CN103694866A - Photo-cured insulating paint and preparation and application method thereof - Google Patents
Photo-cured insulating paint and preparation and application method thereof Download PDFInfo
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- CN103694866A CN103694866A CN201310696676.4A CN201310696676A CN103694866A CN 103694866 A CN103694866 A CN 103694866A CN 201310696676 A CN201310696676 A CN 201310696676A CN 103694866 A CN103694866 A CN 103694866A
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- insullac
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
- C09D175/04—Polyurethanes
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D3/00—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials
- B05D3/06—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials by exposure to radiation
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
- C09D133/04—Homopolymers or copolymers of esters
- C09D133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
- C09D133/08—Homopolymers or copolymers of acrylic acid esters
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
- C09D133/04—Homopolymers or copolymers of esters
- C09D133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
- C09D133/10—Homopolymers or copolymers of methacrylic acid esters
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- Wood Science & Technology (AREA)
- Organic Chemistry (AREA)
- Physics & Mathematics (AREA)
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- Paints Or Removers (AREA)
- Organic Insulating Materials (AREA)
- Polyurethanes Or Polyureas (AREA)
Abstract
The invention discloses a photo-cured insulating paint which comprises photo-active resin, a photo-active diluent, a photo-initiator, a crosslinking agent, an antifoaming agent, a leveling agent and a coupling agent. The photo-cured insulating paint can be cured under the ultraviolet irradiation with certain power density to form an insulating paint film with certain electric insulating property and mechanical property. Without VOC in the formula, the prepared product does not pollute the environment when in use and has outstanding environmental performance. The invention also discloses a preparation method and an application method of the photo-cured insulating paint.
Description
Technical field
The invention belongs to insulating material field.Specifically belong to enamel covered wire, enamel insulated aluminium wire and composite type varnished wire insullac used; Varnished insulation insullac; Bonding with insullac; Covering insullac; The insulate manufacture field of the aspect insullac such as insullac used of siliconized plate (silieonized plate).
Background technology
Paint is the general name that filmogen is dispersed in the colloidal solution forming in solvent.Insullac is a special kinds in paint class.Insullac is to take macromolecular material as basis, can be solidified under certain conditions insulating film or the whole important insulating material of insulation.Insullac belongs to a kind of in five large clasp Y insulation Y materials (being insullac, impregnation of fibers, veneer sheet, mica products and compression molding material), a kind of typical dielectric substance, its essential characteristic be respond to rather than with conduction mode transmit electric role and influence.Its performance characteristics is presented as: insulating property are good; Sticking power is good, physical strength is higher; String stress is little; Thermotolerance can meet the different requirements of transformer; To open air or particular surroundings, can meet its particular requirement, radioprotective, protection against corrosion, antiultraviolet etc.; Manufacturability is good, good operability, nontoxic or low toxicity, time of drying are short etc.Thereby obtain a wide range of applications, well behaved insullac is one of prerequisite guaranteeing the normal work of electric installation, in electric insulation field, occupies critical role.
But traditional insullac is solvent-borne type product, its solid content only has 33% left and right even lower, and VOC(volatile organic matter is mainly a series of organic solvent in this series products) content is up to nearly 70%, a large amount of VOC evaporate in air when product is used, and environment is caused serious injury.For minimizing is polluted, most producers reclaim afterfire by VOC and process, but still have strong irritating smell, and a certain amount of carcinogenic, teratogen of partial organic substances burning meeting generation, and near resident's health operator and plant area is had to certain influence; It is also a kind of huge wasting of resources that valuable organism is burnt, and especially petrochemical industry resource is gradually exhausted, and organic solvent price rises steadily, and reduces the meaning that VOC content has environment benefits and economic gains two aspects.
Ultraviolet light polymerization (often solidifying referred to as UV) paint is a kind of novel environmental protection paint.By preparation, with special resin and the thinner of this process matching and make special-purpose paint vehicle, this kind of paint can, under the irradiation of UV-light, form dry paint film by the curing of coating with the paint of mobility within the several seconds to the time of tens of seconds.Because set time is extremely short and resin and diluent system all have light reaction, VOC content when paint vehicle is used can be reduced to the degree that approaches zero.Thereby ultraviolet-cured paint is a kind of environmental protection and high efficiency novel paint.If change resin and the diluent system thereof of existing insullac, make it to meet the requirement of UV curing technology, by the VOC content greatly reducing in insullac use, obtain the New insulated paint of environmental protection.
Summary of the invention
Poor for existing insullac VOC too high levels, environmental-protecting performance, use in to defects such as atmospheric pollution are serious, operator's working conditions is severe, the object of the invention is to prepare a kind of resin that contains UV-light active group (simultaneously containing the functional group that aspects such as can meeting insulation paint film mechanical property, chemical property, thermal characteristics requires in resin) and the diluent system matching thereof and be mixed with paint vehicle, this paint vehicle can be under certain UV-light of power and the effect of finite concentration light trigger fast setting, form dry paint film.This paint vehicle is the almost release of VOC free in use, and environmental-protecting performance is splendid, can fundamentally solve a series of environmental issues of traditional insullac.
Above-mentioned purpose of the present invention is achieved by the following technical solution: a kind of photocuring insullac, comprises the raw material of following weight part:
Photolytic activity resin 100 weight parts;
Photolytic activity thinner 20 ~ 60 weight parts;
Light trigger 0.5 ~ 10 weight part;
Linking agent 0.1 ~ 1.5 weight part;
Defoamer 0.1 ~ 1 weight part;
Flow agent 0.1 ~ 1 weight part;
Coupling agent 0.1 ~ 1 weight part.
In the present invention, described photolytic activity resin refers to one or more in photolytic activity vibrin, photolytic activity urethane resin or both modified products.Wherein, described photolytic activity vibrin or its modified resin refer to the photolytic activity resin that contains certain proportion ester bond (COO-) in molecular structure, and it is by containing two key raw materials, hydroxyl (or amino) raw material, obtaining containing carboxyl raw material or containing several process polyreactions in acid anhydrides raw material.Photolytic activity urethane resin or its modified resin refer to the photolytic activity resin that contains certain proportion carbamate (NHCOO-) group in molecular structure, and it obtains by containing two key raw materials, contain reactive hydrogen raw material (being mainly hydroxyl or amino raw material) and containing isocyano raw material reaction.
Particularly, described photolytic activity vibrin or its modified resin are by a certain proportion of several being contained to two key raw materials, hydroxyl (or amino) raw material, carrying out at a certain temperature polyreaction containing carboxyl raw material or containing acid anhydrides raw material, the degree of being undertaken by measurement acid number detection reaction.Question response stops heating while being tending towards complete, cooling, adds photolytic activity thinner and stopper, stirs, and discharging prepares.
Particularly, described photolytic activity urethane resin or its modified resin be by by a certain proportion of several containing two key raw materials, containing reactive hydrogen raw material (being mainly hydroxyl or amino raw material) with containing isocyano raw material, in the situation that a certain amount of catalyzer exists, under certain temperature, carry out polymerization, the degree of utilizing Di-n-Butyl Amine volumetry detection reaction to carry out.Question response stops heating while being tending towards complete, cooling, adds photolytic activity thinner and stopper, stirs, and discharging prepares.
In technique scheme, the described unsaturated materials that contains two keys in those structures that refers to containing pair key raw materials, can be alkene or the unsaturated acid that contains two keys, alcohol, ammonia, ester, acid anhydrides etc.Particularly, described in the present invention, containing two key raw materials, include but not limited to: Propylene glycol monoacrylate, Hydroxyethyl acrylate, vinylformic acid hydroxy butyl ester, cis maleic anhydride, trans maleic anhydride, vinyl carbinol (also claiming vinylcarbinol), dicyclopentadiene etc.
In technique scheme, described hydroxyl (or amino) raw material refers to the material that contains hydroxyl (or amino) in those structures, can be alcohol, comprises monohydroxy-alcohol, polyvalent alcohol; Phenol, comprises monohydric phenol, polyphenol; Or amine, amino acid etc.Particularly, hydroxyl described in the present invention (or amino) raw material includes but not limited to: urea, trimeric cyanamide, hexanediamine, cyclohexanediamine, ethylene glycol, propylene glycol, glycerol, dihydroxyphenyl propane, Macrogol 200, poly(oxyethylene glycol) 400, Polyethylene Glycol-600, neopentyl glycol, vinyl carbinol (also claiming vinylcarbinol), various commercially available polyether Glycols or polyether glycol, various commercially available polyester diol or polyester polyol etc.
In technique scheme, the described material that contains carboxyl raw material or refer to the acid anhydride structure that contains carboxyl or carboxyl dehydration formation in those structures containing acid anhydrides raw material.Can be saturated acid or unsaturated acid, can be that monoprotic acid can be also polyprotonic acid.Particularly, describedly containing carboxyl raw material or containing acid anhydrides raw material, include but not limited to Tetra hydro Phthalic anhydride, terephthalic acid, m-phthalic acid, phthalic acid, cis maleic anhydride, trans maleic anhydride, hexanodioic acid etc.
In technique scheme, the described isocyano raw material that contains includes but not limited to: tolylene diisocyanate, isophorone diisocyanate, diphenylmethanediisocyanate, hexamethylene diisocyanate etc.
In the present invention, described photolytic activity thinner refers to double bond containing small molecular ester, includes but not limited to butyl acrylate, ethyl propenoate, carbamate mono acrylic ester, hexanediyl ester, butylene glycol diacrylate, neopentylglycol diacrylate, double pentaerythritol methacrylate, Viscoat 295, vinylbenzene, methyl methacrylate etc.Its consumption can be 20,25,30,35,40,45,50 or 55 weight parts.
In the present invention, described stopper refer to molecule can with chain free radical reaction, form the low activity free radical that non-free radical material maybe can not cause, thus the material that polymerization is stopped.Can be phenolic inhibitor, quinones stopper, arene nitro compound stopper, mineral compound stopper.Particularly, described stopper includes but not limited to Resorcinol, para benzoquinone, phenothiazine, beta-phenyl naphthylamines, p-ten.-butylcatechol, methylene blue, 1, the bitter hydrazine, 2 of 1-phenylbenzene-2-, 2,6,6-tetramethyl piperidine nitrogen oxygen free radical, toluhydroquinone, MEHQ, 2-Tert. Butyl Hydroquinone, 2,5 di tert butyl hydroquinone etc.
In photolytic activity vibrin or the preparation of its modified resin, controlling hydroxyl in raw material is 1.3:1 ~ 0.9:1 with the amount of substance ratio of carboxyl; Can be particularly 0.95:1,1.0:1,1.05:1,1.1:1,1.15:1,1.2:1 or 1.25:1; Or in control raw material, hydroxyl is that 1.3:0.5 ~ 0.9:0.5 can be particularly 0.95:0.5,1.0:0.5,1.05:0.5,1.1:0.5,1.15:0.5,1.2:0.5 or 1.25:0.5 with the amount of substance ratio of acid anhydrides; Or the amount of substance of hydroxyl and (summations of carboxyl and 2 times of acid anhydrides) is than for 1.3:1 ~ 0.9:1, can be particularly 0.95:1,1.0:1,1.05:1,1.1:1,1.15:1,1.2:1 or 1.25:1.The temperature of reaction is 140 ~ 230 ℃.
In photolytic activity vibrin or the preparation of its modified resin, the mensuration of acid number is specially: in Erlenmeyer flask, add the sample 0.5g through accurate weighing, add proper amount of acetone to dissolve, then add 2 phenolphthalein ethanolic solns.With the KOH standardized solution of 0.1mol/l, be titrated in pink and red 20s and do not take off.The acid number of sample is pressed following formula 1 and is calculated.
In formula 1:
AN is the acid number of sample, the mg/g of unit.
N is the concentration of KOH standardized solution, the mol/l of unit.
The volume of the KOH solution that l consumes while being titration, units/ml.
W is the quality of add of sample, the g of unit.
S is the solid content of sample.
In photolytic activity urethane resin or the preparation of its modified resin, controlling containing reactive hydrogen raw material (hydroxyl or amino raw material) is 1.02:1 ~ 1.15:1 with containing reactive hydrogen in isocyano raw material with the amount of substance ratio of isocyano, can be particularly 1.05:1,1.08:1,1.1:1,1.12:1 etc.Temperature of reaction is 50 ~ 120 ℃.Described catalyzer can be the organic tins such as dibutyl tin laurate.Its ratio is 0.2% ~ 1% of total quality of material mark.Be preferably 0.5%.
In the preparation of photolytic activity urethane resin or its modified resin, the concrete grammar that degree is carried out in the reaction of Di-n-Butyl Amine titration measuring is: in Erlenmeyer flask, adding 4ml concentration is the Di-n-Butyl Amine toluene standardized solution of 0.1mol/L, weigh, and peeling.Get the 0.5g left and right sample of accurate weighing in this Erlenmeyer flask, stirring shakes up, after reaction 15min, add 2 bromophenol blue indicators, then add the isopropanol of about 15ml, with the HCl standardized solution titration of 0.01mol/L, color is green by blue flavescence, separately does blank test.The content of isocyano is pressed following formula 2 and is calculated.
（2）。
In formula 2:
W
nCOfor the content of isocyano in system, the mmol/g of unit.
V
1the amount of the standard hydrochloric acid consuming for blank sample, units/ml.
V
2the amount of the standard hydrochloric acid consuming for testing sample, units/ml.
C is the volumetric molar concentration of standard hydrochloric acid, the mol/L of unit.
M is the quality of sample, the g of unit.
In the present invention, in above-mentioned two resinoids, photolytic activity thinner is 1:5 ~ 3:5 with the mass ratio of synthetic resins.The mass ratio of stopper and resin is 1:1000 ~ 1:100.
Photocuring insullac of the present invention is prepared by the following method: the above-mentioned photolytic activity resin having made is added to light trigger, linking agent, defoamer, flow agent, coupling agent in proportion, stir, by three-roll grinder, grind, discharging, obtains insullac.Wherein, photolytic activity resin can be in photolytic activity vibrin or photolytic activity urethane resin or its modified resin any one or multiple.
In the present invention, described light trigger is preferably cracking type initiator, includes but not limited to 1173,184,907,369,1490,1700 etc.Light trigger is preferably 0.5 in insullac, 0.8,1.0,1.2,2,4,6,8,9 weight parts.
In the present invention, thus linking agent refer to and can make the mutual bonding cross-linking of a plurality of thread-like molecules become the material of network structure at intermolecular bridging action of line style, be mainly promote or telomerized polymer molecular chain between covalent linkage or ionic linkage form.For example: in molecule, contain often the material of a plurality of functional groups, as organic dibasic acid, polyvalent alcohol etc.; Or molecule contains the compound of a plurality of unsaturated double-bonds, as Vinylstyrene and vulcabond, N,N methylene bis acrylamide (MBA) etc.Particularly, linking agent of the present invention includes but not limited to: Vinylstyrene, N,N methylene bis acrylamide (MBA), butyl (tetra) titanate, titanium ethanolate, dibutyl tin laurate.Its consumption can be 0.5,0.8,1.0,1.2 weight parts in photocuring insullac.
In the present invention, described defoamer can be commercially available for painting organo-siloxane, polyethers, silicon and the ether grafting of froth breaking, containing the defoamer such as amine, imines and amides, particularly, defoamer of the present invention includes but not limited to: polydimethylsiloxane, tributyl phosphate, silicone antifoam agent etc.Its consumption can be 0.3,0.5,0.8 weight part in photocuring insullac.
In the present invention, described flow agent can be the commercially available various flow agents for photo-cured coating system, comprise organosilicon type, for example silicone oil, polydimethylsiloxane, polyether polyester modified organic silicon oxygen alkane, alkyl-modified organo-siloxane, terminal groups modification organosilicon; Also can be acrylate type, acrylic resin for example, urea-formaldehyde resin and terpolycyantoamino-formaldehyde resin etc.Its consumption can be 0.3,0.5,0.8 weight part in photocuring insullac.
In the present invention, described coupling agent can be the commercially available various coupling agents for photo-cured coating system, comprises organic chromium complex, silicane, titanate ester and aluminic acid compound etc.Its consumption can be 0.3,0.5,0.8 weight part in photocuring insullac.
Another object of the present invention is to provide a kind of using method of above-mentioned photocuring insullac, comprises the steps:
(1) by the parts annealing of insullac to be coated, at its surface daub on a wall paint film, and carry out levelling;
(2) utilize UV-light to carry out hardening with radiation to paint film.
In the present invention, parts described in aforesaid method can be enameled wire bare wires to be produced, include but not limited to copper cash, aluminum steel, alloy wire; Outward appearance is circle or the flat of various size.Also can be other parts that need to carry out insulation processing.
In aforesaid method, flow time is 3 ~ 600s described in step 1; Described in step 2, UV-light is provided by the ultraviolet lamp of certain power, and its power can be 0.2 ~ 25kW; Paint film is preferably 5 ~ 80cm apart from the distance of ultraviolet lamp, and the time of hardening with radiation is preferably 5 ~ 600s.
In aforesaid method of the present invention, sometimes in order further to improve the performances such as sticking power, paint film softening of snappiness, paint film and the base material of paint film punctures, at some, product performance there is the field of particular requirement, the step of heat cross-linking can also be set after ultraviolet light polymerization, comprise the parts after ultraviolet light polymerization are sent in the stove with thermograde and heated, complete the heat cross-linking of paint film.
In above-mentioned heat cross-linking step, thermograde is the gradient of the even variation from low temperature to high temperature.Low-temperature end is 120 ~ 300 ℃, and temperature end is 250 ~ 550 ℃.The length of thermograde is 2 ~ 10m, to guarantee there is therein certain heat-up time by the parts of enamel-cover.Be 0.2 ~ 45min heat-up time.
For different insulative grade and the different requirements to insullac film thickness, the parameters such as envrionment temperature during according to the viscosity of the active insullac of dissimilar UV-light and production, the step that repeats above-mentioned photocuring, heat cross-linking capable of circulation, finally obtains satisfactory, to have certain thickness insulation paint film parts.
Aforesaid method of the present invention can be widely used in the production technique of enameled wire.Because the production technique of enameled wire in prior art (is generally conductor material by bare wire, conventional have copper, aluminium and an alloy etc.) after annealing softening, " paint, cure " through circulation repeatedly forms again, and the insullac that can be used for preparing enameled wire be take solvent-thinned paint as main.Therefore,, in the manufacturing processed of enameled wire, the component of 80% left and right evaporate in air when product is used, and environment is caused serious injury.And adopt aforesaid method to produce enameled wire, by the VOC content greatly reducing in insullac use procedure.
Beneficial effect of the present invention is:
1) described photocuring insullac can occur to solidify under the ultraviolet light irradiation of certain power density, forms the insulation paint film with certain electrical insulation properties and mechanical property.This is invented in prepared formula for a product and is not contained VOC, can be to environment in use, and environmental-protecting performance is outstanding.
2) using method of photocuring insullac of the present invention can complete solidifying of paint film in Production of Enamel Wires in the several seconds to tens of seconds time, can make the VOC discharging in enameled wire manufacturing processed close to zero.Simultaneously, for meeting the particular requirement of some field to product performance, the method has been carried out heat cross-linking after the stage at ultraviolet light polymerization, sticking power, paint film softening of further having improved snappiness, paint film and the base material of paint film such as punctures at the performance, product and several indifferences of traditional enameled wire performance, can meet the needs of winding wire.Particularly importantly, the method does not discharge VOC in the manufacturing processed of enameled wire, a series of environmental issues while fundamentally having solved traditional enameled wire manufacture.And products obtained therefrom performance is not compared with the prepared product performance of traditional insullac and is declined.As ultraviolet curing type insullac provided by the invention is coated on the circular copper cash that nominal diameter is 1mm and makes enamel insulated round copper wire by supporting technology provided by the invention, its indices is all better than national standard.It to insullac film thickness, is the enameled wire product of 0.04mm left and right (diameter of enameled wire is 1.08mm), more than its normal temperature voltage breakdown can reach 10kV, winding diameter is that 1mm does not ftracture, in film integrity, pinhole number is zero, softening puncture 10min at 240 ℃ and do not puncture, under 3 times of diameters of thermal shocking, do not ftracture, jerk have no progeny coat of paint and copper cash and do not depart from.
Accompanying drawing explanation
Fig. 1 is preparation technology's schema of photocuring insullac of the present invention.
Embodiment
embodiment 1
Stainless steel cauldron at 1000L (is furnished with fractional column, the fractionation ability of 3 theoretical trays of tool; By heat-conducting oil heating, and can provide the temperature of 140 ~ 230 ℃ to material in reactor) in add successively cis-butenedioic anhydride 93kg, phthalic anhydride 240kg, hexanodioic acid 92kg, propylene glycol 144kg, dihydroxyphenyl propane 144kg, glycerol 87kg.Off-response still, passes into the rare gas elementes such as nitrogen or argon gas.Start agitator motor.Open heat conduction oil circulating pump, material in reactor is heated, regulate material temperature 160 ℃ of left and right, controlling fractionating tube temperature out must not be over 100 ℃.Temperature of charge starts timing while reaching 160 ℃, every 60min measures an acid number, and acid number is measured the acid number time after lower than 160mg/g and changed every 15min into once.After acid number is lower than 130mg/g, system is carried out to underpressure distillation, acid number fast-descending.After acid number is lower than 50mg/g, stop heating, stop distillation, reaction product is pumped in cooling reactor, naturally lower the temperature or utilize hypothermic saline cooling by coil pipe.
Until temperature of charge, add 200kg vinylbenzene and 200kg methyl methacrylate during lower than 100 ℃, 1kg Resorcinol, continues to stir, cool to room temperature.Add again 0.7kg titanium ethanolate, 0.5kg silicone antifoam agent, 0.5kg flow agent, 0.5kg coupling agent, 30kg light trigger 1173, pumping material grinds 15min in three-roll grinder, and discharging packs lighttight osculum metal bucket or plastic tank into.Product is preserved in low temperature below 10 ℃, shading.
embodiment 2
Stainless steel cauldron at 2000L (is furnished with fractional column, the fractionation ability of 3 theoretical trays of tool; By heat-conducting oil heating, and can provide the temperature of 50 ~ 120 ℃ to material in reactor) in add successively 700kg ethyl acetate, 550kg tolylene diisocyanate, 85kg vinylformic acid hydroxy propyl ester, 800kg poly(oxyethylene glycol) 400, ethylene glycol 118kg, glycerol 30kg.Off-response still, passes into the rare gas elementes such as nitrogen or argon gas.Start agitator motor.Open heat conduction oil circulating pump, material in reactor is heated, regulate material temperature 65 ℃ of left and right, controlling fractionating tube temperature out must not be over 50 ℃.Temperature of charge starts timing while reaching 65 ℃, control temperature and react 3h.Then in reactor, add 5kg dibutyl tin laurate, be warmed up to 95 ℃ and continue reaction.After reaction mass temperature reaches 95 ℃, start timing, survey the content of isocyanic ester in a system per half an hour, after isocyanate content is lower than 20mg/g, system is carried out to underpressure distillation, steam ethyl acetate.When fractional column head temperature obviously rises, stop heating, stop distillation, reaction product is pumped in cooling reactor, naturally lower the temperature or utilize hypothermic saline cooling by coil pipe.
Until temperature of charge, add 150kg butyl acrylate and 250kg methyl methacrylate during lower than 100 ℃, 1.2kg Resorcinol, continues to stir, cool to room temperature.Add again 1.0 kg butyl (tetra) titanates, 0.6 kg silicone antifoam agent, 0.6kg flow agent, 0.6kg coupling agent, 35kg light trigger 1173, pumping material grinds 15min in three-roll grinder, and discharging packs lighttight osculum metal bucket or plastic tank into.Product is preserved in low temperature below 10 ℃, shading.
embodiment 3
Circular copper cash outside surface after annealed, that nominal diameter is 1.0mm is coated with and is decorated with the UV-light active polyester clasp Y insulation Y paint paint film that thickness is 8 μ m left and right, levelling 10s.The ultraviolet lamp that is 500w with four power respectively from four direction (copper cash japanning is positioned at Si Zhideng center) apart from paint film 20cm, to the copper cash irradiation 30s after japanning, complete solidifying of insullac.Enameled wire after solidifying is put into process furnace, and the temperature of process furnace one end is 200 ℃, and the other end is 350 ℃, and length is 4m.Enameled wire therein uniform motion 5min completes the heat cross-linking of paint film.Taking-up, cooling, obtaining film thickness is the enameled wire of 8 μ m left and right.Repeat this photocuring, heat cross-linking step 8 time, obtaining film thickness is the polyester enamelled wire product of 60 μ m left and right.
embodiment 4
Circular copper cash outside surface after annealed, that nominal diameter is 2.0mm is coated with and is decorated with the UV-light active polyurethane clasp Y insulation Y paint paint film that thickness is 10 μ m left and right, levelling 10s.The ultraviolet lamp that is 1000w with four power respectively from four direction (copper cash japanning is positioned at Si Zhideng center) apart from paint film 10cm, to the copper cash irradiation 10s after japanning, complete solidifying of insullac.Enameled wire after solidifying is put into process furnace, and the temperature of process furnace one end is 180 ℃, and the other end is 420 ℃, and length is 6m.Enameled wire therein uniform motion 4min completes the heat cross-linking of paint film.Taking-up, cooling, obtaining film thickness is the enameled wire of 10 μ m left and right.Repeat this photocuring, heat cross-linking step 10 time, obtaining film thickness is the polyurethane enamelled wire product of 100 μ m left and right.
Claims (10)
1. a photocuring insullac, comprises the raw material of following weight part:
Photolytic activity resin 100 weight parts;
Photolytic activity thinner 20-60 weight part;
Light trigger 0.5 ~ 10 weight part;
Linking agent 0.1-1.5 weight part;
Defoamer 0.1-1 weight part;
Flow agent 0.1-1 weight part;
Coupling agent 0.1-1 weight part.
2. photocuring insullac as claimed in claim 1, described photolytic activity resin is selected from one or more in photolytic activity vibrin, photolytic activity urethane resin or both modified products.
3. photocuring insullac as claimed in claim 2, described photolytic activity vibrin or its modified product are by containing two key raw materials, hydroxyl (or amino) raw material, obtain containing carboxyl raw material or containing several reactions in acid anhydrides raw material; Described photolytic activity urethane resin or its modified product are by containing two key raw materials, contain reactive hydrogen raw material (hydroxyl or amino raw material), obtaining containing isocyano raw material reaction.
4. photocuring insullac as claimed in claim 3, in described photolytic activity vibrin or the preparation of its modified resin, controls hydroxyl in raw material and compares for 1.3:1 ~ 0.9:1 with the amount of substance of carboxyl; In described photolytic activity urethane resin or the preparation of its modified resin, controlling containing reactive hydrogen raw material (hydroxyl or amino raw material) is 1.02:1 ~ 1.15:1 with containing reactive hydrogen in isocyano raw material with the amount of substance ratio of isocyano.
5. the photocuring insullac as described in claim 1-3 any one, described photolytic activity thinner is selected from one or more in butyl acrylate, ethyl propenoate, carbamate mono acrylic ester, hexanediyl ester, butylene glycol diacrylate, neopentylglycol diacrylate, double pentaerythritol methacrylate, Viscoat 295, vinylbenzene, methyl methacrylate; Described linking agent is selected from one or more in Vinylstyrene, N,N methylene bis acrylamide (MBA), butyl (tetra) titanate, titanium ethanolate, dibutyl tin laurate; Described defoamer is selected from one or more in polydimethylsiloxane, tributyl phosphate, silicone antifoam agent; Described flow agent is selected from silicone oil, polydimethylsiloxane, polyether polyester modified organic silicon oxygen alkane, alkyl-modified organo-siloxane, terminal groups modification organosilicon, acrylic resin, one or more in urea-formaldehyde resin and terpolycyantoamino-formaldehyde resin; Described coupling agent is selected from one or more in organic chromium complex compound, silicane, titanate ester and aluminic acid compound; Described light trigger is selected from one or more of 1173,184,907,369,1490,1700.
6. the preparation method of the photocuring insullac as described in claim 1-5 any one, comprise adding light trigger, linking agent, defoamer, flow agent, coupling agent in photolytic activity resin, stir, by three-roll grinder, grind, discharging, obtains insullac.
7. a using method for the photocuring insullac as described in claim 1-5 any one, comprises the steps:
(1), by the parts annealing of insullac to be coated, at its surface daub on a wall photocuring insulation paint film, and carry out levelling;
(2) utilize UV-light to carry out hardening with radiation to paint film.
8. using method as claimed in claim 7, wherein described in step 1, flow time is 3 ~ 600s; Described in step 2, UV-light is provided by ultraviolet lamp, and its power is 0.2 ~ 25kW; Paint film is preferably 5 ~ 80cm apart from the distance of ultraviolet lamp, and the time of hardening with radiation is preferably 5 ~ 600s.
9. using method as claimed in claim 7 can arrange heat cross-linking step after step 2 again, comprises the parts after ultraviolet light polymerization are sent in the stove with thermograde and heated, and completes the heat cross-linking of paint film.
10. the using method of stating as claim 9, described thermograde is 120 ~ 300 ℃ of low-temperature end, 250 ~ 550 ℃ of temperature end; The length of thermograde is 2 ~ 10m, and be 0.2 ~ 45min heat-up time.
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
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| CN201310696676.4A CN103694866B (en) | 2013-12-18 | 2013-12-18 | A kind of photocuring insullac and preparation and application thereof |
| PCT/CN2014/093444 WO2015090150A1 (en) | 2013-12-18 | 2014-12-10 | Photo-curable insulating varnish, preparation method therefor and application method thereof |
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| CN201310696676.4A CN103694866B (en) | 2013-12-18 | 2013-12-18 | A kind of photocuring insullac and preparation and application thereof |
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| WO2015090150A1 (en) | 2015-06-25 |
| CN103694866B (en) | 2016-06-22 |
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