CN117264183A - Bio-based polyester polyol and preparation method thereof - Google Patents
Bio-based polyester polyol and preparation method thereof Download PDFInfo
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- CN117264183A CN117264183A CN202311240057.4A CN202311240057A CN117264183A CN 117264183 A CN117264183 A CN 117264183A CN 202311240057 A CN202311240057 A CN 202311240057A CN 117264183 A CN117264183 A CN 117264183A
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- polyester polyol
- based polyester
- polyol
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- 229920005906 polyester polyol Polymers 0.000 title claims abstract description 75
- 238000002360 preparation method Methods 0.000 title claims abstract description 32
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 claims abstract description 52
- 229920005862 polyol Polymers 0.000 claims abstract description 46
- 150000003077 polyols Chemical class 0.000 claims abstract description 46
- 239000004359 castor oil Substances 0.000 claims abstract description 31
- 235000019438 castor oil Nutrition 0.000 claims abstract description 31
- ZEMPKEQAKRGZGQ-XOQCFJPHSA-N glycerol triricinoleate Natural products CCCCCC[C@@H](O)CC=CCCCCCCCC(=O)OC[C@@H](COC(=O)CCCCCCCC=CC[C@@H](O)CCCCCC)OC(=O)CCCCCCCC=CC[C@H](O)CCCCCC ZEMPKEQAKRGZGQ-XOQCFJPHSA-N 0.000 claims abstract description 31
- 239000003963 antioxidant agent Substances 0.000 claims abstract description 28
- 239000003054 catalyst Substances 0.000 claims abstract description 28
- 230000003078 antioxidant effect Effects 0.000 claims abstract description 27
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 26
- 238000003756 stirring Methods 0.000 claims description 73
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 60
- 238000006243 chemical reaction Methods 0.000 claims description 60
- 238000010438 heat treatment Methods 0.000 claims description 44
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 40
- 238000002156 mixing Methods 0.000 claims description 34
- 229940126062 Compound A Drugs 0.000 claims description 28
- NLDMNSXOCDLTTB-UHFFFAOYSA-N Heterophylliin A Natural products O1C2COC(=O)C3=CC(O)=C(O)C(O)=C3C3=C(O)C(O)=C(O)C=C3C(=O)OC2C(OC(=O)C=2C=C(O)C(O)=C(O)C=2)C(O)C1OC(=O)C1=CC(O)=C(O)C(O)=C1 NLDMNSXOCDLTTB-UHFFFAOYSA-N 0.000 claims description 28
- PJUIMOJAAPLTRJ-UHFFFAOYSA-N monothioglycerol Chemical compound OCC(O)CS PJUIMOJAAPLTRJ-UHFFFAOYSA-N 0.000 claims description 22
- 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 22
- 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 22
- FDTBETCIPGWBHK-UHFFFAOYSA-N hydroxy-dimethyl-phenylsilane Chemical compound C[Si](C)(O)C1=CC=CC=C1 FDTBETCIPGWBHK-UHFFFAOYSA-N 0.000 claims description 21
- KCTAHLRCZMOTKM-UHFFFAOYSA-N tripropylphosphane Chemical compound CCCP(CCC)CCC KCTAHLRCZMOTKM-UHFFFAOYSA-N 0.000 claims description 21
- 229910052757 nitrogen Inorganic materials 0.000 claims description 20
- 239000002253 acid Substances 0.000 claims description 14
- 238000000034 method Methods 0.000 claims description 14
- 238000001816 cooling Methods 0.000 claims description 12
- 238000001914 filtration Methods 0.000 claims description 12
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 12
- 239000002994 raw material Substances 0.000 claims description 6
- 238000004519 manufacturing process Methods 0.000 claims description 3
- BGYHLZZASRKEJE-UHFFFAOYSA-N [3-[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxy]-2,2-bis[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxymethyl]propyl] 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical group CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)OCC(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 BGYHLZZASRKEJE-UHFFFAOYSA-N 0.000 claims description 2
- 150000001875 compounds Chemical class 0.000 claims description 2
- FATBGEAMYMYZAF-KTKRTIGZSA-N oleamide Chemical compound CCCCCCCC\C=C/CCCCCCCC(N)=O FATBGEAMYMYZAF-KTKRTIGZSA-N 0.000 claims description 2
- FATBGEAMYMYZAF-UHFFFAOYSA-N oleicacidamide-heptaglycolether Natural products CCCCCCCCC=CCCCCCCCC(N)=O FATBGEAMYMYZAF-UHFFFAOYSA-N 0.000 claims description 2
- 239000000463 material Substances 0.000 abstract description 7
- 229920002635 polyurethane Polymers 0.000 abstract description 3
- 239000004814 polyurethane Substances 0.000 abstract description 3
- 238000004132 cross linking Methods 0.000 abstract description 2
- 239000008204 material by function Substances 0.000 abstract description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 abstract description 2
- 230000032050 esterification Effects 0.000 abstract 1
- 238000005886 esterification reaction Methods 0.000 abstract 1
- 239000000178 monomer Substances 0.000 abstract 1
- 238000006068 polycondensation reaction Methods 0.000 abstract 1
- 238000006116 polymerization reaction Methods 0.000 abstract 1
- 230000000052 comparative effect Effects 0.000 description 10
- 238000005303 weighing Methods 0.000 description 10
- 238000012360 testing method Methods 0.000 description 9
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 4
- 238000007792 addition Methods 0.000 description 3
- 239000003209 petroleum derivative Substances 0.000 description 3
- 238000006555 catalytic reaction Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- IBOFVQJTBBUKMU-UHFFFAOYSA-N 4,4'-methylene-bis-(2-chloroaniline) Chemical compound C1=C(Cl)C(N)=CC=C1CC1=CC=C(N)C(Cl)=C1 IBOFVQJTBBUKMU-UHFFFAOYSA-N 0.000 description 1
- 241001112258 Moca Species 0.000 description 1
- 229910018557 Si O Inorganic materials 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229920013724 bio-based polymer Polymers 0.000 description 1
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 description 1
- 238000012650 click reaction Methods 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- XOFYZVNMUHMLCC-ZPOLXVRWSA-N prednisone Chemical compound O=C1C=C[C@]2(C)[C@H]3C(=O)C[C@](C)([C@@](CC4)(O)C(=O)CO)[C@@H]4[C@@H]3CCC2=C1 XOFYZVNMUHMLCC-ZPOLXVRWSA-N 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Inorganic materials [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 239000005028 tinplate Substances 0.000 description 1
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 description 1
- 235000015112 vegetable and seed oil Nutrition 0.000 description 1
- 239000008158 vegetable oil 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
- C08G63/68—Polyesters containing atoms other than carbon, hydrogen and oxygen
- C08G63/695—Polyesters containing atoms other than carbon, hydrogen and oxygen containing silicon
- C08G63/6954—Polyesters containing atoms other than carbon, hydrogen and oxygen containing silicon derived from polxycarboxylic acids and polyhydroxy 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
- 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)
- Polyesters Or Polycarbonates (AREA)
Abstract
The invention relates to a bio-based polyester polyol and a preparation method thereof, belonging to the technical field of functional materials, wherein the bio-based polyester polyol comprises 10-12 parts of sebacic acid, 82.1-98.5 parts of modified bio-based polyol, 0.05 part of antioxidant, 0.005 part of catalyst and 0.05 part of slipping auxiliary agent in parts by weight; the bio-based polyester polyol is prepared by using sebacic acid and modified bio-based polyol as polymerization monomers, adding a catalyst, an antioxidant and a slipping auxiliary agent, and performing esterification polycondensation, wherein the introduction of benzene ring and organosilicon improves the thermal stability of the bio-based polyester polyol, simultaneously improves the mechanical property of the bio-based polyester polyol, introduces polyhydroxy structure branched chains, improves the reactive sites, and simultaneously has a polyhydroxy castor oil polyol molecular structure, thereby also playing a crosslinking role and improving the mechanical property and thermal stability of the polyurethane material.
Description
Technical Field
The invention belongs to the technical field of functional materials, and particularly relates to a polyester polyol and a preparation method thereof.
Background
Polyester polyols are the main raw materials for preparing polyurethane materials, the raw materials used for the current polyester polyols are basically from petroleum products, and with the increasing consumption of petroleum resources, bio-based polymer materials are receiving a great deal of attention because of their ability to get rid of the dependence on petroleum products.
Castor oil is a low-value industrial vegetable oil, can effectively reduce dependence on petroleum products, and can obviously improve the defects of petroleum-based polyester polyol in terms of water resistance, flexibility and the like due to the unique long aliphatic hydrophobic chain segment.
The bio-based dibasic acid is produced by taking castor oil as a raw material through the processes of hydrolysis, cracking, neutralization, decoloration, crystallization, drying and the like, but the reactivity of the castor oil is reduced due to the fact that the castor oil has a linear soft chain segment structure and a small number of hydroxyl groups on molecules, so that the synthesized polyurethane material has low mechanical strength and thermal stability, and the application of the castor oil in production and life is further limited.
Disclosure of Invention
In order to solve the technical problems mentioned in the background art, the invention aims to provide a bio-based polyester polyol and a preparation method thereof.
The aim of the invention can be achieved by the following technical scheme:
the bio-based polyester polyol comprises the following raw materials in parts by weight:
10-12 parts of sebacic acid, 82.1-98.5 parts of modified bio-based polyol, 0.05 part of antioxidant, 0.005 part of catalyst and 0.05 part of slipping auxiliary agent.
The modified bio-based polyol is prepared by the following method:
step A1: mixing castor oil, dimethylphenyl silanol and tetraisopropyl titanate, feeding into a reaction kettle, controlling the stirring speed to be 150-180r/min, heating to 110-125 ℃ under the protection of nitrogen, and stirring for reacting for 1.5-2h to obtain a compound A;
further, the dosage ratio of castor oil, dimethylphenyl silanol and tetraisopropyl titanate is 500-700mL:1.7-2.4mol:10-15mL.
Dimethyl phenyl silanol is grafted onto castor oil molecular chain under the catalysis of tetrabutyl titanate. The specific reaction process is as follows:
step A2: mixing and feeding a compound A, 1-thioglycerol, tripropylphosphine and methanol into a reaction kettle, controlling the stirring rate to be 200-260r/min, heating to 30-35 ℃ under the protection of nitrogen, and stirring and reacting for 0.5-1h to obtain modified bio-based polyol;
further, the dosage ratio of compound a, 1-thioglycerol, tripropylphosphine and methanol was 500mL:2-2.2mol:0.1-0.3g:20-30mL.
The 1-thioglycerol is subjected to click reaction under the catalysis of the catalyst tripropyl phosphorus, and more hydroxyl groups are introduced into the castor oil molecular chain, wherein the specific reaction process is as follows:
a bio-based polyester polyol prepared by the process of:
step S1: mixing sebacic acid, modified bio-based polyol, a catalyst, an antioxidant and a slipping auxiliary agent, feeding into a reaction kettle, controlling the stirring speed to be 500-600r/min, heating to 140-160 ℃ under the protection of nitrogen atmosphere, continuously heating to 200-210 ℃ after stirring for 0.5-1h, adjusting the vacuum degree of the reaction kettle to 0.06Mpa, cooling to 95-105 ℃ after stirring for 1.5-2h, and filtering to obtain bio-based polyester polyol;
further, the acid value of the bio-based polyester polyol is not higher than 0.5mgKOH/g.
The invention has the beneficial effects that:
the invention discloses a bio-based polyester polyol and a preparation method thereof.
Compared with unmodified polyester polyol, the addition of organic silicon in the bio-based polyester polyol has the Si-O bond energy larger than C-C bond and C-0 bond, so that the thermal stability of the polyester polyol is effectively improved; meanwhile, the side chain of the bio-based polyester polyol introduces a benzene ring rigid structure, so that the steric hindrance of molecules is increased, the polymer is entangled in a physical structure, and the mechanical strength of the polymer is improved; the introduction of the 1-thioglycerol introduces a polyhydroxy structure branched chain on a linear soft molecular chain of the polyester polyol, reduces the regularity of the polyester structure, increases the number of hydroxyl groups, can improve the reactive active sites of the polyester polyol, and simultaneously can achieve the crosslinking effect by the polyhydroxy castor oil polyol molecular structure, thereby further improving the mechanical strength and the thermal stability of the bio-based polyester polyol.
Detailed Description
The technical solutions of the embodiments of the present invention will be clearly and completely described below in conjunction with the embodiments of the present invention, and it is apparent that the described embodiments are only some embodiments of the present invention, 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.
The bio-based polyester polyol raw material prepared in this example is referred to as follows:
catalyst (tetraisopropyl titanate);
antioxidants (Irganox-1010);
slip aids (oleamide, shanghai Jizhui Biochemical technologies Co., ltd.).
