CN106146858B - A kind of tetrapropanate fluorine rubber composition - Google Patents

A kind of tetrapropanate fluorine rubber composition Download PDF

Info

Publication number
CN106146858B
CN106146858B CN201610522832.9A CN201610522832A CN106146858B CN 106146858 B CN106146858 B CN 106146858B CN 201610522832 A CN201610522832 A CN 201610522832A CN 106146858 B CN106146858 B CN 106146858B
Authority
CN
China
Prior art keywords
fluorine rubber
tetrapropanate fluorine
crosslinking agent
tetrapropanate
divinylbenzene
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
CN201610522832.9A
Other languages
Chinese (zh)
Other versions
CN106146858A (en
Inventor
丛川波
孟晓宇
周琼
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
China University of Petroleum Beijing
Original Assignee
China University of Petroleum Beijing
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by China University of Petroleum Beijing filed Critical China University of Petroleum Beijing
Priority to CN201610522832.9A priority Critical patent/CN106146858B/en
Publication of CN106146858A publication Critical patent/CN106146858A/en
Application granted granted Critical
Publication of CN106146858B publication Critical patent/CN106146858B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • 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

Landscapes

  • 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 tetrapropanate fluorine rubber compositions, the composition material based on tetrapropanate fluorine rubber, using organic peroxide as crosslinking agent, using multi-functional crosslinked microsphere as assistant crosslinking agent, the microballoon is divinylbenzene homopolymer microballoon, or divinylbenzene and styrene, acrylate, three kinds one kind of vinylpyridine or two kinds of copolymer microsphere, or using above-mentioned copolymer as core, divinylbenzene is the hud typed crosslinked microsphere of shell, 50nm-100 μm of its diameter, the microballoon can not only be such that tetrapropanate fluorine rubber is crosslinked, and can also improve the processing fluidity of rubber.

Description

A kind of tetrapropanate fluorine rubber composition
Technical field
The present invention relates to a kind of new cross-linking methods of high molecular material, specifically, having invented one kind contains divinylbenzene Polymer microballoon, can be used for being crosslinked tetrapropanate fluorine rubber, obtain 4 third fluorine vulcanizates haveing excellent performance.
Background technique
Tetrapropanate fluorine rubber is the wider polar rubber of scope of use, be can be applied in the hot environment of oil-containing water.4 third fluorine Rubber not only needs main vulcanizing agent in sulfidation, it is necessary to auxiliary curing agent be added, so its vulcanizing system is by peroxidating Object and auxiliary curing agent composition, peroxide are 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 allyl Acid esters (TAIC), triallyl cyanurate (TAC) and polybutadiene, are also proposed novel assistant crosslinking agent recently, such as eight second Alkenyl silsesquioxane (OVPOSS), novel crosslinker use OVPOSS to obtain as assistant crosslinking agent compared with traditional crosslinking agent Vulcanizate in harsh environment have better stability.Compare these types of assistant crosslinking agent, it has been found that second is connected on molecule The compound of alkenyl can become assistant crosslinking agent.The present invention is total using emulsion method or suspension method as monomer using divinylbenzene Poly- or homopolymerization forms various sizes of polymer microballoon, such microsphere surface has vinyl groups, the property class of the group The double bond being similar in OVPOSS and TAIC can be used as assistant crosslinking agent vulcanization tetrapropanate fluorine rubber, the extraordinary vulcanization prepared Glue stability with higher in harsh environment.
Summary of the invention
The present invention relates to a kind of new methods for being crosslinked tetrapropanate fluorine rubber, specifically, by emulsion polymerization or suspending poly- Synthesis different-grain diameter size polymer microballoon, the microsphere surface have vinyl group, can be used to be crosslinked tetrapropanate fluorine rubber.
The present invention it is characterized in that, the composition material based on tetrapropanate fluorine rubber, using organic peroxide as crosslinking agent, Using carbon black as reinforcing filler, using containing divinylbenzene microspheres as assistant crosslinking agent, using stearic acid or its salt as processing aid, group At, by tetrapropanate fluorine rubber be 100 parts by weight in terms of, comprising:
The fluorine content of tetrapropanate fluorine rubber used in it is 54.8~58.3%, and the high polymer main chain of such fluorubber is main It is made of C-F key, there is relatively high stability in harsh environment, such as, Japan AGC be company and upper for specific product Like the tetrapropanate fluorine rubber of rich (3F) company production in sea three.There is no double bond on the strand of this kind of rubber, it is necessary to higher using activity Peroxide and assistant crosslinking agent vulcanized, organic peroxide DCP, BIBP and BPO, dosage is with tetrapropanate fluorine rubber 100 parts by weight meters, preferably 1-6 parts by weight, dosage is excessive, forms excessively crosslinking, and it is unfavorable to generate to the performance of final products It influences, and the residue of peroxide decomposition will affect the performance of tetrapropanate fluorine rubber, therefore peroxide has dosage to be not easy It is more.General auxiliary curing agent uses TAIC or TAC, and there are unstable groups in both compounds can occur in harsh environment Decomposition reaction, and reduce use value of the tetrapropanate fluorine rubber in acidic environment.The present invention, which is used, contains two in more stable Vinyl benzene (DVB) microballoon is assistant crosslinking agent, improves the stability of tetrapropanate fluorine rubber in acid condition, also improves simultaneously The processing fluidity performance of tetrapropanate fluorine rubber.What is used contains divinylbenzene microspheres, mainly passes through emulsion polymerization and suspension Polymerization preparation, which can be the individual copolymer microsphere of DVB, can also be DVB and styrene, acrylate, vinylpyridine One kind or two kinds of copolymer microsphere that three kinds of pyridine, can also be with styrene, acrylate, vinylpyridine polymer For core, DVB is the hud typed crosslinked microsphere of shell, and the common feature of such microballoon is exactly that microsphere surface has vinyl group, can be with Tetrapropanate fluorine rubber forms cross-linked network.According to different polymerizations, the diameter range of such microballoon is 50nm-100 μm, according to The requirement of different crosslink density and the hardness of tetrapropanate fluorine rubber, the dosage of such microballoon are 2-20 parts.In the formula of invention Anti-aging agent is 2-mercaptobenzimidazole and 2, and the compound system of 2,4- trimethyl -1,2- dihyaroquinolines, dosage is respectively 0.5-2 Part.In order to obtain suitable hardness and higher tensile strength, elongation at break, the present invention using different-grain diameter carbon black or Other fillers carry out reinforcement, to meet the needs of different.
Specific embodiment
1. different types of crosslinked microsphere
Table 1
aThe diameter of crosslinked microsphere is 500nm, and dosage is 10 parts
Table 2
bIt can not be crosslinked
2. the influence of crosslinked microsphere diameter
Table 3
cThe dosage of crosslinked microsphere is 10 parts
Table 4
3. crosslinked microsphere dosage changes
Table 3
cThe dosage of crosslinked microsphere is 10 parts
Table 4

Claims (5)

1. a kind of tetrapropanate fluorine rubber composition, characterized in that the composition material based on tetrapropanate fluorine rubber, with organic peroxy Compound is crosslinking agent, using the microballoon containing poly- divinylbenzene as assistant crosslinking agent, using hard (carbon) black as reinforcing filler, with 4 third fluorine rubbers Glue is 100 parts by weight meters, comprising:
Tetrapropanate fluorine rubber 100
Anti-aging agent 1-4
Stearate 1-2
Organic peroxide 1-6
Reinforcing filler 15-80
Assistant crosslinking agent 2-20；
The assistant crosslinking agent is the crosslinked microsphere that surface has vinyl group, and composition is divinylbenzene homopolymer microballoon； Divinylbenzene and styrene, acrylate, three kinds one kind of vinylpyridine or two kinds of copolymer microsphere；Or Using above-mentioned copolymer as core, divinylbenzene is the hud typed crosslinked microsphere of shell.
2. tetrapropanate fluorine rubber composition according to claim 1, characterized in that the fluorine content of the tetrapropanate fluorine rubber is 54.8~58.3wt%。
3. tetrapropanate fluorine rubber composition according to claim 1, characterized in that the reinforcing filler is hard (carbon) black N330 and/or N550.
4. tetrapropanate fluorine rubber composition according to claim 1, characterized in that the organic peroxide is peroxidating One of diisopropylbenzene (DIPB) (DCP), dual-tert-butyl dicumyl peroxide (BIBP) and benzoyl peroxide (BPO) are a variety of Be used in combination.
5. tetrapropanate fluorine rubber composition according to claim 1-4, characterized in that the microballoon of the 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)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201610522832.9A CN106146858B (en) 2016-07-05 2016-07-05 A kind of tetrapropanate fluorine rubber composition

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201610522832.9A CN106146858B (en) 2016-07-05 2016-07-05 A kind of tetrapropanate fluorine rubber composition

Publications (2)

Publication Number Publication Date
CN106146858A CN106146858A (en) 2016-11-23
CN106146858B true CN106146858B (en) 2019-02-12

Family

ID=58061869

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201610522832.9A Active CN106146858B (en) 2016-07-05 2016-07-05 A kind of tetrapropanate fluorine rubber composition

Country Status (1)

Country Link
CN (1) CN106146858B (en)

Families Citing this family (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)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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.
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
CN102617959A (en) * 2011-03-30 2012-08-01 中国石油化工股份有限公司 Sulfur-resistant rubber composition

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
《VULCANIZATION OF A FLUOROELASTOMER DERIVED FROM TETRAFLUOROETHYLENE AND PROPYLENE》;Kojima G, Wachi H;《Rubber Chemistry & Technology》;19781231;第51卷(第5期);全文
《四氟乙烯-丙烯共聚橡胶组成对其结构和力学性能的影响》;左威武, 包永忠, 刘进朝,等;《化工生产与技术》;20151231;第22卷(第4期);全文
四氟乙烯-丙烯共聚橡胶的制备、结构和性能;左威武;《中国优秀硕士学位论文全文数据库（电子期刊）.工程科技I辑》;20160215;全文

Also Published As

Publication number Publication date
CN106146858A (en) 2016-11-23

Similar Documents

Publication Publication Date Title
CN101338047B (en) Low rigidity, low compression permanent deformation cold tolerant butadiene nitrile rubber compositions
KR101150016B1 (en) Styrenic themoplastic resin compositions with good mechanical properties and low gloss
KR20180073062A (en) Thermoplastic resin composition, method for preparing the resin composition and molding product comprising the resin composition
CN105355312B (en) A kind of ageing-resistant power cable of oil resistant
TW201945425A (en) Additive for rubbers, uncrosslinked rubber composition, crosslinked rubber and tire
JP2016006135A (en) Rubber composition and pneumatic tire using the same
CN106146858B (en) A kind of tetrapropanate fluorine rubber composition
JP2008222845A (en) Rubber composition for tire
CN106009440B (en) A kind of tetrapropanate fluorine rubber composition
KR101817435B1 (en) SBR rubber and the tire using this
KR100962630B1 (en) Rubber composition for low heat build up under tread
KR100733927B1 (en) Impact strength modifiers for polyvinyl chloride and preparation method thereof
CN106117926B (en) With the method for poly- 1,2 butadiene rubber crosslinking and reinforcement tetrapropanate fluorine rubber
JP4168189B2 (en) Composite of acrylic rubber and fluororubber, method for producing the same, and vulcanizable rubber composition
KR20190017766A (en) Rubber composition and molded article
JP2021515831A (en) A core-shell copolymer, a method for producing the same, and a thermoplastic resin composition containing the same.
KR102143893B1 (en) Compositions, containing thermoplastics based on polyvinyl chloride and containing cross-linked nbr microgels modified with hydroxyl groups
KR101584844B1 (en) Method of preparing alkyl acrylate-vinyl aromatic compound-vinylcyan compound copolymer and thermoplastic resin composition comprising the same having excellent impact strength
KR101620134B1 (en) Graft copolymer using water-soluble comonomer and method of preparing the same and polyvinyl chloride resin composition comprising copolymer
Chuayjujit et al. Preparation of thermoplastic elastomer from epoxidised natural rubber and polystyrene
KR101775749B1 (en) Modifier for rubber composition, manufacturing method thereof and rubber composition comprising the modifier
JP6641402B2 (en) Curable elastomer composition
JP4742406B2 (en) Thermoplastic resin composition
KR20100113841A (en) Impact strength modifiers for thermoplastic polyester and thermoplastic resin composition containing the same
KR101200644B1 (en) Multi-layered rubber copolymer having good resistance to whitening and preparation method thereof

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant