CN102775581B - Preparation method and application of end isocyanate polyurethane - Google Patents
Preparation method and application of end isocyanate polyurethane Download PDFInfo
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- CN102775581B CN102775581B CN201210293313.1A CN201210293313A CN102775581B CN 102775581 B CN102775581 B CN 102775581B CN 201210293313 A CN201210293313 A CN 201210293313A CN 102775581 B CN102775581 B CN 102775581B
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Abstract
The invention relates to a preparation method and application of novel end isocyanate polyurethane, belonging to the field of comprehensive utilization of adhesives and recovered resources, novel environmental-friendly processes and composite materials. The preparation method comprises the steps of recovering polyethylene glycol terephthalate, biodiesel by-product crude glycerine and dihydric alcohol as the raw materials to prepare polyester-polyether polyatomic alcohol, and reacting the polyester-polyether polyatomic alcohol with isocyanate so as to prepare the novel end isocyanate polyurethane which is used for adhering polystyrene foam laminboards.
Description
Technical field
The present invention relates to a kind of preparation method and application of Novel end isocyanate polyurethane, be specifically related to a kind of take reclaim a kind of Novel end isocyanate polyurethane that polyethylene terephthalate (PET) and biological diesel oil byproduct raw glycerine are prepared as raw material, this urethane, for gluing polystyrene foam sandwich board, belongs to tackiness agent, comprehensive utilization of resources, environmental friendliness novel process and technical field of composite materials.
Background technology
Polystyrene foam sandwich board, claims again EPS sandwich board, is to do top layer by color steel, and closed pore self-extinguishing type polystyrene foam is made core, by automatization continuous forming machine, by after color steel die mould, binds a kind of new high-efficiency composite architectural materials forming with sizing agent.This sandwich board is widely used in roofing, metope and the clean room of public building, industrial premises and combines freezer, building Jie Ceng, shopping arcade etc.; The feature such as there is light weight, heat insulation, sound insulation, waterproof, antidetonation, fire prevention, the life-span is long, non-maintaining, elegant in appearance, speed of application fast, construction once completes.
Application number is that the patent of CN200410013331.5 discloses a kind of adhesive for polyurethane, this sizing agent is for gluing color-painted steel strip and polyester film, cohesive force is strong, cohere film shearing resistance high, but this sizing agent belongs to acrylic acid copolymer grafted polyurethane type, its raw material forms except vulcabond and polyester polyol, also has acrylic monomer, viscosity increaser, softening agent and solvent etc., raw material and synthesis technique are complicated, use toluene solvant all to produce pollution to operator and environment.
PET is a kind of wrapping material that food, medicine equipment, electric parts etc. are conventional, along with the continuous increase of social demand, and volume of production and marketing day by day.Since two thousand three, global PET production capacity is with the speed expansion of average annual 9% left and right, and 2005 annual capacities reach 5,470 ten thousand tons (output is 4,100 ten thousand tons).At present, China's output surpasses 2,000 ten thousand tons, becomes world PET productive consumption the first big country.Along with the increase day by day of PET volume of production and marketing, discarded PET is also more and more, and Devoting Major Efforts To Developing recycled PET reutilization technology can make this resource utilization recycling, can play the effect of preserving the ecological environment again.
Biofuel is that to take the Vegetable oil lipoprotein such as oil crops, Wild oil plant and engineering microalgae and animal grease, food garbage wet goods be raw material, the reproducibility diesel oil making by alcoholysis (transesterify) technique, because the normal alcohol adopting of alcoholysis is methyl alcohol, so, the chemical composition of biofuel is the longer chain fatty acid methyl esters that Series Molecules amount is different, and its Main By product is raw glycerine.As the substitute products of petrifaction diesel, biofuel is typical green novel energy source, and in recent years, this industry development is very fast, and the output of raw glycerine also increases sharply.
Underpressure distillation is one of raw glycerine method of purifying, but the boiling point of glycerine is up to 290 ℃, and its decompression distillates still needs 180 ℃, this temperature easily causes the side reactions such as its polymerization, and foreign pigment can not be removed completely, in addition, in vacuum distillation process, the impurity parcel glycerine such as concentrated biofuel and fatty acid soaps, be unfavorable for the vaporization of glycerine, therefore, need first to its pre-treatment, underpressure distillation again, just can make the glycerine that purity is higher.
In sum, the by product raw glycerine of recycled PET and production biofuel of take is raw material, the production of preparation to the less demanding polystyrene foam sandwich board of material purity sizing agent, the Sustainable development to waste PET resource and Biodiesel, has great importance.
Summary of the invention
One of technical assignment of the present invention is in order to make up the deficiencies in the prior art, and a kind of preparation method of Novel end isocyanate polyurethane is provided, and it is that main raw material makes that this preparation adopts recycled PET and raw glycerine, and raw materials cost is low, and technique is simple, and technology maturation is reliable.
Two of technical assignment of the present invention is to provide the purposes of this Novel end isocyanate polyurethane, and this urethane is for gluing polystyrene foam sandwich board, and its cured article snappiness is good and shrinking percentage is high, high to two-phase interface bonding action.
Technical scheme of the present invention is as follows:
1. a preparation method for Novel end isocyanate polyurethane, step is as follows:
(1) raw glycerine is refining
The raw glycerine of 100 mass parts, adds the low boiling point organic solvent of 10-15 mass parts, then with acid, neutralizes centrifugation, lower floor is for the preparation of soap, upper strata liquid underpressure distillation, and the low boiling point organic solvent obtaining recycles, temperature rises to 105-110 ℃, and underpressure distillation 1h, obtains refining glycerine.
Described raw glycerine is by product raw glycerin phase separated in biofuel Exchange Ester Process; It is one of following that the raw material that biofuel transesterify is used is selected from: wild plant grease, engineering microalgae waterplant grease, animal grease, food garbage oil;
Described organic solvent, is selected from one of following: methyl alcohol, ethanol, acetone, butanone, methyl acetate and ethyl acetate;
Described acid is hydrochloric acid or sulfuric acid;
The present invention adds organic solvent at glycerine in mutually, not only plays diluting effect, also has the glutinous effect of falling;
The present invention drips acid at glycerine in mutually, makes to be coated on biofuel and the glycerine desorption in glycerine on the one hand, in addition, can react with soap and generate lipid acid, and the emulsifying effect of destruction soap, makes the rate of recovery increase of glycerine.
(2) polyester-polyether glycol is synthetic
Recycled PET is broken, and screening drop, stone, metal solid thing, obtain PET fragment; To the PET fragment, refining glycerine 40-60 mass parts, dibasic alcohol 100 mass parts, the catalyzer 0.05-0.10 mass parts that add 60-80 mass parts in reactor, turn on agitator, is heated to 210-220 ℃, reaction 2h; In reactor, add dicarboxylic anhydride 15-30 mass parts, react 4-6h to anhydrous distillating at 210-220 ℃, vacuumize, vacuum keep is at-0.09MPa, and temperature is 100-110 ℃, and insulated and stirred 30min is cooling, obtains polyester-polyether glycol.
It is one of following that described dibasic alcohol is selected from: ethylene glycol, propylene glycol, glycol ether, triglycol;
It is one of following that described dicarboxylic anhydride is selected from: Succinic anhydried, Pyroglutaric acid, adipic anhydride, MALEIC ANHYDRIDE, Tetra hydro Phthalic anhydride;
Described catalyzer is comprised of zinc acetate and titanic acid ester, and the mass ratio of zinc acetate and titanic acid ester is 1: 1.0-1.5, and it is one of following that titanic acid ester is selected from: butyl (tetra) titanate, isopropyl titanate, iso-butyl titanate;
Described vacuumizing, is that moisture residual in polyester-polyether glycol is distillated, and the polyester-polyether glycol room temperature obtaining is like this clear state.
(3) preparation of isocyanate terminated urethane
In reactor, add polyphenyl polymethylene polyisocyanates 100 mass parts, under agitation, adding polyester-polyether glycol 80-100 mass parts, polyether glycol-2000 that above-mentioned (2) make is 20-40 mass parts, dibutyl tin dilaurate 0.1-0.5 mass parts, triethylene diamine 0.1-0.5 mass parts, methylene dichloride 30-50 mass parts again, heating, and temperature is controlled at 50-60 ℃, reaction 2-2.5h, be cooled to room temperature, discharging, obtains Novel end isocyanate polyurethane; Pack;
Described polyphenyl polymethylene polyisocyanates, functionality is 2.6-2.7, and viscosity (25 ℃) is 270-370mPa.s, and the quality percentage composition of free isocyanate groups is 31.5%;
Described polyether glycol-2000, hydroxyl value is that 54-58mgKOH/g, molecular weight are 2000, viscosity is 100-300mPa.s/25 ℃.
Described dibutyl tin dilaurate and triethylene diamine are catalyzer, due to dibutyl tin dilaurate and two kinds of catalyst by proportion of triethylene diamine are used, when this adhesive for polyurethane is used for gluing color steel and polystyrene foam plate, just viscous force increases, solidification rate is accelerated, high to two base material bonding actions.
2. the Novel end isocyanate polyurethane of preparation described above is for the gluing of polystyrene foam sandwich board.
During use, this urethane is evenly coated to the surface of color steel or polystyrene foam plate, gluing by automatization continuous forming machine or batch process route; Resin added is 0.5kg/m
2; Color steel and polystyrene foam plate gluing time 3h; 90 ℃ of compression shears are peeled off, and detect the interfacial failure rate of polystyrene foam plate.
The above raw glycerine, zinc acetate, titanic acid ester, PET, dibasic alcohol, dicarboxylic anhydride, dibutyl tin dilaurate, triethylene diamine, polyether glycol-2000, methylene dichloride, be commercially available prod, in industrial chemicals market, buys; Polyphenyl polymethylene polyisocyanates is purchased from Yantai Wan Hua urethane company limited; Polyether glycol is purchased from Shandong blue star Dong great company limited.
Feature outstanding in the technology of the present invention is:
(1) using appropriate recycled PET and the common raw material as the isocyanate terminated urethane of preparation of production biological diesel oil byproduct raw glycerine.Under these processing condition, PET first partial alcoholysis generates hydroxyl telechelic polyester, and dicarboxylic anhydride further reacts with glycerine and hydroxyl telechelic polyester, has generated polyester-polyether glycol; The use of recycled PET and raw glycerine, is recycled PET and raw glycerine resource, and new application approach and field is provided, and polyvalent alcohol raw materials cost is reduced, and added value of product increases; In addition, this polyvalent alcohol can be saved the product of preparing with part petroleum replacing chemical resource.Therefore, the Sustainable development of the industrialization of this polyvalent alcohol to PET recycling economy and biofuel and polyvalent alcohol, has great importance.
(2) polyester-polyether glycol is synthetic, has adopted zinc acetate and titanic acid ester concerted catalysis, causes speed of response to be accelerated, and the reaction times shortens, and the polyester-polyether glycol look obtaining is shallow transparent.
Embodiment
Below in conjunction with embodiment, the invention will be further described, but protection scope of the present invention is not only confined to embodiment, and the change that this field professional does technical solution of the present invention, all should belong in protection scope of the present invention.
Embodiment 1
A kind of preparation method of Novel end isocyanate polyurethane
(1) raw glycerine is refining
The raw glycerine of 100g, adds the methyl alcohol of 10g, then with hydrochloric acid neutralization, centrifugation, and lower floor is for the preparation of soap, upper strata liquid underpressure distillation, the methanol loop obtaining is used, and temperature rises to 105-110 ℃, and underpressure distillation 1h, obtains refining glycerine.
Described raw glycerine, is by product raw glycerin phase separated in biofuel Exchange Ester Process, and biofuel transesterify is used raw material for food garbage oil;
(2) polyester-polyether glycol is synthetic
Recycled PET is broken, and screening drop, stone, metal solid thing, obtain PET fragment; To the PET fragment, refining glycerine 40g, ethylene glycol 100g, the catalyzer 0.05g that add 60g in reactor, turn on agitator, is heated to 210-220 ℃, reaction 2h; In reactor, add Succinic anhydried 15g, react 6h to anhydrous distillating at 210 ℃, vacuumize, vacuum keep, at-0.09MPa, is controlled 100 ℃ of temperature, and insulated and stirred 30min is cooling, obtains polyester-polyether glycol.
Described catalyzer is comprised of zinc acetate and butyl (tetra) titanate, and the mass ratio of zinc acetate and butyl (tetra) titanate is 1: 1;
(3) preparation of isocyanate terminated urethane
In reactor, add successively polyphenyl polymethylene polyisocyanates 100g, under agitation, adding polyester-polyether glycol 80g, polyether glycol-2000 that above-mentioned (2) make is 40g, dibutyl tin dilaurate 0.1g, triethylene diamine 0.5g, methylene dichloride 30g, heating, and temperature is controlled at 50 ℃, reaction 2.5h, be cooled to room temperature, discharging, obtains Novel end isocyanate polyurethane; Pack;
Described polyphenyl polymethylene polyisocyanates, functionality is 2.6-2.7, and viscosity (25 ℃) is 270-370mPa.s, and the quality percentage composition of free isocyanate groups is 31.5%;
Described polyether glycol-2000, hydroxyl value is that 54-58mgKOH/g, molecular weight are 2000, viscosity is 100-300mPa.s/25 ℃.
Embodiment 2
A kind of preparation method of Novel end isocyanate polyurethane
(1) raw glycerine is refining
The raw glycerine of 100g, adds the acetone of 15g, then with sulfuric acid neutralization, centrifugation, and lower floor is for the preparation of soap, upper strata liquid underpressure distillation, the acetone recycle obtaining is used, and temperature rises to 105-110 ℃, and underpressure distillation 1h, obtains refining glycerine.
Described raw glycerine, is by product raw glycerin phase separated in biofuel Exchange Ester Process, and it is Viscotrol C that raw material is used in biofuel transesterify;
(2) polyester-polyether glycol is synthetic
Recycled PET is broken, and screening drop, stone, metal solid thing, obtain PET fragment; To the PET fragment, refining glycerine 60g, propylene glycol 100g, the catalyzer 0.10g that add 80g in reactor, turn on agitator, is heated to 210-220 ℃, reaction 2h; In reactor, add adipic anhydride 30g, react 4h to anhydrous distillating at 220 ℃, vacuumize, vacuum keep, at-0.09MPa, is controlled 100 ℃ of temperature, and insulated and stirred 30min is cooling, obtains polyester-polyether glycol.
Described catalyzer is comprised of zinc acetate and isopropyl titanate, and the mass ratio of zinc acetate and isopropyl titanate is 1
:1.5;
(3) preparation of isocyanate terminated urethane
In reactor, add successively polyphenyl polymethylene polyisocyanates 100g, under agitation, adding polyester-polyether glycol 100g, polyether glycol-2000 that above-mentioned (2) make is 20g, dibutyl tin dilaurate 0.5g, triethylene diamine 0.1g, methylene dichloride 50g again, heating, and temperature is controlled at 60 ℃, reaction 2h, be cooled to room temperature, discharging, obtains Novel end isocyanate polyurethane; Pack;
Described polyphenyl polymethylene polyisocyanates, simultaneously embodiment 1;
Described polyether glycol-2000, with embodiment 1.
Embodiment 3
A kind of preparation method of Novel end isocyanate polyurethane
(1) raw glycerine is refining
The raw glycerine of 100g, adds the ethyl acetate of 13g, then with hydrochloric acid neutralization, centrifugation, and lower floor is for the preparation of soap, upper strata liquid underpressure distillation, the ethyl acetate obtaining recycles, and temperature rises to 105-110 ℃, and underpressure distillation 1h, obtains refining glycerine.
Described raw glycerine is by product raw glycerin phase separated in biofuel Exchange Ester Process; The raw material that biofuel transesterify is used is technical grade animal grease;
(2) polyester-polyether glycol is synthetic
Recycled PET is broken, and screening drop, stone, metal solid thing, obtain PET fragment; To the PET fragment, refining glycerine 50g, glycol ether 100g, the catalyzer 0.75g that add 70g in reactor, turn on agitator, is heated to 215 ℃, reaction 2h; In reactor, add MALEIC ANHYDRIDE 25g, react 5h to anhydrous distillating at 215 ℃, vacuumize, vacuum keep, at-0.09MPa, is controlled 100 ℃ of temperature, and insulated and stirred 30min is cooling, obtains polyester-polyether glycol.
Described catalyzer is comprised of zinc acetate and iso-butyl titanate, and the mass ratio of zinc acetate and iso-butyl titanate is 1: 1.3,
(3) preparation of isocyanate terminated urethane
In reactor, add successively polyphenyl polymethylene polyisocyanates 100g, under agitation, adding polyester-polyether glycol 90g, polyether glycol-2000 that above-mentioned (2) make is 30g, dibutyl tin dilaurate 0.3g mass parts, triethylene diamine 0.2g, methylene dichloride 40g again, heating, and temperature is controlled at 55 ℃, reaction 2h, be cooled to room temperature, discharging, obtains Novel end isocyanate polyurethane; Pack;
Described polyphenyl polymethylene polyisocyanates, with embodiment 1;
Described polyether glycol-2000, with embodiment 1.
Embodiment 4
The application of isocyanate terminated urethane
(1), by batch process route, a kind of isocyanate terminated urethane of embodiment 1 preparation is evenly coated to the surface of color steel, by color steel and polystyrene foam plate gluing; Resin added is 0.5kg/m
2; Color steel and polystyrene foam plate gluing time 3h; 90 ℃ of compression shears are peeled off;
(2) the isocyanate terminated urethane of embodiment 2 preparations is for gluing color steel and polystyrene foam plate, and step is with (1);
(3) the isocyanate terminated urethane of embodiment 3 preparations is for gluing color steel and polystyrene foam plate, and step is with (1);
Color steel and the polystyrene foam plate of embodiment 1-3 gluing, 90 ℃ of compression shears are peeled off, and the interfacial failure rate of polystyrene foam plate is 100%.
Claims (5)
1. a preparation method for isocyanate terminated urethane, is characterized in that, step is as follows:
(1) raw glycerine is refining
The raw glycerine of 100 mass parts, adds the low boiling point organic solvent of 10-15 mass parts, then with acid, neutralizes centrifugation, lower floor is for the preparation of soap, upper strata liquid underpressure distillation, and the low boiling point organic solvent obtaining recycles, temperature rises to 105-110 ℃, and underpressure distillation 1h, obtains refining glycerine;
It is one of following that described organic solvent is selected from: methyl alcohol, ethanol, acetone, butanone, methyl acetate and ethyl acetate;
(2) polyester-polyether glycol is synthetic
Recycled PET is broken, and screening drop, stone, metal solid thing, obtain PET fragment; To the PET fragment, refining glycerine 40-60 mass parts, dibasic alcohol 100 mass parts, the catalyzer 0.05-0.10 mass parts that add 60-80 mass parts in reactor, turn on agitator, is heated to 210-220 ℃, reaction 2h; In reactor, add dicarboxylic anhydride 15-30 mass parts, react 4-6h to anhydrous distillating at 210-220 ℃, vacuumize, vacuum keep is at-0.09MPa, and temperature is 100-110 ℃, and insulated and stirred 30min is cooling, obtains polyester-polyether glycol;
Described catalyzer is comprised of zinc acetate and titanic acid ester, and the mass ratio of zinc acetate and titanic acid ester is 1: 1.0-1.5, and it is one of following that titanic acid ester is selected from: butyl (tetra) titanate, isopropyl titanate, iso-butyl titanate;
(3) preparation of isocyanate terminated urethane
In reactor, add polyphenyl polymethylene polyisocyanates 100 mass parts, under agitation, adding polyester-polyether glycol 80-100 mass parts, polyether glycol-2000 that above-mentioned (2) make is 20-40 mass parts, dibutyl tin dilaurate 0.1-0.5 mass parts, triethylene diamine 0.1-0.5 mass parts, methylene dichloride 30-50 mass parts again, heating, and temperature is controlled at 50-60 ℃, reaction 2-2.5h, be cooled to room temperature, discharging, obtains Novel end isocyanate polyurethane; Pack;
Described polyether glycol-2000, hydroxyl value is that 54-58mgKOH/g, molecular weight are 2000, viscosity is 100-300mPa.s/25 ℃;
Described polyphenyl polymethylene polyisocyanates, functionality is 2.6-2.7, and viscosity is 270-370mPa.s/25 ℃, and the quality percentage composition of free isocyanate groups is 31.5%.
2. the preparation method of isocyanate terminated urethane as claimed in claim 1, is characterized in that, the raw glycerine in described step (1) is by product raw glycerin phase separated in biofuel Exchange Ester Process.
3. the preparation method of isocyanate terminated urethane as claimed in claim 1, is characterized in that, the acid in described step (1) is hydrochloric acid or sulfuric acid.
4. the preparation method of isocyanate terminated urethane as claimed in claim 1, is characterized in that, it is one of following that the dibasic alcohol in described step (2) is selected from: ethylene glycol, propylene glycol, glycol ether, triglycol.
5. the preparation method of isocyanate terminated urethane as claimed in claim 1, is characterized in that, it is one of following that the dicarboxylic anhydride in described step (2) is selected from: Succinic anhydried, Pyroglutaric acid, adipic anhydride, MALEIC ANHYDRIDE, Tetra hydro Phthalic anhydride.
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| CN107793063B (en) * | 2016-12-23 | 2021-03-16 | 湖南大学 | Regenerated high polymer water-based emulsion prepared from waste PET (polyethylene terephthalate) polyester material |
| CN106827609B (en) * | 2016-12-30 | 2018-08-28 | 东莞市佳乾新材料科技有限公司 | A kind of preparation method of the high water-fast polystyrene sandwich panel of heat preservation |
| CN107522832B (en) * | 2017-08-10 | 2020-05-19 | 郑州大学 | Bio-based polyester polyol, preparation method thereof, polyurethane rigid foam prepared from bio-based polyester polyol and preparation method of polyurethane rigid foam |
| CN110452356A (en) * | 2019-07-09 | 2019-11-15 | 广东德美精细化工集团股份有限公司 | A kind of oligomer inhibitor of environment-friendly high-efficiency and preparation method thereof |
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| US5932666A (en) * | 1996-02-02 | 1999-08-03 | Ashland Inc. | Low profile additives for polyester resin systems based on asymmetric glycols and aromatic diacids |
| CN101875834A (en) * | 2009-04-28 | 2010-11-03 | 上海昱龄环保科技有限公司 | Method for synthesizing aqueous adhesive for processing wood by using polyester reclaiming material |
| CN101948669A (en) * | 2010-10-15 | 2011-01-19 | 济南大学 | Preparation method and use of aqueous polymer/isocyanate adhesive |
| CN101967363A (en) * | 2010-10-15 | 2011-02-09 | 济南大学 | Isocyanate/polyethylene terephthalate (PET) aqueous emulsion adhesive, preparation method thereof and use thereof |
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Patent Citations (4)
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| US5932666A (en) * | 1996-02-02 | 1999-08-03 | Ashland Inc. | Low profile additives for polyester resin systems based on asymmetric glycols and aromatic diacids |
| CN101875834A (en) * | 2009-04-28 | 2010-11-03 | 上海昱龄环保科技有限公司 | Method for synthesizing aqueous adhesive for processing wood by using polyester reclaiming material |
| CN101948669A (en) * | 2010-10-15 | 2011-01-19 | 济南大学 | Preparation method and use of aqueous polymer/isocyanate adhesive |
| CN101967363A (en) * | 2010-10-15 | 2011-02-09 | 济南大学 | Isocyanate/polyethylene terephthalate (PET) aqueous emulsion adhesive, preparation method thereof and use thereof |
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