CN110283312B - Polylactam in-situ modified polypropylene carbonate and preparation method thereof - Google Patents
Polylactam in-situ modified polypropylene carbonate and preparation method thereof Download PDFInfo
- Publication number
- CN110283312B CN110283312B CN201811525070.3A CN201811525070A CN110283312B CN 110283312 B CN110283312 B CN 110283312B CN 201811525070 A CN201811525070 A CN 201811525070A CN 110283312 B CN110283312 B CN 110283312B
- Authority
- CN
- China
- Prior art keywords
- polypropylene carbonate
- polylactam
- situ
- modified polypropylene
- modified
- 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.)
- Active
Links
- 229920000379 polypropylene carbonate Polymers 0.000 title claims abstract description 139
- -1 polypropylene carbonate Polymers 0.000 title claims abstract description 121
- 238000011065 in-situ storage Methods 0.000 title claims abstract description 52
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 15
- 239000000126 substance Substances 0.000 claims abstract description 12
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 10
- DVPHDWQFZRBFND-DMHDVGBCSA-N 1-o-[2-[(3ar,5r,6s,6ar)-2,2-dimethyl-6-prop-2-enoyloxy-3a,5,6,6a-tetrahydrofuro[2,3-d][1,3]dioxol-5-yl]-2-[4-[(2s,3r)-1-butan-2-ylsulfanyl-2-(2-chlorophenyl)-4-oxoazetidin-3-yl]oxy-4-oxobutanoyl]oxyethyl] 4-o-[(2s,3r)-1-butan-2-ylsulfanyl-2-(2-chloropheny Chemical group C1([C@H]2[C@H](C(N2SC(C)CC)=O)OC(=O)CCC(=O)OC(COC(=O)CCC(=O)O[C@@H]2[C@@H](N(C2=O)SC(C)CC)C=2C(=CC=CC=2)Cl)[C@@H]2[C@@H]([C@H]3OC(C)(C)O[C@H]3O2)OC(=O)C=C)=CC=CC=C1Cl DVPHDWQFZRBFND-DMHDVGBCSA-N 0.000 claims abstract description 9
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims abstract description 5
- 239000003153 chemical reaction reagent Substances 0.000 claims abstract description 4
- 235000008708 Morus alba Nutrition 0.000 claims description 42
- 240000000249 Morus alba Species 0.000 claims description 42
- 239000000835 fiber Substances 0.000 claims description 42
- 229920000049 Carbon (fiber) Polymers 0.000 claims description 16
- 239000004917 carbon fiber Substances 0.000 claims description 16
- 239000000463 material Substances 0.000 claims description 15
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 14
- 238000006243 chemical reaction Methods 0.000 claims description 13
- 239000000203 mixture Substances 0.000 claims description 13
- 238000002156 mixing Methods 0.000 claims description 12
- JBKVHLHDHHXQEQ-UHFFFAOYSA-N epsilon-caprolactam Chemical compound O=C1CCCCCN1 JBKVHLHDHHXQEQ-UHFFFAOYSA-N 0.000 claims description 10
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 claims description 9
- JHWNWJKBPDFINM-UHFFFAOYSA-N Laurolactam Chemical compound O=C1CCCCCCCCCCCN1 JHWNWJKBPDFINM-UHFFFAOYSA-N 0.000 claims description 9
- 238000007334 copolymerization reaction Methods 0.000 claims description 9
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 9
- 238000001035 drying Methods 0.000 claims description 8
- SJECZPVISLOESU-UHFFFAOYSA-N 3-trimethoxysilylpropan-1-amine Chemical compound CO[Si](OC)(OC)CCCN SJECZPVISLOESU-UHFFFAOYSA-N 0.000 claims description 6
- 230000008859 change Effects 0.000 claims description 6
- 239000013078 crystal Substances 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 6
- 239000005057 Hexamethylene diisocyanate Substances 0.000 claims description 5
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 claims description 5
- 239000006185 dispersion Substances 0.000 claims description 4
- 238000001914 filtration Methods 0.000 claims description 4
- 239000000155 melt Substances 0.000 claims description 4
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 claims description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 3
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 claims description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 3
- 239000001099 ammonium carbonate Substances 0.000 claims description 3
- 235000012501 ammonium carbonate Nutrition 0.000 claims description 3
- 239000002981 blocking agent Substances 0.000 claims description 3
- 238000003763 carbonization Methods 0.000 claims description 3
- 238000005520 cutting process Methods 0.000 claims description 3
- 125000005442 diisocyanate group Chemical group 0.000 claims description 3
- 238000011049 filling Methods 0.000 claims description 3
- 229910002804 graphite Inorganic materials 0.000 claims description 3
- 239000010439 graphite Substances 0.000 claims description 3
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 3
- 230000001590 oxidative effect Effects 0.000 claims description 3
- 239000002245 particle Substances 0.000 claims description 3
- 238000005406 washing Methods 0.000 claims description 3
- 230000035484 reaction time Effects 0.000 claims description 2
- 238000002844 melting Methods 0.000 claims 1
- 230000008018 melting Effects 0.000 claims 1
- 230000009477 glass transition Effects 0.000 abstract description 11
- 238000005979 thermal decomposition reaction Methods 0.000 abstract description 11
- 230000004048 modification Effects 0.000 abstract description 9
- 238000012986 modification Methods 0.000 abstract description 9
- 239000012948 isocyanate Substances 0.000 abstract description 6
- 150000002513 isocyanates Chemical class 0.000 abstract description 6
- 150000001875 compounds Chemical class 0.000 abstract description 3
- 239000002861 polymer material Substances 0.000 abstract description 2
