CN105153409A - Thermoplastic copolyester composition with thermally reversible chemical crosslinking properties and preparation method and application thereof - Google Patents
Thermoplastic copolyester composition with thermally reversible chemical crosslinking properties and preparation method and application thereof Download PDFInfo
- Publication number
- CN105153409A CN105153409A CN201510675294.2A CN201510675294A CN105153409A CN 105153409 A CN105153409 A CN 105153409A CN 201510675294 A CN201510675294 A CN 201510675294A CN 105153409 A CN105153409 A CN 105153409A
- Authority
- CN
- China
- Prior art keywords
- thermoplastic
- polymer
- ester composition
- chemically crosslinked
- crosslinking reaction
- 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
- 0 CC(C)(C*C(C*Cl=C(C)C)=O)C(C)=O Chemical compound CC(C)(C*C(C*Cl=C(C)C)=O)C(C)=O 0.000 description 1
Landscapes
- Polyesters Or Polycarbonates (AREA)
- Processes Of Treating Macromolecular Substances (AREA)
Abstract
The invention discloses a thermoplastic copolyester composition with thermally reversible chemical crosslinking properties and a preparation method and application thereof. The copolyester contains a side functional group, namely 2-furfuryl sulfenyl, and is prepared from dibasic acid or dibasic acid ester containing 2-furfuryl sulfenyl, dibasic acid and dibasic alcohol by a melting copolycondensation method. The 2-furfuryl sulfenyl of the copolyester and a crosslinking agent containing maleimide can carry out Diels-Alder cycloaddition reaction at 50-70 DEG C to realize chemical crosslinking and can realize decrosslinking at high temperature, thereby being convenient for recovery and secondary processing and utilization of the materials and realizing a self-repairing or shape memory function of the materials. The thermally reversible crosslinking copolyester designed in the invention has a saturated main chain structure, has excellent thermal stability and mechanical properties, is not easy to generate an irreversible crosslinking structure in thermal processing and life-time service processes of the materials, and can realize thermoplastic processing many times and keep the mechanical properties unchanged.
Description
Technical field
The present invention relates to a kind of thermoplastic copolyesters composition and method of making the same and the purposes with thermal reversion chemically crosslinked characteristic, particularly relate to the thermal reversion characteristic utilizing Diels-Alder cycloaddition reaction, the thermal reversion realized between the copolyesters containing 2-chaff sulfenyl side base and the linking agent containing maleimide base group is cross-linked, thus prepare there is excellent mechanical performances, recyclable reprocessing utilizes and can thermoplastic co-polymer's ester composition of thermal reversion chemically crosslinked of selfreparing.
Background technology
For polymkeric substance, chemically crosslinked structure and thermoplasticity conflict often, is difficult to coexist.The thermosetting polymer of chemically crosslinked, modal such as vulcanized rubber, there is excellent mechanical property and thermotolerance, but it is shaping that the existence of chemically crosslinked structure causes it to be difficult to carry out secondary addition work, and the method that this just makes the waste product produced in leftover bits a large amount of in production process and use procedure be difficult to be processed by thermoplastic realizes again utilizing and wasting; Thermoplastic elastomers has good thermoplasticity, is easy to machine-shaping and recycling, but its heat-mechanical property is often not as the thermosetting polymer of chemically crosslinked, thus limits its application scenario and scope to a certain extent.
Present stage has the preparation research that the polymkeric substance of thermal reversion chemically crosslinked is devoted in some researchs, but because it is directly selected, the restriction of business-like polymkeric substance or itself Molecular Structure Design etc. are not enough to be caused still containing a large amount of unsaturated carbon-carbon double bonds in the cross-linked polymer main chain finally obtained, and the existence of unsaturated carbon-carbon double bond makes this cross-linked polymer all easily can produce a large amount of irreversible crosslinking structures under the service condition of hot-work and long-term natural light irradiation.Therefore, even if this polymkeric substance itself is the introduction of the crosslinked structure of thermal reversion, but greatly will inevitably be affected in the irreversible crosslinking structure that the later stage produces by unsaturated link(age) the recovery secondary processing of this polymkeric substance is utilized.
In addition, polymer materials in the process used because the reason such as indenture, otch can affect work-ing life of material greatly, and the polymer materials with self-healing properties can issue raw corresponding chemical reaction in the stimulation of the factor such as light, heat and realize the selfreparing of material, thus effectively extend the work-ing life of material.
Need to prepare a kind of polymkeric substance with thermal reversion chemically crosslinked characteristic, both be easy to crosslinking reaction occurs thus there is chemically crosslinked structure and good physical and mechanical properties, thermoplastic processing can be carried out again and reclaim second heat more shaping, and use and not easily produce in reprocessing process extra irreversible chemical be cross-linked, material extends its work-ing life when sustaining damage by selfreparing in addition.
Summary of the invention
The invention provides a kind of thermoplastic copolyesters composition and method of making the same and the purposes with thermal reversion chemically crosslinked characteristic.
