CN117362605A - Bio-based polycaprolactone polyol and preparation method thereof - Google Patents
Bio-based polycaprolactone polyol and preparation method thereof Download PDFInfo
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- CN117362605A CN117362605A CN202311477018.6A CN202311477018A CN117362605A CN 117362605 A CN117362605 A CN 117362605A CN 202311477018 A CN202311477018 A CN 202311477018A CN 117362605 A CN117362605 A CN 117362605A
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- 229920001610 polycaprolactone Polymers 0.000 title claims abstract description 66
- 229920005862 polyol Polymers 0.000 title claims abstract description 66
- 150000003077 polyols Chemical class 0.000 title claims abstract description 66
- 239000004632 polycaprolactone Substances 0.000 title claims abstract description 65
- 238000002360 preparation method Methods 0.000 title abstract description 24
- 238000004917 polyol method Methods 0.000 title description 2
- 239000000178 monomer Substances 0.000 claims abstract description 52
- 239000003054 catalyst Substances 0.000 claims abstract description 27
- 238000011065 in-situ storage Methods 0.000 claims abstract description 24
- 238000006243 chemical reaction Methods 0.000 claims abstract description 22
- 238000000034 method Methods 0.000 claims abstract description 20
- 238000002156 mixing Methods 0.000 claims abstract description 12
- 239000003999 initiator Substances 0.000 claims abstract description 10
- 150000003751 zinc Chemical class 0.000 claims abstract description 10
- 150000003863 ammonium salts Chemical class 0.000 claims abstract description 9
- 238000001556 precipitation Methods 0.000 claims abstract description 5
- 238000010438 heat treatment Methods 0.000 claims abstract description 4
- 239000012716 precipitator Substances 0.000 claims abstract description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 30
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims description 16
- NHGXDBSUJJNIRV-UHFFFAOYSA-M tetrabutylammonium chloride Chemical compound [Cl-].CCCC[N+](CCCC)(CCCC)CCCC NHGXDBSUJJNIRV-UHFFFAOYSA-M 0.000 claims description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 12
- VNDYJBBGRKZCSX-UHFFFAOYSA-L zinc bromide Chemical compound Br[Zn]Br VNDYJBBGRKZCSX-UHFFFAOYSA-L 0.000 claims description 8
- 239000011592 zinc chloride Substances 0.000 claims description 8
- 235000005074 zinc chloride Nutrition 0.000 claims description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 7
- UWFRVQVNYNPBEF-UHFFFAOYSA-N 1-(2,4-dimethylphenyl)propan-1-one Chemical compound CCC(=O)C1=CC=C(C)C=C1C UWFRVQVNYNPBEF-UHFFFAOYSA-N 0.000 claims description 6
- CSDQQAQKBAQLLE-UHFFFAOYSA-N 4-(4-chlorophenyl)-4,5,6,7-tetrahydrothieno[3,2-c]pyridine Chemical compound C1=CC(Cl)=CC=C1C1C(C=CS2)=C2CCN1 CSDQQAQKBAQLLE-UHFFFAOYSA-N 0.000 claims description 6
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 claims description 6
- 239000000292 calcium oxide Substances 0.000 claims description 6
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 claims description 6
- 239000002274 desiccant Substances 0.000 claims description 4
- 229940102001 zinc bromide Drugs 0.000 claims description 4
- SHKUUQIDMUMQQK-UHFFFAOYSA-N 2-[4-(oxiran-2-ylmethoxy)butoxymethyl]oxirane Chemical compound C1OC1COCCCCOCC1CO1 SHKUUQIDMUMQQK-UHFFFAOYSA-N 0.000 claims description 3
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 claims description 3
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 claims description 3
- PSHKMPUSSFXUIA-UHFFFAOYSA-N n,n-dimethylpyridin-2-amine Chemical compound CN(C)C1=CC=CC=N1 PSHKMPUSSFXUIA-UHFFFAOYSA-N 0.000 claims description 3
- 239000012312 sodium hydride Substances 0.000 claims description 3
- 229910000104 sodium hydride Inorganic materials 0.000 claims description 3
- JRMUNVKIHCOMHV-UHFFFAOYSA-M tetrabutylammonium bromide Chemical compound [Br-].CCCC[N+](CCCC)(CCCC)CCCC JRMUNVKIHCOMHV-UHFFFAOYSA-M 0.000 claims description 3
- 239000004246 zinc acetate Substances 0.000 claims description 3
- -1 tetrabutylammonium iodide compound Chemical class 0.000 claims description 2
- 230000003197 catalytic effect Effects 0.000 abstract description 15
- 230000000694 effects Effects 0.000 abstract description 4
- 230000009286 beneficial effect Effects 0.000 abstract description 3
- 231100000956 nontoxicity Toxicity 0.000 abstract description 2
- 239000002861 polymer material Substances 0.000 abstract description 2
- 239000000047 product Substances 0.000 description 21
- 230000000052 comparative effect Effects 0.000 description 12
- 238000001035 drying Methods 0.000 description 9
- 239000002904 solvent Substances 0.000 description 9
- 239000000463 material Substances 0.000 description 7
- 239000004814 polyurethane Substances 0.000 description 6
- 229920002635 polyurethane Polymers 0.000 description 6
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical compound C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 description 4
- 238000007373 indentation Methods 0.000 description 4
- PAPBSGBWRJIAAV-UHFFFAOYSA-N ε-Caprolactone Chemical compound O=C1CCCCCO1 PAPBSGBWRJIAAV-UHFFFAOYSA-N 0.000 description 4
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- 238000004821 distillation Methods 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000003208 petroleum Substances 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 238000007151 ring opening polymerisation reaction Methods 0.000 description 2
- DPKBAXPHAYBPRL-UHFFFAOYSA-M tetrabutylazanium;iodide Chemical compound [I-].CCCC[N+](CCCC)(CCCC)CCCC DPKBAXPHAYBPRL-UHFFFAOYSA-M 0.000 description 2
- LZDXRPVSAKWYDH-UHFFFAOYSA-N 2-ethyl-2-(prop-2-enoxymethyl)propane-1,3-diol Chemical compound CCC(CO)(CO)COCC=C LZDXRPVSAKWYDH-UHFFFAOYSA-N 0.000 description 1
- RZTOWFMDBDPERY-UHFFFAOYSA-N Delta-Hexanolactone Chemical compound CC1CCCC(=O)O1 RZTOWFMDBDPERY-UHFFFAOYSA-N 0.000 description 1
- 239000002879 Lewis base Substances 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 150000002009 diols Chemical class 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 239000010985 leather Substances 0.000 description 1
- 239000002649 leather substitute Substances 0.000 description 1
- 150000007527 lewis bases Chemical class 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 238000007142 ring opening reaction Methods 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
- 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
- C08G63/06—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from hydroxycarboxylic acids
- C08G63/08—Lactones or lactides
-
- 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
- C08G63/82—Preparation processes characterised by the catalyst used
- C08G63/823—Preparation processes characterised by the catalyst used for the preparation of polylactones or polylactides
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 the technical field of high polymer materials, in particular to a bio-based polycaprolactone polyol and a preparation method thereof. The bio-based polycaprolactone polyol has a special structure and can provide better flexibility. The preparation method comprises the following steps: step 1, mixing zinc salt, organic ammonium salt and an initiator, and then heating for reaction to obtain an in-situ catalyst; step 2, firstly removing moisture in the delta-CL monomer, and then purifying the delta-CL monomer to obtain a purified delta-CL monomer; step 3, adding the purified delta-CL monomer into an in-situ catalyst for reaction to obtain a product; and step 4, adding a precipitator for precipitation, and separating to obtain the bio-based polycaprolactone polyol. The method adopts a novel catalytic system, has the advantages of higher reaction activity, no toxicity, low cost, simplicity and easiness in operation, can react under normal pressure, has lower requirements on equipment, has low preparation cost, and is beneficial to popularization and utilization of the catalyst.
Description
Technical Field
The invention relates to the technical field of high polymer materials, in particular to a bio-based polycaprolactone polyol and a preparation method thereof.
Background
Polycaprolactone Polyol (PCL) is aliphatic linear polyester, has extremely high extensibility, has extremely large application and play space in the aspects of resin modification, paint, adhesive, polyurethane artificial leather, leather finishing agent and the like, and is a very good organic material. The polycaprolactone polyol comprises petroleum-based polycaprolactone polyol and bio-based polycaprolactone polyol, wherein the bio-based polycaprolactone polyol has good compatibility with other systems and has good application prospect. However, bio-based polycaprolactone polyols have limited applications due to their relatively high price compared to petroleum-based polycaprolactone polyols. In addition, polycaprolactone polyols having flexible linkages can be used to prepare materials with better flexibility, but the currently available polycaprolactone polyols are of a lesser variety and are not sufficiently flexible.
The polycaprolactone polyol is prepared by ring-opening polymerization of caprolactone serving as a raw material in a certain catalytic system. At present, a common catalytic system is a metal and compound/polyol catalytic system, such as Chinese patent application CN108129645A, and epsilon-caprolactone is taken as a raw material, and epsilon-caprolactone is promoted to be subjected to ring-opening polymerization in an alkaline earth metal/diol catalytic system to prepare polycaprolactone polyol. However, the catalytic system used in the method has low reaction activity, low yield, high equipment requirement and high preparation cost of the final product. As another example, chinese patent application CN108912316a provides a method for preparing polycaprolactone polyol, which uses an initiator (alcohol), a catalyst (organozinc), an inhibitor (organophosphorus) and caprolactone to prepare polycaprolactone polyol under the protection of anhydrous, anaerobic and inert gases, but the method needs to react under inert atmosphere, and has the advantages of complex preparation process, low activity of catalytic system, high requirement on equipment and high preparation cost.
Disclosure of Invention
The invention aims to solve the problems of high preparation cost, poor flexibility and complex preparation method of the bio-based polycaprolactone polyol and unfavorable popularization and application, and provides the bio-based polycaprolactone polyol with simple preparation method, low cost and good flexibility and the preparation method thereof. The specific technical scheme is as follows:
in a first aspect of the invention, a bio-based polycaprolactone polyol is provided having the structural formula:
wherein R isIs->One of the following; m is 3-15, n is 3-15.
In a second aspect of the present invention, there is provided a method for preparing a bio-based polycaprolactone polyol comprising the steps of:
step 1, mixing zinc salt, organic ammonium salt and an initiator, and then heating for reaction to obtain an in-situ catalyst;
step 2, firstly removing moisture in the delta-CL monomer, and then purifying the delta-CL monomer to obtain a purified delta-CL monomer;
step 3, adding the purified delta-CL monomer into an in-situ catalyst for reaction to obtain a product;
and step 4, adding a precipitator for precipitation, and separating to obtain the bio-based polycaprolactone polyol.
Specifically, the method for removing moisture in the step 2 is to add a desiccant to remove water, wherein the desiccant is at least one selected from calcium hydride, sodium hydride and calcium oxide.
Specifically, the catalyst in the step 1 is a combination of zinc salt and organic ammonium salt, and the mass ratio of the zinc salt to the organic ammonium salt is 1:10-1:50.
specifically, the zinc salt is selected from at least one of zinc chloride, zinc bromide and zinc acetate, and the organic ammonium salt is selected from at least one of dimethylaminopyridine, tetrabutylammonium chloride, tetrabutylammonium bromide and tetrabutylammonium iodide compound.
Specifically, the initiator in the step 1 is one of ethylene glycol diglycidyl ether, diglycidyl ether and 1, 4-butanediol diglycidyl ether.
Specifically, the mass ratio of the zinc salt to the initiator is 1:30-1:50.
specifically, the mass ratio of the initiator in step 1 to the delta-CL monomer added in step 2 is 1:36-1:54.
Specifically, the temperature of the heating reaction in the step 1 is 60-80 ℃, and the reaction time is 3-5 h.
Specifically, the delta-CL monomer in the step 2 is delta-caprolactone of biological origin;
specifically, the purification process in the step 2 is to perform reduced pressure distillation on the filtrate, wherein the temperature of the reduced pressure distillation is 80-120 ℃, and the reduced pressure distillation time is 1-3h.
Specifically, the reaction temperature in the step 3 is 130-180 ℃ and the reaction time is 1-2h.
Specifically, the precipitating agent in the step 3 is selected from one of methanol and ethanol; the precipitation process is to add a precipitant into the product, filter, dissolve the product with dichloromethane, add the precipitant to precipitate, and filter.
The reaction mechanism of the bio-based polycaprolactone polyol provided by the invention is as follows:
the Lewis base is an organic ammonium salt; x is halogen.
The beneficial effects brought by the invention are as follows:
(1) The bio-based polycaprolactone polyol provided by the invention has flexible connection sections, can provide a proper degree of crosslinking, and the material prepared by using the bio-based polycaprolactone polyol has good flexibility and good application prospect;
(2) The bio-based polycaprolactone polyol provided by the invention adopts a novel catalytic system, has higher reaction activity, has the advantages of no toxicity and low cost, and can improve the preparation yield and reduce the preparation cost of the polycaprolactone polyol;
(3) The method provided by the invention is simple and easy to operate, can be carried out under normal pressure, has lower equipment requirement, is favorable for further reducing the preparation cost and is convenient for popularization and utilization of the bio-based polycaprolactone polyol.
Detailed Description
The technical solutions of the present application will be clearly and completely described below in connection with embodiments, and it is obvious that the described embodiments are some, but not all, embodiments of the present application. All other embodiments, which can be made by one of ordinary skill in the art without undue burden from the present disclosure, are within the scope of the present application based on the embodiments herein.
Example 1
Step 1, mixing 0.5g of ethylene glycol diglycidyl ether, 0.01g of zinc chloride and 0.3g of tetrabutylammonium chloride, and reacting for 4 hours at the normal pressure and the temperature of 70 ℃ to obtain an in-situ catalyst;
step 2, firstly adding calcium hydride to remove water in the delta-CL monomer, and then purifying the delta-CL monomer to obtain a purified delta-CL monomer;
step 3, adding 18g of purified delta-CL monomer into an in-situ catalyst, and reacting for 1h at 160 ℃ to obtain a product;
and step 4, adding methanol into the product after the reaction is finished to precipitate, removing the solvent, and then drying in vacuum at 40 ℃ for 48 hours to obtain the bio-based polycaprolactone polyol.
Example 2
Step 1, mixing 0.4g of ethylene glycol diglycidyl ether, 0.01g of zinc acetate and 0.3g of dimethylaminopyridine, and reacting for 4 hours at 60 ℃ and normal pressure to obtain an in-situ catalyst;
step 2, firstly adding sodium hydride to remove water in the delta-CL monomer, and then purifying the delta-CL monomer to obtain a purified delta-CL monomer;
step 3, adding 18g delta-CL monomer into the in-situ catalyst, and reacting for 1h at 180 ℃ to obtain a product;
and step 4, adding methanol into the product after the reaction is finished to precipitate, removing the solvent, and then drying in vacuum at 40 ℃ for 48 hours to obtain the bio-based polycaprolactone polyol.
Example 3
Step 1, mixing 0.3g of 1, 4-butanediol diglycidyl ether, 0.01g of zinc chloride and 0.3g of tetrabutylammonium chloride, and reacting for 4 hours at 60 ℃ and normal pressure to obtain an in-situ catalyst;
step 2, firstly adding calcium oxide to remove water in the delta-CL monomer, and then purifying the delta-CL monomer to obtain a purified delta-CL monomer;
step 3, adding 16.2g delta-CL monomer into the in-situ catalyst, and reacting for 2 hours at 130 ℃ to obtain a product;
and step 4, adding methanol into the product after the reaction is finished to precipitate, removing the solvent, and then drying in vacuum at 40 ℃ for 48 hours to obtain the bio-based polycaprolactone polyol.
Example 4
Step 1, mixing 0.5g of diglycidyl ether, 0.01g of zinc chloride and 0.5g of tetrabutylammonium iodide, and reacting for 3 hours at the normal pressure and the temperature of 70 ℃ to obtain an in-situ catalyst;
step 2, firstly adding calcium oxide to remove water in the delta-CL monomer, and then purifying the delta-CL monomer to obtain a purified delta-CL monomer;
step 3, adding 18g delta-CL monomer into the in-situ catalyst, and reacting for 2 hours at 160 ℃ to obtain a product;
and step 4, adding methanol into the product after the reaction is finished to precipitate, removing the solvent, and then drying in vacuum at 40 ℃ for 48 hours to obtain the bio-based polycaprolactone polyol.
Example 5
Step 1, mixing 0.5g of diglycidyl ether, 0.01g of zinc bromide and 0.1g of tetrabutylammonium bromide, and reacting for 4 hours at the normal pressure and the temperature of 80 ℃ to obtain an in-situ catalyst;
step 2, firstly adding calcium oxide to remove water in the delta-CL monomer, and then purifying the delta-CL monomer to obtain a purified delta-CL monomer;
step 3, adding 18g delta-CL monomer into the in-situ catalyst, and reacting for 1h at 160 ℃ to obtain a product;
and step 4, adding ethanol into the product after the reaction is finished to perform precipitation, removing the solvent, and then drying in vacuum at 40 ℃ for 48 hours to obtain the bio-based polycaprolactone polyol.
Example 6
Step 1, mixing 0.5g of diglycidyl ether, 0.01g of zinc bromide and 0.30g of tetrabutylammonium iodide, and reacting for 5 hours at the normal pressure and the temperature of 70 ℃ to obtain an in-situ catalyst;
step 2, firstly adding calcium oxide to remove water in the delta-CL monomer, and then purifying the delta-CL monomer to obtain a purified delta-CL monomer;
step 3, adding 18g delta-CL monomer into the in-situ catalyst, and reacting for 1h at 160 ℃ to obtain a product;
and step 4, adding methanol into the product after the reaction is finished to precipitate, removing the solvent, and then drying in vacuum at 40 ℃ for 48 hours to obtain the bio-based polycaprolactone polyol.
Comparative example 1
Step 1, mixing 0.5g of ethylene glycol diglycidyl ether and 0.01g of zinc chloride, and reacting for 4 hours at the normal pressure and the temperature of 70 ℃ to obtain an in-situ catalyst;
step 2, firstly adding calcium hydride to remove water in the delta-CL monomer, and then purifying the delta-CL monomer to obtain a purified delta-CL monomer;
step 3, adding 18g delta-CL monomer into the in-situ catalyst to react for 1h at 160 ℃ to obtain a product;
and step 4, adding methanol into the product after the reaction is finished to precipitate, removing the solvent, and then drying in vacuum at 40 ℃ for 48 hours to obtain the bio-based polycaprolactone polyol.
Comparative example 2
Step 1, mixing 0.5g of ethylene glycol diglycidyl ether, 0.01g of zinc chloride and 0.05g of tetrabutylammonium chloride, and reacting for 4 hours at the normal pressure and the temperature of 70 ℃ to obtain an in-situ catalyst;
step 2, firstly adding calcium hydride to remove water in the delta-CL monomer, and then purifying the delta-CL monomer to obtain a purified delta-CL monomer;
step 3, adding 18g of purified delta-CL monomer into an in-situ catalyst, and reacting for 1h at 160 ℃ to obtain a product;
and step 4, adding methanol into the product after the reaction is finished to precipitate, removing the solvent, and then drying in vacuum at 40 ℃ for 48 hours to obtain the bio-based polycaprolactone polyol.
Comparative example 3
Step 1, mixing 0.5g of trimethylolpropane monoallyl ether, 0.01g of zinc chloride and 0.3g of tetrabutylammonium chloride, and reacting for 4 hours at the normal pressure and the temperature of 70 ℃ to obtain an in-situ catalyst;
step 2, firstly adding calcium hydride to remove water in the delta-CL monomer, and then purifying the delta-CL monomer to obtain a purified delta-CL monomer;
step 3, adding 18g of purified delta-CL monomer into an in-situ catalyst, and reacting for 1h at 160 ℃ to obtain a product;
and step 4, adding methanol into the product after the reaction is finished to precipitate, removing the solvent, and then drying in vacuum at 40 ℃ for 48 hours to obtain the bio-based polycaprolactone polyol.
At present, the preparation cost of petroleum-based polycaprolactone polyol used in the market is 23-28 yuan/kg, and the cost of bio-based polycaprolactone polyol prepared by the existing preparation method is 30-35 yuan/kg, and the preparation cost of the bio-based polycaprolactone polyol provided by the method is about 19-21 yuan/kg. The method of the invention greatly reduces the preparation cost of the bio-based polycaprolactone polyol and is beneficial to popularization and application of the bio-based polycaprolactone polyol.
The bio-based polycaprolactone polyol prepared in each example and comparative example is mixed with TDI, stannous octoate and water, and the mixture is reacted for 1 to 2 hours at room temperature to prepare the polyurethane material.
The catalytic activity of the catalytic system, the production yield of the bio-based polycaprolactone polyol, and the properties of the produced polyurethane materials during the preparation of the bio-based polycaprolactone polyol in examples and comparative examples were tested, and the test results are shown in table 1.
The flexibility of the polyurethane material may be characterized by the indentation hardness, which is referred to the GB 10807-2006 standard.
Test results
Table 1 test results for examples and comparative examples
| Test item | Yield rate | TOF value | Indentation hardness |
| Example 1 | 91.3％ | 3248h -1 | 1.55 |
| Example 2 | 69.1％ | 2458h -1 | 1.60 |
| Example 3 | 57.6％ | 1024h -1 | 1.54 |
| Example 4 | 98.2％ | 3493h -1 | 1.57 |
| Example 5 | 71.7％ | 2550h -1 | 1.64 |
| Example 6 | 79.8％ | 3838h -1 | 1.52 |
| Comparative example 1 | 12.8％ | 455h -1 | 1.61 |
| Comparative example 2 | 16.7％ | 594h -1 | 1.58 |
| Comparative example 3 | 38.9％ | 1383h -1 | 1.82 |
The test results show that the catalytic activity of the catalytic system of the preparation method is higher, the preparation yield is higher, the bio-based polycaprolactone polyol provided by the embodiment of the invention has flexible connection sections, the bio-based polycaprolactone polyol can provide proper crosslinking degree when used for preparing polyurethane materials, and the polyurethane materials prepared by using the bio-based polycaprolactone polyol have smaller indentation hardness and very good flexibility. Comparative example 1 and comparative example 2 have lower catalytic activity and lower production yield of the catalytic system used in the production process; the bio-based polycaprolactone polyol prepared in comparative example 3 has relatively poor flexibility, the bio-based polycaprolactone polyol prepared by using the bio-based polycaprolactone polyol has relatively high indentation hardness, the selection of a catalytic system of the bio-based polycaprolactone polyol cannot better promote ring opening of delta-CL monomers, and the preparation yield is low.
Claims (10)
1. A bio-based polycaprolactone polyol characterized by the following structural formula:
wherein R isIs->One of the following; m is 3-15, n is 3-15.
2. The method for preparing the bio-based polycaprolactone polyol according to claim 1, comprising the steps of:
step 1, mixing zinc salt, organic ammonium salt and an initiator, and then heating for reaction to obtain an in-situ catalyst;
step 2, firstly removing moisture in the delta-CL monomer, and then purifying the delta-CL monomer to obtain a purified delta-CL monomer;
step 3, adding the purified delta-CL monomer into an in-situ catalyst for reaction to obtain a product;
and step 4, adding a precipitator for precipitation, and separating to obtain the bio-based polycaprolactone polyol.
3. The method for preparing the bio-based polycaprolactone polyol according to claim 2, wherein the mass ratio of zinc salt to organic ammonium salt added in step 1 is 1:10-1:50.
4. the method for preparing a bio-based polycaprolactone polyol according to claim 3, wherein the zinc salt is at least one selected from zinc chloride, zinc bromide and zinc acetate, and the organic ammonium salt is at least one selected from dimethylaminopyridine, tetrabutylammonium chloride, tetrabutylammonium bromide and tetrabutylammonium iodide compound.
5. The method of preparing a bio-based polycaprolactone polyol according to claim 2, wherein the initiator in step 1 is at least one of ethylene glycol diglycidyl ether, and 1, 4-butanediol diglycidyl ether.
6. The method for preparing the bio-based polycaprolactone polyol according to claim 2, wherein the mass ratio of the zinc salt to the initiator added in the step 1 is 1:30-1:50.
7. the method of preparing a bio-based polycaprolactone polyol according to claim 2, wherein the mass ratio of the initiator in step 1 to the delta-CL monomer in step 2 is 1:36-1:54.
8. The method for preparing the bio-based polycaprolactone polyol according to claim 2, wherein the method for removing moisture in the step 2 is adding a drying agent for removing water, and the drying agent is at least one selected from calcium hydride, sodium hydride and calcium oxide.
9. The method for preparing a bio-based polycaprolactone polyol according to claim 2, wherein the reaction temperature in step 3 is 130-180 ℃ for 1-2 hours.
10. The method of preparing a bio-based polycaprolactone polyol according to claim 2, wherein the precipitant in step 4 is selected from one of methanol and ethanol.
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