- 238000011031 large-scale manufacturing process Methods 0.000 abstract 1
- 230000000052 comparative effect Effects 0.000 description 10
- 239000000178 monomer Substances 0.000 description 7
- 230000000694 effects Effects 0.000 description 6
- 238000000034 method Methods 0.000 description 6
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 5
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 4
- 239000002131 composite material Substances 0.000 description 3
- 230000006872 improvement Effects 0.000 description 3
- 229920003023 plastic Polymers 0.000 description 3
- 239000004033 plastic Substances 0.000 description 3
- 229920002292 Nylon 6 Polymers 0.000 description 2
- 239000001569 carbon dioxide Substances 0.000 description 2
- 229910002092 carbon dioxide Inorganic materials 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 150000003951 lactams Chemical class 0.000 description 2
- 238000005453 pelletization Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 241000282414 Homo sapiens Species 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 1
- 150000008065 acid anhydrides Chemical class 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000003889 chemical engineering Methods 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000005431 greenhouse gas Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 230000004630 mental health Effects 0.000 description 1
- 238000002715 modification method Methods 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000002464 physical blending Methods 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 239000012779 reinforcing material Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 230000002522 swelling effect Effects 0.000 description 1
- 230000009897 systematic effect Effects 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
- C08G18/44—Polycarbonates
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G64/00—Macromolecular compounds obtained by reactions forming a carbonic ester link in the main chain of the macromolecule
- C08G64/42—Chemical after-treatment
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
- C08G69/02—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids
- C08G69/08—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from amino-carboxylic acids
- C08G69/14—Lactams
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
- C08G69/02—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids
- C08G69/08—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from amino-carboxylic acids
- C08G69/14—Lactams
- C08G69/16—Preparatory processes
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
- C08G69/44—Polyester-amides
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Polyurethanes Or Polyureas (AREA)
- Polyamides (AREA)
Abstract
The invention relates to the technical field of high polymer materials, and discloses polylactam in-situ modified polypropylene carbonate and a preparation method thereof, aiming at the problems of poor thermal stability and low strength of the polypropylene carbonate in the prior art. The polylactam in-situ modified polypropylene carbonate is prepared by in-situ polymerization of a lactam monomer, an end-capping reagent and polypropylene carbonate. According to the invention, isocyanate, maleic anhydride and other active end capping agents are used for carrying out chemical end capping modification on the polypropylene carbonate, and then the modified polypropylene carbonate is copolymerized with a third group of compounds under a certain condition, so that the polylactam in-situ modified polypropylene carbonate is obtained. The glass transition temperature of the modified polypropylene carbonate is increased by 10-100 ℃, the thermal decomposition temperature is increased by 10-50 ℃, the mechanical property is improved by 10-80%, and the preparation method is simple and suitable for large-scale production.
Description
Technical Field
The invention relates to the technical field of high polymer materials, in particular to polylactam in-situ modified polypropylene carbonate and a preparation method thereof.
Background
Since the twentieth century, with the development of science and technology, more and more plastic products are manufactured, which brings convenience to our lives, and also brings serious 'white pollution' and greenhouse effect due to the fact that most of the plastic products are non-degradable materials, and accordingly, the physical and mental health of human beings is greatly influenced. Therefore, the development of biodegradable materials and the reduction of the greenhouse effect are urgent. The polypropylene carbonate (PPC) is a novel completely biodegradable environment-friendly material obtained by polymerizing carbon dioxide and propylene oxide under certain catalyst, pressure and temperature conditions, and the greenhouse gas carbon dioxide is used as a raw material, so that the white pollution and the environmental pollution caused by greenhouse effect can be reduced simultaneously, and the PPC has obvious application prospect. However, PPC has poor thermal stability and low strength, and the application of PPC in the industries of plastics, chemical engineering and the like is greatly limited. Researchers have now conducted extensive research on the improvement of thermal stability. It is currently essential to improve the thermal properties by conventional means of solution or melt blending.
