CN102633954B - Environment-friendly emulsion modified acrylate pigment dyeing adhesive and manufacturing method thereof - Google Patents
Environment-friendly emulsion modified acrylate pigment dyeing adhesive and manufacturing method thereof Download PDFInfo
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- 239000000839 emulsion Substances 0.000 title claims abstract description 40
- 238000004043 dyeing Methods 0.000 title claims abstract description 28
- 150000001252 acrylic acid derivatives Chemical class 0.000 title claims abstract description 19
- 239000000049 pigment Substances 0.000 title abstract description 23
- 239000000853 adhesive Substances 0.000 title abstract description 17
- 230000001070 adhesive effect Effects 0.000 title abstract description 14
- 238000004519 manufacturing process Methods 0.000 title abstract description 8
- 239000003995 emulsifying agent Substances 0.000 claims abstract description 59
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 claims abstract description 40
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims abstract description 39
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims abstract description 39
- 229920000570 polyether Polymers 0.000 claims abstract description 32
- 239000003921 oil Substances 0.000 claims abstract description 26
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 claims abstract description 20
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims abstract description 20
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 claims abstract description 20
- 239000000463 material Substances 0.000 claims abstract description 18
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims abstract description 15
- 239000004721 Polyphenylene oxide Substances 0.000 claims abstract description 7
- 238000003756 stirring Methods 0.000 claims description 72
- 238000006243 chemical reaction Methods 0.000 claims description 58
- -1 methylsiloxane Chemical class 0.000 claims description 27
- 238000002360 preparation method Methods 0.000 claims description 27
- RZJRJXONCZWCBN-UHFFFAOYSA-N octadecane Chemical compound CCCCCCCCCCCCCCCCCC RZJRJXONCZWCBN-UHFFFAOYSA-N 0.000 claims description 26
- 239000000203 mixture Substances 0.000 claims description 25
- XMPZTFVPEKAKFH-UHFFFAOYSA-P ceric ammonium nitrate Chemical compound [NH4+].[NH4+].[Ce+4].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O XMPZTFVPEKAKFH-UHFFFAOYSA-P 0.000 claims description 24
- 239000003795 chemical substances by application Substances 0.000 claims description 24
- 239000002994 raw material Substances 0.000 claims description 24
- 239000011248 coating agent Substances 0.000 claims description 22
- 238000000576 coating method Methods 0.000 claims description 22
- 238000009413 insulation Methods 0.000 claims description 22
- 239000004593 Epoxy Substances 0.000 claims description 20
- QOSMNYMQXIVWKY-UHFFFAOYSA-N Propyl levulinate Chemical compound CCCOC(=O)CCC(C)=O QOSMNYMQXIVWKY-UHFFFAOYSA-N 0.000 claims description 19
- 239000012874 anionic emulsifier Substances 0.000 claims description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 15
- 229940038384 octadecane Drugs 0.000 claims description 13
- 229920001897 terpolymer Polymers 0.000 claims description 13
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 12
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 12
- 229920001400 block copolymer Polymers 0.000 claims description 12
- 239000008367 deionised water Substances 0.000 claims description 12
- 229910021641 deionized water Inorganic materials 0.000 claims description 12
- XQSFXFQDJCDXDT-UHFFFAOYSA-N hydroxysilicon Chemical compound [Si]O XQSFXFQDJCDXDT-UHFFFAOYSA-N 0.000 claims description 12
- 239000003999 initiator Substances 0.000 claims description 12
- 239000004094 surface-active agent Substances 0.000 claims description 12
- 238000010792 warming Methods 0.000 claims description 12
- 239000006185 dispersion Substances 0.000 claims description 8
- 239000000126 substance Substances 0.000 claims description 7
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 claims description 6
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 6
- 125000001931 aliphatic group Chemical group 0.000 claims description 6
- 229910052783 alkali metal Inorganic materials 0.000 claims description 6
- 230000009435 amidation Effects 0.000 claims description 6
- 238000007112 amidation reaction Methods 0.000 claims description 6
- 229910021529 ammonia Inorganic materials 0.000 claims description 6
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 6
- 238000009835 boiling Methods 0.000 claims description 6
- 239000003054 catalyst Substances 0.000 claims description 6
- 150000001875 compounds Chemical class 0.000 claims description 6
- 239000007822 coupling agent Substances 0.000 claims description 6
- 238000004945 emulsification Methods 0.000 claims description 6
- 230000001804 emulsifying effect Effects 0.000 claims description 6
- 238000011067 equilibration Methods 0.000 claims description 6
- 229910052742 iron Inorganic materials 0.000 claims description 6
- HMMGMWAXVFQUOA-UHFFFAOYSA-N octamethylcyclotetrasiloxane Chemical compound C[Si]1(C)O[Si](C)(C)O[Si](C)(C)O[Si](C)(C)O1 HMMGMWAXVFQUOA-UHFFFAOYSA-N 0.000 claims description 6
- 238000010008 shearing Methods 0.000 claims description 6
- XFTALRAZSCGSKN-UHFFFAOYSA-M sodium;4-ethenylbenzenesulfonate Chemical compound [Na+].[O-]S(=O)(=O)C1=CC=C(C=C)C=C1 XFTALRAZSCGSKN-UHFFFAOYSA-M 0.000 claims description 6
- 239000002904 solvent Substances 0.000 claims description 6
- 239000004744 fabric Substances 0.000 abstract description 17
- 238000000034 method Methods 0.000 abstract description 16
- 230000008569 process Effects 0.000 abstract description 6
- 230000000694 effects Effects 0.000 abstract description 3
- 239000000654 additive Substances 0.000 abstract description 2
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- 230000007774 longterm Effects 0.000 abstract description 2
- 238000006116 polymerization reaction Methods 0.000 abstract description 2
- 206010016322 Feeling abnormal Diseases 0.000 abstract 1
