CN114507306B - Tricarboxylic acid compound and preparation method and application thereof - Google Patents
Tricarboxylic acid compound and preparation method and application thereof Download PDFInfo
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- CN114507306B CN114507306B CN202210219476.9A CN202210219476A CN114507306B CN 114507306 B CN114507306 B CN 114507306B CN 202210219476 A CN202210219476 A CN 202210219476A CN 114507306 B CN114507306 B CN 114507306B
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- acid compound
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- -1 Tricarboxylic acid compound Chemical class 0.000 title claims abstract description 79
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- 239000000463 material Substances 0.000 claims abstract description 28
- 238000006243 chemical reaction Methods 0.000 claims abstract description 21
- 238000000034 method Methods 0.000 claims abstract description 12
- 230000008569 process Effects 0.000 claims abstract description 7
- 229920000098 polyolefin Polymers 0.000 claims description 30
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 24
- 239000003963 antioxidant agent Substances 0.000 claims description 20
- 230000003078 antioxidant effect Effects 0.000 claims description 18
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims description 17
- 150000001413 amino acids Chemical class 0.000 claims description 14
- 239000003054 catalyst Substances 0.000 claims description 14
- 229910052757 nitrogen Inorganic materials 0.000 claims description 12
- 239000002994 raw material Substances 0.000 claims description 12
- 239000000203 mixture Substances 0.000 claims description 9
- 239000011541 reaction mixture Substances 0.000 claims description 9
- 125000000217 alkyl group Chemical group 0.000 claims description 8
- 238000002844 melting Methods 0.000 claims description 8
- 230000008018 melting Effects 0.000 claims description 8
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 claims description 8
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 6
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical group OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 6
- 239000004698 Polyethylene Substances 0.000 claims description 5
- 229910052739 hydrogen Inorganic materials 0.000 claims description 5
- 239000001257 hydrogen Substances 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 5
- 229920000573 polyethylene Polymers 0.000 claims description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 4
- KDXKERNSBIXSRK-UHFFFAOYSA-N Lysine Natural products NCCCCC(N)C(O)=O KDXKERNSBIXSRK-UHFFFAOYSA-N 0.000 claims description 4
- 239000004472 Lysine Substances 0.000 claims description 4
- 238000010438 heat treatment Methods 0.000 claims description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 4
- 150000002668 lysine derivatives Chemical class 0.000 claims description 4
- 239000004743 Polypropylene Substances 0.000 claims description 3
- SRSXLGNVWSONIS-UHFFFAOYSA-N benzenesulfonic acid Chemical compound OS(=O)(=O)C1=CC=CC=C1 SRSXLGNVWSONIS-UHFFFAOYSA-N 0.000 claims description 3
- 229940092714 benzenesulfonic acid Drugs 0.000 claims description 3
- 229920001155 polypropylene Polymers 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims 4
- 150000002431 hydrogen Chemical class 0.000 claims 1
- 239000002131 composite material Substances 0.000 abstract description 35
- 238000012545 processing Methods 0.000 abstract description 16
- 230000015556 catabolic process Effects 0.000 abstract description 12
- 238000006731 degradation reaction Methods 0.000 abstract description 12
- 230000000694 effects Effects 0.000 abstract description 10
- 238000004132 cross linking Methods 0.000 abstract description 6
- 125000000524 functional group Chemical group 0.000 abstract description 5
- 125000004122 cyclic group Chemical group 0.000 abstract description 4
- 230000009467 reduction Effects 0.000 abstract description 4
- 230000000052 comparative effect Effects 0.000 description 9
- 239000000314 lubricant Substances 0.000 description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 8
- 239000007788 liquid Substances 0.000 description 8
- 229920001896 polybutyrate Polymers 0.000 description 7
- 239000004626 polylactic acid Substances 0.000 description 7
- 229920000747 poly(lactic acid) Polymers 0.000 description 6
- 238000001816 cooling Methods 0.000 description 5
- 238000001035 drying Methods 0.000 description 5
- 125000003700 epoxy group Chemical group 0.000 description 5
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 4
- 230000009286 beneficial effect Effects 0.000 description 4
- 125000004432 carbon atom Chemical group C* 0.000 description 4
- 238000007599 discharging Methods 0.000 description 4
- 239000000178 monomer Substances 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- 238000001556 precipitation Methods 0.000 description 4
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 208000034530 PLAA-associated neurodevelopmental disease Diseases 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 229920001577 copolymer Polymers 0.000 description 3
- 230000002349 favourable effect Effects 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 3
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 3
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 3
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 3
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 3
- 229920002961 polybutylene succinate Polymers 0.000 description 3
- 239000004631 polybutylene succinate Substances 0.000 description 3
- 239000002244 precipitate Substances 0.000 description 3
- 238000000746 purification Methods 0.000 description 3
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- 239000004677 Nylon Substances 0.000 description 2
- 231100000209 biodegradability test Toxicity 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000000498 cooling water Substances 0.000 description 2
