CN105001395A - Waste PET-based polyurethane elastomer and preparation method thereof - Google Patents
Waste PET-based polyurethane elastomer and preparation method thereof Download PDFInfo
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- CN105001395A CN105001395A CN201510388285.5A CN201510388285A CN105001395A CN 105001395 A CN105001395 A CN 105001395A CN 201510388285 A CN201510388285 A CN 201510388285A CN 105001395 A CN105001395 A CN 105001395A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/08—Processes
- C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
- C08G18/12—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step using two or more compounds having active hydrogen in the first polymerisation step
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
- C08G18/4266—Polycondensates having carboxylic or carbonic ester groups in the main chain prepared from hydroxycarboxylic acids and/or lactones
- C08G18/4269—Lactones
- C08G18/4277—Caprolactone and/or substituted caprolactone
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
- C08G18/4854—Polyethers containing oxyalkylene groups having four carbon atoms in the alkylene group
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
- C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
- C08G18/6603—Compounds of groups C08G18/42, C08G18/48, or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38
- C08G18/6607—Compounds of groups C08G18/42, C08G18/48, or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3203
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2375/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
- C08J2375/04—Polyurethanes
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Abstract
The invention discloses a waste PET-based polyurethane elastomer which is prepared from the following raw materials, by weight, 20.8-27.7% of polytetramethylene oxide, 10.5-12.4% of methyl diphenylene diisocyanate, 12.6-15.7% of poly (epsilon-caprolactone) di-OH, 10.8-13.4% of 1,4-cyclohexane diisocyanate, 0.2-0.5% of N,N'-dicyclohexylcarbodiimide, 6.5-8.9% of neopentylene glycol, 0.04-0.08% of dibutyltin dilaurate and 27-35.6% of PET alcoholysate. A preparation method of the waste PET-based polyurethane elastomer comprises the following steps: (1) preparation of a polyurethane prepolymer; (2) preparation of a chain extender composition and reaction between the chain extender composition and the polyurethane prepolymer; and (3) preparation of the polyurethane elastomer by a tape casting method. According to the invention, a waste PET bottle is reutilized, and the prepared polyurethane elastomer has high heat resistance and can be applicable to a high-temperature environment. Meanwhile, production cost can be reduced remarkably, and the polyurethane elastomer is suitable for popularization and application.
Description
Technical field
The invention belongs to organic polymer resin synthesis technical field, be specifically related to a kind of polyurethane elastomer based on waste PET and preparation method thereof.
Background technology
Urethane has been widely used in the industries such as leather, coating, sizing agent, ink, cushioning material as a kind of polymer materials that can represent thermoplasticity, thermoset, elastomerics and Shape memory behavior unique when generation, and its structure possesses modularization, the soft section of structure replaced with hard section makes its performance easy-regulating.Polyurethane elastomer is as the important one's share of expenses for a joint undertaking in polyurethane material family, and the regulation and control of its performance and potential application are subject to extremely paying close attention to.Polyurethane elastomer, its surface resistivity lower (109-1013 Ω), flame retardant resistance is slightly good, and have very wide adjustable durometer level (to be low to moderate Shao A10, high to Shao D80), it can improve hardness under the prerequisite keeping caoutchouc elasticity, thus reaches very high supporting capacity.In addition, polyurethane elastomer also has outstanding wear resisting property, has the good title of " abrasive rubber ".Because polyurethane elastomer is a kind of strong polar macromolecule material, so also have fabulous oil-proofness, chemical proofing and water tolerance.And at room temperature the 10%-20% of polyurethane elastomer Absorbable rod vibrational energy, not worse than paracril, namely good absorbing.
Plastic packaging containers application market has a extensive future, and wherein, beverage industry has tempting business opportunity, and the beverages such as carbonated drink, fruit juice, vegetables juice plastic containers demand used grows with each passing day.Although PET bottle is started late in China's plastic wrapping industry, along with the introduction of a large amount of note stretch blow equipment, facilitate the production in enormous quantities of PET bottle, current topmost beverage and edible oil packing container.The widespread use of PET bottle and the huge commercial opportunities contained, will impel the fast development of PET bottle production industry, but waste plastic recycling problem is also following.Along with the annual production of PET bottle constantly increases, the quantity of annual waste PET bottle is also corresponding to be increased with direct ratio progression, the problems such as the environmental pollution that it brings also are far longer than the income that it brings, so the recovery reprocessing problem for the PET bottle of packaging industry is also day by day serious.
Summary of the invention
The object of the present invention is to provide a kind of polyurethane elastomer based on waste PET and preparation method thereof, be intended to the problem of environmental pollution that solution brings because of day by day serious package waste PET bottle, waste PET bottle recycles by the present invention again, remarkable reduction polyurethane elastomer production cost, the environmentally friendly polyurethane elastomer that synthesis application scope is widened day by day.
For achieving the above object, the technical solution adopted in the present invention is as follows:
Based on a polyurethane elastomer for waste PET, be prepared from by the raw material of following mass percent:
Polytetrahydrofuran diol 20.8% ~ 27.7%, diphenylmethanediisocyanate 10.5% ~ 12.4%, polycaprolactone diols 12.6% ~ 15.7%, 1,4-cyclohexyl diisocyanate 10.8% ~ 13.4%, N, N'-dicyclohexylcarbodiimide 0.2% ~ 0.5%, neopentyl glycol 6.5% ~ 8.9%, dibutyl tin dilaurate 0.04% ~ 0.08%, PET alcoholysate 27% ~ 35.6%, above raw materials quality per-cent summation is 100%.
Feature of the present invention is also, above-mentioned PET alcoholysate is prepared from by the raw material of following mass percent:
Waste PET bottle 31%, neopentyl glycol 24%, dipropylene glycol 40%, tetrabutyl titanate 5%, above raw materials quality per-cent summation is 100%.
Meanwhile, the invention provides a kind of elastic polyurethane preparation based on waste PET, this polyurethane elastomer is prepared from by the raw material of following mass percent:
Polytetrahydrofuran diol 20.8% ~ 27.7%, diphenylmethanediisocyanate 10.5% ~ 12.4%, polycaprolactone diols 12.6% ~ 15.7%, 1,4-cyclohexyl diisocyanate 10.8% ~ 13.4%, N, N'-dicyclohexylcarbodiimide 0.2% ~ 0.5%, neopentyl glycol 6.5% ~ 8.9%, dibutyl tin dilaurate 0.04% ~ 0.08%, PET alcoholysate 27% ~ 35.6%, above raw materials quality per-cent summation is 100%.
Described polyurethane elastomer carries out according to following concrete steps:
(1) base polyurethane prepolymer for use as is prepared:
By polytetrahydrofuran diol, diphenylmethanediisocyanate, polycaprolactone diols, 1,4-cyclohexyl diisocyanate is placed in container, warming-in-water to 80 DEG C stirs 2 hours, add catalyzer dibutyl tin dilaurate and continue stirring reaction in 30 minutes, in whole reaction process, maintaining nitrogen purge is protected;
(2) prepare chain extender composition, carry out chain extending reaction with base polyurethane prepolymer for use as:
By N, N'-dicyclohexylcarbodiimide, neopentyl glycol and PET alcoholysate are mixed in container, magnetic agitation makes it mix, then be added in the reaction system of step (1), under container being placed in room temperature after reaction 2min, stopped reaction after continuation stirring 1min;
(3) casting method prepares polyurethane elastomer:
Pour step (2) gained reaction slurry in mould casting film-forming, after solidification, extract residual solvent through vacuum again, then in 120 DEG C, thermal treatment 2.5 hours in 0.05MPa thermostatic drying chamber, can polyurethane elastomer be obtained.
Feature of the present invention is also, the PET alcoholysate of preparation is prepared from by the raw material of following mass percent: waste PET bottle 31%, neopentyl glycol 24%, dipropylene glycol 40%, tetrabutyl titanate 5%, and above raw materials quality per-cent summation is 100%.
Feature of the present invention is also, when preparing PET alcoholysate, carries out in the following manner:
A. package waste PET bottle pre-treatment: the waste PET bottle of recovery is cut into sheet, then carries out clean, obtains waste PET sheet;
B. take according to the mass percent of PET alcoholysate raw materials the waste PET sheet that neopentyl glycol, dipropylene glycol, tetrabutyl titanate and step a obtain respectively, wherein, the mass ratio that waste PET sheet accounts for preparation PET alcoholysate raw materials used according to waste PET bottle takes; Then the waste PET sheet taken is added in container together with neopentyl glycol, dipropylene glycol, be uniformly mixed in the oil bath pan of 180 DEG C, after 30 minutes, oil bath temperature be adjusted to 200 DEG C, and the tetrabutyl titanate dripping half deal is in mixed system, under agitation system reacts 3 hours;
C. in system, drip remaining tetrabutyl titanate, in oil bath pan, continue reaction after 1 hour, at room temperature reaction system is continued stirring 3 hours;
D. after having reacted, be brown viscous shape liquid in reaction system, stop stirring, viscous liquid is taken out, adopt vacuum drying oven to carry out drying, after drying completes, the PET alcoholysate of hydroxyl reaction activity must be possessed.
Feature of the present invention is also, in steps d, adopting vacuum drying oven to carry out dry temperature is 45 DEG C, and vacuum tightness is 0.05MPa, and the time is 12 hours.
Feature of the present invention is also, during the pre-treatment of package waste PET bottle, the waste PET bottle of recovery is cut into the sheet of 5mm × 5mm, is placed in container, stir after adding distil water, then ultrasonic cleaning, recycle 80 order screen filtration, by the process three times repeatedly of the stirring that adds water, ultrasonic cleaning and filtration, finally by waste PET sheet natural air drying after 3 hours in atmosphere, being put in vacuum tightness is again 0.05MPa, and temperature is in the vacuum drying oven of 60 DEG C dry 5 hours.
Now for prior art, beneficial effect of the present invention is as follows:
The present invention can solve the problem of environmental pollution brought because of day by day serious package waste PET bottle, after package waste PET bottle is reclaimed reprocessing by the present invention, it is generated the PET alcoholysate possessing hydroxyl reaction activity through alcoholysis process, use discarded PET alcoholysate as the small molecule chain extender in polyurethane elastomer synthesis, participate in the chain extending reaction of base polyurethane prepolymer for use as, PET alcoholysate is successfully accessed in polyurethane elastomer molecular chain, synthesize the polyurethane elastomer of excellent property, the present invention prepares polyurethane elastomer, the ratio that in raw material, PET alcoholysate accounts for is higher, employ a large amount of waste PET bottle, not only waste PET bottle is recycled, and the polyurethane elastomer thermotolerance of preparation is high, the environment of comparatively high temps can be applicable to.Meanwhile, the present invention significantly can reduce production cost, is suitable for applying.
Accompanying drawing explanation
Fig. 1 is the schema of the embodiment of the present invention based on the elastic polyurethane preparation of waste PET;
Fig. 2 is the infrared spectrogram of PET alcoholysate prepared by the embodiment of the present invention;
Fig. 3 is the GPC spectrogram of PET alcoholysate prepared by the embodiment of the present invention;
Fig. 4 is the infrared spectrogram of polyurethane elastomer prepared by the embodiment of the present invention;
Fig. 5 is the heat-resisting decomposing schematic representation that the embodiment of the present invention prepares polyurethane elastomer.
Embodiment
In order to make object of the present invention, technical scheme and advantage clearly understand, below in conjunction with drawings and Examples, the present invention is elaborated further.Should be appreciated that specific embodiment described herein only in order to explain the present invention, be not intended to limit the present invention.
The polyurethane elastomer based on waste PET that the embodiment of the present invention provides, is prepared from by the raw material of following mass percent:
Polytetrahydrofuran diol 20.8% ~ 27.7%, diphenylmethanediisocyanate 10.5% ~ 12.4%, polycaprolactone diols 12.6% ~ 15.7%, 1,4-cyclohexyl diisocyanate 10.8% ~ 13.4%, N, N'-dicyclohexylcarbodiimide 0.2% ~ 0.5%, neopentyl glycol 6.5% ~ 8.9%, dibutyl tin dilaurate 0.04% ~ 0.08%, PET alcoholysate 27% ~ 35.6%, above raw materials quality per-cent summation is 100%;
PET alcoholysate used is prepared from by the raw material of following mass percent:
Waste PET bottle 31%, neopentyl glycol 24%, dipropylene glycol 40%, tetrabutyl titanate 5%, above raw materials quality per-cent summation is 100%.
Fig. 1 shows the realization flow of embodiment of the present invention preparation based on the polyurethane elastomer of waste PET.The elastic polyurethane preparation based on waste PET that the embodiment of the present invention provides, carries out according to following concrete steps:
(1) base polyurethane prepolymer for use as is prepared:
By polytetrahydrofuran diol, diphenylmethanediisocyanate, polycaprolactone diols, 1,4-cyclohexyl diisocyanate is placed in container, warming-in-water to 80 DEG C stirs 2 hours, add catalyzer dibutyl tin dilaurate and continue stirring reaction in 30 minutes, obtain base polyurethane prepolymer for use as, in whole reaction process, maintaining nitrogen purge is protected;
(2) prepare chain extender composition, carry out chain extending reaction with base polyurethane prepolymer for use as:
By N, N'-dicyclohexylcarbodiimide, neopentyl glycol and PET alcoholysate are mixed in container, magnetic agitation makes it mix, then be added in the reaction system of step (1), under container being placed in room temperature after reaction 2min, stopped reaction after continuation stirring 1min;
(3) casting method prepares polyurethane elastomer:
Pour step (2) gained reaction slurry in mould casting film-forming, after solidification, extract residual solvent through vacuum again, then in 120 DEG C, thermal treatment 2.5 hours in 0.05MPa thermostatic drying chamber, can polyurethane elastomer be obtained.
In embodiments of the present invention, the PET alcoholysate of preparation is prepared from by the raw material of following mass percent: waste PET bottle 31%, neopentyl glycol 24%, dipropylene glycol 40%, tetrabutyl titanate 5%, above raw materials quality per-cent summation is 100%.
In embodiments of the present invention, when preparing PET alcoholysate, carry out in the following manner:
A. package waste PET bottle pre-treatment: the waste PET bottle of recovery is cut into sheet, then carries out clean, obtains waste PET sheet;
B. take according to the mass percent of PET alcoholysate raw materials the waste PET sheet that neopentyl glycol, dipropylene glycol, tetrabutyl titanate and step a obtain respectively, wherein, the mass ratio that waste PET sheet accounts for preparation PET alcoholysate raw materials used according to waste PET bottle takes; Then the waste PET sheet taken is added in container together with neopentyl glycol, dipropylene glycol, be uniformly mixed in the oil bath pan of 180 DEG C, after 30 minutes, oil bath temperature be adjusted to 200 DEG C, and the tetrabutyl titanate dripping half deal is in mixed system, under agitation system reacts 3 hours;
C. in system, drip remaining tetrabutyl titanate, in oil bath pan, continue reaction after 1 hour, at room temperature reaction system is continued stirring 3 hours;
D. after having reacted, be brown viscous shape liquid in reaction system, stop stirring, viscous liquid is taken out, adopt vacuum drying oven to carry out drying, after drying completes, the PET alcoholysate of hydroxyl reaction activity must be possessed.
In embodiments of the present invention, in steps d, adopting vacuum drying oven to carry out dry temperature is 45 DEG C, and vacuum tightness is 0.05MPa, and the time is 12 hours.
In embodiments of the present invention, during the pre-treatment of package waste PET bottle, the waste PET bottle of recovery is cut into the sheet of 5mm × 5mm, is placed in container, stir after adding distil water, then ultrasonic cleaning, recycle 80 order screen filtration, by the process three times repeatedly of the stirring that adds water, ultrasonic cleaning and filtration, finally by waste PET sheet natural air drying after 3 hours in atmosphere, being put in vacuum tightness is again 0.05MPa, and temperature is in the vacuum drying oven of 60 DEG C dry 5 hours.
The present invention can solve the problem of environmental pollution brought because of day by day serious package waste PET bottle, after package waste PET bottle is reclaimed reprocessing by the present invention, it is generated the PET alcoholysate possessing hydroxyl reaction activity through alcoholysis process, use discarded PET alcoholysate as the small molecule chain extender in polyurethane elastomer synthesis, participate in the chain extending reaction of base polyurethane prepolymer for use as, PET alcoholysate is successfully accessed in polyurethane elastomer molecular chain, synthesize the polyurethane elastomer of excellent property, the polyurethane elastomer that the present invention obtains not only recycles waste PET bottle, and the polyurethane elastomer thermotolerance of preparation is high, the environment of comparatively high temps can be applicable to.
In the building-up process of polyurethane elastomer, the selection of raw material is of crucial importance, in the present invention, raw material has used polytetrahydrofuran diol, because polytetrahydrofuran diol molecular chain is comparatively special, containing ehter bond and the methylene radical having considerable regular arrangement, therefore be best oligomer polyol raw material prepared by polyurethane elastomer, but this kind of cost of material costly, in the present invention, by using polycaprolactone glycol and PET alcoholysate as supporting the use, can significantly reduce costs, and reaction between the polyvalent alcohol energy combinationally used and vulcabond raw material is more thorough, can avoid in the course of the polymerization process reacting halfway problem, in addition, use dicyclohexylcarbodiimide and neopentyl glycol as supporting the use raw material, all to make reaction more thorough.
Fig. 2 and Fig. 3 is respectively infrared spectrogram and the GPC spectrogram of the PET alcoholysate that the embodiment of the present invention obtains.As shown in Figure 2, figure middle infrared spectrum crest segment display-C=O peak appears at 1720cm
-1place, thus, can determine to there is ester bond in alcoholysate, illustrate that PET successfully there occurs alcoholysis reaction, 3400cm
-1the peak at place is hydroxyl peak, 1270cm
-1and 1130cm
-1nonsymmetrical vibration and the symmetric vibration peak of the C-O-C in correspondence product on ester bond are distinguished in the peak at place, 726cm
-1that the peak at place is corresponding is=CH on phenyl ring, and the appearance at these peaks all shows that namely alcoholysate may be used for the study on the synthesis of polyurethane elastomer containing hydroxyl and ester group in alcoholysate.
Gel permeation chromatography (GPC) is used to carry out molecular weight determination to alcoholysis product, its result as shown in Figure 3, find that its weight-average molecular weight (Mw) is 1800g/mol, number-average molecular weight (Mn) is 1499g/mol, its molecular weight distribution index Mw/Mn=1.2, alcoholysate narrow molecular weight distribution is described, the product after alcoholysis can be used for the synthesis of polyurethane elastomer as oligomer polyol.
Fig. 4 is the infrared spectrogram of polyurethane elastomer prepared by the embodiment of the present invention.Detect polyurethane elastomer prepared by the present invention through Fourier's infrared radiation detection apparatus, result as shown in Figure 4, finds at 3379cm
-1there is wider characteristic peak in position, for being with the hydroxyl peak of hydrogen bond, at 1720cm
-1and 1551cm
-1position finds comparatively sharp-pointed peak type, is respectively the stretching vibration peak of C=O group in polyureas and C-N, N-H group, shows to generate carbamate groups (-NHCOO-), illustrate that preparation method of the present invention successfully synthesizes polyurethane elastomer.
Fig. 5 is the heat-resisting decomposing schematic representation that the embodiment of the present invention prepares polyurethane elastomer.Thermogravimetric analyzer is used to carry out resistance toheat analysis to polyurethane elastomer sample, detected result as shown in Figure 5, as can be seen from the figure, temperature of initial decomposition is approximately 257 DEG C, stop decomposition temperature and be about 433 DEG C, illustrate that the resistance toheat of the polyurethane elastomer of preparation is good, the environment of comparatively high temps can be applicable to.Therefore, the present invention prepares polyurethane elastomer, not only takes full advantage of package waste PET bottle, makes the polyurethane elastomer prepared have superior heat resistance simultaneously.