Example 1 the procedure for the preparation of a bio-based polyester polyol according to this example is as follows:
preparation of modified biobased polyol
a1: mixing castor oil, dimethylphenyl silanol and tetraisopropyl titanate, feeding into a reaction kettle, controlling the stirring speed to be 150r/min, heating to 110 ℃ under the protection of nitrogen, and stirring and reacting for 1.5h to obtain a compound A; in the above reaction, the dosage ratio of castor oil, dimethylphenylsilanol and tetraisopropyl titanate was 500mL:1.7mol:10mL.
a2: mixing and feeding a compound A, 1-thioglycerol, tripropylphosphine and methanol into a reaction kettle, controlling the stirring speed to be 200r/min, heating to 30 ℃ under the protection of nitrogen, and stirring and reacting for 0.5h to obtain modified bio-based polyol; in the above reaction, the dosage ratio of compound A, 1-thioglycerol, tripropylphosphine and methanol was 500mL:2mol:0.1g:20mL.
Preparation of bio-based polyester polyol
s1: proportioning, namely, weighing the following components in parts by weight:
10 parts of sebacic acid;
82.5 parts of modified bio-based polyol;
0.05 parts of an antioxidant;
0.005 parts of catalyst;
0.05 part of slipping auxiliary agent;
s2: mixing sebacic acid, modified bio-based polyol, a catalyst, an antioxidant and a slipping auxiliary agent, feeding into a reaction kettle, controlling the stirring speed to be 500r/min, heating to 140 ℃ under the protection of nitrogen atmosphere, continuously heating to 200 ℃ after stirring and reacting for 0.5h, adjusting the vacuum degree of the reaction kettle to be 0.06Mpa, cooling to 95 ℃ after stirring and reacting for 1.5h, and filtering to obtain the acid value not higher than 0.5mgKOH/g bio-based polyester polyol.
Example 2 the procedure for the preparation of a bio-based polyester polyol according to this example is as follows:
1) Preparation of modified biobased polyol
a1: mixing castor oil, dimethylphenyl silanol and tetraisopropyl titanate, feeding into a reaction kettle, controlling the stirring speed to be 162r/min, heating to 117 ℃ under the protection of nitrogen, and stirring for reacting for 1.5h to obtain a compound A; in the above reaction, the dosage ratio of castor oil, dimethylphenylsilanol and tetraisopropyl titanate was 600mL:2mol:10mL.
a2: mixing and feeding a compound A, 1-thioglycerol, tripropylphosphine and methanol into a reaction kettle, controlling the stirring speed to be 220r/min, heating to 32 ℃ under the protection of nitrogen, and stirring and reacting for 0.5h to obtain modified bio-based polyol; in the above reaction, the dosage ratio of compound A, 1-thioglycerol, tripropylphosphine and methanol was 500mL:2.1mol:0.2g:22mL.
2) Preparation of bio-based polyester polyol
s1: proportioning, namely, weighing the following components in parts by weight:
10.5 parts of sebacic acid;
86.5 parts of modified bio-based polyol;
0.05 parts of an antioxidant;
0.005 parts of catalyst;
0.05 part of slipping auxiliary agent;
s2: mixing sebacic acid, modified bio-based polyol, a catalyst, an antioxidant and a slipping auxiliary agent, feeding into a reaction kettle, controlling the stirring speed to be 520r/min, heating to 145 ℃ under the protection of nitrogen atmosphere, continuously heating to 200 ℃ after stirring and reacting for 0.5h, adjusting the vacuum degree of the reaction kettle to be 0.06Mpa, cooling to 95 ℃ after stirring and reacting for 1.5h, and filtering to obtain the acid value not higher than 0.5mgKOH/g bio-based polyester polyol.
Example 3 the procedure for the preparation of a bio-based polyester polyol according to this example is as follows:
1) Preparation of modified biobased polyol
a1: mixing castor oil, dimethylphenyl silanol and tetraisopropyl titanate, feeding into a reaction kettle, controlling the stirring speed to be 165r/min, heating to 120 ℃ under the protection of nitrogen, and stirring and reacting for 1.5h to obtain a compound A; in the above reaction, the ratio of castor oil, dimethylphenylsilanol and tetraisopropyl titanate used was 700mL:2.4mol:10mL.
a2: mixing and feeding a compound A, 1-thioglycerol, tripropylphosphine and methanol into a reaction kettle, controlling the stirring speed to be 240r/min, heating to 33 ℃ under the protection of nitrogen, and stirring and reacting for 0.5h to obtain modified bio-based polyol; in the above reaction, the dosage ratio of compound A, 1-thioglycerol, tripropylphosphine and methanol was 500mL:2mol:0.2g:24mL.
2) Preparation of bio-based polyester polyol
s1: proportioning, namely, weighing the following components in parts by weight:
11 parts of sebacic acid;
90.5 parts of modified bio-based polyol;
0.05 parts of an antioxidant;
0.005 parts of catalyst;
0.05 part of slipping auxiliary agent;
s2: mixing sebacic acid, modified bio-based polyol, a catalyst, an antioxidant and a slipping auxiliary agent, feeding into a reaction kettle, controlling the stirring speed to 545r/min, heating to 150 ℃ under the protection of nitrogen atmosphere, continuously heating to 205 ℃ after stirring and reacting for 1h, adjusting the vacuum degree of the reaction kettle to 0.06Mpa, cooling to 100 ℃ after stirring and reacting for 2h, and filtering to obtain the acid value not higher than 0.5mgKOH/g bio-based polyester polyol.
Example 4 the procedure for the preparation of a bio-based polyester polyol according to this example was as follows:
1) Preparation of modified biobased polyol
a1: mixing castor oil, dimethylphenyl silanol and tetraisopropyl titanate, feeding into a reaction kettle, controlling the stirring speed to be 170r/min, heating to 118 ℃ under the protection of nitrogen, and stirring and reacting for 1.5h to obtain a compound A; in the above reaction, the dosage ratio of castor oil, dimethylphenylsilanol and tetraisopropyl titanate was 500mL:2.4mol:13mL.
a2: mixing and feeding a compound A, 1-thioglycerol, tripropylphosphine and methanol into a reaction kettle, controlling the stirring speed to 245r/min, heating to 33 ℃ under the protection of nitrogen, and stirring and reacting for 0.5h to obtain modified bio-based polyol; in the above reaction, the dosage ratio of compound A, 1-thioglycerol, tripropylphosphine and methanol was 500mL:2.1mol:0.2g:25mL.
2) Preparation of bio-based polyester polyol
s1: proportioning, namely, weighing the following components in parts by weight:
11.5 parts of sebacic acid;
94.5 parts of modified bio-based polyol;
0.05 parts of an antioxidant;
0.005 parts of catalyst;
0.05 part of slipping auxiliary agent;
s2: mixing sebacic acid, modified bio-based polyol, a catalyst, an antioxidant and a slipping auxiliary agent, feeding into a reaction kettle, controlling the stirring speed to be 550r/min, heating to 150 ℃ under the protection of nitrogen atmosphere, continuously heating to 205 ℃ after stirring and reacting for 1h, adjusting the vacuum degree of the reaction kettle to be 0.06Mpa, cooling to 100 ℃ after stirring and reacting for 2h, and filtering to obtain the acid value not higher than 0.5mgKOH/g bio-based polyester polyol.
Example 5 the procedure for the preparation of a bio-based polyester polyol according to this example is as follows:
1) Preparation of modified biobased polyol
a1: mixing castor oil, dimethylphenyl silanol and tetraisopropyl titanate, feeding into a reaction kettle, controlling the stirring speed to be 170r/min, heating to 122 ℃ under the protection of nitrogen, and stirring for reacting for 1.5h to obtain a compound A; in the above reaction, the dosage ratio of castor oil, dimethylphenylsilanol and tetraisopropyl titanate was 600mL:2.4mol:10mL.
a2: mixing and feeding a compound A, 1-thioglycerol, tripropylphosphine and methanol into a reaction kettle, controlling the stirring rate to be 250r/min, heating to 34 ℃ under the protection of nitrogen, and stirring and reacting for 0.5h to obtain modified bio-based polyol; in the above reaction, the dosage ratio of compound A, 1-thioglycerol, tripropylphosphine and methanol was 500mL:2mol:0.2g:25mL.
2) Preparation of bio-based polyester polyol
s1: proportioning, namely, weighing the following components in parts by weight:
12 parts of sebacic acid;
98.5 parts of modified bio-based polyol;
0.05 parts of an antioxidant;
0.005 parts of catalyst;
0.05 part of slipping auxiliary agent;
s2: mixing sebacic acid, modified bio-based polyol, a catalyst, an antioxidant and a slipping auxiliary agent, feeding into a reaction kettle, controlling the stirring speed to be 550r/min, heating to 155 ℃ under the protection of nitrogen atmosphere, continuously heating to 208 ℃ after stirring and reacting for 1h, adjusting the vacuum degree of the reaction kettle to be 0.06Mpa, cooling to 102 ℃ after stirring and reacting for 2h, and filtering to obtain the acid value not higher than 0.5mgKOH/g bio-based polyester polyol.
Example 6 the procedure for the preparation of a bio-based polyester polyol according to this example was as follows:
1) Preparation of modified biobased polyol
a1: mixing castor oil, dimethylphenyl silanol and tetraisopropyl titanate, feeding into a reaction kettle, controlling the stirring speed to be 180r/min, heating to 125 ℃ under the protection of nitrogen, and stirring for 2 hours to obtain a compound A; in the above reaction, the ratio of castor oil, dimethylphenylsilanol and tetraisopropyl titanate used was 700mL:2.4mol:15mL.
a2: mixing and feeding a compound A, 1-thioglycerol, tripropylphosphine and methanol into a reaction kettle, controlling the stirring speed to be 260r/min, heating to 35 ℃ under the protection of nitrogen, and stirring and reacting for 1h to obtain modified bio-based polyol; in the above reaction, the dosage ratio of compound A, 1-thioglycerol, tripropylphosphine and methanol was 500mL:2mol:0.3g:30mL.
2) Preparation of bio-based polyester polyol
s1: proportioning, namely, weighing the following components in parts by weight:
10 parts of sebacic acid;
94.5 parts of modified bio-based polyol;
0.05 parts of an antioxidant;
0.005 parts of catalyst;
0.05 part of slipping auxiliary agent;
s2: mixing sebacic acid, modified bio-based polyol, a catalyst, an antioxidant and a slipping auxiliary agent, feeding into a reaction kettle, controlling the stirring speed to be 600r/min, heating to 160 ℃ under the protection of nitrogen atmosphere, continuously heating to 210 ℃ after stirring and reacting for 1h, adjusting the vacuum degree of the reaction kettle to be 0.06Mpa, cooling to 105 ℃ after stirring and reacting for 2h, and filtering to obtain the acid value not higher than 0.5mgKOH/g bio-based polyester polyol.
Example 7 the procedure for the preparation of a bio-based polyester polyol according to this example was as follows:
1) Preparation of modified biobased polyol
a1: mixing castor oil, dimethylphenyl silanol and tetraisopropyl titanate, feeding into a reaction kettle, controlling the stirring speed to be 180r/min, heating to 125 ℃ under the protection of nitrogen, and stirring for 2 hours to obtain a compound A; in the above reaction, the ratio of castor oil, dimethylphenylsilanol and tetraisopropyl titanate used was 700mL:2.4mol:15mL.
a2: mixing and feeding a compound A, 1-thioglycerol, tripropylphosphine and methanol into a reaction kettle, controlling the stirring speed to be 200r/min, heating to 30 ℃ under the protection of nitrogen, and stirring and reacting for 0.5h to obtain modified bio-based polyol; in the above reaction, the dosage ratio of compound A, 1-thioglycerol, tripropylphosphine and methanol was 500mL:2mol:0.1g:20mL.
2) Preparation of bio-based polyester polyol
s1: proportioning, namely, weighing the following components in parts by weight:
11 parts of sebacic acid;
98.5 parts of modified bio-based polyol;
0.05 parts of an antioxidant;
0.005 parts of catalyst;
0.05 part of slipping auxiliary agent;
s2: mixing sebacic acid, modified bio-based polyol, a catalyst, an antioxidant and a slipping auxiliary agent, feeding into a reaction kettle, controlling the stirring speed to be 500r/min, heating to 140 ℃ under the protection of nitrogen atmosphere, continuously heating to 200 ℃ after stirring and reacting for 0.5h, adjusting the vacuum degree of the reaction kettle to be 0.06Mpa, cooling to 95 ℃ after stirring and reacting for 1.5h, and filtering to obtain the acid value not higher than 0.5mgKOH/g bio-based polyester polyol.
Example 8 the procedure for the preparation of a bio-based polyester polyol according to this example is as follows:
1) Preparation of modified biobased polyol
a1: mixing castor oil, dimethylphenyl silanol and tetraisopropyl titanate, feeding into a reaction kettle, controlling the stirring speed to be 150r/min, heating to 110 ℃ under the protection of nitrogen, and stirring for 1.5h to obtain a compound A; in the above reaction, the dosage ratio of castor oil, dimethylphenylsilanol and tetraisopropyl titanate was 500mL:1.7mol:10mL.
a2: mixing and feeding a compound A, 1-thioglycerol, tripropylphosphine and methanol into a reaction kettle, controlling the stirring speed to be 260r/min, heating to 35 ℃ under the protection of nitrogen, and stirring and reacting for 1h to obtain modified bio-based polyol; in the above reaction, the dosage ratio of compound A, 1-thioglycerol, tripropylphosphine and methanol was 500mL:2.2mol:0.3g:30mL.
2) Preparation of bio-based polyester polyol
s1: proportioning, namely, weighing the following components in parts by weight:
10.5 parts of sebacic acid;
90.5 parts of modified bio-based polyol;
0.05 parts of an antioxidant;
0.005 parts of catalyst;
0.05 part of slipping auxiliary agent;
s2: mixing sebacic acid, modified bio-based polyol, a catalyst, an antioxidant and a slipping auxiliary agent, feeding into a reaction kettle, controlling the stirring speed to be 600r/min, heating to 160 ℃ under the protection of nitrogen atmosphere, continuously heating to 210 ℃ after stirring and reacting for 1h, adjusting the vacuum degree of the reaction kettle to be 0.06Mpa, cooling to 105 ℃ after stirring and reacting for 2h, and filtering to obtain the acid value not higher than 0.5mgKOH/g bio-based polyester polyol.
Comparative example 1
The comparative example was carried out as follows to prepare a bio-based polyester polyol:
s1: proportioning, namely, weighing the following components in parts by weight:
11 parts of sebacic acid;
47 parts of castor oil;
0.05 parts of an antioxidant;
0.005 parts of catalyst;
0.05 part of slipping auxiliary agent;
s2: mixing sebacic acid, modified bio-based polyol, a catalyst, an antioxidant and a slipping auxiliary agent, feeding into a reaction kettle, controlling the stirring speed to be 500r/min, heating to 140 ℃ under the protection of nitrogen atmosphere, continuously heating to 200 ℃ after stirring and reacting for 0.5h, adjusting the vacuum degree of the reaction kettle to be 0.06Mpa, cooling to 95 ℃ after stirring and reacting for 1.5h, and filtering to obtain the acid value not higher than 0.5mgKOH/g bio-based polyester polyol.
Comparative example 2
The comparative example was carried out as follows to prepare a bio-based polyester polyol:
s1: proportioning, namely, weighing the following components in parts by weight:
10.5 parts of sebacic acid;
48 parts of castor oil;
0.05 parts of an antioxidant;
0.005 parts of catalyst;
0.05 part of slipping auxiliary agent;
s2: mixing sebacic acid, modified bio-based polyol, a catalyst, an antioxidant and a slipping auxiliary agent, feeding into a reaction kettle, controlling the stirring speed to be 600r/min, heating to 160 ℃ under the protection of nitrogen atmosphere, continuously heating to 210 ℃ after stirring and reacting for 1h, adjusting the vacuum degree of the reaction kettle to be 0.06Mpa, cooling to 105 ℃ after stirring and reacting for 2h, and filtering to obtain the acid value not higher than 0.5mgKOH/g bio-based polyester polyol.
To facilitate testing of the relevant properties of bio-based polyester polyols, the bio-based polyester polyols made in examples 1-8 and comparative examples 1-2 were subjected to performance testing, with specific test data as shown in table 1:
heat resistance test:
the bio-based polyester polyols prepared in examples 1 to 8 and comparative examples 1 to 2 were sprayed onto the same substrate (tin plate), respectively, and the heat resistance of the bio-based polyester polyol was evaluated by taking the color difference (. DELTA.E) of the heat-resistant dry film at 300 ℃ X60 min as a reference on the dry film prepared at 280 ℃ X10 min.
TABLE 1
As can be seen from Table 1, the acid value of the bio-based polyester polyol prepared in examples 1 to 8 was 0.28 to 0.42mgKOH.g -1 Hydroxyl value of 379-470 mg KOH.g -1 The color difference was 3.4 to 4.2, indicating that the bio-based polyester polyols prepared in examples 1 to 8 were superior to the bio-based polyester polyols prepared in comparative examples 1 to 2 in terms of their overall properties.
To facilitate testing of the relevant properties of bio-based polyester polyols, the bio-based polyester polyols made in examples 1-8 and comparative examples 1-2 were subjected to performance testing, with specific test data as shown in table 2:
preparation of test bars:
y1: blending the bio-based polyester polyol prepared in examples 1-8 and comparative examples 1-2 with 2, 4-toluene diisocyanate (TDI-100) according to the molar ratio of-OH/-NCO of 1:1.05, carrying out heat preservation in a water bath kettle at 80 ℃ for 2 hours, measuring the content of-NCO, and sealing and preserving after passing the condition to obtain a prepolymer;
y2: the prepolymer and 3,3 '-dichloro-4, 4' -aminodiphenyl Methane (MOCA) are mixed according to the mass ratio of 20:1, blending and defoaming, then injecting into a mould to pressurize for 35min, demoulding, and vulcanizing for 24h at 120 ℃ to obtain a test sample.
TABLE 2
As is clear from Table 2, the bio-based polyester polyols prepared in examples 1 to 8 had a tensile strength of 33 to 40MPa and an impact resistance of 44 to 52KJ/m 2， It was demonstrated that the bio-based polyester polyols prepared in examples 1-8 were superior to the bio-based polyester polyols prepared in comparative examples 1-2 in both tensile strength and impact strength.
In the description of the present specification, the descriptions of the terms "one embodiment," "example," "specific example," and the like, mean that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the present invention. In this specification, schematic representations of the above terms do not necessarily refer to the same embodiments or examples. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples.
The foregoing is merely illustrative and explanatory of the invention, as various modifications and additions may be made to the particular embodiments described, or in a similar manner, by those skilled in the art, without departing from the scope of the invention or exceeding the scope of the invention as defined in the claims.
In the description of the present specification, the descriptions of the terms "one embodiment," "example," "specific example," and the like, mean that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the present invention. In this specification, schematic representations of the above terms do not necessarily refer to the same embodiments or examples. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples.
The foregoing is merely illustrative and explanatory of the invention, as various modifications and additions may be made to the particular embodiments described, or in a similar manner, by those skilled in the art, without departing from the scope of the invention or exceeding the scope of the invention as defined in the claims.
Claims (7)
1. The bio-based polyester polyol is characterized by comprising the following raw materials in parts by weight: 10-12 parts of sebacic acid, 82.1-98.5 parts of modified bio-based polyol, 0.05 part of antioxidant, 0.005 part of catalyst and 0.05 part of slipping auxiliary agent;
the modified bio-based polyol is prepared by the following method:
step A1: mixing castor oil, dimethylphenylsilanol and tetraisopropyl titanate, feeding, heating to 110-125 ℃ under the protection of nitrogen, and stirring for reaction for 1.5-2h to obtain a compound A;
step A2: and (3) mixing the compound A, the 1-thioglycerol, the tripropylphosphine and the methanol, feeding, heating to 30-35 ℃ under the protection of nitrogen, and stirring for reacting for 0.5-1h to obtain the modified bio-based polyol.
2. The bio-based polyester polyol of claim 1, wherein the castor oil, dimethylphenylsilanol and tetraisopropyl titanate are present in an amount ratio of 500 to 700mL:1.7-2.4mol:10-15mL.
3. The bio-based polyester polyol according to claim 1, wherein the amount ratio of compound a, 1-thioglycerol, tripropylphosphine and methanol is 500mL:2-2.2mol:0.1-0.3g:20-30mL.
4. A process for the preparation of a bio-based polyester polyol according to claim 3, comprising the steps of:
step S1: mixing sebacic acid, modified bio-based polyol, catalyst tetraisopropyl titanate, antioxidant and slipping auxiliary agent, heating to 140-160 ℃ under the protection of nitrogen atmosphere, stirring and reacting for 0.5-1h, continuously heating to 200-210 ℃, adjusting the vacuum degree of a reaction kettle to 0.06Mpa, stirring and reacting for 1.5-2h, cooling to 95-105 ℃, and filtering to obtain bio-based polyester polyol.
5. The method for producing a bio-based polyester polyol according to claim 4, wherein the antioxidant is Irganox-1010.
6. The method for preparing a bio-based polyester polyol according to claim 4, wherein the slip aid is oleamide.
7. The method for producing a bio-based polyester polyol according to claim 4, wherein the acid value of the bio-based polyester polyol is not more than 0.5mgKOH/g.
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