CN1161049A - Reduced solvent process for preparation of aqueous polyurethane dispersions with improved heat and solvent resistance - Google Patents
Reduced solvent process for preparation of aqueous polyurethane dispersions with improved heat and solvent resistance Download PDFInfo
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- CN1161049A CN1161049A CN 96190930 CN96190930A CN1161049A CN 1161049 A CN1161049 A CN 1161049A CN 96190930 CN96190930 CN 96190930 CN 96190930 A CN96190930 A CN 96190930A CN 1161049 A CN1161049 A CN 1161049A
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Abstract
This invention relates to a process for preparing poly(urethane/urea) prepolymers and aqueous poly(urethane/urea) dispersions(PUDs) therefrom, the poly(urethane/urea) polymers having high heat resistance and good water resistance. The method employs a water-soluble volatile organic solvent, such as acetone, at a level of 0.1-5 %, based on final dispersion weight, a level which does not require removal for purposes of flash point considerations. The method includes the steps of: reacting in the presence of a water-soluble volatile organic solvent at a level corresponding to no more than 5 % by weight of the final dispersion, a polyisocyanate component comprising a diisocyanate, with a polyol component to produce an isocyanate terminated polyurethane prepolymer, the polyol component providing both carboxylate groups and sulfonate groups; dispersing the isocyanate terminated prepolymer in aqueous media; reacting said dispersed isocyanate terminated polyurethane prepolymer with at least one amine functional chain extender or chain terminator compound to thereby form said poly(urethane/urea) polymer; neutralizing the carboxylate and sulfonate groups of said isocyanate terminated prepolymer with an alkali hydroxide or a tertiary amine prior to, or simultaneous with, said reaction of said prepolymer and said amine functional chain extender or terminator; wherein the method is performed without a solvent distillation step.
Description
Background of invention
1. invention field
The present invention relates to the method that a kind of preparation has good thermotolerance and water-proof water-based anion polyurethane dispersion liquid binder composition.
2. the description of prior art
Polyurethane aqueous dispersion liquid is well-known.Can be by using outside tensio-active agent or the polyether polyols with reduced unsaturation main chain of oxygen Vinyl Ether (the ethylene oxide ether) part that has non-ionic type being provided or providing the polyether polyols with reduced unsaturation that has neutral positively charged ion or anionic group to disperse.
For anionic aqueous polyurethane dispersion, the ion salt group is carboxylate salt or sulfonate groups.When preparation anion polyurethane dispersion liquid, usually be preferably the polyurethane prepolymer that preparation has the free isocyanate of small portion of residual, this prepolymer is dispersed in the aqueous medium, adds low relatively primary amine of multifunctional molecule amount and/or secondary amine then as chain extension agent.This increases chain process needs, and this is can obtain better high-molecular-weight poly (ammonia ester/urea) more of thermotolerance after the chain because increase.In order to disperse to have isocyanate functional group's polyurethane prepolymer, and, in the reaction that generates prepolymer, use volatile solvent (as acetone, butanone, N-Methyl pyrrolidone or the like) sometimes in order to control the generation polyurethane reaction.If solvent height after disperseing then must be removed by distillation usually basically, this complicated operations step needs expensive equipment.And this solvent removal step causes that volume/time productive rate is low in process of production, and the solvent treatment with removing in the step in a large amount of reaction mediums has been increased blast and incendiary danger in process of production.
Polyurethane prepolymer with aforesaid method production is that compound (polymeric polyisocyanate) and the polyol component that a plurality of isocyanos are arranged (comprises polymerized polyalcohol, as polyether glycol or polyester polyol, and common monomer or the very short oligomeric polyols of chain) reaction product.The urethane that so makes has-(A-B-)-the type block polymer structures, wherein the A segment is relative softer segment, from polymerized polyalcohol, and the B segment is hard segment, from polyisocyanate component and any monomer in polyol component or the very short oligomeric polyols of chain.For nearly all commercially available anionic aqueous polyurethane dispersion product, ionic group is included in the hard segment.
When considering how to produce the polyurethane dispersing liquid product, also must consider the required use properties of final polymkeric substance.When dispersion liquid was used as adhesive product, thermotolerance and water tolerance were important performances, and these performances are subjected to the influence of employed polyol component very big.For example, improve the total amount of the hard segment intermediate ion group of polymkeric substance, can cause the minimizing of the relative quantity of soft chain segment, and the water tolerance and snappiness and the elasticity that reduce final polymkeric substance.Add and comprise that the component of nonionic oxygen Vinyl Ether or other polyether moiety can improve dispersibility, but also reduced thermotolerance and water tolerance.
People such as Henning are at US4, have disclosed use N-(2-aminoethyl)-2-aminoethyl sulfonic acid sodium salt (AAS salt) preparation polyurethane dispersing liquid in 870,129.It is reported that aqueous polyurethane dispersing liquid has satisfactory stability when low pH value (5-7), but thermotolerance then only is general.Poor water resistance based on these monomeric commodity (as Bayer KA-8464).And in the document in the employed method, before acetone solvent was removed in distillation, acetone content was 80% (weight) of this dispersion.The solvent of removing this amount from technical scale is a very complicated process.When using this compound, sulfonic acid group is introduced in the hard segment.
