CN102585150B - Preparation method of anionic aqueous polyurethane dispersoid for fabric coating and decoration - Google Patents
Preparation method of anionic aqueous polyurethane dispersoid for fabric coating and decoration Download PDFInfo
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- CN102585150B CN102585150B CN 201210022948 CN201210022948A CN102585150B CN 102585150 B CN102585150 B CN 102585150B CN 201210022948 CN201210022948 CN 201210022948 CN 201210022948 A CN201210022948 A CN 201210022948A CN 102585150 B CN102585150 B CN 102585150B
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Abstract
The invention relates to a preparation method of an anionic aqueous polyurethane dispersoid for fabric coating and decoration. The preparation method is operated according to the following steps that: (a) polyether polyol, polyester polyol and diisocyanate are subjected to polymerization reaction for 2 to 4 hours at 70 to 90 DEG C under the effect of catalysts; (b) acetone solvents and diamine hydrophilic chain extenders containing picolinic acid structures are added for taking reaction for 5 to 30 minutes at 40 to 65 DEG C, and polyurethane prepolymers are prepared; (c) the temperature is lowered to 20 to 40 DEG C, low-molecular-weight chain extenders and water are added and are emulsified through being stirred at high speed; (d) the acetone solvents are removed through reduced pressure distillation, and the anionic aqueous polyurethane dispersoid for fabric coating and decoration is obtained. Because diamine containing the picolinic acid structures is used as hydrophilic chain extenders, the regular pyridine ring structure is contained, the crystallization performance and the initial bonding intensity can be improved, meanwhile, a pyridine ring is an electron deficiency system, the color deepening caused by oxidation cannot easily occur, and the product has the yellowing resistance performance.
Description
Technical field
The present invention relates to a kind of preparation method of pyridine carboxylic acid type negatively charged ion fabric finish, a kind of fabric is covered with paint, lacquer, colour wash, etc. the preparation method with anion aqueous polyurethane disperse.
Background technology
Aqueous polyurethane has and advantage such as does not fire, smell is little, free from environmental pollution and operation processing is easy, is a kind of eco-friendly macromolecular material, is widely used in fields such as coating, tamanori, leather and fabric coating.In the fabric coating application facet, aqueous polyurethane mainly is used in the coating of fabrics such as Nylon Taffeta, real silk, cotton, canvas, polyester-cotton blend, makes fabric have advantages such as Waterproof Breathable, soft surface, high resilience, good hand feeling after the covering with paint.
As fabric coating use urethane, good flexibility and smooth property to be arranged behind the general requirement dry solidification, but require it to have stronger initial adhesion power simultaneously.In order to make soft film coating, the good hand feeling that obtains after the drying, the polyester of generally selecting the non-ordered structure of aliphatics is as soft section main raw material, but just reduced the initial adhesion power to fabric like this.Have bibliographical information can adopt the aromatic ring diamines as chainextender, crystal property is good, and coating is after the thermal activation bonding, and initial adhesion intensity improves.But the aromatic ring diamines easily causes the product xanthochromia, and this mainly is because phenyl ring is the electron rich conjugated structure, is oxidized to quinones easily and the color burn xanthochromia that causes.
Summary of the invention
The present invention is intended to propose a kind of fabric and covers with paint, lacquer, colour wash, etc. the preparation method who uses anion aqueous polyurethane disperse, and the polyurethane dispersions tack that makes is strong, good film-forming property, and anti-xanthochromia.
This fabric is covered with paint, lacquer, colour wash, etc. with the preparation method's of anion aqueous polyurethane disperse step as follows:
(a) with polyether glycol, the pure and mild vulcabond of polyester polyols, under catalyst action, carried out polyreaction 2～4 hours in 70～90 ℃;
(b) add diamines hydrophilic chain extender and the solvent acetone that contains the pyridine carboxylic acid structure, react 5～30min down at 40～65 ℃, make base polyurethane prepolymer for use as;
(c) be cooled to 20～40 ℃, add lower molecular weight diamine chain stretching agent and water, emulsification under high-speed stirring;
(d) decompression steams solvent acetone, namely obtains fabric covering with paint anion aqueous polyurethane disperse.
Wherein, the structure of the diamines hydrophilic chain extender that contains the pyridine carboxylic acid structure that (b) adds in the step is shown below:
In the formula, n=2,3,4
This fabric cover with paint, lacquer, colour wash, etc. with among the preparation method of anion aqueous polyurethane disperse owing to having used the diamines that contains the pyridine carboxylic acid structure as hydrophilic chain extender, it had both contained regular pyridine ring structure, can improve crystal property and initial adhesion intensity; Pyridine ring is the electron deficiency system at organic chemistry simultaneously, and it is difficult for oxidized and makes color burn, has the performance of anti-xanthochromia.
Embodiment
The preparation method that this fabric is covered with paint, lacquer, colour wash, etc. with anion aqueous polyurethane disperse operates according to the following steps:
(a) with polyether glycol, the pure and mild vulcabond of polyester polyols, under catalyst action, carried out polyreaction 2～4 hours in 70～90 ℃;
(b) add diamines hydrophilic chain extender and the solvent acetone that contains the pyridine carboxylic acid structure, react 5～30min down at 40～65 ℃, make base polyurethane prepolymer for use as;
(c) be cooled to 20～40 ℃, add lower molecular weight diamine chain stretching agent and water, emulsification under high-speed stirring;
(d) decompression steams solvent acetone, namely obtains fabric covering with paint anion aqueous polyurethane disperse.
Wherein, the structure of the diamines hydrophilic chain extender that contains the pyridine carboxylic acid structure that (b) adds in the step is shown below:
In the formula, n=2,3,4 is when n=2, and this chainextender is 2-((2-aminoethylamino) methyl) pyridine-4-sodium formiate; During n=3, this chainextender is 2-((2-amino propyl amino) methyl) pyridine-4-sodium formiate; During n=4, this chainextender is 2-((the amino butyl amino of 2-) methyl) pyridine-4-sodium formiate.
The used diamines hydrophilic chain extender that contains the pyridine carboxylic acid structure can be raw material with 2-chloromethyl iso methyl nicotinate among the preparation method of this fabric covering with paint with anion aqueous polyurethane disperse, with NH
2(CH
2) nNH
2Make with the NaOH reaction again after the reaction.Concrete reaction formula is as follows:
N=2,3,4 in the formula.
This fabric is covered with paint, lacquer, colour wash, etc. with among the preparation method of anion aqueous polyurethane disperse, and (a) polyether glycol described in the step can be polymkeric substance or the multipolymer of tetrahydrofuran (THF), oxyethane, propylene oxide, butylene oxide ring; Described polyester polyol can be polycarbonate diol, polycaprolactone glycol or the polyester diol that is got by di-carboxylic acid and dibasic alcohol polycondensation; Described vulcabond can be one or more the mixture in dicyclohexyl methane diisocyanate, isophorone diisocyanate, hexamethylene diisocyanate, the Methylcyclohexyl diisocyanate.
This fabric is covered with paint, lacquer, colour wash, etc. with among the preparation method of anion aqueous polyurethane disperse, and (a) polyether glycol described in the step can be 800～2500 polytetrahydrofuran dibasic alcohol for molecular weight; Described polyester polyol can be 1000～3000 polycarbonate diol for molecular weight.
This fabric is covered with paint, lacquer, colour wash, etc. with among the preparation method of anion aqueous polyurethane disperse, (a) vulcabond and the polyethers described in the step and polyester polyol react and make in the process of base polyurethane prepolymer for use as, the molar ratio of vulcabond and polyvalent alcohol can for: 1.1～1.6.
This fabric is covered with paint, lacquer, colour wash, etc. with among the preparation method of anion aqueous polyurethane disperse, and (a) catalyzer described in the step can be stannous octoate, and the amount of adding is 0.01～0.1% of prepolymer total mass.Also can be dibutyl tin dilaurate or two sad dibutyl tins.
This fabric is covered with paint, lacquer, colour wash, etc. with among the preparation method of anion aqueous polyurethane disperse, and (b) quality of the diamines hydrophilic chain extender that contains the pyridine carboxylic acid structure that adds in the step can be 0.5～3% of the solid amount in the emulsion; The quality of the solvent acetone that adds can be 50～100% of the solid amount in the emulsion.
This fabric is covered with paint, lacquer, colour wash, etc. with among the preparation method of anion aqueous polyurethane disperse, (c) the lower molecular weight diamines that adds in the step is quadrol, the mole number of add-on is in the raw material-the NCO total mole number deducts-the OH total mole number deducts in the pyridine carboxylic acid salt again-NH total mole number income value 40～110%, also be exactly: (mole number of quadrol)=((in the raw material-NCO total mole number)-(OH total mole number)-(in the pyridine carboxylic acid salt-NH total mole number)) * 40～110%; The quality of the water that adds is 45～55% of aqueous polyurethane emulsion total mass; The time of high-speed stirring emulsification is 0.5～1h.
Provide embodiments of the invention below, to specify a kind of preparation method of pyridine carboxylic acid type anion aqueous polyurethane disperse.But be not limited to this.
Embodiment 1
(be that number-average molecular weight is 2000 with PTMG dibasic alcohol 2000, be called for short PTMEG2000,42.9g down together), PTMG 1000 (be that number-average molecular weight is 1000, be called for short PTMEG1000, down together) 21.5g, polycarbonate diol 2000 (is that number-average molecular weight is 2000, be called for short PCD2000, down together) 14.4g, dicyclohexyl methane diisocyanate (is called for short H
12MDI, 35.3g down together), the inferior tin of octoate catalyst (being called for short T-9, down together) 0.05g is in the 500mL four-hole boiling flask, be heated to 70 ℃, reaction 2.5h is cooled to 60 ℃, adds 2-((2-aminoethylamino) methyl) pyridine-4-sodium formiate 3.3g and acetone 80.0g, reaction 25min makes base polyurethane prepolymer for use as.Be cooled to 40 ℃ then, add quadrol 2.2g, water 120.0g, emulsification 0.5h under high-speed stirring, last, decompression steams solvent acetone, namely gets pyridine carboxylic acid type anion aqueous polyurethane disperse WPU1.
Embodiment 2
With PTMEG200087.5g, PCD200014.4g, H
12MDI 28.2g, catalyzer T-90.06g in the 500mL four-hole boiling flask, is heated to 70 ℃, and reaction 3h is cooled to 60 ℃, adds 2-((2-aminoethylamino) methyl) pyridine-4-sodium formiate 3.3g and acetone 70.0g, and reaction 25min makes base polyurethane prepolymer for use as.Be cooled to 40 ℃ then, add quadrol 0.9g, water 120.0g, emulsification 0.5h under high-speed stirring, last, decompression steams solvent acetone, namely gets pyridine carboxylic acid type anion aqueous polyurethane disperse WPU2.
Embodiment 3
With PTMEG2000 80.0g, PCD2000 20.0g, H
12MDI 35.3g, catalyzer T-90.13g in the 500mL four-hole boiling flask, is heated to 75 ℃, and reaction 2h is cooled to 60 ℃, adds 2-((2-amino propyl amino) methyl) pyridine-4-sodium formiate 3.7g and acetone 80.0g, and reaction 25min makes base polyurethane prepolymer for use as.Be cooled to 35 ℃ then, add quadrol 2.2g, water 120.0g, emulsification 0.5h under high-speed stirring, last, decompression steams solvent acetone, namely gets pyridine carboxylic acid type anion aqueous polyurethane disperse WPU3.
Embodiment 4
With PTMEG2000 22.4g, PTMEG1000 33.8g, PCD2000 10.0g, H
12MDI 33.0g, catalyzer T-90.1g is in the 500mL four-hole boiling flask, be heated to 80 ℃, reaction 1.5h is cooled to 60 ℃, add 2-((the amino butyl amino of 2-) methyl) pyridine-4-sodium formiate 3.0g and acetone 70.0g, reaction 25min makes base polyurethane prepolymer for use as.Be cooled to 40 ℃ then, add quadrol 1.8g, water 120.0g, emulsification 0.5h under high-speed stirring, last, decompression steams solvent acetone, namely gets pyridine carboxylic acid type anion aqueous polyurethane disperse WPU4.
Embodiment 5
With PTMEG200025.0g, PTMEG100037.5g, PCD200020.3g, H
12MDI 30.7g, catalyzer T-9 0.09g is in the 500mL four-hole boiling flask, be heated to 75 ℃, reaction 2.0h is cooled to 60 ℃, add 2-((the amino butyl amino of 2-) methyl) pyridine-4-sodium formiate 2.8g and acetone 70.0g, reaction 30min makes base polyurethane prepolymer for use as.Be cooled to 40 ℃ then, add quadrol 1.2g, water 120.0g, emulsification 0.5h under high-speed stirring, last, decompression steams solvent acetone, namely gets pyridine carboxylic acid type anion aqueous polyurethane disperse WPU5.
Embodiment 6
With PTMEG2000 86.0g, PCD2000 14.4g, H
12MDI 28.5g, catalyzer dibutyl tin dilaurate 0.07g is in the 500mL four-hole boiling flask, be heated to 70 ℃, reaction 2.0h is cooled to 60 ℃, add 2-((2-amino propyl amino) methyl) pyridine-4-sodium formiate 3.8g and acetone 75.0g, reaction 30min makes base polyurethane prepolymer for use as.Be cooled to 40 ℃ then, add quadrol 0.9g, water 120.0g, emulsification 0.5h under high-speed stirring, last, decompression steams solvent acetone, namely gets pyridine carboxylic acid type anion aqueous polyurethane disperse WPU6.
Embodiment 7
With PTMEG2000 21.5g, PTMEG1000 32.3g, PCD2000 12.5g, isophorone diisocyanate 29.1g, catalyzer T-9 0.06g, in the 500mL four-hole boiling flask, be heated to 85 ℃, reaction 3.0h, be cooled to 60 ℃, add 2-((2-aminoethylamino) methyl) pyridine-4-sodium formiate 2.5g and acetone 70.0g, reaction 30min makes base polyurethane prepolymer for use as.Be cooled to 40 ℃ then, add quadrol 1.5g, water 120.0g, emulsification 0.5h under high-speed stirring, last, decompression steams solvent acetone, namely gets pyridine carboxylic acid type anion aqueous polyurethane disperse WPU7.
Embodiment 8
With PTMEG2000 45.0g, PTMEG1000 22.5g, PCD2000 10.1g, hexamethylene diisocyanate 22.0g, catalyzer T-9 0.08g, in the 500mL four-hole boiling flask, be heated to 75 ℃, reaction 2.5h, be cooled to 60 ℃, add 2-((2-aminoethylamino) methyl) pyridine-4-sodium formiate 3.2g and acetone 80.0g, reaction 30min makes base polyurethane prepolymer for use as.Be cooled to 40 ℃ then, add quadrol 1.8g, water 120.0g, emulsification 0.5h under high-speed stirring, last, decompression steams solvent acetone, namely gets pyridine carboxylic acid type anion aqueous polyurethane disperse WPU8.
Above-mentioned 8 embodiment gained aqueous polyurethane dispersion products are carried out performance test, and it the results are shown in Table 1.Wherein the mensuration of elongation at break and tensile strength is carried out with reference to GB/T528-1998, and draw speed is 200mm/min.The mensuration of T-stripping strength is carried out with reference to GB/T27912-1995, and its draw speed is 100mm/min, and base material is PVC.The mensuration of anti-yellowing property is that filming of preparing according to GB1727-1992 carried out (general yellow degree factor Y＞15%, think xanthochromia) with reference to GB2409-80 in irradiation under the ultraviolet lamp after 96 hours.Test result shows that gained pyridine carboxylic acid type anion aqueous polyurethane has stronger adhesive property and film-forming properties, and the solid content height, anti-xanthochromia.
The prepared aqueous polyurethane dispersion The performance test results of table 1 embodiment 1-8
Claims (3)
1. a fabric is covered with paint, lacquer, colour wash, etc. the preparation method who uses anion aqueous polyurethane disperse, it is characterized in that operating according to the following steps:
(a) with polyether glycol, the pure and mild vulcabond of polyester polyols, under catalyst action, carried out polyreaction 2～4 hours in 70～90 ℃;
(b) add diamines hydrophilic chain extender and the solvent acetone that contains the pyridine carboxylic acid structure, react 5～30min down at 40～65 ℃, make base polyurethane prepolymer for use as;
(c) be cooled to 20～40 ℃, add lower molecular weight diamine chain stretching agent and water, emulsification under high-speed stirring;
(d) decompression steams solvent acetone, namely obtains fabric covering with paint anion aqueous polyurethane disperse;
Wherein, the structure of the diamines hydrophilic chain extender that contains the pyridine carboxylic acid structure that (b) adds in the step is shown below:
In the formula, n=2,3,4;
Wherein the polyether glycol described in (a) step is polymkeric substance or the multipolymer of tetrahydrofuran (THF), oxyethane, propylene oxide, butylene oxide ring; Described polyester polyol is polycarbonate diol, polycaprolactone glycol or the polyester diol that got by di-carboxylic acid and dibasic alcohol polycondensation; Described vulcabond is one or more the mixture in dicyclohexyl methane diisocyanate, isophorone diisocyanate, hexamethylene diisocyanate, the Methylcyclohexyl diisocyanate; Vulcabond and polyethers and polyester polyol reaction make in the base polyurethane prepolymer for use as process, and the molar ratio of vulcabond and polyvalent alcohol is: 1.1～1.6; Described catalyzer is stannous octoate, and the amount of adding is 0.01～0.1% of prepolymer total mass; (b) quality of the diamines hydrophilic chain extender that contains the pyridine carboxylic acid structure that adds in the step be in the emulsion solid amount 0.5～3%; The quality of the solvent acetone that adds be in the emulsion solid amount 50～100%; (c) the lower molecular weight diamines that adds in the step is quadrol, the mole number of add-on is in the raw material-the NCO total mole number deducts-the OH total mole number deducts in the pyridine carboxylic acid salt again-NH total mole number income value 40～110%; The quality of the water that adds is 45～55% of aqueous polyurethane emulsion total mass; The time of high-speed stirring emulsification is 0.5～1h.
2. fabric as claimed in claim 1 is covered with paint, lacquer, colour wash, etc. the preparation method with anion aqueous polyurethane disperse, it is characterized in that the described diamines hydrophilic chain extender that contains the pyridine carboxylic acid structure is raw material with 2-chloromethyl iso methyl nicotinate, with NH
2(CH
2) nNH
2Make n=2,3,4 in the formula with the NaOH reaction again after the reaction.
3. fabric as claimed in claim 1 or 2 is covered with paint, lacquer, colour wash, etc. the preparation method with anion aqueous polyurethane disperse, it is characterized in that the polyether glycol described in (a) step is that molecular weight is 800～2500 polytetrahydrofuran dibasic alcohol; Described polyester polyol is that molecular weight is 1000～3000 polycarbonate diol.
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| PL2903968T3 (en) * | 2012-10-02 | 2017-05-31 | Gilead Sciences, Inc. | Inhibitors of histone demethylases |
| JP6514117B2 (en) | 2013-02-27 | 2019-05-15 | エピセラピューティクス アーペーエス | Inhibitors of histone demethylase |
| EP3126345A1 (en) * | 2014-03-31 | 2017-02-08 | Gilead Sciences, Inc. | Inhibitors of histone demethylases |
| KR20170040805A (en) | 2014-08-27 | 2017-04-13 | 길리애드 사이언시즈, 인코포레이티드 | Compounds and methods for inhibiting histone demethylases |
| CN104592882B (en) * | 2015-01-30 | 2017-07-04 | 雅图高新材料有限公司 | Automobile single-component water-based plain color paint and its preparation technology |
| CN110330618B (en) * | 2019-07-30 | 2021-05-18 | 嘉兴学院 | Waterborne polyurethane emulsion, preparation method and application thereof |
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| CN101328383A (en) * | 2008-07-17 | 2008-12-24 | 安徽大学 | Production method for liner gloves aqueous polyurethane coating connection material |
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| CN101328383A (en) * | 2008-07-17 | 2008-12-24 | 安徽大学 | Production method for liner gloves aqueous polyurethane coating connection material |
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Address after: 314001 No. 56 South Yuexiu Road, Zhejiang, Jiaxing Co-patentee after: JIAXING HEDA TECHNOLOGY CO.,LTD. Patentee after: JIAXING University Address before: 314001 No. 56 South Yuexiu Road, Zhejiang, Jiaxing Co-patentee before: JIAXING HEDA TECHNOLOGY CHEMICAL Co.,Ltd. Patentee before: Jiaxing University |
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