CN107955098A - A kind of elastomer and preparation method thereof - Google Patents
A kind of elastomer and preparation method thereof Download PDFInfo
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- CN107955098A CN107955098A CN201711251454.6A CN201711251454A CN107955098A CN 107955098 A CN107955098 A CN 107955098A CN 201711251454 A CN201711251454 A CN 201711251454A CN 107955098 A CN107955098 A CN 107955098A
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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
- C08F251/00—Macromolecular compounds obtained by polymerising monomers on to polysaccharides or derivatives thereof
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
- C08B37/00—Preparation of polysaccharides not provided for in groups C08B1/00 - C08B35/00; Derivatives thereof
- C08B37/0006—Homoglycans, i.e. polysaccharides having a main chain consisting of one single sugar, e.g. colominic acid
- C08B37/0009—Homoglycans, i.e. polysaccharides having a main chain consisting of one single sugar, e.g. colominic acid alpha-D-Glucans, e.g. polydextrose, alternan, glycogen; (alpha-1,4)(alpha-1,6)-D-Glucans; (alpha-1,3)(alpha-1,4)-D-Glucans, e.g. isolichenan or nigeran; (alpha-1,4)-D-Glucans; (alpha-1,3)-D-Glucans, e.g. pseudonigeran; Derivatives thereof
- C08B37/0012—Cyclodextrin [CD], e.g. cycle with 6 units (alpha), with 7 units (beta) and with 8 units (gamma), large-ring cyclodextrin or cycloamylose with 9 units or more; Derivatives thereof
- C08B37/0015—Inclusion compounds, i.e. host-guest compounds, e.g. polyrotaxanes
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Abstract
The invention discloses a kind of method for producing elastomers, comprise the following steps：Step 1：The guest molecule that the more cyclodextrin polymers of host molecule are modified with double bond is included, obtains assembly；Step 2：In the presence of initiator, acrylic ester monomer and the assembly are subjected to copolyreaction, obtain elastomer.The method for producing elastomers is simple, simple operation.By the obtained elastomer of preparation method of the present invention can the non-stimulated carry out selfreparing under room temperature and humidity environment, improve the service life of material.
Description
Technical field
The present invention relates to functional high polymer material field, more particularly to a kind of polyacrylate elastomer and its preparation side
Method.
Background technology
General material is chronically at stress in use, can inevitably be subject to the shadow of the external environments such as light, heat
Ring, the fine crack for being difficult to detect is formed in material internal or surface.Fine crack can weaken material in one side material
Function, the fine crack of another aspect material can form stress concentration point in material internal, can not be applied to answering on material
Power is conducted and disperseed, this will produce material destruction.Furthermore become with the extension of time, fine crack will gradually develop
Macroscopic macroscopic view large fracture, notch etc., this can cause the failure of the 26S Proteasome Structure and Function of material, may produce catastrophic
Consequence.In addition, the aging of the crack meeting accelerated material of material, the service life of serious curtailment material, so as to cause substantial amounts of wave
Take.
In a variety of materials, polymer elastomer material has certain toughness in itself, in use can be by outside
The energy dissipation on boundary avoids causing irreversible damage since instantaneous energy is excessive, has preferable application prospect, in modern society
Also there is preferable application in meeting.Self-repair material be one kind under the conditions of no external influence, material in itself can to internal flaw into
The new material of row self-regeneration, and the preparation of selfreparing elastomer then preferably strengthens the feature of elastomeric material.
Because software or elastomeric material largely can be applied to wearable device, before most of is to be directed to its functionalization
It is modified, assign its conductive, magnetic and dielectric properties.
In recent years, the preparation research of self-repair material has been a great concern, and scientists are based on embedding consolidant, draw
The methods of entering dynamic covalent bond or supramolecular chemistry devises number of types of self-repair material.Wherein, on self-healing elasticity
The research of the materials such as body also result in great interest and extensive concern.At present, these feature soft materials are realized and reviewed one's lessons by oneself
Multiple behavior needs environmental stimuli (light, heat, humidity etc.) mostly, and the research on selfreparing elastomer is had focused largely on using non-common
Valence link such as hydrogen bond and excessive chemical key form network structure.However, for selfreparing elastomer, by parallel hydrogen bond or more heavy hydrogen
The interaction of key realizes that selfreparing behavior is had a great influence by moisture, under humidity environment material self-reparing capability can significantly under
Drop.
The content of the invention
In view of this, it is an object of the invention to provide a kind of elastomer and preparation method thereof, by made from this method
Elastomer has self-repair function, and self-reparing capability is good under humidity environment, can extend the service life of material, reduces material
The waste of material, and preparation method is simple, simple operation.Its concrete technical scheme is as follows：
The present invention provides a kind of method for producing elastomers, comprise the following steps：
Step 1：The guest molecule that the more cyclodextrin polymers of host molecule are modified with double bond is included, obtains assembly；
Step 2：In the presence of initiator, acrylic ester monomer and the assembly are subjected to copolyreaction, obtain bullet
Property body.
Preferably, the guest molecule dosage is 1.0~5eq. of the dosage of the host molecule.
Preferably, the dosage of the assembly is 1~30mol% of the dosage of the acrylic ester monomer；
It is furthermore preferred that 2~10mol% of the dosage of the assembly for the dosage of the acrylic ester monomer.
Preferably, the dosage of the initiator is the 0.05~5wt% for assembling bulk concentration.
Preferably, the guest moieties of guest molecule described in step 1 are selected from adamantane group, azobenzene group, ferrocenyl
Group, polyphenol group, phenolphthalein group or cinnamate group；
The guest moieties are the group that host-guest inclusion can be produced with host molecule.
The guest molecule of double bond before modified include adamantanecarboxylic acid, azobenzoic acid, ferrocenecarboxylic acid, ferrocenyl acetic acid or
Lutidines.
The reaction included described in step 1 is specially the guest molecule for being modified the more cyclodextrin polymers of host molecule and double bond by ring
The molar ratio for the guest molecule that dextrin is modified with double bond is 1：1 is included, and inclusion uses mixed solvent DMSO/H2O (v/v)=
1：1~10：1,18~50 DEG C of 12~24h of stirring obtain assembly.
Preferably, acrylic ester monomer described in step 3 is selected from acrylate, hydroxy-ethyl acrylate, acrylic acid hydroxyl
Butyl ester, hydroxyethyl methacrylate or ethoxyethoxy ethyl acrylate.
Preferably, the initiator described in step 2 is radical reaction initiator；
The radical reaction initiator is selected from two isobutyric acid diformazan of azodiisobutyronitrile, azobisisoheptonitrile and azo
Ester, ammonium persulfate, potassium peroxydisulfate, benzoyl peroxide, the benzoyl peroxide tert-butyl ester or methyl ethyl ketone peroxide.
Preferably, the time of copolyreaction described in step 2 is 12~48h；
The temperature of the copolyreaction is 30~100 DEG C.
Preferably, more cyclodextrin polymers described in step 1 are prepared by least two cyclodextrin by crosslinking agent；
The cyclodextrin includes the cyclic oligomer carbohydrates and their derivative that at least six glucopyranose molecules are formed；
The cyclodextrin is preferably beta-cyclodextrin or alpha-cyclodextrin；
The crosslinking agent is selected from epoxychloropropane, oligomer, binary acid or acid anhydrides；
The oligomer is made by polypropylene glycol and toluene di-isocyanate(TDI).
Present invention also offers the elastomer that a kind of above-mentioned preparation method obtains.
Present invention also offers a kind of application of above-mentioned elastomer in self-healing polymers elastomeric material.
As can be known from the above technical solutions, which prepared by three-step approach：Physical crosslinking point is acted as first
The preparation of host molecule, that is, synthesize the oligomer of more cyclodextrin polymers, is then included with the guest molecule being modified, finally with
Acrylate base monomer is copolymerized to obtain target material.Since the Subjective and Objective crosslinking points in the material are the friendship of oversubscription muon physics
Connection, has invertibity, therefore can be realized by the molecular recognition of Subjective and Objective and the movement of strand under room temperature and humidity environment
Non-stimulated selfreparing, improves the service life of material.The elasticity preparation is simple, simple operation.
