CN103214668A - Preparation method of chain extender for waterborne polyurethane - Google Patents
Preparation method of chain extender for waterborne polyurethane Download PDFInfo
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- CN103214668A CN103214668A CN2013101676801A CN201310167680A CN103214668A CN 103214668 A CN103214668 A CN 103214668A CN 2013101676801 A CN2013101676801 A CN 2013101676801A CN 201310167680 A CN201310167680 A CN 201310167680A CN 103214668 A CN103214668 A CN 103214668A
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Abstract
The invention relates to a preparation method of a chain extender for waterborne polyurethane. The preparation method comprises the following steps of: adding an active monomer in the hydrophilic chain extender, carrying out nitrogen protection at the temperature of 0-160 DEG C, after the hydrophilic chain extender is completely dissolved, adding in a catalyst and a cocatalyst, and carrying out reaction for 1-30 hours and vacuum pumping to obtain the chain extender for the waterborne polyurethane, wherein the molar ratio of the active monomer to the hydrophilic chain extender is (1-30):1. The method provided by the invention is simple and feasible in implementation of the process, and simple in equipment, and the produced waterborne polyurethane does not contain a toxic cosolvent with high boiling point, and is more environment-friendly and safer.
Description
Technical field
The invention belongs to the preparation field of chainextender, particularly a kind of preparation method who is used for the chainextender of aqueous polyurethane.
Background technology
Since the industrialization sixties of 20th century, urethane is extensive in light textile, leather processing sector application with its good performance.Reinforcement along with people's environmental consciousness and environmental regulation, the research of eco-friendly aqueous polyurethane, exploitation come into one's own day by day, it uses the fields such as coating, tamanori that constantly expanded to by hide finishes, progressively capture the market of solvent borne polyurethane, representing the developing direction of coating, tamanori.
The aqueous polyurethane main raw material(s): vulcabond, polyester or polyether glycol, wetting ability chainextender, neutralizing agent, back chainextender etc. are formed .[[1] Kim BK, Lee JC.Waterborne polyurethanes and their properties.J Polym Sci Part A:Polym Chem 1996; 34 (6): 1095-1104.[2] Kim BS, Kim BK.Enhancement of hydrolytic stability and adhesion of waterborne polyurethanes.J Appl Polym Sci 2005; 97 (5): 1961-9.[3] Yang J-E, Kong J-S, Park S-W, Lee D-J, Kim H-D.Preparation and properties of waterborne polyurethane-urea anionomers.I.The influence of the degree of neutralization and counterion.J Appl Polym Sci2002; 86 (9): 2375-2383.[4] high-performance water-based polyurethane and method for making CN1226323C thereof].
Aqueous polyurethane is produced the general technology flow process: earlier the polyvalent alcohol underpressure distillation is dewatered, the back adds polyisocyanates, be reacted to NCO under 70-85 ℃ and reach theoretical value, add wetting ability chainextender and acetone equal solvent, after insulation reaction reaches theoretical value to NCO, be cooled to 40-50 ℃, add neutralizing agent, stir 20-40min, back high speed dispersion adds chainextender simultaneously and carries out chain extension in water, obtain homodisperse stabilized aqueous urethane .[[5] Zhang SB, Lv HT, Zhang H, Wang B, Xu YM.Waterborne polyurethanes:spectroscopy and stability of emulsions.J Appl Polym Sci 2006; 101 (1): 597-602.[6] Yen M-S, Kuo S-C.PCL-PEG-PCL triblock copolydiol based waterborne polyurethane.I.Effects of the soft-segment composition on the structure and physical properties.J Appl Polym Sci 1997; 65 (5): 883-92.[7] Yen M-S, Tsai P-Y.Effects on the structure and properties of membranes formed by blending polydimethylsiloxane polyurethane into different soft-segment waterborne polyurethanes.J Appl Polym Sci 2006; 102 (1): 210-21.]
According to the difference of the type of hydrophilic radical, the wetting ability chainextender can be divided into 3 classes: the cationic chainextender of (1) anionic chainextender (2) (3) nonionic chainextender.Now industrial the most frequently used be anionic chainextender 2,2-dimethylol propionic acid (DMPA) and 2,2-dimethylolpropionic acid (DMBA).DMPA, the molecular structural formula of DMBA is as follows:
DMPA uses hydrophilic chain extender more widely at present, but DMPA fusing point height (160-175 ℃), be difficult to heating for dissolving, this just needs to add solvent such as .[[8 such as N-Methyl pyrrolidone (NMP), dimethyl formamide (DMF) acetone] Zhang GX, Zou MX, Wang SJ, Zhang ZC.Radiation induced dispersion polymerization of methyl methacrylate using waterborne polyurethane as stabilizer.Polym Int 2006; 55 (9): 1099-103.[9] Lee H-T, Hwang J-J, Liu H-J.Effects of ionic interactions between clay and waterborne polyurethanes on the structure and physical properties of their nanocomposite dispersions.J Polym Sci Part A:Polym Chem 2006; 44 (19): 5801-7.[10] Yen M-S, Kuo S-C.PCL-PEG-PCL triblock ester-ether copolydiol-based waterborne polyurethane.II.Effect of NCO/OH mole ratio and DMPA content on the physical properties.J Appl Polym Sci 1998; 67 (7): 130-11.] NMP, DMF boiling point height, be difficult to remove behind the preparation PU, and the solubleness of DMPA in acetone is less, in building-up process, need to add a large amount of acetone, take off ketone process trouble and take off unclean, bring potential safety hazard .[[11 to production process] Xu Gewen. water-base polyurethane material [M]. Beijing: chemical press, 2006], DMBA contrast DMPA solvability again has raising, but improve limited [[12] Ceng Jun of effect, Wang actor playing a martial role in Chinese operas waits relatively [J] leather chemical industry of .DMBA and DMPA polyaminoester emulsion salient features, 1999,16 (5): 19-22].
Summary of the invention
Technical problem to be solved by this invention provides a kind of preparation method who is used for the chainextender of aqueous polyurethane, and this method is simple for process, and equipment is simple; The aqueous polyurethane of producing does not contain high boiling poisonous solubility promoter, environmental protection more, safety.
A kind of preparation method who is used for the chainextender of aqueous polyurethane of the present invention comprises:
To add reactive monomer in the hydrophilic chain extender, nitrogen protection, temperature is 0-160 ℃; after hydrophilic chain extender dissolves fully, add catalyzer and promotor, reaction 1-30h; vacuumize, promptly get the chainextender that is used for aqueous polyurethane, wherein the mol ratio of reactive monomer and hydrophilic chain extender is 1-30:1.
Described hydrophilic chain extender is 2,2-dimethylol propionic acid DMPA or 2,2-dimethylolpropionic acid DMBA.
Described reactive monomer is oxyethane, propylene oxide, caprolactone or tetrahydrofuran (THF).
Described catalyzer is stannous octoate, stannous iso caprylate, tributyl methoxyl group tin, tert.-butoxy tin, phenol oxygen base tin, tin chloride, Tin tetrabromide, acetylize tin, butyl (tetra) titanate, aluminium isopropoxide, sodium hydroxide or potassium hydroxide.
Described promotor is an active hydrogen compounds.
Described active hydride is phosphoric acid, nitric acid, the vitriol oil, hydrochloric acid, zinc chloride, aluminum chloride fluosulfonic acid, methyl fluoride sulfonic acid, fluoroethane sulfonic acid, methyl nitrobenzene-sulfonic acid, a kind of in the methyl methylsulfonate.
The add-on of described catalyzer is 0-50ppm.
The add-on of described promotor is 0-50ppm.
Described being reflected in the reactor carried out.
The present invention utilizes open loop addition principle: under certain condition, reactive group (OH or-NH
2) the active monomer ring-opening reaction of initiation ring-type.With active monomer (CL, EO, PO, THF) ring-opening reaction (OH) takes place in the reactive group with DMPA (DMBA), thereby change the crystal habit of DMPA (DMBA), make it be dissolved in polyethers or polyester polyol system easily, do not contain the poisonous solubility promoter aqueous polyurethane of high boiling point, promote the environmental-protecting performance of product and the security of production technique thereby prepare.
Causing the caprolactone open loop with DMPA is example, and reaction formula is:
Beneficial effect
(1) method technology is simple and easy to do, and equipment is simple;
(2) aqueous polyurethane of Sheng Chaning does not contain high boiling poisonous solubility promoter (N-Methyl pyrrolidone, dimethyl formamide) environmental protection more, safety.
Embodiment
Below in conjunction with specific embodiment, further set forth the present invention.Should be understood that these embodiment only to be used to the present invention is described and be not used in and limit the scope of the invention.Should be understood that in addition those skilled in the art can make various changes or modifications the present invention after the content of having read the present invention's instruction, these equivalent form of values fall within the application's appended claims institute restricted portion equally.
Embodiment 1
DMPA134Kg is added in the reactor, and the back adds caprolactone monomer (CL) 228Kg, nitrogen protection; heat up 100 ℃,, add catalyzer aluminium isopropoxide (40ppm) and promotor phosphoric acid (10ppm) when DMPA melts fully; reacted 12 hours, and vacuumized, cooling gets product.Measure hydroxyl value 310KOHmg/g, acid number 155KOHmg/g.
Embodiment 2
DMBA148Kg is added in the reactor, and the back adds propylene oxide (PO) monomer 58Kg, and nitrogen protection heats up 100 ℃, when DMBA melts fully, adds catalyzer potassium hydroxide (10ppm), reacts 3 hours, vacuumizes, and cooling gets product.Measure hydroxyl 550KOH mg/g, acid number 355KOHmg/g.
Embodiment 3
DMPA134Kg is added in the reactor, and the back adds caprolactone monomer (CL) 336Kg, nitrogen protection; heat up 100 ℃,, add catalyzer aluminium isopropoxide (40ppm) and promotor methyl fluoride sulfonic acid (10ppm) when DMPA melts fully; reacted 6 hours, and vacuumized, cooling gets product.Measure hydroxyl value 115KOHmg/g, acid number 112KOHmg/g.
Embodiment 4
DMBA148Kg is added in the reactor, and the back adds tetrahydrofuran (THF) (THF) monomer 228Kg, nitrogen protection; heat up 40 ℃,, add catalyzer acetylize tin (40ppm) and promotor methyl fluoride sulfonic acid (10ppm) when DMBA melts fully; reacted 6 hours, and vacuumized, cooling gets product.Measure hydroxyl value 308KOHmg/g, acid number 150KOHmg/g.
Embodiment 5
DMBA148Kg is added in the reactor, and the back adds oxyethane (EO) monomer 228Kg, and nitrogen protection heats up 25 ℃, when DMBA melts fully, adds catalyzer potassium hydroxide (40ppm), reacts 16 hours, vacuumizes, and cooling gets product.Measure hydroxyl value 204KOHmg/g, acid number 120KOHmg/g.
Embodiment 6
DMBA148Kg is added in the reactor, and the back adds oxyethane (EO) monomer 228Kg, and nitrogen protection heats up 25 ℃, when DMBA melts fully, adds catalyzer sodium hydroxide (40ppm), reacts 15 hours, vacuumizes, and cooling gets product.Measure hydroxyl value 201KOHmg/g, acid number 118KOHmg/g.
Embodiment 7
DMBA148Kg is added in the reactor, and the back adds oxyethane (EO) monomer 228Kg, and nitrogen protection heats up 25 ℃, when DMBA melts fully, adds catalyzer potassium hydroxide (70ppm), reacts 13 hours, vacuumizes, and cooling gets product.Measure hydroxyl value 207KOHmg/g, acid number 122KOHmg/g.
Embodiment 8
DMPA134Kg is added in the reactor, and the back adds caprolactone monomer (CL) 336Kg, nitrogen protection; heat up 100 ℃,, add catalyzer aluminium isopropoxide (20ppm) and promotor methyl fluoride sulfonic acid (10ppm) when DMPA melts fully; reacted 8 hours, and vacuumized, cooling gets product.Measure hydroxyl value 115KOHmg/g, acid number 111KOHmg/g.
Embodiment 9
DMPA134Kg is added in the reactor, and the back adds caprolactone monomer (CL) 336Kg, nitrogen protection; heat up 100 ℃,, add catalyzer aluminium isopropoxide (40ppm) and promotor methyl fluoride sulfonic acid (3ppm) when DMPA melts fully; reacted 8 hours, and vacuumized, cooling gets product.Measure hydroxyl value 115KOHmg/g, acid number 112KOHmg/g.
Embodiment 10
DMPA134Kg is added in the reactor, and the back adds caprolactone monomer (CL) 672Kg, nitrogen protection; heat up 100 ℃,, add catalyzer aluminium isopropoxide (40ppm) and promotor methyl fluoride sulfonic acid (10ppm) when DMPA melts fully; reacted 22 hours, and vacuumized, cooling gets product.Measure hydroxyl value 76KOHmg/g, acid number 72KOHmg/g.
Embodiment 11
DMPA134Kg is added in the reactor, and the back adds caprolactone monomer (CL) 876Kg, nitrogen protection; heat up 160 ℃,, add catalyzer aluminium isopropoxide (40ppm) and promotor methyl fluoride sulfonic acid (10ppm) when DMPA melts fully; reacted 30 hours, and vacuumized, cooling gets product.Measure hydroxyl value 65KOHmg/g, acid number 57KOHmg/g.
Claims (8)
1. preparation method who is used for the chainextender of aqueous polyurethane comprises:
To add reactive monomer in the hydrophilic chain extender, nitrogen protection, temperature is 0-160 ℃; after hydrophilic chain extender dissolves fully, add catalyzer and promotor, reaction 1-30h; vacuumize, promptly get the chainextender that is used for aqueous polyurethane, wherein the mol ratio of reactive monomer and hydrophilic chain extender is 1-30:1.
2. a kind of preparation method who is used for the chainextender of aqueous polyurethane according to claim 1 is characterized in that: described hydrophilic chain extender is 2,2-dimethylol propionic acid DMPA or 2,2-dimethylolpropionic acid DMBA.
3. a kind of preparation method who is used for the chainextender of aqueous polyurethane according to claim 1 is characterized in that: described reactive monomer is oxyethane, propylene oxide, caprolactone or tetrahydrofuran (THF).
4. a kind of preparation method who is used for the chainextender of aqueous polyurethane according to claim 1 is characterized in that: described catalyzer is stannous octoate, stannous iso caprylate, tributyl methoxyl group tin, tert.-butoxy tin, phenol oxygen base tin, tin chloride, Tin tetrabromide, acetylize tin, butyl (tetra) titanate, aluminium isopropoxide, sodium hydroxide or potassium hydroxide.
5. a kind of preparation method who is used for the chainextender of aqueous polyurethane according to claim 1 is characterized in that: described promotor is an active hydrogen compounds.
6. a kind of preparation method who is used for the chainextender of aqueous polyurethane according to claim 5, it is characterized in that: described active hydride is phosphoric acid, nitric acid, the vitriol oil, hydrochloric acid, zinc chloride, the aluminum chloride fluosulfonic acid, methyl fluoride sulfonic acid, fluoroethane sulfonic acid, the methyl nitrobenzene-sulfonic acid, a kind of in the methyl methylsulfonate.
7. a kind of preparation method who is used for the chainextender of aqueous polyurethane according to claim 1 is characterized in that: the add-on of described catalyzer is 0-50ppm.
8. a kind of preparation method who is used for the chainextender of aqueous polyurethane according to claim 1 is characterized in that: the add-on of described promotor is 0-50ppm.