The invention provides a kind of thermoplastic co-polymer's ester composition with thermal reversion chemically crosslinked characteristic, be made up of the copolyesters not containing carbon-carbon double bond containing 2-chaff sulfenyl side base and on main chain and the linking agent containing maleimide base group, and repeatedly can there is chemically crosslinked reconciliation crosslinking reaction, there is thermoplasticity.
The atactic polyester that described copolyesters is made up of the diprotic acid binary alcohol esters repeating unit containing 2-chaff sulfenyl side base and linear diprotic acid binary alcohol esters repeating unit;
The structure of the described diprotic acid binary alcohol esters repeating unit containing 2-chaff sulfenyl side base is as follows:
The structure of described linear diprotic acid binary alcohol esters repeating unit is as follows:
Wherein X, Y, R are C
2~ C
12alkyl, the mole fraction of the diprotic acid binary alcohol esters repeating unit containing 2-chaff sulfenyl side base in copolyesters is 0.01 ~ 0.25;
Described linking agent has following structure:
Wherein A is aromatic series or aliphatic group, and n is 2 or 3; Described aromatic group is the one in following group:
wherein n is 1-3;
"-" in aromatic group represents the position of substitution, such as
represent phenylene;
Described aliphatic group is C
2~ C
12one in alkyl or following group:
wherein
represent the position of substitution;
In composition, the amount ratio of linking agent and multipolymer measures with the maleimide functionality contained by it and 2-chaff sulfenyl respectively, and the mol ratio of maleimide functionality and 2-chaff sulfenyl is 1:1.1 ~ 1.1:1;
Described chemical crosslink reaction occurs in 50 ~ 70 DEG C of temperature ranges;
Described solution crosslinking reaction occurs in 100 ~ 160 DEG C of temperature ranges;
Level of response >=85% of described chemically crosslinked; Level of response >=85% of described solution crosslinking reaction; Crosslinking reaction is conciliate in described chemically crosslinked repeatedly can occur at least three times, and mechanical property keeps more than 90%.
The invention provides a kind of preparation method with thermoplastic co-polymer's ester composition of thermal reversion chemically crosslinked characteristic, it comprises the following steps:
(1) add dibasic alcohol, diprotic acid in the reactor, containing the functional monomer of 2-chaff sulfenyl and catalyzer, esterification 2-7 hour at 160-220 DEG C, obtains esterification products, esterification yield reaches 98% or more;
Described dibasic alcohol and diprotic acid mol ratio are 1.2-2:1;
Described is (0.01-0.25) containing the functional monomer of 2-chaff sulfenyl and the molar ratio of diprotic acid: 1;
(2) in the esterification products of step (1) gained, add catalyzer, at 190-250 DEG C, polycondensation 2-7 hour under 300 ~ 60Pa condition, obtain described copolyesters;
(3) in the copolyesters of step (2) gained, add described linking agent, mix at the temperature higher than copolyesters fusing point or second-order transition temperature, obtain thermoplastic co-polymer's ester composition with thermal reversion chemically crosslinked characteristic; Wherein, the mol ratio of 2-chaff sulfenyl and dimaleoyl imino is 1:1.1 ~ 1.1:1.
Described dibasic alcohol comprises ethylene glycol, 1,2-PD, 1,3-PD, BDO, 1,5-PD, 1,6-hexylene glycol, neopentyl glycol or 2-methyl isophthalic acid, 3 propylene glycol;
Described diprotic acid comprises succinic acid, pentanedioic acid, hexanodioic acid, suberic acid, nonane diacid, sebacic acid or 12 diacid;
The described functional monomer containing 2-chaff sulfenyl comprises the compound of following structure:
Described catalyzer is selected from stannous octoate, stannous oxalate, butyl stannonic acid, dibutyl tin laurate, tetrabutyl titanate, isopropyl titanate or titanium ethylene glycolate, and consumption is the 0.01-0.5mol% of diprotic acid.
Thermoplastic co-polymer's ester composition with thermal reversion chemically crosslinked characteristic provided by the invention can be used as self-repair material, the plastics of shape-memory material or recycling or elastomer material.
Thermoplastic co-polymer's ester composition provided by the invention is for the preparation of the plastics of recyclable recycling or elastomeric preparation and recovery, and process is as follows:
(1) thermoplastic co-polymer's ester composition with thermal reversion chemically crosslinked characteristic is carried out crosslinking reaction 5-24h at 50-70 DEG C, obtain the goods of chemically crosslinked;
(2) goods in step (1) after usage or the scrap stock of step (1) by-product, first in 100-160 DEG C of temperature range, carry out solution crosslinking reaction 5-60min, crosslinking reaction 5-24h is carried out again in 50-70 DEG C of temperature range, again obtained new goods, complete recycling.
Thermoplastic co-polymer's ester composition provided by the invention is for the preparation of self-repair material, and preparation process is as follows:
(1) the thermoplastic co-polymer's ester composition described in any one of claims 1 to 3 is carried out crosslinking reaction 5-24h at 50-70 DEG C, obtain the goods of chemically crosslinked;
(2) after the goods obtained damage, adopt and carry out selfreparing with the following method:
First in 100-160 DEG C of temperature range, carry out solution crosslinking reaction 5-60min, then in 50-70 DEG C of temperature range, carry out crosslinking reaction or directly in 50-70 DEG C of temperature range, carry out crosslinking reaction 5-24h, complete the selfreparing of impaired goods.
Thermoplastic co-polymer's ester composition provided by the invention is used as shape-memory material, and its preparation and application is as follows:
(1) thermoplastic co-polymer's ester composition with thermal reversion chemically crosslinked characteristic is processed into the goods with predetermined shape through thermoplastic;
(2) goods of step (1) carry out predetermined deformation under external force, then at 50-70 DEG C, carry out crosslinking reaction 5-24h, and fixing deformation, obtains the goods with predetermined temporary shapes;
(3) goods of step (2) carry out solution crosslinking reaction 5-60min in 100-160 DEG C of temperature range, recover original-shape, complete shape recovery process.
Beneficial effect of the present invention is the following aspects:
Thermoplastic co-polymer's ester composition provided by the invention has thermal reversion chemically crosslinked characteristic, thus both there is excellent heat-mechanical property that chemically crosslinked characteristic is brought, be conducive to the raising of material property, also there is the recoverable that thermoplasticity is brought, the reprocessing of scrap stock and the recycling of waste product can be realized, play economize on resources, the object of environmental protection, for high performance or the recycling of thermoplastics and thermoplastic elastomer.
Thermoplastic co-polymer's ester composition provided by the invention, reversible crosslink reconciliation crosslinking degree is high, and due to main chain not containing unsaturated carbon-carbon double bond, can effectively avoid producing irreversible crosslinking structure under the service condition of hot-work and long-term natural light irradiation, thus keep its thermoplasticity, namely can repeatedly recycle, and the heat-mechanical property after recycling remains unchanged substantially.
Thermoplastic co-polymer's ester composition provided by the invention has self-repair function, effectively can extend the work-ing life of material.
Thermoplastic co-polymer's ester composition provided by the invention has shape memory function, provides a kind of method realizing shape memory function newly.
The preparation method of thermoplastic co-polymer's ester composition provided by the invention, technique is simple, and process environment is friendly, is conducive to realizing commercialization.
Accompanying drawing explanation
Fig. 1 is the NMR spectrogram contrast of conciliating copolymerzation with cross-linking ester composition PBASf-BMI in embodiment 1 containing functional monomer DMF-FM, the copolyesters PBASf of 2-chaff sulfenyl.
Fig. 2 is copolyesters PBASf in embodiment 1, copolymerzation with cross-linking ester composition PBASf-BMI and the FTIR spectrogram contrast of separating copolymerzation with cross-linking ester composition PBASf-BMI.
Fig. 3 is copolyesters PBASf in embodiment 1, the polyester composition PBASf-BMI dissolving situation comparison diagram in solvent tetrachloroethane at normal temperature and 120 DEG C: a) copolyesters PBASf copolyesters dissolves situation in tetrachloroethane under normal temperature; B) copolymerzation with cross-linking ester composition PBASf-BMI dissolves situation in tetrachloroethane under normal temperature; C) copolymerzation with cross-linking ester composition PBASf-BMI dissolves situation in tetrachloroethane at 120 DEG C.
Fig. 4 is the mechanical property contrast of the copolymerzation with cross-linking ester composition PBASf-BMI of gained after reclaiming for copolyesters PBASf in embodiment 7, copolymerzation with cross-linking ester composition PBASf-BMI and 3 time.
Embodiment
Below by embodiment, the present invention is specifically described, but the invention is not restricted to these embodiments.
The method for testing and analyzing adopted in following embodiment is as follows:
Polymer architecture: 1) adopt BRUKERAC-80400M nuclear magnetic resonance analyser test polymer structure, take deuterochloroform as solvent, tetramethylsilane is interior mark; 2) adopt Nicolet5700 infrared spectrometer test polymer structure, prepare film in hot-forming mode, test by the pattern of reflection.
Mechanics Performance Testing: adopt hot-forming method to prepare the thick thin plate of about 1mm, thin plate after 50 DEG C of constant temperature 24h, with 2 type cut-off knife dumbbell shaped battens.Batten adopts Zwick company RoellZ020 model universal testing machine, under 25 DEG C of rates of extension with 20mm/min, carry out Elongation test.Each sample test 5 battens, average.
Thermal reversion performance test and evaluation method:
1) can judge intuitively to separate crosslinked characteristic at normal temperature and the solvability of separating under crosslinking temperature in its good solvent by crosslinked sample film;
2) by crosslinked sample at 120 DEG C after constant temperature 1h sampling be dissolved in deuterochloroform and carry out nuclear magnetic resonance analyser test, and the solution crosslinking degree of quantitative Analysis furans-maleimide structure;
A
7.37for the characteristic peak peak area of the upper hydrogen of furan nucleus 4 free on polymer lateral chain.
A
5.37for the characteristic peak peak area of the upper hydrogen of furan nucleus 4 in furans in polymkeric substance-maleimide crosslinking structure.
3) with FT-IR to copolyesters PBASf, copolymerzation with cross-linking ester composition PBASf-BMI (by polyester composition PBASf-BMI constant temperature 24h products therefrom at 50 DEG C) and separate copolymerzation with cross-linking ester PBASf-BMI (by copolymerzation with cross-linking ester composition PBASf-BMI at 120 DEG C after constant temperature 30min quenching to room temperature gained) test, to compare in its maleimide functionality=out-of-plane deformation vibration peak (the 829cm of C-H
-1), the breathing vibration peak (1064cm of furan nucleus
-1) peak intensity change.
Reference example 1: prepared by functional monomer
1) preparation of 2-(2-chaff sulfenyl) diethyl succinate
DEF, furfuryl mercaptan and catalyzer (salt of wormwood) are fed intake with mol ratio 1:1:0.05 and is placed in flask normal temperature 25 DEG C magneton stirring reaction 5h, obtain functional monomer 2-(2-chaff sulfenyl) diethyl succinate (DEF-FM) with after organic membrane filtration of 0.45 μm.
2) preparation of 2-(2-chaff sulfenyl) dimethyl succinate
Dimethyl fumarate and furfuryl mercaptan are dissolved in chloroform by the ratio 1:1 of mole number, with the N of 5mol%, N-diisopropylethylamine is as catalyzer, revolve after normal temperature 25 DEG C reaction 5h and steam removing solvent chloroform, extract 3 removing catalyzer with hexanaphthene again, finally revolve functional monomer 2-(the 2-chaff sulfenyl) dimethyl succinate (DMF-FM) steaming and eliminate remaining hexanaphthene and must contain 2-chaff sulfenyl.
The preparation of embodiment 1:PBASf-BMI composition
(1) in the flask of 250mL, hexanodioic acid (0.5mol is added, 73g), 1,4-butyleneglycol (1.0mol, 90.1g), containing functional monomer DMF-FM (consumption is 5mol%, 10mol%, 15mol%, 20mol% that total acid feeds intake) and the tetrabutyl titanate (consumption is total acid 0.2mol%) of 2-chaff sulfenyl side base, acid-alcohol ratio is 2, at 160-190 DEG C, react 6-7h, obtain esterification products, esterification yield reaches 98%; In esterification products, add tetrabutyl titanate (consumption is total acid 0.1mol%), at 190-220 DEG C, melt polycondensation reaction 4-6 hour under about 100Pa condition, prepare the copolyesters PBASf with 2-chaff sulfenyl side base.
(2) by the obtained copolyesters PBASf in step (1) and the shaping method of bismaleimides (ratio of furans and maleimide base group mole number is 1:1.1 ~ 1.1:1) mixing mould heat pressure, thermoplastic co-polymer's ester composition PBASf-BMI with thermal reversion crosslinking feature is prepared
Fig. 1 is the NMR spectrogram contrast of conciliating copolymerzation with cross-linking ester composition PBASf-BMI containing functional monomer DMF-FM, the copolyesters PBASf of 2-chaff sulfenyl, and the calculation formula according to separating crosslinking degree can the solution crosslinking degree of this solution copolymerzation with cross-linking ester composition PBASf-BMI be 85%;
Fig. 2 is the FTIR spectrogram contrast that copolyesters PBASf, PBASf-BMI and solution thereof are cross-linked PBASf-BMI sample;
Fig. 3 is copolyesters PBASf, the PBASf-BMI dissolving situation comparison diagram in solvent tetrachloroethane at normal temperature 25 DEG C and 120 DEG C: a) PBASf copolyesters dissolves situation in tetrachloroethane under normal temperature; B) PBASf-BMI copolyesters dissolves situation in tetrachloroethane under normal temperature; C) PBASf-BMI copolyesters dissolves situation in tetrachloroethane at 120 DEG C.
The preparation of embodiment 2:PBSf-BMI composition
(1) in the flask of 250mL, succinic acid (0.5mol is added, 59g), 1,4-butyleneglycol (1.0mol, 90.1g), containing functional monomer DMF-FM (consumption is 5mol%, 10mol%, 15mol%, 20mol% that total acid feeds intake) and the tetrabutyl titanate (consumption is total acid 0.2mol%) of 2-chaff sulfenyl side base, acid-alcohol ratio is 2, at 160-190 DEG C, react 3-6h, obtain esterification products, esterification yield reaches 98%; In esterification products, add tetrabutyl titanate (consumption is total acid 0.1mol%), at 190-220 DEG C, melt polycondensation reaction 4-6 hour under about 100Pa condition, prepare the copolyesters PBSf with 2-chaff sulfenyl side base.
(2) the obtained copolyesters PBSf in step (1) and the shaping method (or being dissolved in the method for chloroform solution-cast) of bismaleimides BMI (ratio of furans and maleimide base group mole number is 1:1.1 ~ 1.1:1) mixing mould heat pressure are prepared thermoplastic co-polymer's ester composition PBSf-BMI with thermal reversion crosslinking feature.
The preparation of embodiment 3:PBSASf-BMI composition
(1) in the flask of 250mL, succinic acid (0.25mol is added, 59g), hexanodioic acid (0.25mol, 36.5g) 1,4-butyleneglycol (1.0mol, 90.1g), containing functional monomer DMF-FM (consumption is 5mol%, 10mol%, 15mol%, 20mol% that total acid feeds intake) and the tetrabutyl titanate (consumption is total acid 0.2mol%) of 2-chaff sulfenyl side base, acid-alcohol ratio is 2,4-7h is reacted at 160-190 DEG C, obtain esterification products, esterification yield reaches 98%; In esterification products, add tetrabutyl titanate (consumption is total acid 0.1mol%), at 190-240 DEG C, melt polycondensation reaction 4-6 hour under about 100Pa condition, prepare the copolyesters PBSASf with 2-chaff sulfenyl side base.
(2) the obtained copolyesters PBSASf in step (1) and the shaping method (or being dissolved in the method for chloroform solution-cast) of bismaleimides (ratio of furans and maleimide base group mole number is 1:1.1 ~ 1.1:1) mixing mould heat pressure are prepared thermoplastic co-polymer's ester composition PBSASf-BMI with thermal reversion crosslinking feature.
The preparation of embodiment 4:PMSf-BMI composition
(1) in the flask of 250mL, succinic acid (0.5mol is added, 59g), 2-methyl isophthalic acid, ammediol (1.0mol, 90.1g), containing functional monomer DMF-FM (consumption is 5mol%, 10mol%, 15mol%, 20mol% that the total acid feeds intake) tetrabutyl titanate (consumption is total acid 0.2mol%) of 2-chaff sulfenyl, acid-alcohol ratio is 2, at 160-190 DEG C, react 6-7h, obtain esterification products, esterification yield reaches 98%; In esterification products, add tetrabutyl titanate (consumption total acid 0.1mol%), at 190-220 DEG C, melt polycondensation reaction 4-6 hour under about 100Pa condition, prepare the copolyesters PMSf with furan nucleus side base.
(2) the obtained copolyesters PMSf in step (1) and the shaping method (or being dissolved in the method for chloroform solution-cast) of bismaleimides (ratio of furans and maleimide base group mole number is 1:1.1 ~ 1.1:1) mixing mould heat pressure are prepared thermoplastic co-polymer's ester composition PMSf-BMI with thermal reversion crosslinking feature.
The preparation of embodiment 5:PBSeSf-BMI composition
(1) in the flask of 250mL, sebacic acid (0.5mol is added, 101.1g), 1,4-butyleneglycol (1.0mol, 90.1g), containing functional monomer DMF-FM (consumption is 5mol%, 10mol%, 15mol%, 20mol% that the total acid feeds intake) tetrabutyl titanate (consumption is total acid 0.2mol%) of 2-chaff sulfenyl, acid-alcohol ratio is 2, at 160-200 DEG C, react 6-7h, obtain esterification products, esterification yield reaches 98%; In esterification products, add tetrabutyl titanate (consumption total acid 0.1mol%), at 190-240 DEG C, melt polycondensation reaction 4-6 hour under about 100Pa condition, prepare the copolyesters PBSeSf with furan nucleus side base.
(2) the obtained copolyesters PBSeSf in step (1) and the shaping method (or being dissolved in the method for chloroform solution-cast) of bismaleimides (ratio of furans and maleimide base group mole number is 1:1.1 ~ 1.1:1) mixing mould heat pressure are prepared thermoplastic co-polymer's ester composition PBSeSf-BMI with thermal reversion crosslinking feature.
Embodiment 7: polyester composition PBASf-BMI many meltings are reprocessed
(1) the thermoplastic co-polymer's ester composition PBASf-BMI obtained in embodiment 1 is carried out crosslinking reaction 24h at 50 DEG C, obtain the PBASf-BMI sample of chemically crosslinked;
(2) sample in step (1) after usage or the scrap stock of step (1) by-product, hot-forming after first carrying out solution crosslinking reaction 30min at 120 DEG C, at 50 DEG C, constant temperature 24h carries out crosslinking reaction again, and again obtained new goods, complete recycling;
Fig. 4 is the mechanical property contrast of reclaiming melting reprocessing gained sample for polyester composition PBASf-BMI and three time of chemically crosslinked.
Embodiment 8: the selfreparing of polyester composition PBASf-BMI
(1) the thermoplastic co-polymer's ester composition PBASf-BMI obtained in embodiment 1 is carried out crosslinking reaction 24h at 50 DEG C, obtain the PBASf-BMI sample of chemically crosslinked;
(2), after the PBASf-BMI sample cutter obtained being cut, adopt and carry out selfreparing with the following method:
First at 120 DEG C, carry out solution crosslinking reaction 5min, then constant temperature carries out crosslinking reaction 3-5 days at 50 DEG C of temperature, completes the selfreparing of compromised sample, the conservation rate of selfreparing back draft intensity is 90%.
Embodiment 9: the shape memory of polyester composition PBASf-BMI
(1) the thermoplastic co-polymer's ester composition PBASf-BMI obtained in embodiment 1 is processed into the PBASf-BMI sample of the chemically crosslinked with predetermined shape through thermoplastic;
(2) sample of step (1) carries out predetermined deformation under external force, then at 50 DEG C, carries out crosslinking reaction 24h, and fixing deformation, obtains the goods with predetermined temporary shapes, deformation fixed rate >95%;
(3) sample of step (2) carries out solution crosslinking reaction 5min in 120 DEG C of temperature ranges, recover original-shape, then at 50 DEG C, carry out crosslinking reaction 24h obtain crosslinked products, complete shape recovery process, deformation-recovery rate >90%.
Claims (10)
1. one kind has thermoplastic co-polymer's ester composition of thermal reversion chemically crosslinked characteristic, it is characterized in that, be made up of the copolyesters not containing carbon-carbon double bond containing 2-chaff sulfenyl side base and on main chain and the linking agent containing maleimide base group, and repeatedly can there is chemically crosslinked reconciliation crosslinking reaction, there is thermoplasticity.
2. thermoplastic co-polymer's ester composition with thermal reversion chemically crosslinked characteristic according to claim 1, it is characterized in that, the atactic polyester that described copolyesters is made up of the diprotic acid binary alcohol esters repeating unit containing 2-chaff sulfenyl side base and linear diprotic acid binary alcohol esters repeating unit;
The structure of the described diprotic acid binary alcohol esters repeating unit containing 2-chaff sulfenyl side base is as follows:
The structure of described linear diprotic acid binary alcohol esters repeating unit is as follows:
Wherein X, Y, R are C
2~ C
12alkyl, the mole fraction of the diprotic acid binary alcohol esters repeating unit containing 2-chaff sulfenyl side base in copolyesters is 0.01 ~ 0.25;
Described linking agent has following structure:
Wherein A is aromatic series or aliphatic group, and n is 2 or 3; Described aromatic group is the one in following group:
wherein n is 1-3;
Described aliphatic group is C
2~ C
12one in alkyl or following group:
wherein
represent the position of substitution;
Wherein, the mol ratio of maleimide functionality and 2-chaff sulfenyl is 1:1.1 ~ 1.1:1;
Described chemical crosslink reaction occurs in 50 ~ 70 DEG C of temperature ranges;
Described solution crosslinking reaction occurs in 100 ~ 160 DEG C of temperature ranges.
3. thermoplastic co-polymer's ester composition with thermal reversion chemically crosslinked characteristic according to claim 1 and 2, is characterized in that, level of response >=85% of described chemically crosslinked; Level of response >=85% of described solution crosslinking reaction; Crosslinking reaction is conciliate in described chemically crosslinked repeatedly can occur at least three times, and mechanical property keeps more than 90%.
4. the preparation method with thermoplastic co-polymer's ester composition of thermal reversion chemically crosslinked characteristic as described in any one of claims 1 to 3, is characterized in that, comprise the following steps:
(1) add dibasic alcohol, diprotic acid in the reactor, containing the functional monomer of 2-chaff sulfenyl and catalyzer, esterification 2-7 hour at 160-220 DEG C, obtains esterification products, esterification yield reaches 98% or more;
Described dibasic alcohol and diprotic acid mol ratio are 1.2-2:1;
Described is (0.01-0.25) containing the functional monomer of 2-chaff sulfenyl and the molar ratio of diprotic acid: 1;
(2) in the esterification products of step (1) gained, add catalyzer, at 190-250 DEG C, polycondensation 2-7 hour under 300 ~ 60Pa condition, obtain described copolyesters;
(3) in the copolyesters of step (2) gained, add described linking agent, mix at the temperature higher than copolyesters fusing point or second-order transition temperature, obtain thermoplastic co-polymer's ester composition with thermal reversion chemically crosslinked characteristic; Wherein, the mol ratio of 2-chaff sulfenyl and dimaleoyl imino is 1:1.1 ~ 1.1:1.
5. the preparation method with thermoplastic co-polymer's ester composition of thermal reversion chemically crosslinked characteristic according to claim 4, it is characterized in that, described dibasic alcohol comprises ethylene glycol, 1,2-propylene glycol, 1, ammediol, BDO, 1,5-PD, 1,6-hexylene glycol, neopentyl glycol or 2-methyl isophthalic acid, 3 propylene glycol;
Described diprotic acid comprises succinic acid, pentanedioic acid, hexanodioic acid, suberic acid, nonane diacid, sebacic acid or 12 diacid;
The described functional monomer containing 2-chaff sulfenyl comprises the compound of following structure:
6. the preparation method with thermoplastic co-polymer's ester composition of thermal reversion chemically crosslinked characteristic according to claim 4, it is characterized in that, described catalyzer is selected from stannous octoate, stannous oxalate, butyl stannonic acid, dibutyl tin laurate, tetrabutyl titanate, isopropyl titanate or titanium ethylene glycolate, and consumption is the 0.01-0.5mol% of diprotic acid.
