CN104311713A - Graphene/epoxy acrylic acid composite resin and graphene/epoxy acrylic acid composite resin IMD ink preparation method - Google Patents
Graphene/epoxy acrylic acid composite resin and graphene/epoxy acrylic acid composite resin IMD ink preparation method Download PDFInfo
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Abstract
The present invention discloses a graphene/epoxy acrylic acid composite resin and a graphene/epoxy acrylic acid composite resin IMD ink preparation method. According to the present invention, graphite is adopted as a raw material and an oxidizing agent is adopted to prepare the graphite oxide through a Hummers method, ultrasound waves are adopted to peel the graphite oxide to prepare the graphene oxide, a silane coupling agent is adopted to carry out surface modification on the graphene oxide to obtain the modified graphene, reducing is performed through a reducing agent to obtain the reduced modified graphene, and the reduced modified graphene and an acrylic acid monomer are prepared into the graphene/epoxy acrylic acid resin through an in-situ polymerization method; and the ink of the present invention can not produce the color change for 4 min at the temperature of 300 DEG C, has characteristics of good flexibility, good impact resistance, good adhesion, and good water-acid-alkali-resistance comprehensive performance, and can meet the IMD product processing requirements.
Description
Technical field
The present invention relates to technical field of ink, specifically, relate to a kind of Graphene/epoxy acrylic compound resin and IMD ink thereof and preparation method.
Background technology
The high temperature of IMD ink demand fulfillment plastic prod in-mold decoration Thermal-printing Technology technique and stamping procedure, require that IMD ink need have high thermal resistance (300 degree of 30s are colour-fast for hot injection moulding temperature), and good snappiness, shock-resistance, cohesiveness, water-acid resistance.Will be there is temperature at 200 degree of high temperature and become in traditional ink in the market, be difficult to the performance requriements meeting resistance to 300 degree of high temperature, more cannot meet the requirement of above over-all properties.
Summary of the invention
The object of the invention is to overcome the deficiencies in the prior art, the preparation method of a kind of Graphene/epoxy acrylic compound resin and IMD ink thereof is provided.
To achieve these goals, the present invention adopts following technical scheme:
A kind of Graphene/epoxy acrylic compound resin, be prepared from by the following method: take graphite as raw material, utilize oxygenant by Hummers legal system for graphite oxide, utilize ultrasonic wave to carry out stripping to graphite oxide and prepare graphene oxide, adopt silane coupling agent to carry out surface modification to graphene oxide and prepare modified graphene, after reductive agent reduction, obtain modified with reduction Graphene, and prepare Graphene/epoxy acrylic resin with acrylic monomer by situ aggregation method.
In above-mentioned Graphene/epoxy acrylic compound resin, described oxygenant is potassium bichromate, potassium permanganate, potassium hypochlorite or the vitriol oil.
In above-mentioned Graphene/epoxy acrylic compound resin, described silane coupling agent is vinyl three ('beta '-methoxy oxyethyl group) silane, vinyltrimethoxy silane, vinyltriethoxysilane, methacryloxypropyl trimethoxy silane or acryloxypropyl Trimethoxy silane.
In above-mentioned Graphene/epoxy acrylic compound resin, described acrylic ester monomer is the mixture of one or more in vinylbenzene, methacrylic acid, vinylformic acid, Hydroxyethyl acrylate, Propylene glycol monoacrylate, ethyl propenoate, butyl acrylate, hydroxyethyl methylacrylate, Hydroxyethyl acrylate.
The preparation method of above-mentioned Graphene/epoxy acrylic compound resin, comprises the steps:
(1) preparation method of graphite oxide: the acid adding 50-200 part in there-necked flask, and place it in ice bath, then the nitrite of 1-2 part and the crystalline flake graphite of 2-3 part is added, stir, the oxygenant of 7-8 part is added in flask in batches, mixing process need control its temperature of reaction lower than 10 DEG C, and reacts 2h; Be warming up to 35 ± 2 DEG C again, reaction 30min; Drip deionized water, be warming up to 98 DEG C, reaction 30min; Then add 350 parts of hot water dilutions, then add the 30%H of 5-10 part
2o
2with unreacted oxygenant in solution, the color of dispersion liquid is glassy yellow by brown stain; Filtered while hot dispersion liquid, and remove most metal ion and acid ion with 500-750 part dilute hydrochloric acid (1:10 volume ratio) washing; Graphite oxide after washing is loaded in dialysis tubing, puts into deionized water and dialyse, until dialyzate is aobvious neutral; Finally put it in vacuum drying oven, dry under 70 DEG C of conditions, obtain dry graphite oxide powder, aforesaid number refers to weight part;
(2) recycle ultrasonoscope to carry out stripping to graphite oxide and prepare graphene oxide, get the above 0.2-0.8 part graphene oxide powder prepared, add 2-10 part water and 50-200 part solvent, ultrasonic disperse graphene oxide dispersion;
(3) preparation method of modified graphene oxide: the graphene oxide powder getting 0.2-0.8 part, add 2-6 part water and 100 parts of solvents, ultrasonic disperse, obtains graphene oxide dispersion; With acetic acid or hydrochloric acid, dispersion liquid pH value is transferred between 3-5; 10-40 part (10wt%) properties-correcting agent is added dropwise in graphene oxide dispersion; Then above dispersion liquid is added in flask, after stirring at 50 DEG C, obtain the graphene oxide dispersion of 80-140 part; After finally the dispersion liquid obtained being added the not reacted properties-correcting agent several of alcohol extraction, vacuum-drying obtains modified graphene oxide, again adds in solution, obtains modified graphene oxide dispersion liquid after ultrasonic disperse;
(4) preparation method of modified with reduction graphene oxide: the modified graphene oxide dispersion liquid getting above 123.4 parts, adds 160 parts of H
2o, after ultrasonic 30min, adds 0.5-2 part reductive agent and 20 parts of H
2o, then ultrasonic 30min; Transfer in there-necked flask, stir under 95 DEG C of conditions, wash 3 times with water, cross the salt filtering reaction and generate, then wash once with DMF, be finally dispersed in 52 parts of solvents and obtain modified with reduction graphene oxide dispersion;
Described reductive agent is sodium bisulfite;
(5) situ aggregation method prepares modified graphene/epoxy acrylic resin: get modified with reduction graphene oxide dispersion as still liquid, add mix monomer, add initiator, is obtained by reacting Graphene/epoxy acrylic compound resin at 80 DEG C.
A kind of Graphene/epoxy acrylic based polyurethanes base IMD ink, is made up of the component of following parts by weight:
In above-mentioned Graphene/epoxy acrylic based polyurethanes base IMD ink, described solidifying agent is N3390 or Tetra hydro Phthalic anhydride, described quick dry agent is rosin phenolic resin 2104, described adhesion promoter is Chlorinated Polypropylene III, described pigment is titanium white or carbon black, and described wetting dispersing agent is wetting dispersing agent BYK163, and described flow agent is flow agent BYK-306, described defoamer is defoamer BYK-141, and described solvent is ethyl acetate or butanone.
The preparation method of above-mentioned Graphene/epoxy acrylic based polyurethanes base IMD ink, comprises the steps:
According to proportioning, after pigment, Graphene/epoxy acrylic compound resin, wetting dispersing agent, solvent, obtain mill base to after its grinding distribution, after then adding quick dry agent, adhesion promoter, flow agent, defoamer, solidifying agent mixing and stirring, obtain IMD ink.
Compared with prior art, the present invention has following beneficial effect: ink of the present invention is compared with existing ink, ability 300 degree of nondiscolorations in 4 minutes, and there is good snappiness, shock-resistance, cohesiveness, water-acid resistance over-all properties, the requirement of IMD process for manufacturing product can be met.This IMD ink is the special ink being applied to plastic prod in-mold decoration Thermal-printing Technology technique, can be used for the back up of most PC, PET and PVC film, can be used for the first surface decorating being formed with IMD technical requirements product, be widely used in commercial printing market, as the dial plate etc. of the safety notice of automobile, mobile phone key, electronic product.
Embodiment
Following number refers to weight part.
Embodiment 1: the preparation of Graphene/epoxy acrylic based polyurethanes resin
1. the preparation of graphite oxide
The vitriol oil of 100 parts is slowly added in the there-necked flask that condensation and churned mechanically 500mL drying are housed, and place it in ice bath, then the Sodium Nitrite of 2 parts and the crystalline flake graphite of 3 parts is added, stir, the potassium permanganate oxidant of 8 parts is slowly added in flask in batches, mixing process need control its temperature of reaction lower than 10 DEG C, and reacts 2h; Be warming up to 37 DEG C again, reaction 30min; Continuous dropping deionized water 115mL, is warming up to 98 DEG C, reaction 30min; Then add 350 parts of hot water dilutions, then add the 30%H of 8 parts
2o
2with unreacted potassium permanganate oxidant in solution, the color of dispersion liquid is glassy yellow by brown stain; Filtered while hot dispersion liquid, and remove most metal ion and acid ion with 600 parts of dilute hydrochloric acid (1:10 volume ratio) washing; Graphite oxide after washing is loaded in dialysis tubing, puts into deionized water and to dialyse 2d, until dialyzate is aobvious neutral; Finally put it in vacuum drying oven, dry 2d under 70 DEG C of conditions, obtain dry graphite oxide powder.
2. the preparation of graphene oxide (GEO)
Utilize ultrasonoscope to carry out stripping to graphite oxide and prepare graphene oxide, get the above 0.2 part of graphene oxide powder prepared, add 3 parts of water and 100 parts of DMF solvents, ultrasonic disperse 1.5h.Treat ultrasonic after, can observe in system and not have obvious blackish green oxidize graphite particles, whole system becomes tan molten colloidal suspensions, and this suspension is placed and also sedimentation do not occurred in more than three months.
3. the preparation of modified graphene oxide (MGEO)
Get the graphene oxide powder of 0.5 part, add 3 parts of water and 100 parts of DMF solvents, ultrasonic disperse 1.5h, obtains graphene oxide dispersion; With acetic acid (or hydrochloric acid) dispersion liquid pH value is transferred to 3 ?between 5; Under 600 rotating speeds, be added dropwise in graphene oxide dispersion by 30 parts of (10wt%) methacryloxypropyl trimethoxy silane coupling agents, time for adding is 1h; Then above dispersion liquid is added in flask, at 50 DEG C, after rapid stirring 12h, obtain the graphene oxide dispersion of 90 parts; Finally the dispersion liquid obtained is added the not reacted properties-correcting agent of the alcohol extraction of 200 parts for several times after, vacuum-drying obtains modified graphene oxide, obtains modified graphene oxide dispersion liquid after again adding 123 parts of solution ultrasonic disperse.
4. the preparation of modified with reduction graphene oxide
Get the modified graphene oxide dispersion liquid of above 123.4 parts, add 160 parts of H
2o, after ultrasonic 30min, slowly adds 2 parts of sodium bisulfite reductive agents and 20 parts of H
2o, then ultrasonic 30min.Transfer in there-necked flask, under 95 DEG C of conditions, stir 3h.Wash 3 times with water, cross the salt filtering reaction and generate, then wash once with DMF, be finally dispersed in 52 parts of DMF solvents and obtain modified with reduction graphene oxide dispersion.
5. situ aggregation method prepares modified graphene/epoxy acrylic resin
Get above 0g respectively, 52 parts, 104 parts, as still liquid, (addition of graphite oxide is 0% of monomer total amount to 156 parts of modified with reduction graphene oxide dispersion, 1%, 2%, 3%), add 40 parts of mix monomers (ST/BA/HEMA/EA=18.9/7.8/5.9/7.4), add 0.8 part of Diisopropyl azodicarboxylate initiator.React at 80 DEG C after 5 hours and obtain 35% Graphene admittedly contained/epoxy acrylic resin EPAc/ Graphene (0%), EPAc/ Graphene (1%), EPAc/ Graphene (2%), EPAc/ Graphene (3%).
The preparation method of embodiment 2 Graphenes/epoxy acrylic based polyurethanes base IMD ink
Nano-graphene/epoxy acrylic resin (the EPAc/ Graphene (0%) selecting above synthesis to obtain, EPAc/ Graphene (1%), EPAc/ Graphene (2%), EPAc/ Graphene (3%)) be main body binder 25%, Tetra hydro Phthalic anhydride 0.5%, rosin phenolic resin 21042%, Chlorinated Polypropylene III 1%, titanium white 5%, wetting dispersing agent BYK1631%, flow agent BK-3060.2%, defoamer BYK-1410.2%, solvent ethyl acetate is 65.1%, and solid content is 25%-35%.According to proportioning, after pigment, resin, wetting dispersing agent (BYK163), solvent (ethyl acetate) mixing, utilize Mitsubishi refining mill to obtain mill base to after its grinding distribution 1h, after then adding quick dry agent (rosin phenolic resin), adhesion promoter (Chlorinated Polypropylene III), flow agent (BK-306), defoamer (BYK-141), solidifying agent (N3390) mixing and stirring, obtain IMD ink.With EPAc/ Graphene (0%), EPAc/ Graphene (1%), EPAc/ Graphene (2%), EPAc/ Graphene (3%)) ink for preparing for main body binder is respectively IMD-1, IMD-2, IMD-3, IMD-4.
Embodiment 3 nano-graphenes/epoxy acrylic polyurethane-base IMD ink performance
The thermotolerance of ink film is with reference to standard GB/T/T1735 " paint film Heat-tolerance Determination ", paint film thermotolerance refers to that paint film keeps the ability of its apparent state or mechanical property at a given temperature, employing retort furnace heats, after reaching the temperature and time of regulation, represent the resistance toheat of paint film with physicals change or coating surface variation phenomenon.This experiment adopts resistance to 300 DEG C of ink films that the resistance toheat of the time representation ink film of the phenomenons such as elephant skin, bubbling, cracking or variable color does not occur.The hardness of film measures with reference to standard GB/T/T6739-1996 " hardness of film pencil assay method ", is divided into 6H to 6B totally 13 grades, and wherein 6H is the hardest, and 6B is the softest.Film adhesive with reference to standard GB/T/T9286-1998 " paint and varnish paint film draw lattice experiment " [carry out cross and draw the test of lattice tape pull method, test result represents for 0-5 level, wherein 0 grade best, 5 grades are the poorest.The snappiness of film is with reference to standard GB/T/T6742-1993 " paint film flexibility assay method ", adopt hinge type bending tester to measure, represent the snappiness of paint film with model bending and diameter (mm) of the minimum mandrel rod that do not cause paint film to destroy on the mandrel rod of different diameter.Test result is divided into 2mm-32mm totally 12 grades, and its middle grade is that the snappiness of the paint film of 2mm is best, and grade is that the snappiness of the paint film of 32mm is the poorest.The shock strength of film measures with reference to standard GB/T/T1732 " paint film shock-resistance assay method ".The maximum height destroyed not cause paint film represents the shock-resistance of paint film, represents with centimetre (cm) or joule (J).Its value its impact resistance larger is better, and to be wherein considered as shock-resistance the strongest for 50cm or 4.9J.The water tolerance of film measures with reference to standard GB/T/T1733 " paint film water tolerance assay method ", after adding distilled water, surface-coated is had the tinplate of sample to put into wherein, and make 2/3 of every block plate length to be soaked in water in glass flume.Within the time of regulation test, observe whether have variable color, bubble, the phenomenon such as come off.Film resistance to acids and bases measures with reference to standard GB/T/T9274 " mensuration of paint and varnish resistant to liquid medium ", and tinplate prepares paint film.The H of 0.1mol/L is added in glass flume
2sO
4or the NaOH solution of 0.1mol/L, regulate water temperature to be 25 DEG C, and keep this temperature in whole process of the test.Model is put into wherein, and makes 2/3 of model length to be soaked in solution.Measure after certain hour, model is taken out, observe whether paint film has loss of gloss, variable color, foaming, wrinkling, the phenomenon such as come off.
The performance test results being obtained IMD ink (IMD-1, IMD-2, IMD-3, IMD-4) by above example is shown in Table 1.
Table 1
Claims (9)
1. Graphene/epoxy acrylic compound resin, it is characterized in that being prepared from by the following method: take graphite as raw material, utilize oxygenant by Hummers legal system for graphite oxide, utilize ultrasonic wave to carry out stripping to graphite oxide and prepare graphene oxide, adopt silane coupling agent to carry out surface modification to graphene oxide and prepare modified graphene, after reductive agent reduction, obtain modified with reduction Graphene, and prepare Graphene/epoxy acrylic resin with acrylic monomer by situ aggregation method.
2. Graphene/epoxy acrylic compound resin as claimed in claim 1, it is characterized in that, described oxygenant is potassium bichromate, potassium permanganate, potassium hypochlorite or the vitriol oil.
3. Graphene/epoxy acrylic compound resin as claimed in claim 1, it is characterized in that, described silane coupling agent is vinyl three ('beta '-methoxy oxyethyl group) silane, vinyltrimethoxy silane, vinyltriethoxysilane, methacryloxypropyl trimethoxy silane or acryloxypropyl Trimethoxy silane.
4. Graphene/epoxy acrylic compound resin as claimed in claim 1, it is characterized in that, described acrylic ester monomer is the mixture of one or more in vinylbenzene, methacrylic acid, vinylformic acid, Hydroxyethyl acrylate, Propylene glycol monoacrylate, ethyl propenoate, butyl acrylate, hydroxyethyl methylacrylate, Hydroxyethyl acrylate.
5. the preparation method of Graphene described in claim 1/epoxy acrylic compound resin, is characterized in that comprising the steps:
(1) preparation method of graphite oxide: the acid adding 50-200 part in there-necked flask, and place it in ice bath, then the nitrite of 1-2 part and the crystalline flake graphite of 2-3 part is added, stir, the oxygenant of 7-8 part is added in flask in batches, mixing process need control its temperature of reaction lower than 10 DEG C, and reacts 2h; Be warming up to 35 ± 2 DEG C again, reaction 30min; Drip deionized water, be warming up to 98 DEG C, reaction 30min; Then add 350 parts of hot water dilutions, then add the 30%H of 5-10 part
2o
2with unreacted oxygenant in solution, the color of dispersion liquid is glassy yellow by brown stain; Filtered while hot dispersion liquid, and remove most metal ion and acid ion with the washing of 500-750 part dilute hydrochloric acid; Graphite oxide after washing is loaded in dialysis tubing, puts into deionized water and dialyse, until dialyzate is aobvious neutral; Finally put it in vacuum drying oven, dry under 70 DEG C of conditions, obtain dry graphite oxide powder, aforesaid number refers to weight part;
(2) recycle ultrasonoscope to carry out stripping to graphite oxide and prepare graphene oxide, get the above 0.2-0.8 part graphene oxide powder prepared, add 2-10 part water and 50-200 part solvent, ultrasonic disperse graphene oxide dispersion;
(3) preparation method of modified graphene oxide: the graphene oxide powder getting 0.2-0.8 part, add 2-6 part water and 100 parts of solvents, ultrasonic disperse, obtains graphene oxide dispersion; With acetic acid or hydrochloric acid, dispersion liquid pH value is transferred between 3-5; 10-40 part properties-correcting agent is added dropwise in graphene oxide dispersion; Then above dispersion liquid is added in flask, after stirring at 50 DEG C, obtain the graphene oxide dispersion of 80-140 part; After finally the dispersion liquid obtained being added the not reacted properties-correcting agent several of alcohol extraction, vacuum-drying obtains modified graphene oxide, again adds in solution, obtains modified graphene oxide dispersion liquid after ultrasonic disperse;
(4) preparation method of modified with reduction graphene oxide: the modified graphene oxide dispersion liquid getting above 123.4 parts, adds 160 parts of H
2o, after ultrasonic 30min, adds 0.5-2 part reductive agent and 20 parts of H
2o, then ultrasonic 30min; Transfer in there-necked flask, stir under 95 DEG C of conditions, wash 3 times with water, cross the salt filtering reaction and generate, then wash once with DMF, be finally dispersed in 52 parts of solvents and obtain modified with reduction graphene oxide dispersion; (5) situ aggregation method prepares modified graphene/epoxy acrylic resin: get modified with reduction graphene oxide dispersion as still liquid, add mix monomer, add initiator, is obtained by reacting Graphene/epoxy acrylic compound resin at 80 DEG C.
6. preparation method as claimed in claim 5, it is characterized in that, described reductive agent is sodium bisulfite.
7. Graphene/epoxy acrylic based polyurethanes base IMD ink, is characterized in that, be made up of the component of following parts by weight:
Graphene/epoxy acrylic compound resin 20%-30%,
Solidifying agent 3-5%,
Quick dry agent 1%-2%,
Adhesion promoter 0.5%-1%,
Pigment 5%-10%,
Wetting dispersing agent 0.5%-1%,
Flow agent 0.1%-0.2%,
Defoamer 0.1%-0.2%,
Solvent is surplus.
8. Graphene/epoxy acrylic based polyurethanes base IMD ink as claimed in claim 1, it is characterized in that, described solidifying agent is N3390 or Tetra hydro Phthalic anhydride, described quick dry agent is rosin phenolic resin 2104, and described adhesion promoter is Chlorinated Polypropylene III, and described pigment is titanium white or carbon black, described wetting dispersing agent is wetting dispersing agent BYK163, described flow agent is flow agent BK-306, and described defoamer is defoamer BYK-141, and described solvent is ethyl acetate or butanone.
9. the preparation method of Graphene described in claim 1/epoxy acrylic based polyurethanes base IMD ink, it is characterized in that comprising the steps: according to proportioning, after pigment, Graphene/epoxy acrylic compound resin, wetting dispersing agent, solvent, obtain mill base to after its grinding distribution, after then adding quick dry agent, adhesion promoter, flow agent, defoamer, solidifying agent mixing and stirring, obtain IMD ink.
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