CN103333346B - A kind of can the hyperbranched resilient material and preparation method thereof of self-healing - Google Patents
A kind of can the hyperbranched resilient material and preparation method thereof of self-healing Download PDFInfo
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Abstract
The present invention relates to a kind of can the hyperbranched resilient material and preparation method thereof of self-healing.Preparation method comprises: after the first component containing double bond and carboxyl or ester group and the second component containing more than three amino are reacted 1h ~ 72h at the temperature of-20 ~ 50 DEG C; Be warming up to room temperature ~ 200 DEG C, decompression be lower continues reaction 1h ~ 72h, product through precipitation, filter, be separated, dry, obtaining molecule chain end is amino hyperbranched polymer; Be amino hyperbranched polymer by molecule chain end and three components polyprotonic acid or polyprotonic acid mixture or the oligopolymer containing end carboxyl, at 80 ~ 280 DEG C of temperature, react 1h ~ 120h, obtaining can the hyperbranched resilient material of self-healing.Hyper-branched materials of the present invention at room temperature has elasticity, and containing the abundant amino forming reversible hydrogen bond and amide group, material is at room temperature had can self-healing characteristics, and has thermoplasticity, can reprocessabilty shaping.
Description
Technical field
The invention belongs to Materials science and technical field, be specifically related to a kind of can the hyperbranched resilient material and preparation method thereof of self-healing performance.
Background technology
Self-healing is defined as material or the surface ability that automatically or independently heal (recover/repair) damages without any need for outside intervention.The material of nearly all natural and synthesis, in manufacture or use procedure, inevitably because to be heated or the impact that is external or internal factor such as stressed effect produces the destruction such as tiny crack and damage, causes the performance and used life of material to decline.Therefore there is the investigation of materials of selfreparing and self-healing capability, to the physical strength of strongthener, reliability and wearing quality, reduce production cost to have important practical significance, it is all with a wide range of applications in aerospace, automobile, electronics, the field such as daily, bionical, medical.
Propose the concept of Microcapsules Embedded Self-healing Composites from calendar year 2001 White etc. first, excite the world to the extensive concern of self-healing polymers material and research.Be summed up several forms such as the liquid core fibre method that mainly contains, microcapsule method heat and reversible selfreparing method, after nanometer/microcell that first two method needs the crack of composite system to touch containing linking agent, catalyzer or monomer usually, initiated polymerization stops or healed cracks, and such anti-reverse system has a potential shortcoming to be exactly along with the consumption of renovation agent makes healing number of times limited.Therefore, the reversible material that can repeatedly be destroyed by external stimulus and heal causes the increasing interest of people.
2008, Leibler etc. delivered the interaction by multiple hydrogen bonding between small molecules on Nature, and Supramolecular self assembly becomes to have the thermal reversion rubber of self-healing character, is engaged at normal temperatures, the mechanical property of material can be made substantially to recover by simple section.The feature of this system unlimitedly to repeat healing, and cost is low, easily process, and the thermoplastic behavior under melting and hypotoxicity make it have potential industrial application.This rare character becomes the breakthrough in the self-repair material world, obtains suitable attention at supramolecule and macromolecular material research circle, and the research for self-healing polymer materials provides a new direction.
Patent application document US 2009/0062551A1 and CN 101160359A describes utilization and contains
the molecule of group (wherein A represents oxygen, sulphur or NH) to be associated having rubber-like elasticity and comprising the material of the molecule of molecular mass between 9 and 9000g/mol of preparation by noncovalent interaction.At the paper (Nature that applicants delivers, 2008,451 (7181): 977-980) disclosing prepared in can the second-order transition temperature of self-healing elastomer material be 28 DEG C, show as fragility at a lower temperature, in fact this material is not resilient material truly.
As a new developing direction, by intermolecular multiple hydrogen bonding self assembly self-healing elastomerics, there is very large research space, the hydrogen bond type self-healing elastomerics had compared with lower glass transition temperatures is prepared in research, expands its range of application and has important theory significance and actual application value.
Hyperbranched polymer has the three-dimensional space molecular configuration being different from traditional line polymer, outer containing a large amount of end groups, wherein over-branched polyamidoamine molecule superficies contain the amido (primary amine that can form hydrogen bond in a large number, tertiary amine, acid amides etc.) functional group, by the chemical reaction with polyprotonic acid or polyprotonic acid mixture or the oligopolymer containing end carboxyl, soft segment is introduced in over-branched polyamidoamine molecular chain, prepare second-order transition temperature lower, the hyper-branched materials realizing self-healing by intermolecular interaction of hydrogen bond is that preparation can the effective way of self-healing resilient material.
Summary of the invention
The object of the present invention is to provide that a kind of have can the hyperbranched resilient material and preparation method thereof of self-healing performance, this material forms intermolecular physical crosslinking structure by interaction of hydrogen bond, at room temperature there is elastic performance and can self-healing characteristics, and there is thermoplasticity, can reprocessabilty shaping.
The present invention is with the first component containing double bond and carboxyl or ester group, second component containing the amino of more than three, and the mixture of polyprotonic acid or polyprotonic acid or the oligopolymer of end carboxyl are as three components, synthesize that a series of have can the hyperbranched resilient material of self-healing performance, concrete technical scheme is as follows.
The concrete preparation method of hyperbranched resilient material of the present invention is: step a: reacted at-20 ~ 50 DEG C, after reaction times 1h ~ 72h by the second component of the first component containing double bond and carboxyl or ester group with the amino containing more than three; Continue reaction 1h ~ 72h under being warming up to the vacuum tightness of room temperature ~ 200 DEG C, 0.03MPa ~ 0.095MPa, reaction product precipitated in precipitation agent, after filtration, be separated, dry, obtaining molecule chain end is amino hyperbranched polymer;
Step b: the molecule chain end that step a is obtained be amino hyperbranched polymer and three components at 80 ~ 280 DEG C, the reaction times is after 1h ~ 120h, obtains target product; Described three components be in polyprotonic acid more than one or containing the oligopolymer of end carboxyl.
The first component that the present invention adopts comprise in vinylformic acid, methacrylic acid, methyl acrylate, ethyl propenoate, butyl acrylate, methyl methacrylate, β-dimethyl-aminoethylmethacrylate, butyl methacrylate, Octyl methacrylate, lauryl methacrylate(LMA), octadecyl methacrylate, butenoic acid ethyl, diacrylic acid pentyl diol ester and their homologue, derivative and isomer more than one.
The second component that the present invention adopts comprise in diethylenetriamine, triethylene tetramine, tetraethylene pentamine, five ethene hexamines and other polyamines polyene, polyamino aromatic compound, polyamino heterogeneous ring compound more than one.
The three components polyprotonic acid that the present invention adopts comprise in the lipid acid polymer of propanedioic acid, succinic acid, pentanedioic acid, hexanodioic acid, pimelic acid, suberic acid, nonane diacid, SA, butene dioic acid, ethylenediamine tetraacetic acid (EDTA), diethylene triamine pentacetic acid (DTPA) or plant origin more than one, the lipid acid of plant origin comprise in oleic acid, linolic acid, palmitinic acid, lauric acid, tetradecanoic acid, stearic acid more than one.
The three components that the present invention adopts comprises more than one in carboxyl end of the liquid acrylonitrile-butadiene rubber, carboxyl terminated liquid polybutadiene rubber, end carboxyl liquid styrene butadiene rubber, end carboxyl liquid polypiperylene rubber, end carboxyl acrylate quasi-oligomer, end carboxyl oligosiloxane containing the oligopolymer of end carboxyl.
Charged molar ratio between reaction raw materials first component of the present invention and second component is 1/20 ~ 20/1, and molecule chain end is the-NH of amino hyperbranched polymer
2the charged molar ratio of group and three components-COOH group is 1/10 ~ 10/1.
More than one in the present invention's methyl alcohol, ethanol, butanols, isopropylcarbinol, tetracol phenixin, N, N '-dimethyl formamide, N, N '-N,N-DIMETHYLACETAMIDE, chloroform, dimethyl sulfoxide (DMSO) are as reaction medium.
The present invention in step a with acetone, butanone, more than one in ether as precipitation agent.
Tool of the present invention has the following advantages and beneficial effect:
Prepared by the present invention can the hyperbranched resilient material of self-healing, forms intermolecular physical crosslinking structure by interaction of hydrogen bond, and having can self-healing performance, such as after tension fracture, after section contacts at ambient temperature, observe fusion, and can again stretch to it.Preparation can the hyperbranched resilient material second-order transition temperature of self-healing lower than room temperature, good elastic performance can be kept at normal temperatures, and have thermoplasticity, can reprocessabilty shaping; Can additive be added, change some parameter, as time of relaxation at different temperatures, creep properties, second-order transition temperature, chemical resistant properties etc.
The present invention have raw material sources extensively, low price, technique is simple and easy, and controllability is good, the advantage that preparation cost is low.That prepares can dissolve in part organic solvent by the hyperbranched resilient material of self-healing, can carry out blending and modifying, for the manufacture of tackiness agent, rheologic additive, sealing material, coating, wrapping material, tire, sebific duct, adhesive tape etc. with other polymkeric substance.
Accompanying drawing explanation
Fig. 1 is that hyperbranched resilient material of the present invention is at 1700cm
-1-1450cm
-1temperature-dependent IR spectrogram in scope, wherein a-25 DEG C, b-60 DEG C, c-90 DEG C, d-120 DEG C, be down to room temperature for e-160 DEG C, f-160 DEG C.
Fig. 2 is the stress time curve figure of the stress relaxation of hyperbranched resilient material batten of the present invention.
Fig. 3 is the cyclic tension stress-strain curve of hyperbranched resilient material batten of the present invention.
Specific embodiments
Case study on implementation 1
By the triethylene tetramine mixture of the diethylenetriamine of 0.25mol and 0.25mol and 60mL anhydrous methanol solvent even; the methyl acrylate of 0.5mol and the mixture of 20mL anhydrous methanol is added under nitrogen protection; and 36h is reacted at 20 DEG C; underpressure distillation is except desolventizing; be warming up to again 120 DEG C under the vacuum tightness of 0.05MPa, react 36h after; take acetone as precipitation agent; through precipitation, filter, be separated, obtain product after drying and molecule chain end is amino hyperbranched polymer, by its amine value of determination of acid-basetitration.With-NH
2: the mol ratio of-COOH=1:1 is got after above-mentioned product and linolic acid dimeracid mix, and 160 DEG C of reaction 96h, obtain hyperbranched resilient material after vacuum-drying under nitrogen protection.IR (KBr), ν (cm
-1)=3215 (ν
nH), 2945 (ν
as, CH2), 2835 (ν
s, CH2), 1646 (ν
c=O), 1553 (ν
cNand δ
nH), 1036 (ν
cN).
Accompanying drawing 1 for hyperbranched resilient material sample respectively room temperature, 60 DEG C, 90 DEG C, 120 DEG C, 160 DEG C and after carrying out Infrared spectrum scanning when falling back room temperature at 1700 ~ 1450cm
-1spectrogram changing conditions in scope: along with the rising of temperature, be positioned at 1646cm during room temperature
-1the carbonylic stretching vibration frequency ν at place
c=O1654cm when being offset to 160 DEG C to high frequency region gradually
-1, during room temperature, be positioned at 1553cm
-1the C-N stretching vibration frequency ν at place
c-Nwith-NH in-plane bending vibration frequency δ
nH1537cm when being offset to 160 DEG C gradually to low frequency range
-1, and the characteristic peak intensity at two places declines all to some extent, show-NH-in system,
with
between there is hydrogen bond action and rising with temperature dies down gradually; In curve f after cooling, above-mentioned characteristic peak positions returns to original state, and this illustrates that the hydrogen bond between sample molecule has good reversibility.
Differential scanning calorimetry (DSC) test is carried out to resilient material sample, from room temperature, be warming up to 150 DEG C with the temperature rise rate of 10 DEG C/min, and constant temperature 3min, then-80 DEG C are cooled to, again with identical ramp to 150 DEG C with equal speed.Occur obvious glass transition step near-16 DEG C on second time heating curve, show Tg=-16 DEG C of sample, it at room temperature can keep elastomeric character even at lower temperatures.
By resilient material hot pressing 5min, then coldmoulding, be cut into the standard dog bone batten that 2mm is thick.Cut off from centre by batten blade, section contact engaged at once, after at room temperature parking 48h, can carry out uniaxial extension to batten, eventual failure can occur in non-section joint, and describing that material has qualitatively can healing properties.At room temperature carry out tension test with the rate of extension of 50mm/min to the former state of sample and healing sample, its result is as shown in table 1, and indicating that material has quantitatively can healing properties.
The former state of table 1 sample and the mechanical property of healing sample and healing efficiency *
* healing efficiency=(tensile strength of the tensile strength/former state of healing sample) × 100
Case study on implementation 2
Be after the vinylformic acid of 20:1 and the mixing of five ethene hexamines by mol ratio; at-20 DEG C of reaction 72h under nitrogen protection; the product obtained is warming up to after room temperature reacts 72h under the vacuum tightness of 0.095MPa again; take ether as precipitation agent; through precipitation, to filter, be separated, obtain product after drying be molecule chain end be amino hyperbranched polymer, by its amine value of determination of acid-basetitration.With-NH
2: the mol ratio of-COOH=10:1 is got after above-mentioned product and carboxyl end of the liquid acrylonitrile-butadiene rubber mix, and 80 DEG C of reaction 120h, obtain hyperbranched resilient material after vacuum-drying under nitrogen protection.
Differential scanning calorimetry (DSC) test is carried out to resilient material sample, from room temperature, be warming up to 100 DEG C with the temperature rise rate of 10 DEG C/min, and constant temperature 3min, then-80 DEG C are cooled to, again with identical ramp to 100 DEG C with equal speed.Record Tg=-33 DEG C of sample, it at room temperature can keep elastomeric character even at lower temperatures.
The former state recording sample according to method described in embodiment 1 is as shown in table 2 with the drafting results of healing sample.
The former state of table 2 sample and the mechanical property of healing sample and healing efficiency
Case study on implementation 3
By the triaminobenzene of 4.0 mol and 80mL N; dinethylformamide solvent is even; the Octyl methacrylate of 0.1mol and the mixture of 0.1mol Isooctyl methacrylate is added under nitrogen protection; and 1h is reacted at 50 DEG C; underpressure distillation is except desolventizing; be warming up to again 180 DEG C be aggregated in the vacuum tightness of 0.03MPa under react 1h after; take butanone as precipitation agent; through precipitation, to filter, be separated, obtain product after drying be molecule chain end be amino hyperbranched polymer; by its amine value of determination of acid-basetitration, with-NH
2: the mol ratio of-COOH=1:8, get above-mentioned product and diethylene triamine pentacetic acid (DTPA), 280 DEG C of reaction 1h, obtain hyperbranched resilient material after vacuum-drying under nitrogen protection.
Record Tg=-10 DEG C of sample according to method described in case study on implementation 1, it at room temperature can keep elastomeric character.
At room temperature carry out tension test to the former state of sample with healing sample according to method described in case study on implementation 1, its result is as shown in table 3.
The former state of table 3 sample and the mechanical property of healing sample and healing efficiency
Electronic tension tester carries out stress relaxation test, with the speed of 50mm/min, batten is stretched to 100% deformation and constant deformation amount, record stress curve over time.Result as shown in Figure 2;
Be that 1mm sample thin slice is placed in different solvents by thickness, at normal temperature and 50 DEG C, place a couple of days respectively, its solvability is as shown in table 4.
The solubility property of table 4 sample in different solvents
| Water | Methane amide | Dimethyl sulfoxide (DMSO) | N, N '--dimethyl formamide | Methyl alcohol | Ethanol | Chloroform | Acetone | Tetrahydrofuran (THF) | |
| Normal temperature | － | ± | － | － | － | － | ± | － | － |
| 50℃ | － | ＋ | － | － | ± | － | ＋ | － | － |
Note: "+" is solvable, " ± " is partly dissolved, and "-" is soluble.
Case study on implementation 4
The tetraethylene pentamine of 0.2mol is mixed with 50mL alcohol solvent; the mixture of the butenoic acid ethyl of 1mol is added under nitrogen protection; and 48h is reacted at 0 DEG C; underpressure distillation is except desolventizing; being warming up to 50 DEG C again under the vacuum tightness of 0.07MPa, after polyreaction 24h, take ether as precipitation agent, and through precipitation, to filter, be separated, obtain product after drying be molecule chain end be amino hyperbranched polymer; by its amine value of determination of acid-basetitration, with-NH
2: the mol ratio of-COOH=1:4, get above-mentioned product and mol ratio is the oleic acid of 1:1 and linoleic mixture, 120 DEG C of reaction 1h, obtain hyperbranched resilient material after vacuum-drying under nitrogen protection.
Tg=-20 DEG C of sample are recorded according to method described in case study on implementation 1.
According to the method described in case study on implementation 1, tension test is carried out to the former state of material sample and healing sample; And after second time machine-shaping, sample preparation are carried out to sample, tension test is carried out to former state and healing sample, its result is as shown in table 5, and the drafting results difference of twice is not obvious, shows that the material prepared has thermoplasticity.
The former state of table 5 sample and the mechanical property of healing sample and healing efficiency
Case study on implementation 5
The diethylenetriamine of 1mol is mixed with 60mL chloroform solvent; the octadecyl methacrylate of 0.2mol is added under nitrogen protection; and 24h is reacted at 35 DEG C; underpressure distillation is except desolventizing; being warming up to 150 DEG C again under the vacuum tightness of 0.06MPa, after polyreaction 8h, take ether as precipitation agent, and through precipitation, to filter, be separated, obtain product after drying be molecule chain end be amino hyperbranched polymer; by its amine value of determination of acid-basetitration, with-NH
2: the mol ratio of-COOH=4:1, get above-mentioned product and mol ratio is the SA of 2:1 and the mixture of pentanedioic acid, 200 DEG C of reaction 3h, obtain hyperbranched resilient material after vacuum-drying under nitrogen protection.
Tg=-23 DEG C of sample are recorded by method described in case study on implementation 1.
Carry out tension test by method described in case study on implementation 1 to the former state of sample and healing sample, its result is as shown in table 6.
The former state of table 6 sample and the mechanical property of healing sample and healing efficiency
Batten is carried out cyclic tension with the stretching of 10mm/min and recovery rate on electronic tension tester, its result as shown in Figure 3, there is obvious hysteresis phenomenon in sample, the delayed circle of second time circulation is less much than the delayed circle of first time circulation, and the delayed circle circulated with third time is more or less the same.
Claims (4)
1. one kind can the preparation method of hyperbranched resilient material of self-healing, it is characterized in that reacting and carry out as follows: step a: the second component of the first component containing double bond and carboxyl or ester group with the amino containing more than three is reacted, after reaction times 1h ~ 72h at-20 ~ 50 DEG C; Continue reaction 1h ~ 72h under being warming up to the vacuum tightness of room temperature ~ 200 DEG C, 0.03MPa ~ 0.095MPa, reaction product precipitated in precipitation agent, after filtration, be separated, dry, obtaining molecule chain end is amino hyperbranched polymer;
Step b: the molecule chain end that step a is obtained be amino hyperbranched polymer and three components at 80 ~ 280 DEG C, the reaction times is after 1h ~ 120h, obtains target product; Described three components be in polyprotonic acid more than one or containing the oligopolymer of end carboxyl; First component used comprise in vinylformic acid, methacrylic acid, methyl acrylate, ethyl propenoate, butyl acrylate, methyl methacrylate, β-dimethyl-aminoethylmethacrylate, butyl methacrylate, Octyl methacrylate, lauryl methacrylate(LMA), octadecyl methacrylate, butenoic acid ethyl, diacrylic acid pentyl diol ester and their homologue, derivative and isomer more than one;
Second component used comprise in diethylenetriamine, triethylene tetramine, tetraethylene pentamine, five ethene hexamines and other polyethylene polyamine, polyamino aromatic compound, polyamino heterogeneous ring compound more than one; Three components polyprotonic acid used, comprise in the lipid acid polymer of propanedioic acid, succinic acid, pentanedioic acid, hexanodioic acid, pimelic acid, suberic acid, nonane diacid, SA, butene dioic acid, ethylenediamine tetraacetic acid (EDTA), diethylene triamine pentacetic acid (DTPA) or plant origin more than one, the lipid acid of plant origin comprise in oleic acid, linolic acid, palmitinic acid, lauric acid, tetradecanoic acid, stearic acid more than one; Three components used contains the oligopolymer of end carboxyl, comprises more than one in carboxyl end of the liquid acrylonitrile-butadiene rubber, carboxyl terminated liquid polybutadiene rubber, end carboxyl liquid styrene butadiene rubber, end carboxyl liquid polypiperylene rubber, end carboxyl acrylate quasi-oligomer, end carboxyl oligosiloxane; The mol ratio of reaction raw materials first component and second component is 1/20 ~ 20/1, and molecule chain end is the-NH of amino hyperbranched polymer
2the mol ratio of group and three components-COOH group is 1/10 ~ 10/1.
2. according to aforementioned according to claim 1 can the preparation method of the hyperbranched resilient material of self-healing, it is characterized in that step a methyl alcohol, ethanol, butanols, isopropylcarbinol, tetracol phenixin, N, more than one in N '-dimethyl formamide, N, N '-N,N-DIMETHYLACETAMIDE, chloroform, dimethyl sulfoxide (DMSO) are as reaction medium.
3., according to the preparation method of the hyperbranched resilient material of aforementioned self-healing according to claim 1, to it is characterized in that in step a with acetone, butanone, more than one in ether as precipitation agent.
4. by preparation method described in any one of claim 1 ~ 3 obtain can the hyperbranched resilient material of self-healing, it is characterized in that the second-order transition temperature of this material is below room temperature, namely at room temperature there is elastic property, and this material at room temperature has self-healing.
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| CN103113578A (en) * | 2013-01-31 | 2013-05-22 | 华南理工大学 | Modified carboxyl-terminated hyperbranched polyamide resin, as well as preparation method and application thereof |
| CN103130967A (en) * | 2013-02-28 | 2013-06-05 | 西南石油大学 | Hyperbranched hydrophobical-associating water-soluble polymer and its preparation method |
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