CN104945565B

CN104945565B - A kind of electrochemical aluminium gold-stamped foil Subbing resins and preparation method thereof

Info

Publication number: CN104945565B
Application number: CN201510413590.5A
Authority: CN
Inventors: 张爱斌; 陈正宇
Original assignee: Yangzhou Xianghua New Material Technology Co Ltd
Current assignee: Yangzhou Xianghua New Material Technology Co Ltd
Priority date: 2015-07-14
Filing date: 2015-07-14
Publication date: 2018-07-06
Anticipated expiration: 2035-07-14
Also published as: CN104945565A

Abstract

The invention belongs to macromolecule synthesising technology fields, are related to a kind of electrochemical aluminium gold-stamped foil Subbing resins and preparation method thereof.Electrochemical aluminium gold-stamped foil Subbing resins disclosed in this invention gather for ultrabranching polyamide modified water-soluble（Urethane acrylate）（WPUA‑HBPs）Lotion.The invention also discloses the preparation method of lotion, including first preparing AB₂Pre- polycondensation monomer, then prepare the ultrabranching polyamide of different algebraically（HBPs）, then synthesis of super branched is polyamide modified aqueous poly-（Urethane acrylate）Performed polymer and emulsion dispersion, are eventually adding after acrylic ester monomer, acrylate monomer, reactive diluent and the abundant mixing of photoinitiator to obtain the final product.Ultrabranching polyamide viscosity is low, solubility property is good, unique three-dimensional globular structure includes numerous branched chain and terminal amino group, possibility is provided for modified WPUA pre-polymerization precursor emulsions, both with lard type the cutting after lotion film-forming can be caused to greatly improve again with aroma type structure, had excellent performance as electrochemical aluminium gold-stamped foil Subbing resins.

Description

A kind of electrochemical aluminium gold-stamped foil Subbing resins and preparation method thereof

Technical field

The invention belongs to macromolecule synthesising technology fields, are related to electrochemical aluminium gold-stamped foil Subbing resins more particularly to a kind of electricity Change gold stamping foil Subbing resins of aluminium and preparation method thereof.

Background technology

Compared with conventional solvent polyurethane (PU), aqueous poly- (urethane-acrylate) (WPUA) has become current gluing One of upstart of industry, decentralized medium are water, have the characteristics that safe and non-toxic, environmentally protective, even more it marches food, drug The advantageous weapon of packaging material, but single WPUA is faced with compatibility, film cutting property many drawbacks such as poor again, by it During for producing electrochemical aluminium gold-stamped foil glue-line, be extremely difficult to coating uniformly, thermoprint without firkin, without technical indicators such as flashes.Therefore, It needs to take cross-linking modified measure, adjusts WPUA inner molecular structures, requirement when adapting it in production to electrochemical aluminium thermoprinting.

Ultrabranching polyamide (HBPs) has the characteristics that viscosity is low, solubility property is good, and its highly branched three-dimensional space Between structure and numerous active function groups in the end of the chain can generate cross-linking reaction with WPUA systems, different algebraically, dosage HBPs can quantify a certain physicochemical property of modified Subbing resins again, so as to which existing Subbing resins be overcome to dissolve in actual production Property it is poor, optical clarity is low, cutting property many defects such as bad.

At present, the preparation of WPUA-HBPs mainly includes：

(1) preparation of ultrabranching polyamide：AB is synthesized first₂Between the pre- polycondensation monomer of type, wherein A and B functional groups itself not Occur any chemical reaction, and go deep into as the reaction time promotes with reaction process, each functional group for participating in reaction is active It is constant, in polymerization process, some by-products can be inevitably generated, and these by-products do not interfere with anticipation reaction substantially Progress；Again by AB obtained₂Pre- polycondensation monomer autohemagglutination in certain proportion, obtains the ultrabranching polyamide (HBPs- of different algebraically G1、HBPs-G2、HBPs-G3、HBPs-G4……).For example, the patent CN103588976 that inventor submits.For another example, overspend Synthesis, characterization and its influence to aqueous polyurethane film properties of fluidized polymer, material Leader, 2013,27 (11)：85~87, It reports and Michael's addition is carried out at 35 DEG C with diethanol amine (DEA) and methyl methacrylate (MMA), AB is made before this₂ The pre- polycondensation monomer of type, and its autohemagglutination is obtained into a series of dissaving polymer (H1~3) of different algebraically, end group number, with infrared colour (FT-IR spectrum) is composed respectively to AB₂Pre- polycondensation monomer and respectively for polymer carry out structural characterization, and to each generation polymer spy Property viscosity characterization, as a result, it has been found that respectively very much like for molecular structure between dissaving polymer, and its intrinsic viscosity is then with algebraically Increase and continuously decrease, this discovery is not only to prepare the HBPs of different algebraically to provide scientific basis, more improves electrification Aluminium glue layer Resin Flow difference discloses new thinking.

(2) preparation of WPUA-HBPs lotions：It is different with polyfunctionality polyether polyol (NJ-220), isophorone two first Cyanate (IPDI) and dihydromethyl propionic acid (DMPA) preparation-NCO sealing end base polyurethane prepolymer for use as, then using TEA as neutralizer, no Same algebraically, dosage ultrabranching polyamide for modifying agent, be prepared a series of ultrabranching polyamide modified water-solubles it is poly- (urethane- Acrylate) lotion (WPUA-HBPs-G1, WPUA-HBPs-G2, WPUA-HBPs-G3, WPUA-HBPs-G4 ...).For example, Influence of number of functional groups of hyperbranched polyol on cure kinetics and physical properties of polyurethanes,Journal of Polymer Science: Part A:Polymer Chemistry,2009,47(3):731~745, it was recently reported that dissaving structure is introduced into polyaminoester emulsion In the middle.After testing, the introducing of dissaving structure to form more cross-linked networks inside polyaminoester emulsion system, Gu Water resistance, thermal stability, cutting property are also obviously improved after chemical conversion film.The patent CN103588949 that inventor submits for another example.

Existing electrochemical aluminium gold-stamped foil is frequently encountered hot stamping pattern firkin, flash in thermoprint carrier, and finished product solvent is residual The problems such as staying detection unqualified, in the present invention, by using aqueous Subbing resins (WPUA-HBPs lotions) instead of conventional solvent Property resin, so as to overcome problem of solvent residual.

Invention content

The purpose of the present invention is to solve electrochemical aluminium gold-stamped foil Subbing resins dissolvent residuals, disclose a kind of hyperbranched poly Aqueous poly- (urethane-acrylate) (WPUA-HBPs) lotion of amide modifications and preparation method thereof.

A kind of electrochemical aluminium gold-stamped foil Subbing resins are that ultrabranching polyamide modified water-soluble is poly- (urethane-acrylate) (WPUA-HBPs) lotion.

A kind of preparation method of electrochemical aluminium gold-stamped foil Subbing resins measures the poly- (urethane-the third of ultrabranching polyamide modified water-soluble Olefin(e) acid ester) (WPUA-HBPs) pre-polymerization precursor emulsion, it adds in acrylic ester monomer, acrylate monomer, reactive diluent and light and draws Send out the abundant mixing of agent after to obtain the final product, wherein, the quality of poly- (urethane-acrylate) the pre-polymerization precursor emulsion of ultrabranching polyamide modified water-soluble Number is 40~60 parts, and the mass fraction of acrylic ester monomer is 1 part, and the mass fraction of acrylate monomer is 1 part, activity The mass fraction of diluent is 40~65 parts, and the mass fraction of photoinitiator is 1~5 part；

The acrylic ester monomer is acrylic acid (AC), methacrylic acid (MAA), methyl acrylate (MAC) or methyl Hydroxy-ethyl acrylate (HEMA), preferably hydroxyethyl methacrylate (HEMA), add in when preferably system temperature is adjusted to 60 DEG C Hydroxyethyl methacrylate (HEMA)；

The acrylate monomer is methyl acrylate, ethyl acrylate, 2- methyl methacrylates, 2- methacrylic acids Ethyl ester or tri (propylene glycol) diacrylate (TPGDA)；

The reactive diluent is n-butyl acrylate-styrene (BA-St), n-butyl acrylate-tripropylene glycol is double Acrylate (BA-TPGDA) or n-butyl acrylate-trimethylolpropane trimethacrylate (BA-TMPTA)；

The photoinitiator is 2- hydroxy-2-methyl -1- phenyl -1- acetone (Darocur 1173), 1- hydroxy-cyclohexyls Phenyl ketone (Irgacure 184) or 2,2- dimethyl -2- phenyl acetophenones (Irgacure 651).

In the more excellent disclosed example of the present invention, the mass fraction proportioning of each component is pre-polymerization precursor emulsion：Bing olefin(e) acid esters Dan Ti ︰ It is 57 ︰, 1 ︰, 1 ︰, 3 ︰ 40 that third alkene acid ester monomer ︰ light, which draws hair agent ︰ reactive diluents, and reactive diluent contracts for n-butyl acrylate-three Propylene glycol double methacrylate (BA-TPGDA).

Poly- (urethane-acrylate) (WPUA-HBPs) the pre-polymerization precursor emulsion of ultrabranching polyamide modified water-soluble of the present invention, Preparation method, including first preparing AB₂Pre- polycondensation monomer, then the ultrabranching polyamide (HBPs) of different algebraically is prepared, then closed After into poly- (urethane-acrylate) performed polymer of ultrabranching polyamide modified water-soluble and emulsion dispersion to obtain the final product.

Poly- (urethane-acrylate) (WPUA-HBPs) performed polymer of ultrabranching polyamide modified water-soluble disclosed in this invention The preparation method of lotion carries out as steps described below：

Maleic anhydride (MA) and solvent are added in step 1, reaction vessel, stirs to MA be completely dissolved at room temperature, is delayed Slow dropwise addition diethylene triamine (DETA) and solvent, 5~15 DEG C, 5~20min of mixing time of reaction temperature, rotating speed 1000~ 3000r/min, obtains white flock suspension, and vacuum distillation removes dry under room temperature after solvent, obtains white powder；Wherein, The molar ratio of DETA and MA is 1.0~1.2：1, preferred molar ratio 1.05：1, the solvent for acetone, butanone, isopropanol or Isosorbide-5-Nitrae-dioxane, solvent are 5~20mL with the volume mass ratio of corresponding solute:1g, preferably 10mL:Isosorbide-5-Nitrae-dioxane of 1g As the solvent of MA and DETA, preferable reaction temperature is 10 DEG C, time 15min, mixing speed 2000r/min；

Step 2, in the reaction vessel equipped with blender, thermometer, add in p-aminobenzoic acid (PABA) and solvent, room The lower stirring of temperature is slowly added to di-tert-butyl dicarbonate ((Boc) to being completely dissolved₂O), micro iodine powder makees catalyst, 30~60 DEG C Lower reaction 1~4h, 600~1000r/min of mixing speed；Vacuum distillation adds in excessive thionyl chloride after removing most solvents Acyl chloride reaction is carried out, it is sub- that unreacted dichloro is removed under reduced pressure in 0~5 DEG C, 6~8h of reaction time of reaction temperature after reaction Sulfone；Wherein, the molar ratio of di-tert-butyl dicarbonate and p-aminobenzoic acid is 1.0~1.05:1, more excellent molar ratio is 1.02:1, The solvent be Isosorbide-5-Nitrae-dioxane, n,N-Dimethylformamide (DMF) or methyl tertiary butyl ether(MTBE) (MTBE), solvent with to amino The volume mass ratio of benzoic acid (PABA) is 6~10mL:1g, preferably 8mL:The N,N-dimethylformamide (DMF) of 1g is as molten Agent, preferable reaction temperature is 40 DEG C, time 2h, mixing speed 800r/min；During acyl chloride reaction, thionyl chloride and p-aminophenyl The molar ratio of formic acid is 1.5~5.0:1, preferably 4.0:1,60 DEG C of reaction temperature, time 6h；

Step 3,1~2 drop triethylamine (TEA) be catalyzed under, product and step 1 gained white powder acyl is made in step 2 Amination, reaction time are 3~9h, and temperature is 10~80 DEG C, then is removed with the mixed solution of trifluoroacetic acid (TFA) and sodium bicarbonate Di-tert-butyl dicarbonate ((Boc)₂O), 0.5~6h of reaction time, 10~60 DEG C of temperature, products therefrom filtering drying, drying temperature 30~80 DEG C of degree, duration 2~for 24 hours, obtain AB₂Pre- polycondensation monomer；Wherein, step 1 gained white powder and p-aminophenyl first are weighed Sour (PABA) molar ratio is 1:1, the catalysis reaction 6h preferably at 60 DEG C；The molar ratio of the trifluoroacetic acid and p-aminobenzoic acid It is 1.0~1.5:1, more excellent molar ratio is 1.05:1, the molar ratio of sodium bicarbonate and trifluoroacetic acid is 1.0~1.02:1, it is more excellent 1.0:1, preferably 30 DEG C of reaction temperature, time 2h, 50 DEG C of product drying temperature, duration 12h；

Step 4, accurate control material ratio weigh AB₂Pre- polycondensation monomer, ethylenediamine (EDA) and solvent are added in equipped with stirring Stick, reflux condensing tube, thermometer reaction vessel in, AB₂Pre- polycondensation monomer adds in obtain different algebraically polymer in batches, slowly System is warming up to 50~140 DEG C, reacts 4~14h, glassy yellow liquid is obtained, after vacuum distillation removes most solvents, is put into In 60 DEG C~100 DEG C dry 24~72h in vacuum drying chamber, through cooling down, grinding, gained yellow powder is the super of different algebraically Branched polyamide (HBPs-G1, HBPs-G2, HBPs-G3, HBPs-G4)；Wherein, in the synthesis of super branched polyamide stage, strictly Control material ratio, works as AB₂The molar ratio of monomer and ethylenediamine (EDA) is 2:When 1, generation ultrabranching polyamide (HBPs- is made G1)；AB₂The molar ratio of monomer and EDA are 4:When 1, two generation ultrabranching polyamides (HBPs-G2) are made；AB₂Monomer and EDA's rubs You are than being 8:When 1, three generations's ultrabranching polyamide (HBPs-G3) is made；AB₂The molar ratio of monomer and EDA are 16:When 1, it is made four For ultrabranching polyamide (HBPs-G4), polymerization temperature, time unification in 80 DEG C, 8h be it is best, the solvent be deionized water, The volume mass ratio of absolute ethyl alcohol or isopropanol, preferably deionized water, solvent and EDA are 100~200mL:1g；It is preferred that it dries Temperature 70 C, duration 48h；

Step 5, in the dry reaction vessel with agitating device, reflux condensing tube and thermometer, be proportionally added into Macromolecule polyol, polyisocyanates, dihydroxymethyl acids and solvent are warming up to 40~80 DEG C, add in catalyst, slowly heat up To 80~90 DEG C, constant temperature stirs 1~8h；System is cooled to 30~80 DEG C, is slowly added to acrylic ester monomer, specific generation HBPs, the 1~8h of sustained response of number, content, control temperature is at 30~50 DEG C, and it is 7~8 to add in neutralizer regulation system pH, instead After answering 10~90min, deionized water is slowly dropped into carry out emulsion dispersion under high velocity agitation, it is 8~80% to obtain solid content WPUA-HBPs pre-polymerization precursor emulsions, wherein, the macromolecule polyol for Polyoxypropylene diol NJ-210, NJ-220, NJ-330, polyethylene oxide or PolyTHF, preferably NJ-220；The polyisocyanates is aliphatic diisocyanate (ADI) or isophorone diisocyanate (IPDI), the molar ratio 1.5~2.5 of polyisocyanates and macromolecule polyol:1, it is excellent The molar ratio for selecting isophorone diisocyanate (IPDI) and macromolecule polyol is 2.0:1；The dihydroxymethyl acids is two The molar ratio of hydroxymethyl propionic acid (DMPA) or dimethylolpropionic acid (DMBA), dihydroxymethyl acids and macromolecule polyol is 0.9 ~1.02:1, the preferably molar ratio of dihydromethyl propionic acid and macromolecule polyol is 1:1；The solvent be N, N- dimethyl formyls Amine (DMF) or methyl tertiary butyl ether(MTBE) (MTBE), the volume ratio with NJ-220 are 0.5~2:1, preferably solvent be N, N- diformazans Base formamide (DMF), the volume mass ratio with NJ-220 are 1mL:1g；The catalyst is organotin, such as tin dilaurate two Isobutyl group tin (T-12), stannous octoate, two (dodecyl sulphur) dibutyl tins or dibutyltin diacetate, the neutralizer are three Alkyl or alkyl amine, pyridines, pyroles and its mixture preferably select triethylamine (TEA), the rotating speed 2000r/ at 40 DEG C Min is adjusted, and adjusts pH value 7~8；Solid content is excellent 30%.

Optimum operation is in actual mechanical process：System is warming up to 60 DEG C and instills 1 drop tin dilaurate diisobutyl tin (T- 12), and persistently overheating to 85 DEG C, sustained response 6h at such a temperature；The HBPs algebraically added in was one to four generation, and dosage accounts for The 0.1~50% of HBP-WPUA emulsion system total solid contents, is preferably controlled within 1~10%, reaction time 60min.

WPUA-HBPs lotions obtained by the present invention are moved into film-forming in membranous disc, surface drying 10 under natural conditions~ 40h, 20~50s under ultraviolet light, obtain WPUA-HBPs solid films, under natural conditions surface drying for 24 hours, and in ultraviolet lighting Penetrate lower 30s, you can obtain the WPUA-HBPs solid films of optimal properties.

Change Subbing resins system cross-linked state by introducing dissaving structure, WPUA-HBPs cured films are prepared, lead to Overstretching experiment measures the elongation at break of each cured film, filters out best algebraically, the dosage of modifying agent.

Poly- (urethane-the acrylate) (WPUA- of ultrabranching polyamide modified water-soluble according to obtained by the present invention discloses method HBPs) lotion, can be as electrochemical aluminium gold-stamped foil Subbing resins.Subbing resins solid content mainly influences the gold stamping of electrochemical aluminum foil Effect, different pattern and gold stamping area have corresponding solid content, therefore Subbing resins solid content can only pass through practical electrification Aluminium foil production needs to be adjusted.In addition, Subbing resins viscosity mainly influences coating machine working performance, resin viscosity is led compared with conference Cause is unevenly coated, gold stamping to be susceptible to firkin, picking phenomenon, therefore is suitably introduced into entire resin system after dissaving structure Viscosity significantly reduces and is conducive to the uniformity of its coating.Lard type AB disclosed in patent CN201310502908.8₂Type is pre- Polycondensation monomer, the full lard type ultrabranching polyamide that autohemagglutination obtains are used for poly- (urethane-acrylate) lotion of modified water-soluble, curing Film mechanical performance especially elongation at break significantly improves, and is unfavorable for cutting of the Subbing resins during gold stamping.And by the fat Fat type AB₂The pre- polycondensation monomer of type is only as AB in the preparation present invention₂Raw material, with PABA, (Boc)₂O, the multistep reactions such as thionyl chloride Obtained fat/aroma type AB₂Pre- polycondensation monomer is then a kind of new compound, and the ultrabranching polyamide that autohemagglutination obtains is used for Poly- (urethane-acrylate) lotion of modified water-soluble, cured film cutting property will not reduce, this is conducive to gold stamping more accurate figure Case.

The part chemical reagent purity of the present invention, manufacturer are as follows：

MA (chemical pure, Sinopharm Chemical Reagent Co., Ltd.)；(analysis is pure, Chinese medicines group chemistry for Isosorbide-5-Nitrae-dioxane Reagent Co., Ltd)；DETA (analyzes pure, Sinopharm Chemical Reagent Co., Ltd.)；(analysis is pure, the examination of Chinese medicines group chemistry by TEA Agent Co., Ltd)；Deionized water (self-control, Yangzhou Xiang Hua new materials Science and Technology Ltd.)；NJ-220 (industrial goods, Qingdao space Field chemical company)；IPDI (industrial goods, German HUL companies)；DMPA (industrial goods, PERSTOP companies of Switzerland)；DMF (analysis is pure, Sinopharm Chemical Reagent Co., Ltd.)；T-12 (chemical pure, Chinese medicines group chemical reagents corporation)；HEMA (chemical pure, Jiangsu Chemical Co., Ltd. of Wuxi City Unionpay)；BA (chemical pure, Sinopharm Chemical Reagent Co., Ltd.)；TPGDA (chemical pure, traditional Chinese medicines Chemical reagent Co., Ltd of group)；Darocur 1173 (chemical pure, Solution on Chemical Reagents in Shanghai head factory).

Experimental method

(1) with KBr pressed disc methods, to AB₂Monomer, HBPs and pure WPUA lotions, part WPUA-HBPs lotions have carried out infrared Spectrum analysis, INFRARED SPECTRUM collection of illustrative plates are respectively shown in Fig. 1, Fig. 2.

(2) mechanical property of pure WPUA and part WPUA-HBPs cured films is determined, the results are shown in Table 1.

(3) pure WPUA and the ultraviolet-visible light light transmittance of part WPUA-HBPs cured films are determined, as a result such as Fig. 3 institutes Show.

Advantageous effect

The present invention is prepared for a kind of having both the dissaving polymer of lard type and aroma type structure, and be applied to modification Electrochemical aluminium gold-stamped foil Subbing resins.HBPs viscositys itself are low, solubility property is good, and unique three-dimensional globular structure includes numerous Branched chain and terminal amino group, possibility can be provided for modified WPUA pre-polymerization precursor emulsions, both with lard type and aroma type structure Can the cutting after lotion film-forming be greatly improved again, can finally be applied in the industrial production, become electrification The gold stamping foil Subbing resins of aluminium.In addition, WPUA pre-polymerizations precursor emulsion using water as decentralized medium, also functions to environmental protection certain tribute It offers, and the development for following coatings industry provides new approaches.

Description of the drawings

Fig. 1 is AB₂The infared spectrum of monomer and different algebraically HBPs；

Fig. 2 is the infared spectrum of pure WPUA lotions, part WPUA-HBPs lotions；

Fig. 3 is pure WPUA and the ultraviolet-visible light light transmittance curve figure of part WPUA-HBPs cured films.

Specific embodiment

With reference to example, the present invention is described in detail, so that those skilled in the art more fully understand the present invention, But the invention is not limited in following instances.

Blank test

9.81g MA and 98.06ml solvent Isosorbide-5-Nitrae-dioxane is added in a 250mL three-neck flasks, stir at room temperature to After MA is completely dissolved, DETA (10.83g)/Isosorbide-5-Nitrae-dioxane (103.17ml) solution, controlling reaction temperature 10 is slowly added dropwise DEG C, mixing time 15min, rotating speed 2000r/min.White flock suspension is obtained, vacuum distillation removes solvent Isosorbide-5-Nitrae-dioxane And it is dry under room temperature, it is spare to obtain white powder；In the reaction vessel equipped with blender, thermometer, 13.71g is added in PABA and 109.71ml DMF are stirred to it at room temperature after being completely dissolved, and are slowly added to 22.26g (Boc)₂O, and in 1.0mg iodine It is reacted under powder catalytic condition, control mixing speed 800r/min, reacts 2h at 40 DEG C；After vacuum distillation removes most solvents 47.58g thionyl chloride acyl chloride reactions are added in, controlling reaction temperature is removed under reduced pressure after reaction in 5 DEG C, reaction time 8h Unreacted thionyl chloride；Under 1d TEA catalytic conditions, and above-mentioned 20.122g white powders amidation, reaction time 6h, Temperature is 60 DEG C, finally removes Boc with the mixed solution of 11.97g TFA and 8.401g sodium bicarbonates, the reaction time is in 2h, temperature At 30 DEG C, obtained product filtering drying, 50 DEG C, time 12h, obtained AB of drying temperature₂Pre-polymerization monomer powders.It weighs 0.0601g EDA and 8.789g, 17.578g, 35.157g, 70.3136g AB₂Monomer powders, 100ml deionized waters add in dress Have stirring rod, reflux condensing tube, thermometer reaction vessel in, be to slowly warm up to 80 DEG C, react 8h, obtain glassy yellow liquid, subtract It after the most water of pressure distillation removal, is put into vacuum drying chamber and 48h is further dried in 70 DEG C, through cooling down, grinding, gained is yellow Color powder is the ultrabranching polyamide (HBPs-G1, HBPs-G2, HBPs-G3, HBPs-G4) of different algebraically.

In the dry flask with agitating device, reflux condensing tube and thermometer, accurate addition 10g NJ-220, 2.22g IPDI, 0.67g DMPA and 10ml DMF are warming up to 60 DEG C, add in 2d T-12, are to slowly warm up to 85 DEG C, constant temperature stirs Mix 6h；System is cooled to 60 DEG C, is slowly added to 0.66g HEMA, sustained response 8h, control temperature adds in TEA, instead at 40 DEG C After answering 90min, 33.26g deionized waters are slowly dropped into reaction vessel progress emulsion dispersion under the conditions of rotating speed 2000r/min, Obtain the WPUA pre-polymerization precursor emulsions that solid content is 30%；The 5.7g lotions are weighed, add in 0.3g Darocur 1173,2.0g BA And 2.0g TPGDA, move into membranous disc after abundant mixing, under natural conditions surface drying for 24 hours, under ultraviolet light 30s to get To WPUA-HBPs solid films.

Embodiment 1

9.806g MA and 49.03ml solvent Isosorbide-5-Nitrae-dioxane are added in a 250mL three-neck flasks, is stirred at room temperature After being completely dissolved to MA, DETA (10.317g)/Isosorbide-5-Nitrae-dioxane (51.585ml) solution, control reaction temperature is slowly added dropwise 5 DEG C, mixing time 5min, rotating speed 1000r/min of degree.White flock suspension is obtained, vacuum distillation removes solvent Isosorbide-5-Nitrae-dioxy six It is dry under ring and room temperature, it is spare to obtain white powder；In the reaction vessel equipped with blender, thermometer, 13.714g is added in PABA and 82.284ml DMF are stirred to it at room temperature after being completely dissolved, and are slowly added to 21.825g (Boc)₂O, and in 0.5mg It is reacted under iodine powder catalytic condition, control mixing speed 1000r/min, reacts 4h at 60 DEG C；It is molten that vacuum distillation removes the overwhelming majority 59.48g thionyl chloride acyl chloride reactions are added in after agent, controlling reaction temperature depressurizes after reaction in 0 DEG C, reaction time 6h Remove unreacted thionyl chloride；Under 1d TEA catalytic conditions, with above-mentioned 20.122g white powders amidation, reaction time For 3h, temperature is 10 DEG C, finally removes Boc with the mixed solution of 11.402g TFA and 8.401g sodium bicarbonates, the reaction time exists 0.5h, temperature is at 10 DEG C, obtained product filtering drying, 30 DEG C, time 2h, obtained AB of drying temperature₂Pre-polymerization monomer powders. Weigh 0.0601gEDA and 8.789g, 17.578g, 35.157g, 70.3136g AB₂Monomer powders, 100ml deionized waters, add Enter equipped with stirring rod, reflux condensing tube, thermometer reaction vessel in, be to slowly warm up to 50 DEG C, react 4h, obtain glassy yellow liquid Body after vacuum distillation removes most water, is put into vacuum drying chamber and is further dried for 24 hours in 60 DEG C, through cooling down, grinding, Gained yellow powder is the ultrabranching polyamide (HBPs-G1, HBPs-G2, HBPs-G3, HBPs-G4) of different algebraically.

