CN106146858A - The method of polymer microballoon crosslinking 4 third fluorubber containing polydivinylbenezene - Google Patents

The method of polymer microballoon crosslinking 4 third fluorubber containing polydivinylbenezene Download PDF

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Publication number
CN106146858A
CN106146858A CN201610522832.9A CN201610522832A CN106146858A CN 106146858 A CN106146858 A CN 106146858A CN 201610522832 A CN201610522832 A CN 201610522832A CN 106146858 A CN106146858 A CN 106146858A
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microsphere
fluorubber
fluoro
dvb
rubber composites
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CN106146858B (en
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丛川波
孟晓宇
周琼
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China University of Petroleum Beijing
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China University of Petroleum Beijing
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G81/00—Macromolecular compounds obtained by interreacting polymers in the absence of monomers, e.g. block polymers
    • C08G81/02—Macromolecular compounds obtained by interreacting polymers in the absence of monomers, e.g. block polymers at least one of the polymers being obtained by reactions involving only carbon-to-carbon unsaturated bonds
    • C08G81/021—Block or graft polymers containing only sequences of polymers of C08C or C08F
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K13/00—Use of mixtures of ingredients not covered by one single of the preceding main groups, each of these compounds being essential
    • C08K13/02—Organic and inorganic ingredients
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/02—Elements
    • C08K3/04—Carbon
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/09—Carboxylic acids; Metal salts thereof; Anhydrides thereof
    • C08K5/098—Metal salts of carboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/34—Heterocyclic compounds having nitrogen in the ring
    • C08K5/3412—Heterocyclic compounds having nitrogen in the ring having one nitrogen atom in the ring
    • C08K5/3432—Six-membered rings
    • C08K5/3437—Six-membered rings condensed with carbocyclic rings
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/36—Sulfur-, selenium-, or tellurium-containing compounds
    • C08K5/37—Thiols

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

The present invention relates to a kind of 4 third fluoro-rubber composites, said composition is with 4 third fluorubber as material of main part, with organic peroxide as cross-linking agent, with multi-functional crosslinked microsphere as assistant crosslinking agent, described microsphere is the single copolymer microsphere of DVB, or DVB and styrene, acrylate, a kind of or copolymer microsphere of two kinds of vinylpyridine three kinds, or with above-mentioned copolymer as core, DVB is the hud typed crosslinked microsphere of shell, its diameter 50nm 100 μm, this microsphere not only can make 4 third crosslinked fluororubbers, it is also possible to improves the processing fluidity of rubber.

Description

The method of polymer microballoon crosslinking 4 third fluorubber containing polydivinylbenezene
Technical field
The present invention relates to a kind of new cross-linking method of macromolecular material, specifically, invented a class and contained divinylbenzene Polymer microballoon, can be used for cross-linking 4 third fluorubber, it is thus achieved that 4 third fluorine vulcanizates of excellent performance.
Background technology
4 third fluorubber are the polar rubbers that purposes scope is wider, can be applicable in the hot environment of oil-containing water.4 third fluorine Rubber, in sulfidation, not only needs main vulcanizing agent, it is necessary to add auxiliary curing agent, so its vulcanizing system is by peroxidating Thing and auxiliary curing agent composition, peroxide is generally cumyl peroxide (DCP), dual-tert-butyl cumyl peroxide (BIBP) and some peroxide such as benzoyl peroxide (BPO), and traditional auxiliary curing agent is mainly the different melamine of pi-allyl Acid esters (TAIC), triallyl cyanurate (TAC) and polybutadiene, be the most also proposed novel assistant crosslinking agent, such as eight second Thiazolinyl silsesquioxane (OVPOSS), novel crosslinker, compared with traditional cross-linking agent, obtains as assistant crosslinking agent with OVPOSS Vulcanizate there is in severe rugged environment more preferable stability.Contrast this several assistant crosslinking agents, it has been found that on molecule, be connected with second The compound of thiazolinyl can become assistant crosslinking agent.The present invention uses divinylbenzene to use emulsion method or suspension method altogether as monomer Gathering or homopolymerization forms various sizes of polymer microballoon, such microsphere surface is with vinyl groups, the character class of this group The double bond being similar in OVPOSS and TAIC, can be used as assistant crosslinking agent sulfuration 4 third fluorubber, the extraordinary sulfuration prepared Glue has higher stability in severe rugged environment.
Summary of the invention
The present invention relates to the new method of a kind of crosslinking 4 third fluorubber, specifically, be polymerized by emulsion or suspend poly- Synthesis different-grain diameter size polymer microsphere, this microsphere surface, with vinyl group, can be used to cross-link 4 third fluorubber.
The present invention is characterized in that, said composition is with 4 third fluorubber as material of main part, with organic peroxide as cross-linking agent, With white carbon black as reinforcer, with containing divinylbenzene microspheres as assistant crosslinking agent, with stearic acid or its salt as processing aid, its group Become, be in terms of 100 weight portions by 4 third fluorubber, including:
The Oil repellent of 4 third fluorubber wherein used is 54.8～58.3%, and the high polymer main chain of such fluorubber is main Be made up of C-F key, severe rugged environment have the stability that comparison is high, specific product such as, Japan AGC company and upper 4 third fluorubber that rich (3F) company produces are liked in sea three.Double bond is not had, it is necessary to use activity higher on the strand of this kind of rubber Peroxide and assistant crosslinking agent vulcanize, organic peroxide is DCP, BIBP and BPO, and consumption with 4 third fluorubber is 100 weight portion meters, preferably 1-6 weight portion, consumption is too much, forms excessively crosslinking, and it is unfavorable all to produce the performance of final products Affecting, and the residue of peroxide decomposition can affect the performance of 4 third fluorubber, therefore peroxide has consumption to be difficult to Many.General auxiliary curing agent uses TAIC or TAC, and the group that there is instability in both compounds can occur in severe rugged environment Decomposition reaction, and reduce 4 third fluorubber use value in sour environment.The present invention uses more stable containing two Vinyl benzene (DVB) microsphere is assistant crosslinking agent, improves 4 third fluorubber stability in acid condition, also improves simultaneously The processing fluidity performance of 4 third fluorubber.Use containing divinylbenzene microspheres, be mainly polymerized by emulsion and suspend Polymerization preparation, but the single copolymer microsphere of this microsphere DVB, it is possible to it is DVB and styrene, acrylate, vinylpyridine A kind of or the copolymer microsphere of two kinds of pyridine three kinds, it is also possible to be with styrene, acrylate, the polymer of vinylpyridine For core, DVB is the hud typed crosslinked microsphere of shell, and the common feature of such microsphere is exactly that microsphere surface has vinyl group, can be with 4 third fluorubber form cross-linked network.According to different polymerizations, the diameter range of such microsphere is 50nm-100 μm, according to The different crosslink density of 4 third fluorubber and the requirement of hardness, the consumption of such microsphere is 2-20 part.In the formula of invention Age resistor is 2-mercaptobenzimidazole and 2,2,4-trimethyl-1, the compound system of 2-dihyaroquinoline, and its consumption is respectively 0.5-2 Part.In order to obtain suitable hardness and higher hot strength, elongation at break, the present invention use different-grain diameter carbon black or Other fillers carry out reinforcement, to meet different demands.
Detailed description of the invention
The most different types of crosslinked microsphere
Table 1
aA diameter of 500nm of crosslinked microsphere, consumption is 10 parts
Table 2
bCannot cross-link
2. the impact of crosslinked microsphere diameter
Table 3
cThe consumption of crosslinked microsphere is 10 parts
Table 4
3. crosslinked microsphere consumption change
Table 3
cThe consumption of crosslinked microsphere is 10 parts
Table 4

Claims (6)

1. 4 third fluoro-rubber composites, is characterized in that, said composition is with 4 third fluorine as material of main part, with organic peroxide For cross-linking agent, with the microsphere containing poly-divinylbenzene as assistant crosslinking agent, with hard (carbon) black as reinforcer, with 4 third fluorubber it is 100 weight portion meters, including:
4 third fluoro-rubber composites the most according to claim 1, is characterized in that, the Oil repellent of described 4 third fluorubber is 54.8～58.3wt%.
4 third fluoro-rubber composites the most according to claim 1, is characterized in that, described reinforcer is hard (carbon) black N330 and/or N550.
4 third fluoro-rubber composites the most according to claim 1, is characterized in that, described organic peroxide is peroxidating One or more in diisopropylbenzene (DIPB) (DCP), dual-tert-butyl dicumyl peroxide (BIBP) and benzoyl peroxide (BPO) And use.
4 third fluoro-rubber composites the most according to claim 1, is characterized in that, described assistant crosslinking agent is that surface is with second The crosslinked microsphere of thiazolinyl group, but the single copolymer microsphere of its composition DVB, it is possible to be DVB and styrene, acrylate, second A kind of or the copolymer microsphere of two kinds of thiazolinyl pyridine three kinds, it is also possible to be with above-mentioned copolymer as core, DVB is the nucleocapsid of shell Type crosslinked microsphere.
6., according to 4 third fluoro-rubber composites described in any one of claim 1-5, it is characterized in that, the microsphere of described assistant crosslinking agent Diameter range is 50nm-100 μm.
CN201610522832.9A 2016-07-05 2016-07-05 A kind of tetrapropanate fluorine rubber composition Active CN106146858B (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109721898A (en) * 2017-10-30 2019-05-07 中国石油化工股份有限公司 4 third fluorine vulcanizates of one kind and preparation method thereof

Citations (6)

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JPS51145482A (en) * 1975-06-10 1976-12-14 Teijin Ltd Ion exchange membrane
IT1125443B (en) * 1978-10-07 1986-05-14 Daikin Ind Ltd COMPOSITION OF MORTGAGE SUSCEPTABLE MIXTURES TRANSVERSAL LINK INCLUDING A FLUOROELASTOMER CONTAINING IODINE
IT1206517B (en) * 1983-09-07 1989-04-27 Montedison Spa COMPOSITIONS COVULCANISABLE FROM FLUOROELASTOMERS BASED ON VINYLIDENE FLUORIDE AND TETRAFLUOEOETHYLENE-PROPYLENE COPOLYMERS.
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CN102250437A (en) * 2011-06-29 2011-11-23 中国石油大学(北京) Acidproof, alkali-proof and hydrogen-sulphide-corrosion-resistant aflas composite
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JPS51145482A (en) * 1975-06-10 1976-12-14 Teijin Ltd Ion exchange membrane
IT1125443B (en) * 1978-10-07 1986-05-14 Daikin Ind Ltd COMPOSITION OF MORTGAGE SUSCEPTABLE MIXTURES TRANSVERSAL LINK INCLUDING A FLUOROELASTOMER CONTAINING IODINE
IT1206517B (en) * 1983-09-07 1989-04-27 Montedison Spa COMPOSITIONS COVULCANISABLE FROM FLUOROELASTOMERS BASED ON VINYLIDENE FLUORIDE AND TETRAFLUOEOETHYLENE-PROPYLENE COPOLYMERS.
CN102617959A (en) * 2011-03-30 2012-08-01 中国石油化工股份有限公司 Sulfur-resistant rubber composition
CN102219977A (en) * 2011-04-29 2011-10-19 南通普力马弹性体技术有限公司 Micro-crosslinking thermoplastic elastomer
CN102250437A (en) * 2011-06-29 2011-11-23 中国石油大学(北京) Acidproof, alkali-proof and hydrogen-sulphide-corrosion-resistant aflas composite

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KOJIMA G, WACHI H: "《VULCANIZATION OF A FLUOROELASTOMER DERIVED FROM TETRAFLUOROETHYLENE AND PROPYLENE》", 《RUBBER CHEMISTRY & TECHNOLOGY》 *
左威武, 包永忠, 刘进朝,等: "《四氟乙烯-丙烯共聚橡胶组成对其结构和力学性能的影响》", 《化工生产与技术》 *
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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109721898A (en) * 2017-10-30 2019-05-07 中国石油化工股份有限公司 4 third fluorine vulcanizates of one kind and preparation method thereof

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