CN113549199A - Bio-based solvent-resistant polyester polyol, polyurethane resin and preparation process thereof - Google Patents
Bio-based solvent-resistant polyester polyol, polyurethane resin and preparation process thereof Download PDFInfo
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- CN113549199A CN113549199A CN202110833487.1A CN202110833487A CN113549199A CN 113549199 A CN113549199 A CN 113549199A CN 202110833487 A CN202110833487 A CN 202110833487A CN 113549199 A CN113549199 A CN 113549199A
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- polyester polyol
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- 229920005906 polyester polyol Polymers 0.000 title claims abstract description 50
- 239000002904 solvent Substances 0.000 title claims abstract description 36
- 229920005749 polyurethane resin Polymers 0.000 title claims abstract description 16
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- 238000004519 manufacturing process Methods 0.000 claims abstract description 6
- 238000000034 method Methods 0.000 claims abstract description 5
- 150000002009 diols Chemical class 0.000 claims abstract 3
- 238000006243 chemical reaction Methods 0.000 claims description 34
- 239000002253 acid Substances 0.000 claims description 30
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 claims description 15
- 239000003054 catalyst Substances 0.000 claims description 15
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 14
- KDYFGRWQOYBRFD-UHFFFAOYSA-N succinic acid Chemical compound OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 claims description 13
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 12
- 239000000203 mixture Substances 0.000 claims description 12
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 claims description 9
- 239000000463 material Substances 0.000 claims description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- 229910052757 nitrogen Inorganic materials 0.000 claims description 6
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 claims description 6
- 239000001384 succinic acid Substances 0.000 claims description 6
- 238000001816 cooling Methods 0.000 claims description 4
- 238000010438 heat treatment Methods 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 4
- 238000005086 pumping Methods 0.000 claims description 4
- 238000003756 stirring Methods 0.000 claims description 4
- 239000004970 Chain extender Substances 0.000 claims description 3
- 238000005070 sampling Methods 0.000 claims description 3
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 2
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 2
- 229910052787 antimony Inorganic materials 0.000 claims description 2
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 claims description 2
- 229910052719 titanium Inorganic materials 0.000 claims description 2
- 239000010936 titanium Substances 0.000 claims description 2
- 229910052726 zirconium Inorganic materials 0.000 claims description 2
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims 1
- 125000004185 ester group Chemical group 0.000 claims 1
- 229920002635 polyurethane Polymers 0.000 abstract description 10
- 239000004814 polyurethane Substances 0.000 abstract description 10
- 229920005862 polyol Polymers 0.000 abstract description 4
- 150000003077 polyols Chemical class 0.000 abstract description 4
- 238000006116 polymerization reaction Methods 0.000 abstract description 3
- 238000004917 polyol method Methods 0.000 abstract description 2
- 230000002194 synthesizing effect Effects 0.000 abstract description 2
- 239000003208 petroleum Substances 0.000 description 8
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 4
- 230000008901 benefit Effects 0.000 description 4
- RLJWTAURUFQFJP-UHFFFAOYSA-N propan-2-ol;titanium Chemical compound [Ti].CC(C)O.CC(C)O.CC(C)O.CC(C)O RLJWTAURUFQFJP-UHFFFAOYSA-N 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- VXUYXOFXAQZZMF-UHFFFAOYSA-N tetraisopropyl titanate Substances CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 description 4
- 239000000126 substance Substances 0.000 description 3
- 238000005299 abrasion Methods 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 230000018044 dehydration Effects 0.000 description 2
- 238000006297 dehydration reaction Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 239000011846 petroleum-based material Substances 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- YPFDHNVEDLHUCE-UHFFFAOYSA-N propane-1,3-diol Chemical compound OCCCO YPFDHNVEDLHUCE-UHFFFAOYSA-N 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 239000001361 adipic acid Substances 0.000 description 1
- 235000011037 adipic acid Nutrition 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- CDQSJQSWAWPGKG-UHFFFAOYSA-N butane-1,1-diol Chemical compound CCCC(O)O CDQSJQSWAWPGKG-UHFFFAOYSA-N 0.000 description 1
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 239000010779 crude oil Substances 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 150000002148 esters Chemical group 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 238000001879 gelation Methods 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000013520 petroleum-based product Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 239000012974 tin catalyst Substances 0.000 description 1
Classifications
-
- 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
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
- C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/16—Dicarboxylic acids and dihydroxy compounds
-
- 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
- C08G18/4236—Polycondensates having carboxylic or carbonic ester groups in the main chain containing only aliphatic groups
- C08G18/4238—Polycondensates having carboxylic or carbonic ester groups in the main chain containing only aliphatic groups derived from dicarboxylic acids and dialcohols
-
- 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
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/78—Preparation processes
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Polyurethanes Or Polyureas (AREA)
Abstract
The invention relates to a bio-based solvent-resistant polyester polyol, a polyurethane resin and a preparation process thereof, and belongs to the technical field of polyurethane polyol and preparation methods thereof. A bio-based solvent-resistant polyester polyol, characterized by comprising a bio-based diol and a bio-based diacid in a molar ratio of (1.05-1.2): 1. the invention provides a method for synthesizing bio-based solvent-resistant polyurethane polyol and adopts a special production process of step-by-step polymerization to produce polyurethane resin, and the prepared polyurethane resin has excellent solvent resistance and high temperature resistance.
Description
Technical Field
The invention relates to a bio-based solvent-resistant polyester polyol, a polyurethane resin and a preparation process thereof, and belongs to the technical field of polyurethane polyol and preparation methods thereof.
Background
The bio-based material is a novel material which is prepared by taking renewable substances, including crops, trees and other plants and residues and inclusions thereof as raw materials through biological, chemical and physical means and the like.
At present, polyester polyol is generally prepared by adopting petroleum-based materials, and the prepared polyester polyol has unsatisfactory mechanical property, tensile strength, tearing strength, abrasion resistance and solvent resistance. Through market research for several years, the price of petroleum fluctuates greatly, the global reserves are also reduced gradually, petroleum-based products are controlled by crude oil and market demands and are in an increasing trend all the time, and the prices of bio-based raw materials are stable all the time and even show a decreasing trend along with the development of technology. For the sustainable development of society, bio-based raw materials will gradually replace petroleum-based materials and become the best substitute thereof.
At present, polyester polyol and polyurethane products prepared by adopting bio-based materials are in blank stages at home and abroad.
Disclosure of Invention
The invention aims to solve the defects of the prior art and provides a method for synthesizing bio-based solvent-resistant polyurethane polyol and a special production process of step-by-step polymerization for producing polyurethane resin, wherein the prepared polyurethane resin has excellent solvent resistance and high temperature resistance.
In order to achieve the purpose, the invention provides the following technical scheme:
the bio-based solvent-resistant polyester polyol is characterized by comprising bio-based dihydric alcohol and bio-based dibasic acid, wherein the molar ratio of the bio-based dihydric alcohol to the bio-based dibasic acid is (1.05-1.2): 1.
the bio-based dihydric alcohol is any one or mixture of bio-based propylene glycol and bio-based 1, 4-butanediol;
the bio-based dibasic acid is any one of bio-based succinic acid and bio-based sebacic acid;
the bio-based solvent-resistant polyester polyol is characterized by comprising the following steps:
1) and the bio-based dihydric alcohol and the bio-based dibasic acid are mixed according to a molar ratio (1.05-1.2): 1, adding the mixture into a reaction kettle, and introducing nitrogen;
2) controlling the temperature at the top of the rectifying tower not to exceed 100 ℃, carrying out gradient heating to 225 ℃, continuing to react for one hour, and then starting to carry out primary vacuum pumping;
the gradient temperature rise comprises the following specific steps: the gradient temperature rise comprises four stages, namely raising the temperature to 140 ℃ for reaction for 2 hours, raising the temperature to 160 ℃ for reaction for 1 hour, raising the temperature to 180 ℃ for reaction for 2 hours, and raising the temperature to 225 ℃ for reaction for 1 hour;
3) sampling and detecting the materials in the reaction kettle after vacuumizing for two hours, adding a catalyst into the reaction kettle, uniformly stirring the mixture after detecting that the acid value is reduced to below 10mgKOH/g, and then vacuumizing for the second time;
4) after ester exchange reaction for 2-6 hours, pumping away water and small molecular alcohol in the system, and detecting that the acid value is less than or equal to 0.8mgKOH/g, the hydroxyl value is 36-116mgKOH/g, and the water content is less than or equal to 0.03%, thus obtaining the bio-based solvent-resistant polyester polyol;
the bio-based dihydric alcohol is any one of bio-based propylene glycol and bio-based 1, 4-butanediol;
the bio-based dibasic acid is any one of bio-based succinic acid and bio-based sebacic acid;
the catalyst is any one of organic titanium catalysts, organic zirconium catalysts, organic tin catalysts and organic antimony catalysts;
the adding amount of the catalyst is 30-80 ppm.
The preparation process of the polyurethane resin is characterized by comprising the following steps:
1. adding bio-based solvent-resistant polyester polyol into a reactor; stirring and heating to 110 ℃, starting vacuumizing for more than 1h until no bubbles escape, stopping vacuumizing, and cooling to 60 ℃;
2. adding TDI, adjusting the TDI according to the hardness of a final product, continuously reacting for at least 1-3h at 75-85 ℃, titrating NCO to reach a preset content, and cooling to prepare a prepolymer A component;
3. then uniformly mixing the micromolecule chain extender and the bio-based polyester polyol at the temperature of 105-115 ℃, and vacuumizing and dehydrating until no bubbles escape to prepare a component B;
4. uniformly mixing the component A and the component B at 70 ℃, pouring the mixture into a mold, vulcanizing at 95-105 ℃ for 1-2h, demoulding, and curing at 95-105 ℃ for 11-13 h to obtain the polyurethane resin.
According to the bio-based solvent-resistant polyester polyol, bio-based succinic acid and bio-based 1, 3-propylene glycol bio-based 1, 4-butanediol are adopted to synthesize the polyester polyol, the content of the bio-based reaches one hundred percent, and energy conservation and environmental protection are realized. The production process of the bio-based solvent-resistant polyester polyol adopts special means such as gradient temperature rise, fractional vacuum and the like to control the COD (chemical oxygen demand) discharge of sewage and catalyst residues, and ensures that the polyester polyol product has stable quality and uniform molecular weight distribution. When the polyurethane resin is prepared, a stepwise polymerization mode is adopted, which is different from the traditional prepolymer synthesis mode, and the process can completely solve the problems of easy gelation, inconvenient operation, too fast curing speed, difficult demoulding and the like caused by high viscosity of the bio-based polyester polyol. The polyurethane resin produced by adopting the bio-based polyester polyol has obvious advantage of solvent resistance which can reach 14 days/(toluene, ethyl acetate and butanone mixed solution), and has high temperature resistance which can reach 240 ℃ and is far higher than that of the common polyurethane resin, and the overall performance is excellent. The invention adopts all the bio-based raw materials to synthesize the polyester polyol, and continues to use the bio-based polyester polyol to synthesize the polyurethane product, because of some characteristics of the bio-based polyester polyol, the special process is needed to synthesize the polyurethane product, and the bio-based polyurethane product has great advantages in solvent resistance compared with the traditional polyurethane product. The invention forms a polyurethane industry industrial chain which is degradable, environment-friendly and meets the market requirements from the synthesis of the bio-based polyester polyol to the downstream application and performance evaluation, can meet the requirements of downstream customers after the project is finished, can fill the domestic blank, and has great economic benefit and ecological benefit.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all 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.
Example 1
The preparation process of the bio-based solvent-resistant polyester polyol of the embodiment comprises the following steps: 1180g of bio-based succinic acid and 800g of bio-based propylene glycol are respectively put into a reactor, nitrogen is introduced and uniformly stirred, a rectifying tower is connected to a reaction kettle, dehydration is controlled by controlling the temperature of the top of the rectifying tower, the temperature of the top of the rectifying tower is controlled not to exceed 100 ℃, the temperature is raised to 140 ℃ for reaction for 2 hours, then the temperature is raised to 160 ℃ for reaction for 1 hour, then the temperature is raised to 180 ℃ for reaction for 2 hours, then the temperature is raised to 225 ℃ for reaction for 1 hour, the vacuum degree is controlled to be less than 0.08MPa, after 2 hours, a sample is taken and the acid value is detected, after the acid value is less than 10mgKOH/g, a catalyst of 50ppm of tetraisopropyl titanate is added, the vacuum degree is controlled to be less than 0.1MPa, after 2 hours of constant temperature, the acid value and the hydroxyl value of the sample are detected every hour, and when the acid value of the sample is less than 0.5 mgKOH/g and the hydroxyl value reaches 54-58mgKOH/g, the temperature is reduced and the material is discharged.
The polyester polyol obtained in this example has the following indices: acid value of 0.36mgKOH/g, hydroxyl value of 56.48mgKOH/g, water content of 0.019%
Example 2
The preparation process of the bio-based solvent-resistant polyester polyol of the embodiment comprises the following steps: 1180g of bio-based succinic acid and 1020g of bio-based 1.4-butanediol are respectively put into a reactor, nitrogen is introduced to the reactor and stirred uniformly, the temperature of the top of a rectifying tower is controlled not to exceed 100 degrees, the temperature is increased to 140 ℃ for reaction for 2 hours, then the temperature is increased to 160 ℃ for reaction for 1 hour, then the temperature is increased to 180 ℃ for reaction for 2 hours, then the temperature is increased to 225 ℃ for reaction for 1 hour, the vacuum degree is controlled to be less than 0.08MPa, after 2 hours, a sample is sampled and the acid value is detected, after the acid value is less than 10mgKOH/g, a catalyst of tetraisopropyl titanate is added for 30ppm, the vacuum degree is controlled to be less than 0.1MPa, after 2 hours of constant temperature, the acid value and the hydroxyl value of the sample are tested every hour, and when the acid value of the sample is less than 0.5 mgKOH/g unit and the hydroxyl value reaches 72-78mgKOH/g, the temperature is reduced and the material is discharged.
The polyester polyol obtained in this example has the following indices: acid value of 0.25mgKOH/g, hydroxyl value of 75.6mgKOH/g, water content of 0.018%
Example 3
The preparation process of the bio-based solvent-resistant polyester polyol of the embodiment comprises the following steps: 1180g of bio-based succinic acid, 400g of bio-based propylene glycol and 480g of bio-based 1.4-butanediol are respectively put into a reactor, nitrogen is introduced into the reactor and uniformly stirred, the temperature of the top of a rectifying tower is controlled not to exceed 100 ℃, the temperature is increased to 140 ℃ for reaction for 2 hours, then the temperature is increased to 160 ℃ for reaction for 1 hour, then the temperature is increased to 180 ℃ for reaction for 2 hours, then the temperature is increased to 225 ℃ for reaction for 1 hour, the vacuum degree is controlled to be less than 0.08MPa, sampling is carried out after 2 hours, the acid value is detected, after the acid value is less than 10mgKOH/g, a catalyst of tetraisopropyl titanate 80ppm is added, the vacuum degree is controlled to be less than 0.1MPa, the acid value and the hydroxyl value of a sample are tested every hour after the temperature is kept for 2 hours, and the temperature is reduced and the material is discharged after the acid value of the sample reaches 36-39 hydroxyl value of the sample.
The polyester polyol indexes of the embodiment are as follows: the acid value is 0.41mgKOH/g, the hydroxyl value is 36.8mgKOH/g, and the water content is 0.018%
Example 4 (comparative example)
1460g of petroleum-based adipic acid and 990g of petroleum-based butanediol are respectively put into a reactor, nitrogen is introduced and uniformly stirred, the temperature of the top of a rectifying tower is controlled not to exceed 100 degrees, the temperature is increased to 140 ℃ for reaction for 2 hours, then the temperature is increased to 160 ℃ for reaction for 1 hour, then the temperature is increased to 180 ℃ for reaction for 2 hours, then the temperature is increased to 225 ℃ for reaction for 1 hour, the vacuum degree is controlled to be less than 0.08MPa, the sample is sampled and detected after 2 hours, after the acid value is less than 10mgKOH/g, a catalyst (in the embodiment, tetraisopropyl titanate) is added for 50ppm, the vacuum degree is controlled to be less than 0.1MPa, the acid value and the hydroxyl value of the sample are tested every hour after the temperature is kept for 2 hours, and when the acid value of the sample is less than 0.5 mgKOH/g and the hydroxyl value reaches 54-58mgKOH/g, the temperature is reduced and the material is discharged.
The polyester polyol obtained in this example has the following indices: the acid value was 0.31mgKOH/g, the hydroxyl value was 55.7mgKOH/g, and the water content was 0.019%.
Example 5
The polyester polyols of the above examples 1, 2 and 4 are applied to the processing of polyurethane resin respectively, and the processing steps are as follows:
1500g of polyester polyol of example 1, 1180g of polyester polyol of example 2 and 1500g of polyester polyol of example 4 are respectively added into a three-neck flask, the mixture is stirred and heated to 110 ℃, the vacuumizing and the dehydration are started until no bubbles escape, the vacuumizing is stopped, the mixture is cooled to 60 ℃, TDI370g, 325g and 370g are respectively added, the reaction is continued for at least 2h at 80 ℃, the NCO content is titrated to 6.2%, the temperature is reduced, three prepolymer A components with 6.2% of NCO content are prepared, then 101g, 78g and 101g of micromolecule chain extender and 500g, 317g and 500g of bio-based polyester polyol are respectively and uniformly mixed at 110 ℃, the mixture is vacuumized and dehydrated until no bubbles escape, three prepolymer B components are prepared, the corresponding charging A, B components are prepared according to the above amount and are all mixed, the mixture is poured into a mould at 70 ℃ and vulcanized for 1 to 2h, and then the film is removed, and curing for 12 hours at 100 ℃ to prepare a bio-based sample 1, a bio-based sample 2 and a petroleum-based sample 3, and testing the mechanical properties such as hardness, strength, wear resistance and the like.
Table 1: mechanical Properties of sample 1, sample 2 and sample 3
Example 6
The bio-based sample 1, bio-based sample 2 and petroleum-based sample 3 were tested for solvent resistance.
Cutting three samples into rectangular test pieces, soaking in mixed solution of toluene, ethyl acetate and butanone, and observing solvent resistance
Table 2: sample 1, sample 2 and sample 3 resist solvent conditions over time
As can be seen from table 1, the bio-based solvent-resistant polyester polyol of the present invention has superior mechanical properties compared to petroleum-based polyester polyol, and the tensile strength, tear strength and abrasion resistance thereof exceed those of the existing petroleum-based polyester polyol; from table 2, the solvent resistance of the bio-based solvent resistant polyester polyols of the present invention can reach 14 days far more than that of petroleum-based polyester polyols.
The principle and features of the present invention are described above, and the embodiments are only preferred embodiments of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art can substitute or change the technical solution and the inventive concept of the present invention within the technical scope of the present invention.
Claims (8)
1. A bio-based solvent-resistant polyester polyol, characterized by comprising a bio-based diol and a bio-based diacid in a molar ratio of (1.05-1.2): 1.
2. a biobased solvent resistant polyester polyol as claimed in claim 1 wherein said biobased diol is any one or a mixture of biobased propylene glycol and biobased 1.4-butanediol.
3. The bio-based solvent-resistant polyester polyol according to claim 1, wherein the bio-based dibasic acid is any one of bio-based succinic acid and bio-based sebacic acid.
4. A process for the preparation of a bio-based solvent resistant polyester polyol as claimed in any of claims 1 to 3 comprising the steps of:
1) and the bio-based dihydric alcohol and the bio-based dibasic acid are mixed according to a molar ratio (1.05-1.2): 1, adding the mixture into a reaction kettle, and introducing nitrogen;
2) controlling the temperature at the top of the rectifying tower not to exceed 100 ℃, carrying out gradient heating to 225 ℃, continuing to react for one hour, and then starting to carry out primary vacuum pumping;
3) sampling and detecting the materials in the reaction kettle after vacuumizing for two hours, adding a catalyst into the reaction kettle, uniformly stirring the mixture after detecting that the acid value is reduced to below 10mgKOH/g, and then vacuumizing for the second time;
4) and after the ester exchange reaction is carried out for 2-6 hours, pumping away the water and the small molecular alcohol in the system, and detecting that the acid value is less than or equal to 0.8mgKOH/g, the hydroxyl value is 36-116mgKOH/g and the water content is less than or equal to 0.03 percent, thus obtaining the bio-based solvent-resistant polyester polyol.
5. The process for preparing bio-based solvent-resistant polyester polyol according to claim 4, wherein the step 2) of gradient temperature rise comprises the following specific steps: the gradient temperature rise comprises four stages, namely raising the temperature to 140 ℃ for reaction for 2 hours, raising the temperature to 160 ℃ for reaction for 1 hour, raising the temperature to 180 ℃ for reaction for 2 hours, and raising the temperature to 225 ℃ for reaction for 1 hour.
6. The process for preparing bio-based solvent-resistant polyester polyol according to claim 4, wherein the catalyst is any one of organic titanium, organic zirconium, organic tin and organic antimony catalysts.
7. The process for preparing bio-based solvent-resistant polyester polyol as claimed in claim 4, wherein the amount of the catalyst added is 30 to 80 ppm.
8. A preparation process of polyurethane resin is characterized by comprising the following steps:
1) adding the bio-based solvent-resistant polyester polyol as defined in any one of claims 1 to 3 into a reactor, stirring and heating to 110 ℃, starting vacuumizing for more than 1h until no bubbles escape, stopping vacuumizing, and cooling to 60 ℃;
2) adding TDI, continuously reacting for at least 1-3h at 75-85 ℃, titrating NCO to reach a predetermined content, and cooling to prepare a prepolymer A component;
3) then uniformly mixing the micromolecule chain extender and the bio-based polyester polyol at the temperature of 105-115 ℃, and vacuumizing and dehydrating until no bubbles escape to prepare a component B;
4) uniformly mixing the component A and the component B at 70 ℃, pouring the mixture into a mold, vulcanizing at 95-105 ℃ for 1-2h, demoulding, and curing at 95-105 ℃ for 11-13 h to obtain the polyurethane resin.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110833487.1A CN113549199B (en) | 2021-07-23 | 2021-07-23 | Bio-based solvent-resistant polyester polyol, polyurethane resin and preparation process thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
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| CN202110833487.1A CN113549199B (en) | 2021-07-23 | 2021-07-23 | Bio-based solvent-resistant polyester polyol, polyurethane resin and preparation process thereof |
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