CN101065414B - Polyurethane foam - Google Patents
Polyurethane foam Download PDFInfo
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- CN101065414B CN101065414B CN2005800408397A CN200580040839A CN101065414B CN 101065414 B CN101065414 B CN 101065414B CN 2005800408397 A CN2005800408397 A CN 2005800408397A CN 200580040839 A CN200580040839 A CN 200580040839A CN 101065414 B CN101065414 B CN 101065414B
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- foam
- double bond
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- reactive double
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/67—Unsaturated compounds having active hydrogen
- C08G18/671—Unsaturated compounds having only one group containing active hydrogen
- C08G18/672—Esters of acrylic or alkyl acrylic acid having only one group containing active hydrogen
Abstract
Polyurethane foam is made by reacting an isocyanate with a polyol and foam forming ingredients in the presence of a reactive double bond component, particularly an acrylate, to give a foamed body which is subjected to radical initiated cross-linking with the reactive double bond component. In one embodiment the foam-formation and cross-linking are carried out in parallel, and an organic peroxide may be included as a cross-linking initiator. In another embodiment the cross-linking is carried out after foam-formation preferably using E-beam activation. In this case different formulations, using polyether polyol with MW greater than 1500, non MDI, polymer modified polyol or non HR formulations are used. In this case also, it is also possible to use selected formulations which give at least 10% hardness increase without scorching, or which, by controlled use of 0.1 to 10 parts double bond component give low density foams with more than 4 parts water as foaming agent, without scorching.
Description
Technical field
The present invention relates to urethane (PU) porous plastics.
The method of making the perforate flexible polyurethane foam is known technically, edits at for example DrG ü enter Oertel, and the Polyurethane Handbook that Hanser press publishes discusses in pp.161～233.
Traditionally; The manufacturing processed of flexible polyurethane foam comprises; The addition reaction that makes polyvalent alcohol and polyfunctional isocyanate react through NCO and OH group generates ammonia ester bond, and reacting through isocyanic ester and water then generates carbonic acid gas on the spot and make polyurethane foam.This traditional method can be used as the method for so-called single stage method and implements, and wherein polyvalent alcohol, isocyanic ester and water mix generation urethane and in same step, foams.
The reaction of isocyanic ester and polyvalent alcohol generates ammonia ester bond through addition reaction.
I.R-NCO+HOR′-->R-NH-CO-O-R′
Isocyanic ester and water react and generate amine and carbonic acid gas.
II.R-NCO+H
2O-->RHNCOOH-->RNH
2+CO
2
Amine and isocyanate-reactive generate the urea key.
III.R-NCO+RNH
2-->R-NH-CO-NH-R
NCO, OH, H
2The interaction of O will produce combined the urea key polyurethane chain as above reaction I, II, the simultaneous result of III.
Typical case's flexible polyurethane foam has block structure, is made up of the long flexible polyol chain that is connecting urethane and urethane and polyureas aromatics hard block, wherein between the NH of polar group such as urea and ammonia ester bond and carbonyl group, has hydrogen bond.
In addition, substituted urea (in III, generating) can generate biuret (IV) with all the other isocyanate-reactive, and the ammonia ester can generate allophanate (V) with all the other isocyanate-reactive:
The generation of biuret and allophanate causes increase and polymer network crosslinked of hard block in the polymer architecture.
The physicals of the porous plastics that obtains depends on structure and interchain crosslinked of polyurethane chain.
For obtaining higher foam body hardness, particularly make firm closed-cell foamed plastics, the crosslinked of polyurethane chain is to adopt than the short chain polyvalent alcohol and/or through comprising that into the high functionality isocyanic ester is realized.Adding unsaturated compound also is known as free-radical crosslinking agent.
For many purposes, stable and hard, that is, the open-celled polyurethane foams with high bearing capacity is an ideal.
So-called high resilience (' HR ') urethane foam was known as the cold-curing porous plastics in the past, be the flexible polyurethane foam classification known and with, compare with so-called " standard " or " tradition " porous plastics, higher bearing factor and resilience are characteristic.Make the be chosen in performance that to a great extent determined porous plastics of this kind porous plastics to raw materials used or prescription; As editing at DrG ü enter Oertel; The Polyurethane Handbook that Hanser press publishes, p.182 (first version), p.198,202 and 220 (second editions) and other are local is discussed.Raw material or the material combination used in the HR urethane foam prescription possibly be different from those that use in the standard foam plastic formula, so HR is regarded as a uniqueness in the urethane foam field, independent technology.Referring to the pg.202 of above second edition, form 5.3.
The HR porous plastics is defined by combination and even its surface structure of its physicals and chemical structure usually.The HR porous plastics has foam structure more irregular than other urethane foam and at random.For example, a definition of HR porous plastics is that the characteristic through being known as " SAG coefficient " is confirmed, it 65% with in 25% deflection the time " indenting load deflection " ratio (ASTM D-1564-64T) (ILD).The SAG coefficient of standard foam plastics is between about 1.7～2.2, and the coefficient of HR porous plastics is then between about 2.2～3.2.The HR porous plastics also has the feature difference aspect other physicals.For example, the wetting ability of HR porous plastics and fatigue property maybe be better than standard foam plastics.Relevant this respect and other difference are referring to handbook above-mentioned.
Originally, the HR porous plastics was processed by the isocyanic ester of the functionality of " reactivity " polyether glycol and higher or raising.The molecular weight of polyvalent alcohol generally be higher than common molecular weight (4000～6000) have the certain level proportion of primary OH groups oxygen ethene and/or oxypropylene polyether glycol (for example; Surpass 50%; As what mention among the pg 182 in the above-mentioned first version handbook), and its isocyanic ester is MDI (NSC 9596) (or the mixture of MDI and TDI (tolylene diisocyanate), or prepolymer TDI); And not merely be TDI (referring to the pg 220 of top second edition handbook, cold-curing moulding one joint).(pg 221) are subsequently developed and one type of new polyvalent alcohol, are called polymer-modified polyols (also being called polymer polyatomic alcohol) now, it based on a kind of molecular weight between about 4000～5000 and proportion of primary OH groups surpass 70% special polyether glycol.In the production of the HR of this a new generation porous plastics, using these (polyvalent alcohol---annotations of translation), with different isocyanic ester, but mainly is pure TDI at present, (as raw material) together, and cooperate linking agent, catalyzer and the one type of new HR siloxanes of selecting.
This one type of new HR porous plastics has the performance that the original route of the employing of being similar to obtains, but their physicals comprises carrying, can in relative broad range, change at present.The processing safety of new porous plastics is greatly improved, and this just allows to use the TDI that more is easy to get in the industry to produce these porous plastics, by contrast, then must use originally and mix or isocyanuric acid ester.
The polyvalent alcohol of polymer modification is included in the polymer packing material in the basic polyvalent alcohol.Filler material can be used as the inert packing material that is dispersed in the basic polyvalent alcohol, and perhaps the multipolymer of conduct and basic polyvalent alcohol adds at least in part.The example filler material is the reaction product (" PHD " polyvalent alcohol) of acrylonitrile-styrene polymer polyatomic alcohol, vulcabond and the diamines of copolymerization, and vulcabond and amine alcohol gather adduct (" PIPA " polyvalent alcohol).
Polymer-modified polyols also is applied in preparation standard foam plastics, and it can give porous plastics higher load-carrying properties.
As everyone knows, production perforate low-density foam, play the reaction of the big relatively water gaging of additional whipping agent effect, as; For example at USP 4,950, describe in 694; In extensive manufacturing processed, be difficult to control especially, and generate soft relatively porous plastics usually.Situation is especially true when the polyvalent alcohol of polyureas that used a large amount of special polyols such as polyol or filling.In addition, use big water gaging, mean that isocyanate index can not arbitrarily improve so that influence the hardness of porous plastics with this for whipping agent is provided; Sometimes will prove that thermal discharge is excessive because react, thereby cause too early, the oxidative degradation of plastic foam material, or " incipient scorch "; That is the variable color of material.
For this reason, thermopositive reaction undue, out of control must be avoided in extensive the manufacturing, because the danger that possibly occur catching fire.Even if but the oxidative degradation of low degree also is undesirable relatively; Because, in fact, requirement to obtain a kind of " white " urethane foam; Promptly; Look pure white and foams homogeneous are not seen browning or other variable color along section, be known as in this article to have basically no (or not) variable color foams.Term " white " is to adopt for convenience, although these foams possibly have yellow hue.
