CN102775581A - Preparation method and application of novel end isocyanate polyurethane - Google Patents
Preparation method and application of novel end isocyanate polyurethane Download PDFInfo
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- CN102775581A CN102775581A CN2012102933131A CN201210293313A CN102775581A CN 102775581 A CN102775581 A CN 102775581A CN 2012102933131 A CN2012102933131 A CN 2012102933131A CN 201210293313 A CN201210293313 A CN 201210293313A CN 102775581 A CN102775581 A CN 102775581A
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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 isocyanate terminated urethane; Being specifically related to a kind of is a kind of novel isocyanate terminated urethane of feedstock production to reclaim polyethylene terephthalate (PET) and biological diesel oil byproduct raw glycerine; This urethane is used 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
The polystyrene foam sandwich board is claimed the EPS sandwich board again, is to do the top layer by color steel, and closed pore self-extinguishing type polystyrene foam is made core, through the robotization continuous forming machine with the color steel die mould after, bind a kind of new high-efficiency composite architectural materials form with sizing agent.Roofing, metope and clean room and combination freezer, building that this sandwich board is widely used in public building, industrial premises meet layer, shopping arcade etc.; Have 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 characteristics such as completion once.
Application number is that the patent of CN200410013331.5 discloses a kind of adhesive for polyurethane, and this sizing agent is used for gluing color-painted steel strip and polyester film, and cohesive force is strong; It is high to cohere the film shearing resistance; But this sizing agent belongs to acrylic acid copolymer grafted polyurethane type, and its raw material is formed except that 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 that operator and environment are all produced pollution.
PET is a kind of wrapping material commonly used such as food, medicine equipment, electric parts, and along with the continuous increase of social demand, volume of production and marketing increases day by day.Since two thousand three, global PET production capacity is with average annual about 9% speed expansion, 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 first big country.Along with the increase day by day of PET volume of production and marketing, depleted PET is also more and more, and the PET reutilization technology is reclaimed in exploitation energetically, and this resource utilization is utilized again, can play the effect of preserving the ecological environment again.
Biofuel is to be raw material with Vegetable oil lipoprotein such as oil crops, wild oilseed plant and engineering microalgae and animal oil and fat, food garbage wet goods; The reproducibility diesel oil that makes through alcoholysis (transesterify) technology; Because the normal alcohol that adopts of alcoholysis is methyl alcohol; So the chemical ingredients of biofuel is the different longer chain fatty acid methyl esters of serial molecular weight, its main by product is a 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 and needs 180 ℃, and this temperature is prone to cause side reactions such as its polymerization; And foreign pigment can not be removed fully, in addition, and in vacuum distillation process; Impurity such as spissated biofuel and fatty acid soaps parcel glycerine is unfavorable for the vaporization of glycerine, therefore; Need elder generation to its pre-treatment, underpressure distillation more just can make the higher glycerine of purity.
In sum; By product raw glycerine to reclaim PET and production biofuel is a raw material; Preparation is to the production of the less demanding polystyrene foam sandwich board sizing agent of material purity, and the Sustainable development to waste PET resource and biofuel industry has great importance.
Summary of the invention
One of technical assignment of the present invention is in order to remedy the deficiency of prior art, a kind of preparation method of novel isocyanate terminated urethane to be provided, and this preparation is adopted and reclaimed PET and raw glycerine is that main raw material makes, and raw materials cost is low, and technology is simple, and technology maturation is reliable.
Two of technical assignment of the present invention provides the purposes of this novel isocyanate terminated urethane, and this urethane is used for gluing polystyrene foam sandwich board, and its cured article snappiness is good and shrinking percentage is high, high to the two-phase interface bonding action.
Technical scheme of the present invention is following:
1. the preparation method of a novel isocyanate terminated urethane, step is following:
(1) raw glycerine is refining
The raw glycerine of 100 mass parts, the low boiling point organic solvent of adding 10-15 mass parts is again with acid neutralization, spinning; Lower floor is used to prepare soap, upper strata liquid underpressure distillation, and the low boiling point organic solvent that obtains recycles; Temperature rises to 105-110 ℃, and underpressure distillation 1h gets refining glycerine.
Said raw glycerine is isolating by product raw glycerine phase in the biofuel transesterify process; It is one of following that the raw material that the biofuel transesterify is used is selected from: wild plant grease, engineering microalgae waterplant grease, animal oil and fat, food garbage oil;
Said organic solvent is selected from one of following: methyl alcohol, ethanol, acetone, butanone, methyl acetate and ETHYLE ACETATE;
Said 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 biofuel and the glycerine desorption that is coated in the glycerine on the one hand, in addition, can generate lipid acid with the soap reaction, destroys the emulsifying effect of soap, makes the recovery increase of glycerine.
(2) polyester-polyether glycol is synthetic
It is broken to reclaim PET, and screening drop, stone, metal solid thing get the PET fragment; In reaction kettle, add PET fragment, refining glycerine 40-60 mass parts, divalent alcohol 100 mass parts, the catalyzer 0.05-0.10 mass parts of 60-80 mass parts, turn on agitator is heated to 210-220 ℃, reaction 2h; Adding dicarboxylic anhydride 15-30 mass parts in reaction kettle is reacted 4-6h down to anhydrous distillating at 210-220 ℃, vacuumizes, and vacuum tightness remains on-0.09MPa, and temperature is 100-110 ℃, insulated and stirred 30min, and cooling gets polyester-polyether glycol.
It is one of following that said divalent alcohol is selected from: terepthaloyl moietie, Ucar 35, glycol ether, triglycol;
It is one of following that said dicarboxylic anhydride is selected from: Succinic anhydried, Pyroglutaric acid, adipic anhydride, MALEIC ANHYDRIDE, Tetra hydro Phthalic anhydride;
Said catalyzer is made up 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;
Said vacuumizing is that moisture residual in polyester-polyether glycol is distillated, and the polyester that obtains like this-polyether glycol room temperature is clear state.
(3) preparation of isocyanate terminated urethane
In reaction kettle, add polyphenyl polymethylene polyisocyanates 100 mass parts, under agitation; Add polyester-polyether glycol 80-100 mass parts, the polyether glycol-2000 that above-mentioned (2) make again and be 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, heating, temperature is controlled at 50-60 ℃; Reaction 2-2.5h; Be cooled to room temperature, discharging gets novel isocyanate terminated urethane; Pack;
Said polyphenyl polymethylene polyisocyanates, functionality are 2.6-2.7, and viscosity (25 ℃) is 270-370mPa.s, and the quality percentage composition of free isocyanate groups is 31.5%;
Said polyether glycol-2000, hydroxyl value are that 54-58mgKOH/g, molecular weight are 2000, and viscosity is 100-300mPa.s/25 ℃.
Said dibutyl tin dilaurate and triethylene diamine are catalyzer; Because 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, and solidification rate is accelerated, and is high to two base material bonding actions.
2. the novel isocyanate terminated urethane of above-mentioned described preparation is used for the gluing of polystyrene foam sandwich board.
During use, this urethane evenly is coated to the surface of color steel or polystyrene foam plate, gluing through robotization continuous forming machine or batch process route; Resin added is 0.5kg/m
2Color 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, divalent alcohol, dicarboxylic anhydride, dibutyl tin dilaurate, triethylene diamine, polyether glycol-2000, methylene dichloride are the commercially available prod, buy in industrial chemicals market; Polyphenyl polymethylene polyisocyanates is available from the magnificent urethane in Yantai ten thousand ltd; Polyether glycol is available from the big ltd in Shandong blue star east.
The technical outstanding characteristics of the present invention are:
(1) will reclaim PET in right amount and produce the common raw material of biological diesel oil byproduct raw glycerine as the isocyanate terminated urethane of preparation.Under these processing condition, PET at first partial alcoholysis generates hydroxyl telechelic polyester, and dicarboxylic anhydride and glycerine and hydroxyl telechelic polyester further react, and have generated polyester-polyether glycol; Reclaim the use of PET and raw glycerine, for reclaiming PET and raw glycerine resource, new application approach and field is provided, and make the polyvalent alcohol raw materials cost reduce, added value of product increases; In addition, this polyvalent alcohol can be practiced thrift the product that substitutes the preparation of petrochemical complex resource with part.Therefore, the industrialization of this polyvalent alcohol has great importance to the Sustainable development of PET recycling economy and biofuel and polyvalent alcohol.
(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 that obtains-polyether glycol look shallow is transparent.
Embodiment
Below in conjunction with embodiment the present invention is further described, but protection scope of the present invention not only is confined to embodiment, the change that this field professional does technical scheme of the present invention all should belong in protection scope of the present invention.
Embodiment 1
A kind of preparation method of novel isocyanate terminated urethane
(1) raw glycerine is refining
The raw glycerine of 100g, the methyl alcohol of adding 10g, again with the hydrochloric acid neutralization, spinning, lower floor is used to prepare soap, upper strata liquid underpressure distillation, the methanol loop that obtains is used, and temperature rises to 105-110 ℃, and underpressure distillation 1h gets refining glycerine.
Said raw glycerine is isolating by product raw glycerine phase in the biofuel transesterify process, and the biofuel transesterify uses raw material to be food garbage oil;
(2) polyester-polyether glycol is synthetic
It is broken to reclaim PET, and screening drop, stone, metal solid thing get the PET fragment; In reaction kettle, add PET fragment, refining glycerine 40g, terepthaloyl moietie 100g, the catalyzer 0.05g of 60g, turn on agitator is heated to 210-220 ℃, reaction 2h; Adding Succinic anhydried 15g in reaction kettle reacts 6h down to anhydrous distillating at 210 ℃, vacuumizes, and vacuum tightness remains on-0.09MPa, 100 ℃ of controlled temperature, and insulated and stirred 30min, cooling gets polyester-polyether glycol.
Said catalyzer is made up 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 reaction kettle, add polyphenyl polymethylene polyisocyanates 100g successively, under agitation; Add polyester-polyether glycol 80g, the polyether glycol-2000 that above-mentioned (2) make and be 40g, dibutyl tin dilaurate 0.1g, triethylene diamine 0.5g, methylene dichloride 30g, heating, temperature is controlled at 50 ℃; Reaction 2.5h; Be cooled to room temperature, discharging gets novel isocyanate terminated urethane; Pack;
Said polyphenyl polymethylene polyisocyanates, functionality are 2.6-2.7, and viscosity (25 ℃) is 270-370mPa.s, and the quality percentage composition of free isocyanate groups is 31.5%;
Said polyether glycol-2000, hydroxyl value are that 54-58mgKOH/g, molecular weight are 2000, and viscosity is 100-300mPa.s/25 ℃.
Embodiment 2
A kind of preparation method of novel isocyanate terminated urethane
(1) raw glycerine is refining
The raw glycerine of 100g, the acetone of adding 15g, again with the sulfuric acid neutralization, spinning, lower floor is used to prepare soap, upper strata liquid underpressure distillation, the acetone recycle that obtains is used, and temperature rises to 105-110 ℃, and underpressure distillation 1h gets refining glycerine.
Said raw glycerine is isolating by product raw glycerine phase in the biofuel transesterify process, and the biofuel transesterify uses raw material to be Viscotrol C;
(2) polyester-polyether glycol is synthetic
It is broken to reclaim PET, and screening drop, stone, metal solid thing get the PET fragment; In reaction kettle, add PET fragment, refining glycerine 60g, Ucar 35 100g, the catalyzer 0.10g of 80g, turn on agitator is heated to 210-220 ℃, reaction 2h; Adding adipic anhydride 30g in reaction kettle reacts 4h down to anhydrous distillating at 220 ℃, vacuumizes, and vacuum tightness remains on-0.09MPa, 100 ℃ of controlled temperature, and insulated and stirred 30min, cooling gets polyester-polyether glycol.
Said catalyzer is made up 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 reaction kettle, add polyphenyl polymethylene polyisocyanates 100g successively, under agitation; Add polyester-polyether glycol 100g, the polyether glycol-2000 that above-mentioned (2) make again and be 20g, dibutyl tin dilaurate 0.5g, triethylene diamine 0.1g, methylene dichloride 50g, heating, temperature is controlled at 60 ℃; Reaction 2h; Be cooled to room temperature, discharging gets novel isocyanate terminated urethane; Pack;
Said polyphenyl polymethylene polyisocyanates, embodiment 1 simultaneously;
Said polyether glycol-2000 is with embodiment 1.
Embodiment 3
A kind of preparation method of novel isocyanate terminated urethane
(1) raw glycerine is refining
The raw glycerine of 100g, the ETHYLE ACETATE of adding 13g, again with the hydrochloric acid neutralization, spinning, lower floor is used to prepare soap, upper strata liquid underpressure distillation, the ETHYLE ACETATE that obtains recycles, and temperature rises to 105-110 ℃, and underpressure distillation 1h gets refining glycerine.
Said raw glycerine is isolating by product raw glycerine phase in the biofuel transesterify process; The raw material that the biofuel transesterify is used is the technical grade animal oil and fat;
(2) polyester-polyether glycol is synthetic
It is broken to reclaim PET, and screening drop, stone, metal solid thing get the PET fragment; In reaction kettle, add PET fragment, refining glycerine 50g, glycol ether 100g, the catalyzer 0.75g of 70g, turn on agitator is heated to 215 ℃, reaction 2h; Adding MALEIC ANHYDRIDE 25g in reaction kettle reacts 5h down to anhydrous distillating at 215 ℃, vacuumizes, and vacuum tightness remains on-0.09MPa, 100 ℃ of controlled temperature, and insulated and stirred 30min, cooling gets polyester-polyether glycol.
Said catalyzer is made up 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 reaction kettle, add polyphenyl polymethylene polyisocyanates 100g successively, under agitation; Add polyester-polyether glycol 90g, the polyether glycol-2000 that above-mentioned (2) make again and be 30g, dibutyl tin dilaurate 0.3g mass parts, triethylene diamine 0.2g, methylene dichloride 40g, heating, temperature is controlled at 55 ℃; Reaction 2h; Be cooled to room temperature, discharging gets novel isocyanate terminated urethane; Pack;
Said polyphenyl polymethylene polyisocyanates is with embodiment 1;
Said polyether glycol-2000 is with embodiment 1.
Embodiment 4
The application of isocyanate terminated urethane
(1), a kind of isocyanate terminated urethane of embodiment 1 preparation evenly is coated to the surface of color steel, with color steel and polystyrene foam plate gluing through the batch process route; Resin added is 0.5kg/m
2Color 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 used for gluing color steel and polystyrene foam plate, and step is with (1);
(3) the isocyanate terminated urethane of embodiment 3 preparations is used for gluing color steel and polystyrene foam plate, and step is with (1);
The 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 (9)
1. the preparation method of a novel isocyanate terminated urethane is characterized in that, step is following:
(1) raw glycerine is refining
The raw glycerine of 100 mass parts, the low boiling point organic solvent of adding 10-15 mass parts is again with acid neutralization, spinning; Lower floor is used to prepare soap, upper strata liquid underpressure distillation, and the low boiling point organic solvent that obtains recycles; Temperature rises to 105-110 ℃, and underpressure distillation 1h gets refining glycerine.
(2) polyester-polyether glycol is synthetic
It is broken to reclaim PET, and screening drop, stone, metal solid thing get the PET fragment; In reaction kettle, add PET fragment, refining glycerine 40-60 mass parts, divalent alcohol 100 mass parts, the catalyzer 0.05-0.10 mass parts of 60-80 mass parts, turn on agitator is heated to 210-220 ℃, reaction 2h; Adding dicarboxylic anhydride 15-30 mass parts in reaction kettle is reacted 4-6h down to anhydrous distillating at 210-220 ℃, vacuumizes, and vacuum tightness remains on-0.09MPa, and temperature is 100-110 ℃, insulated and stirred 30min, and cooling gets polyester-polyether glycol.
(3) preparation of isocyanate terminated urethane
In reaction kettle, add polyphenyl polymethylene polyisocyanates 100 mass parts, under agitation; Add polyester-polyether glycol 80-100 mass parts, the polyether glycol-2000 that above-mentioned (2) make again and be 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, heating, temperature is controlled at 50-60 ℃; Reaction 2-2.5h; Be cooled to room temperature, discharging gets novel isocyanate terminated urethane; Pack.
2. the preparation method of novel isocyanate terminated urethane as claimed in claim 1 is characterized in that, the raw glycerine in the said step (1) is an isolating by product raw glycerine phase in the biofuel transesterify process.
3. the preparation method of novel isocyanate terminated urethane as claimed in claim 1 is characterized in that, it is one of following that the organic solvent in the said step (1) is selected from: methyl alcohol, ethanol, acetone, butanone, methyl acetate and ETHYLE ACETATE.
4. the preparation method of novel isocyanate terminated urethane as claimed in claim 1 is characterized in that, the acid in the said step (1) is hydrochloric acid or sulfuric acid.
5. the preparation method of novel isocyanate terminated urethane as claimed in claim 1 is characterized in that, it is one of following that the divalent alcohol in the said step (2) is selected from: terepthaloyl moietie, Ucar 35, glycol ether, triglycol.
6. the preparation method of novel isocyanate terminated urethane as claimed in claim 1 is characterized in that, it is one of following that the dicarboxylic anhydride in the said step (2) is selected from: Succinic anhydried, Pyroglutaric acid, adipic anhydride, MALEIC ANHYDRIDE, Tetra hydro Phthalic anhydride.
7. the preparation method of novel isocyanate terminated urethane as claimed in claim 1; It is characterized in that; Catalyzer in the said step (2) is made up of zinc acetate and titanic acid ester; The mass ratio of zinc acetate and titanic acid ester is 1: 1.0-1.5, it is one of following that titanic acid ester is selected from: butyl(tetra)titanate, isopropyl titanate, iso-butyl titanate.
8. the preparation method of novel isocyanate terminated urethane as claimed in claim 1; It is characterized in that, the polyphenyl polymethylene polyisocyanates in the said step (3), functionality is 2.6-2.7; Viscosity (25 ℃) is 270-370mPa.s, and the quality percentage composition of free isocyanate groups is 31.5%
9. the preparation method of novel isocyanate terminated urethane as claimed in claim 1 is characterized in that, the polyether glycol-2000 in the said step (3), and hydroxyl value is that 54-58mgKOH/g, molecular weight are 2000, viscosity is 100-300mPa.s/25 ℃.
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| CN106827609A (en) * | 2016-12-30 | 2017-06-13 | 东莞市佳乾新材料科技有限公司 | A kind of preparation method of the water-fast polystyrene sandwich panel of insulation high |
| CN107522832A (en) * | 2017-08-10 | 2017-12-29 | 郑州大学 | A kind of bio-based polyurethane polyalcohol and preparation method thereof and the hard polyurethane foam and the method for preparation using its preparation |
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| 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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| 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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| CN102775581B (en) | 2014-02-05 |
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