CN117843848A - Bio-based itaconic acid chain extender, and synthetic method and application thereof - Google Patents
Bio-based itaconic acid chain extender, and synthetic method and application thereof Download PDFInfo
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- CN117843848A CN117843848A CN202311854178.8A CN202311854178A CN117843848A CN 117843848 A CN117843848 A CN 117843848A CN 202311854178 A CN202311854178 A CN 202311854178A CN 117843848 A CN117843848 A CN 117843848A
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- itaconic acid
- monomer
- chain extender
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- acid chain
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- 239000004970 Chain extender Substances 0.000 title claims abstract description 38
- LVHBHZANLOWSRM-UHFFFAOYSA-N itaconic acid Chemical group OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 title claims abstract description 29
- 238000010189 synthetic method Methods 0.000 title description 2
- 239000000178 monomer Substances 0.000 claims abstract description 26
- 239000002904 solvent Substances 0.000 claims abstract description 16
- 239000000463 material Substances 0.000 claims abstract description 14
- 239000003999 initiator Substances 0.000 claims abstract description 11
- 238000000034 method Methods 0.000 claims abstract description 11
- 238000002360 preparation method Methods 0.000 claims abstract description 5
- 238000012545 processing Methods 0.000 claims abstract description 5
- 238000003756 stirring Methods 0.000 claims abstract description 4
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 12
- 239000012986 chain transfer agent Substances 0.000 claims description 10
- 229920001896 polybutyrate Polymers 0.000 claims description 9
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 8
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical group C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 8
- NRTSLUOVGBFANI-UHFFFAOYSA-N bis(oxiran-2-ylmethyl) 2-methylidenebutanedioate Chemical group C1OC1COC(=O)C(=C)CC(=O)OCC1CO1 NRTSLUOVGBFANI-UHFFFAOYSA-N 0.000 claims description 7
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 claims description 6
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims description 6
- -1 acrylic ester Chemical class 0.000 claims description 5
- 239000000126 substance Substances 0.000 claims description 5
- 239000004342 Benzoyl peroxide Substances 0.000 claims description 4
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 claims description 4
- 235000019400 benzoyl peroxide Nutrition 0.000 claims description 4
- 238000006116 polymerization reaction Methods 0.000 claims description 4
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 4
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 claims description 3
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 claims description 3
- 238000006243 chemical reaction Methods 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- 150000002989 phenols Chemical class 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 239000008096 xylene Substances 0.000 claims description 2
- 238000011161 development Methods 0.000 abstract description 7
- 239000000155 melt Substances 0.000 abstract description 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 3
- 229910052799 carbon Inorganic materials 0.000 abstract description 3
- 229920000728 polyester Polymers 0.000 abstract description 3
- 230000009467 reduction Effects 0.000 abstract description 3
- 238000001308 synthesis method Methods 0.000 abstract description 3
- 239000003795 chemical substances by application Substances 0.000 abstract 1
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 6
- 230000018109 developmental process Effects 0.000 description 6
- WNAHIZMDSQCWRP-UHFFFAOYSA-N dodecane-1-thiol Chemical compound CCCCCCCCCCCCS WNAHIZMDSQCWRP-UHFFFAOYSA-N 0.000 description 4
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 description 4
- 239000002861 polymer material Substances 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 3
- 229920006238 degradable plastic Polymers 0.000 description 3
- 229910001873 dinitrogen Inorganic materials 0.000 description 3
- 238000004821 distillation Methods 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 238000003760 magnetic stirring Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000004033 plastic Substances 0.000 description 3
- 229920003023 plastic Polymers 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 239000002028 Biomass Substances 0.000 description 2
- 239000004593 Epoxy Substances 0.000 description 2
- 239000006057 Non-nutritive feed additive Substances 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 150000001356 alkyl thiols Chemical class 0.000 description 2
- 239000003963 antioxidant agent Substances 0.000 description 2
- 230000003078 antioxidant effect Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000006722 reduction reaction Methods 0.000 description 2
- 230000008929 regeneration Effects 0.000 description 2
- 238000011069 regeneration method Methods 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 description 1
- 241001465754 Metazoa Species 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 238000000071 blow moulding Methods 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 125000003700 epoxy group Chemical group 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 238000005187 foaming Methods 0.000 description 1
- 238000005469 granulation Methods 0.000 description 1
- 230000003179 granulation Effects 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 238000002074 melt spinning Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
Landscapes
- Biological Depolymerization Polymers (AREA)
Abstract
The invention discloses a bio-based itaconic acid chain extender, a synthesis method and application thereof. The invention provides a bio-based itaconic acid chain extender with a structural formula shown in the specification, wherein the bio-based itaconic acid chain extender adopts a method of converting a first monomer, a second monomer and a chainMixing the transfer agent, the initiator and the solvent uniformly, reacting under the stirring condition, and then distilling under reduced pressure to remove the solvent. The synthesis method disclosed by the invention is simple in process and convenient to operate, and the obtained bio-based itaconate chain extender can improve the melt strength of polyester, can be applied to preparation and processing of biodegradable materials, and has the advantages of carbon emission reduction, reproducibility, development promotion and the like.
