CN111499850A - Carbon dioxide-based polyol, and preparation method and application thereof - Google Patents
Carbon dioxide-based polyol, and preparation method and application thereof Download PDFInfo
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- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
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- C08G18/00—Polymeric products of isocyanates or isothiocyanates
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- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
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- 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
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- C08G18/6622—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 C08G18/3225 or C08G18/3271 and/or polyamines of C08G18/38 with compounds of group C08G18/3271
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- 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
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- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
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- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/24—Acids; Salts thereof
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Abstract
The invention relates to the technical field of chemical production, in particular to a preparation method and application of carbon dioxide-based polyol. The carbon dioxide-based polyol provided by the invention has the structure shown in the formula (I), wherein m is more than or equal to 3 and less than or equal to 60. The carbon dioxide-based polyol provided by the invention is alkali-resistant and oxidation-resistant, simultaneously realizes the recycling of PET, is green and environment-friendly, and the waterborne polyurethane adhesive finally prepared from the carbon dioxide-based polyol has excellent bonding performance and alkali-resistant and oxidation-resistant performances. Experiments show that the T-shaped peeling strength of the waterborne polyurethane adhesive is not lower than 80N/50 mm; the T-type peel strength (alkali resistance 360h) is higher than 70N/50mm, the retention rate of the T-type peel strength (alkali resistance 360h) is not lower than 90.0%, the T-type peel strength (oxidation resistance 360h) is higher than 70N/50mm, and the retention rate of the T-type peel strength (oxidation resistance 360h) is higher than 89N/50 mm.
Description
Technical Field
The invention relates to the technical field of chemical production, in particular to a preparation method and application of carbon dioxide-based polyol.
Background
PET (polyethylene terephthalate) as a thermoplastic polymer material has excellent performance, is widely applied to the fields of synthetic fibers, plastic packaging bottles, engineering plastics, films and the like, particularly the application field of food packaging bottles, and realizes industrial production for the first time in 1953 by DuPont company. However, PET has extremely strong chemical inertness and cannot be biodegraded under natural conditions, and a great amount of used PET products are disposable consumer products, so that the production amount of waste PET is huge, which causes huge waste on human material resources and serious white pollution to the environment. Also, the production of PET comes at the cost of consuming non-renewable resources of petroleum. Therefore, the recycling and reusing of the waste PET is significant, and the waste of petrochemical resources is reduced while the environmental pollution is reduced. In recent years, the virtuous cycle of recycling resources in the PET industry has become an important technical development direction with the gradual increase of the production and waste of PET.
Up to now, the recycling method of PET is divided into physical method and chemical method, the physical method is that the waste PET is heated and melted, and after purification, the waste PET is extruded and molded by a screw extruder, and the method can be used for the recycling of spinning, drawing film, engineering plastics and the like, and has the advantages of simple process, low cost, less investment and little influence on environment. However, in the recovery process, side reactions are likely to occur and degrade, the intrinsic viscosity and the molecular weight are reduced, and the mechanical properties of the material are reduced. The recycled regenerated fiber has poor quality and cannot meet the performance requirements of high-grade products. And the recovery of PET by a chemical method is an efficient recycling mode, can be reused to manufacture a new PET raw material of a PET product, and is a sustainable development scheme. The main processes used for chemically recycling PET materials are alcoholysis processes. The Easterman company of the U.S. uses methanol as an alcoholysis agent to establish an industrial recovery unit for recovering PET. Waste PET is subjected to methanolysis reaction at the temperature of 200 ℃ and under proper high pressure to generate dimethyl terephthalate and ethylene glycol, and the dimethyl terephthalate is purified through crystallization and distillation to obtain a pure product. However, dimethyl terephthalate cannot necessarily be further converted to terephthalic acid in order to be useful in the preparation of PET. And the product contains more derivatives, and the separation series equipment for the classification and purification of the substances has higher cost and high cost. The methanolysis process is therefore limited. The ethylene glycol is used as an alcoholysis agent for alcoholysis, so that the reaction condition is mild, continuous production can be realized under normal pressure, and the main product, namely the ethylene terephthalate can be directly used for producing PET products, unsaturated polyester resins and the like. The Dupont company firstly provides a technology for alcoholysis of waste PET by ethylene glycol, and heats the waste PET, excessive ethylene glycol and tetrabutyl titanate catalyst to 170-190 ℃ under normal pressure, reacts for 2.5-3 h, dissolves ethylene terephthalate with hot water at 90 ℃, then removes insoluble substances and oligomers by filtration, and separates out an ethylene terephthalate product by cooling and crystallization. In 2000, the Japanese Imperial group recovered waste PET by glycolysis, the waste PET bottles were first physically crushed, washed and dissolved in ethylene glycol, the PET bottles were depolymerized at the boiling temperature of ethylene glycol and under a pressure of 0.1MPa to produce ethylene terephthalate, and then subjected to transesterification with methanol to produce dimethyl terephthalate and ethylene glycol. The invention patent 008036276 reports a glycolysis process for post consumer PET recycling that provides a process for depolymerizing and purifying used contaminated polyester by glycolysis comprising the steps of reacting the contaminated polyester with an amount of glycol of greater than about 1 to 5 total glycol units: the molar ratio of total dicarboxylic acid units is accomplished at a temperature of from about 150 to about 300 ℃ and an absolute pressure of from about 0.5 to about 3 bar. The purification is carried out by separation by density differences: the upper layer of reaction product is the lower density contaminant and the depolymerization product is the higher density, and is in the lower layer, and then the layers are separated by siphoning, vacuum suction, etc. the upper layer (contaminant) is removed from the reactor in stream 1 and the lower layer (polyester depolymerization product) is removed from the reactor in stream 2. A Lvxingmi research team of the institute of Process engineering of the Chinese academy of sciences provides an invention patent (application number: 201410016503.8), which takes ionic liquid as a catalyst and takes micromolecular dihydric alcohol such as ethylene glycol, diethylene glycol and the like as an alcoholysis agent to prepare the ethylene glycol terephthalate through the steps of degradation, crystallization, filtration, dissolution and the like. These reports are based on the alcoholysis of PET with a small-molecule diol as the alcoholysis agent to produce dimethyl terephthalate, the main raw material of PET. Shujie et al (Shujie, Yutianshi, Gemingqiao, mechanism of different polyols for degrading PET polyester, material guide, 2011, 25 (17): 398 & 401) report that ethylene terephthalate, butylene terephthalate and monomers containing epoxy structures are respectively obtained by three different polyol (ethylene glycol, 1, 4-butanediol and glycerol) alcoholysis waste PET, the prices of the monomers are low, the cost for preparing the corresponding monomers by the methods is 4800-5700 yuan/ton, the sale price of the response monomer obtained by a petrochemical method is 3000-3500 yuan/ton, and the method is higher than 160% of the production cost of a petrochemical method, so that the monomers prepared by the methods have no popularization value.
Disclosure of Invention
In view of the above, the technical problem to be solved by the present invention is to provide a carbon dioxide-based polyol, a preparation method and an application thereof, the carbon dioxide-based polyol provided by the present invention is alkali-resistant and oxidation-resistant, and the finally prepared aqueous polyurethane adhesive has excellent adhesion performance, alkali-resistant and oxidation-resistant performance.
The invention provides a carbon dioxide-based polyol which has a structure shown in a formula (I):
wherein m is more than or equal to 3 and less than or equal to 60.
Preferably, m is 3, 15, 40 or 60.
The invention also provides a preparation method of the carbon dioxide-based polyol, which comprises the following steps:
A1) mixing a PET material, poly (carbonate-ether) dihydric alcohol and a first catalyst, and stirring and reacting for 2-10 h at 180-220 ℃;
B1) and cooling the reacted product to 130-150 ℃, and vacuumizing for 1h to obtain the carbon dioxide-based polyol.
Preferably, the mass ratio of the PET material, the poly (carbonate-ether) glycol and the first catalyst is 150-230: 380-1200: 0.28 to 0.96;
the first catalyst comprises zinc acetate, manganese phosphate, zinc phosphate, calcium phosphate, a 3A molecular sieve, stannous chloride or butyl titanate;
the PET material comprises waste PET beverage bottle sheets and/or waste PET transparent packaging box sheets;
the number average molecular weight of the poly (carbonate-ether) glycol is 2000-7000;
in the poly (carbonate-ether) glycol, the content of carbonate is 30 wt% -70 wt%.
The invention also provides an aqueous polyurethane dispersion which is prepared from the following raw materials in parts by weight:
the carbon dioxide-based polyol is the carbon dioxide-based polyol or the carbon dioxide-based polyol prepared by the preparation method;
the first chain extender is selected from carboxylic acid and/or amine compounds;
the second chain extender is selected from alcohol compounds.
Preferably, the diisocyanate is selected from one or more of toluene diisocyanate, xylene methane diisocyanate, p-phenylene diisocyanate, 4' -diphenylmethane diisocyanate, isophorone diisocyanate, 1, 5-naphthalene diisocyanate and dicyclohexylmethane diisocyanate;
the first chain extender is selected from one or more of dimethylolpropionic acid, dimethylolbutyric acid, N-methyldiethanolamine, N-butyldiethanolamine, 2' -iminodiethanol and triethanolamine;
the second chain extender is selected from one or more of ethylene glycol, butanediol and diethylene glycol;
the second catalyst is selected from N, N-dimethylhexadecylamine, N-methylmorpholine, stannous octoate, dibutyltin dilaurate, zinc isooctanoate, nickel isooctanoate or zinc naphthoate;
the neutralizing agent is selected from one or more of triethylamine, ammonia water, dimethylethanolamine, N-methyldiethanolamine, trifluoroacetic acid and concentrated hydrochloric acid;
the solvent is selected from butanone, cyclohexanone or acetone.
The invention also provides a preparation method of the aqueous polyurethane dispersion, which comprises the following steps:
A2) under the condition of protective gas, reacting carbon dioxide-based polyol with diisocyanate in a partial solvent to obtain a first intermediate; the carbon dioxide-based polyol is the carbon dioxide-based polyol or the carbon dioxide-based polyol prepared by the preparation method;
B2) reacting the first intermediate, the first chain extender, the second chain extender and the second catalyst in a residual solvent to obtain a second intermediate;
C2) and mixing the second intermediate and a neutralizing agent, then mixing with water for emulsification, and distilling under reduced pressure to obtain the aqueous polyurethane dispersion.
Preferably, in the step B1), the reaction temperature is 85-90 ℃, and the reaction time is 2-4 h;
in the step B2), the reaction temperature is 60-65 ℃, and the reaction time is 1.5-3 h.
The invention also provides a waterborne polyurethane adhesive which is prepared from the following raw materials in parts by weight:
the aqueous polyurethane dispersion is the aqueous polyurethane dispersion or the aqueous polyurethane dispersion prepared by the preparation method.
The invention also provides a preparation method of the waterborne polyurethane adhesive, which comprises the following steps:
A3) mixing the aqueous polyurethane dispersion, heavy calcium carbonate, fumed silica and an aqueous defoaming agent, and sanding to obtain a first component;
B3) and stirring the first component, the water-based dispersant and the water-based thickener at the rotating speed of 1800-2200 rpm for 2-4 h to obtain the water-based polyurethane adhesive.
The invention provides a carbon dioxide-based polyol which has a structure shown in a formula (I), wherein m is more than or equal to 3 and less than or equal to 60. The carbon dioxide-based polyol provided by the invention is alkali-resistant and oxidation-resistant, simultaneously realizes the recycling of PET, is green and environment-friendly, and the waterborne polyurethane adhesive finally prepared from the carbon dioxide-based polyol has excellent bonding performance and alkali-resistant and oxidation-resistant performances.
Experimental results show that the T-shaped peel strength of the waterborne polyurethane adhesive prepared by the invention is not lower than 80N/50mm, and the adhesive property is excellent; the T-type peel strength (alkali resistance 360h) is higher than 70N/50mm, the retention rate of the T-type peel strength (alkali resistance 360h) is not lower than 90.0%, the T-type peel strength (oxidation resistance 360h) is higher than 70N/50mm, the retention rate of the T-type peel strength (oxidation resistance 360h) is higher than 89N/50mm, and the alkali resistance and the oxidation resistance are excellent.
In addition, the technical scheme provided by the invention is to synthesize a polymer polyol (carbon dioxide-based polyol), the synthesis cost is 2300-2600 yuan/ton, and the market price of similar products is more than 1 ten thousand yuan/ton.
Drawings
FIG. 1 is a NMR spectrum of a carbon dioxide based polyol of example 1;
FIG. 2 is an IR spectrum of the carbon dioxide based polyol of example 1.
Detailed Description
The technical solutions of the present invention will be described clearly and completely with reference to the following embodiments of the present invention, and it should be understood that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The invention provides a carbon dioxide-based polyol which has a structure shown in a formula (I):
wherein m is more than or equal to 3 and less than or equal to 60.
In certain embodiments of the invention, m is 3, 15, 40 or 60.
The carbon dioxide-based polyol provided by the invention is prepared from raw materials comprising a PET material, a poly (carbonate-ether) diol and a first catalyst.
In certain embodiments of the invention, the PET material comprises PET scrap pieces. In certain embodiments of the invention, the PET material comprises waste PET beverage bottle flakes and/or waste PET clear pack flakes.
In certain embodiments of the present invention, the poly (carbonate-ether) glycol has a number average molecular weight of 2000 to 7000. In certain embodiments, the poly (carbonate-ether) glycol has a number average molecular weight of 2000. In certain embodiments of the present invention, the polycarbonate-ether diol has a carbonate content of 30 wt% to 70 wt%. In certain embodiments, the polycarbonate-ether diol has a carbonate content of 30 wt%, 70 wt%, 40 wt%, or 50 wt%. In certain embodiments of the present invention, the poly (carbonate-ether) glycol is prepared according to the method disclosed in chinese patent application No. 201110231493.6.
In certain embodiments of the invention, the first catalyst comprises zinc acetate, manganese phosphate, zinc phosphate, calcium phosphate, 3A molecular sieve, stannous chloride, or butyl titanate. The first catalyst is used for promoting poly (carbonate-ether) dihydric alcohol to carry out alcoholysis on the PET sheet, and a macromolecular chain segment of the PET sheet is cracked into micromolecular polymer polyol.
In certain embodiments of the present invention, the mass ratio of the PET material, the poly (carbonate-ether) glycol, and the first catalyst is 150-230: 380-1200: 0.28 to 0.96. In certain embodiments of the invention, the mass ratio of the PET material, the poly (carbonate-ether) glycol, and the first catalyst is 150: 380: 0.28, 230: 1200: 0.96, 200: 1000: 0.45 or 205: 800: 0.72.
in some embodiments of the present invention, the hydroxyl value of the carbon dioxide-based polyol is 20-60 mg KOH/g, the acid value is 1-5 mg KOH/g, and the viscosity is 800-3000 cps (@30 ℃). In certain embodiments, the carbon dioxide-based polyol has a hydroxyl value of 20mg KOH/g, 60mg KOH/g, 40mg KOH/g, or 35mg KOH/g, an acid value of 1mg KOH/g, 5mg KOH/g, 3mg KOH/g, or 3.2mg KOH/g, a viscosity of 800cps (@30 ℃), 3000cps (@30 ℃), 2000cps (@30 ℃), or 1500cps (@30 ℃).
The carbon dioxide-based polyol provided by the invention is alkali-resistant and oxidation-resistant, simultaneously realizes the recycling of PET, is green and environment-friendly, and the waterborne polyurethane adhesive finally prepared from the carbon dioxide-based polyol has excellent bonding performance and alkali-resistant and oxidation-resistant performances.
The invention also provides a preparation method of the carbon dioxide-based polyol, which comprises the following steps:
A1) mixing a PET material, poly (carbonate-ether) dihydric alcohol and a first catalyst, and stirring and reacting for 2-10 h at 180-220 ℃;
B1) and cooling the reacted product to 130-150 ℃, and vacuumizing for 0.5-1 h to obtain the carbon dioxide-based polyol.
In the preparation method of the carbon dioxide-based polyol provided by the invention, the components and the proportion of the adopted raw materials are the same as those in the above, and are not described again.
In some embodiments of the present invention, the PET material further comprises, prior to mixing with the poly (carbonate-ether) glycol and the first catalyst, cutting, washing, and drying the PET material, in some embodiments, the cut size is (4-6) mm × (4-6) mm, in some embodiments, the cut size is 5mm × 5 mm.
In certain embodiments of the present invention, the step a1), the stirring reaction is performed under oil bath heating.
In certain embodiments of the present invention, the temperature of the stirring reaction in the step a1) is 180 ℃, 220 ℃, 200 ℃. In certain embodiments of the invention, the stirring reaction time is 10 hours, 2 hours, or 3 hours.
In certain embodiments of the present invention, in the step B1), the temperature after temperature reduction is 130 ℃, 150 ℃ or 140 ℃.
In step B1), the vacuum is applied to remove the generated small molecule polyol.
In certain embodiments of the invention, the evacuation is for a period of 1 hour.
The invention also provides an aqueous polyurethane dispersion which is prepared from the following raw materials in parts by weight:
the carbon dioxide-based polyol is the carbon dioxide-based polyol or the carbon dioxide-based polyol prepared by the preparation method. In certain embodiments of the present invention, the carbon dioxide based polyol is present in 140 parts, 85 parts, 120 parts, 110 parts, or 135 parts by weight.
In certain embodiments of the present invention, the weight portion of the diisocyanate is 45 parts, 23 parts, 40 parts, 34 parts, or 38 parts. In certain embodiments of the present invention, the diisocyanate is selected from one or more of toluene diisocyanate, xylene methane diisocyanate, p-xylylene diisocyanate, 4' -diphenylmethane diisocyanate, isophorone diisocyanate, 1, 5-naphthalene diisocyanate, and dicyclohexylmethane diisocyanate.
In certain embodiments of the present invention, the weight fraction of the first chain extender is 16.5 parts, 3.5 parts, 5 parts, 8.2 parts, or 7.5 parts. The first chain extender is a carboxylic acid and/or an amine compound. In certain embodiments of the present invention, the first chain extender is selected from one or more of dimethylolpropionic acid, dimethylolbutyric acid, N-methyldiethanolamine, N-butyldiethanolamine, 2' -iminodiethanol, and triethanolamine.
In certain embodiments of the present invention, the weight fraction of the second chain extender is 3.5 parts, 2.1 parts, 3 parts, 2.3 parts, or 3.2 parts. The second chain extender is selected from alcohol compounds. In certain embodiments of the present invention, the second chain extender is selected from one or more of ethylene glycol, butanediol, and diethylene glycol.
In certain embodiments of the present invention, the weight fraction of the second catalyst is 0.18 parts, 0.01 parts, 0.1 parts, 0.14 parts, or 0.13 parts. The second catalyst is selected from metal alkyl compounds, fatty amine compounds, alicyclic amine compounds or alcohol amine compounds, and is preferably N, N-dimethylhexadecylamine, N-methylmorpholine, stannous octoate, dibutyltin dilaurate, zinc isooctanoate, nickel isooctanoate or zinc naphthoate. The second catalyst is used to catalyze the reaction of the isocyanate with the polyol.
In certain embodiments of the present invention, the weight part of the neutralizing agent is 10.2 parts, 1.8 parts, 4.8 parts, 7.5 parts, or 8.2 parts. In certain embodiments of the present invention, the neutralizing agent is an amine compound or an inorganic acid, preferably one or more of triethylamine, ammonia, dimethylethanolamine, N-methyldiethanolamine, trifluoroacetic acid and concentrated hydrochloric acid. In certain embodiments of the invention, the concentrated hydrochloric acid has a mass concentration of 36% to 38%. In certain embodiments, the concentrated hydrochloric acid has a mass concentration of 36%.
In certain embodiments of the present invention, the solvent is present in an amount of 75 parts, 48 parts, 70 parts, 55 parts, or 60 parts by weight. In certain embodiments of the invention, the solvent is selected from butanone, cyclohexanone, or acetone.
In certain embodiments of the present invention, the weight parts of the deionized water is 160 parts, 110 parts, 140 parts, 125 parts, or 145 parts.
The invention also provides a preparation method of the aqueous polyurethane dispersion, which comprises the following steps:
A2) under the condition of protective gas, reacting carbon dioxide-based polyol with diisocyanate in a partial solvent to obtain a first intermediate; the carbon dioxide-based polyol is the carbon dioxide-based polyol or the carbon dioxide-based polyol prepared by the preparation method;
B2) reacting the first intermediate, the first chain extender, the second chain extender and the second catalyst in a residual solvent to obtain a second intermediate;
C2) and mixing the second intermediate and a neutralizing agent, then mixing with water for emulsification, and distilling under reduced pressure to obtain the aqueous polyurethane dispersion.
In the preparation method of the aqueous polyurethane dispersion provided by the invention, the components and the proportion of the adopted raw materials are the same as those in the above, and are not described again.
In certain embodiments of the invention, the shielding gas is nitrogen.
In some embodiments of the invention, in the step a2), the reaction temperature is 85 to 90 ℃, and the reaction time is 2 to 4 hours.
In certain embodiments of the invention, in the step B2), the reaction temperature is 60-65 ℃, and the reaction time is 1.5-3 h.
In certain embodiments of the present invention, the mass ratio of the partial solvent to the residual solvent is 30 to 45: 15 to 30. In certain embodiments, the mass ratio of the partial solvent to the remaining solvent is 45: 30. 30: 18. 40: 30. 35: 20 or 45: 15.
in certain embodiments of the invention, step B2) is performed under a nitrogen blanket.
In certain embodiments of the invention, step C2) is performed under a nitrogen blanket.
In certain embodiments of the present invention, in the step C2), the mass ratio of the deionized water to the neutralizing agent is 110 to 160: 1.5 to 10.5. In certain embodiments, in step C2), the mass ratio of deionized water to neutralizing agent is 160: 10.2, 110: 1.8, 140: 4.8, 125: 7.5 or 145: 8.2.
the method of distillation under reduced pressure is not particularly limited in the present invention, and a method of distillation under reduced pressure known to those skilled in the art may be used.
The invention also provides a waterborne polyurethane adhesive which is prepared from the following raw materials in parts by weight:
the aqueous polyurethane dispersion is the aqueous polyurethane dispersion described above. In certain embodiments of the invention, the parts by weight of the aqueous polyurethane dispersion is 100 parts, 140 parts, 160 parts, 200 parts, or 240 parts.
In certain embodiments of the present invention, the heavy calcium carbonate is present in an amount of 20 parts, 25 parts, 32 parts, 65 parts, or 85 parts by weight. The heavy calcium carbonate can improve the cohesion and the peel strength of the adhesive.
In certain embodiments of the present invention, the fumed silica is 0.08, 0.15, 0.28, 0.45, or 0.55 parts by weight. The fumed silica can prevent the heavy calcium carbonate powder from settling.
In certain embodiments of the present invention, the aqueous dispersant is present in an amount of 0.03 parts, 0.18 parts, 0.27 parts, 0.38 parts, or 0.58 parts by weight. In certain embodiments of the present invention, the aqueous dispersant is selected from BYK-034, BYK-085, BYK-190, BYK-180, or BYK-182.
In certain embodiments of the present invention, the aqueous defoamer is present in an amount of 0.11 parts, 0.20 parts, 0.28 parts, 0.15 parts, or 0.32 parts by weight. In certain embodiments of the present invention, the aqueous defoamer is selected from BYK-1615, BYK-024, BYK-020 or BYK-028.
In certain embodiments of the present invention, the aqueous thickener is present in an amount of 0.35 parts, 0.58 parts, 0.92 parts, 1.05 parts, or 1.28 parts by weight. In certain embodiments of the present invention, the aqueous thickener is selected from BYK-420, BYK-425, BYK-428, or BYK-430.
The invention also provides a preparation method of the waterborne polyurethane adhesive, which comprises the following steps:
A3) mixing the aqueous polyurethane dispersion, heavy calcium carbonate, fumed silica and an aqueous defoaming agent, and sanding to obtain a first component;
B3) and stirring the first component, the water-based dispersant and the water-based thickener at the rotating speed of 1800-2200 rpm for 2-4 h to obtain the water-based polyurethane adhesive.
In the preparation method of the aqueous polyurethane dispersion provided by the invention, the components and the proportion of the adopted raw materials are the same as those in the above, and are not described again.
In certain embodiments of the present invention, step a3), the mixing is performed at ambient temperature. In certain embodiments, the mixing is performed in a high speed disperser.
The ground calcium carbonate is ground in the aqueous polyurethane dispersion, so that the dispersion is more uniform.
In some embodiments of the invention, the sanding time is 3.5 to 5 hours. In some embodiments, the sanding time is 4 hours.
In certain embodiments of the invention, in step B3), the stirring speed is 2000rpm and the stirring time is 3 h.
In certain embodiments of the present invention, step B3) further comprises filtration after the stirring. In some embodiments, the filtering is performed with a 200 mesh screen.
The source of the above-mentioned raw materials is not particularly limited in the present invention, and may be generally commercially available.
Experimental results show that the T-shaped peel strength of the waterborne polyurethane adhesive prepared by the invention is not lower than 80N/50mm, and the adhesive property is excellent.
In order to further illustrate the present invention, the following examples are provided to describe the preparation and application of the carbon dioxide-based polyol of the present invention in detail, but they should not be construed as limiting the scope of the present invention.
The starting materials used in the following examples are all generally commercially available.
Example 1
Preparation of carbon dioxide-based polyol:
the method comprises the steps of cutting waste PET beverage bottle chips into chips with the size of 5mm × 5mm, cleaning and drying for later use, weighing 150g of PET chips, putting the PET chips into a three-neck flask, weighing 380g of poly (carbonate-ether) dihydric alcohol (the number average molecular weight is 2000, the content of carbonate units is 30 wt%), weighing 0.28g of zinc acetate, pouring the zinc acetate into the three-neck flask, putting the three-neck flask into an oil bath, starting a heating device and stirring, heating to 180 ℃, reacting for 10 hours, reducing the temperature to 130 ℃, starting a vacuum pump, vacuumizing for 1 hour, and discharging to obtain a product carbon dioxide-based polyol, wherein the carbon dioxide-based polyol has the structure shown in a formula (I), wherein m is 3, the hydroxyl value is 20mg KOH/g, the acid value is 1mg KOH/g, the viscosity is 800cps (@30 ℃), and a nuclear magnetic resonance hydrogen spectrum (H NMR) of the carbon dioxide-based polyol in example 1 is shown in a figure 1, and a figure 2 is an infrared spectrum (FTIR) of the carbon dioxide-based polyol in example 1.
H NMR(CDCl3As deuterated reagent): 1.43ppm, 2.32ppm, 3.66ppm, 3.75ppm, 3.86ppm, 4.00ppm, 4.52ppm, 4.71ppm, 7.27ppm, 8.04ppm, 8.13 ppm.
FTIR (KBr pellet): 498.4cm-1，731.5cm-1，882.6cm-1，944.6cm-1，1022.8cm-1，1100.3cm-1，1276.9cm-1，1370.6cm-1，1411.7cm-1，1453.6cm-1，1510.9cm-1，1582.9cm-1，1614.7cm-1，1718.5cm-1，1951.7cm-1，2875.9cm-1，2948.7cm-1，3057.8cm-1，3467.7cm-1。
Example 2
Preparation of carbon dioxide-based polyol:
the waste PET beverage bottle chips are cut into chips with the size of 5mm × 5mm, the chips are cleaned and dried for standby, 230g of PET chips are weighed and placed into a three-neck flask, 1200g of poly (carbonate-ether) dihydric alcohol (the number average molecular weight is 7000, the content of carbonate units is 70 wt%) is weighed, 0.96g of manganese acetate is weighed and poured into the three-neck flask, the three-neck flask is placed in an oil bath, a heating device and stirring are started, the temperature is increased to 220 ℃, the reaction is carried out for 2h, the temperature is reduced to 150 ℃, a vacuum pump is started, the vacuum pumping is carried out for 1h, discharging is carried out, the product carbon dioxide-based polyhydric alcohol is obtained, and the detection proves that the carbon dioxide-based polyhydric alcohol has the structure shown in the formula (I), wherein m is 60, the hydroxyl value is 60mg KOH/g, the acid value is 5mg KOH/g, and the viscosity is 3000 cps.
H NMR(CDCl3As deuterated reagent): 1.47ppm, 2.36ppm, 3.71ppm, 3.78ppm, 3.85ppm, 3.98ppm, 4.51ppm, 4.74ppm, 7.26ppm, 8.01ppm, 8.15 ppm.
FTIR (KBr pellet): 496.5cm-1，730.5cm-1，886.4cm-1，946.8cm-1，1023.4cm-1，1102.5cm-1，1278.1cm-1，1371.5cm-1，1412.4cm-1，1454.5cm-1，1512.4cm-1，1584.5cm-1，1610.3cm-1，1720.4cm-1，1953.8cm-1，2874.5cm-1，2945.2cm-1，3053.2cm-1，3469.8cm-1。
Example 3
Preparation of carbon dioxide-based polyol:
the waste PET transparent packaging box piece is cut into pieces of 5mm × 5mm, the pieces are cleaned and dried for standby, 200g of PET pieces are weighed and placed into a three-mouth flask, 1000g of poly (carbonate-ether) dihydric alcohol (the number average molecular weight is 5000, the content of carbonate units is 40 wt%) is weighed, 0.45g of 3A molecular sieve is weighed and poured into the three-mouth flask, the three-mouth flask is placed in an oil bath, a heating device and stirring are started, the temperature is increased to 200 ℃ by heating, the reaction time is 3h, the temperature is reduced to 140 ℃, a vacuum pump is started, the vacuum pumping is carried out for 1h, discharging is carried out, the product of the carbon dioxide-based polyhydric alcohol is obtained, and the carbon dioxide-based polyhydric alcohol has the structure shown in the formula (I), wherein m is 15, the hydroxyl value is 40mg KOH/g, the acid value is 3mg KOH/g, and the viscosity is 2000cps (@30 ℃).
H NMR(CDCl3As deuterated reagent): 1.39ppm, 2.38ppm, 3.69ppm, 3.82ppm, 3.89ppm, 4.01ppm, 4.55ppm, 4.78ppm, 7.26ppm, 8.01ppm, 8.17 ppm.
FTIR (KBr pellet): 493.2cm-1，729.5cm-1，881.7cm-1，944.3cm-1，1017.8cm-1，1103.7cm-1，1281.0cm-1，1375.4cm-1，1410.3cm-1，1457.5cm-1，1519.1cm-1，1579.2cm-1，1614.3cm-1，1724.54cm-1，1955.8cm-1，2879.1cm-1，2947.2cm-1，3048.5cm-1，3472.5cm-1。
Example 4
Preparation of carbon dioxide-based polyol:
the waste PET transparent packaging box sheet is cut into pieces of 5mm × 5mm, the pieces are cleaned and dried for standby, 205g of PET pieces are weighed and put into a three-mouth flask, 800g of poly (carbonate-ether) dihydric alcohol (the number average molecular weight is 3000, the content of carbonate units is 50 wt%) is weighed, 0.72g of stannous chloride is weighed and poured into the three-mouth flask, the three-mouth flask is placed in an oil bath, a heating device and stirring are started, the temperature is increased to 180 ℃ for reaction for 3h, the temperature is reduced to 140 ℃, a vacuum pump is started, the vacuum pumping is carried out for 1h, discharging is carried out, the product of the carbon dioxide-based polyhydric alcohol is obtained, and the detection proves that the carbon dioxide-based polyhydric alcohol has the structure shown in the formula (I), wherein m is 40, the hydroxyl value is 35mg KOH/g, the acid value is 3.2mg KOH/g, and the viscosity is 1500cps (@30 ℃).
H NMR(CDCl3As deuterated reagent): 1.45ppm, 2.31ppm, 3.75ppm, 3.81ppm，3.88ppm，4.07ppm，4.49ppm，4.68ppm，7.25ppm，8.00ppm，8.14ppm。
FTIR (KBr pellet): 497.5cm-1，728.9cm-1，889.1cm-1，948.5cm-1，1027.2cm-1，1105.4cm-1，1283.1cm-1，1375.7cm-1，1418.1cm-1，1463.2cm-1，1518.7cm-1，1586.2cm-1，1615.0cm-1，1723.8cm-1，1957.2cm-1，2879.3cm-1，2948.1cm-1，3057.2cm-1，3461.5cm-1。
Example 5
Preparation of aqueous polyurethane dispersion:
1) under the protection of nitrogen, 140g of carbon dioxide-based polyol, 45g of diisocyanate and 45g of acetone are added into a reaction vessel and react for 2 hours at 85 ℃ to obtain a first intermediate;
2) adding 16.5g of dimethylolpropionic acid, 3.5g of ethylene glycol, 0.18g of stannous octoate and 30g of acetone into the first intermediate, and reacting at 65 ℃ for 3 hours to obtain a second intermediate;
3) the second intermediate was neutralized with 10.2g of triethylamine, and then emulsified with 160g of deionized water, and distilled under reduced pressure to obtain an aqueous polyurethane dispersion (WPU 01).
Example 6
Preparation of aqueous polyurethane dispersion:
1) under the protection of nitrogen, 85g of carbon dioxide-based polyol, 23g of xylene methane diisocyanate and 30g of butanone are added into a reaction vessel and react for 4 hours at 90 ℃ to obtain a first intermediate;
2) adding 3.5g of dimethylolbutyric acid, 2.1g of butanediol, 0.01g of dibutyltin dilaurate and 18g of butanone into the first intermediate to react at the temperature of 60 ℃ for 1.5h to obtain a second intermediate;
3) the second intermediate was neutralized with 1.8g N-methyldiethanolamine, and then emulsified with 110g of deionized water, and distilled under reduced pressure to obtain an aqueous polyurethane dispersion (WPU 02).
Example 7
Preparation of aqueous polyurethane dispersion:
1) under the protection of nitrogen, adding 120g of carbon dioxide-based polyol, 40g of p-xylylene diisocyanate and 40g of cyclohexanone into a reaction vessel, and reacting at 88 ℃ for 3h to obtain a first intermediate;
2) adding 5g N-methyldiethanolamine, 3g of diethylene glycol, 0.1g of nickel diisooctanoate and 30g of cyclohexanone into the first intermediate, and reacting at the temperature of 62 ℃ for 2 hours to obtain a second intermediate;
3) the second intermediate was neutralized with 4.8g of trifluoroacetic acid, and then emulsified with 140g of deionized water, and distilled under reduced pressure to obtain an aqueous polyurethane dispersion (WPU 03).
Example 8
Preparation of aqueous polyurethane dispersion:
1) under the protection of nitrogen, 110g of carbon dioxide-based polyol, 34g of isophorone diisocyanate and 35g of acetone are added into a reaction vessel and react for 2.5 hours at 90 ℃ to obtain a first intermediate;
2) adding 8.2g of N-butyldiethanolamine, 2.3g of butanediol, 0.14g of zinc isooctanoate and 20g of acetone into the first intermediate, and reacting at the temperature of 60 ℃ for 2 hours to obtain a second intermediate;
3) the second intermediate was neutralized with 7.5g of concentrated hydrochloric acid (mass concentration: 36%), and then emulsified with 125g of deionized water, followed by distillation under reduced pressure to obtain an aqueous polyurethane dispersion (WPU 04).
Example 9
Preparation of aqueous polyurethane dispersion:
1) under the protection of nitrogen, 135g of carbon dioxide-based polyol, 38g of dicyclohexylmethane diisocyanate and 45g of butanone are added into a reaction vessel and react for 3.5 hours at 85 ℃ to obtain a first intermediate;
2) adding 7.5g of dimethylolpropionic acid, 3.2g of ethylene glycol, 0.13g of zinc naphthanate and 15g of butanone into the first intermediate to react at 65 ℃ for 1.5h to obtain a second intermediate;
3) the second intermediate was neutralized with 8.2g of aqueous ammonia, and then 145g of deionized water was added to emulsify the neutralized intermediate, followed by distillation under reduced pressure to obtain an aqueous polyurethane dispersion (WPU 05).
Comparative example 1
An aqueous polyurethane dispersion was prepared as in example 5, except that the carbon dioxide-based polyol in example 5 was replaced with polybutylene adipate, and the others were unchanged.
Comparative example 2
An aqueous polyurethane dispersion was prepared as in example 5, except that the carbon dioxide-based polyol in example 5 was replaced with polypropylene glycol, and the others were unchanged.
Example 10
Methods for testing alkali resistance and oxidation resistance of the aqueous polyurethane dispersions of examples 5 to 9 and comparative examples 1 to 2: the aqueous polyurethane dispersion was placed in a teflon pan at 25 ℃ and a relative humidity of 50% for 72 hours, and then placed in a vacuum oven at 40 ℃ for 48 hours to form a support film. Alkali resistance: and (3) placing the self-supporting membrane in a 3.5% sodium hydroxide aqueous solution to be soaked for 360h, and testing the mechanical property retention rate of the membrane. Oxidation resistance: and (3) placing the self-supporting membrane in 6% hydrogen peroxide for soaking for 360h, and testing the mechanical property retention rate of the membrane. The results of alkali resistance and oxidation resistance are shown in table 1.
TABLE 1 alkali and Oxidation resistance results of the aqueous polyurethane dispersions of examples 5-9 and comparative examples 1-2
As can be seen from Table 1, the tensile strength retention (alkali resistance 360h) of the aqueous polyurethane dispersion prepared by the invention is higher than 80%, and the elongation at break retention (alkali resistance 360h) is not lower than 80%; the tensile strength retention (oxidation resistance 360h) of the aqueous polyurethane dispersion is higher than 80%, and the elongation at break retention (oxidation resistance 360h) is higher than 80%.
Example 11
Preparing a water-based polyurethane adhesive:
1) adding the aqueous polyurethane dispersion prepared in the embodiment 5 into a high-speed dispersion machine, adding ground limestone, fumed silica and an aqueous defoaming agent, and sanding for 4 hours to obtain a first component;
2) and (3) putting the first component into a high-speed stirrer, adding the aqueous dispersant and the aqueous thickening agent, stirring at 2000rpm for 3h, and filtering by using a 200-mesh filter screen to obtain the aqueous polyurethane adhesive.
Then, the aqueous polyurethane dispersions of examples 5 were replaced with the aqueous polyurethane dispersions of examples 6 to 9, and the above-described experiment was repeated, wherein the specific formulations of the raw materials used are shown in table 2, and the aqueous polyurethane adhesives obtained from the aqueous polyurethane dispersions of examples 5 to 9 were designated as ADH1, ADH2, ADH3, ADH4, and ADH 5. Comparative example 1 and comparative example 2 were prepared according to the formulation proportions of ADH1, labeled DB1 and DB2, respectively.
TABLE 2 examples 5-9 formulations for preparing waterborne polyurethane adhesives
Respectively and uniformly coating aqueous polyurethane adhesive (ADH 1, ADH2, ADH3, ADH4 or ADH5) on PVC soft leather at a coating weight of 85g/m2And after the water-based adhesive is dried, placing the water-based adhesive in a 55 ℃ oven for 5min, butting two PVC soft skins, and carrying out T-shaped peel strength test after 24h to detect the bonding property of the water-based polyurethane adhesive. T-type peel strength: according to the GB/T2791-1995 standard, a tensile testing machine is adopted for testing (the testing temperature is 23-27 ℃). The adhesive properties of the aqueous polyurethane adhesive are shown in table 3. The alkali resistance and oxidation resistance of the waterborne polyurethane adhesive are characterized by T-type peel strength, and the testing method comprises the steps of placing a bonded sample piece for 24 hours, then soaking the bonded sample piece into 3.5 wt% of sodium hydroxide aqueous solution for 360 hours, then washing the sample piece with deionized water for 5 times, airing at room temperature, placing the sample piece for 24 hours at room temperature, and then testing by using a tensile testing machine according to the GB/T2791 + 1995 standard (the testing temperature is 23-27 ℃). T-peel strength test was performed and the T-peel strength was designated (alkali resistance)360h) In that respect In a similar manner, the oxidation resistance test was performed by simply replacing the 3.5% aqueous sodium hydroxide solution with 6% hydrogen peroxide and was labeled as T-peel strength (oxidation resistance 360 h). And the retention rates of T-type peel strength are respectively marked as retention rate of T-type peel strength (alkali resistance 360h) and retention rate of T-type peel strength (oxidation resistance 360 h).
TABLE 3 bonding Properties of aqueous polyurethane Adhesives
As can be seen from Table 3, the T-type peel strength of the waterborne polyurethane adhesive prepared by the invention is not lower than 80N/50mm, and the adhesive property is better; the T-type peel strength (alkali resistance 360h) is higher than 70N/50mm, the retention rate of the T-type peel strength (alkali resistance 360h) is not lower than 90.0%, the T-type peel strength (oxidation resistance 360h) is higher than 70N/50mm, the retention rate of the T-type peel strength (oxidation resistance 360h) is higher than 89N/50mm, and the alkali resistance and the oxidation resistance are excellent.
The previous description of the disclosed embodiments is provided to enable any person skilled in the art to make or use the present invention. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the invention. Thus, the present invention is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.
Claims (10)
1. A carbon dioxide-based polyol having the structure of formula (I):
wherein m is more than or equal to 3 and less than or equal to 60.
2. The carbon dioxide-based polyol of claim 1, wherein m is 3, 15, 40, or 60.
3. A preparation method of carbon dioxide-based polyol comprises the following steps:
A1) mixing a PET material, poly (carbonate-ether) dihydric alcohol and a first catalyst, and stirring and reacting for 2-10 h at 180-220 ℃;
B1) and cooling the reacted product to 130-150 ℃, and vacuumizing for 1h to obtain the carbon dioxide-based polyol.
4. The carbon dioxide-based polyol according to claim 3, wherein the mass ratio of the PET material, the poly (carbonate-ether) glycol and the first catalyst is 150-230: 380-1200: 0.28 to 0.96;
the first catalyst comprises zinc acetate, manganese phosphate, zinc phosphate, calcium phosphate, a 3A molecular sieve, stannous chloride or butyl titanate;
the PET material comprises waste PET beverage bottle sheets and/or waste PET transparent packaging box sheets;
the number average molecular weight of the poly (carbonate-ether) glycol is 2000-7000;
in the poly (carbonate-ether) glycol, the content of carbonate is 30 wt% -70 wt%.
5. The aqueous polyurethane dispersion is prepared from the following raw materials in parts by weight:
the carbon dioxide-based polyol is the carbon dioxide-based polyol as defined in any one of claims 1 to 2 or the carbon dioxide-based polyol prepared by the preparation method as defined in any one of claims 3 to 4;
the first chain extender is selected from carboxylic acid and/or amine compounds;
the second chain extender is selected from alcohol compounds.
6. The aqueous polyurethane dispersion according to claim 5, wherein the diisocyanate is one or more selected from the group consisting of toluene diisocyanate, xylene methane diisocyanate, p-xylylene diisocyanate, 4' -diphenylmethane diisocyanate, isophorone diisocyanate, 1, 5-naphthalene diisocyanate, and dicyclohexylmethane diisocyanate;
the first chain extender is selected from one or more of dimethylolpropionic acid, dimethylolbutyric acid, N-methyldiethanolamine, N-butyldiethanolamine, 2' -iminodiethanol and triethanolamine;
the second chain extender is selected from one or more of ethylene glycol, butanediol and diethylene glycol;
the second catalyst is selected from N, N-dimethylhexadecylamine, N-methylmorpholine, stannous octoate, dibutyltin dilaurate, zinc isooctanoate, nickel isooctanoate or zinc naphthoate;
the neutralizing agent is selected from one or more of triethylamine, ammonia water, dimethylethanolamine, N-methyldiethanolamine, trifluoroacetic acid and concentrated hydrochloric acid;
the solvent is selected from butanone, cyclohexanone or acetone.
7. A method for preparing an aqueous polyurethane dispersion comprising the steps of:
A2) under the condition of protective gas, reacting carbon dioxide-based polyol with diisocyanate in a partial solvent to obtain a first intermediate; the carbon dioxide-based polyol is the carbon dioxide-based polyol as defined in any one of claims 1 to 2 or the carbon dioxide-based polyol prepared by the preparation method as defined in any one of claims 3 to 4;
B2) reacting the first intermediate, the first chain extender, the second chain extender and the second catalyst in a residual solvent to obtain a second intermediate;
C2) and mixing the second intermediate and a neutralizing agent, then mixing with water for emulsification, and distilling under reduced pressure to obtain the aqueous polyurethane dispersion.
8. The preparation method according to claim 7, wherein in the step B1), the reaction temperature is 85-90 ℃, and the reaction time is 2-4 h;
in the step B2), the reaction temperature is 60-65 ℃, and the reaction time is 1.5-3 h.
9. The waterborne polyurethane adhesive is prepared from the following raw materials in parts by weight:
the aqueous polyurethane dispersion is the aqueous polyurethane dispersion of claim 5 or the aqueous polyurethane dispersion prepared by the preparation method of any one of claims 7 to 8.
10. A preparation method of a water-based polyurethane adhesive comprises the following steps:
A3) mixing the aqueous polyurethane dispersion, heavy calcium carbonate, fumed silica and an aqueous defoaming agent, and sanding to obtain a first component;
B3) and stirring the first component, the water-based dispersant and the water-based thickener at the rotating speed of 1800-2200 rpm for 2-4 h to obtain the water-based polyurethane adhesive.
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| CN113150735A (en) * | 2021-04-14 | 2021-07-23 | 陈壹铭 | Polyurethane adhesive prepared from recovered solvent for shoes and processing method |
| CN113493598A (en) * | 2021-08-16 | 2021-10-12 | 中国科学院长春应用化学研究所 | Biodegradable polyester and preparation method thereof |
| CN113493598B (en) * | 2021-08-16 | 2022-11-01 | 中国科学院长春应用化学研究所 | Biodegradable polyester and preparation method thereof |
| CN116355174A (en) * | 2023-04-17 | 2023-06-30 | 中山大学 | Biodegradable polyurethane based on semi-aromatic polyester polycarbonate diol and preparation method thereof |
| CN116355174B (en) * | 2023-04-17 | 2024-01-02 | 中山大学 | Biodegradable polyurethane based on semi-aromatic polyester polycarbonate diol and preparation method thereof |
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