CN102559120A - Temperature-resistant, corrosion-resistant and high-adhesion adhesive and preparation method thereof - Google Patents
Temperature-resistant, corrosion-resistant and high-adhesion adhesive and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a temperature-resistant, corrosion-resistant and high-adhesion adhesive and a preparation method thereof, and belongs to the technical field of adhesives. The temperature-resistant, corrosion-resistant and high-adhesion adhesive consists of two components, i. e., an adhesive A and an adhesive B, in the weight ratio of 100:1-10, wherein the adhesive A consists of chemical plasticizing vinyl ester resin, a polymerization inhibitor, a low shrinkage agent, a free radical curing solvent, gas-phase silicon dioxide, inorganic filler, a coupling agent, a defoaming agent, color paste or paint, a promoter and a promotion additive; and the adhesive B consists of phthalic ester, peroxide and inertial powder filler. The adhesive provided by the invention has the performance of heat resistance, corrosion resistance, penetration resistance, adhesion, positioning, impact resistance and the like, can be formed into different types at normal temperature, and medium and high temperature, is easy and convenient to operate, can bring the unique advantage of the adhesive into full play on some occasions requiring to paying attention to corrosion resistance, adhesion, heat resistance and the like, and is suitable for mutual adhesion among a continuous cellulose material, a concrete material, a metal material, stone, FRP (Fiber Reinforce Plastic), thermoplastic plastic and the like.
Description
Technical field
The invention belongs to the sizing agent technical field, be specifically related to sizing agent of a kind of heatproof corrosion resistant high-adhesion ability and preparation method thereof.
Background technology
Vinyl ester resin is that a kind of vinyl ester product that is obtained by epoxy resin and methylacrylic acid ring-opening reaction is dissolved in and obtains a kind of radically curing thermosetting resin in the vinylbenzene; Vinyl groups is contained at the two ends of the main body ester molecule chain of bisphenol A-type vinyl ester resin, and middle skeleton is bisphenol A type epoxy resin structured.The molecular side chain end that each phenyl ring of the body portion subchain of phenolic vinyl ester resin links to each other has a vinyl groups, and skeleton is the phenol aldehyde type epoxy resin structure.Final vinyl ester resin has the advantage of epoxy resin and unsaturated polyester resin concurrently: mechanical property excellence, excellent anti-corrosion performance, heat resistance excellence, Job Operations property excellence etc. are mainly used in the corrosion-resistant FRP equipment and the goods such as storage tank, tower, pipeline, groove, liner, blower fan, grid of environment such as chemical field acid-and base-resisting, salt, organic solvent, Oxidant, mixed solvent.
With the different matrix resin is carrier; The sizing agent, the sealer that are aided with filler, auxiliary agent preparation are the important use directions in thermosetting resin downstream; Comparatively common in the market that sizing agent has: solvent-based adhesive mainly comprises X 050, tree elastomer, butyl rubber, styrene-butadiene rubber(SBR), paracril etc.; Acrylate adhesive mainly contains two-component acrylicester glue, anaerobic glue, unsaturated polyester resin glue etc.; The agent of epoxy resin gluing mainly contains the epoxy resin glue of single-component and two components; The agent of organosilicon gluing mainly contains the Zylox, phenolic resin adhesive, silicon resin glue, sealer, joint sealant, laminated adhesive of single-component and two components etc.; Adhesive for polyurethane mainly contains the polyurethane adhesive of single-component and two components; Also have sizing agents such as sizing agent such as radiation curing, water-soluble emulsion sizing agent, hot melt adhesive, pressure sensitive adhesive.These sizing agents have a lot of segmentations classification again according to bonding, location, different effects such as heat-resisting, corrosion-resistant.
It is the stone material tackiness agent of the positioning action of carrier by standard bisphenol type epoxy vinyl ester resin that Chinese patent CN 101974304 A have proposed a kind of; Form the first component by vinyl ester resin, filler and auxiliary agent; The component B solidifying agent adopts methylethyl ketone peroxide, and its stone material bond effect, shrinkability all will be got well than cloud stone glue common on the market.It is carrier that Chinese patent CN 101338173 A have proposed a kind of mixture by oligopolymer urethane resin, bisphenol A-type vinyl ester resin, adjacent benzene or metaphenylene unsaturated polyester resin; Be aided with filler and auxiliary agent make anaerobic glue; Adopt hydrogen phosphide cumene as solidifying agent, be mainly used in the plane bonding between metal and different solid material.It is carrier by the heat-proof corrosion-resistant vinyl ester resin that Chinese patent CN101725270A has proposed a kind of; Be aided with rock wool, elastomer-filled dose, auxiliary agent and make concrete base liner chimney expansion joint sealing corrosion sizing agent; Fitted seal film, foamed bricks use together, and that the resist of formation has is corrosion-resistant, heat-resisting, ageing-resistant, sealing, advantage that globality is strong.The polymer blend that Chinese patent CN101089039 has proposed a kind of chlorinatedpolyethylene and neoprene latex is a matrix resin; Be aided with the cementing agent that vulcanizing agent, filler, promotor, anti-aging agent, softening agent and scorch retarder stablizer are processed, have advantages such as low cost, anti-ozone, heat-resisting, ageing-resistant, fire-retardant, anti-corrosion, oil resistant, anti-bacterium, anti-rat eaten.Chinese patent CN1046772 proposed a kind of by acid resistance filler, water glass or/and the sizing agent that potassium silicate water glass, solidifying agent are formed, have anti-corrosion, heat-resisting, advantage cheaply.Chinese patent CN101602927 has proposed a kind of by the bond scheme of polyfluortetraethylene plate and flue inner wall of stack of nanometer SiOx and TiO2 modified silicon rubber; It is effectively bonding that this matrix material can provide, and makes that whole preservative coat heat resistance is good, strong adhesion, superpower acid resistance, resistance to heat shocks is good, weather resistance good, anti-permeability performance is strong, antifouling property is strong, abrasion resistance can be good.
Existing sizing agent, opinion single variety sizing agent does not generally possess and takes into account adhesive property, corrosion resistance nature, anti-medium osmosis performance, resistance toheat, tough and good fix effect and operative weldability simultaneously.This big limitations the development of tackiness agent of heavy corrosion-resistant field matrix material, be necessary to develop a kind of easy and simple to handle, can take into account the sizing agent of adhesive property, corrosion resisting property, heat-resisting, anti-permeability performance and favorable shock resistance again simultaneously.
Summary of the invention
To the problems referred to above that exist in the prior art; The object of the present invention is to provide sizing agent of a kind of heatproof corrosion resistant high-adhesion ability and preparation method thereof; With polyurethane toughened vinyl ester resin is vector resin; Be aided with other fillers, auxiliary agent and solidifying agent, prepare the sizing agent of different heat-resisting, anti-corrosion, adhesive properties, be used for the continuous fibre cellulosic material, mix mutual sizing agent materials such as earth material, metallic substance, stone material, FRP, thermoplastics.
Described a kind of heatproof corrosion resistant high-adhesion can sizing agent, it is characterized in that by weight proportion being that sizing agent first and sizing agent second two components of 100:1-10 are formed,
Described sizing agent first comprises following compositions in weight portion: chemical toughening type vinyl ester resin 100-200, stopper 0.1-3, shrinking agent 1-20, preferred 3-10; Radically curing solvent 1-10, preferred 2-5, aerosil is hydrophobic type aerosil 2-20, preferred 2-10; Mineral filler 30-600 is preferably 100-500, coupling agent 0.2-5, skimmer 0.2-5, mill base or pigment 0.1-20; Preferred 2-10, promotor 0.2-6, preferred 1-4; Secondary accelerator 0.1-3, preferred 0.5-2
Described sizing agent second comprises following compositions in weight portion: phthalic ester 10-50; Peroxidase 12 0-40; Inert powder filler 10-100, wherein said superoxide are cyclohexanone peroxide, Lucidol or peroxidized t-butyl perbenzoate, and the self cure that is applicable to that superoxide is selected for use cyclohexanone peroxide and other to mix for two kinds and obtained is used; Select for use Lucidol to be applicable to middle temperature sulfuration usefulness, select for use peroxidized t-butyl perbenzoate to be applicable to high temperature vulcanized usefulness.
The sizing agent of described a kind of heatproof corrosion resistant high-adhesion ability; It is characterized in that the chemical toughening type vinyl ester resin described in the sizing agent first is the toughness reinforcing bisphenol A-type vinyl ester resin of polyurethane elastomer; Being called for short TH-460, is that 0.5-2:3 mixes by A part and B part weight proportion
Described A part is made up of the component of following important umber:
W 166 400 30-40, W 166 2000 300-400, diphenylmethanediisocyanate (being called for short MDI) 130-160; Dibutyl tin dilaurate 0.5-2; Thiodiphenylamine 0.1-2, (methyl) senecioate-hydroxyl ethyl ester 60-80, vinylbenzene 400-600
Described B part is made up of the component of following important umber:
Liquid bisphenol A type epoxy resin 370-380, methylacrylic acid 90-130, dihydroxyphenyl propane 60-110; Vinylbenzene 400-600, stopper 2 0.1-2, catalyst B 0.5-2; Benzyl trimethyl ammonium chloride 1-3; Described catalyst B is for being prone to this alkali, phase-transfer catalyst, caustic alkali or triphenylphosphine, and described stopper 2 is a benzoquinones, 1,4-naphthoquinones, Resorcinol or Pyrogentisinic Acid.
The sizing agent of described a kind of heatproof corrosion resistant high-adhesion ability; It is characterized in that the shrinking agent described in the sizing agent first is organic shrinking agent, be one or more the mixture in PS, thermoplastic polyester, PVA, the acrylonitrile-butadiene-styrene copolymer etc.
The sizing agent of described a kind of heatproof corrosion resistant high-adhesion ability; It is characterized in that the radically curing solvent described in the sizing agent first is one or more mixtures in vinylbenzene, Vinylstyrene, TEB 3K, 1,6 hexanediol diacrylate, propylene glycol diacrylate, tripropylene glycol diacrylate, the Viscoat 295 etc.
The sizing agent of described a kind of heatproof corrosion resistant high-adhesion ability; It is characterized in that the mineral filler described in the sizing agent first is two or more mixtures of permanent white, white titanium pigment, talcum powder, silica powder, mica powder, glass flake, thin calcium powder, white lake, be preferably particle size and be 20 orders, 320 orders and 600 orders and above powder according to mass ratio 1:2-3:1 mixture.
The sizing agent of described a kind of heatproof corrosion resistant high-adhesion ability; It is characterized in that the promotor described in the sizing agent first is cobalt naphthenate or cobalt iso-octoate or both mixtures; Secondary accelerator is the N of purity more than 98%; N '-xylidine, N, one or both mixtures of N '-Diethyl Aniline, dimethyl-p-toluidine; Stopper is one or more mixtures of benzoquinones, naphthoquinones, Resorcinol, 2,6 di tert butyl 4 methyl phenol, p-ten.-butylcatechol, quinhydrones, toluhydroquinone, dinitrobenzene, trotyl.
The sizing agent of described a kind of heatproof corrosion resistant high-adhesion ability is characterized in that the phthalic ester described in the sizing agent second is one or more mixtures in Witcizer 300, diethyl phthalate, the DOP.
The sizing agent of described a kind of heatproof corrosion resistant high-adhesion ability is characterized in that the inert powder filler described in the sizing agent second is order number one or more mixtures at 200-800 purpose talcum powder, thin calcium powder, silica powder, mica powder.
The preparation method of the sizing agent of described a kind of heatproof corrosion resistant high-adhesion ability is characterized in that comprising the steps:
1) by said ratio; Chemical toughening type vinyl ester resin, shrinking agent, mineral filler, radically curing solvent, coupling agent, skimmer, promotor and secondary accelerator, stopper are added in the stainless vacuum high speed dispersion still, and it is pre-dispersed to carry out vacuum under 650-750 rev/mins the rotating speed, adds aerosil again; High-speed vacuum disperses under 1200-1400 rev/min the rotating speed; Obtain masterbatch, in masterbatch, add mill base or pigment, obtain the sizing agent first;
2) by said ratio,, obtain sizing agent second with phthalic ester, superoxide and inert powder filler thorough mixing;
3) the sizing agent first and the step 2 that step 1) are obtained) the sizing agent second that obtains is that 100:1-5 mixes by weight ratio, obtain the heatproof corrosion resistant high-adhesion can sizing agent, described sizing agent first and sizing agent second preferred weight proportioning are the 100:2-5 mixing.
The sizing agent of described a kind of heatproof corrosion resistant high-adhesion ability is characterized in that the synthesis technique of described chemical toughening type vinyl ester resin is following:
1) A part: press charge ratio, the diphenylmethanediisocyanate adding is had stirring system, condensing surface, Dropping feeder, heating and cooling temperature control unit reaction kettle, system is warming up to 60 ℃; W 166 400 is added drop-wise in the reaction flask at 25-35min with W 166 2000 mixtures and stirs it, after dripping, drips dibutyl tin dilaurate; And keep temperature of reaction system at 60-65 ℃, reacted the concentration of sampling analysis free isocyanate groups group about 3-4 hour; When the density loss of free isocyanate groups group is also stablized the concentration that reaches the vinylbenzene metering, in 30min, drip (methyl) senecioate-hydroxyl ethyl ester solution that is dissolved with thiodiphenylamine, the temperature of the hierarchy of control is lower than 80 ℃; After dripping; 65 ℃-70 ℃ reactions of maintenance system 2-3 hour add vinylbenzene again, are cooled to 40 ℃; Obtain the A part, for a kind of colourless to light yellow low-viscosity (mobile) liquid;
2) B part: press charge ratio, liquid bisphenol A type epoxy resin and dihydroxyphenyl propane input are had the reaction kettle of stirring system, condensing surface, Dropping feeder, heating and cooling temperature control unit, it is transparent to dissolving fully to keep 68-72 ℃ of insulation; Add catalyst B, be warming up to 120-160 ℃, insulation 30-90min; Reaction is cooled to 110 ± 3 ℃ after finishing, and drips the methacrylic acid solution that is dissolved with stopper and benzyl trimethyl ammonium chloride in the 45min, is warming up to 120-140 ℃ after dripping off; Reaction is reduced to below the 16mgKOH/g until acid number, be cooled to 80 ℃ after, add vinylbenzene; Be cooled to 40 ℃ again, obtain the B part, be a kind of light yellow viscous liquid;
3) with step 1) and step 2) A that obtains part is that 0.5-2:3 mixes with the weight proportion partly with B, obtains chemical toughening type vinyl ester resin.
Through adopting above-mentioned technology, compare with conventional epoxy adhesive, the agent of vinylformic acid gluing, neoprene sizing agent etc., the present invention has following beneficial effect:
1) the highly anti-corrosion vinyl ester resin of the present invention's selection is a matrix resin; Through polyurethane toughened modification; Difference according to corrosive medium; Selectivity must be used mineral filler, has better corrosion resistance nature, obtains a kind of sizing agent vector resin of impact resistance excellence, excellent anti-corrosion performance, heat-resisting excellence;
2) this courage has solved the resistance toheat and the anti-permeability performance of the use processing property of final sizing agent, the shrinking percentage that has reduced sizing agent, raising sizing agent through fillers such as adding glass flakes;
3) the present invention is through adding auxiliary agent, reasonably room temperature, middle temperature, the use of pyritous vulcanizing agent; Solve the flexibility of the sizing agent under the different application occasion; Can select the sizing agent color, not only can satisfy industrial sizing agent purposes, and can satisfy the demand of civil area decorative effect;
4) corrosion resistance nature, compactness, adhesive property, heat-resisting taking into account; Can select the chemical toughening type vinyl ester resin of different series, prepare the sizing agent of different temperature classifications, different impact resistances;
5) sizing agent positioning action of the present invention is good, and cohesive strength is high, and operative weldability is good, and environmental compatibility is strong, but wet environment use down, and the distortion of coming unstuck differs; Have strong corrosive medium excellent performances such as anti-medium osmosis property is strong, acid-and base-resisting, salt, organic solvent, strong oxidizing property medium, heat-resisting, strong adhesion, wear resistance is good, snappiness is good, be prone to plurality of advantages such as construction; Its key technical indexes accords with or surpasses concerned countries coating technology quality standard set quota, is the heavy anticorrosion sizing agent of no-solvent type of the heavy antiseptic project in a kind of ideal petrochemical industry, chemical industry, iron and steel, boats and ships, field such as coloured.
Embodiment
Below in conjunction with embodiment the present invention is done further description, but protection scope of the present invention is not limited in this, ratio involved in the present invention all is weight percentage or the relative weight ratio.
Embodiment 1 room temperature vulcanization sizing agent
(1) MDI of 140g adding has stirring system, condensing surface, Dropping feeder, heating and cooling temperature control unit reaction kettle, and system is warming up to 60 ℃, and 32g W 166 400 is added drop-wise in the reaction flask at about 30min with 320g W 166 2000 mixtures and stirs it; After dripping, drip catalyzer 1g dibutyl tin dilaurate, and keep temperature of reaction system at 60 ℃ to 65 ℃; After reacting about 3.5h, the sampling and testing free isocyanate groups is rolled into a ball less than 150ppm, in 30min, drips 70g (methyl) senecioate-hydroxyl ethyl ester that is dissolved with the 0.5g thiodiphenylamine again; System temperature is no more than 80 ℃ in the control reaction flask, after dripping, and 65 ℃ to 70 ℃ about 2.5h of maintenance system; Add 300g vinylbenzene; Be cooled to 40 ℃ again, obtain a pale yellow thin fluid body, subsequent use.
(2) 2 of the liquid bisphenol A type epoxy resin 370-380 Epikote 828 (DOW Chemical Ltd. commodity) of weighing 372g, 107g, 2-(4,4'-dihydroxyl phenylbenzene) propane input has stirring system, condensing surface, Dropping feeder, heating and cooling temperature control unit reaction kettle; Keep 70 degree left and right sides temperature, transparent until dissolving fully, drop into the triphenylphosphine that micro ethanol dissolves good 0.8g; Be warming up to 120-160 ℃, sampling online sampling titration equivalent weight value is in theoretical equivalent value scope ± 5% behind the 45min, and the real reaction time is that 60min reaches terminal point; Be cooled to 110 ± 3 ℃, drip in the 45min and be dissolved with 0.3g thiodiphenylamine, the 32g methacrylic acid solution of 4-naphthoquinones and 3g benzyl trimethyl ammonium chloride; Drip and be warming up to 125 ℃; Reduce to below the 16mgKOH/g until acid number, be cooled to 80 ℃ after, add 450g vinylbenzene; Be cooled to 40 ℃ again, obtain a light yellow viscous liquid.
(3) with the material of preceding two portions preparation according to 1/6,1/3,2/3 ratio uniform mixing, obtain the toughness reinforcing vinyl ester resin TH-460A of TH-460 Series of Polyurethane chemistry, TH-460B, TH-460C respectively.
(4) get glass flake 20g, 20 purpose permanent white 10g, 600 purpose white titanium pigment 20g, 200 purpose talcum powder 10g, 20 purpose silica powder 10g, 120 purpose mica powder 10g, the thin calcium powder 10g of 20 purposes, 80 purpose white lake 10g, vinylbenzene 20g, KBM-503 coupling agent 1g (KCC of Japanese SHIN-ETSU HANTOTAI commodity), BYK-A 515 skimmer 1g (BYK Ltd. commodity), BYK-A 555 treating compound 1g (BYK Ltd. commodity), TZ-13 (sky and resin company commodity) cobalt iso-octoate promotor 1.2g, the xylidine 0.5g, 1 that above-mentioned subsequent use TH-460A/B/C resin 200g, LPA-1EVA PVA shrinking agent 5g (day with resin company commodity), 320 orders are crossed through coupling agent treatment respectively; 4-naphthoquinones 0.5g adds in the stainless vacuum high speed dispersion still; It is pre-dispersed to carry out vacuum under 650-750 rev/mins of the rotating speeds; Add TS-720 hydrophobic type aerosil 8g (Cabot Ltd. commodity) again; Rotating speed 1200-1400 rev/min of following high-speed vacuum disperses to process masterbatch; Again masterbatch is prepared for use; According to the difference of sizing agent of the present invention application scenario to the requirement of sizing agent thickness state; The filler that adds the different ratios amount again; TH-70000 (ash/white) (day with resin company commodity) or TH-48508 (day with the resin company commodity) mill base that is aided with the 2-5% addition again, the first component of sizing agent of heatproof corrosion resistant high-adhesion ability of processing different series is serial.
(5) cooperate the component B solidifying agent preparation of (4) self cure gluing agent: Witcizer 300/cyclohexanone peroxide CYLONOX 1000P (AkzoNobel Ltd. commodity)/200 purpose mica powders according to 30/40/50 uniform mixing to paste; Pack in the plastics tubing; The sealing cryopreservation, for use.
Embodiment [2]-in high temperature vulcanized sizing agent
(1) MDI of 120g adding has stirring system, condensing surface, Dropping feeder, heating and cooling temperature control unit reaction kettle, and system is warming up to 60 ℃, and 30g W 166 400 is added drop-wise in the reaction flask at about 30min with 300g W 166 2000 mixtures and stirs it; After dripping, drip catalyzer 1g dibutyl tin dilaurate, and keep temperature of reaction system at 60 ℃ to 65 ℃; After reacting about 3.5h, the sampling and testing free isocyanate groups is rolled into a ball less than 150ppm, in 30min, drips 70g (methyl) senecioate-hydroxyl ethyl ester that is dissolved with the 0.5g thiodiphenylamine again; System temperature is no more than 80 ℃ in the control reaction flask, after dripping, and 65 ℃ to 70 ℃ about 2.5h of maintenance system; Add 280g vinylbenzene; Be cooled to 40 ℃ again, obtain a pale yellow thin fluid body, subsequent use.
(2) 2 of the liquid bisphenol A type epoxy resin 370-380 Epikote 828 (DOW Chemical Ltd. commodity) of weighing 372g, 80g, 2-(4,4'-dihydroxyl phenylbenzene) propane input has stirring system, condensing surface, Dropping feeder, heating and cooling temperature control unit reaction kettle; Keep 70 degree left and right sides temperature, transparent until dissolving fully, the triphenylphosphine of input micro ethanol dissolved 0.6g; Be warming up to 120-160 ℃, sampling online sampling titration equivalent weight value is in theoretical equivalent value scope ± 5% behind the 45min, and the real reaction time is that 60min reaches terminal point; Be cooled to 110 ± 3 ℃, drip in the 45min and be dissolved with 0.3g thiodiphenylamine, the methacrylic acid solution of the 120g of 4-naphthoquinones and 3g benzyl trimethyl ammonium chloride; Drip and be warming up to 125 ℃; Reduce to below the 16mgKOH/g until acid number, be cooled to 80 ℃ after, add 450g vinylbenzene; Be cooled to 40 ℃ again, obtain a light yellow viscous liquid.
(3) with the material of preceding two portions preparation according to 1/6,1/3,2/3 ratio uniform mixing, obtain the toughness reinforcing vinyl ester resin TH-460A of TH-460 Series of Polyurethane chemistry, TH-460B, TH-460C.
(4) get above-mentioned subsequent use TH-460A/B/C resin 200g, LPA-2EVA PVA shrinking agent 6g (day and resin company commodity), 320 orders add in the stainless vacuum high speed dispersion still through glass flake 10g, 20 purpose permanent white 5g, 600 purpose white titanium pigment 30g, 200 purpose talcum powder 15g, 20 purpose silica powder 15g, 120 purpose mica powder 15g, the thin calcium powder 5g of 20 purposes, 80 purpose white lake 5g, vinylbenzene 15g, KBM-503 coupling agent 1.5g (KCC of Japanese SHIN-ETSU HANTOTAI commodity), BYK-A 515 skimmer 1.5g (BYK Ltd. commodity), BYK-A 555 treating compound 1.5g (BYK Ltd. commodity), the naphthoquinones 0.6g that coupling agent treatment is crossed; It is pre-dispersed to carry out vacuum under 650-750 rev/mins of the rotating speeds; Add TS-720 hydrophobic type aerosil 10g (Cabot Ltd. commodity) again; Rotating speed 1200-1400 rev/min of following high-speed vacuum disperses to process masterbatch; Again masterbatch is prepared for use; According to the difference of sizing agent of the present invention application scenario to the requirement of sizing agent thickness state; The filler that adds the different ratios amount again; TH-70000 (ash/white) (day with resin company commodity) or TH-48508 (day with the resin company commodity) mill base that is aided with the 2-5% addition again, the first component of sizing agent of heatproof corrosion resistant high-adhesion ability of processing different series is serial.
(5) cooperate the component B solidifying agent of the middle temperature sulfuration sizing agent of (4) to prepare: Witcizer 300/Lucidol powder PERKADOX CH-50 (AkzoNobel Ltd. commodity)/200 purpose mica powders according to 50/40/50 uniform mixing to paste; Pack in the plastics tubing; The sealing cryopreservation, for use; Cooperate the component B solidifying agent preparation of the high temperature vulcanized sizing agent of (4): Witcizer 300/peroxidized t-butyl perbenzoate TRIGONOX C (AkzoNobel Ltd. commodity)/200 purpose mica powders according to 10/20/100 uniform mixing to paste; Pack in the plastics tubing; The sealing cryopreservation, for use.
In the foregoing description; Described catalyst B is with being prone to this alkali, phase-transfer catalyst, caustic alkali or triphenylphosphine replacement; Described stopper 2 usefulness benzoquinones, 1; 4-naphthoquinones, Resorcinol or Pyrogentisinic Acid's replacement; Shrinking agent is with one or more the mixture replacement in PS, thermoplastic polyester, PVA, the acrylonitrile-butadiene-styrene copolymer etc., and the radically curing solvent is replaced with one or more mixtures in vinylbenzene, Vinylstyrene, TEB 3K, 1,6 hexanediol diacrylate, propylene glycol diacrylate, tripropylene glycol diacrylate, the Viscoat 295 etc.; Mineral filler is with two or more mixtures of permanent white, white titanium pigment, talcum powder, silica powder, mica powder, glass flake, thin calcium powder, white lake; Being preferably particle size is that 20 orders, 320 orders and 600 orders and above powder are replaced according to mass ratio 1:2-3:1 mixture, and promotor is with cobalt naphthenate or cobalt iso-octoate or the replacement of both mixtures, and secondary accelerator is with the N of purity more than 98%; N '-xylidine, N, one or both mixture replacements of N '-Diethyl Aniline, dimethyl-p-toluidine; Stopper is with benzoquinones, naphthoquinones, Resorcinol, 2; One or more mixture replacements of 6-di-tert-butyl-4-methy phenol, p-ten.-butylcatechol, quinhydrones, toluhydroquinone, dinitrobenzene, trotyl; Phthalic ester is with one or more mixture replacements in Witcizer 300, diethyl phthalate, the DOP; The inert powder filler all can be obtained same beneficial effect with the corresponding compounds of order number in one or more mixture replacement the foregoing descriptions of 200-800 purpose talcum powder, thin calcium powder, silica powder, mica powder.
Claims (10)
- A heatproof corrosion resistant high-adhesion can sizing agent, it is characterized in that by weight proportion being that sizing agent first and sizing agent second two components of 100:1-10 are formed,Described sizing agent first comprises following compositions in weight portion: chemical toughening type vinyl ester resin 100-200, stopper 0.1-3, shrinking agent 1-20; Radically curing solvent 1-10, aerosil 2-20, mineral filler 30-600; Coupling agent 0.2-5, skimmer 0.2-5, mill base or pigment 0.1-20; Promotor 0.2-6, secondary accelerator 0.1-3Described sizing agent second comprises following compositions in weight portion: phthalic ester 10-50; Peroxidase 12 0-40; Inert powder filler 10-100, wherein said superoxide are cyclohexanone peroxide, Lucidol or peroxidized t-butyl perbenzoate.
- 2. the sizing agent of described a kind of heatproof corrosion resistant high-adhesion ability; It is characterized in that the chemical toughening type vinyl ester resin described in the sizing agent first is the toughness reinforcing bisphenol A-type vinyl ester resin of polyurethane elastomer; By A part and B part weight proportion is that 0.5-2:3 mixesDescribed A part is made up of the component of following important umber:W 166 400 30-40, W 166 2000 300-400, diphenylmethanediisocyanate 130-160, dibutyl tin dilaurate 0.5-2, thiodiphenylamine 0.1-2, (methyl) senecioate-hydroxyl ethyl ester 60-80, vinylbenzene 400-600Described B part is made up of the component of following important umber:Liquid bisphenol A type epoxy resin 370-380, methylacrylic acid 90-130, dihydroxyphenyl propane 60-110; Vinylbenzene 400-600, stopper 2 0.1-2, catalyst B 0.5-2; Benzyl trimethyl ammonium chloride 1-3; Described catalyst B is for being prone to this alkali, phase-transfer catalyst, caustic alkali or triphenylphosphine, and described stopper 2 is a benzoquinones, 1,4-naphthoquinones, Resorcinol or Pyrogentisinic Acid.
- 3. the sizing agent of described a kind of heatproof corrosion resistant high-adhesion ability; It is characterized in that the shrinking agent described in the sizing agent first is organic shrinking agent, be one or more the mixture in PS, thermoplastic polyester, PVA, the acrylonitrile-butadiene-styrene copolymer etc.
- 4. the sizing agent of described a kind of heatproof corrosion resistant high-adhesion ability; It is characterized in that the radically curing solvent described in the sizing agent first is one or more mixtures in vinylbenzene, Vinylstyrene, TEB 3K, 1,6 hexanediol diacrylate, propylene glycol diacrylate, tripropylene glycol diacrylate, the Viscoat 295 etc.
- 5. the sizing agent of described a kind of heatproof corrosion resistant high-adhesion ability; It is characterized in that the mineral filler described in the sizing agent first is two or more mixtures of permanent white, white titanium pigment, talcum powder, silica powder, mica powder, glass flake, thin calcium powder, white lake, be preferably particle size and be 20 orders, 320 orders and 600 orders and above powder according to mass ratio 1:2-3:1 mixture.
- 6. the sizing agent of described a kind of heatproof corrosion resistant high-adhesion ability; It is characterized in that the promotor described in the sizing agent first is cobalt naphthenate or cobalt iso-octoate or both mixtures; Secondary accelerator is the N of purity more than 98%; N '-xylidine, N, one or both mixtures of N '-Diethyl Aniline, dimethyl-p-toluidine; Stopper is one or more mixtures of benzoquinones, naphthoquinones, Resorcinol, 2,6 di tert butyl 4 methyl phenol, p-ten.-butylcatechol, quinhydrones, toluhydroquinone, dinitrobenzene, trotyl.
- 7. the sizing agent of described a kind of heatproof corrosion resistant high-adhesion ability is characterized in thatPhthalic ester described in the sizing agent second is one or more mixtures in Witcizer 300, diethyl phthalate, the DOP.
- 8. the sizing agent of described a kind of heatproof corrosion resistant high-adhesion ability is characterized in thatInert powder filler described in the sizing agent second is order number one or more mixtures at 200-800 purpose talcum powder, thin calcium powder, silica powder, mica powder.
- 9. the preparation method of the sizing agent of described a kind of heatproof corrosion resistant high-adhesion ability is characterized in that comprising the steps:1) by said ratio; Chemical toughening type vinyl ester resin, shrinking agent, mineral filler, radically curing solvent, coupling agent, skimmer, promotor and secondary accelerator, stopper are added in the stainless vacuum high speed dispersion still, and it is pre-dispersed to carry out vacuum under 650-750 rev/mins the rotating speed, adds aerosil again; High-speed vacuum disperses under 1200-1400 rev/min the rotating speed; Obtain masterbatch, in masterbatch, add mill base or pigment, obtain the sizing agent first;2) by said ratio,, obtain sizing agent second with phthalic ester, superoxide and inert powder filler thorough mixing;3) the sizing agent first and the step 2 that step 1) are obtained) the sizing agent second that obtains is that 100:1-5 mixes by weight ratio, obtain the heatproof corrosion resistant high-adhesion can sizing agent, described sizing agent first and sizing agent second preferred weight proportioning are the 100:2-5 mixing.
- 10. the sizing agent of described a kind of heatproof corrosion resistant high-adhesion ability is characterized in that the synthesis technique of described chemical toughening type vinyl ester resin is following:1) A part: press charge ratio, the diphenylmethanediisocyanate adding is had stirring system, condensing surface, Dropping feeder, heating and cooling temperature control unit reaction kettle, system is warming up to 60 ℃; W 166 400 is added drop-wise in the reaction flask at 25-35min with W 166 2000 mixtures and stirs it, after dripping, drips dibutyl tin dilaurate; And keep temperature of reaction system at 60-65 ℃, reacted the concentration of sampling analysis free isocyanate groups group about 3-4 hour; When the density loss of free isocyanate groups group is also stablized the concentration that reaches the vinylbenzene metering, in 30min, drip (methyl) senecioate-hydroxyl ethyl ester solution that is dissolved with thiodiphenylamine, the temperature of the hierarchy of control is lower than 80 ℃; After dripping; 65 ℃-70 ℃ reactions of maintenance system 2-3 hour add vinylbenzene again, are cooled to 40 ℃; Obtain the A part, for a kind of colourless to light yellow low-viscosity (mobile) liquid;2) B part: press charge ratio, liquid bisphenol A type epoxy resin and dihydroxyphenyl propane input are had the reaction kettle of stirring system, condensing surface, Dropping feeder, heating and cooling temperature control unit, it is transparent to dissolving fully to keep 68-72 ℃ of insulation; Add catalyst B, be warming up to 120-160 ℃, insulation 30-90min; Reaction is cooled to 110 ± 3 ℃ after finishing, and drips the methacrylic acid solution that is dissolved with stopper and benzyl trimethyl ammonium chloride in the 45min, is warming up to 120-140 ℃ after dripping off; Reaction is reduced to below the 16mgKOH/g until acid number, be cooled to 80 ℃ after, add vinylbenzene; Be cooled to 40 ℃ again, obtain the B part, be a kind of light yellow viscous liquid;3) with step 1) and step 2) A that obtains part is that 0.5-2:3 mixes with the weight proportion partly with B, obtains chemical toughening type vinyl ester resin.
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