CN104945891A - Alumite adhesive layer resin containing hyperbranched polyamide and preparing method thereof - Google Patents
Alumite adhesive layer resin containing hyperbranched polyamide and preparing method thereof Download PDFInfo
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Abstract
The invention belongs to the field of high-polymer materials and relates to alumite adhesive layer resin containing hyperbranched polyamide and a preparing method thereof. The alumite adhesive layer resin containing the hyperbranched polyamide comprises, by mass, 1-10 parts of hyperbranched polyamide, 25-40 parts of polyurethane resin, 5-15 parts of other resin, 8-20 parts of ganister sand, 0.5-1.0 part of auxiliaries and 40-70 parts of solvent. The invention further discloses a method for preparing the alumite adhesive layer resin containing the hyperbranched polyamide. According to the method, firstly, different generations of hyperbranched polyamide and polyurethane prepolymer emulsion are prepared respectively; secondly, the different generations of hyperbranched polyamide with different contents serve as modifying agents to be mixed with the polyurethane prepolymer emulsion and other auxiliary materials, and the alumite adhesive layer resin can be obtained after the mixture is mixed evenly. The prepared adhesive layer resin has lower viscosity and better dissolvability; at the solidifying stage, a large number of tail end active groups of the hyperbranched polyamide participate in a cross-linking reaction, the number of net points of the whole solidifying system is increased, the associativity of a solidifying film is higher, and the solidifying film is not prone to fracturing and peeling off during gold blocking operation.
Description
Technical field
The invention belongs to polymeric material field, relate to anodized aluminium Subbing resins, particularly relate to a kind of anodized aluminium Subbing resins containing ultrabranching polyamide and preparation method thereof.
Background technology
Electrochemical aluminium gold-stamped technology constantly by scientific workers' reformed AHP to be applicable to gold stamping field more widely, because its gold stamping carrier, gold stamping picture and text etc. are quite numerous and diverse, seek a kind of anodized aluminium that can meet specific gold stamping demand most important.Wherein, big area is gold stamping because it is to anodized aluminium scalding property, cutting property requirement harshness, is difficult to accomplish that full, nothing leakage is scalded, edge clear on the spot, is known as technical barrier already by industry in the gold stamping operation of reality.
In current Subbing resins the most widely used acrylic resin because of its fragility too high, scald property on while meeting cutting property greatly to reduce, in contrast, toughness after urethane (PU) resin film forming is better, after certain properties-correcting agent of introducing, certain fragility can be taken into account again, therefore its can to meet big area as anodized aluminium Subbing resins gold stamping.
Ultrabranching polyamide (HBPs) contains a large amount of end active functional group due to numerous branching end of the chain, and itself molecular chain is low without winding, viscosity, can be dissolved in multi-solvents, may be used for modification PU to improve the degree of crosslinking in its solidification process.For convenience of suitability for industrialized production consider that HBPs has good solubility, generally first by HBPs and PU performed polymer emulsion physical blending, crosslinking reaction can be produced again in cure stage.
The synthesis of hyperbranched polymer and applied research, master thesis, 2012, Jiangsu: Jiangsu University, reports to be reacted by methyl methacrylate and diethanolamine and makes AB
2monomer, then by introducing centronucleus TriMethylolPropane(TMP), under the condition of Catalyzed by p-Toluenesulfonic Acid, preparing the hyper-branched polyester of different algebraically, using it for modified aqueous polyurethane dispersion liquid.Characterize dispersion liquid, found that modified emulsion particle diameter increases and surface tension reduction, this is conducive to the even painting exhibition of emulsion; Tension test is carried out to film after its solidification, found that modified cured film mechanical property slightly strengthens.
Improve the most capable and effective means of the phenomenons such as gold stamping unreal, the firkin of big area, namely seek boiling hot property and all splendid Subbing resins of cutting property.
Summary of the invention
Scalding property and cutting property to improve on anodized aluminium, an object of the present invention is to disclose the anodized aluminium Subbing resins containing ultrabranching polyamide.
Containing the anodized aluminium Subbing resins of ultrabranching polyamide, its component and mass fraction as follows:
Ultrabranching polyamide 1 ~ 10 part,
Urethane resin 25 ~ 40 parts,
Other resins 5 ~ 15 parts,
Silica flour 8 ~ 20 parts,
Auxiliary agent 0.5 ~ 1.0 part,
Solvent 40 ~ 70 parts;
Wherein, described ultrabranching polyamide be one to four generation full fragrant ultrabranching polyamide or fragrance-lard type ultrabranching polyamide, can make by oneself, also can purchased from commercially available, such as by 3, the full fragrant ultrabranching polyamide that 5-diaminobenzoic acid autohemagglutination obtains, the fragrance obtained by MALEIC ANHYDRIDE and diethylene triamine condensation polymerization-lard type ultrabranching polyamide, preferred class is similar to the former by one matter as 3, the full fragrant ultrabranching polyamide that 5-diaminobenzoic acid autohemagglutination obtains, and account for 5 parts of whole Subbing resins system quality number;
Described urethane (PU) resin is the high molecular polymer of multicomponent isocyanate and multi-hydroxy compound polymerization, multicomponent isocyanate can be tolylene diisocyanate, vulcabond ditane, multi-hydroxy compound can be polyvalent alcohol, as ethylene glycol, glycerol etc.; Polyester oligomer containing terminal hydroxyl is used for preparing PAUR, containing the polyether oligomers of terminal hydroxyl, is used for preparing polyether(poly)urethane, is preferably polymerizable raw material gained urethane by macromolecule polyol, polyisocyanates and dihydroxymethyl acid;
Other resins described are nitrocellulose, cellulose acetate butyrate or supervinyi chloride resin etc., preferred nitrocellulose, and mass fraction is 6;
Described silica flour mass fraction preferably 10.2 parts;
Described auxiliary agent is one or more combinations referred in flow agent, slip(ping)agent, wetting agent, thermo-stabilizer, wherein flow agent is polyacrylic acid, carboxymethyl cellulose, slip(ping)agent is polyethylene wax, Poly Propylene Wax, wetting agent is sapn, tween, thermo-stabilizer is glyceryl ester, preferably select flow agent polyacrylic acid, mass fraction is 0.8;
Described solvent is one or more any mixed solvents in benzene,toluene,xylene, butanone, pimelinketone, ethyl acetate, propyl carbinol, and preferred propyl carbinol, mass fraction is 50.
Another object of the present invention, the preparation method disclosing the above-mentioned anodized aluminium Subbing resins containing ultrabranching polyamide, first prepare respectively ultrabranching polyamide and the polyurethane prepolymer precursor emulsion of different algebraically, then using the ultrabranching polyamide of different algebraically, content as properties-correcting agent with base polyurethane prepolymer for use as emulsion blending and other auxiliary materials that adulterate mix after and get final product.
Containing a preparation method for the anodized aluminium Subbing resins of ultrabranching polyamide, comprise the steps:
(1) preparation of ultrabranching polyamide: by AB
2type pre-polymerization monomer is dissolved in solvent, passes through AB
2type pre-polymerization monomer autohemagglutination can obtain the ultrabranching polyamide (HBPs-A1, HBPs-A2, HBPs-A3, HBPs-A4) in one to four generation, polymerization temperature 60 ~ 90 DEG C, time 2 ~ 6h;
Wherein AB
2type pre-polymerization monomer can be known organic molecule also can be the novel substance synthesized first, meet between A and B functional group self and any chemical reaction does not occur, and along with level of response, to deepen A, B functional group activity constant, the by product produced in polymerization process can not have an impact to polyreaction itself, so that ultrabranching polyamide quality after controlling autohemagglutination;
The present invention preferably 3,5-diaminobenzoic acids as AB
2monomer, calculates AB needed for certain generation ultrabranching polyamide of synthesis
2the amount of monomer, directly obtains object product by one-step polymerization method;
If AB used when will prepare HBPs-A1
2the gauge of monomeric substance is 3.0eq, then AB used when preparing HBPs-A2, HBPs-A3, HBPs-A4
2the amount of monomeric substance is respectively 7.0eq, 15.0 eq, 31.0 eq; That is, AB needed for two generation ultrabranching polyamides is prepared
2amount and the AB needed for preparation generation ultrabranching polyamide of monomeric substance
2the ratio of the amount of monomeric substance is 7.0:3.0; AB needed for preparation three generations ultrabranching polyamide
2amount and the AB needed for preparation generation ultrabranching polyamide of monomeric substance
2the ratio of the amount of monomeric substance is 15.0:3.0; Prepare AB needed for four generation ultrabranching polyamides
2amount and the AB needed for preparation generation ultrabranching polyamide of monomeric substance
2the ratio of the amount of monomeric substance is 31.0:3.0; Preferably 80 DEG C, 5h, described solvent selects deionized water, dehydrated alcohol, Virahol etc., and preferred deionized water, to make environmental friendliness;
(2) preparation of polyurethane prepolymer precursor emulsion: in the reaction vessel with whipping appts, reflux condensing tube and thermometer of drying, add macromolecule polyol, polyisocyanates, dihydroxymethyl acid and solvent, be warming up to 40 ~ 80 DEG C, add catalyzer, slowly be warming up to 80 ~ 90 DEG C, constant temperature stirs 1 ~ 8h; Reduce temperature to 30 ~ 50 DEG C, add neutralizing agent, after reaction 10 ~ 90min, under high-speed stirring, deionized water is slowly instilled reaction vessel and carry out emulsion dispersion, obtain the polyurethane prepolymer precursor emulsion that solid content is 8 ~ 80%;
Wherein, described macromolecule polyol can be Polyoxypropylene diol NJ-210, NJ-220, NJ-330, polyethylene oxide and polytetrahydrofuran etc., macromolecule polyol amount of substance is counted 1.0eq, preferred NJ-220;
Polyisocyanates can be aliphatic diisocyanate (ADI), isophorone diisocyanate (IPDI) etc., the mol ratio of polyisocyanates and macromolecule polyol is 1.5 ~ 2.5: 1, and preferred molar ratio is the isophorone diisocyanate (IPDI) of 2.0:1;
Dihydroxymethyl acid can be dimethylol propionic acid (DMPA) or dimethylolpropionic acid (DMBA), and dihydroxymethyl acid and the mol ratio of macromolecule polyol are the dimethylol propionic acid (DMPA) of 0.9 ~ 1.0:1, preferred molar ratio 1.0:1;
Solvent can be DMF (DMF) or methyl tertiary butyl ether (MTBE), and itself and macromolecule polyol mass ratio are 0.5 ~ 20:1, the DMF (DMF) of preferred 10:1;
Catalyzer can be organotin, and as tin dilaurate diisobutyl tin (T-12), stannous octoate, two (dodecyl sulphur) dibutyl tin, dibutyltin diacetate etc., consumption is 1 ~ 2;
Optimum operation is: system is warming up to 60 DEG C of instillations, 1 T-12, and persistently overheating to 85 DEG C of sustained reaction 6h;
Neutralizing agent used is trialkyl or alkyl amine, pyridines, pyroles and composition thereof, preferred triethylamine (TEA), and reacts 50min at 40 DEG C, and regulation system pH is 7 ~ 8; The solid content of polyurethane prepolymer precursor emulsion is best 30%;
(3) ultrabranching polyamide and base polyurethane prepolymer for use as emulsion blending: dropped into by solvent in reactor, controls temperature in the kettle 25 ~ 60 DEG C; Add polyurethane prepolymer precursor emulsion and other resins successively, stir 2 ~ 4 h; By silica flour, ultrabranching polyamide (HBPs-A1, HBPs-A2, HBPs-A3, HBPs-A4 ...), auxiliary agent is disposable adds in still, control temperature 25 ~ 70 DEG C, stirs 2 ~ 6 h; The material mixed flows in storage tank for subsequent use by kettle device, keeps storage tank internal temperature 10 ~ 35 DEG C.
Wherein, when described base polyurethane prepolymer for use as quality of the emulsion number is 30, Subbing resins hot stamping effects is best;
Described ultrabranching polyamide is step (1) made ultrabranching polyamide one to four generation, preferred ultrabranching polyamide two generation and mass fraction is 5;
Described solvent can be one or more mixed solvents in benzene,toluene,xylene, butanone, pimelinketone, ethyl acetate, propyl carbinol, preferably selects propyl carbinol, and to control its mass fraction be 50;
Other resins mainly refer to nitrocellulose, cellulose acetate butyrate or supervinyi chloride resin etc., preferred nitrocellulose, and control its mass fraction and be 6, stir 3h;
Auxiliary agent mainly refers to one or more combinations in flow agent, slip(ping)agent, wetting agent, thermo-stabilizer, wherein flow agent selects polyacrylic acid, carboxymethyl cellulose, slip(ping)agent mainly selects polyethylene wax, Poly Propylene Wax, wetting agent mainly selects sapn, tween, thermo-stabilizer mainly selects glyceryl ester, preferably select flow agent to be polyacrylic acid, and its mass fraction is 0.8;
Silica flour mass fraction is 10.2, stirs 4h.
Blending Processes temperature is unified to be controlled at 30 DEG C, and prepared anodized aluminium Subbing resins can the thermoprint gold stamping product that to go out on the spot full.
The Subbing resins of a series of different material, proportioning can be obtained according to preparation technology set forth in the present invention, this series of Subbing resins is coated on basement membrane aluminium lamination face equably by specific coating machine, after coating machine processing, namely obtain electrochemical aluminum foil finished product.
