CN108912515A - A kind of ageing-resistant ship rubber fender and preparation method thereof - Google Patents
A kind of ageing-resistant ship rubber fender and preparation method thereof Download PDFInfo
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- CN108912515A CN108912515A CN201810847453.6A CN201810847453A CN108912515A CN 108912515 A CN108912515 A CN 108912515A CN 201810847453 A CN201810847453 A CN 201810847453A CN 108912515 A CN108912515 A CN 108912515A
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- 229920001971 elastomer Polymers 0.000 title claims abstract description 85
- 239000005060 rubber Substances 0.000 title claims abstract description 85
- 230000032683 aging Effects 0.000 title claims abstract description 26
- 238000002360 preparation method Methods 0.000 title claims abstract description 23
- 239000000835 fiber Substances 0.000 claims abstract description 47
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 28
- 238000004073 vulcanization Methods 0.000 claims abstract description 25
- 238000002156 mixing Methods 0.000 claims abstract description 22
- 239000004734 Polyphenylene sulfide Substances 0.000 claims abstract description 21
- 229920000069 polyphenylene sulfide Polymers 0.000 claims abstract description 21
- 239000007822 coupling agent Substances 0.000 claims abstract description 20
- 229920006389 polyphenyl polymer Polymers 0.000 claims abstract description 20
- 150000003568 thioethers Chemical class 0.000 claims abstract description 20
- 239000005062 Polybutadiene Substances 0.000 claims abstract description 19
- 239000003242 anti bacterial agent Substances 0.000 claims abstract description 19
- 229920005549 butyl rubber Polymers 0.000 claims abstract description 19
- 229920002857 polybutadiene Polymers 0.000 claims abstract description 19
- 239000004408 titanium dioxide Substances 0.000 claims abstract description 14
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000005864 Sulphur Substances 0.000 claims abstract description 13
- GTTSNKDQDACYLV-UHFFFAOYSA-N Trihydroxybutane Chemical compound CCCC(O)(O)O GTTSNKDQDACYLV-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000005995 Aluminium silicate Substances 0.000 claims abstract description 8
- 235000012211 aluminium silicate Nutrition 0.000 claims abstract description 8
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 claims abstract description 8
- 229920001296 polysiloxane Polymers 0.000 claims abstract description 8
- 239000004615 ingredient Substances 0.000 claims abstract description 7
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 claims description 18
- 229910052901 montmorillonite Inorganic materials 0.000 claims description 18
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 13
- 239000003963 antioxidant agent Substances 0.000 claims description 12
- 230000003078 antioxidant effect Effects 0.000 claims description 12
- 239000002131 composite material Substances 0.000 claims description 12
- 150000001875 compounds Chemical class 0.000 claims description 12
- 238000007670 refining Methods 0.000 claims description 12
- 239000002689 soil Substances 0.000 claims description 12
- 238000003756 stirring Methods 0.000 claims description 12
- 238000000465 moulding Methods 0.000 claims description 10
- 239000000203 mixture Substances 0.000 claims description 8
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 7
- 235000021355 Stearic acid Nutrition 0.000 claims description 7
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 claims description 7
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 claims description 7
- 239000008117 stearic acid Substances 0.000 claims description 7
- XOOUIPVCVHRTMJ-UHFFFAOYSA-L zinc stearate Chemical compound [Zn+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O XOOUIPVCVHRTMJ-UHFFFAOYSA-L 0.000 claims description 7
- 238000001354 calcination Methods 0.000 claims description 6
- 238000001816 cooling Methods 0.000 claims description 6
- 238000005470 impregnation Methods 0.000 claims description 6
- ODUCDPQEXGNKDN-UHFFFAOYSA-N nitroxyl Chemical compound O=N ODUCDPQEXGNKDN-UHFFFAOYSA-N 0.000 claims description 6
- 238000010079 rubber tapping Methods 0.000 claims description 6
- 238000007493 shaping process Methods 0.000 claims description 6
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 2
- 239000011701 zinc Substances 0.000 claims description 2
- 229910052725 zinc Inorganic materials 0.000 claims description 2
- 230000003712 anti-aging effect Effects 0.000 claims 1
- 239000003795 chemical substances by application Substances 0.000 claims 1
- 230000003647 oxidation Effects 0.000 claims 1
- 238000007254 oxidation reaction Methods 0.000 claims 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 abstract description 6
- 238000000034 method Methods 0.000 abstract description 3
- 230000009286 beneficial effect Effects 0.000 abstract description 2
- 125000000962 organic group Chemical group 0.000 abstract description 2
- 239000000126 substance Substances 0.000 abstract description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical group [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 10
- 235000019441 ethanol Nutrition 0.000 description 10
- 230000003321 amplification Effects 0.000 description 5
- 238000005336 cracking Methods 0.000 description 5
- 238000003199 nucleic acid amplification method Methods 0.000 description 5
- 239000011787 zinc oxide Substances 0.000 description 5
- 238000001514 detection method Methods 0.000 description 4
- 230000000855 fungicidal effect Effects 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 238000007667 floating Methods 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 1
- 230000003679 aging effect Effects 0.000 description 1
- 230000000844 anti-bacterial effect Effects 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000003115 biocidal effect Effects 0.000 description 1
- 238000013016 damping Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 238000005187 foaming Methods 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 239000011241 protective layer Substances 0.000 description 1
- 230000035882 stress Effects 0.000 description 1
- 239000004636 vulcanized rubber Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/18—Homopolymers or copolymers of hydrocarbons having four or more carbon atoms
- C08L23/20—Homopolymers or copolymers of hydrocarbons having four or more carbon atoms having four to nine carbon atoms
- C08L23/22—Copolymers of isobutene; Butyl rubber; Homopolymers or copolymers of other iso-olefins
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
- D06M11/77—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with silicon or compounds thereof
- D06M11/79—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with silicon or compounds thereof with silicon dioxide, silicic acids or their salts
-
- 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
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2237—Oxides; Hydroxides of metals of titanium
- C08K2003/2241—Titanium dioxide
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/14—Polymer mixtures characterised by other features containing polymeric additives characterised by shape
- C08L2205/16—Fibres; Fibrils
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M2101/00—Chemical constitution of the fibres, threads, yarns, fabrics or fibrous goods made from such materials, to be treated
- D06M2101/16—Synthetic fibres, other than mineral fibres
- D06M2101/30—Synthetic polymers consisting of macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Textile Engineering (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 invention discloses a kind of ageing-resistant ship rubber fenders and preparation method thereof, and wherein the ingredient of rubber fender includes：Butadiene rubber, butyl rubber, titanium dioxide, calcined kaolin, trihydroxy methyl propane, age resister, modified polyphenyl thioether fibre, vulcanization accelerator, sulphur and antibacterial agent.The beneficial effects of the invention are as follows：The present invention mixes butyl rubber with butadiene rubber, in conjunction with the excellent lower temperature resistance of butadiene rubber, wearability, good processing performance, and the good chemical stability of butyl rubber, heat-resisting, resistance to ozone, ageing-resistant performance, butyl rubber, butadiene rubber are blended with modified polyphenyl thioether fibre using mechanical blending method, polyphenylene sulfide fibre is by the modified active organic group of rear surface of silicone coupling agents, there is preferable dispersibility in rubber, it can be organically combined with rubber, improve the mechanical property and tensile strength of rubber.
Description
Technical field
The present invention relates to field of rubber technology, and in particular to a kind of ageing-resistant ship rubber fender and preparation method thereof.
Background technique
Rubber industry is one of important foundation industry of national economy.It is indispensable that it not only provides daily life for people
The light industrys rubber product such as daily, medical, and mentioned to the heavy industry such as digging, traffic, building, machinery, electronics and new industry
For various rubber system production equipments or rubber components.As it can be seen that the product category of rubber industry is various, backward industry is very wide.
Rubber fender is also known as rubber guard timber, is mounted on harbour or ship, is pulling in shore between ship and harbour or ship to absorb
Or collision energy when mooring, protection ship, harbour are against damages.
Usual rubber fender can be divided into two major classes according to structure：Solid rubber fender（Non-floating）It is protected with float type rubber
The side of a ship.Solid rubber fender（Non-floating）It is that applicating history is relatively early, the dock ship Anti-knocking equipment that has a wide range of application.According to rubber
Glue fender stress condition can be divided into shearing-type, rotation and compression-type etc.；According to the structure of fender, solid rubber fender can divide again
For D type, taper, drum type, sector, rectangle, cylinder-shaped fender etc..Float type rubber fender can freely float on the water surface, root
It can be divided into according to the difference of its internal damping medium：Puffer-type rubber fender, fill type rubber fender.Puffer-type rubber fender be with
Compressed air is medium, consumes collision energy by compressed air to do work；Foam filled type fender is also known as solid polyurethane
Fender, inside are mainly closed cell foamed material for buffer medium, such as foaming EVA, polyurathamc and blown rubber etc..
Rubber fender used at present is protected due to being exposed in the sun and air for a long time using rubber in the short period
The side of a ship just will appear mouldy, phenomena such as being hardened, cracking, and then the buffer capacity of rubber fender is caused to substantially reduce.It is wherein main
Problem is that the rubber of composition rubber fender is ageing-resistant and antibiotic property is poor caused.
Summary of the invention
In order to solve existing rubber fender since long-time is exposed with air and solarization, rubber fender is caused to crack
Phenomena such as, the present invention provides a kind of ageing-resistant ship rubber fenders and preparation method thereof.
In order to achieve the above-mentioned object of the invention, the present invention provides a kind of ageing-resistant ship rubber fenders, and ingredient is by weight
Measure part meter：13 ~ 17 parts of butadiene rubber, 90 ~ 120 parts of butyl rubber, 6 ~ 10 parts of titanium dioxide, 45 ~ 70 parts of calcined kaolin, three
5 ~ 8 parts of hydroxymethyl propane, 1 ~ 5 part of age resister, 30 ~ 50 parts of modified polyphenyl thioether fibre, 2 ~ 4 parts of vulcanization accelerator, sulphur
1.0 ~ 1.5 parts and 1 ~ 5 part of antibacterial agent.
In order to preferably realize foregoing invention purpose, the present invention also provides a kind of systems of ageing-resistant ship rubber fender
Preparation Method includes the following steps：
A, it mixes：It is high that butadiene rubber, butyl rubber, trihydroxy methyl propane, titanium dioxide and calcining are weighed by dosage requirement
Ridge soil, stirs 30min in a stirring kettle with the speed of 80 ~ 100r/min, obtains mixed component A；
B, it is kneaded：Uniformly mixed mixed component A is put into mixer and is kneaded, is then added to modified polyphenyl thioether fibre
Continue to be kneaded in mixer, temperature is 100 DEG C, and time 18min obtains rubber compound；
C, rubber tapping turns refining：Roller temperature is risen to 50 ~ 60 DEG C, then by rubber compound packet roller, appropriate amplification roll spacing adds into mixed component A
Enter sulphur, age resister, vulcanization accelerator and antibacterial agent, tap rubber the 30 ~ 40min that turns refining, and stands 24 ~ 26h of cooling, obtains mixing group
Divide B；
D, it forms：By 60 ~ 75 DEG C of hot press mould temperature rise value, then mixed component B is pressed and molded under the pressure of 6 ~ 8MPa, mould
The pressure time is 3 ~ 7min；
E, vulcanize：By mixed component B after molding be sent into vulcanizer vulcanization, curing temperature be 115 ~ 135 DEG C, pressure be 12 ~
15MPa, time are 12 ~ 15min.
Preferably, the preparation method of the modified polyphenyl thioether fibre is as follows：
（1）Nano montmorillonite is subjected to organic coupling agent processing using silicone coupling agents, is then covered to processed nanometer de-
Addition composite antioxidant C206, second alcohol and water are stirred mixing in soil, and mixing speed is 300 ~ 500r/min, and mixing time is
60~90min；
（2）Polyphenylene sulfide fibre is added to step under room temperature（1）Impregnation is carried out in the mixed component of preparation, impregnates 5 ~ 8h
Polyphenylene sulfide fibre is taken out afterwards, and 180 ~ 200 DEG C at a temperature of laxation shaping is dried to fiber, dry 45 ~ 80min
Modified polyphenyl thioether fibre is made afterwards.
Preferably, step（1）The mass ratio of middle nano montmorillonite and coupling agent is 15：1.
Preferably, step（1）Middle nano montmorillonite, composite antioxidant C206, second alcohol and water mass ratio be 15 ~ 20：3~
8：35~60：85~95.
Preferably, the age resister selects ketoamine age resister.
Preferably, the vulcanization accelerator is zinc oxide, stearic acid and zinc stearate in mass ratio 3:2:2 mix.
Preferably, the antibacterial agent selects any one in WS-911 and nano-silver ionic or two kinds.
The beneficial effects of the invention are as follows：The present invention mixes butyl rubber with butadiene rubber, excellent in conjunction with butadiene rubber
Lower temperature resistance, wearability, good processing performance and the good chemical stability of butyl rubber, heat-resisting, resistance to ozone, resistance to
Ageing properties butyl rubber, butadiene rubber are blended with modified polyphenyl thioether fibre using mechanical blending method, polyphenylene sulfide
Ether fiber has preferable dispersibility, energy by the modified active organic group of rear surface of silicone coupling agents in rubber
Enough and rubber organically combines, and improves the mechanical property and tensile strength of rubber, and calcined kaolin and titanium dioxide are easy after being added
Dissociate and form a protective layer to rubber surface, reduce contact of the rubber with air, improves the resistance to ag(e)ing of rubber entirety, oxygen
The addition for changing zinc, stearic acid and zinc stearate, has activated the crosslink density that vulcanizing system improves vulcanized rubber, has improved rubber
Wear and heat resistant, the addition of age resister can further strengthen the ageing-resistant performance of rubber, WS-911 and nano silver
The performance for imparting rubber antimildew and antibacterial is added in the mixing of ion, reduces the risk of the mouldy corruption of rubber.
Specific embodiment
In order to clarify the technical characteristics of the invention, being illustrated below by specific embodiment to this programme.
Embodiment 1：
The embodiment of the invention provides a kind of ageing-resistant ship rubber fenders, and ingredient is by weight：Butadiene rubber 13
Part, 3 parts of age resister, changes 100 parts of butyl rubber, 6 parts of titanium dioxide, 45 parts of calcined kaolin, 7 parts of trihydroxy methyl propane
Property 30 parts of polyphenylene sulfide fibre, 2 parts of vulcanization accelerator, 1.0 parts of sulphur with 2 parts of antibacterial agent.
Preparation method includes the following steps：
A, it mixes：It is high that butadiene rubber, butyl rubber, trihydroxy methyl propane, titanium dioxide and calcining are weighed by dosage requirement
Ridge soil, stirs 30min in a stirring kettle with the speed of 80r/min, obtains mixed component A；
B, it is kneaded：Uniformly mixed mixed component A is put into mixer and is kneaded, is then added to modified polyphenyl thioether fibre
Continue to be kneaded in mixer, temperature is 100 DEG C, and time 18min obtains rubber compound；
C, rubber tapping turns refining：Roller temperature is risen to 50 DEG C, then by rubber compound packet roller, appropriate amplification roll spacing is added into mixed component A
Sulphur, age resister, vulcanization accelerator and antibacterial agent, tap rubber the 30min that turns refining, and stands cooling for 24 hours, obtains mixed component B；
D, it forms：By 60 DEG C of hot press mould temperature rise value, then mixed component B is pressed and molded under the pressure of 6MPa, when molding
Between be 3min；
E, vulcanize：Mixed component B after molding is sent into vulcanizer vulcanization, curing temperature is 115 DEG C, pressure 12MPa, the time
For 12min.
Wherein, the preparation method of modified polyphenyl thioether fibre is as follows：
（1）Nano montmorillonite is subjected to organic coupling agent processing using silicone coupling agents, is then covered to processed nanometer de-
Addition composite antioxidant C206, second alcohol and water are stirred mixing, mixing speed 300r/min in soil, and mixing time is
60min；Wherein, the mass ratio of nano montmorillonite and coupling agent is 15：1；Nano montmorillonite, composite antioxidant C206, ethyl alcohol and
The mass ratio of water is 15：3：35：85；
（2）Polyphenylene sulfide fibre is added to step under room temperature（1）Impregnation is carried out in the mixed component of preparation, after impregnating 5h
Polyphenylene sulfide fibre is taken out, and 180 DEG C at a temperature of laxation shaping is dried to fiber, be made and change after dry 45min
Property polyphenylene sulfide fibre.
Wherein, age resister selects ketoamine age resister.
Vulcanization accelerator is zinc oxide, stearic acid and zinc stearate in mass ratio 3:2:2 mix.
Antibacterial agent selects any one or two kinds in WS-911 and nano-silver ionic.
After tested, the fender rubber hardness prepared by embodiment 1（Continue your A）68, tensile strength 25.5MPa are pulled apart and are stretched
Long rate 485%, tensile strength change rate -6.5%, ozone aging（20%, 40 DEG C, 200pphm, 168h）No cracking, mould proof grade 1
Grade（Rubber fungicidal properties detection method is referring to HG/T 4301-2012）.
Embodiment 2：
The embodiment of the invention provides a kind of ageing-resistant ship rubber fenders, and ingredient is by weight：Butadiene rubber 14
Part, 4 parts of age resister, changes 110 parts of butyl rubber, 7 parts of titanium dioxide, 65 parts of calcined kaolin, 5 parts of trihydroxy methyl propane
Property 35 parts of polyphenylene sulfide fibre, 4 parts of vulcanization accelerator, 1.2 parts of sulphur with 3 parts of antibacterial agent.
Preparation method includes the following steps：
A, it mixes：It is high that butadiene rubber, butyl rubber, trihydroxy methyl propane, titanium dioxide and calcining are weighed by dosage requirement
Ridge soil, stirs 55min in a stirring kettle with the speed of 90r/min, obtains mixed component A；
B, it is kneaded：Uniformly mixed mixed component A is put into mixer and is kneaded, is then added to modified polyphenyl thioether fibre
Continue to be kneaded in mixer, temperature is 100 DEG C, and time 18min obtains rubber compound；
C, rubber tapping turns refining：Roller temperature is risen to 55 DEG C, then by rubber compound packet roller, appropriate amplification roll spacing is added into mixed component A
Sulphur, age resister, vulcanization accelerator and antibacterial agent, tap rubber the 35min that turns refining, and stands cooling 25h, obtains mixed component B；
D, it forms：By 65 DEG C of hot press mould temperature rise value, then mixed component B is pressed and molded under the pressure of 7MPa, when molding
Between be 4min；
E, vulcanize：Mixed component B after molding is sent into vulcanizer vulcanization, curing temperature is 120 DEG C, pressure 13MPa, the time
For 13min.
Wherein, the preparation method of modified polyphenyl thioether fibre is as follows：
（1）Nano montmorillonite is subjected to organic coupling agent processing using silicone coupling agents, is then covered to processed nanometer de-
Addition composite antioxidant C206, second alcohol and water are stirred mixing, mixing speed 350r/min in soil, and mixing time is
70min；The mass ratio of nano montmorillonite and coupling agent is 15：1；The matter of nano montmorillonite, composite antioxidant C206, second alcohol and water
Amount is than being 17：5：45：90；
（2）Polyphenylene sulfide fibre is added to step under room temperature（1）Impregnation is carried out in the mixed component of preparation, after impregnating 6h
Polyphenylene sulfide fibre is taken out, and 185 DEG C at a temperature of laxation shaping is dried to fiber, be made and change after dry 55min
Property polyphenylene sulfide fibre.
Age resister selects ketoamine age resister.
Vulcanization accelerator is zinc oxide, stearic acid and zinc stearate in mass ratio 3:2:2 mix.
Antibacterial agent selects any one or two kinds in WS-911 and nano-silver ionic.
After tested, the fender rubber hardness prepared by embodiment 2（Continue your A）65, tensile strength 26.0MPa are pulled apart and are stretched
Long rate 512%, tensile strength change rate -6.8%, ozone aging（20%, 40 DEG C, 200pphm, 168h）No cracking, mould proof grade 1
Grade（Rubber fungicidal properties detection method is referring to HG/T 4301-2012）.
Embodiment 3：
The embodiment of the invention provides a kind of ageing-resistant ship rubber fenders, and ingredient is by weight：Butadiene rubber 16
Part, is modified 90 parts of butyl rubber, 9 parts of titanium dioxide, 70 parts of calcined kaolin, 6 parts of trihydroxy methyl propane, 5 parts of age resister
45 parts of polyphenylene sulfide fibre, 3 parts of vulcanization accelerator, 1.4 parts and 1 part of antibacterial agent of sulphur.
Preparation method includes the following steps：
A, it mixes：It is high that butadiene rubber, butyl rubber, trihydroxy methyl propane, titanium dioxide and calcining are weighed by dosage requirement
Ridge soil, stirs 30min in a stirring kettle with the speed of 95r/min, obtains mixed component A；
B, it is kneaded：Uniformly mixed mixed component A is put into mixer and is kneaded, is then added to modified polyphenyl thioether fibre
Continue to be kneaded in mixer, temperature is 100 DEG C, and time 18min obtains rubber compound；
C, rubber tapping turns refining：Roller temperature is risen to 55 DEG C, then by rubber compound packet roller, appropriate amplification roll spacing is added into mixed component A
Sulphur, age resister, vulcanization accelerator and antibacterial agent, tap rubber the 35min that turns refining, and stands cooling 26h, obtains mixed component B；
D, it forms：By 70 DEG C of hot press mould temperature rise value, then mixed component B is pressed and molded under the pressure of 7MPa, when molding
Between be 5min；
E, vulcanize：Mixed component B after molding is sent into vulcanizer vulcanization, curing temperature is 130 DEG C, pressure 14MPa, the time
For 14min.
Wherein, the preparation method of modified polyphenyl thioether fibre is as follows：
（1）Nano montmorillonite is subjected to organic coupling agent processing using silicone coupling agents, is then covered to processed nanometer de-
Addition composite antioxidant C206, second alcohol and water are stirred mixing, mixing speed 450r/min in soil, and mixing time is
80min；The mass ratio of nano montmorillonite and coupling agent is 15：1；The matter of nano montmorillonite, composite antioxidant C206, second alcohol and water
Amount is than being 18：7：55：90.
（2）Polyphenylene sulfide fibre is added to step under room temperature（1）Impregnation is carried out in the mixed component of preparation, is impregnated
Polyphenylene sulfide fibre is taken out after 7h, and 190 DEG C at a temperature of laxation shaping is dried to fiber, made after dry 70min
Obtain modified polyphenyl thioether fibre.
Age resister selects ketoamine age resister.
Vulcanization accelerator is zinc oxide, stearic acid and zinc stearate in mass ratio 3:2:2 mix.
Antibacterial agent selects any one or two kinds in WS-911 and nano-silver ionic.
After tested, the fender rubber hardness prepared by embodiment 3（Continue your A）67, tensile strength 25.8MPa are pulled apart and are stretched
Long rate 490%, tensile strength change rate -5.2%, ozone aging（20%, 40 DEG C, 200pphm, 168h）No cracking, mould proof grade 1
Grade（Rubber fungicidal properties detection method is referring to HG/T 4301-2012）.
Embodiment 4：
The embodiment of the invention provides a kind of ageing-resistant ship rubber fenders, and ingredient is by weight：Butadiene rubber 17
Part, 1 part of age resister, changes 120 parts of butyl rubber, 10 parts of titanium dioxide, 55 parts of calcined kaolin, 8 parts of trihydroxy methyl propane
Property 50 parts of polyphenylene sulfide fibre, 3 parts of vulcanization accelerator, 1.5 parts of sulphur with 5 parts of antibacterial agent.
Preparation method includes the following steps：
A, it mixes：It is high that butadiene rubber, butyl rubber, trihydroxy methyl propane, titanium dioxide and calcining are weighed by dosage requirement
Ridge soil, stirs 30min in a stirring kettle with the speed of 100r/min, obtains mixed component A；
B, it is kneaded：Uniformly mixed mixed component A is put into mixer and is kneaded, is then added to modified polyphenyl thioether fibre
Continue to be kneaded in mixer, temperature is 100 DEG C, and time 18min obtains rubber compound；
C, rubber tapping turns refining：Roller temperature is risen to 60 DEG C, then by rubber compound packet roller, appropriate amplification roll spacing is added into mixed component A
Sulphur, age resister, vulcanization accelerator and antibacterial agent, tap rubber the 40min that turns refining, and stands cooling 26h, obtains mixed component B；
D, it forms：By 75 DEG C of hot press mould temperature rise value, then mixed component B is pressed and molded under the pressure of 8MPa, when molding
Between be 7min；
E, vulcanize：Mixed component B after molding is sent into vulcanizer vulcanization, curing temperature is 135 DEG C, pressure 15MPa, the time
For 15min.
Wherein, the preparation method of modified polyphenyl thioether fibre is as follows：
（1）Nano montmorillonite is subjected to organic coupling agent processing using silicone coupling agents, is then covered to processed nanometer de-
Addition composite antioxidant C206, second alcohol and water are stirred mixing, mixing speed 500r/min in soil, and mixing time is
90min；The mass ratio of nano montmorillonite and coupling agent is 15：1；The matter of nano montmorillonite, composite antioxidant C206, second alcohol and water
Amount is than being 20：8：60：95；
（2）Polyphenylene sulfide fibre is added to step under room temperature（1）Impregnation is carried out in the mixed component of preparation, after impregnating 8h
Polyphenylene sulfide fibre is taken out, and 200 DEG C at a temperature of laxation shaping is dried to fiber, be made and change after dry 80min
Property polyphenylene sulfide fibre.
Wherein, age resister selects ketoamine age resister.
Vulcanization accelerator is zinc oxide, stearic acid and zinc stearate in mass ratio 3:2:2 mix.
Antibacterial agent selects any one or two kinds in WS-911 and nano-silver ionic.
After tested, the fender rubber hardness prepared by embodiment 4（Continue your A）64, tensile strength 25.5MPa are pulled apart and are stretched
Long rate 500%, tensile strength change rate -5.4%, ozone aging（20%, 40 DEG C, 200pphm, 168h）No cracking, mould proof grade 1
Grade（Rubber fungicidal properties detection method is referring to HG/T 4301-2012）.
The foregoing is merely presently preferred embodiments of the present invention, is not intended to limit the invention, it is all in spirit of the invention and
Within principle, any modification, equivalent replacement, improvement and so on be should all be included in the protection scope of the present invention.
Claims (8)
1. a kind of ageing-resistant ship rubber fender, which is characterized in that its ingredient is by weight：13 ~ 17 parts of butadiene rubber,
It is 90 ~ 120 parts of butyl rubber, 6 ~ 10 parts of titanium dioxide, 45 ~ 70 parts of calcined kaolin, 5 ~ 8 parts of trihydroxy methyl propane, anti-aging
1 ~ 5 part of agent, 30 ~ 50 parts of modified polyphenyl thioether fibre, 2 ~ 4 parts of vulcanization accelerator, 1.0 ~ 1.5 parts and 1 ~ 5 part of antibacterial agent of sulphur.
2. the preparation method of ageing-resistant ship rubber fender according to claim 1, which is characterized in that including following step
Suddenly：
A, it mixes：It is high that butadiene rubber, butyl rubber, trihydroxy methyl propane, titanium dioxide and calcining are weighed by dosage requirement
Ridge soil, stirs 30min in a stirring kettle with the speed of 80 ~ 100r/min, obtains mixed component A；
B, it is kneaded：Uniformly mixed mixed component A is put into mixer and is kneaded, then modified polyphenyl thioether fibre is added
Continue to be kneaded into mixer, temperature is 100 DEG C, and time 18min obtains rubber compound；
C, rubber tapping turns refining：Roller temperature is risen to 50 ~ 60 DEG C, it is appropriate to amplify roll spacing into mixed component A then by rubber compound packet roller
Sulphur, age resister, vulcanization accelerator and antibacterial agent is added, tap rubber the 30 ~ 40min that turns refining, and stands 24 ~ 26h of cooling, must mix
Component B；
D, it forms：By 60 ~ 75 DEG C of hot press mould temperature rise value, then mixed component B is pressed and molded under the pressure of 6 ~ 8MPa,
Clamp time is 3 ~ 7min；
E, vulcanize：By mixed component B after molding be sent into vulcanizer vulcanization, curing temperature be 115 ~ 135 DEG C, pressure be 12 ~
15MPa, time are 12 ~ 15min.
3. ageing-resistant ship rubber fender according to claim 1, it is characterised in that：The modified polyphenyl thioether fibre
Preparation method it is as follows：
（1）Nano montmorillonite is subjected to organic coupling agent processing using silicone coupling agents, is then covered to processed nanometer de-
Addition composite antioxidant C206, second alcohol and water are stirred mixing in soil, and mixing speed is 300 ~ 500r/min, and mixing time is
60~90min；
（2）Polyphenylene sulfide fibre is added to step under room temperature（1）Impregnation is carried out in the mixed component of preparation, impregnates 5 ~ 8h
Polyphenylene sulfide fibre is taken out afterwards, and 180 ~ 200 DEG C at a temperature of laxation shaping is dried to fiber, dry 45 ~ 80min
Modified polyphenyl thioether fibre is made afterwards.
4. ageing-resistant ship rubber fender according to claim 3, it is characterised in that：Step（1）Middle nano montmorillonite
Mass ratio with coupling agent is 15：1.
5. ageing-resistant ship rubber fender according to claim 3, it is characterised in that：Step（1）Middle nano montmorillonite,
Composite antioxidant C206, second alcohol and water mass ratio be 15 ~ 20：3~8：35~60：85~95.
6. ageing-resistant ship rubber fender according to claim 1, it is characterised in that：The age resister selects ketoamine
Age resister.
7. ageing-resistant ship rubber fender according to claim 1, it is characterised in that：The vulcanization accelerator is oxidation
Zinc, stearic acid and zinc stearate in mass ratio 3:2:2 mix.
8. ageing-resistant ship rubber fender according to claim 1, it is characterised in that：The antibacterial agent be WS-911 and
Any one in nano-silver ionic or two kinds.
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| CN101537280A (en) * | 2009-04-07 | 2009-09-23 | 厦门三维丝环保股份有限公司 | Preparation method of nano-particle modified polyphenyl thioether filter material |
| WO2012119526A1 (en) * | 2011-03-04 | 2012-09-13 | 中国石油化工股份有限公司 | Electrically conductive, fully vulcanized, thermoplastic elastomer and preparation method thereof |
| CN105400031A (en) * | 2015-12-08 | 2016-03-16 | 黄涌芮 | Anti-aging rubber and preparation method thereof |
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| CN107903514A (en) * | 2017-12-20 | 2018-04-13 | 罗伟 | Nontoxic antibacterial medical rubber and preparation method thereof |
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| WO2012119526A1 (en) * | 2011-03-04 | 2012-09-13 | 中国石油化工股份有限公司 | Electrically conductive, fully vulcanized, thermoplastic elastomer and preparation method thereof |
| CN105400031A (en) * | 2015-12-08 | 2016-03-16 | 黄涌芮 | Anti-aging rubber and preparation method thereof |
| CN106349694A (en) * | 2016-08-24 | 2017-01-25 | 桂林浩新科技服务有限公司 | High-strength polyphenylene sulfide composition and preparation method thereof |
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Application publication date: 20181130 |