CN114507306A - Tricarboxylic acid compound and preparation method and application thereof - Google Patents
Tricarboxylic acid compound and preparation method and application thereof Download PDFInfo
- Publication number
- CN114507306A CN114507306A CN202210219476.9A CN202210219476A CN114507306A CN 114507306 A CN114507306 A CN 114507306A CN 202210219476 A CN202210219476 A CN 202210219476A CN 114507306 A CN114507306 A CN 114507306A
- Authority
- CN
- China
- Prior art keywords
- tricarboxylic acid
- acid compound
- antioxidant
- composite material
- preparation
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- -1 Tricarboxylic acid compound Chemical class 0.000 title claims abstract description 68
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- 239000000463 material Substances 0.000 claims abstract description 28
- 238000000034 method Methods 0.000 claims abstract description 14
- 229920000098 polyolefin Polymers 0.000 claims description 31
- 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 20
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims description 18
- 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 11
- 238000002844 melting Methods 0.000 claims description 10
- 230000008018 melting Effects 0.000 claims description 10
- 239000011541 reaction mixture Substances 0.000 claims description 9
- 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
- 239000004698 Polyethylene Substances 0.000 claims description 7
- 125000000217 alkyl group Chemical group 0.000 claims description 7
- 229920000573 polyethylene Polymers 0.000 claims description 7
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 6
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 6
- 229910052739 hydrogen Inorganic materials 0.000 claims description 5
- 239000001257 hydrogen Substances 0.000 claims description 5
- 150000003628 tricarboxylic acids Chemical class 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
- 150000001875 compounds Chemical class 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
- 150000002431 hydrogen Chemical class 0.000 claims 1
- 239000002131 composite material Substances 0.000 abstract description 39
- 238000006243 chemical reaction Methods 0.000 abstract description 18
- 238000012545 processing Methods 0.000 abstract description 16
- 230000015556 catabolic process Effects 0.000 abstract description 14
- 238000006731 degradation reaction Methods 0.000 abstract description 14
- 230000000694 effects Effects 0.000 abstract description 10
- 239000000314 lubricant Substances 0.000 abstract description 10
- 238000004132 cross linking Methods 0.000 abstract description 6
- 125000000524 functional group Chemical group 0.000 abstract description 5
- 230000000052 comparative effect Effects 0.000 description 9
- 239000007788 liquid Substances 0.000 description 8
- 229920001896 polybutyrate Polymers 0.000 description 7
- 239000004626 polylactic acid Substances 0.000 description 6
- 238000003860 storage Methods 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
- 230000002349 favourable effect Effects 0.000 description 5
- 229920000747 poly(lactic acid) Polymers 0.000 description 5
- 239000002244 precipitate Substances 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- 208000034530 PLAA-associated neurodevelopmental disease Diseases 0.000 description 4
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 4
- 150000001721 carbon Chemical group 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- 125000004122 cyclic group Chemical group 0.000 description 4
- 238000007599 discharging Methods 0.000 description 4
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 4
- 239000000178 monomer Substances 0.000 description 4
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- 229920001577 copolymer Polymers 0.000 description 3
- IDGUHHHQCWSQLU-UHFFFAOYSA-N ethanol;hydrate Chemical compound O.CCO IDGUHHHQCWSQLU-UHFFFAOYSA-N 0.000 description 3
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 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
- 125000004108 n-butyl group Chemical group [H]C([H])([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
- 238000001556 precipitation Methods 0.000 description 3
- 238000000746 purification Methods 0.000 description 3
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 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
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 239000004677 Nylon Substances 0.000 description 2
- 238000005452 bending Methods 0.000 description 2
- 238000006065 biodegradation reaction Methods 0.000 description 2
- 238000013329 compounding Methods 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
- 238000001914 filtration Methods 0.000 description 2
- 238000002329 infrared spectrum Methods 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
- 230000001376 precipitating effect Effects 0.000 description 2