The purity of the reagent of subparticipation reaction, manufacturer (as follows).
3,5-diaminobenzoic acid (analytical pure, Chemical Reagent Co., Ltd., Sinopharm Group); Dehydrated alcohol (industrial goods, Suo Pu group); Deionized water (self-control, Yangzhou Xiang Hua novel material Science and Technology Ltd.); NJ-220(industrial goods, Qingdao Yu Tian chemical company); IPDI(industrial goods, German HUL company); ADI(industrial goods, German HUL company); DMPA(industrial goods, PERSTOP company of Switzerland); ; DMBA(industrial goods, PERSTOP company of Switzerland); DMF(analytical pure, Chemical Reagent Co., Ltd., Sinopharm Group); MTBE(analytical pure, Chemical Reagent Co., Ltd., Sinopharm Group) T-12(chemical pure, chemical reagents corporation of traditional Chinese medicines group); TEA(chemical pure, chemical reagents corporation of traditional Chinese medicines group); Silica flour (analytical pure, Aladdin reagent company limited); Flow agent (industrial goods, the sub-Chemical Co., Ltd. of Shanghai Songyuan); Slip(ping)agent (industrial goods, the sub-Chemical Co., Ltd. of Shanghai Songyuan); Wetting agent (industrial goods, the sub-Chemical Co., Ltd. of Shanghai Songyuan); Thermo-stabilizer (industrial goods, the sub-Chemical Co., Ltd. of Shanghai Songyuan); Nitrocellulose (chemical pure, Nanjing Olympic Duo Fu Buddhist nun bio tech ltd).
Experimental technique
(1) with KBr pressed disc method, carried out Infrared spectroscopy to pure polyaminoester emulsion and partially modified polyaminoester emulsion, its INFRARED SPECTRUM as shown in Figure 1.
(2) professional die-stamping machine (MK1050YM-11 is utilized, Tianjin long queue) by electrochemical aluminum foil thermoprint on particular bearer thing, wherein carrier can be cork paper, paperboard etc., for convenience of description the big area hot stamping effects of Subbing resins, and the present invention uses paperboard as test carrier without exception.
The operating panel that gold stamping template is respectively Xuzhou Hua Yi multicolor printing company limited, Jiangsu Zhong Yinyinwu Group Co., Ltd provides, setting gold stamping pressure is 100Pa, temperature 180 DEG C, speed 110 mmin
-1, bronzing effect figure as shown in Figure 2.
Beneficial effect
When urethane is used for anodized aluminium Subbing resins in the past, often can run into the gold stamping unreal problem of big area, and dissaving structure is creatively introduced in polyurethane system by physical blending mode by the present invention, obtained electrochemical aluminum foil Subbing resins.In Subbing resins cure stage, a large amount of terminal reactive group of ultrabranching polyamide participate in crosslinking reaction, and whole curing system net point increases, and therefore the associativity of cured film is stronger, not easily chaps, peels off when gold stamping operation.In addition the three-dimensional near-spherical structure of ultrabranching polyamide uniqueness makes it have more low-viscosity and better solubility property, and this is also conducive to the mutual pardon between each component.The present invention provides new technical scheme for improving anodized aluminium in thermoprint big area picture and text effect.
Accompanying drawing explanation
Fig. 1 is pure polyaminoester emulsion and partially modified polyaminoester emulsion infrared spectrogram;
Fig. 2 be not containing ultrabranching polyamide Subbing resins with containing the corresponding electrochemical aluminium gold-stamped design sketch of ultrabranching polyamide Subbing resins, wherein (a) is the gold stamping template design sketch of Xuzhou Hua Yi multicolor printing company limited, and (b) is the gold stamping template design sketch of Jiangsu Zhong Yinyinwu Group Co., Ltd.
Embodiment
Below in conjunction with specific embodiment, the present invention is described in detail, and following examples will contribute to those skilled in the art and understand the present invention further, but not limit the present invention in any form.It should be pointed out that to those skilled in the art, without departing from the inventive concept of the premise, can also make some distortion and improvement, these all belong to protection category of the present invention.
Blank test
In the flask with whipping appts, reflux condensing tube and thermometer of drying, disposablely add 10g NJ-220,2.223g IPDI, 0.671g DMPA and 10gDMF, be warming up to 60 DEG C, add 1 T-12, be slowly warming up to 85 DEG C, constant temperature stirs 6 h; Reduce temperature to 40 DEG C, add TEA and adjust pH to 7, after reaction 50min, under 2000r/min high-speed stirring, 32.98g deionized water is slowly instilled reaction vessel and carry out emulsion dispersion, obtain the PU performed polymer emulsion that solid content is 30%.
48g propyl carbinol is dropped in reactor, control temperature in the kettle 30 DEG C; Add 30g urethane resin and 6g nitrocellulose sequentially successively, control stir speed (S.S.) between 300 r/min, stir 3 h; By 10.2g silica flour, 0.8g polyacrylic acid is disposable adds in reactor, control temperature 30 DEG C, and stir speed (S.S.), at 600 r/min, stirs 4 h; The material mixed is flowed in storage tank for subsequent use by kettle device, controls internal temperature 30 DEG C.
Embodiment 1
Be equipped with in 250 mL three-necked flasks of thermometer, whipping appts one and add 22.82g 3,5-diaminobenzoic acid and 98.06 ml deionized waters, autohemagglutination 5h at 80 DEG C, obtains glassy yellow liquid, and drying gained yellow powder is HBPs-A1.
In the flask with whipping appts, reflux condensing tube and thermometer of drying, disposablely add 10g NJ-220,2.223g IPDI, 0.671g DMPA and 10gDMF, be warming up to 60 DEG C, add 1 T-12, be slowly warming up to 85 DEG C, constant temperature stirs 6 h; Reduce temperature to 40 DEG C, add TEA and adjust pH to 7, after reaction 50min, under 2000r/min high-speed stirring, 32.98g deionized water is slowly instilled reaction vessel and carry out emulsion dispersion, obtain the PU performed polymer emulsion that solid content is 30%.
48g propyl carbinol is dropped in reactor, control temperature in the kettle 30 DEG C; Add 30g urethane resin and 6g nitrocellulose sequentially successively, control stir speed (S.S.) between 300 r/min, stir 3 h; By 1g HBPs-A1,10.2g silica flour, 0.8g glyceryl ester is disposable adds in reactor, control temperature 30 DEG C, and stir speed (S.S.), at 600 r/min, stirs 4 h; The material mixed is flowed in storage tank for subsequent use by kettle device, controls internal temperature 30 DEG C.
Embodiment 2
Be equipped with in 250 mL three-necked flasks of thermometer, whipping appts one and add 53.25g 3,5-diaminobenzoic acid and 98.06 ml deionized waters, autohemagglutination 1h at 60 DEG C, obtains glassy yellow liquid, and drying gained yellow powder is HBPs-A2.
In the flask with whipping appts, reflux condensing tube and thermometer of drying, disposablely add 10g NJ-220,1.67g IPDI, 0.60g DMPA and 5gDMF, be warming up to 40 DEG C, add 1 T-12, be slowly warming up to 80 DEG C, constant temperature stirs 1 h; Reduce temperature to 30 DEG C, add TEA and adjust pH to 7, after reaction 10min, under 1000r/min high-speed stirring, 151.18g deionized water is slowly instilled reaction vessel and carry out emulsion dispersion, obtain the PU performed polymer emulsion that solid content is 8%.
70g propyl carbinol is dropped in reactor, control temperature in the kettle 25 DEG C; Add 25g urethane resin and 5g nitrocellulose sequentially successively, control stir speed (S.S.) between 200 r/min, stir 2 h; By 1g HBPs-A2,8g silica flour, 0.5g carboxymethyl cellulose is disposable adds in reactor, control temperature 25 DEG C, and stir speed (S.S.), at 200 r/min, stirs 2 h; The material mixed is flowed in storage tank for subsequent use by kettle device, controls internal temperature 10 DEG C.
Embodiment 3
Be equipped with in 250 mL three-necked flasks of thermometer, whipping appts one and add 114.11g 3,5-diaminobenzoic acid and 98.06 ml deionized waters, autohemagglutination 6h at 90 DEG C, obtains glassy yellow liquid, and drying gained yellow powder is HBPs-A3.
In the flask with whipping appts, reflux condensing tube and thermometer of drying, disposablely add 10g NJ-220,2.78g IPDI, 0.68g DMPA and 20gDMF, be warming up to 80 DEG C, add 2 T-12, be slowly warming up to 90 DEG C, constant temperature stirs 8 h; Reduce temperature to 50 DEG C, add TEA and adjust pH to 8, after reaction 90min, under 3000r/min high-speed stirring, 5.34g deionized water is slowly instilled reaction vessel and carry out emulsion dispersion, obtain the PU performed polymer emulsion that solid content is 80%.
40g propyl carbinol is dropped in reactor, control temperature in the kettle 60 DEG C; Add 40g urethane resin and 15g nitrocellulose sequentially successively, control stir speed (S.S.) between 500 r/min, stir 4 h; By 10g HBPs-A3,20g silica flour, 1.0g Poly Propylene Wax is disposable adds in reactor, control temperature 70 DEG C, and stir speed (S.S.), at 700 r/min, stirs 6 h; The material mixed is flowed in storage tank for subsequent use by kettle device, controls internal temperature 35 DEG C.
Embodiment 4
Be equipped with in 250 mL three-necked flasks of thermometer, whipping appts one and add 235.83g 3,5-diaminobenzoic acid and 98.06 ml deionized waters, autohemagglutination 5h at 80 DEG C, obtains glassy yellow liquid, and drying gained yellow powder is HBPs-A4.
In the flask with whipping appts, reflux condensing tube and thermometer of drying, disposablely add 10g NJ-220,2.223g IPDI, 0.671g DMPA and 10gDMF, be warming up to 60 DEG C, add 1 T-12, be slowly warming up to 85 DEG C, constant temperature stirs 6 h; Reduce temperature to 40 DEG C, add TEA and adjust pH to 7, after reaction 50min, under 2000r/min high-speed stirring, 32.98g deionized water is slowly instilled reaction vessel and carry out emulsion dispersion, obtain the PU performed polymer emulsion that solid content is 30%.
48g propyl carbinol is dropped in reactor, control temperature in the kettle 30 DEG C; Add 30g urethane resin and 6g nitrocellulose sequentially successively, control stir speed (S.S.) between 300 r/min, stir 3 h; By 1g HBPs-A4,10.2g silica flour, 0.8g sapn is disposable adds in reactor, control temperature 30 DEG C, and stir speed (S.S.), at 600 r/min, stirs 4 h; The material mixed is flowed in storage tank for subsequent use by kettle device, controls internal temperature 30 DEG C.
Embodiment 5
Be equipped with in 250 mL three-necked flasks of thermometer, whipping appts one and add 22.82g 3,5-diaminobenzoic acid and 98.06 ml deionized waters, autohemagglutination 5h at 80 DEG C, obtains glassy yellow liquid, and drying gained yellow powder is HBPs-A1.
In the flask with whipping appts, reflux condensing tube and thermometer of drying, disposablely add 10g NJ-210,2.223g IPDI, 0.671g DMPA and 10gDMF, be warming up to 60 DEG C, add 1 T-12, be slowly warming up to 85 DEG C, constant temperature stirs 6 h; Reduce temperature to 40 DEG C, add TEA and adjust pH to 7, after reaction 50min, under 2000r/min high-speed stirring, 32.98g dehydrated alcohol is slowly instilled reaction vessel and carry out emulsion dispersion, obtain the PU performed polymer emulsion that solid content is 30%.
48g propyl carbinol is dropped in reactor, control temperature in the kettle 30 DEG C; Add 30g urethane resin and 6g cellulose acetate butyrate sequentially successively, control stir speed (S.S.) between 300 r/min, stir 3 h; By 1g HBPs-A1,10.2g silica flour, 0.8g tween is disposable adds in reactor, control temperature 30 DEG C, and stir speed (S.S.), at 600 r/min, stirs 4 h; The material mixed is flowed in storage tank for subsequent use by kettle device, controls internal temperature 30 DEG C.
Embodiment 6
Be equipped with in 250 mL three-necked flasks of thermometer, whipping appts one and add 53.25g 3,5-diaminobenzoic acid and 98.06 ml deionized waters, autohemagglutination 5h at 80 DEG C, obtains glassy yellow liquid, and drying gained yellow powder is HBPs-A2.
In the flask with whipping appts, reflux condensing tube and thermometer of drying, disposablely add 10g NJ-220,2.223g IPDI, 0.671g DMPA and 10gDMF, be warming up to 60 DEG C, add 1 T-12, be slowly warming up to 85 DEG C, constant temperature stirs 6 h; Reduce temperature to 40 DEG C, add TEA and adjust pH to 7, after reaction 50min, under 2000r/min high-speed stirring, 32.98g deionized water is slowly instilled reaction vessel and carry out emulsion dispersion, obtain the PU performed polymer emulsion that solid content is 30%.
48g propyl carbinol is dropped in reactor, control temperature in the kettle 30 DEG C; Add 30g urethane resin and 6g nitrocellulose sequentially successively, control stir speed (S.S.) between 300 r/min, stir 3 h; By 1g HBPs-A2,10.2g silica flour, 0.8g polyethylene wax is disposable adds in reactor, control temperature 30 DEG C, and stir speed (S.S.), at 600 r/min, stirs 4 h; The material mixed is flowed in storage tank for subsequent use by kettle device, controls internal temperature 30 DEG C.
Embodiment 7
Be equipped with in 250 mL three-necked flasks of thermometer, whipping appts one and add 22.82g 3,5-diaminobenzoic acid and 98.06 ml deionized waters, autohemagglutination 5h at 80 DEG C, obtains glassy yellow liquid, and drying gained yellow powder is HBPs-A1.
In the flask with whipping appts, reflux condensing tube and thermometer of drying, disposablely add 10g NJ-220,2.223g IPDI, 0.671g DMBA and 10gMTBE, be warming up to 60 DEG C, add 1 T-12, be slowly warming up to 85 DEG C, constant temperature stirs 6 h; Reduce temperature to 40 DEG C, add TEA and adjust pH to 7, after reaction 50min, under 2000r/min high-speed stirring, 32.98g deionized water is slowly instilled reaction vessel and carry out emulsion dispersion, obtain the PU performed polymer emulsion that solid content is 30%.
48g propyl carbinol is dropped in reactor, control temperature in the kettle 30 DEG C; Add 30g urethane resin and 6g nitrocellulose sequentially successively, control stir speed (S.S.) between 300 r/min, stir 3 h; By 1g HBPs-A1,10.2g silica flour, 0.8g glyceryl ester is disposable adds in reactor, control temperature 30 DEG C, and stir speed (S.S.), at 600 r/min, stirs 4 h; The material mixed is flowed in storage tank for subsequent use by kettle device, controls internal temperature 30 DEG C.
Embodiment 8
Be equipped with in 250 mL three-necked flasks of thermometer, whipping appts one and add 22.82g 3,5-diaminobenzoic acid and 98.06 ml deionized waters, autohemagglutination 5h at 80 DEG C, obtains glassy yellow liquid, and drying gained yellow powder is HBPs-A1.
In the flask with whipping appts, reflux condensing tube and thermometer of drying, disposablely add 10g NJ-330,2.223g IPDI, 0.671g DMPA and 10gDMF, be warming up to 60 DEG C, add 1 stannous octoate, slowly be warming up to 85 DEG C, constant temperature stirs 6 h; Reduce temperature to 40 DEG C, add TEA and adjust pH to 8, after reaction 50min, under 2500r/min high-speed stirring, 32.98g deionized water is slowly instilled reaction vessel and carry out emulsion dispersion, obtain the PU performed polymer emulsion that solid content is 30%.
48g ethyl acetate is dropped in reactor, control temperature in the kettle 30 DEG C; Add 30g urethane resin and 6g nitrocellulose sequentially successively, control stir speed (S.S.) between 300 r/min, stir 3 h; By 1g HBPs-A1,10.2g silica flour, 0.8g carboxymethyl cellulose is disposable adds in reactor, control temperature 30 DEG C, and stir speed (S.S.), at 500 r/min, stirs 4 h; The material mixed is flowed in storage tank for subsequent use by kettle device, controls internal temperature 30 DEG C.
Embodiment 9
Be equipped with in 250 mL three-necked flasks of thermometer, whipping appts one and add 22.82g 3,5-diaminobenzoic acid and 98.06 ml deionized waters, autohemagglutination 5h at 80 DEG C, obtains glassy yellow liquid, and drying gained yellow powder is HBPs-A1.
In the flask with whipping appts, reflux condensing tube and thermometer of drying, disposablely add 10g NJ-220,2.223g IPDI, 0.671g DMPA and 10gDMF, be warming up to 60 DEG C, add 1 T-12, be slowly warming up to 85 DEG C, constant temperature stirs 6 h; Reduce temperature to 40 DEG C, add TEA and adjust pH to 7, after reaction 50min, under 2000r/min high-speed stirring, 32.98g dehydrated alcohol is slowly instilled reaction vessel and carry out emulsion dispersion, obtain the PU performed polymer emulsion that solid content is 30%.
48g pimelinketone is dropped in reactor, control temperature in the kettle 30 DEG C; Add 30g urethane resin and 6g nitrocellulose sequentially successively, control stir speed (S.S.) between 300 r/min, stir 3 h; By 1g HBPs-A1,10.2g silica flour, 0.8g polyethylene wax is disposable adds in reactor, control temperature 30 DEG C, and stir speed (S.S.), at 500 r/min, stirs 4 h; The material mixed is flowed in storage tank for subsequent use by kettle device, controls internal temperature 30 DEG C.
Embodiment 10
Be equipped with in 250 mL three-necked flasks of thermometer, whipping appts one and add 22.82g 3,5-diaminobenzoic acid and 98.06 ml deionized waters, autohemagglutination 5h at 80 DEG C, obtains glassy yellow liquid, and drying gained yellow powder is HBPs-A1.
In the flask with whipping appts, reflux condensing tube and thermometer of drying, disposablely add 10g NJ-220,2.223g IPDI, 0.671g DMPA and 10gDMF, be warming up to 60 DEG C, add 2 dibutyltin diacetates, slowly be warming up to 85 DEG C, constant temperature stirs 6 h; Reduce temperature to 40 DEG C, add TEA and adjust pH to 8, after reaction 50min, under 2000r/min high-speed stirring, 32.98g deionized water is slowly instilled reaction vessel and carry out emulsion dispersion, obtain the PU performed polymer emulsion that solid content is 30%.
48g toluene is dropped in reactor, control temperature in the kettle 30 DEG C; Add 30g urethane resin and 6g nitrocellulose sequentially successively, control stir speed (S.S.) between 300 r/min, stir 3 h; By 1g HBPs-A1,10.2g silica flour, 0.8g Poly Propylene Wax is disposable adds in reactor, control temperature 30 DEG C, and stir speed (S.S.), at 400 r/min, stirs 4 h; The material mixed is flowed in storage tank for subsequent use by kettle device, controls internal temperature 35 DEG C.
Embodiment 11
Be equipped with in 250 mL three-necked flasks of thermometer, whipping appts one and add 22.82g 3,5-diaminobenzoic acid and 98.06 ml deionized waters, autohemagglutination 5h at 70 DEG C, obtains glassy yellow liquid, and drying gained yellow powder is HBPs-A1.
In the flask with whipping appts, reflux condensing tube and thermometer of drying, disposablely add 10g NJ-220,2.223g IPDI, 0.671g DMPA and 10gDMF, be warming up to 60 DEG C, add 1 T-12, be slowly warming up to 85 DEG C, constant temperature stirs 5h; Reduce temperature to 40 DEG C, add TEA and adjust pH to 7, after reaction 50min, under 2500r/min high-speed stirring, 32.98g deionized water is slowly instilled reaction vessel and carry out emulsion dispersion, obtain the PU performed polymer emulsion that solid content is 30%.
48g propyl carbinol is dropped in reactor, control temperature in the kettle 30 DEG C; Add 30g urethane resin and 6g nitrocellulose sequentially successively, control stir speed (S.S.) between 300 r/min, stir 3 h; By 1g HBPs-A1,10.2g silica flour, 0.8g Poly Propylene Wax is disposable adds in reactor, control temperature 30 DEG C, and stir speed (S.S.), at 500 r/min, stirs 4 h; The material mixed is flowed in storage tank for subsequent use by kettle device, controls internal temperature 30 DEG C.
Embodiment 12
Be equipped with in 250 mL three-necked flasks of thermometer, whipping appts one and add 22.82g 3,5-diaminobenzoic acid and 98.06 ml deionized waters, autohemagglutination 5h at 80 DEG C, obtains glassy yellow liquid, and drying gained yellow powder is HBPs-A1.
In the flask with whipping appts, reflux condensing tube and thermometer of drying, disposablely add 10g NJ-220,2.223g IPDI, 0.671g DMPA and 10gDMF, be warming up to 60 DEG C, add 2 T-12, be slowly warming up to 85 DEG C, constant temperature stirs 6 h; Reduce temperature to 40 DEG C, add TEA and adjust pH to 7, after reaction 50min, under 2000r/min high-speed stirring, 32.98g deionized water is slowly instilled reaction vessel and carry out emulsion dispersion, obtain the PU performed polymer emulsion that solid content is 30%.
48g butanone is dropped in reactor, control temperature in the kettle 30 DEG C; Add 30g urethane resin and 6g nitrocellulose sequentially successively, control stir speed (S.S.) between 300 r/min, stir 3 h; By 1g HBPs-A1,10.2g silica flour, 0.8g tween is disposable adds in reactor, control temperature 30 DEG C, and stir speed (S.S.), at 400 r/min, stirs 4 h; The material mixed is flowed in storage tank for subsequent use by kettle device, controls internal temperature 30 DEG C.
Embodiment 13
Be equipped with in 250 mL three-necked flasks of thermometer, whipping appts one and add 22.82g 3,5-diaminobenzoic acid and 98.06 ml deionized waters, autohemagglutination 5h at 80 DEG C, obtains glassy yellow liquid, and drying gained yellow powder is HBPs-A1.
In the flask with whipping appts, reflux condensing tube and thermometer of drying, disposablely add 10g NJ-220,2.223g IPDI, 0.671g DMPA and 10gDMF, be warming up to 60 DEG C, add 1 T-12, be slowly warming up to 85 DEG C, constant temperature stirs 6 h; Reduce temperature to 40 DEG C, add TEA and adjust pH to 7, after reaction 50min, under 2000r/min high-speed stirring, 32.98g deionized water is slowly instilled reaction vessel and carry out emulsion dispersion, obtain the PU performed polymer emulsion that solid content is 30%.
48g propyl carbinol is dropped in reactor, control temperature in the kettle 30 DEG C; Add 30g urethane resin and 6g supervinyi chloride resin sequentially successively, control stir speed (S.S.) between 300 r/min, stir 3 h; By 1g HBPs-A1,10.2g silica flour, 0.8g polyethylene wax is disposable adds in reactor, control temperature 30 DEG C, and stir speed (S.S.), at 400 r/min, stirs 4 h; The material mixed is flowed in storage tank for subsequent use by kettle device, controls internal temperature 30 DEG C.
Embodiment 14
Be equipped with in 250 mL three-necked flasks of thermometer, whipping appts one and add 22.82g 3,5-diaminobenzoic acid and 98.06 ml deionized waters, autohemagglutination 5h at 80 DEG C, obtains glassy yellow liquid, and drying gained yellow powder is HBPs-A1.
In the flask with whipping appts, reflux condensing tube and thermometer of drying, disposablely add 10g NJ-220,2.223g IPDI, 0.671g DMPA and 10gDMF, be warming up to 60 DEG C, add 1 T-12, be slowly warming up to 85 DEG C, constant temperature stirs 6 h; Reduce temperature to 40 DEG C, add TEA and adjust pH to 7, after reaction 50min, under 2000r/min high-speed stirring, 32.98g deionized water is slowly instilled reaction vessel and carry out emulsion dispersion, obtain the PU performed polymer emulsion that solid content is 30%.
48g propyl carbinol is dropped in reactor, control temperature in the kettle 30 DEG C; Add 30g urethane resin and 6g nitrocellulose sequentially successively, control stir speed (S.S.) between 300 r/min, stir 3 h; By 1g HBPs-A1,10.2g silica flour, 0.8g Poly Propylene Wax is disposable adds in reactor, control temperature 30 DEG C, and stir speed (S.S.), at 500 r/min, stirs 4 h; The material mixed is flowed in storage tank for subsequent use by kettle device, controls internal temperature 30 DEG C.
As can be seen from accompanying drawing 1, the infrared curve basic simlarity of pure PU and blending resin and PU-HBPs-A1 ~ 4 and blending resin thereof, shows that this patent adopts blending and modifying mode can't cause radical change to Subbing resins molecular system.2270cm
-1the isocyano stretching vibration at place disappears, and this shows that the conversion of isocyanate-monomer is complete.Simultaneously at the 1730cm of each sample
-1all having there is very strong absorption peak in left and right place, corresponding to the stretching vibration peak of carbonyl in carbamate (C=O), can prove the urethane segment had in synthesized product containing ammonia ester bond thus; At 2945cm
-1there is very strong absorption peak left and right, corresponding to absorption peak hydrocarbon in carbamate.3430cm in spectrogram
-1hydroxyl peak disappear, 3315cm
-1there is hydrogen bonding N-H stretching vibration peak, 1533cm
-1there are the mixing bands of a spectrum of N-H flexural vibration and C-N stretching vibration absorption peak, show that-NCO base and hydroxyl total overall reaction generate carbamate groups.1727cm
-1for the characteristic peak of ester carbonyl group, owing to forming hydrogen bond with amino-formate bond, characteristic peak is offset.1242cm
-1for C-O stretching vibration in carbamate and ester bond, 1457 cm
-1for methylene radical formation vibration absorption peak.
As can be seen from accompanying drawing 2, the Subbing resins that pure PU makes, the more probability ground of its gold stamping product has occurred leaking boiling hot, grinning effect, and the Subbing resins that PU-HBPs makes, its gold stamping pattern is full, large on the spot without grinning effect.For (a), the corresponding gold stamping product of pure PU, multiple English alphabets in gold stamping region all occur that leakage is in various degree scalded, and PU-HBPs-A2-5% corresponding gold stamping product, greatly on the spot full, clear patterns; For (b), the corresponding gold stamping product of pure PU, gold stamping regional area is seriously show-through, and such phenomenon does not then appear in the corresponding gold stamping product of PU-HBPs-A2-5%.This is mainly because after introducing dissaving structure in Subbing resins curing system, whole system molecular chain cross-linking set increases, and therefore in bronzing effect, the pattern globality introducing dissaving structure modified is better.
The foregoing is only embodiments of the invention; not thereby the scope of the claims of the present invention is limited; every utilize specification sheets of the present invention to do equivalent structure or the conversion of equivalent flow process, or be directly or indirectly used in other relevant technical fields, be all in like manner included in scope of patent protection of the present invention.
Claims (10)
1. containing the anodized aluminium Subbing resins of ultrabranching polyamide, its component and mass fraction as follows:
Ultrabranching polyamide 1 ~ 10 part,
Urethane resin 25 ~ 40 parts,
Other resins 5 ~ 15 parts,
Silica flour 8 ~ 20 parts,
Auxiliary agent 0.5 ~ 1.0 part,
Solvent 40 ~ 70 parts.
2. the anodized aluminium Subbing resins containing ultrabranching polyamide according to claim 1, is characterized in that: described ultrabranching polyamide be one to four generation full fragrant ultrabranching polyamide or fragrance-lard type ultrabranching polyamide;
Described urethane resin is the high molecular polymer of multicomponent isocyanate and multi-hydroxy compound polymerization;
Other resins described are nitrocellulose, cellulose acetate butyrate or supervinyi chloride resin;
Described auxiliary agent is refer to one or more arbitrary combination in flow agent, slip(ping)agent, wetting agent, thermo-stabilizer, wherein flow agent is polyacrylic acid or carboxymethyl cellulose, slip(ping)agent is polyethylene wax or Poly Propylene Wax, and wetting agent is sapn or tween, and thermo-stabilizer is glyceryl ester;
Described solvent is one or more any mixed solvents in benzene,toluene,xylene, butanone, pimelinketone, ethyl acetate, propyl carbinol.
3. the anodized aluminium Subbing resins containing ultrabranching polyamide according to claim 2, it is characterized in that: described ultrabranching polyamide is that one to four generation is by 3, the full fragrant ultrabranching polyamide that 5-diaminobenzoic acid autohemagglutination obtains, and account for 5 parts of whole Subbing resins system quality number;
Other resins described are nitrocellulose, and mass fraction is 6;
Described silica flour mass fraction 10.2 parts;
Described auxiliary agent is flow agent polyacrylic acid, and mass fraction is 0.8;
Described solvent is propyl carbinol, and mass fraction is 50.
4. prepare the method for the claims 1-3 anodized aluminium Subbing resins containing ultrabranching polyamide described arbitrarily, it is characterized in that: ultrabranching polyamide and the polyurethane prepolymer precursor emulsion of first preparing different algebraically respectively, then using the ultrabranching polyamide of different algebraically, content as properties-correcting agent with base polyurethane prepolymer for use as emulsion blending and other auxiliary materials that adulterate mix after and get final product.
5. preparation, containing the method for the anodized aluminium Subbing resins of ultrabranching polyamide, is characterized in that, comprises the steps: according to claim 4
(1) preparation of ultrabranching polyamide: by AB
2type pre-polymerization monomer is dissolved in solvent, passes through AB
2type pre-polymerization monomer autohemagglutination can obtain the ultrabranching polyamide in one to four generation, polymerization temperature 60 ~ 90 DEG C, autohemagglutination time 2 ~ 6h;
Wherein, described AB
2type pre-polymerization monomer is 3,5-diaminobenzoic acid;
Prepare AB needed for two generation ultrabranching polyamides
2amount and the AB needed for preparation generation ultrabranching polyamide of monomeric substance
2the ratio of the amount of monomeric substance is 7.0:3.0; AB needed for preparation three generations ultrabranching polyamide
2amount and the AB needed for preparation generation ultrabranching polyamide of monomeric substance
2the ratio of the amount of monomeric substance is 15.0:3.0; Prepare AB needed for four generation ultrabranching polyamides
2amount and the AB needed for preparation generation ultrabranching polyamide of monomeric substance
2the ratio of the amount of monomeric substance is 31.0:3.0;
Described solvent is deionized water, dehydrated alcohol or Virahol;
(2) preparation of polyurethane prepolymer precursor emulsion: in the reaction vessel with whipping appts, reflux condensing tube and thermometer of drying, add macromolecule polyol, polyisocyanates, dihydroxymethyl acid and solvent, be warming up to 40 ~ 80 DEG C, add catalyzer, slowly be warming up to 80 ~ 90 DEG C, constant temperature stirs 1 ~ 8h; Reduce temperature to 30 ~ 50 DEG C, add neutralizing agent, after reaction 10 ~ 90min, under high-speed stirring, deionized water is slowly instilled reaction vessel and carry out emulsion dispersion, obtain the polyurethane prepolymer precursor emulsion that solid content is 8 ~ 80%;
Wherein, described macromolecule polyol is Polyoxypropylene diol NJ-210, NJ-220, NJ-330, polyethylene oxide and polytetrahydrofuran;
Described polyisocyanates is aliphatic diisocyanate, isophorone diisocyanate, and the mol ratio of polyisocyanates and macromolecule polyol is 1.5 ~ 2.5: 1;
Described dihydroxymethyl acid is dimethylol propionic acid or dimethylolpropionic acid, and dihydroxymethyl acid is 0.9 ~ 1.0:1 with the mol ratio of macromolecule polyol;
Described solvent is DMF or methyl tertiary butyl ether, and itself and macromolecule polyol mass ratio are 0.5 ~ 20:1;
Described catalyzer is organotin, and as tin dilaurate diisobutyl tin, stannous octoate, two (dodecyl sulphur) dibutyl tin, dibutyltin diacetate, consumption is 1 ~ 2;
Described neutralizing agent is trialkyl or alkyl amine, pyridines, pyroles and composition thereof;
(3) ultrabranching polyamide and base polyurethane prepolymer for use as emulsion blending: dropped into by solvent in reactor, controls temperature in the kettle 25 ~ 60 DEG C; Add polyurethane prepolymer precursor emulsion and other resins successively, stir 2 ~ 4 h; By silica flour, ultrabranching polyamide, auxiliary agent is disposable adds in still, control temperature 25 ~ 70 DEG C, stirs 2 ~ 6 h; The material mixed flows in storage tank for subsequent use by kettle device, keeps storage tank internal temperature 10 ~ 35 DEG C;
Wherein, described base polyurethane prepolymer for use as quality of the emulsion number is 30;
Described ultrabranching polyamide is step (1) made ultrabranching polyamide one to four generation;
Described solvent is one or more mixed solvents in benzene,toluene,xylene, butanone, pimelinketone, ethyl acetate, propyl carbinol;
Other resins described are nitrocellulose, cellulose acetate butyrate or supervinyi chloride resin;
Described auxiliary agent is one or more combinations in flow agent, slip(ping)agent, wetting agent, thermo-stabilizer, wherein flow agent is polyacrylic acid, carboxymethyl cellulose, slip(ping)agent is polyethylene wax, Poly Propylene Wax, and wetting agent is sapn, tween, and thermo-stabilizer is glyceryl ester.
6. described preparation, containing the method for the anodized aluminium Subbing resins of ultrabranching polyamide, is characterized in that according to claim 5, in the preparation process of step (1) ultrabranching polyamide, and polymerization temperature 80 DEG C, time 5h; Described solvent is deionized water.
7. described preparation is containing the method for the anodized aluminium Subbing resins of ultrabranching polyamide according to claim 5, and it is characterized in that, in the preparation process of step (2) polyurethane prepolymer precursor emulsion, described macromolecule polyol is NJ-220; Described polyisocyanates is isophorone diisocyanate, and the mol ratio of polyisocyanates and macromolecule polyol is 2.0: 1; Described dihydroxymethyl acid is dimethylol propionic acid, and the mol ratio of itself and macromolecule polyol is 1.0:1; Described solvent is DMF, and itself and macromolecule polyol mass ratio are 10:1; Described neutralizing agent is triethylamine.
8. described preparation contains the method for the anodized aluminium Subbing resins of ultrabranching polyamide according to claim 5, it is characterized in that, in the preparation process of step (2) polyurethane prepolymer precursor emulsion, system is warming up to 60 DEG C of instillation catalyst dibutyltin cinnamic acid diisobutyl tin, and persistently overheating to 85 DEG C of sustained reaction 6h; After adding neutralizing agent, at 40 DEG C, react 50min, regulation system pH is 7 ~ 8; Base polyurethane prepolymer for use as emulsion solid content 30%.
9. described preparation contains the method for the anodized aluminium Subbing resins of ultrabranching polyamide according to claim 5, it is characterized in that, in step (3) ultrabranching polyamide and base polyurethane prepolymer for use as emulsion blending process, described ultrabranching polyamide is step (1) made ultrabranching polyamide two generation, and mass fraction is 5; Described solvent is propyl carbinol, and its mass fraction is 50; Other resins described are nitrocellulose, and its mass fraction is 6; Described auxiliary agent is flow agent polyacrylic acid, and its mass fraction is 0.8; Silica flour mass fraction is 10.2.
10. described preparation contains the method for the anodized aluminium Subbing resins of ultrabranching polyamide according to claim 5, it is characterized in that, in step (3) ultrabranching polyamide and base polyurethane prepolymer for use as emulsion blending process, temperature 30 DEG C time blended, stirs 3 h after adding polyurethane prepolymer precursor emulsion and other resins successively; Disposable add silica flour, ultrabranching polyamide, auxiliary agent after stir 4h.
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105667109A (en) * | 2016-01-13 | 2016-06-15 | 宁波创源文化发展股份有限公司 | Gold blocking method for printing paper |
| CN109337466A (en) * | 2018-09-26 | 2019-02-15 | 江苏乘鹰新材料股份有限公司 | A kind of anodized aluminium chromatograph coating of the high hiding rare of environment-friendly type and preparation method thereof |
| CN111087962A (en) * | 2019-12-26 | 2020-05-01 | 扬州市祥华新材料科技有限公司 | Preparation and method of aqueous back adhesive for alumite gold stamping foil |
| CN111234157A (en) * | 2020-03-09 | 2020-06-05 | 江苏科技大学 | Reactive extrusion preparation method of flame-retardant hyperbranched polyamide 6 elastomer |
| CN114806162A (en) * | 2022-04-18 | 2022-07-29 | 江阴市宏丰塑业有限公司 | Glass fiber reinforced low-melting-point nylon 56 material and preparation method thereof |
| CN116144137A (en) * | 2023-03-14 | 2023-05-23 | 绍兴君合新材料科技有限公司 | Preparation method of hyperbranched polyurethane amide toughened ABS plastic |
| CN117416113A (en) * | 2023-10-11 | 2024-01-19 | 常州佳尔科仿真器材有限公司 | Lightweight multilayer multiband high-reflection TPU composite material for false target |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1511907A (en) * | 2002-12-30 | 2004-07-14 | 罗运军 | Double component anion water polyurethane dispersion |
| CN101177475A (en) * | 2007-11-02 | 2008-05-14 | 湖南大学 | Method for synthesizing branch polyurethane capable of being ultraviolet solidified |
| CN103588976A (en) * | 2013-10-24 | 2014-02-19 | 江苏大学 | Synthesis method of unsaturated hyperbranched polyamides |
-
2015
- 2015-07-14 CN CN201510410186.2A patent/CN104945891B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1511907A (en) * | 2002-12-30 | 2004-07-14 | 罗运军 | Double component anion water polyurethane dispersion |
| CN101177475A (en) * | 2007-11-02 | 2008-05-14 | 湖南大学 | Method for synthesizing branch polyurethane capable of being ultraviolet solidified |
| CN103588976A (en) * | 2013-10-24 | 2014-02-19 | 江苏大学 | Synthesis method of unsaturated hyperbranched polyamides |
Non-Patent Citations (1)
| Title |
|---|
| YUICHI ISHIDA ET AL: ""synthesis of hyperbranched aromatic polyamides starting from dendrons as ABx monomers:effect of monomer multiplicity on the degree of branching"", 《MACROMOLECULES》 * |
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| CN105667109A (en) * | 2016-01-13 | 2016-06-15 | 宁波创源文化发展股份有限公司 | Gold blocking method for printing paper |
| CN109337466A (en) * | 2018-09-26 | 2019-02-15 | 江苏乘鹰新材料股份有限公司 | A kind of anodized aluminium chromatograph coating of the high hiding rare of environment-friendly type and preparation method thereof |
| CN111087962A (en) * | 2019-12-26 | 2020-05-01 | 扬州市祥华新材料科技有限公司 | Preparation and method of aqueous back adhesive for alumite gold stamping foil |
| CN111234157A (en) * | 2020-03-09 | 2020-06-05 | 江苏科技大学 | Reactive extrusion preparation method of flame-retardant hyperbranched polyamide 6 elastomer |
| CN111234157B (en) * | 2020-03-09 | 2021-10-19 | 江苏科技大学 | Reactive extrusion preparation method of flame-retardant hyperbranched polyamide 6 elastomer |
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