CN102391485A - Preparation method for water-tolerant cold-resistant polyester polyol - Google Patents
Preparation method for water-tolerant cold-resistant polyester polyol Download PDFInfo
- Publication number
- CN102391485A CN102391485A CN2011103010374A CN201110301037A CN102391485A CN 102391485 A CN102391485 A CN 102391485A CN 2011103010374 A CN2011103010374 A CN 2011103010374A CN 201110301037 A CN201110301037 A CN 201110301037A CN 102391485 A CN102391485 A CN 102391485A
- Authority
- CN
- China
- Prior art keywords
- polyester polyol
- water
- resistant polyester
- preparation
- fast cold
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Landscapes
- Polyesters Or Polycarbonates (AREA)
Abstract
The invention relates to a preparation method for water-tolerant cold-resistant polyester polyol, in particular to a method for preparing the polyester polyol from triethylene glycol, neopentyl glycol and adipic acid through reaction at high temperature. The method comprises the following steps of: adding the triethylene glycol, the neopentyl glycol, the adipic acid and a catalyst into a polycondensation kettle; introducing nitrogen from the upper part of the reaction kettle; heating gradually; keeping constant temperature; heating again; dehydrating; reducing pressure under the vacuum condition; distilling, dehydrating and dealcohoizing at high temperature under negative pressure; and cooling at normal temperature and discharging to obtain the product, namely the water-tolerant cold-resistant polyester polyol. The polyester polyol with excellent water tolerance and cold resistance is prepared by the method. Compared with the similar polyol, the polyester polyol has excellent performance, in particular excellent water tolerance and cold resistance. Thermoplastic polyurethane elastomer rubber (TPU) synthesized by the water-tolerant cold-resistant polyester polyol does not have any crack when the TPU is twisted at the temperature of below -20 DEG C for 200,000 times and does not have surface change when the TPU is put into a 10 percent aqueous solution of sodium hydroxide at the temperature of 60 DEG C for 48 hours.
Description
Technical field
The present invention relates to a kind of preparation method of water-fast cold-resistant polyester polyol, being specifically related to a kind of is raw material with Tri Ethyleneglycol, NSC 6366 and hexanodioic acid, at high temperature the method for prepared in reaction polyester polyol.
Background technology
Polyol compound is a polyurethane leather with one of main raw material of resin, and polyurethane leather contains two hydroxyls with the employed polyol compound of resin in its molecular structure, and molecular weight in 600 to 4500 scopes, is a kind of oligomerisation compound generally.Be used for polyurethane leather mainly comprises polyester polyol, polyether glycol and some other hydroxyl with the polyol compound of resin polyol compound.Comparatively speaking, the polyether glycol polymkeric substance has hydrolysis and the good characteristics of low-temperature pliability; Polyol polyester polymer has the advantages that physical strength is good and solvent resistance is good.Intensity is preferably PTMG relatively in the polyether glycol, and hydrolysis is preferably polycarbonate polyol, polycaprolactone and pinakon-hexanodioic acid series etc. relatively in the polyester polyol.The hydrolysis and the physical strength of Tri Ethyleneglycol in numerous polyvalent alcohols-hexanodioic acid series polyhydric alcohol polymer are all better relatively, thereby application prospect is better on hydrolysis resistant polyurethane is removed from office with resin.
Polyurethane leather is made up of soft chain segment and hard segment with its molecular structure of resin, and the consistency between the soft or hard section has determined the intensity of polyurethane leather with resin.In general the polarity of polyester polyol is higher than polyether glycol; Thereby the consistency of the hard section of polyester polyol and high polar is than good many of polyether glycol; So most polyurethane leathers select for use polyester polyol to prepare with resin, in the hope of obtaining the better goods of intensity.The kind of polyol compound has determined the hydrolytic resistance of polyurethane leather with resin, and polyurethane leather mainly is made up of carbamate with hard section of resin, and its structure hydrolysis stability is fine; Soft section mainly is to be made up of polyol compound, and its hydrolysis stability is changed greatly by the influence of polyvalent alcohol kind, and comparatively speaking, polyester polyol is than polyether glycol poor water resistance.
Tri Ethyleneglycol-NSC 6366-hexanodioic acid series polyvalent alcohol is a kind of polyester series polyvalent alcohol.This polyester polyol is close with hard section polarity, and overall compatibility is better, so better with the intensity of resin by Tri Ethyleneglycol-NSC 6366-hexanodioic acid series polyvalent alcohol synthetic polyurethane leather.Tri Ethyleneglycol contains two ehter bonds; The molecule flexibility is good; Lower temperature resistance is good, and ester group content is less in Tri Ethyleneglycol-NSC 6366-hexanodioic acid series polyvalent alcohol, symmetrical configuration; Two methyl in the NSC 6366 molecule have played the certain protection effect to ester group simultaneously, so better with its hydrolysis ability of resin with the polyurethane leather of this polyvalent alcohol preparation.
Summary of the invention
The preparation method who the purpose of this invention is to provide a kind of water-fast cold-resistant polyester polyol, this polyester polyol is to be that raw material prepared in reaction under hot conditions forms with Tri Ethyleneglycol, NSC 6366, hexanodioic acid.
According to technical scheme of the present invention: the preparation method of said water-fast cold-resistant polyester polyol comprises the steps:
Get 34.1～37.1 parts of Tri Ethyleneglycols, 2.9～5.9 parts of NSC 6366s, 34.2～35.2 parts of hexanodioic acids and catalyzer and drop in the polycondensation vessel for 0.0024～0.003 part, feeding nitrogen to pressure from reaction kettle top is 0.1～0.2MPa, progressively is warmed up to 130～140 ℃; Constant temperature 0.5～1.5h, the speed with 8～12 ℃/min progressively is warmed up to 220～230 ℃ subsequently, dewater to moisture content be 0.3%～0.5%; Feed nitrogen from the polycondensation vessel bottom, keep pressure 0.1～0.2MPa, vacuum decompression; High temperature vacuum distillation dehydration dealcoholysis; 220～230 ℃ of temperature, pressure are 0.8～0.9MPa, to product moisture be 0.01%～0.02%; The normal temperature cooling discharging promptly gets the water-fast cold-resistant polyester polyol of product.Unit is a weight part.
Said catalyzer is a tetra isopropyl titanate.
The mol ratio that said Tri Ethyleneglycol and NSC 6366 feed intake is 9: 1～8: 2.
Said Tri Ethyleneglycol and NSC 6366: the molar ratio of alcohol to acid of hexanodioic acid is 1.14～1.2.
Water-fast cold-resistant polyester polyol acid number after the said dehydration is 0.3～0.8mgKOH/g, and hydroxyl value is 53～58mgKOH/g.
Beneficial effect of the present invention: the present invention has prepared the superior polyester polyol of a kind of water-fast cold tolerance, and this polyvalent alcohol is compared performance with similar polyvalent alcohol all has preferable performance, and especially water-fast cold tolerance is superior.Be raw material synthetic TPUE rubber TPU thus at-20 ℃ of tortuous down flawlesses more than 200,000 times, 60 ℃ of 48h of the aqueous sodium hydroxide solution 10% are with the upper surface no change.
Embodiment
The present invention is elaborated through following instance.
Embodiment 1
Get Tri Ethyleneglycol 37.1kg, NSC 6366 2.9kg, hexanodioic acid 35.2kg and tetra isopropyl titanate (Tipt) 2.4g and drop in the polycondensation vessel, molar ratio of alcohol to acid is 1.14 in the raw material, and Tri Ethyleneglycol and NSC 6366 molar ratio are 9: 1, and feeding nitrogen to pressure from reaction kettle top is 0.1MPa; Progressively be warmed up to 130 ℃, constant temperature 0.5h, the speed with 8 ℃/min progressively is warmed up to 220 ℃ subsequently; Dewater to moisture content be 0.3%, feed nitrogen from the polycondensation vessel bottom, keep pressure 0.2MPa; Vacuum decompression, high temperature vacuum distillation dehydration dealcoholysis, 220 ℃ of temperature; Pressure is 0.9MPa, to product moisture be 0.018%, the normal temperature cooling discharging; Promptly get the water-fast cold-resistant polyester polyol of product, its acid number is 0.3mgKOH/g, and hydroxyl value is 53mgKOH/g.
Use this kind polyester polyol to synthesize TPU, be processed into the TPU epithelium of thick 1mm * 2cm * 6cm, this epithelium is tested on leather alternating bending tests machine ,-20 ℃ of down tortuous 200,000 flawlesses; In 10% aqueous sodium hydroxide solution, soak 60 ℃/48h surface no change.
Embodiment 2
Get Tri Ethyleneglycol 37.1kg, NSC 6366 2.9kg, hexanodioic acid 34.6kg and Tipt 2.4g and drop in the polycondensation vessel, molar ratio of alcohol to acid is 1.16 in the raw material, and Tri Ethyleneglycol and NSC 6366 molar ratio are 9: 1, and feeding nitrogen to pressure from reaction kettle top is 0.1MPa; Progressively be warmed up to 130 ℃, constant temperature 0.8h, the speed with 9 ℃/min progressively is warmed up to 230 ℃ subsequently; Dewater to moisture content be 0.4%, feed nitrogen from the polycondensation vessel bottom, keep pressure 0.2MPa; Vacuum decompression, high temperature vacuum distillation dehydration dealcoholysis, 220 ℃ of temperature; Pressure is 0.9MPa, to product moisture be 0.02%, the normal temperature cooling discharging; Promptly get the water-fast cold-resistant polyester polyol of product, its acid number is 0.4mgKOH/g, and hydroxyl value is 54mgKOH/g.
Use this kind polyester polyol to synthesize TPU, be processed into the TPU epithelium of thick 1mm * 2cm * 6cm, this epithelium is tested on leather alternating bending tests machine ,-20 ℃ of down tortuous 200,000 flawlesses; In 10% aqueous sodium hydroxide solution, soak 60 ℃/48h surface no change.
Embodiment 3
Get Tri Ethyleneglycol 35.6kg, NSC 6366 4.4kg, hexanodioic acid 35.5kg and Tipt 2.4g and drop in the polycondensation vessel, molar ratio of alcohol to acid is 1.15 in the raw material, and Tri Ethyleneglycol and NSC 6366 molar ratio are 8.5: 1.5, and feeding nitrogen to pressure from reaction kettle top is 0.1MPa; Progressively be warmed up to 135 ℃, constant temperature 1.0h, the speed with 10 ℃/min progressively is warmed up to 225 ℃ subsequently; Dewater to moisture content be 0.5%, feed nitrogen from the polycondensation vessel bottom, keep pressure 0.1MPa; Vacuum decompression, high temperature vacuum distillation dehydration dealcoholysis, 225 ℃ of temperature; Pressure is 0.85MPa, to product moisture be below 0.01%, the normal temperature cooling discharging; Promptly get the water-fast cold-resistant polyester polyol of product, its acid number is 0.5mgKOH/g, and hydroxyl value is 56mgKOH/g.
Use this kind polyester polyol to synthesize TPU, be processed into the TPU epithelium of thick 1mm * 2cm * 6cm, this epithelium is tested on leather alternating bending tests machine ,-20 ℃ of down tortuous 200,000 flawlesses; In 10% aqueous sodium hydroxide solution, soak 60 ℃/48h surface no change.
Embodiment 4
Get Tri Ethyleneglycol 35.6kg, NSC 6366 4.4kg, hexanodioic acid 34.6kg and Tipt 3.0g and drop in the polycondensation vessel, molar ratio of alcohol to acid is 1.18 in the raw material, and Tri Ethyleneglycol and NSC 6366 molar ratio are 8.5: 1.5, and feeding nitrogen to pressure from reaction kettle top is 0.2MPa; Progressively be warmed up to 140 ℃, constant temperature 1.5h, the speed with 11 ℃/min progressively is warmed up to 225 ℃ subsequently; Dewater to moisture content be 0.5%, feed nitrogen from the polycondensation vessel bottom, keep pressure 0.1MPa; Vacuum decompression, high temperature vacuum distillation dehydration dealcoholysis, 225 ℃ of temperature; Pressure is 0.85MPa, to product moisture be 0.015%, the normal temperature cooling discharging; Promptly get the water-fast cold-resistant polyester polyol of product, its acid number is 0.8mgKOH/g, and hydroxyl value is 58mgKOH/g.
Use this kind polyester polyol to synthesize TPU, be processed into the TPU epithelium of thick 1mm * 2cm * 6cm, this epithelium is tested on leather alternating bending tests machine ,-20 ℃ of down tortuous 200,000 flawlesses; In 10% aqueous sodium hydroxide solution, soak 60 ℃/48h surface no change.
Embodiment 5
Get Tri Ethyleneglycol 34.1kg, NSC 6366 5.9kg, hexanodioic acid 34.9kg and Tipt 3.0kg and drop in the polycondensation vessel, molar ratio of alcohol to acid is 1.19 in the raw material, and Tri Ethyleneglycol and NSC 6366 molar ratio are 8: 2, and feeding nitrogen to pressure from reaction kettle top is 0.2MPa; Progressively be warmed up to 140 ℃, constant temperature 1.5h, the speed with 12 ℃/min progressively is warmed up to 230 ℃ subsequently; Dewater to moisture content be 0.3%, feed nitrogen from the polycondensation vessel bottom, keep pressure 0.15MPa; Vacuum decompression, high temperature vacuum distillation dehydration dealcoholysis, 220 ℃ of temperature; Pressure is 0.8MPa, to product moisture be 0.014%, the normal temperature cooling discharging; Promptly get the water-fast cold-resistant polyester polyol of product, its acid number is 0.6mgKOH/g, and hydroxyl value is 57mgKOH/g.
Use this kind polyester polyol to synthesize TPU, be processed into the TPU epithelium of thick 1mm * 2cm * 6cm, this epithelium is tested on leather alternating bending tests machine ,-20 ℃ of down tortuous 200,000 flawlesses; In 10% aqueous sodium hydroxide solution, soak 60 ℃/48h surface no change.
Embodiment 6
Get Tri Ethyleneglycol 34.1kg, NSC 6366 5.9kg, hexanodioic acid 34.6kg and Tipt 3.0g and drop in the polycondensation vessel, molar ratio of alcohol to acid is 1.2 in the raw material, and Tri Ethyleneglycol and NSC 6366 molar ratio are 8: 2, and feeding nitrogen to pressure from reaction kettle top is 0.15MPa; Progressively be warmed up to 130 ℃, constant temperature 0.5, the speed with 8 ℃/min progressively is warmed up to 230 ℃ subsequently; Dewater to moisture content be 0.4%, feed nitrogen from the polycondensation vessel bottom, keep pressure 0.15MPa; Vacuum decompression, high temperature vacuum distillation dehydration dealcoholysis, 230 ℃ of temperature; Pressure is 0.8MPa, to product moisture be 0.012%, the normal temperature cooling discharging; Promptly get the water-fast cold-resistant polyester polyol of product, its acid number is 0.6mgKOH/g, and hydroxyl value is 56mgKOH/g.
Use this kind polyester polyol to synthesize TPU, be processed into the TPU epithelium of thick 1mm * 2cm * 6cm, this epithelium is tested on leather alternating bending tests machine ,-20 ℃ of down tortuous 200,000 flawlesses; In 10% aqueous sodium hydroxide solution, soak 60 ℃/48h surface no change.
Claims (5)
1. the preparation method of a water-fast cold-resistant polyester polyol, it is characterized in that: step is following by weight:
Get 34.1～37.1 parts of Tri Ethyleneglycols, 2.9～5.9 parts of NSC 6366s, 34.2～35.2 parts of hexanodioic acids and catalyzer and drop in the polycondensation vessel for 0.0024～0.003 part, feeding nitrogen to pressure from reaction kettle top is 0.1～0.2MPa, progressively is warmed up to 130～140 ℃; Constant temperature 0.5～1.5h, the speed with 8～12 ℃/min progressively is warmed up to 220～230 ℃ subsequently, dewater to moisture content be 0.3%～0.5%; Feed nitrogen from the polycondensation vessel bottom, keep pressure 0.1～0.2MPa, vacuum decompression; High temperature vacuum distillation dehydration dealcoholysis; 220～230 ℃ of temperature, pressure are 0.8～0.9MPa, to product moisture be 0.01%～0.02%; The normal temperature cooling discharging promptly gets the water-fast cold-resistant polyester polyol of product.
2. according to the preparation method of the said water-fast cold-resistant polyester polyol of claim 1, it is characterized in that: said catalyzer is a tetra isopropyl titanate.
3. according to the preparation method of the said water-fast cold-resistant polyester polyol of claim 1, it is characterized in that: the mol ratio that said Tri Ethyleneglycol and NSC 6366 feed intake is 9: 1～8: 2.
4. according to the preparation method according to the said water-fast cold-resistant polyester polyol of claim 1, it is characterized in that: said Tri Ethyleneglycol and NSC 6366: the molar ratio of alcohol to acid of hexanodioic acid is 1.14～1.2.
5. according to the preparation method of the said water-fast cold-resistant polyester polyol of claim 1, it is characterized in that: the water-fast cold-resistant polyester polyol acid number after the said dehydration is 0.3～0.8mgKOH/g, and hydroxyl value is 53～58mgKOH/g.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 201110301037 CN102391485B (en) | 2011-09-30 | 2011-09-30 | Preparation method for water-tolerant cold-resistant polyester polyol |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 201110301037 CN102391485B (en) | 2011-09-30 | 2011-09-30 | Preparation method for water-tolerant cold-resistant polyester polyol |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102391485A true CN102391485A (en) | 2012-03-28 |
| CN102391485B CN102391485B (en) | 2012-12-05 |
Family
ID=45858882
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 201110301037 Active CN102391485B (en) | 2011-09-30 | 2011-09-30 | Preparation method for water-tolerant cold-resistant polyester polyol |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102391485B (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103642010A (en) * | 2013-10-23 | 2014-03-19 | 江苏盈天化学有限公司 | Method for preparing adipic acid polyester polyol by utilizing recycled alcohol |
| CN109161008A (en) * | 2018-08-08 | 2019-01-08 | 山东诺威聚氨酯股份有限公司 | The preparation method of cold-resistant polyester polyol |
| CN111433249A (en) * | 2017-12-07 | 2020-07-17 | 路博润先进材料公司 | Thermoplastic polyurethane with high moisture vapor transmission and low water absorption |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101134809A (en) * | 2007-05-21 | 2008-03-05 | 李鹏 | Technical method for preparing aliphatic polyester |
| CN101508769A (en) * | 2009-03-23 | 2009-08-19 | 东华大学 | Process for producing non-crystalline polyester polyol for preparing thermosetting type adhesion agent |
-
2011
- 2011-09-30 CN CN 201110301037 patent/CN102391485B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101134809A (en) * | 2007-05-21 | 2008-03-05 | 李鹏 | Technical method for preparing aliphatic polyester |
| CN101508769A (en) * | 2009-03-23 | 2009-08-19 | 东华大学 | Process for producing non-crystalline polyester polyol for preparing thermosetting type adhesion agent |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103642010A (en) * | 2013-10-23 | 2014-03-19 | 江苏盈天化学有限公司 | Method for preparing adipic acid polyester polyol by utilizing recycled alcohol |
| CN103642010B (en) * | 2013-10-23 | 2015-09-30 | 江苏盈天化学有限公司 | A kind of method utilizing recovery alcohol to prepare hexanodioic acid kind polyester polyvalent alcohol |
| CN111433249A (en) * | 2017-12-07 | 2020-07-17 | 路博润先进材料公司 | Thermoplastic polyurethane with high moisture vapor transmission and low water absorption |
| US11827737B2 (en) | 2017-12-07 | 2023-11-28 | Lubrizol Advanced Materials, Inc. | Thermoplastic polyurethanes with high moisture vapor transmission and low water absorption |
| CN109161008A (en) * | 2018-08-08 | 2019-01-08 | 山东诺威聚氨酯股份有限公司 | The preparation method of cold-resistant polyester polyol |
| CN109161008B (en) * | 2018-08-08 | 2020-10-02 | 山东一诺威聚氨酯股份有限公司 | Preparation method of cold-resistant polyester polyol |
Also Published As
| Publication number | Publication date |
|---|---|
| CN102391485B (en) | 2012-12-05 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN105504215B (en) | A kind of aqueous polyurethane emulsion of color inhibition and preparation method thereof | |
| CN110885435B (en) | Process for preparing high functionality polyether polyols | |
| CN101824299B (en) | Method for preparing single-component high-solid content water-based polyurethane adhesive | |
| CN102391485B (en) | Preparation method for water-tolerant cold-resistant polyester polyol | |
| CN103642024B (en) | A kind of preparation method of terephthalic acid polyester polyether polyol | |
| CN112955563A (en) | Hydroformylated triglycerides and use thereof | |
| CN101967222A (en) | Preparation method of epoxidized castor oil modified water-borne polyurethane | |
| CN102408525B (en) | Acrylate modified maleopimaric acid aqueous polyurethane emulsion and preparation method thereof | |
| CN102633975A (en) | Epoxidized soybean oil based modified waterborne polyurethane gloss oil and preparation method thereof | |
| CN113583611A (en) | Bi-component solvent-free polyurethane adhesive and preparation method thereof | |
| GB2589033A (en) | Vegetable oil polyol and preparation method and application thereof in polyurethane material | |
| CN109232896B (en) | Epoxy resin toughening agent and preparation method and application thereof | |
| CN106519180A (en) | High-temperature self-repairing polyurethane emulsion and preparation method thereof | |
| CN111057224B (en) | High molecular weight high cis content polymaleic acid dihydric alcohol ester and preparation method thereof | |
| CN110172134B (en) | Hydrolysis-resistant polyurethane pultrusion resin composite material and preparation method thereof | |
| CN115594830B (en) | Bio-based polyester elastomer, preparation method and deformation-induced crystallization polyester elastomer | |
| CN114920914B (en) | Preparation and application of bio-based polyester based on 1, 3-butanediol | |
| CN102796063A (en) | Preparation method of novel monohydroxy biology-based epoxy resin | |
| CN102675585A (en) | Polyurethane microporous elastomer added with alcohol and amine compound, and preparation method and application of polyurethane microporous elastomer added with alcohol and amine compound | |
| CN113698587A (en) | Preparation method of hard foam polyether polyol | |
| US9676893B2 (en) | Polyurethane materials formed from epoxidized plant oils | |
| CN106986979A (en) | A kind of synchronous chain extension preparation technology of cationic aromatic aqueous polyurethane | |
| CN114031763A (en) | Cellulose polyether polyol, preparation method and application thereof, and preparation method of cellulose polyether polyol polyurethane foam | |
| CN109355055B (en) | Aqueous polyurethane adhesive emulsion composition and preparation method thereof | |
| CN101619127B (en) | Method for preparing polyurethane resin |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |