CN114031759A - Unsaturated fatty diacid-based polyester polyol and preparation method thereof - Google Patents
Unsaturated fatty diacid-based polyester polyol and preparation method thereof Download PDFInfo
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- CN114031759A CN114031759A CN202111518431.3A CN202111518431A CN114031759A CN 114031759 A CN114031759 A CN 114031759A CN 202111518431 A CN202111518431 A CN 202111518431A CN 114031759 A CN114031759 A CN 114031759A
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- 229920005906 polyester polyol Polymers 0.000 title claims abstract description 36
- 238000002360 preparation method Methods 0.000 title claims abstract description 8
- 239000002253 acid Substances 0.000 claims abstract description 53
- 238000005886 esterification reaction Methods 0.000 claims abstract description 32
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 31
- 238000000034 method Methods 0.000 claims abstract description 29
- 239000000463 material Substances 0.000 claims abstract description 18
- 239000003054 catalyst Substances 0.000 claims abstract description 16
- 238000007599 discharging Methods 0.000 claims abstract description 15
- 238000006068 polycondensation reaction Methods 0.000 claims abstract description 14
- 238000010438 heat treatment Methods 0.000 claims abstract description 13
- 239000000203 mixture Substances 0.000 claims abstract description 7
- 229920005862 polyol Polymers 0.000 claims abstract description 7
- 150000003077 polyols Chemical class 0.000 claims abstract description 7
- 238000002156 mixing Methods 0.000 claims abstract description 4
- 238000006243 chemical reaction Methods 0.000 claims description 60
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 claims description 22
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 claims description 19
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 19
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 16
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 claims description 14
- WLJVNTCWHIRURA-UHFFFAOYSA-N pimelic acid Chemical compound OC(=O)CCCCCC(O)=O WLJVNTCWHIRURA-UHFFFAOYSA-N 0.000 claims description 14
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims description 13
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 11
- 239000001530 fumaric acid Substances 0.000 claims description 11
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 claims description 9
- 239000002994 raw material Substances 0.000 claims description 9
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 8
- BGNXCDMCOKJUMV-UHFFFAOYSA-N Tert-Butylhydroquinone Chemical compound CC(C)(C)C1=CC(O)=CC=C1O BGNXCDMCOKJUMV-UHFFFAOYSA-N 0.000 claims description 8
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 claims description 8
- 239000011976 maleic acid Substances 0.000 claims description 8
- NWVVVBRKAWDGAB-UHFFFAOYSA-N p-methoxyphenol Chemical compound COC1=CC=C(O)C=C1 NWVVVBRKAWDGAB-UHFFFAOYSA-N 0.000 claims description 8
- CNHDIAIOKMXOLK-UHFFFAOYSA-N toluquinol Chemical compound CC1=CC(O)=CC=C1O CNHDIAIOKMXOLK-UHFFFAOYSA-N 0.000 claims description 8
- RTBFRGCFXZNCOE-UHFFFAOYSA-N 1-methylsulfonylpiperidin-4-one Chemical compound CS(=O)(=O)N1CCC(=O)CC1 RTBFRGCFXZNCOE-UHFFFAOYSA-N 0.000 claims description 7
- 239000001361 adipic acid Substances 0.000 claims description 7
- 235000011037 adipic acid Nutrition 0.000 claims description 7
- JFCQEDHGNNZCLN-UHFFFAOYSA-N anhydrous glutaric acid Natural products OC(=O)CCCC(O)=O JFCQEDHGNNZCLN-UHFFFAOYSA-N 0.000 claims description 7
- AZQWKYJCGOJGHM-UHFFFAOYSA-N 1,4-benzoquinone Chemical compound O=C1C=CC(=O)C=C1 AZQWKYJCGOJGHM-UHFFFAOYSA-N 0.000 claims description 6
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 claims description 6
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 6
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 claims description 6
- JVLRYPRBKSMEBF-UHFFFAOYSA-K diacetyloxystibanyl acetate Chemical compound [Sb+3].CC([O-])=O.CC([O-])=O.CC([O-])=O JVLRYPRBKSMEBF-UHFFFAOYSA-K 0.000 claims description 6
- 229910052681 coesite Inorganic materials 0.000 claims description 5
- 229910052906 cristobalite Inorganic materials 0.000 claims description 5
- 229920006395 saturated elastomer Polymers 0.000 claims description 5
- 239000000377 silicon dioxide Substances 0.000 claims description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 5
- 239000003381 stabilizer Substances 0.000 claims description 5
- 229910052682 stishovite Inorganic materials 0.000 claims description 5
- 150000005846 sugar alcohols Polymers 0.000 claims description 5
- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical compound CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 claims description 5
- 229910052905 tridymite Inorganic materials 0.000 claims description 5
- 229940044119 2-tert-butylhydroquinone Drugs 0.000 claims description 4
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 claims description 4
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 claims description 4
- YPFDHNVEDLHUCE-UHFFFAOYSA-N propane-1,3-diol Chemical compound OCCCO YPFDHNVEDLHUCE-UHFFFAOYSA-N 0.000 claims description 4
- 229940083957 1,2-butanediol Drugs 0.000 claims description 3
- 229940015975 1,2-hexanediol Drugs 0.000 claims description 3
- 229940043375 1,5-pentanediol Drugs 0.000 claims description 3
- JZODKRWQWUWGCD-UHFFFAOYSA-N 2,5-di-tert-butylbenzene-1,4-diol Chemical compound CC(C)(C)C1=CC(O)=C(C(C)(C)C)C=C1O JZODKRWQWUWGCD-UHFFFAOYSA-N 0.000 claims description 3
- ALQSHHUCVQOPAS-UHFFFAOYSA-N Pentane-1,5-diol Chemical compound OCCCCCO ALQSHHUCVQOPAS-UHFFFAOYSA-N 0.000 claims description 3
- BMRWNKZVCUKKSR-UHFFFAOYSA-N butane-1,2-diol Chemical compound CCC(O)CO BMRWNKZVCUKKSR-UHFFFAOYSA-N 0.000 claims description 3
- FHKSXSQHXQEMOK-UHFFFAOYSA-N hexane-1,2-diol Chemical compound CCCCC(O)CO FHKSXSQHXQEMOK-UHFFFAOYSA-N 0.000 claims description 3
- WCVRQHFDJLLWFE-UHFFFAOYSA-N pentane-1,2-diol Chemical compound CCCC(O)CO WCVRQHFDJLLWFE-UHFFFAOYSA-N 0.000 claims description 3
- 229960004063 propylene glycol Drugs 0.000 claims description 3
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 claims description 3
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Inorganic materials O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 claims description 2
- 230000032050 esterification Effects 0.000 claims description 2
- YBMRDBCBODYGJE-UHFFFAOYSA-N germanium oxide Inorganic materials O=[Ge]=O YBMRDBCBODYGJE-UHFFFAOYSA-N 0.000 claims description 2
- 239000011261 inert gas Substances 0.000 claims description 2
- 150000001875 compounds Chemical class 0.000 claims 2
- -1 2,2,6, 6-tetramethyl-4-hydroxypiperidine nitroxide free radical Chemical class 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 claims 1
- 230000035945 sensitivity Effects 0.000 abstract description 17
- 229920002635 polyurethane Polymers 0.000 abstract description 14
- 239000004814 polyurethane Substances 0.000 abstract description 14
- 230000002194 synthesizing effect Effects 0.000 abstract 1
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 25
- 229910052740 iodine Inorganic materials 0.000 description 25
- 239000011630 iodine Substances 0.000 description 25
- 150000002148 esters Chemical class 0.000 description 24
- 238000003756 stirring Methods 0.000 description 14
- 238000005070 sampling Methods 0.000 description 12
- 150000007513 acids Chemical class 0.000 description 3
- 238000006116 polymerization reaction Methods 0.000 description 3
- DNIAPMSPPWPWGF-VKHMYHEASA-N (+)-propylene glycol Chemical compound C[C@H](O)CO DNIAPMSPPWPWGF-VKHMYHEASA-N 0.000 description 2
- DNIAPMSPPWPWGF-GSVOUGTGSA-N (R)-(-)-Propylene glycol Chemical compound C[C@@H](O)CO DNIAPMSPPWPWGF-GSVOUGTGSA-N 0.000 description 2
- 229940035437 1,3-propanediol Drugs 0.000 description 2
- 229920005830 Polyurethane Foam Polymers 0.000 description 2
- 150000008064 anhydrides Chemical class 0.000 description 2
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 150000002009 diols Chemical class 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 229920000166 polytrimethylene carbonate Polymers 0.000 description 2
- 239000011496 polyurethane foam Substances 0.000 description 2
- 235000013772 propylene glycol Nutrition 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- KDYFGRWQOYBRFD-UHFFFAOYSA-N succinic acid Chemical compound OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 2
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 2
- STGNLGBPLOVYMA-MAZDBSFSSA-N (E)-but-2-enedioic acid Chemical compound OC(=O)\C=C\C(O)=O.OC(=O)\C=C\C(O)=O STGNLGBPLOVYMA-MAZDBSFSSA-N 0.000 description 1
- STGNLGBPLOVYMA-TZKOHIRVSA-N (z)-but-2-enedioic acid Chemical compound OC(=O)\C=C/C(O)=O.OC(=O)\C=C/C(O)=O STGNLGBPLOVYMA-TZKOHIRVSA-N 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- 150000008065 acid anhydrides Chemical class 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 230000001476 alcoholic effect Effects 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000000539 dimer Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- ACCCMOQWYVYDOT-UHFFFAOYSA-N hexane-1,1-diol Chemical compound CCCCCC(O)O ACCCMOQWYVYDOT-UHFFFAOYSA-N 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- UWJJYHHHVWZFEP-UHFFFAOYSA-N pentane-1,1-diol Chemical compound CCCCC(O)O UWJJYHHHVWZFEP-UHFFFAOYSA-N 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000001384 succinic acid Substances 0.000 description 1
- RINCXYDBBGOEEQ-UHFFFAOYSA-N succinic anhydride Chemical compound O=C1CCC(=O)O1 RINCXYDBBGOEEQ-UHFFFAOYSA-N 0.000 description 1
- 238000003786 synthesis reaction Methods 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
- C08G63/52—Polycarboxylic acids or polyhydroxy compounds in which at least one of the two components contains aliphatic unsaturation
-
- 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
- C08G63/66—Polyesters containing oxygen in the form of ether groups
- C08G63/668—Polyesters containing oxygen in the form of ether groups derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/676—Polyesters containing oxygen in the form of ether groups derived from polycarboxylic acids and polyhydroxy compounds in which at least one of the two components contains aliphatic unsaturation
-
- 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 unsaturated fatty diacid polyester polyol and a preparation method thereof, wherein the polyester polyol is prepared by the following method: (1) taking unsaturated fatty diacid and polyol, proportioning and mixing the materials in proportion, putting the mixture into a reactor, and heating the reactor to perform esterification reaction; (2) and after the esterification reaction is finished, adding a catalyst into the reactor, carrying out polycondensation reaction, and discharging when the acid value and the hydroxyl value of the materials in the reactor meet the index requirements to obtain the target product unsaturated fatty diacid polyester polyol. Compared with the prior art, the polyurethane obtained when the polyester polyol is used for synthesizing the polyurethane has temperature sensitivity, rebound resilience and the like.
