CN102766431A - High-adhesion silicone sealant - Google Patents
High-adhesion silicone sealant Download PDFInfo
- Publication number
- CN102766431A CN102766431A CN2012102652439A CN201210265243A CN102766431A CN 102766431 A CN102766431 A CN 102766431A CN 2012102652439 A CN2012102652439 A CN 2012102652439A CN 201210265243 A CN201210265243 A CN 201210265243A CN 102766431 A CN102766431 A CN 102766431A
- Authority
- CN
- China
- Prior art keywords
- component
- weight
- parts
- silicone sealant
- weight part
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Abstract
The invention relates to a novel single-component room-temperature vulcanized silicone sealant material and belongs to the field of chemical materials. The traditional silicone sealant is mainly made of hydroxyl-terminated polysiloxane. During silicone sealant synthesis, a sulfur-containing group is introduced to a main chain of the hydroxyl-terminated polysiloxane. The hydroxyl-terminated polysiloxane is used with mercapto polysiloxane, and accordingly adhesion of the silicone sealant, especially adhesion with base materials such as metals and glass, is improved evidently. The process of the novel single-component room-temperature vulcanized silicone sealant material is important to industrial production of silicone adhesive.
Description
Technical field
The present invention relates to a kind of novel single-component high-adhesion silicone sealant, belong to chemical material field.
Background technology
Silicone sealant is to be a kind of sealing material that base-material is processed with hydroxy-end capped ZGK 5, belongs to the high molecular chemical product.The high polymer main chain of silicone sealant mainly is made up of silicon-oxygen-silicon bound; The reaction of linking agent and base polymer forms netted Si-O-Si skeleton structure in solidification process; Compare with the molecular organic sealer of other high scores; Its bonding force is stronger, and tensile strength is big, has the characteristics of UV resistant, vibration resistance and protection against the tide, anti-foul smell, high-low temperature resistant, weathering resistance simultaneously again.Sealing glue does not contain organic solvent, and is free from environmental pollution, and cured glue body volumetric shrinkage property is little, good airproof performance; Ambient cure can be used separately, and is easy to use; It is than extensive applicability in addition, and it is substituted to realize that bonding between most of building material products, the effect of being played are that other synthetic materialss are difficult to; It is reported that domestic about 80% building curtain wall all adopts silicone sealant at present, and also is widely used in fields such as weaving, machinery, automobile, electronics.
According to the number of components of product, silicone sealant can be divided into single component and two-pack two big classes usually: the silicone adhesive of single-component, its curing are to be abutted against the change of touching airborne moisture-crosslinking curing and producing physical properties; Two components are meant that then silicone adhesive is divided into two groups of A, B, and any one group of exist singly all can not form curing, but two groups of rubber cements are in case mix just generation curing.
Mostly common single-component silicone sealant is to take off oxime, depickling and dealcoholizing-type; Promptly with α, alpha, omega-dihydroxy polydimethyl siloxane (being commonly called as 107 glue) is a base-material, and methyl tributanoximo silane, vinyl tributanoximo silane and their partial hydrolysate are linking agent; Organo-tin compound is a catalyzer; Aerosil is a filler, and requires to add each analog assistant according to reality, like softening agent, sanitas, fire retardant etc.
In order to change apparent brightness, to reduce cost; Silicone adhesive product in the market all can be more or less some additives of mixing; Such as softening agent white oil, methyl-silicone oil etc.; It can make the curing speed of sealer slow down, cause mechanical properties decrease, has especially influenced the cohesive strength of sealer and some base material; And what more need come into the picture is that some new high-tech industries such as automobile, electron trade etc. at present are because the widening of its application conditions; Cohesive strength to sealer also has higher requirement, in addition, and building curtain wall material and for example; Because long-term exposure out of doors; Very easily receive the influence of external environment, be easy to the problem that cohesive strength descends occur, the application of silicone adhesive is restricted.Therefore, the sticking power that effectively improves silicone sealant becomes one of focus that present people pay close attention to.
CN101652442A discloses a kind of antireflective coating film formation that contains the ZGK 5 of modified with mercapto group and has used coating fluid; It contains polysiloxane (A); Said ZGK 5 (A) is to have the ZGK 5 of the organic group of sulfydryl through the main chain be combined into of siloxane bond and ZGK 5 (a); Sulfydryl organic group wherein is preferably:
HS－(CH
2)
y－；HS－CH
2－CH
2－CH
2－
In the formula, y is the integer of 1-6, the integer of preferred 1-3.
This invention has solved polysiloxane coated when having water repellent surface hard coat base material; The problem of adaptation, scuff resistance difference; Disclose and had only, realized the scheme of this invention technique effect under the main chain bonded situation of the organic group with sulfydryl through siloxane bond and ZGK 5.
EP0781814A2 discloses a kind of curable constituent polyorganosiloxane composition and the method for using its bonding substrates; Said composition comprises the silicone resin that contains alkenyl-functional groups (A) of 30-75% (weight percentage); The sulfydryl polydiorganosiloxane (B) of 70-25% (weight percentage), (A) of per 100 parts of weight and (B) contain the condensation catalyst of 0.01-10% (weight percentage) in the component.
EP0781813A2 discloses a kind of curable constituent polyorganosiloxane composition and the method for using its bonding substrates; Compsn comprises the silicone resin (A) of 30-75% (weight percentage); The sulfydryl polydiorganosiloxane (B) of 5-65% (weight percentage); The organopolysiloxane that contains the alkene chain (C) of 5-65% (weight percentage); (A) of per 100 parts of weight, (B) and (C) in the condensation catalyst of 0.01-10% (weight percentage) is arranged at most, catalyzer is four alkoxy titanium compounds and tin carboxylic acid cpd such as dibutyl tin laurate and stannous octoate.This constituent polyorganosiloxane composition keeps flowable state under anhydrous, the situation of be in the light (not touching high-octane ultraviolet ray, electron beam); But behind the high-octane ultraviolet ray of contact, electron beam; Be exposed to again and then solidify to form glue in the air rapidly; Can be used as tackiness agent, embedding agent etc., this tackiness agent can be used for various base materials, like glass, metal, paper, synthetic resins, fiber etc.
The viscosity that the sulfydryl polydiorganosiloxane is pointed out in this invention is during less than 0.1Pa.s, and the viscosity of compsn then can be low excessively, and when the viscosity of sulfydryl polydiorganosiloxane during greater than 100Pa.s, the viscosity of compsn then can be too high.
The hydrosulphonyl functionalized ZGK 5 that above document uses is the end capped diorganosiloxane that gathers of sulfydryl, and side chain does not contain or contains sulfydryl hardly, that is to say that they contain sulfydryl at the two ends of main chain.
US5278228A discloses the sticker that is used for textiles, and it is formed on hydroxy terminal, the hydrosulphonyl functionalized organopolysiloxane by specific vinyl monomer-grafted.
Summary of the invention
The object of the present invention is to provide a kind of novel high-adhesion can silicone sealant; Promptly in hydroxy-end capped polysiloxane backbone, introduce the functional groups of sulfur-bearing; Because the special charge distribution of sulphur atom, this base polymer can improve the adhesive property of silicone sealant and some base material effectively.Especially for metal base, the introducing of sulfur-bearing siloxanes makes silicone sealant improve greatly the sticking power of metal base, and the silicone adhesive product performance that make are stable, suitability is more extensive.
" silicone sealant ", " silicone adhesive " and " ZGK 5 sealer " interchangeable use in this application.
According to the first embodiment of the present invention, a kind of silicone sealant is provided, it comprises following component: component A: end capped hydrosulphonyl functionalized ZGK 5 100 ~ 20 weight parts of dihydroxyl; Preferred 90 ~ 35 parts by weight of component B: α; Alpha, omega-dihydroxy ZGK 50 ~ 80 weight part, preferred 10 ~ 65 parts by weight of component C: linking agent 1 ~ 20 weight part, preferred 3 ~ 16 weight parts; More preferably 4-14 weight part
Further preferred 5-12 weight part, preferred again 6-10 weight part;
Component D: catalyzer 0.01 ~ 5 weight part, preferred 0.03 ~ 4.5 weight part, more preferably 0.05 ~ 4.2 weight part,
Further preferred 0.1 ~ 4.5 weight part, preferred 0.15 ~ 4.2 weight part, preferred 0.20 ~ 4.0 weight part,
Preferred 0.25 ~ 3.5 weight part, preferred 0.30 ~ 3.2 weight part, preferred 0.40 ~ 2.8 weight part,
Preferred 0.45 ~ 2.5 weight part, preferred 0.5 ~ 2.0 weight part, preferred 0.6 ~ 1.5 weight part;
Wherein, End capped hydrosulphonyl functionalized ZGK 5 of dihydroxyl (component A) and α; The weight part sum of alpha, omega-dihydroxy ZGK 5 (B component) is 100 weight parts, and linking agent and catalyzer weight part separately is with respect to the component A of 100 weight parts and the weight part for the B component.
Preferably, the ratio of component A and B component (weight meter) is 2:8 ~ 10:0, preferred 2.5:7.5 ~ 10:1, preferred 3:7 ~ 9:1, more preferably 3.5:6.5 ~ 8:2,4:6 ~ 7:3 more preferably, further preferred 4:6 ~ 6:4 or 4:6 ~ 7:3 or 4:6 ~ 6.5:3.5.
Preferably, component A is the end capped hydrosulphonyl functionalized ZGK 5 of dihydroxyl with following general formula (I):
In the formula:
R
1Expression has the alkyl of 1-24 carbon atom or has the aryl of 6-10 carbon atom,
R
2Expression has the divalent alkyl of 1-8 carbon atom,
R
3Expression has the alkyl of 1-24 carbon atom, and the aryl of 6-10 carbon atom has the alkoxyl group of 1-6 carbon atom or hydroxyl or R
2And R
3With the Siliciumatom that they were keyed to form contain 1-8 carbon atom trivalent not branching or branched-alkyl 5 Yuans or 6 Yuans rings and
A representes 80-99mol%,
B represent 1-20mol% and
a+b＝100mol%。
Preferably, a representes that 85-93mol% and b represent 7-15mol%, and more preferably a representes that 87-91mol% and b represent 9-13mol%.
Generally, the viscosity that under 25 ℃, records the component A (being the end capped hydrosulphonyl functionalized ZGK 5 of dihydroxyl) of general formula (I) is 100-100,000mPa.s, 500-90 preferably, 000mPa.s; More preferably 1000-60,000mPa.s, further preferred 2000-50,000mPa.s, more preferably 5000-40; 000mPa.s, still more preferably 10,000-35,000mPa.s, preferred again 12; 000-30,000mPa.s, more more preferably 15,000-20,000mPa.s.
Referring to US5278228A (especially embodiment 1), the document is introduced among this paper with full content, as describing in this article as the compound method of the end capped hydrosulphonyl functionalized ZGK 5 of dihydroxyl of the general formula (I) of component A.
Sulfhydryl content among the component A (wt%) generally is 0.02wt%-6wt%, preferably 0.05wt%-5.5wt%, preferably 0.08wt%-5.0wt%; More preferably 0.1wt%-4.5wt%, further preferred 0.2wt%-4.3wt%, further preferred 0.4wt%-4.0wt%; Further preferred 0.5wt%-3.5wt%, further preferred 0.7wt%-3.4wt%, further preferred 0.8wt%-3.3wt%; Further preferred 1.0wt%-3.0wt%, further preferred 1.2wt%-2.8wt%.
The weight-average molecular weight of component A generally is 30,000-200, and between 000, preferably 50,000-100 is between 000.
Said B component (being α, the alpha, omega-dihydroxy ZGK 5) generally is to have general formula HO-[SiOR
2] α of n-SiOH, the alpha, omega-dihydroxy ZGK 5, wherein R is methyl, ethyl, propyl group, vinyl or phenyl.
Above-described B component (being α, the alpha, omega-dihydroxy ZGK 5) generally is α usually used in this field, alpha, omega-dihydroxy ZGK 5, α preferably, alpha, omega-dihydroxy polydimethyl siloxane.The weight-average molecular weight of above-described B component is normally 10,000-250, and between 000, more preferably 30,000-200, between 000, preferably 50,000-100 is between 000.
Further preferred, are 1000-70 in the viscosity of 25 ℃ of following B component, 000mPa.s, further preferred 2000-50; 000mPa.s, more preferably 5000-40,000mPa.s, still more preferably 10; 000-35,000mPa.s, preferred again 12,000-30; 000mPa.s, more more preferably 15,000-20,000mPa.s.
In general, above-described linking agent is a general formula R '-Si (R ")
3Compound,
Wherein R ' is an alkyl, and C1-C10 alkyl for example is like methyl, ethyl, propyl group, butyl, amyl group, 2-ethylhexyl, octyl group, decyl; Thiazolinyl, C2-C6 alkenyl for example is like vinyl, allyl group, hexenyl; Perhaps naphthenic base, C3-C8 naphthenic base for example is like cyclopentyl, cyclohexyl and suberyl; Aryl, C6-C8 aromatic hydrocarbyl for example is like phenyl, tolyl and xylyl; R " be alkoxyl group, C1-C6 alkoxyl group for example, like methoxyl group, oxyethyl group, propoxy-, butoxy, pentyloxy, aminooxy, C1-C4 acyloxy, C2-C5 alkene oxygen base group or C1-C5 alkyl ketone oximido.
Used " alkyl " of the present invention is meant the complete saturated alkyl of straight or branched, can be the C1-C10 alkyl, preferred C1-C8 alkyl, more preferably C1-C7 alkyl, especially preferably C1-C6 alkyl, most preferably C1-C6 alkyl.Instance includes but not limited to methyl, ethyl, propyl group, normal-butyl, isobutyl-etc.
Used " thiazolinyl " of the present invention is meant the alkyl that in side chain or straight chain hydrocarbon chain, comprises one or more pairs of keys, can be the C2-C6 thiazolinyl, preferred C2-C5 thiazolinyl, more preferably C2-C4 thiazolinyl, especially preferably C2-C3 thiazolinyl, most preferably vinyl.Instance includes but not limited to vinyl, allyl group, 1-propenyl, 2-propenyl, hexenyl etc.
Used " naphthenic base " of the present invention is meant saturated hydrocarbon ring fully, can be the naphthenic base of C3-C8, the naphthenic base of preferred C4-C7.The instance of group of naphthene base includes but not limited to cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl etc.
Used " alkoxyl group " of the present invention is meant the alkoxyl group of side chain or straight chain.Can be the C1-C6 alkoxyl group, preferred C1-C4 alkoxyl group, instance includes but not limited to methoxyl group, oxyethyl group, propoxy-, butoxy, isobutoxy, pentyloxy etc.
Linking agent is many alkoxyl silicones alkanes preferably; For example methyltrimethoxy silane, vinyltrimethoxy silane, Union carbide A-162, vinyltriethoxysilane, tetramethoxy-silicane, tetraethoxysilane, tetrapropoxysilane, four butoxy silanes, phenyltrimethoxysila,e or phenyl triethoxysilane; With the ketoximinosilanes class, for example methyl tributanoximo silane, vinyl tributanoximo silane, methyl three (mibk oximido) silane, vinyl three (mibk oximido) silane, methyl tri acetylacetonate oximino silane, phenyl tributanoximo silane, phenyl trimethylammonium isobutyl ketone oximino silane, phenyl tri acetylacetonate oximino silane, four Diacetylmonoxime base silanes or tetramethyl-isobutyl ketone oximino silane.
Linking agent is more preferably the ketoximinosilanes class, particularly preferably be selected from methyl tributanoximo silane, vinyl tributanoximo silane, methyl three (mibk oximido) silane, vinyl three (mibk oximido) silane, methyl tri acetylacetonate oximino silane, phenyl tributanoximo silane, phenyl trimethylammonium isobutyl ketone oximino silane, phenyl tri acetylacetonate oximino silane, four Diacetylmonoxime base silanes or the tetramethyl-isobutyl ketone oximino silane one or both or multiple.
Preferably, said catalyzer is an organo-tin compound.Further preferred, said organo-tin compound be selected from dibutyl tin laurate, two LAURIC ACID 99 MIN diamyl tin, two LAURIC ACID 99 MIN dihexyl tin, two LAURIC ACID 99 MIN dioctyl tins, dibutyltin diacetate, two acetic acid diamyl tin, two acetic acid dihexyl tin, two acetic acid dioctyl tins, dimethoxy dibutyl tin, dimethoxy diamyl tin, dimethoxy dihexyl tin, dimethoxy dioctyl tin, diethoxy dibutyl tin, diethoxy diamyl tin, diethoxy dihexyl tin, diethoxy dioctyl tin, dipropoxy dibutyl tin, dipropoxy diamyl tin, dipropoxy dihexyl tin, dipropoxy dioctyl tin, dibutoxy dibutyl tin, dibutoxy diamyl tin, dibutoxy dihexyl tin, dibutoxy dioctyl tin, dibutyl tin diacetyl acetonate, the stannous octoate any one, two kinds or multiple.
Organo-tin compound is more preferably any one in dibutyl tin laurate, dibutyltin diacetate, the two LAURIC ACID 99 MIN dioctyl tins.
In addition, above-described silicone adhesive also comprises (based on the component A and the B component of 100 weight parts):
Optional filler 0～60 weight part or 1 ~ 60 weight part, preferred 2 ~ 50 weight parts,
More preferably 5 ~ 40 weight parts, more preferably 7 ~ 30 weight parts,
Still further preferred 8 ~ 20 weight parts or 8 ~ 15 weight parts;
Optional softening agent 0 ~ 180 or 1 ~ 180 weight part, preferred 2 ~ 150 weight parts,
More preferably 5 ~ 120 weight parts, more preferably 7 ~ 100 weight parts,
Further preferred 8 ~ 80 weight parts, 10 ~ 70 weight parts; Preferred 12 ~ 50 weight parts,
Preferred 15 ~ 40 weight parts, preferred 18 ~ 30 weight parts;
Optional coupling agent 0 ~ 6 weight part or 0.1 ~ 6 weight part, preferred 0.5 ~ 5 weight part,
Preferred 1.0 ~ 4.5 weight parts, preferred 1.2 ~ 4 weight parts, preferred 1.5 ~ 3 weight parts.
Preferably, said filler is aerosil or precipitated silica.
In general, said softening agent is selected from one or more in the middle of the softening agent commonly used of sealer field.It is mainly used in the viscosity of improving product.Softening agent includes but not limited to dimethyl silicone oil (dimethyl silicone), MO such as industrial white oil, or in the liquid polybutadiene one or more, preferred industrial white oil.
Said coupling agent is preferably silane coupling agent, is more preferably any one or two kinds in γ-chloropropyl triethoxysilane, γ-An Bingjisanyiyangjiguiwan, gamma-methyl allyl acyloxypropyl trimethoxysilane, vinyltrimethoxy silane, the vinyltriethoxysilane.
Above-described silicone sealant can also add other auxiliary agent, as in adhesive accelerant, inhibitor, pigment and the fire retardant one or both or multiple.
Second embodiment according to the present invention provides a kind of method for preparing above-described silicone sealant, and it may further comprise the steps:
(1) with end capped hydrosulphonyl functionalized ZGK 5 of dihydroxyl (component A) and α; Alpha, omega-dihydroxy ZGK 5 (B component) is totally 100 weight parts, and optional filler adds in the mixing tank (for example planetary mixer), (for example vacuumizes; Vacuum tightness 0.09MPa); Mix (for example 45-100 minute) then such as under rotating speed 25-60rpm, stirring 45 ~ 90 minutes preferred 60 minutes;
(2) in the gained mixture, add linking agent 1-20 weight part (preferred 3-15 part); Catalyzer 0.01 ~ 5 weight part (preferred 0.05-1 part); Optional coupling agent, optional softening agent, under vacuum (for example; Vacuum tightness 0.09MPa) mixes (for example under rotating speed 25-60rpm) with react (for example 30～150 minutes), make silicone sealant.
Preferably, in above-described method, the relative consumption of various components is:
Component A: end capped hydrosulphonyl functionalized ZGK 5 100 ~ 20 weight parts of dihydroxyl, preferred 90 ~ 35 weight parts
B component: α, alpha, omega-dihydroxy ZGK 50 ~ 80 weight part, preferred 10 ~ 65 weight parts
Component C: linking agent 1 ~ 20 weight part, preferred 3 ~ 16 weight parts, more preferably 4-14 weight part,
Further preferred 5-12 weight part, preferred again 6-10 weight part;
Component D: catalyzer 0.01 ~ 5 weight part, preferred 0.03 ~ 4.5 weight part,
More preferably 0.05 ~ 4.2 weight part, further preferred 0.1 ~ 4.5 weight part,
Preferred 0.15 ~ 4.2 weight part, preferred 0.20 ~ 4.0 weight part,
Preferred 0.25 ~ 3.5 weight part, preferred 0.30 ~ 3.2 weight part,
Preferred 0.40 ~ 2.8 weight part, preferred 0.45 ~ 2.5 weight part,
Preferred 0.5 ~ 2.0 weight part, preferred 0.6 ~ 1.5 weight part, preferred 0.7-1 weight part;
Wherein, End capped hydrosulphonyl functionalized ZGK 5 of dihydroxyl (component A) and α; The weight part sum of alpha, omega-dihydroxy ZGK 5 (B component) is 100 weight parts, and linking agent and catalyzer weight part separately is with respect to the component A of 100 weight parts and the weight part for the B component.
Preferably, the ratio of component A and B component (weight meter) is 2:8 ~ 10:0, preferred 2.5:7.5 ~ 10:1, preferred 3:7 ~ 9:1, more preferably 3.5:6.5 ~ 8:2,4:6 ~ 7:3 more preferably, further preferred 4:6 ~ 6:4.
In addition, in above-described method, the relative consumption of other component is (based on the component A and the B component of 100 weight parts):
Optional filler 0～60 weight part or 1 ~ 60 weight part, preferred 2 ~ 50 weight parts,
More preferably 5 ~ 40 weight parts, more preferably 7 ~ 30 weight parts,
Still further preferred 8 ~ 20 weight parts or 8 ~ 15 weight parts;
Optional softening agent 0 ~ 180 or 1 ~ 180 weight part, preferred 2 ~ 150 weight parts,
More preferably 5 ~ 120 weight parts, more preferably 7 ~ 100 weight parts,
Further preferred 8 ~ 80 weight parts, 10 ~ 70 weight parts;
Preferred 12 ~ 50 weight parts, preferred 15 ~ 40 weight parts, preferred 18 ~ 30 weight parts;
Optional coupling agent 0 ~ 6 weight part or 0.1 ~ 6 weight part, preferred 0.5 ~ 5 weight part,
Preferred 1.0 ~ 4.5 weight parts, preferred 1.2 ~ 4 weight parts, preferred 1.5 ~ 3 weight parts.
" optional " that the present invention is used is meant optional or can not select.
The present invention compared with prior art has following characteristics: the preparation method of silicone adhesive provided by the invention improves common single-component room temperature vulcanized silicone adhesive; Thiylation group in the main chain of hydroxy-end capped ZGK 5 base-material; Can obviously improve silicone adhesive and special base material, especially the sticking power between the metal base.This method is with a wide range of applications in suitability for industrialized production.
According to the present invention, the purposes of above silicone sealant also is provided, wherein silicone sealant is as sealing agent, tackiness agent, embedding agent or joint sealant (for building or joint sealant that electronics is used).
The basic silicone sealant that uses such as the filleting of civil aluminum alloy door and window, building curtain wall, stone material and decorations.
Silicone sealant belongs to silicone based product; High polymer main chain mainly is made up of silicon-oxygen-silicon bound; The reaction of linking agent and base polymer forms netted Si-O-Si skeleton structure in solidification process, and outstanding feature is exactly to have excellent high and low temperature resistance and weather resistance, and its bonding force is strong; Tensile strength is big, has characteristics such as UV resistant, shock resistance and protection against the tide, anti-ozone simultaneously again.Silicone sealant does not contain organic solvent, and is free from environmental pollution, and cured glue body volumetric shrinkage property is little, good airproof performance, and ambient cure, it is than extensive applicability in addition, can realize bonding between most of building material products, so using value is very big.Can be used as sealing agent, tackiness agent, embedding agent etc., be widely used in building, machinery, automobile, electronic applications.
Silicone adhesive according to the invention, silicone sealant, silicone gums or ZGK 5 sealer are the notions of interchangeable use.
Embodiment
All characteristics of describing among the present invention's (comprising claim and specification sheets) can make up by mode arbitrarily, and no matter whether the description of these characteristics is in same paragraph or the same context, but except the mutually exclusive array mode of this category feature., but be not limited thereto understanding the present invention better below in conjunction with embodiment.Except as otherwise noted, all umbers are weight part among the embodiment, and the raw material of use is the commercially available material.
Below in conjunction with preferred embodiment the present invention is further specified:
The sticking power method of testing:
1, be pressed on the electrophoresis test plate (panel) relevant with sealing glue with standard form (specification: 150 * 70 * 3mm, bore size: 70 * 10mm, 2 holes), scraping thickness is the two seals adhesive tape of 3mm.
2, test plate (panel) is lain in a horizontal plane in taking-up after 30 minutes in 140 ± 3 ℃ of baking ovens, at room temperature placed 24 hours.
3, take off the sealant layer on the test plate (panel) as possible with hand,
If glue-line is destroyed, but can not get any more, then qualified, the sticking power that sealer is described is greater than force of cohesion.
If cohesive failure, glue-line can take off on a small quantity, and is qualified basically;
Destroy if adhere to, then defective
The sticking power testing standard: sticking power is greater than force of cohesion, and cohesive failure destroys greater than adhering to.
Shearing resistance assay method (GB7124-86):
Sample is single bridging arrangement.On the faying surface of sample, apply the longitudinal stretching shearing force, measure the maximum load that sample can bear.Average shearing stress on the faying surface is the tensile shear strength of sealer:
1, with the length and the width of gage measuring sample faying surface, is accurate to 0.05mm.
2, be clipped in sample symmetrically in the upper and lower clamper, the distance of clamping place to lapped butt is 50 ± 1mm.
3, start trier, in 5 ± 1mm/min, load with steady speed.The maximum load of record sample shear fracture.The type of record glue-joint failure (cohesive failure, adhesion destruction, metal destroy).
Shearing resistance is calculated as follows:
τ is a tensile shear strength in the formula, and MPa, P are the maximum load of sample shear fracture, N; B is a sample faying surface width, mm; L is a sample faying surface length, mm.
The end capped hydrosulphonyl functionalized ZGK 5 of employed dihydroxyl (being called for short " hydroxy-end capped sulfydryl ZGK 5 ") is according to preparing in the method described in the embodiment 1 of US5278228A among the embodiment below; The viscosity that under 25 ℃, records is 50; 000mPa.s; The weight-average molecular weight that is recorded by GPC is 81,000; Sulfhydryl content in the polymkeric substance is according to (also can be measured by other ordinary method) measured in method described in the 25th page in the specification sheets of CN1376185A, and sulfhydryl content is about 2wt%.
Embodiment 1 (contrast)
With α, 100 parts of alpha, omega-dihydroxy polydimethyl siloxanes (weight-average molecular weight 90,000), aerosil adds in the planetary mixer for 20 parts, vacuumizes, vacuum tightness 0.09MPa, rotating speed 25-60rpm stirred 60 minutes down; Add 5 parts of methyl tributanoximo silanes, 2 parts of γ-chloropropyl triethoxysilanes, 2 parts of trimethylammonium YSR 3286s; 0.6 part of dibutyl tin laurate; 2 parts of white oils are to carry out chemical reaction under 0.09MPa, the rotating speed 25-60rpm in vacuum tightness, 1 hour reaction times.Through the sticking power method of testing, adhere to and destroy, defective; Shearing resistance τ is 0.85MPa.
Embodiment 2 (contrast)
With α, 100 parts of ω-dimercapto YSR 3286 (number-average molecular weight 4600), aerosil adds in the planetary mixer for 20 parts, vacuumizes, vacuum tightness 0.09MPa, rotating speed 25-60rpm stirred 60 minutes down; Add 5 parts of methyl tributanoximo silanes, 2 parts of γ-chloropropyl triethoxysilanes, 2 parts of trimethylammonium YSR 3286s; 0.6 part of dibutyl tin laurate; 2 parts of white oils are to carry out chemical reaction under 0.09MPa, the rotating speed 25-60rpm in vacuum tightness, 1 hour reaction times.Through the sticking power method of testing, adhere to and destroy, defective; Shearing resistance τ is 0.87MPa.
Embodiment 3 (contrast)
With α, 90 parts of alpha, omega-dihydroxy polydimethyl siloxanes (weight-average molecular weight 90,000); (viscosity that records under 25 ℃ is 50 to hydroxy-end capped sulfydryl ZGK 5,000mPa.s, weight-average molecular weight 81; 000) 10 parts, aerosil adds in the planetary mixer for 20 parts, vacuumizes; Vacuum tightness 0.09MPa, rotating speed 25-60rpm stirred 60 minutes down; Add 5 parts of methyl tributanoximo silanes, 2 parts of γ-chloropropyl triethoxysilanes, 2 parts of trimethylammonium YSR 3286s; 0.6 part of dibutyl tin laurate; 2 parts of white oils carry out chemical reaction under vacuum tightness 0.09MPa, rotating speed 25-60rpm, 1 hour reaction times.Through the sticking power method of testing, adhere to and destroy, defective; Shearing resistance τ is 0.90MPa.
Embodiment 4 (reference)
With α, 80 parts of alpha, omega-dihydroxy polydimethyl siloxanes, 20 parts of hydroxy-end capped sulfydryl ZGK 5, aerosil adds in the planetary mixer for 20 parts, vacuumizes, vacuum tightness 0.09MPa, rotating speed 25-60rpm stirred 60 minutes down; Add 5 parts of methyl tributanoximo silanes, 2 parts of γ-chloropropyl triethoxysilanes, 2 parts of trimethylammonium YSR 3286s; 0.6 part of dibutyl tin laurate; 2 parts of white oils carry out chemical reaction under vacuum tightness 0.09MPa, rotating speed 25-60rpm, 1 hour reaction times.Through the sticking power method of testing, cohesive failure, glue-line can take off on a small quantity, and be qualified basically; Shearing resistance τ is 0.95MPa.
Embodiment 5 (reference)
With α, 70 parts of alpha, omega-dihydroxy polydimethyl siloxanes, 30 parts of hydroxy-end capped sulfydryl ZGK 5, aerosil adds in the planetary mixer for 20 parts, vacuumizes, vacuum tightness 0.09MPa, rotating speed 25-60rpm stirred 60 minutes down; Add 5 parts of methyl tributanoximo silanes, 2 parts of γ-chloropropyl triethoxysilanes, 2 parts of trimethylammonium YSR 3286s; 0.6 part of dibutyl tin laurate; 2 parts of white oils carry out chemical reaction under vacuum tightness 0.09MPa, rotating speed 25-60rpm, 1 hour reaction times.Through the sticking power method of testing, cohesive failure, glue-line can take off on a small quantity, and be qualified basically; Shearing resistance τ is 1.00MPa.
Embodiment 6
With α, 60 parts of alpha, omega-dihydroxy polydimethyl siloxanes (weight-average molecular weight 90,000), 40 parts of hydroxy-end capped sulfydryl ZGK 5, aerosil adds in the planetary mixer for 20 parts, vacuumizes, vacuum tightness 0.09MPa, rotating speed 25-60rpm stirred 60 minutes down; Add 5 parts of methyl tributanoximo silanes, 2 parts of γ-chloropropyl triethoxysilanes, 2 parts of trimethylammonium YSR 3286s; 0.6 part of dibutyl tin laurate; 2 parts of white oils carry out chemical reaction under vacuum tightness 0.09MPa, rotating speed 25-60rpm, 1 hour reaction times.Through the sticking power method of testing, cohesive failure, glue-line can not take off, and is qualified; Shearing resistance τ is 1.10MPa.
Embodiment 7
With α, 50 parts of alpha, omega-dihydroxy polydimethyl siloxanes, 50 parts of hydroxy-end capped sulfydryl ZGK 5, aerosil adds in the planetary mixer for 20 parts, vacuumizes, vacuum tightness 0.09MPa, rotating speed 25-60rpm stirred 60 minutes down; Add 5 parts of methyl tributanoximo silanes, 2 parts of γ-chloropropyl triethoxysilanes, 2 parts of trimethylammonium YSR 3286s; 0.6 part of dibutyl tin laurate; 2 parts of white oils carry out chemical reaction under vacuum tightness 0.09MPa, rotating speed 25-60rpm, 1 hour reaction times.Through the sticking power method of testing, cohesive failure, glue-line can not take off, and is qualified; Shearing resistance τ is 1.12MPa.
Embodiment 8
With α, 40 parts of alpha, omega-dihydroxy polydimethyl siloxanes, 60 parts of hydroxy-end capped sulfydryl ZGK 5, aerosil adds in the planetary mixer for 20 parts, vacuumizes, vacuum tightness 0.09MPa, rotating speed 25-60rpm stirred 60 minutes down; Add 5 parts of methyl tributanoximo silanes, 2 parts of γ-chloropropyl triethoxysilanes, 2 parts of trimethylammonium YSR 3286s; 0.6 part of dibutyl tin laurate; 2 parts of white oils carry out chemical reaction under vacuum tightness 0.09MPa, rotating speed 25-60rpm, 1 hour reaction times.Through the sticking power method of testing, cohesive failure, glue-line can not take off, and is qualified; Shearing resistance τ is 1.25MPa.
Embodiment 9
With α, 30 parts of alpha, omega-dihydroxy polydimethyl siloxanes, 70 parts of hydroxy-end capped sulfydryl ZGK 5, aerosil adds in the planetary mixer for 20 parts, vacuumizes, vacuum tightness 0.09MPa, rotating speed 25-60rpm stirred 60 minutes down; Add 5 parts of methyl tributanoximo silanes, 2 parts of γ-chloropropyl triethoxysilanes, 2 parts of trimethylammonium YSR 3286s; 0.6 part of dibutyl tin laurate; 2 parts of white oils carry out chemical reaction under vacuum tightness 0.09MPa, rotating speed 25-60rpm, 1 hour reaction times.Through the sticking power method of testing, cohesive failure, glue-line can not take off, and is qualified; Shearing resistance τ is 1.30MPa.
Embodiment 10
With α, 20 parts of alpha, omega-dihydroxy polydimethyl siloxanes, 80 parts of hydroxy-end capped sulfydryl ZGK 5, aerosil adds in the planetary mixer for 20 parts, vacuumizes, vacuum tightness 0.09MPa, rotating speed 25-60rpm stirred 60 minutes down; Add 5 parts of methyl tributanoximo silanes, 2 parts of γ-chloropropyl triethoxysilanes, 2 parts of trimethylammonium YSR 3286s; 0.6 part of dibutyl tin laurate; 2 parts of white oils carry out chemical reaction under vacuum tightness 0.09MPa, rotating speed 25-60rpm, 1 hour reaction times.Through the sticking power method of testing, cohesive failure, glue-line can not take off, and is qualified; Shearing resistance τ is 1.40MPa.
Embodiment 11
With α, 10 parts of alpha, omega-dihydroxy polydimethyl siloxanes, 90 parts of hydroxy-end capped sulfydryl ZGK 5, aerosil adds in the planetary mixer for 20 parts, vacuumizes, vacuum tightness 0.09MPa, rotating speed 25-60rpm stirred 60 minutes down; Add 5 parts of methyl tributanoximo silanes, 2 parts of γ-chloropropyl triethoxysilanes, 2 parts of trimethylammonium YSR 3286s; 0.6 part of dibutyl tin laurate; 2 parts of white oils carry out chemical reaction under vacuum tightness 0.09MPa, rotating speed 25-60rpm, 1 hour reaction times.Through the sticking power method of testing, cohesive failure, glue-line can not take off, and is qualified; Shearing resistance τ is 1.30MPa.
Embodiment 12
With 100 parts of hydroxy-end capped sulfydryl ZGK 5, aerosil adds in the planetary mixer for 20 parts, vacuumize, and vacuum tightness 0.09MPa, rotating speed 25-60rpm stirred 60 minutes down; Add 5 parts of methyl tributanoximo silanes, 2 parts of γ-chloropropyl triethoxysilanes, 2 parts of trimethylammonium YSR 3286s; 0.6 part of dibutyl tin laurate; 2 parts of white oils carry out chemical reaction under vacuum tightness 0.09MPa, rotating speed 25-60rpm, 1 hour reaction times.Through the sticking power method of testing, cohesive failure, glue-line can not take off, and is qualified; Shearing resistance τ is 1.28MPa.
Embodiment 1 to embodiment 12 has adopted the α of different ratios, and alpha, omega-dihydroxy polydimethyl siloxane and hydroxy-end capped sulfydryl ZGK 5 prepare silicone adhesive, sums up as follows:
Can know that by above embodiment result along with the add-on of sulfydryl ZGK 5 increases, the sticking power of prepared silicone adhesive is good more, improve generally cohesiveness with the silicone adhesive of ZGK 5 preparation.
Claims (10)
1. silicone sealant, it comprises following component:
Component A: end capped hydrosulphonyl functionalized ZGK 5 100 ~ 20 weight parts of dihydroxyl, preferred 90 ~ 35 weight parts;
B component: α, alpha, omega-dihydroxy ZGK 50 ~ 80 weight part, preferred 10 ~ 65 weight parts;
Component C: linking agent 1 ~ 20 weight part;
Component D: catalyzer 0.01 ~ 5 weight part;
Wherein, The end capped hydrosulphonyl functionalized ZGK 5 of dihydroxyl is component A and α; The alpha, omega-dihydroxy ZGK 5 is that the weight part sum of B component is 100 weight parts, and linking agent and catalyzer weight part separately is with respect to the component A of 100 weight parts and the weight part for the B component; Preferably, wherein the part by weight of component A and B component is 2:8 ~ 10:0, more preferably 2.5:7.5 ~ 10:1.
2. according to the silicone sealant of claim 1, wherein component A is the end capped hydrosulphonyl functionalized ZGK 5 of dihydroxyl with following general formula (I):
In the formula:
R
1Expression has the alkyl of 1-24 carbon atom or has the aryl of 6-10 carbon atom,
R
2Expression has the divalent alkyl of 1-8 carbon atom,
R
3Expression has the alkyl of 1-24 carbon atom, and the aryl of 6-10 carbon atom has the alkoxyl group of 1-6 carbon atom or hydroxyl or R
2And R
3With the Siliciumatom that they were keyed to form contain 1-8 carbon atom trivalent not branching or branched-alkyl 5 Yuans or 6 Yuans rings and
A representes 80-99mol%,
B represent 1-20mol% and
a+b＝100mol%。
3. according to the silicone sealant of claim 1 or 2, wherein the sulfydryl wt% content among the component A is 0.02wt%-6wt%, preferably 0.05wt%-5.5wt%.
4. according to any one silicone sealant among the claim 1-3, wherein the weight-average molecular weight of component A is 30,000-200, and between 000, preferably 50,000-100 is between 000.
5. according to any one silicone sealant among the claim 1-4, wherein the weight-average molecular weight of B component is 10,000-250, and between 000, more preferably 30,000-200 is between 000.
6. according to any one silicone sealant among the claim 1-5, wherein linking agent is a general formula R '-Si (R ")
3Compound,
Wherein R ' is an alkyl, and C1-C10 alkyl for example is like methyl, ethyl, propyl group, butyl, amyl group, 2-ethylhexyl, octyl group, decyl; Thiazolinyl, C2-C6 alkenyl for example is like vinyl, allyl group, hexenyl; Perhaps naphthenic base, C3-C8 naphthenic base for example is like cyclopentyl, cyclohexyl and suberyl; Aryl, C6-C8 aromatic hydrocarbyl for example is like phenyl, tolyl and xylyl; R " be alkoxyl group, C1-C6 alkoxyl group for example, like methoxyl group, oxyethyl group, propoxy-, butoxy, pentyloxy, aminooxy, C1-C4 acyloxy, C2-C5 alkene oxygen base group or C1-C5 alkyl ketone oximido;
Linking agent is many alkoxyl silicones alkanes and ketoximinosilanes class preferably, is more preferably the ketoximinosilanes class.
7. according to any one silicone sealant among the claim 1-6, wherein catalyzer is an organo-tin compound.
8. according to any one silicone sealant among the claim 1-7, component A and B component based on 100 weight parts also comprise:
Optional filler 0～60 weight part or 1 ~ 60 weight part, preferred 2 ~ 50 weight parts;
Optional softening agent 0 ~ 180 or 1 ~ 180 weight part, preferred 2 ~ 150 weight parts;
Optional coupling agent 0 ~ 6 weight part or 0.1 ~ 6 weight part, preferred 0.5 ~ 5 weight part.
9. preparation is according to the method for the silicone sealant of any one among the 1-8, and it may further comprise the steps:
(1) be component A and α with the end capped hydrosulphonyl functionalized ZGK 5 of dihydroxyl, the alpha, omega-dihydroxy ZGK 5 is B component totally 100 weight parts, and optional filler adds in the mixing tank, vacuumizes, and mixes then;
(2) in the gained mixture, add linking agent 3-15 part, catalyzer 0.05-1 part, optional coupling agent, optional softening agent mixes to react under vacuum, makes silicone sealant.
10. according to the purposes of the silicone sealant of any one among the claim 1-8, wherein silicone sealant is as sealing agent, tackiness agent, embedding agent or joint sealant.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 201210265243 CN102766431B (en) | 2012-07-27 | 2012-07-27 | High-adhesion silicone sealant |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 201210265243 CN102766431B (en) | 2012-07-27 | 2012-07-27 | High-adhesion silicone sealant |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102766431A true CN102766431A (en) | 2012-11-07 |
| CN102766431B CN102766431B (en) | 2013-07-31 |
Family
ID=47094020
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 201210265243 Active CN102766431B (en) | 2012-07-27 | 2012-07-27 | High-adhesion silicone sealant |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102766431B (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108611048A (en) * | 2016-12-12 | 2018-10-02 | 广东杰果新材料有限公司 | Dry-type transformer dealcoholized type organic silicon potting adhesive and preparation method thereof |
| CN112457819A (en) * | 2019-09-09 | 2021-03-09 | 广州以恒有机硅有限公司 | High-adhesion silicone sealant |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4234697A (en) * | 1979-01-18 | 1980-11-18 | Dow Corning Corporation | Method of preparing cross-linked polydiorganosiloxane using organic isocyanates and products prepared therefrom |
| CN1371953A (en) * | 2001-02-23 | 2002-10-02 | 成都硅宝科技实业有限责任公司 | Neutral silicone sealant for stone material and making method thereof |
| CN1687288A (en) * | 2005-04-13 | 2005-10-26 | 成都硅宝科技实业有限责任公司 | Flameproofing silicone structure sealant and mfg. method thereof |
| WO2008090458A1 (en) * | 2007-01-25 | 2008-07-31 | Henkel Kgaa | Aqueous silylated polymer emulsion and its preparation method and uses thereof |
| CN101600979A (en) * | 2007-01-22 | 2009-12-09 | 住友化学株式会社 | The optical thin film and the optical laminate that have bonding agent |
| CN101851486A (en) * | 2010-06-04 | 2010-10-06 | 江苏天辰硅材料有限公司 | Two-component solar sealant and preparation method thereof |
| CN102181262A (en) * | 2011-03-28 | 2011-09-14 | 镇江天源华威核能新材料有限公司 | Foam fireproof sealant |
-
2012
- 2012-07-27 CN CN 201210265243 patent/CN102766431B/en active Active
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4234697A (en) * | 1979-01-18 | 1980-11-18 | Dow Corning Corporation | Method of preparing cross-linked polydiorganosiloxane using organic isocyanates and products prepared therefrom |
| CN1371953A (en) * | 2001-02-23 | 2002-10-02 | 成都硅宝科技实业有限责任公司 | Neutral silicone sealant for stone material and making method thereof |
| CN1687288A (en) * | 2005-04-13 | 2005-10-26 | 成都硅宝科技实业有限责任公司 | Flameproofing silicone structure sealant and mfg. method thereof |
| CN101600979A (en) * | 2007-01-22 | 2009-12-09 | 住友化学株式会社 | The optical thin film and the optical laminate that have bonding agent |
| WO2008090458A1 (en) * | 2007-01-25 | 2008-07-31 | Henkel Kgaa | Aqueous silylated polymer emulsion and its preparation method and uses thereof |
| CN101851486A (en) * | 2010-06-04 | 2010-10-06 | 江苏天辰硅材料有限公司 | Two-component solar sealant and preparation method thereof |
| CN102181262A (en) * | 2011-03-28 | 2011-09-14 | 镇江天源华威核能新材料有限公司 | Foam fireproof sealant |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108611048A (en) * | 2016-12-12 | 2018-10-02 | 广东杰果新材料有限公司 | Dry-type transformer dealcoholized type organic silicon potting adhesive and preparation method thereof |
| CN112457819A (en) * | 2019-09-09 | 2021-03-09 | 广州以恒有机硅有限公司 | High-adhesion silicone sealant |
Also Published As
| Publication number | Publication date |
|---|---|
| CN102766431B (en) | 2013-07-31 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN104903404B (en) | Hardening resin composition and solidfied material thereof | |
| JP5860473B2 (en) | Fluid-coated silicone air and water barrier system and process | |
| CN101173101B (en) | Single-component ketoxime removing type room temperature vulcanized silicone rubber composition | |
| CN102796381B (en) | Condensation type RTV silicone rubber composition with matte surface, its preparation method and application | |
| CN101565600A (en) | Low-hardness high-flexibility double-component condensed type organic silicon potting adhesive composition | |
| CN101235203B (en) | Room temperature curable organopolysiloxane compositions | |
| MX2012003993A (en) | Organosiloxane compositions. | |
| JP6601142B2 (en) | Addition condensation combined curable silicone resin sheet, wavelength conversion sheet, and light emitting device manufacturing method | |
| CN101679750B (en) | Architectural unit possessing rapid deep-section cure silicone rubber component | |
| JPWO2017030128A1 (en) | Room temperature curable polyorganosiloxane composition and preparation method thereof | |
| US9228119B2 (en) | Two-component silicone composition | |
| JP2015165035A (en) | Room-temperature-curable polyorganosiloxane composition | |
| CN104508029B (en) | Weatherability organosilicon mixture with improved green strength | |
| CN102295836A (en) | Addition silicone resin composition | |
| CN102766431B (en) | High-adhesion silicone sealant | |
| JP5882851B2 (en) | Discolorable organopolysiloxane composition and structure bonded with the composition | |
| JP6400904B2 (en) | Curable resin composition | |
| KR20150013174A (en) | Curable resin composition and primer composition | |
| KR20160075489A (en) | Silicone adhesive and manufacturing method for same product | |
| JP2014218558A (en) | Room temperature curable polyorganosiloxane composition | |
| KR102198324B1 (en) | Room-temperature-curable organopolysiloxane composition, construction sealant using cured product of said composition, electrical/electronic component, and automobile oil seal | |
| CN103930490A (en) | Filled silicone composition, in situ preparation and use thereof | |
| JP2018090720A (en) | Condensation-curable silicone resin composition sheet, method for producing condensation-curable silicone resin composition sheet, and method for producing light emitting device | |
| JP5106914B2 (en) | Room temperature curable organopolysiloxane composition | |
| CN112457819A (en) | High-adhesion silicone sealant |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |