CN107973886A - A kind of preparation of thermal reversion self-healing polymers material and restorative procedure - Google Patents
A kind of preparation of thermal reversion self-healing polymers material and restorative procedure Download PDFInfo
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F293/00—Macromolecular compounds obtained by polymerisation on to a macromolecule having groups capable of inducing the formation of new polymer chains bound exclusively at one or both ends of the starting macromolecule
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/12—Esters of monohydric alcohols or phenols
- C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
- C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/26—Esters containing oxygen in addition to the carboxy oxygen
- C08F220/32—Esters containing oxygen in addition to the carboxy oxygen containing epoxy radicals
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F8/00—Chemical modification by after-treatment
- C08F8/30—Introducing nitrogen atoms or nitrogen-containing groups
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/12—Esters of monohydric alcohols or phenols
- C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
- C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
- C08F220/1804—C4-(meth)acrylate, e.g. butyl (meth)acrylate, isobutyl (meth)acrylate or tert-butyl (meth)acrylate
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/12—Esters of monohydric alcohols or phenols
- C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
- C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
- C08F220/1812—C12-(meth)acrylate, e.g. lauryl (meth)acrylate
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/12—Esters of monohydric alcohols or phenols
- C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
- C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
- C08F220/1818—C13or longer chain (meth)acrylate, e.g. stearyl (meth)acrylate
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Abstract
Preparation and restorative procedure the invention discloses a kind of thermal reversion self-repair type polymer material.The material carries out Invertible ideal (RAFT) at 60~80 DEG C by a kind of methacrylic acid chaff ester with 40~60 parts in 20~30 parts of lauryl methacrylate, octadecyl methacrylate, tetrahydrofurfuryl methacrylate, butyl methacrylate and obtains.By obtained block copolymer and 10~20 parts of diphenylmethylene bismaleimide in 60~80 DEG C of reactions, obtained preform will pour into mould and dry after reaction, that is, obtain a kind of side chain with thermal reversion Diels Alder keys, there is the polyacrylate materials of self-healing properties.By damaged material in the presence of an inert gas, it is heat-treated 10~30 minutes at 90~110 DEG C, is cooled to room temperature, the reparation to material damage is reached by the collective effects reacted of Diels Alder and the retro DA in this body structure.The material has that self-repair efficiency is high, and can carry out multiple selfreparing in same place in theory, it is not necessary to the advantages that extra catalyst.
Description
Technical field
The present invention relates to organic polymer technical field, more particularly to a kind of preparation of thermal reversion self-healing polymers material
And restorative procedure.
Background technology
High molecular material is easily integrated destruction during processing and use by extraneous factor, and inside produces micro-crack meeting
The mechanical property of material is reduced, shortens its service life.As a kind of novel intelligence structure functional material, self-healing polymers
Material can realize the selfreparing of material micro-crack itself by simulating the mechanism of organism wound healing, avoid its be subject into
One step is destroyed, so as to extend the service life of material.
The approach of high molecular material selfreparing at present has very much, is wherein implanted into thermal reversion in high molecular material body construction
Diels-Alder (DA) covalent bond is a kind of more effective method.This material with thermal reversion chemical bond is being damaged
, can be under conditions of heat treatment after wound, it is not necessary to which extra catalyst, passes through the inverse Diels-Alder in this body structure
(retro-DA) collective effect of reaction and Dles-Alder (DA) reactions is with regard to that can reach the repairing effect to material damage.
The performances such as polyacrylate is heat-resisting, water-fast, ultraviolet resistance and be widely applied in various fields, particularly make
For fields such as coating, adhesive, rubber.Destruction is integrated by extraneous factor, the micro-crack that these material internals produce can shorten
Its service life.If these material self-repair functions can be assigned, you can significantly improve the security of product, extend its use
Service life.
The content of the invention
Destruction caused by order to overcome polyacrylate material in use, the present invention provides a kind of thermal reversion certainly
The preparation of repairing type polyacrylate material, and further provide for the restorative procedure of the material.
The present invention is the principle based on Intrinsical self-healing polymers material, from molecular structure angle, be have devised
A kind of self-repair type polyacrylate material containing thermal reversibility covalent bond, i.e., by methacrylic acid chaff ester side chain furan nucleus
Conjugated double bond and the double bond of bismaleimide inverse Diels-Alder (retro-DA) reactions and Dles-Alder (DA) occurs
Reaction, one kind, which is prepared, has thermal reversion selfreparing polyacrylate material.The material, which has, to be prepared simply, is not required to additional
What renovation agent, can be achieved the features such as repeatedly reparation.
Technical solution：
The technical scheme is that a kind of preparation method of thermal reversion selfreparing polyacrylate material is provided, comprising such as
Lower step：：
(1) lauryl methacrylate, octadecyl methacrylate, methacrylic acid tetrahydrochysene chaff are added in the reactor
Ester, butyl methacrylate one kind, chain-transferring agent, solvent and initiator therein, carry out polymerisation in a nitrogen environment, and 60
It is after~80 DEG C of 4~12h of reaction, obtained polymer precipitation is dry multiple, obtain polymer A；
(2) polymer, solvent, initiator and methacrylic acid chaff ester obtained in the previous step are added in the reactor, in nitrogen ring
Polymerisation is carried out under border, it is after 60~80 DEG C are reacted 4~8h, obtained polymer precipitation is dry multiple, obtain block copolymerization
Thing B；
(3) block copolymer B and diphenylmethylene bismaleimide (BMI) are reacted under the conditions of 60~80 DEG C,
Obtained preform it will pour into mould and dry after reaction, that is, obtain the polyacrylate material with selfreparing intelligent characteristic
Material.
Inert gas of the present invention is nitrogen or argon gas.
Wherein, the solvent be tetrahydrofuran, N, in N- methylene formamide, toluene, dioxane, dichloromethane
One kind, or their any combination；
The method of reparation comprises the following steps, by the material of damage in 90~110 DEG C, in the presence of an inert gas, at heat
Reason 10~30 minutes, is cooled to room temperature.Its principle is based on Diels-Alder (DA) reactions and inverse Diels-Alder
(retro-DA) the thermal reversion reaction system of reaction.After material produces damage (such as micro-crack, cut etc.), by the material in 90
Heat treatment a period of time is carried out at a temperature of~110 DEG C, the bond energy of DA adducts is minimum in covalent bond, occurs when temperature is high
Scission of link.After being down to 60~80 DEG C, the divinyl macromer of depolymerization and dienophile can recombine the crosslinked polymerization of generation under hot conditions
Thing network structure so that the damage of material is repaired.
Technical solution of the present invention further includes a kind of thermal reversion selfreparing polyacrylate material that the method for being prepared as described above obtains
Material.
The beneficial effects of the present invention are：
1. the hot self-repair type polyacrylate material of gained is simple in structure, organic solvent is dissolved in, preparation process is relatively simple；
2. due to containing thermal reversion response DA adduct covalent bonds in material, by simple heat treatment, material can have
Multiple repair ability；
3. the preparation method of thermal reversion selfreparing polyacrylate material provided by the invention has, technique is simple, highly practical,
The features such as applicability is wide.
Embodiment
Embodiment 1：
(1) add in the reactor lauryl methacrylate 2g, chain-transferring agent dithiobenzoic acid cyano group isopropyl ester 0.009g,
Solvents tetrahydrofurane 2g and initiator A IBN 0.0050g, carries out polymerisation in a nitrogen environment, after 70 DEG C are reacted 5h, will
The polymer precipitation arrived is dry multiple, obtains polymer A；
(2) polymer A 1g, solvents tetrahydrofurane 2.5g, initiator A IBN 0.002g and metering system are added in the reactor
Sour chaff ester 1.5g, carries out polymerisation in a nitrogen environment, after 70 DEG C are reacted 4h, obtained polymer precipitation is dry multiple,
Obtain block copolymer B；
(3) block copolymer B 1g, solvents tetrahydrofurane 2.0g, diphenylmethylene bismaleimide are added in the reactor
(BMI) 0.5g is reacted under the conditions of 70 DEG C, obtained preform will be poured into mould and be dried after reaction, that is, be had
There is the polyacrylate material C of selfreparing intelligent characteristic.
(4) after cutting thin-film material with knife, by damaged material in the presence of an inert gas, it is heat-treated 20 minutes, cools down at 100 DEG C
To room temperature, the tool marks of film surface obtain part reparation, and repair rate reaches 81%.Cut by repeatedly circulation, which can
Multiple self-regeneration is carried out in same place.
Embodiment 2：
(1) add in the reactor butyl methacrylate 1.8g, chain-transferring agent dithiobenzoic acid cyano group isopropyl ester 0.01g,
Solvents tetrahydrofurane 1.8g and initiator A IBN 0.0040g, carries out polymerisation in a nitrogen environment, will after 70 DEG C are reacted 6h
Obtained polymer precipitation is dry multiple, obtains polymer A；
(2) polymer A 1g, solvents tetrahydrofurane 2.0g, initiator A IBN 0.002g and metering system are added in the reactor
Sour chaff ester 2g, carries out polymerisation in a nitrogen environment, after 70 DEG C are reacted 4h, obtained polymer precipitation is dry multiple, obtains
To block copolymer B；
(3) block copolymer B 1g, solvents tetrahydrofurane 2.0g, diphenylmethylene bismaleimide are added in the reactor
(BMI) 0.5g is reacted under the conditions of 70 DEG C, obtained preform will be poured into mould and be dried after reaction, that is, be had
There is the polyacrylate material C of selfreparing intelligent characteristic.
(4) after cutting thin-film material with knife, by damaged material in the presence of an inert gas, it is heat-treated 30 minutes, cools down at 110 DEG C
To room temperature, the tool marks of film surface obtain part reparation, and repair rate reaches 75%.Cut by repeatedly circulation, which can
Multiple self-regeneration is carried out in same place.
Embodiment 3：
(1) octadecyl methacrylate 2.4g, chain-transferring agent dithiobenzoic acid cyano group isopropyl ester are added in the reactor
0.008g, solvents tetrahydrofurane 2.4g and initiator A IBN 0.0040g, carry out polymerisation, 80 DEG C of reactions in a nitrogen environment
It is after 4h, obtained polymer precipitation is dry multiple, obtain polymer A；
(2) polymer A 1.5g, solvents tetrahydrofurane 2.0g, initiator A IBN 0.002g and methyl-prop are added in the reactor
Olefin(e) acid chaff ester 1.5g, carries out polymerisation in a nitrogen environment, after 70 DEG C are reacted 4h, the precipitation drying of obtained polymer is more
It is secondary, obtain block copolymer B；
(3) block copolymer B 1.2g, solvents tetrahydrofurane 2.4g, diphenylmethylene bismaleimide are added in the reactor
Amine (BMI) 0.5g is reacted under the conditions of 80 DEG C, obtained preform will be poured into mould and be dried after reaction, that is, obtain
Polyacrylate material C with selfreparing intelligent characteristic.
(4) after cutting thin-film material with knife, by damaged material in the presence of an inert gas, it is heat-treated 20 minutes, cools down at 110 DEG C
To room temperature, the tool marks of film surface obtain part reparation, and repair rate reaches 87%.Cut by repeatedly circulation, which can
Multiple self-regeneration is carried out in same place.
Embodiment 4：
(1) add in the reactor lauryl methacrylate 2g, chain-transferring agent dithiobenzoic acid cyano group isopropyl ester 0.009g,
Solvents tetrahydrofurane 2g and initiator A IBN 0.0050g, carries out polymerisation in a nitrogen environment, after 80 DEG C are reacted 5h, will
The polymer precipitation arrived is dry multiple, obtains polymer A；
(2) polymer A 1g, solvents tetrahydrofurane 2.5g, initiator A IBN 0.002g and metering system are added in the reactor
Sour chaff ester 1.5g, carries out polymerisation in a nitrogen environment, after 80 DEG C are reacted 4h, obtained polymer precipitation is dry multiple,
Obtain block copolymer B；
(3) block copolymer B 1g, solvents tetrahydrofurane 2.0g, diphenylmethylene bismaleimide are added in the reactor
(BMI) 0.5g is reacted under the conditions of 65 DEG C, obtained preform will be poured into mould and be dried after reaction, that is, be had
There is the polyacrylate material C of selfreparing intelligent characteristic.
(4) after cutting thin-film material with knife, by damaged material in the presence of an inert gas, it is heat-treated 20 minutes, cools down at 100 DEG C
To room temperature, the tool marks of film surface obtain part reparation, and repair rate reaches 78%.Cut by repeatedly circulation, which can
Multiple self-regeneration is carried out in same place.
Embodiment 5：
(1) the double thiobenzoate-Alpha-Methyl benzyl esters of lauryl methacrylate 2g, chain-transferring agent are added in the reactor
0.015g, solvents tetrahydrofurane 2g and initiator A IBN 0.0030g, carry out polymerisation, 80 DEG C of reaction 4h in a nitrogen environment
Afterwards, it is obtained polymer precipitation is dry multiple, obtain polymer A；
(2) polymer A1.4g, solvents tetrahydrofurane 3.0g, initiator A IBN 0.002g and metering system are added in the reactor
Sour chaff ester 1.5g, carries out polymerisation in a nitrogen environment, after 80 DEG C are reacted 4h, obtained polymer precipitation is dry multiple,
Obtain block copolymer B；
(3) block copolymer B 2g, solvents tetrahydrofurane 2.0g, diphenylmethylene bismaleimide are added in the reactor
(BMI) 1g is reacted under the conditions of 70 DEG C, obtained preform will be poured into mould and be dried after reaction, that is, be had
The polyacrylate material C of selfreparing intelligent characteristic.
(4) after cutting thin-film material with knife, by damaged material in the presence of an inert gas, it is heat-treated 20 minutes, cools down at 95 DEG C
To room temperature, the tool marks of film surface obtain part reparation, and repair rate reaches 79%.Cut by repeatedly circulation, which can
Multiple self-regeneration is carried out in same place.
Embodiment 6：
(1) double thiobenzoate isobutyronitrile ester 0.02g of lauryl methacrylate 2g, chain-transferring agent, molten are added in the reactor
Agent tetrahydrofuran 2g and initiator A IBN 0.0030g, carries out polymerisation, after 70 DEG C are reacted 8h, will obtain in a nitrogen environment
Polymer precipitation it is dry multiple, obtain polymer A；
(2) polymer A 1.5g, solvents tetrahydrofurane 3.0g, initiator A IBN 0.002g and methyl-prop are added in the reactor
Olefin(e) acid chaff ester 2g, carries out polymerisation in a nitrogen environment, after 70 DEG C are reacted 4h, obtained polymer precipitation is dry multiple,
Obtain block copolymer B；
(3) block copolymer B 2g, solvents tetrahydrofurane 2.0g, diphenylmethylene bismaleimide are added in the reactor
(BMI) 1g is reacted under the conditions of 60 DEG C, obtained preform will be poured into mould and be dried after reaction, that is, be had
The polyacrylate material C of selfreparing intelligent characteristic.
(4) after cutting thin-film material with knife, by damaged material in the presence of an inert gas, it is heat-treated 20 minutes, cools down at 110 DEG C
To room temperature, the tool marks of film surface obtain part reparation, and repair rate reaches 86%.Cut by repeatedly circulation, which can
Multiple self-regeneration is carried out in same place.
Claims (7)
1. a kind of thermal reversion self-repair type polymer material, it is characterised in that self-repair resin is by all acrylic ester class monomer group
Into；Wherein selfreparing thermoplastic resin matrix is prepared by monomer, initiator and chain-transferring agent；Monomer, initiator, chain-transferring agent
Percetage by weight is：Monomer 80~90%, initiator 0.1~1.0%, chain-transferring agent 0.5~1%, crosslinking agent 10~20%.
2. material as claimed in claim 1, it is characterised in that the monomer is lauryl methacrylate, methacrylic acid ten
Eight Arrcostabs, tetrahydrofurfuryl methacrylate, butyl methacrylate are therein a kind of with the mixture of methacrylic acid chaff ester.
3. material as claimed in claim 1, it is characterised in that the initiator is azodiisobutyronitrile (AIBN), azo two is different
Heptonitrile (ABVN), azobisisovaleronitrile, azo diisopropyl imidazoline hydrochloride, benzoyl peroxide (BPO), potassium peroxydisulfate (KPS), over cure
One or more of mixtures in sour ammonium (APS).
4. material as claimed in claim 1, it is characterised in that the chain-transferring agent is dithiobenzoic acid cyano group isopropyl ester, 2-
(dodecyl trithiocarbonic acid ester group) -2 Methylpropionic acid, double thiobenzoates-Alpha-Methyl benzyl ester, double thio phenyl isopropyl acetates
Phenyl ester, double thiobenzoate isobutyronitrile esters, double thiobenzoate isopropyl phenyl esters, S- dodecyls-S '-(α, α '-dimethyl-α "-
Acetic acid) one or more of mixtures in trithiocarbonate.
5. material as claimed in claim 1, it is characterised in that the material can be under conditions of heat treatment, it is not necessary to extra
Catalyst realizes the advantages that repeatedly repairing, so as to extend the service life of polymeric material.
6. material as claimed in claim 1, it is characterised in that polyacrylate material of the side chain with furan nucleus end group passes through
Two-step method synthesizes, and synthesizes lauryl methacrylate, methyl-prop first by reversible addion-fragmentation chain transfer polymerization (RAFT)
A kind of regular homopolymer in olefin(e) acid stearyl, tetrahydrofurfuryl methacrylate, butyl methacrylate, then reuses
The method of RAFT connects methacrylic acid chaff ester, synthesizes a kind of regularity block copolymer.The block that will finally obtain
Copolymer is reacted with diphenylmethylene bismaleimide (BMI) under the conditions of 60~80 DEG C, will be made after reaction
The preform obtained, which is poured into mould, dries, that is, obtains the polyacrylate material with selfreparing intelligent characteristic.
7. the preparation method of material as claimed in claim 1, it is characterised in that include the following steps：1. add in the reactor
Lauryl methacrylate, octadecyl methacrylate, tetrahydrofurfuryl methacrylate, butyl methacrylate are therein
One kind, chain-transferring agent, solvent and initiator, carry out polymerisation in an inert atmosphere, after 60~80 DEG C are reacted 4~12h,
Obtained polymer precipitation is dry multiple；2. polymer, solvent, initiator and first obtained in the previous step are added in the reactor
Base acrylic acid chaff ester, carries out polymerisation in a nitrogen environment, and after 60~80 DEG C are reacted 4~8h, obtained polymer is precipitated
It is dry multiple；3. the block copolymer that second step is obtained is with diphenylmethylene bismaleimide (BMI) at 60~80 DEG C
Under the conditions of reacted, obtained preform will pour into mould and dry after reaction, that is, obtain special with selfreparing intelligence
The polyacrylate material of property.
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Cited By (7)
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| CN109053949A (en) * | 2018-06-19 | 2018-12-21 | 复旦大学 | A kind of graphene/polymer self-repair material and preparation method thereof |
| CN109535626A (en) * | 2018-10-27 | 2019-03-29 | 华南理工大学 | A kind of rubber and preparation method thereof with reversible crosslink key |
| CN109705382A (en) * | 2018-12-14 | 2019-05-03 | 张家港康得新光电材料有限公司 | Self-repair resin, coating, film and method for manufacturing thin film and application |
| CN110627934A (en) * | 2019-09-19 | 2019-12-31 | 青岛科技大学 | Isotactic polypropylene with dithiobenzoic acid alpha-methylbenzyl ester as end group, and preparation method and application thereof |
| JP2020015779A (en) * | 2018-07-23 | 2020-01-30 | 国立研究開発法人物質・材料研究機構 | Functional composition and thermo-reversible adhesive |
| CN111440269A (en) * | 2020-04-28 | 2020-07-24 | 青岛科技大学 | Self-repairing rubber based on Diels-Alder reaction and preparation method thereof |
| CN113429958A (en) * | 2021-07-01 | 2021-09-24 | 华美孚泰油气增产技术服务有限责任公司 | Self-repairing fracturing fluid thickening agent and preparation method thereof |
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2016
- 2016-10-24 CN CN201610922492.9A patent/CN107973886A/en active Pending
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109053949A (en) * | 2018-06-19 | 2018-12-21 | 复旦大学 | A kind of graphene/polymer self-repair material and preparation method thereof |
| CN109053949B (en) * | 2018-06-19 | 2021-01-26 | 复旦大学 | Graphene/polymer self-repairing material and preparation method thereof |
| JP2020015779A (en) * | 2018-07-23 | 2020-01-30 | 国立研究開発法人物質・材料研究機構 | Functional composition and thermo-reversible adhesive |
| JP7138923B2 (en) | 2018-07-23 | 2022-09-20 | 国立研究開発法人物質・材料研究機構 | Functional composition and temperature reversible adhesive |
| CN109535626A (en) * | 2018-10-27 | 2019-03-29 | 华南理工大学 | A kind of rubber and preparation method thereof with reversible crosslink key |
| CN109705382A (en) * | 2018-12-14 | 2019-05-03 | 张家港康得新光电材料有限公司 | Self-repair resin, coating, film and method for manufacturing thin film and application |
| CN109705382B (en) * | 2018-12-14 | 2021-08-10 | 张家港康得新光电材料有限公司 | Self-repairing resin, coating, film preparation method and application |
| CN110627934A (en) * | 2019-09-19 | 2019-12-31 | 青岛科技大学 | Isotactic polypropylene with dithiobenzoic acid alpha-methylbenzyl ester as end group, and preparation method and application thereof |
| CN111440269A (en) * | 2020-04-28 | 2020-07-24 | 青岛科技大学 | Self-repairing rubber based on Diels-Alder reaction and preparation method thereof |
| CN111440269B (en) * | 2020-04-28 | 2022-08-09 | 青岛科技大学 | Self-repairing rubber based on Diels-Alder reaction and preparation method thereof |
| CN113429958A (en) * | 2021-07-01 | 2021-09-24 | 华美孚泰油气增产技术服务有限责任公司 | Self-repairing fracturing fluid thickening agent and preparation method thereof |
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