Description
Technical Field
The invention belongs to the technical field of polymer material processing aids, and particularly relates to a bio-based itaconic acid chain extender, a synthesis method and application thereof.
Background
The chain extender is a novel polymer material processing aid. The chain extender reacts with the chain end group of the polymer material in the molten state in situ, regulates and controls the melt viscosity and the melt strength of the polymer material, improves and recovers the mechanical property and the thermal property of the resin, meets the requirements of forming processes such as melt spinning, casting, blow molding, coating, foaming and the like on the material viscosity, especially the melt strength, and is widely applied to polymerization, processing and recycling of polyester (PET, PBT, PC, PBAT, PLA, PBS, PHA) and polyamide (PA 6, PA 66) resins.
At present, most of the chain extenders at home and abroad are epoxy chain extenders, mainly comprise copolymers of Glycidyl Methacrylate (GMA) and other vinyl monomers, and can replace the bio-based monomers of the GMA. Bio-based Materials (Bio-based Materials) refer to Materials manufactured by biological, chemical and physical means using renewable biomass (including the content of crops, trees and other animals and plants and their residues). The chain extender is mainly used in the industries of degradable plastics and recycled plastics, so that development of the bio-based chain extender for replacing GMA has the advantages of carbon emission reduction, regeneration, development promotion and the like in the existing industries of degradable plastics and recycled plastics.
Itaconic acid is a biological-based platform compound with development potential, and itaconic acid derivative itaconic acid diglycidyl ester, the structure of which contains double bonds and epoxy groups, is a relatively ideal molecule for synthesizing a chain extender. It provides the possibility for the synthesis of bio-based chain extenders.
Glycidyl methacrylate (left) and itaconic acid derivative diglycidyl itaconate (right) structural formula
Disclosure of Invention
The first object of the invention is to provide a bio-based itaconic acid chain extender, which has a chemical structural formula as shown in the following formula, aiming at the defects of the prior art:
wherein m, n and p are the polymerization degree and are 5 to 100 respectively.
The second object of the invention is to provide a preparation method of a bio-based itaconic acid chain extender, comprising the following steps:
uniformly mixing a first monomer, a second monomer, a chain transfer agent, an initiator and a solvent, reacting under the stirring condition, and then distilling under reduced pressure to remove the solvent to obtain the bio-based itaconic acid chain extender; the first monomer is itaconic acid diglycidyl ester, and the second monomer is one or a combination of more of methyl methacrylate, acrylic ester, styrene, alpha-methyl styrene and acrylonitrile.
Preferably, the reaction temperature is 100-110 ℃ and the reaction time is 12-15h.
Preferably, the molar proportion of the first monomer is from 10 to 60%.
Preferably, the molar proportion of the second monomer is 33 to 88.9%.
Preferably, the chain transfer agent includes, but is not limited to, alkyl thiols or phenols, preferably dodecyl mercaptan or hydroquinone, preferably in a molar ratio of 1 to 5%.
Preferably, the initiator is one of azodiisobutyronitrile and benzoyl peroxide, and the molar ratio is preferably 0.1-2%.
Preferably, the solvent is tetrahydrofuran or xylene.
A third object of the present invention is to provide the use of the above-described bio-based itaconic acid chain extender in the preparation and processing of biodegradable materials.
Preferably, the biodegradable material is PBAT.
Compared with the prior art, the invention has the main advantages that:
(1) The bio-based itaconic acid chain extender provided by the invention develops new application of biomass resources, realizes sustainable development, reduces the pressure of chemical energy demand and promotes green economic development.
(2) The invention has simple synthesis steps, mild process conditions and high yield, and can be used for industrialized mass production.
(3) The bio-based itaconic acid chain extender synthesized by the invention can effectively improve the melt strength of polyester.
Detailed Description
The invention is further illustrated by the following examples.
In a first aspect, the present invention provides a bio-based itaconic acid chain extender having the chemical structural formula:
wherein m, n, p are the degree of polymerization and are about 5 to 100.
In a second aspect, the invention provides a method for preparing a bio-based itaconic acid chain extender, comprising the steps of:
uniformly mixing the first monomer, the second monomer, the chain transfer agent, the initiator and the solvent, reacting for 12-15 hours at 100-110 ℃ under the stirring condition, and then distilling under reduced pressure to remove the solvent, thus obtaining the bio-based itaconic acid chain extender;
wherein the first monomer is diglycidyl itaconate; the second monomer is one or a combination of more of methyl methacrylate, acrylic ester, styrene, alpha-methyl styrene and acrylonitrile; the chain transfer agent includes, but is not limited to, alkyl thiols or phenols, preferably dodecyl mercaptan or hydroquinone; the initiator is one of azodiisobutyronitrile and benzoyl peroxide; the solvent is tetrahydrofuran or dimethylbenzene; the mole percentages of the first monomer, the second monomer, the chain transfer agent, the initiator and the solvent are as follows:
10 to 60 percent of first monomer
Second monomer 33-88.9%
Chain transfer agent 1-5%
Initiator 0.1-2%.
In a third aspect, the present invention provides the use of the above-described bio-based itaconic acid chain extender in the preparation or processing of a biodegradable material, said biodegradable material being PBAT.
The invention will be further illustrated with reference to specific examples. It is to be understood that these examples are illustrative of the present invention and are not intended to limit the scope of the present invention. The experimental methods, in which specific conditions are not noted in the following examples, are generally conducted under conventional conditions or under conditions recommended by the manufacturer. Percentages and parts are by weight unless otherwise indicated.
Example 1
Under the protection of nitrogen gas, 11.2g of itaconic acid diglycidyl ester, 42g of styrene, 25g of methyl methacrylate, 0.8g of dodecyl mercaptan, 0.5g of azodiisobutyronitrile and 50mL of tetrahydrofuran are sequentially added into a dry three-necked bottle, and the mixture is reacted for 12 hours at 100 ℃ under the condition of magnetic stirring, and the excess solvent is removed by reduced pressure distillation, so that the light yellow solid itaconic acid ester chain extender is obtained.
The reaction scheme of this example is shown below:
example 2
Under the protection of nitrogen gas, 35.1g of itaconic acid diglycidyl ester, 28g of styrene, 12g of methyl methacrylate, 1.6g of dodecyl mercaptan, 1g of azodiisobutyronitrile and 50mL of dimethylbenzene are sequentially added into a dry three-necked bottle, and the mixture is reacted for 12 hours at 100 ℃ under the condition of magnetic stirring, and then the excess solvent is removed by reduced pressure distillation, so that the light yellow solid itaconic acid ester chain extender is obtained.
Example 3
26.3g of itaconic acid diglycidyl ester, 32g of styrene, 12.5g of methyl methacrylate, 1.2g of hydroquinone, 0.8g of benzoyl peroxide and 60mL of dimethylbenzene are sequentially added into a dry three-necked bottle under the protection of nitrogen gas, and the mixture is reacted for 12 hours at 100 ℃ under the condition of magnetic stirring, and the excess solvent is removed by reduced pressure distillation, so that the light yellow solid itaconic acid ester chain extender is obtained.
Example 4: chain extension effect experiment of itaconic acid ester chain extender
Raw materials:
PBAT blown film material, 100
EXAMPLES 1-3 itaconic acid ester chain extender, 0.5
Antioxidant 1010,0.5
The PBAT is firstly dried in an oven at 80 ℃ for 8 hours to constant weight, then the PBAT and the chain-extended block particles of the example 2 are added into a high-speed mixer to be mixed uniformly, a double-screw extruder is adopted for extrusion granulation, the temperature of each zone is set at 150-170 ℃, and the melt flow is 40-60r/min. The results are shown in Table 1.
Comparative example 1: no chain extender is added
Raw materials:
PBAT blown film material, 100
Antioxidant 1010,0.5
The other conditions were the same as in example 4 without adding a chain extender; the results are shown in Table 1.
TABLE 1 chain extension experiment results
Epoxy equivalent test method refers to ASTM D1652-11e1, melt index test conditions of 190 ℃/2.16kg, acid number test method refers to GB/T14190-2008.
From Table 1, it can be seen that the itaconic acid ester chain extender reduces the melt index and acid value of the blown film material of PBAT, has obvious chain extending effect, namely, successfully develops a bio-based chain extender, and has the advantages of carbon emission reduction, regeneration, development promotion and the like for the existing degradable plastics and recycled plastics industries.
All documents mentioned in this application are incorporated by reference as if each were individually incorporated by reference. Further, it will be appreciated that various changes and modifications may be made by those skilled in the art after reading the above teachings, and such equivalents are intended to fall within the scope of the invention as defined in the appended claims.
Claims (10)
1. The bio-based itaconic acid chain extender is characterized by having a chemical structural formula as shown in the specification:
wherein m, n and p are the polymerization degree and are 5 to 100 respectively.
2. A process for preparing the biobased itaconic acid chain extender of claim 1 comprising the steps of:
uniformly mixing a first monomer, a second monomer, a chain transfer agent, an initiator and a solvent, reacting under the condition of stirring, and then distilling under reduced pressure to remove the solvent, thus obtaining the bio-based itaconic acid chain extender; the first monomer is itaconic acid diglycidyl ester, and the second monomer is one or a combination of more of methyl methacrylate, acrylic ester, styrene, alpha-methyl styrene and acrylonitrile.
3. The process according to claim 2, wherein the chain transfer agent is an alkyl mercaptan or a phenolic compound.
4. The method according to claim 2, wherein the initiator is one of azobisisobutyronitrile and benzoyl peroxide.
5. The method according to claim 2, wherein the solvent is tetrahydrofuran or xylene.
6. The method according to any one of claims 2 to 5, wherein the mole percentages of the first monomer, the second monomer, the chain transfer agent, the initiator, and the solvent are as follows:
10 to 60 percent of first monomer
Second monomer 33-88.9%
Chain transfer agent 1-5%
Initiator 0.1-2%.
7. The method according to claim 2, wherein the reaction time is 12-15h.
8. The process of claim 2, wherein the reaction temperature is 100-110 ℃.
9. Use of the biobased itaconic acid chain extender of claim 1 in the preparation and processing of biodegradable materials.
10. Use according to claim 9, characterized in that the biodegradable material is PBAT.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202311854178.8A CN117843848A (en) | 2023-12-29 | 2023-12-29 | Bio-based itaconic acid chain extender, and synthetic method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202311854178.8A CN117843848A (en) | 2023-12-29 | 2023-12-29 | Bio-based itaconic acid chain extender, and synthetic method and application thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN117843848A true CN117843848A (en) | 2024-04-09 |
Family
ID=90547657
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202311854178.8A Pending CN117843848A (en) | 2023-12-29 | 2023-12-29 | Bio-based itaconic acid chain extender, and synthetic method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN117843848A (en) |
-
2023
- 2023-12-29 CN CN202311854178.8A patent/CN117843848A/en active Pending
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