable situation of ad hoc rules, and wherein the aperture can from very tiny (hole count be greater than 80ppi) to very thick (hole count is reduced to 6ppi).Term " ppi " is measured for abscess (hole) size, confirms through the abscess number on foam surface per inch (every 2.54cm) length.But this embodiment adopts the method for large-scale commercial prodn to produce above-mentioned flexible PU foam, and the foam that makes has predetermined required aperture or hole count and/or pore size distribution.
About this respect, up to now, use the raw material that can get usually on the market in industry, can not produce flexible polyethers-polyurethane foam with very fine hole (greater than 80ppi).On the other hand, if known, can obtain very fine hole with polyester polyol foaming preparation polyester-polyurethane foam.
But; In the present invention, as mentioned below, use prepolymer of the present invention; Preferred highly viscous prepolymer as herein described confirms also can polyether glycol (it has been generally acknowledged that and be very low viscous material) be processed into the very PUR foam of pore surprisingly.
Unless otherwise indicated, otherwise term " highly viscous " is meant that the viscosity of material or material blends is equal to or greater than 5,000, particularly greater than 7, and 000mPas.
The salient point of resulting flexible block foam is following characteristic usually, in the field relevant with the PU foam of polyether glycol base, does not reach these characteristics up to now:
Thereby-can control the viscosity of prepolymer through control texture, may command hole count and structure (thin/gross porosity number and rule/irregular structure).
-excellent hydrolysis aging property; With
-density is 10-100, is preferably 14-70kg/m
3
A special advantage of method of manufacture of the present invention is to be convenient to the systematicness or the irregularity of preset aperture on purpose or hole count and aperture or pore structure.According to required quality, froth, for example in order to foam, mainly to utilize air or nitrogen to change aerating and realize this advantage, if desired, to base mateiral or at least the part base mateiral carry out the degassing more or less.
The hole count that term " pore structure " is interpreted as comprising with regard to aperture, distribution and this paper and the structure of the foam base plate with regard to the type.Even or regular pore structure is meant that the aperture in most of holes is identical or roughly the same.
Because the supposition HV can be depending on the structure of prepolymer; Thereby and become with polymkeric substance, compare with low viscosity reaction mixture, the possibility of the diffusion particularly rate of diffusion of bubble significantly reduces; Thereby but bubble or the coalescence of water vapour bubble form than macrostructure not too apace.Particularly can increase the viscosity based on the foaming system of polyether glycol, and polyether glycol is generally the LV system, therefore control is a surprising characteristic of the present invention with accurately definite aperture.
It is shocking, also can carry out aerating to foam, perhaps on the other hand, even isocyanic ester and/or prepolymer carried out the controlled degassing, produce and have the very foam of macropore through having a mind to restriction.In this case, bigger degassing degree makes the aperture increase and reduce the hole count of end product.Can for example in closed circuit system, under vacuum, outgas.
The viscosity of HV prepolymer is greater than 5,000mPas, particularly greater than 7,000mPas is preferably 15,000-35,000mPas, or even up to about 50,000mPas.
The present invention further specify the present invention in order to explain better with reference to following examples.
Embodiment 1
Adopt interrupter method to prepare prepolymer.
96.24% polyether glycol [DESMOPHEN 20WB56 (Bayer)], hydroxyl value: 56, viscosity: about 700mPas (20 ℃);
3.75% tolylene diisocyanate 80/20 (TDI 80/20)
0.00385% dibutyl tin dilaurate (DBTL)
Under room temperature, polyether glycol is placed mixing vessel, under agitation add dibutyl tin dilaurate subsequently.Tolylene diisocyanate slowly is stirred in this mixture.
After about 24 hours, the viscosity of resulting prepolymer (25 ℃) is about 30,000mPas.
But this prepolymer also can adopt continuous processing to prepare similarly.
Embodiment 2
Compare foamy preparation of the present invention and characteristic with the known conventional product of prior art.
Adopt single stage method, (Messrs.Hennecke, Germany) preparation foam in standard industry flexible block foam offset plate workshop.In this embodiment, according to prescription raw material is directly measured to mixing section from magazine with pump (for example piston pump or toothed gear pump), this mixing section is equipped with whisking appliance and vomit pipe.
Adopt methods known in the art metering and mixing raw material.In this embodiment, with temperature regulation to 25 ± 3 of raw material ℃.
The overall rate of discharge of prepolymer or polyvalent alcohol is 50kg/ minute.For extra nucleogenesis (that is to say that extra nucleation forms bubble), the nitrogen metering is added to mixing section.Low whipping speed is no more than 6, and 000rpm preferably is lower than 6, and 000rpm is foaming down, and the pressure of mixing section is no more than 2.5 crust, preferably is lower than 2.5 crust.
Use following table 1 described each component as foaming raw material, 1 preparation is used for prepolymer of the present invention according to embodiment, and the polyether glycol of reference implementation example is identical with embodiment's 1, and its viscosity is about 700mPas.
Table 1
*The weight part of the per 100 weight part polyvalent alcohols of php=part (or prepolymer or prepolymer/polyol blends).
The flexible PU foam that will under these conditions, prepare carries out following test:
A) because the compressive hardness (compression hardness) that causes of accelerated weathering test descends and
B) measure pore structure (ppi).
Before and after accelerated weathering test, measure compressive hardness, the kPas of unit.According to EN ISO3386-1, measure down in 40% deformation.Under 120 ℃,, in autoclave, carry out accelerated weathering test (wet method is aging) 5 hours (digestion period) with saturated vapor pressure according to EN ISO 2440.
The hole count that counting is positioned on the straight line is confirmed pore structure.Unit is ppi (hole count of every linear inch or 2.54cm).
Table 2 test result
| Compressive hardness [kPa] before the accelerated weathering test | Compressive hardness after the accelerated weathering test [kPa] | Compressive hardness decline [%] | Hole count (ppi) | |
| The prepolymer of foaming | 3.37 | 3.37 | 0％ | 92 |
| The polyether glycol of foaming (reference implementation example) | 3.67 | 3.41 | 7.08％ | 45 |
It is visible to compare (table 2) by this, and flexible PU foamy density prepared in accordance with the present invention is about 25kg/m
3, not only the hole has obviously thinner aperture, and beguine is more ageing-resistant according to the foam with equal densities of the typical method preparation of prior art simultaneously.
Also find; Compare through the foam with identical or essentially identical preparation that the prior art currently known methods prepares under suitable condition with those, all various foam articles prepared according to the methods of the invention up to now are moisture-proof method aging (according to the standard of above-mentioned accelerated weathering test) more obviously.
Although the foamy compressive hardness according to the currently known methods preparation descends up to 35%, and for identical with polyol component or the essentially identical preparation of main isocyanic ester prepared in accordance with the present invention, the foamy compressive hardness descends and is no more than 15%.Greater than 80ppi, and density is 20-30kg/m in the foamy hole count
3Situation under, compressive hardness descends even is 0-5% only.
The decline of the compressive hardness of common product prepared in accordance with the present invention is hanged down 10-50% than the reference product of prior art for preparing at least.This point has explained that profoundly foam prepared in accordance with the present invention has significantly improved stability to aging, and particularly the moisture-proof method is aging.
In context, select to make with the density and hardness characteristic of product prepared in accordance with the present invention basic identical with reference to the prescription of product.
More particularly, selection is feasible roughly the same with foamy volume density prepared in accordance with the present invention and hardness with reference to the prescription of product, and tolerance zone is ± 10%.
Embodiment 3
Prepare the gross porosity flexible block foam through reducing bubble nucleating.
According to embodiment 2 another response preparations of preparation, adopt identical prescription to use prepolymer through the degassing prepares flexible block foam to raw material (being mainly used isocyanic ester), the density of this flexible block foam is 18kg/m
3, hole count is 8ppi.
Provide these and other embodiment with reference to following table 3; It is identical with table 1 with B wherein to be listed as A; Row C is the foregoing description 3; Other are classified as and use the preparation identical with table 1 and other embodiment of method, and difference is in the mixing machine of laboratory, to process in each case, but not mix like the machine of table 1.
Each embodiment of table 3A (mixing based on the 200g polyvalent alcohol), all amounts are php
(part per hundred weight part polyvalent alcohol and/or prepolymers)
| A | B | C | D | ?E | F | G | ?H | ?I | J | |
| Polyvalent alcohol .OH=56 | 100 | 100 | ?100 | |||||||
| Prepolymer | 100 | 100 | 100 | 100 | 100 | ?100 | 100 | |||
| TDI?80/20 | 47.8 | 17.8 | 24.2 | ?23.2 | 23.2 | 22.8 | ?48 | ?47.7 | 46.9 | |
| TDI?65/35 | 17.8 | 45.2 | 24.2 | ?23.2 | 23.2 | 22.6 | ||||
| Water | 3.8 | 3 | 4.2 | 3.8 | ?3.8 | 3.8 | 3.8 | ?3.8 | ?3.8 | 3.8 |
| Dabco?33lv | 0.05 | 0.05 | ?0.05 | ?0.05 | 0.05 | |||||
| Niax?A1 | 0.12 | 0.12 | ?0.12 | ?0.12 | 0.12 | |||||
| Stannous octoate 33% | 0.18 | 0.2 | 0.2 | ?0.3 | ?0.3 | 0.3 | ||||
| Tegoamln?ZE-1 | 0.3 | ?0.3 | 0.3 | 0.3 | ||||||
| Kosmos?EF | 1.5 | ?1.5 | 1.5 | 1.5 | ||||||
| Polysiloxane surfactant | 1.05 | 1.05 | 1.05 | 1.5 | ?1.5 | 1.5 | 1.5 | ?1.05 | ?1.05 | 1.05 |
| The amount of isocyanic ester in prepolymer, php | nll | 3.89 | 3.89 | nil | ?0.5 | 1 | 2 | ?nil | ?1 | 2 |
| The viscosity of polymkeric substance or prepolymer, mpa | 700 | 30.000 | 30.000 | 700 | ?800 | 1.440 | 2.000 | ?700 | ?1.450 | 2.010 |
| Density, Kg/M3 | 24.8 | 25 | 18 | 22.7 | ?22.6 | 22.5 | 23 | ?23.6 | ?23.9 | 26 |
| CLD?40％(Kpa) | 3.67 | 3.37 | 3.9 | 3.31 | ?2.46 | 3.03 | 2.98 | ?3 | ?3.44 | 3.91 |
| CLD decline (%) behind the humid ageing | 7.08 | 0 | 2.5 | 19.3 | ?12.1 | 6.6 | 14.4 | ?21 | ?9.3 | 9.8 |
| Aperture (ppi) | 45 | 92 | 8 | 54 | ?48 | 50 | 55 | ?55 | ?52 | 56 |
Each embodiment of table 3B (mixing based on the 200g polyvalent alcohol), all measure php (as stated)
| K | ?L | ?M | ?N | ?O | ?P | ?Q | ?R | |
| Polyvalent alcohol, OH=56 | 100 | ?50 | ||||||
| Prepolymer | ?100 | ?100 | ?100 | ?100 | ?100 | ?100 | ?50 | |
| TDI?80/20 | 20.2 | ?18.3 | ?18.2 | ?18.2 | ?18.2 | ?18.8 | ?20 | ?20 |
| TDI?65/35 | 20.2 | ?18.2 | ?18.2 | ?18.2 | ?18.2 | ?19.8 | ?20 | ?20 |
| Water | 3.1 | ?3.1 | ?3.1 | ?3.1 | ?3.1 | ?3.1 | ?3.1 | ?3.1 |
| Dabco?33lv | ||||||||
| Niax?A1 | ||||||||
| Stannous octoate 33% | ||||||||
| Tegoamin?ZE-1 | 0.3 | ?0.3 | ?0.3 | ?0.3 | ?0.3 | ?0.3 | ?0.3 | ?0.3 |
| Kosmos?EF | 1.5 | ?0.8. | ?1.5 | ?1.5 | ?1.5 | ?1.5 | ?1.5 | ?1.5 |
| Polysiloxane surfactant | 1.5 | ?1 | ?1.5 | ?1.5 | ?1.5 | ?1.5 | ?1.5 | ?1.5 |
| The amount .php of isocyanic ester in prepolymer | nil | ?3.5 | ?2 | ?1 | ?3.9 | ?0.8 | ?0.27 | ?1 |
| The viscosity of polymkeric substance or prepolymer, mpa | 700 | ?17.000 | ?2.000 | ?1.440 | ?8.850 | ?750 | ?700 | ?1.440 |
| Density .kg/m 3 | 28.6 | ?30.9 | ?28.3 | ?29.3 | ?27.1 | ?29.2 | ?28 | ?27.5 |
| CLD?40％(Kpa) | 2.76 | ?4.4 | ?2.88 | ?2.37 | ?4.65 | ?3.34 | ?3.1 | ?2.8 |
| CLD decline (%) behind the humid ageing | 24.5 | ?12.6 | ?9 | ?0.8 | ?11.6 | ?11.1 | ?11 | ?10.4 |
| Aperture (ppi) | 52 | ?49 | ?51 | ?48 | ?53 | ?50 | ?49 | ?47 |
Each embodiment of table 3C (mixing based on the 200g polyvalent alcohol), all measure php (as stated)
| S | ?T | |
| Polyvalent alcohol, OH=56 | 100 | |
| Prepolymer | 100 | |
| TDI?80/20 | 15.2 | 14.5 |
| TDI?65/35 | 15.2 | 14.5 |
| Water | 2.3 | 2.3 |
| Tegoamin?ZE-1 | 0.3 | 0.3 |
| Kosmos?EF | 1.5 | 1.5 |
| ZGK 5 | 1 | 1 |
| The amount .php of isocyanic ester in prepolymer | 2 | |
| The viscosity of polymkeric substance or prepolymer, mPa | 600 | 3.700 |
| Density, kg/m 3 | 34.8 | 37.6 |
| CLD?40％(Kpa) | 2.31 | 4.13 |
| CLD decline (%) behind the humid ageing | 19.5 | 11.1 |
| Aperture (ppi) | 46 | 46 |
Tegoamin ZE-1 and KOAMOS EF are respectively amine and tin catalyst, and be different with Niax A1 with Dabco33lv, but have required low fogging performance.
The explanation of his-and-hers watches 3
Row A and B are the foregoing description 1, and row C is embodiment 3.That is to say; Row B and C are for using the foam that (use HV prepolymer) prepares according to the present invention of machine production; Row A is for adopting and be used to prepare routine that the identical basic polyvalent alcohol of prepolymer that be listed as B prepares with reference to the machine production foam, and the density that is mixed with is with to be listed as B foamy density identical.
Show the remarkable hydrolysis aging that improved, have controlled thin and thick pore structure (row B and C).
Row D-G is for having the foam of similar density and similar water content preparation at foaming stages.Use identical isocyanic ester and catalyzer (TDI and DBTL) preparation prepolymer, but the ratio of isocyanic ester is different, the viscosity of the prepolymer that obtains is different.Basis polyvalent alcohol and identical (MW=3,000) that is used for embodiment 1.Kicker is different with the catalyzer that is used for embodiment 1, for production is used for the low fogging catalyzer that the foam of automobile industry preferably uses.
D compares with reference columns, and foam of the present invention (row E-G) has improved stability to aging.
Row H-J and row category-A be like (using identical polyvalent alcohol, identical isocyanic ester and catalyzer to prepare prepolymer), but the ratio of isocyanic ester that is used to prepare prepolymer is different, and be the laboratory mixing, non-machine mixing.H compares with reference columns, foam of the present invention (row I,
J) has improved stability to aging.
Row K-R be other embodiment (using the polyvalent alcohol identical with embodiment 1), but is used to prepare the ratio difference of the isocyanic ester of prepolymer, and is lower than the water-content that is used to foam of embodiment 1, following parameter variation as follows:
I) be used to prepare the isocyanic ester/catalyzer of prepolymer:
K-N、Q、R：TDI+DBTL
The O:TDI+ stannous octoate
P: polymeric MDI (for example Voranate M220, available from Dow Chemical)+DBTL
Ii) K is the reference implementation example, and basic polyvalent alcohol is not converted into prepolymer; The identical basic polyvalent alcohol that L-Q has same amount is converted into prepolymer; The identical basic polyvalent alcohol of half amount is converted into prepolymer among the P, with the identical basic polyvalent alcohol dilution that is not converted into prepolymer of equivalent.
K compares with reference columns, and foam of the present invention (row L-R) has improved stability to aging.
S is different with embodiment 1 with T for row; Particularly polyvalent alcohol is EO/PO polyvalent alcohol (but not the specific PO polyvalent alcohol of embodiment 1); Can be the polyether glycol of trifunctional, contain a large amount of secondary hydroxyls, MW=3; 500, be specially LUPRANOL
2084 (BASF).Isocyanic ester/the catalyzer that is used to prepare prepolymer is TDI/DBTL.
(row S) compares with reference, and foam of the present invention (row T) has improved stability to aging.
Identical by table 3 part with table 1 and 2 (repeating) with the row A and the B of table 3, to compare with the reference preparation that does not use prepolymer of the present invention, preparation of the present invention has significantly improved decrease of hardness.
The ratio of isocyanic ester that is used to prepare prepolymer is different, the viscosity of the prepolymer that obtains from 700mPas than the paramount levels of viscosity of LV (30,000mPas).But, in each case, to compare with corresponding reference preparation, decrease of hardness has surprisingly to be improved significantly, explains that important factor wherein is the hydroxy-end capped isocyanic ester/polyol prepolymer of use.The result shows that also the viscosity increase also can be acting factor in some cases.Can in wide prepolymer range of viscosities, obtain high-quality available foam.
As stated, higher isocyanate content makes that the viscosity of prepolymer is higher, makes final foamy density high slightly.
Foam of the present invention is particularly with the diversified purposes that has of the cystose of industrial-scale production.Its purposes extends to electrical isolation, sound insulation and thermal-insulating system; For example be used for building and civil engineering and be used for automobile production; Produce the cleaning supplies of the burnisher of cleaning sponge or outfit cleaning sponge; Can produce cosmetic sponge and comfortable foam, for example mattress and upholstery foam are particularly useful as the carrier foam of printing ink or as ink pad in recording unit or printing press.
Certainly, it should be understood that the present invention is not limited to the details of the foregoing description preparation, the foregoing description only is used to illustrate.
As stated, the present invention also provides the novel prepolymers that is used to prepare said foamy stable storing except method for producing polyurethanes is provided.
Claims (5)
1. method for preparing flexible polyurethane foam by prepolymer and the mixture that forms the foamy component; Wherein said prepolymer is through at least a polyvalent alcohol and at least a polyfunctional isocyanate reaction preparation; Said prepolymer is that viscosity is lower than 20; 000mPas and have the not foaming polyol prepolymer of available hydroxyl; Said viscosity uses brookfield's viscometer under 25 ℃ temperature, to measure, and said prepolymer prepares through making the isocyanate reaction with the 0.1-30% of the required in theory isocyanic ester weight of all available hydroxyl reactions of said polyvalent alcohol, and said formation foamy component comprises at least a polyfunctional isocyanic ester and water.
2. the method for claim 1 is characterized in that said polyvalent alcohol at least mainly is propylene oxide deutero-polyether glycol.
3. method for preparing flexible polyurethane foam by prepolymer and the mixture that forms the foamy component; Wherein said prepolymer is through at least a polyvalent alcohol and at least a polyfunctional isocyanate reaction preparation; Said prepolymer is that viscosity is 7; 000-50; 000mPas and have the not foaming polyol prepolymer of available hydroxyl; Said viscosity uses brookfield's viscometer under 25 ℃ temperature, to measure, and said prepolymer prepares through making the isocyanate reaction with the 30-99% of the required in theory isocyanic ester weight of all available hydroxyl reactions of said polyvalent alcohol, and said formation foamy component comprises at least a polyfunctional isocyanic ester and water.
4. the method for claim 3, wherein said polyvalent alcohol at least mainly is a propylene oxide deutero-polyether glycol.
5. claim 3 or 4 method; Wherein said prepolymer is that viscosity is 15; 000-35; 000mPas and have the not foaming polyol prepolymer of available hydroxyl, said prepolymer prepares through making the isocyanate reaction with the 30-50% of the required in theory isocyanic ester weight of all available hydroxyl reactions of said polyvalent alcohol.
Applications Claiming Priority (5)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CH00841/04 | 2004-05-12 | ||
| CH8412004 | 2004-05-12 | ||
| GBGB0508091.6A GB0508091D0 (en) | 2005-04-22 | 2005-04-22 | Flexible polyurethane foam |
| GB0508091.6 | 2005-04-22 | ||
| PCT/EP2005/005314 WO2005108455A2 (en) | 2004-05-12 | 2005-05-12 | Flexible polyurethane foam |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1980967A CN1980967A (en) | 2007-06-13 |
| CN1980967B true CN1980967B (en) | 2012-03-28 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2005800228178A Active CN1980967B (en) | 2004-05-12 | 2005-05-12 | Flexible polyurethane foam |
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|---|---|
| CN (1) | CN1980967B (en) |
| ZA (1) | ZA200610324B (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN105764945A (en) * | 2013-12-04 | 2016-07-13 | 科思创德国股份有限公司 | Reaction system for a low-monomer one-component polyurethane foam |
| CN105899564A (en) * | 2013-12-04 | 2016-08-24 | 科思创德国股份有限公司 | Reaction system for a low-monomer-content single-component polyurethane foam ii |
| CN107759758A (en) * | 2017-10-31 | 2018-03-06 | 山东诺威聚氨酯股份有限公司 | Low temperature resistant modified polyalcohol and preparation method thereof |
| CN111019081A (en) * | 2019-12-31 | 2020-04-17 | 江苏谦胜合成材料有限公司 | Production process of PU (polyurethane) continuous foaming sports mat |
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| US8722753B2 (en) * | 2007-08-21 | 2014-05-13 | Lear Corporation | Hydroxyl terminated precursor and method of making the same |
| US8394868B2 (en) * | 2008-06-12 | 2013-03-12 | Dow Global Technologies Llc | Polyol prepolymers of natural oil based polyols |
| CN105579484B (en) * | 2013-02-26 | 2019-06-04 | 霍尼韦尔国际公司 | Polyurethane foam pre-composition containing halogenated olefin blowing agents and the foam being produced from it |
| US9695266B2 (en) * | 2013-03-06 | 2017-07-04 | Foamtec International Co., Ltd. | Wettable, high strength foam especially for ink holders |
| KR101600393B1 (en) | 2015-05-20 | 2016-03-07 | 에프엔에스테크 주식회사 | Polishing pad and preparing method thereof |
| EP3442007B1 (en) * | 2016-04-06 | 2020-11-25 | KPX Chemical Co., Ltd. | Method for manufacturing polishing pad |
| CN109836551B (en) * | 2019-01-28 | 2021-12-10 | 上海鸿得聚氨酯有限公司 | Polyurethane foam gasket composition for sport protection and preparation method thereof |
| CN112225869B (en) * | 2020-10-14 | 2022-04-12 | 广德祥源新材科技有限公司 | Polyurethane microporous foam with uniform pore diameter and preparation method thereof |
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| EP1380608A1 (en) * | 2001-02-06 | 2004-01-14 | Toyo Quality One Corporation | Lowly air-permeable flexible polyurethane foam block and process for producing the same |
-
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- 2005-05-12 CN CN2005800228178A patent/CN1980967B/en active Active
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- 2006-12-11 ZA ZA200610324A patent/ZA200610324B/en unknown
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1380608A1 (en) * | 2001-02-06 | 2004-01-14 | Toyo Quality One Corporation | Lowly air-permeable flexible polyurethane foam block and process for producing the same |
| CN1491244A (en) * | 2001-02-06 | 2004-04-21 | ����Ʒ�ʵ�һ�ɷ�����˾ | Lowly air-permeable flexible polyurethane foam block and process for producing the same |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105764945A (en) * | 2013-12-04 | 2016-07-13 | 科思创德国股份有限公司 | Reaction system for a low-monomer one-component polyurethane foam |
| CN105899564A (en) * | 2013-12-04 | 2016-08-24 | 科思创德国股份有限公司 | Reaction system for a low-monomer-content single-component polyurethane foam ii |
| CN107759758A (en) * | 2017-10-31 | 2018-03-06 | 山东诺威聚氨酯股份有限公司 | Low temperature resistant modified polyalcohol and preparation method thereof |
| CN111019081A (en) * | 2019-12-31 | 2020-04-17 | 江苏谦胜合成材料有限公司 | Production process of PU (polyurethane) continuous foaming sports mat |
| CN111019081B (en) * | 2019-12-31 | 2021-12-14 | 江苏谦胜合成材料有限公司 | Production process of PU (polyurethane) continuous foaming sports mat |
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| Publication number | Publication date |
|---|---|
| CN1980967A (en) | 2007-06-13 |
| ZA200610324B (en) | 2008-09-25 |
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