The present invention is raw materials used as follows:
| Title | Grade | Source |
| Neopentyl glycol | Analytical pure | Tianjin recovery fine chemistry industry institute |
| Dipropylene glycol | Analytical pure | Tianjin recovery fine chemistry industry institute |
| Tetrabutyl titanate | Chemical pure | Brassica rapa L analyses Chemical Industry Science Co., Ltd |
| Dibutyl tin dilaurate | Chemical pure | Brassica rapa L analyses Chemical Industry Science Co., Ltd |
| Isosorbide-5-Nitrae-cyclohexyl diisocyanate | Industrial goods | Shanghai Sheng Yu Chemical Co., Ltd. |
| Polycaprolactone diols | Chemical pure | Daicel chemical industry bead commercial firm of Japan |
| Diphenylmethanediisocyanate | Chemical pure | Aladdin reagent |
| Polytetrahydrofuran diol | Chemical pure | Aladdin reagent |
| Neopentyl glycol | Chemical pure | Aladdin reagent |
| N, N'-dicyclohexylcarbodiimide | Analytical pure | Chengdu Ke Long chemical reagent factory |
In order to there be understanding clearly to technical characteristic of the present invention, object and effect, now describe the specific embodiment of the present invention in detail with embodiment.
Embodiment 1
Preparation PET alcoholysate: utilize waste PET bottle to recycle and generate alcoholysate, adopt the raw material of mass fraction in table 1:
The recycling of table 1 waste PET bottle generates alcoholysate proportioning raw materials table (mass percent)
| Waste PET bottle | Neopentyl glycol | Dipropylene glycol | Tetrabutyl titanate |
| NPG | (DPG) | ||
| 31％ | 24％ | 40％ | 5％ |
Preparation method:
A, the waste PET bottle of recovery is cut into the sheet of 5mm × 5mm, is positioned in beaker, in beaker, pours distilled water glass stick into stir, beaker is put into Ultrasonic Cleaners cleaning 20 minutes, then the discarded sheet PET in beaker is poured out, use 80 order screen filtration, unwatering.By said process three times repeatedly, finally waste PET sheet is placed in 80 order mesh screens dry, natural air drying is after 3 hours in atmosphere, then to be put in vacuum tightness be 0.05MPa, and temperature is in the vacuum drying oven of 60 DEG C dry 5 hours;
B, according to raw materials quality per-cent, by the PET sheet of 31% with 24% neopentyl glycol, 40% dipropylene glycol together with throw in and be connected with in the there-necked flask of whipping appts, be uniformly mixed in the oil bath pan of 180 DEG C, after 30 minutes, oil bath temperature is adjusted to 200 DEG C, and the tetrabutyl titanate dripping 2.5% is in mixed system, under agitation system reacts 3 hours;
C, drip in system remaining 2.5% tetrabutyl titanate, tune up rotating speed, in oil bath pan, continue reaction 1 hour, then there-necked flask is taken out oil bath pan, at room temperature reaction system is continued stirring 3 hours;
After having reacted under d, room temperature, be brown viscous shape liquid in reaction system, stop stirring, viscous liquid is poured in 100ml beaker, put into the vacuum drying oven that vacuum tightness is 0.05MPa, temperature is 45 DEG C to take out after dry 12 hours, obtain the PET alcoholysate possessing hydroxyl reaction activity.
Embodiment 2
The present embodiment 2 prepares the polyurethane elastomer based on waste PET, adopts the raw material of mass percent in following table:
Concrete preparation process is as follows:
A, by diphenylmethanediisocyanate (MDI), polytetrahydrofuran diol (PTMEG), polycaprolactone diols (PCL) and 1,4-cyclohexyl diisocyanate (CHDI) puts into the four-hole boiling flask with whipping appts, thermometer, nitrogen tube, put into oil bath pan and be warming up to 80 DEG C of stirrings 2 hours, add catalyzer dibutyl tin dilaurate (DBTDL) and continue stirring reaction in 30 minutes, in whole reaction process, maintaining nitrogen purge is protected;
B, by N, N'-dicyclohexylcarbodiimide (DCC), the mixture of neopentyl glycol (NPG) and PET alcoholysate stirs 20min under magnetic stirrer effect, make it mix, modest viscosity, then uniform mixture is added in the reaction system of a fast, under react 2min under the rotating speed of 900 revs/min after, taking-up four-hole boiling flask is placed in room temperature fast, stopped reaction after continuation stirring 1min;
C, reacted after, to slow down rotating speed discharging, be poured into casting film-forming in clean Teflon mould, place in the thermostatic drying chamber of 65 DEG C and solidify week age, film after solidification extracts residual solvent through vacuum again, 120 DEG C, thermal treatment 2.5 hours in 0.05MPa thermostatic drying chamber, can synthesis of polyurethane elastomerics.
Embodiment 3
The present embodiment 3 prepares the polyurethane elastomer based on waste PET, and preparation method is identical with embodiment 2, different unlike proportioning raw materials, in the present embodiment, adopts the raw material of following mass percent:
| PTMEG | MDI | PCL | CHDI | DCC | NPG | DBTDL | PET alcoholysate |
| 27.7％ | 12.4％ | 12.6％ | 13.4％ | 0.2％ | 6.5％ | 0.04％ | 27.16％ |
Embodiment 4
The present embodiment 4 prepares the polyurethane elastomer based on waste PET, and preparation method is identical with embodiment 2, different unlike proportioning raw materials, in the present embodiment, adopts the raw material of following mass percent:
| PTMEG | MDI | PCL | CHDI | DCC | NPG | DBTDL | PET alcoholysate |
| 20.8％ | 10.5％ | 15.7％ | 10.8％ | 0.4％ | 7.2％ | 0.06％ | 34.54％ |
Embodiment 5
The present embodiment 5 prepares the polyurethane elastomer based on waste PET, and preparation method is identical with embodiment 2, different unlike proportioning raw materials, in the present embodiment, adopts the raw material of following mass percent:
| PTMEG | MDI | PCL | CHDI | DCC | NPG | DBTDL | PET alcoholysate |
| 20.8％ | 10.76％ | 12.6％ | 10.8％ | 0.5％ | 8.9％ | 0.04％ | 35.6％ |
Embodiment 6
The present embodiment 6 prepares the polyurethane elastomer based on waste PET, and preparation method is identical with embodiment 2, different unlike proportioning raw materials, in the present embodiment, adopts the raw material of following mass percent:
| PTMEG | MDI | PCL | CHDI | DCC | NPG | DBTDL | PET alcoholysate |
| 25.26％ | 10.5％ | 12.6％ | 12.5％ | 0.3％ | 8％ | 0.04％ | 30.8％ |
Above-described embodiment 2-6 has all successfully prepared the polyurethane elastomer that the present invention is based on waste PET, visual inspection is carried out by the five groups of polyurethane elastomers prepared embodiment 2-6, find that obtained polyurethane elastomer appearance transparence is higher, and it is better to be affectedly bashful feel, inviscid.
The foregoing is only preferred embodiment of the present invention, not in order to limit the present invention, all any amendments done within the spirit and principles in the present invention, equivalent replacement and improvement etc., all should be included within protection scope of the present invention.
Claims (7)
1. based on a polyurethane elastomer for waste PET, it is characterized in that, be prepared from by the raw material of following mass percent:
Polytetrahydrofuran diol 20.8% ~ 27.7%, diphenylmethanediisocyanate 10.5% ~ 12.4%, polycaprolactone diols 12.6% ~ 15.7%, 1,4-cyclohexyl diisocyanate 10.8% ~ 13.4%, N, N'-dicyclohexylcarbodiimide 0.2% ~ 0.5%, neopentyl glycol 6.5% ~ 8.9%, dibutyl tin dilaurate 0.04% ~ 0.08%, PET alcoholysate 27% ~ 35.6%, above raw materials quality per-cent summation is 100%.
2. a kind of polyurethane elastomer based on waste PET according to claim 1, is characterized in that, described PET alcoholysate is prepared from by the raw material of following mass percent:
Waste PET bottle 31%, neopentyl glycol 24%, dipropylene glycol 40%, tetrabutyl titanate 5%, above raw materials quality per-cent summation is 100%.
3. based on an elastic polyurethane preparation for waste PET, it is characterized in that, described polyurethane elastomer is prepared from by the raw material of following mass percent:
Polytetrahydrofuran diol 20.8% ~ 27.7%, diphenylmethanediisocyanate 10.5% ~ 12.4%, polycaprolactone diols 12.6% ~ 15.7%, 1,4-cyclohexyl diisocyanate 10.8% ~ 13.4%, N, N'-dicyclohexylcarbodiimide 0.2% ~ 0.5%, neopentyl glycol 6.5% ~ 8.9%, dibutyl tin dilaurate 0.04% ~ 0.08%, PET alcoholysate 27% ~ 35.6%, above raw materials quality per-cent summation is 100%;
Described polyurethane elastomer carries out according to following concrete steps:
(1) base polyurethane prepolymer for use as is prepared:
By polytetrahydrofuran diol, diphenylmethanediisocyanate, polycaprolactone diols, 1,4-cyclohexyl diisocyanate is placed in container, warming-in-water to 80 DEG C stirs 2 hours, add catalyzer dibutyl tin dilaurate and continue stirring reaction in 30 minutes, obtain base polyurethane prepolymer for use as, in whole reaction process, maintaining nitrogen purge is protected;
(2) prepare chain extender composition, carry out chain extending reaction with base polyurethane prepolymer for use as:
By N, N'-dicyclohexylcarbodiimide, neopentyl glycol and PET alcoholysate are mixed in container, magnetic agitation makes it mix, obtain chain extender composition, then be added in the reaction system of step (1), under container being placed in room temperature after reaction 2min, stopped reaction after continuation stirring 1min;
(3) casting method prepares polyurethane elastomer:
Pour step (2) gained reaction slurry in mould casting film-forming, after solidification, extract residual solvent through vacuum again, then in 120 DEG C, thermal treatment 2.5 hours in 0.05MPa thermostatic drying chamber, can polyurethane elastomer be obtained.
4. a kind of elastic polyurethane preparation based on waste PET according to claim 3, it is characterized in that, PET alcoholysate is prepared from by the raw material of following mass percent: waste PET bottle 31%, neopentyl glycol 24%, dipropylene glycol 40%, tetrabutyl titanate 5%, and above raw materials quality per-cent summation is 100%.
5. a kind of elastic polyurethane preparation based on waste PET according to claim 4, is characterized in that, during preparation PET alcoholysate, carries out in the following manner:
A. package waste PET bottle pre-treatment: the waste PET bottle of recovery is cut into sheet, then carries out clean, obtains waste PET sheet;
B. take according to the mass percent of PET alcoholysate raw materials the waste PET sheet that neopentyl glycol, dipropylene glycol, tetrabutyl titanate and step a obtain respectively, wherein, the mass ratio that waste PET sheet accounts for preparation PET alcoholysate raw materials used according to waste PET bottle takes; Then the waste PET sheet taken is added in container together with neopentyl glycol, dipropylene glycol, be uniformly mixed in the oil bath pan of 180 DEG C, after 30 minutes, oil bath temperature be adjusted to 200 DEG C, and the tetrabutyl titanate dripping half deal is in mixed system, under agitation system reacts 3 hours;
C. in system, drip remaining tetrabutyl titanate, in oil bath pan, continue reaction after 1 hour, at room temperature reaction system is continued stirring 3 hours;
D. after having reacted, be brown viscous shape liquid in reaction system, stop stirring, viscous liquid is taken out, adopt vacuum drying oven to carry out drying, after drying completes, the PET alcoholysate of hydroxyl reaction activity must be possessed.
6. a kind of elastic polyurethane preparation based on waste PET according to claim 5, is characterized in that, in steps d, adopting vacuum drying oven to carry out dry temperature is 45 DEG C, and vacuum tightness is 0.05MPa, and the time is 12 hours.
7. a kind of elastic polyurethane preparation based on waste PET according to claim 5, it is characterized in that, during the pre-treatment of package waste PET bottle, the waste PET bottle of recovery is cut into the sheet of 5mm × 5mm, be placed in container, stir after adding distil water, then ultrasonic cleaning, recycle 80 order screen filtration, by the process three times repeatedly of the stirring that adds water, ultrasonic cleaning and filtration, finally by waste PET sheet natural air drying after 3 hours in atmosphere, then to be put in vacuum tightness be 0.05MPa, and temperature is in the vacuum drying oven of 60 DEG C dry 5 hours.
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