Brief description of the drawings
In order to illustrate more clearly about the embodiment of the present invention or technical scheme of the prior art, below will be to embodiment or existing
There is attached drawing needed in technology description to be briefly described, it should be apparent that, drawings in the following description are only this
Some embodiments of invention, for those of ordinary skill in the art, without having to pay creative labor, may be used also
To obtain other attached drawings according to these attached drawings.
Fig. 1 is comparison diagram directly perceived before and after elastomer selfreparing provided by the invention.
Fig. 2 surpasses depth image comparison diagram for 3D before and after elastomer selfreparing provided by the invention.
Embodiment
Below in conjunction with the embodiment of the present invention, technical scheme is clearly and completely described, it is clear that institute
The embodiment of description is only part of the embodiment of the present invention, instead of all the embodiments.Based on the embodiments of the present invention,
The other embodiment that those of ordinary skill in the art are obtained without making creative work, belongs to guarantor of the present invention
The scope of shield.
Raw material and reagent used can be bought by market in elastomer provided by the invention and preparation method thereof.
Just a kind of elastomer provided by the present invention and preparation method thereof is described further below.
Embodiment one
The preparation of more cyclodextrin polymers：The beta-cyclodextrin of 10g is dissolved in the NaOH solution of 15ml.Add the ring of 5mol%
Oxygen chloropropane, continues stirring reaction 3h at 35 DEG C, solution is poured into the isopropanol of 200ml and precipitated, filtered, then will slightly produce
Thing is soluble in water, and is neutralized with dilute hydrochloric acid, dialyses one week, finally freezes product.
It is prepared by modified guest molecule：40ml thionyl chlorides, 80 DEG C of conditions are added to adamantanecarboxylic acid (18.4g, 102mmol)
Lower stirring 2h, revolving remove excessive thionyl chloride and obtain adamantane formyl chloride；By hydroxyethyl meth acrylate (HEMA)
(2g, 15mmol), tripropyl amine (TPA) (3.3g, 23mmol) are dissolved in 200mL anhydrous methylene chlorides (0-5eq.), are added dropwise dissolved with 3.7g gold
The dichloromethane of firm alkane formyl chloride (18.6mmol), continues to stand overnight after stirring 5h, suction filtration obtains light yellow liquid.Washing,
It is dry, as modified guest molecule hydroxyethyl meth acrylate-adamantane (HEMA-Ad).
The preparation of assembly；The more cyclodextrin polymers of 4g (poly-CD) are dissolved in 10ml water, by cyclodextrin (CD) with
HEMA-Ad molar ratios 1：1 is included, and inclusion uses mixed solvent DMSO/H2O (v/v)=1：1,24h is vigorously stirred at room temperature
Obtain modified monomer solution.
The preparation of polymer elastomer：The above-mentioned solution 20ml containing functional monomer is pipetted, adds 6.045ml
The hydroxyethyl hydroxyl ethyl ester (HEMA) of (57.6mmol), then adds initiator potassium persulfate (KPS) 138mg
(0.6mmol), is passed through bubbling argon 20min, room temperature reaction is overnight after mixing.It will be done at products therefrom in an oven 50 DEG C
Dry 12h, it is then 3 days dry under room temperature and normal pressure, obtain polymer elastomer.
Selfreparing is tested：As depicted in figs. 1 and 2, with scalpel by dried polymer elasticity manufactured in the present embodiment
Body cuts the breach that a depth is 2 millimeters, and after placing 12h under room temperature and 70% damp condition, it is micro- to surpass the depth of field with 3D
Mirror observes section, it is found that crackle substantially shoals, elastomer is gradually restored to original shape.Remediation efficiency=breach healing
Product=95% behind preceding area/healing.
Embodiment two
The preparation of more cyclodextrin polymers：Polyethylene glycol 400 (0.1mol) and toluene di-isocyanate(TDI) (0.2mol) room temperature first
React 5 it is small when obtain poly- diisocyanate.Obtained when 0.1mol alpha-cyclodextrins and the small poly- diisocyanate room temperature reactions 6 of 0.2mol
More cyclodextrin polymers, wherein average each more cyclodextrin polymers contain 4 cyclodextrin.
It is prepared by modified guest molecule：40ml thionyl chlorides are added to azobenzoic acid (102mmol), are stirred under the conditions of 80 DEG C
2h, revolving remove excessive thionyl chloride and obtain adamantane formyl chloride；Hydroxy ethyl methacrylate (HEA) (15mmol) is dissolved in
In 200ml anhydrous methylene chlorides (0-5eq.), the dichloromethane dissolved with azo chlorobenzoyl chloride (18.6mmol) is instilled, is dripped off follow-up
Stood overnight after continuous stirring 5h, suction filtration obtains light yellow liquid.Washing, dry, filtering, it is single to be modified to obtain lurid solid
Body hydroxy ethyl methacrylate-azobenzene (HEA-Azo).
The preparation of assembly；Using mixed solvent DMSO/H2O=1：3 are included.Concrete operations are as follows, by 4g
Poly-CD is dissolved in 30ml water, wherein each poly-CD contains 4 CD, by CD and HEA-Azo molar ratios 1：1 is wrapped
Close, calculate HEA-Ad mass, inclusion uses mixed solvent DMSO/H2O=1：3, by the mixed system after inclusion in 50 DEG C of stirrings
Stay overnight to obtain functional monomer solution.
The preparation of polymer elastomer：Above-mentioned functional monomer solution 10ml is pipetted to the hydroxy-ethyl acrylate of 4eq.CD amounts
(HEA), 200mg KPS initiators are then added, are passed through bubbling argon 20min after mixing, 45 DEG C of reactions are overnight.By institute
Product drying is obtained, obtains polymer elastomer.
Selfreparing is tested：As depicted in figs. 1 and 2, dried polymer elastomer is cut into a depth as 2 with scalpel
The breach of millimeter, after placing 12h under room temperature and 70% damp condition, surpasses depth-of-field microscope with 3D and section is seen
Examine, it is found that crackle substantially shoals, elastomer is gradually restored to original shape.Area/healing before remediation efficiency=breach healing
=98% is accumulated below.
Embodiment three
The preparation of more cyclodextrin polymers：With embodiment 1.
It is prepared by modified guest molecule：40ml thionyl chlorides are added to ferrocenecarboxylic acid (102mmol), are stirred under the conditions of 80 DEG C
2h, revolving remove excessive thionyl chloride and obtain ferrocene formyl chloride；Hydroxy-ethyl acrylate (HEA) (17mmol) is dissolved in
In 200ml anhydrous methylene chlorides (0-5eq.), the dichloromethane dissolved with 3.7g ferrocene formyl chloride (18.6mmol) is added dropwise, continues
Stood overnight after stirring 5h, filter, wash, be dried to obtain brown solid, it is modified monomer hydroxy-ethyl acrylate-ferrocene
(HEA-Fc)。
The preparation of assembly；CD contents are 68wt% in poly-CD, by CD and HEMA-Fc molar ratios 1：1 is included,
Inclusion uses mixed solvent DMSO/H2O=10：1,24h is vigorously stirred at room temperature obtains functional monomer solution.
The preparation of polymer elastomer：Pipette the butyl acrylate that the above-mentioned functional monomers of 20ml add 57.6mmol
(BA), 350mg initiator As IBN is then added, when 60 DEG C of reactions 7 are small.It is polymer elastomer by products therefrom drying.
Selfreparing is tested：As depicted in figs. 1 and 2, dried polymer elastomer is cut into a depth as 2 with scalpel
The breach of millimeter, after placing 12h under room temperature and 50% damp condition, surpasses depth-of-field microscope with 3D and section is seen
Examine, it is found that crackle substantially shoals, elastomer is gradually restored to original shape.Area/healing before remediation efficiency=breach healing
=91% is accumulated below.
Example IV
The preparation of more cyclodextrin polymers：With embodiment 1.
It is prepared by modified guest molecule：In the environment of ice bath, 978mg n-isopropyl acrylamide, 1250mgAlCl3And 1mg
Thiophene is dissolved in 4ml acetone, is then slowly added dropwise into the phenolphthalein 7.5ml acetone dissolved with 3980mg, is reacted overnight at 40 DEG C.
Then reaction liquid is cooled to room temperature, is diluted with deionized water, then at least extracted with dichloromethane 3 times, take organic layer,
Vacuum distillation, it is modified monomer phenolphthalein-N-isopropylacrylamide (Am-PP) to obtain white solid.
The preparation of assembly；CD contents are 68wt% in poly-CD, and 4g poly-CD are dissolved in 30ml water, wherein
Each poly-CD contains 4 CD, by CD and Am-PP molar ratios 1：1 is included, and calculates Am-PP mass, includes mixed solvent
DMSO/H2O=10：11, the mixed system after inclusion is stirred overnight to obtain functional monomer solution at 50 DEG C.
The preparation of polymer elastomer：The functional monomer solution of 10ml is pipetted, adds the acrylic acid ethoxy of 57.6mmol
Base oxethyl ethyl ester, then adds 480mg initiator A IBN, is passed through bubbling argon 20min, room temperature reaction 6 after mixing
Hour.It is polymer elastomer after products therefrom is dried.
Selfreparing is tested：As depicted in figs. 1 and 2, dried polymer elastomer is cut into a depth as 2 with scalpel
The breach of millimeter, is placed on after placing 12h under room temperature and 70% damp condition, surpasses depth-of-field microscope with 3D and section is seen
Examine, it is found that crackle substantially shoals, elastomer is gradually restored to original shape.Area/healing before remediation efficiency=breach healing
=96% is accumulated below.
The above, the above embodiments are merely illustrative of the technical solutions of the present invention, rather than its limitations；Although with reference to before
Embodiment is stated the present invention is described in detail, it will be understood by those of ordinary skill in the art that：It still can be to preceding
State the technical solution described in each embodiment to modify, or equivalent substitution is carried out to which part technical characteristic；And these
Modification is replaced, and the essence of appropriate technical solution is departed from the spirit and scope of various embodiments of the present invention technical solution.
Claims (10)
1. a kind of method for producing elastomers, it is characterised in that comprise the following steps：
Step 1：The guest molecule that the more cyclodextrin polymers of host molecule are modified with double bond is included, obtains assembly；
Step 2：In the presence of initiator, acrylic ester monomer and the assembly are subjected to copolyreaction, obtain elastomer.
2. preparation method according to claim 1, it is characterised in that the guest molecule dosage is the host molecule
1.0~5eq. of dosage.
3. preparation method according to claim 1, it is characterised in that the dosage of the assembly is the esters of acrylic acid
1~30mol% of the dosage of monomer.
4. according to the preparation method described in claim 1, it is characterised in that the dosage of initiator described in step 2 is the assembly
0.05~5wt% of concentration.
5. preparation method according to claim 1, it is characterised in that the guest moieties of guest molecule described in step 1 are selected from
Adamantane group, azobenzene group, ferrocene group, polyphenol group, phenolphthalein group or cinnamate group.
6. preparation method according to claim 1, it is characterised in that acrylic ester monomer described in step 2 is selected from propylene
Sour hydroxyl methyl esters, hydroxy-ethyl acrylate, hy-droxybutyl, hydroxyethyl methacrylate or ethoxyethoxy ethyl acrylate.
7. preparation method according to claim 1, it is characterised in that initiator described in step 2 triggers for radical reaction
Agent；
The radical reaction initiator is selected from azodiisobutyronitrile, azobisisoheptonitrile and azo-bis-iso-dimethyl, mistake
Ammonium sulfate, potassium peroxydisulfate, benzoyl peroxide, the benzoyl peroxide tert-butyl ester or methyl ethyl ketone peroxide；
The time of the copolyreaction is 12~48h；
The temperature of the copolyreaction is 30~100 DEG C.
8. preparation method according to claim 1, it is characterised in that more cyclodextrin polymers are pasted by least two ring described in step 1
It was proficient in crosslinking agent to be prepared；
The cyclodextrin includes the cyclic oligomer carbohydrates and their derivative that at least six glucopyranose molecules are formed；
The crosslinking agent is selected from epoxychloropropane, oligomer, binary acid or acid anhydrides；
The oligomer is made by polypropylene glycol and toluene di-isocyanate(TDI).
9. the elastomer that the preparation method according to claim 1 to 8 any one obtains.
10. application of the elastomer according to claim 9 in self-healing polymers elastomeric material.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108395509A (en) * | 2018-03-21 | 2018-08-14 | 广东电网有限责任公司电力科学研究院 | A kind of high molecular polymer and its preparation method and application with self-repair function |
| CN109134951A (en) * | 2018-08-28 | 2019-01-04 | 广东电网有限责任公司 | A kind of self-healing cable outer sheath material, preparation method and its method for coating |
| CN109765755A (en) * | 2019-01-25 | 2019-05-17 | 武汉华星光电半导体显示技术有限公司 | A kind of photoresist and preparation method thereof |
| CN111040079A (en) * | 2019-12-03 | 2020-04-21 | 广东电网有限责任公司 | High-crosslinking-degree topological structure self-repairing elastomer and preparation method and application thereof |
| CN111848984A (en) * | 2020-07-27 | 2020-10-30 | 广州大学 | Cyclodextrin hydrogel and preparation method and application thereof |
| CN109705290B (en) * | 2018-12-28 | 2021-01-01 | 陕西师范大学 | Temperature-responsive side-chain photosensitive block copolymer and preparation method thereof |
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| CN101538373A (en) * | 2009-04-08 | 2009-09-23 | 武汉理工大学 | Method for surface modification of polyurethane material by graft copolymerization |
| CN103665246A (en) * | 2013-12-17 | 2014-03-26 | 深圳市乐普泰科技股份有限公司 | Cationic rigid macromonomer, preparation method and toner |
| CN104592702A (en) * | 2014-12-26 | 2015-05-06 | 四川大学 | Self-healing organic matter/inorganic nanoparticle hybrid material and preparation method thereof |
| CN106590310A (en) * | 2017-02-21 | 2017-04-26 | 中国科学院成都生物研究所 | Uvioresistant paint with self-repairing function and preparation method and application thereof |
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| CN101538373A (en) * | 2009-04-08 | 2009-09-23 | 武汉理工大学 | Method for surface modification of polyurethane material by graft copolymerization |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108395509A (en) * | 2018-03-21 | 2018-08-14 | 广东电网有限责任公司电力科学研究院 | A kind of high molecular polymer and its preparation method and application with self-repair function |
| CN109134951A (en) * | 2018-08-28 | 2019-01-04 | 广东电网有限责任公司 | A kind of self-healing cable outer sheath material, preparation method and its method for coating |
| CN109705290B (en) * | 2018-12-28 | 2021-01-01 | 陕西师范大学 | Temperature-responsive side-chain photosensitive block copolymer and preparation method thereof |
| CN109765755A (en) * | 2019-01-25 | 2019-05-17 | 武汉华星光电半导体显示技术有限公司 | A kind of photoresist and preparation method thereof |
| CN111040079A (en) * | 2019-12-03 | 2020-04-21 | 广东电网有限责任公司 | High-crosslinking-degree topological structure self-repairing elastomer and preparation method and application thereof |
| CN111848984A (en) * | 2020-07-27 | 2020-10-30 | 广州大学 | Cyclodextrin hydrogel and preparation method and application thereof |
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Application publication date: 20180424 |