CN110330796A

CN110330796A - A kind of silicon rubber and preparation method thereof of boiling non-whitening

Info

Publication number: CN110330796A
Application number: CN201910515935.6A
Authority: CN
Inventors: 成家新
Original assignee: DONGGUAN TIAN'AN SILICONES TECHNOLOGY Co Ltd
Current assignee: DONGGUAN TIAN'AN SILICONES TECHNOLOGY Co Ltd
Priority date: 2019-06-14
Filing date: 2019-06-14
Publication date: 2019-10-15

Abstract

The present invention relates to silicon rubber technical fields, and in particular to a kind of silicon rubber and preparation method thereof of boiling non-whitening.The silicon rubber includes the raw material of following parts by weight: 100 parts of silicon rubber, 25-40 parts of reinforcing agent, 1.5-2.5 parts of dimethicone, silicon powder 8-12 parts modified, 5-10 parts of constitution controller, 1-2 parts of coupling agent, 1-5 parts of high temperature resistant agent, 12-16 parts of synergist, 0.5-2.0 parts of release agent and 0.5-1.5 parts of vulcanizing agent.Silicone rubber high temperature resistant of the invention is excellent, can be the phenomenon that moieties will not be precipitated inside silicon rubber after boiling, effectively surface is inhibited to whiten, and has the mechanical strengths such as preferable tensile strength, tearing strength, expansion and contraction, and stability is high.

Description

A kind of silicon rubber and preparation method thereof of boiling non-whitening

Technical field

The present invention relates to silicon rubber technical fields, and in particular to a kind of silicon rubber and preparation method thereof of boiling non-whitening.

Background technique

Current silicon rubber, after by boiling water, surface can generate one layer of white substance, these whiteness bases Originally be as caused by containing zinc stearate in silicon rubber, simultaneously because material dispersion in silicon rubber is uneven, heat resistance compared with It is low, so that at high temperature, the partial material in silicon rubber is precipitated, and main SiO₂Ingredient is then easy in conjunction with water, generates knot Brilliant hydrate, and then form whiteness.And the whiteness that this is precipitated in terms of be used in baby child and kitchen utensils for, very Puzzlement is brought to big degree to user, or even is had an impact to health, and the silicon rubber of whiteness is precipitated also due to its material Dispersion it is uneven, performances, the durability such as that there are intensity is low, tearing toughness is low are lower.

Summary of the invention

In order to overcome shortcoming and defect existing in the prior art, the purpose of the present invention is to provide a kind of boiling non-whitenings Silicon rubber, the silicone rubber high temperature resistant is excellent, moieties will not be precipitated inside silicon rubber after boiling, effectively inhibit The phenomenon that surface is whitened, and there are the mechanical strengths such as preferable tensile strength, tearing strength, expansion and contraction, stability is high.

Another object of the present invention is to provide a kind of preparation method of the silicon rubber of boiling non-whitening, the preparation method works Skill is simple, convenient operation and control, and quality is stablized, and high production efficiency, production cost is low, and silicon rubber obtained can be made by boiling Moieties will not be precipitated inside silicon rubber afterwards, it is suppressed that the phenomenon that surface is whitened, and have preferable tensile strength, tearing strong The mechanical strengths such as degree, expansion and contraction, stability is high, can large-scale industrial production.

The purpose of the invention is achieved by the following technical solution: a kind of silicon rubber of boiling non-whitening, the silicon rubber packet Include the raw material of following parts by weight:

The present invention prepares high-temperature-resisting silicon rubber by using above-mentioned raw materials, and asepsis environment-protecting, high temperature resistance is excellent, have compared with The performances such as good tensile strength, elongation at break, tearing strength, high mechanical strength；Wherein, by using reinforcing agent, silicon is improved The mechanical performances such as the hardness and tensile strength of rubber, and its powder shaped structure can promote the dispersibility of each material of silicon rubber；And it adopts Dimethicone can improve the plasticity of silicon rubber, increase flexibility, increase silicon rubber and reinforcing agent, modified silicon powder etc. The compatibility of powder shaped material, and the anti-aging phenomenon of silicon rubber can be effectively improved, reduce silicon rubber and occurs hardening after boiling, The aging phenomena such as cracking, and the demolding performace of silicon rubber is improved to a certain extent；And use through modified silicon powder, it can mention The dispersibility of high silicon rubber promotes the compatibility between each material, is easy to be uniformly mixed, avoids synergy in silicon rubber preparation process Phenomena such as conglomeration is reunited, occurs for the materials such as the dimethicone of the powder shapeds such as agent, reinforcing agent material and oily, and dispersibility is splendid, with Release agent and high temperature resistant agent three's mating reaction can effectively improve the phenomenon that whiteness is precipitated after silicon rubber high temperature boiling, suppression Silastic surface processed whitens；And the constitution controller used is avoided that silicon rubber is hardened in storage placement process, is plastic Property lower, processing performance the structuring phenomenons such as reduce, the stability of silastic-layer is improved, (if having there is the silicon rubber of structuring It then needs to re-start mixing or heat treatment goes to improve structuring phenomenon, but increase process costs simultaneously, and reduce production Efficiency and quality)；The coupling agent of use can improve the crosslink density and crosslinking agent centrostigma of silicon rubber, and improve material in silicon rubber Wetability and dispersibility in colloid system inhibit form and aspect variation of silicon rubber material during sulfidization molding, make that silicon rubber is made Film surface without stick sense, it is dry and comfortable, improve the performances such as tensile strength, elongation at break, the tearing strength of silicon rubber；What is used is resistance to High temperature agent can effectively be capable of the trace acidic of catalytic degradation reaction inside neutralized silicone rubber and alkaline matter prevents the oxidation of side chain The cyclisation depolymerization of crosslinking and main chain, the segment of large volume is introduced in the main chain of silicon rubber, caused by preventing backbone cyclized depolymerization Degradation, and the crosslinking due to caused by the oxygenolysis of organic side group of silicon rubber can be prevented and degraded, change the structure of side group, mentions The heat resistance of high silicon rubber；The synergist of use can effectively improve the heat resistance, anti-flammability, mechanical strength, ruler of silastic-layer The performances such as very little stability；If the not anxious demolding performace that can improve silicon rubber of material, improves its processing forming and stability, makes Whiteness is not precipitated after high temperature boiling in silicon rubber obtained, it is suppressed that the phenomenon that silastic product surface is whitened；It uses Vulcanizing agent can promote the sulfidization molding of material.

Preferably, the silicon rubber is phenylene silicone rubber, and the penylene base content of the phenylene silicone rubber is 55-60%, second Amount vinyl content is 0.06-0.12%, molecular weight is 680,000-78 ten thousand.

The phenylene silicone rubber that the present invention uses is the silicon rubber that penylene base is introduced in polysiloxane backbone, due to penylene base Introducing and strict control penylene base content, the high temperature resistance and heat radiation performance of silicon rubber can be significantly improved, and The content of strict control vinyl can improve the crosslink density of silicon rubber and the quantity of Concentrative crosslinking point, improve silicon rubber Mechanical strength reduces the crosslink density of silicon rubber, Concentrative crosslinking point quantity reduces, to drop if contents of ethylene is very few The mechanical performances such as the low hardness of silicon rubber, tearing strength can make the crosslink density of silicon rubber if contents of ethylene is excessive Excessively high, brittleness increases, and elongation rate of tensile failure reduces, and the tensile strength and tearing strength of silicon rubber decline；And pass through strict control The molecular weight of silicon rubber, using the long characteristic of high molecular weight, main chain, intermolecular active force is larger, can make silicon rubber obtained With preferable mechanical strength and processing forming；Simultaneously because containing aromatic ring in phenylene silicone rubber, so that silicon rubber strand Rigidity increase, flexibility reduces, and glass transition temperature improves, and improves high temperature resistance, up to 280-300 DEG C, and has moisture-proof The performances such as mildew-proof water-resistant steam are not easy that moieties are precipitated after boiling, inhibit the phenomenon that silastic surface whitens.

Preferably, every portion of reinforcing agent include 3-5 parts of partial sizes 6-12 μm titanium dioxide, 2-3 parts of partial sizes are at 8-10 μm Powdered whiting and 5-6 parts of specific surface areas in 250-350m²The precipitated silica of/g.

The present invention is used as reinforcing agent, and strict control by using titanium dioxide, powdered whiting and precipitated silica compounding The partial size and specific surface area of each material, can significantly improve the performances such as tensile strength, the elongation at break of silicon rubber.

Preferably, the constitution controller is to block poly- methyl-silicone oil and aminomethyl phenyl methoxy by hydroxy silicon oil, ethyoxyl Base silicone oil is with the mixture that weight ratio is that 3-5:1.5-2.0:1 is formed.

The present invention can make silicon rubber generate Concentrative crosslinking point by using the constitution controller of mentioned kind, improve silicon The crosslink density of rubber improves mechanical performance, and is avoided that silicon rubber is hardened (white carbon black surface in storage placement process Hydroxyl and silicon rubber molecule terminal condensation), the structuring phenomenons such as plasticity is lower, processing performance reduces, improve silicon rubber Stability, and avoid silicon rubber occur after high temperature boiling hardening, cracking etc. aging phenomena；Wherein, the hydroxy silicon oil of use Having the characteristics that viscosity is low, hydroxy radical content is high, activity is big, and anti-structured effect is obvious, and when use can save heat treatment procedure, and The transparency of product can be improved；The ethyoxyl of use block poly- methyl-silicone oil and methyl phenyl methoxy silicone oil can to silicon rubber into Row grafting is modified, improves its crosslinking points, improves the mechanical strength of silicon rubber.

Preferably, every part of coupling agent includes 1-3 parts of vinyltrimethoxysilanes, 1.2-1.8 parts of two oil of isopropyl Acid esters oxygroup (dioctyl phosphoric acid acyloxy titanate esters) and 2-4 parts of γ-aminopropyltrimethoxysilanes.

The present invention by using mentioned kind compounding be used as coupling agent, can significantly improve silicon rubber system tensile strength, The performances such as elongation at break, heat-resisting weatherability improve hygrometric state physical mechanical strength, the hygrometric state electric property of silastic material, change Kind wetability and dispersibility of the material in silicon rubber system, promotes the polymerization crosslinking of silicon rubber material.

Preferably, the high temperature resistant agent is with weight ratio by nano modification cerium oxide, di-iron trioxide and glass powder for 3- The mixture of 5:1-2:1 composition.

The present invention is used as high temperature resistant agent by using above-mentioned material compounding, and connection can be played between the matrix of silicon rubber and is made With can improve the high temperature resistance of silicon rubber, improve thermal stability of the silicon rubber in high temperature boiling, white is not precipitated after boiling Substance avoids its surface from whitening；Wherein, the nano modification cerium oxide of use can prevent the polysiloxanes oxide side chain of silicon rubber Crosslinking and backbone cyclized degradation, can effectively improve the heat resistance and thermal stability of silastic-layer；The di-iron trioxide of use can press down The polysiloxanes oxide side chain degradation of silastic-layer processed come improve silicon rubber heat resistance (in silicon rubber by Heat Ageing, The side chain of polysiloxanes is oxidized, and forms group, and during oxide side chain, di-iron trioxide can prevent the shape of group At, and then improve the heat resistance of silicon rubber)；For the glass powder of use after melted by heating, stickiness with higher makes silicon rubber shape At ceramic, heat resistant fire-proof system is formed, the heat resistance of silicon rubber is improved.

Preferably, the nano modification cerium oxide is made by following steps:

Step is 1.: ethyl alcohol, 1,2- butanediol and deionized water is mixed evenly with volume ratio for 15-18:3-8:1, Solvent A is made, then titanate coupling agent is added into solvent A, 25-30min is mixed, modified solution is made；

Step (2): ethyl alcohol and isopropanol are mixed evenly with volume ratio for 3-5:1, and solvent B is made, then will receive Rice cerium oxide is added into solvent B, and nanometer is made in ultrasonic disperse 30-40min under conditions of frequency is 12000-20000HZ Cerium oxide solution；

Step (3): by nano-cerium oxide solution made from step (2) in temperature be 65-70 DEG C at stirring in water bath, side stirring While modified solution made from step (1) is added dropwise in nano-cerium oxide solution, continue to stir 20-23min after being added dropwise, so Mixture is filtered afterwards, filter residue is washed 2-4 times with cleaning solution, is then to dry at 65-80 DEG C in temperature by the filter residue after washing Nano modification cerium oxide is made in 6-8h, grinding.

The present invention prepares nano modification cerium oxide by using above-mentioned steps, makes it have higher activity and reinforcement is made With the high temperature resistance of silicon rubber can be significantly improved；Wherein, step (1) is by using ethyl alcohol, 1,2- butanediol and deionized water Mixing is used as solvent A, can fully disperse titanate coupling agent to promote its subsequent with wherein and mix with nano-cerium oxide solution Reaction process；And step (2) by using ethyl alcohol and isopropanol as solvent A, nano-cerium oxide can fully be dispersed with Wherein, and by the way of ultrasonic disperse, and strict control supersonic frequency and time, being uniformly dispersed for nano-cerium oxide can be promoted Degree promotes its subsequent and modified solution hybrid reaction process；And step (3) is nano oxidized by the way that modified solution to be slowly dropped into In cerium solution, the completeness of modified-reaction can be promoted, keep titanate coupling agent sufficiently modified to nano-cerium oxide, and is solvent A, molten Contain a large amount of ethyl alcohol in agent B, the ingredient of the two solvent is similar, and the two can be made to be sufficiently mixed dispersion, is less prone to layering etc. Phenomenon, and the later period dries readily volatilized removal, and is washed using ethanol water, and the purity of nano modification cerium oxide is improved And quality.

Preferably, in the step (1), the mass ratio of titanate coupling agent and solvent A is 1:20-22, the titanate esters Coupling agent is isopropyl dioleate oxygroup (dioctyl phosphoric acid acyloxy titanate esters)；In the step (2), nano-cerium oxide Partial size is 20-150nm, and for nano-cerium oxide in advance through 60-70 DEG C of drying 4-6h, the mass ratio of nano-cerium oxide and solvent B is 1: 16-20；In the step (3), the revolving speed of stirring in water bath is 500-1000rpm, the modified solution and nano-cerium oxide solution Volume ratio be 1:6-12, the cleaning solution is the mixture that forms of 15-18:1 with volume ratio by ethyl alcohol and deionized water.

The present invention is by using isopropyl dioleate oxygroup (dioctyl phosphoric acid acyloxy titanate esters) as modified coupling Agent, and its solid-liquid ratio with solvent A is controlled, modification efficiency is high, can carry out sufficient surface to nano-cerium oxide and be modified, with nanometer Condensation reaction occurs for the hydroxyl on cerium oxide surface, forms chemical bonds, makes nano modification cerium oxide obtained that can promote silicon The dispersibility of gum material, the agglomeration for reducing material occurs, and nano modification cerium oxide can be made to absorb silicon rubber macromolecular The free radical that chain is generated due to heat ageing, improves the thermal stability of silicon rubber, and then improves its high temperature resistance.

And pass through the partial size of strict control nano-cerium oxide, and by preparatory drying and processing, it can be made to be well-dispersed in molten In agent A, keep its subsequent progress high effective and modified；And pass through the revolving speed of strict control stirring in water bath, titanate coupling agent can be made and received Rice cerium oxide come into full contact with, to nano-cerium oxide surface carry out it is high effective and modified, if revolving speed is slower, reduce modified reaction into Journey reduces the contact frequency and contact area of titanate coupling agent and nano-cerium oxide if revolving speed is very fast, reduces modified effect Fruit.

Preferably, every part of synergist includes 1.0-1.5 parts of montmorillonites, 3-8 parts of silicon carbide, 2-6 parts of zinc oxide and 5- 10 parts of zinc borates.

The present invention can significantly improve thermal stability anti-flammability, the machinery of silicon rubber by using the synergist of mentioned kind The performances such as intensity, dimensional stability；Wherein, the structure cell in the crystal structure of the montmorillonite of use is by two layers of oxygen-octahedron Between one layer of alumina octahedral of folder constitute, there is preferable layered nano-structure and cation exchange properties, make it have preferably Dispersibility improves the dispersibility of each material of silicon rubber, and then improves the dimensional stability and thermal resistance performance of silicon rubber, thermostabilization Property it is high；The silicon carbide of use plays the role of inert material, inhibits the contraction of firing product in silicon rubber burning cracking process, The dimensional stability for improving silastic-layer, makes it have preferable high temperature resistant, fire retardant performance；The zinc oxide used is both sexes Oxide can absorb Determining Micro Acid or alkaline matter that silicon rubber system can be catalyzed silicon rubber degradation, slow down the decomposition of silicon rubber, mention The heat resistance and acid-alkali-corrosive-resisting of high silastic-layer；The zinc borate of use is nontoxic, has preferable high thermal stability and divides Property is dissipated, the anti-flammability and thermal stability of silicon rubber can be effectively improved, it is heat-resist, it is not easy to deform because of high temperature or spontaneous combustion, so that Whiteness is not precipitated after high temperature boiling in silicon rubber.

Preferably, every part of release agent include 2-4 parts of polytetrafluoroethylene (PTFE), 2-5 parts of fluorinated ethylene propylene copolymers and 0.5-1.0 parts of metlyl branching silicone oils.

The present invention can reduce the surface energy of silicon rubber, isolation performance is good, dosage by using the release agent of mentioned kind It is few, the release property between silicon rubber and mold is improved, and few to the pollution of mold；Wherein, the polytetrafluoroethylene (PTFE) high temperature resistant of use Excellent performance, and it is ageing-resistant, phenomena such as being less prone to cracking in an atmosphere or under high temperature boiling, harden, coefficient of friction is low, interior lubrication Property is good, can improve the release property of silicon rubber；The fluorinated ethylene propylene copolymer of use has preferable heat resistance and chemically-resistant Stability improves its heat resistance while improving silicon rubber demoulding effect, analyses silicon rubber obtained not after high temperature boiling Whiteness out；The metlyl branching silicone oil of use can directly apply in silicon rubber demoulding, and processing performance is excellent.

Preferably, the vulcanizing agent be by t-butyl perbenzoate and 2,5- dimethyl -2,5- di-tert-butyl peroxide oneself Alkane is with the mixture that weight ratio is that 1-2:3-5 is formed.

The present invention is used in compounding by using the vulcanizing agent of mentioned kind, can be improved the vulcanization crosslinking effect of silicon rubber, be shown It writes and shortens vulcanization time, vulcanization effect is good, and silicon rubber obtained can be made to have preferable tensile strength, elongation at break, tearing The mechanical strengths such as intensity and stability.

Preferably, the modified silicon powder is made by following steps:

Step (1): silicon powder is heated to 100-108 DEG C, stirring, being added while stirring to mass fraction is 16-20% Ammonia spirit in, adjust pH value to 7.8-8.2, return stirring 2-5h at being then 115-120 DEG C in temperature keeps the temperature, is made Mixture is 1.；

Step (2): coupling modifier is added into alcoholic solution, is mixed, and mixture is made 2.；

Step (3): by mixture made from step (2) be 2. added to mixture made from step (1) 1. in, while stirring It is added, then return stirring 90-180min at being 103-108 DEG C in temperature after addition is filtered, washed, is in temperature It is dry at 120-125 DEG C, modified silicon powder is made.

The present invention prepares modified silicon powder by using above-mentioned steps, is acted on using the functional group of modifying agent so that silicon powder Firm covalent bond interface cohesion is realized with silicon rubber, the hydrophily of silicon powder can be changed into organophilic surface, is improved Silicon powder is modified to the dispersion performance of silicon rubber system, and reduces the section thermal resistance of silicon rubber, improves the heat resistance of silicon rubber, Make it that moieties should not be precipitated after high temperature boiling, always silastic surface blushing.

Wherein, by first heating silicon powder, make its pre-activate, recycle the ammonia spirit of partial ionization to its into 1. row hydrolysis, and strict control response parameter form it into the mixture of surface hydroxylation system, while utilizing alcoholic solvent antithesis Connection agent B is hydrolyzed, so that reacting with Si three hydrolysising groups being connected with water in coupling modifier, generates silanol, and silanol Between be dehydrated, be condensed into the oligosiloxane of Si-OH so that hydrolyze after mixture be 1. 2. easily dispersed with mixture It is even, it solves the problems, such as the dispersion unevenness of coupling agent and silicon powder, promotes modified process and efficiency；Finally the coupling after hydrolysis is changed Property agent is gradually added into silicon powder, and carrying out sufficient surface with it contacts, and is modified, so that the mixture containing Si-OH 2. reacting with the OH on the hydroxylated surface of silicon powder, hydrogen bond is formed, condensation, dehydration finally occur during being heated to reflux And curing reaction, firm Covalent bonding together is formed with silicon powder, improves the organophilic of silicon powder, silicon rubber is promoted to be adsorbed on The surface of modified silicon powder, and promote the dispersion of material, so that modified silicon powder and reinforcing agent cooperate, reinforcement is only used in improvement Agent to silicon rubber carry out reinforcement and caused by viscosity is excessive, poor fluidity, processing forming is poor, hardness is low the problems such as, and modification Silicon powder afterwards can effectively improve the heat resistance of silicon rubber, make silicon rubber obtained that whiteness not be precipitated after high temperature boiling, Inhibit the phenomenon that surface is whitened.

Preferably, in the step (1), the mixing mass ratio of the silicon powder and ammonia spirit is 2:2.5-3, the silicon The partial size of micro mist is 20-80 μm；In the step (2), the coupling modifier is by N- β (aminoethyl)-γ-aminopropyltriethoxy With the mixture that weight ratio is that 1.5-2.0:1 is formed, the alcohol is molten for dimethoxysilane and phenylaminomethyl trimethoxy silane The mixture that liquid is made of n-butanol and ethyl alcohol with volume ratio for 1:1.5-2.0, the coupling modifier and alcoholic solution mix Conjunction mass ratio is 0.5-1.0:18；In the step (3), 1. mixture is 8-15:1- with the mixing mass ratio of mixture 2. 1.5。

The present invention passes through the mixed proportion of strict control silicon powder and ammonia spirit, and the ionic activity of ammonium hydroxide is high, utilizes ammonia Silicon powder is hydrolyzed in the hydroxyl that water section ionizes out, makes its surface hydroxylation, promotes its coupling modifier with sequential hydrolysis Agent is bonded, and promotes to be modified；And pass through the partial size of strict control silicon powder, preferable specific surface area is made it have, it is promoted The hydroxylating on surface, and silicon rubber is improved in the adsorbance of silicon micropowder surface, and then improves the mechanical performance of silicon rubber；And pass through Coupling modifier is used as using above-mentioned amino silane coupling agent compounding, the hydrolysing activity base of Si is contained in one end in molecule Group hydrolyzes when it is in above-mentioned alcoholic solution of the invention, and hydrolysising group then react generation Si- with water in coupling modifier OH, and the Si-OH generated then reacts to form hydrogen bond with the hydroxylated OH of silicon micropowder surface, while contracting under heating conditions Dehydration is closed, Covalent bonding together is formed, and the other end contains non-hydrolytic amino in the silane coupled agent molecule of above-mentioned amino Functional group reactions in active group, with silicon rubber promote coupling modifier and the connection with silicon rubber, inhale so that silicon rubber is stablized The surface for investing silicon powder, improves the mechanical performance of silicon rubber, and promotes the dispersibility of each material and silicon rubber, so that silicon powder Effect is matched with release agent, high temperature resistant agent, is improved dispersibility of three's material in silicon rubber strand, is improved silicon rubber Heat resistance, it is non-aging after high temperature boiling, whiteness is not precipitated, inhibit the phenomenon that silastic surface whitens.

And by strict control mixture, 1. the mixing mass ratio with mixture 2., the amino one type of silane after capable of making hydrolysis are even Connection agent react with hydroxylated silicon micropowder surface, generate hydrogen bond, and amino then with the functional group reactions of silicon rubber, the two cooperate rush Into silicon rubber in the adsorption capacity of silicon micropowder surface, the mechanical performance and heat resistance of silicon rubber are improved, if the dosage mistake of mixture 1. It is few, then the reaction active sites and amount of hydroxyl groups of silicon micropowder surface are reduced, so that the OH and hydroxyl of the coupling modifier after hydrolysis The hydrogen bonding degree of SiClx micro mist is lower, and the crosslinking for reducing coupling modifier and silicon powder is binding affinity, and the idol that dosage is more The amino of connection modifying agent is then reacted with silicon rubber, so that coupling modifier is with silicon rubber associativity good but is bonded with silicon powder Property is lower, reduces silicon rubber in the adsorption capacity of silicon micropowder surface, thereby reduce the mechanical performance of silicon rubber, heat resistance and The dispersibility of material in system；On the contrary, on the one hand reducing the hydrogen with hydroxylating silicon powder if the dosage of mixture 2. is very few Key bonding, on the other hand then reduce functional group reactions with silicon rubber, so that adsorption capacity of the silicon rubber in silicon micropowder surface, Reduce the mechanical performance and heat resistance of silicon rubber.

Another object of the present invention is achieved through the following technical solutions: a kind of silicon rubber of boiling non-whitening as described above Preparation method includes the following steps:

A, silicon rubber and constitution controller in parts by weight, are stirred mixing, material A is made；

B, in parts by weight, reinforcing agent is added in five times into material A made from step A, reinforcing agent is added every time After stir to reinforcing agent and be thoroughly mixed into step A, material B are all made after mixing；

C, in parts by weight, coupling agent, high temperature resistant agent and synergist are added into material B made from step B, mixed Obtained material C after uniformly；

D, in parts by weight, dimethicone, modified silicon powder and release agent are added to material C made from step C In, material D is made after mixing；

E, it by the agglomerating rear material D heating refining glue obtained of step D mixing, is made to mediate and expect；Then material discharging will be mediated, is opened Uniformly, lower roll stands 8-12h after filtering for refining, and base rubber is made；

F, base rubber mill made from step E is uniform, vulcanizing agent is then added, mill is uniformly dispersed again, clot lower roll, Sizing material is made, for use；

G, sizing material made from step F is vulcanized by five sections of hot drying tunnels, it is cooling, the silicon rubber of boiling non-whitening is made Glue.

The present invention prepares silicon rubber by using above-mentioned steps, and simple process, convenient operation and control, quality is stable, production High-efficient, production cost is low, and silicon rubber obtained can be made to have high temperature resistance, whiteness is not precipitated after high temperature boiling, Phenomena such as being less prone to hardening, cracking, and there is preferable mechanical strength and stability, it can large-scale industrial production；Wherein, By the addition sequence and processing parameter of strict control unclassified stores, first constitution controller and silicon rubber are stirred, can be mentioned The inhibition structuring performance of high silicon rubber system when avoiding subsequent addition reinforcing agent, improves silicone rubber mechanical performance in reinforcing agent When make silicon rubber be easy to structuring phenomenon occur, and reinforcing agent is added portionwise, and can gradually adjust, improve the machinery of silicon rubber Intensity and toughness easily cause the structuring phenomenon of silicon rubber system, reduce silicon rubber if reinforcing agent is once all added The intensity of system.Then coupling agent, high temperature resistant agent and synergist is added, the high temperature resistance, heat-resisting of silicon rubber can be significantly improved Property, anti-flammability, mechanical strength, dimensional stability, the performances such as interior release property, and promote under the action of coupling agent reinforcing agent, resistance to The cross-linked polymeric of high temperature agent, synergist and composite silicone rubber acts on.Thereafter dimethicone, modified silicon powder and demoulding are added Agent improves the high temperature resistance and heat of silicon rubber by modified silicon powder, high temperature resistant agent and release agent three's phase coordinative role Stability, and modified silicon powder can promote the dispersibility of each material, avoid that agglomeration occurs.

Heating refining glue and vacuum processing are finally carried out, the subsequent processing curingprocess rate of silicon rubber and stability is improved, reduces The dosage of vulcanizing agent shortens vulcanization time and reduces curing temperature, and then effectively improves the mechanical performance of silicon rubber.

Preferably, in the step A, the time for stirring mixing is 3-8min；In the step E, the filtering is used The filtering of 180-220 mesh filter screen；In the step E, the heating refining glue specific steps are as follows: step D mixing is agglomerating rear obtained Material D is warming up to 90-100 DEG C, and full open end mediates 50-60min, then carries out vacuumize process, is made and mediates material；It is described to take out very The time of vacancy reason is 65-75min, and vacuum degree is -0.06MPa~-0.08MPa.

The present invention by the mixing time of strict control silicon rubber, can make silicon rubber it is subsequent be blended with material in compatibility Preferably, it is uniformly dispersed, improves the mechanical strength of silicon rubber；It is filtered by using 180-220 mesh filter screen, removes object during mill Dough consor at bulky grain, improve the uniformity of the subsequent mixing with other raw materials and material during sulfidization molding be thin Greasy degree.And by that can improve kneading processing in air after material D heating the intersolubility between each raw material, effectively improve silicon The stability of rubbery system improves subsequent curingprocess rate, and is vacuum-treated, and can improve the agglomerating effect of kneading of material, Improve the intensity of silicon rubber.And the time and vacuum degree, the inside that can improve silicon rubber being vacuum-treated by strict control bond Polymerism, be easy to carry out following process prolongs pressure etc. processes, processing forming is good, make silicon rubber have preferable tensile strength, The mechanical strengths such as elongation at break, tearing strength.

Preferably, in the step G, the temperature that five sections of hot drying tunnel temperatures of vulcanization are respectively as follows: first segment is 225-235 DEG C, the temperature of second segment is 235-245 DEG C, and the temperature of third section is 250-260 DEG C, and the 4th section of temperature is 240-250 DEG C, the Five sections of temperature is 230-240 DEG C.

The temperature of each section that the present invention is vulcanized by strict control can gradually heat up to base rubber and vulcanize, and vulcanization is promoted to hand over Connection sufficiently, improves mechanical strengths and the thermal stability such as tensile strength, elongation at break, the tearing strength of silicon rubber obtained；If Curing temperature is too low, then reduces the vulcanization crosslinking efficiency and effect of silicon rubber system, make silicon rubber mechanical strength obtained compared with It is low, stability is low, if curing temperature is excessively high, phenomena such as silicon rubber is burnt, and it is old to be easy to produce hardening, cracking etc. Change phenomenon, using effect is poor.

The beneficial effects of the present invention are: the silicone rubber high temperature resistant of boiling non-whitening of the present invention is excellent, is passing through boiling The phenomenon that moieties will not be precipitated inside silicon rubber afterwards, effectively surface is inhibited to whiten, and there is preferable tensile strength, tear The mechanical strengths such as resistance to spalling, expansion and contraction, stability are high.

The preparation method simple process of the silicon rubber of boiling non-whitening of the present invention, convenient operation and control, quality are stablized, production High-efficient, production cost is low, can make silicon rubber obtained that moieties not be precipitated inside silicon rubber after boiling, it is suppressed that The phenomenon that surface is whitened, and there are the mechanical strengths such as preferable tensile strength, tearing strength, expansion and contraction, stability is high, can advise greatly Mould industrialized production.

Specific embodiment

For the ease of the understanding of those skilled in the art, below with reference to embodiment, the present invention is further illustrated, real The content that the mode of applying refers to not is limitation of the invention.

Embodiment 1

A kind of silicon rubber of boiling non-whitening, the silicon rubber includes the raw material of following parts by weight:

The silicon rubber is phenylene silicone rubber, and the penylene base content of the phenylene silicone rubber is 55%, contents of ethylene is 0.12%, molecular weight is 680,000；

Every portion of reinforcing agent include 3 parts of partial sizes 6 μm titanium dioxide, 2 parts of partial sizes are in 8 μm of powdered whiting and 5 parts Specific surface area is in 350m²The precipitated silica of/g.

The constitution controller be blocked by hydroxy silicon oil, ethyoxyl poly- methyl-silicone oil and methyl phenyl methoxy silicone oil with Weight ratio is the mixture of 3:1.5:1 composition；Every part of coupling agent includes 1 part of vinyltrimethoxysilane, 1.2 parts of isopropyls Base dioleate oxygroup (dioctyl phosphoric acid acyloxy titanate esters) and 2 parts of γ-aminopropyltrimethoxysilanes.

The high temperature resistant agent is made of nano modification cerium oxide, di-iron trioxide and glass powder with weight ratio for 3:1:1 Mixture；Every part of synergist includes 1.0 parts of montmorillonites, 3 parts of silicon carbide, 2 parts of zinc oxide and 5 parts of zinc borates.

The nano modification cerium oxide is made by following steps:

Step is 1.: ethyl alcohol, 1,2- butanediol and deionized water being mixed evenly with volume ratio for 15:8:1, are made molten Agent A, then titanate coupling agent is added into solvent A, and 25min is mixed, and modified solution is made；

Step is 2.: ethyl alcohol and isopropanol being mixed evenly with volume ratio for 3:1, solvent B is made, then by nano oxygen Change cerium to be added into solvent B, nano-cerium oxide solution is made in ultrasonic disperse 40min under conditions of frequency is 12000HZ；

Step is 3.: by step, 2. nano-cerium oxide solution obtained in temperature is stirring in water bath at 65 DEG C, while stirring will 1. modified solution obtained is added dropwise in nano-cerium oxide solution step, continues to stir 20min after being added dropwise, then will mixing Object filtering, filter residue are washed 4 times with cleaning solution, are then to dry 8h at 65 DEG C in temperature by the filter residue after washing, grind, be made and receive The modified oxidized cerium of rice.

The step 1. in, the mass ratio of titanate coupling agent and solvent A is 1:20, and the titanate coupling agent is isopropyl Base dioleate oxygroup (dioctyl phosphoric acid acyloxy titanate esters)；The step 2. in, the partial size of nano-cerium oxide is 20nm, is received For rice cerium oxide in advance through 60 DEG C of drying 6h, the mass ratio of nano-cerium oxide and solvent B are 1:16；The step 3. in, water-bath is stirred The revolving speed mixed is 500rpm, and the volume ratio of the modified solution and nano-cerium oxide solution is 1:6, and the cleaning solution is by ethyl alcohol The mixture formed with deionized water with volume ratio for 15:1.

Every part of release agent includes 2 parts of polytetrafluoroethylene (PTFE), 2 parts of fluorinated ethylene propylene copolymers and 0.5 part of methyl branch Silicone oil；The vulcanizing agent is by t-butyl perbenzoate and 2,5- dimethyl -2,5- di-t-butyl hexane peroxide with weight ratio For the mixture of 1:3 composition.

The modified silicon powder is made by following steps:

Step (1): silicon powder is heated to 100 DEG C, it is molten that the ammonium hydroxide for being 16% to mass fraction is added in stirring while stirring In liquid, pH value is adjusted to 7.8, mixture is made 1. in return stirring 5h at being then 115 DEG C in temperature, heat preservation；

Step (3): by mixture made from step (2) be 2. added to mixture made from step (1) 1. in, while stirring It is added, then return stirring 180min at being 103 DEG C in temperature after addition is filtered, washed, do at being 120 DEG C in temperature It is dry, modified silicon powder is made.

In the step (1), the mixing mass ratio of the silicon powder and ammonia spirit is 2:2.5, the grain of the silicon powder Diameter is 20 μm；In the step (2), the coupling modifier is by N- β (aminoethyl)-γ-aminopropyltriethoxy dimethoxy silicon Alkane and phenylaminomethyl trimethoxy silane with the mixture that weight ratio is that 1.5:1 form, the alcoholic solution be by n-butanol with The mixing mass ratio of the mixture that ethyl alcohol is formed with volume ratio for 1:2.0, the coupling modifier and alcoholic solution is 0.5:18；Institute It states in step (3), 1. mixture is 8:1.5 with the mixing mass ratio of mixture 2..

A kind of preparation method of the silicon rubber of boiling non-whitening as described above, includes the following steps:

E, it by the agglomerating rear material D heating refining glue obtained of step D mixing, is made to mediate and expect；Then material discharging will be mediated, is opened Uniformly, lower roll stands 8h after filtering for refining, and base rubber is made；

In the step A, the time for stirring mixing is 3min；In the step E, the filtering uses 180 mesh filter screen mistakes Filter；In the step E, the heating refining glue specific steps are as follows: the agglomerating rear material D obtained of step D mixing is warming up to 90 DEG C, Full open end mediates 60min, then carries out vacuumize process, is made and mediates material；The time of the vacuumize process is 65min, very Reciprocal of duty cycle is -0.08MPa.

In the step G, the temperature that five sections of hot drying tunnel temperatures of vulcanization are respectively as follows: first segment is 225 DEG C, the temperature of second segment Degree is 235 DEG C, and the temperature of third section is 250 DEG C, and the 4th section of temperature is 240 DEG C, and the 5th section of temperature is 230 DEG C.

Embodiment 2

The silicon rubber is phenylene silicone rubber, and the penylene base content of the phenylene silicone rubber is 56%, contents of ethylene is 0.10%, molecular weight is 700,000；Every portion of reinforcing agent include 3.5 parts of partial sizes 8 μm titanium dioxide, 2.2 parts of partial sizes are at 8.5 μm Powdered whiting and 5.2 parts of specific surface areas in 320m²The precipitated silica of/g.

The constitution controller be blocked by hydroxy silicon oil, ethyoxyl poly- methyl-silicone oil and methyl phenyl methoxy silicone oil with Weight ratio is the mixture of 3.5:1.6:1 composition；Every part of coupling agent includes 1.5 parts of vinyltrimethoxysilanes, 1.3 parts Isopropyl dioleate oxygroup (dioctyl phosphoric acid acyloxy titanate esters) and 2.5 parts of γ-aminopropyltrimethoxysilanes.

The high temperature resistant agent is with weight ratio by nano modification cerium oxide, di-iron trioxide and glass powder for 3.5:1.2:1 The mixture of composition；Every part of synergist includes 1.2 parts of montmorillonites, 4 parts of silicon carbide, 3 parts of zinc oxide and 6 parts of zinc borates.

The nano modification cerium oxide is made by following steps:

Step is 1.: ethyl alcohol, 1,2- butanediol and deionized water being mixed evenly with volume ratio for 16:7:1, are made molten Agent A, then titanate coupling agent is added into solvent A, and 26min is mixed, and modified solution is made；

Step is 2.: ethyl alcohol and isopropanol being mixed evenly with volume ratio for 3.5:1, solvent B is made, then by nanometer Cerium oxide is added into solvent B, and nano-cerium oxide solution is made in ultrasonic disperse 38min under conditions of frequency is 14000HZ；

Step is 3.: by step, 2. nano-cerium oxide solution obtained in temperature is stirring in water bath at 66 DEG C, while stirring will 1. modified solution obtained is added dropwise in nano-cerium oxide solution step, continues to stir 21min after being added dropwise, then will mixing Object filtering, filter residue are washed 3 times with cleaning solution, are then to dry 7.5h at 68 DEG C in temperature by the filter residue after washing, grind, be made Nano modification cerium oxide.

The step 1. in, the mass ratio of titanate coupling agent and solvent A is 1:20.5, and the titanate coupling agent is different Propyl dioleate oxygroup (dioctyl phosphoric acid acyloxy titanate esters)；The step 2. in, the partial size of nano-cerium oxide is 50nm, For nano-cerium oxide in advance through 62 DEG C of drying 5.5h, the mass ratio of nano-cerium oxide and solvent B are 1:17；The step 3. in, water The revolving speed of bath stirring is 600rpm, and the volume ratio of the modified solution and nano-cerium oxide solution is 1:8, the cleaning solution be by The mixture that ethyl alcohol and deionized water are formed with volume ratio for 16:1.

Every part of release agent includes 2.5 parts of polytetrafluoroethylene (PTFE), 3 parts of fluorinated ethylene propylene copolymers and 0.6 part of methyl branch Chain silicone oil；The vulcanizing agent is by t-butyl perbenzoate and 2,5- dimethyl -2,5- di-t-butyl hexane peroxide with weight Than the mixture formed for 1.2:3.5.

The modified silicon powder is made by following steps:

Step (1): silicon powder is heated to 102 DEG C, it is molten that the ammonium hydroxide for being 17% to mass fraction is added in stirring while stirring In liquid, pH value is adjusted to 7.9, mixture is made 1. in return stirring 4h at being then 116 DEG C in temperature, heat preservation；

Step (3): by mixture made from step (2) be 2. added to mixture made from step (1) 1. in, while stirring It is added, then return stirring 165min at being 104 DEG C in temperature after addition is filtered, washed, do at being 121 DEG C in temperature It is dry, modified silicon powder is made.

In the step (1), the mixing mass ratio of the silicon powder and ammonia spirit is 2:2.6, the grain of the silicon powder Diameter is 40 μm；In the step (2), the coupling modifier is by N- β (aminoethyl)-γ-aminopropyltriethoxy dimethoxy silicon Alkane and phenylaminomethyl trimethoxy silane with the mixture that weight ratio is that 1.6:1 form, the alcoholic solution be by n-butanol with The mixing mass ratio of the mixture that ethyl alcohol is formed with volume ratio for 1:1.9, the coupling modifier and alcoholic solution is 0.6:18；Institute It states in step (3), 1. mixture is 10:1.3 with the mixing mass ratio of mixture 2..

E, it by the agglomerating rear material D heating refining glue obtained of step D mixing, is made to mediate and expect；Then material discharging will be mediated, is opened Uniformly, lower roll stands 9h after filtering for refining, and base rubber is made；

In the step A, the time for stirring mixing is 4min；In the step E, the filtering uses 190 mesh filter screen mistakes Filter；In the step E, the heating refining glue specific steps are as follows: the agglomerating rear material D obtained of step D mixing is warming up to 92 DEG C, Full open end mediates 58min, then carries out vacuumize process, is made and mediates material；The time of the vacuumize process is 68min, very Reciprocal of duty cycle is -0.065MPa.

In the step G, the temperature that five sections of hot drying tunnel temperatures of vulcanization are respectively as follows: first segment is 228 DEG C, the temperature of second segment Degree is 238 DEG C, and the temperature of third section is 252 DEG C, and the 4th section of temperature is 242 DEG C, and the 5th section of temperature is 232 DEG C.

Embodiment 3

The silicon rubber is phenylene silicone rubber, and the penylene base content of the phenylene silicone rubber is 58%, contents of ethylene is 0.09%, molecular weight is 720,000；The weight that every portion of reinforcing agent includes 4 parts of partial sizes in 9 μm of titanium dioxide, 2.5 parts of partial sizes at 9 μm Matter calcium carbonate and 5.5 parts of specific surface areas are in 300m²The precipitated silica of/g.

The constitution controller be blocked by hydroxy silicon oil, ethyoxyl poly- methyl-silicone oil and methyl phenyl methoxy silicone oil with Weight ratio is the mixture of 4:1.8:1 composition；Every part of coupling agent includes 2 parts of vinyltrimethoxysilanes, 1.5 parts of isopropyls Base dioleate oxygroup (dioctyl phosphoric acid acyloxy titanate esters) and 3 parts of γ-aminopropyltrimethoxysilanes.

The high temperature resistant agent is with weight ratio by nano modification cerium oxide, di-iron trioxide and glass powder for 4:1.5:1 group At mixture；Every part of synergist includes 1.3 parts of montmorillonites, 5 parts of silicon carbide, 4 parts of zinc oxide and 8 parts of zinc borates.

The nano modification cerium oxide is made by following steps:

Step is 1.: ethyl alcohol, 1,2- butanediol and deionized water being mixed evenly with volume ratio for 16.5:6:1, are made Then solvent A titanate coupling agent is added into solvent A, 28min is mixed, and modified solution is made；

Step is 2.: ethyl alcohol and isopropanol being mixed evenly with volume ratio for 4:1, solvent B is made, then by nano oxygen Change cerium to be added into solvent B, nano-cerium oxide solution is made in ultrasonic disperse 35min under conditions of frequency is 16000HZ；

Step is 3.: by step, 2. nano-cerium oxide solution obtained in temperature is stirring in water bath at 68 DEG C, while stirring will 1. modified solution obtained is added dropwise in nano-cerium oxide solution step, continues to stir 22min after being added dropwise, then will mixing Object filtering, filter residue are washed 3 times with cleaning solution, are then to dry 7h at 72 DEG C in temperature by the filter residue after washing, grind, be made and receive The modified oxidized cerium of rice.

The step 1. in, the mass ratio of titanate coupling agent and solvent A is 1:21, and the titanate coupling agent is isopropyl Base dioleate oxygroup (dioctyl phosphoric acid acyloxy titanate esters)；The step 2. in, the partial size of nano-cerium oxide is 80nm, is received For rice cerium oxide in advance through 65 DEG C of drying 5h, the mass ratio of nano-cerium oxide and solvent B are 1:18；The step 3. in, water-bath is stirred The revolving speed mixed is 800rpm, and the volume ratio of the modified solution and nano-cerium oxide solution is 1:9, and the cleaning solution is by ethyl alcohol The mixture formed with deionized water with volume ratio for 16.5:1.

Every part of release agent includes 3 parts of polytetrafluoroethylene (PTFE), 3.5 parts of fluorinated ethylene propylene copolymers and 0.8 part of methyl branch Chain silicone oil；The vulcanizing agent is by t-butyl perbenzoate and 2,5- dimethyl -2,5- di-t-butyl hexane peroxide with weight Than the mixture formed for 1.5:4.

The modified silicon powder is made by following steps:

Step (1): silicon powder is heated to 104 DEG C, it is molten that the ammonium hydroxide for being 18% to mass fraction is added in stirring while stirring In liquid, pH value is adjusted to 8.0, mixture is made 1. in return stirring 3.5h at being then 118 DEG C in temperature, heat preservation；

Step (3): by mixture made from step (2) be 2. added to mixture made from step (1) 1. in, while stirring It is added, then return stirring 140min at being 105 DEG C in temperature after addition is filtered, washed, do at being 122 DEG C in temperature It is dry, modified silicon powder is made.

In the step (1), the mixing mass ratio of the silicon powder and ammonia spirit is 2:2.8, the grain of the silicon powder Diameter is 50 μm；In the step (2), the coupling modifier is by N- β (aminoethyl)-γ-aminopropyltriethoxy dimethoxy silicon Alkane and phenylaminomethyl trimethoxy silane with the mixture that weight ratio is that 1.8:1 form, the alcoholic solution be by n-butanol with The mixing mass ratio of the mixture that ethyl alcohol is formed with volume ratio for 1:1.8, the coupling modifier and alcoholic solution is 0.8:18；Institute It states in step (3), 1. mixture is 13:1.2 with the mixing mass ratio of mixture 2..

E, it by the agglomerating rear material D heating refining glue obtained of step D mixing, is made to mediate and expect；Then material discharging will be mediated, is opened Uniformly, lower roll stands 10h after filtering for refining, and base rubber is made；

In the step A, the time for stirring mixing is 5min；In the step E, the filtering uses 200 mesh filter screen mistakes Filter；In the step E, the heating refining glue specific steps are as follows: the agglomerating rear material D obtained of step D mixing is warming up to 95 DEG C, Full open end mediates 55min, then carries out vacuumize process, is made and mediates material；The time of the vacuumize process is 70min, very Reciprocal of duty cycle is -0.07MPa.

In the step G, the temperature that five sections of hot drying tunnel temperatures of vulcanization are respectively as follows: first segment is 230 DEG C, the temperature of second segment Degree is 240 DEG C, and the temperature of third section is 255 DEG C, and the 4th section of temperature is 245 DEG C, and the 5th section of temperature is 235 DEG C.

Embodiment 4

The silicon rubber is phenylene silicone rubber, and the penylene base content of the phenylene silicone rubber is 59%, contents of ethylene is 0.08%, molecular weight is 750,000；Every portion of reinforcing agent include 4.5 parts of partial sizes 10 μm titanium dioxide, 2.8 parts of partial sizes are in 9.5 μ The powdered whiting of m and 5.8 parts of specific surface areas are in 280m²The precipitated silica of/g.

The constitution controller be blocked by hydroxy silicon oil, ethyoxyl poly- methyl-silicone oil and methyl phenyl methoxy silicone oil with Weight ratio is the mixture of 4.5:1.9:1 composition；Every part of coupling agent includes 2.3 parts of vinyltrimethoxysilanes, 1.6 parts Isopropyl dioleate oxygroup (dioctyl phosphoric acid acyloxy titanate esters) and 3.5 parts of γ-aminopropyltrimethoxysilanes.

The high temperature resistant agent is with weight ratio by nano modification cerium oxide, di-iron trioxide and glass powder for 4.5:1.8:1 The mixture of composition；Every part of synergist includes 1.4 parts of montmorillonites, 6 parts of silicon carbide, 5 parts of zinc oxide and 9 parts of zinc borates.

The nano modification cerium oxide is made by following steps:

Step is 1.: ethyl alcohol, 1,2- butanediol and deionized water being mixed evenly with volume ratio for 17:5:1, are made molten Agent A, then titanate coupling agent is added into solvent A, and 29min is mixed, and modified solution is made；

Step is 2.: ethyl alcohol and isopropanol being mixed evenly with volume ratio for 4.5:1, solvent B is made, then by nanometer Cerium oxide is added into solvent B, and nano-cerium oxide solution is made in ultrasonic disperse 32min under conditions of frequency is 18000HZ；

Step is 3.: by step, 2. nano-cerium oxide solution obtained in temperature is stirring in water bath at 69 DEG C, while stirring will 1. modified solution obtained is added dropwise in nano-cerium oxide solution step, continues to stir 22min after being added dropwise, then will mixing Object filtering, filter residue are washed 2 times with cleaning solution, are then to dry 6.5h at 76 DEG C in temperature by the filter residue after washing, grind, be made Nano modification cerium oxide.

The step 1. in, the mass ratio of titanate coupling agent and solvent A is 1:21.5, and the titanate coupling agent is different Propyl dioleate oxygroup (dioctyl phosphoric acid acyloxy titanate esters)；The step 2. in, the partial size of nano-cerium oxide is 120nm, for nano-cerium oxide in advance through 68 DEG C of drying 4.5h, the mass ratio of nano-cerium oxide and solvent B are 1:19；The step is 3. In, the revolving speed of stirring in water bath is 900rpm, and the volume ratio of the modified solution and nano-cerium oxide solution is 1:10, the washing The mixture that liquid is made of ethyl alcohol and deionized water with volume ratio for 17:1.

Every part of release agent includes 3.5 parts of polytetrafluoroethylene (PTFE), 4 parts of fluorinated ethylene propylene copolymers and 0.9 part of methyl branch Chain silicone oil；The vulcanizing agent is by t-butyl perbenzoate and 2,5- dimethyl -2,5- di-t-butyl hexane peroxide with weight Than the mixture formed for 1.8:4.5.

The modified silicon powder is made by following steps:

Step (1): silicon powder is heated to 106 DEG C, it is molten that the ammonium hydroxide for being 19% to mass fraction is added in stirring while stirring In liquid, pH value is adjusted to 8.1, mixture is made 1. in return stirring 3h at being then 119 DEG C in temperature, heat preservation；

Step (3): by mixture made from step (2) be 2. added to mixture made from step (1) 1. in, while stirring It is added, then return stirring 115min at being 106 DEG C in temperature after addition is filtered, washed, do at being 123 DEG C in temperature It is dry, modified silicon powder is made.

In the step (1), the mixing mass ratio of the silicon powder and ammonia spirit is 2:2.9, the grain of the silicon powder Diameter is 60 μm；In the step (2), the coupling modifier is by N- β (aminoethyl)-γ-aminopropyltriethoxy dimethoxy silicon With the mixture that weight ratio is that 1.5-2.0:1 is formed, the alcoholic solution is by positive fourth for alkane and phenylaminomethyl trimethoxy silane The mixing mass ratio of the mixture that pure and mild ethyl alcohol is formed with volume ratio for 1:1.6, the coupling modifier and alcoholic solution is 0.9: 18；In the step (3), 1. mixture is 14:1.1 with the mixing mass ratio of mixture 2..

E, it by the agglomerating rear material D heating refining glue obtained of step D mixing, is made to mediate and expect；Then material discharging will be mediated, is opened Uniformly, lower roll stands 11 after filtering for refining, and base rubber is made；

In the step A, the time for stirring mixing is 6min；In the step E, the filtering uses 210 mesh filter screen mistakes Filter；In the step E, the heating refining glue specific steps are as follows: the agglomerating rear material D obtained of step D mixing is warming up to 98 DEG C, Full open end mediates 52min, then carries out vacuumize process, is made and mediates material；The time of the vacuumize process is 73min, very Reciprocal of duty cycle is -0.075MPa.

In the step G, the temperature that five sections of hot drying tunnel temperatures of vulcanization are respectively as follows: first segment is 232 DEG C, the temperature of second segment Degree is 243 DEG C, and the temperature of third section is 258 DEG C, and the 4th section of temperature is 248 DEG C, and the 5th section of temperature is 238 DEG C.

Embodiment 5

The silicon rubber is phenylene silicone rubber, and the penylene base content of the phenylene silicone rubber is 60%, contents of ethylene is 0.06%, molecular weight is 780,000；The weight that every portion of reinforcing agent includes 5 parts of partial sizes in 11 μm of titanium dioxide, 3 parts of partial sizes at 10 μm Matter calcium carbonate and 6 parts of specific surface areas are in 250m²The precipitated silica of/g.

The constitution controller be blocked by hydroxy silicon oil, ethyoxyl poly- methyl-silicone oil and methyl phenyl methoxy silicone oil with Weight ratio is the mixture of 5:2.0:1 composition；Every part of coupling agent includes 3 parts of vinyltrimethoxysilanes, 1.8 parts of isopropyls Base dioleate oxygroup (dioctyl phosphoric acid acyloxy titanate esters) and 4 parts of γ-aminopropyltrimethoxysilanes.

The high temperature resistant agent is made of nano modification cerium oxide, di-iron trioxide and glass powder with weight ratio for 5:2:1 Mixture；Every part of synergist includes 1.5 parts of montmorillonites, 8 parts of silicon carbide, 6 parts of zinc oxide and 10 parts of zinc borates.

The nano modification cerium oxide is made by following steps:

Step is 1.: ethyl alcohol, 1,2- butanediol and deionized water being mixed evenly with volume ratio for 18:3:1, are made molten Agent A, then titanate coupling agent is added into solvent A, and 30min is mixed, and modified solution is made；

Step is 2.: ethyl alcohol and isopropanol being mixed evenly with volume ratio for 5:1, solvent B is made, then by nano oxygen Change cerium to be added into solvent B, nano-cerium oxide solution is made in ultrasonic disperse 30min under conditions of frequency is 20000HZ；

Step is 3.: by step, 2. nano-cerium oxide solution obtained in temperature is stirring in water bath at 70 DEG C, while stirring will 1. modified solution obtained is added dropwise in nano-cerium oxide solution step, continues to stir 23min after being added dropwise, then will mixing Object filtering, filter residue are washed 2 times with cleaning solution, are then to dry 6h at 80 DEG C in temperature by the filter residue after washing, grind, be made and receive The modified oxidized cerium of rice.

The step 1. in, the mass ratio of titanate coupling agent and solvent A is 1:22, and the titanate coupling agent is isopropyl Base dioleate oxygroup (dioctyl phosphoric acid acyloxy titanate esters)；The step 2. in, the partial size of nano-cerium oxide is 150nm, For nano-cerium oxide in advance through 70 DEG C of drying 4h, the mass ratio of nano-cerium oxide and solvent B are 1:20；The step 3. in, water-bath The revolving speed of stirring is 1000rpm, and the volume ratio of the modified solution and nano-cerium oxide solution is 1:12, the cleaning solution be by The mixture that ethyl alcohol and deionized water are formed with volume ratio for 18:1.

Every part of release agent includes 4 parts of polytetrafluoroethylene (PTFE), 5 parts of fluorinated ethylene propylene copolymers and 1.0 parts of methyl branches Silicone oil；The vulcanizing agent is by t-butyl perbenzoate and 2,5- dimethyl -2,5- di-t-butyl hexane peroxide with weight ratio For the mixture of 2:5 composition.

The modified silicon powder is made by following steps:

Step (1): silicon powder is heated to 108 DEG C, it is molten that the ammonium hydroxide for being 20% to mass fraction is added in stirring while stirring In liquid, pH value is adjusted to 8.2, mixture is made 1. in return stirring 2h at being then 120 DEG C in temperature, heat preservation；

Step (3): by mixture made from step (2) be 2. added to mixture made from step (1) 1. in, while stirring It is added, then return stirring 90min at being 108 DEG C in temperature after addition is filtered, washed, do at being 125 DEG C in temperature It is dry, modified silicon powder is made.

In the step (1), the mixing mass ratio of the silicon powder and ammonia spirit is 2:3, the partial size of the silicon powder It is 80 μm；In the step (2), the coupling modifier is by N- β (aminoethyl)-γ-aminopropyltriethoxy dimethoxysilane The mixture formed with phenylaminomethyl trimethoxy silane with weight ratio for 1.9:1, the alcoholic solution is by n-butanol and second The mixing mass ratio of the mixture that alcohol is formed with volume ratio for 1:1.5, the coupling modifier and alcoholic solution is 0.5-1.0:18； In the step (3), 1. mixture is 16:1 with the mixing mass ratio of mixture 2..

E, it by the agglomerating rear material D heating refining glue obtained of step D mixing, is made to mediate and expect；Then material discharging will be mediated, is opened Uniformly, lower roll stands 12h after filtering for refining, and base rubber is made；

In the step A, the time for stirring mixing is 8min；In the step E, the filtering uses 220 mesh filter screen mistakes Filter；In the step E, the heating refining glue specific steps are as follows: the agglomerating rear material D obtained of step D mixing is warming up to 100 DEG C, full open end mediates 50min, then carries out vacuumize process, is made and mediates material；The time of the vacuumize process is 75min, Vacuum degree is -0.08MPa.

In the step G, the temperature that five sections of hot drying tunnel temperatures of vulcanization are respectively as follows: first segment is 235 DEG C, the temperature of second segment Degree is 245 DEG C, and the temperature of third section is 250-260 DEG C, and the 4th section of temperature is 250 DEG C, and the 5th section of temperature is 240 DEG C.

Comparative example 1

This comparative example and the difference of above-described embodiment 3 are:

The silicon powder is the silicon powder without any modification.

Comparative example 2

The modified silicon powder is made by following steps:

Step (1): coupling modifier is added into alcoholic solution, is mixed, and mixture is made 1.；

Step (2): being heated to 104 DEG C for silicon powder, stirring, be then added to mixture made from step (1) 1. in, side It stirs side to be added, then it is 122 in temperature that return stirring 140min at being 105 DEG C in temperature after addition is filtered, washed It is dry at DEG C, modified silicon powder is made.

In the step (1), the coupling modifier is by N- β (aminoethyl)-γ-aminopropyltriethoxy dimethoxysilane The mixture formed with phenylaminomethyl trimethoxy silane with weight ratio for 1.8:1, the alcoholic solution is by n-butanol and second The mixing mass ratio of the mixture that alcohol is formed with volume ratio for 1:1.8, the coupling modifier and alcoholic solution is 0.8:18；It is described In step (2), the partial size of the silicon powder is 50 μm, and silicon powder and the mixing mass ratio of mixture 1. are 32:1.2.

Comparative example 3

Comparative example 4

The release agent is zinc stearate.

Comparative example 5

The high temperature resistant agent is what 4:1.5:1 was formed with weight ratio by nano-cerium oxide, di-iron trioxide and glass powder Mixture；The nano-cerium oxide is the cerium oxide without any modification.

Comparative example 6

In the preparation step of the nano modification cerium oxide, processing, specially market are modified using silane coupling agent The silane resin acceptor kh-550 of sale.

Comparative example 7

The release agent is zinc stearate；The high temperature resistant agent be by nano-cerium oxide, di-iron trioxide and glass powder with Weight ratio is the mixture of 4:1.5:1 composition；The nano-cerium oxide is the cerium oxide without any modification.

Silicon rubber made from above-described embodiment 1-5 and comparative example 1-7 is subjected to hardness, tensile strength, elongation at break, is torn The performance tests such as resistance to spalling, heat distortion temperature, it is shown that test result is as follows:

Wherein, the shore hardness test is measured using GB/T 531.1-2008 standard；The tensile strength uses GB/T528-2009 standard is measured；The tearing strength is measured using GB/T 529-2008 standard；The thermal deformation Temperature test is measured using " GB/T 1633-2000 vicat softening temperature " standard.

There are above-mentioned data it is found that silicon rubber produced by the present invention has preferable resistance to high-performance, by high temperature boiling The phenomenon that moieties will not be precipitated after 300h inside silicon rubber, effectively surface is inhibited to whiten, while there is preferable drawing The mechanical strengths such as intensity, tearing strength, expansion and contraction are stretched, stability is high.

Wherein, compared with Example 3, used silicon powder is without any modification, silicon rubber obtained for comparative example 1 Glue then occurs a small amount of whiteness in 100 DEG C of high temperature boiling 281h, and heat distortion temperature is 302 DEG C, hence it is evident that decline, and it is hard The mechanical performances such as degree, tensile strength, elongation and tearing strength are decreased obviously, and illustrate the present invention by changing to silicon powder Property, silicon rubber can be improved in the adsorption capacity on its surface, promote the compatibility between each material, be easy to be uniformly mixed, avoid silicon rubber Conglomeration reunion etc. occurs for the materials such as dimethicone of the powder shapeds such as synergist, reinforcing agent material and oily existing in glue preparation process As, dispersibility is splendid, and release agent and high temperature resistant agent three's mating reaction, can effectively improve be precipitated after silicon rubber high temperature boiling it is white The phenomenon that color substance, inhibits silastic surface to whiten.

And in the silicon powder modified technique step of comparative example 2, silicon powder is not dissolved using solvent, is directly added to water It is modified in the coupling modifier of solution, silicon rubber obtained a small amount of white object then occurs in 100 DEG C of high temperature boiling 289h Matter, and heat distortion temperature is 304 DEG C, and the mechanical performances such as hardness, tensile strength, elongation and tearing strength are decreased obviously, Illustrate that the present invention is hydrolyzed silicon powder by using ammonia spirit, the surface hydroxylation of silicon powder can be made, be easy to and hydrolyze Si-OH reaction in coupling modifier afterwards, forms hydrogen bond, and it is anti-that condensation, dehydration and solidification occur during being heated to reflux It answers, forms firm Covalent bonding together with silicon powder, improve the organophilic of silicon powder, promote silicon rubber to be adsorbed on modified The surface of silicon powder promotes the heat resistance that silicon rubber is effectively improved while the dispersion of material, makes silicon rubber obtained in high temperature Whiteness is not precipitated after boiling, inhibits the phenomenon that surface is whitened.

Modified silicon powder is not used in the silicon rubber of comparative example 3, silicon rubber obtained is analysed in 100 DEG C of high temperature boiling 278h Partial white substance out, heat distortion temperature are 298 DEG C, and heat resistance is lower, and precipitation substance is relatively more, while hardness, drawing The mechanical performances such as intensity, elongation and tearing strength are stretched to be decreased obviously, illustrate the present invention by using modified silicon powder, With release agent and high temperature resistant agent three's mating reaction, the phenomenon that whiteness is precipitated after silicon rubber high temperature boiling can effectively improve, Silastic surface is inhibited to whiten.

The release agent of comparative example 4 uses zinc stearate, and silicon rubber obtained is precipitated on a small quantity in 100 DEG C of high temperature boiling 283h Under whiteness, heat distortion temperature are 306 DEG C, and the mechanical performances such as hardness, tensile strength, elongation and tearing strength are obvious Drop, illustrates to be used in compounding by using release agent of the invention, can reduce the surface energy of silicon rubber, and isolation performance is good, and dosage is few, The release property between silicon rubber and mold is improved, and few to the pollution of mold, and can solve since zinc stearate leads to silicon rubber The problem of substance is precipitated.

Cerium oxide in the high temperature resistant agent of comparative example 5 is without any modification, silicon rubber heat distortion temperature obtained It is 300 DEG C, and a small amount of whiteness, and hardness, tensile strength, elongation and tearing is precipitated in 100 DEG C of high temperature boiling 277h The mechanical performances such as intensity are decreased obviously, and are illustrated by carrying out modification of the invention to cerium oxide, make silicon rubber have compared with High activity and reinforcing effect, can significantly improve the high temperature resistance of silicon rubber, be not easy that white is precipitated under the conditions of high temperature boiling Substance inhibits the phenomenon that silastic surface whitens.

And changed in the nano-cerium oxide modified technique step of comparative example 6 using commercially available silane resin acceptor kh-550 Property, silicon rubber obtained is precipitated a small amount of whiteness in 100 DEG C of high temperature boiling 291h, and heat distortion temperature is 305 DEG C, and hard The mechanical performances such as degree, tensile strength, elongation and tearing strength are decreased obviously, and illustrate the present invention by using two oil of isopropyl Acid esters oxygroup (dioctyl phosphoric acid acyloxy titanate esters) is modified nano-cerium oxide, sends out with the hydroxyl on nano-cerium oxide surface Raw condensation reaction, forms chemical bonds, makes nano modification cerium oxide obtained that can promote the dispersibility of silicon rubber material, subtracts The agglomeration of few material occurs, and nano modification cerium oxide can be made to absorb silicon rubber macromolecular chain and generated due to heat ageing Free radical improves the thermal stability of silicon rubber, and the polysiloxanes oxide side chain of silicon rubber is inhibited to be crosslinked and backbone cyclized degradation, energy Effectively improve the heat resistance and high temperature resistance of silicon rubber.

And in the silicon rubber of comparative example 7, using zinc stearate, cerium oxide does not use silicon without modification in high temperature resistant agent Micro mist, silicon rubber obtained is remarkably decreased in mechanical performances such as hardness, tensile strength, elongation and tearing strengths, and thermal change Shape temperature is remarkably decreased, and only 271 DEG C, and whiteness is then precipitated in 100 DEG C of high temperature boiling 229h, in combination with the present invention Embodiment 1-5 and comparative example 3-5 illustrates the type of release agent, the material variety of high temperature resistant agent and modification, silicon powder Addition, three have an impact to the heat resistance of silicon rubber, water boiling resistance, and when three's variable does not use (comparative example 7), Silicone Rubber be far below the embodiment of the present invention and comparative example 3-5, illustrate the present invention by using modified silicon powder, The specific high temperature resistant agent of the present invention and the specific release agent of the present invention, can improve the heat resistance and water boiling resistance of silicon rubber, show The phenomenon that whiteness is precipitated after improving the boiling of silicon rubber high temperature is write, inhibits the phenomenon that silastic surface whitens.

Above-described embodiment is the preferable implementation of the present invention, and in addition to this, the present invention can be realized with other way, Do not depart under the premise of present inventive concept it is any obviously replace it is within the scope of the present invention.

Claims

1. a kind of silicon rubber of boiling non-whitening, it is characterised in that: the silicon rubber includes the raw material of following parts by weight:

2. a kind of silicon rubber of boiling non-whitening according to claim 1, it is characterised in that: the silicon rubber is penylene silicon Rubber, the penylene base content of the phenylene silicone rubber is 55-60%, contents of ethylene 0.06-0.12%, molecular weight 68 Ten thousand -78 ten thousand；The heavy carbon that every portion of reinforcing agent includes 3-5 parts of partial sizes in 6-12 μm of titanium dioxide, 2-3 parts of partial sizes at 8-10 μm Sour calcium and 5-6 parts of specific surface areas are in 250-350m²The precipitated silica of/g.

3. a kind of silicon rubber of boiling non-whitening according to claim 1, it is characterised in that: the constitution controller be by It is that 3-5:1.5-2.0:1 is formed that hydroxy silicon oil, ethyoxyl, which block poly- methyl-silicone oil and methyl phenyl methoxy silicone oil with weight ratio, Mixture；Every part of coupling agent includes 1-3 parts of vinyltrimethoxysilanes, 1.2-1.8 parts of isopropyl dioleate oxygen Base (dioctyl phosphoric acid acyloxy titanate esters) and 2-4 parts of γ-aminopropyltrimethoxysilanes.

4. a kind of silicon rubber of boiling non-whitening according to claim 1, it is characterised in that: the high temperature resistant agent is by receiving The modified oxidized cerium of rice, di-iron trioxide and glass powder are with the mixture that weight ratio is that 3-5:1-2:1 is formed；Every part of synergist Including 1.0-1.5 parts of montmorillonites, 3-8 parts of silicon carbide, 2-6 parts of zinc oxide and 5-10 parts of zinc borates.

5. a kind of silicon rubber of boiling non-whitening according to claim 1, it is characterised in that: every part of release agent includes 2-4 parts of polytetrafluoroethylene (PTFE), 2-5 parts of fluorinated ethylene propylene copolymers and 0.5-1.0 parts of metlyl branching silicone oils；The vulcanizing agent be by The mixing that t-butyl perbenzoate and 2,5- dimethyl -2,5- di-t-butyl hexane peroxide are formed with weight ratio for 1-2:3-5 Object.

6. a kind of silicon rubber of boiling non-whitening according to claim 1, it is characterised in that: the modified silicon powder is by such as Lower step is made:

Step (1): silicon powder is heated to 100-108 DEG C, the ammonia for being 16-20% to mass fraction is added in stirring while stirring In aqueous solution, pH value is adjusted to 7.8-8.2, mixing is made in return stirring 2-5h at being then 115-120 DEG C in temperature, heat preservation Object is 1.；

Step (3): by mixture made from step (2) be 2. added to mixture made from step (1) 1. in, while stirring plus Enter, then it is 120- in temperature that return stirring 90-180min at being 103-108 DEG C in temperature after addition is filtered, washed It is dry at 125 DEG C, modified silicon powder is made.

7. a kind of silicon rubber of boiling non-whitening according to claim 6, it is characterised in that: described in the step (1) The mixing mass ratio of silicon powder and ammonia spirit is 2:2.5-3, and the partial size of the silicon powder is 20-80 μm；The step (2) In, the coupling modifier is by N- β (aminoethyl)-γ-aminopropyltriethoxy dimethoxysilane and phenylaminomethyl trimethoxy Base silane is with volume ratio by n-butanol and ethyl alcohol for 1 with the mixture that weight ratio is that 1.5-2.0:1 is formed, the alcoholic solution: The mixing mass ratio of the mixture of 1.5-2.0 composition, the coupling modifier and alcoholic solution is 0.5-1.0:18；The step (3) in, 1. mixture is 8-15:1-1.5 with the mixing mass ratio of mixture 2..

8. a kind of preparation method of the silicon rubber of the boiling non-whitening as described in claim any one of 1-7, it is characterised in that: including Following steps:

B, in parts by weight, reinforcing agent is added in five times into material A made from step A, is stirred after reinforcing agent is added every time It mixes to reinforcing agent and is thoroughly mixed into step A, material B is all made after mixing；

C, in parts by weight, coupling agent, high temperature resistant agent and synergist are added into material B made from step B, are uniformly mixed Material C is made afterwards；

D, in parts by weight, dimethicone, modified silicon powder and release agent are added into material C made from step C, mixed Obtained material D after closing uniformly；

E, it by the agglomerating rear material D heating refining glue obtained of step D mixing, is made to mediate and expect；Then material discharging will be mediated, mill is equal Even, lower roll stands 8-12h after filtering, and base rubber is made；

F, base rubber mill made from step E is uniform, vulcanizing agent is then added, mill is uniformly dispersed again, clot lower roll, is made Sizing material, for use；

G, sizing material made from step F is vulcanized by five sections of hot drying tunnels, it is cooling, the silicon rubber of boiling non-whitening is made.

9. a kind of preparation method of the silicon rubber of boiling non-whitening according to claim 8, it is characterised in that: the step In A, the time for stirring mixing is 3-8min；In the step E, the filtering is filtered using 180-220 mesh filter screen；The step In E, the heating refining glue specific steps are as follows: the agglomerating rear material D obtained of step D mixing is warming up to 90-100 DEG C, full open end 50-60min is mediated, vacuumize process is then carried out, is made and mediates material；The time of the vacuumize process is 65-75min, very Reciprocal of duty cycle is -0.06MPa~-0.08MPa.

10. a kind of preparation method of the silicon rubber of boiling non-whitening according to claim 8, it is characterised in that: the step In rapid G, the temperature that five sections of hot drying tunnel temperatures of vulcanization are respectively as follows: first segment is 225-235 DEG C, and the temperature of second segment is 235- 245 DEG C, the temperature of third section is 250-260 DEG C, and the 4th section of temperature is 240-250 DEG C, and the 5th section of temperature is 230-240 ℃。