CN102936319A - Fluororubber-grated-maleic anhydride bulking agent and preparing method thereof - Google Patents
Fluororubber-grated-maleic anhydride bulking agent and preparing method thereof Download PDFInfo
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- CN102936319A CN102936319A CN201210447767XA CN201210447767A CN102936319A CN 102936319 A CN102936319 A CN 102936319A CN 201210447767X A CN201210447767X A CN 201210447767XA CN 201210447767 A CN201210447767 A CN 201210447767A CN 102936319 A CN102936319 A CN 102936319A
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- maleic anhydride
- viton
- expanding material
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Abstract
The invention discloses a fluororubber-grated-maleic anhydride bulking agent and a preparing method thereof. The preparing method is that: raw fluororubber, fluororubber, initiating agents, vulcanizing agents and accelerants are filled into an internal mixer for reacting for 10-30min at temperature of 120-160 DEG C and with rotating speed to be 50-100r/min to obtain the fluororubber-grated-maleic anhydride (KFM-g-MAH) bulking agent. KFM-g-MAH performance of the bulking agent and carbonyl groups/carboxyl groups and other polar groups in polar acrylic polymer have strong interaction, and simultaneously can react with polar groups (amino groups and carboxyl groups) of acrylic polymer (ACM) and epoxy groups to achieve the reactive compatibilization effect. By aid of selection of the initiating agents, reactant activation energy is reduced, and accordingly high grating efficiency is achieved. The fluororubber-grated-maleic anhydride bulking agent and the preparing method thereof have the advantages that grating efficiency is obviously improved and compatibilization effect is good and stable.
Description
Technical field
The present invention relates to expanding material, is a kind of viton grafted maleic anhydride expanding material specifically, also relates to its preparation method.
Background technology
Viton (FKM) is the synthetic macromolecule elastomerics that contains fluorine atom on the carbon atom of main chain or side chain, and it is widely used in many fields such as space flight, military project, national defence, automobile, petrochemical complex.The viton goods are mainly used in sealing member, packing ring, pad, barrier film, sebific duct, oil sealing, lining, anticorrosive products and electrical isolation goods.
Viton is most widely used to be automotive field, accounts for to use 60～70% of total amount.On automobile component, can be used as motor spirit flexible pipe, refueling hose, petrolift, air-conditioning plant O shape circle, reach the sealing material of jet apparatus, power piston, valve stem, bent axle, compressor of air conditioner.The automotive sealant that rubber is made in use, except the effect that is subjected to stress, strain, high temperature and low temperature, also be subjected to the erosion of oil product (oil fuel, lubricating oil), chemicals (alcohol, deicing fluid, scavenging solution, braking fluid, sulfuric acid, nitric acid) and biology (mould, bacterium, insect) etc.During product design, as can not consider the independent and synergy of working conditions comprehensively, will cause damage intensity to be accelerated, cause shorten work-ing life.Particularly along with the development of automotive industry and motorway, the travel speed of automobile significantly improves, so that the use temperature of oil sealing significantly rises, the oil temperature at the bent axle place of engine is substantially more than 110 ℃, therefore to the also corresponding raising of specification of quality of the rubber seal of automobile accessories.Traditional viton elaxtic seal can't satisfy high temperature, at a high speed, the actual operation requirements of high abrasion.
China begins to develop viton from the sixties in 20th century, successively successfully develops 23 types, 26 types, 246 types, TP-2 type etc. take polyolefine as main viton and the basic viton of the inferior pin of carboxyl.Develop again perfluoroelastomers the eighties in 20th century and fluoridized phosphorus rubber etc.
In order to improve the performance of viton and goods, a large amount of research work have been carried out in modification and the processing of viton both at home and abroad.At present, the modification of viton mainly contains both direction: the one,, pass through backbone modification, exploitation such as fluoroether rubber, trifluoropropyl siloxane, ehter bond is introduced the viton main chain, increased the flexibility of molecule, kept the original characteristics of viton when its low-temperature performance is improved greatly, but because the Development and Production high cost has greatly limited its promotion and application; The 2nd,, rubber blending, with viton and some conventional rubbers, specialty elastomer and usefulness, so that it is more excellent to obtain performance, the material that cost is lower.
Blending and modifying is a kind of preferably method, but has the following disadvantages: the cost performance that (1) makes novel type fluorubber is not high.Fluoroether rubber, trifluoropropyl siloxane make its price even are higher than viton because cost of development is too high, can only be used under the relatively harsher environment of condition, and promotion and application are restricted; (2) blending and modifying between the viton is restricted to the modification of viton performance.Rubber of the same type has determined that it causes that by the rubber self structure performance deficiency is restricted in improvement.Its cost is difficult to be reduced.Though and the blend of viton and fluoroether rubber can well improve the low-temperature performance of viton, cost is higher; (3) blend of viton and other rubber is difficult kind to the low-temperature performance of viton.Blending and modifying can improve the elasticity of viton, the improvement of the single performance such as processing characteristics, but very few to improving the viton low-temperature performance and considering the aspect research of a plurality of defectives.
When viton and double activated acrylic elastomer (AECM) blend, because the difference of blend on molecular structure, polarity causes the consistency of the two not good enough, have a strong impact on and the colloidality energy, therefore, need by the consistency between two kinds of glue of expanding material improvement.
Summary of the invention
For the deficiency that prior art exists, problem to be solved by this invention is a kind of method that can promote viton expanding material consistency of preparation.
Technical scheme of the present invention is achieved in that a kind of viton grafted maleic anhydride expanding material, by the following method preparation: crude fluororubber, maleic anhydride, initiator, vulcanizing agent, promotor are joined in the Banbury mixer, at 120～160 ℃, under the condition of rotating speed 50～100r/min, reaction 10～30min obtains viton grafted maleic anhydride (KFM-g-MAH) expanding material.
Further, described crude fluororubber 80～130 weight parts, maleic anhydride 3～8 weight parts, initiator 0.5～2 weight part, vulcanizing agent 0.2～0.5 weight part, promotor 0.1～0.3 weight part.
Described initiator is one or more of benzoyl peroxide (BPO), dilauroyl peroxide (LPO), Diisopropyl azodicarboxylate (AIBN), Potassium Persulphate (KPS), dicumyl peroxide (DCP) or oxidation di-t-butyl.
Described vulcanizing agent be benzoyl peroxide (BPO), BPP (BPP), calcium hydroxide or magnesian one or more.
Described promotor is 2-benzothiazolyl mercaptan (accelerator M), 2, one or more of 2 '-dithio-bis-benzothiazole (accelerator DM), N-cyclohexyl-2-benzothiazole sulfonamide (vulcanization accelerator CBS), N tert butyl benzothiazole 2 sulfenamide (vulcanization accelerator TBBS), tetramethyl-thiuram disulfide (vulcanization accelerator TMTD), N-cyclohexyl-2-benzene (accelerator CZ).
The percentage of grafting of above-mentioned resulting viton grafted maleic anhydride (KFM-g-MAH) expanding material is 1.5～3.5%.
The structure of above-mentioned resulting viton grafted maleic anhydride (KFM-g-MAH) expanding material adopts Fourier's infrared measurement; Percentage of grafting adopts chemical titration, and concrete " with reference to preparation and the applied research of maleic anhydride graft natural rubber " (" elastomerics ", 2010,20(2), 10～15).
Above-mentioned unreacted maleic anhydride and oligopolymer thereof are removed by the soxhlet extraction of ethanol.
Compared with prior art, the present invention has the following advantages:
1, viton grafted maleic anhydride of the present invention (KFM-g-MAH) expanding material has added a small amount of vulcanizing agent and promotor, and percentage of grafting obviously improves.
2, the present invention is by the interaction generation block of some functional group between component or the expanding material of graft copolymer, and compatibilization effect is good and stable.
Expanding material viton grafted maleic anhydride can with polar acrylate's rubber in carbonyl/carboxyl isopolarity base strong interaction occurs, can also, epoxy group(ing) react the effect of realization response increase-volume so that being arranged with the polar group (amino, hydroxyl) of acrylic elastomer (ACM) simultaneously.By selecting of initiator, reduce the activation energy of reactant, thereby realize the grafting high efficiency.
Embodiment
Below among each embodiment the umber of material all express with weight part.
Embodiment 1
0.1 part of 80 parts of crude fluororubber, 3 parts of maleic anhydrides, 0.5 part of dicumyl peroxide (DCP), 0.2 part in magnesium oxide, tetramethyl-thiuram disulfide (vulcanization accelerator TMTD) is joined in the Banbury mixer, be that 120 ℃, rotating speed are under the condition of 50r/min in temperature, reaction 15min, obtain viton grafted maleic anhydride (KFM-g-MAH) expanding material, recording its percentage of grafting is 1.65%.
Embodiment 2
With 0.3 part of 120 parts of crude fluororubber, 6 parts of maleic anhydrides, 1 part of Potassium Persulphate (KPS), benzoyl peroxide (BPO), 2,0.2 part of 2 '-dithio-bis-benzothiazole (accelerator DM) joins in the Banbury mixer, be that 140 ℃, rotating speed are under the condition of 80r/min in temperature, reaction 18min, obtain viton grafted maleic anhydride (KFM-g-MAH) expanding material, recording its percentage of grafting is 3.5%.
Embodiment 3
0.3 part of 130 parts of viton, 7 parts of maleic anhydrides, 1.5 parts of dilauroyl peroxides (LPO), 0.5 part of BPP (BPP), N tert butyl benzothiazole 2 sulfenamide (vulcanization accelerator TBBS) is joined in the Banbury mixer, be that 160 ℃, rotating speed are under the condition of 100r/min in temperature, react 20 min, obtain viton grafted maleic anhydride (KFM-g-MAH) expanding material, recording its percentage of grafting is 3.15%.
Claims (7)
1. the preparation method of a viton grafted maleic anhydride expanding material, it is characterized in that: crude fluororubber, maleic anhydride, initiator, vulcanizing agent, promotor are joined in the Banbury mixer, at 120～160 ℃, under the condition of rotating speed 50～100r/min, reaction 10～30min.
2. the preparation method of viton grafted maleic anhydride expanding material according to claim 1 is characterized in that, described crude fluororubber 80～130 weight parts, maleic anhydride 3～8 weight parts, initiator 0.5～2 weight part, vulcanizing agent 0.2～0.5 weight part, promotor 0.1～0.3 weight part.
3. the preparation method of viton grafted maleic anhydride expanding material according to claim 1, it is characterized in that described initiator is one or more of benzoyl peroxide, dilauroyl peroxide, Diisopropyl azodicarboxylate, Potassium Persulphate, dicumyl peroxide or oxidation di-t-butyl.
4. the preparation method of viton grafted maleic anhydride expanding material according to claim 1 is characterized in that, described vulcanizing agent be benzoyl peroxide, BPP, calcium hydroxide or magnesian one or more.
5. the preparation method of viton grafted maleic anhydride expanding material according to claim 1, it is characterized in that, described promotor is 2-benzothiazolyl mercaptan, 2, one or more of 2 '-dithio-bis-benzothiazole, N-cyclohexyl-2-benzothiazole sulfonamide, N tert butyl benzothiazole 2 sulfenamide, tetramethyl-thiuram disulfide, N-cyclohexyl-2-benzene.
6. the preparation method of viton grafted maleic anhydride expanding material according to claim 1 is characterized in that, the percentage of grafting of the viton grafted maleic anhydride expanding material that obtains is 1.5～3.5%.
7. a viton grafted maleic anhydride expanding material is characterized in that, is made by preparation method claimed in claim 1.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201210447767XA CN102936319A (en) | 2012-11-09 | 2012-11-09 | Fluororubber-grated-maleic anhydride bulking agent and preparing method thereof |
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| CN201210447767XA CN102936319A (en) | 2012-11-09 | 2012-11-09 | Fluororubber-grated-maleic anhydride bulking agent and preparing method thereof |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103897314A (en) * | 2014-04-01 | 2014-07-02 | 安庆丰源化工有限公司 | Method for preparing high-performance fluorine rubber |
| CN105086303A (en) * | 2015-08-10 | 2015-11-25 | 安徽锦洋氟化学有限公司 | Fluororubber sealing gasket used for engine and preparation method of fluororubber sealing gasket |
| CN106632868A (en) * | 2016-10-21 | 2017-05-10 | 兰州理工大学 | Maleic anhydride-grafted compatibilizer and its preparation method, and polytetrafluoroethylene composite |
| CN113444208A (en) * | 2021-09-02 | 2021-09-28 | 宁波能之光新材料科技股份有限公司 | Compatilizer of fluorinated ethylene propylene and preparation method and application thereof |
-
2012
- 2012-11-09 CN CN201210447767XA patent/CN102936319A/en active Pending
Non-Patent Citations (1)
| Title |
|---|
| 董丽杰等: "《氟橡胶接枝马来酸酐的研究》", 《特种橡胶制品》 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103897314A (en) * | 2014-04-01 | 2014-07-02 | 安庆丰源化工有限公司 | Method for preparing high-performance fluorine rubber |
| CN105086303A (en) * | 2015-08-10 | 2015-11-25 | 安徽锦洋氟化学有限公司 | Fluororubber sealing gasket used for engine and preparation method of fluororubber sealing gasket |
| CN106632868A (en) * | 2016-10-21 | 2017-05-10 | 兰州理工大学 | Maleic anhydride-grafted compatibilizer and its preparation method, and polytetrafluoroethylene composite |
| CN113444208A (en) * | 2021-09-02 | 2021-09-28 | 宁波能之光新材料科技股份有限公司 | Compatilizer of fluorinated ethylene propylene and preparation method and application thereof |
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Application publication date: 20130220 |