7. the purposes with thermoplastic co-polymer's ester composition of thermal reversion chemically crosslinked characteristic as described in any one of claims 1 to 3, is characterized in that, as plastics or the elastomer material of self-repair material, shape-memory material or recycling.
8. the purposes with thermoplastic co-polymer's ester composition of thermal reversion chemically crosslinked characteristic according to claim 7, it is characterized in that, described thermoplastic co-polymer's ester composition is for the preparation of the plastics of recyclable recycling or elastomeric preparation and recovery, and process is as follows:
(1) thermoplastic co-polymer's ester composition with thermal reversion chemically crosslinked characteristic is carried out crosslinking reaction 5-24h at 50-70 DEG C, obtain the goods of chemically crosslinked;
(2) goods in step (1) after usage or the scrap stock of step (1) by-product, first in 100-160 DEG C of temperature range, carry out solution crosslinking reaction 5-60min, crosslinking reaction 5-24h is carried out again in 50-70 DEG C of temperature range, again obtained new goods, complete recycling.
9. the purposes with thermoplastic co-polymer's ester composition of thermal reversion chemically crosslinked characteristic according to claim 7, is characterized in that, described thermoplastic co-polymer's ester composition is for the preparation of self-repair material, and preparation process is as follows:
(1) the thermoplastic co-polymer's ester composition described in any one of claims 1 to 3 is carried out crosslinking reaction 5-24h at 50-70 DEG C, obtain the goods of chemically crosslinked;
(2) after the goods obtained damage, adopt and carry out selfreparing with the following method:
First in 100-160 DEG C of temperature range, carry out solution crosslinking reaction 5-60min, then in 50-70 DEG C of temperature range, carry out crosslinking reaction or directly in 50-70 DEG C of temperature range, carry out crosslinking reaction 5-24h, complete the selfreparing of impaired goods.
10. the purposes with thermoplastic co-polymer's ester composition of thermal reversion chemically crosslinked characteristic according to claim 7, is characterized in that, described thermoplastic co-polymer's ester composition is used as shape-memory material, and its preparation and application is as follows:
(1) thermoplastic co-polymer's ester composition with thermal reversion chemically crosslinked characteristic is processed into the goods with predetermined shape through thermoplastic;
(2) goods of step (1) carry out predetermined deformation under external force, then at 50-70 DEG C, carry out crosslinking reaction 5-24h, and fixing deformation, obtains the goods with predetermined temporary shapes;
(3) goods of step (2) carry out solution crosslinking reaction 5-60min in 100-160 DEG C of temperature range, recover original-shape, complete shape recovery process.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510675294.2A CN105153409B (en) | 2015-10-16 | 2015-10-16 | Thermoplastic copolyester composition with thermally reversible chemical crosslinking properties and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510675294.2A CN105153409B (en) | 2015-10-16 | 2015-10-16 | Thermoplastic copolyester composition with thermally reversible chemical crosslinking properties and preparation method and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN105153409A true CN105153409A (en) | 2015-12-16 |
| CN105153409B CN105153409B (en) | 2017-03-22 |
Family
ID=54794481
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201510675294.2A Active CN105153409B (en) | 2015-10-16 | 2015-10-16 | Thermoplastic copolyester composition with thermally reversible chemical crosslinking properties and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN105153409B (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108586715A (en) * | 2018-04-20 | 2018-09-28 | 浙江大学 | A kind of biological poly ester elastomer and preparation method thereof |
| CN109971138A (en) * | 2019-03-22 | 2019-07-05 | 江门市德山复合材料科技有限公司 | A kind of selfreparing PCBT composite material and preparation method |
| CN110804165A (en) * | 2019-11-13 | 2020-02-18 | 苏州大学 | Photocrosslinkable and crosslinked thermoplastic PET copolyester and preparation and application thereof |
| CN112625415A (en) * | 2020-12-14 | 2021-04-09 | 东华大学 | Dynamic thermosetting material, elastic conductive composite material, preparation and application thereof |
| CN115305596A (en) * | 2022-07-21 | 2022-11-08 | 山东华纶新材料有限公司 | Marine creep-resistant high-strength polyester fiber and preparation method and application thereof |
| CN115397886A (en) * | 2020-04-01 | 2022-11-25 | 出光兴产株式会社 | Resin, resin precursor composition, coating liquid composition, electrophotographic photoreceptor, molded article, electronic device, and method for producing electrophotographic photoreceptor |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101889039A (en) * | 2007-11-16 | 2010-11-17 | 日本电气株式会社 | Shape memory resin, shaped article using the same and method of using the shaped article |
-
2015
- 2015-10-16 CN CN201510675294.2A patent/CN105153409B/en active Active
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101889039A (en) * | 2007-11-16 | 2010-11-17 | 日本电气株式会社 | Shape memory resin, shaped article using the same and method of using the shaped article |
Non-Patent Citations (1)
| Title |
|---|
| MITSUHIRO SHIBATA ETC: "High-performance hybrid materials prepared by the thermo-reversible Diels–Alder polymerization of furfuryl ester-terminated butylene succinate oligomers and maleimide compounds", 《POLYMER JOURNAL》 * |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108586715A (en) * | 2018-04-20 | 2018-09-28 | 浙江大学 | A kind of biological poly ester elastomer and preparation method thereof |
| CN109971138A (en) * | 2019-03-22 | 2019-07-05 | 江门市德山复合材料科技有限公司 | A kind of selfreparing PCBT composite material and preparation method |
| CN109971138B (en) * | 2019-03-22 | 2021-08-17 | 江门市德山复合材料科技有限公司 | Self-repairing PCBT composite material and preparation method thereof |
| CN110804165A (en) * | 2019-11-13 | 2020-02-18 | 苏州大学 | Photocrosslinkable and crosslinked thermoplastic PET copolyester and preparation and application thereof |
| CN110804165B (en) * | 2019-11-13 | 2021-09-07 | 苏州大学 | Photocrosslinkable and crosslinked thermoplastic PET copolyester and preparation and application thereof |
| CN115397886A (en) * | 2020-04-01 | 2022-11-25 | 出光兴产株式会社 | Resin, resin precursor composition, coating liquid composition, electrophotographic photoreceptor, molded article, electronic device, and method for producing electrophotographic photoreceptor |
| CN112625415A (en) * | 2020-12-14 | 2021-04-09 | 东华大学 | Dynamic thermosetting material, elastic conductive composite material, preparation and application thereof |
| CN115305596A (en) * | 2022-07-21 | 2022-11-08 | 山东华纶新材料有限公司 | Marine creep-resistant high-strength polyester fiber and preparation method and application thereof |
| CN115305596B (en) * | 2022-07-21 | 2023-09-29 | 山东华纶新材料有限公司 | Ocean creep-resistant high-strength polyester fiber and preparation method and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN105153409B (en) | 2017-03-22 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN105153409A (en) | Thermoplastic copolyester composition with thermally reversible chemical crosslinking properties and preparation method and application thereof | |
| Xie et al. | Modification of poly (ethylene 2, 5-furandicarboxylate) with biobased 1, 5-pentanediol: significantly toughened copolyesters retaining high tensile strength and O2 barrier property | |
| Hong et al. | Fully bio-based high-performance thermosets with closed-loop recyclability | |
| Fei et al. | Biobased poly (ethylene 2, 5-furancoate): No longer an alternative, but an irreplaceable polyester in the polymer industry | |
| Zhou et al. | Synthesis of vanillin-based polyimine vitrimers with excellent reprocessability, fast chemical degradability, and adhesion | |
| Tu et al. | Biobased high-performance aromatic–aliphatic polyesters with complete recyclability | |
| Tao et al. | Sustainable alternative to bisphenol A epoxy resin: high-performance recyclable epoxy vitrimers derived from protocatechuic acid | |
| Wu et al. | High molecular weight poly (butylene succinate-co-butylene furandicarboxylate) copolyesters: from catalyzed polycondensation reaction to thermomechanical properties | |
| Xu et al. | Catalyst-free self-healing fully bio-based vitrimers derived from tung oil: Strong mechanical properties, shape memory, and recyclability | |
| CN104341585B (en) | Taking the flexible atactic polyester of furandicarboxylic acid as the triblock copolymer of soft section and preparation method thereof | |
| Bhanderi et al. | Recycling of polyethylene terephthalate (PET Or PETE) plastics–An alternative to obtain value added products: A review | |
| CN102558515A (en) | Method for continuously preparing biodegradable plastic | |
| CN102516513A (en) | Preparation method of low-yellowing 2,5-furandicarboxylic acid-based polyester | |
| CN112300372B (en) | Preparation and application of sulfur-containing copolyester partially derived from biomass | |
| CN110078903A (en) | A method of continuously preparing Biodegradable resin side by side | |
| CN102746500A (en) | Method for synthesizing high-molecular-weight poly(lactic acid) through melt polycondensation of lactic acid under catalysis of three-way composite catalyst | |
| Xu et al. | Tough self-healing polyurethane elastomers based on interpenetrating networks containing multiple hydrogen bond networks, flexible blocks, metal coordination and covalent cross-linking | |
| Zhang et al. | Mechanically robust, stretchable, recyclable, and biodegradable ionogels reinforced by polylactide stereocomplex nanocrystals | |
| Wang et al. | Dynamics-Driven Controlled polymerization to synthesize fully renewable poly (ester–ether) s | |
| CN108219121A (en) | A kind of biology base high barrier polyester material and its synthetic method | |
| CN101628972A (en) | Method for preparing poly (ethylene succinate) | |
| Ding et al. | Eco-plastics derived from low-purity plant oil monomer and their sustainable recycling | |
| CN116554436A (en) | Self-repairable bio-based crosslinked polyurethane material and preparation method thereof | |
| Qin et al. | Dynamic reversible mechanism of phenol-carbamate bonds and their potential for the development of thermo-healing, recyclable and high-performance epoxy thermosets | |
| CN110591058A (en) | Method for catalytic polycondensation of degradable packaging material |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |