CN102587132A - 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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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 of modifying.
Background technology
Aramid fiber can be divided into Fanglun 1313 (abbreviation meta-aramid), Fanglun 1414's (abbreviation p-aramid fiber) and heteroaromatic polyamide fiber kinds such as (being called for short the aramid fiber III) substantially.Because aramid fiber has characteristics such as ultra high modulus, high strength, high temperature resistant, light weight, thereby have widely in fields such as Aero-Space, military clothes, material enhancings and to use.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 through hydrogen bond, skin zone by the high rigid molecule chain of degree of crystallinity along fiber axis to being arranged in parallel, 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 the amide functional group, makes this hydrogen not live and dials, be difficult to substituted, and surface crystallinity is high by other group, and smooth surface, wettability is poor, has limited its application in field of compound material.Thereby aramid fiber surface 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.The physics method comprises face coat, high-energy ray (X-ray, gamma-rays, high-power electron beam etc.), plasma, ultrasonic immersing etc. again; Chemical method comprises surface activation (etching, introducing functional group etc.), surface grafting etc. again.Wherein, surface grafting is divided into supercritical CO again
2Method, solwution method and solid phase method etc.In the solution grafting, studying maximum is Na metal reaction grafting method.It is to adopt the Na salt of dimethyl sulfoxide (DMSO) (DMSO) right with the generation of the active hydrogen reaction on amido link zwitterion; 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 anionic initiator again and causes anionic polymerisation.What another research was more is isocyanates grafting method; It is that aramid fiber is placed the toluene solution that is dissolved with a certain amount of isocyanates or directly places isocyanate solution; Make hydrogen and isocyanate reaction on the fiber amido link under the uniform temperature, the NCO in the grafting can react with water, alcohol, ammonia etc. again.Though two kinds of solution modification methods can both be carried out modification to aramid fiber surface, exist complicated operation, solvent poisonous, exist pollute, shortcomings such as the bad control of reaction, so 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, shortcoming such as uncontrollable, the complicated operation of reaction, rate of vaccination are low, generally aramid fiber is carried out modification without it.
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 has important use in fields such as extract drugs, foaming, sewage disposals.Utilize supercritical CO
2It is a kind of method that new development is got up that fluid technique carries out polymer modification.Existing both at home and abroad in a large number about at supercritical CO
2The report of middle polypropylene polymer surfaces grafting such as (PP).Supercritical CO
2Fluid can dissolve most of small organic molecules, minority is fluorine-containing and the big molecule of silicon, can not dissolve most polymer, but most polymers is had swelling action in various degree.Utilize this character, can be with in the slotting embedded polymer things such as monomer and initator.Polymerization in inert atmosphere after direct intensification polymerization in back or the release can embed the various polymerization thing on the inside and the surface of polymer, thereby reach the purpose that the inside and the surface of polymer are carried out modification and modification simultaneously.This method has not to be destroyed the polymer outward appearance, evenly embeds few advantages such as interparticle adhesion, caking phenomenon that take place after incompatible polymers, the polymerization; Very help realizing large-scale continuous production; And operation with separates simple, the reaction time is short, grafting efficiency is high, can wait percent grafting etc. through adjusting temperature, pressure, processing time, can effectively improve the performance of material.
Summary of the invention
Technical problem to be solved by this invention provides a kind of aramid fiber at supercritical CO
2In the environmental protection simple to operate, economic of surface grafting polymerization method of modifying method of modifying, percent grafting controlled, the surface of the aramid fiber after the modification becomes coarse because of there being polymer, can increase the 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 of modifying, comprising:
(1) aramid fiber is put into apparatus,Soxhlet's, add hot acetone to 70 ℃, acetone cleans the aramid fiber surface behind condensing reflux, take out fiber behind the 24h, and the vacuumize fiber is subsequent use;
(2) glycerol polymerization on aramid fiber surface:
In reaction vessel, add monomer and initator, put into aramid fiber then, wherein aramid fiber does not contact with monomer and initator; Closed reaction container behind the deaeration, at the following 1-30 of decomposition of initiator temperature ℃, charges into CO in reaction vessel
2, make system be in supercritical CO
2State, swelling 2-8h; Then
A. the above 1-30 of heating systems to decomposition of initiator temperature ℃, make monomer polymerization, obtain the aramid fiber of surface aggregate modification;
Or the b. release is taken out behind the aramid fiber at N
2Be heated to the above 1-30 of decomposition of initiator temperature ℃ polymerization under the protection, obtain the aramid fiber of surface aggregate modification;
(3) the not cleaning of graft polymers of aramid fiber surface:
With the aramid fiber of above-mentioned surface aggregate modification with acetone to constant weight, last vacuumize fiber gets final product.
Monomer described in the step (2) is one or more in styrene (St), methyl methacrylate (MMA), the maleic anhydride (MAH).
Initator described in the step (2) is azo-initiator or peroxide initator; Described azo-initiator is azodiisobutyronitrile AIBN; Described peroxide initator is dibenzoyl peroxide BPO.
Monomer described in the 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 the 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 the 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 the 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.
The concrete operations of use acetone to the constant weight described in the step (3) are: the aramid fiber of described surface aggregate modification is placed acetone, add hot acetone to 70 ℃ condensing reflux washing sample, till fibre weight is constant.
The present invention can carry out polymerization at aramid fiber surface effectively, and grafting embeds different polymer, reaches the purpose of improving aramid fiber interface connectivity difference.
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, helps aramid fiber and use as the composite reinforcing material.
The present invention adds aramid fiber, monomer and monomer initator in autoclave, below the decomposition of initiator temperature, in autoclave, charge into CO
2And make it reach supercriticality, utilize supercritical CO
2Swelling and rolling action, carry in the aramid fiber with the aramid fiber swelling and with initator and monomer; After make monomer polymerization more than directly being warming up to the decomposition of initiator temperature, or take out aramid fiber after the release, and under nitrogen atmosphere, be warming up to and make the polymerization of initator trigger monomer more than the decomposition of initiator temperature; Last at a certain temperature with the acetone flush 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 big application potential;
(2) the present invention surface of obtaining the aramid fiber after the modification becomes coarse because of there being polymer, can increase itself and composite wood
The adhesion and the compatibility of material matrix help 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 to be used to the present invention is described and be not used in the restriction scope of the present invention.Should be understood that in addition those skilled in the art can do various changes or modification to 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 institute restricted portion equally.
Embodiment 1
(1) cleaning on aramid fiber surface:
Put into acetone soln in the there-necked flask, put into aramid fiber in the apparatus,Soxhlet's.Add hot acetone to 70 ℃, acetone cleans the aramid fiber surface behind condensing reflux, and it is subsequent use to take out the vacuumize fiber behind the scavenging period 24h.
(2) aramid fiber surface grafting polymerization styrene
At the bottom of the initator (is example with BPO) and monomer St adding autoclave with a certain amount of (BPO/St=0.3-1wt%), add the aramid fiber (with monomer and initator do not contact) of surface through cleaning.Close autoclave, in still, charge into CO
2And discharge CO
2Three times, to discharge air.In still, charge into CO
2, and heating systems, make pressure reach 13-30MPa, temperature is 45-50 ℃, makes system be in supercritical CO
2State.Behind the swelling aramid fiber 4-8h, directly system is heated to 70-100 ℃, trigger monomer styrene polymerization 4-5h; Or behind the release taking-up aramid fiber, fiber is placed there-necked flask, N
2Be heated to 100 ℃ of polymerization 2-3h in the atmosphere, take out fiber.
The styrene polymerization reaction equation is following:
(3) the not cleaning of graft polymers of aramid fiber surface:
To place acetone through the aramid fiber of surface aggregate, 70 ℃ of condensing reflux washing sample, till fibre weight is constant, the vacuumize fiber sample.
Embodiment 2
(1) cleaning on aramid fiber surface:
Put into acetone soln in the there-necked flask, put into aramid fiber in the apparatus,Soxhlet's.Add hot acetone to 70 ℃, acetone cleans the aramid fiber surface behind condensing reflux, and it is subsequent use to take out the vacuumize fiber behind the scavenging period 24h.
(2) aramid fiber surface grafting polymerization methyl methacrylate
At the bottom of the initator and monomer M MA adding autoclave with a certain amount of (BPO/MMA=0.4-3wt%), add the aramid fiber (with monomer and initator do not contact) of surface through cleaning.Close autoclave, in still, charge into CO
2And discharge CO
2Three times, to discharge air.In still, charge into CO
2, and heating systems, make pressure reach 8-30MPa, temperature is 45-50 ℃, makes system be in supercritical CO
2State.Behind the swelling aramid fiber 4-8h, directly system is heated to 80-100 ℃, trigger monomer methyl methacrylate polymerization 4-8h; Or behind the release taking-up aramid fiber, fiber is placed there-necked flask, N
2Be heated to 100 ℃ of polymerization 2-3h in the atmosphere, take out fiber.
The methyl methacrylate polymerization reaction equation is following:
(3) the not cleaning of graft polymers of aramid fiber surface:
To place acetone through the aramid fiber of surface aggregate, 70 ℃ of condensing reflux washing sample, till fibre weight is constant, the vacuumize fiber sample.
Embodiment 3
(1) cleaning on aramid fiber surface:
Put into acetone soln in the there-necked flask, put into aramid fiber in the apparatus,Soxhlet's.Add hot acetone to 70 ℃, acetone cleans the aramid fiber surface behind condensing reflux, and it is subsequent use to take out the vacuumize fiber behind the scavenging period 24h.
(2) aramid fiber surface grafting polymerization maleic anhydride
At the bottom of the initator and monomer M AH adding autoclave with a certain amount of (BPO/MAH=0.4-3wt%), add the aramid fiber (with monomer and initator do not contact) of surface through cleaning.Close autoclave, in still, charge into CO
2And discharge CO
2Three times, to discharge air.In still, charge into CO
2, and heating systems, make pressure reach 13-30MPa, temperature is 45-50 ℃, makes system be in supercritical CO
2State.Behind the swelling aramid fiber 4-8h, directly system is heated to 125 ℃, trigger monomer maleic anhydride polymerization 4-8h; Or behind the release taking-up aramid fiber, fiber is placed there-necked flask, N
2Be heated to 125 ℃ of polymerization 2-3h in the atmosphere, take out fiber.
Maleic anhydride polymerisation formula is following:
(3) the not cleaning of graft polymers of aramid fiber surface:
To place acetone through the aramid fiber of surface aggregate, 70 ℃ of condensing reflux washing sample, till fibre weight is constant, the vacuumize fiber sample.
Embodiment 4
(1) cleaning on aramid fiber surface:
Put into acetone soln in the there-necked flask, put into aramid fiber in the apparatus,Soxhlet's.Add hot acetone to 70 ℃, acetone cleans the aramid fiber surface behind condensing reflux, and it is subsequent use to take out the vacuumize fiber behind the scavenging period 24h.
(2) aramid fiber surface grafting polymerization styrene and maleic anhydride
(monomer mass is than St/MAH=1: 1wt%) add at the bottom of the 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, in still, charge into CO
2And discharge CO
2Three times, to discharge air.In still, charge into CO
2, and heating systems, make pressure reach 8-30MPa, temperature is 45-50 ℃, makes system be in supercritical CO
2State.Behind the swelling aramid fiber 4-8h, directly system is heated to 100-125 ℃, trigger monomer styrene and maleic anhydride polymerization 4-8h; Or behind the release taking-up aramid fiber, fiber is placed there-necked flask, N
2Be heated to 125 ℃ of polymerization 2-3h in the atmosphere, take out fiber after the cooling system.
Maleic anhydride of styrene polymerisation formula is following:
(3) the not cleaning of graft polymers of aramid fiber surface:
To place acetone through the aramid fiber of surface aggregate, 70 ℃ of condensing reflux washing sample, till fibre weight is constant, the vacuumize fiber.
Claims (8)
1. an aramid fiber is at supercritical CO
2In the surface grafting polymerization method of modifying, comprising:
(1) aramid fiber is put into apparatus,Soxhlet's, add hot acetone to 70 ℃, acetone cleans the aramid fiber surface behind condensing reflux, take out fiber behind the 24h, and the vacuumize fiber is subsequent use;
(2) in reaction vessel, add monomer and initator, put into aramid fiber then, wherein aramid fiber does not contact with monomer and initator; Closed reaction container behind the deaeration, at the following 1-30 of decomposition of initiator temperature ℃, charges into a certain amount of CO in reaction vessel
2, make system be in supercritical CO
2State, swelling 2-8h; Then
A. the above 1-30 of heating systems to decomposition of initiator temperature ℃, make monomer polymerization, obtain the aramid fiber of surface aggregate modification;
Or the b. release is taken out behind the aramid fiber at N
2Be heated to the above 1-30 of decomposition of initiator temperature ℃ polymerization under the protection, obtain the aramid fiber of surface aggregate modification;
(3) with the aramid fiber of above-mentioned surface aggregate modification with acetone to constant weight, 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 of modifying, it is characterized in that: the monomer described in the step (2) is one or more among styrene St, methyl methacrylate MMA, the maleic anhydride MAH.
3. a kind of aramid fiber according to claim 1 is at supercritical CO
2In the surface grafting polymerization method of modifying, it is characterized in that: the initator described in the step (2) is azo-initiator or peroxide initator; Described azo-initiator is azodiisobutyronitrile AIBN; Described peroxide initator is dibenzoyl peroxide BPO.
4. a kind of aramid fiber according to claim 1 is at supercritical CO
2In the surface grafting polymerization method of modifying; It is characterized in that: the monomer described in the 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.
5. a kind of aramid fiber according to claim 1 is at supercritical CO
2In the surface grafting polymerization method of modifying; It is characterized in that: the monomer described in the 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.
6. a kind of aramid fiber according to claim 1 is at supercritical CO
2In the surface grafting polymerization method of modifying; It is characterized in that: the monomer described in the 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.
7. a kind of aramid fiber according to claim 1 is at supercritical CO
2In the surface grafting polymerization method of modifying; It is characterized in that: the monomer described in the 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.
8. a kind of aramid fiber according to claim 1 is at supercritical CO
2In the surface grafting polymerization method of modifying; It is characterized in that: the concrete operations of use acetone to the constant weight described in the step (3) are: the aramid fiber of described surface aggregate modification is placed acetone; Add hot acetone to 70 ℃ condensing reflux washing sample; Till fibre weight is constant, the vacuumize fiber.
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| CN111118894A (en) * | 2020-01-14 | 2020-05-08 | 贵州大学 | Method for modifying carbon fiber |
| 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 |
| CN112521703A (en) * | 2020-11-03 | 2021-03-19 | 上海工程技术大学 | Method for preparing modified aramid pulp/PTFE composite material by supercritical carbon dioxide polymerization |
| CN112941916A (en) * | 2021-02-03 | 2021-06-11 | 贵州理工学院 | Supercritical CO2Method for assisting surface grafting treatment of aramid fiber |
| CN114008117A (en) * | 2019-04-16 | 2022-02-01 | 原子能与替代能源委员会 | Method for surface functionalization in supercritical fluid media |
| 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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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114008117A (en) * | 2019-04-16 | 2022-02-01 | 原子能与替代能源委员会 | Method for surface functionalization in supercritical fluid media |
| CN111118894A (en) * | 2020-01-14 | 2020-05-08 | 贵州大学 | Method for modifying carbon fiber |
| 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 |
| CN112521703A (en) * | 2020-11-03 | 2021-03-19 | 上海工程技术大学 | Method for preparing modified aramid pulp/PTFE composite material by supercritical carbon dioxide polymerization |
| 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 |
| CN112941916A (en) * | 2021-02-03 | 2021-06-11 | 贵州理工学院 | Supercritical CO2Method for assisting surface grafting treatment of aramid fiber |
| 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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