When, except gathering the reactant that the addition polyurethane reaction uses, comprise also that so that when strengthening or increasing the unsaturated compound that polyurethane substrates stability adds, this point will be more obvious in order to generate additive-crosslinking.Giving open-cell foamed plastics stability or the high-mechanic aspect of performance can run into variety of problems, specifically, but common practices is to remove as far as possible or reduce to promote the crosslinked radical that possibly cause softening and/or incipient scorch.
About in the polyurethane material preparation, strengthening crosslinked measure, the known verivate that uses vinylformic acid VI with reactive double bond:
VI.CH
2＝CH-COOH
EP 262488B describes the urethane filler material through the prepared in reaction of hydroxyl (methyl) propenoate and isocyanic ester, and wherein adopt about 1: 1 OH: NCO ratio can not be by solvent-extracted reactive double bond so that this material is had.The polyurethane material that obtains uses with the pressed powder form, and this powder can mix with silicon-dioxide, and free-radical curable generates the hard transparent solid that can be used for dentistry then.
EP 1129121B also describes isocyanic ester and hydroxyl (methyl) propenoate reacts so that generate radical curable polyurethane material, and having can not be by solvent-extracted reactive double bond.Here, material is as moulding bodies rather than powder forming, and the main body that is shaped is subsequently through being exposed to heat and/or blue or UV-light realization radically curing.The main body that forms can be made into the ventilation property porous plastics.
USP 6699916A and USP 6803390 descriptions react through isocyanic ester and multifunctional (methyl) propenoate and generate the method that prepolymer prepares urethane foam.This prepolymer will form composition with polyvalent alcohol and foam subsequently and react.The foams that obtain are a kind of crosslinked closed pore rigid foams.
US2004/0102538A (EP 1370597A) openly reacts in the presence of (methyl) propenoate polyvalent alcohol through POLYMETHYLENE POLYPHENYLISOCYANATE and polyethers or polyester polyol and prepares the method for flexible polyurethane foam.
USP 4250005A description reacts in the presence of acrylate cross linked promotor with organic isocyanate or foam formation composition through polyester polyol or lower molecular weight polyether glycol (1500 or lower) and prepares the method for urethane foam.The porous plastics that obtains is accepted the performance of ionization radiation irradiation with the improvement porous plastics.
DE 3127945 A-1 have described the reaction of mixture in the presence of the small amount of hydroxyl groups methacrylate compound of hyperergy polyvalent alcohol and TDI or MDI isocyanic ester particularly in the embodiment that provides, the foams of producing are handled to improve its performance with high energy beam subsequently.Its composition provides those compositions that very soft HR porous plastics will use corresponding to those with non-polymer modified polyalcohol system.
According to the present invention, have now found that the open-celled polyurethane foams with good physical can cause crosslinked processing through the radical of porous plastics being implemented control by the mixture of polyvalent alcohol, isocyanic ester and reactive double bond component such as propenoate.
Particularly, have now found that and to process stable and the perforate of high bearing capacity, nondiscoloration porous plastics basically.
This kind porous plastics can be the elasticity flexible foam plastic; For example, be used for furniture buffering cushion, or have flexible open-celled structure but have enough deflections to keep the semihard porous plastics of the shape between the usage period; For example; Decorative structure component in riding motor vehicle cabin, for example, panel board etc.
Even might process the perforate rigid foam, in addition, the present invention also advantageously is applied to the manufacturing of closed pore rigid foam.
So; According to one aspect of the invention; A kind of method of making urethane foam is provided, wherein at least a polyfunctional isocyanate, at least a polyvalent alcohol, the latter is a kind of molecular weight greater than 1500 polyether glycol fully or mainly; And foam forms, and polyaddition takes place in composition in the presence of at least a reactive double bond component and foam forms reaction; Thereby generate the urethane main body of foaming, wherein at least a polyfunctional isocyanate is substantially free of or does not comprise MDI, and the urethane main body of foaming is carried out the crosslinked of radical initiation with the reactive double bond component.
Therefore, said reaction is under the situation that does not have MDI basically or fully, to carry out.Can use single a kind of polyether glycol, also can use the mixture of polyether glycol.Whole polyvalent alcohols of use promptly, with the polyvalent alcohol of isocyanate-reactive except that said pair of key component, are molecular weight or molecular-weight average greater than 1500 polyether glycol fully or mainly yet preferably.
This porous plastics can be HR type as discussed above or can not be the HR type.
So; According to second aspect present invention; A kind of method of making urethane foam is provided, wherein at least a polyfunctional isocyanate, at least a polyvalent alcohol, the latter is a kind of molecular weight greater than 1500 polyether glycol fully or mainly; And foam forms, and polyaddition takes place in composition in the presence of at least a reactive double bond component and foam forms reaction; Thereby generate the urethane main body of foaming, wherein porous plastics is not the HR porous plastics, and this polyurathamc main body is carried out the crosslinked of radical initiation with the reactive double bond component.
The polyvalent alcohol that uses in the inventive method can contain or comprise at least a as polymer-modified polyols described above, no matter whether these foams are prepared according to the HR porous plastics.
So; According to third aspect present invention; A kind of method of making urethane foam is provided; Wherein at least a polyfunctional isocyanate, at least a polyvalent alcohol and foam form composition polyaddition and foam formation reaction take place in the presence of at least a reactive double bond component; Thereby generate the urethane main body of foaming, wherein the polyvalent alcohol urethane main body that contains or comprises at least a polymer-modified polyols and foaming with the reactive double bond component carry out that radical causes crosslinked.
For the present invention second and the third aspect, preferably, isocyanic ester is gone up basically and is not contained or do not comprise MDI, as first aspect present invention.
It is shocking that the inventive method can be produced the stabilizing polyurethane foams plastics with superior physical properties, the incipient scorch problem must not occur.
This be with radical cause cross-linking step be applied on these specific 3 components (polyvalent alcohol, isocyanic ester, reactive double bond component) urethane foam system effect.
Do not intend and be limited to any specific mechanisms; But it is believed that; The reactive double bond component provides the crosslinked of dependence carbon-carbon double bond in the existence that radical causes in the environment, rather than polarity is crosslinked, to such an extent as to can reach desired compressive hardness; Slowed down the again simultaneously availability of radical has reduced the incipient scorch that caused by thermopositive reaction or the danger of variable color whereby.This pair key component works the free radical activity that slows down, and for example, by reacting with radical initiation material such as superoxide, the latter adds for the purpose that causes is special, also can be natural a small amount of existence, for example, in raw polyol.Quantitative requirement for playing two key components of aversion response with initiator will correspondingly change.
In other words; Adopt specific " basically " urethane to generate component (that is, isocyanic ester, polyvalent alcohol and foaming ingredient), then add two key components and use radical initiation step ability; Even if under extensive situation about making; Produce the urethane foam that can accept " in vain ", this porous plastics is than single situation of basal component (that is, unparalleled key component and radical cause step) of using is harder basically.
The raising of hardness can be within least 10%, discusses as following.Actual hardness will depend on requirement and will depend on basal component or other parameter of use.
As described above, hardness can improve through improving isocyanate index (surpassing the desired stoichiometry of polyvalent alcohol) in conventional urethane porous plastics system, but this will increase the danger of incipient scorch.In the present invention, hardness can improve not requiring under the situation that increases isocyanate index similarly, thereby can alleviate more conveniently or avoid incipient scorch.
Only as an example, can obtain compressive hardness easily is the stable open-celled polyurethane foams of 5kPa at least, even if in low density, that is, is equal to or less than 20～25kg/m
3Situation under.
So; According to fourth aspect of the present invention; A kind of method of making urethane foam is provided; Polyaddition takes place in the presence of at least a reactive double bond component the basal component that wherein comprises at least a polyfunctional isocyanate, at least a polyvalent alcohol and foam formation composition and thereby foam formation reaction generates the non-discoloring basically polyurathamc main body of a kind of stable perforate; It is characterized in that; The non-discoloring basically polyurathamc main body of this perforate with the reactive double bond component carry out that radical causes crosslinked, thereby produce than adopting comparable said basal component but do not add the compressive hardness of the comparable rigidity big at least 10% of the basic nondiscoloration polyurathamc of stable perforate that said pair of key component form.So-called comparable said basal component refers to substantially the same basal component, that is, same polyvalent alcohol, isocyanic ester and main foam form composition, but on catalyzer or other additive, take the circumstances into consideration to make certain change so that contain the omission of two key components.
This pair key component can have unexpected superior effect usually, and when promptly box lunch is with a small amount of use, that is, it can prevent incipient scorch when using higher dosage water to become bubble so that producing than low density foam.When using higher dosage water but when not having volatility foaming ingredient (evaporation rather than with isocyanate-reactive and have cooling performance) basically, incipient scorch is a serious problems normally.
In view of this, water constituent content greater than 4 parts and do not have basically the present invention of volatility foaming ingredient various above-mentioned aspect, especially in the production of low-density foam, for example, less than 25kg/m
3, particularly less than 22 or 20kg/m
3The time, two key components can 0.1～10 part, and preferred 0.1～5 part, particularly about 3 parts quantity is used, so that produce the low-density foam that has premium properties, has basically no incipient scorch.All umbers are benchmark in 100 weight part polyvalent alcohols.
So; According to fifth aspect present invention; A kind of method of making urethane foam is provided, wherein comprises at least a polyfunctional isocyanate, at least a polyvalent alcohol and comprise water but do not contain the foam that any volatility foam forms component basically and form the basal component of composition, react and generate the non-discoloring basically polyurathamc main body of a kind of stable perforate thereby polyaddition and foam formation take place under at least a reactive double bond component; It is characterized in that; The non-discoloring basically polyurathamc main body of this perforate with the reactive double bond component carry out that radical causes crosslinked, and wherein the consumption of two key components between 0.1～10 part, preferred 0.1～5 part; Particularly about 3 parts, and the consumption of water is greater than 4 parts.
The the of the present invention the 4th and the 5th aspect can make up with any or all aspect of the present invention of front; So can also can not use MDI; Molecular weight is greater than 1500 polyether glycol, polymer-modified polyols polyvalent alcohol; And can be can not be the HR porous plastics also, decide as required.Preferably, do not use MDI.
Preferably, polymer-modified polyols has a kind of basic polyvalent alcohol, and it is a polyether glycol fully or mainly.Preferably, isocyanic ester does not also contain or comprises MDI basically.
In one embodiment, radical causes, and crosslinked being put on subsequently saidly gathered addition and formed in the reaction with foam, and this can occur in any time easily, perhaps in the later any occasion easily of polyurathamc main body shaping.
In another kind of embodiment, radical cause cross-linking step with said gather addition with foam formation react and carry out abreast.
So; According to sixth aspect present invention; A kind of method of making urethane foam is provided; Polyaddition takes place in composition in the presence of at least a reactive double bond component and foam formation reaction generates a kind of polyurathamc main body thereby wherein at least a polyfunctional isocyanate, at least a polyvalent alcohol and foam form; It is characterized in that, this polyurathamc main body with the reactive double bond component carry out that radical causes crosslinked, it with said gather addition with foam formation react and carry out abreast.This can take the circumstances into consideration combination with the characteristic of the above-mentioned aspect of the present invention on the one hand the present invention.For example, polyvalent alcohol can comprise polyether glycol and can be used in polymer-modified polyols, the high resilience system of no MDI.Yet other composition, prescription and system comprise, for example, non-HR polyester polyol system also can be used.
Aspect any one, radical causes cross-linking step can be implemented in the presence of radical initiator on the present invention, and this initiator can be a superoxide.This causes under the crosslinked situation of carrying out abreast particularly useful at radical as mentioned above.Yet, also can add radical initiator causing subsequently under the crosslinked situation, because have now found that,, still might keep stability and delay radical causing crosslinked although in gathering addition and foam forming process, have initiator.
So; According to seventh aspect present invention; A kind of method of making urethane foam is provided; Polyaddition takes place in the presence of the reactive double bond component for wherein at least a multifunctional POLYMETHYLENE POLYPHENYLISOCYANATE, at least a polyvalent alcohol and foam formation composition and thereby foam formation reaction generates a kind of polyurathamc main body, it is characterized in that, this urethane main body is carried out the crosslinked of radical initiation with the reactive double bond component in the presence of radical initiator.This respect of the present invention can make up with the characteristic of aspect of the present invention above-mentioned, as long as suitable.So for example, polyvalent alcohol can comprise polyether glycol and can be used for polymer-modified polyols does not have the high resilience system of MDI.Yet other composition, prescription and system comprise, for example, non-HR polyester polyol system also can be used.
Cause step about the radical of the above all respects of the present invention, its enforcement is intended to cause the modification of two key components so that strengthen or make the reactivity of (or each) two keys be able in the polyurathamc main body, realize crosslinked.
This can be because radical initiator acts on two keys or destroys or result that the modification energy is produced through applying.
This kind energy can be made up of one or more of following energy: heat, visible or near visual range (for example, ultraviolet) ionizing rays, high-energy ionization radiation.
In a kind of particularly preferred embodiment, only use high-energy ionization radiation, perhaps with the heat combination and/or in the presence of radical initiator.This kind radiation is known technically and can constitutes any suitable particle or the ionizing rays form of ripple.Relevantly be fit to this kind radiation, for example, γ-radiation, description, can be referring to USP 4250005.Preferred especially radiation is electron beam (E-bundle) radiation.The radiation of E-bundle constitutes the high-energy electron that is produced by powerful electron-beam accelerator.The electron impact molecule also produces the displacement to the higher-energy molecular state, so just causes and support can produce alternate manner the crosslinked of mechanical property levels that be beyond one's reach.
Preferably, basic polyurethane component (as top definition) with concentration and/or quantity use, they should produce the heat release that is enough to form radical and, meanwhile, controlled, anti-oxidant, the anti-incipient scorch effect of a kind of pair of key component.
Be the speed and/or the degree of control response intensity and/or radical crosslinking, the component concentrations with reactive double bond can change, and in other words, regulates particularly or sets according to the expection function.
For controlling the hardness and/or the supporting capacity of the porous plastics of being produced, the component concentrations with reactive double bond can change, and in other words, regulates particularly or sets according to the function of expection.
The oxidative degradation of the porous plastics of producing for preventing, the component concentrations with reactive double bond can change, and in other words, regulates particularly or sets according to the defencive function of expection.
In those mixtures, also add in basal component; As above-mentioned; Can be under the situation of at least a radical-forming agent of organo-peroxide; Can the component concentrations with reactive double bond be adjusted to the concentration of the radical-forming agent of adding, and/or can in the mixture of basal component, add at least a radical and capture material, particularly at least a inhibitor.
The invention of above-mentioned chemical substance can adopt following component to implement, and its ratio is with php (umbers of per 100 weight parts), and with total polymer content, (that is, following a)+b)) is the benchmark meter, is:
A) the highest by 99, particularly the highest 95 or 97php have the polyethers and/or the polyester polyol of OH group, its functionality is 2 at least, preferred 2～5;
B) 1 or multiple polymkeric substance with reactive double bond, particularly propenoate or the methacrylic ester of the highest by 99 (particularly at least 0.1 or 1, preferably at least 3) php are polymer based, as following description;
C) the NCO functionality is 2 at least, preferred 2～5 isocyanic ester;
D) 0.5～20, the water of 2～12php particularly is as whipping agent;
E) in case of necessity, at least a radical initiator of 0.05～5php or radical-forming agent, preferred organo-peroxide;
F) any catalyzer; And
G) any other auxiliary
The quantity of isocyanic ester and water should be regulated proper each other; Make should being chosen as in typical case: the calculating OH of acquisition: nco index is between 50～130; Preferred 70～120, particularly 85～120, wherein index equals 100 and shows that OH and NCO group meet the formula weight ratio; 90 index shows that NCO is not enough with respect to the OH group, and 110 index then shows its relatively excessive (index=OH is by the saturated percentage ratio of NCO group).
Preferably; The mixture of all components comprises the polymkeric substance of the reactive double bond with hydroxyl group; The propenoate or the methacrylate polymers that particularly contain oh group; Though outside the hydroxyl-removal group, other can with the group of isocyanate-reactive such as amine groups also can exist or substitute it and exist.So except the free-radical crosslinking agent effect that relies on the carbon-carbon bond that plays formation and polyurethane chain with two key reactions, this type of component can also be passed through urethanum and/or other key and isocyanate-reactive and generate polymer chain.
Through adopt can with two key components of isocyanate-reactive, this type of component can be incorporated in the polyurethane substrates along with the formation of urethane main body.Therefore, this pair key component is retained as active, non-volatile anti-incipient scorch additive.
The inventive method can adopt prepolymer to implement; Promptly; Be employed in the first step polymer materials of preparation that reacts, thereby generate a kind of prepolymer that will be in second step reacts with further polyvalent alcohol and/or reactive double bond component and polyfunctional isocyanate with hydroxyl or isocyanic ester end through polyvalent alcohol and/or reactive double bond component and polyfunctional isocyanate (latter can to form the isocyanic ester that uses in the reaction identical or different with foam).These two steps can adopt identical or different polyvalent alcohol, reactive double bond component or polyfunctional isocyanate.Particularly, component above-mentioned a) and b) arbitrary combination all can with c) isocyanic ester react in advance.Be the production and/or the improvement foam performance that promote urethane foam, the use of prepolymer is known on polyurethanes technology.
Employed polyvalent alcohol also comprises polymer-modified polyols, as known in making at HR porous plastics (also be called, as discussed above, " high resilience " or " high comfortable " porous plastics).These polyvalent alcohols can be through additional polymer chemistry or physics comprise and reach modification.The present invention provides the prescription of the HR porous plastics of hardness raising.
In further embodiment, 120～250 ℃ TR, the transformation period of organo-peroxide above-mentioned is between about 15min～about 5s.
This organo-peroxide can be selected from hydroperoxide, dialkyl peroxide, diacyl peroxide, peracid, ketone peroxide and epidioxy thing.Dialkyl peroxide; For example, Trigonox 101 (trade(brand)name of AKZO Nobel) or Peroxan HX (trade(brand)name of Pergan) promptly, 2; 5-dimethyl--2; 5-two (t-butyl peroxy) hexane, or dicumyl peroxide (PeroxanDC) is especially suitable, because they have high relatively temperature stability.
Carbon dioxide liquid or gas (or other material) can be used as additional whipping agent.
In further embodiment, foaming can be less than or equal to enforcement under the pressure of barometric point.
In further embodiment, all components can add separately, in mixing machine or mixing head, mix, and with post-foaming, preferably are shaped simultaneously.
The present invention relates to, particularly, a kind of like this method, it is adapted at making on the technical scale urethane foam, especially for the industry manufacturing of urethane foam piece material.
Adopt the present invention; Might produce a kind of strand end, stabilization, crosslinked urethane foam, it is under given density and abscess number; Have; Compare with the identical or comparable prescription conventional foam plastics of top discussion, exceed at least 10%, preferred at least 15% hardness and/or supporting capacity.
As an example, the present invention can provide a kind of urethane foam, and it has at least a feature:
5～120kg/m
3Overall consistency (gross density);
The abscess number of
10～120ppi;
Yet, adopt the inventive method also can make closed-cell foamed plastics.
Urethane foam of the present invention can be used as, for example, and matrix material; Be used for packaging field, be used for heat insulation and/or sound insulation, be used to make indicating meter, strainer, cushion and mattress; Be used for many different industrial circles and/or transportation purpose, especially for motor vehicle industry and construction industry.
Urethane foam flexible foam plastic normally made in accordance with the present invention; Yet, adopt the inventive method, also can make rigid foam.
In one aspect of the invention, this brings up one type of new urethane foam, by 2 respectively but the crosslinking reaction of carrying out abreast simultaneously process.A kind of reaction, polyaddition (polyurethane reaction) are based on the conventional urethane chemistry, and second reaction is based on the crosslinking reaction of the free yl induction of two keys.These two kinds of reactions occur in 1 operation during the foaming of porous plastics; Usually cause a kind of characteristic synthetic characteristic; It is characterized in that; With according to identical or comparable at least prescription but compare with this type of foam of free-radical crosslinking agent order manufacturing with conventional urethane, the hardness and the supporting capacity that obviously improve.
Generation and traditional concept are inconsistent in the time of two kinds of chemical reactions, because foams will take place too early, oxidative degradation.For example; Expectation will occur; Because due to the height heat release; Impaired and the possible spontaneous ignition of unsettled color and luster, mechanical characteristics (is for example edited referring to Dr
Oertel; The Polyurethane Handbook that Hanser press publishes, joint 3.4.8P104 and joint 5.1.1.3, P169).
Yet employing the present invention, this kind phenomenon can controlled and suppress to proof wittingly astoundingly; Do like this, because the law of mass action and heat transfer phenomenon, the only scale more than the laboratory; In other words; Only, particularly on technical scale, especially in the industry manufacturing of foam plastics block, play an important role in the scale that constantly increases.For promoting this point; The annexing ingredient (fraction) of same or other pair key component; And any be generally used for chemically combining and/or in and/or the alternative inhibitor that makes the radical that generates between the reaction period before their degradation effect begins to work, just become harmless; As required, can be used as additive and basal component: polyvalent alcohol, isocyanic ester and two key component add together.
It is the radical of realizing free-radical crosslinking agent spontaneous generation in heat release polyurethane reaction process that this program not only allows to have a mind to controlledly using any; And allow use to add radical-forming agent; For example; Organo-peroxide so that accelerated reaction and/or reach the crosslinked of greater strength, and unlikely in this process the whole foam generation structure of infringement.Concern each other through the conditioned reaction component; Particularly two key component concentrations and isocyanic ester and polyvalent alcohol; And and additional radical-forming agent and/or radical capture the relation between material or the inhibitor; Might not only successfully overcome the above-mentioned shortcoming and the prejudice of prior art, and particularly produce so-called " high bearing capacity " porous plastics of a new generation.The distinct characteristic of this kind porous plastics of new generation is it, with crosslinked the comparing of order, different three-dimensional structures; And the conventional foam plastics of or comparable prescription identical with (as discussed above) are compared and are exceeded; At least 10%, preferably at least 15, usually even exceed 20% hardness and/or supporting capacity.
In addition, the inventive method is not only applicable to than low density polyurethane foam, compare with adopting traditional method, and easier, quick or cheap manufacturing, and also suitable efficient is produced semihard to the rigid foam grade much higherly.As stated, this also makes, and with regard to given density, the porous plastics of producing is how firmly or supporting capacity is much higher compared with what describe in the document up to now.
The key factor of this kind urethane foam of new generation is particularly:
Through fully high polyurethane reaction heat release and/or through the activity that further adds or the activatory radical generates material on the spot, they will produce radical, and the two keys through free yl induction react and carry out forming crosslinked with polyurethane reaction parallel thus.
Under necessary and favourable situation, the inventive method can generate material (" radical-forming agent ") through in the mixture of basal component, adding radical, particularly quickens through adding superoxide, and radical crosslinking is strengthened.For example, suitable superoxide is those decomposition temperatures and the reactive superoxide that is fit to the urethane foam manufacturing.Yet; Other suitable superoxide comprises can not depend merely on or can not lean at all the adding of hot measure or other energy to decompose; But also must lean on chemical substance; For example, promotor, amine, metals ion, strong bronsted lowry acids and bases bronsted lowry, reduction or oxidizing substance by force, or even lean on those that could decompose with some metallic contact.It is especially preferred in the fully rapid decomposition of about 130～180 ℃ of range temperature the organo-peroxide of about 2～5min foamed time being provided.Therefore, the typical transformation period of suitable organo-peroxide is in the scope in several seconds, for example, at 180 ℃ of 5s, until several minutes, for example, at 130 ℃ of 10～15min.This type of superoxide is that those skilled in the art are familiar with and available commercial arranged.Except superoxide; So-called superoxide-coinitiator also can use; For example, with trade(brand)name Saret
-coagents (Sartomer company) available commercial.
Two key components of using among the present invention play a part through the crosslinked hardness of improving, and the generation of the radical that can also slow down simultaneously is to prevent unacceptable variable color, and is as discussed above.
As what explained, utilized crosslinked both can the generation substantially parallelly or subsequently of this kind of two key components to cause, and this can perhaps realize in the presence of living radical initiator such as superoxide through depending merely on heating or ionizing rays with porous plastics.
Under the situation of using radical initiator, this can be to come into force, and perhaps it can be in dormancy and have only the activation that when it receives the heat of activation, just can become, and the heat of activation can be derived by the thermopositive reaction of foamed polyurethane-generation component.
Generally speaking, with adopting the higher-energy ionizing rays to substitute the radical initiator of thermal activation, though except can also can not being the radical initiator of thermal activation, not get rid of the possibility of also using ionizing rays.
No matter adopt which kind of program, rely on two key components, radical initiator and the crosslinked and retarding action to the ionizing rays that causes crosslinked alternative measure is provided with controlled way, can produce favourable plastic foam material.
Mentioned above, during use, ionizing rays can be an electron beam irradiation, and the latter is according to traditional method, with preferably applying with energy dose fixing, regulation.
Make the method for urethane foam except the mixture of employing base substance above-mentioned such as polyvalent alcohol methacrylic ester and polyvalent alcohol methacrylic ester and polyethers and/or polyester polyol system, the invention still further relates to the urethane foam of manufactured thus.These relate to but never are limited to, and polyurethane semihard is to rigid foam, and it also has following notable feature in addition except the raising of hardness and/or supporting capacity:
5～120kg/m
3Overall consistency (gross density);
The abscess number of
10～120ppi (the abscess number of ppi=per inch).
These characteristics can be through polyvalent alcohol methacrylic ester or polyvalent alcohol methacrylic ester and polyvalent alcohol (ether and/or ester) the foaming of mixture obtain easily.
The performance of urethane foam of new generation above-mentioned, for example, high firmness, high bearing capacity and/or high compression hardness/density ratio is to be realized by the new prescription based on the combination of and the following:
A) polyvalent alcohol, preferred ether and/or ester are (it comprises polymer-modified polyols) on basis;
B) contain compound, particularly methacrylic ester and/or the acrylic ester polymer of reactive double bond;
C) aliphatic series or aromatic polyisocyanate;
D) water is as whipping agent;
E) any radical h substance, for example, organo-peroxide;
F) catalyzer; With
G) any further additive.
Discuss below maybe with preferred part by weight.
Preferably also as the component of group (b), although be different from (a), these polyvalent alcohols must contain reactive double bond to polyvalent alcohol.Except component (a)～(e); New prescription also can comprise other additive (f), radical is captured (g) of agent form; For example; Inhibitor, superoxide-auxiliary agent and/or the common additives that the manufacturing urethane foam is used that is useful on, for example, whipping agent, catalyzer, stablizer, pigment etc.
Hydroxy functionality is 2 at least; Preferred 2～5 and molecular weight can be used as group (a) basal component between 400～9000 hydroxyl group polyethers and/or polyester polyol; Although it is as discussed above; Polyether glycol preferably perhaps must be used perhaps to account for the overwhelming majority in some cases uniquely, particularly surpasses under 1500 the situation at molecular weight.
Preferably use those urethane foams to make the polyvalent alcohol of common general knowledge.Suitable polyether glycol comprises polymer-modified polyols, is described in, and for example Dr G ü enter Oertel edits, the Polyurethane Handbook that Hanser press publishes, pp.44～53 and 74～76 (polyvalent alcohol of filling).
Containing the polyether glycol that includes catalyzer in addition also can use.The mixture of polyether glycol above-mentioned and polyester polyol also can use.Suitable polyester polyol for example is that Dr
Oertel edits; The Polyurethane Handbook that Hanser press publishes, those that describe in pp.54～60.
The prepolymer of being processed by polyol component above-mentioned equally also is preferred.
Comprise 2 or the POLYMETHYLENE POLYPHENYLISOCYANATE of more a plurality of isocyanate groups be used as group (c) component.Two of common use standard available supply-and/or triisocyanate.The example of suitable isocyanic ester is aliphatic series, cyclic aliphatic, araliphatic and/or aromatic isocyanate; For example; 2 of the two isocyanato-toluene (=tolylene diisocyanate TDI) of available commercial; 4-and 2; The 6-mixture of isomers, it is with trade(brand)name Caradate
T80 (Shell) or Voronate
T80 and T65 (Dow Chemical) sale.4,4 '-two isocyanato-ditanes (=4,4 '-methylene-bis (phenyl isocyanate) is (MDI); And the mixture of TDI and MDI also can use, as long as occasion allows.Yet, also can use isocyanate prepolymer based on TDI or MDI and polyvalent alcohol.Modified isocyanate (for example; Desmodur
MT58, Baeyer is produced) also can use.The example of aliphatic isocyanate is 1; 6-hexamethylene diisocyanate or triisocyanate; For example; Desmodur
N100 or N330, Baeyer is produced.
Double bond content 2～4DB/mol, molecular weight 400～10,000 and preferably the double bond-contained polymer of hydroxy functionality 2～5 be used as the component of group (b) usually.Yet; Substitute this base polymer perhaps additionally; Also can use the functional monomer with reactive double bond component, this monomer can be a kind, or two or more monomeric mixtures; For example, propenoate and/or methacrylate monomers, acrylic amide, vinyl cyanide, toxilic anhydride, vinylbenzene; Vinylstyrene, vinyl pyridine, vinyl silanes, vinyl ester, vinyl ether, divinyl, dimethylbutadiene etc. are only lifted several examples.
Can use hydroxy functionality be higher than 2 and OH value between 5～350 hydroxyl (methyl) origoester acrylate.The product classification comprises: aliphatic series or aromatics epoxy diacrylate, polyester acrylate, oligo-ether propenoate.Key parameter is a viscosity, so that can process and reactivity with polyurethane form.Preferred methacrylate but propenoate has proved also passable.
The additional examples of hydroxyl-functional (methyl) propenoate is: two (methacryloxy-2-hydroxypropyl) esters of sebacic acid, two (methacryloxy-2-hydroxypropyl) esters of hexanodioic acid, two (methacryloxy-2-hydroxypropyl) esters of succsinic acid, two-GMA (methacrylic esters of dihydroxyphenyl propane-glycidyl), methacrylic ester hydroxyl ethyl ester (HEMA), the methacrylic ester of polyoxyethylene glycol, methylacrylic acid 2-hydroxyl and 2; The triacrylate of 3-two hydroxypropyl acrylates and tetramethylolmethane.
A kind of suitable material is Laromer LR8800, and it is that a kind of molecular weight is about 900, two key functionality is about 3.5, OH value 80mg KOH/g and viscosity 6000mPa.s, 23 ℃, polyester acrylate.
Another kind of material is Laromer LR9007, and it is that a kind of molecular weight is about 600, two key functionality is about 4.0, OH value 130mg KOH/g and viscosity 1000mPa.s, 23 ℃, polyether acrylate.
Polyethers and/or polyester polyol particularly based on propenoate those, preferably also are used for this purpose.Polyethers and polyester acrylate have available commercial; For example, trade(brand)name Photomer
(Cognis company) and Laromer
are (BASF).Other spendable polymkeric substance is known; For example, so-called Sartomer
(Total Fina).
Necessity or hope, the organo-peroxide of available commercial for example, also can be used as group (e) reactive component and uses.Preferred superoxide be stable and be lower than under the temperature of reaction that causes by the polyurethane reaction heat release sluggish those; In other words; It has the long as far as possible transformation period and radical transfer and its radical systematic function of performance only just take place rapidly when the temperature of the exothermic temperature scope that surpasses the polyurethane polyureas addition reaction for it; This kind synchronization allows and guarantees to cause to greatest extent rapid generation, the radical initiation and catalytic crosslinked of crosslinked (polyaddition) and reactive double bond component, to process final product.In about 120～180 ℃ exothermic temperature scope, the transformation period of suitable superoxide is: for example, 5s arrives 15min at 120 ℃ at 180 ℃.
Component as group (g); Superoxide-auxiliary agent (for example, Saret
product), radical is captured material; For example; Unsaturated, particularly aromatics, organic cpds and/or inhibitor, for example; Divalent iron salt, bisulfite solution, sodium metal, triphenyl phosphine etc. can join in the mixture of basal component so that control radical crosslinking wittingly.
Needs or favourable, the catalyzer that the isocyanic ester addition reaction is used, particularly tin compound, for example, two stannous octoates or dibutyl tin laurate, but also have tertiary amine as 1,4-two azos (2,2,2) double-octane all can be used as group (f) additive and uses.Meanwhile, also can use various different catalysts.
The further example of spendable group of (g) additive is an auxiliary, for example, and chain extension agent, linking agent, chain terminator, filler and/or pigment.
The example of suitable chain extension agent is lower molecular weight, isocyanic ester-reactivity, two functional substances such as diethylolamine and water.
Low-molecular-weight isocyanate-reactivity three or more high functionality material such as trolamine, glycerine and sorbyl alcohol can be used as linking agent and use.
Suitable chain terminator is isocyanic ester-reactive monofunctional species, for example, and single hydroxyl alcohol, primary and secondary amine.
The organic or inorganic solid, for example, lime carbonate, trimeric cyanamide or Nano filling can be used as filler and use.
The example of other spendable auxiliary is fire retardant and/or pigment.
Foaming can adopt the conventional plastic technological facilities to implement; For example be described in; For example Dr
Oertel edits, and the Polyurethane Handbook that Hanser press publishes is in pp.162～171; For example, adopt the foam-plastic blocks materials device.
Example prescription and the composition discussed above can be used for the present invention any one or all aspect, as long as appropriate.
Now with further describing the present invention among the embodiment below.
Embodiment 1: according to the comparison of foaming of the present invention with the traditional method of using prior art formula
According to the porous plastics of the prescription in the table 1 through in the laboratory, accomplishing the manufacturing of porous plastics based on the manual mixing of 500g polyvalent alcohol.It is basic identical that two kinds of situation are participated in the prescription of component of reaction, the adding of different is listed radical-forming agent.
Table 1:
TP:
-compressive hardness is measured under 40% deformation according to EN ISO 3386-1.
-foam structure is confirmed through the hole count that counting is positioned on the straight line.Data are represented with ppi (per inch hole count).
As can seeing from table 1, urethane foam product that the inventive method the is produced density under the situation of comparable abscess number is than according to the urethane foam low about 25% of the comparable prescription manufacturing of traditional method but compressive hardness is the 3 times big of latter.
Embodiment 2: the antioxidant effect of two key components.
Table 2:
| Characteristic foams color | Pale yellow, foams are stable | Characteristic foams color | Brown deeply, foam falls slag |
| ΔE | 9.6 | ΔE | 40.68 |
Test conditions:
-prepare based on the 50g polyvalent alcohol;
-mixing all ingredients 30s, but except stannous octoate and the TDI;
-introduce stannous octoate, mix 5s;
-introduce TDI, mix 5s;
-let the mixture reaction and the 1min that in the Vestolen PP 7052 box, foams;
-mixture 800W microwave oven internal heating 40s (NN-E222M of Panasonic, 20L);
-let it react 2h at least;
-foam plastics block is cut in half and tests the core zone, particularly use hand test mechanical quality, and
-mensuration Δ E, L
*, a
*, b
*, adopt Microflash color analysis appearance (DatacolorInternational).
Utilize microwave heating in the heat release of simulating the foamable reaction that others in addition will carry out on the laboratory scale on technical scale.The result confirms; According to the present invention, the impression quite deep provide protection of two key components in the present embodiment of Laromer
LR8800.
Table 3A～G:
The explanation of the material of relevant use provides at the table end.
Under the situation of mark, after the polyurathamc main body is shaped, adopt various controlled electron-beam doses to implement electron radiation-activated.
The energy (radiation) that is applied on the porous plastics is big or small as the dosage that absorbs.The energy that the unit weight product absorbs is measured with Gray (Gy).Typical doses among the embodiment is 50kGy (being equivalent to 50kJ/kg).Yet, (observe influence in 2～80+mGy) to hardness in the energy region of wide absorption.On the facility that has 10MeV (million-electron-volt) the LC energy (IBA SA (Belgium) manufacturing), implement electrocuring.
| Table 3A | A | B |
| (corresponding to table 1) | ||
| Laromer?LR?8800(oh＝80) | 25 | 25 |
| Desmophen?3223(oh＝35) | 75 | 75 |
| TDI(80/20) | 55 | 54.3 |
| Iso?Index | 95 | 95 |
| Water | 5 | 5 |
| Peroxan?PK295V-90 | 0 | 1 |
| Niax?A1 | 0.2 | 0.2 |
| DMEA | ||
| Stannous octoate | 0.23 | 0.23 |
| Silicone surfactant | 0.7 | 0.8 |
| Density kg/m3 | 23 | 17 |
| Compressive hardness kPa | 5.9 | 20 |
| (not having circulation in advance) | ||
| Compressive hardness kPa | ND | ND |
| (ENISO?3386-1) | ||
| The abscess number | 53 | 51 |
| ND: undetermined |
| Table 3E | AA | BB |
| 1，6?DEXA | 100 | 100 |
| PIPA?97/10 | 10 | 10 |
| Desmodur?N?100 | 100 | 100 |
| Water | 4.4 | 4.4 |
| Niax?A1 | 0.6 | 0.6 |
| NIAXA?30 | 0.6 | 0.6 |
| Peroxan?BHP | 0 | 0.5 |
| Silicone surfactant | 0.6 | 0.6 |
| EM | 1 | 1 |
| Density Kg/M3 | 66.8 | 74.1 |
| Compressive hardness Kpa | 1.92 | Irrelevant |
| (ENISO?3386-1) | ||
| Activation | Electron beam (50+32 mGy) | Superoxide on the spot |
| Compressive hardness Kpa | ||
| (not having circulation in advance) | 104 | 227.4 |
| Table 3F | A1 | B1 |
| Desmophen?3223(oh＝35) | 100 | 97 |
| Laromer?LR?8800(oh＝80) | 3 | |
| TDI(80/20) | 65 | 65.6 |
| Water | 6 | 6 |
| Niax?A1 | 0.12 | 0.1 |
| Stannous octoate | 0.23 | 0.23 |
| Siloxanes | 0.8 | 0.8 |
| Methylene dichloride | 1 | 1 |
| Without microwave | ||
| Density Kg/M3 | 21.3 | 21 |
| 40％CLD?kPa | 3.76 | 3.56 |
| The foam color | In vain | In vain |
| L */a */b * | 86.73/-0.39/- 0.78 | 84.72/-0.25/- 0.54 |
| With microwave 40 seconds | 800 | 800 |
| Density Kg/M3 | 19 | 16.5 |
| 40％CLD(kPa) | Can't survey | 3.7 |
| The foam integrity | Fall slag | Intact |
| The foam color | Vandyke brown | Light yellow |
| L */a */b * | 64.01/9.28/31.55 | 84.35/-1.89/8.91 |
| ΔE | 40.68 | 9.6 |
| Table 3H | A3 | B3 |
| Laromer?LR?9007 | 0 | 20 |
| Prepolymer 30 | 100 | 80 |
| TDI(80/20) | 32.3 | 33.9 |
| The Iso index | 105 | 100 |
| Water | 2.6 | 2.6 |
| Peroxan?PK295V-90 | 0 | 0.9 |
| Urea | 0.4 | 0.35 |
| DMEA | 0.06 | 0.06 |
| Stannous octoate | 0.13 | 0.08 |
| Silicone surfactant | 0.6 | 0.4 |
| Density Kg/m3 | 37.7 | 37.5 |
| Compressive hardness Kpa | 5.41 | 8.68 |
| (ENISO?3386-1) |
| Table 3I | A4 | B4 | C4 | D4 | E4 |
| Laromer?LR?9007 | 0 | 30 | 0 | 15 | 30 |
| Desmophen?3223 | 50 | 20 | 15 | 0 | 0 |
| PIPA?97/10 | 50 | 50 | 85 | 85 | 70 |
| TDI(80/20) | 50.2 | 51.0 | 51.1 | 49.7 | 51.5 |
| The Iso index | 105 | 95 | 102 | 95 | 95 |
| Water | 3.86 | 3.86 | 3.0 | 3.0 | 3.0 |
| Peroxan?PK295V-90 | 0 | 1.0 | 0 | 0 | 0 |
| Sorbyl alcohol | 0.6 | 0.6 | 0.8 | 0.8 | 0.8 |
| Stannous octoate | 0.05 | 0.05 | 0.05 | 0.05 | 0.05 |
| The low activity silicone surfactant | 0.3 | 0.3 | 0.3 | 0.3 | 0.3 |
| Silicone surfactant | 0 | 0.5 | 0 | 0 | 0 |
| Diethylolamine | 1.0 | 1.0 | 1.0 | 1.0 | 1.0 |
| Urea | 0.4 | 0.4 | 0.4 | 0.4 | 0.4 |
| Density Kg/m3 | 26.9 | 25.1 | 24.5 | 27.6 | 27.8 |
| Compressive hardness Kpa (ENISO 3386-1) | 3.88 | 34.82 | 3.47 | 4.78 | 5.44 |
| Compressive hardness Kpa (ENISO 3386-1) electron radiation-activated 32mGy | - | - | - | 6.71 | 10.91 |
The material explanation
Propenoate
Laromer 9007: oligo-ether propenoate, molecular weight are about 600, and acrylate functionalities is about 4DB/mol, is made by BASF AG
Laromer 8800: gather hydroxy acrylate, molecular weight is about 900, and acrylate functionalities is about 3.5DB/mol, is made by BASF AG
1,6-dexa:1, two (3 acryls-2-hydroxyl propoxy-) hexanes of 6-, 2DB/mol, by Mitsuya Boeki, (Osaka, Japan) makes
Laromer 8986: the aromatics epoxy diacrylate, and molecular weight 650, acrylate functionalities is about 2.5db/mol, is made by BASF AG
Polyvalent alcohol/carrier
PIPA 97/10: be that POLYMETHYLENE POLYPHENYLISOCYANATE gathers 10% dispersion-s of addition (PIPA) affixture in the polyether glycol of 4800 terminal molecular weight of a kind of oxygen ethene, by shell chemical company manufacturing-a kind of polymer-modified polyols
Dispersion agent EM: nonionic emulsifying agent, by the Rheinchemie manufactured
Desmophen 3223: reactive polyether polyols, and it is terminal to have oxygen ethene, and molecular weight is about 5000, is made by Bayer AG
Lupranol 4700:40% solid, the styrene/acrylonitrile copolymer polyvalent alcohol is made by BASF AG, based on main right and wrong EO terminated polyether polyvalent alcohol---polymer-modified polyols
Voranol CP 755: non-reacted polyether glycol, molecular weight 700 is made by Dow Chemical
Voranol CP 1421: reactive high ethylene content polyether glycol, molecular weight is about 5000, is made by Dow Chemical
Prepolymer 30
Prepare prepolymer by discontinuous method
96.24% polyether glycol (DESMOPHEN 20WB56 (Bayer AG)), OH value: 56, viscosity: about 700mPa.s, 20 ℃)
3.75% 2 isocyanato-toluene 80/20 (TDI 80/20)
0.00385% dibutyl tin laurate (DBTL)
This polyether glycol is placed in the mixing vessel under the room temperature, under agitation adds dibutyl tin laurate subsequently.In this mixture, slowly stir and add two isocyanato-toluene.
Behind about 24h, it is about 30 that the viscosity of the prepolymer of generation reaches, 000mPa.s, and 25 ℃, OH value reaches 30 simultaneously.
Isocyanic ester
TDI (80/20): tolylene diisocyanate, isomer 2,4: 2,6 ratio 80%/20%
TDI (65/35): tolylene diisocyanate, isomer 2,4: 2,6 ratio 65%/35%
Desmodur 100: be a kind of aliphatic isocyanate (NCO content 20%), made by Bayer AG
Voranate M 220: polymkeric substance MDI, made by Dow Chemical
Superoxide
PEROXAN PK295V-90:1,1-(at 128 ℃ transformation period 13min, made by Pergan (Germany) for two (t-butyl peroxy)-3,3,5-trimethyl-cyclohexane by 90% solution in OMS (nothing is smelt white spirit) or Permethyl 99A.
Perozan HX (2,5-dimethyl--2,5-di-t-butyl peroxide) hexane
The solution of Perozan BHP70:70% tert-butyl peroxide in water.Transformation period 1min at 222 ℃
Peroxan DC: dicumyl peroxide, at 172 ℃ transformation period 1min, by Pergan, Germany makes
Amine catalyst
Niax A1: air products company (USA)
DMEA: dimethylethanolamine
Dabco 33LV: triethylenediamine, by the air products manufactured
Silicone surfactant
The example of silicone surfactant (being used for the standard foam prescription) is Silbyk 9001 or 9025, by Byk chemical company, or Tegostab BF 2370 or B 8002, make by Goldschmidt.
The example of low activity silicone surfactant is Silbyk 9705 or 9710, from Byk chemical company, and Tegostab B 8681, from Goldschmidt, or L-2100, from GE advanced material company.These products are used to the high-elastic foam plastic manufacturing.
They are different from above-described silicone surfactant part and are, because ZGK 5 is lower with short their activity of dying of T 46155 molecular chain.
Mersolat?H-40
Alkyl sodium sulfonate is made by Lanxess (Germany)
Explanation of tables
Table 3A (corresponding to last table 1)
Embodiment A and B show prescription of equal value, and the two all contains propenoate.But Embodiment B with regard to activatable, is caused foams hardness to increase greatly by existing superoxide.
Table 3B
Comprise a series of suitable prescriptions.
Embodiment C is the preparation with zero acrylate content, owing to add propenoate (embodiment D) but do not apply energy (electron beam) or radical (superoxide) activates propenoate, the foams hardness between C and the D differs minimum.In embodiment E, propenoate is increased so observe little hardness by electron radiation-activated, and in embodiment F, propenoate is by peroxide activated, so the significantly increase of foams hardness occurs.
Table 3C
Or a series of suitable prescriptions
Embodiment G, H and I are not embodiments of the invention, but below different polyvalent alcohols combinations in the form effect difference of foams hardness clearly reflected show.
Embodiment J and K have the propenoate of existence, but the propenoate in J does not have (by electron beam or superoxide) activation, are therefore showing very little variation aspect the foams hardness.Embodiment K is through the porous plastics heat activation to processing, and hardness increases considerably less.
Embodiment M and J are suitable, but the electron beam activated, and embodiment L (also being similar to J) is by superoxide activatory on the spot.
Embodiment N, O or P are by the activation under different activation temperatures of different superoxide.In embodiment N, select superoxide, so that propenoate is not activated during foamable reaction.Embodiment O uses superoxide, and the postheating activation is so foams hardness has had increase.In embodiment P, used superoxide and foams by electron radiation-activated, foams hardness further sharply increases.
Table 3D
This form logically is similar to table 3C, and different is to use different propenoate.
Embodiment Y and Z show that if the heat release of foam formation reaction is insufficient, the heat dissipation of emitting is too fast, and then superoxide is with unable to get up reaction (Y).Yet the porous plastics of processing can heat, and can be activated, so foams hardness will show increase.
Table 3E
Embodiment reading beam and peroxide activated influence to the preparation that uses aliphatic isocyanate.
Table 3F (this embodiment is corresponding to top table 2)
Most of polyvalent alcohols comprise a small amount of superoxide, and during the foam formation reaction, will produce some extra a small amount of superoxide.In having the preparation of high heat release, such trace superoxide can cause the variable color (incipient scorch) of porous plastics.In extreme occasion, but porous plastics very fast spontaneous combustion after making.Can cause spontaneous combustion at hectic fever weather with the placement condition of the high heat release preparation of the raw material manufacturing of high-content impurity.The porous plastics of table among the 3F is to adopt the very high water yield (6php) to make, and produces very high heat release with activation, and this porous plastics is put in the microwave oven to highlight this kind variable color immediately, also stops exothermic dissipation simultaneously.
Table 3G
This table shows that B2, C2 and D2 are as embodiments of the invention.A2 is not embodiments of the invention, because it is a standard flexible foam plastic preparation.B2 shows that gathering the hydroxyl acrylic ester cpds joins the influence among the preparation A2.A spot of hardness increase is the typical effect when in prescription A1, adding lower molecular weight high functionality polyvalent alcohol.
C2 shows a kind of propenoate activatory method (electron beam) that makes.Here, hardness increases about 40 times.
D2 shows the peroxide activated of propenoate, as second step (not being during foaming).This is because therefore the too fast cause of sample heat radiation of laboratory size, has implemented subordinate phase activation (through baking oven for heating) so that the effect that simulation obtains on technical scale.
Table 3H shows that this notion also is applicable to disclosed prepolymer in common pending application application (PCT/EP2005/005314).Embodiment A 3 is not embodiments of the invention.B3 shows, the application of some Laromer in prescription improved the supporting capacity of porous plastics through peroxide activated effect.
Table 31 shows that the present invention also is applicable to the high resilience technology raw material with a kind of isocyanic ester and polymer-modified polyols.The low activity silicone surfactant is a kind of known high resilient surface promoting agent.Prescription A4 is not embodiments of the invention, provides the soft low density porous plastics.Rely on hydroxy acrylate and peroxide activated, hardness increases by 10 times.Prescription C4 is not embodiments of the invention.Prescription D4 and E4 show, the electron radiation-activated through two keys can obtain tangible hardness increase.
Claims (30)
1. method of making urethane foam; Wherein at least a polyfunctional isocyanate, at least a polyvalent alcohol; The latter is a kind of molecular weight greater than 1500 polyether glycol fully or mainly; And foam form composition under at least a reactive double bond component, takes place polyaddition with foam formation react, thereby the urethane main body that generation is foamed, wherein said polyfunctional isocyanate is substantially free of or does not comprise MDI; And the urethane main body of foaming is carried out the crosslinked of radical initiation with the reactive double bond component; Said reactive double bond component is the two key components of polyol reaction property that react with the polyfunctional isocyanate, thereby introduces in the polyurethane substrates, wherein the reactive double bond component be hydroxy functionality be higher than 2 and OH value between hydroxyl (methyl) origoester acrylate of 5～350mgKOH/g.
2. the process of claim 1 wherein that porous plastics is formulated into the HR porous plastics.
3. the process of claim 1 wherein that porous plastics is formulated into non-HR porous plastics.
4. the process of claim 1 wherein that polyvalent alcohol contains or comprises at least a polymer-modified polyols.
5. the process of claim 1 wherein that crosslinked that said radical causes carries out in the presence of at least a radical-forming agent.
6. the method for claim 5, wherein at least a radical-forming agent is an organo-peroxide.
7. the method for claim 1; The urethane main body of wherein said foaming is the non-discoloring basically polyurathamc main body of a kind of stable perforate; It is characterized in that; The non-discoloring basically polyurathamc main body of this perforate with the reactive double bond component carry out that radical causes crosslinked, thereby producing than adopting comparable comprises that at least a polyfunctional isocyanate, at least a polyvalent alcohol and foam form the basal component of composition but the compressive hardness that do not add the comparable rigidity big at least 10% of the basic nondiscoloration foaming of the stable perforate main body that said pair of key component form.
8. the process of claim 1 wherein that foam is formed into branch and comprises water, said polyaddition and foam form reaction and do not exist any volatility foam to form component basically, and wherein the consumption of two key components is between 0.1～10 part, and the consumption of water is greater than 4 parts.
9. the method for claim 1 is characterized in that, the working concentration and/or the consumption that comprise the basal component of at least a polyfunctional isocyanate, at least a polyvalent alcohol and foam formation composition should be able to produce the heat release that is enough to form radical.
10. the method for claim 1 is characterized in that, changes or regulate to have the component concentrations of reactive double bond, so that the degree of control response intensity and/or speed and/or radical crosslinking.
11. the method for claim 1 is characterized in that, changes or regulate to have the component concentrations of reactive double bond, so that the hardness and/or the supporting capacity of the porous plastics that control is produced.
12. the method for claim 1 is characterized in that, changes or regulate to have the component concentrations of reactive double bond, so that the oxidative degradation of the porous plastics that prevents to be produced.
13. the method for claim 5; It is characterized in that; Component concentrations with reactive double bond is adjusted to the concentration that adds radical-forming agent, and/or at least a radical of adding is captured material at least a polyfunctional isocyanate, at least a polyvalent alcohol and the foam formation mixture of ingredients.
14. the method for claim 1 is characterized in that, reactive component with total polymer content, promptly a)+b), is the benchmark meter:
A) the polyether glycol of the highest 99php with OH group, its functionality is 2～5;
B) the hydroxy functionality of the highest 99php be higher than 2 and OH value between hydroxyl (methyl) origoester acrylate of 5～350mgKOH/g;
C) the NCO functionality is 2～5 POLYMETHYLENE POLYPHENYLISOCYANATE, and consumption is according to 50～120 OH:NCO Index for Calculation;
D) water of 0.5～20php is as whipping agent;
E) at least a reaction initiator of 0.05～5php or radical-forming agent;
F) any catalyzer; And
G) any other auxiliary
Mix each other and react.
15. the method for claim 1 is characterized in that, at least a portion polyvalent alcohol and/or two key component are used as the prepolymer form that generates through the pre-reaction with the polyfunctional isocyanate.
16. the method for claim 6 is characterized in that, the transformation period of organo-peroxide is between 15min～5s, in 120～250 ℃ TR.
17. the method for claim 6 is characterized in that, organo-peroxide is selected from hydroperoxide, dialkyl peroxide, diacyl peroxide, peracid, ketone peroxide and epidioxy thing.
18. the method for claim 1 is characterized in that, the polyurathamc main body issues living radical in the influence of ionizing rays and causes crosslinked.
19. the method for claim 18 is characterized in that, ionizing rays is an electron beam irradiation.
20. the method for claim 1 is characterized in that, carbon dioxide gas is used as additional whipping agent and uses.
21. the method for claim 1 is characterized in that, comprises the individually adding of basal component quilt that at least a polyfunctional isocyanate, at least a polyvalent alcohol and foam form composition, in mixing machine or mixing head, mixes subsequently to be shaped simultaneously.
22. the method for claim 1 is characterized in that, the molecular weight of said reactive double bond component is 400-10000.
23. the process of claim 1 wherein to form reaction abreast with said addition and the foam of gathering, the polyurathamc main body is carried out radical with the reactive double bond component and is caused crosslinked.
24. the urethane foam that obtains according to the method for claim 1.
25. the urethane foam of producing according to the method for claim 23.
26. the urethane foam of claim 25; It is characterized in that; Under given density and abscess number, its hardness and/or its supporting capacity are than comprising the conventional foam plastics height at least 10% that identical at least a polyfunctional isocyanate, at least a polyvalent alcohol and foam form the comparable prescription of composition.
27. the urethane foam of claim 25 is characterized in that, it has at least a feature:
The abscess number of
10～120ppi;
accounts for the perforate of the overwhelming majority at least.
28. method of making urethane foam; Wherein at least a polyfunctional isocyanate, at least a polyvalent alcohol and foam form composition polyaddition and foam formation reaction take place in the presence of at least a reactive double bond component; Thereby generate the urethane main body of foaming; Wherein said polyfunctional isocyanate is substantially free of or does not comprise MDI; The urethane main body of foaming is carried out the crosslinked of radical initiation with the reactive double bond component under the influence of ionizing rays, said reactive double bond component is the two key components of polyol reaction property that react with the polyfunctional isocyanate, thereby introduces in the polyurethane substrates; Wherein the reactive double bond component be hydroxy functionality be higher than 2 and OH value between hydroxyl (methyl) origoester acrylate of 5～350mg KOH/g, said at least a polyvalent alcohol all or mainly is a molecular weight greater than 1500 polyether glycol.
29. the method for claim 28 is characterized in that, ionizing rays is an electron beam irradiation.
30. the method for claim 28 is characterized in that, the molecular weight of said reactive double bond component is 400-10000.
Applications Claiming Priority (5)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CH01962/04 | 2004-11-29 | ||
| CH19622004 | 2004-11-29 | ||
| GBGB0513473.9A GB0513473D0 (en) | 2005-07-01 | 2005-07-01 | Polyurethane foam |
| GB0513473.9 | 2005-07-01 | ||
| PCT/EP2005/012880 WO2006056485A1 (en) | 2004-11-29 | 2005-11-29 | Polyurethane foam |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101065414A CN101065414A (en) | 2007-10-31 |
| CN101065414B true CN101065414B (en) | 2012-06-13 |
Family
ID=34974741
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2005800408397A Expired - Fee Related CN101065414B (en) | 2004-11-29 | 2005-11-29 | Polyurethane foam |
Country Status (2)
| Country | Link |
|---|---|
| CN (1) | CN101065414B (en) |
| ZA (1) | ZA200704462B (en) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| TWI460196B (en) * | 2008-07-18 | 2014-11-11 | Univ Nat Taiwan | Polyurethane-acrylate material for forming viscoelastic damping polymers |
| WO2014089387A2 (en) * | 2012-12-07 | 2014-06-12 | Inoac Usa, Inc. | Hydrophilic thermal reticulated polyurethane foam useable for creation of a molten metal filter |
| DE102013019388A1 (en) * | 2013-11-18 | 2015-05-21 | GM Global Technology Operations LLC (n. d. Ges. d. Staates Delaware) | Instrument panel for a vehicle, vehicle with the instrument panel and method of manufacturing the instrument panel |
| CN109021808A (en) * | 2018-06-07 | 2018-12-18 | 上海沐皿新材料科技有限公司 | Water-repellent paint and one-piece type three-level block flexibly plate using the coating |
| CN114057985B (en) * | 2021-12-24 | 2023-05-12 | 湖北世丰新材料有限公司 | Hydrophilic high PPI polyurethane porous material, preparation method and application thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1251596A (en) * | 1997-04-02 | 2000-04-26 | 三洋化成工业株式会社 | Polyurethane foam, process for producing same and foam forming composition |
| CN1423668A (en) * | 2000-01-17 | 2003-06-11 | 亨茨曼国际有限公司 | Process for preparing a free rise or slabstock flexible polyurethane foam |
-
2005
- 2005-11-29 CN CN2005800408397A patent/CN101065414B/en not_active Expired - Fee Related
-
2007
- 2007-05-30 ZA ZA200704462A patent/ZA200704462B/en unknown
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1251596A (en) * | 1997-04-02 | 2000-04-26 | 三洋化成工业株式会社 | Polyurethane foam, process for producing same and foam forming composition |
| CN1423668A (en) * | 2000-01-17 | 2003-06-11 | 亨茨曼国际有限公司 | Process for preparing a free rise or slabstock flexible polyurethane foam |
Also Published As
| Publication number | Publication date |
|---|---|
| ZA200704462B (en) | 2008-07-30 |
| CN101065414A (en) | 2007-10-31 |
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