CN113004242A - Sorbitol-based aqueous cyclic carbonate, and preparation method and application thereof - Google Patents
Sorbitol-based aqueous cyclic carbonate, and preparation method and application thereof Download PDFInfo
- Publication number
- CN113004242A CN113004242A CN202110225126.9A CN202110225126A CN113004242A CN 113004242 A CN113004242 A CN 113004242A CN 202110225126 A CN202110225126 A CN 202110225126A CN 113004242 A CN113004242 A CN 113004242A
- Authority
- CN
- China
- Prior art keywords
- sorbitol
- cyclic carbonate
- reaction
- aqueous
- epoxy resin
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 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 title claims abstract description 109
- 239000000600 sorbitol Substances 0.000 title claims abstract description 109
- 150000005676 cyclic carbonates Chemical class 0.000 title claims abstract description 78
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- 238000006243 chemical reaction Methods 0.000 claims abstract description 50
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 36
- 239000003822 epoxy resin Substances 0.000 claims abstract description 23
- 229920000647 polyepoxide Polymers 0.000 claims abstract description 23
- KZMGYPLQYOPHEL-UHFFFAOYSA-N Boron trifluoride etherate Chemical compound FB(F)F.CCOCC KZMGYPLQYOPHEL-UHFFFAOYSA-N 0.000 claims abstract description 20
- 239000006185 dispersion Substances 0.000 claims abstract description 20
- 239000003054 catalyst Substances 0.000 claims abstract description 18
- -1 sorbitol cyclic carbonate Chemical class 0.000 claims abstract description 16
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims abstract description 14
- 229910002092 carbon dioxide Inorganic materials 0.000 claims abstract description 14
- JRMUNVKIHCOMHV-UHFFFAOYSA-M tetrabutylammonium bromide Chemical compound [Br-].CCCC[N+](CCCC)(CCCC)CCCC JRMUNVKIHCOMHV-UHFFFAOYSA-M 0.000 claims abstract description 13
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 claims abstract description 10
- 150000003512 tertiary amines Chemical class 0.000 claims abstract description 9
- 239000001569 carbon dioxide Substances 0.000 claims abstract description 5
- FBPFZTCFMRRESA-JGWLITMVSA-N D-glucitol Chemical compound OC[C@H](O)[C@@H](O)[C@H](O)[C@H](O)CO FBPFZTCFMRRESA-JGWLITMVSA-N 0.000 claims abstract description 3
- 150000008064 anhydrides Chemical class 0.000 claims abstract description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 36
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 30
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 21
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 12
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical group CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 12
- 238000003756 stirring Methods 0.000 claims description 11
- LRWZZZWJMFNZIK-UHFFFAOYSA-N 2-chloro-3-methyloxirane Chemical compound CC1OC1Cl LRWZZZWJMFNZIK-UHFFFAOYSA-N 0.000 claims description 10
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 10
- 239000002253 acid Substances 0.000 claims description 10
- 239000000126 substance Substances 0.000 claims description 10
- 239000002904 solvent Substances 0.000 claims description 9
- 238000010438 heat treatment Methods 0.000 claims description 8
- 239000000376 reactant Substances 0.000 claims description 8
- 238000001816 cooling Methods 0.000 claims description 7
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 6
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 6
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical group CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 6
- 150000008065 acid anhydrides Chemical class 0.000 claims description 6
- 238000000034 method Methods 0.000 claims description 6
- FFRBMBIXVSCUFS-UHFFFAOYSA-N 2,4-dinitro-1-naphthol Chemical compound C1=CC=C2C(O)=C([N+]([O-])=O)C=C([N+]([O-])=O)C2=C1 FFRBMBIXVSCUFS-UHFFFAOYSA-N 0.000 claims description 5
- 239000004593 Epoxy Substances 0.000 claims description 5
- 238000004821 distillation Methods 0.000 claims description 5
- 239000007789 gas Substances 0.000 claims description 5
- 239000007788 liquid Substances 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 5
- 238000006386 neutralization reaction Methods 0.000 claims description 5
- 229910052757 nitrogen Inorganic materials 0.000 claims description 5
- 238000002390 rotary evaporation Methods 0.000 claims description 5
- 238000004448 titration Methods 0.000 claims description 5
- JGFZNNIVVJXRND-UHFFFAOYSA-N N,N-Diisopropylethylamine (DIPEA) Chemical compound CCN(C(C)C)C(C)C JGFZNNIVVJXRND-UHFFFAOYSA-N 0.000 claims description 4
- UEEJHVSXFDXPFK-UHFFFAOYSA-N N-dimethylaminoethanol Chemical compound CN(C)CCO UEEJHVSXFDXPFK-UHFFFAOYSA-N 0.000 claims description 4
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 claims description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 4
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 claims description 4
- 229960002887 deanol Drugs 0.000 claims description 4
- 239000012972 dimethylethanolamine Substances 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 4
- 239000003960 organic solvent Substances 0.000 claims description 4
- FALRKNHUBBKYCC-UHFFFAOYSA-N 2-(chloromethyl)pyridine-3-carbonitrile Chemical group ClCC1=NC=CC=C1C#N FALRKNHUBBKYCC-UHFFFAOYSA-N 0.000 claims description 3
- GAWIXWVDTYZWAW-UHFFFAOYSA-N C[CH]O Chemical group C[CH]O GAWIXWVDTYZWAW-UHFFFAOYSA-N 0.000 claims description 3
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims description 3
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 claims description 3
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 3
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 claims description 3
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 3
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims description 3
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 3
- 229940014800 succinic anhydride Drugs 0.000 claims description 3
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 2
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical compound C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 claims description 2
- 238000011049 filling Methods 0.000 claims description 2
- 238000001914 filtration Methods 0.000 claims description 2
- 239000000463 material Substances 0.000 claims description 2
- CRVGTESFCCXCTH-UHFFFAOYSA-N methyl diethanolamine Chemical compound OCCN(C)CCO CRVGTESFCCXCTH-UHFFFAOYSA-N 0.000 claims description 2
- 230000003472 neutralizing effect Effects 0.000 claims description 2
- 239000007787 solid Substances 0.000 claims description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 2
- 239000004971 Cross linker Substances 0.000 claims 1
- 150000001875 compounds Chemical class 0.000 abstract description 7
- 238000004132 cross linking Methods 0.000 abstract description 6
- 239000002028 Biomass Substances 0.000 abstract description 2
- 239000002994 raw material Substances 0.000 abstract description 2
- 239000012948 isocyanate Substances 0.000 description 13
- 150000002513 isocyanates Chemical class 0.000 description 13
- 239000004814 polyurethane Substances 0.000 description 13
- 229920002635 polyurethane Polymers 0.000 description 13
- 239000000047 product Substances 0.000 description 13
- 239000002245 particle Substances 0.000 description 7
- 229920000768 polyamine Polymers 0.000 description 6
- 239000003431 cross linking reagent Substances 0.000 description 4
- 238000000354 decomposition reaction Methods 0.000 description 4
- 239000000853 adhesive Substances 0.000 description 3
- 230000001070 adhesive effect Effects 0.000 description 3
- 230000007613 environmental effect Effects 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- 239000012528 membrane Substances 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 150000003141 primary amines Chemical class 0.000 description 3
- 230000035484 reaction time Effects 0.000 description 3
- 238000010992 reflux Methods 0.000 description 3
- 238000000967 suction filtration Methods 0.000 description 3
- RNLHGQLZWXBQNY-UHFFFAOYSA-N 3-(aminomethyl)-3,5,5-trimethylcyclohexan-1-amine Chemical compound CC1(C)CC(N)CC(C)(CN)C1 RNLHGQLZWXBQNY-UHFFFAOYSA-N 0.000 description 2
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 description 2
- 239000004721 Polyphenylene oxide Substances 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 229920000570 polyether Polymers 0.000 description 2
- 230000002195 synergetic effect Effects 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- YGYAWVDWMABLBF-UHFFFAOYSA-N Phosgene Chemical compound ClC(Cl)=O YGYAWVDWMABLBF-UHFFFAOYSA-N 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 231100000206 health hazard Toxicity 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 238000007142 ring opening reaction Methods 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D317/00—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms
- C07D317/08—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3
- C07D317/10—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3 not condensed with other rings
- C07D317/32—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3 not condensed with other rings with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D317/34—Oxygen atoms
- C07D317/36—Alkylene carbonates; Substituted alkylene carbonates
-
- 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
- C08G71/00—Macromolecular compounds obtained by reactions forming a ureide or urethane link, otherwise, than from isocyanate radicals in the main chain of the macromolecule
- C08G71/04—Polyurethanes
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Epoxy Resins (AREA)
Abstract
Sorbitol-based aqueous cyclic carbonate and a preparation method and application thereof, sorbitol and epichlorohydrin are reacted in the presence of boron trifluoride diethyl etherate serving as a catalyst to obtain sorbitol epoxy resin; in the presence of a catalyst tetrabutylammonium bromide, reacting sorbitol epoxy resin with carbon dioxide to obtain sorbitol-based cyclic carbonate; reacting sorbitol cyclic carbonate with anhydride to obtain carboxylated sorbitol cyclic carbonate; and (3) reacting the carboxylated sorbitol cyclic carbonate with tertiary amine, and then adding water to disperse to obtain the slightly transparent sorbitol-based aqueous cyclic carbonate dispersoid. According to the invention, the biomass resource sorbitol is used as a raw material, and the cyclic carbonate structure and the hydrophilic group structure are introduced in sequence on the basis to obtain the sorbitol aqueous cyclic carbonate derivative, so that the sorbitol aqueous cyclic carbonate derivative can participate in the cross-linking reaction of amine compounds, the hydrophilicity of the compounds is improved, and the sorbitol aqueous cyclic carbonate derivative can be effectively dispersed in water to form a stable and uniform dispersion.
Description
Technical Field
The invention belongs to the technical field of cross-linking agents, and particularly relates to sorbitol-based water-based cyclic carbonate and a preparation method and application thereof.
Background
At present, the environmental protection problem has attracted wide attention of all countries in the world, and all countries not only put forward the expectation that the final product is nontoxic and pollution-free, but also gradually require the expectation of no toxicity and pollution in the production process. The traditional polyurethane has excellent performance and is widely applied to the fields of coatings, adhesives and the like. Although polyurethanes have good properties. However, the preparation of polyurethane requires the use of isocyanate-NCO, and the preparation of isocyanate requires the use of phosgene, which is a significant environmental and human health hazard. In addition, isocyanate is sensitive to water and is easy to react with water, so that the processes of polyurethane preparation, isocyanate storage, isocyanate transportation and the like are influenced.
In contrast, cyclocarbonate-based non-isocyanate polyurethane has great advantages, and the preparation of the non-isocyanate polyurethane is obtained by ring opening of cyclocarbonate and amine, wherein five-membered cyclic carbonate is the most main monomer for preparing the non-isocyanate polyurethane, and the cyclocarbonates are an organic material with (-O- (C ═ O) -O-) as a characteristic functional group and have the advantages of degradability, high boiling point, environmental protection and the like.
However, most of the processes for preparing non-isocyanate polyurethane by using common cyclic carbonate use DMF as solvent, the current research is mainly focused on solvent-type cyclic carbonate non-isocyanate polyurethane, and the research and production of water-based cyclic carbonate non-isocyanate polyurethane rarely see related reports. The common cyclic carbonate structural compound has the defects of high viscosity, difficult dispersion, limited reaction, difficult construction and the like in a water system.
Disclosure of Invention
The technical problem to be solved is as follows: aiming at the defects, the invention provides a sorbitol-based water-based cyclic carbonate and a preparation method and application thereof.
The technical scheme is as follows: a sorbitol-based aqueous cyclic carbonate having the molecular formula:
wherein R is methyl, ethyl, butyl, isopropyl, hydroxyethyl, cyclohexyl or benzyl.
The preparation method of the sorbitol-based aqueous cyclic carbonate comprises the following steps: (1) in the presence of boron trifluoride diethyl etherate serving as a catalyst, sorbitol and epoxy chloropropane react to obtain sorbitol epoxy resin, wherein the molar ratio of the epoxy chloropropane to the sorbitol is (4.0-7.5): 1.0; (2) reacting the sorbitol epoxy resin obtained in the step (1) with carbon dioxide in the presence of a catalyst tetrabutylammonium bromide (TBAB) to obtain sorbitol-based cyclic carbonate, wherein the pressure of the reacted carbon dioxide is 10-20 atmospheric pressures; (3) reacting the sorbitol-based cyclic carbonate obtained in the step (2) with acid anhydride to obtain carboxylated sorbitol cyclic carbonate, wherein the molar ratio of the acid anhydride to the sorbitol-based cyclic carbonate is (2.5-4.0): 1.0; (4) and (3) reacting the carboxylated sorbitol cyclic carbonate obtained in the step (3) with tertiary amine, and then adding water to disperse to obtain a slightly transparent sorbitol-based aqueous cyclic carbonate dispersion, wherein the neutralization degree of the reaction of the carboxylated sorbitol cyclic carbonate and the tertiary amine is 60-100%.
The reaction equation is:
wherein R is methyl, ethyl, butyl, isopropyl, hydroxyethyl, cyclohexyl and benzyl.
The step (1) is specifically as follows: dissolving sorbitol in an organic solvent, adding epoxy chloropropane and boron trifluoride diethyl etherate serving as a catalyst to react for 2-4h at the temperature of 60-80 ℃ to obtain sorbitol epoxy resin; the organic solvent is ethyl acetate, diethyl ether, acetone, acetonitrile, dioxane, dichloromethane or tetrahydrofuran; the catalyst boron trifluoride diethyl etherate accounts for 1-6 per mill of the total mass of reactants.
Purifying the sorbitol epoxy resin obtained in the step (1) according to the following steps: cooling the reaction material obtained in the step (1) to 40-50 ℃, removing the solvent, adding sodium hydroxide with the mass of epoxy chloropropane and the like, wherein the concentration of the sodium hydroxide is 40 wt.%, and reacting for 4 hours at 35 ℃; filtering the solution obtained in the step one to remove insoluble substances, then carrying out reduced pressure distillation to remove water and unreacted epichlorohydrin substances, wherein the remainder is the target product sorbitol glycidyl ether, and the theoretical epoxy value of the product is 0.68mol/100g-0.99mol/100 g.
The step (2) is specifically as follows: adding the sorbitol epoxy resin obtained in the step (1) into a pressure reaction kettle, and filling CO2 to the pressure of 1.0-2.0 MPa; continuously stirring at the reaction temperature of 90-130 ℃ for 1-11 hours, finishing the reaction, cooling to 60 ℃, then exhausting CO2 gas in the reaction kettle, and taking out the product to obtain a golden yellow viscous liquid sorbitol-based cyclic carbonate sample; the catalyst tetrabutylammonium bromide was added in an amount of 0.5 wt.% of the sorbitol epoxy resin.
The step (3) is specifically as follows: putting the sorbitol base cyclic carbonate and the anhydride obtained in the step (2) into a 1L three-neck flask and protecting with dry nitrogen; heating the mixture to 90-130 ℃ for reaction, and stopping the reaction when the acid value of the product is reduced to a theoretical value through potassium hydroxide titration; the acid anhydride is succinic anhydride, maleic anhydride or phthalic anhydride, and the theoretical acid value is 25-40mg KOH/g.
The step (4) is specifically as follows: reducing the temperature of the carboxylated sorbitol cyclic carbonate obtained in the step (3) to 40 ℃, and adding acetone in the midway to reduce the viscosity to be not higher than 6000mPa & s; neutralizing the modified carboxylated cyclic carbonate by adding tertiary amine at 40 ℃, wherein the neutralization degree is 60-100%, then gradually dripping water for dispersion, and finally removing acetone by rotary evaporation to obtain 30-40 wt.% solid cyclic carbonate aqueous dispersion; the tertiary amine is triethylamine, dimethylethanolamine, triethanolamine, N-methyldiethanolamine or N, N-diisopropylethylamine.
The application of the sorbitol-based water-based cyclic carbonate in a water-based system crosslinking agent.
Has the advantages that: according to the preparation method, sorbitol serving as a biomass resource is used as a raw material, a cyclic carbonate structure and a hydrophilic group structure are introduced in sequence on the basis to obtain the sorbitol waterborne cyclic carbonate derivative, so that the sorbitol waterborne cyclic carbonate derivative can participate in a crosslinking reaction of amine compounds, the hydrophilicity of the compounds is improved, the compounds can be effectively dispersed in water to form a stable and uniform dispersion, a good dispersion and solidification synergistic effect is achieved, and the additional value of sorbitol is improved at the same time; the sorbitol aqueous cyclic carbonate has excellent water dispersibility, and different dispersed particle sizes can be realized by controlling different acid values, for example, the acid value is controlled to be 25mgKOH/g, so that stable dispersion with the particle size of 115nm is obtained, and the acid value is controlled to be 40KOH/g, so that stable dispersion with the particle size of 75nm is obtained; the traditional MDI (diphenylmethane diisocyanate) crosslinking agent can exist in micron scale only when being dispersed in water, and is unstable, and compared with sorbitol waterborne cyclic carbonate, the dispersibility and stability of the sorbitol waterborne cyclic carbonate in a waterborne system are greatly improved. When the isocyanate curing agent is added in an equivalent amount (0.5 wt%), when the isocyanate curing agent is applied to a water-based polyamine system, compared with a traditional isocyanate crosslinking agent, the crosslinking density is improved from 48% to 85%, the pencil hardness of a cured film is improved from HB to 2H, and meanwhile, the initial decomposition temperature of the cured film is improved from 243 ℃ to 273 ℃, so that the synergistic effect of dispersion and curing is realized.
Drawings
FIG. 1 is the nuclear magnetic hydrogen spectrum of sorbitol aqueous cyclic carbonate prepared by the present invention.
FIG. 2 is a graph showing the particle size distribution of an aqueous sorbitol aqueous cyclic carbonate dispersion prepared according to the present invention.
Detailed Description
The technical solution of the present invention is further illustrated by the following examples, which are not intended to limit the scope of the present invention. In the examples, all percentages are by weight unless otherwise indicated.
Example 1
Preparation of compound sorbitol aqueous cyclic carbonate:
0.1mol (18.2g) of sorbitol is weighed, dissolved in 30g of ether solvent in advance and added into a three-neck flask, then the three-neck flask is placed into a water bath kettle provided with a constant-temperature magnetic stirrer, a reflux condenser and a temperature measuring device, and 0.6mol (55.51g) of epichlorohydrin is added into the three-neck flask. Stirring is started, when the temperature of the water bath rises and is constant at 60 ℃, the catalyst boron trifluoride diethyl etherate (0.60 percent of the total mass of reactants) is quickly added into a three-neck flask and is tightly plugged by a plug, and the reaction time is 4 hours. After the reactants are cooled to room temperature, sodium hydroxide (prepared into 40 wt.% sodium hydroxide solution) with the same mass as the epoxy chloropropane is added, and the reaction is carried out for 4 hours at 35 ℃. And after insoluble substances are removed by suction filtration, substances such as water, solvent, unreacted epichlorohydrin and the like are removed by reduced pressure distillation, and the remainder is the target product sorbitol epoxy resin. Epoxy value 0.99mol/100g, yield 71.6%.
100g of sorbitol-based epoxy resin is weighed, a catalyst TBAB (the addition amount of tetrabutylammonium bromide accounts for 0.5 wt.% of the sorbitol-based epoxy resin) is added into a high-pressure reaction kettle, and the reaction kettle is filled with CO2Then emptying again, repeating the above steps for 3 times in total, aiming at emptying the air in the reaction kettle and finally introducing CO2Heating to 1.5MPa, heating to a predetermined reaction temperature of 130 ℃, continuously stirring for 10 hours, cooling to 60 ℃ after the reaction is finished, and exhausting CO in the reaction kettle2And (4) gas and taking out the product to obtain a golden yellow viscous liquid sorbityl cyclic carbonate sample.
100g of sorbitol cyclic carbonate and 35g of succinic anhydride were placed in a three-necked flask and protected with dry nitrogen. The mixture was heated to 125 ℃ and the reaction was stopped when the acid number of the product had fallen to the theoretical value, as determined by titration with potassium hydroxide. The reaction temperature was then lowered to 40 ℃ and acetone was added midway to reduce the viscosity. The modified cyclic carbonates were neutralized at 40 ℃ to a degree of 100% by addition of Triethylamine (TEA), dispersed by gradually dropping water and finally the acetone was removed by rotary evaporation to give a 30 wt.% aqueous sorbitol-based cyclic carbonate aqueous dispersion.
The sorbitol-based water-based cyclic carbonate participates in polyamine crosslinking reaction and curing membrane application:
mixing an aqueous sorbitol-based cyclic carbonate dispersion with a polyether polyamine ED-600, wherein the cyclic carbonate functionality to primary amine is carried out in a molar ratio of 1: 1. After stirring for 5 minutes, a film was scraped off from the glass plate with a 50 μm coater, and the film was cured at 90 ℃ for 1 hour and then at 120 ℃ for 2 hours to give a sorbitol-based aqueous cyclic carbonate polyurethane cured film.
The sorbitol aqueous cyclic carbonate dispersoid has the particle diameter of 83nm and is semitransparent; the hardness of the cured film pencil is 2H, the 60-degree gloss is 95, the adhesive force is first grade, and the initial decomposition temperature is 269 ℃.
Example 2
Preparation of compound sorbitol aqueous cyclic carbonate:
0.15mol (27.3g) of sorbitol is weighed, dissolved in 40g of ether solvent in advance and added into a three-neck flask, then the three-neck flask is placed into a water bath kettle provided with a constant-temperature magnetic stirrer, a reflux condenser and a temperature measuring device, and 0.9mol (83.27g) of epichlorohydrin is added into the three-neck flask. Stirring is started, when the temperature of the water bath rises and is constant at 60 ℃, the catalyst boron trifluoride diethyl etherate (0.5 percent of the total mass of reactants) is quickly added into a three-neck flask and is tightly plugged by a plug, and the reaction time is 4 hours. After the reactants are cooled to room temperature, sodium hydroxide (prepared into 40 wt.% sodium hydroxide solution) with the same mass as the epoxy chloropropane is added, and the reaction is carried out for 4 hours at 35 ℃. And after insoluble substances are removed by suction filtration, substances such as water, solvent, unreacted epichlorohydrin and the like are removed by reduced pressure distillation, and the remainder is the target product sorbitol epoxy resin. Epoxy value 1.03mol/100g, yield 72.1%.
100g of sorbitol-based epoxy resin is weighed, a catalyst TBAB (the addition amount of tetrabutylammonium bromide accounts for 0.5 wt.% of the sorbitol-based epoxy resin) is added into a high-pressure reaction kettle, and the reaction kettle is filled with CO2Then emptying again, repeating the above steps for 3 times in total, aiming at emptying the air in the reaction kettle and finally introducing CO2Heating to 2MPa, heating to a preset reaction temperature of 125 ℃, continuously stirring for 11 hours, cooling to 60 ℃ after the reaction is finished, and exhausting CO in the reaction kettle2And (4) gas and taking out the product to obtain a golden yellow viscous liquid sorbityl cyclic carbonate sample.
100g of sorbitol cyclic carbonate and 34g of maleic anhydride were placed in a three-necked flask and protected with dry nitrogen. The mixture was heated to 130 ℃ and the reaction was stopped when the acid number of the product had fallen to the theoretical value, as determined by titration with potassium hydroxide. The reaction temperature was then lowered to 40 ℃ and acetone was added midway to reduce the viscosity. The modified cyclic carbonate was neutralized to 90% neutralization by addition of Dimethylethanolamine (DMEA) at 40 ℃, then dispersed by gradually dropping water and finally the acetone was removed by rotary evaporation to give 35 wt.% aqueous sorbitol-based cyclic carbonate dispersion in water.
The sorbitol-based water-based cyclic carbonate participates in polyamine crosslinking reaction and curing membrane application:
mixing an aqueous sorbitol-based cyclic carbonate dispersion and Isophoronediamine (IPDA), wherein the cyclic carbonate functionality: the primary amine was carried out in a molar ratio of 1: 1. After stirring for 5 minutes, a film was scraped off from the glass plate with a 50 μm coater, and the film was cured at 90 ℃ for 1 hour and then at 120 ℃ for 2 hours to give a sorbitol-based aqueous cyclic carbonate polyurethane cured film.
The sorbitol aqueous cyclic carbonate dispersoid has the particle diameter of 106nm and is in a slightly transparent state; the cured film had pencil hardness of H, 60 ℃ gloss of 93, first order adhesion, and initial decomposition temperature of 253 ℃.
Example 3
Preparation of compound sorbitol aqueous cyclic carbonate:
0.3mol (54.6g) of sorbitol is weighed, dissolved in 45g of ether solvent in advance and added into a three-neck flask, then the three-neck flask is placed into a water bath kettle provided with a constant-temperature magnetic stirrer, a reflux condenser and a temperature measuring device, and 2.1mol (194.29g) of epichlorohydrin is added into the three-neck flask. Stirring is started, when the temperature of the water bath rises and is constant at 60 ℃, the catalyst boron trifluoride diethyl etherate (0.55 percent of the total mass of reactants) is quickly added into a three-neck flask and is tightly plugged by a plug, and the reaction time is 3.5 hours. After the reactant is cooled to room temperature, sodium hydroxide (prepared into 40% sodium hydroxide solution) with the same mass as the epichlorohydrin is added, and the reaction is carried out for 4 hours at the temperature of 35 ℃. And after insoluble substances are removed by suction filtration, substances such as water, solvent, unreacted epichlorohydrin and the like are removed by reduced pressure distillation, and the remainder is the target product sorbitol epoxy resin. Epoxy value 1.01mol/100g, yield 71.2%.
100g of sorbitol-based epoxy resin is weighed, a catalyst TBAB (the addition amount of tetrabutylammonium bromide accounts for 0.5 wt.% of the sorbitol-based epoxy resin) is added into a high-pressure reaction kettle, and the reaction kettle is filled with CO2Then emptying again, repeating the above steps for 3 times in total, aiming at emptying the air in the reaction kettle and finally introducing CO2Heating to 2MPa, heating to a preset reaction temperature of 125 ℃, continuously stirring for 11 hours, cooling to 60 ℃ after the reaction is finished, and exhausting CO in the reaction kettle2And (4) gas and taking out the product to obtain a golden yellow viscous liquid sorbityl cyclic carbonate sample.
100g of sorbitol cyclic carbonate and 51g of Phthalic Anhydride (PA) were placed in a three-necked flask and protected with dry nitrogen. The mixture was heated to 120 ℃ and the reaction was stopped when the acid number of the product had fallen to the theoretical value, as determined by titration with potassium hydroxide. The reaction temperature was then lowered to 40 ℃ and acetone was added midway to reduce the viscosity. The modified cyclic carbonate was neutralized at 40 ℃ to 100% by adding triethanolamine, then dispersed by gradually dropping water, and finally the acetone was removed by rotary evaporation to give 40 wt.% aqueous sorbitol-based cyclic carbonate aqueous dispersion.
The sorbitol-based water-based cyclic carbonate participates in polyamine crosslinking reaction and curing membrane application:
mixing an aqueous sorbitol-based cyclic carbonate dispersion with a polyether polyamine M-2005, wherein the cyclic carbonate functionality to primary amine was carried out in a molar ratio of 1: 1. After stirring for 5 minutes, a film was scraped off from the glass plate with a 50 μm coater, and the film was cured at 90 ℃ for 1 hour and then at 120 ℃ for 2 hours to give a sorbitol-based aqueous cyclic carbonate polyurethane cured film.
The sorbitol aqueous cyclic carbonate dispersoid has the particle diameter of 96nm and is semitransparent; the hardness of the cured film pencil is 2H, the 60-degree gloss is 95, the adhesive force is first grade, and the initial decomposition temperature is 273 ℃.
Claims (8)
1. A sorbitol-based aqueous cyclic carbonate characterized by a molecular structural formula:
wherein R is methyl, ethyl, butyl, isopropyl, hydroxyethyl, cyclohexyl or benzyl.
2. A process for the preparation of a sorbitol-based aqueous cyclic carbonate according to claim 1, comprising the steps of: (1) in the presence of boron trifluoride diethyl etherate serving as a catalyst, sorbitol and epoxy chloropropane react to obtain sorbitol epoxy resin, wherein the molar ratio of the epoxy chloropropane to the sorbitol is (4.0-7.5): 1.0; (2) reacting the sorbitol epoxy resin obtained in the step (1) with carbon dioxide in the presence of a catalyst tetrabutylammonium bromide (TBAB) to obtain sorbitol-based cyclic carbonate, wherein the pressure of the reacted carbon dioxide is 10-20 atmospheric pressures; (3) reacting the sorbitol-based cyclic carbonate obtained in the step (2) with acid anhydride to obtain carboxylated sorbitol cyclic carbonate, wherein the molar ratio of the acid anhydride to the sorbitol-based cyclic carbonate is (2.5-4.0): 1.0; (4) and (3) reacting the carboxylated sorbitol cyclic carbonate obtained in the step (3) with tertiary amine, and then adding water to disperse to obtain a slightly transparent sorbitol-based aqueous cyclic carbonate dispersion, wherein the neutralization degree of the reaction of the carboxylated sorbitol cyclic carbonate and the tertiary amine is 60-100%.
3. The method for producing a sorbitol-based aqueous cyclic carbonate according to claim 2, wherein the step (1) is specifically: dissolving sorbitol in an organic solvent, adding epoxy chloropropane and boron trifluoride diethyl etherate serving as a catalyst to react for 2-4h at the temperature of 60-80 ℃ to obtain sorbitol epoxy resin; the organic solvent is ethyl acetate, diethyl ether, acetone, acetonitrile, dioxane, dichloromethane or tetrahydrofuran; the catalyst boron trifluoride diethyl etherate accounts for 1-6 per mill of the total mass of reactants.
4. The process for producing a sorbitol-based aqueous cyclic carbonate according to claim 2, wherein the sorbitol epoxy resin obtained in the step (1) is purified by the following steps: cooling the reaction material obtained in the step (1) to 40-50 ℃, removing the solvent, adding sodium hydroxide with the mass of epoxy chloropropane and the like, wherein the concentration of the sodium hydroxide is 40 wt.%, and reacting for 4 hours at 35 ℃; filtering the solution obtained in the step one to remove insoluble substances, then carrying out reduced pressure distillation to remove water and unreacted epichlorohydrin substances, wherein the remainder is the target product sorbitol glycidyl ether, and the theoretical epoxy value of the product is 0.68mol/100g-0.99mol/100 g.
5. The method for producing a sorbitol-based aqueous cyclic carbonate according to claim 2, wherein the step (2) is specifically: adding the sorbitol epoxy resin obtained in the step (1) into a pressure reaction kettle and filling CO2To the pressure of 1.0-2.0 MPa; ② continuously stirring at the reaction temperature of 90-130 ℃ for 1-11 hours, after the reaction is finished, cooling to 60 ℃, evacuating CO in the reaction kettle2Gas is generated, and a product is taken out to obtain a golden yellow viscous liquid sorbityl cyclic carbonate sample; the catalyst tetrabutylammonium bromide was added in an amount of 0.5 wt.% of the sorbitol epoxy resin.
6. The method for preparing a sorbitol-based aqueous cyclic carbonate according to claim 2, wherein the step (3) is specifically: putting the sorbitol base cyclic carbonate and the anhydride obtained in the step (2) into a 1L three-neck flask and protecting with dry nitrogen; heating the mixture to 90-130 ℃ for reaction, and stopping the reaction when the acid value of the product is reduced to a theoretical value through potassium hydroxide titration; the acid anhydride is succinic anhydride, maleic anhydride or phthalic anhydride, and the theoretical acid value is 25-40mg KOH/g.
7. The method for preparing a sorbitol-based aqueous cyclic carbonate according to claim 2, wherein the step (4) is specifically: reducing the temperature of the carboxylated sorbitol cyclic carbonate obtained in the step (3) to 40 ℃, and adding acetone in the midway to reduce the viscosity to be not higher than 6000mPa & s; neutralizing the modified carboxylated cyclic carbonate by adding tertiary amine at 40 ℃, wherein the neutralization degree is 60-100%, then gradually dripping water for dispersion, and finally removing acetone by rotary evaporation to obtain 30-40 wt.% solid cyclic carbonate aqueous dispersion; the tertiary amine is triethylamine, dimethylethanolamine, triethanolamine, N-methyldiethanolamine or N, N-diisopropylethylamine.
8. Use of the sorbitol-based aqueous cyclic carbonate according to claim 1 in an aqueous system crosslinker.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110225126.9A CN113004242A (en) | 2021-03-01 | 2021-03-01 | Sorbitol-based aqueous cyclic carbonate, and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110225126.9A CN113004242A (en) | 2021-03-01 | 2021-03-01 | Sorbitol-based aqueous cyclic carbonate, and preparation method and application thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN113004242A true CN113004242A (en) | 2021-06-22 |
Family
ID=76387272
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202110225126.9A Pending CN113004242A (en) | 2021-03-01 | 2021-03-01 | Sorbitol-based aqueous cyclic carbonate, and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN113004242A (en) |
Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1386126A (en) * | 2000-06-05 | 2002-12-18 | 长濑化成株式会社 | Crosslinking agent for water-absorbing resin and water-absorbing material obtained with the same |
| CN103232428A (en) * | 2013-05-02 | 2013-08-07 | 中国林业科学研究院林产化学工业研究所 | Preparation method of terpenyl cyclocarbonate and non-isocyanate polyurethane thereof |
| CN105917044A (en) * | 2014-02-03 | 2016-08-31 | 长濑化成株式会社 | Adhesive composition for organic fibers, and method for treating the organic fibers |
| CN107075308A (en) * | 2014-10-28 | 2017-08-18 | 长濑化成株式会社 | Paint composite |
| CN108546262A (en) * | 2018-04-12 | 2018-09-18 | 华南理工大学 | Aqueous syrups cyclic carbonate ester lotion and preparation method thereof and the application in water-based non-isocyanate polyurethane coating |
| CN108603071A (en) * | 2016-03-18 | 2018-09-28 | 长濑化成株式会社 | Coating resin combination |
| CN108659689A (en) * | 2018-04-12 | 2018-10-16 | 华南理工大学 | A kind of sorb alcohol radical non-isocyanate polyurethane coating and preparation method thereof |
| US20190092964A1 (en) * | 2017-09-22 | 2019-03-28 | EVERGREEN C&T Corporation | Uv curable coating composition |
-
2021
- 2021-03-01 CN CN202110225126.9A patent/CN113004242A/en active Pending
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1386126A (en) * | 2000-06-05 | 2002-12-18 | 长濑化成株式会社 | Crosslinking agent for water-absorbing resin and water-absorbing material obtained with the same |
| CN103232428A (en) * | 2013-05-02 | 2013-08-07 | 中国林业科学研究院林产化学工业研究所 | Preparation method of terpenyl cyclocarbonate and non-isocyanate polyurethane thereof |
| CN105917044A (en) * | 2014-02-03 | 2016-08-31 | 长濑化成株式会社 | Adhesive composition for organic fibers, and method for treating the organic fibers |
| CN107075308A (en) * | 2014-10-28 | 2017-08-18 | 长濑化成株式会社 | Paint composite |
| CN108603071A (en) * | 2016-03-18 | 2018-09-28 | 长濑化成株式会社 | Coating resin combination |
| US20190092964A1 (en) * | 2017-09-22 | 2019-03-28 | EVERGREEN C&T Corporation | Uv curable coating composition |
| CN108546262A (en) * | 2018-04-12 | 2018-09-18 | 华南理工大学 | Aqueous syrups cyclic carbonate ester lotion and preparation method thereof and the application in water-based non-isocyanate polyurethane coating |
| CN108659689A (en) * | 2018-04-12 | 2018-10-16 | 华南理工大学 | A kind of sorb alcohol radical non-isocyanate polyurethane coating and preparation method thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| TWI257933B (en) | Polymeric urea-urethane rheology control agent and preparation process | |
| US4230824A (en) | Sucrose based polyether polyols | |
| CN105968331B (en) | A kind of miscellaneous multi-arm star hydroxyl polyester of low viscosity and the preparation method and application thereof | |
| JPH08501329A (en) | Polyurethane, its use and water-based paint containing polyurethane as a thickener | |
| CN107216761A (en) | The preparation method of the water soluble acrylic resin of high solid | |
| CN106519158B (en) | A kind of end group is the preparation method of the hyperbranched poly (urethane-amine) of hydroxyl, interior branch unit with vinyl | |
| CN107189053B (en) | Preparation method and application under a kind of polynary carbonic ester resin and its normal pressure | |
| CN107987611A (en) | A kind of hyperbranched resin base UV cures jetted ink and its preparation method and application | |
| CN104693994A (en) | Ultraviolet photocuring coating containing inorganic pigment and filler and preparation method thereof | |
| US11932774B2 (en) | Waterborne isocyanate-free polyurethane epoxy hybrid coatings | |
| CN109265646A (en) | A kind of aqueous polyurethane emulsion and preparation method thereof with high tensile | |
| US5319055A (en) | Non-aqueous thickening agents | |
| JPH09235352A (en) | Curing agent for resin | |
| US4171423A (en) | Derivatives of ester diol alkoxylates and compositions thereof | |
| US4059549A (en) | Moisture-hardenable sealing and coating compounds | |
| CN113004242A (en) | Sorbitol-based aqueous cyclic carbonate, and preparation method and application thereof | |
| CN100430424C (en) | Process for preparing acrylate resin for powder paint | |
| CN108546262A (en) | Aqueous syrups cyclic carbonate ester lotion and preparation method thereof and the application in water-based non-isocyanate polyurethane coating | |
| CN108117832A (en) | Double curing type one-component carbamide paints and preparation method thereof | |
| EP3914635A1 (en) | Dihydroxy lactam based polymers, compositions and applications thereof | |
| WO1999020666A1 (en) | Polymers of 3-butene esters, their preparation and use | |
| CN105061685A (en) | Preparation method of yellow urethane acrylate dye | |
| CN109486470A (en) | A kind of epoxidized soybean oil adhesive and preparation method thereof of imidazoles blocked polyurethane effect | |
| CN111471424B (en) | Waterborne polyurethane adhesive and preparation method thereof | |
| JPH02174750A (en) | Secondary polyetheramine,preparation thereof and preparationof polyurehtnane therefrom in the absence of catalyst |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20210622 |
|
| RJ01 | Rejection of invention patent application after publication |