CN116574377A - Anti-structuring mixed silicon rubber and production process thereof - Google Patents
Anti-structuring mixed silicon rubber and production process thereof Download PDFInfo
- Publication number
- CN116574377A CN116574377A CN202310461878.4A CN202310461878A CN116574377A CN 116574377 A CN116574377 A CN 116574377A CN 202310461878 A CN202310461878 A CN 202310461878A CN 116574377 A CN116574377 A CN 116574377A
- Authority
- CN
- China
- Prior art keywords
- parts
- silicone rubber
- structuring
- rubber
- carbon black
- 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.)
- Pending
Links
- 229920002379 silicone rubber Polymers 0.000 title claims abstract description 58
- 238000004519 manufacturing process Methods 0.000 title abstract description 11
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 64
- 239000004945 silicone rubber Substances 0.000 claims abstract description 52
- 239000006229 carbon black Substances 0.000 claims abstract description 46
- 229920001971 elastomer Polymers 0.000 claims abstract description 46
- 238000002156 mixing Methods 0.000 claims abstract description 41
- -1 vinyl methoxy siloxane Chemical class 0.000 claims abstract description 38
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 32
- 229920002545 silicone oil Polymers 0.000 claims abstract description 27
- XOOUIPVCVHRTMJ-UHFFFAOYSA-L zinc stearate Chemical compound [Zn+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O XOOUIPVCVHRTMJ-UHFFFAOYSA-L 0.000 claims abstract description 15
- 239000002253 acid Substances 0.000 claims abstract description 12
- 239000007864 aqueous solution Substances 0.000 claims abstract description 12
- 239000002994 raw material Substances 0.000 claims abstract description 12
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 18
- 229920002554 vinyl polymer Polymers 0.000 claims description 17
- 238000000034 method Methods 0.000 claims description 16
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 14
- 239000000243 solution Substances 0.000 claims description 12
- 150000001875 compounds Chemical class 0.000 claims description 11
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 10
- 238000010438 heat treatment Methods 0.000 claims description 9
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 8
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 8
- 230000008569 process Effects 0.000 claims description 8
- 238000007670 refining Methods 0.000 claims description 8
- 230000001105 regulatory effect Effects 0.000 claims description 8
- 238000001816 cooling Methods 0.000 claims description 7
- 229910052757 nitrogen Inorganic materials 0.000 claims description 7
- 238000003756 stirring Methods 0.000 claims description 6
- 239000011260 aqueous acid Substances 0.000 claims description 5
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 14
- 238000003860 storage Methods 0.000 abstract description 6
- 238000005516 engineering process Methods 0.000 abstract description 2
- 230000002035 prolonged effect Effects 0.000 abstract description 2
- 230000000052 comparative effect Effects 0.000 description 18
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 14
- 239000003795 chemical substances by application Substances 0.000 description 13
- 239000006185 dispersion Substances 0.000 description 10
- 229910052710 silicon Inorganic materials 0.000 description 8
- 239000010703 silicon Substances 0.000 description 8
- 239000000377 silicon dioxide Substances 0.000 description 8
- 239000000945 filler Substances 0.000 description 7
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 7
- 230000000694 effects Effects 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- BPYFPNZHLXDIGA-UHFFFAOYSA-N diphenylsilicon Chemical compound C=1C=CC=CC=1[Si]C1=CC=CC=C1 BPYFPNZHLXDIGA-UHFFFAOYSA-N 0.000 description 5
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 238000004513 sizing Methods 0.000 description 4
- 230000008859 change Effects 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 230000007062 hydrolysis Effects 0.000 description 3
- 238000006460 hydrolysis reaction Methods 0.000 description 3
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 239000004636 vulcanized rubber Substances 0.000 description 3
- 229910020175 SiOH Inorganic materials 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000000903 blocking effect Effects 0.000 description 2
- DKAGJZJALZXOOV-UHFFFAOYSA-N hydrate;hydrochloride Chemical compound O.Cl DKAGJZJALZXOOV-UHFFFAOYSA-N 0.000 description 2
- 230000035699 permeability Effects 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 230000002787 reinforcement Effects 0.000 description 2
- 235000012239 silicon dioxide Nutrition 0.000 description 2
- 229910018557 Si O Inorganic materials 0.000 description 1
- 229910008051 Si-OH Inorganic materials 0.000 description 1
- 229910006358 Si—OH Inorganic materials 0.000 description 1