In the dry flask with agitating device, reflux condensing tube and thermometer, accurate addition 10g NJ-220, 1.667g IPDI, 0.604g DMPA and 5ml DMF are warming up to 40 DEG C, add in 1d T-12, are to slowly warm up to 80 DEG C, constant temperature stirs Mix 1h；System is cooled to 30 DEG C, is slowly added to 0.521g HEMA, 0.139g HBPs-G1-1%, sustained response 1h, control Temperature adds in TEA at 30 DEG C, after reacting 10min, is slowly dropped into 171.05g deionized waters under the conditions of rotating speed 1000r/min Reaction vessel carries out emulsion dispersion, obtains the WPUA-HBPs pre-polymerization precursor emulsions that solid content is 8%；The 5.7g lotions are weighed, are added in 0.3g Darocur 1173,2.0g BA and 2.0g TPGDA are moved into membranous disc after abundant mixing, surface drying under natural conditions 10h, 20s is to get to WPUA-HBPs solid films under ultraviolet light.

Embodiment 2

9.81g MA and 196.12ml solvent Isosorbide-5-Nitrae-dioxane are added in a 250mL three-neck flasks, is stirred at room temperature After being completely dissolved to MA, DETA (12.38g)/Isosorbide-5-Nitrae-dioxane (247.61ml) solution, controlling reaction temperature is slowly added dropwise 15 DEG C, mixing time 20min, rotating speed 3000r/min.White flock suspension is obtained, vacuum distillation removes solvent Isosorbide-5-Nitrae-dioxy six It is dry under ring and room temperature, it is spare to obtain white powder；In the reaction vessel equipped with blender, thermometer, 13.71g is added in PABA and 137.14ml DMF are stirred to it at room temperature after being completely dissolved, and are slowly added to 22.92g (Boc)₂O, and in 2.0mg iodine It is reacted under powder catalytic condition, control mixing speed 600r/min, reacts 1h at 30 DEG C；After vacuum distillation removes most solvents 17.844g thionyl chloride acyl chloride reactions are added in, controlling reaction temperature is removed under reduced pressure after reaction in 5 DEG C, reaction time 8h Unreacted thionyl chloride；Under 2d TEA catalytic conditions, and above-mentioned 20.122g white powders amidation, reaction time 9h, Temperature is 80 DEG C, finally removes Boc with the mixed solution of 17.10g TFA and 12.85g sodium bicarbonates, the reaction time is in 6h, temperature At 60 DEG C, obtained product filtering drying, 80 DEG C of drying temperature, the time for 24 hours, obtained AB₂Pre-polymerization monomer powders.It weighs 0.0601gEDA and 8.789g, 17.578g, 35.157g, 70.3136g AB₂Monomer powders, 100ml deionized waters add in dress Have stirring rod, reflux condensing tube, thermometer reaction vessel in, be to slowly warm up to 140 DEG C, react 14h, obtain glassy yellow liquid, After the most water of vacuum distillation removal, it is put into vacuum drying chamber and is further dried for 24 hours in 60 DEG C, through cooling down, grinding, gained Yellow powder is the ultrabranching polyamide (HBPs-G1, HBPs-G2, HBPs-G3, HBPs-G4) of different algebraically.

In the dry flask with agitating device, reflux condensing tube and thermometer, accurate addition 10g NJ-220, 2.78g IPDI, 0.68g DMPA and 20ml DMF are warming up to 80 DEG C, add in 2d T-12, are to slowly warm up to 90 DEG C, constant temperature stirs Mix 8h；System is cooled to 80 DEG C, is slowly added to 0.66g HEMA, 0.71g HBPs-G2-5%, sustained response 8h, control temperature Degree adds in TEA at 40 DEG C, after reacting 90min, is slowly dropped into 33.26g deionized waters instead under the conditions of rotating speed 3000r/min Container is answered to carry out emulsion dispersion, obtains the WPUA-HBPs pre-polymerization precursor emulsions that solid content is 30%；The 5.7g lotions are weighed, are added in 0.3g Darocur 1173,2.0g BA and 2.0g TPGDA are moved into membranous disc after abundant mixing, surface drying under natural conditions 10h, 20s is to get to WPUA-HBPs solid films under ultraviolet light.

Embodiment 3

In the dry flask with agitating device, reflux condensing tube and thermometer, accurate addition 10g NJ-220, 2.78g IPDI, 0.68g DMPA and 20ml DMF are warming up to 80 DEG C, add in 2d T-12, are to slowly warm up to 90 DEG C, constant temperature stirs Mix 8h；System is cooled to 80 DEG C, is slowly added to 0.66g HEMA, 1.505g HBPs-G3-10%, sustained response 8h, control Temperature adds in TEA at 40 DEG C, after reacting 90min, is slowly dropped into 3.76g deionized waters instead under the conditions of rotating speed 3000r/min Container is answered to carry out emulsion dispersion, obtains the WPUA-HBPs pre-polymerization precursor emulsions that solid content is 80%；The 5.0g lotions are weighed, are added in 1.0g Darocur 1173,2.0g BA and 2.0g TPGDA are moved into membranous disc after abundant mixing, surface drying under natural conditions 40h, 50s is to get to WPUA-HBPs solid films under ultraviolet light.

Embodiment 4

In the dry flask with agitating device, reflux condensing tube and thermometer, accurate addition 10g NJ-220, 2.22g IPDI, 0.67g DMPA and 10ml DMF are warming up to 60 DEG C, add in 2d T-12, are to slowly warm up to 85 DEG C, constant temperature stirs Mix 6h；System is cooled to 60 DEG C, is slowly added to 0.66g HEMA, 0.71g HBPs-G4-10%, sustained response 8h, control temperature Degree adds in TEA at 40 DEG C, after reacting 90min, is slowly dropped into 33.26g deionized waters instead under the conditions of rotating speed 2000r/min Container is answered to carry out emulsion dispersion, obtains the WPUA-HBPs pre-polymerization precursor emulsions that solid content is 30%；The 5.7g lotions are weighed, are added in 0.3g Darocur 1173,2.0g BA and 2.0g TPGDA are moved into membranous disc after abundant mixing, surface drying under natural conditions For 24 hours, under ultraviolet light 30s to get to WPUA-HBPs solid films.

Embodiment 5

9.81g MA and 98.06ml solvent isopropanols are added in a 250mL three-neck flasks, are stirred at room temperature complete to MA After dissolving, DETA (10.83g)/isopropanol (103.17ml) solution, 10 DEG C of controlling reaction temperature, mixing time is slowly added dropwise 15min, rotating speed 2000r/min.White flock suspension is obtained, vacuum distillation is removed and done under solvent Isosorbide-5-Nitrae-dioxane and room temperature It is dry, it is spare to obtain white powder；In the reaction vessel equipped with blender, thermometer, add in 13.71g PABA and 109.71ml DMF are stirred to it at room temperature after being completely dissolved, and are slowly added to 22.26g (Boc)₂O, and be catalyzed in 1.0mg iodine powder Under the conditions of react, control mixing speed 800r/min reacts 2h at 40 DEG C；Vacuum distillation adds in after removing most solvents 47.58g thionyl chloride acyl chloride reactions, controlling reaction temperature are removed under reduced pressure not anti-after reaction at 5 DEG C, reaction time 8h The thionyl chloride answered；Under 1d TEA catalytic conditions, with above-mentioned 20.122g white powders amidation, reaction time 6h, temperature It is 60 DEG C, finally removes Boc with the mixed solution of 11.97g TFA and 8.401g sodium bicarbonates, the reaction time, temperature was 30 in 2h DEG C, obtained product filtering drying, 50 DEG C, time 12h, obtained AB of drying temperature₂Pre-polymerization monomer powders.Weigh 0.0601g EDA and 8.789g, 17.578g, 35.157g, 70.3136g AB₂Monomer powders, 100ml deionized waters are added in equipped with stirring Stick, reflux condensing tube, thermometer reaction vessel in, be to slowly warm up to 80 DEG C, react 8h, obtain glassy yellow liquid, be evaporated under reduced pressure After the most water of removal, it is put into vacuum drying chamber and 48h is further dried in 70 DEG C, through cooling down, grinding, gained yellow powder The ultrabranching polyamide (HBPs-G1, HBPs-G2, HBPs-G3, HBPs-G4) of as different algebraically.

In the dry flask with agitating device, reflux condensing tube and thermometer, accurate addition 10g NJ-220, 2.22g IPDI, 0.67g DMPA and 10ml DMF are warming up to 60 DEG C, add in 2d T-12, are to slowly warm up to 85 DEG C, constant temperature stirs Mix 6h；System is cooled to 60 DEG C, is slowly added to 0.66g MAC, 0.71g HBPs-G4-10%, sustained response 8h, control temperature Degree adds in TEA at 40 DEG C, after reacting 90min, is slowly dropped into 33.26g deionized waters instead under the conditions of rotating speed 2000r/min Container is answered to carry out emulsion dispersion, obtains the WPUA-HBPs pre-polymerization precursor emulsions that solid content is 30%；The 5.7g lotions are weighed, are added in 0.3g Irgacure 184,2.0g BA and 2.0g TPGDA are moved into membranous disc after abundant mixing, surface drying under natural conditions For 24 hours, under ultraviolet light 30s to get to WPUA-HBPs solid films.

Embodiment 6

9.81g MA and 98.06ml solvent Isosorbide-5-Nitrae-dioxane is added in a 250mL three-neck flasks, stir at room temperature to After MA is completely dissolved, DETA (10.83g)/Isosorbide-5-Nitrae-dioxane (103.17ml) solution, controlling reaction temperature 10 is slowly added dropwise DEG C, mixing time 15min, rotating speed 2000r/min.White flock suspension is obtained, vacuum distillation removes solvent Isosorbide-5-Nitrae-dioxane And it is dry under room temperature, it is spare to obtain white powder；In the reaction vessel equipped with blender, thermometer, 13.71g is added in PABA and 109.71ml Isosorbide-5-Nitraes-dioxane, are stirred to it at room temperature after being completely dissolved, and are slowly added to 22.26g (Boc)₂O, and It is reacted under 1.0mg iodine powder catalytic conditions, control mixing speed 800r/min, reacts 2h at 40 DEG C；Vacuum distillation removes big absolutely 47.58g thionyl chloride acyl chloride reactions are added in after partial solvent, at 5 DEG C, reaction time 8h, reaction terminates controlling reaction temperature After unreacted thionyl chloride is removed under reduced pressure；Under 1d TEA catalytic conditions, and above-mentioned 20.122g white powders amidation, instead It is 6h between seasonable, temperature is 60 DEG C, finally removes Boc with the mixed solution of 11.97g TFA and 8.401g sodium bicarbonates, during reaction Between in 2h, temperature is at 30 DEG C, obtained product filtering drying, 50 DEG C, time 12h, obtained AB of drying temperature₂Pre- polycondensation monomer powder End.Weigh 0.0601g EDA and 8.789g, 17.578g, 35.157g, 70.3136g AB₂Monomer powders, 100ml deionizations Water, add in equipped with stirring rod, reflux condensing tube, thermometer reaction vessel in, be to slowly warm up to 80 DEG C, react 8h, obtain bright orange Color liquid after vacuum distillation removes most water, is put into vacuum drying chamber and 48h is further dried in 70 DEG C, through cooling down, grinding Mill, gained yellow powder is the ultrabranching polyamide (HBPs-G1, HBPs-G2, HBPs-G3, HBPs-G4) of different algebraically.

In the dry flask with agitating device, reflux condensing tube and thermometer, accurate addition 10g NJ-220, 2.22g IPDI, 0.67g DMPA and 10ml DMF are warming up to 60 DEG C, add in 2d bis- (dodecyl sulphur) dibutyl tin, slowly 85 DEG C are warming up to, constant temperature stirring 6h；System is cooled to 60 DEG C, is slowly added to 0.66g HEMA, 0.71g HBPs-G4-10%, Sustained response 8h, control temperature add in TEA at 40 DEG C, after reacting 90min, remove 33.26g under the conditions of rotating speed 2000r/min Ionized water is slowly dropped into reaction vessel and carries out emulsion dispersion, obtains the WPUA-HBPs pre-polymerization precursor emulsions that solid content is 30%；It weighs The 5.7g lotions add in 0.3g Irgacure 651,2.0g BA and 2.0g TPGDA, are moved into after abundant mixing into membranous disc, For 24 hours, 30s is to get to WPUA-HBPs solid films under ultraviolet light for surface drying under natural conditions.

Embodiment 7

9.81g MA and 98.06ml solvent butanone is added in a 250mL three-neck flasks, is stirred at room temperature completely molten to MA After solution, DETA (10.83g)/butanone (103.17ml) solution, 10 DEG C of controlling reaction temperature, mixing time is slowly added dropwise 15min, rotating speed 2000r/min.White flock suspension is obtained, vacuum distillation is removed and done under solvent Isosorbide-5-Nitrae-dioxane and room temperature It is dry, it is spare to obtain white powder；In the reaction vessel equipped with blender, thermometer, add in 13.71g PABA and 109.71ml DMF are stirred to it at room temperature after being completely dissolved, and are slowly added to 22.26g (Boc)₂O, and be catalyzed in 1.0mg iodine powder Under the conditions of react, control mixing speed 800r/min reacts 2h at 40 DEG C；Vacuum distillation adds in after removing most solvents 47.58g thionyl chloride acyl chloride reactions, controlling reaction temperature are removed under reduced pressure not anti-after reaction at 5 DEG C, reaction time 8h The thionyl chloride answered；Under 1d TEA catalytic conditions, with above-mentioned 20.122g white powders amidation, reaction time 6h, temperature It is 60 DEG C, finally removes Boc with the mixed solution of 11.97g TFA and 8.401g sodium bicarbonates, the reaction time, temperature was 30 in 2h DEG C, obtained product filtering drying, 50 DEG C, time 12h, obtained AB of drying temperature₂Pre-polymerization monomer powders.Weigh 0.0601g EDA and 8.789g, 17.578g, 35.157g, 70.3136g AB₂Monomer powders, 100ml deionized waters are added in equipped with stirring Stick, reflux condensing tube, thermometer reaction vessel in, be to slowly warm up to 80 DEG C, react 8h, obtain glassy yellow liquid, be evaporated under reduced pressure After the most water of removal, it is put into vacuum drying chamber and 48h is further dried in 70 DEG C, through cooling down, grinding, gained yellow powder The ultrabranching polyamide (HBPs-G1, HBPs-G2, HBPs-G3, HBPs-G4) of as different algebraically.

In the dry flask with agitating device, reflux condensing tube and thermometer, accurate addition 10g NJ-330, 2.22g ADI, 0.67g DMPA and 10ml DMF are warming up to 60 DEG C, add in 2d T-12, are to slowly warm up to 85 DEG C, constant temperature stirring 6h；System is cooled to 60 DEG C, is slowly added to 0.66g HEMA, 0.71g HBPs-G4-10%, sustained response 8h controls temperature At 40 DEG C, TEA is added in, after reacting 90min, 33.26g deionized waters are slowly dropped into reaction under the conditions of rotating speed 2000r/min Container carries out emulsion dispersion, obtains the WPUA-HBPs pre-polymerization precursor emulsions that solid content is 30%；The 5.7g lotions are weighed, are added in 0.3g Irgacure 651,2.0g BA and 2.0g St are moved into membranous disc after abundant mixing, under natural conditions surface drying for 24 hours, 30s is to get to WPUA-HBPs solid films under ultraviolet light.

Embodiment 8

9.81g MA and 98.06ml solvent Isosorbide-5-Nitrae-dioxane is added in a 250mL three-neck flasks, stir at room temperature to After MA is completely dissolved, DETA (10.83g)/Isosorbide-5-Nitrae-dioxane (103.17ml) solution, controlling reaction temperature 10 is slowly added dropwise DEG C, mixing time 15min, rotating speed 2000r/min.White flock suspension is obtained, vacuum distillation removes solvent Isosorbide-5-Nitrae-dioxane And it is dry under room temperature, it is spare to obtain white powder；In the reaction vessel equipped with blender, thermometer, 13.71g is added in PABA and 109.71ml MTBE are stirred to it at room temperature after being completely dissolved, and are slowly added to 22.26g (Boc)₂O, and in 1.0mg It is reacted under iodine powder catalytic condition, control mixing speed 800r/min, reacts 2h at 40 DEG C；Vacuum distillation removes most solvents 47.58g thionyl chloride acyl chloride reactions are added in afterwards, and at 5 DEG C, reaction time 8h, decompression after reaction removes controlling reaction temperature Remove unreacted thionyl chloride；Under 1d TEA catalytic conditions, with above-mentioned 20.122g white powders amidation, the reaction time is 6h, temperature are 60 DEG C, finally remove Boc with the mixed solution of 11.97g TFA and 8.401g sodium bicarbonates, the reaction time is in 2h, temperature It spends at 30 DEG C, obtained product filtering drying, 50 DEG C, time 12h, obtained AB of drying temperature₂Pre-polymerization monomer powders.It weighs 0.0601g EDA and 8.789g, 17.578g, 35.157g, 70.3136g AB₂Monomer powders, 120ml remove absolute ethyl alcohol, add in Equipped with stirring rod, reflux condensing tube, thermometer reaction vessel in, be to slowly warm up to 80 DEG C, react 8h, obtain glassy yellow liquid, After the most water of vacuum distillation removal, it is put into vacuum drying chamber and 48h is further dried in 70 DEG C, through cooling down, grinding, gained Yellow powder is the ultrabranching polyamide (HBPs-G1, HBPs-G2, HBPs-G3, HBPs-G4) of different algebraically.

In the dry flask with agitating device, reflux condensing tube and thermometer, accurate addition 10g NJ-220, 2.22g IPDI, 0.67g DMPA and 10ml DMF are warming up to 60 DEG C, add in 2d dibutyltin diacetates, are to slowly warm up to 85 DEG C, constant temperature stirring 6h；System is cooled to 60 DEG C, is slowly added to 0.66g HEMA, 0.71g HBPs-G4-10%, sustained response 8h, control temperature add in TEA at 40 DEG C, after reacting 90min, delay 33.26g deionized waters under the conditions of rotating speed 2000r/min The slow reaction vessel that instills carries out emulsion dispersion, obtains the WPUA-HBPs pre-polymerization precursor emulsions that solid content is 30%；Weigh the 5.7g breasts Liquid adds in 0.3g Darocur 1173,2.0g BA and 2.0g TPGDA, is moved into after abundant mixing into membranous disc, natural conditions For 24 hours, 30s is to get to WPUA-HBPs solid films under ultraviolet light for lower surface drying.

Embodiment 9

9.81g MA and 196.12ml solvent Isosorbide-5-Nitrae-dioxane are added in a 250mL three-neck flasks, is stirred at room temperature After being completely dissolved to MA, DETA (10.83g)/Isosorbide-5-Nitrae-dioxane (103.17ml) solution, controlling reaction temperature is slowly added dropwise 10 DEG C, mixing time 15min, rotating speed 2000r/min.White flock suspension is obtained, vacuum distillation removes solvent Isosorbide-5-Nitrae-dioxy six It is dry under ring and room temperature, it is spare to obtain white powder；In the reaction vessel equipped with blender, thermometer, 13.71g is added in PABA and 109.71ml DMF are stirred to it at room temperature after being completely dissolved, and are slowly added to 22.26g (Boc)₂O, and in 1.0mg iodine It is reacted under powder catalytic condition, control mixing speed 800r/min, reacts 2h at 40 DEG C；After vacuum distillation removes most solvents 47.58g thionyl chloride acyl chloride reactions are added in, controlling reaction temperature is removed under reduced pressure after reaction in 5 DEG C, reaction time 8h Unreacted thionyl chloride；Under 1d TEA catalytic conditions, and above-mentioned 20.122g white powders amidation, reaction time 6h, Temperature is 60 DEG C, finally removes Boc with the mixed solution of 11.97g TFA and 8.401g sodium bicarbonates, the reaction time is in 2h, temperature At 30 DEG C, obtained product filtering drying, 50 DEG C, time 12h, obtained AB of drying temperature₂Pre-polymerization monomer powders.It weighs 0.0601g EDA and 8.789g, 17.578g, 35.157g, 70.3136g AB₂Monomer powders, 100ml deionized waters add in dress Have stirring rod, reflux condensing tube, thermometer reaction vessel in, be to slowly warm up to 80 DEG C, react 8h, obtain glassy yellow liquid, subtract It after the most water of pressure distillation removal, is put into vacuum drying chamber and 48h is further dried in 70 DEG C, through cooling down, grinding, gained is yellow Color powder is the ultrabranching polyamide (HBPs-G1, HBPs-G2, HBPs-G3, HBPs-G4) of different algebraically.

In the dry flask with agitating device, reflux condensing tube and thermometer, accurate addition 10g NJ-220, 2.22g IPDI, 0.67g DMPA and 10ml DMF are warming up to 60 DEG C, add in 2d T-12, are to slowly warm up to 85 DEG C, constant temperature stirs Mix 6h；System is cooled to 60 DEG C, is slowly added to 0.66g HEMA, 0.71g HBPs-G4-10%, sustained response 8h, control temperature Degree adds in TEA at 40 DEG C, after reacting 90min, is slowly dropped into 33.26g deionized waters instead under the conditions of rotating speed 2000r/min Container is answered to carry out emulsion dispersion, obtains the WPUA-HBPs pre-polymerization precursor emulsions that solid content is 30%；The 5.7g lotions are weighed, are added in 0.3g Darocur 1173,2.0g BA and 2.0g TMPTA are moved into membranous disc after abundant mixing, surface drying under natural conditions For 24 hours, under ultraviolet light 30s to get to WPUA-HBPs solid films.

Embodiment 10

In the dry flask with agitating device, reflux condensing tube and thermometer, accurate addition 10g NJ-210, 2.22g IPDI, 0.67g DMPA and 10ml DMF are warming up to 60 DEG C, add in 2d T-12, are to slowly warm up to 85 DEG C, constant temperature stirs Mix 6h；System is cooled to 60 DEG C, is slowly added to 0.66g HEMA, 0.71g HBPs-G4-10%, sustained response 8h, control temperature Degree adds in TEA at 40 DEG C, after reacting 90min, is slowly dropped into 33.26g deionized waters instead under the conditions of rotating speed 2000r/min Container is answered to carry out emulsion dispersion, obtains the WPUA-HBPs pre-polymerization precursor emulsions that solid content is 30%；The 5.7g lotions are weighed, are added in 0.3g Darocur 1173,2.0g BA and 2.0g TPGDA are moved into membranous disc after abundant mixing, surface drying under natural conditions For 24 hours, under ultraviolet light 30s to get to WPUA-HBPs solid films.

Embodiment 11

9.81g MA and 98.06ml solvent Isosorbide-5-Nitrae-dioxane is added in a 250mL three-neck flasks, stir at room temperature to After MA is completely dissolved, DETA (10.83g)/Isosorbide-5-Nitrae-dioxane (103.17ml) solution, controlling reaction temperature 10 is slowly added dropwise DEG C, mixing time 15min, rotating speed 2000r/min.White flock suspension is obtained, vacuum distillation removes solvent Isosorbide-5-Nitrae-dioxane And it is dry under room temperature, it is spare to obtain white powder；In the reaction vessel equipped with blender, thermometer, 13.71g is added in PABA and 109.71ml DMF are stirred to it at room temperature after being completely dissolved, and are slowly added to 22.26g (Boc)₂O, and in 1.0mg iodine It is reacted under powder catalytic condition, control mixing speed 800r/min, reacts 2h at 40 DEG C；After vacuum distillation removes most solvents 17.844g thionyl chloride acyl chloride reactions are added in, controlling reaction temperature is removed under reduced pressure after reaction in 5 DEG C, reaction time 8h Unreacted thionyl chloride；Under 1d TEA catalytic conditions, and above-mentioned 20.122g white powders amidation, reaction time 6h, Temperature is 60 DEG C, finally removes Boc with the mixed solution of 11.97g TFA and 8.401g sodium bicarbonates, the reaction time is in 2h, temperature At 30 DEG C, obtained product filtering drying, 50 DEG C, time 12h, obtained AB of drying temperature₂Pre-polymerization monomer powders.It weighs 0.0601g EDA and 8.789g, 17.578g, 35.157g, 70.3136g AB₂Monomer powders, 100ml deionized waters add in dress Have stirring rod, reflux condensing tube, thermometer reaction vessel in, be to slowly warm up to 80 DEG C, react 8h, obtain glassy yellow liquid, subtract It after the most water of pressure distillation removal, is put into vacuum drying chamber and 48h is further dried in 70 DEG C, through cooling down, grinding, gained is yellow Color powder is the ultrabranching polyamide (HBPs-G1, HBPs-G2, HBPs-G3, HBPs-G4) of different algebraically.

Embodiment 12

9.81g MA and 98.06ml solvent Isosorbide-5-Nitrae-dioxane is added in a 250mL three-neck flasks, stir at room temperature to After MA is completely dissolved, DETA (10.83g)/Isosorbide-5-Nitrae-dioxane (103.17ml) solution, controlling reaction temperature 10 is slowly added dropwise DEG C, mixing time 15min, rotating speed 2000r/min.White flock suspension is obtained, vacuum distillation removes solvent Isosorbide-5-Nitrae-dioxane And it is dry under room temperature, it is spare to obtain white powder；In the reaction vessel equipped with blender, thermometer, 13.71g is added in PABA and 109.71ml DMF are stirred to it at room temperature after being completely dissolved, and are slowly added to 22.26g (Boc)₂O, and in 1.0mg iodine It is reacted under powder catalytic condition, control mixing speed 800r/min, reacts 2h at 40 DEG C；After vacuum distillation removes most solvents 47.58g thionyl chloride acyl chloride reactions are added in, controlling reaction temperature is removed under reduced pressure after reaction in 5 DEG C, reaction time 8h Unreacted thionyl chloride；Under 1d TEA catalytic conditions, and above-mentioned 20.122g white powders amidation, reaction time 6h, Temperature is 60 DEG C, finally removes Boc with the mixed solution of 11.97g TFA and 8.401g sodium bicarbonates, the reaction time is in 2h, temperature At 30 DEG C, obtained product filtering drying, 50 DEG C, time 12h, obtained AB of drying temperature₂Pre-polymerization monomer powders.It weighs 0.0601g EDA and 8.789g, 17.578g, 35.157g, 70.3136g AB₂Monomer powders, 150ml absolute ethyl alcohols add in dress Have stirring rod, reflux condensing tube, thermometer reaction vessel in, be to slowly warm up to 80 DEG C, react 8h, obtain glassy yellow liquid, subtract It after the most water of pressure distillation removal, is put into vacuum drying chamber and 48h is further dried in 70 DEG C, through cooling down, grinding, gained is yellow Color powder is the ultrabranching polyamide (HBPs-G1, HBPs-G2, HBPs-G3, HBPs-G4) of different algebraically.

In the dry flask with agitating device, reflux condensing tube and thermometer, accurate addition 10g NJ-220, 2.22g IPDI, 0.67g DMPA and 10ml MTBE are warming up to 60 DEG C, add in 2d T-12, are to slowly warm up to 85 DEG C, constant temperature stirs Mix 6h；System is cooled to 60 DEG C, is slowly added to 0.66g MAA, 0.71g HBPs-G4-10%, sustained response 8h, control temperature Degree adds in TEA at 40 DEG C, after reacting 90min, is slowly dropped into 33.26g deionized waters instead under the conditions of rotating speed 2000r/min Container is answered to carry out emulsion dispersion, obtains the WPUA-HBPs pre-polymerization precursor emulsions that solid content is 30%；The 5.7g lotions are weighed, are added in 0.3g Darocur 1173,2.0g BA and 2.0g TPGDA are moved into membranous disc after abundant mixing, surface drying under natural conditions For 24 hours, under ultraviolet light 30s to get to WPUA-HBPs solid films.

Embodiment 13

9.81g MA and 100.20ml solvent Isosorbide-5-Nitrae-dioxane are added in a 250mL three-neck flasks, is stirred at room temperature After being completely dissolved to MA, DETA (10.83g)/Isosorbide-5-Nitrae-dioxane (103.17ml) solution, controlling reaction temperature is slowly added dropwise 10 DEG C, mixing time 15min, rotating speed 2000r/min.White flock suspension is obtained, vacuum distillation removes solvent Isosorbide-5-Nitrae-dioxy six It is dry under ring and room temperature, it is spare to obtain white powder；In the reaction vessel equipped with blender, thermometer, 13.71g is added in PABA and 109.71ml DMF are stirred to it at room temperature after being completely dissolved, and are slowly added to 20.05g (Boc)₂O, and in 1.0mg iodine It is reacted under powder catalytic condition, control mixing speed 800r/min, reacts 2h at 40 DEG C；After vacuum distillation removes most solvents 47.58g thionyl chloride acyl chloride reactions are added in, controlling reaction temperature is removed under reduced pressure after reaction in 5 DEG C, reaction time 8h Unreacted thionyl chloride；Under 1d TEA catalytic conditions, and above-mentioned 20.122g white powders amidation, reaction time 6h, Temperature is 60 DEG C, finally removes Boc with the mixed solution of 11.97g TFA and 8.401g sodium bicarbonates, the reaction time is in 2h, temperature At 30 DEG C, obtained product filtering drying, 50 DEG C, time 12h, obtained AB of drying temperature₂Pre-polymerization monomer powders.It weighs 0.0601g EDA and 8.789g, 17.578g, 35.157g, 70.3136g AB₂Monomer powders, 100ml deionized waters add in dress Have stirring rod, reflux condensing tube, thermometer reaction vessel in, be to slowly warm up to 80 DEG C, react 8h, obtain glassy yellow liquid, subtract It after the most water of pressure distillation removal, is put into vacuum drying chamber and 48h is further dried in 70 DEG C, through cooling down, grinding, gained is yellow Color powder is the ultrabranching polyamide (HBPs-G1, HBPs-G2, HBPs-G3, HBPs-G4) of different algebraically.

From attached drawing 1 as can be seen that AB₂Monomer is basically identical on position of functional group with HBPs-G1~4, especially each generation Dissaving polymer, infrared chromatography height is similar, shows the similitude of each generation polymer molecular structure.In addition, in 3420cm^-1 The spike of appearance is free-NH₂Stretching vibration peak, 1680cm^-1There are-C=O the stretching vibrations from amide structure in place Peak, in 1630cm^-1There is the absorption peak of C=C double bonds, show in entire reaction process, come from the C=in DETA structures C double bonds are not destroyed.

From attached drawing 2 as can be seen that with different algebraically, dosage HBPs modified WPUA lotions infrared spectrum and blank test In pure WPUA lotions obtained it is substantially similar, this shows that the emulsion modified fore-and-aft architecture structure of entire performed polymer has no apparent change Change.2275cm^-1There is not the stretching vibration peak of isocyano in raw material in place, this shows that the group has been completed to convert.By in figure It is shown, in 1730cm^-1All there is absorption peak to some extent in neighbouring each sample, this may be because carbonyl stretches in amido bond Caused by contracting vibration；3430cm can not be clearly found from spectrogram^-1Any absorption peak is contained at place, exactly because and this case Carboxylic hydroxyl is combined with segment in WPUA in ultrabranching polyamide, caused by hydroxyl reaction completely；Compared with pure WPUA, also not It can be in 3500~3300cm^-1Interior discovery-NH₂Stretching vibration peak, this is primarily due to-the NH for coming from dissaving structure₂It is complete Full association.

The light transmission of partially cured film can be analyzed, be measured by UV-VIS spectrum.It can be seen that from attached drawing 3 As λ≤500nm, pure WPUA cured films are not obvious with modified WPUA-HBPs cured film differences, and light transmittance all exists Within 20%；And after λ >=600nm, WPUA-HBPs cured film light transmittances are apparently higher than pure WPUA cured films before modified, Middle WPUA-HBPs-G2-5% highests (83%), this shows optical lens of the ultrabranching polyamide as modifying agent to raising cured film Lightness is most important.It analyzes from microcosmic, dissaving structure is introduced in pre-polymerization precursor emulsion segment, not only so that system grain size drop It is low, and mutually winding is reduced between chain and chain, is conducive to short wavelength light and is penetrated, is solidified into film property and greatly improves, with this Meanwhile excellent light transmission is also beneficial to improve the aesthetics of electrochemical aluminium gold-stamped product.

The elongation at break of 1. pure WPUA of table and part WPUA-HBPs cured films

Table 1 is pure WPUA and the elongation at break of part WPUA-HBPs cured films, as can be seen from the table, utilizes over-expense Change it is structurally-modified after the purer WPUA cured films of its elongation at break of cured film of WPUA-HBPs-G1~4 significantly reduce, and with The increase of HBPs algebraically and dosage, corresponding cured film elongation at break is gradually lowered, wherein pure WPUA cured films are broken Elongation highest (21.59%) is split, WPUA-HBPs-G3-5% cured film elongation at breaks are minimum (6.13%), and WPUA- The cured film elongation at break of HBPs-G4-1~10% is then held essentially constant (being respectively 7.52%, 7.66%, 8.51%), this It is primarily due to introduce after dissaving structure so that system internal crosslinking point increases in pre-polymerization precursor emulsion, destroys original line Property chain structure, the rigidity of system reduces, therefore modified cured film elongation at break reduces now, when using different content Cured film elongation at break is basically unchanged when HBPs-G4 is as modifying agent, this is primarily due to HBPs-G4 and contains more over-expenses Change structure and terminal amino group, excessive dissaving structure can not be associated completely with terminal amino group, therefore its cured film is broken Elongation is held essentially constant.

Embodiment 14

Using WPUA-HBPs lotions made from above-described embodiment 1-13 as electrochemical aluminium gold-stamped foil Subbing resins, applied to electricity Change aluminium gilding technology, cutting property improves.From above-described embodiment it is found that blank test corresponds to Subbing resins cured film elongation at break It is 21.59%, for modified Subbing resins cured film generally between 6~17%, this shows dissaving structure for modified, glue Layer resin cured film elongation at break significantly reduces, so as to which cutting property significantly improves.

The foregoing is merely the embodiment of the present invention, are not intended to limit the scope of the invention, every to utilize this hair The equivalent structure or equivalent flow shift that bright specification is made directly or indirectly is used in other related technical areas, Similarly it is included within the scope of the present invention.

Claims

1. a kind of preparation method of electrochemical aluminium gold-stamped foil Subbing resins, the electrochemical aluminium gold-stamped foil Subbing resins are hyperbranched polyamides Amine modified water-soluble gathers（Urethane-acrylate）Lotion, which is characterized in that measure ultrabranching polyamide modified water-soluble and gather（Urethane-the third Olefin(e) acid ester）It is fully mixed to add in acrylic ester monomer, acrylate monomer, reactive diluent and photoinitiator for pre-polymerization precursor emulsion After even to obtain the final product, wherein：

The ultrabranching polyamide modified water-soluble gathers（Urethane-acrylate）The mass fraction of pre-polymerization precursor emulsion is 40~60 parts, The mass fraction of acrylic ester monomer is 1 part, and the mass fraction of acrylate monomer is 1 part, the mass parts of reactive diluent Number is 40~65 parts, and the mass fraction of photoinitiator is 1~5 part；

The acrylic ester monomer is methyl acrylate or hydroxyethyl methacrylate；

The acrylate monomer is methyl acrylate, ethyl acrylate, 2- methyl methacrylates, ethyl 2-methacrylate Or tri (propylene glycol) diacrylate；

The reactive diluent is n-butyl acrylate-styrene, n-butyl acrylate-tripropylene glycol double methacrylate or third Olefin(e) acid N-butyl-trimethylolpropane trimethacrylate；

The photoinitiator is 2- hydroxy-2-methyl -1- phenyl -1- acetone, 1- hydroxycyclohexyl phenyl ketones or 2,2- diformazans Base -2- phenyl acetophenones；

The ultrabranching polyamide modified water-soluble gathers（Urethane-acrylate）The preparation method of pre-polymerization precursor emulsion, first prepares AB₂In advance Then polycondensation monomer prepares the ultrabranching polyamide of different algebraically, be finally synthesizing ultrabranching polyamide modified water-soluble and gather（Urethane-the third Olefin(e) acid ester）After performed polymer and emulsion dispersion to obtain the final product, include the following steps：

Maleic anhydride and solvent are added in step 1, reaction vessel, stirs to maleic anhydride be completely dissolved at room temperature, Diethylene triamine and solvent, 5~15 DEG C, 5~20min of mixing time, 1000~3000r/ of rotating speed of reaction temperature is slowly added dropwise Min, obtains white flock suspension, and vacuum distillation removes dry under room temperature after solvent, obtains white powder；

Wherein, the molar ratio of diethylene triamine and maleic anhydride is 1.0~1.2：1, the solvent for acetone, butanone, Isopropanol or Isosorbide-5-Nitrae-dioxane, solvent are 5~20mL with the volume mass ratio of corresponding solute:1g；

Step 2, in the reaction vessel equipped with blender, thermometer, add in p-aminobenzoic acid and solvent, stir at room temperature to It is completely dissolved, is slowly added to di-tert-butyl dicarbonate, micro iodine powder makees catalyst, reacts 1~4h, mixing speed at 30~60 DEG C 600~1000r/min；The excessive thionyl chloride of addition carries out acyl chloride reaction, reaction after vacuum distillation removes most solvents Unreacted thionyl chloride is removed under reduced pressure in 0~5 DEG C of temperature, 6~8h of reaction time after reaction；

Wherein, the molar ratio of di-tert-butyl dicarbonate and p-aminobenzoic acid is 1.0~1.05:1, the solvent is Isosorbide-5-Nitrae-dioxy The volume mass ratio of six rings, n,N-Dimethylformamide or methyl tertiary butyl ether(MTBE), solvent and p-aminobenzoic acid is 6~10mL: 1g；During acyl chloride reaction, the molar ratio of thionyl chloride and p-aminobenzoic acid is 1.5~5.0:1；

Step 3,1~2 drop triethylamine catalysis under, product and step 1 gained white powder amidation is made in step 2, reaction Time is 3~9h, and temperature is 10~80 DEG C, then removes two dimethyl dicarbonate fourths with the mixed solution of trifluoroacetic acid and sodium bicarbonate Ester, 0.5~6h of reaction time, 10~60 DEG C of temperature, products therefrom filtering drying, 30~80 DEG C of drying temperature, duration 2~for 24 hours, Obtain AB₂Pre- polycondensation monomer；

Wherein, it is 1 to weigh step 1 gained white powder with p-aminobenzoic acid molar ratio:1；The trifluoroacetic acid with to amino The molar ratio of benzoic acid is 1.0~1.5:1, the molar ratio of sodium bicarbonate and trifluoroacetic acid is 1.0~1.02:1；

Step 4, accurate control material ratio weigh AB₂Pre- polycondensation monomer, ethylenediamine and solvent are added in equipped with stirring rod, reflux condensation mode It manages, in the reaction vessel of thermometer, AB₂Pre- polycondensation monomer adds in obtain different algebraically polymer in batches, and slowly system heats up To 50~140 DEG C, 4~14h is reacted, glassy yellow liquid is obtained, after vacuum distillation removes most solvents, is put into vacuum drying chamber In in 60 DEG C~100 DEG C dry 24~72h, through cooling down, grinding, gained yellow powder is the hyperbranched polyamides of different algebraically Amine；

Wherein, work as AB₂The molar ratio of monomer and ethylenediamine is 2:When 1, generation ultrabranching polyamide is made；AB₂Monomer and ethylenediamine Molar ratio be 4:When 1, two generation ultrabranching polyamides are made；AB₂The molar ratio of monomer and ethylenediamine is 8:When 1, three generations is made Ultrabranching polyamide；AB₂The molar ratio of monomer and ethylenediamine is 16:When 1, four generation ultrabranching polyamides are made, the solvent is The volume mass ratio of deionized water, absolute ethyl alcohol or isopropanol, solvent and ethylenediamine is 100~200mL:1g；

Step 5, in the dry reaction vessel with agitating device, reflux condensing tube and thermometer, be proportionally added into high score Sub- polyalcohol, polyisocyanates, dihydroxymethyl acids and solvent are warming up to 40~80 DEG C, add in catalyst, are to slowly warm up to 80 ~90 DEG C, constant temperature stirs 1~8h；System is cooled to 30~80 DEG C, acrylic ester monomer is slowly added to, specific algebraically, contains The ultrabranching polyamide of amount, 1~8h of sustained response, for control temperature at 30~50 DEG C, it is 7~8 to add in neutralizer regulation system pH, After reacting 10~90min, deionized water is slowly dropped into carry out emulsion dispersion under high velocity agitation, obtain solid content for 8~ 80% ultrabranching polyamide modified water-soluble gathers（Urethane-acrylate）Pre-polymerization precursor emulsion；

Wherein, the macromolecule polyol for Polyoxypropylene diol NJ-210, NJ-220, NJ-330, polyethylene oxide or PolyTHF；The polyisocyanates be aliphatic diisocyanate or isophorone diisocyanate, polyisocyanates with The molar ratio 1.5~2.5 of macromolecule polyol:1；The dihydroxymethyl acids be dihydromethyl propionic acid or dimethylolpropionic acid, The molar ratio of dihydroxymethyl acids and macromolecule polyol is 0.9~1.02:1；The solvent for N,N-dimethylformamide or Methyl tertiary butyl ether(MTBE), the volume ratio with NJ-220 are 0.5~2:1；The catalyst is tin dilaurate diisobutyl tin, octanoic acid Stannous, two (dodecyl sulphur) dibutyl tins or dibutyltin diacetate, the neutralizer are alkyl amine, pyridines, pyrroles Class and its mixture.

2. the preparation method of electrochemical aluminium gold-stamped foil Subbing resins according to claim 1, it is characterised in that：The acrylate Class monomer is hydroxyethyl methacrylate, is added in when system temperature is adjusted to 60 DEG C.

3. the preparation method of electrochemical aluminium gold-stamped foil Subbing resins according to claim 1, it is characterised in that：The quality of each component Number proportioning is pre-polymerization precursor emulsion：It is 57 ︰, 1 ︰, 1 ︰ that third olefin(e) acid esters list body ︰ the third alkene acid ester monomer ︰ light, which draws hair agent ︰ reactive diluents, 3 ︰ 40, reactive diluent are n-butyl acrylate-tripropylene glycol double methacrylate.

4. the preparation method of electrochemical aluminium gold-stamped foil Subbing resins according to claim 1, it is characterised in that：In the step 1, The molar ratio of diethylene triamine and maleic anhydride is 1.05：1.

5. the preparation method of electrochemical aluminium gold-stamped foil Subbing resins according to claim 1, it is characterised in that：The step 1 In, solvent is 10 mL with the volume mass ratio of corresponding solute:Isosorbide-5-Nitrae-dioxane of 1g is as maleic anhydride and divinyl The solvent of base triamine, reaction temperature is 10 DEG C, time 15min, 2000 r/min of mixing speed.

6. the preparation method of electrochemical aluminium gold-stamped foil Subbing resins according to claim 1, it is characterised in that：In the step 2, The molar ratio of di-tert-butyl dicarbonate and p-aminobenzoic acid is 1.02:1.

7. the preparation method of electrochemical aluminium gold-stamped foil Subbing resins according to claim 1, it is characterised in that：The step 2 In, the volume mass ratio of solvent and p-aminobenzoic acid is 8 mL:The n,N-Dimethylformamide of 1g is as solvent, reaction temperature For 40 DEG C, time 2h, 800 r/min of mixing speed.

8. the preparation method of electrochemical aluminium gold-stamped foil Subbing resins according to claim 1, it is characterised in that：In the step 3, The catalysis reaction 6h at 60 DEG C.

9. the preparation method of electrochemical aluminium gold-stamped foil Subbing resins according to claim 1, it is characterised in that：In the step 3, The molar ratio of the trifluoroacetic acid and p-aminobenzoic acid is 1.05:1, the molar ratio of sodium bicarbonate and trifluoroacetic acid is 1.0:1.

10. the preparation method of electrochemical aluminium gold-stamped foil Subbing resins according to claim 1, it is characterised in that：The step 3 In, 30 DEG C of reaction temperature, time 2h, 50 DEG C of product drying temperature, duration 12h.

11. the preparation method of electrochemical aluminium gold-stamped foil Subbing resins according to claim 1, it is characterised in that：The step 4 In, 80 DEG C of polymerization temperature, time 8h, the solvent is deionized water.

12. the preparation method of electrochemical aluminium gold-stamped foil Subbing resins according to claim 1, it is characterised in that：The step 4 In, 70 DEG C of drying temperature, duration 48h.

13. the preparation method of electrochemical aluminium gold-stamped foil Subbing resins according to claim 1, it is characterised in that：The step 5 In, the macromolecule polyol is Polyoxypropylene diol NJ-220.

14. the preparation method of electrochemical aluminium gold-stamped foil Subbing resins according to claim 1, it is characterised in that：The step 5 In, the molar ratio of the isophorone diisocyanate and macromolecule polyol is 2.0:1.

15. the preparation method of electrochemical aluminium gold-stamped foil Subbing resins according to claim 1, it is characterised in that：The step 5 In, the molar ratio of the dihydromethyl propionic acid and macromolecule polyol is 1:1.

16. the preparation method of electrochemical aluminium gold-stamped foil Subbing resins according to claim 1, it is characterised in that：The step 5 In, the neutralizer is triethylamine.

17. the preparation method of electrochemical aluminium gold-stamped foil Subbing resins according to claim 1, it is characterised in that：The step 5 In, control temperature is 7~8 in 40 DEG C of 2000 r/min of rotating speed, addition neutralizer regulation system pH, after 10~90min of reaction, Deionized water is slowly dropped into carry out emulsion dispersion under high-speed stirred, obtains the ultrabranching polyamide modified water that solid content is 30% Property is gathered（Urethane-acrylate）Pre-polymerization precursor emulsion.

18. the preparation method of electrochemical aluminium gold-stamped foil Subbing resins according to claim 1, it is characterised in that：The step 5 In, system is warming up to 60 DEG C and instills 1 drop tin dilaurate diisobutyl tin, 85 DEG C is warming up to, reacts 6h；The HBPs generations added in Number was one to four generation, and dosage accounts for ultrabranching polyamide modified water-soluble and gathers（Urethane-acrylate）Pre-polymerization precursor emulsion total solid content 0.1~50%.

19. the preparation method of electrochemical aluminium gold-stamped foil Subbing resins according to claim 1, it is characterised in that：The step 5 In, HBPs dosages account for ultrabranching polyamide modified water-soluble and gather（Urethane-acrylate）The 1~10% of pre-polymerization precursor emulsion total solid content Within, reaction time 60min.