CN102587132B - Modification method of aramid fiber in supercritical CO2 by surface grafting polymerization - Google Patents
Modification method of aramid fiber in supercritical CO2 by surface grafting polymerization Download PDFInfo
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- Y02P20/54—Improvements relating to the production of bulk chemicals using solvents, e.g. supercritical solvents or ionic liquids
Abstract
The invention relates to a modification method of aramid fiber in supercritical CO2 by surface grafting polymerization. The method comprises the steps of: (1) cleaning aramid fiber surface with acetone and vacuum-drying fiber; (2) adding monomers and an initiator to a reaction vessel, then adding the aramid fiber, closing the reaction vessel, removing air, introducing CO2 into the reaction vessel at the temperature lower than the decomposition temperature of the initiator so that the system is in a supercritical CO2 state, swelling and heating for polymerizing the monomers to obtain surface-polymerization-modified aramid fiber, wherein the aramid fiber does not contact the monomers and the initiator; and (3) cleaning the surface-polymerization-modified aramid fiber with acetone until constant weight, and finally vacuum-drying the fiber. According to the invention, the method is simple in operation, economical, environmentally friendly and controllable in grafting ratio; and the obtained modified aramid fiber has rough surface due to the existence of the polymer, so that the adhesion and compatibility between the fiber and a composite material substrate are improved and the application of the fiber as a composite material reinforcing agent is facilitated.
Description
Technical field
The invention belongs to the modification field of aramid fiber, particularly a kind of aramid fiber is at supercritical CO
2In the surface grafting polymerization method.
Background technology
Aramid fiber can be divided into the kinds such as Fanglun 1313 (abbreviation meta-aramid), Fanglun 1414's (abbreviation p-aramid fiber) and heteroaromatic polyamide fiber (being called for short the aramid fiber III) substantially.Because aramid fiber has the characteristics such as ultra high modulus, high strength, high temperature resistant, light weight, thereby in fields such as Aero-Space, military clothes, Material reinforcements, have a wide range of applications.Because aramid fiber is to be formed by the rigid molecule chain, it has unique " skin-core " structure, the core rodlike molecule is arranged in parallel by hydrogen bond, and skin zone is by the high rigid molecule chain of degree of crystallinity along fiber axis to being arranged in parallel, and skin zone's thickness is about the 1%-40% of whole fibre diameter.In the rigid molecule chain, phenyl ring has shielding action to the hydrogen on amide functional group, makes this hydrogen not live and dial, be difficult to be substituted by other group, and surface crystallinity is high, and smooth surface, wettability is poor, has limited its application in field of compound material.Thereby aramid fiber surface is carried out modification, increase surperficial lipophilicity and roughness and seem particularly important.
At present, aramid fiber surface modification can be divided into two kinds of methods substantially, and a kind of is physical method, and a kind of is chemical method.Physical comprises again face coat, high-energy ray (X-ray, gamma-rays, high-power electron beam etc.), plasma, ultrasonic immersing etc.; Chemical method comprises again surface activation (etching, introducing functional group etc.), surface grafting etc.Wherein, surface grafting is divided into again supercritical CO
2Method, solwution method and solid phase method etc.In solution grafting, most study be Na metal reaction Graft Method.It is to adopt the Na salt of dimethyl sulfoxide (DMSO) (DMSO) and the active hydrogen reaction on amido link to produce zwitterion pair, this zwitterion was to both reacting with halogenated hydrocarbons, the functional group that will have ad hoc structure is grafted to fiber surface, can be used as again anionic initiator and causes anionic polymerisation.What another research was more is the isocyanates Graft Method, it is that aramid fiber is placed in the toluene solution that is dissolved with a certain amount of isocyanates or directly is placed in isocyanate solution, make hydrogen and isocyanate reaction on the fiber amido link under uniform temperature, the isocyanate group in grafting can react with water, alcohol, ammonia etc. again.Though two kinds of solution modification methods can be carried out modification to aramid fiber surface, exist complicated operation, solvent poisonous, exist pollute, the shortcomings such as the bad control of reaction, therefore also application on a large scale.The research of solid phase grafting method modification of aramid fiber is less, and have that reaction temperature is higher, the shortcoming such as uncontrollable, the complicated operation of reaction, rate of vaccination are low, generally without it, aramid fiber is carried out modification.
Supercritical CO
2Have asepsis environment-protecting, density is bordering on liquid, it is 100 times of liquid, surprising advantages such as solution pervasion ability that viscosity is bordering on gas, diffusion coefficient, thereby in fields such as medicine extraction, foaming, sewage disposals, has important use.Utilize supercritical CO
2It is a kind of method that new development is got up that fluid technique carries out polymer modification.Existing in a large number about at supercritical CO both at home and abroad
2The report of the polymer surfaces grafting such as middle polypropylene (PP).Supercritical CO
2Fluid can dissolve most of small organic molecules, minority is fluorine-containing and the large molecule of silicon, can not dissolve most polymer, but most polymers is had in various degree swelling action.Utilize this character, can be with in the slotting embedded polymer things such as monomer and initator.Polymerization in inert atmosphere after rear directly intensification polymerization or release, can embed different polymer on inside and the surface of polymer, thereby reach, the purpose of modification and modification carried out on inside and the surface of polymer simultaneously.The method has not to be destroyed the polymer outward appearance, evenly embeds few advantages such as interparticle adhesion, caking phenomenon that occur after incompatible polymers, polymerization, extremely be conducive to realize large-scale continuous production, and operation with separates simple, the reaction time is short, grafting efficiency is high, can regulate and control percent grafting etc. by adjusting temperature, pressure, processing time etc., can effectively improve the performance of material.
Summary of the invention
Technical problem to be solved by this invention is to provide a kind of aramid fiber at supercritical CO
2In the environmental protection simple to operate, economic of surface grafting polymerization method method of modifying, percent grafting controlled, the surface of the aramid fiber after modification is because existing polymer to become coarse, can increase adhesion and the compatibility of itself and matrices of composite material.
A kind of aramid fiber of the present invention is at supercritical CO
2In the surface grafting polymerization method, comprising:
(1) aramid fiber is put into apparatus,Soxhlet's, add hot acetone to 70 ℃, acetone cleans the aramid fiber surface after condensing reflux, take out fiber after 24h, and the vacuumize fiber is standby;
(2) glycerol polymerization on aramid fiber surface:
Add monomer and initator in reaction vessel, then put into aramid fiber, wherein aramid fiber does not contact with monomer and initator; Closed reaction container, after deaeration,, at the following 1-30 ℃ of decomposition of initiator temperature, be filled with CO in reaction vessel
2, make system be in supercritical CO
2State, swelling 2-8h; Then
A. heating systems, to the above 1-30 ℃ of decomposition of initiator temperature, makes monomer polymerization, obtains the aramid fiber of surface aggregate modification;
Or the b. release is taken out after aramid fiber at N
2Be heated to the above 1-30 of decomposition of initiator temperature ℃ polymerization under protection, obtain the aramid fiber of surface aggregate modification;
(3) the not cleaning of graft polymers of aramid fiber surface:
The aramid fiber of above-mentioned surface aggregate modification is cleaned to constant weight with acetone, and last vacuumize fiber gets final product.
Monomer described in step (2) is one or more in styrene (St), methyl methacrylate (MMA), maleic anhydride (MAH).
Initator described in step (2) is azo-initiator or peroxide initator; Described azo-initiator is azodiisobutyronitrile AIBN; Described peroxide initator is dibenzoyl peroxide BPO.
Monomer described in step (2) is styrene St, initator is dibenzoyl peroxide BPO, and its reaction condition is: BPO/St=0.3-1wt%, swelling temperature are that 45-50 ℃, pressure are that 8-30MPa, swelling time are that 4-8h, polymerization temperature are that 70-100 ℃, polymerization time are 4-5h.
Monomer described in step (2) is methyl methacrylate MMA, initator is dibenzoyl peroxide BPO, and its reaction condition is: BPO/MMA=0.4-3wt%, swelling temperature are that 45-50 ℃, pressure are that 8-30MPa, swelling time are that 4-8h, polymerization temperature are that 80-100 ℃, polymerization time are 4-8h.
Monomer described in step (2) is maleic anhydride MAH, initator is dibenzoyl peroxide BPO, and its reaction condition is: BPO/MAH=0.4-3wt%, swelling temperature are that 45-50 ℃, pressure are that 8-30MPa, swelling time are that 4-8h, polymerization temperature are that 125 ℃, polymerization time are 4-8h.
Monomer described in step (2) is styrene St and maleic anhydride MAH, initator is dibenzoyl peroxide BPO, wherein the mass ratio of St and MAH is 1: 1, and its reaction condition is: BPO/St=0.2-1.5wt%, BPO/MAH=0.2-1.5wt%, swelling temperature are that 45-50 ℃, pressure are that 8-30MPa, swelling time are that 4-8h, polymerization temperature are that 100-125 ℃, polymerization time are 4-8h.
With acetone, cleaning to the concrete operations of constant weight described in step (3) is: the aramid fiber of described surface aggregate modification is placed in acetone, adds hot acetone to 70 ℃ condensing reflux washing sample, until fibre weight is constant.
The present invention can carry out polymerization at aramid fiber surface effectively, and grafting embeds different polymer, reaches and improves the poor purpose of aramid fiber interface connectivity.
The present invention it can increase aramid fiber rough surface, lipophilicity effectively at smooth aramid fiber surface grafting polymerization thing, improved the interfacial bonding property of aramid fiber and composite resin matrix, is conducive to aramid fiber and uses as the composite reinforcing material.
The present invention adds aramid fiber, monomer and monomer initator in autoclave, below the decomposition of initiator temperature, be filled with CO in autoclave
2And make it reach supercriticality, utilize supercritical CO
2Swelling and rolling action, carry in aramid fiber with the aramid fiber swelling and with initator and monomer; Make monomer polymerization more than directly being warming up to the decomposition of initiator temperature afterwards, or take out aramid fiber after release, and under nitrogen atmosphere, be warming up to more than the decomposition of initiator temperature and make the polymerization of initator trigger monomer; Last at a certain temperature with acetone wash away be not grafted on aramid fiber surface polymer.
Beneficial effect:
(1) method of modifying of the present invention environmental protection simple to operate, economic, percent grafting are controlled, have larger application potential;
(2) the present invention obtain the aramid fiber after modification surface because existing polymer to become coarse, can increase itself and composite wood
Adhesion and the compatibility of material matrix, be conducive to fiber and use as the composite reinforce.
The specific embodiment
, below in conjunction with specific embodiment, further set forth the present invention.Should be understood that these embodiment only are not used in and limit the scope of the invention for explanation the present invention.Should be understood that in addition those skilled in the art can make various changes or modifications the present invention after the content of having read the present invention's instruction, these equivalent form of values fall within the application's appended claims limited range equally.
Embodiment 1
(1) cleaning on aramid fiber surface:
Put into acetone soln in there-necked flask, put into aramid fiber in apparatus,Soxhlet's.Add hot acetone to 70 ℃, acetone cleans the aramid fiber surface after condensing reflux, takes out the vacuumize fiber after scavenging period 24h standby.
(2) aramid fiber surface grafting polymerization styrene
At the bottom of the initator of a certain amount of (BPO/St=0.3-1wt%) (take BPO as example) and monomer St are added autoclave, add the aramid fiber (with monomer and initator do not contact) of surface through cleaning.Close autoclave, be filled with CO in still
2And discharge CO
2Three times, to discharge air.Be filled with CO in still
2, and heating systems, make pressure reach 13-30MPa, temperature is 45-50 ℃, makes system be in supercritical CO
2State.After swelling aramid fiber 4-8h, directly system is heated to 70-100 ℃, trigger monomer styrene polymerization 4-5h; Or after release taking-up aramid fiber, fiber is placed in there-necked flask, N
2Be heated to 100 ℃ of polymerization 2-3h in atmosphere, take out fiber.
The styrene polymerization reaction equation is as follows:
(3) the not cleaning of graft polymers of aramid fiber surface:
To be placed in acetone through the aramid fiber of surface aggregate, 70 ℃ of condensing reflux washing sample, until fibre weight is constant, the vacuumize fiber sample.
Embodiment 2
(1) cleaning on aramid fiber surface:
Put into acetone soln in there-necked flask, put into aramid fiber in apparatus,Soxhlet's.Add hot acetone to 70 ℃, acetone cleans the aramid fiber surface after condensing reflux, takes out the vacuumize fiber after scavenging period 24h standby.
(2) aramid fiber surface grafting polymerization methyl methacrylate
At the bottom of the initator of a certain amount of (BPO/MMA=0.4-3wt%) and monomer M MA are added autoclave, add the aramid fiber (with monomer and initator do not contact) of surface through cleaning.Close autoclave, be filled with CO in still
2And discharge CO
2Three times, to discharge air.Be filled with CO in still
2, and heating systems, make pressure reach 8-30MPa, temperature is 45-50 ℃, makes system be in supercritical CO
2State.After swelling aramid fiber 4-8h, directly system is heated to 80-100 ℃, trigger monomer methyl methacrylate polymerization 4-8h; Or after release taking-up aramid fiber, fiber is placed in there-necked flask, N
2Be heated to 100 ℃ of polymerization 2-3h in atmosphere, take out fiber.
The methyl methacrylate polymerization reaction equation is as follows:
(3) the not cleaning of graft polymers of aramid fiber surface:
To be placed in acetone through the aramid fiber of surface aggregate, 70 ℃ of condensing reflux washing sample, until fibre weight is constant, the vacuumize fiber sample.
Embodiment 3
(1) cleaning on aramid fiber surface:
Put into acetone soln in there-necked flask, put into aramid fiber in apparatus,Soxhlet's.Add hot acetone to 70 ℃, acetone cleans the aramid fiber surface after condensing reflux, takes out the vacuumize fiber after scavenging period 24h standby.
(2) aramid fiber surface grafting polymerization maleic anhydride
At the bottom of the initator of a certain amount of (BPO/MAH=0.4-3wt%) and monomer M AH are added autoclave, add the aramid fiber (with monomer and initator do not contact) of surface through cleaning.Close autoclave, be filled with CO in still
2And discharge CO
2Three times, to discharge air.Be filled with CO in still
2, and heating systems, make pressure reach 13-30MPa, temperature is 45-50 ℃, makes system be in supercritical CO
2State.After swelling aramid fiber 4-8h, directly system is heated to 125 ℃, trigger monomer maleic anhydride polymerization 4-8h; Or after release taking-up aramid fiber, fiber is placed in there-necked flask, N
2Be heated to 125 ℃ of polymerization 2-3h in atmosphere, take out fiber.
Maleic anhydride polymerisation formula is as follows:
(3) the not cleaning of graft polymers of aramid fiber surface:
To be placed in acetone through the aramid fiber of surface aggregate, 70 ℃ of condensing reflux washing sample, until fibre weight is constant, the vacuumize fiber sample.
Embodiment 4
(1) cleaning on aramid fiber surface:
Put into acetone soln in there-necked flask, put into aramid fiber in apparatus,Soxhlet's.Add hot acetone to 70 ℃, acetone cleans the aramid fiber surface after condensing reflux, takes out the vacuumize fiber after scavenging period 24h standby.
(2) aramid fiber surface grafting polymerization styrene and maleic anhydride
(monomer mass is than St/MAH=1: 1wt%) at the bottom of adding autoclave, add the aramid fiber (with monomer and initator do not contact) of surface through cleaning with a certain amount of (BPO/St=0.2-1.5%wt, BPO/MAH=0.2-1.5%wt) initiator B PO and monomer St and MAH.Close autoclave, be filled with CO in still
2And discharge CO
2Three times, to discharge air.Be filled with CO in still
2, and heating systems, make pressure reach 8-30MPa, temperature is 45-50 ℃, makes system be in supercritical CO
2State.After swelling aramid fiber 4-8h, directly system is heated to 100-125 ℃, trigger monomer styrene and maleic anhydride polymerization 4-8h; Or after release taking-up aramid fiber, fiber is placed in there-necked flask, N
2Be heated to 125 ℃ of polymerization 2-3h in atmosphere, take out fiber after cooling system.
Maleic anhydride of styrene polymerisation formula is as follows:
(3) the not cleaning of graft polymers of aramid fiber surface:
To be placed in acetone through the aramid fiber of surface aggregate, 70 ℃ of condensing reflux washing sample, until fibre weight is constant, the vacuumize fiber.
Claims (5)
1. an aramid fiber is at supercritical CO
2In the surface grafting polymerization method, comprising:
(1) aramid fiber is put into apparatus,Soxhlet's, add hot acetone to 70 ℃, acetone cleans the aramid fiber surface after condensing reflux, take out fiber after 24h, and the vacuumize fiber is standby;
(2) add monomer and initator in reaction vessel, then put into aramid fiber, wherein aramid fiber does not contact with monomer and initator; Closed reaction container, after deaeration,, at the following 1-30 ℃ of decomposition of initiator temperature, be filled with a certain amount of CO in reaction vessel
2, make system be in supercritical CO
2State, swelling 2-8h; Then
A. heating systems, to the above 1-30 ℃ of decomposition of initiator temperature, makes monomer polymerization, obtains the aramid fiber of surface aggregate modification;
Or the b. release is taken out after aramid fiber at N
2Be heated to the above 1-30 of decomposition of initiator temperature ℃ polymerization under protection, obtain the aramid fiber of surface aggregate modification;
Wherein above-mentioned monomer is one or more in styrene St, methyl methacrylate MMA, maleic anhydride MAH; Initator is azo-initiator or peroxide initator; Described azo-initiator is azodiisobutyronitrile AIBN; Described peroxide initator is dibenzoyl peroxide BPO;
(3) aramid fiber of above-mentioned surface aggregate modification is cleaned to constant weight with acetone, final drying gets final product.
2. a kind of aramid fiber according to claim 1 is at supercritical CO
2In the surface grafting polymerization method, it is characterized in that: the monomer described in step (2) is styrene St, initator is dibenzoyl peroxide BPO, and its reaction condition is: BPO/St=0.3-1wt%, swelling temperature are that 45-50 ℃, pressure are that 8-30MPa, swelling time are that 4-8h, polymerization temperature are that 70-100 ℃, polymerization time are 4-5h.
3. a kind of aramid fiber according to claim 1 is at supercritical CO
2In the surface grafting polymerization method, it is characterized in that: the monomer described in step (2) is methyl methacrylate MMA, initator is dibenzoyl peroxide BPO, and its reaction condition is: BPO/MMA=0.4-3wt%, swelling temperature are that 45-50 ℃, pressure are that 8-30MPa, swelling time are that 4-8h, polymerization temperature are that 80-100 ℃, polymerization time are 4-8h.
4. a kind of aramid fiber according to claim 1 is at supercritical CO
2In the surface grafting polymerization method, it is characterized in that: the monomer described in step (2) is styrene St and maleic anhydride MAH, initator is dibenzoyl peroxide BPO, wherein the mass ratio of St and MAH is 1:1, and its reaction condition is: BPO/St=0.2-1.5wt%, BPO/MAH=0.2-1.5wt%, swelling temperature are that 45-50 ℃, pressure are that 8-30MPa, swelling time are that 4-8h, polymerization temperature are that 100 ℃, polymerization time are 4-8h.
5. a kind of aramid fiber according to claim 1 is at supercritical CO
2In the surface grafting polymerization method, it is characterized in that: with acetone, cleaning to the concrete operations of constant weight described in step (3) is: the aramid fiber of described surface aggregate modification is placed in acetone, add hot acetone to 70 ℃ condensing reflux washing sample, until fibre weight is constant, the vacuumize fiber.
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| FR3095207B1 (en) * | 2019-04-16 | 2021-04-23 | Commissariat Energie Atomique | Surface functionalization process in a supercritical fluid medium |
| CN111118894B (en) * | 2020-01-14 | 2022-09-23 | 贵州大学 | Method for modifying carbon fiber |
| CN112521703B (en) * | 2020-11-03 | 2022-11-04 | 上海工程技术大学 | Method for preparing modified aramid pulp/PTFE composite material by supercritical carbon dioxide polymerization |
| CN112521705A (en) * | 2020-11-03 | 2021-03-19 | 上海工程技术大学 | Method for preparing modified aramid pulp/PMMA (polymethyl methacrylate) composite material by supercritical carbon dioxide polymerization |
| CN112941916B (en) * | 2021-02-03 | 2022-11-04 | 贵州理工学院 | Supercritical CO 2 Method for assisting surface grafting treatment of aramid fiber |
| CN115093626A (en) * | 2022-08-25 | 2022-09-23 | 广东粤港澳大湾区黄埔材料研究院 | Civil aviation tire body rubber and preparation method and application thereof |
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