CN108676144B - Water-proof moisture-permeable aqueous polyurethane dispersoid and preparation method and application thereof - Google Patents
Water-proof moisture-permeable aqueous polyurethane dispersoid and preparation method and application thereof Download PDFInfo
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- CN108676144B CN108676144B CN201810569770.6A CN201810569770A CN108676144B CN 108676144 B CN108676144 B CN 108676144B CN 201810569770 A CN201810569770 A CN 201810569770A CN 108676144 B CN108676144 B CN 108676144B
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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
- C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
- C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
- C08G18/6666—Compounds of group C08G18/48 or C08G18/52
- C08G18/667—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38
- C08G18/6674—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3203
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- 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
- C08G18/30—Low-molecular-weight compounds
- C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
- C08G18/3203—Polyhydroxy compounds
- C08G18/3206—Polyhydroxy compounds aliphatic
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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
- C08G18/30—Low-molecular-weight compounds
- C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
- C08G18/3225—Polyamines
- C08G18/3228—Polyamines acyclic
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- 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
- C08G18/48—Polyethers
- C08G18/4825—Polyethers containing two hydroxy groups
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- C08G18/00—Polymeric products of isocyanates or isothiocyanates
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- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
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- C08G18/48—Polyethers
- C08G18/4833—Polyethers containing oxyethylene units
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- 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
- C08G18/48—Polyethers
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- 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
- C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
- C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
- C08G18/6666—Compounds of group C08G18/48 or C08G18/52
- C08G18/667—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38
- C08G18/6674—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3203
- C08G18/6677—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3203 having at least three hydroxy groups
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- 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
- C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
- C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
- C08G18/6666—Compounds of group C08G18/48 or C08G18/52
- C08G18/667—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38
- C08G18/6681—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/32 or C08G18/3271 and/or polyamines of C08G18/38
- C08G18/6685—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/32 or C08G18/3271 and/or polyamines of C08G18/38 with compounds of group C08G18/3225 or polyamines of C08G18/38
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
- C09D175/04—Polyurethanes
- C09D175/08—Polyurethanes from polyethers
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
- D06N3/00—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof
- D06N3/12—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof with macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. gelatine proteins
- D06N3/14—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof with macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. gelatine proteins with polyurethanes
- D06N3/146—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof with macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. gelatine proteins with polyurethanes characterised by the macromolecular diols used
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Abstract
The invention provides a water-based polyurethane dispersion for a waterproof and moisture-permeable fabric coating, and a preparation method and application thereof. According to the aqueous polyurethane dispersion, a strong hydrophilic hydroxyl side group aggregated into clusters is introduced into a main chain through a special micromolecule chain extender, and the aqueous polyurethane dispersion and a weak hydrophilic ether bond on a branched chain form a synergistic effect, so that the one-way movement of water in a fabric from inside to outside is facilitated, the problem of mutual restriction of water pressure and moisture permeability is balanced, and meanwhile, good waterproof and moisture permeability performances are obtained.
Description
Technical Field
The invention belongs to the field of waterborne polyurethane materials, and particularly relates to a waterproof moisture-permeable waterborne polyurethane dispersion as well as a preparation method and application thereof.
Background
With the improvement of living standard of people, outdoor exercises are increased, the requirements on outdoor exercise clothes are higher and higher, and the water resistance and moisture permeability are a great trend. The polyurethane resin is a commonly used waterproof moisture-permeable resin at present, but the existing waterproof moisture-permeable polyurethane resin also has the problem of poor moisture permeability.
The research shows that the perspiration volume of a person during activity is 11500g/24h, and the fabric needs about 4000g/m2The corresponding moisture permeability of 24 h; meanwhile, in order to achieve the ideal waterproof effect, the hydrostatic pressure of the fabric is required to be not lower than 5.58 KPa. The increase of the hydrostatic pressure resistance value of the fabric often causes the reduction of the moisture permeability. Therefore, on the premise of ensuring that the coated fabric has certain hydrostatic pressure resistance, the improvement of moisture permeability becomes the focus of attention of related researchers. Researchers at home and abroad prepare the waterproof moisture-permeable waterborne polyurethane coating agent, in particular the low-VOC waterborne polyurethane coating agent, by introducing hydrophilic chain segments or groups and other technologies on molecular chains, but the introduction of the hydrophilic chain segments or groups can also bring preventionThe water performance is reduced.
US6613867 discloses a method for preparing moisture permeable waterborne polyurethane, the component a is bifunctional isocyanate, the component B is ethylene glycol, diethylene glycol, 1, 3-propylene glycol, the component C is diol, diamine, amino alcohol with molecular weight less than 400, the component D is ethoxy alcohol or ethoxy/propoxy copolyol. US2011312237A1 discloses a preparation method of thermoplastic aqueous polyurethane resin with moisture permeability, which adopts copolyol and polyethoxy diol as soft blocks (wherein the copolyol is a copolymer of ethoxy and C3-C6 alkoxy), and the polyethoxy diol and the copolyol in the two soft blocks are 70-97% and 3-30%. The aqueous polyurethane using polyethylene glycol as the breathable layer has the disadvantages that the prepared emulsion has high viscosity and poor construction process, and the resin has poor washing resistance due to hydrolysis resistance.
CN10883803 discloses an aqueous polyurethane dispersion prepared by using a polyol containing polyoxyethylene side chains as a hydrophilic monomer and PEG1000 as a soft segment, which has good moisture permeability and mechanical strength, but does not improve the water pressure resistance and has a large resin viscosity.
The above-mentioned published patents show that most of the current water-proof moisture-permeable aqueous polyurethane resins employ polyethoxy diol in the main chain or introduce hydrophilic groups in the side chains. However, experiments also find that when an ethoxy (-EO-) hydrophilic group is on the main chain, although the-EO-segment can play a good role in moisture permeability for transferring water molecules, the water pressure resistance of the resin is obviously reduced along with the increase of the-EO-segment on the main chain due to the self-hydrophilicity. When the hydrophilic-EO-group is on the side chain, although the water pressure resistance and the moisture permeability can be balanced, the water pressure resistance tends to be affected when the moisture permeability is improved. Therefore, the needs of improving the moisture permeability and keeping the performance of the fabric not significantly reduced after multiple water washes under the condition of ensuring certain water pressure resistance performance all present new challenges for related researchers.
Disclosure of Invention
The invention aims to provide a novel water-proof moisture-permeable aqueous polyurethane dispersion. According to the dispersoid, a strong hydrophilic hydroxyl side group aggregated into clusters is introduced into a main chain through a special micromolecule chain extender, and the dispersoid and a weak hydrophilic ether bond on a branched chain form a synergistic effect, so that the unidirectional movement of water in a fabric from inside to outside is facilitated, the problem of mutual restriction of water pressure and moisture permeability is balanced, and good waterproof and moisture permeability performances can be obtained simultaneously.
The invention also aims to provide a preparation method of the water-based polyurethane waterproof moisture-permeable dispersion.
The invention further aims to provide application of the water-proof moisture-permeable aqueous polyurethane dispersion.
In order to achieve the purpose, the invention adopts the following technical scheme:
an aqueous polyurethane dispersion for a waterproof moisture-permeable coating, which is prepared from the following raw materials:
a. at least two diisocyanates, added in an amount of 19 to 29% by weight, preferably 22 to 25% by weight;
b. at least two polyether diols and/or polyester diols, in an amount of 28 to 41 wt.%, preferably 32 to 38 wt.%;
c. at least one polyether or polyester polyol with functionality not less than 3, the addition amount is 10-20 wt%, preferably 10.5-15 wt%;
d. at least one active hydrogen-containing small molecular weight polyol chain extender, with the addition amount of 0.5-4 wt%, preferably 1.5-3 wt%;
e. at least one active hydrogen-containing nonionic hydrophilic chain extender in an amount of 14 to 30 wt%, preferably 20 to 25 wt%;
f. at least two small molecular polyamine chain-expanding agents containing active hydrogen, the adding amount is 3.8-5.3 wt%, and the preferential amount is 4-5 wt%;
g. at least two auxiliary agents containing two or more of an antioxidant, a light stabilizer and an ultraviolet absorber, wherein the addition amount is 0.2-2.0 wt%, and preferably 0.4-1.0 wt%;
the weight of the raw materials is based on the solid content of the waterborne polyurethane resin.
In the present invention, component a is selected from aliphatic and/or alicyclic isocyanates, preferably two or more of isophorone diisocyanate, 1, 6-hexyl diisocyanate, dicyclohexylmethane diisocyanate and tetramethylxylylene diisocyanate, more preferably dicyclohexylmethane diisocyanate and 1, 6-hexyl diisocyanate. The two isocyanates can be subjected to synergistic reaction, so that the molecular structure design and the molecular weight control of the dispersion are facilitated, and the comprehensive performance of the dispersion is better.
In the invention, the component b is selected from two or more of polytetrahydrofuran dihydric alcohol, polyethylene glycol dihydric alcohol, polypropylene glycol dihydric alcohol and polyethylene glycol-propylene glycol dihydric alcohol; preferably two or more of polypropylene glycol and/or polytetrahydrofuran glycol with the number average molecular weight of 300-3000; more preferably a mixture of polypropylene glycol with number average molecular weight of 1500-2500 and two polytetrahydrofuran glycol with different molecular weight of 1000-2500, wherein the mass ratio of the mixture of polypropylene glycol and polytetrahydrofuran glycol is 0.2: 1-0.7: 1. The polypropylene glycol has low cost, mild reaction and excellent polytetrahydrofuran glycol performance, and the matching use of the polypropylene glycol and the polytetrahydrofuran glycol can meet the requirement of batch production.
In the present invention, component c is preferably a polyether polyol, more preferably a polyglycerol of molecular weight 2000 and 3000, and most preferably a polyglycerol of molecular weight 3000. The trifunctional polyglycerol is introduced from the aspects of molecular architecture and molecular weight control, so that good fabric hand feeling is obtained, and the water pressure resistance of the fabric can be obviously improved.
In the invention, the molecular weight of the component d is 30-200; one or more selected from 1, 3-propanediol, 1, 4-butanediol, diethylene glycol, neopentyl glycol, 1, 6-hexanediol and 1, 4-cyclohexanedimethanol, preferably 1, 4-butanediol and/or 1, 6-hexanediol.
In the invention, the molecular weight of the component e is 500-3000; selected from TegoChemie
D-3403, Ymer by PerstropTMN120 and one or more of MPEG1200 of Letian Corp, Korea, preferably Ymer of PerstropTMAnd (4) N120. By introducing an ether bond into a side chain of a molecule by N120 or the like, a weakly hydrophilic ether bond can be extendedThe strong hydrophilic hydroxyl in the chain agent forms a synergistic effect, thereby effectively balancing the problem of mutual restriction between water pressure and moisture permeability.
In the invention, the molecular weight of the component f is 30-300; two or more selected from the group consisting of ethylenediamine, hexamethylenediamine, 4-diphenylmethanediamine, hydroxyethylethylenediamine, di-n-butylamine, isophoronediamine and 1, 3-bis [ (trimethylol) methylamino ] propane, preferably a mixture of 1, 3-bis [ (trimethylol) methylamino ] propane and ethylenediamine, or a mixture of 1, 3-bis [ (trimethylol) methylamino ] propane and isophoronediamine; wherein the structural formula of the 1, 3-bis [ (trihydroxymethyl) methylamino ] propane is as follows:
the introduced 1, 3-bis [ (trihydroxymethyl) methylamino ] propane structure contains 6 strongly hydrophilic hydroxyl side groups, clustered hydroxyl groups are gathered at the position of the chain extender in the main chain, the chain extender can form a strong hydrogen bond effect with water to adsorb moisture, an effective channel is provided for conduction of water molecules, unidirectional movement of the moisture from inside to outside is facilitated, the moisture permeability of resin is obviously improved, and different moisture permeability can be obtained by adjusting the adding amount of the chain extender.
In the present invention, the component g is selected from two or more of hindered amines and hindered phenols, and a combination of an antioxidant 1010 and a light stabilizer 292 is preferred.
In the invention, a catalyst is added when the resin is prepared, and the catalyst comprises but is not limited to an organic bismuth or organic zinc catalyst, preferably an organic bismuth catalyst 8108 which is the leading catalyst in the United states, and the addition amount is a known catalyst amount.
In the invention, the solid content of the dispersion is 30-45 wt%, preferably 35-40 wt%, and the particle size of the dispersion is 30-100 nm, preferably 40-80 nm.
The preparation method comprises the following preparation steps:
(1) mixing the components a, b, c and e for reaction to generate an isocyanate-terminated prepolymer, wherein the reaction temperature is 75-85 ℃;
(2) adding the component d, acetone and a catalyst into the prepolymer for reaction, further increasing the molecular weight of the prepolymer, reducing the temperature after the reaction temperature reaches 75-85 ℃ and theoretical NCO%, and adding acetone for dilution;
(3) adding acetone diluted solution of component g, wherein the addition amount of acetone is 5-8 times of g, and adding deionized water for dispersion under high-speed shearing;
(4) and (3) adding a water diluted solution of the component f for chain extension, wherein the addition amount of water is 3-5 times of that of the component f, and removing acetone after the chain extension is finished to obtain the aqueous polyurethane dispersion product.
The dispersion prepared by the method can be used for waterproof and moisture permeable fabric coatings, and the coatings can be applied to the fields of sports wear, outdoor clothing, fire-fighting clothing, military clothing, leisure wind clothing, breathable poncho, military tents, sleeping bags, postal bags, protective articles and medical and protective articles.
The positive effects of the invention are mainly reflected in the following aspects:
(1) the waterproof and moisture permeable effect of the invention is realized by a novel hydrophilic structure of waterborne polyurethane: mixed polyether glycol is taken as a main chain, strong hydrophilic hydroxyl side groups aggregated into clusters are introduced into partial positions on the main chain, and weak hydrophilic ether bonds are introduced into the side chains, so that a synergistic effect can be formed, the problem of mutual restriction between water pressure and moisture permeability is balanced, unidirectional movement of water from inside to outside is facilitated, and the functions of water resistance and moisture permeability are realized simultaneously;
(2) the hydrostatic pressure resistance of the fabric coated with the resin is more than 5100mmH2O, moisture permeability > 6000g/m224h, after washing for five times, the water pressure resistance and the moisture permeability are reduced by not more than 18 percent and 4 percent;
(3) the invention has simple production process, convenient operation, safety and no toxicity.
Detailed Description
The test method in the invention is as follows:
the solid content testing method comprises the following steps: weighing appropriate amount of the emulsion in a container made of tinfoil paper, weighing the weight change at 150 deg.C for 20min, and calculating the solid content.
The particle size test method comprises the following steps: a malvern particle size instrument was used.
pH test method: a pH meter was used.
Viscosity test method: a BROOKFIELD viscometer, rotor No. 3, at 30rpm was used.
The appearance test method comprises the following steps: and judging the eye sight.
Moisture permeability: according to ASTM-E96-05, the test conditions are 50 ℃, 23% RH, 5-10h,2.5m/s wind speed, the unit is g/m2/24h。
Hydrostatic pressure: according to GB/T4744-1997, the unit is mmH2O。
Washing with water for 5 times: and (3) washing for five times by a washing machine according to GB/T8629-2001 at 40 ℃ for 45min for 5 times, and determining that the water pressure and the moisture permeability are reduced by less than 80 percent.
Softness: grading is carried out according to 1-5, 5 represents the best, 1 represents the worst, and the judgment is carried out by touching.
Surface dryness: grading is carried out according to 1-5, 5 represents the best, 1 represents the worst, and the judgment is carried out by touching.
Rebound resilience: grading is carried out according to 1-5, 5 represents the best, 1 represents the worst, and the judgment is carried out by touching.
The construction process for preparing the fabric coating by using the dispersion is as follows:
coating sizing agent on semi-matte nylon cloth by using a circular knife, drying for 1min at 150 ℃, and coating two knives together to ensure that the total sizing amount of the two knives is 20-30 g/m2. The samples were tested after curing in an oven at 50 ℃ for 24 h.
The construction formula of the fabric coating is as follows:
the raw materials used in the examples were as follows:
PPG2000 (Polypropylene glycol, hydroxyl number 56mgKOH/g, number average molecular weight ≈ 2000, functionality of 2, great east Chemicals);
PTMG2000 (polytetrahydrofuran ether glycol, hydroxyl value 56mgKOH/g, number average molecular weight 2000, functionality of 2, Tahitawa Daochien);
PTMG1000 (polytetrahydrofuran ether glycol, hydroxyl value 112mgKOH/g, number average molecular weight 1000, functionality of 2, dawsonia macrochemical);
YmerTMn120 (polyethylene oxide ether glycol, hydroxyl value 110mgKOH/g, number average molecular weight ≈ 1000, Perstorp, Sweden);
MN3050 (polyglycerol, hydroxyl group 56mgKOH/g, number average molecular weight 3000, functionality 3, great east china);
HDO (1, 6-hexanediol, BASF, germany);
BDO (1, 4-butanediol, BASF, Germany);
IPDA (isophoronediamine, BASF, Germany);
EDA (ethylenediamine, BASF, germany);
1, 3-bis [ (trihydroxymethyl) methylamino ] propane (chain extender, Dalian Meiren Biotech Co., Ltd.);
292 (light stabilizers, Ciba, USA);
1010 (antioxidant, Ciba, USA);
silok43 (handle, siloco chemical, guang);
white paste (pigment and filler, Jiangsu Fuchuang leather-resistant company).
Example 1
Into a four-necked flask equipped with a reflux condenser, a thermometer and mechanical stirring was charged 40g
HMDI、25.2g
HDI, 70g N120, 35g of PPG2000, 50g of PTMEG2000, 15g of PTMEG1000, 30g of MN3050, reached a theoretical NCO% of 6.13% after 1h of reaction at 80 ℃.
And (3) cooling to 60 ℃, adding 6g of BDO, 0.08136g of catalyst 8108 and 40g of acetone for dilution, uniformly stirring, heating to 80 ℃, reacting for 4.5-6.5 h (timing is started at 75 ℃), and stopping the reaction when the theoretical NCO% reaches 2.51%. Cooling to 60 ℃, adding 54g of acetone for dilution, stirring and mixing for 5min to fully mix the prepolymer and the acetone, and continuously cooling to 30-35 ℃.
Adding 1010/292 acetone solution, stirring for 5min to mix uniformly, stirring at 1200-1500 rpm, and adding 656g deionized water within 6 min.
Diluting 2g of ethylenediamine and 10g of 1, 3-bis [ (trihydroxymethyl) methylamino ] propane with 48g of deionized water, slowly adding the diluted materials into a system, reacting for 5min at a constant temperature of 35 ℃, and distilling the prepared emulsion under reduced pressure to remove acetone to obtain the blue-light-evident waterborne polyurethane emulsion with the solid content of 35 wt% and the particle size of 40 nm.
Example 2
41g of a four-necked flask equipped with a reflux condenser, a thermometer and mechanical stirring was charged into the flask
HMDI、25g
HDI, 60g N120, 36g of PPG2000, 47g of PTMEG2000, 17g of PTMEG1000, 30g of MN3050, reached a theoretical NCO% of 6.53% after 1h of reaction at 85 ℃.
And (3) cooling to 60 ℃, adding 7g of BDO, 0.0789g of catalyst 8108 and 39.6g of acetone for dilution, uniformly stirring, heating to 85 ℃, reacting for 4.5-6.5 h (timing is started at 75 ℃), and stopping the reaction when the theoretical NCO% reaches 2.61%. Cooling to 60 ℃, adding 52.6g of acetone for dilution, stirring and mixing for 5min to fully mix the prepolymer and the acetone, and continuously cooling to 30-35 ℃.
Adding 1010/292 acetone solution, stirring for 5min to mix uniformly, stirring at 1200-1500 rpm, and adding 637g deionized water within 6min to obtain the aqueous polyurethane dispersion.
Diluting 2g of ethylenediamine and 10g of 1, 3-bis [ (trihydroxymethyl) methylamino ] propane with 48g of deionized water, slowly adding the diluted materials into a system, reacting for 5min at a constant temperature of 35 ℃, and distilling the prepared emulsion under reduced pressure to remove acetone to obtain the blue-light-evident waterborne polyurethane emulsion with the solid content of 35 wt% and the particle size of 60 nm.
Example 3
38g of a four-necked flask equipped with a reflux condenser, a thermometer and mechanical stirring was charged into the flask
HMDI、24g
HDI, 80g N120, 50g of PPG2000, 60g of PTMEG2000, 15g of PTMEG1000, 38g of MN3050, reached a theoretical NCO% of 4.41% after 1h of reaction at 75 ℃.
And (3) cooling to 60 ℃, adding 3.5g of BDO, 0.09255g of catalyst 8108 and 46g of acetone for dilution, uniformly stirring, heating to 75 ℃, reacting for 4.5-6.5 h (timing is started at 75 ℃), and stopping the reaction when the theoretical NCO% reaches 1.89%. Cooling to 60 ℃, adding 61g of acetone for dilution, stirring and mixing for 5min to fully mix the prepolymer and the acetone, and continuously cooling to 30-35 ℃.
Adding 1010/292 acetone solution, stirring for 5min to mix uniformly, stirring at 1200-1500 rpm, and adding 730g deionized water within 6min to obtain the aqueous polyurethane dispersion.
Diluting 4g of isophorone diamine and 10g of 1, 3-bis [ (trihydroxymethyl) methylamino ] propane with 56g of deionized water, slowly adding the diluted materials into a system, reacting for 5min at a constant temperature of 35 ℃, and distilling the prepared emulsion under reduced pressure to remove acetone to obtain the blue-light-evident waterborne polyurethane emulsion with the solid content of 30 wt% and the particle size of 40 nm.
Example 4
To a four-necked flask equipped with a reflux condenser, a thermometer and mechanical stirring was added 50g
HMDI、26g
HDI, 50g N120, 20g of PPG2000, 40g of PTMEG2000, 25g of PTMEG1000 and 30g of MN3050, reached a theoretical NCO% of 8.52% after 1h of reaction at 80 ℃.
And (3) cooling to 60 ℃, adding 10g of BDO, 0.0753g of catalyst 8108 and 37g of acetone for dilution, uniformly stirring, heating to 80 ℃, reacting for 4.5-6.5 h (timing is started at 75 ℃), and stopping the reaction when the theoretical NCO% reaches 3.33%. Cooling to 60 ℃, adding 50g of acetone for dilution, stirring and mixing for 5min to fully mix the prepolymer and the acetone, and continuously cooling to 30-35 ℃.
Adding 1010/292 acetone solution, stirring for 5min to mix uniformly, stirring at 1200-1500 rpm, and adding 609g deionized water within 6min to obtain the aqueous polyurethane dispersion.
Diluting 3.5g of ethylenediamine and 10g of 1, 3-bis [ (trihydroxymethyl) methylamino ] propane with 54g of deionized water, slowly adding the diluted materials into a system, reacting for 5min at a constant temperature of 35 ℃, and distilling the prepared emulsion under reduced pressure to remove acetone to obtain the blue-light-evident waterborne polyurethane emulsion with the solid content of 40 wt% and the particle size of 80 nm.
Example 5
To four-port furnace equipped with reflux condenser tube, thermometer and mechanical stirringAdding 30g of the mixture into a bottle
HMDI、20g
HDI, 35g N120, 45g of PPG2000, 40g of PTMEG2000, 15g of PTMEG1000, 45g of MN3050, reached a theoretical NCO% of 4.86% after 1h of reaction at 80 ℃.
And (3) cooling to 60 ℃, adding 3.5g of BDO, 0.07005g of catalyst 8108 and 35g of acetone for dilution, uniformly stirring, heating to 80 ℃, reacting for 4.5-6.5 h (timing is started at 75 ℃), and stopping the reaction when the theoretical NCO% reaches 2.49%. Cooling to 60 ℃, adding 46g of acetone for dilution, stirring and mixing for 5min to fully mix the prepolymer and the acetone, and continuously cooling to 30-35 ℃.
Adding 1010/292 acetone solution, stirring for 5min to mix uniformly, stirring at 1200-1500 rpm, and adding 568g deionized water within 6min to obtain the aqueous polyurethane dispersion.
Diluting 1.5g of ethylenediamine and 10g of 1, 3-bis [ (trihydroxymethyl) methylamino ] propane with 46g of deionized water, slowly adding the diluted materials into a system, reacting for 5min at a constant temperature of 35 ℃, and distilling the prepared emulsion under reduced pressure to remove acetone to obtain the blue-light-evident waterborne polyurethane emulsion with the solid content of 45 wt% and the particle size of 92 nm.
Example 6
Into a four-necked flask equipped with a reflux condenser, a thermometer and mechanical stirring was charged 40g
HMDI、25g
HDI, 80g N120, 35g of PPG2000, 35g of PTMEG2000, 10g of PTMEG1000, 45g of MN3050, reached a theoretical NCO% of 6.20% after 1h of reaction at 80 ℃.
And (3) cooling to 60 ℃, adding 6g of HDO, 0.0813g of catalyst 8108 and 40g of acetone for dilution, uniformly stirring, heating to 80 ℃, reacting for 4.5-6.5 h (timing is started at 75 ℃), and stopping the reaction when the theoretical NCO% reaches 2.84%. Cooling to 60 ℃, adding 54g of acetone for dilution, stirring and mixing for 5min to fully mix the prepolymer and the acetone, and continuously cooling to 30-35 ℃.
Adding 1010/292 acetone solution, stirring for 5min to mix uniformly, stirring at 1200-1500 rpm, and adding 640g deionized water within 6min to obtain the aqueous polyurethane dispersion.
Diluting 3g of ethylenediamine and 10g of 1, 3-bis [ (trihydroxymethyl) methylamino ] propane with 52g of deionized water, slowly adding the diluted materials into a system, reacting for 5min at a constant temperature of 35 ℃, and distilling the prepared emulsion under reduced pressure to remove acetone to obtain the blue-light-evident waterborne polyurethane emulsion with the solid content of 30 wt% and the particle size of 42 nm.
Comparative example 1
This comparative example did not add 1, 3-bis [ (trihydroxymethyl) methylamino-]Propane. Into a four-necked flask equipped with a reflux condenser, a thermometer and mechanical stirring was charged 40g
HMDI、25.2g
HDI, 70g N120, 35g of PPG2000, 50g of PTMEG2000, 15g of PTMEG1000, 30g of MN3050, reached a theoretical NCO% of 6.13% after 1h of reaction at 80 ℃.
And (3) cooling to 60 ℃, adding 6g of BDO, 0.0813g of catalyst 8108 and 40g of acetone for dilution, uniformly stirring, heating to 80 ℃, reacting for 4.5-6.5 h (timing is started at 75 ℃), and stopping the reaction when the theoretical NCO% reaches 2.51%. Cooling to 60 ℃, adding 54g of acetone for dilution, stirring and mixing for 5min to fully mix the prepolymer and the acetone, and continuously cooling to 30-35 ℃.
Adding 1010/292 acetone solution, stirring for 5min to mix uniformly, stirring at 1200-1500 rpm, and adding 642g deionized water within 6min to obtain the aqueous polyurethane dispersion.
Diluting 4g of ethylenediamine with 16g of deionized water, slowly adding the diluted ethylenediamine into the system, reacting at the constant temperature of 35 ℃ for 5min, and distilling the prepared emulsion under reduced pressure to remove acetone to obtain the aqueous polyurethane emulsion with the solid content of 30 wt% and the particle size of 50nm and obvious blue light.
Comparative example 2
This comparative example was made with PEG1000 and no N120. Into a four-necked flask equipped with a reflux condenser, a thermometer and mechanical stirring was charged 40g
HMDI、25.2g
HDI, 70g of PEG1000, 35g of PPG2000, 50g of PTMEG2000, 15g of PTMEG1000, 30g of MN3050, reached a theoretical NCO% of 6.13% after 1h of reaction at 80 ℃.
And (3) cooling to 60 ℃, adding 6g of BDO, 0.08136g of catalyst 8108 and 40g of acetone for dilution, uniformly stirring, heating to 80 ℃, reacting for 4.5-6.5 h (timing is started at 75 ℃), and stopping the reaction when the theoretical NCO% reaches 2.51%. Cooling to 60 ℃, adding 54g of acetone for dilution, stirring and mixing for 5min to fully mix the prepolymer and the acetone, and continuously cooling to 30-35 ℃.
Adding 1010/292 acetone solution, stirring for 5min to mix uniformly, stirring at 1200-1500 rpm, and adding 656g deionized water within 6min to obtain the aqueous polyurethane dispersion.
Diluting 2g of ethylenediamine and 10g of 1, 3-bis [ (trihydroxymethyl) methylamino ] propane with 48g of deionized water, slowly adding the diluted materials into a system, reacting for 5min at a constant temperature of 35 ℃, and distilling the prepared emulsion under reduced pressure to remove acetone to obtain the blue-light-evident waterborne polyurethane emulsion with the solid content of 30 wt% and the particle size of 45 nm.
Comparative example 3
This comparative example used a single isocyanate. To a four-necked flask equipped with a reflux condenser, a thermometer and mechanical stirring was added 50g
HDI, 70g PEG1000, 35g PPG2000, 50g PTMEG2000, 15g PTMEG1000, 30g MN3050, after reaction for 1h at 80 ℃ reached a theoretical NCO% of 6.32%.
And (3) cooling to 60 ℃, adding 6g of BDO, 0.0768g of catalyst 8108 and 38g of acetone for dilution, uniformly stirring, heating to 80 ℃, reacting for 4.5-6.5 h (timing is started at 75 ℃), and stopping the reaction when the theoretical NCO% reaches 2.52%. Cooling to 60 ℃, adding 51g of acetone for dilution, stirring and mixing for 5min to fully mix the prepolymer and the acetone, and continuously cooling to 30-35 ℃.
Adding 1010/292 acetone solution, stirring for 5min to mix uniformly, stirring at 1200-1500 rpm, and adding 606g deionized water within 6min to obtain the aqueous polyurethane dispersion.
2g of ethylenediamine and 10g of 1, 3-bis [ (trihydroxymethyl) methylamino ] propane are diluted with 48g of deionized water and slowly added into the system, so that the obtained emulsion is unstable and has coagulation phenomenon after 12 hours.
The dispersions of the examples and comparative examples were used to prepare fabric coatings, and the properties of the samples after construction are shown in Table 1:
TABLE 1 Properties of Dispersion prepared Fabric coating samples in examples and comparative examples
Comparing the performance data of comparative example 1 and example 1 shows that: compared with example 1, the hydrostatic pressure of comparative example 1 is equivalent, the moisture permeability is poorer, and the performance is obviously reduced after 5 times of water washing. Mainly, 1, 3-bis [ (trihydroxymethyl) methylamino ] propane is not added in the comparative example 1, and the substance has better hydrophilic moisture permeability and can effectively transmit water molecules.
As can be seen by comparing the performance data of comparative example 2 and example 1: compared with example 1, comparative example 2 has better moisture permeability, very poor water pressure resistance, and obviously poor dryness and rebound elasticity of the surface of the paint film. Mainly because PEG1000 is introduced into the main chain of the polyurethane resin in the comparative example 2 to replace N120 of a nonionic hydrophilic part, and because ether bonds are introduced into molecular side chains of the N120, weak hydrophilic ether bonds can form a synergistic effect with strong hydrophilic hydroxyl groups in the special chain extender, and the unidirectional movement of water from inside to outside is facilitated, the moisture permeability and the water pressure resistance of the resin in the comparative example 2 are poorer than those of the resin in the example 1, and the emulsion in the comparative example 2 has higher viscosity and is not easy to construct.
The above description is only a part of the embodiments of the present invention, and is not intended to limit the scope of the present invention; it is intended that the following claims be interpreted as including all such alterations, modifications, and equivalents as fall within the true spirit and scope of the invention.
Claims (18)
1. An aqueous polyurethane dispersion for a waterproof moisture-permeable coating, which is prepared by reacting the following raw materials:
a. at least two diisocyanates, the addition amount is 19-29 wt%;
b. at least two polyether diols and/or polyester diols, the addition amount is 28-41 wt%;
c. at least one polyether or polyester polyol with functionality more than or equal to 3, the adding amount is 10-20 wt%;
d. at least one micromolecular polyalcohol chain extender containing active hydrogen, the adding amount is 0.5-4 wt%;
e. at least one nonionic hydrophilic chain extender containing active hydrogen, the adding amount is 14-30 wt%;
f. at least two micromolecular polyamine chain-expanding agents containing active hydrogen, the adding amount is 3.8-5.3 wt%;
g. at least two auxiliary agents, which comprise two or more of antioxidant, light stabilizer and ultraviolet absorbent, and the addition amount is 0.2-2.0 wt%;
the weight of the raw materials is calculated by the solid content of the waterborne polyurethane resin;
wherein the raw material e is a dimerTMN120, the raw material f is 1, 3-bis [ (trihydroxymethyl) methylamino)]Mixtures of propane and ethylenediamine, or 1, 3-bis [ (trihydroxymethyl) methylamino-]A mixture of propane and isophorone diamine; wherein, 1, 3-bis [ (trihydroxymethyl) methylamino group]The structural formula of propane is:
2. the dispersion of claim 1, prepared by reacting the following starting materials:
a. at least two diisocyanates, the addition amount is 22-25 wt%;
b. at least two polyether diols and/or polyester diols, the addition amount is 32-38 wt%;
c. at least one polyether or polyester polyol with functionality more than or equal to 3, the adding amount is 10.5-15 wt%;
d. at least one micromolecular polyalcohol chain extender containing active hydrogen, the adding amount is 1.5-3 wt%;
e. at least one nonionic hydrophilic chain extender containing active hydrogen, the adding amount is 20-25 wt%;
f. at least two small molecular polyamine chain extenders containing active hydrogen, the addition amount is 4-5 wt%;
g. at least two auxiliary agents, which comprise two or more of antioxidant, light stabilizer and ultraviolet absorbent, and the addition amount is 0.4-1.0 wt%;
the weight of the raw materials is based on the solid content of the waterborne polyurethane resin.
3. Dispersion according to claim 1 or 2, characterized in that component a is selected from aliphatic and/or cycloaliphatic isocyanates.
4. A dispersion according to claim 3, characterised in that component a is selected from two or three of 1, 6-hexyl diisocyanate, isophorone diisocyanate and dicyclohexylmethane diisocyanate.
5. The dispersion according to claim 4, wherein the isocyanate in component a is 1, 6-hexyl diisocyanate or dicyclohexylmethane diisocyanate.
6. The dispersion according to claim 1, wherein component b is selected from two or more of polytetrahydrofuran diol, polyethylene glycol diol, polypropylene glycol diol and polyethylene glycol-propylene glycol diol.
7. The dispersion according to claim 6, wherein component b is selected from two or more of polypropylene glycol and/or polytetrahydrofuran glycol having a number average molecular weight of 300 to 3000.
8. The dispersion according to claim 7, wherein component b is selected from the group consisting of polypropylene glycol having a number average molecular weight of 1500 to 2500 and a mixture of two different polytetrahydrofuran glycols having a number average molecular weight of 1000 to 2500, wherein the mass ratio of the mixture of polypropylene glycol and polytetrahydrofuran glycol is 0.2:1 to 0.7: 1.
9. The dispersion of claim 1, wherein component c is a polyether polyol.
10. Dispersion according to claim 9, characterized in that component c is a polyglycerol with a number average molecular weight of 2000 and/or 3000.
11. A dispersion according to claim 10, characterised in that component c is a polyglycerol with a number average molecular weight of 3000.
12. The dispersion of claim 1, wherein component d has a number average molecular weight of from 30 to 200.
13. The dispersion of claim 12, wherein component d is selected from one or more of 1, 3-propanediol, 1, 4-butanediol, diethylene glycol, neopentyl glycol, 1, 6-hexanediol, and 1, 4-cyclohexanedimethanol.
14. Dispersion according to claim 13, characterized in that component d is selected from 1, 4-butanediol and/or 1, 6-hexanediol.
15. The dispersion according to claim 1 or 2, wherein the solid content of the dispersion is 30 to 45 wt% and the particle size of the dispersion is 30 to 100 nm.
16. The dispersion as claimed in claim 15, wherein the solid content of the dispersion is 35 to 40 wt%, and the particle size of the dispersion is 40 to 80 nm.
17. Method for preparing a dispersion according to any one of claims 1 to 16, characterized in that it comprises the following preparation steps:
(1) mixing the components a, b, c and e for reaction to generate an isocyanate-terminated prepolymer, wherein the reaction temperature is 75-85 ℃;
(2) adding the component d, acetone and a catalyst into the prepolymer for reaction, further increasing the molecular weight of the prepolymer, reducing the temperature after the reaction temperature reaches 75-85 ℃ and theoretical NCO%, and adding acetone for dilution;
(3) adding acetone diluted solution of component g, wherein the addition amount of acetone is 5-8 times of g, and adding deionized water for dispersion under high-speed shearing;
(4) and (3) adding a water diluted solution of the component f for chain extension, wherein the addition amount of water is 3-5 times of that of the component f, and removing acetone after the chain extension is finished to obtain the aqueous polyurethane dispersion product.
18. Use of the dispersion according to any one of claims 1 to 16 or the dispersion prepared by the process according to claim 17 for waterproof moisture-permeable textile coatings which can be applied in the field of sports wear, outdoor wear, military wear, leisure wind wear, breathable poncho, military tents, sleeping bags, postal bags, protective goods, medical and health goods.
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| CN109749405B (en) * | 2018-12-19 | 2021-04-09 | 上海汇得科技股份有限公司 | Preparation method of thickened nonionic aqueous polyurethane emulsion with pseudoplasticity for synthetic leather |
| CN111363186B (en) * | 2018-12-25 | 2023-01-13 | 万华化学集团股份有限公司 | Polyurethane foam material, preparation method thereof and application thereof in wound dressing |
| CN110684171A (en) * | 2019-10-29 | 2020-01-14 | 兰州科天水性高分子材料有限公司 | Waterborne polyurethane emulsion and preparation method and application thereof |
| CN110606930A (en) * | 2019-10-29 | 2019-12-24 | 兰州科天水性高分子材料有限公司 | Waterborne polyurethane resin and preparation method and application thereof |
| CN111057209A (en) * | 2019-12-27 | 2020-04-24 | 辽宁恒星精细化工有限公司 | Water-based moisture-permeable flame-retardant polyurethane coating adhesive for textiles and preparation method thereof |
| CN111040660A (en) * | 2019-12-27 | 2020-04-21 | 辽宁恒星精细化工有限公司 | Water-based moisture-permeable flame-retardant polyurethane film for textiles and preparation method thereof |
| CN111019084A (en) * | 2019-12-27 | 2020-04-17 | 辽宁恒星精细化工有限公司 | Water-based moisture-permeable flame-retardant polyurethane emulsion for textiles and preparation method thereof |
| CN111349210A (en) * | 2020-05-07 | 2020-06-30 | 邦弗特新材料股份有限公司 | High-strength nonionic aqueous polyurethane emulsion and preparation method thereof |
| CN111560110B (en) * | 2020-06-05 | 2022-04-15 | 旭川化学（苏州）有限公司 | Moisture-absorption-resistant aqueous polyurethane dispersion and preparation method and application thereof |
| CN112851898B (en) * | 2021-03-01 | 2022-08-05 | 万华化学集团股份有限公司 | Self-extinction waterborne polyurethane resin, preparation method and application |
| CN113045725A (en) * | 2021-04-08 | 2021-06-29 | 东莞市米儿塑胶原料有限公司 | Preparation method of antifogging TPU material and preparation method of film |
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| CN101424045A (en) * | 2008-12-05 | 2009-05-06 | 武汉科技学院 | Method for preparing polyurethane loomage water proof and moisture permeable dressing agent |
| CN105622894A (en) * | 2014-11-05 | 2016-06-01 | 中国石油化工集团公司 | One-component non-ionic polyurethane water dispersion |
| CN104530370B (en) * | 2014-12-26 | 2017-07-07 | 上海材料研究所 | A kind of solvent-free method for preparing non-ion aqueous polyurethane |
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