CN1429252A - Reinforcing polymers containing polyurethanes - Google Patents
Reinforcing polymers containing polyurethanes Download PDFInfo
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- CN1429252A CN1429252A CN01809351A CN01809351A CN1429252A CN 1429252 A CN1429252 A CN 1429252A CN 01809351 A CN01809351 A CN 01809351A CN 01809351 A CN01809351 A CN 01809351A CN 1429252 A CN1429252 A CN 1429252A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/0061—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof characterized by the use of several polymeric components
-
- 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
- C08G18/40—High-molecular-weight compounds
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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
- C08G18/40—High-molecular-weight compounds
- C08G18/4009—Two or more macromolecular compounds not provided for in one single group of groups C08G18/42 - C08G18/64
- C08G18/4072—Mixtures of compounds of group C08G18/63 with other macromolecular compounds
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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
- C08G18/40—High-molecular-weight compounds
- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
- C08G18/4266—Polycondensates having carboxylic or carbonic ester groups in the main chain prepared from hydroxycarboxylic acids and/or lactones
- C08G18/4269—Lactones
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
- C08L75/04—Polyurethanes
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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
- C08G2110/00—Foam properties
- C08G2110/0008—Foam properties flexible
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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
- C08G2110/00—Foam properties
- C08G2110/0083—Foam properties prepared using water as the sole blowing agent
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2375/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
- C08J2375/04—Polyurethanes
Abstract
Polyurethane and/or polyurea polymers are reinforced using certain crystalline and amorphous reinforcing polymers. The reinforcing polymers have crystalline melting temperatures and/or glass transition temperatures from about 40-200 DEG C, and are relatively miscible with the reacting polyurethane and/or polyurea formulation.
Description
The present invention relates to polyether polyols with reduced unsaturation.
Urethane and polyurea polymer are widely used in many application.Elastic polyurethane is widely used in various application, in the panel board and many other application such as dynamic elasticity body (such as wheel, travelling belt, pad), automobile.Flexible PU foam is used for the application of many seats and cushion, such as family and office furniture, mattress and automotive seat.These urethane nearly all are to make with the reaction between the polyvalent alcohol of organic polymeric polyisocyanate and high equivalent weight or polyamines and chain extension agent or the linking agent.The component of high equivalent weight is prevailing to be about 800～about 3, the 000 daltonian polyethers of each isocyanate reactive group.
In addition, hard polyurethane foams is used for various insulating to be used, and particularly in the insulation of household electrical appliance, in these were used, they are foam-in-site in household appliance shell, formed fluid insulation.Laminated rigid foam commercial also be very important.
Can obtain high-quality urethane by the less expensive raw material of extensive acquisition.Yet, wish to have the physicals of improvement under the situation about having.Such example is exactly the weight capacity of flexible PU foam.Weight capacity is generally forced deflection (IFD) or pressure deflection (CFD) expression with impression, and it can be described to the supporting capacity of foam to the load that applies, the people's that these duty ratios are seated in this way weight on the foam pad of chair or car seat.Provide the weight capacity of improvement that several potential benefits are arranged.Can obtain same product performance with lower foam density by let us such as better weight capacity, therefore just reduce raw materials cost, make foam more cheap.Similarly, the foam of higher weight capacity can use thinner cross section, and this also causes reducing the foamy cost.
Improve the foamy weight capacity several known technology are arranged.Such as can in prescription, adding mineral filler.Yet this can cause foam elongation and the sizable decline of shear strength, and density increases simultaneously.Can reduce the equivalent of polyol component, but this can cause the loss of elongation, and make the T of urethane
g(second-order transition temperature) rises.Other method is to add linking agent or use dissimilar polymer poly ether products, but these methods cause the loss of elongation and make the foamy compression set variation of manufacturing.
Therefore, any method of improving weight capacity, the most desirablely provide the required improvement on weight capacity, will keep other important performance simultaneously, such as tensile strength, shearing resistance, elongation, density, compression set and air flow property within acceptable limit.Have, special hope can be with common general available foaming machine again, and when making flexible PU foam, enforcement improves the technology of weight capacity under similar other processing condition of the current processing condition of generally using.
Wish that hard polyurethane foams also has the performance of improvement.
In first aspect, the present invention is a kind of urethane and/or polyureas foam of making by following reaction:
(a) at least a organic polymeric polyisocyanate; With
(b) a kind of isocyanate-reactive components, this component comprises:
(i) at least a isocyanate-reactive material that is in a liquid state under 25 ℃ on average has at least 2 isocyanate reactive groups in each molecule, and equivalent is 500～8, and 000, and
(ii) at least a high-melting-point polymer, its fusing point are about 45 ℃～about 200 ℃, with the T of K calculating
g/ T
mLess than 0.75, and calculating interaction parameter χ under 300K and other polyurethane component is greater than 1.6, and this parameter is less than 2.0 under 400K.
In second aspect, the present invention is a kind of method, and this method comprises:
(I) by following component is mixed, obtain reaction mixture:
(a) a kind of polymeric polyisocyanate and
(b) a kind of isocyanate-reactive components, this component comprises:
(i) at least a isocyanate-reactive material that is in a liquid state under 25 ℃ on average has at least 2 isocyanate reactive groups in each molecule, and equivalent is 500～8, and 000, and
(ii) at least a high-melting-point polymer, its fusing point are about 45 ℃～about 200 ℃, with the T of K calculating
g/ T
mLess than 0.75, and calculating interaction parameter χ under 300K and other polyurethane component is greater than 1.6, and this parameter is less than 2.0 under 400K.
(II) reaction mixture is heated to the above temperature of component (b) fusing point (ii) and keeps time enough, make (ii) fusion of component (b), and optional make (b) (ii) with the polymeric polyisocyanate reaction,
(III) make reaction mixture cured, obtain urethane and/or polyureas, and
(IV) urethane and/or polyureas are cooled to be lower than (ii) T of component (b)
mTemperature.
In the third aspect, the present invention a kind ofly has the external phase of isocyanate-reactive material and a dispersion that disperse phase is formed by at least a, external phase comprises the isocyanate-reactive material, under 25 ℃, be liquid, each molecule on average has at least 2 isocyanate reactive groups, and equivalent is 500～8000, and disperse phase contains at least a dystectic polymer beads, its fusing point is about 45 ℃～about 200 ℃, T
g/ T
mLess than 0.75, the χ that calculates under 300K is greater than 1.6, and the χ that calculates under 400K is less than 2.0.
In fourth aspect, the present invention is urethane and/or the polyurea polymer of being made by the reaction between the following material:
(a) at least a organic polymeric polyisocyanate and
(b) a kind of isocyanate-reactive components, it comprises:
(i) at least a isocyanate-reactive material that is in a liquid state under 25 ℃ on average has at least 2 isocyanate reactive groups in each molecule, and equivalent is 500～8, and 000, and
(ii) at least a unbodied polymkeric substance, its T
gBe higher than about 45 ℃, its T
g/ T
mGreater than 0.65.
Aspect the 5th, the present invention is a kind of method, and this method comprises:
(I) by following component is mixed, obtain reaction mixture:
(a) a kind of polymeric polyisocyanate and
(b) a kind of isocyanate-reactive components, this component comprises:
(i) at least a isocyanate-reactive material that is in a liquid state under 25 ℃ on average has at least 2 isocyanate reactive groups in each molecule, and equivalent is 500～8, and 000, and
(ii) at least a unbodied polymkeric substance, its T
gBe higher than about 45 ℃, its T
g/ T
mGreater than 0.65.
