CN118406222B - Bio-based polyester polyol and preparation method and application thereof - Google Patents
Bio-based polyester polyol and preparation method and application thereof Download PDFInfo
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- CN118406222B CN118406222B CN202410882516.7A CN202410882516A CN118406222B CN 118406222 B CN118406222 B CN 118406222B CN 202410882516 A CN202410882516 A CN 202410882516A CN 118406222 B CN118406222 B CN 118406222B
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- polyester polyol
- dihydric alcohol
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- 229920005906 polyester polyol Polymers 0.000 title claims abstract description 68
- 238000002360 preparation method Methods 0.000 title claims abstract description 32
- 239000000853 adhesive Substances 0.000 claims abstract description 68
- 230000001070 adhesive effect Effects 0.000 claims abstract description 68
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 62
- 239000002253 acid Substances 0.000 claims abstract description 44
- 239000002608 ionic liquid Substances 0.000 claims abstract description 42
- 125000000168 pyrrolyl group Chemical group 0.000 claims abstract description 39
- 150000002009 diols Chemical class 0.000 claims abstract description 18
- 239000002994 raw material Substances 0.000 claims abstract description 14
- SMAZMUALKFIBFI-UHFFFAOYSA-N 6-hydroxy-6-oxohexanoate;triethylazanium Chemical compound CCN(CC)CC.OC(=O)CCCCC(O)=O SMAZMUALKFIBFI-UHFFFAOYSA-N 0.000 claims abstract description 11
- 125000003118 aryl group Chemical group 0.000 claims abstract description 9
- 238000004806 packaging method and process Methods 0.000 claims description 40
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 claims description 29
- 239000000463 material Substances 0.000 claims description 28
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims description 25
- 239000003054 catalyst Substances 0.000 claims description 22
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 claims description 20
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 18
- 238000001816 cooling Methods 0.000 claims description 18
- OXHNLMTVIGZXSG-UHFFFAOYSA-N 1-Methylpyrrole Chemical compound CN1C=CC=C1 OXHNLMTVIGZXSG-UHFFFAOYSA-N 0.000 claims description 17
- 238000006243 chemical reaction Methods 0.000 claims description 16
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 claims description 15
- 238000010438 heat treatment Methods 0.000 claims description 13
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 13
- 239000005057 Hexamethylene diisocyanate Substances 0.000 claims description 11
- QORUGOXNWQUALA-UHFFFAOYSA-N N=C=O.N=C=O.N=C=O.C1=CC=C(C(C2=CC=CC=C2)C2=CC=CC=C2)C=C1 Chemical compound N=C=O.N=C=O.N=C=O.C1=CC=C(C(C2=CC=CC=C2)C2=CC=CC=C2)C=C1 QORUGOXNWQUALA-UHFFFAOYSA-N 0.000 claims description 11
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical group O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 claims description 11
- 238000004821 distillation Methods 0.000 claims description 10
- 238000000034 method Methods 0.000 claims description 10
- SIBFQOUHOCRXDL-UHFFFAOYSA-N 3-bromopropane-1,2-diol Chemical compound OCC(O)CBr SIBFQOUHOCRXDL-UHFFFAOYSA-N 0.000 claims description 9
- 238000005406 washing Methods 0.000 claims description 9
- 239000012298 atmosphere Substances 0.000 claims description 8
- 239000012948 isocyanate Substances 0.000 claims description 8
- 150000002513 isocyanates Chemical class 0.000 claims description 8
- 238000002156 mixing Methods 0.000 claims description 8
- 239000000178 monomer Substances 0.000 claims description 8
- TVIDDXQYHWJXFK-UHFFFAOYSA-N dodecanedioic acid Chemical compound OC(=O)CCCCCCCCCCC(O)=O TVIDDXQYHWJXFK-UHFFFAOYSA-N 0.000 claims description 7
- 239000003960 organic solvent Substances 0.000 claims description 7
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 6
- 229910052751 metal Inorganic materials 0.000 claims description 6
- 239000002184 metal Substances 0.000 claims description 6
- LWBHHRRTOZQPDM-UHFFFAOYSA-N undecanedioic acid Chemical compound OC(=O)CCCCCCCCCC(O)=O LWBHHRRTOZQPDM-UHFFFAOYSA-N 0.000 claims description 6
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 4
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 claims description 4
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 claims description 4
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 claims description 4
- 239000007788 liquid Substances 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 3
- SSZWWUDQMAHNAQ-UHFFFAOYSA-N 3-chloropropane-1,2-diol Chemical compound OCC(O)CCl SSZWWUDQMAHNAQ-UHFFFAOYSA-N 0.000 claims description 2
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 claims description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 2
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 claims description 2
- 125000002524 organometallic group Chemical group 0.000 claims description 2
- 239000000126 substance Substances 0.000 claims description 2
- 239000010936 titanium Substances 0.000 claims description 2
- 229910052719 titanium Inorganic materials 0.000 claims description 2
- 238000010411 cooking Methods 0.000 abstract 1
- 229920000642 polymer Polymers 0.000 abstract 1
- 230000000052 comparative effect Effects 0.000 description 18
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 13
- 239000012299 nitrogen atmosphere Substances 0.000 description 11
- RLJWTAURUFQFJP-UHFFFAOYSA-N propan-2-ol;titanium Chemical compound [Ti].CC(C)O.CC(C)O.CC(C)O.CC(C)O RLJWTAURUFQFJP-UHFFFAOYSA-N 0.000 description 11
- VXUYXOFXAQZZMF-UHFFFAOYSA-N tetraisopropyl titanate Substances CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 description 11
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 description 9
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 9
- 239000012975 dibutyltin dilaurate Substances 0.000 description 9
- 239000002131 composite material Substances 0.000 description 8
- 238000007599 discharging Methods 0.000 description 8
- 238000012360 testing method Methods 0.000 description 7
- 238000001291 vacuum drying Methods 0.000 description 6
- QFGCFKJIPBRJGM-UHFFFAOYSA-N 12-[(2-methylpropan-2-yl)oxy]-12-oxododecanoic acid Chemical compound CC(C)(C)OC(=O)CCCCCCCCCCC(O)=O QFGCFKJIPBRJGM-UHFFFAOYSA-N 0.000 description 5
- 239000005025 cast polypropylene Substances 0.000 description 5
- 238000010025 steaming Methods 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 description 4
- 239000001361 adipic acid Substances 0.000 description 4
- 235000011037 adipic acid Nutrition 0.000 description 4
- 229910052782 aluminium Inorganic materials 0.000 description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 4
- 238000013329 compounding Methods 0.000 description 4
- 239000011888 foil Substances 0.000 description 4
- 239000004033 plastic Substances 0.000 description 4
- 229920003023 plastic Polymers 0.000 description 4
- -1 polyethylene terephthalate Polymers 0.000 description 4
- 230000007613 environmental effect Effects 0.000 description 3
- DNIAPMSPPWPWGF-VKHMYHEASA-N (+)-propylene glycol Chemical compound C[C@H](O)CO DNIAPMSPPWPWGF-VKHMYHEASA-N 0.000 description 2
- DNIAPMSPPWPWGF-GSVOUGTGSA-N (R)-(-)-Propylene glycol Chemical compound C[C@@H](O)CO DNIAPMSPPWPWGF-GSVOUGTGSA-N 0.000 description 2
- YPFDHNVEDLHUCE-UHFFFAOYSA-N 1,3-propanediol Substances OCCCO YPFDHNVEDLHUCE-UHFFFAOYSA-N 0.000 description 2
- 229940035437 1,3-propanediol Drugs 0.000 description 2
- 102000009027 Albumins Human genes 0.000 description 2
- 108010088751 Albumins Proteins 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- 239000004743 Polypropylene Substances 0.000 description 2
- 229920001328 Polyvinylidene chloride Polymers 0.000 description 2
- 241000519995 Stachys sylvatica Species 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000005266 casting Methods 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000000855 fermentation Methods 0.000 description 2
- 230000004151 fermentation Effects 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 229920000139 polyethylene terephthalate Polymers 0.000 description 2
- 239000005020 polyethylene terephthalate Substances 0.000 description 2
- 229920001155 polypropylene Polymers 0.000 description 2
- 229920000166 polytrimethylene carbonate Polymers 0.000 description 2
- 239000005033 polyvinylidene chloride Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 239000004677 Nylon Substances 0.000 description 1
- 241000218602 Pinus <genus> Species 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000004359 castor oil Substances 0.000 description 1
- 235000019438 castor oil Nutrition 0.000 description 1
- 238000012937 correction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000006477 desulfuration reaction Methods 0.000 description 1
- 230000023556 desulfurization Effects 0.000 description 1
- 230000029087 digestion Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 238000009459 flexible packaging Methods 0.000 description 1
- 239000005021 flexible packaging material 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
- 239000011261 inert gas Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- 239000012785 packaging film Substances 0.000 description 1
- 229920006280 packaging film Polymers 0.000 description 1
- 238000007719 peel strength test Methods 0.000 description 1
- 239000002985 plastic film Substances 0.000 description 1
- 229920006255 plastic film Polymers 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Landscapes
- Polyesters Or Polycarbonates (AREA)
Abstract
The invention relates to the technical field of polymers, in particular to a bio-based polyester polyol and a preparation method and application thereof. The polyester polyol comprises the following raw materials: dibasic acid, dihydric alcohol and ionic liquid; wherein the dibasic acid comprises bio-based dibasic acid and aromatic dibasic acid; the dihydric alcohol comprises bio-based dihydric alcohol and dihydric alcohol containing pyrrole structure; the mol ratio of the bio-based dibasic acid, the aromatic dibasic acid and the ionic liquid is 1: (0.1-0.5): (0.05-0.3); the molar ratio of the bio-based diol to the diol containing the pyrrole structure is 1: (0.05-0.3); the ratio of the total molar quantity of the dibasic acid and the ionic liquid to the molar quantity of the dihydric alcohol is 100: (140-200); the ionic liquid is triethylamine adipate. The adhesive containing the bio-based polyester polyol has excellent peel strength, cooking resistance and appearance.
Description
Technical Field
The invention belongs to the field of high polymer materials, relates to a bio-based polyester polyol, a preparation method and application thereof, and in particular relates to a bio-based polyester polyol, a preparation method thereof and application thereof in adhesives for food packaging.
Background
The use of bio-based polyester polyols in adhesives is becoming increasingly widespread, mainly thanks to their unique properties and environmental protection properties, which can give adhesives excellent adhesion properties.
The food flexible package refers to a package with a changeable shape, such as aluminum foil, plastic film or a compound thereof, when no filler is present, the packaging film is compounded by using an adhesive in the flexible package, and proper adhesive is selected to have a key effect on the quality of the flexible package, so that more flexible package adhesives are polyurethane adhesives at present, but the adhesives waste raw materials excessively.
The soft package solvent-free adhesive is an adhesive type with excellent performance and wide application prospect, the application of the soft package solvent-free adhesive in the field of soft packages is favorable for improving the quality and environmental protection performance of packages, the sustainable development of the packaging industry is promoted, the requirements on the peel strength of the adhesive are higher and higher along with the increase of the requirements and the wider application range of the soft packages, and in practical application, white spots can appear on the appearance of the solvent-free adhesive when the solvent-free adhesive is used, which is a relatively obvious disadvantage.
Disclosure of Invention
The first aspect of the present invention provides a bio-based polyester polyol comprising the following raw materials: the ratio of the total molar quantity of the dibasic acid and the ionic liquid to the molar quantity of the dibasic alcohol is 100: (140-200);
Wherein the dibasic acid is bio-based dibasic acid and aromatic dibasic acid, and the mol ratio of the bio-based dibasic acid, the aromatic dibasic acid and the ionic liquid is 1: (0.1-0.5): (0.05-0.3);
The dihydric alcohol is bio-based dihydric alcohol and dihydric alcohol containing a pyrrole structure, and the molar ratio of the bio-based dihydric alcohol to the dihydric alcohol containing the pyrrole structure is 1: (0.05-0.3);
the preparation method of the dihydric alcohol containing the pyrrole structure comprises the following steps: in an inert atmosphere in the presence of an organic solvent, the molar ratio is (1-1.2): 1, reacting N-methylpyrrole with halogenated dihydric alcohol at 50-70 ℃ for 12-20 hours to obtain a product material, removing an organic solvent and unreacted N-methylpyrrole by reduced pressure distillation, washing and drying the product material to obtain dihydric alcohol containing a pyrrole structure;
the chemical general formula of the dihydric alcohol containing the pyrrole structure is shown as the formula (1):
Formula (1);
In the formula (1), X is Cl or Br;
the ionic liquid is triethylamine adipate.
The method for synthesizing the ionic liquid (triethylamine adipate) in the context of the present invention is referred to as: li Xueliang, yang Le. Preparation of ionic liquid R 3NANR3 and desulfurization performance [ J ]. Environmental engineering report, 2012, 6 (9): preparation of 1.2 preparation part of ionic liquid in 3233-3237, specifically, the synthetic method comprises: the molar ratio of adipic acid to triethylamine is 1:2, ethanol is used as a solvent, and the amount of ethanol is 5 times of the mass of adipic acid. And (3) dropwise adding triethylamine at the temperature of 35 ℃ for reaction for 8 hours, and carrying out reduced pressure rotary distillation on the mixed liquid at the temperature of 70 ℃ to remove unreacted raw materials and solvent, thereby obtaining the ionic liquid (triethylamine adipate).
In the present invention, adipic acid (CAS number 124-04-9), triethylamine (CAS number 121-44-8) and ethanol are commercially available, for example, adipic acid, triethylamine and ethanol in the context of the present invention are purchased from Shanghai Ala Biochemical technologies Co., ltd.) and all have analytically pure purity.
As a preferable technical scheme of the invention, the mol ratio of the bio-based dibasic acid, the aromatic dibasic acid and the ionic liquid is 1: (0.2-0.3): (0.1-0.2), preferably 1: (0.2-0.3): (0.14-0.18).
As a preferable technical scheme of the invention, the mol ratio of the bio-based dihydric alcohol to the dihydric alcohol containing the pyrrole structure is 1: (0.1-0.2), preferably 1: (0.15-0.19).
As a preferred embodiment of the present invention, the halogenated diol is selected from 3-chloro-1, 2-propanediol and 3-bromo-1, 2-propanediol. 3-bromo-1, 2-propanediol is preferred.
N-methylpyrrole in the present invention is commercially available, for example, N-methylpyrrole in the context of the present invention (CAS number: 96-54-8) is available from Shanghai Ala Biotechnology Co., ltd. In analytical purity.
In the present invention, 3-bromo-1, 2-propanediol (CAS number 4704-77-2) is commercially available, e.g., 3-bromo-1, 2-propanediol in the context of the present invention is available from Shanghai Ala Biotechnology Co., ltd.) in analytical purity.
In the present invention, the inert atmosphere is an inert gas atmosphere commonly used in the art, such as nitrogen.
As a preferable technical scheme of the invention, when preparing dihydric alcohol containing pyrrole structure, the organic solvent is at least one selected from chloroform, dichloromethane or carbon tetrachloride, preferably carbon tetrachloride.
In the present invention, carbon tetrachloride and ethyl acetate are commercially available, for example, in the context of the present invention, both are purchased from Shanghai Ala Biotechnology Co., ltd, and are all analytically pure.
As a preferable technical scheme of the invention, when preparing dihydric alcohol containing pyrrole structure, the mass ratio of the organic solvent to N-methyl pyrrole is 1: (1-2), for example, 1:1. 1:1.2, 1:1.3, 1:1.4, 1:1.5, 1:1.6, 1:1.7, 1:1.8, 1:1.9, 1:2.
As a preferred embodiment of the present invention, conditions for reduced pressure distillation include: the temperature is 120-140 ℃ and the pressure is 0.5-1.2Pa.
As a preferable technical scheme of the invention, the washing liquid is ethyl acetate, the washing times are 2-5 times, and the washing operation means are conventional means in the field, and are not repeated here.
In the present invention, in the preparation of the diol having a pyrrole structure, the drying mode is not particularly limited, and vacuum drying may be selected, for example, vacuum drying is performed at a temperature of 75 ℃ and a vacuum degree of 0.01MPa, wherein the end point of the vacuum drying is: the washing liquid is removed, and a detailed description is omitted.
As a more preferable technical scheme of the invention, the preparation method of the dihydric alcohol containing a pyrrole structure comprises the following steps: the mass ratio of the N-methyl pyrrole to the N-methyl pyrrole is 1:1-2 of carbon tetrachloride, the molar ratio of which is (1-1.2): 1 and 3-bromo-1, 2-propanediol, heating to 50-70 ℃ in nitrogen atmosphere, and reacting for 12-20 hours to obtain a product material; the product material is distilled under reduced pressure at the temperature of 120-140 ℃ and the pressure of 0.5-1.2Pa to remove carbon tetrachloride and unreacted N-methylpyrrole, the material after reduced pressure distillation is collected and washed for 2-5 times by ethyl acetate, and then vacuum drying is carried out at the temperature of 75 ℃ and the vacuum degree of 0.01MPa to obtain the dihydric alcohol containing pyrrole structure.
In the invention, the bio-based dibasic acid can ensure that the polyester polyol has a certain bio-based component and also has a certain biodegradability, and as a preferable technical scheme of the invention, the bio-based dibasic acid is at least one selected from bio-based succinic acid, bio-based sebacic acid, bio-based undecanedioic acid and bio-based dodecanedioic acid, and is preferably bio-based sebacic acid and/or bio-based dodecanedioic acid.
In the present invention, bio-based dibasic acid refers to dibasic acid derived from biological matrix, such as succinic acid, also called succinic acid, the natural source of which is amber formed by burying resin of Pinus plant in the ground for a long time; sebacic acid occurs naturally in castor oil; undecanedioic acid is mainly produced by biological fermentation.
The bio-based sebacic acid (CAS number 111-20-6) in the present invention is commercially available, for example, from Albumin Biotechnology Co., ltd. In Shanghai, with a purity of 99%.
The bio-based dodecanedioic acid (CAS number 693-23-2) of the present invention is commercially available, for example, from Albumin Biotechnology Co., ltd. Shanghai, at 99% purity.
As a preferred embodiment of the present invention, the aromatic dibasic acid is at least one selected from phthalic anhydride, isophthalic acid and terephthalic acid, and preferably terephthalic acid.
Terephthalic acid (CAS number 100-21-0) in this invention is commercially available, e.g., from Shanghai Seiyaku Biotechnology Co., ltd., purity 99% in the context of this invention.
As a preferred embodiment of the present invention, the bio-based diol is selected from bio-based 1, 4-butanediol and/or bio-based 1, 3-propanediol, preferably bio-based 1, 4-butanediol.
The biobased 1, 4-butanediol (CAS number 110-63-4) of the present invention is commercially available, e.g., 1, 4-butanediol in the context of the present invention is available from Shanghai Ala Biotechnology Co., ltd. In 98% purity.
In the present invention, 1, 4-butanediol, 1, 3-propanediol may be produced in nature, for example, by fermentation synthesis of some microorganisms.
As a preferable technical scheme of the invention, the acid value of the polyester polyol is 0.1-0.5mgKOH/g, and the hydroxyl value is 25-225mgKOH/g.
As a more preferable embodiment of the present invention, the polyester polyol has an acid value of 0.1 to 0.5mgKOH/g and a hydroxyl value of 50 to 150mgKOH/g.
The raw materials in the invention can also contain or not contain a catalyst according to the need, and are used for promoting the synthesis of the polyester polyol from the dibasic acid and the dihydric alcohol, and preferably, the raw materials of the polyester polyol also contain the catalyst; preferably, the catalyst is used in an amount of 0 to 400ppm, preferably 100 to 220ppm, based on the total mass of diacid and diol.
The second aspect of the present invention provides a process for producing the bio-based polyester polyol, comprising:
(1) In inert atmosphere, mixing dibasic acid, dihydric alcohol and ionic liquid, and reacting for 1-2 h at 150-170 ℃;
(2) Continuously heating to 210-230 ℃, adding a catalyst, and continuously reacting for 3-4 hours;
(3) The pressure is reduced to 10-15torr, and the reaction is continued at 210-230 ℃ until the acid value of the system is 0.1-0.5mgKOH/g and the hydroxyl value is 25-225mgKOH/g, thus obtaining the bio-based polyester polyol.
The inert atmosphere in the present invention is an inert atmosphere conventional in the art, such as nitrogen.
In the present invention, the catalyst is added, which means that the catalyst can be added according to the reaction requirement, and as a preferable technical scheme of the present invention, the catalyst is used in an amount of 0-400ppm, preferably 100-220ppm, based on the total mass of the dibasic acid and the dibasic alcohol.
As a preferred embodiment of the present invention, the catalyst is selected from organic titanium catalysts, preferably from n-butyl titanate and/or tetraisopropyl titanate, preferably tetraisopropyl titanate.
The tetraisopropyl titanate in the present invention is commercially available, for example, from the company Shanghai Ala Biotechnology Co., ltd, with a purity of 95%.
In a third aspect, the invention provides the use of the bio-based polyester polyol of the invention in an adhesive for food packaging.
According to a fourth aspect of the present invention, there is provided an adhesive for food packaging, the raw materials of the adhesive for food packaging comprising: the bio-based polyester polyol, isocyanate monomer and organic metal catalyst are disclosed.
As a preferable technical scheme of the invention, the raw materials of the adhesive for food packaging comprise the following components in parts by weight: 100 parts of bio-based polyester polyol, 30-60 parts of isocyanate monomer and 0.01-1 part of organic metal catalyst.
As a more preferable technical scheme of the invention, the raw materials of the adhesive for food packaging comprise, by weight: 100 parts of bio-based polyester polyol, 45-55 parts of isocyanate monomer and 0.02-0.04 part of organic metal catalyst.
As a preferred technical scheme of the invention, the weight ratio of hexamethylene diisocyanate to triphenylmethane triisocyanate is preferably 1: (0.1-1), more preferably 1: (0.2-0.3).
The organometallic catalysts in the present invention may be of the type conventional in the art, and dibutyltin dilaurate is exemplified in the present invention, but are not to be construed as limiting the invention.
The fifth aspect of the present invention provides a method for preparing an adhesive for food packaging, the method comprising:
S1, dehydrating bio-based polyester polyol and an organic metal catalyst at the temperature of 110-120 ℃ and the vacuum degree of-0.06 to-0.1 MPa for 40-60min;
s2, cooling to 50-90 ℃, and adding isocyanate monomer to react until the NCO weight percent of the system is 1-7 weight percent, thus obtaining the adhesive.
The adhesive for food packaging can be applied to food flexible packaging bonding.
The flexible packaging material in the invention comprises one or a combination of at least two of PET (polyethylene terephthalate), PA, (polyamide), NY (nylon), aluminum foil, CPP (cast polypropylene film), RCPP (high temperature steam resistant cast polypropylene film), PE (polyethylene) and PVDC (polyvinylidene chloride).
The components of aluminum foil and RCPP (high temperature retort cast polypropylene film) are used as non-limiting illustration in the present invention.
When the adhesive for food packaging is used, the film layer is compounded by a compounding machine at the temperature of 60-70 ℃, the coating dry weight is generally 1-2g/m 2, and after the film is compounded, the film is cured at the temperature of 45-50 ℃ for 10-15 hours to obtain the composite film.
Compared with the prior art, the invention has at least the following beneficial effects:
the bio-based polyester polyol has better performance balance and leveling property when in use, and the adhesive containing the bio-based polyester polyol has excellent peel strength and steaming resistance, has excellent appearance, and can better meet the actual production requirements, and particularly:
1. According to the invention, the ionic liquid or the dihydric alcohol of the pyrrole is independently added into the raw material of the polyester polyol, so that the peel strength of the adhesive can be increased when the polyester polyol is used for the adhesive, but the peel strength of the adhesive can be further increased and the steaming resistance of the adhesive can be increased when the ionic liquid or the dihydric alcohol of the pyrrole is simultaneously used.
2. When the ionic liquid can enable the polyester polyol to increase the peeling strength of the adhesive for food packaging, the introduction of the dihydric alcohol containing the pyrrole structure can further enable the polyester polyol to increase the peeling strength of the adhesive for food packaging, and simultaneously increase the boiling resistance of the adhesive for food packaging; when the dihydric alcohol containing the pyrrole structure can enable the polyester polyol to increase the peeling strength of the adhesive for food packaging, the ionic liquid is introduced to further enable the polyester polyol to increase the peeling strength of the adhesive for food packaging, and meanwhile the appearance of the composite film is obviously improved.
3. In the invention, the ionic liquid and the dihydric alcohol containing the pyrrole structure need to be controlled, the excessive material is unfavorable for the overall performance of the adhesive, presumably because the excessive addition of the ionic liquid can influence the viscosity of the adhesive at room temperature, the compounding fastness is unfavorable, and the excessive addition of the dihydric alcohol containing the pyrrole structure can influence the leveling property.
Detailed Description
The present invention is described in detail below by way of examples, which are only illustrative of specific technical solutions of the present invention and do not limit the scope of the present invention, i.e., it should be understood that insubstantial simple corrections, adaptations and combinations made by those skilled in the art based on the inventive concept of the present invention are within the scope of the present invention as claimed.
In the following examples, all materials were commercially available unless otherwise specified.
Examples
Example 1
An embodiment of the invention provides a method for preparing a diol containing a pyrrole structure, comprising the following steps:
The mass ratio of the N-methyl pyrrole to the N-methyl pyrrole is 1:1.2 carbon tetrachloride in a molar ratio of 1.05:1 and 3-bromo-1, 2-propanediol, heating to 60 ℃ in nitrogen atmosphere, and reacting for 14 hours to obtain a product material; the product material is subjected to reduced pressure distillation at 120 ℃ and the pressure is 1.2Pa to remove carbon tetrachloride and unreacted N-methylpyrrole, the material subjected to reduced pressure distillation is collected and washed 3 times by ethyl acetate, and then the material is subjected to vacuum drying at 75 ℃ and the vacuum degree is 0.01MPa to obtain the dihydric alcohol A containing the pyrrole structure.
The chemical reaction equation involved in the preparation of the pyrrole structure-containing diol includes:
the preparation of the bio-based polyester polyol according to an embodiment of the present invention comprises the steps of:
(1) In a nitrogen atmosphere, the molar ratio is 70:20:10:120:20, namely mixing biological base sebacic acid, terephthalic acid, ionic liquid (the ionic liquid is triethylamine adipate), biological base 1, 4-butanediol and dihydric alcohol A containing a pyrrole structure to obtain a mixed material, and reacting at 170 ℃ for 1h;
(2) After continuously heating to 230 ℃, adding tetraisopropyl titanate (the dosage is 150ppm based on the total mass of the mixed materials), and continuously reacting for 4 hours;
(3) And (3) reducing the pressure to 10torr, continuously reacting at 230 ℃ until the acid value of the system is 0.5mgKOH/g and the hydroxyl value is 50mgKOH/g, and cooling and discharging to obtain the bio-based polyester polyol A.
Example 2
An embodiment of the invention provides a method for preparing a diol containing a pyrrole structure, comprising the following steps:
The mass ratio of the N-methyl pyrrole to the N-methyl pyrrole is 1:1.5 carbon tetrachloride in a molar ratio of 1.2:1 and 3-bromo-1, 2-propanediol, heating to 65 ℃ in nitrogen atmosphere, and reacting for 13 hours to obtain a product material; and (3) carrying out reduced pressure distillation on the product material at the temperature of 140 ℃ and the pressure of 0.8Pa to remove carbon tetrachloride and unreacted N-methylpyrrole, collecting the material subjected to reduced pressure distillation, washing 3 times by using ethyl acetate, and then carrying out vacuum drying at the temperature of 75 ℃ and the vacuum degree of 0.01MPa to obtain the dihydric alcohol B containing the pyrrole structure.
The chemical reaction equation involved in the preparation of the pyrrole structure-containing diol includes:
the preparation of the bio-based polyester polyol according to an embodiment of the present invention comprises the steps of:
(1) In a nitrogen atmosphere, the molar ratio was 75:15:10:160:30, terephthalic acid, an ionic liquid (the ionic liquid is triethylamine adipate), bio-based 1, 4-butanediol and dihydric alcohol B containing a pyrrole structure, and reacting for 1.5h at 160 ℃;
(2) After continuously heating to 220 ℃, adding tetraisopropyl titanate (the dosage is 120ppm based on the total mass of the mixed materials), and continuously reacting for 3 hours;
(3) And (3) reducing the pressure to 12torr, continuously reacting at 220 ℃ until the acid value of the system is 0.4mgKOH/g and the hydroxyl value is 110mgKOH/g, and cooling and discharging to obtain the bio-based polyester polyol B.
Example 3
The preparation of the bio-based polyester polyol according to an embodiment of the present invention comprises the steps of:
(1) In a nitrogen atmosphere, the molar ratio is 70:18:12:175:25, namely mixing biological base sebacic acid, terephthalic acid, ionic liquid (the ionic liquid is triethylamine adipate), biological base 1, 4-butanediol and dihydric alcohol A containing a pyrrole structure to obtain a mixed material, and reacting for 2 hours at 150 ℃;
(2) After continuously heating to 210 ℃, adding tetraisopropyl titanate (the dosage is 150ppm based on the total mass of the mixed materials), and continuously reacting for 4 hours;
(3) And (3) reducing the pressure to 10torr, continuously reacting at 210 ℃ until the acid value of the system is 0.1mgKOH/g and the hydroxyl value is 150mgKOH/g, and cooling and discharging to obtain the bio-based polyester polyol C.
Comparative example 1
The preparation of the bio-based polyester polyol of a comparative example of the present invention comprises the steps of:
(1) In a nitrogen atmosphere, the molar ratio was 83:17:190, mixing the bio-based dodecanedioic acid, terephthalic acid and bio-based 1, 4-butanediol, and reacting at 160 ℃ for 1.5h;
(2) After continuously heating to 220 ℃, adding tetraisopropyl titanate (the dosage is 120ppm based on the total mass of the mixed materials), and continuously reacting for 3 hours;
(3) The pressure is reduced to 12torr, the reaction is continued at 220 ℃ until the acid value of the system is 0.4mgKOH/g and the hydroxyl value is 110mgKOH/g, and the bio-based polyester polyol D1 is obtained after cooling and discharging.
Comparative example 2
The preparation of the bio-based polyester polyol of a comparative example of the present invention comprises the steps of:
(1) In a nitrogen atmosphere, the molar ratio was 83:17:160:30, mixing bio-based dodecanedioic acid, terephthalic acid, bio-based 1, 4-butanediol and dihydric alcohol B containing a pyrrole structure, and reacting for 1.5h at 160 ℃;
(2) After continuously heating to 220 ℃, adding tetraisopropyl titanate (the dosage is 120ppm based on the total mass of the mixed materials), and continuously reacting for 3 hours;
(3) And (3) reducing the pressure to 12torr, continuously reacting at 220 ℃ until the acid value of the system is 0.4mgKOH/g and the hydroxyl value is 110mgKOH/g, and cooling and discharging to obtain the bio-based polyester polyol D2.
Comparative example 3
The preparation of the bio-based polyester polyol of a comparative example of the present invention comprises the steps of:
(1) In a nitrogen atmosphere, the molar ratio was 75:15:10:190, performing a reaction for 1.5 hours at 160 ℃ on a mixed material obtained by mixing bio-based dodecanedioic acid, terephthalic acid, ionic liquid (the ionic liquid is triethylamine adipate) and bio-based 1, 4-butanediol;
(2) After continuously heating to 220 ℃, adding tetraisopropyl titanate (the dosage is 120ppm based on the total mass of the mixed materials), and continuously reacting for 3 hours;
(3) And (3) reducing the pressure to 12torr, continuously reacting at 220 ℃ until the acid value of the system is 0.4mgKOH/g and the hydroxyl value is 110mgKOH/g, and cooling and discharging to obtain the bio-based polyester polyol D3.
Comparative example 4
The preparation of the bio-based polyester polyol of a comparative example of the present invention comprises the steps of:
(1) In a nitrogen atmosphere, the molar ratio is 65:13:22:160:30, terephthalic acid, an ionic liquid (the ionic liquid is triethylamine adipate), bio-based 1, 4-butanediol and dihydric alcohol B containing a pyrrole structure, and reacting for 1.5h at 160 ℃;
(2) After continuously heating to 220 ℃, adding tetraisopropyl titanate (the dosage is 120ppm based on the total mass of the mixed materials), and continuously reacting for 3 hours;
(3) And (3) reducing the pressure to 12torr, continuously reacting at 220 ℃ until the acid value of the system is 0.4mgKOH/g and the hydroxyl value is 110mgKOH/g, and cooling and discharging to obtain the bio-based polyester polyol D4.
Comparative example 5
The preparation of the bio-based polyester polyol of a comparative example of the present invention comprises the steps of:
(1) In a nitrogen atmosphere, the molar ratio was 75:15:10:130:60, namely mixing biological base dodecanedioic acid, terephthalic acid, ionic liquid (the ionic liquid is triethylamine adipate), biological base 1, 4-butanediol and dihydric alcohol B containing a pyrrole structure to obtain a mixed material, and reacting at 160 ℃ for 1.5h;
(2) After continuously heating to 220 ℃, adding tetraisopropyl titanate (the dosage is 120ppm based on the total mass of the mixed materials), and continuously reacting for 3 hours;
(3) And (3) reducing the pressure to 12torr, continuously reacting at 220 ℃ until the acid value of the system is 0.4mgKOH/g and the hydroxyl value is 110mgKOH/g, and cooling and discharging to obtain the bio-based polyester polyol D5.
Application example 1
The preparation of the adhesive A for food packaging in an embodiment of the invention comprises the following steps:
S1: 100 parts of bio-based polyester polyol A and 0.02 part of dibutyltin dilaurate are dehydrated for 45min under the conditions of the temperature of 115 ℃ and the vacuum degree of-0.09 MPa in parts by weight;
s2: cooling to 60 ℃, adding 45 parts of hexamethylene diisocyanate and 10 parts of triphenylmethane triisocyanate for reaction until the NCO weight percent of the system is 3.3 weight percent, and obtaining the adhesive A for food packaging.
Application example 2
The preparation of the adhesive B for food packaging in an embodiment of the invention comprises the following steps:
S1: 100 parts of bio-based polyester polyol B and 0.03 part of dibutyltin dilaurate are dehydrated for 60min under the conditions of the temperature of 115 ℃ and the vacuum degree of-0.09 MPa in parts by weight;
s2: cooling to 65 ℃, adding 40 parts of hexamethylene diisocyanate and 8 parts of triphenylmethane triisocyanate for reaction until the NCO weight percent of the system is 3.6 weight percent, and obtaining the adhesive B for food packaging.
Application example 3
The preparation of the adhesive C for food packaging in an embodiment of the invention comprises the following steps:
S1: 100 parts of bio-based polyester polyol C and 0.02 part of dibutyltin dilaurate are dehydrated for 60min under the conditions of the temperature of 120 ℃ and the vacuum degree of-0.07 MPa in parts by weight;
s2: cooling to 80 ℃, adding 42 parts of hexamethylene diisocyanate and 12 parts of triphenylmethane triisocyanate for reaction until the NCO weight percent of the system is 4.2 weight percent, and obtaining the adhesive C for food packaging.
Application example 4
The preparation of the adhesive D1 for food packaging of a comparative example comprises the following steps:
S1: 100 parts of bio-based polyester polyol D1 and 0.03 part of dibutyltin dilaurate are dehydrated for 60min under the conditions of the temperature of 115 ℃ and the vacuum degree of-0.09 MPa in parts by weight;
s2: cooling to 65 ℃, adding 40 parts of hexamethylene diisocyanate and 8 parts of triphenylmethane triisocyanate for reaction until the NCO weight percent of the system is 3.6 weight percent, and obtaining the adhesive D1 for food packaging.
Application example 5
The preparation of the adhesive D2 for food packaging of a comparative example comprises the following steps:
S1: 100 parts of bio-based polyester polyol D2 and 0.03 part of dibutyltin dilaurate are dehydrated for 60min under the conditions of the temperature of 115 ℃ and the vacuum degree of-0.09 MPa in parts by weight;
s2: cooling to 65 ℃, adding 40 parts of hexamethylene diisocyanate and 8 parts of triphenylmethane triisocyanate for reaction until the NCO weight percent of the system is 3.6 weight percent, and obtaining the adhesive D2 for food packaging.
Application example 6
The preparation of the adhesive D3 for food packaging of a comparative example comprises the following steps:
S1: 100 parts of bio-based polyester polyol D3 and 0.03 part of dibutyltin dilaurate are dehydrated for 60min under the conditions of the temperature of 115 ℃ and the vacuum degree of-0.09 MPa in parts by weight;
S2: cooling to 65 ℃, adding 40 parts of hexamethylene diisocyanate and 8 parts of triphenylmethane triisocyanate for reaction until the NCO weight percent of the system is 3.6 weight percent, and obtaining the adhesive D3 for food packaging.
Application example 7
The preparation of the adhesive D4 for food packaging of a comparative example comprises the following steps:
s1: 100 parts of bio-based polyester polyol D4 and 0.03 part of dibutyltin dilaurate are dehydrated for 60min under the conditions of the temperature of 115 ℃ and the vacuum degree of-0.09 MPa in parts by weight;
s2: cooling to 65 ℃, adding 40 parts of hexamethylene diisocyanate and 8 parts of triphenylmethane triisocyanate for reaction until the NCO weight percent of the system is 3.6 weight percent, and obtaining the adhesive D4 for food packaging.
Application example 8
The preparation of the adhesive D5 for food packaging of a comparative example comprises the following steps:
s1: 100 parts of bio-based polyester polyol D5 and 0.03 part of dibutyltin dilaurate are dehydrated for 60min under the conditions of the temperature of 115 ℃ and the vacuum degree of-0.09 MPa in parts by weight;
s2: cooling to 65 ℃, adding 40 parts of hexamethylene diisocyanate and 8 parts of triphenylmethane triisocyanate for reaction until the NCO weight percent of the system is 3.6 weight percent, and obtaining the adhesive D5 for food packaging.
Test case
Preparing a composite film by using adhesives A, B, C, D, D2, D3, D4 and D5 for food packaging, wherein the preparation steps are as follows: at 65 ℃, using an adhesive for food packaging to compound an RCPP/AL film (namely compounding a high-temperature-resistant steaming casting polypropylene film and an aluminum foil, wherein the high-temperature-resistant steaming casting polypropylene film is 50cm long, 50cm wide, 50um thick, 50cm long, 50cm wide and 12um thick) on a compounding machine, the machine speed is 100m/min, the coating amount is 1.8g/m 2, after the food packaging adhesive is compounded, curing the film in a curing chamber at 50 ℃ for 15 hours to obtain an aluminum-plastic composite film, observing the appearance bubble white point condition of the cured aluminum-plastic composite film, and simultaneously testing the peeling strength and the steaming resistance.
Peel strength test: the Al layer and the CPP layer in the aluminum-plastic composite film were tested according to GB/T8808-1988 (test sample is a sample cut into 200 mm. Times.15 mm) at a speed of 300mm/min, and the longitudinal peel strength thereof was tested.
Retort resistance: the aluminum-plastic composite film is steamed for 40min at 135 ℃ and then the peeling strength is tested according to the method, the reduction rate of the longitudinal peeling strength is calculated, the reduction rate of the peeling strength is less than or equal to 8 percent, and the grade 1 is recorded; the drop rate is more than 8 percent and less than 12 percent, which is marked as grade 2; the rate of decrease was 12 or more, designated as level 3.
The test results are shown in Table 1.
TABLE 1
From the test results of comparative example 1 and examples 1 to 3, it can be seen that the addition of ionic liquid and diol containing pyrrole structure can increase the peel strength and retort resistance of polyester polyol for adhesive for food packaging, and can overcome the defect that the appearance of the adhesive is easy to generate white spots.
As can be seen from the test results of comparative examples 2 to 3 and examples 1 to 3, the ionic liquid has a synergistic effect with the diol containing the pyrrole structure, and when the ionic liquid can increase the peel strength of the adhesive, the introduction of the diol containing the pyrrole structure can further increase the peel strength of the adhesive, and the digestion resistance of the adhesive is also increased; when the dihydric alcohol containing the pyrrole structure can increase the peeling strength of the adhesive, the ionic liquid can further increase the peeling strength of the adhesive, and meanwhile, the appearance of the composite film is obviously improved.
As can be seen from the test results of comparative examples 4 to 5 and examples 1 to 3, the amounts of the ionic liquid and the diol having a pyrrole structure added were not as large as possible.
Claims (10)
1. A bio-based polyester polyol, characterized in that the polyester polyol comprises the following raw materials: diacid, diol and ionic liquid, the ratio of the total molar amount of the diacid and the ionic liquid to the molar amount of the diol is 100: (140-200);
Wherein the dibasic acid is bio-based dibasic acid and aromatic dibasic acid, and the molar ratio of the bio-based dibasic acid to the aromatic dibasic acid to the ionic liquid is 1: (0.1-0.5): (0.05-0.3);
The dihydric alcohol is bio-based dihydric alcohol and dihydric alcohol containing a pyrrole structure, and the molar ratio of the bio-based dihydric alcohol to the dihydric alcohol containing the pyrrole structure is 1: (0.05-0.3);
the preparation method of the dihydric alcohol containing the pyrrole structure comprises the following steps: in an inert atmosphere in the presence of an organic solvent, the molar ratio is (1-1.2): 1, reacting N-methylpyrrole with halogenated dihydric alcohol at 50-70 ℃ for 12-20 hours to obtain a product material, and then sequentially carrying out reduced pressure distillation, washing and drying on the product material to obtain dihydric alcohol containing a pyrrole structure;
the chemical general formula of the dihydric alcohol containing the pyrrole structure is shown as the formula (1):
Formula (1);
In the formula (1), X is Cl or Br;
The ionic liquid is triethylamine adipate;
The bio-based diol is selected from bio-based 1, 4-butanediol.
2. The bio-based polyester polyol of claim 1, wherein the halogenated diol is selected from 3-chloro-1, 2-propanediol or 3-bromo-1, 2-propanediol.
3. The bio-based polyester polyol of claim 2, wherein the organic solvent is selected from at least one of chloroform, dichloromethane, or carbon tetrachloride; the mass ratio of the organic solvent to the N-methyl pyrrole is 1: (1-2); conditions for the reduced pressure distillation include: the temperature is 120-140 ℃ and the pressure is 0.5-1.2Pa; the washing liquid is ethyl acetate, and the washing times are 2-5 times.
4. The bio-based polyester polyol of claim 2, wherein the bio-based diacid is selected from at least one of bio-based succinic acid, bio-based sebacic acid, bio-based undecanedioic acid, or bio-based dodecanedioic acid; the aromatic dibasic acid is at least one selected from phthalic anhydride, isophthalic acid or terephthalic acid.
5. The bio-based polyester polyol according to claim 1, wherein the polyester polyol has an acid value of 0.1 to 0.5mgKOH/g and a hydroxyl value of 25 to 225mgKOH/g; the raw material of the polyester polyol also contains a catalyst, the dosage of the catalyst is 100-220ppm based on the total mass of the dibasic acid, the dihydric alcohol and the ionic liquid, and the catalyst is selected from organic titanium catalysts.
6. A process for the preparation of the bio-based polyester polyol according to any one of claims 1 to 5, comprising:
(1) In inert atmosphere, mixing dibasic acid, dihydric alcohol and ionic liquid, and reacting for 1-2 h at 150-170 ℃;
(2) Continuously heating to 210-230 ℃, adding a catalyst, and continuously reacting for 3-4 hours;
(3) The pressure is reduced to 10-15torr, and the reaction is continued at 210-230 ℃ until the acid value of the system is 0.1-0.5mgKOH/g and the hydroxyl value is 25-225mgKOH/g, thus obtaining the bio-based polyester polyol.
7. Use of the bio-based polyester polyol according to any one of claims 1 to 5 in adhesives for food packaging.
8. The adhesive for food packaging is characterized by comprising the following raw materials: the bio-based polyester polyol, isocyanate monomer and organometallic catalyst of any of claims 1-5.
9. The adhesive for food packaging according to claim 8, wherein the raw materials of the adhesive for food packaging comprise, in parts by weight: 100 parts of bio-based polyester polyol, 30-60 parts of isocyanate monomer and 0.01-1 part of organic metal catalyst; the isocyanate monomer is selected from hexamethylene diisocyanate and triphenylmethane triisocyanate, and the weight ratio of the hexamethylene diisocyanate to the triphenylmethane triisocyanate is 1: (0.1-1).
10. A method for preparing the adhesive for food packaging according to claim 8 or 9, characterized in that the method comprises:
S1, dehydrating bio-based polyester polyol and an organic metal catalyst at the temperature of 110-120 ℃ and the vacuum degree of-0.06 to-0.1 MPa for 40-60min;
s2, cooling to 50-90 ℃, adding isocyanate monomer, and reacting until the NCO weight percent of the system is 1-7 weight percent, thus obtaining the adhesive.
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| CN102784664A (en) * | 2011-05-19 | 2012-11-21 | 常州市华润复合材料有限公司 | Catalytic composition containing ionic liquid and application thereof |
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