- 230000000996 additive effect Effects 0.000 abstract 1
- 230000009286 beneficial effect Effects 0.000 abstract 1
- RPQRDASANLAFCM-UHFFFAOYSA-N oxiran-2-ylmethyl prop-2-enoate Chemical compound C=CC(=O)OCC1CO1 RPQRDASANLAFCM-UHFFFAOYSA-N 0.000 abstract 1
- 230000010148 water-pollination Effects 0.000 abstract 1
- 238000007639 printing Methods 0.000 description 25
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical class O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 13
- 238000005516 engineering process Methods 0.000 description 8
- 230000007613 environmental effect Effects 0.000 description 7
- 239000000975 dye Substances 0.000 description 5
- 235000019256 formaldehyde Nutrition 0.000 description 5
- 239000004753 textile Substances 0.000 description 5
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical class OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- 150000001408 amides Chemical class 0.000 description 3
- 239000012752 auxiliary agent Substances 0.000 description 3
- 239000011230 binding agent Substances 0.000 description 3
- 238000001514 detection method Methods 0.000 description 3
- 239000000835 fiber Substances 0.000 description 3
- 239000004816 latex Substances 0.000 description 3
- 229920000126 latex Polymers 0.000 description 3
- 239000003973 paint Substances 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 230000005855 radiation Effects 0.000 description 2
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- 229920005989 resin Polymers 0.000 description 2
- 230000008719 thickening Effects 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- DUIOKRXOKLLURE-UHFFFAOYSA-N 2-octylphenol Chemical compound CCCCCCCCC1=CC=CC=C1O DUIOKRXOKLLURE-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 1
- 235000016623 Fragaria vesca Nutrition 0.000 description 1
- 240000009088 Fragaria x ananassa Species 0.000 description 1
- 235000011363 Fragaria x ananassa Nutrition 0.000 description 1
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
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- 210000000981 epithelium Anatomy 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
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- 238000009776 industrial production Methods 0.000 description 1
- 235000015110 jellies Nutrition 0.000 description 1
- 239000008274 jelly Substances 0.000 description 1
- 239000004530 micro-emulsion Substances 0.000 description 1
- HQVFKSDWNYVAQD-UHFFFAOYSA-N n-hydroxyprop-2-enamide Chemical compound ONC(=O)C=C HQVFKSDWNYVAQD-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
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- Silicon Polymers (AREA)
- Paints Or Removers (AREA)
- Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
Abstract
The invention relates to an environment-friendly emulsion modified acrylate pigment dyeing adhesive and a manufacturing method of the environment-friendly emulsion modified acrylate pigment dyeing adhesive. Through improvement of additive order and relavent process parameters of materials such as a combination of methyl methacrylate, methyl acrylate, ethyl acrylate, glycidyl acrylate and acrylic acid, linear block polyether octodecane amino ternary polymerization modified silicon oil, emulsifier and the like, the environment-friendly emulsion modified acrylate pigment dyeing adhesive and the manufacturing method aim at solving the long-term technical problems that fabric feels hard, crockfastness is poor, rubbing fastness is low, hardness of dyed fabric is higher, adhesive force is low and environment is polluted, so as to realize the beneficial technical effects of good crockfastness, high rubbing fastness, soft feeling on dyed fabric, good hydrophily of the dyed fabric, better adhesive force and environment-friendly production process.
Description
Technical field
The present invention relates to the pigment dyeing binding agent technical field, relate in particular to a kind of environmental-friendly type emulsion shape modified acrylate coating material dyeing tackiness agent and preparation method thereof.
Background technology
Pigment dyeing is that coating is made dispersion liquid, makes fabric homogeneous band liquid by padding, then through pyroprocessing, effect by means of tackiness agent, form layer of transparent and tough and tensile resin film at fabric, thus with paint machine be bonded on the fiber, coating itself does not have avidity to fiber.
Coating is widely used at stamp for a long time as a kind of pigment, in recent years, because the range of application of coating has been expanded in improving constantly of dyeing and printing auxiliary (as tackiness agent) performance, makes pigment dyeing technique obtain developing rapidly.Pigment dyeing also has weak point, has determined its crock fastness as mechanical set, and it is not high especially to wash fastness by rubbing with the hands, dyes the back fabric feeling and hardens etc.
The quality of pigment dyeing quality, key are selecting for use of tackiness agent.The pigment dyeing tackiness agent, should not wear out and yellowing etc. at performance requriements such as good film-forming properties and stability, suitable clinging power, higher chemically-resistant medicament stability, epithelium water white transparency, high resilience and toughness.Higher to fastness and feel requirement, and be difficult for sticking roll etc.Adhesive agent emulsion does not contain the N-methylol, does not contain APEO, energy-conserving and environment-protective.
In recent years, be devoted to seek new green type environment-friendly adhesive both at home and abroad, patent has been prepared a kind of environmentally-friendly acrylic ester coating printing adhesive both at home and abroad, but can not solve the problems such as the back fabric feeling hardens of dying, the domestic patent that also has has been prepared a kind of environment protection type microemulsion interpenetrating network pigment resin printing adhesive agent, solved feel, problems such as environmental protection, but can not solve problems such as dying the back fabric hydrophilic.