(II) reaction mixture is heated to component (b) T (ii)
gAbove temperature keeps time enough, and make component (b) (ii) take place to be transformed into rubbery state mutually, and anisotropically be dispersed in the reaction mixture,
(III) make reaction mixture cured, obtain urethane and/or polyureas, and
(IV) urethane and/or polyureas are cooled to be lower than (ii) T of component (b)
gTemperature.
Aspect the 6th, the present invention is a kind of urethane and/or polyurea polymer, they have one by being liquid under 25 ℃, and have at least 2 isocyanate functionalities and 500～8,000 the normal isocyanate-reactive material and the reaction product of polymeric polyisocyanate are formed mutually, with a common continuous anisotropy of forming by at least a amorphous polymer or with the reaction product of organic polymeric polyisocyanate mutually, the T of this polymkeric substance
gBe about 45 ℃～about 200 ℃, T
g/ T
mGreater than 0.65, perhaps a kind of reaction product of organic polymeric polyisocyanate.
Aspect the 7th, the present invention is a kind of dispersion of being made up of external phase and disperse phase, this external phase comprises at least a isocyanate-reactive material, under 25 ℃, be liquid, its each molecule on average has at least 2 isocyanate reactive groups, and equivalent is 500～8,000, this disperse phase contains the particle of at least a amorphous polymer, the T of this polymkeric substance
gBe about 45 ℃～about 200 ℃, and T
g/ T
mGreater than 0.65.
In eight aspect, the present invention for high-melting-point polymer/organic polymeric polyisocyanate to being respectively 1.6～4.0 and 0.74～2.0 at the χ of 300K and 400K calculated value in the above-mentioned each side of the present invention.
In the present invention, urethane and/or polyureas are to be made by the prescription that contains some polymeric additive.These additives can be high-melting-point crystalline polymer (being abbreviated as " high-melting-point polymer " in this article), also can be the high Tg amorphous polymers with some performance that will more discuss fully below.These polymkeric substance of stack up all are called " enhancing " polymkeric substance in this article.
As employed in this article, " crystallization " or " high-melting-point " polymkeric substance be a kind of like this polymkeric substance (a) at room temperature as mass polymer, it demonstrates the crystalline content of at least 0.3 (weight part that every parts by weight polymer contains); (b) work as T
gAnd T
mWhen all representing with standard(thermodynamic)scale, the T that it demonstrates
g/ T
mRatio is less than about 0.75; Perhaps satisfy simultaneously (a) and (b); Perhaps (c) because the processing conditions that before crystallization polymkeric substance quenched, and can not present amorphous in urethane and/or polyurea polymer.Recognized already that it was exactly partial crystallization at most that all " crystallization " polymkeric substance are gone up substantially, all contains crystallization phases and amorphous phase.
Term " amorphous " polymkeric substance that uses represent be following a kind of polymkeric substance (a) at room temperature as mass polymer, it demonstrates and is less than 0.3 crystalline content; (b) work as T
gAnd T
mWhen all representing with standard(thermodynamic)scale, the T that it demonstrates
g/ T
mRatio is greater than about 0.65; Perhaps (c) is a kind of normal crystalline material, because the processing conditions that before crystallization, polymkeric substance is quenched, and can in urethane and/or polyurea polymer, present amorphous.The T of amorphous polymer
g/ T
mBe preferably greater than 0.70, more preferably greater than 0.75.
The crystalline melting point of the high-melting-point polymer that be fit to use herein is higher than about 45 ℃, preferably is higher than about 70 ℃, more preferably is higher than about 80 ℃, up to the high processing temperature of urethane and/or polyureas moulding prescription.This fusing point generally is not higher than about 200 ℃, preferably is not higher than about 180 ℃, even preferably is not higher than about 160 ℃, most preferably is not higher than about 150 ℃.
In addition, in the processing temperature scope of using under the temperature that is higher than the high-melting-point polymer fusing point with in this urethane and/or polyureas moulding formulation cured the time, this high-melting-point polymer is relative mixable with the reaction mixture of isocyanate-reactive material and organic polymeric polyisocyanate.For other main ingredient of high-melting-point polymer and use in urethane and/or polyureas moulding prescription, " but relative compatibility " relates to the calculating of interaction parameter (χ value).The χ value is a dimentionless quantity, generally uses Molecular Simulations, the software product Cerius of Inc. company
2The 3rd edition or more highest version calculate.In Macromolecules30:1509～1514 (1997), narrated the details of computation program at K.Choi and W.H.Jo, quoted disclosure as a reference at this.The χ value reduces indicating that but compatibility improves relatively.When the χ value of calculating is 1.0 or more hour, but mean reasonable relative compatibility.Preferably derive the χ value of the high-melting-point polymer of use and organic polymeric polyisocyanate under maximum concentration and/or isocyanate-reactive components.All be to derive the χ value when the maximum concentration more preferably to high-melting-point polymer and organic polymeric polyisocyanate and isocyanate-reactive components.In addition, preferably derive the χ value in the whole temperature range that in the process of this prescription of processing, will run into, in other words from about 300K～about 473K, more preferably from about 350K～about 453K.For at least a high-melting-point polymer/main isocyanate-reactive components to or high-melting-point polymer/polymeric polyisocyanate right, the χ value of calculating at 300K is preferably greater than 1.6, when cooling off, can be separated, χ value when 400K is carried out so that the reaction between all components is easier in whole temperature range preferably less than 2.0.For at least a high-melting-point polymer/main isocyanate-reactive components to or the χ value of high-melting-point polymer/polymeric polyisocyanate to calculating, be more preferably less than 2.0 in the value of 400K, and greater than 0.74.For at least a high-melting-point polymer/main isocyanate-reactive components to or the χ value of high-melting-point polymer/polymeric polyisocyanate to calculating, in the value of 400K even be more preferably less than 1.75.In a preferred embodiment, be 0.75～1.5 for high-melting-point polymer/polymeric polyisocyanate to χ value in the calculating of 400K.The example of this polymeric polyisocyanate is MDI, TDI or their blend.
The χ value that provides above will be normalized to the high-melting-point polymer or the amorphous polymer of 3,000 molecular weight by calculating.But also can use identical compatibility threshold value to differentiate other preferred embodiment of the present invention when different molecular weight,, just use (χ molecular weight)/3,000 to replace χ value basis as a comparison itself if this moment, molecular weight was not 3,000.This value is also used a hypothesis, and Here it is high-melting-point amorphous polymer constitutes about 0.1 volume component of total prescription, and the weight component of urethane or polyurethane/urea hard segment approximately is 0.8.
The feature of significant especially high-melting-point polymer is to work as T
gAnd T
mWhen all being expressed as K with standard(thermodynamic)scale, it has lower T
g/ T
mThis T
g/ T
mIt is about 0.75 that value generally is lower than, and preferably is lower than approximately 0.70, more preferably less than about 0.65, most preferably is lower than about 0.60.This T
g/ T
mValue can be hanged down to 0.35 or lower, though it is believed that and work as T
g/ T
mValue is low can't see also what benefit can be arranged again to this value when following.T
g/ T
mValue preferably 0.35 or bigger is more preferably about 0.40 or bigger, even more preferably about 0.45 or bigger.For polymkeric substance, when under static isothermal condition, carrying out crystallization, T
g/ T
mRelevant with the maximum crystalline content of the polymkeric substance of expection.Ask for an interview Bicerano.J. " Crystallization of Polypropylene andPoly (Ethylene Terephthalate) ", J.Macromol.Sci.Review, C38, p.391～479 (1998).In addition, it is believed that, tend to show the bigger ability that in urethane and/or polyurea polymer, forms crystallization phases at the polymkeric substance that forms higher maximum crystalline content under the static isothermal condition.When crystallization under static isothermal condition, has the T in above-mentioned scope
g/ T
mThe polymkeric substance of ratio tends to have maximum crystalline content, and its content is about 0.5～1.0 in every parts by weight polymer, the crystallization of preferably approximately 0.6～about 0.8 weight part.
The crystallization phases that is formed by high-melting-point polymer can be isotropic (promptly low long-width ratio), perhaps preferably anisotropic (being that long-width ratio is 2 or bigger, preferably is 3 at least, more preferably is 5 at least).Herein " long-width ratio " of Shi Yonging mean the longest size of crystal divided by with the perpendicular direction of longest dimension on the size in cross section of the maximum of being got.
T
gValue is to measure with the differential scanning calorimeter expediently.
In addition, have been found that the number-average molecular weight about at least 1 of working as high-melting-point polymer, 000, preferably approximately 1,000～20,000, more preferably about 1,500～about 15,000, particularly about 2,000～about 12,000, most preferably be to see its benefit best at about 2,000～about 6,000 o'clock.
In the high-melting-point polymer that is suitable for, have:
(A) general formula is [C (O)-(CHR)
x-C (O)-O-]
jThe aliphatics polyanhydride, wherein R is alkyl, particularly methyl or the ethyl that hydrogen atom or unsubstituted or inertia replace, and most preferably is hydrogen, x is approximately not 8 or bigger numeral, preferably from about 10 to about 14, j provides a numeral of molecular weight as mentioned above.Calculating based on interaction parameter, preferably every weight part isocyanate-reactive components is used these polymkeric substance up to about 0.1 weight part, use MDI or TDI as polymeric polyisocyanate and use poly-(propylene oxide) polymkeric substance fill a prescription as main isocyanate-reactive material ground in the time, weight content is about 0.8 or higher.
(B) comprise that general formula is [(CHR)
y-O-CHR-O-]
jThe aliphatic poly acetal, wherein y is about 8 or bigger numeral, is preferably 12～20, R and j are as top.Described calculating based on interaction parameter, using MDI or TDI as polymeric polyisocyanate, in the poly-prescription of (propylene oxide) polymkeric substance as main isocyanate-reactive material, every weight part isocyanate-reactive components is preferably used up to the such polymkeric substance of about 0.2 weight part.
(C) comprise that general formula is [(CHR)
x-C (O)-O-]
jAliphatic polyester, wherein x, R are identical with the front with j.Calculating based on interaction parameter, using MDI or TDI as polymeric polyisocyanate, in the poly-prescription of (propylene oxide) polymkeric substance as main isocyanate-reactive material, every weight part isocyanate-reactive components is preferably used up to the such polymkeric substance of about 0.2 weight part.
(D) comprise that general formula is [(CHR)
x-O-]
jSend out aliphatic polyether, wherein x, R are identical with the front with j.Calculating based on interaction parameter, using MDI or TDI as polymeric polyisocyanate, in the poly-prescription of (propylene oxide) polymkeric substance as main isocyanate-reactive components, every weight part isocyanate-reactive components is preferably used about 0.5 weight part or more polymkeric substance like this.
(E) comprise that general formula is [(CHR
2)
o-C (O) O-]
jPolyhydroxyalkanoatefrom, R wherein
2Be hydrogen or C
1～C
4Alkyl, o are 0～3 numerals, and j is identical with the front.Poly(lactic acid) (L and/or D isomer), poly-(3-hydroxybutyric acid) and poly-(3-hydroxypentanoic acid) are arranged in suitable polyhydroxyalkanoatefrom.Calculating based on interaction parameter, using MDI or TDI as polymeric polyisocyanate, in the poly-prescription of (propylene oxide) polymkeric substance as main isocyanate-reactive material, every weight part isocyanate-reactive components is preferably used the such polymkeric substance up to about 0.5 weight part.
(F) general formula is [(CHR)
x-C (O)-NH-]
jFatty polyamide, wherein x, R are identical with the front with j.Based on the calculating of interaction parameter, using MDI or TDI as polymeric polyisocyanate, in the poly-prescription of (propylene oxide) polymkeric substance as main isocyanate-reactive material, every weight part isocyanate-reactive components is preferably used such polymkeric substance of about 0.8 weight part
(G) comprise that general formula is [O-{ (CHR)
m-O-}
n-(CHR)
m-OC (O)-Ph-C (O)]
jThe aromatic/aliphatic polyester, wherein each m is at least 2 to about 30 numeral independently, preferably about 6 to about 24, n is 0～about 5 numeral, preferably 1,2 or 3, Ph is an arylidene unsubstituted or that replace, R and j are with top identical; And
(H) general formula is [(CHR)
1-X]
jOther polymkeric substance also be suitable, wherein l is 8 or bigger numeral, is more preferably about 10 to about 20, X is a polarity link group, R is identical with the front with j.
High-melting-point polymer preferably or (B) from (B), (C), (D), (C) and combination (D).Though to the present invention is not crucial, this high-melting-point polymer preferably contains isocyanate reactive group, makes it to react with the polymeric polyisocyanate group, to be attached in the polymer network by covalent linkage (being the link of urethanum and/or urea).Best is to be any isocyanate reactive group on the terminated end group.Preferred isocyanate reactive group is primary hydroxyl, secondary hydroxyl, primary amino and secondary amino group.When high-melting-point polymer contains isocyanate reactive group, its functionality (being the average activity group number of each molecule) preferably is 2.0 at least, be more preferably about 2.0～about 8.0, even be more preferably about 2.0～about 4.0, most preferably be about 2.0～about 3.0.This functionality is easy to obtain by selective polymerization initiator suitably.The functionality that produces such as, dibasic alcohol is 2, and the functionality of trivalent alcohol is 3, and perhaps the functionality that produces of tetramethylolmethane is 4 or the like.
Some amorphous polymer can use or replaces them with high-melting-point polymer.Suitable amorphous polymer is that second-order transition temperature is about 45 ℃ at least, is not higher than 200 ℃, preferably approximately 50～about 120 ℃ polymkeric substance.Suitable amorphous polymer also preferably is mixable relatively in reaction mixture, and this reaction mixture is included in organic polymeric polyisocyanate and the liquid isocyanate active substance on the meaning discussed above.When urethane and/or polyurea polymer will be used to expose to the open air when using under the temperature that is being higher than envrionment temperature, the Tg of high-melting-point polymer generally should be higher than the use temperature of expection.
This amorphous polymer forms anisotropic domain structure in urethane and/or polyurea polymer matrix.These domain structure are common successive with urethane and/or polyureas matrix preferably.In order to make the easier formation of these domain structure, this amorphous polymer preferably is low viscous liquid under processing temperature.The suitable means of estimating viscosity are to carry out the solution flow index test, for example narrate in ASTM D1238, are applying under the load of 2.16kg, carry out the solution flow index test under the processing temperature of hope.Under these conditions, the amorphous polymer with 10dg/min or bigger, particularly 20dg/min or bigger melt flow index is preferred.
As mentioned above, this amorphous polymer preferably contains isocyanate reactive group.
This enhancing polymkeric substance joins in urethane and/or the polyureas and forms admixtion.This can realize with several method.Because strengthening polymkeric substance is solid at ambient temperature, preferably it is mixed with liquid ingredient, they are sent in the polyurethane foam processing units with the form of fluid stream.A kind of method of particularly suitable is strengthening polymer dispersed in polyether polyatomic alcohol component, and then with it with the polymeric polyisocyanate merging and with mixture solidified.Yet this strengthens polymkeric substance and also can add with other ratio of component such as chain extension agent, water and/or tensio-active agent logistics.If this strengthens polymkeric substance at room temperature is not isocyanate-reactive, even it can be blended in the polyisocyanate component and to add as this method.
In addition, this enhancing polymkeric substance can be used for making in the isocyanate-terminated prepolymer, can use separately, also can mix use with polyethers.
This isocyanate-reactive material, each molecule on average has at least two isocyanate reactive groups.Isocyanate reactive group be with isocyanate reaction and with any heteroatomic group of its formation covalent linkage.Preferred isocyanate reactive group is hydroxyl, primary amino or stretches amino, preferred primary hydroxyl and secondary hydroxyl.As known in the prior art of making urethane and/or polyurea polymer, popular isocyanate-reactive material has broad variety, selects specific type to carry out according to the performance that hope occurs in product.In prior art, isocyanate activity compound is known, be included in this narration (PIPA is the product that olamine and polymeric polyisocyanate reaction obtain addition polymerization with other commercial polyvalent alcohol and/or SAN, PIPA or PHD polyol, see United States Patent (USP) 4,374,209, PHD represents Polyharn-stoffdispersion.In the Polyurethane of G.Oertel Handbook (polyurethane handbook, the 2nd edition, Hanser press), these polyvalent alcohols have been narrated.Also can use the mixture of one or more polyvalent alcohols and/or one or more polyols to make polyurethane foam of the present invention.At United States Patent (USP) 4,394, narrated many suitable isocyanate-reactive materials in 491 the 3rd～5 hurdle, this patent is hereby incorporated by reference.Yet, the preferred polyol of making flexible foam be the equivalent of each isocyanate reactive group be about 500～about 8,000, preferably approximately 800～about 3,000, more preferably about 1,000～about 2,500 polyethers and polyester polyol.That these preferred polyethers and polyester polyol also advantageously have is about 2～and about 6, preferably approximately 2～about 4, more preferably about nominal functionality of 2～about 3 (number of the isocyanate reactive group in each molecule).Particularly preferably be polyether glycol, this is C
2～C
4The polymkeric substance of alkylene oxide or tetrahydrofuran (THF).For making molding or high resilience sizing material foam, the preferred polymkeric substance that uses propylene oxide, its for and account for randomcopolymer or the segmented copolymer of gross weight until the oxyethane of about 20wt%, the ethylene oxide-capped and proportion of primary OH groups that particularly contains about 8～20wt% is 50% or more polyvalent alcohol.For traditional sizing material foam, most preferably the trifunctional polymkeric substance of propylene oxide and propylene oxide and be not higher than the randomcopolymer of the oxyethane of about 15wt% have and are less than 30%, particularly are less than 15% primary hydroxyl.
Operable other polyvalent alcohol comprises the polyvalent alcohol of polymerized thylene carbonate alkyl ester group and the polyvalent alcohol of polyphosphoric acid ester group.Preferably have 2～8 by epoxy alkane is added to such as oxyethane, propylene oxide, butylene oxide ring or their mixture, on the initiator of preferred 2～6 active hydrogen atoms and the preparation polyvalent alcohol.For catalytic polymerization, can use anionic or cationic catalyzer, such as KOH, CsOH, Ba (OH)
2, boron trifluoride or two cyanide complex (DMC) catalyzer, such as six cyano group cobalts acid zinc.
As discussing in front, because it is preferably mixable relatively in urethane that reacts and/or polyureas prescription to strengthen polymkeric substance, so preferably select together, make in their the described in front scope of interaction parameter (χ value) to strengthening polymkeric substance and isocyanate-reactive components.
Urethane and/or polyurea polymer are can react under the condition that generates high-molecular weight polymer at isocyanate-reactive material and polymeric polyisocyanate, enhancing polymkeric substance, isocyanate-reactive material and polymeric polyisocyanate are put together make.Along with each component reacts, the temperature of reaction mixture surpasses fusing point or the second-order transition temperature that strengthens polymkeric substance, stops time enough under this temperature, makes the transformation mutually of high-melting-point polymer fusion or generation amorphous polymer.Essential heat can be provided by the reaction heat of mixture, also can be provided by the heat that adds, and is perhaps provided by both combinations.
Since in reaction process, the necessary fusion of high-melting-point polymer, this polymkeric substance preferably uses with the form of finely divided particulate, in case make the temperature of reaction mixture surpass its fusing point, these particles are fusion rapidly just.Similarly, amorphous polymer preferably provides with the form of finely divided particulate, and making promptly to take place easily to change mutually preferably becomes low viscous fluid.
Reaction mixture is cured and forms urethane and/or polyurea polymer.The solidified process generally began before high-melting-point polymer fusion or amorphous polymer take place to change mutually, and lasted till by fusion/phase transition process always and to finish fusion/after changing mutually.Can be cured with any method easily, this is included in makes the various traditional methods of using in urethane and/or the polyurea polymer.Such as when making molded polymeric, polymkeric substance can fully solidify in mould, perhaps be cured to suitable work in-process intensity, make that it can the demoulding and nonvolatil distortion does not take place, then at ambient temperature or carry out after fixing under the high temperature by other mode.If wish or if necessary, can preheated mold so that high-melting-point polymer fusion or amorphous polymer take place to change mutually.Have, the mould of substituting the bad for the good can heat as required to carry out necessary transformation mutually and to finish curing again.When making the flexible PU foam of molding, both can use so-called cold mould technology to the present invention, also can use the hot-die technology.Can use the sizing material foaming technique for making flexible foam.For making rigid foam, traditional casting technique is to be suitable for fully.It is also noted that,, perhaps change mutually with heat that compare with not using the conventional formulation that strengthens polymkeric substance, set time and/or temperature may need have increase slightly for amorphous polymer provides because this method is necessary for high-melting-point polymer melting heat is provided.
Urethane that solidified and/or polyureas under the situation of high-melting-point polymer, be cooled to be lower than the temperature of fusing point, perhaps under the situation of amorphous polymer, be cooled to the following temperature of Tg.It is believed that, in most of the cases, strengthen polymkeric substance and will in urethane and/or polyureas matrix, form high dispersive, but still be the separate areas structure.At polymkeric substance is under the preferable case of crystalline polymer, it is believed that the crystalline texture that has formed high dispersive in urethane and/or polyureas matrix.Therefore, high-melting-point polymer is not to form the low long-width ratio particle of dispersive, and thinks that it has formed the high surface area crystallization that is dispersed in widely in whole urethane and/or the polyureas matrix.Similarly, amorphous polymer forms anisotropic domain structure, and they preferably are total to successive with urethane and/or polyureas matrix.
Most of urethane and/or polyurea polymer both contained " firmly " domain structure and also contained " soft " domain structure, different to a certain degree processing conditions from according to specific reactant, and they are more or less isolating phases.In traditional urethane and/or polyurea polymer, " firmly " domain structure generally is counted as the domain structure that mainly comprises any water, chain extension agent and/or linking agent (as following definition) and polymeric polyisocyanate reaction product, and " soft " domain structure to be counted as mainly be the resistates of high equivalent weight isocyanate-reactive components.Performance (in flexible foam) such as weight capacity generally is owing to formed the hard segment that clearly limits.Therefore, in the present invention, do not destroy significantly by the domain structure that strengthens polymer formation preferably that the normal of hard segment forms in urethane and/or polyureas.Therefore, by strengthening domain structure that polymer residues forms preferably mainly in the soft chain segment of urethane and/or polyurea polymer.
Organic polymeric polyisocyanate that can use in the present invention comprises aliphatics, the aromatic isocyanic ester of alicyclic and fragrant fat and their mixture.The optimization aromatic isocyanic ester, particularly aromatic polymeric polyisocyanate.
The example of suitable aromatic isocyanate comprises 4 of diphenylmethanediisocyanate, 4 '-, 2,4 '-and 2,2 '-isomer and their blend and polymeric and monomeric MDI blend, toluene 2,4-and 2,6-vulcabond (TDI), m-and p-phenylene vulcabond, chloro phenylene-2, the 4-vulcabond, diphenylene-4,4 '-vulcabond, 4,4 '-two isocyanic acids-3,3 '-dimethyl diphenyl ester, 3-MDPM-4,4 '-vulcabond and diphenyl ether vulcabond and 2,4,6-triisocyanate base toluene and 2,4,4 '-triisocyanate yl diphenyl ether.
Can use the mixture of isocyanic ester, such as 2 of commercial toluene diisocyanate, 4-and 2,6-isomer mixture.Implementing to use thick polymeric polyisocyanate when of the present invention, such as crude toluene diisocynate that obtains by the phosgenation of tolylene diamine mixture or the thick diphenylmethanediisocyanate that obtains by thick methylene dianiline (MDA) phosgenation.Also can use the blend of TDI/MDI.Can also use with polyvalent alcohol (b1) or the MDI of aforesaid any other polyvalent alcohol manufacturing or the prepolymer of TDI base.Isocyanate-terminated prepolymer be by excessive polymeric polyisocyanate and comprise aminating polyvalent alcohol or and the reaction of imines/enamine or polyamines prepare.
The example of aliphatic polymeric isocyanate comprises ethylidene diisocyanate, 1,6-hexamethylene diisocyanate, isophorone diisocyanate, hexanaphthene-1,4-vulcabond, 4, the saturated analogues of 4 '-dicyclohexyl methane diisocyanate, above-mentioned aromatic diisocyanate and their mixture.
In order to make flexible foam, preferred polymeric polyisocyanate is a Toluene-2,4-diisocyanate, 4-and 2,6-vulcabond or MDI, the perhaps combination of TDI/MDI, the perhaps prepolymer of being made by them.
For flexible foam, the amount that organic polymeric polyisocyanate and isocyanate activity compound react, make that multiply by 100 defined isocyanate index with the number of NCO group or equivalent again divided by the normal sum of the hydrogen atom of isocyanate-reactive is 50～120, preferred 75～110.
Except isocyanate-reactive material, polymeric polyisocyanate and high-melting-point polymer,, can use various other additive and reactants according to the urethane that will make and/or polyurea polymer type difference.
Such as, most of urethane and/or polyurea polymer are to use the mixture of isocyanate-reactive components to prepare.This mixture will comprise that generally polyethers of one or more high equivalent weights (＞500) or polyester use with one or more chain extension agents and/or linking agent.Chain extension agent is an equivalent less than about 250, preferably less than about 125, and has the material of two isocyanate reactive groups in each molecule.Linking agent has similar equivalent, and each molecule has at least three isocyanate reactive groups.For the application of flexible foam, general water is as difunctionality whipping agent and chain extension agent.In addition, linking agent generally uses such as monoethanolamine, phenylenediamine, two (3-chloro-4-aminophenyl) methane, 2,4-diamino-3,5-diethyl toluene, Yi Bingchunan, diisopropanolamine (DIPA), N-(2-hydroxypropyl) quadrol and N, N '-two (2-hydroxypropyl)-quadrol.
The general whipping agent that uses is made the honeycomb polymkeric substance.Whipping agent can be water (forming carbonic acid gas with isocyanate reaction), low boiling hydrocarbon is such as pentane, hexane, heptane, amylene, heptene, pentamethylene, hexanaphthene, gas ratio such as carbonic acid gas, azo-compound such as azo hexahydrobenzene dintrile or halohydrocarbon such as dichloro C2H4F2 C2H4F2, vinylidene chloride and methylene dichloride.
When making polyurethane flexible foam, preferred water is as whipping agent.The consumption of per 100 weight part polyvalent alcohols ((b1)+(b2)) water is preferably 0.5～10 weight part, more preferably 2～7 weight parts.Carboxylic acid or salt also can be used as whipping agent.Obviously with isocyanate reaction the time in the foam formulation content of water to have influence on total heat release of foams, water-content is high more in foam formulation, heat release is just many more, fast more.Therefore, moisture more prescription is with easier fusion high-melting-point polymer or amorphous polymer (b2).When using hydro carbons, Chlorofluorocarbons (CFCs) or hydrofluoric ether as whipping agent, generally be not higher than 40 weight parts of component (b), preferably be not higher than 30 weight parts of component (b).Also can make the combination of water and hydro carbons, Chlorofluorocarbons (CFCs) or hydrofluoric ether as whipping agent.
Generally to use catalyzer.Representational catalyzer comprises: (a) tertiary amine, such as Trimethylamine 99, triethylamine, N-methylmorpholine, N-ethylmorpholine, N, N-dimethyl benzylamine, N, N-dimethylethanolamine, N, N, N ', N '-tetramethyl--1,4-butanediamine, N, N-dimethyl-piperazine, 1,4-diaza-ring-2,2,2-octane, two (dimethylaminoethyl) ether and triethylenediamine; (b) tertiary phosphine is such as trialkyl phosphine and triakyl benzyl phosphine; (c) various metallo-chelates are such as the inner complex that can be obtained such as Be, Mg, Zn, Cd, Pd, Ti, Zr, Sn, As, Bi, Cr, Mo, Mn, Fe, Co and Ni by Acetyl Acetone, benzoyl acetone, trifluoroacetyl benzylacetone, ethylacetoacetone(EAA,HEAA) etc. and metal; (d) the acid metal-salt of strong acid is such as iron(ic) chloride, tin chloride, tin protochloride, butter of antimony, nitric acid molybdenum and molybdenum chloride; (e) highly basic is such as oxyhydroxide, alkoxide and the phenoxide of basic metal and alkaline-earth metal; (f) alcoholate of various metals and phenolate thing are such as Ti (OR)
4, Sn (OR)
4And Al (OR)
3, R is an alkyl or aryl here, the reaction product of alcoholate and carboxylic acid, beta-diketon and 2 (N, N-dialkyl amido) alcohol; (g) organic acid and various metal are such as the salt of basic metal, alkaline-earth metal, Al, Sn, Pb, Mn, Co, Ni and Cu, such as sodium-acetate, stannous octoate, stannous oleate, lead octoate 36 and metal drier, such as manganese naphthenate and naphthoic acid cobalt; (h) Organometallic derivatives of the As of tetravalent tin, trivalent and pentavalent, Sb and Bi, and iron carbonyl and cobalt-carbonyl and (i) their mixture.
The general consumption of catalyzer is very little, such as about 0.0015～approximately 5wt% that accounts for polyurethane reactive mixture (promptly be used for making foamy all components).Amine catalyst tends to be used in the high-end of above-mentioned scope and uses, and metal catalyst tend to 1% or lower quantity use.
In addition, if desired, can use other useful additive, such as tensio-active agent, chain extension agent, filler such as lime carbonate, pigment ratio such as titanium dioxide, ferric oxide, chromic oxide, azo/diazo dyes, phthalocyanine, dioxazines and carbon black and other polyvalent alcohol.
Such as Herrington, R. the Dow Polyurethanes-FlexibleFoams (urethane-flexible foam of Dow) that waits the people to edit, the 2nd edition, 1997, and in the reference of this narration, all narrated the appropriate means of making molding and sizing material polyurethane flexible foam.
Under identical density, polyurethane flexible foam tends to have excellent weight capacity made in accordance with the present invention, when obtaining this performance, the physicals of other hope of great majority does not all have significantly loss, particularly tensile strength, shearing resistance, elongation and deterioration with moisture compression set.The present invention provides the manufacture method of the high resilience foamy with following performance combination especially:
The core density of measuring according to ASTM 3574-95 is 30～50kg/m.
That measure according to Peugeot D-41 1008-861 and force the ratio of deflection and the core density of representing with kg/m greater than 0.15 with 50% compression that KPa represents.
That measure according to ISO 2439-97 and to force the deflection and the ratio of the core density of representing with kg/m with 40% impression that N represents be about 7.1 at least.
The tensile strength of measuring according to ASTM 3547-95 is 150kPa at least, and elongation is 90% at least.
The shearing resistance of measuring according to ASTM D 3547-95 is 1.8N/m at least.
75% humidity wears out compression set less than 30%, and
The air flow quantity of measuring according to ASTM D 3574-95 is 1.0ft/min at least.
Can be used in seat according to urethane of the present invention and/or polyureas flexible foam such as carrier vehicle, vehicle (mobile or non-maneuverable), ship, snowmobile, land vehicle, aircraft such as automobile, two-wheeled are first-class, also are used for cushion and the mat or the upward application of other bed of furniture.
Method of the present invention is suitable for the application of reactive injection molding, wherein main isocyanate-reactive material is ethylene oxide-capped poly-(propylene oxide) polyvalent alcohol or amine terminated polyether, chain extension agent be aromatic diamine such as diethyl toluene diamine, and polymeric polyisocyanate is MDI or polymeric MDI.
Similarly, the present invention can be used for making polyurethane film, coating and caking agent.
Embodiment given below is used to illustrate the present invention, should not limit the present invention by any way.Except as otherwise noted, all umber and per-cent all are based on weight.
The raw material that uses in each embodiment is described as follows.SPECFLEX NC632 is with ethylene oxide-capped being caused by glycerine/Sorbitol Powder
Epoxypropane polymer, by Dow Chemical Company
Sell with trade(brand)name SPECFLEX.The average hydroxyl value is 32,
Average equivalent is about 1726, and functionality is 4～5.SPECFLEX NC700 is the polyol of 40%SAN base, and the average hydroxyl value is
20, sell by Dow Chemical Company.NIAX A-300 is enjoying of CK-Witco-OSI Specialties company sale
The amine catalyst that the delayed action of patent is arranged.NIAX A-400 is enjoying of CK-Witco-OSI Specialties company sale
The amine catalyst that the delayed action of patent is arranged.DABCO 38LV is that Air Products and Chemicals Inc. is with the merchant
The triethylenediamine catalyzer that name of an article DABCO sells is two
33% solution in the propylene glycol.DEOA is a diethanolamine.TEGOSTAB B8708 is the polysiloxane group that following Goldschmidt Ag company sells
Tensio-active agent.VORANATE T-80 is that Dow Chemical Company is with trade(brand)name VORANTE
2,4/2,6 isomer of the tolylene diisocyanate of selling
80/20 blend.PPDL2 is by poly-ten of 15 carbon lactones and glycol initiators preparation
The polymkeric substance of five carbon lactone polyester based has been narrated in this article
Its preparation method.The T of PPDL2
gApproximately be 92 ℃, T
g/ T
m
(K) be 0.578, in the many units of PDDL2/ that 400K calculates
The χ value of alcohol/MDI blend is 1.46, calculates at 300K
Be 3.27.DYNACOLL 7380 is polyester polyols that Degussa Huels company sells,
Its hydroxyl value is 29, about 67 ℃ of fusing point, T
g/ T
mBe 0.62,
DYNACOLL/ polyvalent alcohol/TDI blending 400 times calculating
The χ value of thing is 1.13, is 2.79 at 300K.FOMREZ 66-56 is the polyester as the same chemical constitution of DYNACOLL 7380
Polyvalent alcohol, but chain is lacked (hydroxyl value 56).Its fusing point is
About 64 ℃, T
g/ T
mBe 0.61, FOMREZ/ polyvalent alcohol/TDI
Blend is 0.60 in the χ of 400K value, 300K's
Be 1.47.FOMREZ 66-56 is Cromton-Witco
Company sells.
General experiment condition is as follows:
Preparation PPDL2. at nitrogen atmosphere with under stirring, in container, add 15 carbon lactones, i.e. PDL (100g) and 1,6-hexylene glycol (6.0g), mol ratio is 10: 1, and is heated to 150 ℃.Add catalyzer stannous 2-ethylhexoate (0.5g), temperature of reaction is raised to 190 ℃.The disappearance of observing PDL monitors the process of polyreaction.When polymerization is finished, the thermopolymer melt that obtains is poured in the 700mL dry toluene.Solution cooling with obtaining allows polymer precipitation come out.The precipitation that filtering separation obtains arrives constant weight with hexane wash and vacuum-drying at room temperature.Separate the polyester diol white crystalline solid that obtains, its T
gBe-50 ℃, T
mIt is 89 ℃.Obtain number-average molecular weight 2,770 with the MALDI-TOF mass-spectrometer measurement.
General foam formulation, HR molding and free foaming
Except each component of in work embodiment, listing, be used for the basic foam formulation of HR foamy and contain following component, be the weight percentage of polyvalent alcohol and/or polyvalent alcohol blend.
Prescription A
Water 3.7
DEOA???????????????????1.0
NIAX A-300 0.25 (containing 50% water)
NIAX A-400 0.1 (containing 30% water)
DABCO?33LV?????????????0.3
TEGOSTAB?B?8708????????0.80
DABCO?DC?5164??????????0.20
Table top and machine molding and free foaming
For the embodiment 1～4 and 5 that contains high-melting-point polymer, product is added in the NC632 polyvalent alcohol, water, catalyzer, silicone premix of fine powdered, then 3, the rotating speed of 000rpm stirs down and disperseed in 30 seconds, adds isocyanic ester then, restir 5 seconds, under the situation of free foaming, reactant is poured in the cardboard case, perhaps under the situation of molding, poured into being heated in 60 ℃ the aluminum dipping form, of 30 * 30 * 10mm then with the mould closure.
Test procedure
Density is carried out according to ISO 845-95, and unit is kg/m.
Air flow quantity is measured with the testing method of ASTM D3574-95, table
Be shown ft/min (cfm).
IFD is that impression is forced deflection, surveys by clear ISO 2439-97
Amount is reported as the newton number under 40% foam deflection.
CFD is that deflection is forced in compression, according to Peugeot D-41-
The testing method test of 1003-86 is reported as
25%, the kPa number under 50% and 65% deflection.
CS is dry compression set, according to Peugeot D-45-
The testing method of 1046-83 (70%CD) test, newspaper
The road is a per-cent.
75%CS is the dry compression set of measuring according to ISO 1856-80.
Elongation is surveyed according to Peugeot D-41.1050.85 testing method
Amount is reported as percentage ratio.
Tensile strength is surveyed according to Peugeot D-41.1050.85 testing method
Amount is reported as kPa.
Shearing resistance is surveyed according to Peugeot D-41.1048.81 testing method
Amount is reported as N/m.
Rebound resilience is measured according to the testing method of ASTM 3574-95, newspaper
The road is a percentage ratio.
The deterioration with moisture compression set is surveyed according to the method for ASTM ground 574-95 (75%CD)
Amount is reported as percentage ratio.
Embodiment 1～4
The experiment of carrying out the operator's console scale is to determine to use the influence of PPDL2 instead of part high functionality polyvalent alcohol in the flexible foam prescription.Foam formulation A that uses and the moulded foam that obtains and the foamy performance of free foaming provide in table 1, table 2 and table 3 respectively.
The research of the initial operation platform scale of table 1. pair molding and free foaming
| ??1 | ??RefA | ??1 | ??2 | ??3 | ??4 |
| ??NC632 | ??80 | ??75 | ??70 | ??65 | ??60 |
| ??NC700 | ??20 | ??20 | ??20 | ??20 | ??20 |
| The PPDL2 powder | ??0 | ??5 | ??10 | ??15 | ??20 |
| T-80 | 44.8 | ?44.8 | ?44.8 | ?44.8 | ?44.8 |
| Index | 100 | ?100 | ?100 | ?100 | ?99 |
| The die sinking time (min) | 4 | ?4 | ?4 | ?5 | ?5 |
| Mould-filling time (sec) | 43 | ?44 | ?44 | ?47 | ?47 |
| (weight part) | 333 | ?332 | ?340 | ?338 | ?336 |
| Molding density | 37 | ?37 | ?37.8 | ?37.6 | ?37.3 |
| The mold filling temperature (℃) | 70 | ?68 | ?69 | ?67 | ?73 |
| Reach 90 ℃ time (sec) | 80 | ?87 | ?87 | ?87 | ?86 |
| The die sinking temperature (℃) | 133 | ?130 | ?129 | ?123 | ?122 |
| Free foaming | |||||
| The creaminess time (sec) | 10～11 | ?9 | ?10 | ?10 | ?10 |
| Gel time (sec) | 66 | ?65 | ?63 | ?68 | ?80 |
| Foamed time (sec) | 85 | ?105 | ?104 | ?100 | ?91 |
Mould-filling time is the time when foam begins to emerge from the venting hole of mould.The mold filling temperature is when mould is filled, the temperature of using very thin thermopair to note from the foamy core.The time that reaches 90 ℃ is the time of thermopair when pointing out that the temperature of foam core reaches 90 ℃, and this is the fusing point of PPDL-2.Therefore, seeing PPDL-2 fusion, is before foam arrives the top and after mould is full of.The die sinking temperature is the temperature of time record just before opening mold lid, shows that core temperature is higher than the fusing point of PPDL-2.
The free foaming activity data demonstrates, and replaces liquid NC-632 the process of reaction not to be had miraculous change with solid PDDL-2.Just solidify and tend to slow down, not unexpected, this is longer and show by the die sinking time under high PPDL-2 concentration.
Table 2. is according to the performance of the moulded foam of the prescription manufacturing of table 1
| Foam number | RefA | ?1 | ?2 | ?3 | ?4 |
| 40％IFD | ?244 | ?247 | ?303 | ?330 | ?380 |
| Core density | ?34.7 | ?33.7 | ?35.0 | ?35.4 | ?36.9 |
| 25％CFD | ?3.5 | ?3.4 | ?4.3 | ?4.9 | ?5.4 |
| 50％CFD | ?5.2 | ?5.2 | ?6.5 | ?7.5 | ?9.0 |
| 65％CFD | ?8.4 | ?8.7 | ?11 | ?12.5 | ?15.9 |
| Air flow quantity | ?3.4 | ?3.2 | ?3.1 | ?3.7 | ?3.5 |
Result in table 2 demonstrates, and as testing at CFD and IFD, adds the PPDL-2 polymkeric substance and has increased foamy hardness.When replacing high functionality polyvalent alcohol (NC632), observe the increase of this hardness of not expected with dibasic alcohol (PPDL-2).Also require not reduce during with PPDL-2 instead of part high functionality polyvalent alcohol by the foamy air flow quantity.
Table 3. is according to the free foaming foamy performance of table 1 formulation
| Foam number | RefA | ?1 | ?2 | ?3 | ?4 |
| Core density | 28.3 | ?28.7 | ?29.3 | ?29.4 | ?31.8 |
| 50％CFD | 3.4 | ?4.0 | ?4.5 | ?4.8 | ?6.3 |
| Air flow quantity | 4.4 | ?4.3 | ?4.3 | ?4.5 | ?4.4 |
As viewed at moulded foam, in case when replacing a part of high functionality polyvalent alcohol with PPDL-2, the increase of the foam hardness of not expected.
Embodiment 5
The experiment of carrying out the operator's console scale is to determine to use the influence of Dynacoll 7380 instead of part high functionality polyvalent alcohols in the flexible foam prescription.The foamy performance that table 4 provides foam formulation and obtains.
Table 4. is about the research of moulded foam initial operation platform scale
| Foam number | ?RefB* | ?RefC* | ?5 |
| ?NC632 | ?80 | ?72 | ?72 |
| ?NC700 | ?20 | ?20 | ?20 |
| ?Dynacoll?7380 | ?0 | ?0 | ?8 |
| ?Fomrez?66-56 | ?0 | ?8 | ?0 |
| Index | ?100 | ?100 | ?100 |
| The die sinking time (min) | ?4 | ?4 | ?4 |
| (weight part) | ?331 | ?328 | ?335 |
| ?40％IFD(N) | ?236 | ?235 | ?279 |
| Core density (kg/m) | ?34.7 | ?34.0 | ?36.4 |
| ?50％CFD | ?5.0 | ?5.3 | ?6.2 |
| Air flow quantity (cfm) | 4.6 | ?4.5 | ?4.6 |
| 75% deterioration with moisture compression set | 16.8 | ?19.7 | ?19.9 |
The result of table 4 shows, its χ value when 300K is less than 1.6 Fomrez66-56, and not producing hardness increases, and the χ value when 300K is 2.79 Dynacoll 7380, then shows higher foam weight capacity.
Consider specification sheets and embodiments of the present invention disclosed herein, other embodiment of the present invention will be self-evident to those skilled in the art.Should think that these explanations and embodiment only are for example, and following claim is just pointed out real scope and spirit of the present invention.
Claims (7)
1. a urethane and/or polyureas foam made from following reaction:
(a) at least a organic polymeric polyisocyanate; With
(b) a kind of isocyanate-reactive components, it comprises:
(i) at least a isocyanate-reactive material that is in a liquid state under 25 ℃ on average has at least 2 isocyanate reactive groups in each molecule, and equivalent is 500～8, and 000, and
(ii) at least a high-melting-point polymer, its fusing point are about 45 ℃～about 200 ℃, T
g/ T
mLess than 0.75, and calculating interaction parameter χ under 300K and other polyurethane component is greater than 1.6, and this parameter is less than 2.0 under 400K.
2. method, this method comprises:
(I) by following component is mixed, obtain reaction mixture:
(a) a kind of polymeric polyisocyanate and
(b) a kind of isocyanate-reactive components, this component comprises:
(i) at least a isocyanate-reactive material that is in a liquid state under 25 ℃ on average has at least 2 isocyanate reactive groups in each molecule, and equivalent is 500～8, and 000, and
(ii) at least a high-melting-point polymer, its fusing point are about 45 ℃～about 200 ℃, T
g/ T
mLess than 0.75, and the calculating interaction parameter χ under 300K is greater than 1.6, under 400K this parameter less than 2.0,
(II) reaction mixture is heated to the above temperature of component (b) fusing point (ii) and keeps time enough, make (ii) fusion of component (b),
(III) make reaction mixture cured, obtain urethane and/or polyureas, and
(IV) urethane and/or polyureas are cooled to be lower than the (ii) temperature of fusing point of component (b).
3. one kind by at least a external phase of isocyanate-reactive material and the dispersion that disperse phase is formed of containing, the isocyanate-reactive material is a liquid under 25 ℃, each molecule on average has at least 2 isocyanate reactive groups, and equivalent is 500～8000, disperse phase contains at least a dystectic polymer beads, its fusing point is about 45 ℃～about 200 ℃, T
g/ T
mLess than 0.75, the χ that calculates under 300K is greater than 1.6, and the χ that calculates under 400K is less than 2.0.
4. a urethane and/or polyurea polymer made from following reaction:
(a) at least a organic polymeric polyisocyanate; With
(b) a kind of isocyanate-reactive components, it comprises:
(i) at least a isocyanate-reactive material, it is a liquid under 25 ℃, each molecule on average has at least 2 isocyanate reactive groups, and equivalent is 500～8, and 000; And
(ii) at least a amorphous polymer, its T
gBe higher than about 45 ℃, T
g/ T
mLess than 0.75.
5. method, this method comprises:
(I) by following component is mixed, obtain reaction mixture:
(a) a kind of polymeric polyisocyanate and
(b) a kind of isocyanate-reactive components, this component comprises:
(i) at least a isocyanate-reactive material that is in a liquid state under 25 ℃ on average has at least 2 isocyanate reactive groups in each molecule, and equivalent is 500～8, and 000, and
(ii) at least a unbodied polymkeric substance, its T
gBe higher than about 45 ℃, up to about 200 ℃, its T
g/ T
mGreater than 0.65,
(II) reaction mixture is heated to component (b) T (ii)
gThe above time enough that keeps of temperature makes component (b) (ii) take place to be transformed into rubbery state mutually, and anisotropically is dispersed in the reaction mixture,
(III) make reaction mixture cured, obtain urethane and/or polyureas, and
(IV) urethane and/or polyureas are cooled to be lower than component (b) T (ii)
gTemperature.
6. urethane and/or polyurea polymer, it has one by being liquid under 25 ℃, and have at least 2 isocyanate functionalities and 500～8,000 the normal isocyanate-reactive material and the reaction product of polymeric polyisocyanate are formed mutually, with one by at least a amorphous polymer or the common continuous anisotropy formed mutually, the T of this polymkeric substance
gBe about 45 ℃～about 200 ℃, T
g/ T
mGreater than 0.65, the perhaps reaction product of organic polymeric polyisocyanate.
7. dispersion of forming by external phase and disperse phase, this external phase comprises at least a isocyanic ester, it is a liquid under 25 ℃, and its each molecule on average has at least 2 isocyanate reactive groups, and equivalent is 500～8,000, this disperse phase contains the particle of at least a amorphous polymer, the T of this polymkeric substance
gBe about 45 ℃～about 200 ℃, and T
g/ T
mGreater than 0.65.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US20422300P | 2000-05-15 | 2000-05-15 | |
| US60/204,223 | 2000-05-15 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN1429252A true CN1429252A (en) | 2003-07-09 |
Family
ID=22757101
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN01809351A Pending CN1429252A (en) | 2000-05-15 | 2001-05-15 | Reinforcing polymers containing polyurethanes |
Country Status (8)
| Country | Link |
|---|---|
| EP (1) | EP1299476A2 (en) |
| JP (1) | JP2003533577A (en) |
| KR (1) | KR20030003734A (en) |
| CN (1) | CN1429252A (en) |
| AU (1) | AU2001263137A1 (en) |
| CA (1) | CA2408735A1 (en) |
| MX (1) | MXPA02011230A (en) |
| WO (1) | WO2001088036A2 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111109931A (en) * | 2020-01-06 | 2020-05-08 | 江苏众恒可来比家具有限公司 | Self-adaptive adjusting mattress |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2003064491A1 (en) * | 2002-01-28 | 2003-08-07 | Woodbridge Foam Corporation | Foam isocyanate-based polymer having improved toughness and process for production thereof |
| EP1959171B1 (en) * | 2005-12-06 | 2018-09-12 | NOK Corporation | Rod sealing system |
| JP2008074914A (en) * | 2006-09-20 | 2008-04-03 | Bridgestone Corp | Polyurethane foam-molded article and method for producing the same |
| RU2014102979A (en) | 2011-06-30 | 2015-08-10 | ДАУ ГЛОБАЛ ТЕКНОЛОДЖИЗ ЭлЭлСи | POLYMER CONTAINING SILANE END GROUPS USED FOR COATING, ADHESIVES, SEALANTS AND ELASTOMERS |
| CN112225873B (en) * | 2020-09-15 | 2022-04-22 | 万华化学集团股份有限公司 | High-transparency fast-forming degradable thermoplastic polyurethane elastomer and preparation method thereof |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE2913458A1 (en) * | 1979-04-04 | 1980-10-16 | Bayer Ag | DISPERSIONS OF HIGH-MELTING POLYESTERS IN POLYHYDROXYL COMPOUNDS, METHOD FOR THE PRODUCTION THEREOF AND THEIR USE IN THE PRODUCTION OF POLYURETHANE PLASTICS |
| US4994503A (en) * | 1989-09-13 | 1991-02-19 | The Dow Chemical Company | Particulate polymer and polymer compositions therewith |
-
2001
- 2001-05-15 AU AU2001263137A patent/AU2001263137A1/en not_active Abandoned
- 2001-05-15 JP JP2001585248A patent/JP2003533577A/en active Pending
- 2001-05-15 MX MXPA02011230A patent/MXPA02011230A/en unknown
- 2001-05-15 EP EP01937395A patent/EP1299476A2/en not_active Withdrawn
- 2001-05-15 CA CA002408735A patent/CA2408735A1/en not_active Abandoned
- 2001-05-15 KR KR1020027015428A patent/KR20030003734A/en not_active Application Discontinuation
- 2001-05-15 CN CN01809351A patent/CN1429252A/en active Pending
- 2001-05-15 WO PCT/US2001/015647 patent/WO2001088036A2/en not_active Application Discontinuation
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111109931A (en) * | 2020-01-06 | 2020-05-08 | 江苏众恒可来比家具有限公司 | Self-adaptive adjusting mattress |
Also Published As
| Publication number | Publication date |
|---|---|
| KR20030003734A (en) | 2003-01-10 |
| AU2001263137A1 (en) | 2001-11-26 |
| MXPA02011230A (en) | 2004-08-19 |
| CA2408735A1 (en) | 2001-11-22 |
| JP2003533577A (en) | 2003-11-11 |
| EP1299476A2 (en) | 2003-04-09 |
| WO2001088036A3 (en) | 2002-07-18 |
| WO2001088036A2 (en) | 2001-11-22 |
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