CN110396182A - One kind polyester resin and the preparation method and application thereof as made from organism-based raw material - Google Patents
One kind polyester resin and the preparation method and application thereof as made from organism-based raw material Download PDFInfo
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- CN110396182A CN110396182A CN201910807180.7A CN201910807180A CN110396182A CN 110396182 A CN110396182 A CN 110396182A CN 201910807180 A CN201910807180 A CN 201910807180A CN 110396182 A CN110396182 A CN 110396182A
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- polyester resin
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- organism
- raw material
- based raw
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- 239000004645 polyester resin Substances 0.000 title claims abstract description 27
- 229920001225 polyester resin Polymers 0.000 title claims abstract description 25
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- 239000002994 raw material Substances 0.000 title claims abstract description 18
- JAABVEXCGCXWRR-UHFFFAOYSA-N norcantharidin Chemical compound C1CC2C3C(=O)OC(=O)C3C1O2 JAABVEXCGCXWRR-UHFFFAOYSA-N 0.000 claims abstract description 17
- KLDXJTOLSGUMSJ-JGWLITMVSA-N Isosorbide Chemical compound O[C@@H]1CO[C@@H]2[C@@H](O)CO[C@@H]21 KLDXJTOLSGUMSJ-JGWLITMVSA-N 0.000 claims abstract description 13
- 229960002479 isosorbide Drugs 0.000 claims abstract description 13
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 7
- 150000005846 sugar alcohols Polymers 0.000 claims abstract description 7
- 239000000463 material Substances 0.000 claims abstract description 6
- 230000009477 glass transition Effects 0.000 claims abstract description 4
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 4
- 238000006243 chemical reaction Methods 0.000 claims description 19
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 18
- 238000003756 stirring Methods 0.000 claims description 13
- 238000010792 warming Methods 0.000 claims description 10
- 229910052757 nitrogen Inorganic materials 0.000 claims description 9
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 claims description 8
- 239000006227 byproduct Substances 0.000 claims description 7
- 238000006068 polycondensation reaction Methods 0.000 claims description 7
- 238000005070 sampling Methods 0.000 claims description 7
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 6
- HYBBIBNJHNGZAN-UHFFFAOYSA-N furfural Chemical compound O=CC1=CC=CO1 HYBBIBNJHNGZAN-UHFFFAOYSA-N 0.000 claims description 6
- 238000009413 insulation Methods 0.000 claims description 6
- 229920000642 polymer Polymers 0.000 claims description 6
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 claims description 4
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 claims description 4
- 239000003054 catalyst Substances 0.000 claims description 3
- DNXDYHALMANNEJ-UHFFFAOYSA-N furan-2,3-dicarboxylic acid Chemical compound OC(=O)C=1C=COC=1C(O)=O DNXDYHALMANNEJ-UHFFFAOYSA-N 0.000 claims description 3
- 235000011187 glycerol Nutrition 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 claims description 3
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 claims description 3
- 239000001361 adipic acid Substances 0.000 claims description 2
- 235000011037 adipic acid Nutrition 0.000 claims description 2
- 239000003381 stabilizer Substances 0.000 claims description 2
- YPFDHNVEDLHUCE-UHFFFAOYSA-N 1,3-propanediol Substances OCCCO YPFDHNVEDLHUCE-UHFFFAOYSA-N 0.000 abstract description 9
- 125000003367 polycyclic group Chemical group 0.000 abstract description 4
- 239000002253 acid Substances 0.000 abstract description 2
- 230000007613 environmental effect Effects 0.000 abstract description 2
- DNIAPMSPPWPWGF-VKHMYHEASA-N (+)-propylene glycol Chemical compound C[C@H](O)CO DNIAPMSPPWPWGF-VKHMYHEASA-N 0.000 abstract 1
- 229920000166 polytrimethylene carbonate Polymers 0.000 abstract 1
- 230000003335 steric effect Effects 0.000 abstract 1
- 239000011248 coating agent Substances 0.000 description 22
- 238000000576 coating method Methods 0.000 description 22
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 13
- 239000000047 product Substances 0.000 description 10
- 238000012360 testing method Methods 0.000 description 9
- YBMRDBCBODYGJE-UHFFFAOYSA-N germanium dioxide Chemical compound O=[Ge]=O YBMRDBCBODYGJE-UHFFFAOYSA-N 0.000 description 8
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Natural products OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 7
- 229910052787 antimony Inorganic materials 0.000 description 5
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 5
- 230000006837 decompression Effects 0.000 description 5
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 5
- 238000004321 preservation Methods 0.000 description 5
- 229910001220 stainless steel Inorganic materials 0.000 description 5
- 239000010935 stainless steel Substances 0.000 description 5
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Natural products CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 4
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 4
- 239000000853 adhesive Substances 0.000 description 4
- 230000001070 adhesive effect Effects 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 229940119177 germanium dioxide Drugs 0.000 description 4
- 239000003973 paint Substances 0.000 description 4
- XZZNDPSIHUTMOC-UHFFFAOYSA-N triphenyl phosphate Chemical compound C=1C=CC=CC=1OP(OC=1C=CC=CC=1)(=O)OC1=CC=CC=C1 XZZNDPSIHUTMOC-UHFFFAOYSA-N 0.000 description 4
- 238000005452 bending Methods 0.000 description 3
- 229920013724 bio-based polymer Polymers 0.000 description 3
- 238000009835 boiling Methods 0.000 description 3
- 238000004080 punching Methods 0.000 description 3
- 238000007711 solidification Methods 0.000 description 3
- 230000008023 solidification Effects 0.000 description 3
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 2
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 235000013305 food Nutrition 0.000 description 2
- 239000011976 maleic acid Substances 0.000 description 2
- -1 maleic acid Acid anhydride Chemical class 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 239000001384 succinic acid Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 2
- POAOYUHQDCAZBD-UHFFFAOYSA-N 2-butoxyethanol Chemical compound CCCCOCCO POAOYUHQDCAZBD-UHFFFAOYSA-N 0.000 description 1
- AORTZIIKTZPIQU-UHFFFAOYSA-N 3-butyl-4-methyloxolane-2,5-dione Chemical compound CCCCC1C(C)C(=O)OC1=O AORTZIIKTZPIQU-UHFFFAOYSA-N 0.000 description 1
- 229920000742 Cotton Polymers 0.000 description 1
- 241000220324 Pyrus Species 0.000 description 1
- YSMRWXYRXBRSND-UHFFFAOYSA-N TOTP Chemical compound CC1=CC=CC=C1OP(=O)(OC=1C(=CC=CC=1)C)OC1=CC=CC=C1C YSMRWXYRXBRSND-UHFFFAOYSA-N 0.000 description 1
- XSTXAVWGXDQKEL-UHFFFAOYSA-N Trichloroethylene Chemical compound ClC=C(Cl)Cl XSTXAVWGXDQKEL-UHFFFAOYSA-N 0.000 description 1
- 239000002390 adhesive tape Substances 0.000 description 1
- 229920003180 amino resin Polymers 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000000593 degrading effect Effects 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 150000002240 furans Chemical class 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 1
- 235000021017 pears Nutrition 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- LLHKCFNBLRBOGN-UHFFFAOYSA-N propylene glycol methyl ether acetate Chemical compound COCC(C)OC(C)=O LLHKCFNBLRBOGN-UHFFFAOYSA-N 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- BAZAXWOYCMUHIX-UHFFFAOYSA-M sodium perchlorate Chemical compound [Na+].[O-]Cl(=O)(=O)=O BAZAXWOYCMUHIX-UHFFFAOYSA-M 0.000 description 1
- 229910001488 sodium perchlorate Inorganic materials 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 239000005028 tinplate Substances 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
- C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/52—Polycarboxylic acids or polyhydroxy compounds in which at least one of the two components contains aliphatic unsaturation
- C08G63/56—Polyesters derived from ester-forming derivatives of polycarboxylic acids or of polyhydroxy compounds other than from esters thereof
- C08G63/58—Cyclic ethers; Cyclic carbonates; Cyclic sulfites ; Cyclic orthoesters
-
- 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
- C08G63/85—Germanium, tin, lead, arsenic, antimony, bismuth, titanium, zirconium, hafnium, vanadium, niobium, tantalum, or compounds thereof
- C08G63/86—Germanium, antimony, or compounds thereof
- C08G63/863—Germanium or compounds thereof
-
- 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
- C08G63/85—Germanium, tin, lead, arsenic, antimony, bismuth, titanium, zirconium, hafnium, vanadium, niobium, tantalum, or compounds thereof
- C08G63/86—Germanium, antimony, or compounds thereof
- C08G63/866—Antimony or compounds thereof
-
- 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
- C08G63/87—Non-metals or inter-compounds thereof
Abstract
The present invention provides one kind polyester resin and preparation method thereof as made from organism-based raw material, the polyester resin passes through 7- oxabicyclo [2.2.1] heptane -2,3- dicarboxylic anhydride, isobide, 1,3-propanediol, and polyalcohol from biology base and polyacid carry out polymerization preparation, 7- oxabicyclo [2.2.1] heptane -2,3- dicarboxylic anhydride accounts for the 50-100% of all sour molar contents, the isobide accounts for the 20-60% of all alcohol molar contents, the 1,3-PD accounts for the 10-30% of all alcohol molar contents.Polyester resin of the invention uses the material of biology base, environmental protection and energy saving completely.The combination of the polycyclic binary acid and polycyclic isobide that use this rigidity of 7- oxabicyclo [2.2.1] heptane -2,3- dicarboxylic anhydride strong simultaneously, so that product has very high glass transition temperature.Due to the presence of multiring structure, the space steric effect of product is very high, can be well protected and is easy ester bond under attack, so that product has good resistance.
Description
Technical field
The invention belongs to technical field of macromolecule polymerization, and in particular to a kind of polyester resin as made from organism-based raw material and
Preparation method and application.
Background technique
Bio-based polymers are the environmentally protective polymer of one kind synthesized by biomonomer.Bio-based polymers generally have
Source is green, it is cheap and easy to get, be easy to the features such as degrading.Also, for saving petroleum resources, protection environment, development circulation warp
Ji etc. considers, replaces petrochemical production high molecular material to have become the hot spot that people study with reproducible living resources,
The synthesis and application of bio-based polymers are also increasingly valued by people.
During the polyester resin of biology base is also rapidly developing at present, but most product all also only partially makes
With bio-based materials, it is less able to replace completely, otherwise service performance has bigger decline.Can-coating, due to food
Directly contact the mechanical performance for resin, resistance, security performance has very high requirement, at present raw material of its synthesis still with
Based on petroleum-based raw material.
Summary of the invention
The present invention provides one kind polyester resin and the preparation method and application thereof as made from organism-based raw material.
The purpose of the present invention is achieved through the following technical solutions:
A kind of preparation method of the polyester resin as made from organism-based raw material passes through 7- oxabicyclo [2.2.1] heptane -2,3- bis-
Carboxylic acid anhydrides, isobide, 1,3-PD, and the polyalcohol from biology base and polyacid carry out polymerization preparation, wherein institute
The 50-100% that 7- oxabicyclo [2.2.1] heptane -2,3- dicarboxylic anhydride accounts for all sour molar contents is stated, the isobide accounts for
The 20-60% of all alcohol molar contents, the 1,3-PD account for the 10-30% of all alcohol molar contents.
Preferably, the preparation method of above-described a kind of polyester resin as made from organism-based raw material, including walk as follows
Suddenly,
S1, by 7- oxabicyclo [2.2.1] heptane -2,3- dicarboxylic anhydride, isobide, 1,3-PD, and from biology
The polyalcohol and polyacid of base are put into reaction kettle under nitrogen protection, and stirring reaches through temperature reaction three times to amount of by-products
Theoretical value；
S2, addition catalyst and stabilizer carry out being continuously heating to 275~295 DEG C in a kettle, and are decompressed to 100Pa or less
Polycondensation reaction is carried out, sampling analysis to polymer viscosity reaches desired value, discharges.
Preferably, in the S1 under nitrogen protection, it is warming up to 60~100 DEG C of insulation reactions for the first time, second of heating
To 220 DEG C of insulation reactions, it is warming up to 230~270 DEG C of insulation reactions for the third time.
Preferably, 7- oxabicyclo [2.2.1] heptane -2,3- dicarboxylic anhydride is prepared from bio-based materials furfural
And it obtains.It is oxidized to maleic acid specifically, first reacting with sodium perchlorate by furfural, then dehydration production maleic anhydride, maleic acid
Acid anhydride reacts back end hydrogenation with furans and 7- oxabicyclo [2.2.1] heptane -2,3- dicarboxylic anhydride is prepared.
Preferably, the polyalcohol from biology base be selected from 1,6- hexylene glycol, 1,4-butanediol, 1,2-PD, third
The one such or two or more any combination of triol.
Preferably, the polyacid from biology base is selected from 1, 4- succinic acid, adipic acid, furandicarboxylic acid wherein one
Kind or two kinds any combination.
Preferably, a kind of preparation method preparation of the polyester resin as made from organism-based raw material described in any of the above is poly-
Ester resin.
Preferably, the polyester resin number-average molecular weight is 15000~45000, and glass transition temperature is 80~120
℃。
The beneficial effects of the present invention are embodied in: polyester resin of the invention uses the material of biology base, environmental protection and energy saving completely.
Simultaneously using the strong polycyclic binary acid of this rigidity of 7- oxabicyclo [2.2.1] heptane -2,3- dicarboxylic anhydride and polycyclic different mountain
The combination of pears alcohol, so that product has very high glass transition temperature.Due to the presence of multiring structure, the steric hindrance of product
Effect is very high, can be well protected and is easy ester bond under attack, so that product has good resistance.7- oxabicyclo
The multiring structure of [2.2.1] heptane -2,3- dicarboxylic anhydride is improving the rigidity of product simultaneously, moreover it is possible to certain flexibility is provided,
So that the machinability of product is preferably promoted.
Specific embodiment
Below by way of specific embodiment, the present invention will be further elaborated.
Embodiment 1
By 7- oxabicyclo [2.2.1] heptane -2,3- dicarboxylic anhydride 9.3kg, furandicarboxylic acid 7kg, 1,3- propylene glycol 1.5kg,
Isobide 8kg, 1,6- hexylene glycol 3.5kg are put into 100L stainless steel cauldron, under nitrogen protection, with 55~
The stirring of 80rpm revolving speed, is rapidly heated to 60~100 DEG C after reacting 0.3 hour, is gradually warmed up to 220 DEG C of heat preservations that carry out reaction 1 small
When, then be warming up to 230~270 DEG C and react 2.2 hours or so, when amount of by-products reaches theoretical value out, reaction was completed.21g is added
Antimony glycol, the triphenyl phosphate of 10g germanium dioxide and 16g continues to heat up and slowly depressurize, revolving speed is adjusted to 30~
50rpm, temperature are controlled between 275~295 DEG C, and decompression step by step to 100Pa or less carries out polycondensation reaction.Sampling analysis, when poly-
It closes when object viscosity reaches desired value and stops stirring, eliminate vacuum, product discharge.
Embodiment 2
By 7- oxabicyclo [2.2.1] heptane -2,3- dicarboxylic anhydride 11.8kg, 1,4- succinic acid 3.5kg, 1,3- propylene glycol
1.6kg, isobide 7.3kg, 1,4-butanediol 2.8kg are put into 100L stainless steel cauldron, under nitrogen protection, with
The stirring of 55~80rpm revolving speed, is rapidly heated to 60~100 DEG C after reacting 0.3 hour, is gradually warmed up to 220 DEG C of heat preservations and carries out instead
It answers 1 hour, then is warming up to 230~270 DEG C and reacts 2.2 hours or so, reaction was completed when amount of by-products reaches theoretical value out.Add
Enter the antimony glycol of 21g, the triphenyl phosphate of 10g germanium dioxide and 16g continues to heat up and slowly depressurize, and revolving speed is adjusted to 30
~50rpm, temperature are controlled between 275~295 DEG C, and decompression step by step to 100Pa or less carries out polycondensation reaction.Sampling analysis, when
Polymer viscosity stops stirring when reaching desired value, eliminates vacuum, product discharge.
Embodiment 3
By 7- oxabicyclo [2.2.1] heptane -2,3- dicarboxylic anhydride 14.3kg, 1,4- succinic acid 1.8kg, 1,3- propylene glycol
2.1kg, isobide 9.2kg, 1,4-butanediol 1.4kg, glycerine 0.2kg are put into 100L stainless steel cauldron, are used
Under nitrogen protection, with the stirring of 55~80rpm revolving speed, it is rapidly heated to 60~100 DEG C after reacting 0.3 hour, is gradually warmed up to 220
DEG C heat preservation carry out reaction 1 hour, then be warming up to 230~270 DEG C react 2.2 hours or so, when amount of by-products reaches theoretical value out
When reaction was completed.The antimony glycol of 21g is added, the triphenyl phosphate of 10g germanium dioxide and 16g continues to heat up and slowly depressurize,
Revolving speed is adjusted to 30~50rpm, and temperature is controlled between 275~295 DEG C, and decompression step by step to 100Pa or less carries out polycondensation reaction.
Sampling analysis stops stirring when polymer viscosity reaches desired value, eliminates vacuum, product discharge.
Embodiment 4
By 7- oxabicyclo [2.2.1] heptane -2,3- dicarboxylic anhydride 16.8kg, 1,3- propylene glycol 1.4kg, isobide
4.6kg, 1,2-PD 4.5kg, glycerine 0.3kg are put into 100L stainless steel cauldron, under nitrogen protection, with 55
The stirring of~80rpm revolving speed, is rapidly heated to 60~100 DEG C after reacting 0.3 hour, is gradually warmed up to 220 DEG C of heat preservations and carries out reaction 1
Hour, then be warming up to 230~270 DEG C and react 2.2 hours or so, when amount of by-products reaches theoretical value out, reaction was completed.It is added
The antimony glycol of 21g, the triphenyl phosphate of 10g germanium dioxide and 16g continue to heat up and slowly depressurize, and revolving speed is adjusted to 30~
50rpm, temperature are controlled between 275~295 DEG C, and decompression step by step to 100Pa or less carries out polycondensation reaction.Sampling analysis, when poly-
It closes when object viscosity reaches desired value and stops stirring, eliminate vacuum, product discharge.
Comparative example
By terephthalic acid (TPA) 8.3kg, M-phthalic acid 8.3kg, 1,3-PD 1.4kg, ethylene glycol 4.6kg, neopentyl glycol
4.5kg is put into 100L stainless steel cauldron, under nitrogen protection, with the stirring of 55~80rpm revolving speed, be rapidly heated to
It after 60~100 DEG C are reacted 0.3 hour, is gradually warmed up to 220 DEG C of heat preservations and carries out reaction 1 hour, then be warming up to 230~270 DEG C instead
It answers 2.2 hours or so, when amount of by-products reaches theoretical value out, reaction was completed.The antimony glycol of 21g and the tricresyl phosphate of 16g is added
Phenyl ester continues to heat up and slowly depressurize, and revolving speed is adjusted to 30~50rpm, and temperature is controlled between 275~295 DEG C, decompression step by step
Polycondensation reaction is carried out to 100Pa or less.Sampling analysis stops stirring when polymer viscosity reaches desired value, eliminates vacuum, produces
Object discharging.
The configuration of coating:
Propylene glycol methyl ether acetate, ethylene glycol monobutyl ether, Solvesso100(mass ratio 1:1:4 are added into mixing kettle)
18kg embodiment 1-4 and comparative example resin are added in mixing kettle by mixed solvent 40kg respectively under stirring, are stirred
Uniformly, coating is presented transparent；Then catalyst (NACURE 4046) 1.5kg, levelling agent (BKY016) 1.1kg, curing agent is added
Amino resins (cymel303) 2.4kg high-speed stirred mixes 1h, obtains food cover inner-wall paint.
The preparation of coating:
It by the embodiment coating and comparative example coating of preparation, is coated on tinplate with 20# bar, and under the conditions of 200 DEG C
12min is toasted, after cooling, in case test.
Performance test:
Solvent resistant wiping:
It with the absorbent cotton for occupying butanone, is pinned with one kilogram of power, in coating surface, straight line is wiped back and forth, and one is denoted as 1 back and forth
It is secondary, the number for wiping and exposing substrate is calculated, higher than 100 times be denoted as greater than 100.
Anti- citric acid test:
By the plate after paint solidification, slitting dress, and after bending several times, be put into 2% citric acid solution boil 121 DEG C/
30min, lustrous surface and smooth degree after then observation is boiled, scores according to glossiness and smooth degree, if
Surface is smooth not to have loss of gloss, then is 10；If surface loss of gloss, coating shedding if is 0, and score is unqualified lower than 7.
Anti- acetic acid test
By the plate after paint solidification, slitting dress, and after bending several times, be put into 2% acetum boil 121 DEG C/
30min, lustrous surface and smooth degree after then observation is boiled, scores according to glossiness and smooth degree, if
Surface is smooth not to have loss of gloss, then is 10；If surface loss of gloss, coating shedding if is 0, and score is unqualified lower than 7；
Resistance to boiling test:
By the plate after paint solidification, slitting dress, and after bending several times, it is put into 85 DEG C/30min in distilled water, is then seen
The lustrous surface after boiling and smooth degree are examined, is scored according to glossiness and smooth degree, if surface is smooth not to be had
Loss of gloss is then 10；If surface loss of gloss, coating shedding if is 0, and score is unqualified lower than 7；
Resistance to deep-draw test:
206 basic lids are made using punching machine punching press in clad plate, whether the coating in observation punching stretch region has rupture, do not break
It is excellent for splitting, have be broken at one it is good, greater than one at be broken into difference.
Adhesive force test:
On the coating of specimen surface, the checkerboard type checker pattern that each direction is 11 notch is cut out with cutter, and always
Base is switched to, adhesive tape is attached on grid, is then torn, falling off area and evaluate the adhesive force of coating by coating is commented
Valence mode is as shown in table 1:
Table 1: adhesive force test evaluation table
| Grade | Coating shedding degree |
| 0 | The side of notch is completely smooth, does not have grid to fall off on grid |
| 1 | There is small sheet coating shedding in crosspoint, the coating area that falls off, which accounts for, draws lattice area no more than 5% |
| 2 | There is small sheet coating shedding along the side and crosspoint of notch, the coating area that falls off, which accounts for, draws 6% one the 50% of lattice area |
| 3 | Coating severe detachment, the coating area that falls off, which accounts for, draws lattice area greater than 50 % |
Test result performance comparison is as shown in table 2.
Table 2: each embodiment test result contrast table.
| Number | Solvent resistant wiping | Anti- citric acid | Anti- acetic acid | Resistance to boiling | Resistance to deep-draw | Adhesive force |
| Embodiment 1 | >100 | 10 | 9 | 9 | It is excellent | 0 |
| Embodiment 2 | >100 | 10 | 10 | 10 | It is excellent | 0 |
| Embodiment 3 | >100 | 9 | 9 | 10 | It is excellent | 0 |
| Embodiment 4 | >100 | 10 | 10 | 9 | It is excellent | 0 |
| Comparative example | >100 | 6 | 7 | 8 | It is good | 0 |
It is compared by above data, the polyester resin that raw material provided by the invention is synthesized entirely from biology base has very
Good resistance and processing performance can satisfy tank and listen the interior use for applying coating.
Still there are many specific embodiments by the present invention.All all skills formed using equivalent replacement or equivalent transformation
Art scheme, all falls within the scope of protection of present invention.
Claims (9)
1. a kind of preparation method of the polyester resin as made from organism-based raw material, it is characterised in that: pass through 7- oxabicyclo
[2.2.1] heptane -2,3- dicarboxylic anhydride, isobide, 1,3-PD, and the polyalcohol from biology base and polyacid into
Row polymerization preparation, wherein 7- oxabicyclo [2.2.1] heptane -2,3- dicarboxylic anhydride accounts for the 50- of all sour molar contents
100%, the isobide accounts for the 20-60% of all alcohol molar contents, and the 1,3-PD accounts for the 10- of all alcohol molar contents
30%。
2. a kind of preparation method of the polyester resin as made from organism-based raw material as described in claim 1, it is characterised in that: packet
Include following steps,
S1, by 7- oxabicyclo [2.2.1] heptane -2,3- dicarboxylic anhydride, isobide, 1,3-PD, and from biology
The polyalcohol and polyacid of base are put into reaction kettle under nitrogen protection, and stirring reaches through temperature reaction three times to amount of by-products
Theoretical value；
S2, addition catalyst and stabilizer carry out being continuously heating to 275~295 DEG C in a kettle, and are decompressed to 100Pa or less
Polycondensation reaction is carried out, sampling analysis to polymer viscosity reaches desired value, discharges.
3. a kind of preparation method of the polyester resin as made from organism-based raw material as claimed in claim 2, it is characterised in that: institute
It states in S1 under nitrogen protection, is warming up to 60~100 DEG C of insulation reactions for the first time, be warming up to 220 DEG C of insulation reactions for the second time, the
It is warming up to 230~270 DEG C of insulation reactions three times.
4. a kind of preparation method of the polyester resin as made from organism-based raw material as described in claim 1, it is characterised in that: institute
7- oxabicyclo [2.2.1] heptane -2,3- dicarboxylic anhydride is stated to be prepared from bio-based materials furfural.
5. a kind of preparation method of the polyester resin as made from organism-based raw material as described in claim 1, it is characterised in that: institute
It states the polyalcohol from biology base and is selected from 1,6- hexylene glycol, 1,4-butanediol, 1,2-PD, glycerine is one such or two
Kind or more any combination.
6. a kind of preparation method of the polyester resin as made from organism-based raw material as described in claim 1, it is characterised in that: institute
The polyacid stated from biology base is selected from 1, 4- succinic acid, and adipic acid, furandicarboxylic acid is one of or two or more to appoint
Meaning combination.
7. a kind of preparation method of polyester resin as made from organism-based raw material as described in claim 1-4 is any is prepared poly-
Ester resin.
8. polyester resin as claimed in claim 5, it is characterised in that: the polyester resin number-average molecular weight be 15000~
45000, glass transition temperature is 80~120 DEG C.
9. polyester resin as claimed in claim 5, it is characterised in that: the polyester resin is applied to tank and listens inside courtyard.
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102190782A (en) * | 2010-03-17 | 2011-09-21 | 东丽纤维研究所（中国）有限公司 | Copolyester compound and method for preparing same |
| JP6407600B2 (en) * | 2014-07-23 | 2018-10-17 | 国立大学法人群馬大学 | Biodegradable polyester |
-
2019
- 2019-08-29 CN CN201910807180.7A patent/CN110396182B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102190782A (en) * | 2010-03-17 | 2011-09-21 | 东丽纤维研究所（中国）有限公司 | Copolyester compound and method for preparing same |
| JP6407600B2 (en) * | 2014-07-23 | 2018-10-17 | 国立大学法人群馬大学 | Biodegradable polyester |
Non-Patent Citations (4)
| Title |
|---|
| XIAOPENG YU等: "Unraveling substituent effects on the glass transition temperatures of", 《NATURE COMMUNICATIONS》 * |
| YUYA TACGUBANA等: "Synthesis, Physical Properties, and Biodegradability of Biobased", 《ACS SUSTAINABLE CHEMISTRY & ENGINEERING》 * |
| YUYA TACHIBANA等: "Biodegradability of polyesters comprising a bio-based monomer derived", 《POLYMER DEGRADATION AND STABILITY》 * |
| YUYA TACHIBANA等: "Synthesis and characterization of a renewable polyester containing oxabicyclic dicarboxylate derived from furfural", 《GREEN CHEMISTRY》 * |
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