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Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN104910342A (en) * | 2015-06-30 | 2015-09-16 | 东华大学 | Preparation method of waterborne polyurethane |
| CN104211898B (en) * | 2014-08-13 | 2016-08-17 | 佛山市顺德区巴德富实业有限公司 | A kind of Amino End Group aqueous pu dispersions and preparation method thereof |
| CN104211890B (en) * | 2014-09-01 | 2016-09-28 | 福建宝利特科技股份有限公司 | A kind of aqueous polyurethane hydrophilic chain extender and preparation method thereof |
| CN106750126A (en) * | 2016-12-19 | 2017-05-31 | 东华大学 | A kind of preparation method of co-solvent aqueous polyurethane |
| CN108084423A (en) * | 2017-11-15 | 2018-05-29 | 孝感市锐思新材科技有限公司 | A kind of preparation method for increase-volume chain extension material |
| CN108222401A (en) * | 2018-04-11 | 2018-06-29 | 王正恒 | Composite insulation boards integrated board and preparation process |
| CN109972413A (en) * | 2019-04-02 | 2019-07-05 | 浙江诚迅新材料有限公司 | A kind of aqueous imitative sheep bar suede water-base resin of high viscosity and its preparation process |
| CN110041483A (en) * | 2019-04-02 | 2019-07-23 | 浙江诚迅新材料有限公司 | A kind of aqueous skin feel treatment agent of aqueous polyurethane and its preparation method and application the aqueous polyurethane |
| CN112646162A (en) * | 2020-12-14 | 2021-04-13 | 山东一诺威新材料有限公司 | Preparation method of polyether chain extender for waterborne polyurethane |
| CN113105602A (en) * | 2020-01-13 | 2021-07-13 | 浙江诚迅新材料有限公司 | Microfiber superfine fold line bonding layer resin and production process thereof |
| CN114805783A (en) * | 2021-01-18 | 2022-07-29 | 万华化学集团股份有限公司 | Preparation method of hydrophilic chain extender and application of chain extender in waterborne polyurethane |
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| CN104211898B (en) * | 2014-08-13 | 2016-08-17 | 佛山市顺德区巴德富实业有限公司 | A kind of Amino End Group aqueous pu dispersions and preparation method thereof |
| CN104211890B (en) * | 2014-09-01 | 2016-09-28 | 福建宝利特科技股份有限公司 | A kind of aqueous polyurethane hydrophilic chain extender and preparation method thereof |
| CN104910342B (en) * | 2015-06-30 | 2018-01-19 | 东华大学 | A kind of preparation method of aqueous polyurethane |
| CN104910342A (en) * | 2015-06-30 | 2015-09-16 | 东华大学 | Preparation method of waterborne polyurethane |
| CN106750126A (en) * | 2016-12-19 | 2017-05-31 | 东华大学 | A kind of preparation method of co-solvent aqueous polyurethane |
| CN106750126B (en) * | 2016-12-19 | 2019-04-09 | 东华大学 | A kind of preparation method of co-solvent aqueous polyurethane |
| CN108084423A (en) * | 2017-11-15 | 2018-05-29 | 孝感市锐思新材科技有限公司 | A kind of preparation method for increase-volume chain extension material |
| CN108222401B (en) * | 2018-04-11 | 2020-06-23 | 济南正恒聚氨酯材料有限公司 | Composite insulation board integrated board and preparation process |
| CN108222401A (en) * | 2018-04-11 | 2018-06-29 | 王正恒 | Composite insulation boards integrated board and preparation process |
| CN109972413A (en) * | 2019-04-02 | 2019-07-05 | 浙江诚迅新材料有限公司 | A kind of aqueous imitative sheep bar suede water-base resin of high viscosity and its preparation process |
| CN110041483A (en) * | 2019-04-02 | 2019-07-23 | 浙江诚迅新材料有限公司 | A kind of aqueous skin feel treatment agent of aqueous polyurethane and its preparation method and application the aqueous polyurethane |
| CN113105602A (en) * | 2020-01-13 | 2021-07-13 | 浙江诚迅新材料有限公司 | Microfiber superfine fold line bonding layer resin and production process thereof |
| CN112646162A (en) * | 2020-12-14 | 2021-04-13 | 山东一诺威新材料有限公司 | Preparation method of polyether chain extender for waterborne polyurethane |
| CN112646162B (en) * | 2020-12-14 | 2022-10-04 | 山东一诺威新材料有限公司 | Preparation method of polyether chain extender for waterborne polyurethane |
| CN114805783A (en) * | 2021-01-18 | 2022-07-29 | 万华化学集团股份有限公司 | Preparation method of hydrophilic chain extender and application of chain extender in waterborne polyurethane |
| CN114805783B (en) * | 2021-01-18 | 2023-05-26 | 万华化学集团股份有限公司 | Preparation method of hydrophilic chain extender and application of chain extender in waterborne polyurethane |
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