CN117534825A - Method for synthesizing bio-based polyol - Google Patents
Method for synthesizing bio-based polyol Download PDFInfo
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- CN117534825A CN117534825A CN202210920221.5A CN202210920221A CN117534825A CN 117534825 A CN117534825 A CN 117534825A CN 202210920221 A CN202210920221 A CN 202210920221A CN 117534825 A CN117534825 A CN 117534825A
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- 229920005862 polyol Polymers 0.000 title claims abstract description 74
- 150000003077 polyols Chemical class 0.000 title claims abstract description 74
- 238000000034 method Methods 0.000 title claims abstract description 21
- 230000002194 synthesizing effect Effects 0.000 title claims description 7
- 229920000570 polyether Polymers 0.000 claims abstract description 33
- 239000004721 Polyphenylene oxide Substances 0.000 claims abstract description 32
- 238000006243 chemical reaction Methods 0.000 claims abstract description 32
- 229920013724 bio-based polymer Polymers 0.000 claims abstract description 26
- 239000000463 material Substances 0.000 claims abstract description 23
- 239000011550 stock solution Substances 0.000 claims abstract description 13
- 229920001577 copolymer Polymers 0.000 claims abstract description 10
- 239000000243 solution Substances 0.000 claims abstract description 10
- 230000003472 neutralizing effect Effects 0.000 claims abstract description 5
- 239000012295 chemical reaction liquid Substances 0.000 claims abstract description 4
- HYBBIBNJHNGZAN-UHFFFAOYSA-N furfural Chemical compound O=CC1=CC=CO1 HYBBIBNJHNGZAN-UHFFFAOYSA-N 0.000 claims description 24
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 18
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 18
- XPFVYQJUAUNWIW-UHFFFAOYSA-N furfuryl alcohol Chemical compound OCC1=CC=CO1 XPFVYQJUAUNWIW-UHFFFAOYSA-N 0.000 claims description 18
- 239000003054 catalyst Substances 0.000 claims description 15
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 12
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 claims description 10
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 10
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 9
- GKTNLYAAZKKMTQ-UHFFFAOYSA-N n-[bis(dimethylamino)phosphinimyl]-n-methylmethanamine Chemical compound CN(C)P(=N)(N(C)C)N(C)C GKTNLYAAZKKMTQ-UHFFFAOYSA-N 0.000 claims description 8
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 claims description 7
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 6
- 150000001875 compounds Chemical class 0.000 claims description 5
- 238000006386 neutralization reaction Methods 0.000 claims description 5
- 239000004593 Epoxy Substances 0.000 claims description 4
- 230000035484 reaction time Effects 0.000 claims description 4
- 150000002240 furans Chemical class 0.000 claims description 3
- FBPFZTCFMRRESA-FSIIMWSLSA-N D-Glucitol Natural products OC[C@H](O)[C@H](O)[C@@H](O)[C@H](O)CO FBPFZTCFMRRESA-FSIIMWSLSA-N 0.000 claims description 2
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 claims description 2
- 239000003795 chemical substances by application Substances 0.000 claims description 2
- 230000000977 initiatory effect Effects 0.000 claims description 2
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 claims description 2
- 238000007142 ring opening reaction Methods 0.000 claims description 2
- 239000000600 sorbitol Substances 0.000 claims description 2
- 150000005846 sugar alcohols Polymers 0.000 claims description 2
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 claims 1
- 229920000642 polymer Polymers 0.000 abstract description 30
- 238000002360 preparation method Methods 0.000 abstract description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 18
- 239000007787 solid Substances 0.000 description 16
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 12
- 229920005830 Polyurethane Foam Polymers 0.000 description 10
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 10
- 239000002585 base Substances 0.000 description 10
- 229910052757 nitrogen Inorganic materials 0.000 description 10
- 239000011496 polyurethane foam Substances 0.000 description 10
- 238000003756 stirring Methods 0.000 description 10
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 9
- 239000006260 foam Substances 0.000 description 8
- 238000010438 heat treatment Methods 0.000 description 8
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 8
- 239000000047 product Substances 0.000 description 8
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 7
- 238000012360 testing method Methods 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 6
- 229910001873 dinitrogen Inorganic materials 0.000 description 6
- 239000002994 raw material Substances 0.000 description 6
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 5
- 229910052799 carbon Inorganic materials 0.000 description 5
- 238000005187 foaming Methods 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 239000003381 stabilizer Substances 0.000 description 5
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- 239000011259 mixed solution Substances 0.000 description 4
- -1 patent CN107722258A Chemical class 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 239000003153 chemical reaction reagent Substances 0.000 description 3
- 239000013065 commercial product Substances 0.000 description 3
- 239000002131 composite material Substances 0.000 description 3
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 description 3
- 239000012948 isocyanate Substances 0.000 description 3
- 150000002513 isocyanates Chemical class 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 238000006068 polycondensation reaction Methods 0.000 description 3
- 239000004604 Blowing Agent Substances 0.000 description 2
- 239000001569 carbon dioxide Substances 0.000 description 2
- 229910002092 carbon dioxide Inorganic materials 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 229920001228 polyisocyanate Polymers 0.000 description 2
- 239000005056 polyisocyanate Substances 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 229920002635 polyurethane Polymers 0.000 description 2
- 239000004814 polyurethane Substances 0.000 description 2
- 239000007962 solid dispersion Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000004094 surface-active agent Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- IMNIMPAHZVJRPE-UHFFFAOYSA-N triethylenediamine Chemical compound C1CN2CCN1CC2 IMNIMPAHZVJRPE-UHFFFAOYSA-N 0.000 description 2
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 description 2
- HXKKHQJGJAFBHI-UHFFFAOYSA-N 1-aminopropan-2-ol Chemical compound CC(O)CN HXKKHQJGJAFBHI-UHFFFAOYSA-N 0.000 description 1
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- UEEJHVSXFDXPFK-UHFFFAOYSA-N N-dimethylaminoethanol Chemical compound CN(C)CCO UEEJHVSXFDXPFK-UHFFFAOYSA-N 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- ISKQADXMHQSTHK-UHFFFAOYSA-N [4-(aminomethyl)phenyl]methanamine Chemical compound NCC1=CC=C(CN)C=C1 ISKQADXMHQSTHK-UHFFFAOYSA-N 0.000 description 1
- JJLKTTCRRLHVGL-UHFFFAOYSA-L [acetyloxy(dibutyl)stannyl] acetate Chemical compound CC([O-])=O.CC([O-])=O.CCCC[Sn+2]CCCC JJLKTTCRRLHVGL-UHFFFAOYSA-L 0.000 description 1
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000004359 castor oil Substances 0.000 description 1
- 235000019438 castor oil Nutrition 0.000 description 1
- 229920000891 common polymer Polymers 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- 229960002887 deanol Drugs 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 239000012975 dibutyltin dilaurate Substances 0.000 description 1
- 239000012972 dimethylethanolamine Substances 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 239000004872 foam stabilizing agent Substances 0.000 description 1
- 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 description 1
- 150000008282 halocarbons Chemical class 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229940102253 isopropanolamine Drugs 0.000 description 1
- 239000004611 light stabiliser Substances 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000013518 molded foam Substances 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 229940049964 oleate Drugs 0.000 description 1
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 1
- 150000002902 organometallic compounds Chemical class 0.000 description 1
- NWVVVBRKAWDGAB-UHFFFAOYSA-N p-methoxyphenol Chemical compound COC1=CC=C(O)C=C1 NWVVVBRKAWDGAB-UHFFFAOYSA-N 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 239000012258 stirred mixture Substances 0.000 description 1
- KSBAEPSJVUENNK-UHFFFAOYSA-L tin(ii) 2-ethylhexanoate Chemical compound [Sn+2].CCCCC(CC)C([O-])=O.CCCCC(CC)C([O-])=O KSBAEPSJVUENNK-UHFFFAOYSA-L 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
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
- C08G65/32—Polymers modified by chemical after-treatment
- C08G65/329—Polymers modified by chemical after-treatment with organic compounds
- C08G65/331—Polymers modified by chemical after-treatment with organic compounds containing oxygen
- C08G65/3311—Polymers modified by chemical after-treatment with organic compounds containing oxygen containing a hydroxy group
- C08G65/3318—Polymers modified by chemical after-treatment with organic compounds containing oxygen containing a hydroxy group heterocyclic
-
- 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
- C08G18/48—Polyethers
-
- 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
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
- C08G65/32—Polymers modified by chemical after-treatment
- C08G65/329—Polymers modified by chemical after-treatment with organic compounds
- C08G65/331—Polymers modified by chemical after-treatment with organic compounds containing oxygen
-
- 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
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
- C08G65/32—Polymers modified by chemical after-treatment
- C08G65/329—Polymers modified by chemical after-treatment with organic compounds
- C08G65/331—Polymers modified by chemical after-treatment with organic compounds containing oxygen
- C08G65/3311—Polymers modified by chemical after-treatment with organic compounds containing oxygen containing a hydroxy group
- C08G65/3314—Polymers modified by chemical after-treatment with organic compounds containing oxygen containing a hydroxy group cyclic
- C08G65/3315—Polymers modified by chemical after-treatment with organic compounds containing oxygen containing a hydroxy group cyclic aromatic
- C08G65/3317—Polymers modified by chemical after-treatment with organic compounds containing oxygen containing a hydroxy group cyclic aromatic phenolic
-
- 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
- C08G2101/00—Manufacture of cellular products
-
- 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
- C08G2110/00—Foam properties
- C08G2110/0008—Foam properties flexible
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Polyethers (AREA)
Abstract
The invention discloses a preparation method of bio-based polymer polyol, which comprises the following steps: (1) The bio-based material and the optional copolymer are catalytically reacted in the base polyether to generate a bio-based polymer polyol stock solution; (2) Solidifying the raw solution of the bio-based polymer polyol at high temperature to generate a reaction solution of the bio-based polymer polyol; (3) And (3) neutralizing and devolatilizing the bio-based polymer polyol reaction liquid to obtain the synthetic bio-based polyol. The method can obviously improve the bio-based content of the polymer polyol under the condition of not affecting the performance of the polymer polyol, and the bio-based polymer polyol synthesized by the method is a green and environment-friendly bio-based material.
Description
Technical Field
The invention belongs to the field of polymer polyols, and particularly relates to a method for synthesizing bio-based polyols.
Background
Compared with polyether polyol, the prepared polyurethane foam plastic has higher hardness, is mainly used for high resilience, high bearing capacity and molded foam, and is widely used in the fields of automobile seats, mattresses, furniture and the like.
In recent years, with the rising of carbon peak and carbon neutralization concepts, china also puts forward a 'two-carbon' strategic goal to strive for carbon dioxide emission to reach a peak before 2030 and to realize carbon neutralization before 2060. The bio-based material has the characteristics of environmental protection, renewable raw materials and biodegradability, and can greatly reduce carbon emission.
At present, bio-based polymer polyol is synthesized by bio-based polyether polyol, such as patent CN107722258A, using bio-based oil-based substances as an initiator, continuously polymerizing propylene oxide under the action of potassium hydroxide or a bimetallic catalyst, and then synthesizing polymer polyol by using the bio-based polyether polyol. The polymer polyol prepared by the method has a certain bio-based content, but the solid dispersion in the polymer polyol is still a copolymer of styrene and acrylonitrile. Since the solid particles are petrochemical-based materials, the higher the solids content, the lower the biobased content in the polymer polyol, relative.
Disclosure of Invention
In order to solve the above problems, the present invention provides a method for synthesizing bio-based polyols, which enables the solid dispersion in the synthesized polymer polyol to have a high bio-based content. In preparing high solids polymer polyols, the biobased content is greatly increased without altering their properties.
In order to solve the technical problems, the invention provides a method for synthesizing bio-based polyol, which comprises the following steps:
(1) The bio-based material and the optional copolymer are catalytically reacted in the base polyether to generate a bio-based polymer polyol stock solution;
(2) Solidifying the raw solution of the bio-based polymer polyol at high temperature to generate a reaction solution of the bio-based polymer polyol;
(3) And (3) neutralizing and devolatilizing the bio-based polymer polyol reaction liquid to obtain the synthetic bio-based polyol.
In the present invention, the bio-based material in the step (1) is furan derivative, including but not limited to furfural, furfuryl alcohol, etc., when the bio-based material is furfural, the copolymer is selected from one or more of phenol, formaldehyde or acetone, and when the bio-based material is furfuryl alcohol, the raw material does not contain the copolymer.
In the invention, the mass ratio of the bio-based material to the base polyether in the step (1) is 5:95-50:50, preferably 20:80-50:50.
In the present invention, when the bio-based material in the step (1) is furfural, the molar ratio of furfural to copolymer is 1.05:1-2:1, preferably 1.05:1-1.2:1.
In the present invention, the base polyether in the step (1) is not particularly limited, and a polymer polyether polyol obtained by initiating the ring-opening reaction of the epoxy compound with a small molecular polyol in the presence of a catalyst is preferable. The small molecular polyalcohol is one or more of glycerol, trimethylolpropane, pentaerythritol, hexaol and sorbitol, and the epoxy compound is ethylene oxide and propylene oxide. Preferably, the molecular weight of the base polyether is 3000 to 12000, preferably 3000 to 5000, and the functionality is 3 to 8, preferably 3 to 5.
In the invention, the catalyst in the step (1) is preferably a phosphazene catalyst from the standpoint of the difficulty of post-treatment, the phosphazene catalyst can provide a strong alkaline environment with pH of more than 11 required by biological base material polycondensation, and after the reaction is finished, the product does not contain sodium, potassium and other ions which affect foaming, and the dosage of the phosphazene catalyst is 0.5-2wt% of the mass of the base polyether.
In the invention, the reaction temperature in the step (1) is 40-150 ℃, preferably 120-150 ℃; the reaction time is 1 to 12 hours, preferably 3 to 5 hours. Through the reaction, the bio-based material is firstly reacted in the basic polyether at a lower temperature to generate a linear structure, and at the moment, the reaction liquid is usually a homogeneous liquid with lower viscosity and easy transportation because a bulk structure is not formed.
In the invention, the curing reaction temperature in the step (2) is 150-220 ℃, preferably 200-220 ℃; the curing reaction time is 1 to 12 hours, preferably 4 to 8 hours. In this step, the bio-based polymer in the bio-based polymer polyol stock solution is cured at a high temperature to form a solid, i.e., to produce a polymer polyol.
In the invention, the neutralizing agent in the step (3) is one or more selected from hydrochloric acid, acetic acid and citric acid, preferably acetic acid, and the pH value after neutralization is 5-8; the curing process is dehydration reaction, and the system contains a small amount of unreacted phenol or acetone, volatile acid and other small molecular compounds used for neutralization, and the product needs to be subjected to devolatilization treatment, wherein the devolatilization is carried out in a reaction kettle, the devolatilization temperature is 220-220 ℃, and the devolatilization pressure is 5-25 kPa.
In the present invention, polymer polyols are well suited for polyurethane foam synthesis. The present invention therefore also provides for the use of the polyether polyols prepared by the process described above in the synthesis of polyurethane foams, preferably of flexible polyurethane foams, in particular by foaming a composition of the polymer polyol and the polyisocyanate.
Methods for preparing flexible polyurethane foams are known in the art, and in particular flexible polyurethane foams are obtained by reacting polyurethane catalysts, polyols, cross-linking agents, blowing agents, foam stabilizers, auxiliaries with polyisocyanates, as described in CN 106519148A. The present invention is not particularly limited with respect to the selection of the components required for preparing the flexible polyurethane foam, and the corresponding components suitable for preparing the flexible polyurethane foam in the art may be employed. In some embodiments, the polyurethane catalyst is preferably an organometallic compound, such as stannous octoate, stannous oleate, dibutyltin dilaurate, dibutyltin acetate, and/or dibutyltin diacetate, and/or an organoamine catalyst; organic amine catalysts such as bis (2, 2' -dimethylamino) ethyl ether, trimethylamine, triethylamine, triethylenediamine and/or dimethylethanolamine. The blowing agent is preferably water, acetone, carbon dioxide, halogenated hydrocarbons, aliphatic alkanes and/or alicyclic alkanes. The foam stabilizer is preferably an organopolysiloxane surfactant. In addition, the flexible polyurethane foam may further contain a flame retardant, a filler, a light stabilizer, an antioxidant, and the like.
Compared with the prior art, the application has the following beneficial effects:
the polymer polyol containing the bio-based material is produced by performing polycondensation on the bio-based furan derivative material in polyether polyol. The two-step polycondensation method can also prevent the too fast polymerization reaction and the formation of unstable large particle precipitation by explosion polymerization. And as the basic polyether contains hydroxyl, the basic polyether can react with bio-based substances to a certain extent, plays a good role in dispersion and stabilization, effectively reduces large particles generated in the reaction, and improves the stability of the polymer polyol. When the reaction is carried out in the bio-based polyether, the bio-based material is used for replacing the original petrochemical-based material styrene/acrylonitrile, so that the bio-based content of the whole polymer polyol is improved on the premise of not influencing the performance, and the bio-based content is not reduced along with the improvement of the solid content of the polymer polyol. Solves the problem of low biobased content of high solid content polymer polyol, and is an environment-friendly biobased material.
Detailed Description
Some of the raw materials used in the examples or comparative examples are described below:
base polyether a: polyether prepared by reacting castor oil having a functionality of 3 with propylene oxide and ethylene oxide, having an ethylene oxide content of 15% and a number average molecular weight of 3000. Commercial product FB340 (vancomic).
Base polyether b: polyethers prepared by reacting glycerol having a functionality of 3 with propylene oxide and ethylene oxide, having an ethylene oxide content of 15% and a number average molecular weight of 3000. Commercial product F3156 (vancomic).
Base polyether c: polyether prepared by reacting glycerol having a functionality of 3 with propylene oxide and ethylene oxide, having an ethylene oxide content of 18%, an ethylene oxide capping rate of 70% and a number average molecular weight of 4800. Such as commercial product F3135 (vancomic).
Macromolecular stabilizer: f3135 and maleic anhydride with equal molar weight are subjected to esterification reaction to form polyether half-ester, and then are blocked by propylene oxide or ethylene oxide.
Furfural: the reagent is pure and 99 percent, and the Ala is.
Furfuryl alcohol: the reagent is pure and 98 percent, and the Alatine.
Phenol: the reagent is pure, and the Alatine.
Formaldehyde: 40% aqueous solution, wanhua chemistry.
Acetone: wanhua chemistry.
Styrene: 99% containing 10-15ppm TBC inhibitor and Alatine.
Acrylonitrile: 99%, contains MEHQ, aletin.
Isopropyl alcohol: 99%, allatin.
Performance testing
And (3) solid content testing: GB 12005.2-1989
Viscosity test: GB/T12008.8-1992
Hydroxyl value test: GB/T7383-2007
Bio-based content testing: GB/T39715.4-2021
Example 1
200g of basic polyether a and 61.7g of furfuryl alcohol are mixed, 1.5g of methanol solution (35%) of phosphazene is added into a reaction kettle, 3bar nitrogen is replaced for three times, stirring and heating are carried out to 120 ℃, reaction is carried out for 8h, and the bio-based polymer polyol stock solution is obtained after cooling, wherein the stock solution is brownish red semitransparent liquid without solid content.
And continuously heating the polymer polyol stock solution to 220 ℃, stirring and reacting for 8 hours, keeping 220 ℃, adding acetic acid to adjust the pH to 7, and devolatilizing the reaction system. And (3) after devolatilizing for 2 hours in 5kPa, carrying out nitrogen gas stripping for 2 hours to obtain the bio-based polymer polyol A. The solid content of the product is 18.7%, the viscosity is 4856cp@25 ℃, the hydroxyl value is 45.5mgKOH/g, and the biobased content is 45.8%.
Example 2
122g of basic polyether b, 87g of furfural and 29g of formaldehyde are mixed, 1.5g of methanol solution (35%) of phosphazene is added into a reaction kettle, 3bar nitrogen is replaced for three times, stirring and heating are carried out to 150 ℃, reaction is carried out for 4h, and the bio-based polymer polyol stock solution is obtained after cooling.
And continuously heating the polymer polyol stock solution to 200 ℃, stirring and reacting for 4 hours, maintaining the temperature at 200 ℃, adding hydrochloric acid to adjust the pH to 7, and devolatilizing the reaction system. And (3) after devolatilizing for 4 hours at 25kPa, carrying out nitrogen gas stripping for 2 hours to obtain the bio-based polymer polyol B. The solid content of the product is 44.6%, the viscosity is 8207 cp@25deg.C, the hydroxyl value is 31mgKOH/g, and the biobased content is 31.88%.
Example 3
122g of basic polyether b, 50g of furfural and 59g of phenol are mixed, 1.5g of methanol solution (35%) of phosphazene is added into a reaction kettle, 3bar nitrogen is replaced for three times, stirring and heating are carried out to 140 ℃, reaction is carried out for 5h, and the bio-based polymer polyol stock solution is obtained after cooling.
And continuously heating the polymer polyol stock solution to 210 ℃, stirring and reacting for 6 hours, keeping 210 ℃, adding citric acid to adjust the pH to 7, and devolatilizing the reaction system. And (3) after devolatilizing for 3 hours at 15kPa, carrying out nitrogen gas stripping for 2 hours to obtain the bio-based polymer polyol C. The solid content of the product is 45.2%, the viscosity is 9764cp@25 ℃, the hydroxyl value is 30.6mgKOH/g, and the biobased content is 18.4%.
Example 4
150g of basic polyether c, 67g of furfural and 45g of acetone are mixed, 1.5g of methanol solution (35%) of phosphazene is added into a reaction kettle, 3bar nitrogen is replaced for three times, stirring and heating are carried out to 130 ℃, reaction is carried out for 6h, and the bio-based polymer polyol stock solution is obtained after cooling.
And continuously heating the polymer polyol stock solution to 200 ℃, stirring and reacting for 6 hours, maintaining the temperature at 200 ℃, adding acetic acid to adjust the pH to 7, and devolatilizing the reaction system. And (3) after devolatilizing for 2 hours in 5kPa, carrying out nitrogen gas stripping for 2 hours to obtain the bio-based high-resilience polymer polyol D. The solid content of the product is 40.3 percent, the viscosity is 7765cp@25 ℃, the hydroxyl value is 20.8mgKOH/g, and the biobased content is 22 percent.
Comparative example 1
550g of base polyether b and 30g of isopropanol and 10g of macromolecular stabilizer are mixed and then added into a reaction kettle, 3bar of nitrogen is replaced for three times, and the mixture is stirred and heated to 120 ℃.
A mixed solution composed of 315g of styrene, 135g of acrylonitrile and 5g of azobisisobutyronitrile was placed in a bottle, and the mixed solution was fed into a reaction vessel at a rate of 3 g/min. After the addition is completed, the temperature is raised to 135 ℃, and the reaction system is devolatilized after stirring reaction is carried out for 1 h. And (3) after devolatilizing for 2 hours in 5kPa, carrying out nitrogen gas stripping for 2 hours to obtain the common polymer polyol E. The product measured solids content was 45% with a viscosity of 4315cp@25℃and a hydroxyl value of 30.8mgKOH/g.
Comparative example 2
600g of basic polyether c and 26g of isopropanol and 8g of macromolecular stabilizer are mixed and then added into a reaction kettle, 3bar of nitrogen is replaced for three times, and the mixture is stirred and heated to 120 ℃.
A mixed solution of 300g of styrene, 100g of acrylonitrile and 4.2g of azobisisobutyronitrile was placed in a bottle, and the mixed solution was fed into a reaction vessel at a rate of 3 g/min. After the addition is completed, the temperature is raised to 135 ℃, and the reaction system is devolatilized after stirring reaction is carried out for 1 h. And (3) after devolatilizing for 2 hours in 5kPa, carrying out nitrogen gas stripping for 2 hours to obtain the high-resilience polymer polyol F. The solid content of the product is 40% by measurement, the viscosity is 49567 cp@25 ℃, and the hydroxyl value is 21mgKOH/g.
The polymer polyols prepared in examples 1, 2, 3, 4 and comparative examples 1, 2 were subjected to foaming tests.
Wherein examples 1, 2, 3 and comparative example 1 were foamed as follows:
preparing a composite material according to the raw materials and weight percentages shown in Table 1 (the mass percentages in the table are based on 100% of the total mass of the composite material), mixing the composite material and isocyanate raw materials8001 was kept at constant temperature for 3 hours in an environment of 22 ℃. Then 100g of the combination is taken and mixed with 60g +.>8001 was stirred and mixed in a stirrer (revolution number 3000 rpm) for 6 seconds. The stirred mixture was then rapidly poured into an aluminum open mold (dimensions: 300mm long, 300mm wide, 50mm thick) preheated to 60℃to foam the mixture. After 7 minutes, the foam was removed to obtain a polyurethane foam.
TABLE 1
| Raw materials | Proportioning of |
| Polymer polyols | 33.59 |
| WANOL F3156 | 59.56 |
| Diethanolamine (DEA) | 0.50 |
| Water and its preparation method | 4.16 |
| N, N-bis (dimethylaminopropyl) isopropanolamine (CAS No.: 67151-63-7) | 0.40 |
| N, N, N '-trimethyl-N-' -hydroxyethyl-diaminoethyl ether | 0.50 |
| Organobismuth catalyst BiCAT 8106 | 0.10 |
| Foam stabilizer B-8715LF2 | 1.19 |
Wherein example 4 and comparative example 2 were foamed as follows:
the polymer polyol, surfactant, water, catalyst and diethanolamine were mixed in a vessel according to the composition of table 2 and stirred at high speed for 55 seconds. A specified amount of isocyanate (calculated as 100 isocyanate index) was added, mixed for 5 seconds and the reaction mixture was quickly poured into a 65 ℃ water jacketed mold. After 4.5 minutes, the foam was removed from the mold, compressed to break the cells, and aged at room temperature for 24 hours to test the physical properties of the foam.
TABLE 2
The foaming activity and foam properties were measured as shown in Table 3.
TABLE 3 Soft foam Polymer polyol foaming basic index
It can be seen that the same solids content of bio-based polymer polyol B, C is greatly improved in bio-based content compared with polymer polyol E, and has almost no difference in properties such as density, apparent hardness, tear and tensile strength, and only an increase in viscosity.
It can be seen that the high rebound bio-based polymer polyol D with the same solid content is improved by about 22% in bio-based content compared with the high rebound polymer polyol F, and almost has no difference in properties such as density, elongation, tear and tensile strength, and only has an increase in viscosity.
It will be readily appreciated that the above embodiments are merely examples given for clarity of illustration and are not meant to limit the invention thereto. Other variations or modifications of the above teachings will be apparent to those of ordinary skill in the art. It is not necessary here nor is it exhaustive of all embodiments. While still being apparent from variations or modifications that may be made by those skilled in the art are within the scope of the invention.
Claims (9)
1. A method of synthesizing a bio-based polyol comprising the steps of:
(1) The bio-based material and the optional copolymer are catalytically reacted in the base polyether to generate a bio-based polymer polyol stock solution;
(2) Solidifying the raw solution of the bio-based polymer polyol at high temperature to generate a reaction solution of the bio-based polymer polyol;
(3) And (3) neutralizing and devolatilizing the bio-based polymer polyol reaction liquid to obtain the synthetic bio-based polyol.
2. The method of claim 1, wherein the bio-based material in step (1) is a furan derivative, including but not limited to furfural, furfuryl alcohol, and the like, and when the bio-based material is furfural, the copolymer is selected from one or more of phenol, formaldehyde, or acetone, and when the bio-based material is furfuryl alcohol, the feedstock does not comprise the copolymer.
3. The method according to claim 1 or 2, wherein the mass ratio of bio-based material to base polyether in step (1) is 5:95 to 50:50, preferably 20:80 to 50:50.
4. A method according to any one of claims 1 to 3, wherein when the biobased material in step (1) is furfural, the molar ratio of furfural to copolymer is from 1.05:1 to 2:1, preferably from 1.05:1 to 1.2:1.
5. The method according to any one of claims 1 to 4, wherein the base polyether in the step (1) is a high molecular polyether polyol obtained by initiating a ring-opening reaction of an epoxy compound with a small molecular polyol in the presence of a catalyst; the small molecular polyalcohol is one or more of glycerol, trimethylolpropane, pentaerythritol, hexaol and sorbitol, and the epoxy compound is ethylene oxide and propylene oxide.
6. The process of any one of claims 1-5, wherein the catalyst in step (1) is a phosphazene catalyst.
7. The process according to any one of claims 1 to 6, wherein the reaction temperature in step (1) is 40 ℃ to 150 ℃, preferably 120 ℃ to 150 ℃; the reaction time is 1 to 12 hours, preferably 3 to 5 hours.
8. The method of any one of claims 1 to 7, wherein the curing reaction temperature of step (2) is 150 ℃ to 220 ℃, preferably 200 ℃ to 220 ℃; the curing reaction time is 1 to 12 hours, preferably 4 to 8 hours.
9. The method according to any one of claims 1 to 8, wherein the neutralizing agent in the step (3) is one or more selected from hydrochloric acid, acetic acid and citric acid, preferably acetic acid, and the pH after neutralization is 5 to 8.
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