CN104530719A - Vinyl blocked poly(trifluoropropyl)methylsiloxane fluororubber compatibilizer and preparation method thereof - Google Patents

Vinyl blocked poly(trifluoropropyl)methylsiloxane fluororubber compatibilizer and preparation method thereof Download PDF

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Publication number
CN104530719A
CN104530719A CN201410831578.1A CN201410831578A CN104530719A CN 104530719 A CN104530719 A CN 104530719A CN 201410831578 A CN201410831578 A CN 201410831578A CN 104530719 A CN104530719 A CN 104530719A
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China
Prior art keywords
viton
parts
trifluoro propyl
fluororubber
methyl trifluoro
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CN201410831578.1A
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Chinese (zh)
Inventor
杜明欣
杜华太
张志刚
张春梅
崔俞
宫志欣
邹德广
庞明磊
张斌
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No 53 Institute of China North Industries Group Corp
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No 53 Institute of China North Industries Group Corp
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Priority to CN201410831578.1A priority Critical patent/CN104530719A/en
Publication of CN104530719A publication Critical patent/CN104530719A/en
Pending legal-status Critical Current

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Abstract

The invention belongs to the technical field of rubber materials. By introducing vinyl blocked poly(trifluoropropyl)methylsiloxane on a main chain of fluororubber, the purpose of improving the compatibility of blend of fluororubber and fluorinated silicone rubber is realized by means of the characteristic that vinyl blocked poly(trifluoropropyl)methylsiloxane is compatible with fluororubber and fluorinated silicone rubber. Meanwhile, crosslinking reaction is carried out on unreacted vinyl and fluorinated silicone rubber, so that reactive compatibilization is realized. The invention relates to a fluororubber-vinyl blocked poly(trifluoropropyl)methylsiloxane compatibilizer which at least comprises the following materials in parts by weight: 100 parts of fluororubber, 3-15 parts of vinyl blocked poly(trifluoropropyl)methylsiloxane, 0.5-2 parts of an initiator and 0.2-1.5 parts of an accelerant. The fluororubber-vinyl blocked poly(trifluoropropyl)methylsiloxane compatibilizer prepared by using a high-temperature mechanochemical grafting method has good compatibility with fluororubber and fluorinated silicone rubber, so that the compatibilization effect is obvious and stable.

Description

Ethenyl blocking gathers methyl trifluoro propyl siloxanes fluorine glue expanding material and preparation method
Technical field
The invention belongs to technical field of rubber material, relate to fluorine/trifluoropropyl siloxane blend modification technology, particularly fluorine/trifluoropropyl siloxane capacity increasing technique.
Background technology
Viton has excellent thermotolerance, ozone resistance, oil-proofness, chemical resistance and resistance to gas permeability.The industries such as aerospace, army material, motor vehicles for civilian use manufacture can be widely used in.But owing to containing fluorine atom in viton molecular chain, its molecular chain rigidity is large, makes viton there is resistance to low temperature difference, seriously constrains the use range of viton material.
Trifluoropropyl siloxane main chain is-Si-O-, and Chain Flexibility is good, main chain bond energy is high, and have excellent high and low temperature resistance, side chain is methyl and trifluoro propyl, has good medium-resistance, and its medium-resistance is only second to the material such as viton, paracril.
Adopt viton and trifluoropropyl siloxane blended, obviously can improve the resistance to low temperature of viton.Because viton belongs to charcoal chain polymer, trifluoropropyl siloxane is silicon-oxygen backbone polymer, does not possess thermodynamic compatibility between two-phase, consistency is to each other poor, microcosmic point is difficult to form molecular level blended, blended rear phase interface bonding effect power is less, and blend mechanical property is not high.
Adopt suitable expanding material, the consistency of viton and trifluoropropyl siloxane can be improved, improve dispersion effect and accelerate rate of dispersion, improving the mechanical property of viton/trifluoropropyl siloxane blend.
CN 102936319 discloses a kind of viton grafted maleic anhydride expanding material and preparation method thereof, and this patent is reactive grafting maleic anhydride on viton molecular chain, for improving viton and acrylic elastomer comixing compatibility.Specifically join in Banbury mixer by crude fluororubber, maleic anhydride, initiator etc., at 120 ~ 160 DEG C, under the condition of rotating speed 50 ~ 100r/min, reaction 10 ~ 30min, obtains viton grafted maleic anhydride expanding material.This expanding material is mainly used in viton/acrylate blend glue, powerful interaction can be there is with the carbonyl in polar acrylate's rubber/carboxyl isopolarity group, can also react with the polar group of acrylic elastomer (amino, hydroxyl) and epoxy group(ing) simultaneously, the effect of realization response increase-volume.
Have no about viton/trifluoropropyl siloxane Blend rubber viton-ethenyl blocking gathers the report of methyl trifluoro propyl siloxanes expanding material.
Summary of the invention
The object of the invention is to the defect existed for prior art, a kind of viton and trifluoropropyl siloxane expanding material and preparation method thereof are provided.
The object of the present invention is achieved like this, viton (FR) main chain is introduced the poly-methyl trifluoro propyl siloxanes (FMQ) of ethenyl blocking, utilize the feature that itself and viton and trifluoropropyl siloxane all can be well compatible, reach the object improving viton/trifluoropropyl siloxane Blend rubber consistency, simultaneously unreacted vinyl in sulfidation can with trifluoropropyl siloxane generation crosslinking reaction, the object of realization response increase-volume.
Viton-the ethenyl blocking that the present invention relates to gathers methyl trifluoro propyl siloxanes expanding material, and quality of materials composition at least comprises:
Viton 100 parts
Ethenyl blocking gathers methyl trifluoro propyl siloxanes 3 ~ 15 parts
Initiator 0.5 ~ 2 part
Promotor 0.2 ~ 1.5 part
Wherein, described viton is containing one or more the compound system in olefin rubber, fluorine ethers rubber; The molecular weight that described ethenyl blocking gathers methyl trifluoro propyl siloxanes is 2000 ~ 20000; Described initiator is one or more in benzoyl peroxide, 2,4-dichlorobenzoperoxides, dicumyl peroxide, 2,5-dimethyl-2,5-di-t-butyl hexane peroxides; Described promotor is cyanacrylate or triallylcyanurate.
Viton-the ethenyl blocking that the present invention relates to gathers methyl trifluoro propyl siloxanes expanding material, and for ethenyl blocking gathers the polysiloxane grafted viton of methyl trifluoro propyl, raw material quality composition at least comprises:
Viton 100 parts
Ethenyl blocking gathers methyl trifluoro propyl siloxanes 5 ~ 15 parts
Initiator 0.5 ~ 1.5 part
Promotor 0.2 ~ 1 part.
Viton-the ethenyl blocking that the present invention relates to gathers methyl trifluoro propyl siloxanes expanding material (FR-g-FMQ), adopt the preparation of high temperature mechanochemical grafting method, in Haake torque rheometer or Banbury mixer 110 ~ 170 DEG C, under the condition of rotating speed 30 ~ 100r/min, reaction 10 ~ 35min, the viton-ethenyl blocking obtaining the present invention relates to gathers methyl trifluoro propyl siloxanes expanding material.
The viton grafting vinyl end-blocking that the present invention relates to gathers methyl trifluoro propyl siloxanes expanding material, with the consistency of viton and trifluoropropyl siloxane is good, compatibilization ability is strong, can significantly improve the mechanical properties such as the tensile strength of Blend rubber, tensile yield, compatibilization effect is obvious.Be applicable to viton and the blended increase-volume of trifluoropropyl siloxane.
Embodiment
Below in conjunction with embodiment, not add the viton/trifluoropropyl siloxane (for 7.1MPa, elongation is 205% to tensile strength, and shore a hardness is 63 degree) of expanding material for contrast, the technical scheme that the present invention relates to and compatibilization effect are further described, but not as the restriction to summary of the invention.
Do not do in embodiment illustrate be mass parts.
embodiment one
By viton FE2602 rubber 100 parts, ethenyl blocking gathers methyl trifluoro propyl siloxanes (molecular weight 2000) 3 parts, benzoyl peroxide 0.5 part, cyanacrylate 0.2 part joins in Banbury mixer evenly mixing, under the condition of temperature temperature 110 DEG C, rotating speed 30r/min, reaction 10min, obtains viton grafting vinyl end-blocking and gathers methyl trifluoro propyl siloxanes.
The tensile strength adding the viton/trifluoropropyl siloxane Blend rubber of 3 parts of these embodiment expanding materials is 7.5MPa, and elongation is 240%, and shore a hardness is 64 degree.
embodiment two
By viton FE2462 rubber 100 parts, ethenyl blocking gathers methyl trifluoro propyl siloxanes (molecular weight 6000) 5 parts, 2,4-dichlorobenzoperoxide 1 part, cyanacrylate 0.5 part joins in Haake torque rheometer evenly mixing, under the condition of temperature temperature 130 DEG C, rotating speed 50r/min, reaction 30min, obtains viton grafting vinyl end-blocking and gathers methyl trifluoro propyl siloxanes.
The tensile strength adding the viton/trifluoropropyl siloxane Blend rubber of 5 parts of these embodiment expanding materials is 7.7MPa, and elongation is 255%, and shore a hardness is 64 degree.
embodiment three
By fluoroether rubber PL855 rubber 100 parts, ethenyl blocking gathers methyl trifluoro propyl siloxanes (molecular weight 20000) 10 parts, dicumyl peroxide 2 parts, triallylcyanurate 1 part joins in Haake torque rheometer evenly mixing, under the condition of temperature temperature 140 DEG C, rotating speed 80r/min, reaction 20min, obtains viton grafting vinyl end-blocking and gathers methyl trifluoro propyl siloxanes.
The tensile strength adding the viton/trifluoropropyl siloxane Blend rubber of 8 parts of these embodiment expanding materials is 8.2MPa, and elongation is 245%, and shore a hardness is 65 degree.
embodiment four
By viton FE2602 rubber 80 parts, viton FE2462 rubber 20 parts, ethenyl blocking gathers methyl trifluoro propyl siloxanes (molecular weight 5000) 15 parts, 2,5-dimethyl-2,5-di-t-butyl hexane peroxide 0.8 part, triallylcyanurate 1.5 parts joins in Haake torque rheometer evenly mixing, under the condition of temperature temperature 170 DEG C, rotating speed 100r/min, reaction 15min, obtains viton grafting vinyl end-blocking and gathers methyl trifluoro propyl siloxanes.
The tensile strength adding the viton/trifluoropropyl siloxane Blend rubber of 10 parts of these embodiment expanding materials is 7.7MPa, and elongation is 260%, and shore a hardness is 66 degree.
embodiment five
By viton FE2462 rubber 80 parts, fluoroether rubber PL855 rubber 20 parts, ethenyl blocking gathers methyl trifluoro propyl siloxanes (molecular weight 5000) 8 parts, 2,4-dichlorobenzoperoxide 1 part, benzoyl peroxide 0.5 part, triallylcyanurate 2 parts joins in Haake torque rheometer evenly mixing, under the condition of temperature temperature 120 DEG C, rotating speed 70r/min, reaction 35min, obtains viton grafting vinyl end-blocking and gathers methyl trifluoro propyl siloxanes.
The tensile strength adding the viton/trifluoropropyl siloxane Blend rubber of 8 parts of these embodiment expanding materials is 9.1MPa, and elongation is 310%, and shore a hardness is 65 degree.
embodiment six
By fluoroether rubber Viton GLT rubber 80, fluoroether rubber PL855 rubber 20 parts, hydroxy terminated fluorosilicone oil 5 parts, ethenyl blocking gathers methyl trifluoro propyl siloxanes (molecular weight 15000) 12 parts, 2,4-dichlorobenzoperoxide 0.7 part, dicumyl peroxide 1 part, triallylcyanurate 0.8 part joins in Haake torque rheometer evenly mixing, under the condition of temperature temperature 160 DEG C, rotating speed 90r/min, reaction 25min, obtains viton grafting vinyl end-blocking and gathers methyl trifluoro propyl siloxanes.
The tensile strength adding the viton/trifluoropropyl siloxane Blend rubber of 8 parts of these embodiment expanding materials is 8.3MPa, and elongation is 270%, and shore a hardness is 66 degree.

Claims (3)

1. viton-ethenyl blocking gathers a methyl trifluoro propyl siloxanes expanding material, and quality of materials composition at least comprises:
Viton 100 parts
Ethenyl blocking gathers methyl trifluoro propyl siloxanes 3 ~ 15 parts
Initiator 0.5 ~ 2 part
Promotor 0.2 ~ 1.5 part;
Wherein, described viton is containing one or more the compound system in olefin rubber, fluorine ethers rubber; The molecular weight that described ethenyl blocking gathers methyl trifluoro propyl siloxanes is 2000 ~ 20000; Described initiator is one or more in benzoyl peroxide, 2,4-dichlorobenzoperoxides, dicumyl peroxide, 2,5-dimethyl-2,5-di-t-butyl hexane peroxides; Described promotor is cyanacrylate or triallylcyanurate.
2. viton-ethenyl blocking according to claim 1 gathers methyl trifluoro propyl siloxanes expanding material, and raw material quality composition at least comprises:
Viton 100 parts
Ethenyl blocking gathers methyl trifluoro propyl siloxanes 5 ~ 15 parts
Initiator 0.5 ~ 1.5 part
Promotor 0.2 ~ 1 part.
3. any one viton-ethenyl blocking according to claim 1 and 2 gathers the preparation method of methyl trifluoro propyl siloxanes expanding material, adopt the preparation of high temperature mechanochemical grafting method, in Haake torque rheometer or Banbury mixer 110 ~ 170 DEG C, under the condition of rotating speed 30 ~ 100r/min, reaction 10 ~ 35min, the viton-ethenyl blocking obtaining the present invention relates to gathers methyl trifluoro propyl siloxanes expanding material.
CN201410831578.1A 2014-12-29 2014-12-29 Vinyl blocked poly(trifluoropropyl)methylsiloxane fluororubber compatibilizer and preparation method thereof Pending CN104530719A (en)

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108473685A (en) * 2016-01-20 2018-08-31 国立大学法人御茶水女子大学 fluorine-containing silicon-containing compound
CN109734924A (en) * 2019-01-15 2019-05-10 安徽大学 A kind of rubber blending macromolecular expanding material and its preparation method and application
CN111073304A (en) * 2019-12-31 2020-04-28 山东华夏神舟新材料有限公司 Fluorosilicone rubber composition and preparation method thereof
CN116209685A (en) * 2020-09-04 2023-06-02 大金美国股份有限公司 Reactive fluoropolymer compatibilizers and uses thereof

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101412835A (en) * 2008-11-28 2009-04-22 华南理工大学 Blend of fluorubber and silastic, and preparation thereof
CN102617956A (en) * 2012-03-30 2012-08-01 青岛科技大学 Fluorine rubber, silicone rubber and fluorinated silicone rubber ter-blending high/low temperature resistant oil-proof material and preparation method thereof
CN103601940A (en) * 2013-10-28 2014-02-26 青岛嘉利福环保科技有限公司 Oil resistant rubber tube for floor scrubbing machine

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101412835A (en) * 2008-11-28 2009-04-22 华南理工大学 Blend of fluorubber and silastic, and preparation thereof
CN102617956A (en) * 2012-03-30 2012-08-01 青岛科技大学 Fluorine rubber, silicone rubber and fluorinated silicone rubber ter-blending high/low temperature resistant oil-proof material and preparation method thereof
CN103601940A (en) * 2013-10-28 2014-02-26 青岛嘉利福环保科技有限公司 Oil resistant rubber tube for floor scrubbing machine

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108473685A (en) * 2016-01-20 2018-08-31 国立大学法人御茶水女子大学 fluorine-containing silicon-containing compound
US10745524B2 (en) * 2016-01-20 2020-08-18 Ochanomizu University Fluorine-containing and silicon containing compound
CN108473685B (en) * 2016-01-20 2021-07-16 国立大学法人御茶水女子大学 Fluorine-containing silicon-containing compound
CN109734924A (en) * 2019-01-15 2019-05-10 安徽大学 A kind of rubber blending macromolecular expanding material and its preparation method and application
CN111073304A (en) * 2019-12-31 2020-04-28 山东华夏神舟新材料有限公司 Fluorosilicone rubber composition and preparation method thereof
CN116209685A (en) * 2020-09-04 2023-06-02 大金美国股份有限公司 Reactive fluoropolymer compatibilizers and uses thereof

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Application publication date: 20150422