Description
Technical Field
The invention belongs to the technical field of preparation of polyols, and relates to unsaturated fatty diacid polyester polyol and a preparation method thereof.
Background
Polymer polyol is one of important raw materials in the polyurethane industry, and in addition to polyether polyol, polyester polyol imparts unique properties to polyurethane, is an important synthetic raw material in the polyurethane field and the like, and plays an important role in the chemical industry.
Along with the improvement of the quality of social life, higher requirements are put forward on the service performance of polyurethane, for example, the polyurethane can be softened above a certain service temperature, and when the temperature is lower than a certain service temperature, the polyurethane foam is hardened from soft, so that the polyurethane foam has the characteristic of good temperature sensitivity. Meanwhile, the polyurethane is required to be capable of being restored to the original form slowly after being extruded and deformed, and has a good rebound resilience characteristic. It is important to combine the two properties of polyurethane, which are closely related to the raw materials for preparing polyurethane, and therefore, the present invention is proposed based on the above.
Disclosure of Invention
The invention aims to provide unsaturated fatty dibasic acid polyester polyol and a preparation method thereof, wherein polyurethane obtained when the unsaturated fatty dibasic acid polyester polyol is used for polyurethane synthesis has temperature sensitivity, rebound resilience and the like.
The purpose of the invention can be realized by the following technical scheme:
a preparation method of unsaturated fatty diacid polyester polyol comprises the following steps:
(1) taking unsaturated fatty diacid and polyol, proportioning and mixing the materials in proportion, putting the mixture into a reactor, and heating the reactor to perform esterification reaction;
(2) and after the esterification reaction is finished, adding a catalyst into the reactor, carrying out polycondensation reaction, and discharging when the acid value and the hydroxyl value of the materials in the reactor meet the index requirements to obtain the target product unsaturated fatty diacid polyester polyol.
Further, in the step (1), the addition amount mass ratio (here, the molar ratio) of the unsaturated fatty diacid to the polyhydric alcohol is 0.88 to 0.99: 1.
further, in the step (1), the unsaturated fatty dibasic acid is one or a mixture of maleic acid (maleic acid), fumaric acid (fumaric acid) and maleic anhydride, and when a plurality of dibasic acids are mixed, the proportion can be any. Preferably, in order to obtain better 'temperature sensitivity and rebound resilience' performance of the polyurethane, saturated dibasic acid such as glutaric acid, adipic acid or pimelic acid is added into the system during polymerization so as to adjust the content and distribution of double bonds on a polyester chain. The proportion of saturated dibasic acids such as glutaric acid, adipic acid or pimelic acid is generally not less than 45% by mole of the total mass of all the diacids (i.e. the total amount of saturated unsaturated dibasic acids).
Further, the polyalcohol is one or a mixture of more of ethylene glycol, diethylene glycol, triethylene glycol, 1, 2-propanediol, 1, 3-propanediol, 1, 2-butanediol, 1, 4-butanediol, 1, 2-pentanediol, 1, 5-pentanediol, 1, 2-hexanediol and 1, 6-hexanediol. The use of the diol and the matching of the diacid are one of the elements for obtaining the polyurethane with the temperature sensitivity and the rebound resilience, and when the diacid used is succinic acid (anhydride) (the succinic acid refers to maleic acid, maleic anhydride and fumaric acid), the diol is preferably pentanediol or hexanediol.
Furthermore, in the step (1), when the unsaturated fatty diacid is maleic anhydride, the unsaturated fatty diacid is firstly heated to 50-90 ℃ for reaction for 0.5-3 h, and then the temperature is raised to 150-200 ℃ for reaction for 1-10 h; when the unsaturated fatty diacid is maleic acid or fumaric acid, the unsaturated fatty diacid and the polyhydric alcohol are mixed and dissolved, and simultaneously, the temperature is raised to 150-200 ℃ for reaction for 1-10 hours.
Specifically, the esterification reaction process depends on different raw materials of the diacid, when the raw material of the diacid is maleic anhydride, the maleic anhydride is added into dihydric alcohol, the esterification reaction is carried out on the acid anhydride and alcoholic hydroxyl for 0.5 to 3 hours at the temperature of between 50 and 90 ℃ to generate dimer alcohol acid, the temperature is increased to between 150 and 200 ℃, the esterification reaction is carried out on carboxylic acid and hydroxyl for 1 to 10 hours, the generated small molecular water is separated and removed through a rectifying tower arranged at the top of a reaction kettle, the preferred temperature range is between 170 and 190 ℃, the preferred reaction time is between 5 and 8 hours, and when no water is generated basically, the small molecular water enters the polycondensation process. When the used dibasic acid is maleic acid or fumaric acid, adding diacid into a reactor containing glycol, gradually heating to 150-200 ℃ while stirring, mixing and dissolving, carrying out esterification reaction on carboxylic acid and hydroxyl for 1-10 h, separating and removing generated micromolecular water through a rectifying tower arranged at the top of a reaction kettle, wherein the preferable temperature range is 170-190 ℃, and the preferable reaction time is 5-8 h. When substantially no water is formed, the polycondensation process is entered.
Further, in the step (1), a rectifying tower is arranged at the top of the reactor to separate and remove water generated in the esterification reaction.
Further, in the step (2), in order to prevent the adverse effect of oxygen in the air during the polymerization, N needs to be introduced into the system during the polymerization2And the like, keeping the reaction under substantially oxygen-free conditions. In the polycondensation stage, it is necessary to work under a relatively high vacuum, typically at a pressure of less than 2kPa, in order to increase the molecular weight of the polyester polyol. N may also be introduced into the system2Under an inert gas, using N2The gas flow carries the small analytes produced out of the system to increase molecular weight.
Further, in the step (2), the catalyst mainly contains Sb2O3Antimony acetate, GeO2N-butyl titanate, isopropyl titanate, TiO2/SiO2The composite has better catalytic performance in the polycondensation reaction disclosed by the invention, and antimony acetate, isopropyl titanate and TiO2/SiO2The composite has excellent catalytic performance. The dosage of the catalyst is 7ppm to 350ppm of the total mass of the dibasic acid and the dihydric alcohol, and the preferred dosage is 10ppm to 200 ppm. The temperature in the polycondensation process is 190-250 ℃, the preferred temperature range is 200-230 ℃, the temperature is gradually increased in the polycondensation process, the temperature increasing speed is controlled to be 0.5-2 ℃/min, the constant temperature is maintained for 1-15 h after the temperature is increased to the specified temperature, and the preferred time range is 5-10 h. The acid value of the obtained product is not higher than 2mgKOH/g, the hydroxyl value is 30-60 mgKOH/g, and the iodine value range is 5-65g/100 g. The molecular weight range is 2000-12000 g/mol.
Further, in the step (2), the temperature of the polycondensation reaction is 190-250 ℃ and the time is 1-15 h.
Further, in the above esterification and polycondensation reaction, in order to prevent the double bond in the unsaturated acid (anhydride) from being destroyed, a stabilizer is required to be added to the reaction system, and the stabilizer may be hydroquinone, p-hydroxyanisole, 2, 5-di-tert-butylhydroquinone, 2-tert-butylhydroquinone, p-benzoquinone, methylhydroquinone, 2,6, 6-tetramethyl-4-hydroxypiperidine nitroxide radical (also referred to as ZM-701), and one of them may be added or a plurality of them may be mixed for use. The addition amount is 0.05-1.5% of the mass of the unsaturated raw materials including unsaturated anhydride and unsaturated fatty diacid in the reaction system, and the preferable dosage is 0.1-1.0%.
Detailed Description
The present invention will be described in detail with reference to specific examples. The present embodiment is implemented on the premise of the technical solution of the present invention, and a detailed implementation manner and a specific operation process are given, but the scope of the present invention is not limited to the following embodiments.
In the following examples, unless otherwise specified, all the conventional commercially available raw materials or conventional processing techniques in the art are indicated.
Example 1
0.798kg of 1, 3-propanediol and 0.049g of hydroquinone were charged into a reactor, N2 was slowly introduced to remove air from the reactor, and N was slowly introduced with stirring2To remove air from the reactor, the temperature was raised to 50 ℃.
98g of maleic anhydride and 1188g of glutaric acid were charged into the reactor, and reacted while being dissolved, at 50 ℃ for 0.5 hour. Then the temperature is raised to 150 ℃ within 45min, the dibasic acid and the dihydric alcohol start to react in the temperature raising process, the water generated by the reaction is separated from the reaction system through a rectifying tower at the top of the kettle, the temperature of the top of the rectifying tower is controlled to be 100 +/-1 ℃, and the constant temperature reaction is continued for 1h at 150 ℃.
After the esterification reaction was completed, 14.6mg of antimony acetate as a catalyst was charged into the reactor and reacted at 150 ℃ for 30 min.
Vacuumizing, keeping the pressure of the reactor lower than 2kPa, gradually heating to 230 ℃ at the speed of 2 ℃/min, and reacting for 6h at constant temperature. Slowly introducing N into the reactor2And simultaneously closing the vacuum system, opening a discharge valve after the reactor is heated to normal pressure, and discharging the materials to obtain the required polyester polyol. Sampling and analyzing acid ester, hydroxyl value, iodine value and molecular weight. The acid ester has a hydroxyl value of 60mgKOH/g, an iodine value of 12.2, a molecular weight of 2300g/mol and a temperature sensitivity index of 5.2 and is 1.9 mgKOH/g.
Example 2
197kg of 1, 2-hexanediol and 2.94g of 2-tert-butylhydroquinone were charged into the reactor, and N was slowly introduced with stirring2To remove air from the reactor, the temperature was raised to 50 ℃.
196g of maleic anhydride and 1168g of adipic acid were charged into a reactor, and reacted while being dissolved, at 90 ℃ for 3 hours. Then the temperature is raised to 200 ℃ within 45min, the dibasic acid and the dihydric alcohol start to react in the temperature raising process, the water generated by the reaction is separated from the reaction system through a rectifying tower at the top of the kettle, the temperature of the top of the rectifying tower is controlled to be 100 +/-1 ℃, and the constant temperature reaction is continued for 10 hours at 200 ℃.
After the esterification reaction was completed, 921.375mg of isopropyl titanate as a catalyst was charged into the reactor, and the reaction was carried out at 200 ℃ for 90 min.
Introduction of N2Gradually heating to 240 ℃ at the speed of 2 ℃/min, and reacting for 2h at constant temperature. Slowly introducing N into the reactor2And simultaneously closing the vacuum system, opening a discharge valve after the reactor is heated to normal pressure, and discharging the materials to obtain the required polyester polyol. Sampling and analyzing acid ester, hydroxyl value, iodine value and molecular weight. The acid ester has a hydroxyl value of 59mgKOH/g, an iodine value of 19.28, a molecular weight of 3000g/mol and a temperature sensitivity index of 4.9 and is 1.5 mgKOH/g.
Example 3
Into the reactor, 1.166kg of diethylene glycol and 2.94g of ZM-701 were charged, and N was slowly introduced while stirring2To remove air from the reactor, the temperature was raised to 50 ℃.
294g of maleic anhydride and 1120g of pimelic acid were charged into a reactor, and reacted while dissolving, at 75 ℃ for 1 hour. Then the temperature is raised to 155 ℃ within 45min, the dibasic acid and the dihydric alcohol start to react in the temperature raising process, the water generated by the reaction is separated from the reaction system through a rectifying tower at the top of the kettle, the temperature of the top of the rectifying tower is controlled to be 100 +/-1 ℃, and the reaction is continued for 2 hours at the constant temperature of 155 ℃.
After the esterification reaction was completed, 38.7mg of Sb as a catalyst was charged into the reactor2O3The reaction was carried out at 155 ℃ for 45 min.
Vacuumizing, keeping the pressure of the reactor lower than 2kPa, gradually heating to 260 ℃ at the speed of 2 ℃/min, and reacting for 5 hours at constant temperature. Slowly introducing N into the reactor2And simultaneously closing the vacuum system, opening a discharge valve after the reactor is heated to normal pressure, and discharging the materials to obtain the required polyester polyol. Sampling and analyzing acid ester, hydroxyl value, iodine value and molecular weight. The acid ester has a hydroxyl value of 45mgKOH/g and an iodine value of 29.51, a molecular weight of 3500g/mol and a temperature sensitivity index of 6.1.
Example 4
1.0125kg of 1, 4-butanediol and 0.435g of methylhydroquinone are introduced into a reactor, and N is slowly introduced with stirring2To remove air from the reactor, the temperature was raised to 50 ℃.
58g of maleic acid and 1254g of glutaric acid were charged to the reactor. Then the temperature is raised to 200 ℃ within 45min, the dibasic acid and the dihydric alcohol are subjected to esterification reaction in the temperature raising process, water generated by the reaction is separated from a reaction system through a rectifying tower at the top of the kettle, the temperature of the top of the rectifying tower is controlled to be 100 +/-1 ℃, and the constant temperature reaction is continued for 5 hours at 200 ℃.
After the esterification reaction was completed, 697.35mg of GeO as a catalyst was charged into the reactor2The reaction was carried out at 200 ℃ for 60 min.
Vacuumizing, keeping the pressure of the reactor lower than 2kPa, gradually heating to 240 ℃ at the speed of 2 ℃/min, and reacting for 6h at constant temperature. Slowly introducing N into the reactor2And simultaneously closing the vacuum system, opening a discharge valve after the reactor is heated to normal pressure, and discharging the materials to obtain the required polyester polyol. Sampling and analyzing acid ester, hydroxyl value, iodine value and molecular weight. The acid ester is 1.2mgKOH/g,Hydroxyl value of 58mgKOH/g, iodine value of 5.46, molecular weight of 7500g/mol, and temperature sensitivity index of 5.0.
Example 5
1.357kg of 1, 6-hexanediol and 0.2784g of p-hydroxyanisole were charged into a reactor, and N was slowly introduced under stirring2To remove air from the reactor, the temperature was raised to 50 ℃.
464g of maleic acid and 876g of adipic acid were charged into the reactor. Then the temperature is raised to 150 ℃ within 45min, the dibasic acid and the dihydric alcohol are subjected to esterification reaction in the temperature raising process, water generated by the reaction is separated from a reaction system through a rectifying tower at the top of the kettle, the temperature of the top of the rectifying tower is controlled to be 100 +/-1 ℃, and the constant temperature reaction is continued for 4 hours at 150 ℃.
After the esterification reaction was completed, 80.91mg of antimony acetate as a catalyst was charged into the reactor and reacted at 150 ℃ for 80 min.
Introduction of N2Gradually heating to 220 ℃ at the speed of 2 ℃/min, and reacting for 0.5h at constant temperature. Slowly introducing N into the reactor2And simultaneously closing the vacuum system, opening a discharge valve after the reactor is heated to normal pressure, and discharging the materials to obtain the required polyester polyol. Sampling and analyzing acid ester, hydroxyl value, iodine value and molecular weight. The acid ester is 0.5mg KOH/g, the hydroxyl value is 65mg KOH/g, the iodine value is 37.64, the molecular weight is 10000g/mol, and the temperature sensitivity index is 7.0.
Example 6
0.893kg of 1, 2-propanediol and 0.87g of 2-tert-butylhydroquinone are introduced into a reactor, and N is slowly introduced with stirring2To remove air from the reactor, the temperature was raised to 50 ℃.
580g of maleic acid and 800g of pimelic acid were charged to the reactor. Then the temperature is raised to 155 ℃ within 45min, the dibasic acid and the dihydric alcohol are subjected to esterification reaction in the temperature raising process, water generated by the reaction is separated from a reaction system through a rectifying tower at the top of the kettle, the temperature of the top of the rectifying tower is controlled to be 100 +/-1 ℃, and the thermostatic reaction is continued for 6 hours at 155 ℃.
After the esterification reaction was completed, 454.6mg of n-butyl titanate as a catalyst was charged into the reactor, and the reaction was carried out at 155 ℃ for 75 min.
Vacuumizing, keeping the pressure of the reactor lower than 2kPa, gradually heating to 235 ℃ at the speed of 2 ℃/min, and reacting for 3.5h at constant temperature. Slowly introducing N into the reactor2And simultaneously closing the vacuum system, opening a discharge valve after the reactor is heated to normal pressure, and discharging the materials to obtain the required polyester polyol. Sampling and analyzing acid ester, hydroxyl value, iodine value and molecular weight. The acid ester has a hydroxyl value of 57mgKOH/g, an iodine value of 55.83, a molecular weight of 4500g/mol and a temperature sensitivity index of 6.3 and is 0.8 mgKOH/g.
Example 7
1.248kg of 1, 5-pentanediol and 6.264g of p-hydroxyanisole are added into a reactor, and N is slowly introduced into the reactor under stirring2To remove air from the reactor, the temperature was raised to 50 ℃.
696g of fumaric acid and 528g of glutaric acid were charged into the reactor. Then the temperature is raised to 160 ℃ within 45min, the dibasic acid and the dihydric alcohol are subjected to esterification reaction in the temperature raising process, water generated by the reaction is separated from a reaction system through a rectifying tower at the top of the kettle, the temperature of the top of the rectifying tower is controlled to be 100 +/-1 ℃, and the constant temperature reaction is continued at 160 ℃ for 8 hours.
After the esterification reaction was completed, 123.6mg of Sb as a catalyst was charged into the reactor2O3The reaction was carried out at 160 ℃ for 65 min.
Vacuumizing, keeping the pressure of the reactor lower than 2kPa, gradually heating to 250 ℃ at the speed of 2 ℃/min, and reacting for 7h at constant temperature. Slowly introducing N into the reactor2And simultaneously closing the vacuum system, opening a discharge valve after the reactor is heated to normal pressure, and discharging the materials to obtain the required polyester polyol. Sampling and analyzing acid ester, hydroxyl value, iodine value and molecular weight. The acid ester has a hydroxyl value of 70mgKOH/g, an iodine value of 61.60, a molecular weight of 2600g/mol and a temperature sensitivity index of 4.6 of 2.1 mgKOH/g.
Example 8
0.7595kg of ethylene glycol and 3.828g of p-benzoquinone were put into a reactor, and N was slowly introduced into the reactor while stirring2To remove air from the reactor, the temperature was raised to 50 ℃.
348g of fumaric acid and 1022g of adipic acid were charged into the reactor. Then the temperature is raised to 165 ℃ within 45min, the dibasic acid and the dihydric alcohol are subjected to esterification reaction in the temperature raising process, water generated by the reaction is separated from a reaction system through a rectifying tower at the top of the kettle, the temperature of the top of the rectifying tower is controlled to be 100 +/-1 ℃, and the thermostatic reaction is continued for 9 hours at 165 ℃.
After the esterification reaction was completed, 212.95mg of TiO was charged into the reactor2/SiO2The reaction was carried out at 165 ℃ for 50 min.
Introduction of N2Gradually raising the temperature to 260 ℃ at the speed of 2 ℃/min, and reacting for 10 hours at constant temperature. Slowly introducing N into the reactor2And simultaneously closing the vacuum system, opening a discharge valve after the reactor is heated to normal pressure, and discharging the materials to obtain the required polyester polyol. Sampling and analyzing acid ester, hydroxyl value, iodine value and molecular weight. The acid ester has the advantages of 1.85mgKOH/g, the hydroxyl value of 35mgKOH/g, the iodine value of 35.76, the molecular weight of 8500g/mol and the temperature sensitivity index of 4.4.
Example 9
0.954kg of 1, 2-butanediol and 3.48g of methylhydroquinone are introduced into a reactor, while stirring, N is slowly passed through the reactor while stirring2To remove air from the reactor, the temperature was raised to 50 ℃.
290g of fumaric acid and 1200g of pimelic acid were charged into the reactor. Then the temperature is raised to 150 ℃ within 45min, the dibasic acid and the dihydric alcohol are subjected to esterification reaction in the temperature raising process, water generated by the reaction is separated from a reaction system through a rectifying tower at the top of the kettle, the temperature of the top of the rectifying tower is controlled to be 100 +/-1 ℃, and the constant temperature reaction is continued for 10 hours at 150 ℃.
After the esterification reaction was completed, 48.88mg of isopropyl titanate as a catalyst was charged into the reactor, and the reaction was carried out at 150 ℃ for 85 min.
Vacuumizing, keeping the pressure of the reactor lower than 2kPa, gradually heating to 250 ℃ at the speed of 2 ℃/min, and reacting for 8h at constant temperature. Slowly introducing N into the reactor2And simultaneously closing the vacuum system, opening a discharge valve after the reactor is heated to normal pressure, and discharging the materials to obtain the required polyester polyol. Sampling and analyzing acid ester, hydroxyl value, iodine value and molecular weight. The acid ester has a hydroxyl value of 42mgKOH/g, an iodine value of 25.96, a molecular weight of 2500g/mol and a temperature sensitivity index of 9.7 and is 1.56 mgKOH/g.
Example 10
1.3098kg of 1, 6-hexanediol and 2.584g of ZM-701 were charged into a reactor, and N was slowly introduced into the reactor while stirring2To remove air from the reactor, the temperature was raised to 50 ℃.
98g of maleic anhydride, 174g of fumaric acid and 990g of glutaric acid were charged into a reactor, and reacted while dissolving, followed by reaction at 60 ℃ for 2 hours. Then the temperature is raised to 155 ℃ within 45min, the dibasic acid and the dihydric alcohol start to react in the temperature raising process, the water generated by the reaction is separated from the reaction system through a rectifying tower at the top of the kettle, the temperature of the top of the rectifying tower is controlled to be 100 +/-1 ℃, and the constant temperature reaction is continued for 1.5h at 155 ℃.
After the esterification reaction was completed, 205.744mg of GeO as a catalyst was charged into the reactor2The reaction was carried out at 155 ℃ for 65 min.
Vacuumizing, keeping the pressure of the reactor lower than 2kPa, gradually heating to 245 ℃ at the speed of 2 ℃/min, and reacting for 6h at constant temperature. Slowly introducing N into the reactor2And simultaneously closing the vacuum system, opening a discharge valve after the reactor is heated to normal pressure, and discharging the materials to obtain the required polyester polyol. Sampling and analyzing acid ester, hydroxyl value, iodine value and molecular weight. The acid ester has the advantages of 1.35mgKOH/g, 52mgKOH/g hydroxyl value, 24.67 iodine value, 3600g/mol molecular weight and 6.6 temperature sensitivity index.
Example 11
Into a reactor, 1.74kg of triethylene glycol and 1.683g of 2, 5-di-tert-butylhydroquinone were charged, and N was slowly introduced while stirring2To remove air from the reactor, the temperature was raised to 50 ℃.
58.8g of maleic anhydride, 139.2g of fumaric acid and 1197.2 g of adipic acid were charged into a reactor, and reacted while being dissolved, at 70 ℃ for 1.5 hours. Then the temperature is raised to 160 ℃ within 45min, the dibasic acid and the dihydric alcohol start to react in the temperature raising process, the water generated by the reaction is separated from the reaction system through a rectifying tower at the top of the kettle, the temperature at the top of the rectifying tower is controlled to be 100 +/-1 ℃, and the constant temperature reaction is continued for 5.5 hours at 160 ℃.
After the esterification reaction was completed, 203.788mg of antimony acetate as a catalyst was charged into the reactor, and the reaction was carried out at 160 ℃ for 55 min.
Introduction of N2Gradually raising the temperature to 260 ℃ at the speed of 2 ℃/min, and reacting for 9 hours at constant temperature. Slowly introducing N into the reactor2And simultaneously closing the vacuum system, opening a discharge valve after the reactor is heated to normal pressure, and discharging the materials to obtain the required polyester polyol. Sampling and analyzing acid ester, hydroxyl value, iodine value and molecular weight. The acid ester has a hydroxyl value of 56mgKOH/g, an iodine value of 14.57, a molecular weight of 4200g/mol and a temperature sensitivity index of 8.5, and is 0.78 mgKOH/g.
Example 12
1.3kg of 1, 2-pentanediol and 3.4454g of ZM-701 were charged into a reactor, and N was slowly introduced into the reactor while stirring2To remove air from the reactor, the temperature was raised to 50 ℃.
137.2g of maleic anhydride, 162.4g of fumaric acid and 1152 g of pimelic acid were charged into the reactor, and reacted while being dissolved, and reacted at 80 ℃ for 2.5 hours. Then the temperature is raised to 180 ℃ within 45min, the dibasic acid and the dihydric alcohol start to react in the temperature raising process, the water generated by the reaction is separated from the reaction system through a rectifying tower at the top of the kettle, the temperature of the top of the rectifying tower is controlled to be 100 +/-1 ℃, and the constant temperature reaction is continued for 7.5 hours at 180 ℃.
After the esterification reaction was completed, 275.16mg of TiO was charged into the reactor2/SiO2The reaction was carried out at 180 ℃ for 40 min.
Introduction of N2Gradually raising the temperature to 250 ℃ at the speed of 2 ℃/min, and reacting for 8 hours at constant temperature. Slowly introducing N into the reactor2And simultaneously closing the vacuum system, opening a discharge valve after the reactor is heated to normal pressure, and discharging the materials to obtain the required polyester polyol. Sampling and analyzing acid ester, hydroxyl value, iodine value and molecular weight. The acid ester has a hydroxyl value of 59mgKOH/g, an iodine value of 25.83, a molecular weight of 3200g/mol and a temperature sensitivity index of 6.9 and is 1.1 mgKOH/g.
The embodiments described above are described to facilitate an understanding and use of the invention by those skilled in the art. It will be readily apparent to those skilled in the art that various modifications to these embodiments may be made, and the generic principles described herein may be applied to other embodiments without the use of the inventive faculty. Therefore, the present invention is not limited to the above embodiments, and those skilled in the art should make improvements and modifications within the scope of the present invention based on the disclosure of the present invention.
Claims (10)
1. A preparation method of unsaturated fatty diacid polyester polyol is characterized by comprising the following steps:
(1) taking unsaturated fatty diacid and polyol, proportioning and mixing the materials in proportion, putting the mixture into a reactor, and heating the reactor to perform esterification reaction;
(2) and after the esterification reaction is finished, adding a catalyst into the reactor, carrying out polycondensation reaction, and discharging when the acid value and the hydroxyl value of the materials in the reactor meet the index requirements to obtain the target product unsaturated fatty diacid polyester polyol.
2. The method for preparing unsaturated fatty diacid-based polyester polyol according to claim 1, wherein in the step (1), the molar ratio of the unsaturated fatty diacid to the polyol is 0.8-0.99: 1.
3. the method for preparing unsaturated fatty diacid-based polyester polyol as claimed in claim 1, wherein in the step (1), the unsaturated fatty diacid is one or a mixture of maleic acid, fumaric acid or maleic anhydride;
the polyalcohol is one or a mixture of more of ethylene glycol, diethylene glycol, triethylene glycol, 1, 2-propylene glycol, 1, 3-propylene glycol, 1, 2-butanediol, 1, 4-butanediol, 1, 2-pentanediol, 1, 5-pentanediol, 1, 2-hexanediol and 1, 6-hexanediol.
4. The method for preparing unsaturated fatty diacid based polyester polyol as claimed in claim 3, wherein in the step (1), when the unsaturated fatty diacid is maleic anhydride, the unsaturated fatty diacid is firstly heated to 50-90 ℃ for reaction for 0.5-3 h, and then the temperature is raised to 150-200 ℃ for reaction for 1-10 h;
when the unsaturated fatty diacid is maleic acid or fumaric acid, the unsaturated fatty diacid and the polyhydric alcohol are mixed and dissolved, and simultaneously, the temperature is raised to 150-200 ℃ for reaction for 1-10 hours.
5. The method for preparing unsaturated fatty diacid-based polyester polyol as claimed in claim 1, wherein, in the step (1), the reactor is added with saturated diacid before esterification, and the addition amount is not less than 45 percent of the total molar amount of all the diacid;
the saturated dibasic acid is one or more of glutaric acid, adipic acid or pimelic acid.
6. The method for preparing unsaturated fatty diacid-based polyester polyol as claimed in claim 1, wherein in the step (1), the top of the reactor is further provided with a rectifying tower for separating and removing water generated in the esterification reaction;
in the step (2), the polycondensation reaction is carried out under the anaerobic condition, and in the process of the polycondensation reaction, the reactor is vacuumized or inert gas is introduced into the reaction system.
7. The method for preparing unsaturated fatty diacid-based polyester polyol as claimed in claim 1, wherein in step (2), the catalyst is Sb2O3Antimony acetate, GeO2N-butyl titanate, isopropyl titanate, TiO2/SiO2One or more of the compounds are combined, and the dosage of the compound is 7ppm to 350ppm of the total mass of the polyatomic alcohol and the diacid raw material.
8. The method for preparing unsaturated fatty diacid-based polyester polyol as claimed in claim 1, wherein in the step (2), the temperature of the polycondensation reaction is 190-250 ℃ and the time is 1-15 h.
9. The method for preparing unsaturated fatty diacid-based polyester polyol as claimed in claim 1, wherein in the whole reaction process, a stabilizer is added into the reactor, and the addition amount of the stabilizer is 0.05-1.5 percent of the mass of unsaturated raw materials including unsaturated fatty diacid;
the stabilizer is one or a combination of more of hydroquinone, p-hydroxyanisole, 2, 5-di-tert-butylhydroquinone, 2-tert-butylhydroquinone, p-benzoquinone, methyl hydroquinone and 2,2,6, 6-tetramethyl-4-hydroxypiperidine nitroxide free radical.
10. An unsaturated fatty dibasic acid based polyester polyol produced by the production method according to any one of claims 1 to 9.
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