- 239000012043 crude product Substances 0.000 description 2
- YSMODUONRAFBET-UHFFFAOYSA-N delta-DL-hydroxylysine Natural products NCC(O)CCC(N)C(O)=O YSMODUONRAFBET-UHFFFAOYSA-N 0.000 description 2
- YSMODUONRAFBET-UHNVWZDZSA-N erythro-5-hydroxy-L-lysine Chemical compound NC[C@H](O)CC[C@H](N)C(O)=O YSMODUONRAFBET-UHNVWZDZSA-N 0.000 description 2
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 229920001778 nylon Polymers 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 239000012925 reference material Substances 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 238000009423 ventilation Methods 0.000 description 2
- BSHGVWRQILWEKK-GDVGLLTNSA-N (2s)-2,6-diamino-5-methylhexanoic acid Chemical compound NCC(C)CC[C@H](N)C(O)=O BSHGVWRQILWEKK-GDVGLLTNSA-N 0.000 description 1
- 125000004398 2-methyl-2-butyl group Chemical group CC(C)(CC)* 0.000 description 1
- 125000004493 2-methylbut-1-yl group Chemical group CC(C*)CC 0.000 description 1
- 125000004917 3-methyl-2-butyl group Chemical group CC(C(C)*)C 0.000 description 1
- 229940117976 5-hydroxylysine Drugs 0.000 description 1
- LCWXJXMHJVIJFK-UHFFFAOYSA-N Hydroxylysine Natural products NCC(O)CC(N)CC(O)=O LCWXJXMHJVIJFK-UHFFFAOYSA-N 0.000 description 1
- 229920000168 Microcrystalline cellulose Polymers 0.000 description 1
- 229920000881 Modified starch Polymers 0.000 description 1
- 239000004368 Modified starch Substances 0.000 description 1
- JKIJEFPNVSHHEI-UHFFFAOYSA-N Phenol, 2,4-bis(1,1-dimethylethyl)-, phosphite (3:1) Chemical compound CC(C)(C)C1=CC(C(C)(C)C)=CC=C1OP(OC=1C(=CC(=CC=1)C(C)(C)C)C(C)(C)C)OC1=CC=C(C(C)(C)C)C=C1C(C)(C)C JKIJEFPNVSHHEI-UHFFFAOYSA-N 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- BGYHLZZASRKEJE-UHFFFAOYSA-N [3-[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxy]-2,2-bis[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxymethyl]propyl] 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)OCC(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 BGYHLZZASRKEJE-UHFFFAOYSA-N 0.000 description 1
- 239000012190 activator Substances 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 238000007112 amidation reaction Methods 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 238000006065 biodegradation reaction Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 150000001721 carbon Chemical group 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000000593 degrading effect Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 229920000578 graft copolymer Polymers 0.000 description 1
- 238000005469 granulation Methods 0.000 description 1
- 230000003179 granulation Effects 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- QJHBJHUKURJDLG-UHFFFAOYSA-N hydroxy-L-lysine Natural products NCCCCC(NO)C(O)=O QJHBJHUKURJDLG-UHFFFAOYSA-N 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 125000001972 isopentyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 description 1
- 150000003951 lactams Chemical class 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 238000010128 melt processing Methods 0.000 description 1
- 238000010309 melting process Methods 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 235000019813 microcrystalline cellulose Nutrition 0.000 description 1
- 239000008108 microcrystalline cellulose Substances 0.000 description 1
- 229940016286 microcrystalline cellulose Drugs 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 235000019426 modified starch Nutrition 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 125000001280 n-hexyl group Chemical group C(CCCCC)* 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- 125000003538 pentan-3-yl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000012466 permeate Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920002959 polymer blend Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 230000000638 stimulation Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 150000003628 tricarboxylic acids Chemical class 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F8/00—Chemical modification by after-treatment
- C08F8/30—Introducing nitrogen atoms or nitrogen-containing groups
- C08F8/32—Introducing nitrogen atoms or nitrogen-containing groups by reaction with amines
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/26—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers modified by chemical after-treatment
- C08L23/36—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers modified by chemical after-treatment by reaction with compounds containing nitrogen, e.g. by nitration
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/06—Biodegradable
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W90/00—Enabling technologies or technologies with a potential or indirect contribution to greenhouse gas [GHG] emissions mitigation
- Y02W90/10—Bio-packaging, e.g. packing containers made from renewable resources or bio-plastics
Landscapes
- Chemical & Material Sciences (AREA)
- General Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention relates to a tricarboxylic acid compound, a preparation method and application thereof. The tricarboxylic acid compound has the structural characteristics shown in the formula (I). The structure of the tricarboxylic acid compound does not contain a cyclic reactive functional group, and the tricarboxylic acid compound is used as a compatibilizer in a degradable composite material, so that the problems of poor fluidity and degradation performance reduction caused by cross-linking reaction of the material can be avoided, the compatibilizer effect is good, the processing fluidity of the composite material is obviously improved, meanwhile, the composite material has good degradation performance, the thermal stability of the composite material in a high-temperature processing process is improved, and the actual application requirements are better met.
Description
Technical Field
The invention relates to the technical field of high polymer materials, in particular to a tricarboxylic acid compound and a preparation method and application thereof.
Background
Degradable material refers to a material that is degradable in both thermodynamic and kinetic sense over a period of time. Degradable materials are classified into: photodegradable materials, biodegradable materials, and the like, wherein the biodegradable material plays a unique role in environmental protection as a naturally degradable material, and research and development thereof have been rapidly progressed, and are considered as effective solutions for "white pollution".
The common biodegradable materials on the market at present comprise polylactic acid (PLA), a copolymer (PBAT) of adipic acid butanediol ester and terephthalic acid butanediol ester, polybutylene succinate (PBS) and the like, wherein the PLA is derived from natural starch, has rich sources, has the characteristics of no toxicity and no stimulation, good biocompatibility, high strength, good processability, biodegradability and the like, and is most widely applied. However, PLA has the problems of poor toughness and insufficient fluidity, and in practice, PLA, PBAT, PBS and other materials generally need to be melt blended to improve toughness, and meanwhile, a compatilizer or compatibilizer needs to be added to improve compatibility of the composite material, so that mechanical properties of the composite material prepared by blending are improved.
Styrene and maleic anhydride copolymer are used as macromolecular activator, and lactam and initiator are further added to prepare graft copolymer of copolymer and nylon as compatilizer between styrene polymer and nylon; in addition, there is a study on adding modified starch rich in epoxy groups to PLA-PBAT polymer blends to make the compatibility between PLA and PBAT better.
However, the compatilizer contains a large amount of maleic anhydride groups or epoxy groups, so that the compatilizer has more annular active groups, can react with hydroxyl groups on PLA, PBAT and other materials, and can generate cross-linking between degradable materials, thereby obviously reducing the fluidity of a blending system and being unfavorable for subsequent melting and molding processing of the prepared degradable composite material. In addition, after the degradable composite material forms a certain polymer crosslinked network structure, external water vapor is difficult to permeate into the polymer, so that the degradation rate of the material is influenced, and even the material cannot be degraded when the content of the compatilizer is too high.
Disclosure of Invention
Based on the above, the invention provides a non-reactive tricarboxylic acid compound, and a preparation method and application thereof. The tricarboxylic acid compound can be used as a compatibilizing lubricant to effectively improve the fluidity of the degradable composite material, avoid the problem of degrading the material due to crosslinking reaction, and has good compatibilizing effect.
The specific technical scheme is as follows:
in a first aspect of the present invention, there is provided a tricarboxylic acid compound having structural characteristics represented by formula (I):
wherein R is 1 Selected from hydrogen, hydroxy and C 1 ～C 5 One of the alkyl groups;
R 2 and R is 3 Each independently is a polyolefin-based group.
In one embodiment, the tricarboxylic acid compound has structural characteristics shown in formulas (II-1) to (II-4):
wherein n is 15 to 30.
The invention provides a preparation method of a tricarboxylic acid compound, which comprises the following raw materials in parts by mass:
the amino acid is selected from one or more of lysine and lysine derivatives.
In one embodiment, the preparation raw materials of the tricarboxylic acid compound comprise the following components in parts by mass:
in one embodiment, the polyolefin wax is selected from one or more of polyethylene wax and polypropylene wax; and/or
The carbon chain length of the polyolefin wax is C15-C30.
In one embodiment, the antioxidant is a phosphite antioxidant and a hindered phenol antioxidant.
In one embodiment, the weight ratio of the phosphite antioxidant to the hindered phenol antioxidant is (1:1) - (2:1).
In one embodiment, the catalyst is selected from one or more of p-toluene sulfonic acid and benzene sulfonic acid.
In one embodiment, the preparation method of the tricarboxylic acid compound comprises the following steps:
mixing the polyolefin wax and the antioxidant, carrying out melting treatment under the protection of nitrogen at the temperature of 105-125 ℃, heating to 150-170 ℃ after the polyolefin wax is melted, and stirring to prepare a pre-reaction mixture;
adding the maleic anhydride into the pre-reaction mixture, reacting for 3-4 hours, adding the mixture of the catalyst and the amino acid, and reacting for 2-3 hours;
introducing nitrogen to continue the reaction for 2-3 h to prepare the tricarboxylic acid compound.
In one embodiment, the stirring speed is 30rpm/min to 100rpm/min.
In one embodiment, the maleic anhydride is added at a rate of 20mL/min to 50mL/min; and/or
The speed of adding the mixture of the catalyst and the amino acid is 20 mL/min-50 mL/min.
In a third aspect of the invention, there is provided the use of the above-described tricarboxylic acid compound or the tricarboxylic acid compound prepared by the above-described preparation method in a degradable material.
Compared with the prior art, the invention has the following beneficial effects:
the ternary carboxylic acid compound provided by the invention does not contain cyclic reactive functional groups such as maleic anhydride groups or epoxy groups, is used as a compatibilizing lubricant in a degradable composite material, can avoid the problems of poor fluidity and degradation performance reduction caused by cross-linking reaction of the material, and the polyolefin structure is beneficial to improving the processing fluidity of the composite material, and the polycarboxylic groups are introduced into the molecular terminal, so that the compatibility among different types of degradable materials is improved, the compatibilizing effect is good, and the processing fluidity of the composite material is obviously improved and has better degradation performance.
In addition, the tricarboxylic acid compound increases the molecular weight of the composite material, introduces the polycarboxylic group with hydrogen bond function, is beneficial to improving the thermal stability of the composite material in the high-temperature processing process, has a certain branching structure, reduces the relative sliding among high molecular chains, greatly reduces the possibility of precipitation in the composite material, and better meets the actual application requirements.
Drawings
For a clearer description of embodiments of the invention or of the prior art, the drawings that are needed in the description of the embodiments or of the prior art will be briefly described, it being apparent that the drawings in the description below are some embodiments of the invention, from which, without inventive effort, other drawings can be obtained for a person skilled in the art;
FIG. 1 is an infrared spectrum of the tricarboxylic acid compound prepared in example 1.
Detailed Description
In order that the invention may be understood more fully, a more particular description of the invention will be rendered by reference to specific embodiments thereof which are illustrated in the appended claims. This invention may, however, be embodied in many different forms and should not be construed as limited to the embodiments set forth herein. These embodiments are provided so that this disclosure will be thorough and complete.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used in the description of the invention herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention.
The term "and/or," "and/or," as used herein, includes any one of two or more of the listed items in relation to each other, as well as any and all combinations of the listed items in relation to each other, including any two of the listed items in relation to each other, any more of the listed items in relation to each other, or all combinations of the listed items in relation to each other.
In the present invention, "first aspect", "second aspect", "third aspect", etc. are used for descriptive purposes only and are not to be construed as indicating or implying a relative importance or quantity, nor as implying an importance or quantity of the indicated technical features. Moreover, "first," "second," "third," etc. are for non-exhaustive list description purposes only, and it should be understood that no closed limitation on the number is made.
Unless otherwise indicated or contradicted, terms or phrases used herein have the following meanings:
"alkyl" means containing a primary (n) carbon atom, orSaturated hydrocarbons of secondary carbon atoms, or tertiary carbon atoms, or quaternary carbon atoms, or combinations thereof lose one hydrogen atom to form a monovalent residue. Phrases containing this term, e.g., "C 1 ～C 5 Alkyl "means an alkyl group containing 1 to 5 carbon atoms, which at each occurrence may be, independently of one another, C 1 Alkyl, C 2 Alkyl, C 3 Alkyl, C 4 Alkyl or C 5 An alkyl group. Suitable examples include, but are not limited to: methyl (Me, -CH) 3 ) Ethyl (Et, -CH) 2 CH 3 ) 1-propyl (n-Pr, n-propyl, -CH 2 CH 2 CH 3 ) 2-propyl (i-Pr, i-propyl, -CH (CH) 3 ) 2 ) 1-butyl (n-Bu, n-butyl, -CH) 2 CH 2 CH 2 CH 3 ) 2-methyl-1-propyl (i-Bu, i-butyl, -CH) 2 CH(CH 3 ) 2 ) 2-butyl (s-Bu, s-butyl, -CH (CH) 3 )CH 2 CH 3 ) 2-methyl-2-propyl (t-Bu, t-butyl, -C (CH) 3 ) 3 ) 1-pentyl (n-pentyl, -CH) 2 CH 2 CH 2 CH 2 CH 3 ) 2-pentyl (-CH (CH 3) CH2CH2CH 3), 3-pentyl (-CH (CH) 2 CH 3 ) 2 ) 2-methyl-2-butyl (-C (CH) 3 ) 2 CH 2 CH 3 ) 3-methyl-2-butyl (-CH (CH) 3 )CH(CH 3 ) 2 ) 3-methyl-1-butyl (-CH) 2 CH 2 CH(CH 3 ) 2 ) 2-methyl-1-butyl (-CH) 2 CH(CH 3 )CH 2 CH 3 ) And 1-hexyl (-CH) 2 CH 2 CH 2 CH 2 CH 2 CH 3 )。
In the invention, the technical characteristics described in an open mode comprise a closed technical scheme composed of the listed characteristics and also comprise an open technical scheme comprising the listed characteristics.
In the present invention, the numerical ranges are referred to as continuous, and include the minimum and maximum values of the ranges, and each value between the minimum and maximum values, unless otherwise specified. Further, when a range refers to an integer, each integer between the minimum and maximum values of the range is included. Further, when multiple range description features or characteristics are provided, the ranges may be combined. In other words, unless otherwise indicated, all ranges disclosed herein are to be understood to include any and all subranges subsumed therein.
The temperature parameter in the present invention is not particularly limited, and may be a constant temperature treatment or a treatment within a predetermined temperature range. The constant temperature process allows the temperature to fluctuate within the accuracy of the instrument control.
The invention provides a tricarboxylic acid compound, which has the structural characteristics shown in a formula (I):
wherein R is 1 Selected from hydrogen, hydroxy and C 1 ～C 5 One of the alkyl groups;
R 2 and R is 3 Each independently is a polyolefin-based group.
The tricarboxylic acid compound provided by the invention can be used as a non-reactive compatibilizer lubricant, has good compatibilizer effect on common degradable composite materials, and can improve the processing fluidity of the materials. The structure of the tricarboxylic acid compound does not contain cyclic reactive functional groups such as maleic anhydride groups or epoxy groups, and the like, and is applied to the degradable composite material, so that the problem of poor fluidity caused by the formation of a high molecular cross-linked network structure between materials can be avoided, the melt index of the degradable composite material is not obviously reduced after processing, and the problem of degradation performance reduction caused by cross-linking reaction of the material is avoided.
The tricarboxylic acid compound provided by the invention has the structural characteristics of the tricarboxylic acid Y-shaped polyolefin, wherein the polyolefin structure is favorable for improving the processing fluidity of the composite material, and the polycarboxylic group is introduced at the molecular terminal by utilizing the principle of similar compatibility, so that the compatibility among different types of degradable materials is improved, the compatibilization effect is good, and the processing fluidity of the composite material is obviously improved and has better degradation performance.
In the invention, the tricarboxylic acid compound increases the molecular weight of the composite material on one hand, and introduces the polycarboxylic group with hydrogen bond function on the other hand, thereby being beneficial to improving the thermal stability of the composite material in the high-temperature processing process, having a certain branching structure, reducing the relative sliding among high polymer chains, greatly reducing the possibility of separating out the tricarboxylic acid compound in the composite material, and having better application effect.
In one example, the polyolefin-based carbon chain length is from C15 to C30.
In one example, the tricarboxylic acid compound has structural features represented by formulas (II-1) to (II-4):
wherein n is 7 to 30. Further, n is 7 to 15.
In one example, n is 15 to 30.
The invention also provides a preparation method of the tricarboxylic acid compound, which comprises the following raw materials in parts by mass:
the amino acid is selected from one or more of lysine and lysine derivatives.
It can be understood that the invention takes polyolefin wax as matrix resin, firstly grafts maleic anhydride group on the polyolefin wax to obtain polyolefin wax-maleic anhydride graft, and then carries out amidation reaction with specific kind of amino acid to prepare tricarboxylic acid compound, the reaction route is as follows:
wherein R' is a polyolefin group.
In one example, the lysine derivative is selected from, but not limited to: 5-hydroxy lysine, 5-methyl lysine, 5-ethyl lysine.
In one embodiment, the preparation raw materials of the tricarboxylic acid compound comprise the following components in parts by mass:
in one example, the polyolefin wax is selected from one or more of polyethylene wax and polypropylene wax.
In one example, the polyolefin wax has a carbon chain length of from C15 to C30.
In one example, the antioxidant is a combination of phosphite antioxidants and hindered phenol antioxidants.
In one example, the weight ratio of phosphite antioxidant to hindered phenol antioxidant is (1:1) - (2:1).
In one example, the catalyst is selected from one or more of p-toluene sulfonic acid and benzene sulfonic acid.
In one example, the method for preparing the tricarboxylic acid compound comprises the following steps:
mixing polyolefin wax and an antioxidant, carrying out melting treatment under the protection of nitrogen at the temperature of 105-125 ℃, heating to 150-170 ℃ after the polyolefin wax is melted, and stirring to prepare a pre-reaction mixture;
adding maleic anhydride into the pre-reaction mixture, reacting for 3-4 hours, adding a mixture of a catalyst and amino acid, and reacting for 2-3 hours;
introducing nitrogen to continue the reaction for 2-3 h to prepare the tricarboxylic acid compound.
Further, the temperature of the melt processing includes, but is not limited to: 105 ℃, 107 ℃, 110 ℃, 113 ℃, 115 ℃, 117 ℃, 120 ℃, 123 ℃, 125 ℃.
Further, after the polyolefin wax is melted, the temperature to which it is raised includes, but is not limited to: 150 ℃, 153 ℃, 155 ℃, 157 ℃,160 ℃, 163 ℃, 165 ℃, 167 ℃,170 ℃.
In one example, the stirring speed is 30rpm/min to 100rpm/min. Further, rotational speeds of agitation include, but are not limited to: 30rpm/min, 40rpm/min, 50rpm/min, 60rpm/min, 70rpm/min, 80rpm/min, 90rpm/min, 100rpm/min.
In one example, the rate of addition of maleic anhydride is 20mL/min to 50mL/min.
In one example, the catalyst and amino acid mixture is added at a rate of 20mL/min to 50mL/min.
In one example, the method for preparing the tricarboxylic acid compound further comprises the following steps:
adding the mixture of the catalyst and the amino acid to continue to react for 2 to 3 hours, cooling, purifying and drying to prepare the tricarboxylic acid compound.
In one example, the purification is performed in a 95% aqueous ethanol solution. Understandably, the reaction is finished to obtain a crude product of the tricarboxylic acid compound, the crude product is placed in a 95% ethanol aqueous solution for standing and precipitation, and the purified tricarboxylic acid compound is obtained by filtering and taking the precipitate.
In one example, the drying conditions include: the temperature is 85-95 ℃ and the time is 2.5-3.5 h. It will be appreciated that the tricarboxylic acid compound is obtained by drying and pulverizing, and is in the form of pale yellow powder.
The invention also provides application of the tricarboxylic acid compound or the tricarboxylic acid compound prepared by the preparation method in degradable materials. Further, the degradable material is a composite material of PLA and PBAT.
The tricarboxylic acid compound provided by the invention does not contain cyclic reactive functional groups such as maleic anhydride groups or epoxy groups, can be used as a compatibilizing lubricant to be applied to degradable composite materials, avoids the problems of poor fluidity and degradation performance reduction caused by cross-linking reaction of the materials, and has the advantages that the polyolefin structure is favorable for improving the processing fluidity of the composite materials, the carboxyl groups are introduced at the molecular terminals, the compatibility among different types of degradable materials is favorable, the compatibilizing effect is good, and the processing fluidity of the composite materials is obviously improved and has better degradation performance.
The present invention will be described in further detail with reference to specific examples. The raw materials, reagents and the like used in the following examples were obtained from commercial products unless otherwise specified.
The raw material components in the following examples are as follows:
polyethylene wax: qingdao bany chemical industry Co., ltd., brand BN200;
maleic anhydride: shanghai Kaijin chemical Co., ltd., trademark MA;
antioxidant 168: kaiyin chemical Co., ltd;
antioxidant 1010: kaiyin chemical Co., ltd;
p-toluene sulfonic acid (catalyst): jinan Hui jin Chuan chemical Co., ltd, industrial grade;
lysine: jinan Hui jin Chuan chemical Co., ltd, industrial grade;
hydroxylysine: shanghai source leaf Biotechnology Inc., analytical purity;
PLA grafted maleic anhydride: zhongshan Hua plastic technology Co., ltd;
domestic PLA compatilizer: ke Aisi chemical Co., ltd., brand BP-1.
Examples 1 to 4
Examples 1 to 4 each provide a tricarboxylic acid compound, the raw material components and proportions of the tricarboxylic acid compound of each example are shown in Table 1, and the total amount of all the raw material components in each example is 100 parts.
TABLE 1
The preparation method comprises the following steps:
(1) Putting polyolefin wax and an antioxidant into a reaction kettle, replacing nitrogen for three times, and performing melting treatment under the condition of nitrogen protection and 117 ℃;
(2) Placing maleic anhydride monomer into a storage tank A, and placing a catalyst and amino acid into a storage tank B to obtain a mixture of the catalyst and the amino acid;
(3) After the polyolefin wax in the step (1) is completely melted, the temperature is increased to 170 ℃, and a stirrer is started, wherein the rotating speed is 100rpm/min;
(4) Opening a liquid pump communicated with the storage tank A, adding maleic anhydride monomer into the pre-reaction mixture at the speed of 20mL/min, and closing the liquid pump after the addition is finished;
(5) Closing the valve of the horizontal condenser, opening the cooling water and the ventilation valve of the vertical condenser pipe, and continuing the reaction at 170 ℃ for 4 hours;
(6) Opening a liquid pump communicated with the storage tank B, adding a mixture of the catalyst and the amino acid at a speed of 20mL/min, closing the liquid pump after the addition is finished, and then continuing the reaction for 3 hours;
(7) Opening an oil-water separator, discharging redundant liquid, opening a door of a horizontal condenser, and introducing nitrogen into the kettle for continuous reaction for 2.5h;
(8) And after the reaction is finished, cooling the reaction kettle to 110 ℃, discharging, cooling, then placing in a 95% ethanol aqueous solution for purification, standing for precipitation, filtering, taking the precipitate, drying at 90 ℃ for 3 hours, and crushing to prepare the tricarboxylic acid compound.
Wherein, the infrared spectrogram of the tricarboxylic acid compound prepared in the example 1 is shown in figure 1. 2914.82cm in the figure -1 、2848.97cm -1 And 719.73cm -1 Is a characteristic peak of C-H structure, and is derived from polyethylene group introduced by polyethylene wax, and 1735.14cm -1 Is a characteristic peak of C=O structure, and is derived from tricarboxyl functional group in the structure, 1600-1659.43cm -1 The left and right spectral bands are-CO-NH 2 A small number of amide structural characteristic peaks, the remainder being C-H and C-N vibrational peaks.
Comparative examples 1 to 5
Comparative examples 1 to 5 each provide a compatibilizing lubricant, the raw material components and the proportions of the compatibilizing lubricants in each comparative example or the kinds of the compatibilizing lubricants are shown in table 2, and the total amount of the raw material components in all comparative examples is 100 parts.
TABLE 2
Comparative example 1 was prepared as follows:
(1) Putting polyolefin wax and an antioxidant into a reaction kettle, replacing nitrogen for three times, and performing melting treatment under the condition of nitrogen protection and 105 ℃;
(2) Placing maleic anhydride monomer into a storage tank A;
(3) After the polyolefin wax in the step (1) is completely melted, the temperature is increased to 170 ℃, and in the heating and melting process of the polyolefin wax, a stirrer is started, and the rotating speed is 100rpm/min, so as to prepare a pre-reaction mixture;
(4) Opening a liquid pump communicated with the storage tank A, adding maleic anhydride monomer into the pre-reaction mixture at the speed of 20mL/min, and closing the liquid pump after the addition is finished;
(5) Closing the valve of the horizontal condenser, opening the cooling water and the ventilation valve of the vertical condenser pipe, and continuing the reaction at 170 ℃ for 4 hours;
(6) Opening an oil-water separator, discharging redundant liquid, opening a door of a horizontal condenser, and introducing nitrogen into the kettle for continuous reaction for 2.5h;
(7) And after the reaction is finished, cooling the reaction kettle to 110 ℃, discharging, cooling, then placing in a 95% ethanol aqueous solution for purification, standing for precipitation, filtering, taking the precipitate, drying at 90 ℃ for 3 hours, and crushing to prepare the tricarboxylic acid compound.
The preparation methods of comparative examples 2 and 3 are the same as those of examples.
Mechanical property test
The extrusion process comprises the following steps:
according to mass percent, 3 percent of the tricarboxylic acid compound obtained in examples 1-4 or the compatibilizing lubricant obtained in comparative examples 1-5, 68 percent of PLA and 29 percent of PBAT are respectively and uniformly mixed, and are put into a double-screw extruder for granulation, so that the degradable composite material is prepared, and the processing temperature is 200 ℃. The degradable composite material was subjected to performance test, and the test results are shown in tables 3 and 4.
TABLE 3 Table 3
| Test item | Test standard | Unit (B) | Example 1 | Example 2 | Example 3 | Example 4 |
| Melting point temperature | DSC | ℃ | 133 | 131 | 134 | 130 |
| Tensile Strength | GB/T 1040 | MPa | 50.3 | 48.6 | 48.1 | 50.2 |
| Elongation at break | GB/T 1040 | ％ | 46.2 | 31.3 | 44.7 | 38.4 |
| Flexural Strength | GB/T 9341 | MPa | 3260 | 3300 | 3120 | 3200 |
| Notched impact Strength | GB/T 1843 | kJ/m 2 | 26.8 | 27.4 | 26.4 | 25.5 |
| Melt index | GB/T 3682 | g/10min | 17.3 | 16.6 | 16.5 | 17.1 |
TABLE 4 Table 4
Biodegradation performance test
Biodegradable composites prepared in each example and comparative example were subjected to a biodegradability test according to the method of GB/T19277.1-2011, and the results are shown in Table 5 and Table 6. The reference material is microcrystalline cellulose, the biological decomposition rate of the reference material after 45 days is 75%, and the requirement of GB/T20197-2006 on the effectiveness of the degradation material is met.
TABLE 5
TABLE 6
The results show that compared with comparative examples 1-5, the tricarboxylic acid compounds prepared in examples 1-4 of the invention have good compatibilization effect when being applied to the degradable composite material, and the degradable composite material has higher tensile strength, elongation at break, bending strength and notch impact strength, shows better processing fluidity, has better melting point temperature and melt index, and realizes the effect of remarkably improving the processing fluidity of the degradable composite material and simultaneously has better degradation performance. In addition, in the biodegradability test, the degradable composite material added with the tricarboxylic acid compounds prepared in the examples 1-4 shows better degradation performance, which shows that the tricarboxylic acid compound provided by the invention can be used as a compatibilizer lubricant to have obvious application effect in the degradable composite material.
The technical features of the above-described embodiments may be arbitrarily combined, and all possible combinations of the technical features in the above-described embodiments are not described for brevity of description, however, as long as there is no contradiction between the combinations of the technical features, they should be considered as the scope of the description.
The above examples illustrate only a few embodiments of the invention, which are described in detail and are not to be construed as limiting the scope of the invention. It should be noted that it will be apparent to those skilled in the art that several variations and modifications can be made without departing from the spirit of the invention, which are all within the scope of the invention. Accordingly, the scope of protection of the present invention is to be determined by the appended claims.
Claims (12)
1. A tricarboxylic acid compound is characterized by having a structural feature represented by formula (I):
wherein R is 1 Selected from hydrogen, hydroxy and C 1 ～C 5 One of the alkyl groups;
R 2 and R is 3 Each independently is a polyolefin-based group.
2. The tricarboxylic acid compound of claim 1, which has structural characteristics represented by formulas (II-1) to (II-4):
wherein n is 15 to 30.
3. A method for preparing the tricarboxylic acid compound as in claim 1 or 2, wherein the preparation raw materials of the tricarboxylic acid compound comprise the following components in parts by mass:
the amino acid is selected from one or more of lysine and lysine derivatives.
4. The preparation method of the tricarboxylic acid compound as in claim 3, wherein the preparation raw materials of the tricarboxylic acid compound comprise the following components in parts by mass:
5. a process for the preparation of a tricarboxylic acid compound as claimed in claim 3, wherein the polyolefin wax is selected from one or more of polyethylene wax and polypropylene wax; and/or
The carbon chain length of the polyolefin wax is C15-C30.
6. The method for preparing a tricarboxylic acid compound of claim 3, wherein the antioxidant is a phosphite antioxidant and a hindered phenol antioxidant.
7. The method for producing a tricarboxylic acid compound of claim 6, wherein the weight ratio of the phosphite antioxidant to the hindered phenol antioxidant is (1:1) to (2:1).
8. A process for the preparation of a tricarboxylic acid compound as defined in claim 3, wherein the catalyst is selected from one or more of p-toluene sulfonic acid and benzene sulfonic acid.
9. The method for producing a tricarboxylic acid compound according to any one of claims 3 to 8, comprising the steps of:
mixing the polyolefin wax and the antioxidant, carrying out melting treatment under the protection of nitrogen at the temperature of 105-125 ℃, heating to 150-170 ℃ after the polyolefin wax is melted, and stirring to prepare a pre-reaction mixture;
adding the maleic anhydride into the pre-reaction mixture, reacting for 3-4 hours, adding the mixture of the catalyst and the amino acid, and reacting for 2-3 hours;
introducing nitrogen to continue the reaction for 2-3 h to prepare the tricarboxylic acid compound.
10. The method for producing a tricarboxylic acid compound of claim 9, wherein the stirring speed is 30rpm/min to 100rpm/min.
11. The method for producing a tricarboxylic acid compound of claim 9, wherein the speed of adding the maleic anhydride is 20mL/min to 50mL/min; and/or
The speed of adding the mixture of the catalyst and the amino acid is 20 mL/min-50 mL/min.
12. Use of a tricarboxylic acid compound as defined in any one of claims 1 to 2 or a tricarboxylic acid compound prepared by the preparation method as defined in any one of claims 3 to 11 in a degradable material.
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Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS59197459A (en) * | 1983-04-26 | 1984-11-09 | Ube Ind Ltd | Production of polyamide composition |
| US5342886A (en) * | 1988-03-24 | 1994-08-30 | Atochem | α-monoolefinic graft copolymers |
| CN1495209A (en) * | 2002-08-30 | 2004-05-12 | ������ѧ��ʽ���� | Polyolefine macromonomer, graftmer obtained by utilizing polyolefine macromonomer and its application |
| CA2620633A1 (en) * | 2005-09-06 | 2007-03-15 | Trung Bui-Khac | Modified biodegradable polymers, preparation and use thereof for making biomaterials and dressings |
| CN110551337A (en) * | 2019-10-14 | 2019-12-10 | 上海联景高分子材料有限公司 | EVA and TPU melt blending to prepare elastomer alloy and composition foaming material thereof |
| CN111621025A (en) * | 2020-06-15 | 2020-09-04 | 山东省高速路桥养护有限公司 | Solid warm-mix modified double-effect asphalt modifier and preparation method thereof |
| CN113234307A (en) * | 2021-06-29 | 2021-08-10 | 山东农业大学 | Full-degradable antibacterial food packaging film and preparation method thereof |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CA2518298A1 (en) * | 2005-09-06 | 2007-03-06 | Chaimed Technologies Inc. | Biodegradable polymers, their preparation and their use for the manufacture of bandages |
-
2022
- 2022-03-02 CN CN202210219476.9A patent/CN114507306B/en active Active
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS59197459A (en) * | 1983-04-26 | 1984-11-09 | Ube Ind Ltd | Production of polyamide composition |
| US5342886A (en) * | 1988-03-24 | 1994-08-30 | Atochem | α-monoolefinic graft copolymers |
| CN1495209A (en) * | 2002-08-30 | 2004-05-12 | ������ѧ��ʽ���� | Polyolefine macromonomer, graftmer obtained by utilizing polyolefine macromonomer and its application |
| CA2620633A1 (en) * | 2005-09-06 | 2007-03-15 | Trung Bui-Khac | Modified biodegradable polymers, preparation and use thereof for making biomaterials and dressings |
| CN110551337A (en) * | 2019-10-14 | 2019-12-10 | 上海联景高分子材料有限公司 | EVA and TPU melt blending to prepare elastomer alloy and composition foaming material thereof |
| CN111621025A (en) * | 2020-06-15 | 2020-09-04 | 山东省高速路桥养护有限公司 | Solid warm-mix modified double-effect asphalt modifier and preparation method thereof |
| CN113234307A (en) * | 2021-06-29 | 2021-08-10 | 山东农业大学 | Full-degradable antibacterial food packaging film and preparation method thereof |
Non-Patent Citations (2)
| Title |
|---|
| 益小苏，李岩编著.《生物质树脂、纤维及生物复合材料》.中国建材工业出版社,2017,第10页. * |
| 颜彩繁主编.《固体物理专题实验》.南开大学出版社,2020,第160-161页. * |
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