CN103122068B - Polyimide acrylic ester oligomer for UV (ultraviolet) paint - Google Patents
Polyimide acrylic ester oligomer for UV (ultraviolet) paint Download PDFInfo
- Publication number
- CN103122068B CN103122068B CN201210569582.6A CN201210569582A CN103122068B CN 103122068 B CN103122068 B CN 103122068B CN 201210569582 A CN201210569582 A CN 201210569582A CN 103122068 B CN103122068 B CN 103122068B
- Authority
- CN
- China
- Prior art keywords
- polyimide
- acrylate
- acrylic ester
- paint
- containing amino
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
Abstract
The invention provides a preparation method and application of polyimide acrylic ester oligomer for a UV (ultraviolet) paint. The photo-curable polyimide acrylic ester oligomer is synthetized by leading an acrylate monomer with a double-bond reaction group at the tail end of polyimide, and corresponding UV paint is prepared. Thus, the excellent performance of the polyimide resin is applied to the UV paint; defects of the UV paint on a special base material (especially glass) are solved; the polyimide acrylic ester oligomer provides the performances, such as excellent high temperature resistance, water resistance and high hardness, to the prepared UV paint, and has good adhesion force on the base materials such as glass, metal, ceramics and plastic; and the blank of the polyimide resin in the field of the UV paint is filled.
Description
Technical field
The present invention relates to a kind of photocurable oligopolymer, be specifically related to the application of a kind of preparation method of UV coating polyimide origoester acrylate and the polyimide origoester acrylate with the method production.
Technical background
Polyimide is one of organic polymer material of over-all properties the best.Polyimide is the macromolecular material containing imide ring on a class main chain.Due to main chain containing aromatic nucleus, it is as advanced composite material matrix, and having outstanding heat resistance and excellent mechanical property, is one of material that in current polymer matrix composites, temperature tolerance is the highest.As electronic information material, polyimide, except having outstanding resistance to elevated temperatures, also has outstanding dielectric properties and radiation resistance, is one of encapsulation and coating material best in current microelectronics message area.In addition, polyimide resin is used as the feature that the aspects such as tackiness agent, fiber, plastics and photoresist material also show excellent combination property.
Polyimide, as the special engineered material of one, has been widely used in the fields such as Aeronautics and Astronautics, microelectronics, nanometer, liquid crystal, separatory membrane, laser.Recently, one of in 21 century most promising engineering plastics are all being listed the research of polyimide, development and utilization by each state.Polyimide, because of its outstanding feature in performance and synthesis, no matter be as structured material or as functional material, its huge application prospect is familiar with fully.
Since polyimide (PI) moulding compound (Vespei SP) appearance in 1964, experienced by the development of forties years: the 60's ~ 70, goods mainly supplied war industry to develop high-temperature polymer, especially aerospace industry application; The new variety improving PI processing characteristics are there are the eighties, such as poly-(amide-imide) (PAI), polyetherimide (PEI); The nineties, the kinds such as transparent PI, photosensitivity PI continue to bring out; Up to the present, PI developed into covering extensive fields, goods are various, primary articles comprises: moulding resin/part, insulated wire, film, fiber, preimpregnation material/matrix material, coating, tackiness agent and foam etc.
Polyimide also can be applied to paint field, mainly contains following aspect: CN1197925C has prepared a kind of polyimide based high-temp-resistant radiation hardness slip coating; CN100492173C has prepared a kind of coating composition that can be used for the polyimide of the positive light sensitivity of indicating meter insulation layer; CN102516868A has prepared a kind of polyimide material surface protection coating being suitable for space environment and using; It is corrosionproof lubricant coating based that CN1450139A has prepared a kind of high temperature resistant thixotropic polyimide; CN101139501B has prepared a kind of polyimide thermostable aqueous dispersion coating material; CN102492320A has prepared a kind of Quick-curing polyimide coating for high-temperature-resistant optical fiber; CN102516867A has prepared a kind of polyimide paint for optical fiber; CN102220085A has prepared a kind of polyimide coating with high-temperature resistance.But also there is no polyimide resin in the related application of UV paint field at present.
UV photo-cured coating be a kind ofly have that set time is short, solidification value is low, volatile matter is low, economize the energy, the coating new variety of the advantage such as resource-saving, nuisanceless, high-level efficiency, there is very vast potential for future development.But there is the defects such as poor adhesive force, temperature tolerance is poor, water boiling resistance is poor, hardness is low, particularly on glass in UV coating at present on some special base materials (glass, metal, pottery, plastic cement).
The excellent properties of polyimide resin is applied to UV coating by the present invention innovatively, solves some defects that UV coating exists at non-absorbability base material (particularly glass).
Summary of the invention
The object of the invention is to fill up the blank that polyimide resin is applied in UV paint field, a kind of polyimide origoester acrylate for UV coating is provided.This oligopolymer gives high temperature resistant, performance and the sticking power good on the base materials such as glass, metal, pottery, plastic cement such as water boiling resistance, high rigidity of UV coating excellence prepared therefrom.
The present invention discloses simultaneously and protects this application of polyimide origoester acrylate in UV coating.
For achieving the above object, a kind of UV coating polyimide origoester acrylate is now provided, it is characterized in that being obtained by following methods:
S1. add in polar solvent by tetracarboxylic dianhydride, diamine and the organic silicon acrylic ester containing amino, reaction generates intermediate;
S2. in intermediate, add dewatering agent (also having dehydration catalyst) and polar solvent, carry out chemical imidization reaction obtained.
After described S2 reaction terminates, reaction solution is poured in dehydrated alcohol, be precipitated thing; Throw out, through washing, drying, obtains photocurable polyimide origoester acrylate.
Tetracarboxylic dianhydride described in step S1, diamine and the organic silicon acrylic ester containing amino are calculated in molar ratio as n+1:n:2, and described n is 1≤n≤20.
Described tetracarboxylic dianhydride is 1,2,4,5-pyromellitic acid anhydride, 3,3 ', 4,4 '-BPDA, 3,3 ', 4,4 '-benzophenone tetracarboxylic dianhydride, 3,3 ', 4,4 '-oxydiphthalic, 2,2 '-bis-[4-(3,4-dicarboxyl phenoxy group) phenyl] propane tetracarboxylic dianhydride, 2, one or more in 2 '-bis-(3,4-bis-carboxyphenyl) HFC-236fa tetracarboxylic dianhydride, preferably 1,2,4,5-pyromellitic acid anhydride, 4,4 '-BPDA or 4, one or more in 4 '-oxydiphthalic; Structural formula is as follows.
Described diamine is 1, 6-hexanediamine, 1, two (the 3-aminopropan alkyl) tetramethyl disiloxane of 3-, 1, two (the 4-amino-benzene oxygen methane)-1 of 3-, 1, 3, 3-tetramethyl disiloxane, 3, 4 '-diaminodiphenyl oxide, 4, 4 '-diaminodiphenyl oxide, 4, 4 '-diaminodiphenylsulfone(DDS), 1, two (4-amino-benzene oxygen) benzene of 4-, 2, two [(4-amino-benzene oxygen) phenyl] propane of 2-, one or more in two [4-(4-phenoxy group) phenyl] sulfone, preferably 1, two (the 3-aminopropan alkyl) tetramethyl disiloxane of 3-, 4, 4 '-diaminodiphenyl oxide or 4, one or more in 4 '-diaminodiphenylsulfone(DDS), structural formula is as follows,
Described polar solvent is METHYLPYRROLIDONE, N, N '-dimethyl methane amide, N, one or more the mixing in N '-dimethyl ethanamide, dimethyl sulfoxide (DMSO).
In described S1, after adding polar solvent, solids content is 25 grams per milliliter solvents; In S2, described in the material that adds also comprise dehydration catalyst; After adding dewatering agent, dehydration catalyst and polar solvent in S2, solids content is 15 grams per milliliter solvents.
Described dewatering agent is diacetyl oxide, and dehydration catalyst is pyridine.Described dewatering agent consumption is 2 ~ 4 times of diamine amount of substance; Described dehydration catalyst consumption is 0.2 ~ 1 times of dewatering agent amount of substance.
Described S1 is under protection of inert gas, reacts 8 ~ 24 hours at 20 ~ 30 DEG C; S2 reacts 4 ~ 16 hours at 30 ~ 90 DEG C.
Described throw out absolute ethanol washing, then wash with anhydrous diethyl ether.
Described is obtained by the acrylate reactions containing amino organoalkoxysilane and hydroxyl containing amino organic silicon acrylic ester; Described is 3-TSL 8330 or APTES containing amino organoalkoxysilane; The acrylate of described hydroxyl is one or more in the Hydroxyethyl acrylate of processed, hydroxyethyl methylacrylate, Propylene glycol monoacrylate, Rocryl 410.
The described preparation method containing amino organic silicon acrylic ester is: add in reactor by the acrylate containing amino organoalkoxysilane and hydroxyl; add the strong basic ion exchange resin accounting for above-mentioned two material total masses 5% ~ 15% again; under protection of inert gas; be preferably nitrogen; stir at 70 DEG C ~ 150 DEG C, allow this alcoholysis reaction carry out 6 ~ 18 hours, then carry out underpressure distillation at 130 DEG C ~ 180 DEG C; filter, to obtain final product.
In order to understand the present invention better, do further explaination to the present invention program's association reaction formula below, listed reaction formula is only theory deduction gained, and it can not as the restriction of scope.
Preparation process of the present invention is: by tetracarboxylic dianhydride, diamine and being calculated in molar ratio as (n+1) containing amino organic silicon acrylic ester: n:2 successively joins in polar solvent, its solids content is made to be 25 grams per milliliter solvents, under nitrogen protection, stir at 20 ~ 30 DEG C after 8 ~ 24 hours, generate intermediate polyamic acid, add dewatering agent diacetyl oxide and dehydration catalyst pyridine and polar solvent immediately, its solids content is made to reduce to 15 grams per milliliter solvents, at 30 DEG C ~ 90 DEG C, chemical imidization is reacted 4 ~ 16 hours again, reaction solution is poured in the dehydrated alcohol of high-speed stirring, be precipitated thing, after gained throw out priority dehydrated alcohol and anhydrous diethyl ether fully wash, namely vacuum-drying obtain photocurable polyimide origoester acrylate, reaction process is (for monobasic containing amido organosilicon acrylate) as the formula (1),
In formula, n is resin polymerization degree, 1≤n≤20.
Tetracarboxylic dianhydride monomer O (CO) selected in formula (1) reaction
2r
2(CO)
2o, the R be wherein suitable for
2as the formula (2).Wherein X is O, S, SO
2, CO, CH
2, C (CH
3)
3, CF
2, C (CF
3)
2or do not exist.Wherein preferred tetracarboxylic dianhydride is 1,2,4,5-pyromellitic acid anhydride (PMDA), 3,3 ', 4,4 '-BPDA (BPDA), 3,3 ', 4,4 '-benzophenone tetracarboxylic dianhydride (BTDA), 3,3 ', 4,4 '-oxydiphthalic (ODPA), 2,2 '-bis-[4-(3,4-dicarboxyl phenoxy group) phenyl] propane tetracarboxylic dianhydride (BPADA), 2, one or more mixing in 2 '-bis-(3,4-bis-carboxyphenyl) HFC-236fa tetracarboxylic dianhydride (6FDA).
Diamine H selected in formula (1) reaction
2n-R
3-NH
2, the R be wherein suitable for
3as the formula (3).Wherein Z is O, S, SO
2, CO, CH
2, C (CH
3)
3, CF
2, C (CF
3)
2or do not exist, R
4for C
1~ C
12alkyl or-oxyl.Wherein preferred diamine is 1, 6-hexanediamine, 1, two (the 3-aminopropan alkyl) tetramethyl disiloxane of 3-, 1, two (the 4-amino-benzene oxygen methane)-1 of 3-, 1, 3, 3-tetramethyl disiloxane, 3, 4 '-diaminodiphenyl oxide (3, 4 '-ODA), 4, 4 '-diaminodiphenyl oxide (4, 4 '-ODA), 4, 4 '-diaminodiphenylsulfone(DDS) (4, 4 '-DDS), 1, two (4-amino-benzene oxygen) benzene (1 of 4-, 4-BAB), 2, two [(4-amino-benzene oxygen) phenyl] propane (4-BAPP) of 2-, one or more mixing in two [4-(4-phenoxy group) phenyl] sulfone (BAPS).
The preparation process containing amido organosilicon acrylate being used as end-capping reagent in formula (1) reaction is: the acrylate containing amino organoalkoxysilane and hydroxyl is calculated in molar ratio as 1:3 and adds in the reactor of band water trap and condenser, add the strong basic ion exchange resin accounting for above-mentioned two material total masses 10% again, under nitrogen protection, stir at 70 DEG C ~ 150 DEG C and react, the small molecules methyl alcohol generated or ethanol are constantly separated by water trap, this alcoholysis reaction is allowed to carry out 6 ~ 18 hours, underpressure distillation is carried out again at 130 DEG C ~ 180 DEG C, remove the acrylate of unreacted hydroxyl, filter, obtain monobasic containing amido organosilicon acrylate and dibasic mix products containing amido organosilicon acrylate, reaction process as the formula (4),
In formula, R
1for CH
3or C
2h
5.
Used in formula (4) reaction is 3-TSL 8330 (silane coupling agent KH-540) or APTES (silane resin acceptor kh-550) containing amino organoalkoxysilane; The acrylate of hydroxyl used is one or more the mixing in the Hydroxyethyl acrylate of processed, hydroxyethyl methylacrylate, Propylene glycol monoacrylate and Rocryl 410.
UV coating polyimide origoester acrylate of the present invention, can be used for being prepared in the UV coating that the base materials such as glass, metal, pottery, plastic cement use; As a kind of preferred version, described base material is preferably glass baseplate.
Oligopolymer used is the photocurable polyimide origoester acrylate that the present invention synthesizes;
Light trigger is 2, one or more mixing in 4,6-trimethylbenzoy-dipheny phosphine oxide, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-2-hydroxyl-1-phenyl-1-acetone, 2-methyl isophthalic acid-(4-methylthio group phenyl)-2-morpholine-1-acetone, 2-isopropyl thioxanthone;
Auxiliary agent is one or more the mixing in defoamer, flow agent, mould inhibitor, dispersion moisture agent;
Diluting monomer is NVP, vinylbenzene, butyl acrylate, tri (propylene glycol) diacrylate, 1, one or more mixing in 3-butylene glycol diacrylate, Viscoat 295, pentaerythritol triacrylate, PDDA, 1,4 butanediol diacrylate, phthalic acid three propanedioic acid diacrylate.
This UV coating can be prepared as follows: first join in high speed dispersor by oligopolymer, dispersion agent, amount of activated thinner, color stuffing and other part of auxiliary by certain proportioning, it is allowed to disperse 0.5 ~ 1 hour, after reaching required fineness, add reactive thinner and the auxiliary agent of light trigger and remainder, continue to be uniformly mixed until evenly, i.e. obtained UV coating.
UV coating prepared by the polyimide origoester acrylate that described use the present invention synthesizes, comprises following component: color stuffing, polyimide origoester acrylate, reactive thinner, light trigger, auxiliary agent etc.
Pigment used is one or more the mixing in titanium dioxide, carbon black, iron oxide pigment, cadmium pigment, chromate pigments, pearly pigment, the blue or green pigment of phthalein, azo pigment, Heterocyclics Pigments; Filler is one or more the mixing in calcium carbonate, talcum powder, kaolin, calcium sulfate, barium sulfate, silicon-dioxide, mica, Calucium Silicate powder.
Major advantage of the present invention is:
1., by introducing the acrylate monomer with double bond reactive group at polyimide end, synthesized a kind of photo curable polyimide origoester acrylate, and prepared corresponding UV coating.Therefore, the excellent properties of polyimide resin is applied to UV coating, solves some defects that UV coating (particularly glass) on special base material exists.
2. this polyimide origoester acrylate gives high temperature resistant, performance and the sticking power good on the base materials such as glass, metal, pottery, plastic cement such as water boiling resistance, high rigidity of UV coating excellence prepared therefrom.
3. filled up the blank that polyimide resin is applied in UV paint field.
embodiment:
Below in conjunction with specific embodiment, the invention will be further described, but embodiments of the present invention is not limited in any way.
Embodiment 1
By 3-TSL 8330 8.96 grams (0.05 mole) and through the Propylene glycol monoacrylate 19.52 grams (0.15 mole) of processed add band water trap and condenser reactor in, add strong basic ion exchange resin 2.85 grams again, under nitrogen protection, stir at 130 DEG C and react, the small molecules methyl alcohol generated constantly is separated by water trap, this alcoholysis reaction is allowed to carry out 14 hours, underpressure distillation is carried out again at 150 DEG C, remove unreacted Propylene glycol monoacrylate, filter, obtain monobasic containing amido organosilicon acrylate and dibasic mix products containing amido organosilicon acrylate.
By 1, 2, 4, 5-pyromellitic acid anhydride 47.98 grams (0.22 mole), 4, 4 '-diaminodiphenyl oxide 40.04 grams (0.20 mole) and the above-mentioned organic silicon acrylic ester 13.06 grams (0.04 mole) containing amino successively join in 404 milliliters of DMF, under nitrogen protection, stir at 20 DEG C ~ 30 DEG C after 12 hours, add dewatering agent diacetyl oxide 40.84 grams (0.40 mole), dehydration catalyst pyridine 31.64 grams (0.40 mole) and 270 milliliters of DMF, at 90 DEG C, chemical imidization reacts 10 hours, reaction solution is poured in the dehydrated alcohol of high-speed stirring, be precipitated thing, after gained throw out priority dehydrated alcohol and anhydrous diethyl ether fully wash, namely vacuum-drying obtain photocurable polyimide origoester acrylate,
Take above-mentioned polyimide origoester acrylate 25 grams, dissolve with 12.5 grams of NVPs (NVP) and 10 grams of tri (propylene glycol) diacrylates (TPGDA), add 2.5 grams of light trigger 1-hydroxycyclohexyl phenyl ketone (184) again, be uniformly dispersed on high speed dispersor.By this UV paint on glass and stainless steel plate, then under UV-irradiation, carry out photocuring, then carry out performance characterization and test, result is as shown in table 1.
Embodiment 2
By 3-TSL 8330 8.96 grams (0.05 mole) and through the Rocryl 410 21.63 grams (0.15 mole) of processed add band water trap and condenser reactor in, add strong basic ion exchange resin 3.06 grams again, under nitrogen protection, stir at 120 DEG C and react, the small molecules methyl alcohol generated constantly is separated by water trap, this alcoholysis reaction is allowed to carry out 14 hours, underpressure distillation is carried out again at 150 DEG C, remove unreacted Rocryl 410, filter, obtain monobasic containing amido organosilicon acrylate and dibasic mix products containing amido organosilicon acrylate.
By 3, 3 ', 4, 4 '-BPDA 52.96 grams (0.18 mole), 1, two (the 3-aminopropan alkyl) tetramethyl disiloxane 39.76 grams (0.16 mole) of 3-and the above-mentioned organic silicon acrylic ester 13.90 grams (0.04 mole) containing amino successively join in 426 milliliters of NMP, under nitrogen protection, stir at 20 DEG C ~ 30 DEG C after 12 hours, add dewatering agent diacetyl oxide 32.67 grams (0.32 mole), dehydration catalyst pyridine 25.31 grams (0.32 mole) and 284 milliliters of NMP, at 80 DEG C, chemical imidization reacts 8 hours, reaction solution is poured in the dehydrated alcohol of high-speed stirring, be precipitated thing, after gained throw out priority dehydrated alcohol and anhydrous diethyl ether fully wash, namely vacuum-drying obtain photocurable polyimide origoester acrylate,
Take above-mentioned polyimide origoester acrylate 25 grams, dissolve with 12.5 grams of NVPs (NVP) and 10 grams of tri (propylene glycol) diacrylates (TPGDA), add 2.5 grams of light trigger 1-hydroxycyclohexyl phenyl ketone (184) again, be uniformly dispersed on high speed dispersor.By this UV paint on glass and stainless steel plate, then under UV-irradiation, carry out photocuring, then carry out performance characterization and test, result is as shown in table 1.
Embodiment 3
By APTES 11.07 grams (0.05 mole) and through the Hydroxyethyl acrylate 17.42 grams (0.15 mole) of processed add band water trap and condenser reactor in, add strong basic ion exchange resin 2.85 grams again, under nitrogen protection, stir at 140 DEG C and react, the small molecules ethanol generated constantly is separated by water trap, this alcoholysis reaction is allowed to carry out 14 hours, underpressure distillation is carried out again at 150 DEG C, remove unreacted Hydroxyethyl acrylate, filter, obtain monobasic containing amido organosilicon acrylate and dibasic mix products containing amido organosilicon acrylate.
By 3, 3 ', 4, 4 '-benzophenone tetracarboxylic dianhydride 45.11 grams (0.14 mole), 1, 6-hexanediamine 13.94 grams (0.12 mole) and the above-mentioned organic silicon acrylic ester 13.06 grams (0.04 mole) containing amino successively join in 288 milliliters of DMAc, under nitrogen protection, stir at 20 DEG C ~ 30 DEG C after 12 hours, add dewatering agent diacetyl oxide 24.50 grams (0.24 mole), dehydration catalyst pyridine 19.98 grams (0.24 mole) and 192 milliliters of DMAc, at 70 DEG C, chemical imidization reacts 9 hours, reaction solution is poured in the dehydrated alcohol of high-speed stirring, be precipitated thing, after gained throw out priority dehydrated alcohol and anhydrous diethyl ether fully wash, namely vacuum-drying obtain photocurable polyimide origoester acrylate,
Take above-mentioned polyimide origoester acrylate 25 grams, dissolve with 12.5 grams of NVPs (NVP) and 10 grams of tri (propylene glycol) diacrylates (TPGDA), add 2.5 grams of light trigger 1-hydroxycyclohexyl phenyl ketone (184) again, be uniformly dispersed on high speed dispersor.By this UV paint on glass and stainless steel plate, then under UV-irradiation, carry out photocuring, then carry out performance characterization and test, result is as shown in table 1.
Embodiment 4
By APTES 11.07 grams (0.05 mole) and through the hydroxyethyl methylacrylate 19.53 grams (0.15 mole) of processed add band water trap and condenser reactor in, add strong basic ion exchange resin 3.06 grams again, under nitrogen protection, stir at 150 DEG C and react, the small molecules ethanol generated constantly is separated by water trap, this alcoholysis reaction is allowed to carry out 14 hours, underpressure distillation is carried out again at 150 DEG C, remove unreacted hydroxyethyl methylacrylate, filter, obtain monobasic containing amido organosilicon acrylate and dibasic mix products containing amido organosilicon acrylate.
By 3, 3 ', 4, 4 '-oxydiphthalic 31.02 grams (0.10 mole), 4, 4 '-diaminodiphenylsulfone(DDS) 18.58 grams (0.08 mole) and the above-mentioned organic silicon acrylic ester 13.90 grams (0.04 mole) containing amino successively join in 254 milliliters of DMSO, under nitrogen protection, stir at 20 DEG C ~ 30 DEG C after 12 hours, add dewatering agent diacetyl oxide 16.34 grams (0.16 mole), dehydration catalyst pyridine 12.66 grams (0.16 mole) and 169 milliliters of DMSO, at 80 DEG C, chemical imidization reacts 11 hours, reaction solution is poured in the dehydrated alcohol of high-speed stirring, be precipitated thing, after gained throw out priority dehydrated alcohol and anhydrous diethyl ether fully wash, namely vacuum-drying obtain photocurable polyimide origoester acrylate,
Take above-mentioned polyimide origoester acrylate 25 grams, dissolve with 12.5 grams of NVPs (NVP) and 10 grams of tri (propylene glycol) diacrylates (TPGDA), add 2.5 grams of light trigger 1-hydroxycyclohexyl phenyl ketone (184) again, be uniformly dispersed on high speed dispersor.By this UV paint on glass and stainless steel plate, then under UV-irradiation, carry out photocuring, then carry out performance characterization and test, result is as shown in table 1.
Table 1
| Test event | Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Testing method |
| Paint film appearance | Light yellow clear | Light yellow clear | Light yellow clear | Light yellow clear | Range estimation |
| Weightless 5% temperature/DEG C | 372 | 365 | 360 | 353 | TG |
| Second-order transition temperature/DEG C | 238 | 246 | 225 | 221 | DSC |
| Hardness/H | 5 | 4 | 4 | 4 | GB/T 6739-1996 |
| Attachment fastness/level on glass | 0 | 0 | 0 | 0 | GB/T 9286-1998 |
| Attachment fastness/level on stainless steel plate | 0 | 0 | 0 | 0 | GB/T 9286-1998 |
| 1h(25 DEG C is soaked) in water | Do not come off, do not whiten | Do not come off, do not whiten | Do not come off, do not whiten | Do not come off, do not whiten | GB/T 1733-1993 |
| 1h(100 DEG C is soaked) in water | Do not come off, do not whiten | Do not come off, do not whiten | Do not come off, do not whiten | Do not come off, do not whiten | GB/T 1733-1993 |
| Water-intake rate/% | <1.0 | <1.0 | <1.0 | <1.0 | HG/T 3344-1985 |
Claims (7)
1. a UV coating polyimide origoester acrylate, is characterized in that, obtained by following methods:
S1. add in polar solvent by tetracarboxylic dianhydride, diamine and the organic silicon acrylic ester containing amino, reaction generates intermediate;
S2. in intermediate, add dewatering agent and polar solvent, carry out chemical imidization reaction obtained,
Described is obtained by the acrylate reactions containing amino organoalkoxysilane and hydroxyl containing amino organic silicon acrylic ester; Described is 3-TSL 8330 or APTES containing amino organoalkoxysilane; The acrylate of described hydroxyl is one or more in the Hydroxyethyl acrylate of processed, hydroxyethyl methylacrylate, Propylene glycol monoacrylate, Rocryl 410,
The described preparation method containing amino organic silicon acrylic ester is: add in reactor by the acrylate containing amino organoalkoxysilane and hydroxyl; add the strong basic ion exchange resin accounting for above-mentioned two material total masses 5% ~ 15% again; under protection of inert gas; stir at 70 DEG C ~ 150 DEG C; allow this alcoholysis reaction carry out 6 ~ 18 hours, then carry out underpressure distillation at 130 DEG C ~ 180 DEG C, filter; obtain
Tetracarboxylic dianhydride described in S1, diamine and the organic silicon acrylic ester containing amino are calculated in molar ratio as n+1:n:2, and described n is 1≤n≤20.
2. UV coating polyimide origoester acrylate according to claim 1, is characterized in that, after S2 reaction terminates, is poured into by reaction solution in dehydrated alcohol, is precipitated thing; Throw out, through washing, drying, obtains photocurable polyimide origoester acrylate.
3. UV coating polyimide origoester acrylate according to claim 1, is characterized in that:
Described tetracarboxylic dianhydride is 1,2,4,5-pyromellitic acid anhydride, 3,3 ', 4,4 '-BPDA, 3,3 ', 4,4 '-benzophenone tetracarboxylic dianhydride, 3,3 ', 4,4 '-oxydiphthalic, 2,2 '-bis-[4-(3,4-dicarboxyl phenoxy group) phenyl] propane tetracarboxylic dianhydride, 2, one or more in 2 '-bis-(3,4-bis-carboxyphenyl) HFC-236fa tetracarboxylic dianhydride;
Described diamine is 1,6-hexanediamine, 1, two (the 3-aminopropan alkyl) tetramethyl disiloxane, 1 of 3-, two (the 4-amino-benzene oxygen methane)-1 of 3-, 1,3,3-tetramethyl disiloxane, 3,4 '-diaminodiphenyl oxide, 4,4 '-diaminodiphenyl oxide, 4, one or more in 4 '-diaminodiphenylsulfone(DDS), Isosorbide-5-Nitrae-bis-(4-amino-benzene oxygen) benzene, 2,2-two [(4-amino-benzene oxygen) phenyl] propane, two [4-(4-phenoxy group) phenyl] sulfone;
Described polar solvent is METHYLPYRROLIDONE, N, N '-dimethyl methane amide, N, one or more in N '-dimethyl ethanamide, dimethyl sulfoxide (DMSO);
Described dewatering agent is diacetyl oxide.
4. UV coating polyimide origoester acrylate according to claim 1, is characterized in that, in S2, described in the material that adds also comprise dehydration catalyst, described dehydration catalyst is pyridine.
5. UV coating polyimide origoester acrylate according to claim 4, is characterized in that, in S1, after adding polar solvent, solids content is 25 grams per milliliter solvents; After adding dewatering agent, dehydration catalyst and polar solvent in S2, solids content is 15 grams per milliliter solvents.
6. UV coating polyimide origoester acrylate according to claim 1, it is characterized in that, S1 is under protection of inert gas, reacts 8 ~ 24 hours at 20 ~ 30 DEG C; S2 reacts 4 ~ 16 hours at 30 ~ 90 DEG C.
7. UV coating polyimide origoester acrylate according to claim 2, is characterized in that, described throw out absolute ethanol washing, then washs with anhydrous diethyl ether.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210569582.6A CN103122068B (en) | 2012-12-25 | 2012-12-25 | Polyimide acrylic ester oligomer for UV (ultraviolet) paint |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210569582.6A CN103122068B (en) | 2012-12-25 | 2012-12-25 | Polyimide acrylic ester oligomer for UV (ultraviolet) paint |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103122068A CN103122068A (en) | 2013-05-29 |
| CN103122068B true CN103122068B (en) | 2015-07-08 |
Family
ID=48453237
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201210569582.6A Expired - Fee Related CN103122068B (en) | 2012-12-25 | 2012-12-25 | Polyimide acrylic ester oligomer for UV (ultraviolet) paint |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103122068B (en) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106916486A (en) * | 2017-03-03 | 2017-07-04 | 华南农业大学 | Polysiloxane modified polyimide photosensitive-ink and its preparation method and application |
| MX2019012405A (en) | 2017-04-21 | 2020-01-27 | Henkel IP & Holding GmbH | (meth) acrylate functionalized poly (meth) acrylate-block-polyimi de-block-poly (meth) acrylate copolymer, preparation method and use thereof. |
| TWI666670B (en) * | 2018-05-18 | 2019-07-21 | 致伸科技股份有限公司 | Keycap structure and manufacturing method thereof |
| CN108795315B (en) * | 2018-05-30 | 2021-02-12 | 宁波科莱恩新材料科技有限公司 | UV anti-adhesion acid-resistant protective film based on active fluorine-containing polyimide |
| CN115197399B (en) * | 2022-07-12 | 2023-06-16 | 中山大学 | Preparation method and application of alicyclic epoxy polyimide |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5310862A (en) * | 1991-08-20 | 1994-05-10 | Toray Industries, Inc. | Photosensitive polyimide precursor compositions and process for preparing same |
| JPH07242822A (en) * | 1994-03-08 | 1995-09-19 | Sumitomo Bakelite Co Ltd | Resin composition improved in physical property at high temperature |
| CN1137043A (en) * | 1996-01-09 | 1996-12-04 | 河北工业大学 | Thermostable photosensitive polyimide |
| US5629358A (en) * | 1991-12-27 | 1997-05-13 | Imperial Chemical Industries Plc | Photocurable resin composition containing acrylate silane and epoxy silane and/or their hydrolysis products |
| CN1583835A (en) * | 2003-06-02 | 2005-02-23 | 信越化学工业株式会社 | Siloxane copolymer, making method, and thermosetting resin composition |
| CN101151579A (en) * | 2005-03-30 | 2008-03-26 | 新日铁化学株式会社 | Photosensitive resin composition and circuit substrate employing the same |
| CN102439521A (en) * | 2009-10-15 | 2012-05-02 | 株式会社Lg化学 | Light-sensitive resin composition and a dry film comprising the same |
-
2012
- 2012-12-25 CN CN201210569582.6A patent/CN103122068B/en not_active Expired - Fee Related
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5310862A (en) * | 1991-08-20 | 1994-05-10 | Toray Industries, Inc. | Photosensitive polyimide precursor compositions and process for preparing same |
| US5629358A (en) * | 1991-12-27 | 1997-05-13 | Imperial Chemical Industries Plc | Photocurable resin composition containing acrylate silane and epoxy silane and/or their hydrolysis products |
| JPH07242822A (en) * | 1994-03-08 | 1995-09-19 | Sumitomo Bakelite Co Ltd | Resin composition improved in physical property at high temperature |
| CN1137043A (en) * | 1996-01-09 | 1996-12-04 | 河北工业大学 | Thermostable photosensitive polyimide |
| CN1583835A (en) * | 2003-06-02 | 2005-02-23 | 信越化学工业株式会社 | Siloxane copolymer, making method, and thermosetting resin composition |
| CN101151579A (en) * | 2005-03-30 | 2008-03-26 | 新日铁化学株式会社 | Photosensitive resin composition and circuit substrate employing the same |
| CN102439521A (en) * | 2009-10-15 | 2012-05-02 | 株式会社Lg化学 | Light-sensitive resin composition and a dry film comprising the same |
Non-Patent Citations (2)
| Title |
|---|
| Synthesis and characterization of low-dielectric photosensitive polyimide/silica hybrid materials;Suttisak Srisuwan,et al.;《Journal of applied polymer science》;20100815;第117卷(第4期);第2422-2427页 * |
| UV固化环氧丙烯酸酯/聚酰亚胺树脂粉复合涂层的制备及性能研究;高鹏等;《材料导报》;20100825;第24卷(第8期);第25-28页 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN103122068A (en) | 2013-05-29 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103122068B (en) | Polyimide acrylic ester oligomer for UV (ultraviolet) paint | |
| JP5845911B2 (en) | Polyimide precursor aqueous solution composition and method for producing polyimide precursor aqueous solution composition | |
| CN103261278B (en) | Polyamic acid resin composition and method of producing the same | |
| CN110028670A (en) | Low-dielectric loss negative light-sensitive poly amic acid ester resin, resin combination, preparation method and application | |
| CN103842408A (en) | Polyamic acid resin composition, polyimide resin composition, polyimide oxazole resin composition, and flexible substrate containing same | |
| CN101959935A (en) | Polyimide precursor composition, polyimide film and transparent flexible film | |
| CN102260480B (en) | High-temperature-resistant modified epoxy resin adhesive and preparation method thereof | |
| CN112876680B (en) | Polyamide acid slurry, preparation method thereof and polyimide film | |
| KR100676331B1 (en) | Polyimide Hybrid Adhesives | |
| CN101700474A (en) | Polyimide gas separation membrane with high molecular weight and preparation method thereof | |
| CN103119085A (en) | Resin composition and manufacturing process therefor | |
| Que et al. | Synthesis and characterization of trifluoromethyl-containing polyimide-modified epoxy resins | |
| CN102120820B (en) | A kind of method of performing aqueous synthesis of thermosetting polyimide | |
| CN110419001A (en) | Photosensitive polymer combination, photosensitive polymer combination film, insulating film and electronic component | |
| CN106046373B (en) | A kind of solvable polyimide film and preparation method with anti-flammability | |
| CN108822317A (en) | A kind of preparation method of graphene polyimide heating film | |
| CN111072962B (en) | Synthesis and application of photosensitive polyimide for high-temperature-resistant optical fiber coating | |
| WO2022004583A1 (en) | Isocyanate-modified polyimide resin, resin composition and cured product of same | |
| GB2101149A (en) | Process for producing polyamide acid silicon type intermediate and polyimide silicon copolymer resin | |
| Liu et al. | Novel UV-curable epoxy resins modified with alkyne: Cured through thiol-yne click reaction | |
| WO2004096919A1 (en) | Resin composition and adhesive film | |
| CN104861162A (en) | Soluble polyimide with tert-butyl and triphenylamine structure and preparation method of soluble polyimide | |
| CN107163248A (en) | Phosphorous and trifluoromethyl soluble polyimide of one class and preparation method thereof | |
| CN103159954B (en) | Preparation method of polyimide resin and application in two-layer binder-free flexible copper clad | |
| JPH07109438A (en) | Polyimide varnish |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| PP01 | Preservation of patent right | ||
| PP01 | Preservation of patent right |
Effective date of registration: 20170928 Granted publication date: 20150708 |
|
| PD01 | Discharge of preservation of patent | ||
| PD01 | Discharge of preservation of patent |
Date of cancellation: 20200928 Granted publication date: 20150708 |
|
| CF01 | Termination of patent right due to non-payment of annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20150708 Termination date: 20211225 |