People such as Reiff are at US4, have disclosed the waterborne sulfonated polyurethane dispersing liquid based on sulfonated polyether two pure and mild water soluble sulfonated diamines in no-solvent process in 108,814.Yet this no-solvent process has produced the polymkeric substance that does not have high crystallization rate, high heat resistance or excellent water tolerance.
People such as Schafheutle are at US5, have disclosed to use in 334,690 to have the polyester of anionic group or the method that polyether glycol prepares polyurethane dispersing liquid.Mentioning urethane in the document can prepare in the presence of solvent, perhaps with solvent-free melting method preparation.In the embodiment of the document, use about 40% carboxylation polyester polyvalent alcohol and acetone.Also for example understand the melting method that uses sulfonated polyester polyol.Yet, in melting method, use high temperature can cause as vulcabond react with carboxylic acid and/or urethano group and even the generation of the side reactions such as trimerization reaction of isocyanic ester, make final product may not have good linear structure, thus this polymkeric substance may have poor crystallization rate, the difference not slaking the time intensity and unfavorable thermotolerance.Therefore melting method is not too selected for the preparation aqueous polyurethane dispersing liquid.
People such as Pedain are at US4, disclosed the method for the solvent-free or a small amount of solvent that is used to prepare aqueous polyurethane dispersing liquid in 829,122, but this method are used the end capped amine chain extension agent of protecting group.
People such as Duan submitted on November 22nd, 1994 conduct on September 24th, 1993 submitted 08/126, the patent application 08/343 of the part continuation application of 508 (now abandoning), disclosed in 676 based on the aqueous polyurethane dispersing liquid that uses sulfonated polyester polyol and hydroxycarboxylic acid, the suitable α that is to use, α-dihydroxymethyl paraffinic acid (as dimethylol propionic acid) obtains having the polyether polyols with reduced unsaturation of anionic group on the hard segment of polymkeric substance and soft chain segment.Acetone and no-solvent process are used for polyurethane preformed polymer, when using acetone method, boil off acetone after disperseing and increasing chain.In no-solvent process, owing to use glycol ether in polyester, therefore used polyester comprises oxygen Vinyl Ether part in these prescriptions, and fusing point is lower than 50 ℃, is preferably at room temperature to be those of liquid.Urethane according to the no-solvent process preparation has poor thermotolerance and water tolerance.
The patent application No.08/304 that people such as Duan submitted on September 9th, 1994 has disclosed in 653 a kind of based on the sulfonated polyester polyol and the sulfonated polyester aqueous polyurethane of higher molecular weight and the dispersion liquid of the non-carboxylation dibasic alcohol of lower molecular weight (having high thermotolerance and excellent water tolerance) that use with the solvent (as acetone, NMP or DPMA) of water compatible.When using NMP or DPMA, the scope that has disclosed solvent is about 3-15%, is benchmark with the weight of final dispersion liquid.When using acetone, after disperseing and increasing chain, boil off acetone, make the final content of acetone can reach 1.1% low or lower.
The present inventor is surprisingly found out that now, with patent application No.08/304,653 similarly have high thermotolerance and water-proof polymkeric substance can prepare by low acetone solvent method, this method can be controlled the prepolymer formation reaction well, but does not introduce the too much solvent that must remove from final dispersion liquid.
Summary of the invention
The present invention relates to be used for improving one's methods of poly-(ammonia ester/urea) prepolymer of preparation, and poly-(ammonia ester/urea) dispersion liquid (PUDs) of water-based therefrom, this poly-(ammonia ester/urea) polymkeric substance has high thermotolerance and excellent water tolerance.The consumption of water-soluble volatile organic solvent (as acetone) is 0.1 to about 5% in the method for the present invention, is preferably and is not more than 3%, is preferably 0.5 to 2%, is benchmark with the weight of final dispersion liquid, considers that from flash-point the quantity of solvent of this level need not to remove.Therefore, the invention provides a kind of method that generates poly-(ammonia ester/urea) polymer aqueous dispersion of stable negatively charged ion, this dispersion liquid contains the dispersion liquid of 0.1 to 5% (weight) volatile solvent of having an appointment, and this poly-(ammonia ester/urea) has high heat resistance and water-proof feature when drying, and this method comprises:
With respect to final dispersion liquid weight be not more than 5% water-soluble volatile organic solvent in the presence of, make the polyisocyanate component and the polyol component reaction that contain vulcabond, generating end is the polyurethane prepolymer of isocyanic ester, and this polyol component has carboxylic acid group and sulfonic group;
With this end is that the prepolymer of isocyanic ester is dispersed in the aqueous medium;
Make described dispersive terminal, generate described poly-(ammonia ester/urea) polymkeric substance for the polyurethane prepolymer of isocyanic ester and functional chain extension agent of at least a amine or the reaction of chain terminator compound;
Before described prepolymer and the functional chain extension agent of described amine or chain terminator reaction or simultaneously, with in alkali metal hydroxide or the tertiary amine and described end be the carboxylic acid group and the sulfonic group of the prepolymer of isocyanic ester;
Wherein, there is not the solvent distilation steps in the described method.
Suitable polyhydroxy component comprises at least a sulfonated polyester, and the feature of this sulfonated polyester is that number-average molecular weight is about 500 to 10,000, and melt temperature is about 10 ℃ to 100 ℃; The hydroxycarboxylic acid of at least a following formula:
(HO)
xR (COOH)
yWherein R represents the alkyl that contains 1 to 12 carbon atom of straight or branched, x and y represent 1 to 3 numerical value, but condition is when the x value is 1, in polyisocyanate component, use the trifunctional isocyanates of equivalent, and when x is 3, use the monofunctional isocyanates of equivalent, thereby make the polyurethane prepolymer that obtains keep not crosslinked basically.This polyhydroxy component also can randomly contain the polyester of unsulfonated and/or the low molecular weight diols of non-carboxylation.Require described polyol component not contain the compound of band vinyloxy group ethylidene (ethyleneoxyethylene) group, be preferably polyhydroxy component and do not contain any polyether moiety.
Detailed Description Of The Invention
What preferably be used is that the sulfonated polyester polyol of the polyurethane prepolymer of isocyanic ester is to introduce sulfonic polyester polyol by functional dicarboxylic acid residue of sulfonic acid and/or the functional diol residue of sulfonic acid to generate end.The functional group of sulfonic acid can be the form of acid or salt.Suitable salt form is an alkali metal salt or tertiary ammonium salt.Typical functional dicarboxylic acid residue of these sulfonic acid and/or the functional diol residue of sulfonic acid are the glycol of polyester and/or the small portion in two acid moieties, are preferably the 1.0%-10.0% (weight) that accounts for polyester.The diacid of used unsulfonated and glycol can be aromatics or aliphatic in generating sulfonated polyester.The example of the diacid of unsulfonated comprises hexanodioic acid, nonane diacid, succsinic acid, suberic acid and phthalic acid.The example of the glycol of unsulfonated comprises ethylene glycol, butyleneglycol, butylene glycol, propylene glycol, neopentyl glycol, hexylene glycol, 1,4 cyclohexane dimethanol, 1,2-propylene glycol and 2-methyl isophthalic acid, ammediol.The example of sulfonation diacid comprises sulfoisophthalic acid, 1,3-dihydroxyl fourth sulfonic acid and sulfo-succinic acid.The example of sulfonation glycol comprises 1,4-dihydroxyl fourth sulfonic acid and succinic aldehyde bisulfite disodium.
Preferred sulfonated polyester polyol comprises polyester polyol, the hexanodioic acid and 1 based on 5-sulfoisophthalic acid one sodium salt, 6-hexylene glycol.
What useful in the present invention sulfonated polyester polyol was suitable is that number-average molecular weight is about 500 to 10,000, is preferably 1,000-4, and 000, melt temperature is about 10 ℃ to 100 ℃.The fusing point that is preferably sulfonated polyester polyol is 40 ℃ to 60 ℃.Particularly preferably be sulfonated polyester polyol by the derivatives reaction preparation of the short-chain diol of sulfonation diacid or glycol and unsulfonated and short chain diacid or diacid.
The polyol component that is used to prepare poly-(ammonia ester/urea) dispersion liquid of the present invention also comprises hydroxycarboxylic acid except sulfonated polyester polyol, can also randomly comprise the pure and mild nonacid low molecular weight diols of nonacid polyester polyols.For the purposes of the present invention, the used best oxygen-free Vinyl Ether of polyvalent alcohol part in poly-(ammonia ester/urea) polymkeric substance of preparation, these parts can cause the wet fastness and the poor heat resistance of final polymkeric substance.Most preferably this polyol component does not contain the compound that has any polyether moiety.
Except that the sulfonic group of sulfonated polyester polyol, the water dispersible of the urethane that the carboxylic acid group of hydroxyl alkane acid obtains increase.Hydroxyl alkane acid provides anionic group for the hard segment of polyether polyols with reduced unsaturation, and sulfonated polyester polyol provides anionic group for the soft chain segment of this polymkeric substance.Irrelevant therewith is, it is believed that by hard segment and soft chain segment to polymkeric substance provides anionic group, and this anionic group can more effectively influence the prepolymer dispersion liquid, thus only used a small amount of solvent have high heat resistance and a water-proof polymer dispersion liquid.Carboxylic acid group in the urethane that obtains also can be used as the cross-linking set with the polyfunctional aziridine reaction.The hydroxycarboxylic acid that is used to generate terminal polyurethane prepolymer for isocyanic ester is a following formula: compound:
(HO)
xR (COOH)
yWherein R represents the alkyl that contains 1 to 12 carbon atom of straight or branched, x and y represent 1 to 3 numerical value, but condition is when the x value is 1, use the trifunctional isocyanates of equivalent, and when x is 3, use the monofunctional isocyanates of equivalent, thereby make the polyurethane prepolymer that obtains keep not crosslinked basically.Being preferably x is 2, and being more preferably hydroxycarboxylic acid is the α that is expressed from the next, α-dihydroxymethyl paraffinic acid:
R wherein
1Represent hydrogen or contain high alkyl to 9 carbon atoms.These examples for compounds have 2,2-dihydroxymethyl acetate, 2,2-dimethylol propionic acid, 2,2-dimethylolpropionic acid and 2,2-dihydroxymethyl valeric acid.Preferred dihydroxymethyl paraffinic acid is 2,2-dimethylol propionic acid (DMPA).
The optional preparation end that uses is more inexpensive than sulfonated polyester polyol usually as the unsulfonated polyester polyol of isocyanate prepolymer in polyol component.That be used to generate the unsulfonated diacid of unsulfonated polyester polyol and glycol and can be aromatics or aliphatic series.The example of the diacid of unsulfonated comprises hexanodioic acid, nonane diacid, succsinic acid, suberic acid and phthalic acid.The example of the glycol of unsulfonated comprises ethylene glycol, butyleneglycol, butylene glycol, propylene glycol, neopentyl glycol, hexylene glycol, 1,4 cyclohexane dimethanol, 1,2-propylene glycol and 2-methyl isophthalic acid, ammediol.
In some instances, low molecular weight diols also can be used as the part polyol component.The low molecular weight diols that is used to generate terminal polyurethane prepolymer for isocyanic ester is an aliphatic diol, especially aklylene glycol.Its molecular weight is 60 to 400.Low molecular weight diols is C preferably
2To C
8Aklylene glycol is preferably C
3To C
6Aklylene glycol, the example of low molecular weight diols has ethylene glycol, 1, ammediol, more preferably 1, the 4-butyleneglycol (1,4-BD) and 1, the 6-hexylene glycol.The effect of this low molecular weight diols is to improve crystallization rate, the intensity when obtaining high not slaking, water tolerance and good thermotolerance.
The vulcabond that is used to generate terminal polyurethane prepolymer for isocyanic ester can be aliphatic series or aromatic diisocyanate or its mixture.The example of suitable aliphatic vulcabond has isophorone diisocyanate (IPDI), cyclopentylidene vulcabond, cyclohexylidene vulcabond, methyl cyclohexylidene vulcabond, dicyclohexyl methane diisocyanate, hexamethylene diisocyanate (HDI), dicyclohexyl methane diisocyanate (H12MDI) and tetramethylxylene diisocyanate (TMXDI).The example of suitable aromatic diisocyanate has phenylene diisocyanate, tolylene diisocyanate (TDI), Xylene Diisocyanate, two biphenylene isocyanates, naphthalene diisocyanate and '-diphenylmethane diisocyanate (MDI).
Be lower than at a small amount of boiling point 100 ℃ volatile water-soluble organic solvent (wherein acetone is preferred) in the presence of the generation polyurethane prepolymer.Its amount depends on the chain that increases of dissemination and prepolymer, makes to contain the solvent that is not more than about 5% (being preferably 0.5-3%) in the final dispersion liquid, thereby does not need solvent removal step.The example of other operable solvent comprises 1-Methyl-2-Pyrrolidone (NMP), dipropylene glycol methyl ether acetate (DPMA) and butanone (MEK).
The flash-point that contains the polyurethane dispersing liquid of different concns acetone is listed in the following table 1.
Table 1
| Acetone content (weight %) | Flash-point *(°F) | |
| ????ASTM?D-56 | ????ASTM?D-3278 | |
| ????7 | ????62 | ????77 |
| ????5 | ????75 | ????90 |
| ????3 | ????102 | ????130 |
| ????2 | ????＞140 | ????＞140 |
| ????1 | ????＞150 ** | ????＞150 ** |
*The flash-point of pure acetone is 15 °F
*Therefore water vapour can influence flash-point when the temperature that is higher than 150 in the aqueous polyurethane dispersing liquid that contains 1% (weight) acetone, and 150 expressions are with the detectable flash-point maximum value of this method.
This shows that acetone content is not more than 5%, be preferably and be not more than 3%, be preferably and be not more than at 2% o'clock, is the ideal prescription, almost or does not fully have the potential flash burn.
In polyol component, polyvalent alcohol uses with following relative weight ratio aptly: sulfonated polyester polyol/hydroxycarboxylic acid/nonacid low molecular weight diols/unsulfonated polyvalent alcohol: 10-50/0.5-5/0.1-2/0-20 is preferably 20-40/1-3/0.5-1.5/0-10.When generating polyurethane prepolymer, the NCO group is suitably 1.1-1.9 to the ratio of OH group in the polyol component in the vulcabond component, is preferably 1.2-1.6.
This prepolymer reaction back NCO content is advisable with 1-5% (weight).
Polyurethane prepolymer is in room temperature to 100 ℃, is generally to generate under 50-80 ℃ the temperature.If desired, can use as catalyzer such as tertiary amine or pink salts.
Prepolymer is dispersed in it in water after generating.In order to finish dispersion, with in the tertiary amine and at least a portion hydroxy-acid group in sulfonic group (if also not salify) and the prepolymer.This tertiary amine can add with water, neutralizes but be more preferably before adding water, and suitable is directly to add in prepolymer/solvent mixture.
Add after the tertiary amine, the acid number of dispersion liquid should be not more than 15, is preferably less than 5, and more preferably tertiary amine is in excess in acidic group, makes not have free acid when disperseing.
In aqueous liquid dispersion, terminal prepolymer for isocyanic ester increases chain and chain termination by reacting with primary amine or the functional compound of secondary amine.Therefore, final dispersive polymkeric substance is poly-(ammonia ester/urea).Used chain extension agent is preferably water-soluble cpds, because this will improve the dispersiveness of polymkeric substance final product in water.Organic diamine is preferred the use, and this is because they can improve molecular weight usually to greatest extent, and can not make poly-(ammonia ester/urea) dispersion liquid gelation.Useful chain extension agent comprises aliphatic series, alicyclic and aromatic diamine.The example of suitable diamines has 1,2-quadrol (EDA), propylene diamine, 1,4-butanediamine, piperazine, 1,4-cyclohexyl dimethyl diamines, hexamethylene-diamine (HDI), N-methyl propylene diamine, diamino-phenyl sulfone, diamino-diphenyl ether, diamino-diphenyl dimethylmethane, 2,4-diamino-6-phenyl triazine, isophorone diamine, dimer (fatty acid) yl diamines, N-isodecyl oxygen base propyl group-1, the functional diamines of 3-diaminopropanes and imidazolone.Also can use the polyamine compounds that has primary amine end group and interior secondary amine group, for example diethylenetriamine (DETA), Triethylenetetramine (TETA).Can the secondary amine by these compounds carry out in poly-(ammonia ester/urea) polymkeric substance of dispersive that some is crosslinked, but should crosslinkedly can remain low by suitable stoichiometry adjusting.
The example of useful chain terminator comprises alkamine, as thanomin, Propanolamine, butanolamine, N-Mono Methyl Ethanol Amine, N-methyl isopropyl hydramine, taurine and isethionic acid.
Composition of the present invention can by be applied to base material and when dry (or this not long ago) in dispersion liquid, add linking agent and crosslinked.Conventional polyisocyanate crosslinking agent may be inapplicable at this, because this polymkeric substance preferably has or do not have fully amino end group hardly.Yet, crosslinked can finishing by the carboxylic acid group who imports in the sulfonated polyurethane polymkeric substance via the hydroxycarboxylic acid component in the polyol component.The carboxylic acid group with can with the reaction of the linking agent of carboxylic acid reaction, this linking agent at room temperature be have active, as polyfunctional aziridine compound, zinc carbonate ammonium, zirconium carbonate or multifunctional carbodiimide compound.The add-on of typical linking agent is 1-10% (weight).
Said composition can be used for automotive industry, be about under 90-110 ℃ the activation temperature polypropylene foam and polyvinyl chloride is bonding; In space industry, under the activation temperature of room temperature to 100 ℃ with DuPontTedlar
The matrix material of PVF and phenol is bonding; In footwear are already made, with leather and SBR bonding (activation temperature 60-90 ℃), and the PVC of highly plasticized mistake from bonding or with other base material bonding (activation temperature 60-90 ℃); In wood working, with the fiberboard of PVC and intermediate density bonding (activation temperature 60-90 ℃); In book-binding, use the activation temperature of room temperature to 95 ℃ that paper and paper is bonding; In siding is made, be used for Tedlar
Bonding with PVC, timber, Wood composite material, regeneration timber and/or paper product; And be used for pet film and polypropylene, polyethylene film or aluminium or other sheet metal are carried out lamination (activation temperature 50-70 ℃).
Composition of the present invention and other aqueous-based polymers dispersion liquid (even have low pH value (pH4-7) those) have good consistency.This consistency makes composition of the present invention can be used for mixing with acrylate copolymer, epoxy polymer and vinyl acetate polymer or other vinyl polymer dispersion liquid and other polyether polyols with reduced unsaturation dispersion liquid.Can be used for footwear and glass fibre pressure-sizing processing with the water-based acrylic mixture of polymers.Can be used for automotive industry, wood working and book-binding with the mixture of vinyl-acetic ester or other vinyl polymer dispersion liquid.
The present invention is further illustrated with non-limiting example below, and except as otherwise noted, wherein used umber and percentage number average are by weight.
Embodiment
Thermotolerance
The thermotolerance of the polyurethane dispersing liquid tackiness agent of being mentioned in the following embodiments obtains by the following method: dispersion liquid is gone up at the PVC film (polyvinyl chloride film of LairdPlastics) of 10mil cleaning with (or not with) linking agent to paint initial area with the #28Mylar rod be that 2.5 * 2.5cm (1 * 1 inch) wide is the PVC film tape of 2.5cm.Treat that the tackiness agent hand feels after the drying, cuts into the rectangular of 2.5 * 5cm (1 * 2 inch) with initial p VC film.Will this initial rectangular and rectangular maintenance of PVC another 2.5 uncoated * 5cm residence time in 30 seconds under 345kPa (50psi) pressure rolling pressure with Sentinal Heat Sealer.Selected heat-sealing temperature (activation temperature) is listed in table 2.This adherend was left standstill 7 days, measure heat resisting temperature then.
Add 100g weight to each PVC adherend, be T type configuration, place the Tenney stove then.The bond area of these T type things is 1 square inch.Make these T type things experience 25 ℃ of processes that per hour heat up until 127 ℃ (260).Damage until adherend with Tenney sensor record temperature.
The abbreviation explanation
Use following abbreviation among the present invention:
Rucoflex XS-5483-55 is based on 5-sulfoisophthalic acid list sodium salt, hexanodioic acid and 1, and the sulfonated polyester polyol of 6-hexylene glycol, OH number are 49.0
The DMPA dimethylol propionic acid
1,4-BD 1, the 4-butyleneglycol
The IPDI isophorone diisocyanate
The HDI hexamethylene diisocyanate
The TMXDI tetramethylxylene diisocyanate
The EDA quadrol
The TEA triethylamine
The MEK butanone
Embodiment 1
In the presence of 18.1g acetone, make 213.8g XS-5483-55,10.05g DMPA and 11.25g 1 at 70 ℃, 4-BD and 31.08g IPDI and 47.04g HDI reaction 3 hours are with the preparation prepolymer.In this pre-polymer solution, add 6.0g TEA then, with in and hydroxy-acid group in the prepolymer.Add 554.3g water then,, and then be added in the 5.4g EDA in the 50.0g water, to generate aqueous polyurethane dispersing liquid to disperse this through the neutral prepolymer.Obtain solids content and be the 34.9%pH value and be 7.0 and acetone content be the dispersion liquid of 1.9% segmentation.
With this aqueous polyurethane dispersing liquid casting film.The film of some parts of casting at room temperature flooded 7 days with water retting 24 hours with in MEK respectively.In both cases, the film after the dipping is still very firm, shows to have good water tolerance and solvent resistance.
It is stable on heating that the results are shown in Table 2.
Embodiment 2
In the presence of 18.1g acetone, make 213.8g XS-5483,10.05g DMPA and 9.0g1 at 70 ℃, 4-BD and 25.83g IPDI and 42.84g HDI reaction 3 hours are with the preparation prepolymer.In this pre-polymer solution, add 8.0g TEA then, with in and part hydroxy-acid group in the prepolymer.Add 520.9g water,, add 4.95g EDA and 50.0g water then immediately, to generate aqueous polyurethane dispersing liquid to disperse this through the neutral prepolymer.Obtain solids content and be the 34.9%pH value and be 8.6 and acetone content be the dispersion liquid of 2.0% segmentation.
The some portions of film difference waters that made by this dispersion liquid flooded 24 hours and flooded 7 days in MEK.They are still very firm after the dipping.
It is stable on heating that the results are shown in Table 2.
Embodiment 3
The preparation method of embodiment 3 is identical with method among the embodiment 1, under stirring in the plastic containers of opening, the neutral prepolymer is dispersed in the water.Obtain solids content and be the 35.0%pH value and be 7.2 and acetone content be the dispersion liquid of 1.0% segmentation.
The some portions of film difference waters that made by this dispersion liquid flooded 24 hours or flooded 7 days in MEK.They are still very firm after the dipping.
It is stable on heating that the results are shown in Table 2.
Embodiment 4 (reference examples)
In this embodiment, by based on Dispercoll KA-8464 (the aqueous polyurethane dispersing liquid product of Bayer Corporation), the HDI of sulfonated aliphatic diamines and IPDI (according to United States Patent (USP) 4,870,129, make with the 40-80% acetone method) casting film.After at room temperature flooding 24 hours in the water, the film that is made by this dispersion liquid becomes very weak, and loses proof stress fully.To in MEK, flood 7 days by another film that this dispersion liquid makes, fully dissolving.It is stable on heating that the results are shown in Table 2.
Table 2. heat resisting temperature (°F) (PVC/PVC)
| Activation temperature (°F) | ????125 | ????150 | ????175 | ????200 |
| Embodiment 1 | ????＞260 | ????＞260 | ????＞260 | ????＞260 |
| Embodiment 2 | ????242 | ????242 | ????247 | ????242 |
| Embodiment 3 | ????＞260 | ????＞260 | ????＞260 | ????＞260 |
| Embodiment 4 | ????199 | ????220 | ????221 | ????223 |
Embodiment 5
In the presence of 4.24kg acetone, make 45.39kg XS-5483,2.13kg DMPA and 2.39kg 1 at 70 ℃, 4-BD and 6.60kg IPDI and 9.99kg HDI reaction 2.5 hours are with the preparation prepolymer.In this prepolymer, add 1.27kg TEA then, with in and hydroxy-acid group in the prepolymer.This neutralizing agent was mixed 15 minutes.
Be used in the method for continuously stirring in the pipeline, this prepolymer is dispersed in the water.The mixing tank that is used to obtain dispersion liquid is by Tokushu Kika Kogyo Co., the T.K.Homomic Line Flow100S that Ltd. makes.Prepolymer is added in this mixing tank under 80 ℃ temperature by the speed of toothed gear pump with 3.60kg/min.Speed with 6.40kg/min adds water in this mixing tank under 60 ℃ temperature.Average retention time in mixing tank remained on 61 seconds, and stir speed (S.S.) is 3600RPMs.
This dispersion liquid is transferred in the refining container that turbine type agitator is housed, with 5 to 10min
-1Rate loop.The solution of EDA in water of adding 9.78% in this refining container.Add after dispersion liquid and two amine aqueous solutions, the purified dispersion liquid was mixed 30 minutes under 60 ℃ temperature.
Obtaining solids content is 31.38%, and the pH value is 7.9, and mean particle size is that 189nm and viscosity are the aqueous polyurethane dispersing liquid of the segmentation of 36cps.
The foregoing description and narration are illustrative, rather than limit.For a person skilled in the art, can make many variations and alternative to these embodiment and narration.All these substitute and change and should be included in the scope of appended claim.The person skilled in the art can expect the method with the specific examples equivalence described in the present invention, and these equivalent methods also should be included in the scope of appended claim.
Claims (15)
1. generate the method for poly-(ammonia ester/urea) the prepolymer dispersion liquid of stabilized aqueous anionic, this dispersion liquid contains the volatile solvent of 1.1 to 5% (weight) of dispersion liquid, this method comprises: be not higher than under 100 ℃ the temperature, with respect to final dispersion liquid weight be not more than 5% water-soluble volatile organic solvent in the presence of, make the polyisocyanate component and the polyol component reaction that contain two isocyanos, generating end is the polyurethane prepolymer of isocyano, and this polyol component then has carboxylic acid group and sulfonic group;
With this end is that the prepolymer of isocyano is dispersed in the aqueous medium;
Make described dispersive terminal, generate described poly-(ammonia ester/urea) polymkeric substance for the polyurethane prepolymer of isocyano and functional chain extension agent of at least a amine or the reaction of chain terminator compound;
Before described prepolymer and the functional chain extension agent of described amine or chain terminator reaction or simultaneously, with in alkali metal hydroxide or the tertiary amine and described end be the carboxylic acid group and the sulfonic group of the prepolymer of isocyano;
Wherein, there is not the solvent distilation steps in the described method.
2. the method for claim 1, the consumption that it is characterized in that described solvent is for respect to about 1.1 to 3% of final dispersion liquid weight.
3. the method for claim 1 is characterized in that polyhydroxy component comprises at least a sulfonated polyester, and the feature of this sulfonated polyester is that number-average molecular weight is about 500 to 10,000, and melt temperature is about 10 ℃ to 100 ℃; And the hydroxycarboxylic acid of at least a following formula:
(HO)
xR (COOH)
yWherein R represents the alkyl that contains 1 to 12 carbon atom of straight or branched, x and y represent 1 to 3 numerical value, but condition is when the x value is 1, in polyisocyanate component, use the trifunctional isocyanates of equivalent, and when x is 3, use the monofunctional isocyanates of equivalent, thereby make the polyurethane prepolymer that obtains keep not crosslinked basically.
4. method as claimed in claim 5 is characterized in that hydroxycarboxylic acid is the α that is expressed from the next, α-dihydroxymethyl paraffinic acid:
R wherein
1Represent hydrogen or contain high alkyl to 9 carbon atoms.
5. method as claimed in claim 7 is characterized in that hydroxycarboxylic acid is 2, the 2-dimethylol propionic acid.
6. method as claimed in claim 6 is characterized in that described polyol component comprises that also molecular weight is about 60 to 400 nonacid glycol.
7. as claim 1 or 5 described methods, it is characterized in that described sulfonated polyester polyol is the polyester of sulfonation dicarboxylic acid or sulfonation diol polyester, unsulfonated dicarboxylic acid and unsulfonated glycol.
8. as method as described in the claim 7, it is characterized in that sulfonation diacid or sulfonation glycol are selected from sulfoisophthalic acid, sulfo-succinic acid, 1,4-dihydroxyl fourth sulfonic acid and succinic aldehyde bisulfite disodium.
9. as claim 1 or 5 described methods, it is characterized in that sulfonated polyester polyol is 5-sulfoisophthalic acid one sodium salt, 1, the polyester of 6-hexylene glycol and hexanodioic acid.
10. the method for claim 1 is characterized in that polyisocyanate component comprises hexamethylene diisocyanate (HDI).
11. method as claimed in claim 11, it is characterized in that polymeric polyisocyanate is the mixture of HDI and second kind of vulcabond, described second kind of vulcabond is selected from isophorone diisocyanate (IPDI), the cyclopentylidene vulcabond, the cyclohexylidene vulcabond, methyl cyclohexylidene vulcabond, dicyclohexyl methane diisocyanate, dicyclohexyl methane diisocyanate (H12MDI), tetramethylxylene diisocyanate (TMXDI), phenylene diisocyanate, tolylene diisocyanate (TDI), Xylene Diisocyanate, two biphenylene isocyanates, naphthalene diisocyanate and '-diphenylmethane diisocyanate (MDI).
12. the method for claim 1, it is characterized in that the functional chain extension agent of described amine is selected from 1,2-quadrol (EDA), propylene diamine, 1, the 4-butanediamine, piperazine, 1,4-cyclohexyl dimethyl diamines, hexamethylene-diamine (HDA), N-methyl propylene diamine, the diamino-phenyl sulfone, diamino-diphenyl ether, the diamino-diphenyl dimethylmethane, 2,4-diamino-6-phenyl triazine, isophorone diamine, the dimer (fatty acid) yl diamines, N-isodecyl oxygen base propyl group-1, the 3-diaminopropanes, the functional diamines of imidazolone, diethylenetriamine (DETA), Triethylenetetramine (TETA), and composition thereof.
13. the method for claim 1 is characterized in that described end is the prepolymer of isocyano and the mixture reaction of functional chain extender compound of at least a amine and at least a chain terminator compound.
14. method as claimed in claim 13 is characterized in that described chain extension agent is selected from 1, diethylenetriamine, and composition thereof, described chain terminator is a thanomin.
15., it is characterized in that not containing in the described polyol component compound of band vinyloxy group ethylidene group as claim 1 or 6 described methods.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 96190930 CN1161049A (en) | 1995-09-15 | 1996-09-11 | Reduced solvent process for preparation of aqueous polyurethane dispersions with improved heat and solvent resistance |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US08/528,936 | 1995-09-15 | ||
| CN 96190930 CN1161049A (en) | 1995-09-15 | 1996-09-11 | Reduced solvent process for preparation of aqueous polyurethane dispersions with improved heat and solvent resistance |
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| Publication Number | Publication Date |
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| CN1161049A true CN1161049A (en) | 1997-10-01 |
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|---|---|---|---|
| CN 96190930 Pending CN1161049A (en) | 1995-09-15 | 1996-09-11 | Reduced solvent process for preparation of aqueous polyurethane dispersions with improved heat and solvent resistance |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100354329C (en) * | 2003-07-30 | 2007-12-12 | 三井武田化学株式会社 | Polyurethane resin,water polyurethane resin,hydrophilic modifier,moisture resin and process for producing polyurethaneresin |
| CN100480349C (en) * | 2007-01-05 | 2009-04-22 | 华南理工大学 | Method for preparing modified aqueous adhesion agent of polyurethane |
| TWI500756B (en) * | 2012-07-17 | 2015-09-21 | ||
| CN107383332A (en) * | 2017-08-22 | 2017-11-24 | 广东电网有限责任公司电力科学研究院 | A kind of polyether polyols and its preparation method and application |
| CN114621416A (en) * | 2020-12-09 | 2022-06-14 | 万华化学集团股份有限公司 | Aqueous polyurethane dispersion, preparation method and application thereof in two-component spray glue |
-
1996
- 1996-09-11 CN CN 96190930 patent/CN1161049A/en active Pending
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100354329C (en) * | 2003-07-30 | 2007-12-12 | 三井武田化学株式会社 | Polyurethane resin,water polyurethane resin,hydrophilic modifier,moisture resin and process for producing polyurethaneresin |
| CN100480349C (en) * | 2007-01-05 | 2009-04-22 | 华南理工大学 | Method for preparing modified aqueous adhesion agent of polyurethane |
| TWI500756B (en) * | 2012-07-17 | 2015-09-21 | ||
| CN107383332A (en) * | 2017-08-22 | 2017-11-24 | 广东电网有限责任公司电力科学研究院 | A kind of polyether polyols and its preparation method and application |
| US11053345B2 (en) | 2017-08-22 | 2021-07-06 | Electric Power Research Institute Of Guangdong Power Grid Co., Ltd. | Polyurethane polymer, method for preparing the same and use thereof |
| CN114621416A (en) * | 2020-12-09 | 2022-06-14 | 万华化学集团股份有限公司 | Aqueous polyurethane dispersion, preparation method and application thereof in two-component spray glue |
| CN114621416B (en) * | 2020-12-09 | 2023-08-11 | 万华化学集团股份有限公司 | Aqueous polyurethane dispersion, preparation method and application thereof in double-component spray adhesive |
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