CN104845565B - The preparation process of high performance and solvent type copolymer acrylate pressure sensitive adhesive - Google Patents
The preparation process of high performance and solvent type copolymer acrylate pressure sensitive adhesive Download PDFInfo
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- CN104845565B CN104845565B CN201410050746.3A CN201410050746A CN104845565B CN 104845565 B CN104845565 B CN 104845565B CN 201410050746 A CN201410050746 A CN 201410050746A CN 104845565 B CN104845565 B CN 104845565B
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- solvent
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- 239000002904 solvent Substances 0.000 title claims abstract description 44
- 239000004820 Pressure-sensitive adhesive Substances 0.000 title claims abstract description 29
- 238000002360 preparation method Methods 0.000 title claims abstract description 27
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 title claims abstract description 24
- 229920001577 copolymer Polymers 0.000 title claims abstract description 22
- 239000000178 monomer Substances 0.000 claims abstract description 46
- 238000006243 chemical reaction Methods 0.000 claims abstract description 30
- 239000003999 initiator Substances 0.000 claims abstract description 14
- 238000004132 cross linking Methods 0.000 claims abstract description 11
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 45
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 42
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 18
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 18
- 239000007787 solid Substances 0.000 claims description 18
- 239000003795 chemical substances by application Substances 0.000 claims description 17
- 238000001723 curing Methods 0.000 claims description 17
- 239000003292 glue Substances 0.000 claims description 16
- 239000007788 liquid Substances 0.000 claims description 16
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 14
- 238000002156 mixing Methods 0.000 claims description 13
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 claims description 12
- 239000004848 polyfunctional curative Substances 0.000 claims description 11
- 238000010438 heat treatment Methods 0.000 claims description 10
- 238000003756 stirring Methods 0.000 claims description 10
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 9
- 229910052757 nitrogen Inorganic materials 0.000 claims description 9
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 claims description 8
- 230000006641 stabilisation Effects 0.000 claims description 8
- 238000011105 stabilization Methods 0.000 claims description 8
- 229940117958 vinyl acetate Drugs 0.000 claims description 8
- 238000010792 warming Methods 0.000 claims description 8
- 238000000034 method Methods 0.000 claims description 7
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 claims description 6
- 239000012948 isocyanate Substances 0.000 claims description 6
- 230000004044 response Effects 0.000 claims description 6
- 230000002459 sustained effect Effects 0.000 claims description 6
- -1 azo compound Chemical class 0.000 claims description 5
- 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
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-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
- 150000002148 esters Chemical class 0.000 claims description 4
- 230000006698 induction 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
- 238000006116 polymerization reaction Methods 0.000 claims description 4
- 230000008569 process Effects 0.000 claims description 4
- 229940090181 propyl acetate Drugs 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
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 3
- 239000002253 acid Substances 0.000 claims description 3
- 239000002131 composite material Substances 0.000 claims description 3
- 150000002513 isocyanates Chemical class 0.000 claims description 3
- 150000003254 radicals Chemical class 0.000 claims description 3
- 229920002818 (Hydroxyethyl)methacrylate Polymers 0.000 claims description 2
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-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
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 claims description 2
- 238000009835 boiling Methods 0.000 claims description 2
- 150000001875 compounds Chemical class 0.000 claims description 2
- 238000000354 decomposition reaction Methods 0.000 claims description 2
- 230000009477 glass transition Effects 0.000 claims description 2
- 239000005416 organic matter Substances 0.000 claims description 2
- 150000001451 organic peroxides Chemical class 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
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims description 2
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims description 2
- 150000005846 sugar alcohols Polymers 0.000 claims description 2
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 2
- 229920002554 vinyl polymer Polymers 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims 5
- 239000003054 catalyst Substances 0.000 claims 2
- AYOHIQLKSOJJQH-UHFFFAOYSA-N dibutyltin Chemical compound CCCC[Sn]CCCC AYOHIQLKSOJJQH-UHFFFAOYSA-N 0.000 claims 1
- 238000007599 discharging Methods 0.000 claims 1
- 125000002485 formyl group Chemical group [H]C(*)=O 0.000 claims 1
- 239000013557 residual solvent Substances 0.000 claims 1
- 238000009826 distribution Methods 0.000 abstract description 7
- 238000005227 gel permeation chromatography Methods 0.000 abstract description 2
- 229920002799 BoPET Polymers 0.000 description 11
- 238000003483 aging Methods 0.000 description 10
- 230000032683 aging Effects 0.000 description 10
- 239000011248 coating agent Substances 0.000 description 9
- 238000000576 coating method Methods 0.000 description 9
- DXPPIEDUBFUSEZ-UHFFFAOYSA-N 6-methylheptyl prop-2-enoate Chemical group CC(C)CCCCCOC(=O)C=C DXPPIEDUBFUSEZ-UHFFFAOYSA-N 0.000 description 7
- 238000007664 blowing Methods 0.000 description 7
- 238000007334 copolymerization reaction Methods 0.000 description 7
- 235000021050 feed intake Nutrition 0.000 description 6
- 230000035484 reaction time Effects 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 5
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 230000001070 adhesive effect Effects 0.000 description 3
- 239000006087 Silane Coupling Agent Substances 0.000 description 2
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
- 238000004026 adhesive bonding Methods 0.000 description 2
- 239000002390 adhesive tape Substances 0.000 description 2
- 150000001336 alkenes Chemical class 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- LRDFRRGEGBBSRN-UHFFFAOYSA-N isobutyronitrile Chemical compound CC(C)C#N LRDFRRGEGBBSRN-UHFFFAOYSA-N 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 1
- KXKVLQRXCPHEJC-UHFFFAOYSA-N acetic acid trimethyl ester Natural products COC(C)=O KXKVLQRXCPHEJC-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 239000002585 base Substances 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
- 230000007547 defect Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005755 formation reaction Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 210000003739 neck Anatomy 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 238000005191 phase separation Methods 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 229920005862 polyol Polymers 0.000 description 1
- 150000003077 polyols Chemical class 0.000 description 1
- 230000001737 promoting effect Effects 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
- 238000012546 transfer Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Abstract
The preparation process of high performance and solvent type copolymer acrylate pressure sensitive adhesive, is made of the component of following weight：Its 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, accounting example early period of rise period is 10% 20%wt, the later stage ratio of rise period is 40% 60%wt, reaction terminating phase toatl proportion for 138 163%wt of monomer weight solvent and account for 0.03 0.5%wt initiators of total monomer weight and matched.The copolymer acrylate average molecular weight of the invention is big, and molecular weight distribution is wide, and copolymer acrylate molecular weight can be tested by gel permeation chromatography, and for weight average molecular weight in 450 900 kg/mol, molecular weight distributing index is 4 20.
Description
Technical field
The present invention relates to a kind of preparation processes of high performance and solvent type copolymer acrylate pressure sensitive adhesive, belong to chemical field.
Background technology
Pressure sensitive adhesive is a kind of without that in solvent, heat or other means, only need to apply slight pressure, you can with adherend
Bond firm adhesive.Pressure-sensitive is showed by its adhesion properties, and adhesion properties are made of four big bond properties,
Respectively initial bonding strength（tack）T, bonding force（adhesion）A, cohesive force（cohesion）C and base adhesion force（keying）K.Just
Viscous force T is also known as fast viscous force, refers to that quick separating is showed immediately after pressure sensitive adhesive product and adherend are with very light pressure contact
The resistant to separation ability gone out.Bonding force A refers to after being pasted with appropriate pressure and time, glue and by institute's table between maxxaedium
Reveal the ability for the resistance interfacial separation come；Cohesive force C refers to the intensity of gluing oxidant layer in itself；Base adhesion force K refers to adhesive
Bonding force between base material or adhesive and silane coupling agent and silane coupling agent and base material.The pressure sensitive adhesive good as one must be expired
The balance of four big bond properties of foot, T<A<C<K.Its middle-molecular-weihydroxyethyl and its distribution are the principal elements for influencing each bonding force.Nanjing
The Li Chuncheng of chemical engineering institute and Zheng Changren existChemical industry and bondingMagazine is published an article, and " molecular weight is to the shadow of pressure sensitive adhesive bond properties
It rings "（1996, the 3rd phase, 163）Illustrate, usual adhesive property is improved with the increase of molecular weight.When pressure sensitive adhesive keeps sufficiently high
When molecular weight and wider molecular weight distribution, the preferable pressure sensitive adhesive of comprehensive performance could be obtained.
Pressure-sensitive acrylate formula is simple, bonding range is wide, weatherability is good, light resistance is strong, oil resistivity is excellent, water resistance
It is good, there is no phenomena such as phase separation and migration, thus be widely used in every field.It can be divided into solvent according to different type
Type, emulsion-type, heat molten type, water-soluble glue-type and radiation curing etc., solvent-type acrylic esters pressure sensitive adhesive is by acrylate monomer
It carries out sticking thick liquid obtained by free radical polymerization in organic solvent, adds or be not added with what other additives were formed（It is divided into non-
Three kinds of cross-linking type, cross-linking type and non-aqueous dispersion type）.Solvent-type acrylic esters pressure sensitive adhesive is with wetability is good, initial bonding strength is big, dry
Dry rate is fast and many advantages, such as water-tolerant, is still widely used in the necks such as medical adhesive tape, pressure-sensitive label and double faced adhesive tape so far
Domain.The Chinese patent of application number " 201210311025.9 " discloses a kind of preparation method of solvent-type acrylic esters pressure sensitive adhesive
And application.But the major defect of country's solvent-type acrylic esters pressure sensitive adhesive is that holding power is not high under high temperature at present, main former
Because being that average molecular weight is relatively low, this is because take traditional solution processes, be compared to bulk polymerization, chain tra nsfer and
Chain termination easily by solvent effect, causes molecular weight to be difficult to reach sufficiently large, and the molecular weight propagation process time is long, is unfavorable for
Industrialized production.When polymerizeing in a solvent simultaneously, how a step realizes that wider molecular weight distribution is also a technical barrier.
Invention content
The purpose of the present invention is being directed to the deficiency of existing preparation process at present, a kind of high performance and solvent type copolymerization third is provided
The preparation process of olefin(e) acid ester pressure-sensitive, its object is to：Average molecular weight and the molecular weight distribution for increasing copolymer acrylate are wide
Degree, and then the comprehensive performances such as tack, holding power, high temperature resistance for improving pressure sensitive adhesive.
The preparation process of high performance and solvent type copolymer acrylate pressure sensitive adhesive, it is characterised in that：Including hard monomer, soft list
The raw material proportionings such as body, function monomer, solvent and initiator including another independent curing agent component, are additionally included in customization
The condition control of reaction process in stirred autoclave, the present invention is achieved by the following technical solutions.
(1) Monomer Formations technology
The soft monomer for copolymerization of the present invention, it is characterized in that referring to glass transition temperature between -20 DEG C~-70 DEG C of vinyl
Monomer, including ethyl acrylate（-22℃）, butyl acrylate（-55℃）, Isooctyl acrylate monomer（-70℃）；For the hard of copolymerization
Monomer includes methyl acrylate, vinylacetate, styrene, acrylonitrile, methyl methacrylate, for the crosslinking of copolymerization
Monomer includes acrylic acid, hydroxyethyl methacrylate, methacrylic acid.Its general structure of all comonomers is as follows.
The comonomer raw material proportioning of the present invention, soft monomer content are 65-90%wt.Hard monomer content is 10-30%wt,
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 are soft
Content of monomer 0-40%wt.
(2) initiator elicitation technique
For the present invention for the initiator of copolymerization, structure feature is organic peroxide or azo compound, is heated and divides
Solution causes monomer polymerization into free radical, including benzoyl peroxide, azodiisobutyronitrile, azobisisoheptonitrile.
Initiator feature dosage is the 0.03-0.5%wt of total monomer weight, preferably 0.06-0.3%wt.
(3) solvent burden ratio technology
The present invention is used to dissolve the solvent that copolymer acrylate is applicable in, it is characterised in that one or more of boiling point 60-120
Organic matter in the range of DEG C, including toluene, chlorobenzene, isopropanol, methyl acetate, ethyl acetate, propyl acetate.High performance pressure sensitive glue
Solvent ratios, it is characterised in that initial reaction stage accounts for the 10%wt of monomer ratio, and accounting example early period of rise period is 10%-20%wt,
The later stage ratio of rise period is 40%-60%wt, and reaction terminating phase toatl 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 characterised in that and agitating paddle takes double-layer structure to design,
Containing sped structure and overhead gage；With temperature measuring equipment entrance, nitrogen inlet, solid feed inlet, liquid addition port, reflux column and under
Discharge port；It also resides in and takes jacket type heating means.
The copolyreaction of the present invention, it is characterised in that by increasing the temperature to 72-96 DEG C, decomposition of initiator is promoted to be formed certainly
By base, so as to induced polymerization, basic process is divided into induction period, rise period and amortization period.Induction period temperature is set as 76-84
DEG C, after autoacceleration, the latter temperature of rise period is set as 88-96 DEG C, and fundamental reaction structural formula is as follows：
(5) curing technology
High performance pressure sensitive glue of the present invention, further includes the curing agent chemically reacted with cross-linking monomer, feature
Including the chemical combination compound containing isocyanate structural and polyalcohol, solvent ethyl acetate and for promoting urging for curing reaction
Agent dibutyl tin laurate（Its dosage is the 3% of isocyanate compound）, solid content 4.5%wt.Hardener dose is
Pressure sensitive adhesive solubilizer composite glue（Solid content 40%wt）1.5%wt.
The present invention has the advantages that compared with prior art：
The copolymer acrylate average molecular weight of the invention is big, and molecular weight distribution is wide, and copolymer acrylate molecular weight can lead to
It crosses gel permeation chromatography to be tested, weight average molecular weight is in 450-900 kg/mol, molecular weight distributing index 4-20.It will copolymerization
Acrylate is uniformly mixed with curing agent according to fixed proportion, and coated in PET film surface, thickness about 25-50 is measured after drying
Micron；After cured, tack 14-23 balls hold 2 hours peeling≤0.5cm of viscosity.Pressure sensitive adhesive coated on PET film,
After 71 DEG C of hot air agings 72 hours, adhesion strength and adhesion property keep stablizing.The bright pressure of these application data sheets
The tack of quick glue is good, and holding power is strong, and high temperature resistance is improved significantly.It is a kind of high solvent type copolymerization third of comprehensive performance
Olefin(e) acid ester pressure-sensitive.
Specific embodiment
Illustrate the present invention, but the present invention is not merely defined in these embodiments below by way of specific embodiment.
Embodiment 1
1200 grams, Isooctyl acrylate monomer 400g, styrene 140g, vinylacetate 200g of butyl acrylate, acrylic acid
60g, toluene 400g, azodiisobutyronitrile 1g are dosed into 50L mechanic whirl-nett reaction kettles, after replacing nitrogen three times, setting stirring
Speed 100r/min is warming up to 82 DEG C, 5 DEG C/min of heating rate, about 20 minutes stabilizations to set temperature.
After 82 DEG C of reactions 2.5 hours, feed intake azodiisobutyronitrile 1.5g from solid feeding port, add first from liquid feed mouth
Benzene 400g sets mixing speed 50r/min, and the reaction was continued 1 hour.
88 DEG C are raised the temperature to again, from liquid addition port plus ethyl acetate 1000g, are fed intake azo two from solid feeding port
Isobutyronitrile 1.5g, sustained response cool down after 1 hour, add ethyl acetate 1200g, enter container from feed opening blowing after stirring evenly
In, it is sealed to be measured.
After solvent is dried, measure infrared and molecular weight and see attached drawing 1 and subordinate list 1.
The preparation method of curing agent component is as follows, according to molar ratio as n at a temperature of setting 60 DEG CNCO：nOH= 2:1 ratio
Example input toluene di-isocyanate(TDI) and polyether polyol（Hydroxyl value 130mgKOH/g, functionality 2.2）.12 hours postcoolings are reacted,
Measure isocyanate content is 12%wt, adds the dibutyl tin laurate of 3% ratio, and be diluted to total solid content with ethyl acetate
4.5%wt。
Hardener dose 4.5% through coating machine is coated onto PET film surface after being mixed with glue, and it is just viscous and hold viscous strong to measure it
Degree, and through 71 DEG C of hot air agings, its applicable cases is measured, concrete outcome sees attached list 2.
Embodiment 2
1000 grams, Isooctyl acrylate monomer 600g, styrene 100g, vinylacetate 240g of butyl acrylate, acrylic acid hydroxyl
Ethyl ester 60g, toluene 400g, azobisisoheptonitrile 0.75g are dosed into 50L mechanic whirl-nett reaction kettles, after replacing nitrogen three times, if
Determine mixing speed 100r/min, be warming up to 82 DEG C, 5 DEG C/min of heating rate.About 20 minutes stabilizations are to set temperature.
After 76 DEG C of 2.5 hours reaction time, feed intake azobisisoheptonitrile 1g from solid feeding port, add from liquid feed mouth
Toluene 400g sets mixing speed 50r/min, and the reaction was continued 2 hours.
84 DEG C are raised the temperature to again, from liquid addition port plus ethyl acetate 1000g, are fed intake azo two from solid feeding port
Different heptonitrile 1.5g, sustained response cool down after 2 hours, add ethyl acetate 1200g, enter container from feed opening blowing after stirring evenly
In, it is sealed to be measured.
After solvent is dried, measure molecular weight and see attached list 1.
The preparation method is the same as that of Example 1 for curing agent component.
Hardener dose 4.5% through coating machine is coated onto PET film surface after being mixed with glue, and it is just viscous and hold viscous strong to measure it
Degree, and through 71 DEG C of hot air agings, its applicable cases is measured, concrete outcome sees attached list 2.
Embodiment 3
1600 grams, methyl methacrylate 340g, methacrylic acid 60g, chlorobenzene 400g of butyl acrylate, two different heptan of azo
Nitrile 0.75g is dosed into 50L mechanic whirl-nett reaction kettles, after replacing nitrogen three times, is set mixing speed 100r/min, is warming up to 82
DEG C, 5 DEG C/min of heating rate.About 20 minutes stabilizations are to set temperature.
After 76 DEG C of 4.5 hours reaction time, feed intake azobisisoheptonitrile 0.25g from solid feeding port, from liquid feed
Mouth plus toluene 400g set mixing speed 50r/min, and the reaction was continued 2 hours.
84 DEG C are raised the temperature to again, from liquid addition port plus propyl acetate 1000g, are fed intake azo two from solid feeding port
Different heptonitrile 1.5g, sustained response cool down after 2 hours, add propyl acetate 1200g, enter container from feed opening blowing after stirring evenly
In, it is sealed to be measured.
After solvent is dried, measure molecular weight and see attached list 1.
The preparation method is the same as that of Example 1 for curing agent component.
Hardener dose 4.5% through coating machine is coated onto PET film surface after being mixed with glue, and it is just viscous and hold viscous strong to measure it
Degree, and through 71 DEG C of hot air agings, its applicable cases is measured, concrete outcome sees attached list 2.
Embodiment 4
1200 grams, Isooctyl acrylate monomer 400g, styrene 150g, vinylacetate 150g of butyl acrylate, acrylic acid
100g, toluene 400g, remaining reaction method is the same as embodiment 1.
After solvent is dried, measure molecular weight and see attached list 1.
The preparation method is the same as that of Example 1 for curing agent component.
Hardener dose 4.5% through coating machine is coated onto PET film surface after being mixed with glue, and it is just viscous and hold viscous strong to measure it
Degree, and through 72 DEG C of hot air agings, its applicable cases is measured, concrete outcome sees attached list 2.
Embodiment 5
1400 grams, Isooctyl acrylate monomer 400g, styrene 60g, vinylacetate 80g, acrylic acid 60g of butyl acrylate,
Reaction process control condition is the same as embodiment 1.After solvent is dried, measure molecular weight and see attached list 1.
The preparation method is the same as that of Example 1 for curing agent component.
Hardener dose 4.5% through coating machine is coated onto PET film surface after being mixed with glue, and it is just viscous and hold viscous strong to measure it
Degree, and through 71 DEG C of hot air agings, its applicable cases is measured, concrete outcome sees attached list 2.
Embodiment 6
1200 grams, Isooctyl acrylate monomer 400g, styrene 140g, vinylacetate 200g of butyl acrylate, acrylic acid
60g, toluene 400g, benzoyl peroxide 1g are dosed into 50L mechanic whirl-nett reaction kettles, after replacing nitrogen three times, setting stirring
Speed 100r/min is warming up to 84 DEG C, 5 DEG C/min of heating rate.About 20 minutes stabilizations are to set temperature.
After 84 DEG C of 3.5 hours reaction time, feed intake benzoyl peroxide 1.5g from solid feeding port, from liquid feed mouth
Add toluene 400g, set mixing speed 50r/min, the reaction was continued 1 hour.
88 DEG C are raised the temperature to again, from liquid addition port plus ethyl acetate 1000g, are fed intake azo two from solid feeding port
Isobutyronitrile 1.5g, sustained response cool down after 1 hour, add ethyl acetate 1600g, enter container from feed opening blowing after stirring evenly
In, it is sealed to be measured.
After solvent is dried, molecular weight subordinate list 1 is measured.
The preparation method is the same as that of Example 1 for curing agent component.
Hardener dose 4.5% through coating machine is coated onto PET film surface after being mixed with glue, and it is just viscous and hold viscous strong to measure it
Degree, and through 71 DEG C of hot air agings, its applicable cases is measured, concrete outcome sees attached list 2.
Embodiment 7
1200 grams, Isooctyl acrylate monomer 600g, styrene 140g, acrylic acid 60g, toluene 400g of butyl acrylate, azo
Two different heptonitrile 1g are dosed into 50L mechanic whirl-nett reaction kettles, after replacing nitrogen three times, set mixing speed 100r/min, heating
To 82 DEG C, 5 DEG C/min of heating rate.About 20 minutes stabilizations are to set temperature.
After 82 DEG C of 2.5 hours reaction time, feed intake azobisisoheptonitrile 1.5g from solid feeding port, from liquid feed mouth
Add toluene 400g, set mixing speed 50r/min, the reaction was continued 1 hour.
88 DEG C are raised the temperature to again, from liquid addition port plus ethyl acetate 1000g, are fed intake azo two from solid feeding port
Different heptonitrile 1.5g, sustained response cool down after 1 hour, add ethyl acetate 2000g, enter container from feed opening blowing after stirring evenly
In, it is sealed to be measured.
After solvent is dried, molecular weight subordinate list 1 is measured.
The preparation method is the same as that of Example 1 for curing agent component.
Hardener dose 4.5% through coating machine is coated onto PET film surface after being mixed with glue, and it is just viscous and hold viscous strong to measure it
Degree, and through 71 DEG C of hot air agings, its applicable cases is measured, concrete outcome sees attached list 2.
Comparative example 1
It is synthesized, is compared with embodiment 1,1200 grams of butyl acrylate, propylene according to feeding method of tradition
Sour different monooctyl ester 400g, styrene 160g, vinylacetate 180g, acrylic acid 60g, toluene 400g, azodiisobutyronitrile 2g feed intake
Into 50L mechanic whirl-nett reaction kettles, after replacing nitrogen three times, mixing speed 100r/min is set, is warming up to 82 DEG C, heating rate
5℃/min.About 20 minutes stabilizations are to set temperature.After 82 DEG C of 6 hours reaction time, from liquid addition port plus ethyl acetate
2600g enters from feed opening blowing in container after stirring evenly, and is sealed to be measured.
After solvent is dried, measure molecular weight and see attached list 1.
The preparation method is the same as that of Example 1 for curing agent.
Hardener dose 4.5% through coating machine is coated onto PET film surface after being mixed with glue, and it is just viscous and hold viscous strong to measure it
Degree, and through 71 DEG C of hot air agings, its applicable cases is measured, concrete outcome sees attached list 2.
Comparative example 2
It is compared with embodiment 3,1600 grams, methyl methacrylate 340g, acrylic acid 60g of butyl acrylate, toluene
400g, azodiisobutyronitrile 2g are dosed into 50L mechanic whirl-nett reaction kettles, after replacing nitrogen three times, set mixing speed 100r/
Min is warming up to 82 DEG C, 5 DEG C/min of heating rate.About 20 minutes stabilizations are to set temperature.After 82 DEG C of 6 hours reaction time,
From liquid addition port plus ethyl acetate 2600g, enter in container from feed opening blowing after stirring evenly, be sealed to be measured.
After solvent is dried, measure molecular weight and see attached list 1.
The preparation method is the same as that of Example 1 for curing agent.
Hardener dose 4.5% through coating machine is coated onto PET film surface after being mixed with glue, and it is just viscous and hold viscous strong to measure it
Degree, and through 71 DEG C of hot air agings, its applicable cases is measured, concrete outcome sees attached list 2.
The present invention is not limited solely to above-mentioned specific embodiment.
Subordinate list 1：Each batch molecular weight product and molecular weight distribution list.
Subordinate list 2：Application situation table.
Claims (9)
1. the preparation process of high performance and solvent type copolymer acrylate pressure sensitive adhesive, which is characterized in that by following weight
Component forms：Soft monomer content is 65-90%wt；Hard monomer content is 10-30%wt；Cross-linking monomer content is 3%-5%wt, is owned
Content of monomer is 100%wt；Initial reaction stage accounts for the 20%wt of monomer ratio, accounts for monomer ratio as 10%-20%wt the early period of rise period,
The later stage of rise period accounts for monomer ratio as 40%-60%wt, and the reaction terminating phase accounts for monomer ratio as 60%wt or 80%wt or 100%wt
Solvent and account for the 0.03-0.5%wt initiators of total monomer weight and matched, further include that chemistry occurs with cross-linking monomer is anti-
The curing agent answered, the preparation process of the high performance and solvent type copolymer acrylate pressure sensitive adhesive are：Hard monomer, soft is weighed by proportioning
Monomer, initiator, cross-linking monomer and solvent, put into reaction kettle step by step, and keep stirring in reaction kettle, is allowed to gradual
72-96 DEG C is warming up to, decomposition of initiator is promoted to form free radical, so as to induced polymerization, basic process is divided into induction period, increases
Phase and amortization period；Induction period temperature is set as 76-84 DEG C, and after autoacceleration, the latter temperature of rise period is set as 88-96 DEG C,
It is sufficiently stirred, naturally cools to 50 DEG C or so dischargings after reacting 3 ~ 4h, the substep, which feeds intake, to be referred to soft monomer, hard list first
Body, cross-linking monomer, partial solvent, part initiator mixing are thrown into reaction kettle, after replacing nitrogen three times, set mixing speed
100r/min is warming up to 76-84 DEG C, 5 DEG C/min of heating rate, about 20 minutes stabilizations to set temperature；Secondly, at 76-84 DEG C
It after reaction 2.5 hours or 4.5 hours, feeds intake part initiator from solid feeding port, adds partial solvent from liquid feed mouth, set
Mixing speed 50r/min, the reaction was continued 1 hour or 2 hours；Temperature is risen to 88-96 DEG C again, adds part molten from liquid feed mouth
Agent feeds intake part initiator from solid feeding port, and sustained response cools down after 1 hour or 2 hours, adds residual solvent.
2. the preparation process of high performance and solvent type copolymer acrylate pressure sensitive adhesive according to claim 1, it is characterised in that：Institute
It is glass transition temperature between -20 DEG C~-70 DEG C of vinyl monomer to state soft monomer, is ethyl acrylate, butyl acrylate, propylene
One or more of the different monooctyl ester of acid mixture.
3. the preparation process of high performance and solvent type copolymer acrylate pressure sensitive adhesive according to claim 1, it is characterised in that：Institute
Hard monomer is stated, includes one kind or several in methyl acrylate, vinylacetate, styrene, acrylonitrile, methyl methacrylate
Kind mixture.
4. the preparation process of high performance and solvent type copolymer acrylate pressure sensitive adhesive according to claim 1, it is characterised in that：Institute
It states cross-linking monomer and includes one or more of acrylic acid, hydroxyethyl methacrylate, methacrylic acid mixture.
5. the preparation process of high performance and solvent type copolymer acrylate pressure sensitive adhesive according to claim 1, it is characterised in that：Institute
Initiator is stated as organic peroxide or azo compound, free radical is thermally decomposed into and causes monomer polymerization, is benzoyl peroxide
One or more of formyl, azodiisobutyronitrile, azobisisoheptonitrile mixture.
6. the preparation process of high performance and solvent type copolymer acrylate pressure sensitive adhesive according to claim 1, it is characterised in that：Institute
It is the organic matter in the range of one or more of 60-120 DEG C of boiling points to state solvent, is toluene, isopropanol, ethyl acetate, propyl acetate
One or more of mixture.
7. the preparation process of high performance and solvent type copolymer acrylate pressure sensitive adhesive according to claim 1, it is characterised in that：Institute
State curing agent include the chemical combination compound containing isocyanate structural and polyalcohol, solvent ethyl acetate and for promote cure
The catalyst dibutyltin dilaurylate of reaction, catalyst amount are the 3% of isocyanate compound, and curing agent solid content is
4.5%wt。
8. the preparation process of high performance and solvent type copolymer acrylate pressure sensitive adhesive according to claim 1, it is characterised in that：Institute
State the 0.06-0.3%wt that initiator amount is total monomer weight.
9. the preparation process of high performance and solvent type copolymer acrylate pressure sensitive adhesive according to claim 1, it is characterised in that：Institute
The 1.5%wt that hardener dose is composite glue is stated, composite glue is combined by the pressure sensitive adhesive solubilizer that solid content is 40%wt.
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| CN105219316B (en) * | 2015-11-12 | 2017-09-19 | 四川厚生天佐药业有限公司 | A kind of high adhesiveness energy medical polyacrylate pressure-sensitive adhesive sticks agent |
| CN105419688A (en) * | 2015-12-02 | 2016-03-23 | 安徽金信地首饰有限公司 | Modified acrylate adhesive |
| CN105400464B (en) * | 2015-12-24 | 2017-02-08 | 广州市金万正印刷材料有限公司 | Freeze-tolerant acrylate pressure-sensitive adhesive, preparation method thereof, and application thereof in production of freeze-tolerant acrylate pressure-sensitive labels |
| CN105778833A (en) * | 2016-03-21 | 2016-07-20 | 苏州华周胶带有限公司 | Pressure-sensitive adhesive for pressure-sensitive adhesive tapes |
| CN107142034A (en) * | 2017-05-09 | 2017-09-08 | 北京化工大学 | A kind of heat conduction pressure sensitive adhesive and preparation method that graphene is peeled off comprising physics |
| CN107610585B (en) * | 2017-09-18 | 2021-04-20 | 江苏景宏新材料科技有限公司 | Preparation of washable transparent heat-shrinkable beer bottle label and label washing process thereof |
| CN109054701A (en) * | 2018-07-11 | 2018-12-21 | 江苏景宏新材料科技有限公司 | Low temperature resistant pressure-sensitive adhesive agent and preparation method thereof |
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