- 239000012925 reference material Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000009423 ventilation Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 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
- AXKZIDYFAMKWSA-UHFFFAOYSA-N 1,6-dioxacyclododecane-7,12-dione Chemical compound O=C1CCCCC(=O)OCCCCO1 AXKZIDYFAMKWSA-UHFFFAOYSA-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
- WSQZNZLOZXSBHA-UHFFFAOYSA-N 3,8-dioxabicyclo[8.2.2]tetradeca-1(12),10,13-triene-2,9-dione Chemical compound O=C1OCCCCOC(=O)C2=CC=C1C=C2 WSQZNZLOZXSBHA-UHFFFAOYSA-N 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
- 241000252233 Cyprinus carpio Species 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 group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 231100000209 biodegradability test Toxicity 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 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
- QJHBJHUKURJDLG-UHFFFAOYSA-N hydroxy-L-lysine Natural products NCCCCC(NO)C(O)=O QJHBJHUKURJDLG-UHFFFAOYSA-N 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
- 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
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 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
- 230000010355 oscillation Effects 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
- 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
- 229930195734 saturated hydrocarbon Natural products 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
Images
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 nitrogen-containing compounds, 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 and a preparation method and application thereof. The tricarboxylic acid compound has the structural characteristics shown in the formula (I). The structure of the ternary carboxylic acid compound does not contain an annular reactive functional group, and the ternary carboxylic acid compound is applied to a degradable composite material as a compatibilization lubricant, so that the problems of poor fluidity and reduced degradation performance caused by a cross-linking reaction of the material can be solved, the compatibilization effect is good, the processing fluidity of the composite material is obviously improved, the composite material has better degradation performance, the thermal stability of the composite material in a high-temperature processing process is favorably 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
By degradable material is meant a material that is degradable in both thermodynamic and kinetic terms over a period of time. According to the external factors of degradation, the degradable materials are divided into: a photodegradable material, a biodegradable material, etc., wherein the biodegradable material, as a naturally degradable material, plays a unique role in environmental protection, and research and development thereof have been rapidly developed and are considered as an effective solution to "white pollution".
Common biodegradable materials in the market at present comprise polylactic acid (PLA), a copolymer (PBAT) of butylene adipate and butylene terephthalate, polybutylene succinate (PBS) and the like, wherein the PLA is derived from natural starch, has rich sources, has the characteristics of no toxicity, no stimulation, good biocompatibility, high strength, good processability, biodegradability and the like, and is most widely applied. However, PLA has problems of poor toughness and insufficient fluidity, and in practice, PLA, PBAT, PBS, and other materials are usually required to be melt-blended to improve toughness, and a compatibilizer or compatibilizer is required to be added to improve compatibility of the composite material, so as to improve mechanical properties of the composite material prepared by blending.
The research is carried out to prepare a graft copolymer of the copolymer and the nylon as a compatilizer between the styrene polymer and the nylon by taking the copolymer of the styrene and the maleic anhydride as a macromolecular activator and further adding lactam and an initiator; in addition, researches have been made on adding modified starch rich in epoxy groups into the PLA-PBAT blend polymer, so that the compatibility between PLA and PBAT is better.
However, these compatibilizers contain a large amount of maleic anhydride groups or epoxy groups, so that the compatibilizers have more cyclic active groups, and can react with hydroxyl groups on materials such as PLA and PBAT, and cross-linking can occur among degradable materials, so that the fluidity of a blending system is obviously reduced, and the subsequent melting and molding processing of the prepared degradable composite material is not facilitated. In addition, after the degradable composite material forms a certain polymer cross-linked network structure, external moisture is difficult to permeate into the polymer, so that the degradation rate of the material is influenced, and when the content of the compatilizer is too high, the material can not be degraded.
Disclosure of Invention
Based on the above, the invention provides a non-reactive ternary carboxylic acid compound, and a preparation method and application thereof. The tricarboxylic acid compound can be used as a compatibilization lubricant to effectively improve the fluidity of the degradable composite material, and the problem that the degradation performance of the material is reduced due to a crosslinking reaction is solved, so that the compatibilization effect is good.
The specific technical scheme is as follows:
in a first aspect of the present invention, there is provided a tricarboxylic acid compound having a structural feature represented by formula (I):
wherein R is1Selected from hydrogen, hydroxy and C1～C5One of alkyl groups;
R2and R3Each independently a polyolefin group.
In one embodiment, the tricarboxylic acid compounds have structural characteristics shown in formulas (II-1) to (II-4):
wherein n is 15-30.
The second aspect of the invention provides a preparation method of a tricarboxylic acid compound, 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.
In one embodiment, the raw materials for preparing the tricarboxylic acid compounds 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 combination of 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-toluenesulfonic acid and benzenesulfonic acid.
In one embodiment, the preparation method of the tricarboxylic acid compound comprises the following steps:
mixing the polyolefin wax and an antioxidant, carrying out melting treatment under the conditions of nitrogen protection and 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 h, adding the mixture of the catalyst and the amino acid, and reacting for 2-3 h;
and introducing nitrogen to continue reacting for 2-3 h to prepare the tricarboxylic acid compound.
In one embodiment, the stirring speed is 30rpm/min to 100 rpm/min.
In one embodiment, the speed of adding the maleic anhydride is 20mL/min to 50 mL/min; and/or
The rate of adding the mixture of the catalyst and the amino acid is 20mL/min to 50 mL/min.
In a third aspect of the present invention, there is provided an application of the tricarboxylic acid compounds or the tricarboxylic acid compounds prepared by the above preparation method in degradable materials.
Compared with the prior art, the invention has the following beneficial effects:
the tricarboxylic 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 compatibilization lubricant to be applied to degradable composite materials, can avoid the problems of poor fluidity and degradation performance reduction caused by cross-linking reaction of materials, is favorable for improving the processing fluidity of the composite materials due to a polyolefin structure, is favorable for increasing the compatibility among different types of degradable materials due to the introduction of a multi-carboxyl group at the tail end of a molecule, has a good compatibilization effect, and has good degradation performance while the processing fluidity of the composite materials is remarkably improved.
In addition, the molecular weight of the composite material is increased by the tricarboxylic acid compound, and the multi-carboxyl group with hydrogen bond function is introduced, so that the thermal stability of the composite material in the high-temperature processing process is improved, a certain branched structure is realized, the relative sliding between high molecular chains is reduced, the possibility of precipitation of the composite material in the composite material is greatly reduced, and the actual application requirement is better met.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings needed to be used in the description of the embodiments or the prior art will be briefly introduced below, and it is obvious that the drawings in the following description are some embodiments of the present invention, and for those skilled in the art, other drawings can be obtained according to the drawings without creative efforts;
FIG. 1 is an infrared spectrum of a tricarboxylic acid compound prepared in example 1.
Detailed Description
In order that the invention may be more readily understood, reference will now be made to the following more particular description of the invention, examples of which are set forth below. 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.
As used herein, the term "and/or", "and/or" includes any one of two or more of the associated listed items, as well as any and all combinations of the associated listed items, including any two of the associated listed items, any more of the associated listed items, or all combinations of the associated listed items.
In the present invention, "first aspect", "second aspect", "third aspect" and the like are used for descriptive purposes only and are not to be construed as indicating or implying a relative importance or quantity, nor are they to be construed as implicitly indicating the importance or quantity of the technical feature indicated. Also, "first," "second," "third," etc. are for non-exhaustive enumeration description purposes only and should not be construed as constituting a closed limitation to the number.
Unless otherwise stated or contradicted, terms or phrases used herein have the following meanings:
"alkyl" refers to a monovalent residue resulting from the loss of one hydrogen atom from a saturated hydrocarbon containing a primary (normal) carbon atom, or a secondary carbon atom, or a tertiary carbon atom, or a quaternary carbon atom, or a combination thereof. Phrases containing the term, e.g., "C1～C5The alkyl group "means an alkyl group having 1 to 5 carbon atoms, and may be C independently at each occurrence1Alkyl radical, C2Alkyl radical, C3Alkyl radical, C4Alkyl or C5An alkyl group. Suitable examples include, but are not limited to: methyl (Me, -CH)3) Ethyl (Et-CH)2CH3) 1-propyl (n-Pr, n-propyl, -CH)2CH2CH3) 2-propyl (i-Pr, i-propyl, -CH (CH)3)2) 1-butyl (n-Bu, n-butyl, -CH)2CH2CH2CH3) 2-methyl-1-propyl (i-Bu, i-butyl, -CH)2CH(CH3)2) 2-butyl (s-Bu, s-butyl, -CH (CH)3)CH2CH3) 2-methyl-2-propyl (t-Bu, t-butyl, -C (CH)3)3) 1-pentyl (n-pentyl, -CH)2CH2CH2CH2CH3) 2-pentyl (-CH (CH3) CH2CH2CH3), 3-pentyl (-CH (CH)2CH3)2) 2-methyl-2-butyl (-C (CH)3)2CH2CH3) 3-methyl-2-butyl (-CH (CH)3)CH(CH3)2) 3-methyl-1-butyl (-CH)2CH2CH(CH3)2) 2-methyl-1-butyl (-CH)2CH(CH3)CH2CH3) And 1-hexyl (-CH)2CH2CH2CH2CH2CH3)。
In the present invention, the technical features described in the open type include a closed technical solution composed of the listed features, and also include an open technical solution including the listed features.
In the present invention, the numerical intervals are regarded as continuous, and include the minimum and maximum values of the range 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-describing 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 encompass 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 certain 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 is1Selected from hydrogen, hydroxy and C1～C5One of alkyl groups;
R2and R3Each independently a polyolefin group.
The tricarboxylic acid compound provided by the invention can be used as a non-reactive compatibilization lubricant, has a good compatibilization effect on common degradable composite materials, and can improve the processing fluidity of the materials. The structure of the ternary carboxylic acid compound does not contain cyclic reactive functional groups such as maleic anhydride groups or epoxy groups, and the like, so that the problem of poor fluidity caused by the formation of a macromolecular cross-linked network structure between materials can be solved when the ternary carboxylic acid compound is applied to the degradable composite material, the melt index of the processed degradable composite material is not obviously reduced, and the problem of degradation performance reduction caused by cross-linking reaction of the material is solved.
The tricarboxylic acid compound provided by the invention has the structural characteristics of tricarboxylic acid Y-shaped polyolefin, wherein the polyolefin structure is favorable for improving the processing flowability of the composite material, and by utilizing the principle of similar compatibility, a multi-carboxyl group is introduced into the molecular tail end, so that the compatibility among different types of degradable materials is favorably increased, the compatibilization effect is good, the processing flowability of the composite material is obviously improved, and the composite material has better degradation performance.
In the invention, the molecular weight of the composite material is increased by the tricarboxylic acid compounds, and the multi-carboxyl group with hydrogen bond function is introduced, so that the thermal stability of the composite material in the high-temperature processing process is improved, and the composite material has a certain branched structure, so that the relative sliding among high molecular chains is reduced, the possibility of precipitation of the composite material in the composite material is greatly reduced, and the application effect is better.
In one example, the carbon chain length of the polyolefin group is from C15 to C30.
In one example, tricarboxylic compounds have structural features represented by formulas (II-1) to (II-4):
wherein n is 7 to 30. Further, n is 7-15.
In one example, n is 15-30.
