CN100376633C - Low-modulus high-elongation high-adhesive-strength organosilicon sealing material and its preparing method - Google Patents
Low-modulus high-elongation high-adhesive-strength organosilicon sealing material and its preparing method Download PDFInfo
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Abstract
The present invention discloses organosilicon sealing materials with low modulus, high elongation rates and strong adhesive strength and a preparation method thereof. The organosilicon sealing materials comprise the following components by weight portions: 100 portions of poly-organic radical siloxane, 50 to 200 portions of filler, 1 to 10 portions of chain extender, 2 to 10 portions of crosslinking curing agent, 0.05 to 2 portions of catalyst and 0.1 to 5 portions of silane coupling agent. Ketoxime silicane is added to the components as the chain extender by the present invention, so the characteristics of low modulus and high elongation rates are realized. Meanwhile, the novel silane coupling agent containing cyanogen group and secondary amino group is added to the components to be used as viscosity increaser, so surface drying time is shortened, and the mechanical property of the organosilicon sealing materials and the adhesive strength to basal materials are improved. The obtained sealing materials have the advantages of excellent weather ageing resistance, high temperature resistance, low temperature resistance, favorable adhesive property to various seams, difficult disengagement of adhesive surfaces, favorable water resistance, excellent telescopic recoverability, low modulus and no toxicity or harm or environmental pollution. A breakage elongation rate reaches more than 800%, and the organosilicon sealing materials can bear large level or vertical displacement between concrete slabs.
Description
Technical field
The present invention relates to a kind of low-modulus high-elongation high-adhesive-strength organosilicon sealing material and preparation method thereof.The present invention is specifically related to a kind of have low modulus, high-elongation, the sealing adhesiveproperties is good, stability in storage is high, the elastic telescopic ability is strong, weathering resistance is good self cure (RTV) organosilicon sealing material and preparation method thereof.
Background technology
China's building, communication fast development, heavy construction facility, motorway and Tunnel Engineering etc. are increasing, the problem of concrete extension joint has caused the great attention of engineering circle, requires further to improve ageing resistance, water tolerance, elastic performance, integral adhesive and the intensity of concrete extension joint material.The sealing concrete seams material of present domestic use mainly contains pitch, modifying asphalt, prefabricated chloroprene rubber, poly-sulphur and urethane.These material ageing resistance are poor, work-ing life is short, to the cementability of base material and intensity is lower, displacement capacity is not enough, easily produce problems such as throwing off, rupture, extrude destruction, and mostly have toxicity, easily cause environmental pollution.The organosilicon sealing material that the present invention makes has excellent weather-resistant and high and low temperature resistance, and displacement capacity is strong, and cementability is good, can be widely used in traffic and building field.
Be that basic glue, acetoxysilane are that linking agent, zinc or zirconium compounds are catalyzer with the end capped polysiloxane of silanol among the U.S.P.4410677, in system, add a large amount of silicone oil simultaneously and made the low modulus organosilicon sealing material, and regulate modulus by regulating the silicone oil addition.But because silicone oil does not participate in the vulcanization crosslinking reaction, easily to the sealant surface migration, adhesive power is reduced, seal failure causes environmental pollution simultaneously.
Being that basic glue, organoalkoxysilane are linking agent with alkoxy end-capped polysiloxane among the U.S.P.5053442, is chainextender with the organoalkoxysilane of bifunctional, and is catalyzer with the organic titanium, has made the low modulus organosilicon sealing material.This material non-toxic, tasteless, non-corrosiveness, but exist the problem that the shelf lives lacks, cementability is strong, grow set time.
Being basic glue with hydroxy-end capped polysiloxane among the U.S.P.3996184, is chainextender with N methylacetamide base silane, is linking agent with aminooxy silane, has made the low modulus organosilicon sealing material.This material has amine flavor gas to emit in solidification process, is strong basicity, easily causes basic glue fracture.Simultaneously, amides chainextender price height, active big, poor storage stability have limited its application.
Being basic glue with hydroxy-end capped polysiloxane among the U.S.P.4978706, is chainextender with amide group silane, is linking agent with the tetraketone oximino silane, has made the low modulus organosilicon sealing material.This material non-corrosiveness, curing speed is fast, and is better to substrate bonding.But owing to adopted amide group silane to make chainextender, so also there is poor storage stability, the high deficiency of cost has limited its use range.
U.S.P.5246980 with hydroxy-end capped polysiloxane, filler-calcium carbonate, chainextender N methylacetamide base silane, linking agent aminooxy silane as first component, as second component, made two-pack low modulus organosilicon sealing material with the polysiloxane of hydroxy-end capped polysiloxane, filler-calcium carbonate, methyl blocking.This material cured speed is fast, but and deep layer solidify, but exist the price height of amide group silane equally, problem such as the shelf lives is short, and two-pack is made troubles to construction.
Domestic also have a relevant patent report, publication number CN1149307A is basic glue with hydroxy-end capped poly-diorganosiloxane, the phenyl silane linking agent, adhesion promotor, catalyzer and the softening agent that add filler, tris-functional ketoxime base have made the rubber composition of high elongation low modulus ambient temperature curable.By the specific embodiments in the patent specification as can be known, though this patent reaches the purpose of high elongation, low modulus, soft, tensile strength is very low, has limited its range of application greatly.This patent is not used any chainextender, but realizes high elongation low modulus by adding a large amount of softening agent (plasticizer dosage near basic glue consumption half).This just exists the shortcoming described in the U.S.P.4410677 equally: softening agent does not participate in the vulcanization crosslinking reaction, easily to the sealant surface migration, adhesive power is reduced, and seal failure causes environmental pollution simultaneously.
The many sight reported patent, though made the organosilicon sealing material of low modulus high elongation rate, all exist weak point, and its bonding strength to base material is not high, and its application is restricted.And realize low modulus, high-elongation as chainextender with ketoximinosilanes, improve mechanical property and the bonding strength of base material be yet there are no report as tackifier with the silane coupling agent of cyano-containing and secondary amino group.
Summary of the invention
The purpose of this invention is to provide a kind of low-modulus high-elongation high-adhesive-strength organosilicon sealing material and preparation method thereof.
Low-modulus high-elongation high-adhesive-strength organosilicon sealing material, its component is as follows by weight:
(A) poly-organopolysiloxane is 100 parts,
(B) filler 50-200 part,
(C) chainextender 1-10 part,
(D) crosslinking and curing agent 2-10 part,
(E) catalyzer 0.05-2 part,
(F) silane coupling agent 0.1-5 part.
Described poly-organopolysiloxane is a hydroxyl-terminated injecting two methyl siloxane, and viscosity is 10000-100000Pas in the time of 25 ℃; Filler is the super-fine active calcium carbide of handling through stearic acid, and particle size range is at 0.01-50 μ m; Chainextender is selected hydrolyzable two ketoximinosilanes or polysiloxane based on 2 functional groups for use; But crosslinking and curing agent is ketoximinosilanes or the polysiloxane that contains moisture hydrolyzes more than two; Catalyzer is organic carboxyl acid tin system; Silane coupling agent is (MeO)
3SiC
3H
6NHC
2H
4NHC
2H
4CN and (MeO)
2CH
3SiC
3H
6NHC
2H
4NHC
2H
4CN.
The preparation method's of low-modulus high-elongation high-adhesive-strength organosilicon sealing material step is as follows:
1) filler dry 3-4 in 100-120 ℃ of baking oven is individual hour;
2) with hydroxy-end capped poly-organopolysiloxane and filler in the planet mixing machine, in vacuum seal down mixed 2-3 hour, obtain sizing;
3) in sizing, add chainextender and linking agent, vacuum seal mixed 8-10 minute down;
4) add silane coupling agent and catalyzer then, mixed 8-10 minute, behind the part lower-molecular substance that generates in vacuum removal bubble and the reaction, promptly obtain the good organosilicon sealing material of stable storing.
Advantage of the present invention is: added low price, raw material sources are extensive, stability in storage is good ketoximinosilanes as chainextender in component, realized the low modulus (characteristic of 100% stress at definite elongation＜0.4MPa), high-elongation (elongation at break＞800%); The novel cyano-containing and the silane coupling agent of secondary amino group have also been added in addition in the component, shortened its surface drying time (shortening to 1 hour) greatly by 1 day, significantly improved bonding strength (quite firm with the substrate bonding face, tension specimen destroys and is cohesive failure) to base material.Avoided the various drawbacks mentioned in this paper background technology simultaneously: organoalkoxysilane is as chainextender, and the shelf lives is short, cementability is strong, set time is long; Amide group silane is as chainextender price height, active big, poor storage stability; Softening agent is regulated modulus, does not participate in the vulcanization crosslinking reaction, easily to the sealant surface migration, adhesive power is reduced, and seal failure causes environmental pollution simultaneously.
The preparation method of low-modulus high-elongation high-adhesive-strength room temperature vulcanization organosilicon sealing material: the mode that adopts batch charging, promptly earlier hydroxy-end capped poly-organopolysiloxane and filler are mixed under vacuum seal, add chainextender and linking agent then, add catalyzer and silane coupling agent at last, improved the stability in storage of product.
The present invention has excellent weather-resistant, high and low temperature resistance (keeping good elasticity in-50～200 ℃ of temperature ranges); Various seams had good cementability, the bonding plane difficult drop-off; The excellent water tolerance energy can effectively stop rainwater to immerse from seam, avoids ground softening and corroded; Excellent is flexible restorative, and elongation at break can bear level or the great displacement of vertical direction between the concrete plate more than 800%, so as not to seal gum be stretched for a long time or shear-stress after ftracture; Nontoxic, harmless, environmentally safe; Single component, self cure, easy construction, the easy repairing greatly reduce the long-time maintenance cost of concrete works.
Embodiment
Usually the method that realizes organosilicon sealing material low modulus, high-elongation has: molar mass, adding softening agent, use half reinforcement or the non-reinforced filling etc. that increase basic glue.But use the basic glue of high molecular weight, because its viscosity conference brings difficulty to processing; Add softening agent and can occur the phenomenon of small molecules again to the material surface migration.The present invention mainly is by add a kind of hydrolyzable bifunctional ketoximinosilanes (chainextender) that has in component, utilize its chain extension effect to change network topology structure and reach reduction cross-linking set density degree and distribution, thereby realize the purpose of low modulus, high-elongation.Also added the novel cyano-containing and the silane coupling agent of secondary amino group in addition in the component, shortened its surface drying time greatly, significantly improved performance of science and the bonding strength of base material.
The used organopolysiloxane of low-modulus high-elongation high-adhesive-strength organosilicon sealing material of the present invention mainly is by the poly-diorganosiloxane unit of terminal hydroxy group (RR ' SiO)
nForm.R, R ' can be identical or different univalence hydrocarbyls, or the halogenated monovalent alkyl.Monovalent alkyl is an alkyl, as methyl, ethyl, propyl group, n-octyl; Alkenyl is as allyl group and vinyl; Aromatic base is as phenyl or tolyl; Cycloalkyl is as hexanaphthene; Aralkyl is as the 2-styroyl.The halogenated monovalent alkyl is a perfluoroalkyl, as 3,3, and the 3-trifluoro propyl, another kind of halogeno-group is γ-chloropropyl.Hydroxy-end capped poly-organopolysiloxane used among the present invention mainly is hydroxy-end capped polydimethylsiloxane, and range of viscosities is (25 ℃) 10000-100000Pa.s, and 30000-80000Pa.s is a preferable range.
The used filler of low-modulus high-elongation high-adhesive-strength organosilicon sealing material of the present invention can be one or more fillers.Can be the filler of enhancement type, as the white carbon black of vapor phase process, the white carbon black of the precipitator method, finely disseminated lime carbonate, carbon black.Also can be the increment filler, as lime carbonate, finely disseminated quartz, diatomite, ferric oxide, titanium dioxide and zinc oxide.Used filler is the super-fine active calcium carbide that handled through stearic acid on the surface among the present invention, and particle size range 0.01-50 μ m, 0.04-20 μ m are best.Under the poly-organopolysiloxane of per 100 weight parts, preferably interpolation scope of filler is the 50-150 weight part.
The used crosslinking and curing agent of low-modulus high-elongation high-adhesive-strength organosilicon sealing material of the present invention is silicane and the oligosiloxane class that has in each molecule greater than the hydrolysable group of two silicon key links.The hydrolysable group of silicon key link can be alkoxyl group, acyloxy, ketoxime base, amino, amido, alkenyloxy etc.Alkoxyl group can be methoxyl group, oxyethyl group, positive propoxy, isopropoxy and methoxyethoxy.Acyloxy can be acetoxyl group, hot acyloxy and benzoyloxy group.The ketoxime base can be acetone oximido, butanone oximido and pentanone oximido.Amino can be N, N-diethylamino, N-ethylamino, N-propyl group amino and N, N-methylcyclohexyl amino.Alkene oxygen base can be propenyloxy group, different propenyloxy group, butenyloxy.Amido can be N-methyl kharophen, N-ethyl kharophen, N-butyl kharophen, N-methylbenzene amido.The linking agent that the present invention mainly adopts is a methyl tributanoximo silane, and under the poly-organopolysiloxane of per 100 weight parts, crosslinking and curing agent preferably adds the 3-8 weight part.
