CN102358777B - Water-based polyurethane elastomer emulsion, and preparation method and application thereof - Google Patents
Water-based polyurethane elastomer emulsion, and preparation method and application thereof Download PDFInfo
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Abstract
The invention discloses water-based polyurethane elastomer emulsion, and a preparation method and application thereof. The preparation method comprises the following steps of: (1) mixing organic diisocyanate, polyol with the molecular weight of 600-4,000, hydroxy carboxylic acid and an organotin-containing catalyst, and reacting at the temperature of between 60 and 90DEG C for 2 to 5 hours; (2) adding an active hydrogen-containing chain extender, and continuously reacting until a theoretical value of residual NCO percent is reached; (3) adding a polyhydroxy chain terminator to make the residual NCO percent equal to 0; (4) adding organic amine for neutralization reaction at the temperature of between 30 and 55DEG C, wherein the neutralization degree is 70 to 100 molar percent of hydroxy carboxylic acid; and (5) adding a crosslinking agent and water to obtain aqueous dispersion, namely the water-based polyurethane elastomer emulsion. Products prepared from the emulsion have low modulus, weak bondage feel, and high resistance to yellowing, and can be stably stored.
Description
Technical field
The product that the present invention relates to a kind of aqueous polyurethane elastic precursor emulsion, preparation method and make by this elastomerics.
Background technology
One all is to use the natural rubber latex that collects from para ruber to process for common medical gloves; It has a series of good performances; Like higher inherent elasticity; And the sensitivity sense of good clawing thing article, and as the together effective barrier of pathogenic agent, germ and bacterium, the natural rubber latex gloves equally also can provide effective provide protection.
But some are worn the people who uses the medical gloves of being processed by natural rubber latex and anaphylaxis once occurred, and are serious even produce anaphylactic shock.The reason that causes this reaction and shock is to contain protein in the natural rubber latex.Therefore, the personnel that are engaged in sanitary work begin searching and replace natural rubber latex with synthetic materials, to alleviate the irritated and shock risk of wearing with occurring in the gloves process.The synthetic materials of replaced natural rubber latex commonly used has Vilaterm, nitrile rubber and styrene-butadiene latex.But all there are uncomfortable, the shortcomings such as ventilation property is not good, biocompatibility difference of wearing these materials in one.
Urethane (PU) elastomerics is used for the preparation of protective gloves always by expectation so far, and wherein aqueous polyurethane need not a large amount of organic solvents because of it, and environmental hazard is little and receive much concern.But mostly present business-like water-based PU is linear product or lightly crosslinked product, though have excellent elasticity, intensity is relatively poor, prepares a kind of thermoplastic polyurethane gloves like Chinese patent CN1380358A, and its elongation is good, but tensile strength is not high.
One can carry out modification through crosslinked mode.But make emulsion dispersion inhomogeneous easily through preceding crosslinked mode, the PU intergranular does not merge, and causes gloves generation of cracks when drying and forming-film; Goods after the film forming can't present PU high-performance originally, and crosslinked mode prepares moulding behind therefore many employing high temperature, and method commonly used is to adopt polyamines class material to make linking agent; Utilize quadrol to be chainextender like Chinese patent CN 1807481; Dry film forming down at 90 ℃, but the polyamines taste is bigger, isocyanate groups and polyamine substance reaction belong to diffusion reaction; Can not guarantee that all amine substances all react completely, remain in the polyamines Diazolidinyl Urea in the goods.And can not guarantee polyamines class material participate in fully the reaction, in a single day remaining quadrol retains in the goods, Diazolidinyl Urea.Chinese patent CN 1329624 carries out end-blocking to the part isocyanate groups earlier, uses the polyamine chain extension again, and preparation contains the dispersion liquid of blocked isocyanate groups; And then the high temperature film forming, polyamine makes polyamine react completely as chainextender, linking agent and part neutralizing agent; But the use of polyamines class material can cause introducing a large amount of polyurethane-urea groups equally; Make that the goods modulus is excessive, dress uncomfortablely that tight sense is strong.Chinese patent CN1774459 utilizes water to make chainextender, does not add amine substance and carries out chain extension, does not add linking agent or solidifying agent, though controlled the polyurethane-urea group content, crosslinking degree is low, products made thereby fracture and tensile strength one
In addition, Chinese patent CN 1351620, CN 1942439 and CN 1554685 all are through adding the dispersion effect that tensio-active agent obtains water-based, but the existence meeting of tensio-active agent has a negative impact to the final performance of product.
Summary of the invention
The object of the present invention is to provide a kind of aqueous polyurethane elastic precursor emulsion and preparation method and application, to overcome intensity difference in the prior art, the high deficiency of cross-linking modified back modulus.
The preparation method of aqueous polyurethane elastic precursor emulsion of the present invention comprises the steps:
(1) with organic diisocyanate, molecular weight is 600～4000 polyol, hydroxyl carboxylic acid and organic tin catalyst mix, at 60～90 ℃ of reaction 2～5h; Preferred 70～80 ℃ of reaction 3～4h;
(2) add chainextender, continue reaction to the theoretical value that reaches remaining NCO% with active hydrogen;
(3) add poly-hydroxy class chain terminator, making remaining NCO% content is 0;
(4) add organic amine down at 30～55 ℃ and carry out neutralization reaction, degree of neutralization is 70%～100% of a hydroxyl carboxylic acid molar weight, preferred 80%～90%;
(5) add linking agent and water, obtain a kind of aqueous liquid dispersion, be aqueous polyurethane elastic precursor emulsion of the present invention;
The parts by weight of each component are following:
Preferably, the parts by weight of each component are following:
The weight consumption of organotin catalysts is 0.05～0.2% of an organic diisocyanate;
Described organic diisocyanate is fat (ring) family or aromatic isocyanate; Can be selected from isophorone diisocyanate, hexamethylene diisocyanate, 4, more than one in 4 '-diphenylmethanediisocyanate, dicyclohexyl methane diisocyanate, tolylene diisocyanate or the xylylene diisocyanate; The isocyanic ester of preferred fat (ring) family;
Described molecular weight is that 600～4000 polyol is a macromolecular polyol; Can be in polyester type or the polyether-type more than one, like polyoxyethylene enediol, polyoxypropyleneglycol, polytetrahydrofuran diol, polycaprolactone divalent alcohol, PCDL or poly adipate succinic acid ester; Preferred molecular weight is 1000～2000 macromolecular polyol;
Described hydroxyl carboxylic acid is selected from more than one in dimethylol propionic acid or the dimethylolpropionic acid;
Described chainextender with active hydrogen is selected from 1, more than one in 4-butyleneglycol, 1,3 butylene glycol, terepthaloyl moietie, Ucar 35 or the glycol ether;
Described poly-hydroxy class chain terminator is the poly-hydroxy class material that comprises at least three oh groups, contains the primary amine of at least two hydroxyls or the material of secondary amine group, can be selected from TriMethylolPropane(TMP), glycerine or the diethylolamine one or both;
Described linking agent is a blocked polyisocyanates class material; Comprise at least two end capped isocyanate groups; Its deblocking temperature is between 100～150 ℃; Its end-capping reagent can be acetoxime, Diacetylmonoxime, 3; 5-dimethyl pyrazole, 1; 2; 4-triazole, ethyl malonate, described linking agent does not require wetting ability, can adopt commercially produced product; Like Bayer AG (Bayer) trade mark is BL3175SN, BL4265SN in Desmodur
series, and Baxenden Chemtura Company (Baxenden Chemicals) trade mark is BI7950, BI7987, the BI7963 in Trixene
series.
Described organotin catalysts is selected from dibutyl tin dilaurate or stannous octoate;
Described organic amine is selected from primary, the second month in a season or tertiary amine, and the preferred substituted tertiary amine of trialkyl is like triethylamine, Trimethylamine 99 or triisopropylamine etc.;
The water yield that adds, the solid content that makes described based polyurethane elastomer emulsions is between 10～50wt%; Preferably between 15～45wt%, but can dispersion-s be diluted to any required minimum solid content usually;
Aqueous polyurethane elastic precursor emulsion ability stable existence of the present invention is more than 6 months, and its particle diameter is between 0.01 to 0.6 micron;
Aqueous polyurethane elastic precursor emulsion of the present invention can carry out moulding through prior art, and the dip forming like US5088125 patent documentation report immerses mould in the peptizer liquid, and this coagulant solution is generally the CaCl that massfraction is 10～20wt%
2Ca (NO with 0～10wt%
3)
2Mixed solution is dried 3～5min with this mould at 80～100 ℃ subsequently, this mould is immersed in the polyurethane aqueous dispersion liquid that is preheating to 40～50 ℃ again; Stop 2～3s, take out and in 50～60 ℃ of down dry 15～25min, salt lixiviate in 30～70 ℃ water again; Taking-up is at 50～60 ℃ of down dry 5～10min; Continuation is at 100～150 ℃ of drying 5～30min, and the demoulding obtains the film forming elastomeric article then, said film forming elastomeric article such as gloves, fingerstall, condom or organ bag;
The method of manufacture of aqueous polyurethane elastic body film-forming products of the present invention, its mould comprises pottery, metal or mould of plastics.
The film-forming products of the present invention's preparation; Penetrate easily or deviate from, feel is good when dressing, tensile strength and breaking tenacity are between 15～28MPa, elongation at break is between 600～1200%; 100% stretches modulus surely between 0.8～2.0MPa; 300% stretches modulus surely between 1.9～3.9MPa, and 500% stretches modulus surely between 3.0～6.8MPa, has excellent mechanical property.
The effect of invention
The invention has the advantages that:
(i) do not use polyamine as chainextender, it is remaining not contain the pungency amine in the gained dispersion liquid;
(ii) do not contain urea groups or content extremely low (less than 1wt%) basically, make that the goods modulus is low, a little less than the constraint sense, anti-flavescence property is good simultaneously;
(iii) the hydroxyl carboxylic acid need not extra interpolation N-first class pyrrolidone (NMP) solvent;
The blocked polyisocyanates that (iv) uses does not require wetting ability, and nonaqueous blocked polyisocyanates added before adding emulsifying water, can when emulsification, be coated by emulsion under fully stirring; Can carry out crosslinkedly through heating, sufficient intensity is provided, can also guarantee stably stored; The blocked polyisocyanates of water-based then can add before emulsification, also can add with water.
Concrete embodiment
Below in conjunction with embodiment the present invention is further specified, but do not limit the scope of the invention.
Embodiment 1
150.6g polyoxypropyleneglycol PPG-2000 (molecular weight 2000) 120 ℃ ,-0.96MPa under vacuum hydro-extraction 2h, 67.87g isophorone diisocyanate, 17.21g dimethylol propionic acid and 0.136g dibutyl tin dilaurate at 80 ℃ of reaction 2h down, add 8.44 g1, the 4-butyleneglycol carries out chain extension; Recording NCO% is 0.27 (theoretical value is 0.28), adds the 1.72g diethylolamine, to NCO% be 0; Be cooled to 55 ℃, add in the 10.39g triethylamine and 1h, add 14.84g BL3175 (Bayer AG's product; Be a kind of non-aqueous blocked polyisocyanates; Solid content 75wt%, wherein end-blocking NCO content is 8.33wt%), stir adding 620.1g deionized water down; Stir 3h, promptly obtain the aqueous polyurethane emulsion that solid content is 30wt%.
Mould is immersed in the peptizer liquid, and this coagulant solution is that massfraction is the CaCl of 12wt%
2Ca (NO with 3wt%
3)
2Mixed aqueous solution.Taking out mould immerses this mould in the polyurethane aqueous dispersion that is preheating to 45 ℃ after 3 minutes 100 ℃ of oven dry and stops 2～3s; Take out back dry 20min under 60 ℃, salt lixiviate in 50 ℃ water is again taken out and dry 6min under 60 ℃; Again 150 ℃ of dry 20min, demouldings then.The resulting product performance is seen table 1.
Embodiment 2
200.67g polyoxypropyleneglycol PPG-1000 120 ℃ ,-0.96MPa under vacuum hydro-extraction 2h, 126.63g isophorone diisocyanate, 24.04g dimethylol propionic acid and 0.1266g dibutyl tin dilaurate at 75 ℃ of reaction 3h down, add 16.13g1, the 4-butyleneglycol carries out chain extension; Recording NCO% is 0.24 (theoretical value is 0.25), adds the 2.31g diethylolamine, to NCO% be 0; Be cooled to 50 ℃, add in the 16.32g triethylamine and 1h, add 8.93g BI7963 (Ba Xindun chemical company product; A kind of non-aqueous blocked polyisocyanates; Solid content 70wt%, wherein end-blocking NCO content is 6.16wt%), under agitation add 86.12g BI7987 (a kind of water-based blocked polyisocyanates; Solid content 40wt%; Wherein end-blocking NCO content is 1.8wt%) and the mixed solution of 733.9g deionized water, stir 3h, promptly obtain the aqueous polyurethane emulsion that solid content is 35wt%.
Product preparation method is with embodiment 1, and difference is at last 130 ℃ of dry 25min, demouldings then.The resulting product performance is seen table 1.
Embodiment 3
160.4g polyoxypropyleneglycol PPG-2000 and 20.05g W 166 PPG-1000 120 ℃ ,-0.96MPa under vacuum hydro-extraction 2h, 96.80g isophorone diisocyanate, 25.39g dimethylol propionic acid and 0.1452g stannous octoate at 80 ℃ of reaction 2h down, add 12.23g 1, the 4-butyleneglycol carries out chain extension; Recording NCO% is 0.24 (theoretical value is 0.25), adds the 2.54g TriMethylolPropane(TMP), to NCO% be 0; Be cooled to 55 ℃; Add in the 16.28g triethylamine and 1h, add 31.29g BI7963, stir adding 425.2g deionized water down; Stir 3h, promptly obtain the aqueous polyurethane emulsion that solid content is 45wt%.
Product preparation method is with embodiment 1, and difference is at last 125 ℃ of dry 25min, demouldings then.The resulting product performance is seen table 1.
Embodiment 4
152.3g polyoxypropyleneglycol PPG-1000 120 ℃ ,-0.96MPa under vacuum hydro-extraction 2h, 181.88g4,4 '-diphenylmethanediisocyanate, 40.50g dimethylol propionic acid and 0.1273g dibutyl tin dilaurate add the 27.49g glycol ether and carry out chain extension at 75 ℃ of reaction 3h down; Recording NCO% is 0.28 (theoretical value is 0.28), adds the 2.83g diethylolamine, to NCO% be 0; Be cooled to 50 ℃; Add in the 21.39g triethylamine and 1h, add 24.86g BL3175, stir adding 2515.7g deionized water down; Stir 3h, promptly obtain the aqueous polyurethane emulsion that solid content is 15wt%.
Product preparation method is with embodiment 1.The resulting product performance is seen table 1.
Embodiment 5
177.76g polyoxypropyleneglycol PPG-2000 120 ℃ ,-0.96MPa under vacuum hydro-extraction 2h, 38.53g hexamethylene diisocyanate, 9.46g dimethylolpropionic acid and 0.0578g dibutyl tin dilaurate at 80 ℃ of reaction 3h down, add 4.62g terepthaloyl moietie and carry out chain extension, recording NCO% is 0.07 (theoretical value is 0.07); Add 0.35g glycerine; To NCO% be 0, be cooled to 55 ℃, add in the 8.88g Tributylamine and 1h; Add 4.10g=BI7963; Stir adding 449.1g deionized water down, stir 3h, promptly obtain the aqueous polyurethane emulsion that solid content is 35wt%.
Product preparation method is with embodiment 3.The resulting product performance is seen table 1.
Embodiment 6
102.2g polyoxypropyleneglycol PPG-3000 and 31.08g polyoxypropyleneglycol PPG-600 120 ℃ ,-0.96MPa under vacuum hydro-extraction 2h, 85.81g tolylene diisocyanate (TDI-80/20, wherein 2,4-TDI accounts for 80wt%), 32.80g dimethylolpropionic acid and 0.0968g stannous octoate at 80 ℃ of reaction 2h down; Add the 17.36g glycol ether and carry out chain extension; Recording NCO% is 0.46 (theoretical value is 0.48), adds the 4.10g TriMethylolPropane(TMP), to NCO% be 0; Be cooled to 55 ℃; Add in the 41.04g Tributylamine and 1h, add 41.66g BI7963, stir adding 331.1g deionized water down; Stir 3h, promptly obtain the aqueous polyurethane emulsion that solid content is 50wt%.
Product preparation method is with embodiment 3.The resulting product performance is seen table 1.
Embodiment 7
102.2g polyoxypropyleneglycol PPG-3000 and 31.08g polyoxypropyleneglycol PPG-600 120 ℃ ,-0.96MPa under vacuum hydro-extraction 2h, 85.81g tolylene diisocyanate (TDI-80/20; Wherein 2,4-TDI accounts for 80wt%), 32.80g dimethylolpropionic acid and 0.0968g stannous octoate be at 80 ℃ of reaction 2h down, add the 17.36g glycol ether and carry out chain extension; Recording NCO% is 0.46 (theoretical value is 0.48); Add the 4.10g TriMethylolPropane(TMP), to NCO% be 0, be cooled to 55 ℃; Add in the 41.04g Tributylamine and 1h; Stir the mixed solution that adds 142.60g BI7987 and 471.6g deionized water down, stir 3h, obtain the aqueous polyurethane emulsion that solid content is 40wt%.
Product preparation method is with embodiment 6.The resulting product performance is seen table 1.
Comparative Examples 1
90.05g polyoxypropyleneglycol (molecular weight 2000,120 ℃ ,-0.96MPa under vacuum hydro-extraction 2h), 44.14g isophorone diisocyanate, 10.61g dimethylol propionic acid and 0.0441g stannous octoate be at 80 ℃ of reaction 3h down, adds 6.71g1; 4 butyleneglycols carry out chain extension, when reacting when NCO% is 0, are cooled to 55 ℃; Add in the 6.40g triethylamine and 1h; Stir adding 368.5g deionized water down, stir 3h, obtain the aqueous polyurethane emulsion of 30wt%.
Product preparation method is with embodiment 1, and difference is at last 120 ℃ of dry 15min, demouldings then.The resulting product performance is seen table 1.
Comparative Examples 2
81.10g polyoxypropyleneglycol (molecular weight 1000; 120 ℃ ,-0.96MPa under vacuum hydro-extraction 2h), 53.58g isophorone diisocyanate, 10.69g dimethylol propionic acid and 0.0536g stannous octoate be at 80 ℃ of reaction 2h down, react to NCO% be 4.63 o'clock (theoretical value is 4.64), be cooled to 55 ℃; Add in the 6.45g triethylamine and 1h; Add the 364.9g deionized water that contains the 4.55g quadrol under stirring again, stir 3h, obtain the aqueous polyurethane emulsion that solid content is 30wt%.
Product preparation method is with Comparative Examples 1, the demoulding then.The resulting product performance is seen table 1.
The applied mechanics performance of the made aqueous polyurethane elastic body of table 1
Claims (9)
1. the preparation method of aqueous polyurethane elastic precursor emulsion is characterized in that, comprises the steps:
(1) with organic diisocyanate, molecular weight is 600 ~ 4000 polyol, hydroxyl carboxylic acid and organic tin catalyst mix, at 60 ~ 90 ℃ of reaction 2 ~ 5h;
(2) add chainextender, continue reaction to the theoretical value that reaches remaining NCO% with active hydrogen;
(3) add poly-hydroxy class chain terminator, making remaining NCO% content is 0;
(4) add organic amine down at 30～55 ℃ and carry out neutralization reaction, degree of neutralization is 70% ~ 100% of a hydroxyl carboxylic acid molar weight;
(5) add linking agent and water, obtain a kind of aqueous liquid dispersion, be described aqueous polyurethane elastic precursor emulsion, the parts by weight of each component are following:
The weight consumption of organotin catalysts is 0.05～0.2% of an organic diisocyanate.
2. method according to claim 1 is characterized in that, in the step (1), and 70 ~ 80 ℃ of reaction 3 ~ 4h.
3. method according to claim 1 is characterized in that, in the step (4), degree of neutralization is 80% ~ 90% of a hydroxyl carboxylic acid molar weight.
4. method according to claim 1 is characterized in that, the parts by weight of each component are following:
5. method according to claim 4; It is characterized in that; Described organic diisocyanate is selected from isophorone diisocyanate, hexamethylene diisocyanate, 4, more than one in 4 '-diphenylmethanediisocyanate, dicyclohexyl methane diisocyanate, tolylene diisocyanate or the xylylene diisocyanate;
Described molecular weight is that 600 ~ 4000 polyol is a macromolecular polyol, is polyoxyethylene enediol, polyoxypropyleneglycol, polytetrahydrofuran diol, polycaprolactone divalent alcohol, PCDL or poly adipate succinic acid ester;
Described hydroxyl carboxylic acid is selected from more than one in dimethylol propionic acid or the dimethylolpropionic acid;
Described chainextender with active hydrogen is selected from 1, more than one in 4-butyleneglycol, 1,3 butylene glycol, terepthaloyl moietie, Ucar 35 or the glycol ether;
Described poly-hydroxy class chain terminator is to comprise in the material of the poly-hydroxy class material of at least three oh groups, the primary amine that contains at least two hydroxyls or secondary amine group one or both;
Described linking agent is a blocked polyisocyanates class material, comprises at least two end capped isocyanate groups, and its deblocking temperature is between 100 ~ 150 ℃; Its end-capping reagent is acetoxime, Diacetylmonoxime, 3; 5-dimethyl pyrazole, 1,2,4-triazole or ethyl malonate;
Described organotin catalysts is selected from dibutyl tin dilaurate or stannous octoate;
Described organic amine is selected from primary, the second month in a season or tertiary amine.
6. method according to claim 4 is characterized in that, described poly-hydroxy class chain terminator is selected from one or both in TriMethylolPropane(TMP), glycerine or the diethylolamine.
7. the aqueous polyurethane elastic precursor emulsion for preparing according to each said method of claim 1～6.
8. the application of aqueous polyurethane elastic precursor emulsion according to claim 7 is used to be prepared into film elasticity system article.
9. adopt the film forming elastomeric article of the described aqueous polyurethane elastic precursor emulsion preparation of claim 7.
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