CN113549199B - 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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- CN113549199B CN113549199B CN202110833487.1A CN202110833487A CN113549199B CN 113549199 B CN113549199 B CN 113549199B CN 202110833487 A CN202110833487 A CN 202110833487A CN 113549199 B CN113549199 B CN 113549199B
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- 229920005906 polyester polyol Polymers 0.000 title claims abstract description 45
- 239000002904 solvent Substances 0.000 title claims abstract description 33
- 229920005749 polyurethane resin Polymers 0.000 title claims abstract description 17
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- 239000002253 acid Substances 0.000 claims abstract description 31
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 9
- 238000010438 heat treatment Methods 0.000 claims description 17
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 13
- 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
- 239000003054 catalyst Substances 0.000 claims description 12
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 claims description 10
- 238000006243 chemical reaction Methods 0.000 claims description 9
- 238000001816 cooling Methods 0.000 claims description 8
- 238000003756 stirring Methods 0.000 claims description 7
- 239000000463 material Substances 0.000 claims description 6
- 229910052757 nitrogen Inorganic materials 0.000 claims description 6
- 239000001384 succinic acid Substances 0.000 claims description 6
- 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 claims description 5
- VXUYXOFXAQZZMF-UHFFFAOYSA-N tetraisopropyl titanate Substances CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 4
- 238000005070 sampling Methods 0.000 claims description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 4
- 239000004970 Chain extender Substances 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 3
- 238000007599 discharging Methods 0.000 claims description 2
- 238000005809 transesterification reaction Methods 0.000 claims description 2
- 238000005086 pumping Methods 0.000 claims 1
- 229920002635 polyurethane Polymers 0.000 abstract description 10
- 239000004814 polyurethane Substances 0.000 abstract description 10
- 238000000034 method Methods 0.000 abstract description 4
- 229920005862 polyol Polymers 0.000 abstract description 4
- 150000003077 polyols Chemical class 0.000 abstract description 4
- 238000004519 manufacturing process Methods 0.000 abstract description 3
- 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 1
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 12
- 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
- 239000002994 raw material Substances 0.000 description 4
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 4
- 238000005299 abrasion Methods 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 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
- 238000011161 development Methods 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 239000011846 petroleum-based material Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- DNIAPMSPPWPWGF-VKHMYHEASA-N (+)-propylene glycol Chemical compound C[C@H](O)CO DNIAPMSPPWPWGF-VKHMYHEASA-N 0.000 description 1
- YPFDHNVEDLHUCE-UHFFFAOYSA-N 1,3-propanediol Substances OCCCO YPFDHNVEDLHUCE-UHFFFAOYSA-N 0.000 description 1
- 229940035437 1,3-propanediol Drugs 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- 239000001361 adipic acid Substances 0.000 description 1
- 235000011037 adipic acid Nutrition 0.000 description 1
- 229910052787 antimony Inorganic materials 0.000 description 1
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-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
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 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
- 238000011156 evaluation Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 238000001879 gelation Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000013520 petroleum-based product Substances 0.000 description 1
- 229920000166 polytrimethylene carbonate Polymers 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
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 239000012974 tin catalyst Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 238000004448 titration Methods 0.000 description 1
- 229910052726 zirconium Inorganic materials 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
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- 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, polyurethane resin and a preparation process thereof, belonging to the technical field of polyurethane polyol and preparation methods thereof. A 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 invention provides a method for synthesizing bio-based solvent-resistant polyurethane polyol, which adopts a special production process of 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, polyurethane resin and a preparation process thereof, belonging to the technical field of polyurethane polyol and preparation methods thereof.
Background
The bio-based material refers to a novel material manufactured by biological, chemical, physical and other means by using renewable materials including crops, trees, other plants, residues and contents thereof as raw materials.
At present, petroleum-based materials are generally adopted to prepare polyester polyol, and the mechanical properties, tensile strength, tear strength, abrasion resistance and solvent resistance of the prepared polyester polyol are not ideal. Through market research for several years, the petroleum price is greatly fluctuated, the global reserve is gradually reduced, petroleum-based products are controlled by crude oil and market demands and are always in an increasing trend, and the prices of bio-based raw materials are always relatively stable and even show a decreasing trend along with the development of technology. For sustainable development of society, bio-based raw materials must gradually replace petroleum-based materials, becoming the best substitute for them.
At present, the preparation of polyester polyol and polyurethane products by adopting biological base materials is still in a blank stage at home and abroad.
Disclosure of Invention
The invention aims to solve the defects existing in the prior art, and provides a bio-based solvent-resistant polyurethane polyol synthesis method which adopts a special production process of step polymerization to produce polyurethane resin, and the prepared polyurethane resin has excellent solvent resistance and high temperature resistance.
In order to achieve the above purpose, the present invention provides the following technical solutions:
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 two of bio-based propylene glycol and bio-based 1, 4-butanediol;
the bio-based diacid 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 of:
1) The bio-based dihydric alcohol and the bio-based dibasic acid are mixed according to the mol ratio of (1.05-1.2): 1, adding the mixture into a reaction kettle, and introducing nitrogen;
2) Controlling the temperature of the top of the rectifying tower to be not more than 100 ℃, raising the temperature to 225 ℃ through gradient, and starting to vacuumize once after continuing to react for one hour;
the specific steps of gradient temperature rise are as follows: the gradient heating comprises four stages, namely heating to 140 ℃ for 2 hours, heating to 160 ℃ for 1 hour, heating to 180 ℃ for 2 hours and heating to 225 ℃ for 1 hour;
3) Sampling and detecting materials in the reaction kettle after vacuumizing for two hours, detecting that the acid value is reduced to below 10mgKOH/g, adding a catalyst into the reaction kettle, uniformly stirring, and vacuumizing for the second time;
4) After transesterification reaction for 2-6 hours, removing water and micromolecular alcohol in the system, and detecting the acid value of less than or equal to 0.8mgKOH/g, the hydroxyl value of 36-116mgKOH/g and the water content of less than or equal to 0.03 percent, 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 diacid 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 addition amount of the catalyst is 30-80 ppm.
The preparation process of the polyurethane resin is characterized by comprising the following steps of:
1. adding a bio-based solvent resistant polyester polyol to a reactor; stirring and heating to 110 ℃, 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 the final product, continuously reacting at 75-85 ℃ for at least 1-3h, titrating NCO to reach the preset content, and cooling to prepare a prepolymer A component;
3. uniformly mixing the micromolecular chain extender with the bio-based polyester polyol at 105-115 ℃, 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 mould, vulcanizing at 95-105 ℃ for 1-2 hours, demoulding, and curing at 95-105 ℃ for 11-13 hours to obtain the polyurethane resin.
According to the bio-based solvent-resistant polyester polyol, bio-based succinic acid and bio-based 1, 3-propanediol bio-based 1, 4-butanediol are adopted to synthesize the polyester polyol, the bio-based content 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, controls the COD discharge of sewage and the catalyst residue, and ensures the stable quality and uniform molecular weight distribution of the polyester polyol product. When the polyurethane resin is prepared, the stepwise polymerization mode is adopted, and the process is different from the traditional prepolymer synthesis mode, so that the problems of easy gelation, inconvenient operation, high curing speed, difficult demolding and the like caused by high viscosity of the bio-based polyester polyol can be completely solved. The polyurethane resin produced by the bio-based polyester polyol has obvious advantages in solvent resistance, the solvent resistance can reach 14 days/(toluene, ethyl acetate and butanone mixed solution), the high temperature resistance can reach 240 ℃, and the polyurethane resin is far higher than that of common polyurethane resin, and has excellent overall performance. The invention synthesizes the polyester polyol by adopting all the bio-based raw materials, and continues to synthesize the polyurethane product by using the bio-based polyester polyol, and because of some characteristics of the bio-based polyester polyol, the synthetic polyurethane product needs to adopt a special process, and the bio-based polyurethane product has great advantages in terms of solvent resistance compared with the traditional polyurethane product. The invention forms a polyurethane industry industrial chain which meets the requirements of degradable environment protection and satisfies the market from the synthesis of the bio-based polyester polyol to downstream application and performance evaluation, and after the project is finished, the invention not only can meet the requirements of downstream clients, but also can fill the domestic blank, and has larger economic benefit and ecological benefit.
Detailed Description
The following description of the technical solutions in the embodiments of the present invention will be clear and complete, and it is obvious that the described embodiments are only some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Example 1
The preparation process of the bio-based solvent-resistant polyester polyol 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 into the reactor and is uniformly stirred, a rectifying tower is connected to the reactor, 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 to be not more than 100 ℃, the temperature is increased to 140 ℃ for 2 hours, the temperature is increased to 160 ℃ for 1 hour, the temperature is increased to 180 ℃ for 2 hours, the temperature is increased to 225 ℃ for 1 hour, the vacuum degree is controlled to be less than 0.08Mpa, sampling and detecting the acid value are carried out after 2 hours, the catalyst tetraisopropyl titanate is added after the acid value is less than 10mgKOH/g, the vacuum degree is controlled to be less than 0.1Mpa, the acid value and hydroxyl value of a sample are tested every hour after the temperature is kept for 2 hours, and the acid value of the sample is reduced to be 54-58mgKOH/g after the acid value of the sample is less than 0.5 mgKOH/g.
The polyester polyol indexes obtained in this example are: acid value 0.36mgKOH/g, hydroxyl value 56.48mgKOH/g, moisture 0.019%
Example 2
The preparation process of the bio-based solvent-resistant polyester polyol 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 into the reactor and is uniformly stirred, the temperature at the top of a rectifying tower is controlled to be not more than 100 ℃, the temperature is raised to 140 ℃ for 2 hours, the temperature is raised to 160 ℃ for 1 hour, the temperature is raised to 180 ℃ for 2 hours, the temperature is raised to 225 ℃ for 1 hour, the vacuum degree is controlled to be less than 0.08Mpa, the acid value is detected after 2 hours, the catalyst tetraisopropyl titanate is added after the acid value is less than 10mgKOH/g, the acid value and the hydroxyl value of a sample are tested per hour after the temperature is kept constant for 2 hours, and the sample is cooled and discharged after the acid value of the sample is less than 0.5 mgKOH/g unit and the hydroxyl value reaches 72-78 mgKOH/g.
The polyester polyol indexes obtained in this example are: acid value 0.25mgKOH/g, hydroxyl value 75.6mgKOH/g, moisture 0.018%
Example 3
The preparation process of the bio-based solvent-resistant polyester polyol 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 stirred uniformly, the temperature at the top of a rectifying tower is controlled not to exceed 100 DEG, the temperature is raised to 140 ℃ for 2 hours, the temperature is raised to 160 ℃ for 1 hour, the temperature is raised to 180 ℃ for 2 hours, the temperature is raised to 225 ℃ for 1 hour, the vacuum degree is controlled to be less than 0.08Mpa, the acid value is sampled and detected after 2 hours, the acid value is less than 10mgKOH/g, 80ppm of catalyst tetraisopropyl titanate 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 constant for 2 hours, and the sample is cooled and discharged after the acid value of the sample reaches 36-39.
The polyester polyol index of this example is: acid value 0.41mgKOH/g, hydroxyl value 36.8mgKOH/g, moisture 0.018%
Example 4 (comparative example)
Adding 1460g of petroleum-based adipic acid and 990g of petroleum-based butanediol into a reactor, introducing nitrogen, stirring uniformly, controlling the temperature at the top of a rectifying tower to be not more than 100 ℃, heating to 140 ℃ for reaction for 2 hours, heating to 160 ℃ for reaction for 1 hour, heating to 180 ℃ for reaction for 2 hours, heating to 225 ℃ for reaction for 1 hour, controlling the vacuum degree to be less than 0.08Mpa, sampling and detecting the acid value after 2 hours, adding a catalyst (tetraisopropyl titanate is used in the embodiment) after the acid value is less than 10mgKOH/g, controlling the vacuum degree to be less than 0.1Mpa, testing the acid value hydroxyl value of a sample per hour after the constant temperature is kept for 2 hours, and cooling and discharging after the acid value of the sample is less than 0.5 mgKOH/g hydroxyl value reaches 54-58 mgKOH/g.
The polyester polyol indexes obtained in this example are: acid value 0.31mgKOH/g, hydroxyl value 55.7mgKOH/g, moisture 0.019%.
Example 5
The polyester polyols of examples 1, 2 and 4 were used to process polyurethane resins, respectively, 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, stirring and heating are carried out to 110 ℃, vacuumizing and dewatering are started until no bubbles escape, cooling is carried out to 60 ℃,370g of TDI, 325g and 370g of TDI are respectively added, continuing to react at 80 ℃ for at least 2h, cooling is carried out after titration NCO reaches 6.2%, three prepolymer A components with NCO content of 6.2% are prepared, 101g,78g and 101g of micromolecular chain extender are respectively mixed with 500g,317g and 500g of biobased polyester polyol at 110 ℃, vacuumizing and dewatering are carried out until no bubbles escape to prepare three prepolymer B components, the corresponding A, B components are all mixed after being prepared according to the feeding amount, are poured into a mould after being mixed uniformly at 70 ℃, vulcanized for 1-2h at 100 ℃, and cured for 12 hours to prepare a biobased sample 1, a biobased sample 2, a petroleum based sample, hardness and abrasion resistance are tested, and the like.
Table 1: mechanical Properties of sample 1, sample 2 and sample 3
Example 6
The solvent resistance of the bio-based sample 1, the bio-based sample 2 and the petroleum-based sample 3 was tested.
Cutting three samples into rectangular test pieces, soaking in mixed solution of toluene, ethyl acetate and butanone, and observing solvent resistance
Table 2: solvent resistance of sample 1, sample 2 and sample 3 over time
As can be seen from Table 1, the bio-based solvent-resistant polyester polyol of the present invention has excellent mechanical properties compared with petroleum-based polyester polyol, and has tensile strength, tear strength and abrasion resistance exceeding those of the existing petroleum-based polyester polyol; the solvent resistance of the bio-based solvent resistant polyester polyol of the present invention can be far greater than that of petroleum-based polyester polyol for 14 days from Table 2.
While the principles and features of the present invention have been described in detail, the present embodiments are only preferred embodiments of the present invention, and the scope of the present invention is not limited thereto, but any person skilled in the art should be able to apply equally to the present invention, and any substitution or modification of the technical solution and the inventive concept thereof is intended to be covered by the scope of the present invention.
Claims (1)
1. The preparation process of the polyurethane resin is characterized by comprising the following steps of:
1) Adding 1180g of bio-based solvent-resistant polyester polyol into a reactor, stirring and heating to 110 ℃, starting vacuumizing for more than 1 hour until no bubbles escape, stopping vacuumizing, and cooling to 60 ℃;
2) Adding 325g of TDI, continuously reacting for at least 2 hours at 80 ℃, titrating NCO to 6.2%, and cooling to prepare a prepolymer A component;
3) Uniformly mixing 78g of small molecular chain extender and 317g of bio-based solvent-resistant polyester polyol at 110 ℃, 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 100 ℃ for 1-2 hours, removing the film, and curing at 100 ℃ for 12 hours to obtain polyurethane resin;
the bio-based solvent-resistant polyester polyol comprises the following preparation process:
1) 1180g of bio-based succinic acid and 1020g of bio-based 1, 4-butanediol are respectively taken and put into a reactor, and nitrogen is introduced into the reactor for uniform stirring;
2) Controlling the temperature of the top of the rectifying tower not to exceed 100 ℃, raising the temperature to 225 ℃ through gradient, continuously reacting for one hour, and then starting to vacuumize once, wherein the vacuum degree is controlled to be less than 0.08Mpa; the specific steps of gradient temperature rise are as follows: the gradient heating comprises four stages, namely heating to 140 ℃ for 2 hours, heating to 160 ℃ for 1 hour, heating to 180 ℃ for 2 hours and heating to 225 ℃ for 1 hour;
3) Sampling and detecting materials in the reaction kettle after vacuumizing for two hours, detecting that the acid value is reduced to below 10mgKOH/g, adding a catalyst tetraisopropyl titanate into the reaction kettle, stirring uniformly, then vacuumizing for the second time, and controlling the vacuum degree to be less than 0.1Mpa;
4) And (3) carrying out transesterification for 2 hours, pumping away water and micromolecular alcohol in the system, detecting the acid value and the hydroxyl value of a sample, and cooling and discharging to obtain the bio-based solvent-resistant polyester polyol, wherein the acid value of the bio-based solvent-resistant polyester polyol is 0.25mgKOH/g, the hydroxyl value is 75.6mgKOH/g, and the water content is 0.018%.
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