Chinese patent application publication No. CN107573476A discloses a preparation method of a modified polypropylene carbonate material, which comprises the steps of adding polypropylene carbonate into a solvent for complete dissolution, then adding an acid anhydride end-capping agent, and heating in a water bath for reaction; raising the temperature, adding an isocyanate blocking agent, and continuing the reaction; and dropwise adding the mixture which is completely reacted into absolute ethyl alcohol for precipitation, filtering the obtained solid, and drying in vacuum. The method improves the glass transition temperature and the thermal stability of the polypropylene carbonate, but the improvement effect is not very obvious. The patent of national patent application publication numbers CN108164978A, CN107474502A and CN105924923A also describes the modification of polypropylene carbonate, but the modification effect is not very obvious, and the modification effect is also obviously affected due to the compatibility problem of the mixture components. Some studies for chemically modifying PPC are reported occasionally, but most of them do not have intensive systematic studies and effective application.
Disclosure of Invention
In order to solve the technical problems, the invention provides polylactam in-situ modified polypropylene carbonate and a preparation method thereof. The thermal property and the mechanical property of the polylactam in-situ modified polypropylene carbonate are obviously improved, and compared with the unmodified polypropylene carbonate, the glass transition temperature of the polylactam in-situ modified polypropylene carbonate is improved by 60 ℃; the thermal decomposition temperature is increased by 40 ℃; the mechanical property is improved by 70 percent.
The specific technical scheme of the invention is as follows: the polylactam in-situ modified polypropylene carbonate is prepared by in-situ polymerization of a lactam monomer, a terminating agent and polypropylene carbonate.
The invention is mainly technically characterized in that the poly (propylene carbonate) is subjected to chemical end-capping modification by using an active end-capping agent such as isocyanate, maleic anhydride and the like through a chemical method, and then is copolymerized with a third component compound under a certain condition, so that the poly (propylene carbonate) modified by the polylactam in situ is obtained.
The reason for the poor thermal stability of the polypropylene carbonate is that random fracture occurs to generate oligomers when the polypropylene carbonate is heated, and the polypropylene carbonate is easily unzipped when heated due to the existence of terminal hydroxyl groups of the polypropylene carbonate, and cyclic propylene carbonate is removed at the terminal of the polypropylene carbonate each time. Therefore, in order to improve the thermal stability, the terminal hydroxyl groups need to be subjected to end-capping modification. The polylactam material has small relative density, high strength, good stability, good wear resistance and higher long-term use temperature, and can react with the group on the end capping agent of the polypropylene carbonate. Therefore, the invention selects the polylactam monomer as the third monomer of the modified polypropylene carbonate. Because polylactam is not readily biodegradable, strict control of the amount of polylactam monomer is required. The lactam and the isocyanate-terminated polypropylene carbonate are copolymerized, so that the polypropylene carbonate is chemically modified on a molecular structure, and a composite material with good mechanical property and thermal property is obtained, so that the application field of the polypropylene carbonate material is expanded and extended.
Preferably, the mol ratio of the terminal hydroxyl of the polypropylene carbonate to the end-capping reagent and the lactam monomer is 1: 1-5: 0.05-0.5.
As described above, polypropylene carbonate has poor thermal stability, and in order to improve this problem, terminal hydroxyl groups thereof need to be modified by end capping. Furthermore, in view of the fact that a third component needs to be added for copolymerization reaction, the isocyanate needs to be excessive, and the molar ratio of the isocyanate to the terminal OH of the polypropylene carbonate is preferably 1.0-5.0 after many times of practice. In view of the degradability of the polypropylene carbonate material, the content of the added third monomer polyamide component is not too high. Through multiple practices, the content of the lactam monomer is determined to be 1.0-20.0% (based on the mole number of the polypropylene carbonate).
Preferably, the molecular weight of the polypropylene carbonate is 1000 to 20000. Because the polypropylene carbonate is a novel completely biodegradable environment-friendly material, the molecular weight of the polypropylene carbonate is not too large, the polypropylene carbonate is too large, degrades slowly, and is too small, does not have strength, and cannot be used.
Preferably, the blocking agent is diisocyanate including at least one of toluene 2, 4-diisocyanate, hexamethylene diisocyanate, 4' -dicyclohexylmethane diisocyanate, and diphenylmethane diisocyanate, or maleic anhydride. Preferably, the lactam monomer comprises at least one of caprolactam, decanolactam and laurolactam.
The polylactam in-situ modified polypropylene carbonate also comprises modified mulberry fibers; the addition amount of the modified mulberry fibers is 0.5-1.5% of the weight of the polypropylene carbonate. Preferably, the preparation method of the modified mulberry fiber comprises the following steps: placing mulberry fibers with the diameter of 20-30 nm into a closed container, filling liquid ammonia, increasing the pressure to 2-3 MPa at the pressure increasing rate of 0.6-1 MPa/min, increasing the pressure for 2-3 min at the pressure increasing rate of 0.6-1 MPa/min, maintaining the pressure for 5-7 min, and instantly releasing the mulberry fibers to 0.005-0.008 MPa at the pressure reducing rate of 4-5 MPa/s within 1.5-2 seconds to obtain the crystal change modified mulberry fibers. And (3) placing the crystal change modified mulberry fibers into a hydrothermal reaction kettle, carrying out hydrothermal carbonization for 40-70 min at 160-200 ℃, filtering, washing and drying to obtain the carbon fibers. And (3) oxidizing the obtained carbon fiber serving as an anode and graphite serving as a cathode in an ammonium carbonate solution with the concentration of 4-7% for 1-1.5 min under the condition that the current intensity is 0.8-1A to obtain the oxidized carbon fiber. Dispersing the obtained oxidized carbon fibers into 2-5 mg/mL dispersion, adding aminopropyltrimethoxysilane, reacting for 4-6 hours at 60-80 ℃ with the mass ratio of the oxidized carbon fibers to the aminopropyltrimethoxysilane being 1-3: 1, and thus obtaining the modified mulberry fibers.
The mulberry fiber has high strength and good toughness, but the wear resistance and the compatibility with the polypropylene carbonate are poor, in the embodiment, the mulberry fiber is crystallized, the swelling property of the mulberry fiber is improved, then the mulberry fiber is carbonized to form the carbon fiber, the wear resistance of the mulberry fiber is improved, then the mulberry fiber is subjected to oxidation treatment, the number of active functional groups on the surface of the mulberry fiber is increased, and finally the mulberry fiber is modified by organic siloxane to increase the compatibility with the polypropylene carbonate. The modified mulberry fiber can be crosslinked with isocyanate groups in hexamethylene diisocyanate and amino groups in laurolactam, so that the strength and the wear resistance of the polypropylene carbonate are improved. Because the modified mulberry fibers are uniformly dispersed in the polypropylene carbonate and are combined through chemical bond crosslinking, compared with unmodified mulberry fibers, the modified mulberry fibers have good compatibility with the polypropylene carbonate, surface groups can be combined with functional groups in the polypropylene carbonate and a capping reagent, and the thermal stability and the mechanical strength of the polypropylene carbonate can be obviously enhanced.
A preparation method of polylactam in-situ modified polypropylene carbonate comprises the following steps:
(1) chemical end capping: fully mixing the poly (propylene carbonate) with a terminating agent in proportion, and then putting the mixture into a high-temperature reaction kettle to carry out melt blending while stirring to obtain the chemically terminated poly (propylene carbonate);
(2) in-situ polymerization: and (2) adding lactam into the reaction kettle in the step (1) in proportion, carrying out copolymerization reaction with the chemically terminated polypropylene carbonate, and cutting the discharged material into particles to obtain the polylactam in-situ modified polypropylene carbonate.
Compared with the unmodified polypropylene carbonate, the glass transition temperature of the polypropylene carbonate in-situ modified by the polylactam prepared by the method is increased by 10-100 ℃, the thermal decomposition temperature is increased by 10-50 ℃, and the mechanical property is improved by 10-80%. The heat resistance and the mechanical property are obviously improved, the comprehensive performance of the modified polypropylene carbonate is greatly improved, and the application field of the polypropylene carbonate is effectively widened.
Preferably, in the step (1), the polypropylene carbonate is dried for 8-12 h at the temperature of 30-40 ℃; the melt blending temperature is 50-200 ℃, and the time is 2-12 h. Preferably, the melt blending temperature is 100-200 ℃, and the time is 2-10 h.
Preferably, in the step (2), the polymerization temperature is 100-220 ℃, and the reaction time is 0.5-6 h.
Compared with the prior art, the invention has the following beneficial effects: the invention mainly uses the chemical method, uses the active end capping agent such as isocyanate, maleic anhydride and the like to carry out chemical end capping modification on the poly (propylene carbonate), and then carries out copolymerization with the third component compound under certain conditions, thereby obtaining the poly (propylene carbonate)/high molecular copolymerization composite material, which is obviously different from the traditional physical blending modification method. The in-situ polymerization process is adopted, namely, the polypropylene carbonate terminated by an active agent is directly mixed with a melt of a third component monomer, and then polymerization modification is carried out under a specific polymerization process to obtain a composite material, tests show that the thermal property and the mechanical property of the polylactam in-situ modified polypropylene carbonate are obviously improved, compared with unmodified polypropylene carbonate, the glass transition temperature of the polylactam in-situ modified polypropylene carbonate is improved by 60 ℃, the thermal decomposition temperature is improved by 40 ℃, the mechanical property is improved by 70%, and the application field of the polypropylene carbonate material is expanded and extended.
Detailed Description
The present invention will be further described with reference to the following examples. The devices, connections, and methods referred to in this disclosure are those known in the art, unless otherwise indicated.
Example 1
A preparation method of polylactam in-situ modified polypropylene carbonate comprises the following steps:
(1) chemical end capping: drying 100g of propylene carbonate with molecular weight of 20000 at 35 ℃ for 12h, then fully mixing the propylene carbonate with diphenylmethane diisocyanate according to the molar ratio of 1:2.5 of terminal hydroxyl of the propylene carbonate to the diphenylmethane diisocyanate, and then putting the mixture into a high-temperature reaction kettle to melt and blend for 6h at 150 ℃ while stirring to obtain the chemically-terminated propylene carbonate;
(2) in-situ polymerization: and (2) adding 0.57g of dry caprolactam into the reaction kettle in the step (1) according to the molar ratio of the terminal hydroxyl of the polypropylene carbonate to caprolactam monomer of 1:0.5, carrying out copolymerization reaction with the chemically blocked polypropylene carbonate at 170 ℃ for 1h, and pelletizing the discharged material to obtain the in-situ modified polypropylene carbonate of polycaprolactam.
Example 2
A preparation method of polylactam in-situ modified polypropylene carbonate comprises the following steps:
(1) chemical end capping: drying 100g of polypropylene carbonate with the molecular weight of 10000 at 30 ℃ for 12h, then fully mixing the dried polypropylene carbonate with 2.8g of diphenylmethane diisocyanate according to the molar ratio of the terminal hydroxyl of the polypropylene carbonate to the diphenylmethane diisocyanate of 1:1.6, and then putting the mixture into a high-temperature reaction kettle to melt and blend the mixture for 8h at 130 ℃ while stirring to obtain the chemically-terminated polypropylene carbonate;
(2) in-situ polymerization: and (2) adding 0.79g of dried dodecalactam into the reaction kettle in the step (1) according to the molar ratio of the terminal hydroxyl of the poly (propylene carbonate) to the dodecalactam monomer of 1:0.2, carrying out copolymerization reaction with the chemically end-capped poly (propylene carbonate) at 170 ℃ for 1h, and carrying out particle cutting on the discharged material to obtain the poly (propylene carbonate) modified in situ by the poly (dodecalactam).
Example 3
A preparation method of polylactam in-situ modified polypropylene carbonate comprises the following steps:
(1) chemical end capping: drying 100g of polypropylene carbonate with the molecular weight of 4000 at 35 ℃ for 8h, fully mixing the dried polypropylene carbonate with 4.8g of toluene 2, 4-diisocyanate according to the molar ratio of the hydroxyl at the tail end of the polypropylene carbonate to the toluene 2, 4-diisocyanate of 1:1.1, and then putting the mixture into a high-temperature reaction kettle to melt and blend the mixture for 10h at 100 ℃ while stirring to obtain the chemically end-capped polypropylene carbonate;
(2) in-situ polymerization: and (2) adding 0.3g of dry caprolactam into the reaction kettle in the step (1) according to the molar ratio of the terminal hydroxyl of the polypropylene carbonate to caprolactam monomer of 1:0.05, carrying out copolymerization reaction with the chemically blocked polypropylene carbonate at 130 ℃ for 3h, and pelletizing the discharged material to obtain the in-situ modified polypropylene carbonate of polycaprolactam.
Example 4
A preparation method of polylactam in-situ modified polypropylene carbonate comprises the following steps:
(1) chemical end capping: drying 100g of polypropylene carbonate with the molecular weight of 10000 at 30 ℃ for 12h, then fully mixing the dried polypropylene carbonate with 2.8g of hexamethylene diisocyanate according to the molar ratio of the terminal hydroxyl of the polypropylene carbonate to the hexamethylene diisocyanate of 1:1.6, and then putting the mixture into a high-temperature reaction kettle to be melted and blended for 8h at 130 ℃ while stirring to obtain the chemically-terminated polypropylene carbonate;
(2) in-situ polymerization: adding 0.79g of dried dodecalactam into the reaction kettle in the step (1) according to the molar ratio of the terminal hydroxyl of the polypropylene carbonate to the dodecalactam monomer of 1:0.2, then adding modified mulberry fibers accounting for 0.5 percent of the weight of the polypropylene carbonate, carrying out copolymerization reaction with the chemically terminated polypropylene carbonate at 100 ℃ for 6h, and carrying out strand drawing and dicing on the discharged material to obtain the in-situ modified polypropylene carbonate of the polydodecalactam.
The preparation method of the modified mulberry fiber comprises the following steps: placing mulberry fibers with the diameter of 20nm in a closed container, filling liquid ammonia, increasing the pressure to 3MPa at the pressure increasing rate of 1MPa/min, increasing the pressure for 2min at the pressure increasing rate of 1MPa/min, maintaining the pressure for 5min, and instantly releasing the mulberry fibers to 0.005MPa at the pressure reducing rate of 4MPa/s within 1.5 seconds to obtain the crystal change modified mulberry fibers. And (3) putting the crystal change modified mulberry fibers into a hydrothermal reaction kettle, performing hydrothermal carbonization for 40min at 200 ℃, filtering, washing and drying to obtain the carbon fibers. And oxidizing the obtained carbon fiber serving as an anode and graphite serving as a cathode in an ammonium carbonate solution with the concentration of 7% for 1min under the condition that the current intensity is 1A to obtain the oxidized carbon fiber. Dispersing the obtained oxidized carbon fiber into 4mg/mL dispersion, adding aminopropyltrimethoxysilane, wherein the mass ratio of the oxidized carbon fiber to the aminopropyltrimethoxysilane is 2:1, and reacting at 80 ℃ for 4 hours to obtain the modified mulberry fiber.
Comparative example 1
Comparative example 1 differs from example 1 in that: the polypropylene carbonate was chemically blocked with only diphenylmethane diisocyanate without performing the in situ polymerization reaction of step (2), and the rest was the same as in example 1.
Comparative example 2
Comparative example 2 differs from example 1 in that: in the step (1), the polypropylene carbonate is dried at 35 ℃ for 12 hours, and then is fully mixed with diphenylmethane diisocyanate according to the molar ratio of the terminal hydroxyl group of the polypropylene carbonate to the diphenylmethane diisocyanate of 1:2.5, and the rest is the same as that of the example 1.
Comparative example 3
Comparative example 3 differs from example 4 in that: the modified mulberry fibers were replaced with unmodified mulberry fibers, and the procedure was otherwise the same as in example 4.
The glass transition temperature, the thermal decomposition temperature and the breaking strength of the polylactam in-situ modified polypropylene carbonates prepared in examples 1 to 4 and comparative examples 1 to 3 and the unmodified polypropylene carbonate of the blank group were measured, and the test results are shown in table 1.
TABLE 1
As can be seen from Table 1, the glass transition temperature, the thermal decomposition temperature and the mechanical properties of the polylactam in-situ modified polypropylene carbonate are obviously improved. Compared with unmodified polypropylene carbonate, the glass transition temperature of the poly (propylene carbonate) in-situ modified by the polydodecalactam prepared in the example 1 is increased by 50 ℃, the thermal decomposition temperature is increased by 40 ℃, and the mechanical property is improved by 70%. Compared with the modified polypropylene carbonate prepared in comparative examples 1-2, the glass transition temperature, the thermal decomposition temperature and the mechanical property of the poly (dodecalactam) in-situ modified polypropylene carbonate prepared in example 1 are also obviously improved. The improvement of the performance of the modified polypropylene carbonate is not facilitated by simply carrying out end capping on the polypropylene carbonate or reducing the amount of the end capping agent during end capping. In the embodiment 4, the modified mulberry fibers are used as the reinforcing material, and the glass transition temperature, the thermal decomposition temperature and the mechanical property of the prepared polylactam in-situ modified polypropylene carbonate are obviously improved. Comparative example 3 compared to example 4, the polylactam in-situ modified polypropylene carbonate prepared in comparative example 3 has a large difference in glass transition temperature, thermal decomposition temperature and mechanical properties compared to example 4 because the compatibility of the unmodified mulberry fiber with the polypropylene carbonate is poor, the dispersion of the mulberry fiber in the polypropylene carbonate is not uniform, resulting in poor thermal decomposition temperature and breaking strength of the prepared polypropylene carbonate, even not as high as those of the polypropylene carbonate prepared in example 2 without adding the mulberry fiber.
The above description is only a preferred embodiment of the present invention, and is not intended to limit the present invention, and all simple modifications, changes and equivalent structural changes made to the above embodiment according to the technical spirit of the present invention still belong to the protection scope of the technical solution of the present invention.
Claims (8)
1. The polylactam in-situ modified polypropylene carbonate is characterized in that: the polylactam in-situ modified polypropylene carbonate is prepared by in-situ polymerization of a lactam monomer, an end-capping agent, polypropylene carbonate and modified mulberry fibers, wherein the addition amount of the modified mulberry fibers is 0.5-1.5% of the weight of the polypropylene carbonate;
the preparation method of the modified mulberry fiber comprises the following steps: placing mulberry fibers with the diameter of 20-30 nm in a closed container, filling liquid ammonia, increasing the pressure to 2-3 MPa at the pressure increasing rate of 0.6-1 MPa/min, increasing the pressure for 2-3 min at the pressure increasing rate of 0.6-1 MPa/min, maintaining the pressure for 5-7 min, and instantly releasing the mulberry fibers to 0.005-0.008 MPa at the pressure reducing rate of 4-5 MPa/s within 1.5-2 seconds to obtain crystal change modified mulberry fibers; placing the crystal change modified mulberry fibers in a hydrothermal reaction kettle, performing hydrothermal carbonization for 40-70 min at 160-200 ℃, filtering, washing and drying to obtain carbon fibers; oxidizing the obtained carbon fiber serving as an anode and graphite serving as a cathode in an ammonium carbonate solution with the concentration of 4-7% for 1-1.5 min under the condition that the current intensity is 0.8-1A to obtain oxidized carbon fiber; dispersing the obtained oxidized carbon fibers into 2-5 mg/mL dispersion, adding aminopropyltrimethoxysilane, reacting for 4-6 hours at 60-80 ℃ with the mass ratio of the oxidized carbon fibers to the aminopropyltrimethoxysilane being 1-3: 1, and thus obtaining the modified mulberry fibers.
2. The polylactam in-situ modified polypropylene carbonate according to claim 1, characterized in that: the mol ratio of the hydroxyl at the tail end of the poly (propylene carbonate) to the end-capping reagent and the lactam monomer is 1: 1-5: 0.05-0.5.
3. The polylactam in-situ modified polypropylene carbonate according to claim 2, characterized in that: the molecular weight of the polypropylene carbonate is 1000-20000.
4. The polylactam in-situ modified polypropylene carbonate according to claim 2, characterized in that: the blocking agent is diisocyanate or maleic anhydride, and the diisocyanate comprises at least one of toluene 2, 4-diisocyanate, hexamethylene diisocyanate, 4' -dicyclohexylmethane diisocyanate and diphenylmethane diisocyanate; the lactam monomer comprises at least one of caprolactam, decanolactam and laurolactam.
5. The preparation method of the polylactam in-situ modified polypropylene carbonate according to any one of claims 1 to 4, which is characterized by comprising the following steps:
(1) chemical end capping: fully mixing the poly (propylene carbonate) with a terminating agent in proportion, and then putting the mixture into a reactor to carry out melt blending while stirring to obtain the chemically terminated poly (propylene carbonate);
(2) in-situ polymerization: and (2) adding a lactam monomer and modified mulberry fibers into the reactor in the step (1) in proportion, carrying out copolymerization reaction with the chemically terminated polypropylene carbonate, and cutting the discharged material into particles to obtain the in-situ modified polypropylene carbonate of the polylactam.
6. The preparation method of the polylactam in-situ modified polypropylene carbonate according to claim 5, characterized in that: in the step (1), the polypropylene carbonate is dried for 8-12 h at the temperature of 30-40 ℃; the melt blending temperature is 50-200 ℃, and the time is 2-12 h.
7. The preparation method of the polylactam in-situ modified polypropylene carbonate according to claim 6, characterized in that: the melting reaction temperature is 100-200 ℃, and the time is 2-10 h.
8. The preparation method of the polylactam in-situ modified polypropylene carbonate according to claim 5, characterized in that: in the step (2), the polymerization temperature is 100-220 ℃, and the reaction time is 0.5-6 h.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811525070.3A CN110283312B (en) | 2018-12-13 | 2018-12-13 | Polylactam in-situ modified polypropylene carbonate and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811525070.3A CN110283312B (en) | 2018-12-13 | 2018-12-13 | Polylactam in-situ modified polypropylene carbonate and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN110283312A CN110283312A (en) | 2019-09-27 |
| CN110283312B true CN110283312B (en) | 2021-12-28 |
Family
ID=68000948
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201811525070.3A Active CN110283312B (en) | 2018-12-13 | 2018-12-13 | Polylactam in-situ modified polypropylene carbonate and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN110283312B (en) |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103261260A (en) * | 2010-12-28 | 2013-08-21 | Sk新技术株式会社 | Method for improving thermal stability of polypropylene carbonate |
| CN104479081A (en) * | 2015-01-14 | 2015-04-01 | 河北工业大学 | Method for modifying polypropylene carbonate through reaction extrusion |
| CN105176035A (en) * | 2015-08-10 | 2015-12-23 | 河南大学 | Nylon powder / poly propylene carbonate composite material and preparation method thereof |
| CN107573476A (en) * | 2016-07-05 | 2018-01-12 | 中国石油化工股份有限公司 | The preparation method of modified poly (propylene carbonate) material |
| CN107868425A (en) * | 2017-10-12 | 2018-04-03 | 杭州师范大学 | A kind of high-performance polymethyl ethylene carbonate material and preparation method thereof |
| CN108047678A (en) * | 2017-12-15 | 2018-05-18 | 武汉工程大学 | A kind of modified lignin resin/polypropylene carbonate composite material and preparation method thereof |
| CN108603020A (en) * | 2016-05-31 | 2018-09-28 | Lg化学株式会社 | Polymerized thylene carbonate alkyl ester resin combination, preparation method, the moulding article of formation and the preparation method using its moulding article |
-
2018
- 2018-12-13 CN CN201811525070.3A patent/CN110283312B/en active Active
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103261260A (en) * | 2010-12-28 | 2013-08-21 | Sk新技术株式会社 | Method for improving thermal stability of polypropylene carbonate |
| CN104479081A (en) * | 2015-01-14 | 2015-04-01 | 河北工业大学 | Method for modifying polypropylene carbonate through reaction extrusion |
| CN105176035A (en) * | 2015-08-10 | 2015-12-23 | 河南大学 | Nylon powder / poly propylene carbonate composite material and preparation method thereof |
| CN108603020A (en) * | 2016-05-31 | 2018-09-28 | Lg化学株式会社 | Polymerized thylene carbonate alkyl ester resin combination, preparation method, the moulding article of formation and the preparation method using its moulding article |
| CN107573476A (en) * | 2016-07-05 | 2018-01-12 | 中国石油化工股份有限公司 | The preparation method of modified poly (propylene carbonate) material |
| CN107868425A (en) * | 2017-10-12 | 2018-04-03 | 杭州师范大学 | A kind of high-performance polymethyl ethylene carbonate material and preparation method thereof |
| CN108047678A (en) * | 2017-12-15 | 2018-05-18 | 武汉工程大学 | A kind of modified lignin resin/polypropylene carbonate composite material and preparation method thereof |
Non-Patent Citations (2)
| Title |
|---|
| Research on the Structure and Properties of Mulberry Fiber;wu Hai-liang等;《Journal of Donghua University》;20180228(第2期);第153-158页 * |
| 聚碳酸亚丙酯化学改性研究进展;孙娇等;《中国印刷与包装研》;20140228(第1期);第16-24页 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN110283312A (en) | 2019-09-27 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101358385B (en) | Modified polybenzoxazole fiber and preparation method thereof | |
| CN107513162A (en) | A kind of preparation method of graphene/nylon 6 nano-composite | |
| CN103030766B (en) | Carbon dioxide-based poly (carbonic ester-ether) polyurethane and preparation method thereof | |
| CN109706536B (en) | Preparation method of nylon 6-based polyesteramide fiber | |
| CN111718591B (en) | Lignin-containing bio-based composite material and preparation method thereof | |
| KR101986985B1 (en) | Use of polyethylenimines in the production of polyamides | |
| CN109930230A (en) | A kind of copolyamide industrial yarn and preparation method thereof | |
| CN113527668B (en) | Long-chain polyamide and preparation method and application thereof | |
| CN108250433A (en) | A kind of PA6-56 copolymeric materials and preparation method thereof | |
| CN102911366A (en) | Preparation method of nylon 6 having high hygroscopicity, high dyeing property and high elasticity | |
| CN116355209B (en) | Preparation method and application of high-whiteness meta-aramid polymer | |
| CN108715667A (en) | The preparation method of epoxy resin composite material based on Quadrupolar hydrogen bond supermolecule selfreparing | |
| CN110283312B (en) | Polylactam in-situ modified polypropylene carbonate and preparation method thereof | |
| CN104479127A (en) | Caprolactam hydrolytic polymer and hydrolytic polymerization method thereof | |
| CN109208115A (en) | A method of epoxy-modified high ortho position thermosetting phenolic fiber is prepared using wet spinning | |
| CN115806661A (en) | Method for preparing high-molecular-weight acid-dyeable block copolyester by liquid-phase polycondensation method | |
| CN110093679B (en) | Graphene modified nylon 66/nylon 6 fiber and preparation and application thereof | |
| CN113293512A (en) | Antibacterial skin-friendly non-woven fabric and preparation method thereof | |
| CN108251912B (en) | Preparation method of comfortable polyurethane elastic fiber | |
| KR101180508B1 (en) | Polyurethane composition for high tenacity spandex fiber, and spandex fiber prepared using the polyurethane composition | |
| CN103628172B (en) | A kind of preparation method of ternary copolyimide fiber | |
| CN106977880B (en) | A kind of preparation method and applications of acid anhydride non-covalent modification graphene | |
| CN114479131A (en) | High-toughness PP (polypropylene) particles and preparation method thereof | |
| CN110272538B (en) | Silanized polypropylene carbonate and preparation method thereof | |
| CN1180137C (en) | Modified melt spun spandex and its prepn. process |
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 |