- OBNDGIHQAIXEAO-UHFFFAOYSA-N [O].[Si] Chemical compound [O].[Si] OBNDGIHQAIXEAO-UHFFFAOYSA-N 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 230000001476 alcoholic effect Effects 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 125000004093 cyano group Chemical group *C#N 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 229910021485 fumed silica Inorganic materials 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 125000000962 organic group Chemical group 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 229910052573 porcelain Inorganic materials 0.000 description 1
- SCPYDCQAZCOKTP-UHFFFAOYSA-N silanol Chemical compound [SiH3]O SCPYDCQAZCOKTP-UHFFFAOYSA-N 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Inorganic materials [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 1
- 229920001059 synthetic polymer Polymers 0.000 description 1
- 125000000725 trifluoropropyl group Chemical group [H]C([H])(*)C([H])([H])C(F)(F)F 0.000 description 1
- 238000004073 vulcanization Methods 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
- C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
- C08L83/04—Polysiloxanes
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02T—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO TRANSPORTATION
- Y02T10/00—Road transport of goods or passengers
- Y02T10/80—Technologies aiming to reduce greenhouse gasses emissions common to all road transportation technologies
- Y02T10/86—Optimisation of rolling resistance, e.g. weight reduction
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 invention belongs to the technical field of silicone rubber, and in particular relates to anti-structuring mixed silicone rubber and a production process thereof, wherein the anti-structuring mixed silicone rubber comprises the following raw materials in parts by weight: 110-3 raw rubber 70-80 parts, 220-2 raw rubber 30-40 parts, vinyl methoxy siloxane 6-8 parts, acid aqueous solution 2-4 parts, hydroxyl silicone oil 4-7 parts, zinc stearate 0.06-0.1 part and white carbon black 50-60 parts. The production process provided by the invention comprises the steps of pretreating white carbon black by a certain technology, eliminating hydroxyl on the surface of the white carbon black, and then carrying out batch mixing. On the premise of ensuring that the mixed silicone rubber has stronger mechanical properties, the anti-structuring property of the mixed silicone rubber can be effectively improved, the storage time of the mixed silicone rubber is greatly prolonged, meanwhile, the generation of water in the production process is reduced, the odor is low, the mixed silicone rubber is not stuck to rollers, the processing is easy, and the energy is saved and the consumption is reduced.
Description
Technical Field
The invention belongs to the technical field of silicon rubber, and particularly relates to anti-structuring mixed silicon rubber and a production process thereof.
Background
The kneaded silicone rubber is a rubber having a main chain composed of silicon and oxygen atoms alternately, and the silicon atoms are usually bonded with two organic groups. Conventional silicone rubber is composed mainly of segments of silicone containing methyl groups and small amounts of vinyl groups. The introduction of phenyl can improve the high and low temperature resistance of the silicone rubber, and the introduction of trifluoropropyl and cyano can improve the temperature resistance and oil resistance of the silicone rubber. The silicone rubber has good low temperature resistance and can still work at-55 ℃. After introduction of the phenyl group, the temperature can reach-73 ℃. The heat resistance of the silicone rubber is also outstanding, the silicone rubber can work for a long time at 180 ℃, still has elasticity when being born for a plurality of weeks or longer at a temperature slightly higher than 200 ℃, and can instantaneously resist the high temperature of more than 300 ℃. The silicone rubber has good air permeability, and the oxygen permeability is highest in the synthetic polymer, and is mainly used in the industries of cables, wires, automobiles and the like.
Silica is generally used for reinforcement in a silicone rubber formula, and silica such as fumed silica and precipitated silica has a very good reinforcement effect on silicone rubber, but because the silica has a large specific surface area, a large amount of SiOH groups are contained on the surface, the SiOH groups are easy to react with Si-O bonds or Si-OH bonds in raw rubber molecules to form a silica filler network, a structuring phenomenon is generated, namely Payne effect, so that the silicone rubber has poor processing rheological property, difficult remixing and short storage period, and the problems of unsatisfactory filling mould and the like are easily caused because the Mooney viscosity of the silica filler. The structuring is generally reduced by adding a structuring control agent during kneading. During mixing, the white carbon black is kneaded and dispersed in the raw rubber, and the added structural control agent does not react with the raw rubber, but preferentially gathers on the surface of the white carbon black, so that the formation of a white carbon black filler network is weakened, the white carbon black is better dispersed in the silicone rubber, and the processing rheological property of the silicone rubber is improved.
In the research of the 'influence of silazane on the performance of high-strength silicone rubber' published by Shandong university Du Zuodong, cyclic silazane is used as an anti-structure agent, analysis shows that before silicon dioxide is contacted with silazane, various characteristic peaks of silicon hydroxyl groups are obviously present, and after the silicon dioxide is contacted with the silazane, most of hydroxyl groups disappear, and simultaneously, a characteristic peak of disilyl is added, so that the reaction of the silazane and the silicon hydroxyl groups is illustrated. The compatibility of the filler and the organosilicon raw rubber is greatly increased, so that the filler is uniformly dispersed, and the anti-structuring capability is improved. However, the disadvantages are also evident, firstly the pungent odor and the addition of silazane are an effective means of blocking the silicon hydroxyl groups, but a large amount of addition is required to achieve complete blocking, which is costly and entails a rise in cost.
The research of the influence of diphenyl silicon glycol on the silica gel material of white carbon black and the vulcanized rubber performance thereof shows that both silicon glycol and diphenyl silicon glycol can be used as structural control agents, but the control effect of the silicon glycol is insufficient, the control efficiency of the structure of the diphenyl silicon glycol is high, the obtained vulcanized rubber has better comprehensive performance, but the vulcanized rubber belongs to a crystal compound, has higher melting point and needs to be preheated, and in addition, chen Linshan is published in 1997, journal of electric porcelain lightning arrester, as Al (0H) 3 And diphenyl silicon glycol in the application of silicone rubber, it is found that diphenyl silicon glycol is dehydrated and condensed during heat treatment, and when the thickness of sizing material is increased, the generated free water causes the degradation of silicone rubber molecules, so that the performance of vulcanized products is deteriorated.
The hydroxyl silicone oil is used as a structuring control agent, has the advantages of good anti-structure property, convenient use, transparent obtained rubber compound and the like, but the research of the 'influence of the hydroxyl silicone oil on the performance of peroxide vulcanized silicone rubber' finds that the chain link of the hydroxyl silicone oil is shorter, low-molecular volatile matters are easy to escape after being heated, and the quality of the silicone rubber is greatly influenced; water molecules are generated in the anti-structuring process, so that the water content of the glue is increased; in addition, the hydroxyl silicone oil has plasticizing effect on silicone rubber, and the dosage is slightly large, so that the tensile strength and the tearing strength are reduced, the sizing material becomes sticky, and the problems of easy roll sticking and the like in processing are caused. The common method for using hydroxyl silicone oil as a structuring control agent can reduce the amount of active alcoholic hydroxyl groups on the surface of white carbon black, but the single use of hydroxyl silicone oil as an anti-structuring control agent has the problems of single function, poor stability (often accompanied by dehydration condensation reaction), large dosage, easy stickiness of sizing materials, bad smell during heating or vulcanization molding, slightly more dosage, reduced breaking strength, increased breaking permanent deformation, rebound resilience and the like.
Patent CN200510106541.3 mentions a novel structuring control agent of the formula α -alkoxy- ω -hydroxy-oligosiloxane-methylvinylsiloxane copolymer. The structuring control agent is a multifunctional structuring control agent, but the cost is high and the anti-structuring effect is still less than ideal.
Disclosure of Invention
The invention aims to provide the mixed silicon rubber which can effectively improve the anti-structuring performance and prolong the storage time so as to solve the problems in the prior art.
In order to achieve the technical purpose, the technical scheme of the invention comprises the following steps:
an anti-structuring mixing silicone rubber comprises the following raw materials in parts by weight: 110-3 raw rubber 70-80 parts, 220-2 raw rubber 30-40 parts, vinyl methoxy siloxane 6-8 parts, acid aqueous solution 2-4 parts, hydroxyl silicone oil 4-7 parts, zinc stearate 0.06-0.1 part and white carbon black 50-60 parts.
Raw rubber is a polymer material with unique high elasticity, is a parent material for manufacturing rubber products, and is generally referred to as unvulcanized rubber compound. The 110-3 raw rubber and the 220-2 raw rubber are two types of raw rubber, wherein the vinyl content of the 110-3 raw rubber is about 0.22 percent, and the vinyl content of the 220-2 raw rubber is about 0.16 percent.
Preferably, the acid aqueous solution is one or more of hydrochloric acid aqueous solution, sulfuric acid aqueous solution or phosphoric acid aqueous solution.
Preferably, the pH of the aqueous acid solution is=1 to 5.
Preferably, the vinyl content of the 110-3 raw rubber is 0.22%.
Preferably, the vinyl content of the 220-2 raw rubber is 0.16%.
The invention further aims at providing a production process of the anti-structuring mixing silicon rubber, which comprises the following steps of:
(1) Pretreatment: mixing an acid aqueous solution with vinyl methoxy siloxane, stirring and dispersing in a high-speed dispersing machine to fully hydrolyze the vinyl methoxy siloxane, and then putting the white carbon black into the high-speed dispersing machine to uniformly disperse at a high speed to obtain pretreated white carbon black;
(2) Mixing: nitrogen replacement of the kneader for 15min; putting 110-3 raw rubber, 220-2 raw rubber and zinc stearate into a kneader, and mixing for 5min at 20rpm; adding pretreated white carbon black for four times, wherein the adding amount of each time is the same, adding hydroxyl silicone oil together when adding for the first time, and cold-refining and mixing for 30min after each time; heating to 100-180 ℃, regulating the rotation speed to 25rpm, mixing and preserving heat for 0.5-2 h; cooling and taking out of the pot to obtain the product.
As a modification, in the step (1), the rotation speed of the high-speed dispersing machine is 500-3000 rpm.
As a modification, in the step (1), the aqueous acid solution and the vinylmethoxy siloxane are stirred and dispersed in a high-speed dispersing machine for 0.5-2 h.
By adopting the technical scheme, the invention has the beneficial effects that:
according to the invention, the vinyl methoxy siloxane is compounded on the basis of the hydroxyl silicone oil and reacts with Si-0H groups on the surface of the white carbon black, so that the amount of active alcohol hydroxyl groups on the surface of the white carbon black is reduced, the hydrophobization performance of the white carbon black is improved, the dispersibility and compatibility between raw rubber and filler are further improved, the dispersion of other materials in a silicone rubber system is promoted, and the anti-structuring performance of the silicone rubber is improved. In addition, because the methoxy group in the vinyl methoxy siloxane replaces the hydroxyl group in the hydroxyl silicone oil, compared with the method of singly using the hydroxyl silicone oil as the structural control agent, the compound structural control agent obviously reduces the water generated in the reaction process; and when water is generated in the reaction, terminal methoxy groups and branched methoxy groups in the vinyl methoxy siloxane are continuously hydrolyzed into silicon hydroxyl groups, so that the dispersibility of the filler is further improved, the stability is improved, the water content is reduced, and the problem of sizing stickiness is avoided. In addition, the vinyl methoxy siloxane has vinyl in the branched chain, so that the crosslinking property with the silicone rubber can be improved, the stress can be absorbed, and the tearing strength of the silicone rubber can be improved.
The invention adopts a compound form of vinyl methoxy siloxane and hydroxyl silicone oil, and the proportion is 1-3:1. The structure of the vinylmethoxy siloxane used in the invention is as follows:
the method comprises the steps of premixing vinyl methoxy siloxane with acid water regulated to a certain condition, wherein under the condition, the hydrolysis activation energy of the vinyl methoxy siloxane is 11-16 kcal/mol, the hydrolysis constant is highest, and the vinyl methoxy siloxane is easy to hydrolyze to generate silanol, so that a silicon-oxygen hydrogen bond is formed.
The production process provided by the invention comprises the steps of pretreating white carbon black by a certain technology, eliminating hydroxyl on the surface of the white carbon black, and then carrying out batch mixing. On the premise of ensuring that the mixed silicone rubber has stronger mechanical properties, the anti-structuring property of the mixed silicone rubber can be effectively improved, the storage time of the mixed silicone rubber is greatly prolonged, meanwhile, the generation of water in the production process is reduced, the odor is low, the mixed silicone rubber is not stuck to rollers, the processing is easy, and the energy is saved and the consumption is reduced.
Detailed Description
Example 1
An anti-structuring mixing silicone rubber comprises the following raw materials in parts by weight:
70 parts of 110-3 raw rubber (vinyl 0.22 percent)
220-2 raw rubber (vinyl 0.16%) 30 parts
Vinyl methoxy siloxane 6 parts
2 parts of aqueous hydrochloric acid solution having a pH of 1
5 parts of hydroxy silicone oil
Zinc stearate 0.1 part
50 parts of white carbon black
Mixing the prepared hydrochloric acid aqueous solution with pH=1 with vinyl methoxy siloxane, stirring in a high-speed dispersing machine at a rotating speed of 500rpm for 2 hours to fully hydrolyze the vinyl methoxy siloxane, and then putting all the white carbon black into the high-speed dispersing machine for high-speed uniform dispersion to obtain the pretreated white carbon black.
After 15min of nitrogen replacement of the kneader, 110-3 raw rubber, 220-2 raw rubber and zinc stearate are put into the kneader for initial mixing for 5min at 20rpm; adding the pretreated white carbon black in equal parts for four times, and cold-refining and mixing for 30min after each addition, wherein the hydroxyl silicone oil is added together with the mixture in the first addition; heating to 150 ℃, regulating the rotation speed to 25rpm, mixing and preserving heat for 1h; finally cooling and taking out of the pot.
Example 2
An anti-structuring mixing silicone rubber comprises the following raw materials in parts by weight:
110-3 raw rubber (vinyl 0.22%) 75 parts
220-2 raw rubber (vinyl 0.16%) 35 parts
Vinyl methoxy siloxane 7 parts
3 parts of aqueous sulfuric acid solution having pH of 2
5 parts of hydroxy silicone oil
Zinc stearate 0.06 parts
White carbon black 55 parts
Mixing the prepared sulfuric acid aqueous solution with pH=2 with vinyl methoxy siloxane, stirring in a high-speed dispersing machine at 3000rpm for 0.5h to fully hydrolyze the vinyl methoxy siloxane, and then putting all the white carbon black into the high-speed dispersing machine for high-speed uniform dispersion to obtain the pretreated white carbon black.
After 15min of nitrogen replacement of the kneader, putting raw rubber and zinc stearate into initial mixing for 5min, and rotating at 20rpm; adding the pretreated white carbon black in equal parts for four times, and cold-refining and mixing for 30min after each addition, wherein the hydroxyl silicone oil is added together with the mixture in the first addition; heating to 130 ℃, regulating the rotation speed to 25rpm, mixing and preserving heat for 1h; finally cooling and taking out of the pot.
Example 3
An anti-structuring mixing silicone rubber comprises the following raw materials in parts by weight:
80 parts of 110-3 raw rubber (vinyl 0.22 percent)
220-2 raw rubber (vinyl 0.16%) 40 parts
8 parts of vinyl methoxy siloxane
4 parts of aqueous phosphoric acid solution having a pH of 3
7 parts of hydroxy silicone oil
Zinc stearate 0.1 part
60 parts of white carbon black
Mixing the prepared phosphoric acid aqueous solution with pH=3 with vinyl methoxy siloxane, stirring in a high-speed dispersing machine at a rotating speed of 1500rpm for 1h to fully hydrolyze the vinyl methoxy siloxane, and then putting all the white carbon black into the high-speed dispersing machine for high-speed uniform dispersion to obtain the pretreated white carbon black.
After 15min of nitrogen replacement of the kneader, putting raw rubber and zinc stearate into initial mixing for 5min, and rotating at 20rpm; adding the uniformly treated white carbon black in four times, and cold-refining and mixing for 30min after each addition, wherein the hydroxyl silicone oil is added together with the mixture in the first addition; heating to 100 ℃, regulating the rotation speed to 25rpm, mixing and preserving heat for 2 hours; finally cooling and taking out of the pot.
Example 4
An anti-structuring mixing silicone rubber comprises the following raw materials in parts by weight:
70 parts of 110-3 raw rubber (vinyl 0.22 percent)
220-2 raw rubber (vinyl 0.16%) 30 parts
Vinyl methoxy siloxane 6 parts
2 parts of aqueous hydrochloric acid solution with pH of 5
4 parts of hydroxy silicone oil
Zinc stearate 0.1 part
50 parts of white carbon black
Mixing the prepared hydrochloric acid water with pH=5 with vinyl methoxy siloxane, stirring in a high-speed dispersing machine at 2000rpm for 1h to fully hydrolyze the vinyl methoxy siloxane, and then adding all the white carbon black into the high-speed dispersing machine for high-speed uniform dispersion to obtain the pretreated white carbon black.