The invention also provides a preparation method of the ternary carboxylic acid compound, and the preparation raw materials of the ternary carboxylic acid compound comprise the following components 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 maleic anhydride groups are grafted on the polyolefin wax to obtain polyolefin wax-maleic anhydride grafts, and then the polyolefin wax-maleic anhydride grafts are further subjected to amidation reaction with specific types of amino acids to prepare ternary carboxylic acid compounds, wherein 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-hydroxylysine, 5-methyllysine and 5-ethyllysine.
In one embodiment, the preparation raw materials of the tricarboxylic acid compounds 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 carbon chain length of the polyolefin wax is from C15 to C30.
In one example, the antioxidant is a combination of a phosphite antioxidant and a hindered phenol antioxidant.
In one example, the weight ratio of the phosphite antioxidant to the hindered phenol antioxidant is (1:1) to (2: 1).
In one example, the catalyst is selected from one or more of p-toluenesulfonic acid and benzenesulfonic acid.
In one example, the preparation method of the tricarboxylic acid compound comprises the following steps:
mixing polyolefin wax and an antioxidant, carrying out melting treatment under the conditions of nitrogen protection and 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 h, adding a mixture of a catalyst and amino acid, and reacting for 2-3 h;
and introducing nitrogen to continue reacting for 2-3 h to prepare the tricarboxylic acid compound.
Further, the temperature of the melt processing includes, but is not limited to: 105 deg.C, 107 deg.C, 110 deg.C, 113 deg.C, 115 deg.C, 117 deg.C, 120 deg.C, 123 deg.C, 125 deg.C.
Further, the temperature to which the polyolefin wax is heated after melting 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 100 rpm/min. Further, the rotational speed of the agitation includes, but is not limited to: 30rpm/min, 40rpm/min, 50rpm/min, 60rpm/min, 70rpm/min, 80rpm/min, 90rpm/min, 100 rpm/min.
In one example, the maleic anhydride is added at a rate of 20mL/min to 50 mL/min.
In one example, the mixture of catalyst and amino acid is added at a rate of 20mL/min to 50 mL/min.
In one example, the preparation method of the tricarboxylic acid compound further comprises the following steps:
adding a mixture of a catalyst and amino acid, continuously reacting for 2-3 h, cooling, purifying, and drying to prepare the tricarboxylic acid compound.
In one example, the purification is performed in 95% aqueous ethanol. Understandably, the crude product of the tricarboxylic acid compounds is obtained after the reaction is finished, the crude product is placed in 95 percent ethanol water solution for standing and precipitation, and the precipitate is filtered to obtain the purified tricarboxylic acid compounds.
In one example, the drying conditions include: the temperature is 85-95 ℃ and the time is 2.5-3.5 h. It is understood that the tricarboxylic acid compound is obtained by drying and pulverizing, and is in light yellow powder.
The invention also provides the application of the ternary carboxylic acid compound or the ternary carboxylic 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 compatibilization 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, is favorable for improving the processing fluidity of the composite materials due to a polyolefin structure, is favorable for increasing the compatibility among different types of degradable materials due to the introduction of a multi-carboxyl group at the tail end of a molecule, has a good compatibilization effect, and has good degradation performance while the processing fluidity of the composite materials is remarkably improved.
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 are commercially available products unless otherwise specified.
The raw material components in the following examples are as follows:
polyethylene wax: qingdao Bangni chemical Co., Ltd, brand BN 200;
maleic anhydride: shanghai Kayin chemical Co., Ltd., trade name MA;
antioxidant 168: shanghai Kaiyn chemical Co., Ltd;
antioxidant 1010: shanghai Kaiyn chemical Co., Ltd;
p-toluenesulfonic acid (catalyst): jinan Hui Jinchuan chemical Co., Ltd, industrial grade;
lysine: jinan Hui Jingchuan chemical Co., Ltd, industrial grade;
hydroxy lysine: shanghai-sourced leaf Biotechnology Co., Ltd, analytically pure;
PLA grafted maleic anhydride: hua plastic science and technology Co., Ltd, Zhongshan City;
domestic PLA compatibilizer: koies chemical Co., Ltd, under the designation BP-1.
Examples 1 to 4
Examples 1 to 4 each provide a tricarboxylic acid-based compound, and the raw material components and the compounding ratio of the tricarboxylic acid-based 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 with nitrogen for three times, and then carrying out melting treatment under the conditions of nitrogen protection and 117 ℃;
(2) placing a maleic anhydride monomer in a storage tank A, and placing a catalyst and amino acid in a storage tank B to obtain a mixture of the catalyst and the amino acid;
(3) when the polyolefin wax is completely melted in the step (1), raising the temperature to 170 ℃, and starting a stirrer at the rotating speed of 100 rpm/min;
(4) opening a liquid pump communicated with the storage tank A, adding the 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 the speed of 20mL/min, closing the liquid pump after the addition is finished, and continuing the reaction for 3 hours;
(7) opening the oil-water separator, discharging redundant liquid, opening a door of the horizontal condenser, and introducing nitrogen into the kettle to continue to react for 2.5 hours;
(8) after the reaction is finished, cooling the reaction kettle to 110 ℃, discharging and cooling, then putting the reaction kettle into 95% ethanol water solution for purification, standing and precipitating, filtering, taking precipitate, drying the precipitate for 3 hours at 90 ℃, and then crushing to prepare the tricarboxylic acid compound.
The infrared spectrum of the tricarboxylic acid compound obtained in example 1 is shown in FIG. 1. 2914.82cm in the figure-1、2848.97cm-1And 719.73cm-1Is of C-H structureCharacteristic peak of (A), derived from polyethylene-based polyethylene introduced by polyethylene wax, and 1735.14cm-1Is a characteristic peak of a C ═ O structure, is derived from a tricarboxyl functional group in the structure, and is 1600-1659.43cm-1The left and right spectral bands are-CO-NH2A few characteristic peaks of the amide structure, the remainder being the oscillation peaks of C-H and C-N.
Comparative examples 1 to 5
Comparative examples 1 to 5 each provide a compatibilized lubricant, the raw material components and the compounding ratio of the compatibilized lubricant or the types of the compatibilized lubricant in each comparative example are shown in table 2, and the total amount of the raw material components in all the comparative examples is 100 parts.
TABLE 2
Comparative example 1 the preparation method was as follows:
(1) putting polyolefin wax and an antioxidant into a reaction kettle, replacing with nitrogen for three times, and then carrying out melting treatment under the conditions of nitrogen protection and 105 ℃;
(2) placing maleic anhydride monomers into a storage tank A;
(3) when the polyolefin wax is completely melted in the step (1), raising the temperature to 170 ℃, and starting a stirrer at the rotating speed of 100rpm/min to prepare a pre-reaction mixture in the process of heating and melting the polyolefin wax;
(4) opening a liquid pump communicated with the storage tank A, adding the 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 the oil-water separator, discharging redundant liquid, opening a door of the horizontal condenser, and introducing nitrogen into the kettle to continue to react for 2.5 hours;
(7) after the reaction is finished, cooling the reaction kettle to 110 ℃, discharging and cooling, then putting the reaction kettle into 95% ethanol water solution for purification, standing and precipitating, filtering, taking precipitate, drying the precipitate at 90 ℃ for 3 hours, and then crushing to prepare the tricarboxylic acid compound.
The preparation methods of comparative examples 2 and 3 were the same as those of examples.
Mechanical Property test
The extrusion processing technology comprises the following steps:
respectively and uniformly mixing 3% of the tricarboxylic acid compounds obtained in examples 1-4 or the compatibilization lubricant obtained in comparative examples 1-5, 68% of PLA and 29% of PBAT in percentage by mass, and putting the mixture into a double-screw extruder for granulation to prepare the degradable composite material, wherein the processing temperature is 200 ℃. The degradable composite material was subjected to performance tests, and the test results are shown in tables 3 and 4.
TABLE 3
| Test items | Test standard | Unit of | 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 |
| Bending strength | GB/T 9341 | MPa | 3260 | 3300 | 3120 | 3200 |
| Notched impact strength | GB/T 1843 | kJ/m2 | 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
Biodegradability test
The biodegradable composite materials prepared in each example and comparative example were subjected to a biodegradation rate test according to the method of GB/T19277.1-2011, and the results are shown in tables 5 and 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 degradation materials is met.
TABLE 5
TABLE 6
The results show that compared with comparative examples 1 to 5, after the tricarboxylic acid compounds prepared in examples 1 to 4 of the present invention are applied to the degradable composite material, the compatibilization effect is good, the degradable composite material has higher tensile strength, elongation at break, bending strength and notch impact strength, and shows better processing flowability, and has better melting point temperature and melt index, so that the effect of having better degradation performance while significantly improving the processing flowability of the degradable composite material is achieved. In addition, in a biodegradation performance test, the degradable composite material added with the tricarboxylic acid compounds prepared in the embodiments 1 to 4 shows better degradation performance, and the tricarboxylic acid compounds provided by the invention can be used as a compatibilization lubricant and have a remarkable application effect in the degradable composite material.
The technical features of the embodiments described above may be arbitrarily combined, and for the sake of brevity, all possible combinations of the technical features in the embodiments described above are not described, but should be considered as being within the scope of the present specification as long as there is no contradiction between the combinations of the technical features.
The above-mentioned embodiments only express several embodiments of the present invention, and the description thereof is specific and detailed, but not to be understood as limiting the scope of the invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention. Therefore, the protection scope of the present patent shall be subject to the appended claims.
Claims (12)
1. A tricarboxylic acid compound, which is characterized by having the structural characteristics shown in the formula (I):
wherein R is1Selected from hydrogen, hydroxy and C1～C5One of alkyl groups;
R2and R3Each independently a polyolefin group.
2. The tricarboxylic acid-based compound according to claim 1, which has structural features represented by formulas (II-1) to (II-4):
wherein n is 15-30.
3. The preparation method of the tricarboxylic acid compounds is characterized in that the preparation raw materials of the tricarboxylic acid compounds comprise the following components in parts by mass:
the amino acid is selected from one or more of lysine and lysine derivatives.
4. The method for preparing tricarboxylic acid compounds according to claim 3, wherein the raw materials for preparing the tricarboxylic acid compounds comprise the following components in parts by mass:
5. the method for preparing tricarboxylic acids according to 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 of claim 3, wherein the antioxidant is a combination of a phosphite antioxidant and a hindered phenol antioxidant.
7. The method of claim 6, wherein the weight ratio of the phosphite antioxidant to the hindered phenol antioxidant is (1:1) - (2: 1).
8. The method of claim 3, wherein the catalyst is selected from one or more of p-toluenesulfonic acid and benzenesulfonic acid.
9. The method of any one of claims 3 to 8, comprising the steps of:
mixing the polyolefin wax and an antioxidant, carrying out melting treatment under the conditions of nitrogen protection and 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 h, adding the mixture of the catalyst and the amino acid, and reacting for 2-3 h;
and introducing nitrogen to continue reacting for 2-3 h to prepare the tricarboxylic acid compound.
10. The method of claim 9, wherein the stirring speed is 30rpm/min to 100 rpm/min.
11. The method of claim 9, wherein the maleic anhydride is added at a rate of 20-50 mL/min; and/or
The rate of adding the mixture of the catalyst and the amino acid is 20mL/min to 50 mL/min.
12. Use of the tricarboxylic acid compounds according to any one of claims 1 to 2 or the tricarboxylic acid compounds prepared by the preparation method according to any one of claims 3 to 11 in degradable materials.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210219476.9A CN114507306B (en) | 2022-03-02 | 2022-03-02 | Tricarboxylic acid compound and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210219476.9A CN114507306B (en) | 2022-03-02 | 2022-03-02 | Tricarboxylic acid compound and preparation method and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN114507306A true CN114507306A (en) | 2022-05-17 |
| CN114507306B CN114507306B (en) | 2024-02-27 |
Family
ID=81553537
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202210219476.9A Active CN114507306B (en) | 2022-03-02 | 2022-03-02 | Tricarboxylic acid compound and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN114507306B (en) |
Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS59197459A (en) * | 1983-04-26 | 1984-11-09 | Ube Ind Ltd | Method for manufacturing 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 |
| US20090035356A1 (en) * | 2005-09-06 | 2009-02-05 | 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 |
-
2022
- 2022-03-02 CN CN202210219476.9A patent/CN114507306B/en active Active
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS59197459A (en) * | 1983-04-26 | 1984-11-09 | Ube Ind Ltd | Method for manufacturing 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 |
| US20090035356A1 (en) * | 2005-09-06 | 2009-02-05 | 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 (1)
| Title |
|---|
| 益小苏，李岩编著, 中国建材工业出版社, pages: 160 - 161 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN114507306B (en) | 2024-02-27 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US9206306B2 (en) | Resin composition, film, bag product and production process of resin composition | |
| Chaiwutthinan et al. | Biodegradable plastics prepared from poly (lactic acid), poly (butylene succinate) and microcrystalline cellulose extracted from waste-cotton fabric with a chain extender | |
| CN115058103B (en) | Preparation of epoxy cardanol-based chain extender modified PBAT-PLA composite membrane | |
| CN105838049B (en) | Biodegradable polylactic acid base shape memory composite and preparation method thereof | |
| CN111205604B (en) | Ultrathin high-strength high-toughness biodegradable mulch film material, film, preparation method and application | |
| CN105860468A (en) | Biodegradable supertough polylactic acid (PLA) blend material and preparation method thereof | |
| US5447669A (en) | Melt-processed polymer blends | |
| CN102030861B (en) | Method for preparing epoxy functional acrylate polymer | |
| CN112694730B (en) | A method for preparing high-performance and high-fluidity polylactic acid based on hyperbranched polymers | |
| CN111763410B (en) | Biodegradable PBAT alloy with high starch content and preparation method thereof | |
| CN107880503B (en) | A kind of PHBV/PBAT/EHBP blend and preparation method thereof | |
| CN102492101B (en) | ABS melt-grafting glycidyl methacrylate and preparation method thereof | |
| CN113956627B (en) | Precipitation-resistant and low-haze starch-based fully biodegradable PBAT alloy and preparation method thereof | |
| JPH06184418A (en) | Biodegradable polymer composition | |
| CN111087789A (en) | High-impact polycarbonate/polylactic acid resin composition and preparation method thereof | |
| Gong et al. | In situ grafting approach for preparing PLA/PHBV degradable blends with improved mechanical properties | |
| CN115286867B (en) | Nanometer compatibilized polypropylene polystyrene composition and preparation method thereof | |
| CN114507306B (en) | Tricarboxylic acid compound and preparation method and application thereof | |
| CN102408524B (en) | Multi-monomer melt-grafted acrylonitrile-butadiene-styrene copolymer and preparation method thereof | |
| JPH11240962A (en) | Molded product of polyester resin composition having improved processabillty | |
| Jeziórska | Studies on reactive compatibilisation of polyamide 6/poly (butylene terephthalate) blends by low molecular weight bis-oxazoline | |
| CN111171493A (en) | A kind of heat-resistant and shock-resistant polystyrene/polylactic acid alloy and preparation method thereof | |
| Lee et al. | Preparation of poly (butylene terephthalate)/oxazoline containing polystyrene graft copolymer through melt-blending and their application as a compatibilizer in polycarbonate/polystyrene blend | |
| EP1756211A1 (en) | Polystyrene containing masterbatch composition for polyester modification | |
| CN108641318B (en) | Biodegradable polyhydroxycarboxylic acid alloy material and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |