CN102559120B - 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 energy and preparation method thereof.
Background technology
Vinyl ester resin is that a kind of vinyl ester product that is obtained by epoxy resin and methacrylic acid ring-opening reaction is dissolved in and obtains a kind of radically curing thermosetting resin in 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 phenol aldehyde type vinyl ester resin is connected is with 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 excellence etc. are mainly used in corrosion-resistant FRP equipment and the goods such as storage tank, tower, pipeline, groove, liner, blower fan, grid of the environment such as chemical field acid-and base-resisting, salt, organic solvent, Oxidant, mixed solvent.
Take the different matrix resin as carrier, the sizing agent, the seal gum that are aided with filler, auxiliary agent preparation are the important application directions in one, downstream of thermosetting resin, comparatively common that sizing agent has in the market: solvent-based adhesive mainly comprises chloroprene rubber, natural rubber, isoprene-isobutylene rubber, styrene-butadiene rubber(SBR), paracril etc.; Acrylate adhesive mainly contains two-component acrylicester glue, anaerobic glue, unsaturated polyester resin glue etc.; Epoxy resin adhesive mainly contains the epoxy resin glue of single-component and two components; The agent of organosilicon gluing mainly contains the silicon rubber, phenolic resin adhesive, silicon resin glue, seal gum, 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 the 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 again a lot of segmentations classification according to bonding, location, the not same-action 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 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 and make to get 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 protective layer of formation has advantages of is corrosion-resistant, heat-resisting, ageing-resistant, sealing, globality are strong.The polymer blend that Chinese patent CN101089039 has proposed a kind of chlorinatedpolyethylene and neoprene latex is matrix resin, be aided with the cementing agent that vulcanizing agent, filler, promotor, anti-aging agent, softening agent and scorch retarder stablizer are made, have the 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 form, 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, flushing resistance is good.
Existing sizing agent, opinion single variety sizing agent does not generally possess and takes into account simultaneously adhesive property, corrosion resistance nature, anti-medium osmosis performance, resistance toheat, tough and good fix effect and operative weldability.The development that this has limited the tackiness agent of heavy corrosion-resistant field matrix material greatly is necessary to develop a kind of easy and simple to handle, can take into account simultaneously again the sizing agent of adhesive property, corrosion resisting property, heat-resisting, anti-permeability performance and good shock resistance.
Summary of the invention
For the above-mentioned problems in the prior art, the object of the present invention is to provide sizing agent of a kind of heatproof corrosion resistant high-adhesion energy and preparation method thereof, take polyurethane toughened vinyl ester resin as 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 mutual sizing agent materials such as continuous fibre cellulosic material, mixed earth material, metallic substance, stone material, FRP, thermoplastics.
The sizing agent of described a kind of heatproof corrosion resistant high-adhesion energy is characterized in that being comprised of sizing agent first and sizing agent second two components that weight proportion is 100:1-10,
Described sizing agent first comprises the component of following parts by weight: 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, defoamer 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 the component of following parts by weight: phthalic ester 10-50; peroxidase 12 0-40; inert powder filler 10-100; wherein said superoxide is cyclohexanone peroxide, benzoyl peroxide or peroxidized t-butyl perbenzoate; superoxide selects cyclohexanone peroxide and other the two kinds self cures that are applicable to that are mixed to get to use; select benzoyl peroxide to be applicable to middle temperature sulfuration use, select peroxidized t-butyl perbenzoate to be applicable to high temperature vulcanized use.
The sizing agent of described a kind of heatproof corrosion resistant high-adhesion energy, 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 comprised of the component of following important umber:
Polypropylene glycol 400 30-40, polypropylene glycol 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 comprised of the component of following important umber:
Liquid bisphenol A type epoxy resin 370-380, methacrylic 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 easy this alkali, phase-transfer catalyst, caustic alkali or triphenylphosphine, and described stopper 2 is benzoquinones, 1,4-naphthoquinone, Resorcinol or Pyrogentisinic Acid.
The sizing agent of described a kind of heatproof corrosion resistant high-adhesion energy, 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 polystyrene, thermoplastic polyester, polyvinyl acetate (PVA), acrylonitrile-butadiene-styrene copolymer etc.
The sizing agent of described a kind of heatproof corrosion resistant high-adhesion energy, it is characterized in that the radically curing solvent described in the sizing agent first is one or more mixtures in vinylbenzene, Vinylstyrene, methyl methacrylate, 1,6 hexanediol diacrylate, propylene glycol diacrylate, tripropylene glycol diacrylate, Viscoat 295 etc.
The sizing agent of described a kind of heatproof corrosion resistant high-adhesion energy, it is characterized in that the mineral filler described in the sizing agent first is two or more mixtures of barium sulfate, titanium dioxide, talcum powder, silica powder, mica powder, glass flake, thin calcium powder, aluminium hydroxide, be preferably granular 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 energy, 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 energy is characterized in that the phthalic ester described in sizing agent second is one or more mixtures in dibutyl phthalate, diethyl phthalate, dioctyl phthalate (DOP).
The sizing agent of described a kind of heatproof corrosion resistant high-adhesion energy is characterized in that the inert powder filler described in sizing agent second is that the order number is at one or more mixtures of 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 energy 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, defoamer, promotor and secondary accelerator, stopper are added in stainless vacuum high-speed dispersing kettle, carry out vacuum under the rotating speed of 650-750 rev/mins pre-dispersed, add again aerosil, under the rotating speed of 1200-1400 rev/min, high-speed vacuum disperses, obtain masterbatch, add mill base or pigment in masterbatch, obtain the sizing agent first;
2) by said ratio, phthalic ester, superoxide and inert powder filler are fully mixed, obtain sizing agent second;
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 that 100:2-5 mixes.
The sizing agent of described a kind of heatproof corrosion resistant high-adhesion energy is characterized in that the synthesis technique of described chemical toughening type vinyl ester resin is as follows:
1) A part: press charge ratio, diphenylmethanediisocyanate is added have stirring system, condenser, Dropping feeder, heating and cooling temperature control unit reactor, system is warming up to 60 ℃, polypropylene glycol 400 and polypropylene glycol 2000 mixtures are added drop-wise in reaction flask at 25-35min and stir it, after dripping, drip dibutyl tin dilaurate, and keep temperature of reaction system at 60-65 ℃, reacted approximately 3-4 hour, the concentration of sampling analysis free isocyanate groups group, when the density loss of free isocyanate groups group and the stable concentration that reaches the vinylbenzene metering, drip (methyl) senecioate be dissolved with thiodiphenylamine-hydroxyl ethyl ester solution in 30min, the temperature of the hierarchy of control is lower than 80 ℃, after dripping, 65 ℃-70 ℃ reactions of maintenance system 2-3 hour, add again vinylbenzene, be 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 had stirring system, condenser, Dropping feeder, the reactor of heating and cooling temperature control unit, keep 68-72 ℃ of insulation transparent to dissolving fully, add catalyst B, be warming up to 120-160 ℃, insulation 30-90min, reaction is cooled to 110 ± 3 ℃ after finishing, drip the methacrylic acid solution that is dissolved with stopper and benzyl trimethyl ammonium chloride in 45min, be warming up to 120-140 ℃ after dripping off, react until acid number is down to below 16mgKOH/g, after being cooled to 80 ℃, add vinylbenzene, be cooled to again 40 ℃, obtain the B part, be a kind of light yellow viscous liquid,
3) with step 1) and step 2) A that obtains part and B partly mix take weight proportion as 0.5-2:3, obtains chemical toughening type vinyl ester resin.
By 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 matrix resin, through polyurethane toughened modification, difference according to corrosive medium, selectivity must be used mineral filler, have more preferably corrosion resistance nature, obtain a kind of sizing agent vector resin of impact resistance excellence, excellent anti-corrosion performance, heat-resisting excellence;
2) this Hymecromone is crossed fillers such as adding glass flake, has solved 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;
3) the present invention is by adding auxiliary agent, the reasonably vulcanizing agent use of room temperature, middle temperature, high temperature, solve the adaptability 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 civil area to the demand of 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 uses under wet environment, and the distortion of coming unstuck differs; Have the strong corrosive medium excellent performances such as anti-medium osmosis is strong, acid-and base-resisting, salt, organic solvent, strong oxidizing property medium, heat-resisting, strong adhesion, the plurality of advantages such as wear resistance is good, snappiness is good, easy construction, its the 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 desirable petrochemical industry, chemical industry, iron and steel, boats and ships, the field such as coloured.
Embodiment
The invention will be further described below in conjunction with embodiment, but protection scope of the present invention is not limited in this, and 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 adds and has stirring system, condenser, Dropping feeder, heating and cooling temperature control unit reactor, system is warming up to 60 ℃, 32g polypropylene glycol 400 and 320g polypropylene glycol 2000 mixtures stir it in approximately 30min is added drop-wise to reaction flask, after dripping, drip catalyzer 1g dibutyl tin dilaurate, and keep temperature of reaction system at 60 ℃ to 65 ℃, after reacting approximately 3.5h, sampling and testing free isocyanate groups group is less than 150ppm, drip again the 70g(methyl that is dissolved with the 0.5g thiodiphenylamine in 30min) senecioate-hydroxyl ethyl ester, control the interior system temperature of reaction flask and be no more than 80 ℃, after dripping, 65 ℃ to 70 ℃ of maintenance systems are 2.5h approximately, add 300g vinylbenzene, be cooled to again 40 ℃, obtain a pale yellow thin fluid body, standby.
(2) the liquid bisphenol A type epoxy resin 370-380 Epikote 828(DOW Chemical Ltd. commodity of weighing 372g), 2 of 107g, 2-(4, 4'-dihydroxyl phenylbenzene) propane drops into and has stirring system, condenser, Dropping feeder, heating and cooling temperature control unit reactor, keep 70 and spend the left and right temperature, until dissolve transparent fully, drop into the triphenylphosphine that micro ethanol dissolves good 0.8g, be warming up to 120-160 ℃, after 45min, the online sampling of sampling titration equivalent weight value is until in theoretical equivalent value scope ± 5%, the real reaction time is that 60min reaches terminal point, be cooled to 110 ± 3 ℃, drip in 45min and be dissolved with the 0.3g thiodiphenylamine, the 32g methacrylic acid solution of 4-naphthoquinones and 3g benzyl trimethyl ammonium chloride, drip and be warming up to 125 ℃, until acid number is down to below 16mgKOH/g, after being cooled to 80 ℃, add 450g vinylbenzene, be cooled to again 40 ℃, obtain a light yellow viscous liquid.
(3) material with front two portions preparation evenly mixes according to 1/6,1/3,2/3 ratio, obtains respectively the toughness reinforcing vinyl ester resin TH-460A of TH-460 Series of Polyurethane chemistry, TH-460B, TH-460C.
(4) get respectively above-mentioned standby TH-460A/B/C resin 200g, LPA-1EVA polyvinyl acetate (PVA) shrinking agent 5g(days and resin company commodity), the glass flake 20g that 320 orders are crossed through coupling agent treatment, 20 purpose barium sulfate 10g, 600 purpose titanium dioxide 20g, 200 purpose talcum powder 10g, 20 purpose silica powder 10g, 120 purpose mica powder 10g, the 20 thin calcium powder 10g of purpose, 80 purpose aluminium hydroxide 10g, vinylbenzene 20g, KBM-503 coupling agent 1g(Japan KCC of SHIN-ETSU HANTOTAI commodity), BYK-A 515 defoamer 1g(BYK Ltd. commodity), BYK-A 555 treating compound 1g(BYK Ltd. commodity), TZ-13(days and resin company commodity) cobalt iso-octoate promotor 1.2g, xylidine 0.5g, 1,4-naphthoquinones 0.5g adds in stainless vacuum high-speed dispersing kettle, carry out vacuum under 650-750 rev/mins of rotating speeds pre-dispersed, add again TS-720 hydrophobic type aerosil 8g(Cabot Ltd. commodity), rotating speed 1200-1400 rev/min of lower high-speed vacuum disperses to make masterbatch, again masterbatch is prepared stand-by, the difference that sizing agent thickness state is required according to sizing agent of the present invention application scenario, the filler that adds again the different ratios amount, be aided with again the TH-70000(ash of 2-5% addition/white) (day and resin company commodity) or TH-48508(days and resin company commodity) mill base, make different series the heatproof corrosion resistant high-adhesion can the first component series of sizing agent.
(5) coordinate the component B solidifying agent preparation of (4) self cure gluing agent: dibutyl phthalate/cyclohexanone peroxide CYLONOX 1000P(AkzoNobel Ltd. commodity)/200 purpose mica powders evenly are mixed to paste according to 30/40/50, pack in plastics tubing, the sealing cryopreservation, stand-by.
Embodiment [2]-in high temperature vulcanized sizing agent
(1) MDI of 120g adds and has stirring system, condenser, Dropping feeder, heating and cooling temperature control unit reactor, system is warming up to 60 ℃, 30g polypropylene glycol 400 and 300g polypropylene glycol 2000 mixtures stir it in approximately 30min is added drop-wise to reaction flask, after dripping, drip catalyzer 1g dibutyl tin dilaurate, and keep temperature of reaction system at 60 ℃ to 65 ℃, after reacting approximately 3.5h, sampling and testing free isocyanate groups group is less than 150ppm, drip again the 70g(methyl that is dissolved with the 0.5g thiodiphenylamine in 30min) senecioate-hydroxyl ethyl ester, control the interior system temperature of reaction flask and be no more than 80 ℃, after dripping, 65 ℃ to 70 ℃ of maintenance systems are 2.5h approximately, add 280g vinylbenzene, be cooled to again 40 ℃, obtain a pale yellow thin fluid body, standby.
(2) the liquid bisphenol A type epoxy resin 370-380 Epikote 828(DOW Chemical Ltd. commodity of weighing 372g), 2 of 80g, 2-(4, 4'-dihydroxyl phenylbenzene) propane drops into and has stirring system, condenser, Dropping feeder, heating and cooling temperature control unit reactor, keep 70 and spend the left and right temperature, until dissolve transparent fully, drop into the triphenylphosphine of the 0.6g of micro ethanol dissolving, be warming up to 120-160 ℃, after 45min, the online sampling of sampling titration equivalent weight value is until in theoretical equivalent value scope ± 5%, the real reaction time is that 60min reaches terminal point, be cooled to 110 ± 3 ℃, drip in 45min and be dissolved with the 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 ℃, until acid number is down to below 16mgKOH/g, after being cooled to 80 ℃, add 450g vinylbenzene, be cooled to again 40 ℃, obtain a light yellow viscous liquid.
(3) material with front two portions preparation evenly mixes according to 1/6,1/3,2/3 ratio, obtains the toughness reinforcing vinyl ester resin TH-460A of TH-460 Series of Polyurethane chemistry, TH-460B, TH-460C.
(4) get above-mentioned standby TH-460A/B/C resin 200g, LPA-2EVA polyvinyl acetate (PVA) shrinking agent 6g(days and resin company commodity), the glass flake 10g that 320 orders are crossed through coupling agent treatment, 20 purpose barium sulfate 5g, 600 purpose titanium dioxide 30g, 200 purpose talcum powder 15g, 20 purpose silica powder 15g, 120 purpose mica powder 15g, the 20 thin calcium powder 5g of purpose, 80 purpose aluminium hydroxide 5g, vinylbenzene 15g, KBM-503 coupling agent 1.5g(Japan KCC of SHIN-ETSU HANTOTAI commodity), BYK-A 515 defoamer 1.5g(BYK Ltd. commodity), BYK-A 555 treating compound 1.5g(BYK Ltd. commodity), naphthoquinones 0.6g adds in stainless vacuum high-speed dispersing kettle, carry out vacuum under 650-750 rev/mins of rotating speeds pre-dispersed, add again TS-720 hydrophobic type aerosil 10g(Cabot Ltd. commodity), rotating speed 1200-1400 rev/min of lower high-speed vacuum disperses to make masterbatch, again masterbatch is prepared stand-by, the difference that sizing agent thickness state is required according to sizing agent of the present invention application scenario, the filler that adds again the different ratios amount, be aided with again the TH-70000(ash of 2-5% addition/white) (day and resin company commodity) or TH-48508(days and resin company commodity) mill base, make different series the heatproof corrosion resistant high-adhesion can the first component series of sizing agent.
(5) coordinate the component B solidifying agent preparation of the middle temperature sulfuration sizing agent of (4): dibutyl phthalate/benzoyl peroxide powder PERKADOX CH-50(AkzoNobel Ltd. commodity)/200 purpose mica powders evenly are mixed to paste according to 50/40/50, pack in plastics tubing, the sealing cryopreservation, stand-by; Coordinate the component B solidifying agent preparation of the high temperature vulcanized sizing agent of (4): dibutyl phthalate/peroxidized t-butyl perbenzoate TRIGONOX C(AkzoNobel Ltd. commodity)/200 purpose mica powders evenly are mixed to paste according to 10/20/100, pack in plastics tubing, the sealing cryopreservation, stand-by.
in above-described embodiment, easily this alkali of described catalyst B, phase-transfer catalyst, caustic alkali or triphenylphosphine are replaced, and described stopper 2 is used benzoquinones, 1,4-naphthoquinone, Resorcinol or Pyrogentisinic Acid replace, the shrinking agent polystyrene, thermoplastic polyester, polyvinyl acetate (PVA), the mixture of one or more in acrylonitrile-butadiene-styrene copolymer etc. is replaced, radically curing solvent vinylbenzene, Vinylstyrene, methyl methacrylate, 1,6 hexanediol diacrylate, propylene glycol diacrylate, tripropylene glycol diacrylate, in Viscoat 295s etc., one or more mixtures are replaced, mineral filler barium sulfate, titanium dioxide, talcum powder, silica powder, mica powder, glass flake, thin calcium powder, two or more mixtures of aluminium hydroxide, being preferably granular size is 20 orders, 320 orders and 600 orders and above powder are replaced according to mass ratio 1:2-3:1 mixture, and promotor is replaced with cobalt naphthenate or cobalt iso-octoate or both mixtures, and secondary accelerator is with the N of purity more than 98%, N '-xylidine, N, N '-Diethyl Aniline, one or both mixtures of dimethyl-p-toluidine are replaced, the stopper benzoquinones, naphthoquinones, Resorcinol, 2, the 6-di-tert-butyl-4-methy phenol, p-ten.-butylcatechol, quinhydrones, toluhydroquinone, dinitrobenzene, one or more mixtures of trotyl are replaced, the phthalic ester dibutyl phthalate, diethyl phthalate, one or more mixtures in dioctyl phthalate (DOP) are replaced, the inert powder filler with the order number at 200-800 purpose talcum powder, thin calcium powder, silica powder, one or more mixtures of mica powder are replaced the corresponding compound in above-described embodiment, all can obtain same beneficial effect.
Claims (7)
1. the sizing agent of a heatproof corrosion resistant high-adhesion energy, is characterized in that being comprised of sizing agent first and sizing agent second two components that weight proportion is 100:1-10,
Described sizing agent first comprises the component of following parts by weight: 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, defoamer 0.2-5, mill base or pigment 0.1-20, promotor 0.2-6, secondary accelerator 0.1-3;
Described sizing agent second comprises the component of following parts by weight: phthalic ester 10-50, peroxidase 12 0-40, inert powder filler 10-100, wherein said superoxide are cyclohexanone peroxide, benzoyl peroxide or peroxidized t-butyl perbenzoate;
Chemical toughening type vinyl ester resin described in described sizing agent first is the toughness reinforcing bisphenol A-type vinyl ester resin of polyurethane elastomer, is that 0.5-2:3 mixes by A part and B part weight proportion,
Described A part is prepared through reaction by the component of following parts by weight:
Polypropylene glycol 400 30-40, polypropylene glycol 2000 300-400, diphenylmethanediisocyanate 130-160, dibutyl tin dilaurate 0.5-2, thiodiphenylamine 0.1-2, (methyl) senecioate-hydroxyl ethyl ester 60-80, vinylbenzene 400-600
Described B part is prepared through reaction by the component of following parts by weight:
Liquid bisphenol A type epoxy resin 370-380, methacrylic 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 easy this alkali, phase-transfer catalyst, caustic alkali or triphenylphosphine, and described stopper 2 is benzoquinones, 1,4-naphthoquinone, Resorcinol or Pyrogentisinic Acid;
Described shrinking agent is organic shrinking agent, is one or more the mixture in polystyrene, thermoplastic polyester, polyvinyl acetate (PVA), acrylonitrile-butadiene-styrene copolymer;
Described radically curing solvent is one or more mixtures in vinylbenzene, Vinylstyrene, methyl methacrylate, 1,6 hexanediol diacrylate, propylene glycol diacrylate, tripropylene glycol diacrylate, Viscoat 295.
A kind of heatproof corrosion resistant high-adhesion as claimed in claim 1 can sizing agent, it is characterized in that the mineral filler described in the sizing agent first is two or more mixtures of barium sulfate, titanium dioxide, talcum powder, silica powder, mica powder, glass flake, thin calcium powder, aluminium hydroxide, granular size is that 20 orders, 320 orders and 600 orders and above powder are according to mass ratio 1:2-3:1 mixture.
A kind of heatproof corrosion resistant high-adhesion as claimed in claim 1 can sizing agent, 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.
4. the sizing agent of a kind of heatproof corrosion resistant high-adhesion energy as claimed in claim 1, is characterized in that the phthalic ester described in sizing agent second is one or more mixtures in dibutyl phthalate, diethyl phthalate, dioctyl phthalate (DOP).
5. the sizing agent of a kind of heatproof corrosion resistant high-adhesion energy as claimed in claim 1, is characterized in that the inert powder filler described in sizing agent second is that the order number is at one or more mixtures of 200-800 purpose talcum powder, thin calcium powder, silica powder, mica powder.
6. the preparation method of the sizing agent of a kind of heatproof corrosion resistant high-adhesion energy as claimed in claim 1, 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, defoamer, promotor and secondary accelerator, stopper are added in stainless vacuum high-speed dispersing kettle, carry out vacuum under the rotating speed of 650-750 rev/min pre-dispersed, add again aerosil, under the rotating speed of 1200-1400 rev/min, high-speed vacuum disperses, obtain masterbatch, add mill base or pigment in masterbatch, obtain the sizing agent first;
2) by said ratio, phthalic ester, superoxide and inert powder filler are fully mixed, obtain sizing agent second;
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.
A kind of heatproof corrosion resistant high-adhesion as claimed in claim 1 can sizing agent, it is characterized in that the synthesis technique of described chemical toughening type vinyl ester resin is as follows:
1) A part: press charge ratio, diphenylmethanediisocyanate is added have stirring system, condenser, Dropping feeder, heating and cooling temperature control unit reactor, system is warming up to 60 ℃, polypropylene glycol 400 and polypropylene glycol 2000 mixtures are added drop-wise in reaction flask at 25-35min and stir it, after dripping, drip dibutyl tin dilaurate, and keep temperature of reaction system at 60-65 ℃, reacted approximately 3-4 hour, the concentration of sampling analysis free isocyanate groups group, when the density loss of free isocyanate groups group and the stable concentration that reaches the vinylbenzene metering, drip (methyl) senecioate be dissolved with thiodiphenylamine-hydroxyl ethyl ester solution in 30min, the temperature of the hierarchy of control is lower than 80 ℃, after dripping, 65 ℃-70 ℃ reactions of maintenance system 2-3 hour, add again vinylbenzene, be 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 had stirring system, condenser, Dropping feeder, the reactor of heating and cooling temperature control unit, keep 68-72 ℃ of insulation transparent to dissolving fully, add catalyst B, be warming up to 120-160 ℃, insulation 30-90min, reaction is cooled to 110 ± 3 ℃ after finishing, drip the methacrylic acid solution that is dissolved with stopper and benzyl trimethyl ammonium chloride in 45min, be warming up to 120-140 ℃ after dripping off, react until acid number is down to below 16mgKOH/g, after being cooled to 80 ℃, add vinylbenzene, be cooled to again 40 ℃, obtain the B part, be a kind of light yellow viscous liquid,
3) with step 1) and step 2) A that obtains part and B partly mix take weight proportion as 0.5-2:3, obtains chemical toughening type vinyl ester resin.
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