The used catalyzer of low-modulus high-elongation high-adhesive-strength organosilicon sealing material of the present invention is a kind of acceleration solidified catalyzer, and this catalyzer can be one or more mixtures in organic carboxyl acid tin system and inner complex or organic titanate and the inner complex thereof.Wherein, tin based compound catalyzer is mainly organic carboxyl acid tin and organotin inner complex, is inner complex etc. as stannous octoate, dibutyl tin laurate, two sad dibutyl tins, dibutyltin diacetate, dimethoxy dibutyl tin, Dibutyltin oxide and some organotins.The titanium sub-group compound catalyzer is mainly the inner complex of titanic acid ester and titanium, as tetra isopropyl titanate, tetra-n-butyl titanic acid ester, four (trimethylammonium alkoxyl group) titanium, diisopropoxy-two (acetylacetone based) titanium, diisopropoxy-two (methyl aceto acetate base) titanium, propylidene dioxy-two (acetylacetone based) titanium, propylidene dioxy-two (methyl aceto acetate base) titanium etc.The used catalyzer of the present invention is mainly dibutyl tin laurate, and under the poly-organopolysiloxane of per 100 weight parts, catalyzer preferably adds the 0.05-1 weight part.
The used chainextender of low-modulus high-elongation high-adhesive-strength organosilicon sealing material of the present invention is hydrolyzable ketoximinosilanes or polysiloxane based on 2 functional groups, and molecular structural formula is R
1R
2Si (ONCR
3R
4)
2Silane is formed, wherein R
1, R
2Can be identical or different univalence hydrocarbyl, or the halogenated monovalent alkyl.Monovalent alkyl is an alkyl, as methyl, ethyl, propyl group, n-octyl; Alkenyl is as allyl group and vinyl; Aromatic base is as phenyl or tolyl; Cycloalkyl is as hexanaphthene; Aralkyl is as the 2-styroyl.The halogenated monovalent alkyl is a perfluoroalkyl, as 3,3, and the 3-trifluoro propyl, another kind of halogeno-group is γ-chloropropyl.R
3, R
4Can be identical or different univalence hydrocarbyls, as methyl, ethyl, propyl group, n-octyl etc.Used ketoximinosilanes chainextender is mainly dimethyl two Diacetylmonoxime base silanes among the present invention,, methyl ethylene two Diacetylmonoxime base silanes, under the poly-organopolysiloxane of per 100 weight parts, chainextender preferably adds the 3-9 weight part.
The used silane coupling agent of low-modulus high-elongation high-adhesive-strength organosilicon sealing material of the present invention is the silane coupling agent of cyano-containing and secondary amino group, and molecular structural formula is (R
1O)
3-xSiR
2 xR
3NHR
4NH
y(C
2H
4CN)
z, R wherein
1, R
2For the straight or branched alkyl of an identical or different 1-6 carbon atom, as methyl, ethyl, propyl group, n-octyl; R
3, R
4Be the arylmethylene alkyl and the alkyl arylene of alkylidene group, aryl or the 6-10 carbon atom of 1-6 carbon atom, as-C
3H
6-,-C
2H
4-,-CH
2C
6H
4CH
2-,-C
6H
4-,-(CH
2)
2C
6H
4-,-(CH
2)
2C
6H
4(CH
2)
2-,-C
6H
4(CH
2)
2-; X, y are 0 or 1, and z is 1 or 2.The cyano-containing that the present invention is used and the silane coupling agent of secondary amino group are (MeO)
3SiC
3H
6NHC
2H
4NHC
2H
4CN and (MeO)
2CH
3SiC
3H
6NHC
2H
4NHC
2H
4CN, wherein (MeO)
3SiC
3H
6NHC
2H
4NHC
2H
4CN is by (MeO)
3SiC
3H
6NHC
2H
4NH
2(trade names KH-792/ is commercially available) and vinyl cyanide with etc. molar ratio reaction make, be called for short 7A; (MeO)
2CH
3SiC
3H
6NHC
2H
4NHC
2H
4CN is by (MeO)
2SiCH
3C
3H
6NHC
2H
4NH
2(trade names DL-602/ is commercially available) and vinyl cyanide with etc. molar ratio reaction make, be called for short 6A.Under the poly-organopolysiloxane of per 100 weight parts, silane coupling agent preferably adds the 0.1-5 weight part.
Embodiment 1
With (25 ℃ of 100 parts of hydroxy-end capped polydimethylsiloxanes, 53000cP), under the vacuum seal condition, in planetary mixer, the mixing 2-3 hour at the super-fine active calcium carbide of 0.04-20 μ m of 100 parts of dryings through the acid-treated particle size range of tristearin, obtain sizing; Add 8 parts of dimethyl, two Diacetylmonoxime base silane chainextenders and 5 parts of methyl tributanoximo silane linking agents then, mixed 8-10 minute under the vacuum seal condition; Add 0.1 part of dibutyl tin dilaurate catalyzer and 1 part of 7A silane coupling agent at last, mixed 8-10 minute, behind the part lower-molecular substance that generates in vacuum removal bubble and the reaction, sealing is preserved.
Prepare other three groups of organosilicon sealing materials with same method, different is to add 6 parts, 3 parts, 0 part dimethyl, two Diacetylmonoxime base silane chainextenders respectively.The organosilicon sealing material that makes is injected the dark mould of 2mm, and vulcanization crosslinking is 7 days under 25 ℃, 50%RH, makes the dumbbell shape sample, tests its mechanical property by GB/T 528-1998 testing standard, and its test result is as shown in table 1.
Table 1 chainextender dimethyl two Diacetylmonoxime base silane consumptions are to the influence of mechanical property
Annotate: the modulus in the mechanical property table is meant that the dumbbell shape sample is stretched to 100% o'clock stress at definite elongation, and is as follows.
Embodiment 2
With (25 ℃ of 100 parts of hydroxy-end capped polydimethylsiloxanes, 53000cP), under the vacuum seal condition, in planetary mixer, the mixing 2-3 hour at the super-fine active calcium carbide of 0.04-20 μ m of 100 parts of dryings through the acid-treated particle size range of tristearin, obtain sizing; Add 8 parts of methyl ethylenes, two Diacetylmonoxime base silane chainextenders and 4 parts of methyl tributanoximo silane linking agents then, mixed 8-10 minute under the vacuum seal condition; Add 0.1 part of dibutyl tin dilaurate catalyzer and 1 part of 7A silane coupling agent at last, mixed 8-10 minute, behind the part lower-molecular substance that generates in vacuum removal bubble and the reaction, sealing is preserved.
Prepare other three groups of organosilicon sealing materials with same method, different is to add 6 parts, 2 parts, 0 part methyl ethylene, two Diacetylmonoxime base silane chainextenders respectively.The organosilicon sealing material that makes is injected the dark mould of 2mm, and vulcanization crosslinking is 7 days under 25 ℃, 50%RH, makes the dumbbell shape sample, tests its mechanical property by GB/T 528-1998 testing standard, and its test result is as shown in table 2.
Table 2 chainextender methyl ethylene two Diacetylmonoxime base silane consumptions are to the influence of mechanical property
By table 1,2 as seen, along with the increase of two ketoximinosilanes chainextender consumptions, the tensile strength of organosilicon sealing material reduces, elongation at break increases, modulus reduces, surface drying time prolongs, hardness reduces.This explanation adds the topological framework that ketoximinosilanes has changed cross-linked network, has reduced its cross-linking density, has played the effect of chain extension really.
Embodiment 3
With (25 ℃ of 100 parts of hydroxy-end capped polydimethylsiloxanes, 53000cP), under the vacuum seal condition, in planetary mixer, the mixing 2-3 hour at the super-fine active calcium carbide of 0.04-20 μ m of 100 parts of dryings through the acid-treated particle size range of tristearin, obtain sizing.Add 6 parts of dimethyl, two Diacetylmonoxime base silane chainextenders and 5 parts of methyl tributanoximo silane linking agents then, mixed 8-10 minute under the vacuum seal condition; Add 0.1 part of dibutyl tin dilaurate catalyzer and 1 part of 7A silane coupling agent at last, mixed 8-10 minute, behind the part lower-molecular substance that generates in vacuum removal bubble and the reaction, sealing is preserved.
Prepare other four groups of organosilicon sealing materials with same method, different is the type of silane coupling agent.What add respectively is 1 part of KH-792,6A, DL-602 or does not add any silane coupling agent.The organosilicon sealing material that makes is injected the dark mould of 2mm, and vulcanization crosslinking is 7 days under 25 ℃, 50%RH, makes the dumbbell shape sample, tests its mechanical property by GB/T 528-1998 testing standard, and its test result is as shown in table 3.
Table 3 silane coupling agent type is to the influence of organosilicon sealing material mechanical property
Embodiment 4
To prepare five groups of organosilicon sealing materials with embodiment 3 same methods.
Organosilicon sealing material is pressed the sample preparation of GB 1742-79 testing standard, and vulcanization crosslinking is 7 days under 25 ℃, 50%RH, tests its shearing resistance to aluminium flake, and its test result is as shown in table 4.
Table 4 silane coupling agent type is to the influence of organosilicon sealing material and aluminium flake shearing resistance
Embodiment 5
To prepare five groups of organosilicon sealing materials with embodiment 3 same methods.
This organosilicon sealing material is made H type sample, and vulcanization crosslinking is 21 days under 25 ℃, 50%RH, tests its stretching adhesiveproperties by GB/T 13477-92 testing standard, and its test result is shown in table 5, table 6.
Table 5 silane coupling agent type is to the influence of organosilicon sealing material adhesiveproperties
Annotate: modulus is meant the stress at definite elongation of H type sample stretching 100% in 1) showing
2) bonding base material is a reinforced cement-mortar board
Table 6 silane coupling agent type is to the influence of organosilicon sealing material adhesiveproperties
Annotate: modulus is meant the stress at definite elongation of H type sample stretching 100% in 1) showing
2) bonding base material is a glass
Embodiment 6
With (25 ℃ of 100 parts of hydroxy-end capped polydimethylsiloxanes, 53000cP), under the vacuum seal condition, in planetary mixer, the mixing 2-3 hour at the super-fine active calcium carbide of 0.04-20 μ m of 100 parts of dryings through the acid-treated particle size range of tristearin, obtain sizing.Add 6 parts of dimethyl, two Diacetylmonoxime base silane chainextenders and 5 parts of methyl tributanoximo silane linking agents then, mixed 8-10 minute under the vacuum seal condition; Add 0.1 part of dibutyl tin dilaurate catalyzer and 0.5 part of 7A silane coupling agent at last, mixed 8-10 minute, behind the part lower-molecular substance that generates in vacuum removal bubble and the reaction, sealing is preserved.
Prepare other three groups of organosilicon sealing materials with same method, different is to add 1 part, 2 parts, 3 parts 7A respectively.The organosilicon sealing material that makes is injected the dark mould of 2mm, and vulcanization crosslinking is 7 days under 25 ℃, 50%RH, makes the dumbbell shape sample, tests its mechanical property by GB/T 528-1998 testing standard, and its test result is as shown in table 7.
Table 7 silane coupling agent consumption is to the influence of organosilicon sealing material mechanical property
Embodiment 7
The preparation of organosilicon sealing material is with embodiment 6.This organosilicon sealing material is made H type sample, and vulcanization crosslinking is 21 days under 25 ℃, 50%RH, tests its stretching adhesiveproperties by GB/T 13477-92 testing standard, and its test result is as shown in table 8.
Table 8 silane coupling agent consumption is to the influence of organosilicon sealing material adhesiveproperties
Annotate: modulus is meant the stress at definite elongation of H type sample stretching 100% in 1) showing
2) bonding base material is a glass
By table 3-8 as seen, add the mechanical property that silane coupling agent has effectively improved organosilicon sealing material, shortened its surface drying time greatly, significantly improved its bonding strength base materials such as aluminium, concrete, glass.Silane coupling agent 7A, the 6A of wherein homemade cyano-containing and secondary amino group obviously is better than commercially available trade names on effect be KH-792 and DL-602, and different consumptions is also bigger to its Effect on Performance.
Embodiment 8
With (25 ℃ of 100 parts of hydroxy-end capped polydimethylsiloxanes, 53000cP), under the vacuum seal condition, in planetary mixer, the mixing 2-3 hour at the super-fine active calcium carbide of 0.04-20 μ m of 100 parts of dryings through the acid-treated particle size range of tristearin, obtain sizing.Add 8 parts of dimethyl, two Diacetylmonoxime base silane chainextenders and 8 parts of methyl tributanoximo silane linking agents then, mixed 8-10 minute under the vacuum seal condition; Add 0.1 part of dibutyl tin dilaurate catalyzer and 1 part of 7A silane coupling agent at last, mixed 8-10 minute, behind the part lower-molecular substance that generates in vacuum removal bubble and the reaction, sealing is preserved.
Prepare other 3 three groups of organosilicon sealing materials with same method, different is to add 6 parts, 4 parts, 2 parts methyl tributanoximo silane linking agents respectively.The organosilicon sealing material that makes is injected the dark mould of 2mm, and vulcanization crosslinking is 7 days under 25 ℃, 50%RH, makes the dumbbell shape sample, tests its mechanical property by GB/T 528-1998 testing standard, and its test result is as shown in table 9.
Table 9 linking agent methyl tributanoximo silane consumption is to the influence of organosilicon sealing material mechanical property
Table 10 lime carbonate consumption is to the influence of organosilicon sealing material mechanical property
Embodiment 9
With (25 ℃ of 100 parts of hydroxy-end capped polydimethylsiloxanes, 53000cP), under the vacuum seal condition, in planetary mixer, the mixing 2-3 hour at the super-fine active calcium carbide of 0.04-20 μ m of 100 parts of dryings through the acid-treated particle size range of tristearin, obtain sizing.Add 6 parts of dimethyl, two Diacetylmonoxime base silane chainextenders and 5 parts of methyl tributanoximo silane linking agents then, mixed 8-10 minute under the vacuum seal condition; Add 0.1 part of dibutyl tin dilaurate catalyzer and 1 part of 7A silane coupling agent at last, mixed 8-10 minute, behind the part lower-molecular substance that generates in vacuum removal bubble and the reaction, sealing is preserved.
Prepare other three groups of organosilicon sealing materials with same method, different is to add 90 parts, 80 parts, 70 parts lime carbonate respectively.The organosilicon sealing material that makes is injected the dark mould of 2mm, and vulcanization crosslinking is 7 days under 25 ℃, 50%RH, makes the dumbbell shape sample, tests its mechanical property by GB/T 528-1998 testing standard, and its test result is as shown in table 10.
Embodiment 10
With (25 ℃ of 100 parts of hydroxy-end capped polydimethylsiloxanes, 53000cP), under the vacuum seal condition, in planetary mixer, the mixing 2-3 hour at the super-fine active calcium carbide of 0.04-20 μ m of 100 parts of dryings through the acid-treated particle size range of tristearin, obtain sizing; Add 6 parts of dimethyl, two Diacetylmonoxime base silane chainextenders, 5 parts of methyl tributanoximo silane linking agents, 0.1 part of dibutyl tin dilaurate catalyzer and 1 part of 7A silane coupling agent then simultaneously, mixed 8-10 minute; Behind the part lower-molecular substance that generates in vacuum removal bubble and the reaction, sealing is preserved.
Prepare another group organosilicon sealing material with same recipe ingredient, different is after obtaining sizing, and various auxiliary agents are added in batches.Add chainextender and linking agent earlier, vacuum seal was stirred 8-10 minute down, and then added catalyzer and silane coupling agent, mixed 8-10 minute; Behind the part lower-molecular substance that generates in vacuum removal bubble and the reaction, sealing is preserved.The performance of the organosilicon sealing material that two kinds of methods are made is done with contrast, and is as shown in table 11.
The addition sequence of table 11 auxiliary agent is to the influence of organosilicon sealing material stability in storage
| Auxiliary agent adding method | Performance |
| Add in batches simultaneously and add | Product appearance is general, the part is inhomogeneous, occurred good, even, the stable performance more than 1 year of gelatin phenomenon product appearance in about 1 month |
The difference of order of addition(of ingredients) causes the difference on the product performance, analyzing its reason may be: can accelerate the crosslinking curing speed of organosilicon sealing material greatly in view of catalyzer, add when simultaneously fashionable owing to disperse uneven, easily cause partial trace to solidify, reduced the stability in storage of product.And ought add fashionablely in batches, then avoided this phenomenon.
Embodiment 11
With (25 ℃ of 100 parts of hydroxy-end capped polydimethylsiloxanes, 53000cP), under the vacuum seal condition, in planetary mixer, the mixing 2-3 hour at the super-fine active calcium carbide of 0.04-20 μ m of 100 parts of dryings through the acid-treated particle size range of tristearin, obtain sizing.Add 6 parts of dimethyl, two Diacetylmonoxime base silane chainextenders and 5 parts of methyl tributanoximo silane linking agents then, mixed 8-10 minute under the vacuum seal condition; Add 0.1 part of dibutyl tin dilaurate catalyzer and 1 part of 7A silane coupling agent at last, mixed 8-10 minute, behind the part lower-molecular substance that generates in vacuum removal bubble and the reaction, sealing is preserved.
Organosilicon sealing material in the plastic seal tube was placed 1 year respectively at placing under the normality to place under 7 days (acceleration shelf test), the room temperature in 7 days, the 55 ℃ baking ovens, tested its performance then, test result is as shown in table 12.
The package stability of table 12 organosilicon sealing material
| Test event | Prepare sample after 7 days | Place sample after 7 days for 55 ℃ | Room temperature is deposited sample after 1 year |
| Surface drying time/min Shao Er hardness/degree tensile strength/MPa elongation at break/100% 100% tensile modulus/MPa | 80 24 2.01 834 0.14 | 80 23 2.0 830 0.13 | 85 22 1.98 821 0.13 |
Claims (2)
1. a low-modulus high-elongation high-adhesive-strength organosilicon sealing material is characterized in that, its component is as follows by weight:
(A) poly-organopolysiloxane is 100 parts,
(B) filler 50-200 part,
(C) chainextender 1-10 part,
(D) crosslinking and curing agent 2-10 part,
(E) catalyzer 0.05-2 part,
(F) silane coupling agent 0.1-5 part,
Described chainextender is selected hydrolyzable two ketoximinosilanes or polysiloxane based on 2 functional groups for use, two ketoximinosilanes are dimethyl two Diacetylmonoxime base silanes, methyl ethylene two Diacetylmonoxime base silanes, silane coupling agent is the silane coupling agent that contains cyano group and secondary amine, and its molecular structural formula is (R
1O)
3-xSiR
2 xR
3NHR
4NH
y(C
2H
4CN)
z, R wherein
1, R
2Be the straight or branched alkyl of an identical or different 1-6 carbon atom, R
3, R
4Arylmethylene alkyl and alkyl arylene for alkylidene group, aryl or the 6-10 carbon atom of 1-6 carbon atom, x, y are 0 or 1, z is 1 or 2, poly-organopolysiloxane is a hydroxyl-terminated injecting two methyl siloxane, viscosity is 10000-100000Pas in the time of 25 ℃, and filler is the super-fine active calcium carbide of handling through stearic acid, and particle size range is at 0.01-50 μ m, but crosslinking and curing agent is ketoximinosilanes or the polysiloxane that contains moisture hydrolyzes more than two, and catalyzer is organic carboxyl acid tin system.
2. preparation method of low-modulus high-elongation high-adhesive-strength organosilicon sealing material according to claim 1 is characterized in that step is as follows:
1) filler dry 3-4 in 100-120 ℃ of baking oven is individual hour;
2) will gather organopolysiloxane and filler in the planet mixing machine, mix 2-3 hour down, obtain sizing in vacuum seal;
3) in sizing, add chainextender and linking agent, vacuum seal mixed 8-10 minute down;
4) add silane coupling agent and catalyzer then, mixed 8-10 minute, behind the part lower-molecular substance that generates in vacuum removal bubble and the reaction, promptly obtain the good organosilicon sealing material of stable storing.
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| MX2011008279A (en) * | 2009-02-17 | 2011-11-04 | Dow Corning | Silicone gel seal and method for its preparation and use. |
| CN102115604B (en) * | 2009-12-31 | 2013-07-24 | 上海广茂达光艺科技股份有限公司 | Double-component condensed-type organosilicon transparent electronic potting adhesive and component A composition thereof |
| CN102816553A (en) * | 2011-06-08 | 2012-12-12 | 苏州达同新材料有限公司 | Organosilicon adhesive used for edge sealing of solar cell assembly and preparation method thereof |
| CN102746820A (en) * | 2012-07-26 | 2012-10-24 | 广州市白云化工实业有限公司 | Silicone weather-proof sealing gum for fiber reinforcement cement plate and preparation method of silicone weather-proof sealing gum |
| CN108084955B (en) * | 2017-12-20 | 2021-05-28 | 中天东方氟硅材料有限公司 | Single-component self-leveling silicone sealant composition for concrete joint, sealant and preparation method of sealant |
| CN108102598B (en) * | 2018-01-12 | 2021-03-09 | 广东欧利雅化工有限公司 | Preparation method of low-modulus deketoxime type sealant and sealant |
| CN108997759A (en) * | 2018-05-31 | 2018-12-14 | 镇江高美新材料有限公司 | A kind of high-insulativity fluid silicone rubber |
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