CN104193852B - A kind of modified unsaturated rubber and preparation, using method - Google Patents
A kind of modified unsaturated rubber and preparation, using method Download PDFInfo
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- CN104193852B CN104193852B CN201410431458.2A CN201410431458A CN104193852B CN 104193852 B CN104193852 B CN 104193852B CN 201410431458 A CN201410431458 A CN 201410431458A CN 104193852 B CN104193852 B CN 104193852B
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Abstract
The invention provides a kind of modified unsaturated rubber, at least there is the repetitive of a kind of expression in formula (I)～formula (IV): Wherein, R1For halogen, C1～C4 alkyl, hydrogen atom；R2For hydrogen atom, C1～C4 alkyl；R3For hydrogen atom, C1～C4 alkyl；R4For hydrogen atom, C1～C4 alkyl；R5For halogen, C1～C4 alkyl, hydrogen atom；R6For hydrogen atom, C1～C4 alkyl；M=0～4, n=0～4.The method that the invention also discloses above-mentioned modified unsaturated rubber, including, the sulfhydryl compound containing furan structure and unsaturated rubber are dissolved in organic solvent, after stirring, under conditions of ultraviolet lighting, completes graft reaction.Utilize this modification unsaturated rubber can obtain the modified unsaturated rubber of reversible crosslink.The modified unsaturated rubber of this reversible crosslink has an excellent in mechanical performance, and the feature being easily recycled.
Description
Technical field
The present invention relates to technical field of polymer materials, specifically, the present invention relates to a kind of modified unsaturated rubber and
It prepares using method.
Background technology
Rubber has practical application area widely, but is difficult to be utilized owing to it is modified, produced garbage again
To environment, and huge number of rubber-based products is had to be consumed every year.
According to GB GB/T 1924-2003, rubber can be divided into saturated rubber and unsaturated rubber.Unsaturated rubber is
Refer to rubber backbone contains at regular intervals the rubber of a great deal of double bond, such as isoprene rubber, natural rubber, butylbenzene
Rubber, butadiene rubber, nitrile rubber, neoprene.The usage amount of unsaturated rubber is big, applied widely, and due to certainly
Oneself shortcoming needs to add inorganic filler or with other rubber is used with.Such product, with greater need for recovery, is difficult to be returned simultaneously
Receive and utilize.Such as, butadiene rubber is particularly suitable for automobile tire processed and cold-resistant goods, it is also possible to manufacture padded coaming and each brood lac
Footwear, adhesive plaster, adhesive tape and sandwich rubber etc..But it is poor that butadiene rubber exists processing characteristics, rubber has the shortcomings such as certain cold flow tendency.
It is amorphous state when room temperature is zero load, when bearing external force, has the highest deformability, be elastic and that tolerance to cold is best synthesis
Rubber.And owing to strand is more regular, crystallization reinforcement during stretching, can be obtained, add white carbon black and can obtain again significant white carbon black benefit
Potent fruit, is a kind of preferable general purpose rubber of combination property, and at present in synthetic rubber, yield is only second to butadiene-styrene rubber and occupies second
Position.But seldom it is used alone, in most cases needs to add inorganic filler or with other rubber is used with.The product so obtained
Product are difficult to be recycled.Therefore this area needs a kind of new modified rubber being prone to be recycled.
Summary of the invention
In order to overcome above-mentioned problem, the invention provides a kind of new modified unsaturated rubber, and preparation user
Method.Utilizing the modified unsaturated rubber of its reversible crosslink prepared, this rubber has excellent in mechanical performance, and is easily recycled profit
Feature.
Specifically, the invention provides a kind of modified unsaturated rubber, at least there is the one in formula (I)～formula (IV)
The repetitive represented:
Wherein, R1For halogen, C1～C4 alkyl, hydrogen atom；R2For hydrogen atom, C1～C4 alkyl；R3For hydrogen atom, C1～
C4 alkyl；R4For hydrogen atom, C1～C4 alkyl；R5For halogen, C1～C4 alkyl, hydrogen atom；R6For hydrogen atom, C1～C4 alkyl；
M=0～4, n=0～4.
Preferably, R1For chlorine atom, hydrogen atom, methyl；R2For hydrogen atom, methyl；R3For methyl；R4For methyl, hydrogen atom；R5
For chlorine atom, hydrogen atom, methyl；R6For hydrogen atom, methyl；M=1；N=1.
In the present invention, rubbing of the repetitive that during graft ratio is modified unsaturated rubber, formula (I)～formula (IV) are expressed
That number summation and the ratio of the molal quantity of carbon-carbon double bond in unsaturated rubber before modified.In certain embodiments, graft ratio is
10%, 12%, 14%, 16%, 18%, 20%, it is 10～20%.The molal quantity of carbon-carbon double bond in unsaturated rubber before modified,
Can obtain according to various structural formula cubages in the raw material that producer provides.
The invention also discloses the method preparing above-mentioned modified unsaturated rubber, including:
Sulfhydryl compound containing furan structure and unsaturated rubber are dissolved in organic solvent, add light trigger,
After stirring, under conditions of ultraviolet lighting, complete graft reaction.
The described sulfhydryl compound containing furan structure, refers to the mercaptan containing furan structure.Those skilled in the art
It should be appreciated that containing the hydrogen atom of furan structure in the sulfhydryl compound of furan structure can be replaced base (such as alkyl, more excellent
Choosing, C1～C4 alkyl) replace, this is also within protection scope of the present invention.Such as shown in formula (V), formula (VI) containing furan
The sulfhydryl compound of structure.Preferably, the described sulfhydryl compound containing furan structure is, 2-methyl-3-furanthiol, 2,5-
Dimethyl-3-furanthiol, furan-2-methanthiol, 5-methyl-2-furan methanthiol.
Wherein, R2Can be hydrogen atom, C1～C4 alkyl；R3Can be hydrogen atom, C1～C4 alkyl；R4Can be that hydrogen is former
Son, C1～C4 alkyl；M=0～4.
Wherein, R3Can be hydrogen atom, C1～C4 alkyl；R4Can be hydrogen atom, C1～C4 alkyl；R6Can be that hydrogen is former
Son, C1～C4 alkyl；N=0～4.
In the present invention, the addition of the sulfhydryl compound containing furan structure has no particular limits, itself and unsaturated rubber
The molal quantity of the carbon-carbon double bond in glue, and modified intended graft ratio is relevant.Graft ratio in embodiments of the invention
Example is generally 10～20%.
Described unsaturated rubber refers to contain at regular intervals in rubber backbone the rubber of a great deal of double bond.Excellent
Choosing, unsaturated rubber is that isoprene rubber, natural rubber, butadiene-styrene rubber, butadiene rubber, nitrile rubber, neoprene are appointed
A kind of.The present invention concrete model not particularly requirement to unsaturated rubber.
Described organic solvent is alcohols, chloroform, dichloromethane, 1,4-dioxane, dimethyl sulfoxide, N, N '-diformazan
Base Methanamide, N, any one in N '-dimethyl acetamide, N-methyl-pyrrolidon, ketone, benzene and benzene homologues.
Described light trigger is free radical photo-initiation or cationic photoinitiator.Described free radical photo-initiation is
Benzoinum ethers, Dialkoxy acetophenones, Oxoxanthone, Sulfide-containing Hindered benzophenone, thioxanthone, anthraquinone and benzophenone and
One or more in derivant；Described cationic photoinitiator is Diaryl iodonium compound, triaryl sulfide, Diaryl iodonium
Any one or more combination in mantoquita, ferrocene salt.The addition of light trigger be unsaturated rubber weight 0.001～
20%, preferably 0.1～10%.
Preferably, described ultraviolet wavelength is 200～400nm.
The invention also discloses the using method of above-mentioned modified unsaturated rubber, including:
Add containing double (many) maleic anhydrides or double (many) maleoyl in the organic solution of above-mentioned modified unsaturated rubber
The compound of imine structure, after stirring, hot briquetting, obtain the modified unsaturated rubber of reversible crosslink.
Described organic solvent is alcohols, chloroform, dichloromethane, 1,4-dioxane, dimethyl sulfoxide, N, N '-diformazan
Base Methanamide, N, any one in N '-dimethyl acetamide, N-methyl-pyrrolidon, ketone, benzene and benzene homologues.
The total mole number of the repetitive that formula (I) in described modified unsaturated rubber～formula (IV) represent with containing double
Double (many) maleic anhydride construction units and double (many) in the compound of (many) maleic anhydrides or double (many) maleimide structure
The middle mole ratio of maleimide structure unit is 1:1～1.1.Complete in order to react, therein containing double (many) maleic acids
The molal quantity of the compound of acid anhydride or double (many) maleimide structure can increase in right amount.
In the present invention, described contains double (many) maleic anhydrides or the compound of double (many) maleimide structure, refers to
Intramolecular at least contains two maleic anhydride structures or the compound of maleimide structure.Described compound can be single
Body, it is also possible to be polymer.Such as, described compound is the BMI (being called for short BMI) shown in formula (VII),
Wherein, R7 is C1～C6 alkylidene, phenylene, C1～C6 alkylidene diphenyl；R7 can also be made up of oligomer
Group.As forShown polyether-basedOr
Shown polyalkenyl, it is preferable that be 4,4'-methylenediphenyl, polyoxyethanyl, polyoxyethyl propyl, polyvinyl etc..
It is obvious that on double (many) maleic anhydrides or double (many) maleimide structure hydrogen atom be replaced base (include but not
It being limited to, alkyl, halogen, phenyl, benzyl) substituted compound is also within protection scope of the present invention.
The temperature of hot briquetting is 50～120 DEG C.
In general, the reaction equation of the present invention is represented by
Unsaturated rubber in the party's formula is butadiene rubber, and the sulfhydryl compound containing furan structure is furfurylmercaptan, contains
The compound having double (many) maleic anhydrides or double (many) maleimide structure is N, N'-(4,4'-methylenediphenyl) span
Carry out acid imide.
The present invention utilizes sulfydryl-alkene clicking chemistry, utilizes the sulfhydryl compound containing furan structure and unsaturated rubber, as
Butadiene rubber, butadiene-styrene rubber, natural rubber mixes, and under conditions of ultraviolet lighting, the sulfhydryl compound containing furan structure connects
Branch, on rubber molecular chain, obtains modified unsaturated rubber, then adds containing maleic anhydride or maleimide in this system
The compound of structure, under conditions of heating, this system carries out diels Alder reaction, makes molecular chemistry cross-link, and obtaining can
The modified unsaturated rubber of inverse crosslinking.Being thermal reversion due to this crosslinking again, such system then can reach in a heated condition
The effect reclaimed and reinvent.Meanwhile, under the effect of diels Alder reversible reaction, the reversible crosslink after crosslinking
Modified unsaturated rubber has preferable mechanical property, it is not necessary to adding other fillers such as inorganic particulate, this also carries for recycling
Supply good condition.
Accompanying drawing explanation
In Fig. 1 embodiment, graft ratio is the contrast nuclear-magnetism figure of 20% modified butadiene rubber and butadiene rubber before modified.
In Fig. 2 embodiment, graft ratio is the infrared figure of contrast of 20% modified butadiene rubber and butadiene rubber before modified.
The stress-strain curve of the modified butadiene rubber of the reversible crosslink of different graft ratio, grafting in Fig. 3 embodiment
Ratio is respectively 10%, and 12%, 14%, 16%, 18%, 20%.
Detailed description of the invention
Below according to specific embodiment, technical scheme is described further.Protection scope of the present invention does not limits
In following example, enumerate these examples and limit the present invention merely for exemplary purpose never in any form.
Raw material in following example, as being not particularly illustrated, is commercially available.
Embodiment
Butadiene rubber (trade mark: BR9000) and furfurylmercaptan are dissolved in toluene in proportion, and graft ratio is 10%, 12%,
14%, 16%, 18%, 20%, add light trigger 2-methyl isophthalic acid-[(4-methyl mercapto) phenyl]-2-of butadiene rubber weight 8%
Morpholine acetone (Irgacure 907, Ciba Specialty Chemicals), after stirring, carrying out a little of ultraviolet lighting (365nm wavelength)
Hit reaction.Backward reacted solution in add the N corresponding to furfurylmercaptan addition, N'-(4,4'-methylenediphenyl) double
Maleimide, maleimide base group therein is 1:1 with the furan group mol ratio of furfurylmercaptan, after stirring, heating
Cross moulding under the conditions of 80 DEG C, obtains the modified butadiene rubber of reversible crosslink.
Table one is respectively 10% for graft ratio in embodiment, the reversible crosslink of 12%, 14%, 16%, 18%, 20%
The elongation at break of modified butadiene rubber and fracture strength
Table one
| Graft ratio | 10% | 12% | 14% | 16% | 18% | 20% |
| Fracture strength (MPa) | 4.64 | 4.63 | 4.57 | 4.58 | 4.46 | 4.66 |
| Elongation at break (%) | 81.3 | 78.8 | 63.9 | 55.7 | 44.8 | 45.8 |
Those skilled in the art, can be it should be noted that, embodiment described in the invention is the most exemplary
Various other replacement, changes and improvements are made in the scope of the present invention.Thus, the invention is not restricted to above-mentioned embodiment, and only
It is defined by the claims.
Claims (11)
1. the method preparing modified unsaturated rubber, including by the sulfhydryl compound containing furan structure and unsaturated rubber
Dissolve in organic solvent, add light trigger, after stirring, under conditions of ultraviolet lighting, complete graft reaction, obtain
Modified unsaturated rubber；Wherein: described modified unsaturated rubber at least has the repetition of a kind of expression in formula (I)～formula (IV)
Unit:
Wherein, R1For halogen, C1～C4 alkyl, hydrogen atom；R2For hydrogen atom, C1～C4 alkyl；R3For hydrogen atom, C1～C4 alkane
Base；R4For hydrogen atom, C1～C4 alkyl；R5For halogen, C1～C4 alkyl, hydrogen atom；R6For hydrogen atom, C1～C4 alkyl；
M=0～4, n=0～4.
Method the most according to claim 1, it is characterised in that the described sulfhydryl compound containing furan structure is for containing
The mercaptan of furan structure.
Method the most according to claim 2, it is characterised in that the described sulfhydryl compound containing furan structure is 2-first
Base-3-furanthiol, 2,5-dimethyl-3-furanthiols, furan-2-methanthiol, 5-methyl-2-furan methanthiol any one.
Method the most according to claim 1, it is characterised in that described unsaturated rubber is isoprene rubber, natural
Rubber, butadiene-styrene rubber, butadiene rubber, nitrile rubber, neoprene any one.
Method the most according to claim 1, it is characterised in that described organic solvent be alcohols, chloroform, dichloromethane,
1,4-dioxane, dimethyl sulfoxide, N, N '-dimethyl Methanamide, N, in N '-dimethyl acetamide, ketone and benzene homologues
Any one.
Method the most according to claim 1, it is characterised in that described light trigger is free radical photo-initiation or sun
Ion-type light trigger, the addition of light trigger is the 0.001～20% of unsaturated rubber weight.
Method the most according to claim 6, it is characterised in that described free radical photo-initiation is Benzoinum ethers, dioxane
The combination of one or more in epoxide 1-Phenylethanone., Oxoxanthone, thioxanthone, anthraquinone and benzophenone and derivant thereof；Described
Cationic photoinitiator is any one in Diaryl iodonium compound, triaryl sulfide, ferrocene salt.
8. a using method for modified unsaturated rubber, including:
Add containing double (many) maleic anhydrides or double (many) maleimide structure in the organic solution of modified unsaturated rubber
Compound, after stirring, hot briquetting, obtain the modified unsaturated rubber of reversible crosslink；Wherein: described modified unsaturated
Rubber at least has a repetitive of a kind of expression in formula (I)～formula (IV):
Wherein, R1For halogen, C1～C4 alkyl, hydrogen atom；R2For hydrogen atom, C1～C4 alkyl；R3For hydrogen atom, C1～C4 alkane
Base；R4For hydrogen atom, C1～C4 alkyl；R5For halogen, C1～C4 alkyl, hydrogen atom；R6For hydrogen atom, C1～C4 alkyl；
M=0～4, n=0～4.
Method the most according to claim 8, it is characterised in that described contains double (many) maleic anhydrides or double (many) Malaysias
The compound of imide structure, refers to that intramolecular at least contains two maleic anhydride structures or the chemical combination of maleimide structure
Thing.
Method the most according to claim 9, it is characterised in that described contains double (many) maleic anhydrides or double (many) horses
Carry out the compound of imide structure, for the BMI shown in formula (VII),
Wherein R7For C1～C6 alkylidene, phenylene, C1～C6 alkylidene diphenyl, the group being made up of longer chain oligomers.
11. methods according to claim 10, it is characterised in that R7It is 4,4'-methylenediphenyl, polyoxyethanyl, polyoxy
Propyl group, in polyvinyl any one.
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| CN104628895A (en) * | 2015-01-27 | 2015-05-20 | 上海交通大学 | Method for thermally reversibly crosslinking styrenic thermoplastic elastomer material |
| JP6776515B2 (en) * | 2015-08-21 | 2020-10-28 | 日本ゼオン株式会社 | Crosslinkable rubber composition |
| CN105254963B (en) * | 2015-10-31 | 2017-09-29 | 上海交通大学 | Carbon nano-tube modification rubber composite, preparation method and the remodeling recovery method of a kind of recoverable |
| CN105602181A (en) * | 2015-12-28 | 2016-05-25 | 上海交通大学 | Carbon nanotube modified thermoplastic elastomer composite material with solvent resistance and preparing method thereof |
| CN105859920B (en) * | 2016-04-19 | 2018-11-30 | 常熟理工学院 | A kind of high grafting rate functionalization ethylene propylene diene rubber and preparation method thereof |
| CN108017728B (en) * | 2016-11-01 | 2021-04-13 | 中国石油化工股份有限公司 | Rubber composition, modified rubber with self-healing function and preparation method and application thereof |
| CN106832356B (en) * | 2017-01-19 | 2019-06-21 | 北京化工大学 | A kind of thermal reversion crosslinking gutta-percha dual-shaped memory elasticity body and preparation method thereof |
| CN107245134B (en) * | 2017-08-02 | 2019-05-14 | 四川大学 | A kind of styrene copolymer and preparation method thereof with furyl |
| CN107337748B (en) * | 2017-08-02 | 2019-11-26 | 四川大学 | A kind of styrene copolymer and preparation method thereof with reversible crosslink key |
| CN108192082B (en) * | 2018-01-31 | 2020-09-15 | 浙江大学 | Method for preparing reversible crosslinking toughening epoxy resin by using body click chemical reaction |
| CN108299623B (en) * | 2018-01-31 | 2020-09-15 | 浙江大学 | Method for preparing recyclable epoxy resin by using body click chemical reaction |
| CN108570139B (en) * | 2018-04-20 | 2020-10-16 | 上海交通大学 | Method for preparing crosslinked elastomer by utilizing dynamic covalent bond |
| CN110791952B (en) * | 2018-08-01 | 2021-11-30 | 北京化工大学 | Modified cellulose fiber and preparation method and application thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102391424A (en) * | 2011-09-01 | 2012-03-28 | 上海交通大学 | Method for modifying styrene-butadiene-styrene (SBS) block copolymer |
| CN102482245A (en) * | 2009-09-11 | 2012-05-30 | 株式会社理光 | Furan Derivative And Electrophotographic Photoconductor |
| CN103788386A (en) * | 2014-01-26 | 2014-05-14 | 上海交通大学 | Method for modifying elastomer by using click reaction of thiol-ene |
-
2014
- 2014-08-28 CN CN201410431458.2A patent/CN104193852B/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102482245A (en) * | 2009-09-11 | 2012-05-30 | 株式会社理光 | Furan Derivative And Electrophotographic Photoconductor |
| CN102391424A (en) * | 2011-09-01 | 2012-03-28 | 上海交通大学 | Method for modifying styrene-butadiene-styrene (SBS) block copolymer |
| CN103788386A (en) * | 2014-01-26 | 2014-05-14 | 上海交通大学 | Method for modifying elastomer by using click reaction of thiol-ene |
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