After 15min of nitrogen replacement of the kneader, putting raw rubber and zinc stearate into initial mixing for 5min, and rotating at 20rpm; adding the uniformly treated white carbon black in four times, and cold-refining and mixing for 30min after each addition, wherein the hydroxyl silicone oil is added together with the mixture in the first addition; heating to 180 ℃, regulating the rotation speed to 25rpm, mixing and preserving heat for 0.5h; finally cooling and taking out of the pot.
Comparative example 1
An anti-structuring mixing silicone rubber comprises the following raw materials in parts by weight:
70 parts of 110-3 raw rubber (vinyl 0.22 percent)
220-2 raw rubber (vinyl 0.16%) 30 parts
5 parts of hydroxy silicone oil
Zinc stearate 0.1 part
50 parts of white carbon black
After 15min of nitrogen replacement of the kneader, putting raw rubber and zinc stearate into initial mixing for 5min, and rotating at 20rpm; adding the white carbon black in equal parts for four times, and cold-refining and mixing for 30min after each addition, wherein all other ingredients are added together when the white carbon black is added for the first time; heating to 150 ℃, regulating the rotation speed to 25rpm, mixing and preserving heat for 1h; finally cooling and taking out of the pot.
Comparative example 2
On the basis of comparative example 1, the mass part of the raw material hydroxyl silicone oil is 11 parts, and other raw material proportions and operation methods are the same as those of comparative example 1.
Comparative example 3
Based on example 1, the high-speed dispersion operation conditions of hydrochloric acid water and vinyl methoxy siloxane were changed to "100rpm, and stirred for 0.5h", and other raw material ratios and operation methods were the same as in example 1.
Comparative example 4
On the basis of the embodiment 1, the process of adding the white carbon black treated before in equal parts for four times is changed into the process of adding the white carbon black and all auxiliary agents at one time after each time of adding, and the process of cold-refining and mixing for 2 hours, and other raw material proportions and operation methods are the same as the embodiment 1.
The shore a hardness of the compounded silicone rubber prepared in example 1-comparative example 4 is shown in table 1:
table 1 change in shore a hardness of each kneaded silicone rubber
As can be seen from examples 1 to 4, the hardness of the mixed silicone rubber produced by the method of the invention is about 60 Shore A, and the hardness is still about 66 after two years of storage; the Shore hardness change amplitude of the comparative examples after 1-4 years is generally 2-3 times that of the examples, and the difference of anti-structuring performance is very obvious.
In comparison with example 1, comparative example 1 was free of acid water and vinylmethoxy siloxane, no pretreatment step, comparative example 2 was free of acid water and vinylmethoxy siloxane, increased in the amount of hydroxy silicone oil, no pretreatment step, comparative example 3 was reduced in the rotational speed of the disperser, shortened in the pretreatment time, and comparative example 4 was a one-time addition of white carbon black at the production stage.
As can be seen from the comparison of the data in the example 1 and the comparative example 1, the change of Shore A hardness is obviously increased compared with the example 1 without adding acid water and vinyl methoxy siloxane, the structuring phenomenon is serious, and the hydrolytic capacity of the vinyl methoxy siloxane can be enhanced only by the compatibility of the acid water and the vinyl methoxy siloxane as the structuring control agent, thereby being beneficial to treating the silicon hydroxyl on the surface of the white carbon black in the pretreatment stage and reducing the structuring.
As can be seen from the comparison of the data of example 1, comparative example 1 and comparative example 2, the structuring phenomenon of comparative example 2 is greatly improved compared with that of comparative example 1, but still the result is worse than that of example 1, without adding acid water and vinyl methoxy siloxane, while increasing the mass parts of hydroxy silicone oil.
As can be seen from the comparison of the data in example 1 and comparative example 3, the pretreatment time is shortened, the dispersion time is too short, the dispersion is obviously uneven, the hydrolysis degree of the vinyl methoxy siloxane is insufficient, and the late anti-structuring effect is not achieved.
The comparison of the data in the embodiment 1 and the comparative example 4 shows that compared with batch feeding, the one-time feeding and feeding load is larger, the dispersion is uneven, the dispersion of the white carbon black is not facilitated, and the anti-structuring capability in the storage process of the later-stage rubber compound is obviously poorer.
The method has the advantages of simple and convenient scheme and simple facilities, and can obviously improve the anti-structuring performance of the mixed silicone rubber.
The above-described embodiments of the present invention do not limit the scope of the present invention. Any other corresponding changes and modifications made in accordance with the technical idea of the present invention shall be included in the scope of the claims of the present invention.
Claims (8)
1. The anti-structuring mixing silicone rubber is characterized by comprising the following raw materials in parts by weight: 110-3 raw rubber 70-80 parts, 220-2 raw rubber 30-40 parts, vinyl methoxy siloxane 6-8 parts, acid aqueous solution 2-4 parts, hydroxyl silicone oil 4-7 parts, zinc stearate 0.06-0.1 part and white carbon black 50-60 parts.
2. The anti-structuring compound silicone rubber according to claim 1, wherein the aqueous acid solution is one or more of aqueous hydrochloric acid solution, aqueous sulfuric acid solution, and aqueous phosphoric acid solution.
3. The anti-structuring compounded silicone rubber according to claim 1, characterized in that the aqueous acid solution has a pH = 1-5.
4. The anti-structuring compound silicone rubber of claim 1, wherein the vinyl content of the 110-3 green rubber is 0.22%.
5. The anti-structuring compound silicone rubber of claim 1, wherein the vinyl content of the 220-2 green rubber is 0.16%.
6. A process for producing the anti-structuring compounded silicone rubber as defined in claim 1, comprising the steps of:
(1) Pretreatment: mixing an acid aqueous solution with vinyl methoxy siloxane, stirring and dispersing in a high-speed dispersing machine to fully hydrolyze the vinyl methoxy siloxane, and then putting the white carbon black into the high-speed dispersing machine to uniformly disperse at a high speed to obtain pretreated white carbon black;
(2) Mixing: nitrogen replacement of the kneader for 15min; putting 110-3 raw rubber, 220-2 raw rubber and zinc stearate into a kneader, and mixing for 5min at 20rpm; adding pretreated white carbon black for four times, wherein the adding amount of each time is the same, adding hydroxyl silicone oil together when adding for the first time, and cold-refining and mixing for 30min after each time; heating to 100-180 ℃, regulating the rotation speed to 25rpm, mixing and preserving heat for 0.5-2 h; cooling and taking out of the pot to obtain the product.
7. The process for producing an anti-structuring compound silicone rubber according to claim 6, wherein in the step (1), the rotation speed of the high-speed disperser is 500-3000 rpm.
8. The process for producing an anti-structuring compound silicone rubber according to claim 6, wherein in the step (1), the aqueous acid solution and the vinylmethoxy siloxane are stirred and dispersed in a high-speed dispersing machine for 0.5 to 2 hours.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202310461878.4A CN116574377A (en) | 2023-04-26 | 2023-04-26 | Anti-structuring mixed silicon rubber and production process thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202310461878.4A CN116574377A (en) | 2023-04-26 | 2023-04-26 | Anti-structuring mixed silicon rubber and production process thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN116574377A true CN116574377A (en) | 2023-08-11 |
Family
ID=87538809
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202310461878.4A Pending CN116574377A (en) | 2023-04-26 | 2023-04-26 | Anti-structuring mixed silicon rubber and production process thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN116574377A (en) |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1368995A (en) * | 1999-08-19 | 2002-09-11 | 陶氏康宁公司 | Chemically modified silica fillers, process for producing and silicon compositions containing same |
| CN1786053A (en) * | 2005-09-29 | 2006-06-14 | 浙江新安化工集团股份有限公司 | Mixed milling type silicon rubber anti structural agent |
| JP2012172114A (en) * | 2011-02-23 | 2012-09-10 | Sumitomo Bakelite Co Ltd | Silicone rubber curable composition, molded product, medical tube, and surface treatment method of silica filler |
| CN103242534A (en) * | 2013-05-24 | 2013-08-14 | 江苏麒祥高新材料有限公司 | Anti-structuring control agent of white carbon black filling silicon rubber and preparation method of agent |
| CN104559202A (en) * | 2015-01-21 | 2015-04-29 | 宜昌兴之新塑胶电子科技有限公司 | Preparation method of high-tear-resistance silicon compounded rubber |
| JP2015209473A (en) * | 2014-04-25 | 2015-11-24 | 住友理工株式会社 | Silicone rubber composition and silicone rubber crosslinked body |
-
2023
- 2023-04-26 CN CN202310461878.4A patent/CN116574377A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1368995A (en) * | 1999-08-19 | 2002-09-11 | 陶氏康宁公司 | Chemically modified silica fillers, process for producing and silicon compositions containing same |
| CN1786053A (en) * | 2005-09-29 | 2006-06-14 | 浙江新安化工集团股份有限公司 | Mixed milling type silicon rubber anti structural agent |
| JP2012172114A (en) * | 2011-02-23 | 2012-09-10 | Sumitomo Bakelite Co Ltd | Silicone rubber curable composition, molded product, medical tube, and surface treatment method of silica filler |
| CN103242534A (en) * | 2013-05-24 | 2013-08-14 | 江苏麒祥高新材料有限公司 | Anti-structuring control agent of white carbon black filling silicon rubber and preparation method of agent |
| JP2015209473A (en) * | 2014-04-25 | 2015-11-24 | 住友理工株式会社 | Silicone rubber composition and silicone rubber crosslinked body |
| CN104559202A (en) * | 2015-01-21 | 2015-04-29 | 宜昌兴之新塑胶电子科技有限公司 | Preparation method of high-tear-resistance silicon compounded rubber |
Non-Patent Citations (1)
| Title |
|---|
| 张世玲等: "《高压复合绝缘子及其应用》", vol. 1, 中国建材工业出版社, pages: 170 - 76 * |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN112175210B (en) | Preparation method of organic silicon elastomer based on polyphenol compound crosslinking | |
| CN112375262A (en) | Wear-resistant sole material and preparation method thereof | |
| CN116574377A (en) | Anti-structuring mixed silicon rubber and production process thereof | |
| CN108484998B (en) | Wet mixing coprecipitation rubber and preparation method thereof | |
| CN113897171A (en) | Preparation method of high-displacement dealcoholized flame-retardant fireproof sealant | |
| CN110330654B (en) | Methyl vinyl silicone rubber and application thereof | |
| CN110564163A (en) | preparation method of fluorosilicone rubber for high-temperature-resistant layer of high-temperature cable | |
| CN110885560A (en) | Preparation method of silicone rubber composite material for insulator | |
| CN112011185B (en) | Method for preparing organic silicon thermoplastic vulcanized rubber by double-premixing dynamic vulcanization process | |
| CN114410000A (en) | Preparation method of low-cost multifunctional modified polypropylene black master batch | |
| CN113698772A (en) | Antistatic silicone rubber and preparation method thereof | |
| CN114085538A (en) | High-temperature-resistant natural rubber material and preparation method thereof | |
| CN113429807A (en) | Modified graphene and preparation method and application thereof | |
| CN117343690A (en) | Universal green silicone adhesive with stable storage and preparation method thereof | |
| CN113512198A (en) | Method for preparing high-hardness single-component oxime type room temperature vulcanized silicone rubber by using hydrolysis material | |
| CN116444933A (en) | Thermoplastic elastomer with low compression set characteristic and preparation method thereof | |
| CN117510862A (en) | Structure control agent and preparation method thereof | |
| CN110437622A (en) | A kind of self-lubricating silicon rubber and preparation method thereof | |
| CN112980195A (en) | Method for preparing high-hardness single-component alcohol-type room temperature vulcanized silicone rubber by using hydrolyzed material | |
| CN109457494B (en) | Cleaning agent-resistant polyvinyl chloride artificial leather | |
| CN113122004A (en) | Biological silicon rubber and preparation method thereof | |
| CN117534964A (en) | Semiconductive liquid silicone rubber composition, liquid silicone rubber and application thereof | |
| CN107841104A (en) | High temperature resistant PLA graphene composite material and preparation method thereof | |
| CN117050719A (en) | Method for controlling viscosity peak in dealcoholized organosilicon sealant production process | |
| CN118027885A (en) | Organic silicon water-blocking sealant for photovoltaic module and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination |