CN108219111A - Selfreparing, the thermosets that can be reprocessed and can be recycled and its processing method under a kind of temperate condition - Google Patents
Selfreparing, the thermosets that can be reprocessed and can be recycled and its processing method under a kind of temperate condition Download PDFInfo
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- CN108219111A CN108219111A CN201810005368.5A CN201810005368A CN108219111A CN 108219111 A CN108219111 A CN 108219111A CN 201810005368 A CN201810005368 A CN 201810005368A CN 108219111 A CN108219111 A CN 108219111A
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- 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
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/20—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the epoxy compounds used
-
- 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
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/77—Polyisocyanates or polyisothiocyanates having heteroatoms in addition to the isocyanate or isothiocyanate nitrogen and oxygen or sulfur
- C08G18/78—Nitrogen
- C08G18/7862—Nitrogen containing cyano groups or aldimine or ketimine groups
-
- 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
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/04—Polysiloxanes
- C08G77/22—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen and oxygen
- C08G77/26—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen and oxygen nitrogen-containing groups
Abstract
The invention discloses selfreparing, the thermosets that can be reprocessed and can be recycled and its processing methods under a kind of temperate condition, belong to functional high polymer material field.Dynamic key by the reversible fracture that stimuli responsive is introduced in based on the crosslinked thermosetting polymer of commutative chemical bond is prepared selfreparing and can reprocess molding thermosetting polymer.Its principle is when applying mild outside stimulus condition, the reversible fracture of dynamic key temporarily reduces the effective crosslinking density of material internal, covalent bond is accelerated to exchange the recombination with cross-linked network, and then assigns thermoset copolymer material and realizes the Ke Xunhuanliyong ability such as underbead crack selfreparing or material fragment reprocessing molding in a mild condition.The it is proposed of the present invention by for the selfreparing of thermosetting polymer and its composite material, can reprocess and can be recycled a convenient new way is provided.
Description
Technical field
The present invention relates to a kind of thermosets, and in particular to selfreparing under a kind of temperate condition can be reprocessed and can be followed
The thermosets and its processing method that ring utilizes belong to high molecular material processing application field,
Background technology
For thermosetting polymer because of stable structure, mechanical performance is excellent, resistant to chemical etching and produced in construction material, electronics
The fields such as product, automobile component and space flight and aviation are in occupation of the status for being difficult to replace.However thermosets (such as phenoplasts,
Epoxy plastics) because being difficult to reprocess after molding, usually by discarded after structure change or hydraulic performance decline.In high speed development
Electronics industry, due to not can be recycled for thermosetting property electronic package material, a large amount of electronic products become electronic waste.Conventional electricity
For the maximum temperature range of sub- product (including army grade electronic equipment) normal work between -55~125 DEG C, this causes thermosetting
Property electronic package material and electronic component hot repair it is multiple and recycle more difficult.Current a large amount of waste electronic encapsulating materials
It is improper to handle the waste for not only causing non-renewable resources, serious pollution also is caused to the environment around us.
Therefore, inherently solve the problems, such as that the research that the thermosetting polymers such as electronic package material recycle is extremely urgent.
Leibler et al. is prepared for a kind of with covalent bond exchange reaction using epoxy resin and polyacid or acid anhydrides for the first time
Novel hot setting polymer, and therefore obtain the prize of European patent man in 2015.The polymer is because of softening process and glassy state
Silica (vitreous silica) is similar, also referred to as vitrimers (class glass polymer).As permanent organic
Network, the thermosetting polymer exchanged based on covalent bond can realize thermosetting under the premise of polymer architecture and performance is not changed
Property material reparation and reprocessing, since crosslink density remains constant, though at high temperature it still have it is good resistance to
Solvent borne.As temperature increases, the exchange rate of covalent bond is accelerated in the thermosetting polymer exchanged based on covalent bond, cross-linked network
Network recombinates, and polymer modulus and viscosity continuously decrease, and the hot repair so as to fulfill thermosets is multiple and reprocesses.
During it the thermosetting polymer selfreparing exchanged based on covalent bond, can reprocess and can be recycled, covalently
The exchange rate of key plays decisive role, this leads to its selfreparing, can reprocess and can be recycled it is generally necessary to for a long time
High temperature, condition are harsher.Such as prepared based on glutaric anhydride and epoxy resin vitrimers thermosetting polymers (Tg~
80 DEG C, modulus~1.8GPa) need 200 DEG C or more the ability stress that releasable material reprocessing generates in the process completely.Tsing-Hua University is big
It learns crag seminar to introduce carbon nanotubes in the thermosetting polymer exchanged based on ester bond key, passes through the photo-thermal of carbon nanotube
Transformation, realizes the reparation and welding of epoxy material (Tg~45 DEG C, modulus~1.7GPa) using laser, however light laser
The actual temperature of the lower material of irradiation it is still very high (>180℃).Long-time high temperature or strong laser irradiation can not only generate largely
Energy consumption, while can also serious destruction be caused to other important components (such as core electron element) in product, it will be applied from future
Angle is set out, and the temperature that how to be effectively reduced the selfreparing of vitrimers thermosets, can reprocess and can be recycled is extremely
It closes important.
Invention content
The purpose of the present invention is to provide selfreparing, the thermosetting properties that can be reprocessed and can be recycled under a kind of temperate condition
Material and its processing method.
The invention is realized in this way：
Selfreparing under a kind of temperate condition, the processing method for the thermosets that can be reprocessed and can be recycled, including：
The first step, at a certain temperature, with reversible the first compounds precursors for being broken dynamic key and with reversible fracture dynamic key
Second compound forerunner's precursor reactant, be prepared active group sealing end have it is reversible fracture dynamic key compound；Second
Step in polymer monomer, adds in the compound with reversible fracture dynamic key of active group sealing end, curing agent and chemical bond
Exchange reaction catalyst by certain time curing reaction, obtains having reversible fracture dynamic key and the heat of commutative chemical bond
Solidity polymer material, the thermosets have selfreparing, the ability that can be reprocessed and can be recycled in a mild condition.
Further scheme is：
First compounds precursors with reversible fracture dynamic key are furfuryl alcohol or epoxy-capped furans monomer.
Further scheme is：
The epoxy-capped furans monomer is under alkaline condition, to be made by furfuryl alcohol and epoxychloropropane in catalyst
What the condensation reaction under was prepared.
Further scheme is：
The second compound presoma with reversible fracture dynamic key is bismaleimide diphenyl-methane, multifunctional
Spend isocyanate compound or polyfunctionality silicone compounds.
Further scheme is：
The compound with reversible fracture dynamic key of the active group sealing end is epoxy-capped reversible with D-A
The compound of dynamic key is either the compound with the reversible dynamic keys of D-A of isocyano sealing end or is siloxane blocking
The compound with the reversible dynamic keys of D-A.
Further scheme is：
The polymer monomer is bis-phenol A glycidyl ether, isocyanide acid compound, polynary organic silicon monomer.
Further scheme is：
The curing agent be glutaric anhydride be curing agent, triethanolamine is curing agent or dibenzoyl peroxide is curing
Agent.
Further scheme is：
The chemical bond exchange reaction catalyst is zinc acetylacetonate, di-n-butyltin dilaurate or tetramethyl hydroxide
Ammonium.
Further scheme is：
Under the temperate condition carbon nanometer is also added into selfreparing, the thermosets that can be reprocessed and can be recycled
Pipe.
It should be noted that there is no especially limits for the addition of epoxy-capped furans monomer, bismaleimide monomer
System, as long as the thermoset epoxy materials with diels-Alder (D-A) dynamic key and commutative ester bond can be finally obtained,
Realize the purpose of the present invention.
The present invention while claimed pass through selfreparing, the thermosetting that can be reprocessed and can be recycled under above-mentioned temperate condition
Property material the temperate condition that obtains of processing method processing under selfreparing, the thermosets that can reprocess and can be recycled,
Selfreparing, the thermosets that can be reprocessed and can be recycled are to have reversible fracture dynamic key under the temperate condition
With the thermoset copolymer material of commutative chemical bond.
Thermosets of the present invention, can be on 120 DEG C of left sides when internal cracked or rupture becomes fragment
Under conditions of the right side, by applying certain pressure, carrying out selfreparing in 1h to crackle or fragment reprocessing being shaped to intact sample,
And the pattern and performance of material can restore as before, so as to fulfill recycling.
Compared with the recyclable thermosets reported before, the selfreparing of thermosets provided by the invention,
Can reprocess and can be recycled can realize at 120 DEG C in 1h, and selfreparing can reprocess and required temperature can be recycled
Far below other recyclable thermosets.
The present invention cardinal principle be：By introducing stimulation in based on the crosslinked thermosetting polymer of commutative chemical bond
The dynamic key of the reversible fracture of response prepares selfreparing and can reprocess molding thermosetting polymer.It is mild external applying
During incentive condition, the reversible fracture of dynamic key temporarily reduces the effective crosslinking density of material internal, and covalent bond is accelerated to exchange and hand over
The recombination of networking network, and then realize the selfreparing of thermosets in a mild condition, can reprocess and can be recycled, have
Body principle is as shown in Figure 1.The it is proposed of the present invention will be molded for the selfreparing of thermosetting polymer and its composite material, reprocessing
A convenient new way is provided with recycling.
Selection introduces the dynamic of the reversible fracture of stimuli responsive in based on the crosslinked thermosetting polymer of commutative chemical bond
State key, by applying mild outside stimulus condition, the reversible fracture of dynamic key temporarily reduces the effective crosslinking density of material internal,
Covalent bond is accelerated to exchange and the recombination of cross-linked network, realize thermosets selfreparing in a mild condition, can reprocess and
It is Ke Xunhuanliyong.It is realized and reviewed one's lessons by oneself under the harsh conditions such as high temperature or strong light based on the thermosetting polymer needs that covalent bond exchanges
Again, it can reprocess and can be recycled, in contrast, introducing stimuli responsive in the thermosetting polymer exchanged based on covalent bond
Reversible fracture dynamic key, the exchange of covalent bond and the recombination of cross-linked network are can speed up, so as in milder condition
The lower selfreparing for realizing thermosets can be reprocessed and be can be recycled, this will have more advantage in practical applications.
The dynamic key of the reversible fracture of stimuli responsive in the present invention, including arbitrarily response can be generated to environmental stimuli
Dynamic covalent bond or dynamic non-covalent key.
Commutative ester bond in the present invention can arbitrarily occur commutative including ester bond, ethylene ammonia ester bond, boric acid ester bond etc.
The chemical bond of reaction.
Thermosets in the present invention, can also include polyurethane, organosilicon etc. can arbitrarily introduce the poly- of dynamic key
Close object cross-linked network structure.
Environmental stimuli condition in the present invention, temperature, pH including heat, light, ultrasound, magnetic field and particular solution or solvent
The condition that value, redox property etc. can arbitrarily apply.
Description of the drawings
Fig. 1, epoxy vitrimers thermosets the recycling under the conditions of mild outside stimulus with dynamic key
Mechanism schematic diagram.
Fig. 2, epoxy vitrimers thermosets reprocess molding picture in kind under 120 DEG C, 1h.
Specific embodiment
The invention will be further described with reference to the accompanying drawings and examples.But the present invention is not limited to the following example.
Embodiment 1
Precursor compound of the design synthesis with dynamic key first, then reacts with curing agent and is crosslinked, had
There are the hard vitrimers thermosetting polymers of dynamic key.Specific preparation process is as follows：The first step, under alkaline condition,
Epoxy-capped furans monomer is prepared by the condensation reaction of furfuryl alcohol and epoxychloropropane under catalyst action, utilizes it later
D-A occurs at 70 DEG C with bismaleimide diphenyl-methane to react, the epoxide with D-A dynamic keys is prepared；
Second step, using bis-phenol A glycidyl ether and the epoxide with D-A dynamic keys is as reaction monomers, while with penta 2
Acid anhydrides is curing agent, and zinc acetylacetonate is ester bond exchange catalysts, is reacted 48 hours at 70 DEG C, is prepared hard with dynamic key
Matter epoxy vitrimers thermosetting polymers.By inside the hard epoxy vitrimers thermosets with dynamic key
Introduce crackle or by material manual breakage become fragment, when at 120 DEG C apply certain pressure 1 it is small when after, hard epoxy
Crackle can be repaired in vitrimers thermosets, and fragment, which can reprocess, is shaped to complete sample, so as to fulfill that can follow
Ring utilizes, and it is as shown in Figure 2 to recycle process.
Embodiment 2：
Under alkaline condition, it is prepared by the condensation reaction of furfuryl alcohol and epoxychloropropane under catalyst action epoxy-capped
Furans monomer, D-A occurs at 70 DEG C with bismaleimide diphenyl-methane using it later and reacts, is prepared with D-
The epoxide of A dynamic keys；Later, the epoxide using bis-phenol A glycidyl ether and with D-A dynamic keys is as anti-
Monomer is answered, while using glutaric anhydride as curing agent, zinc acetylacetonate is ester bond exchange catalysts, using carbon nanotube as photoresponse
Element reacts 48 hours at 70 DEG C, prepares the hard vitrimers thermosetting polymers with dynamic key.By with
Crackle is introduced inside the hard epoxy vitrimers thermosets of dynamic key or material manual breakage is become into fragment, one
Determine under near infrared light, apply certain pressure after 1 hour, crackle can be repaiied in hard epoxy vitrimers thermosets
Multiple, fragment, which can reprocess, is shaped to complete sample, so as to fulfill Ke Xunhuanliyong.
Embodiment 3：
Polyurethane precursor compound of the design synthesis with dynamic key first, then reacts with curing agent and is crosslinked,
Obtain the vitrimers heat-curable urethanes with dynamic key.Specific preparation process is as follows：The first step utilizes furfuryl alcohol and span
Carry out acid imide diphenyl-methane and D-A reactions occur at 70 DEG C, the precursor compound with D-A dynamic keys is prepared；Second
Step is reacted using the precursor compound with D-A dynamic keys and isocyanide acid compound, obtains the polymer containing isocyano
Precursor compound, adds in ester bond exchange catalysts di-n-butyltin dilaurate, prepared by polyfunctionality curing agent triethanolamine
Vitrimers thermosetting polymers with dynamic key.By in the polyurethane vitrimers thermosets with dynamic key
Inside introduces crackle or material manual breakage is become fragment, after certain pressure is applied at 120 DEG C, polyurethane
Crackle can be repaired in vitrimers thermosets, and fragment, which can reprocess, is shaped to complete sample, so as to fulfill that can follow
Ring utilizes.
Embodiment 4：
Organosilane precursor compound of the design synthesis with dynamic key first, then reacts with curing agent and is crosslinked,
Obtain the vitrimers organosilicon polymers with dynamic key.Specific preparation process is as follows：The first step utilizes furfuryl alcohol and span
Carry out acid imide diphenyl-methane and D-A reactions occur at 70 DEG C, the precursor compound with D-A dynamic keys is prepared；Second
Step is reacted using the precursor compound with D-A dynamic keys and polynary organic silicon monomer, obtained with silane reaction active group
The polymer precursor compound of group adds in siloxanes exchange reaction catalyst tetramethylammonium hydroxide and silane crosslinker peroxide
Change dibenzoyl, prepare the vitrimers thermosetting polymers with dynamic key.By in the organosilicon with dynamic key
Crackle is introduced inside vitrimers thermosets or material manual breakage is become into fragment, when applying a level pressure at 120 DEG C
After power, crackle can be repaired in organosilicon vitrimers thermosets, and fragment, which can reprocess, is shaped to complete sample,
So as to fulfill Ke Xunhuanliyong.
Although reference be made herein to invention has been described for explanatory embodiment of the invention, and above-described embodiment is only this hair
Bright preferable embodiment, embodiments of the present invention are simultaneously not restricted to the described embodiments, it should be appreciated that people in the art
Member can be designed that a lot of other modifications and embodiment, these modifications and embodiment will be fallen in principle disclosed in the present application
Within scope and spirit.
Claims (10)
1. selfreparing under a kind of temperate condition, the processing method for the thermosets that can be reprocessed and can be recycled, feature
It is：The first step, at a certain temperature, the first compounds precursors with reversible fracture dynamic key with reversible fracture with moving
The compound with reversible fracture dynamic key of active group sealing end is prepared in second compound forerunner's precursor reactant of state key；
Second step in polymer monomer, adds in the compound with reversible fracture dynamic key of active group sealing end, curing agent and change
Key exchange reaction catalyst is learned, by certain time curing reaction, obtains that there is reversible fracture dynamic key and commutative chemical bond
Thermoset copolymer material, which has selfreparing in a mild condition, can reprocess and can be recycled
Ability.
2. according to claim 1 selfreparing under temperate condition, the thermosets that can be reprocessed and can be recycled place
Reason method, it is characterised in that：
First compounds precursors with reversible fracture dynamic key are furfuryl alcohol or epoxy-capped furans monomer.
3. according to claim 2 selfreparing under temperate condition, the thermosets that can be reprocessed and can be recycled place
Reason method, it is characterised in that：
The epoxy-capped furans monomer is under alkaline condition, by furfuryl alcohol and epoxychloropropane under catalyst action
Condensation reaction be prepared.
4. according to claim 1 selfreparing under temperate condition, the thermosets that can be reprocessed and can be recycled place
Reason method, it is characterised in that：
The second compound presoma with reversible fracture dynamic key is bismaleimide diphenyl-methane, polyfunctionality is different
Cyanate esters or polyfunctionality silicone compounds.
5. according to claim 1 selfreparing under temperate condition, the thermosets that can be reprocessed and can be recycled place
Reason method, it is characterised in that：
The compound with reversible fracture dynamic key of the active group sealing end, has D-A can inverse kinematics for epoxy-capped
The compound of key be either the compound with the reversible dynamic keys of D-A of isocyano sealing end or be siloxane blocking tool
There is the compound of the reversible dynamic keys of D-A.
6. according to claim 1 selfreparing under temperate condition, the thermosets that can be reprocessed and can be recycled place
Reason method, it is characterised in that：
The polymer monomer is bis-phenol A glycidyl ether, isocyanide acid compound, polynary organic silicon monomer.
7. according to claim 1 selfreparing under temperate condition, the thermosets that can be reprocessed and can be recycled place
Reason method, it is characterised in that：
The curing agent be glutaric anhydride be curing agent, triethanolamine is curing agent or dibenzoyl peroxide is curing agent.
8. according to claim 1 selfreparing under temperate condition, the thermosets that can be reprocessed and can be recycled place
Reason method, it is characterised in that：
The chemical bond exchange reaction catalyst is zinc acetylacetonate, di-n-butyltin dilaurate or tetramethylammonium hydroxide.
9. according to claim 1 selfreparing under temperate condition, the thermosets that can be reprocessed and can be recycled place
Reason method, it is characterised in that：
Under the temperate condition carbon nanotube is also added into selfreparing, the thermosets that can be reprocessed and can be recycled.
10. selfreparing, the thermosets that can be reprocessed and can be recycled under a kind of temperate condition, it is characterised in that be to pass through
What the processing method processing described in claim 1 to 9 any claim obtained, selfreparing under the temperate condition, can be again
Processing and Ke Xunhuanliyong thermosets are the thermosetting polymer with reversible fracture dynamic key and commutative chemical bond
Material.
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| CN109762139A (en) * | 2019-01-22 | 2019-05-17 | 中国工程物理研究院化工材料研究所 | It can weld the preparation method that can repair and can reprocess molding thermosetting polymer under a kind of moderate temperature |
| CN109851973A (en) * | 2019-01-23 | 2019-06-07 | 浙江省仙居县博达异型橡塑有限公司 | A kind of ionomer ethylene propylene diene rubber and preparation method thereof |
| CN110183587A (en) * | 2019-05-05 | 2019-08-30 | 湖北三江航天江河化工科技有限公司 | Photocuring selfreparing polyurethane acrylic resin and preparation method thereof |
| CN110627998A (en) * | 2019-10-14 | 2019-12-31 | 中国工程物理研究院化工材料研究所 | Method for regulating and controlling stress relaxation and reprocessing molding temperature of glass-like polymer material through dynamic bond content |
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| CN110857360A (en) * | 2018-08-23 | 2020-03-03 | 天津大学 | Application of high-tensile high-toughness polysiloxane nano composite elastomer in degradable material |
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| CN109762139B (en) * | 2019-01-22 | 2021-06-22 | 中国工程物理研究院化工材料研究所 | Preparation method of thermosetting polymer capable of being welded, repaired and reprocessed and molded at medium temperature |
| CN109762139A (en) * | 2019-01-22 | 2019-05-17 | 中国工程物理研究院化工材料研究所 | It can weld the preparation method that can repair and can reprocess molding thermosetting polymer under a kind of moderate temperature |
| CN109851973B (en) * | 2019-01-23 | 2021-03-23 | 浙江省仙居县博达异型橡塑有限公司 | Ionic crosslinking ethylene propylene diene monomer rubber and preparation method thereof |
| CN109851973A (en) * | 2019-01-23 | 2019-06-07 | 浙江省仙居县博达异型橡塑有限公司 | A kind of ionomer ethylene propylene diene rubber and preparation method thereof |
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Application publication date: 20180629 |