CN104845565A - Preparation technology for high-performance solvent copolymerization acrylate pressure-sensitive adhesive - Google Patents
Preparation technology for high-performance solvent copolymerization acrylate pressure-sensitive adhesive Download PDFInfo
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- CN104845565A CN104845565A CN201410050746.3A CN201410050746A CN104845565A CN 104845565 A CN104845565 A CN 104845565A CN 201410050746 A CN201410050746 A CN 201410050746A CN 104845565 A CN104845565 A CN 104845565A
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- sensitive adhesive
- pressure sensitive
- solvent
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- 239000002904 solvent Substances 0.000 title claims abstract description 41
- 239000004820 Pressure-sensitive adhesive Substances 0.000 title claims abstract description 33
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 title claims abstract description 26
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- 238000005516 engineering process Methods 0.000 title claims abstract description 13
- 238000007334 copolymerization reaction Methods 0.000 title abstract description 8
- 239000000178 monomer Substances 0.000 claims abstract description 46
- 238000006243 chemical reaction Methods 0.000 claims abstract description 34
- 239000003999 initiator Substances 0.000 claims abstract description 11
- 238000004132 cross linking Methods 0.000 claims abstract description 9
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 45
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 39
- 239000003292 glue Substances 0.000 claims description 25
- 238000003756 stirring Methods 0.000 claims description 22
- 229920001577 copolymer Polymers 0.000 claims description 21
- 239000003795 chemical substances by application Substances 0.000 claims description 18
- 239000007787 solid Substances 0.000 claims description 16
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 claims description 13
- 230000032683 aging Effects 0.000 claims description 12
- 238000001723 curing Methods 0.000 claims description 12
- 239000004848 polyfunctional curative Substances 0.000 claims description 12
- WYGWHHGCAGTUCH-UHFFFAOYSA-N 2-[(2-cyano-4-methylpentan-2-yl)diazenyl]-2,4-dimethylpentanenitrile Chemical compound CC(C)CC(C)(C#N)N=NC(C)(C#N)CC(C)C WYGWHHGCAGTUCH-UHFFFAOYSA-N 0.000 claims description 11
- 239000011248 coating agent Substances 0.000 claims description 11
- 238000000576 coating method Methods 0.000 claims description 11
- DXPPIEDUBFUSEZ-UHFFFAOYSA-N 6-methylheptyl prop-2-enoate Chemical group CC(C)CCCCCOC(=O)C=C DXPPIEDUBFUSEZ-UHFFFAOYSA-N 0.000 claims description 10
- NIXOWILDQLNWCW-UHFFFAOYSA-N Acrylic acid Chemical compound OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 10
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 10
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 claims description 9
- 239000000203 mixture Substances 0.000 claims description 9
- 238000000034 method Methods 0.000 claims description 8
- VVWRJUBEIPHGQF-UHFFFAOYSA-N propan-2-yl n-propan-2-yloxycarbonyliminocarbamate Chemical compound CC(C)OC(=O)N=NC(=O)OC(C)C VVWRJUBEIPHGQF-UHFFFAOYSA-N 0.000 claims description 8
- -1 azo compound Chemical class 0.000 claims description 6
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 claims description 6
- 239000004342 Benzoyl peroxide Substances 0.000 claims description 4
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 claims description 4
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 claims description 4
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims description 4
- 235000019400 benzoyl peroxide Nutrition 0.000 claims description 4
- 230000001939 inductive effect Effects 0.000 claims description 4
- YKYONYBAUNKHLG-UHFFFAOYSA-N n-Propyl acetate Natural products CCCOC(C)=O YKYONYBAUNKHLG-UHFFFAOYSA-N 0.000 claims description 4
- 230000008569 process Effects 0.000 claims description 4
- 229940090181 propyl acetate Drugs 0.000 claims description 4
- 150000003254 radicals Chemical class 0.000 claims description 4
- 239000000126 substance Substances 0.000 claims description 4
- NQPDZGIKBAWPEJ-UHFFFAOYSA-N valeric acid Chemical compound CCCCC(O)=O NQPDZGIKBAWPEJ-UHFFFAOYSA-N 0.000 claims description 4
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 4
- 229920002554 vinyl polymer Polymers 0.000 claims description 4
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 3
- 239000012948 isocyanate Substances 0.000 claims description 3
- 150000002513 isocyanates Chemical class 0.000 claims description 3
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 claims description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 2
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 claims description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 2
- 238000009835 boiling Methods 0.000 claims description 2
- 239000003054 catalyst Substances 0.000 claims description 2
- 239000002131 composite material Substances 0.000 claims description 2
- 238000000354 decomposition reaction Methods 0.000 claims description 2
- AYOHIQLKSOJJQH-UHFFFAOYSA-N dibutyltin Chemical compound CCCC[Sn]CCCC AYOHIQLKSOJJQH-UHFFFAOYSA-N 0.000 claims description 2
- 150000002148 esters Chemical class 0.000 claims description 2
- JUMYIBMBTDDLNG-OJERSXHUSA-N hydron;methyl (2r)-2-phenyl-2-[(2r)-piperidin-2-yl]acetate;chloride Chemical compound Cl.C([C@@H]1[C@H](C(=O)OC)C=2C=CC=CC=2)CCCN1 JUMYIBMBTDDLNG-OJERSXHUSA-N 0.000 claims description 2
- VLCAYQIMSMPEBW-UHFFFAOYSA-N methyl 3-hydroxy-2-methylidenebutanoate Chemical compound COC(=O)C(=C)C(C)O VLCAYQIMSMPEBW-UHFFFAOYSA-N 0.000 claims description 2
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 claims description 2
- 238000006116 polymerization reaction Methods 0.000 claims description 2
- 230000001737 promoting effect Effects 0.000 claims description 2
- 229940099204 ritalin Drugs 0.000 claims description 2
- 230000007704 transition Effects 0.000 claims description 2
- 230000011514 reflex Effects 0.000 claims 2
- 238000005520 cutting process Methods 0.000 claims 1
- 238000007599 discharging Methods 0.000 claims 1
- 239000011521 glass Substances 0.000 claims 1
- 238000009826 distribution Methods 0.000 abstract description 8
- 230000001070 adhesive effect Effects 0.000 abstract description 3
- 238000005227 gel permeation chromatography Methods 0.000 abstract description 2
- 239000000853 adhesive Substances 0.000 abstract 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 16
- 239000007788 liquid Substances 0.000 description 14
- 229920002799 BoPET Polymers 0.000 description 12
- 238000003483 aging Methods 0.000 description 11
- 235000021050 feed intake Nutrition 0.000 description 9
- 229910052757 nitrogen Inorganic materials 0.000 description 8
- 238000007664 blowing Methods 0.000 description 7
- 238000006073 displacement reaction Methods 0.000 description 7
- 238000007789 sealing Methods 0.000 description 7
- 238000010792 warming Methods 0.000 description 7
- 230000001965 increasing effect Effects 0.000 description 6
- 230000035484 reaction time Effects 0.000 description 6
- 230000002459 sustained effect Effects 0.000 description 5
- 238000000926 separation method Methods 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 2
- 239000006087 Silane Coupling Agent Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 description 1
- 241001269238 Data Species 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 239000012790 adhesive layer Substances 0.000 description 1
- 239000002390 adhesive tape Substances 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000012662 bulk polymerization Methods 0.000 description 1
- 238000003889 chemical engineering Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005755 formation reaction Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 230000000176 photostabilization Effects 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 238000003847 radiation curing Methods 0.000 description 1
- 238000010526 radical polymerization reaction Methods 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
Landscapes
- Adhesives Or Adhesive Processes (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
Provided is preparation technology for a high-performance solvent copolymerization acrylate pressure-sensitive adhesive. The adhesive comprises the following components, by weight ratio: 65-90% of a soft monomer, 10-30% of a hard monomer, and 3-5% of a crosslinking monomer. The adhesive also comprises a solvent, the weight of which is 10% of the total weight of monomers at an initial reaction stage, is 10-20% of the total weight of monomers at an early stage of a growth stage, is 40-60% of the total weight of monomers at a later stage of the growth stage, and is 138-163% of the total weight of monomers at a final reaction stage, and an initiator, the weight of which is 0.03-0.5% of the total weight of monomers. According to the invention, the copolymerization acrylate is high in average molecular weight and wide in molecular weight distribution. The molecular weight of the copolymerization acrylate can be measured through gel permeation chromatography, and has a weight-average molecular weight in a range of 450-900 kg/mol and a molecular weight distribution index in a range of 4-20.
Description
Technical field
The present invention relates to a kind of preparation technology of high performance and solvent type copolymer acrylate pressure sensitive adhesive, belong to chemical field.
Background technology
Pressure sensitive adhesive is a class without the need to by means of solvent, heat or other means, only need apply slight pressure, can bond firmly tackiness agent with adherend.Pressure-sensitive is showed by its adhesion properties, and its adhesion properties is made up of four large bond propertiess, is respectively initial bonding strength (tack) T, bonding force (adhesion) A, force of cohesion (cohesion) C and base adhesion force (keying) K.Initial bonding strength T, also known as fast viscous force, to refer to after pressure sensitive adhesive goods contact with very light pressure with adherend the resistant to separation ability that sharp separation immediately shows.After bonding force A refers to and pastes with suitable pressure and time, glue and by between maxxaedium the ability of opposing interfacial separation that shows; Force of cohesion C refers to the intensity of adhesive layer itself; Base adhesion force K refers to tackiness agent and base material, or tackiness agent and silane coupling agent and the bonding force between silane coupling agent and base material.The balance of four large bond propertiess must be met, T<A<C<K as a good pressure sensitive adhesive.Its middle-molecular-weihydroxyethyl and distribution thereof are the principal elements affecting each bounding force.Li Chuncheng and the Zheng Changren of Nanjing Chemical Engineering College exist
chemical industry and bondingmagazine is published an article " molecular weight is on the impact of pressure sensitive adhesive bond properties ", and (the 1996,3rd phase, 163) illustrate, usual adhesiveproperties improves with the increase of molecular weight.When pressure sensitive adhesive keeps sufficiently high molecular weight and wider molecular weight distribution, the good pressure sensitive adhesive of over-all properties could be obtained.
Simple, the bonding scope of pressure-sensitive acrylate formula is wide, weathering resistance is good, photostabilization is strong, oil-proofness is excellent, water-tolerant, do not exist and be separated and the phenomenon such as migration, is thus widely used in every field.Solvent-borne type, emulsion-type, hot-melting type, water-soluble glue-type and radiation curing etc. are divided into according to dissimilar, solvent-type acrylic ester class pressure sensitive adhesive is the glutinous thick liquid carrying out radical polymerization in organic solvent by acrylate monomer and obtain, and adds or does not add (being divided into three kinds, non-crosslinked type, cross-linking type and non-aqueous dispersion type) that other additives are formed.Solvent-type acrylic ester class pressure sensitive adhesive has that wettability is good, initial bonding strength is large, drying rate is fast and the plurality of advantages such as water-tolerant, is still widely used in the fields such as medical adhesive tape, Pressuresensitive Label and double sticky tape so far.The Chinese patent of application number " 201210311025.9 " discloses a kind of preparation method and application of solvent-type acrylic ester class pressure sensitive adhesive.But the main drawback of current domestic solvent-type acrylic ester class pressure sensitive adhesive is that under high temperature, hold tack is not high, its major cause is that molecular-weight average is on the low side, this is owing to taking traditional solution processes, be compared to mass polymerization, its chain tra nsfer and chain termination are easily by solvent effect, cause molecular weight to be difficult to reach enough large, and the molecular weight propagation process time is long, is unfavorable for suitability for industrialized production.When being polymerized in a solvent, how a step realizes wider molecular weight distribution is also a technical barrier simultaneously.
Summary of the invention
The object of the invention is the deficiency for having preparation technology at present, provide a kind of preparation technology of high performance and solvent type copolymer acrylate pressure sensitive adhesive, its object is to: the molecular-weight average and the molecular weight distribution width that increase copolymer acrylate, and then improve the over-all properties such as tack, hold tack, resistance to elevated temperatures of pressure sensitive adhesive.
The preparation technology of high performance and solvent type copolymer acrylate pressure sensitive adhesive, it is characterized in that: comprise the proportioning raw materials such as hard monomer, soft monomer, function monomer, solvent and initiator, comprise another independently curing agent component, the condition being also included in reaction process in the stirred autoclave of customization controls, and the present invention is achieved by the following technical solutions.
(1) Monomer Formations technology
Soft monomer for copolymerization of the present invention, is characterized in that referring to that second-order transition temperature is between the vinyl monomer of-20 DEG C ~-70 DEG C, comprises ethyl propenoate (-22 DEG C), butyl acrylate (-55 DEG C), Isooctyl acrylate monomer (-70 DEG C); For the hard monomer of copolymerization, include methyl acrylate, vinyl acetate, vinylbenzene, vinyl cyanide, methyl methacrylate, the cross-linking monomer for copolymerization comprises vinylformic acid, hydroxyethyl methylacrylate, methacrylic acid.Its general structure of all comonomers is as follows.
Comonomer proportioning raw materials of the present invention, its soft monomer content is 65-90%wt.Hard monomer content is 10-30%wt, and cross-linking monomer content is 3%-5%wt.In soft monomer, butyl acrylate accounts for the 60-100%wt of total soft monomer content, other soft monomer content 0-40%wt.
(2) initiator elicitation technique
The present invention is used for the initiator of copolymerization, and its constitutional features is organo-peroxide or azo compound, and decomposes becomes free radical trigger monomer to be polymerized, and comprises benzoyl peroxide, Diisopropyl azodicarboxylate, 2,2'-Azobis(2,4-dimethylvaleronitrile).
Initiator feature consumption is the 0.03-0.5%wt of total monomer weight, preferred 0.06-0.3%wt.
(3) solvent burden ratio technology
The present invention for dissolve copolymer acrylate the solvent that is suitable for, it is characterized in that the organism within the scope of one or more boiling points 60-120 DEG C, comprise toluene, chlorobenzene, Virahol, ritalin, vinyl acetic monomer, propyl acetate.The solvent ratios of high performance pressure sensitive glue, is characterized in that initial reaction stage accounts for the 10%wt of monomer ratio, and epacmastic early stage, accounting example was 10%-20%wt, and epacmastic later stage ratio is 40%-60%wt, and reaction terminating phase overall proportion is the 138-163%wt of monomer weight.
(4) copolyreaction Row control technology
The present invention is used for the stirred autoclave of acrylic ester copolymer, it is characterized in that stirring rake takes bilayer structure to design, containing sped structure and overhead gage; Join temperature measuring equipment entrance, nitrogen inlet, solid feed inlet, liquid addition port, reflux tower and lower discharge port; Also be to take jacketed type heating means.
Copolyreaction of the present invention, is characterized in that by increasing the temperature to 72-96 DEG C, promotes that decomposition of initiator forms free radical, thus induced polymerization, its primary process is divided into inductive phase, rise period and amortization period.Inductive phase, temperature was set as 76-84 DEG C, and after autoacceleration, epacmastic latter temperature is set as 88-96 DEG C, and its primitive reaction structural formula is as follows:
(5) curing technology
High performance pressure sensitive glue of the present invention, also comprise the solidifying agent with cross-linking monomer generation chemical reaction, its feature comprises the chemical combination mixture containing isocyanate structural and polyvalent alcohol, solvent ethyl acetate, and for promoting the catalyst dibutyltin dilaurylate of curing reaction (its consumption is 3% of isocyanic ester mixture), solid content is 4.5%wt.Hardener dose is the 1.5%wt of pressure sensitive adhesive solubilizing agent composite glue (solid content 40%wt).
The present invention compared with prior art has following beneficial effect:
The copolymer acrylate molecular-weight average of this invention is large, and molecular weight distribution is wide, and copolymer acrylate molecular weight is tested by gel permeation chromatography, and weight-average molecular weight is at 450-900 kg/mol, and molecular weight distributing index is 4-20.By copolymer acrylate and solidifying agent according to fixed proportion Homogeneous phase mixing, be coated in PET film surface, measure thickness after drying and be about 25-50 micron; After solidification, tack 14-23 ball, holds viscosity and peels off≤0.5cm in 2 hours.Be coated on the pressure sensitive adhesive of PET film, through 71 DEG C of hot air agings after 72 hours, cohesive strength and adhesion property keep stable.These application datas show that the tack of this pressure sensitive adhesive is good, and hold tack is strong, and resistance to elevated temperatures is improved significantly.It is the solvent-borne type copolymer acrylate pressure sensitive adhesive that a kind of over-all properties is high.
Accompanying drawing explanation
Fig. 1: particular product performance parameters trend graph of the present invention.
Embodiment
Below by way of specific embodiment, the present invention is described, but the present invention is not merely defined in these embodiments.
embodiment 1
Butyl acrylate 1200 grams, Isooctyl acrylate monomer 400g, vinylbenzene 140g, vinyl acetate 200g, vinylformic acid 60g, toluene 400g, Diisopropyl azodicarboxylate 1g are dosed in 50L mechanic whirl-nett reaction still, after displacement nitrogen three times, setting stirring velocity 100r/min, be warming up to 82 DEG C, heat-up rate 5 DEG C/min, within about 20 minutes, stablize to design temperature.
After 2.5 hours 82 DEG C of reactions, to feed intake Diisopropyl azodicarboxylate 1.5g, add toluene 400g from liquid feed mouth from solid dog-house, setting stirring velocity 50r/min, continues reaction 1 hour.
Again temperature is increased to 88 DEG C, adds ethyl acetate 1000g from liquid addition port, to feed intake Diisopropyl azodicarboxylate 1.5g from solid dog-house, sustained reaction was lowered the temperature after 1 hour, add ethyl acetate 1200g, enter container after stirring from feed opening blowing, sealing is preserved to be measured.
After solvent is dried, measure and infraredly see accompanying drawing 1 and subordinate list 1 with molecular weight.
The preparation method of curing agent component is as follows, is n at setting 60 DEG C of temperature according to mol ratio
nCO: n
oHthe ratio of=2:1 drops into tolylene diisocyanate and polyether glycol (hydroxyl value 130mgKOH/g, functionality 2.2).React after 12 hours and cool, mensuration isocyanate content is 12%wt, adds the dibutyl tin laurate of 3% ratio, and with diluted ethyl acetate to total solid content 4.5%wt.
Be coated onto PET film surface through coating machine after hardener dose 4.5% mixes with glue, measure it and just glue and hold sticky intensity, and through 71 DEG C of hot air agings, measure its applicable cases, concrete outcome see attached list 2.
embodiment 2
Butyl acrylate 1000 grams, Isooctyl acrylate monomer 600g, vinylbenzene 100g, vinyl acetate 240g, Hydroxyethyl acrylate 60g, toluene 400g, 2,2'-Azobis(2,4-dimethylvaleronitrile) 0.75g is dosed in 50L mechanic whirl-nett reaction still, after displacement nitrogen three times, and setting stirring velocity 100r/min, be warming up to 82 DEG C, heat-up rate 5 DEG C/min.Within about 20 minutes, stablize to design temperature.
After 76 DEG C of 2.5 hours reaction times, to feed intake 2,2'-Azobis(2,4-dimethylvaleronitrile) 1g, add toluene 400g from liquid feed mouth from solid dog-house, setting stirring velocity 50r/min, continues reaction 2 hours.
Again temperature is increased to 84 DEG C, adds ethyl acetate 1000g from liquid addition port, to feed intake 2,2'-Azobis(2,4-dimethylvaleronitrile) 1.5g from solid dog-house, sustained reaction was lowered the temperature after 2 hours, add ethyl acetate 1200g, enter container after stirring from feed opening blowing, sealing is preserved to be measured.
After being dried by solvent, determining molecular weight sees attached list 1.
The preparation method of curing agent component is with embodiment 1.
Be coated onto PET film surface through coating machine after hardener dose 4.5% mixes with glue, measure it and just glue and hold sticky intensity, and through 71 DEG C of hot air agings, measure its applicable cases, concrete outcome see attached list 2.
embodiment 3
Butyl acrylate 1600 grams, methyl methacrylate 340g, methacrylic acid 60g, chlorobenzene 400g, 2,2'-Azobis(2,4-dimethylvaleronitrile) 0.75g are dosed in 50L mechanic whirl-nett reaction still, after displacement nitrogen three times, setting stirring velocity 100r/min, is warming up to 82 DEG C, heat-up rate 5 DEG C/min.Within about 20 minutes, stablize to design temperature.
After 76 DEG C of 4.5 hours reaction times, to feed intake 2,2'-Azobis(2,4-dimethylvaleronitrile) 0.25g, add toluene 400g from liquid feed mouth from solid dog-house, setting stirring velocity 50r/min, continues reaction 2 hours.
Again temperature is increased to 84 DEG C, from liquid addition port with propyl acetate 1000g, feeds intake 2,2'-Azobis(2,4-dimethylvaleronitrile) 1.5g from solid dog-house, sustained reaction was lowered the temperature after 2 hours, with propyl acetate 1200g, enter container after stirring from feed opening blowing, sealing is preserved to be measured.
After being dried by solvent, determining molecular weight sees attached list 1.
The preparation method of curing agent component is with embodiment 1.
Be coated onto PET film surface through coating machine after hardener dose 4.5% mixes with glue, measure it and just glue and hold sticky intensity, and through 71 DEG C of hot air agings, measure its applicable cases, concrete outcome see attached list 2.
embodiment 4
Butyl acrylate 1200 grams, Isooctyl acrylate monomer 400g, vinylbenzene 160g, vinyl acetate 200g, vinylformic acid 80g, toluene 400g, remaining reaction method is with embodiment 1.
After solvent is dried, measure and infraredly see accompanying drawing 1 and subordinate list 1 with molecular weight.
The preparation method of curing agent component is with embodiment 1.
Be coated onto PET film surface through coating machine after hardener dose 4.5% mixes with glue, measure it and just glue and hold sticky intensity, and through 71 DEG C of hot air agings, measure its applicable cases, concrete outcome see attached list 2.
embodiment 5
Butyl acrylate 1200 grams, Isooctyl acrylate monomer 400g, vinylbenzene 150g, vinyl acetate 150g, vinylformic acid 100g, toluene 400g, remaining reaction method is with embodiment 1.
After being dried by solvent, determining molecular weight sees attached list 1.
The preparation method of curing agent component is with embodiment 1.
Be coated onto PET film surface through coating machine after hardener dose 4.5% mixes with glue, measure it and just glue and hold sticky intensity, and through 72 DEG C of hot air agings, measure its applicable cases, concrete outcome see attached list 2.
embodiment 6
Butyl acrylate 1400 grams, Isooctyl acrylate monomer 400g, vinylbenzene 60g, vinyl acetate 80g, vinylformic acid 60g, reaction process control condition is with embodiment 1.After being dried by solvent, determining molecular weight sees attached list 1.
The preparation method of curing agent component is with embodiment 1.
Be coated onto PET film surface through coating machine after hardener dose 4.5% mixes with glue, measure it and just glue and hold sticky intensity, and through 71 DEG C of hot air agings, measure its applicable cases, concrete outcome see attached list 2.
embodiment 7
Butyl acrylate 1200 grams, Isooctyl acrylate monomer 400g, vinylbenzene 140g, vinyl acetate 200g, vinylformic acid 60g, toluene 400g, benzoyl peroxide 1g is dosed in 50L mechanic whirl-nett reaction still, after displacement nitrogen three times, and setting stirring velocity 100r/min, be warming up to 84 DEG C, heat-up rate 5 DEG C/min.Within about 20 minutes, stablize to design temperature.
After 84 DEG C of 3.5 hours reaction times, to feed intake benzoyl peroxide 1.5g, add toluene 400g from liquid feed mouth from solid dog-house, setting stirring velocity 50r/min, continues reaction 1 hour.
Again temperature is increased to 88 DEG C, adds ethyl acetate 1000g from liquid addition port, to feed intake Diisopropyl azodicarboxylate 1.5g from solid dog-house, sustained reaction was lowered the temperature after 1 hour, add ethyl acetate 1600g, enter container after stirring from feed opening blowing, sealing is preserved to be measured.
After solvent is dried, determining molecular weight subordinate list 1.
The preparation method of curing agent component is with embodiment 1.
Be coated onto PET film surface through coating machine after hardener dose 4.5% mixes with glue, measure it and just glue and hold sticky intensity, and through 71 DEG C of hot air agings, measure its applicable cases, concrete outcome see attached list 2.
embodiment 8
Butyl acrylate 1200 grams, Isooctyl acrylate monomer 600g, vinylbenzene 140g, vinylformic acid 60g, toluene 400g, 2,2'-Azobis(2,4-dimethylvaleronitrile) 1g are dosed in 50L mechanic whirl-nett reaction still, after displacement nitrogen three times, setting stirring velocity 100r/min, is warming up to 82 DEG C, heat-up rate 5 DEG C/min.Within about 20 minutes, stablize to design temperature.
After 82 DEG C of 2.5 hours reaction times, to feed intake 2,2'-Azobis(2,4-dimethylvaleronitrile) 1.5g, add toluene 400g from liquid feed mouth from solid dog-house, setting stirring velocity 50r/min, continues reaction 1 hour.
Again temperature is increased to 88 DEG C, adds ethyl acetate 1000g from liquid addition port, to feed intake 2,2'-Azobis(2,4-dimethylvaleronitrile) 1.5g from solid dog-house, sustained reaction was lowered the temperature after 1 hour, add ethyl acetate 2000g, enter container after stirring from feed opening blowing, sealing is preserved to be measured.
After solvent is dried, determining molecular weight subordinate list 1.
The preparation method of curing agent component is with embodiment 1.
Be coated onto PET film surface through coating machine after hardener dose 4.5% mixes with glue, measure it and just glue and hold sticky intensity, and through 71 DEG C of hot air agings, measure its applicable cases, concrete outcome see attached list 2.
comparative example 1
Traditionally a feeding method synthesizes, and contrasts with embodiment 1, butyl acrylate 1200 grams, Isooctyl acrylate monomer 400g, vinylbenzene 160g, vinyl acetate 180g, vinylformic acid 60g, toluene 400g, Diisopropyl azodicarboxylate 2g is dosed in 50L mechanic whirl-nett reaction still, after displacement nitrogen three times, and setting stirring velocity 100r/min, be warming up to 82 DEG C, heat-up rate 5 DEG C/min.Within about 20 minutes, stablize to design temperature.After 82 DEG C of 6 hours reaction times, add ethyl acetate 2600g from liquid addition port, enter container after stirring from feed opening blowing, sealing is preserved to be measured.
After being dried by solvent, determining molecular weight sees attached list 1.
Solidifying agent preparation method is with embodiment 1.
Be coated onto PET film surface through coating machine after hardener dose 4.5% mixes with glue, measure it and just glue and hold sticky intensity, and through 71 DEG C of hot air agings, measure its applicable cases, concrete outcome see attached list 2.
comparative example 2
Contrast with embodiment 3, butyl acrylate 1600 grams, methyl methacrylate 340g, vinylformic acid 60g, toluene 400g, Diisopropyl azodicarboxylate 2g are dosed in 50L mechanic whirl-nett reaction still, after displacement nitrogen three times, setting stirring velocity 100r/min, is warming up to 82 DEG C, heat-up rate 5 DEG C/min.Within about 20 minutes, stablize to design temperature.After 82 DEG C of 6 hours reaction times, add ethyl acetate 2600g from liquid addition port, enter container after stirring from feed opening blowing, sealing is preserved to be measured.
After being dried by solvent, determining molecular weight sees attached list 1.
Solidifying agent preparation method is with embodiment 1.
Be coated onto PET film surface through coating machine after hardener dose 4.5% mixes with glue, measure it and just glue and hold sticky intensity, and through 71 DEG C of hot air agings, measure its applicable cases, concrete outcome see attached list 2.
The present invention is not only confined to above-mentioned specific embodiment.
Subordinate list 1: each batch products molecular weight and molecular weight distribution table look-up.
Subordinate list 2: application situation table.
Claims (10)
1. high performance and solvent type copolymer acrylate pressure sensitive adhesive, is characterized in that, is made up of the component of following weight: soft monomer content is 65-90%wt; Hard monomer content is 10-30%wt; Cross-linking monomer content is 3%-5%wt; Initial reaction stage accounts for the 10%wt of monomer ratio, epacmastic early stage, accounting example was 10%-20%wt, epacmastic later stage ratio is 40%-60%wt, reaction terminating phase overall proportion is that the solvent of the 138-163%wt of monomer weight and the 0.03-0.5%wt initiator that accounts for total monomer weight carry out proportioning, also comprises the solidifying agent with cross-linking monomer generation chemical reaction.
2. high performance and solvent type copolymer acrylate pressure sensitive adhesive according to claim 1, it is characterized in that: described soft monomer be second-order transition temperature between the vinyl monomer of-20 DEG C ~-70 DEG C, comprise one or more mixtures in ethyl propenoate (-22 DEG C), butyl acrylate (-55 DEG C), Isooctyl acrylate monomer (-70 DEG C).
3. high performance and solvent type copolymer acrylate pressure sensitive adhesive according to claim 1, is characterized in that: described hard monomer, includes one or more mixtures in methyl acrylate, vinyl acetate, vinylbenzene, vinyl cyanide, methyl methacrylate.
4. high performance and solvent type copolymer acrylate pressure sensitive adhesive according to claim 1, is characterized in that: described cross-linking monomer comprises one or more mixtures in vinylformic acid, hydroxyethyl methylacrylate, methacrylic acid.
5. high performance and solvent type copolymer acrylate pressure sensitive adhesive according to claim 1, it is characterized in that: described initiator is organo-peroxide or azo compound, decomposes becomes free radical trigger monomer to be polymerized, and comprises one or more mixtures in benzoyl peroxide, Diisopropyl azodicarboxylate, 2,2'-Azobis(2,4-dimethylvaleronitrile).
6. high performance and solvent type copolymer acrylate pressure sensitive adhesive according to claim 1, it is characterized in that: described solvent is the organism within the scope of one or more boiling points 60-120 DEG C, comprise one or more mixtures in toluene, chlorobenzene, Virahol, ritalin, vinyl acetic monomer, propyl acetate.
7. high performance and solvent type copolymer acrylate pressure sensitive adhesive according to claim 1, it is characterized in that: described solidifying agent comprises the chemical combination mixture containing isocyanate structural and polyvalent alcohol, solvent ethyl acetate, and for promoting the catalyst dibutyltin dilaurylate of curing reaction, its consumption is 3% of isocyanic ester mixture, and solid content is 4.5%wt.
8. high performance and solvent type copolymer acrylate pressure sensitive adhesive according to claim 1, is characterized in that: described initiator amount is the 0.06-0.3%wt of total monomer weight.
9. high performance and solvent type copolymer acrylate pressure sensitive adhesive according to claim 1, is characterized in that: described hardener dose is the 1.5%wt of the pressure sensitive adhesive solubilizing agent composite glue of solid content 40%wt.
10. the preparation technology of high performance and solvent type copolymer acrylate pressure sensitive adhesive, it is characterized in that: take hard monomer, soft monomer, initiator, cross-linking monomer and solvent by proportioning, disposablely put in reactor, keep stirring in reactor, make it to be warmed up to 72-96 DEG C gradually, promote that decomposition of initiator forms free radical, thus induced polymerization, its primary process is divided into inductive phase, rise period and amortization period; Inductive phase, temperature was set as 76-84 DEG C, after autoacceleration, epacmastic latter temperature is set as 88-96 DEG C, abundant stirring, naturally cools to about 50 DEG C dischargings after reaction 3 ~ 4h, by coating, dries slaking, cutting operation, coated alkaline cell, to the print film of this invention pressure sensitive adhesive be coated with through 75 DEG C of aging 96h, coated glass stick and alkaline cell, testing curved surface reflex action performance; Low temperature 5 DEG C places 96h, coated alkaline cell, testing curved surface reflex action.
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| CN107610585A (en) * | 2017-09-18 | 2018-01-19 | 江苏景宏新材料科技有限公司 | A kind of preparation for washing transparent thermal contraction type beer bottle label and its wash mark technique |
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