Pigment printing is by means of tackiness agent coating to be adhered to the printing technology that fiber surface obtains required pattern, now has been widely used in various textiless, advantage such as have that technology is simple, bright in colour, decorative pattern is clear, energy-and time-economizing, the three wastes are few.The mill base of pigment printing is many to be made up of pigment, tackiness agent, thickening material and other additives etc.Wherein, the weight of tackiness agent is the most key for the influence of the feel of stamp product, vividness, every fastness indexs such as (friction, washing and drycleanings etc.).
Most printing adhesives in the market all contain a certain amount of N-hydroxyacrylamide cross-linking monomer, bake with storage process in can discharge a large amount of free formaldehydes, can't satisfy the requirement of high weight textiles and clothes, have a strong impact on and limited the development of China's rag trade.In addition, alkylphenol polyoxyethylene (APEO) because of security not high and biological degradability difference etc. the potential hazard that environment exists has been studied widely and has been proved, some countries of Europe have just formulated its production of regulation limitations and use from 1976.And European Union has also made clear and definite restriction and regulation in formal promulgation on June 18th, 2003 rules to use, circulation and the discharging of APEO, and is especially stricter to limiting the quantity of of the APEO in textiles and the clothes.The textiles that China exports to Europe every year and clothes are worth and reach more than 100 hundred million dollars, thus must use by careful attention APEO, and effective ways are exactly the substitute of seeking the tensio-active agent and the dyeing and printing auxiliary that contain APEO.Pigment printing development in future trend must be that the direction towards high-performance, environment-friendly type develops.
Pigment printing is a kind of process for cleanly preparing, need not to evaporate and wash, and technology is simple, has lot of advantages, is subjected to printer author's favor deeply.The printing technique development of China is at full speed, and with regard to stamp output, the tprinted Fabrics output of China in 2002 just reaches 43.67 myriametres, accounts for first place, the world.The printing technology technology and equipment that present China adopts, with world level gap and little, we can say, state-of-the-art equipment in the world, can both see in China, traditional printing technology does not have big variation yet on method, but with regard to the stamp product quality, but very big with the international most advanced level gap, why big like this difference is arranged, key is the pigment printing auxiliary agent, special picture tackiness agent, cross linking agent, auxiliary agent quality such as thickening material can not get basic solution, cause the pigment printing network blocking easily, also there are problems such as release formaldehyde in feel not as dye printing, wherein, pigment printing binding agent is the main component of textile printing pigment, crucial kind, consumption is very big, and the quality of pigment printing quality directly is subjected to the printing adhesive Effect on Performance.At present, weaving needs in the process of using could make that with the active group that contains methylol third rare amides in the paint adhesive moiety fabric obtains desirable dried, fastness to wet rubbing more after high temperature bakes.High temperature bakes the physicals of DYED FABRICS is sustained damage, and on the other hand, relies on methylol third rare amides active group producing the release that will be accompanied by formaldehyde in crosslinked and the process of taking inevitably behind the high temperature action, and environment is polluted.Also there is report can produce the formaldehydeless printing adhesive of low temperature recently, but still need bake, just temperature lower (100 ℃～130 ℃), and majority is to bake the active group of crosslinked usefulness with epoxy chloropropionate alkanes replacement N-methylol third rare amides as the later stage.This improving one's methods not only can not fundamentally solve unfavorable factor on the product performance that pyroprocessing brings, but also is attended by the pollution hidden trouble that can absorb organic halogen.
In recent years, be devoted to seek new green type adhesive product both at home and abroad, that its requirement has is wear-resisting, water tolerance and higher draw tensile strength the time, want compliance with environmental protection requirements especially, reaches the many-sided balances such as feel, fastness and Environmental Safety that solve pigment printing.In European patent EP 0,892, reported in the 094A2 communique that the ester modified and nucleocapsid production technique of use side hydroxyl acrylic prepared a kind of core-shell type paint dyeing and printing adhesive agent emulsion, but should invention in polymkeric substance is synthetic, adopt octyl phenol Soxylat A 25-7 (OPEO) as nonionogenic tenside, OPEO is a kind of of APEO, belong to non-feature of environmental protection emulsifying agent category, and the emulsifying agent consumption is usually than other auxiliary agents big (the emulsifying agent consumption is 2%～5% in this invention), so the polymer emulsion that obtains with this method embodies its feature of environmental protection with the textile printing tackiness agent than difficulty; The performance of this patent application gained emulsion depends on the latex particle of its hud typed structure, and because latex particle nucleocapsid structure generation influence factor is more, often obtain snowman's type, strawberry type even the isostructural particle of counter-rotative type, especially circumstance complication is wayward in the industrial production, be difficult to obtain having the latex particle of real nucleocapsid structure, so this technology is used the existence restriction in the scale operation.In addition, Japanese patent laid-open 5-271432 communique discloses a kind of environment-protection coating printing adhesive and preparation method, this method is at first prepared the poly-amino performed polymer of end-vinyl, then aqueous dispersions irradiation 30～50min under 1.5～2.5KGy radiation dose condition that its performed polymer and acrylate monomer and water are mixed with.This invention report is good by the binder performance of this method preparation, and formaldehyde and APEO content satisfy environmental requirement all less than 5ppm.And owing to radio polymerization need carry out under the condition of logical nitrogen deoxidation, and source of radiation is expensive, so this method production cost adhesive agent emulsion solid content higher and that prepare lower (being about 40%).
Summary of the invention
The objective of the invention is the above-mentioned deficiency at prior art, a kind of environmental-friendly type emulsion shape modified acrylate coating material dyeing tackiness agent and preparation method thereof is provided, pass through methyl methacrylate, methyl acrylate, ethyl propenoate, acrylic acid epoxy propyl ester and acrylic acid composition, and the amino terpolymer modified silicon oil of linearity block polyethers octadecane and emulsifying agent etc. add the improvement of order and related process parameter, endeavour to solve fabric feeling is hardened, crock fastness is poor, it is not high to wash fastness by rubbing with the hands, it is higher to dye back fabric hardness, the long-term technical problem of clinging power difference and environmental pollution, thereby it is good to reach crock fastness, especially wash the fastness height by rubbing with the hands, dye the back fabric feeling and feel like jelly, it is good to dye the back fabric hydrophilic, especially the good and production process environmental protection close friend's of clinging power useful technique effect.
For achieving the above object, the present invention is achieved by the following technical solutions:
The preparation method of a kind of environmental-friendly type emulsion shape modified acrylate coating material dyeing tackiness agent of the present invention is characterized in that this preparation method comprises following operation steps:
(1) selects methyl methacrylate, methyl acrylate, ethyl propenoate, acrylic acid epoxy propyl ester and acrylic acid composition for use, described methyl methacrylate, methyl acrylate, ethyl propenoate, acrylic acid epoxy propyl ester and acrylic acid amount ratio are 1.3: 2.4: 3.1 with molar ratio computing: 1.4: 2.6;
(2) with octamethylcyclotetrasiloxane, the mixture of low viscous hydroxy silicon oil is a kind of raw material A, with 1,1,3, it is in 785 rev/mins the high speed rotating stirring tank that the 3-tetramethyl disiloxane drops into the commentaries on classics degree by 4: 20 weight ratio, 35% the initiator ceric ammonium nitrate that adds described raw material A weight simultaneously, stirring reaction is 15 minutes when temperature is 95 ℃, 5% the amidation coupling agent that adds described raw material A weight, when temperature is 18 ℃, carried out equilibration reaction 30 minutes, vacuumize lower-molecular substance again, must hold hydrogeneous methylsiloxane intermediate, described hydroxy silicon oil is 15mpas 25 ℃ viscosity; The hydrogeneous methylsiloxane intermediate of end and allyl polyether with preparation, drop in the reactor by 2: 1 weight ratios, in the presence of solvent, when temperature is 15 ℃, stir, insulation reaction 12 minutes, drip 0.00001% iron catalyst of raw material A weight, stirring reaction 30 minutes gets organopolysiloxane-polyethers linear block copolymers; It is in 1565 rev/mins the low speed rotation stirring tank that above-mentioned organopolysiloxane-polyethers linear block copolymers and capacity strong aqua are dropped into the commentaries on classics degree, when being 65 ℃, temperature stirs, insulation reaction 40 minutes, vacuumize unreacted ammonia, get the amino terpolymer modified silicon oil of linearity block polyethers octadecane;
(3) form mixed emulsifier A by the compound back of anionic emulsifier and nonionic surface active agent, the emulsifying agent B that is formed by emulsifier op-10; Wherein, the weight proportion of mixed emulsifier A is anionic emulsifier: nonionic surface active agent is 1.6: 3.3, and the weight ratio of described emulsifying agent A and emulsifying agent B is 2.6: 1.4;
Described anionic emulsifier is the combination of an alkali metal salt of alkyl vinylformic acid-2-ethanesulfonic acid sodium, sodium p styrene sulfonate and aliphatic dicarboxylic acid;
(4) in the high speed rotating reaction vessel, be to be dissolved in 2.4L deionized water at 2.6: 1.4 emulsifying agent A and emulsifying agent B according to weight ratio, when being 985 rev/mins, stirs the rotating speed of high speed rotating reaction vessel, stir after 5 minutes, stirred when being 685 rev/mins with rotating speed 15 minutes, add described methyl methacrylate, methyl acrylate, ethyl propenoate, acrylic acid epoxy propyl ester and acrylic acid composition then, when the rotating speed of low speed rotation reaction vessel is 285 rev/mins, stir, stir after 5 minutes; Add the amino terpolymer modified silicon oil of described linearity block polyethers octadecane then, by high-shearing dispersion emulsifying machine quick emulsification 26min, make pre-emulsion A and wait to drip;
In four-hole boiling flask, add deionized water, emulsifying agent A, mix and stir 10min, be warming up to 45 ℃ and kept 30 minutes, add the initiator ceric ammonium nitrate; Slowly be warming up to 70 ℃-80 ℃, drip described pre-emulsion A with 35 droplets/minute, drip finish after, 70～72 ℃ of following insulation reaction 2h are cooled to 45～50 ℃, add ammoniacal liquor and regulate pH value 6.5～7.0, continue stirring 15min.
As optimized technical scheme:
Drip described pre-emulsion A with 35 droplets/minute in the step (4), after dropping finished, 71 ℃ of following insulation reaction 2h were cooled to 47 ℃.
Drip described pre-emulsion A with 35 droplets/minute in the step (4), after dropping finished, 71 ℃ of following insulation reaction 2h were cooled to 49 ℃.
The environmental-friendly type emulsion shape modified acrylate coating material dyeing tackiness agent that the preparation method of this environmental-friendly type emulsion shape modified acrylate coating material dyeing tackiness agent prepares.
Embodiment
Below in conjunction with embodiment, further set forth the present invention.
Embodiment 1:
The preparation method of a kind of environmental-friendly type emulsion shape modified acrylate coating material dyeing tackiness agent of the present invention is characterized in that this preparation method comprises following operation steps:
(1) selects methyl methacrylate, methyl acrylate, ethyl propenoate, acrylic acid epoxy propyl ester and acrylic acid composition for use, described methyl methacrylate, methyl acrylate, ethyl propenoate, acrylic acid epoxy propyl ester and acrylic acid amount ratio are 1.3: 2.4: 3.1 with molar ratio computing: 1.4: 2.6;
(2) with octamethylcyclotetrasiloxane, the mixture of low viscous hydroxy silicon oil is a kind of raw material A, with 1,1,3, it is in 785 rev/mins the high speed rotating stirring tank that the 3-tetramethyl disiloxane drops into the commentaries on classics degree by 4: 20 weight ratio, 35% the initiator ceric ammonium nitrate that adds described raw material A weight simultaneously, stirring reaction is 15 minutes when temperature is 95 ℃, 5% the amidation coupling agent that adds described raw material A weight, when temperature is 18 ℃, carried out equilibration reaction 30 minutes, vacuumize lower-molecular substance again, must hold hydrogeneous methylsiloxane intermediate, described hydroxy silicon oil is 15mpas 25 ℃ viscosity; The hydrogeneous methylsiloxane intermediate of end and allyl polyether with preparation, drop in the reactor by 2: 1 weight ratios, in the presence of solvent, when temperature is 15 ℃, stir, insulation reaction 12 minutes, drip 0.00001% iron catalyst of raw material A weight, stirring reaction 30 minutes gets organopolysiloxane-polyethers linear block copolymers; It is in 1565 rev/mins the low speed rotation stirring tank that above-mentioned organopolysiloxane-polyethers linear block copolymers and capacity strong aqua are dropped into the commentaries on classics degree, when being 65 ℃, temperature stirs, insulation reaction 40 minutes, vacuumize unreacted ammonia, get the amino terpolymer modified silicon oil of linearity block polyethers octadecane;
(3) form mixed emulsifier A by the compound back of anionic emulsifier and nonionic surface active agent, the emulsifying agent B that is formed by emulsifier op-10; Wherein, the weight proportion of mixed emulsifier A is anionic emulsifier: nonionic surface active agent is 1.6: 3.3, and the weight ratio of described emulsifying agent A and emulsifying agent B is 2.6: 1.4;
Described anionic emulsifier is the combination of an alkali metal salt of alkyl vinylformic acid-2-ethanesulfonic acid sodium, sodium p styrene sulfonate and aliphatic dicarboxylic acid;
(4) in the high speed rotating reaction vessel, be to be dissolved in 2.4L deionized water at 2.6: 1.4 emulsifying agent A and emulsifying agent B according to weight ratio, when being 985 rev/mins, stirs the rotating speed of high speed rotating reaction vessel, stir after 5 minutes, stirred when being 685 rev/mins with rotating speed 15 minutes, add described methyl methacrylate, methyl acrylate, ethyl propenoate, acrylic acid epoxy propyl ester and acrylic acid composition then, when the rotating speed of low speed rotation reaction vessel is 285 rev/mins, stir, stir after 5 minutes; Add the amino terpolymer modified silicon oil of described linearity block polyethers octadecane then, by high-shearing dispersion emulsifying machine quick emulsification 26min, make pre-emulsion A and wait to drip;
In four-hole boiling flask, add deionized water, emulsifying agent A, mix and stir 10min, be warming up to 45 ℃ and kept 30 minutes, add the initiator ceric ammonium nitrate; Slowly be warming up to 70 ℃-80 ℃, drip described pre-emulsion A with 35 droplets/minute, drip finish after, 71 ℃ of following insulation reaction 2h are cooled to 45～50 ℃, add ammoniacal liquor and regulate pH value 6.5～7.0, continue stirring 15min.
Embodiment 2:
The preparation method of a kind of environmental-friendly type emulsion shape modified acrylate coating material dyeing tackiness agent of the present invention is characterized in that this preparation method comprises following operation steps:
(1) selects methyl methacrylate, methyl acrylate, ethyl propenoate, acrylic acid epoxy propyl ester and acrylic acid composition for use, described methyl methacrylate, methyl acrylate, ethyl propenoate, acrylic acid epoxy propyl ester and acrylic acid amount ratio are 1.3: 2.4: 3.1 with molar ratio computing: 1.4: 2.6;
(2) with octamethylcyclotetrasiloxane, the mixture of low viscous hydroxy silicon oil is a kind of raw material A, with 1,1,3, it is in 785 rev/mins the high speed rotating stirring tank that the 3-tetramethyl disiloxane drops into the commentaries on classics degree by 4: 20 weight ratio, 35% the initiator ceric ammonium nitrate that adds described raw material A weight simultaneously, stirring reaction is 15 minutes when temperature is 95 ℃, 5% the amidation coupling agent that adds described raw material A weight, when temperature is 18 ℃, carried out equilibration reaction 30 minutes, vacuumize lower-molecular substance again, must hold hydrogeneous methylsiloxane intermediate, described hydroxy silicon oil is 15mpas 25 ℃ viscosity; The hydrogeneous methylsiloxane intermediate of end and allyl polyether with preparation, drop in the reactor by 2: 1 weight ratios, in the presence of solvent, when temperature is 15 ℃, stir, insulation reaction 12 minutes, drip 0.00001% iron catalyst of raw material A weight, stirring reaction 30 minutes gets organopolysiloxane-polyethers linear block copolymers; It is in 1565 rev/mins the low speed rotation stirring tank that above-mentioned organopolysiloxane-polyethers linear block copolymers and capacity strong aqua are dropped into the commentaries on classics degree, when being 65 ℃, temperature stirs, insulation reaction 40 minutes, vacuumize unreacted ammonia, get the amino terpolymer modified silicon oil of linearity block polyethers octadecane;
(3) form mixed emulsifier A by the compound back of anionic emulsifier and nonionic surface active agent, the emulsifying agent B that is formed by emulsifier op-10; Wherein, the weight proportion of mixed emulsifier A is anionic emulsifier: nonionic surface active agent is 1.6: 3.3, and the weight ratio of described emulsifying agent A and emulsifying agent B is 2.6: 1.4;
Described anionic emulsifier is the combination of an alkali metal salt of alkyl vinylformic acid-2-ethanesulfonic acid sodium, sodium p styrene sulfonate and aliphatic dicarboxylic acid;
(4) in the high speed rotating reaction vessel, be to be dissolved in 2.4L deionized water at 2.6: 1.4 emulsifying agent A and emulsifying agent B according to weight ratio, when being 985 rev/mins, stirs the rotating speed of high speed rotating reaction vessel, stir after 5 minutes, stirred when being 685 rev/mins with rotating speed 15 minutes, add described methyl methacrylate, methyl acrylate, ethyl propenoate, acrylic acid epoxy propyl ester and acrylic acid composition then, when the rotating speed of low speed rotation reaction vessel is 285 rev/mins, stir, stir after 5 minutes; Add the amino terpolymer modified silicon oil of described linearity block polyethers octadecane then, by high-shearing dispersion emulsifying machine quick emulsification 26min, make pre-emulsion A and wait to drip;
In four-hole boiling flask, add deionized water, emulsifying agent A, mix and stir 10min, be warming up to 45 ℃ and kept 30 minutes, add the initiator ceric ammonium nitrate; Slowly be warming up to 70 ℃-80 ℃, drip described pre-emulsion A with 35 droplets/minute, drip finish after, 71 ℃ of following insulation reaction 2h are cooled to 47 ℃, add ammoniacal liquor and regulate pH value 6.5～7.0, continue stirring 15min.
Embodiment 3:
The preparation method of a kind of environmental-friendly type emulsion shape modified acrylate coating material dyeing tackiness agent of the present invention is characterized in that this preparation method comprises following operation steps:
(1) selects methyl methacrylate, methyl acrylate, ethyl propenoate, acrylic acid epoxy propyl ester and acrylic acid composition for use, described methyl methacrylate, methyl acrylate, ethyl propenoate, acrylic acid epoxy propyl ester and acrylic acid amount ratio are 1.3: 2.4: 3.1 with molar ratio computing: 1.4: 2.6;
(2) with octamethylcyclotetrasiloxane, the mixture of low viscous hydroxy silicon oil is a kind of raw material A, with 1,1,3, it is in 785 rev/mins the high speed rotating stirring tank that the 3-tetramethyl disiloxane drops into the commentaries on classics degree by 4: 20 weight ratio, 35% the initiator ceric ammonium nitrate that adds described raw material A weight simultaneously, stirring reaction is 15 minutes when temperature is 95 ℃, 5% the amidation coupling agent that adds described raw material A weight, when temperature is 18 ℃, carried out equilibration reaction 30 minutes, vacuumize lower-molecular substance again, must hold hydrogeneous methylsiloxane intermediate, described hydroxy silicon oil is 15mpas 25 ℃ viscosity; The hydrogeneous methylsiloxane intermediate of end and allyl polyether with preparation, drop in the reactor by 2: 1 weight ratios, in the presence of solvent, when temperature is 15 ℃, stir, insulation reaction 12 minutes, drip 0.00001% iron catalyst of raw material A weight, stirring reaction 30 minutes gets organopolysiloxane-polyethers linear block copolymers; It is in 1565 rev/mins the low speed rotation stirring tank that above-mentioned organopolysiloxane-polyethers linear block copolymers and capacity strong aqua are dropped into the commentaries on classics degree, when being 65 ℃, temperature stirs, insulation reaction 40 minutes, vacuumize unreacted ammonia, get the amino terpolymer modified silicon oil of linearity block polyethers octadecane;
(3) form mixed emulsifier A by the compound back of anionic emulsifier and nonionic surface active agent, the emulsifying agent B that is formed by emulsifier op-10; Wherein, the weight proportion of mixed emulsifier A is anionic emulsifier: nonionic surface active agent is 1.6: 3.3, and the weight ratio of described emulsifying agent A and emulsifying agent B is 2.6: 1.4;
Described anionic emulsifier is the combination of an alkali metal salt of alkyl vinylformic acid-2-ethanesulfonic acid sodium, sodium p styrene sulfonate and aliphatic dicarboxylic acid;
(4) in the high speed rotating reaction vessel, be to be dissolved in 2.4L deionized water at 2.6: 1.4 emulsifying agent A and emulsifying agent B according to weight ratio, when being 985 rev/mins, stirs the rotating speed of high speed rotating reaction vessel, stir after 5 minutes, stirred when being 685 rev/mins with rotating speed 15 minutes, add described methyl methacrylate, methyl acrylate, ethyl propenoate, acrylic acid epoxy propyl ester and acrylic acid composition then, when the rotating speed of low speed rotation reaction vessel is 285 rev/mins, stir, stir after 5 minutes; Add the amino terpolymer modified silicon oil of described linearity block polyethers octadecane then, by high-shearing dispersion emulsifying machine quick emulsification 26min, make pre-emulsion A and wait to drip;
In four-hole boiling flask, add deionized water, emulsifying agent A, mix and stir 10min, be warming up to 45 ℃ and kept 30 minutes, add the initiator ceric ammonium nitrate; Slowly be warming up to 70 ℃-80 ℃, drip described pre-emulsion A with 35 droplets/minute, drip finish after, 71 ℃ of following insulation reaction 2h are cooled to 49 ℃, add ammoniacal liquor and regulate pH value 6.5～7.0, continue stirring 15min.
Embodiment 4:
The preparation method of a kind of environmental-friendly type emulsion shape modified acrylate coating material dyeing tackiness agent of the present invention is characterized in that this preparation method comprises following operation steps:
(1) selects methyl methacrylate, methyl acrylate, ethyl propenoate, acrylic acid epoxy propyl ester and acrylic acid composition for use, described methyl methacrylate, methyl acrylate, ethyl propenoate, acrylic acid epoxy propyl ester and acrylic acid amount ratio are 1.3: 2.4: 3.1 with molar ratio computing: 1.4: 2.6;
(2) with octamethylcyclotetrasiloxane, the mixture of low viscous hydroxy silicon oil is a kind of raw material A, with 1,1,3, it is in 785 rev/mins the high speed rotating stirring tank that the 3-tetramethyl disiloxane drops into the commentaries on classics degree by 4: 20 weight ratio, 35% the initiator ceric ammonium nitrate that adds described raw material A weight simultaneously, stirring reaction is 15 minutes when temperature is 95 ℃, 5% the amidation coupling agent that adds described raw material A weight, when temperature is 18 ℃, carried out equilibration reaction 30 minutes, vacuumize lower-molecular substance again, must hold hydrogeneous methylsiloxane intermediate, described hydroxy silicon oil is 15mpas 25 ℃ viscosity; The hydrogeneous methylsiloxane intermediate of end and allyl polyether with preparation, drop in the reactor by 2: 1 weight ratios, in the presence of solvent, when temperature is 15 ℃, stir, insulation reaction 12 minutes, drip 0.00001% iron catalyst of raw material A weight, stirring reaction 30 minutes gets organopolysiloxane-polyethers linear block copolymers; It is in 1565 rev/mins the low speed rotation stirring tank that above-mentioned organopolysiloxane-polyethers linear block copolymers and capacity strong aqua are dropped into the commentaries on classics degree, when being 65 ℃, temperature stirs, insulation reaction 40 minutes, vacuumize unreacted ammonia, get the amino terpolymer modified silicon oil of linearity block polyethers octadecane;
(3) form mixed emulsifier A by the compound back of anionic emulsifier and nonionic surface active agent, the emulsifying agent B that is formed by emulsifier op-10; Wherein, the weight proportion of mixed emulsifier A is anionic emulsifier: nonionic surface active agent is 1.6: 3.3, and the weight ratio of described emulsifying agent A and emulsifying agent B is 2.6: 1.4;
Described anionic emulsifier is the combination of an alkali metal salt of alkyl vinylformic acid-2-ethanesulfonic acid sodium, sodium p styrene sulfonate and aliphatic dicarboxylic acid;
(4) in the high speed rotating reaction vessel, be to be dissolved in 2.4L deionized water at 2.6: 1.4 emulsifying agent A and emulsifying agent B according to weight ratio, when being 985 rev/mins, stirs the rotating speed of high speed rotating reaction vessel, stir after 5 minutes, stirred when being 685 rev/mins with rotating speed 15 minutes, add described methyl methacrylate, methyl acrylate, ethyl propenoate, acrylic acid epoxy propyl ester and acrylic acid composition then, when the rotating speed of low speed rotation reaction vessel is 285 rev/mins, stir, stir after 5 minutes; Add the amino terpolymer modified silicon oil of described linearity block polyethers octadecane then, by high-shearing dispersion emulsifying machine quick emulsification 26min, make pre-emulsion A and wait to drip;
In four-hole boiling flask, add deionized water, emulsifying agent A, mix and stir 10min, be warming up to 45 ℃ and kept 30 minutes, add the initiator ceric ammonium nitrate; Slowly be warming up to 70 ℃-80 ℃, drip described pre-emulsion A with 35 droplets/minute, drip finish after, 72 ℃ of following insulation reaction 2h are cooled to 49 ℃, add ammoniacal liquor and regulate pH value 6.5～7.0, continue stirring 15min.
The every Performance Detection data of table 1
The every application performance of table 2 detects data
The formaldehyde detection method is with reference to GB/T2912.1-2009 in the table 1, and median size is utilized the test of Rise-2202 type fully-automatic laser particle-size analyzer, and feel relies on hand to touch, and getting wet property detection method is with reference to GB/T 4745-1997
The fabric crock fastness is with reference to GB/T3920-19970 in the table 2, and brushing fastness is tested with reference to GB/T420-1990, and fastness to washing is tested with reference to GB/T3921.2-1997.
Claims (4)
1. the preparation method of environmental-friendly type emulsion shape modified acrylate coating material dyeing tackiness agent is characterized in that this preparation method comprises following operation steps:
(1) selects methyl methacrylate, methyl acrylate, ethyl propenoate, acrylic acid epoxy propyl ester and acrylic acid composition for use, described methyl methacrylate, methyl acrylate, ethyl propenoate, acrylic acid epoxy propyl ester and acrylic acid amount ratio are 1.3: 2.4: 3.1 with molar ratio computing: 1.4: 2.6;
(2) with octamethylcyclotetrasiloxane, the mixture of low viscous hydroxy silicon oil is a kind of raw material A, with 1,1,3, it is in 785 rev/mins the high speed rotating stirring tank that the 3-tetramethyl disiloxane drops into the commentaries on classics degree by 4: 20 weight ratio, 35% the initiator ceric ammonium nitrate that adds described raw material A weight simultaneously, stirring reaction is 15 minutes when temperature is 95 ℃, 5% the amidation coupling agent that adds described raw material A weight, when temperature is 18 ℃, carried out equilibration reaction 30 minutes, vacuumize lower-molecular substance again, must hold hydrogeneous methylsiloxane intermediate, described hydroxy silicon oil is 15mPas 25 ℃ viscosity; The hydrogeneous methylsiloxane intermediate of end and allyl polyether with preparation, drop in the reactor by 2: 1 weight ratios, in the presence of solvent, when temperature is 15 ℃, stir, insulation reaction 12 minutes, drip 0.00001% iron catalyst of raw material A weight, stirring reaction 30 minutes gets organopolysiloxane-polyethers linear block copolymers; It is in 1565 rev/mins the low speed rotation stirring tank that above-mentioned organopolysiloxane-polyethers linear block copolymers and capacity strong aqua are dropped into the commentaries on classics degree, when being 65 ℃, temperature stirs, insulation reaction 40 minutes, vacuumize unreacted ammonia, get the amino terpolymer modified silicon oil of linearity block polyethers octadecane;
(3) form mixed emulsifier A by the compound back of anionic emulsifier and nonionic surface active agent, the emulsifying agent B that is formed by emulsifier op-10; Wherein, the weight proportion of mixed emulsifier A is anionic emulsifier: nonionic surface active agent is 1.6: 3.3, and the weight ratio of described emulsifying agent A and emulsifying agent B is 2.6: 1.4;
Described anionic emulsifier is the combination of an alkali metal salt of alkyl vinylformic acid-2-ethanesulfonic acid sodium, sodium p styrene sulfonate and aliphatic dicarboxylic acid;
(4) in the high speed rotating reaction vessel, be to be dissolved in 2.4L deionized water at 2.6: 1.4 emulsifying agent A and emulsifying agent B according to weight ratio, when being 985 rev/mins, stirs the rotating speed of high speed rotating reaction vessel, stir after 5 minutes, stirred when being 685 rev/mins with rotating speed 15 minutes, add described methyl methacrylate, methyl acrylate, ethyl propenoate, acrylic acid epoxy propyl ester and acrylic acid composition then, when the rotating speed of low speed rotation reaction vessel is 285 rev/mins, stir, stir after 5 minutes; Add the amino terpolymer modified silicon oil of described linearity block polyethers octadecane then, by high-shearing dispersion emulsifying machine quick emulsification 26min, make pre-emulsion A and wait to drip;
In four-hole boiling flask, add deionized water, emulsifying agent A, mix and stir 10min, be warming up to 45 ℃ and kept 30 minutes, add the initiator ceric ammonium nitrate; Slowly be warming up to 70 ℃-80 ℃, drip described pre-emulsion A with 35 droplets/minute, drip finish after, 70～72 ℃ of following insulation reaction 2h are cooled to 45～50 ℃, add ammoniacal liquor and regulate pH value 6.5～7.0, continue stirring 15min.
2. the preparation method of environmental-friendly type emulsion shape modified acrylate coating material dyeing tackiness agent according to claim 1 is characterized in that, drips described pre-emulsion A with 35 droplets/minute in the step (4), and after dropping finished, 71 ℃ of following insulation reaction 2h were cooled to 47 ℃.
3. the preparation method of environmental-friendly type emulsion shape modified acrylate coating material dyeing tackiness agent according to claim 1 is characterized in that, drips described pre-emulsion A with 35 droplets/minute in the step (4), and after dropping finished, 71 ℃ of following insulation reaction 2h were cooled to 49 ℃.
4. the environmental-friendly type emulsion shape modified acrylate coating material dyeing tackiness agent that obtains of the preparation method of environmental-friendly type emulsion shape modified acrylate coating material according to claim 1 dyeing tackiness agent.
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| CN106567262A (en) * | 2016-11-03 | 2017-04-19 | 东莞市联洲知识产权运营管理有限公司 | Formaldehyde-free adhesive for pigment dyeing and preparation method thereof |
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| CN103541234A (en) * | 2013-10-23 | 2014-01-29 | 合肥聚合辐化技术有限公司 | Thin-film printing adhesive and preparation method thereof |
| CN103924458B (en) * | 2014-03-26 | 2015-12-02 | 东至绿洲环保化工有限公司 | Silicone acrylic emulsion printing adhesive |
| CN103923271B (en) * | 2014-03-26 | 2016-04-27 | 东至绿洲环保化工有限公司 | Silicone modified styrene-acrylate emulsion |
| CN106687484B (en) * | 2014-09-23 | 2019-03-12 | 巴斯夫欧洲公司 | Aqueous polymer-silicone oil hybrid compositions |
| CN107447551B (en) * | 2017-08-16 | 2019-08-13 | 辽宁恒星精细化工有限公司 | Cotton towel fabric hydrophilic acrylic ester coating printing adhesive and preparation method thereof |
| CN112281512A (en) * | 2020-10-15 | 2021-01-29 | 西安工程大学 | Polyester fabric printing method |
| CN116284790A (en) * | 2023-03-27 | 2023-06-23 | 湖北兴瑞硅材料有限公司 | Acrylic ester modified silicone oil, preparation method thereof and packaging adhesive containing acrylic ester modified silicone oil |
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| CN101220563A (en) * | 2007-11-22 | 2008-07-16 | 复旦大学 | Environment protection type pigment resin printing adhesive agent capable of self crosslinking at low-temperature, and preparation thereof |
| CN102391411A (en) * | 2011-08-29 | 2012-03-28 | 华南理工大学 | Low-temperature self-crosslinking polyacrylate pigment printing binding agent and preparation method thereof |
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| CN101220563A (en) * | 2007-11-22 | 2008-07-16 | 复旦大学 | Environment protection type pigment resin printing adhesive agent capable of self crosslinking at low-temperature, and preparation thereof |
| CN102391411A (en) * | 2011-08-29 | 2012-03-28 | 华南理工大学 | Low-temperature self-crosslinking polyacrylate pigment printing binding agent and preparation method thereof |
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