CN111138578B - Hyperbranched polyvinyl acetate and high-stability writing ink based on same - Google Patents
Hyperbranched polyvinyl acetate and high-stability writing ink based on same Download PDFInfo
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- CN111138578B CN111138578B CN201911416872.5A CN201911416872A CN111138578B CN 111138578 B CN111138578 B CN 111138578B CN 201911416872 A CN201911416872 A CN 201911416872A CN 111138578 B CN111138578 B CN 111138578B
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F118/00—Homopolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an acyloxy radical of a saturated carboxylic acid, of carbonic acid or of a haloformic acid
- C08F118/02—Esters of monocarboxylic acids
- C08F118/04—Vinyl esters
- C08F118/08—Vinyl acetate
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/38—Polymerisation using regulators, e.g. chain terminating agents, e.g. telomerisation
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D11/00—Inks
- C09D11/16—Writing inks
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2438/00—Living radical polymerisation
- C08F2438/03—Use of a di- or tri-thiocarbonylthio compound, e.g. di- or tri-thioester, di- or tri-thiocarbamate, or a xanthate as chain transfer agent, e.g . Reversible Addition Fragmentation chain Transfer [RAFT] or Macromolecular Design via Interchange of Xanthates [MADIX]
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Abstract
The invention relates to hyperbranched polyvinyl acetate and high-stability writing ink based on the same. The hyperbranched polyvinyl acetate is synthesized by a simple method, has a symmetrical spherical three-dimensional structure, is not easy to wind molecular chains, has low viscosity and good fluidity, and is easy to form a film. The polyvinyl acetate is used as a polymer additive, a writing ink formula is designed and optimized, on one hand, components in the emulsion ink formula are simplified, on the other hand, the stability of the emulsion ink is greatly improved, and the prepared writing ink has the characteristics of low viscosity, high thixotropic value and the like, and has good writing performance and line appearance.
Description
Technical Field
The invention relates to the technical field of ink manufacturing, in particular to hyperbranched polyvinyl acetate and high-stability writing ink based on the hyperbranched polyvinyl acetate.
Background
The emulsion ink for writing has advantages of oil-based ink and water-based ink, and is increasingly popular with users and markets today when green environmental protection is advocated. At present, aldehyde ketone resin or epoxy resin is generally used as a high molecular additive in the production process of emulsion ink, and mainly plays a role of a connecting material in the ink, and has great influence on the viscosity, adhesive force, luster, dryness and writing adaptability of the ink. The aldehyde ketone resin or the epoxy resin generally needs to be dissolved by a large amount of organic solvent and a certain amount of emulsifier is added, so that the environmental protection of the emulsified ink is reduced. The aldehyde ketone resin or the epoxy resin is generally linear, and is easy to be wound and agglomerated in the long-term storage process, the emulsified state is damaged, the viscosity of the ink is increased, the problems of difficult ink generation, line breakage and the like are easy to occur in the writing process, and the quality of the emulsified ink is influenced.
CN 101891843A discloses a preparation method of hyperbranched polyvinyl acetate, ECTVA is used as RAFT reagent to synthesize hyperbranched polyvinyl acetate, but the application of hyperbranched polyvinyl acetate in the field of ink manufacture is not involved. Therefore, there is a need to develop new hyperbranched polymers that can be used in the field of ink manufacturing.
Disclosure of Invention
In order to solve the technical problems, the invention aims to provide hyperbranched polyvinyl acetate and high-stability writing ink based on the hyperbranched polyvinyl acetate.
The invention discloses a preparation method of hyperbranched polyvinyl acetate, which comprises the following steps:
under the protection of inert atmosphere, carrying out reversible addition-fragmentation chain transfer polymerization on vinyl acetate in an organic solvent at 40-70 ℃ under the action of a thermal initiator and an RAFT reagent to obtain the hyperbranched polyvinyl acetate; wherein the RAFT agent has the following structural formula:
Further, the thermal initiator is one or more of azobisisobutyronitrile, dimethyl azobisisobutyrate and azobisisoheptonitrile.
Further, the reaction time is 5 to 8 hours.
The thermal initiator is used for carrying out thermal polymerization on the vinyl acetate, and the RAFT reagent is used for carrying out thermal polymerization on the vinyl acetate and the thermal initiator in a certain ratio, wherein the molar ratio of the vinyl acetate to the thermal initiator is 1-2: 1, and the molar ratio of the vinyl acetate to the RAFT reagent is 10-80: 1.
Further, the organic solvent is 1, 4-dioxane and/or Tetrahydrofuran (THF).
The synthetic route of the RAFT reagent (PCTVA) used in the invention is as follows:
the preferred solvent for the reaction is dimethylformamide.
The synthesis route of the hyperbranched polyvinyl acetate is as follows:
wherein B in the product represents a vinyl group, and B represents a polymer linkage point; s represents a dithio compound group, and the wavy line represents linear polyvinyl acetate.
The invention also discloses the hyperbranched polyvinyl acetate prepared by the preparation method.
The terminal of the hyperbranched polyvinyl acetate prepared by the invention has functional groups with stronger polarity, is easy to form hydrogen bonds with water, and has good water solubility and emulsification characteristics. And the hyperbranched polyvinyl acetate has a symmetrical spherical three-dimensional structure, molecules are not easy to wind, and the formed emulsion has low viscosity, good fluidity and easy film formation.
The invention also claims the application of the hyperbranched polyvinyl acetate in preparing ink.
The invention also discloses writing ink which comprises the following components in parts by weight:
10.0-30.0 parts of dye; 10.0-30.0 parts by weight of alcohol and/or ether organic solvent; 25.0-50.0 parts of water; 10-30 parts of hyperbranched polyvinyl acetate prepared by the method; 0.5-1.0 part of auxiliary agent.
Further, the dye is selected from solvent type dyes. The dyes of the respective colors having good compatibility are preferable.
Further, the alcohol and/or ether organic solvent is selected from one or more of phenethyl alcohol, ethylene glycol phenyl ether, ethylene glycol butyl ether, diethylene glycol ethyl ether and diethylene glycol methyl ether.
Further, the adjuvant comprises one or more of a thickening agent, a preservative and an emulsifier.
Further, the thickener is preferably hydroxyethyl cellulose. The antiseptic is preferably one or more of benzoic acid, sodium benzoate and sorbic acid.
Further, the emulsifier is selected from tween or OP.
Further, the viscosity of the writing ink is 600-800mpa.s, the thixotropic index is 3.0-3.5, and the writing ink belongs to a high-quality writing emulsified ink with low viscosity and high thixotropic value.
The preparation process and method of the writing ink of the invention comprises the following steps:
(1) Dissolving the dye: dissolving a dye in an alcohol organic solvent at the temperature of 80-90 ℃ to prepare a dye compound liquid A;
(2) preparation of solvent complex liquid: heating water and an alcohol organic solvent and uniformly stirring to obtain a solvent complex liquid B;
(3) preparing a mixed solution of an emulsifying alcohol dye: slowly adding the solvent compound liquid B into the dye compound liquid A, stirring while adding, controlling the stirring speed at 600-900 revolutions per minute, stirring for 30 minutes, continuously accelerating the stirring for 60-80 minutes after all the solvent compound liquid B is added, keeping the system temperature at 60 ℃ at 3000 revolutions per minute, and obtaining the emulsified alcohol dye mixed liquid;
(4) preparing a hyperbranched polyvinyl acetate emulsifier: uniformly stirring hyperbranched polyvinyl acetate, water and an emulsifier at the temperature of 60 ℃ and the rotating speed of 500 plus materials at 700 r/min until the hyperbranched polyvinyl acetate, the water and the emulsifier are completely dissolved to obtain a hyperbranched polyvinyl acetate emulsifier;
(5) preparing writing ink: adding the emulsified alcohol dye mixed solution into the hyperbranched polyvinyl acetate emulsifier, finally adding the auxiliary agent, and uniformly stirring at 600 revolutions per minute under 500 plus materials until the viscosity of the product is 600 plus materials at 800 mpa.s.
By the scheme, the invention at least has the following advantages:
the hyperbranched polyvinyl acetate synthesized by the method is in a good symmetrical spherical three-dimensional structure, the molecular chains are not easy to wind, the viscosity is low, the hyperbranched polyvinyl acetate has good fluidity, and the film is easy to form, so that the hyperbranched polyvinyl acetate is a high-quality emulsion ink high-molecular additive.
The prepared hyperbranched polyvinyl acetate is used as a polymer additive, a writing ink formula is designed and optimized, on one hand, the components in the emulsion ink formula are simplified, on the other hand, the stability of the emulsion ink is greatly improved, and the prepared writing ink has the characteristics of low viscosity, high thixotropic value and the like, and has good writing performance and line appearance.
The writing ink is green and environment-friendly, the hyperbranched polyvinyl acetate is used as a high-molecular emulsifier, the using amount of an organic solvent is greatly reduced, the pre-manufactured ink can be kept stable for a long time (more than 18 months), and the writing performance and indexes are superior to those of common emulsion ink. The produced emulsion ink meets the national standard of writing ink. The finished product of the refill made of the emulsified ink has the advantages of over 320m of marked lines, no obvious phenomena of broken lines and light traces, water resistance: more than or equal to 1.5h, the stitch remains visible, and the light fastness is as follows: and the stitch is kept visible for more than or equal to 72 hours.
The foregoing description is only an overview of the technical solutions of the present invention, and in order to make the technical solutions of the present invention more clearly understood and to implement them in accordance with the contents of the description, the following description is made with reference to the preferred embodiments of the present invention and the accompanying detailed drawings.
Drawings
FIG. 1 is a nuclear magnetic hydrogen spectrum of the synthesized hyperbranched polyvinyl acetate.
Detailed Description
The following examples are given to further illustrate embodiments of the present invention. The following examples are intended to illustrate the invention but are not intended to limit the scope of the invention.
Example 1
The synthesis of the hyperbranched polyvinyl acetate comprises the following steps:
(1) synthesis of RAFT reagent PCTVA: adding 300mL of dimethyl formamide serving as a solvent into a reaction kettle, adding 100g of potassium phenoxy xanthate while stirring, fully dissolving and uniformly mixing, slowly dropwise adding 80g of vinyl chloroacetate, stirring the mixed solution at room temperature for reacting for 3-5 hours, separating and purifying to obtain 110g of a yellow-green product, and calculating the yield to be 63%. The purity of the obtained product can reach 99 percent through HPLC detection.
(2) 500g of monomer vinyl acetate (Vac), 50g of initiator Azobisisobutyronitrile (AIBN), 50 mL of PCTVA (pentatricopeptide disulfide) and 500mL of solvent (1, 4-dioxane) are sequentially added into a reactor, and the reaction is carried out for 5 to 8 hours at a constant temperature (40 to 70 ℃). After the reaction is finished, 540g of hyperbranched polyvinyl acetate is obtained by separation, and the product is subjected to GPC measurement, wherein the molecular weight distribution index (Mw/Mn) is 2.44, and the molecular weight is 7100 (THF is taken as the fluidity, and PMMA is taken as the standard sample). The nuclear magnetic hydrogen spectrum of the hyperbranched resin sample prepared in the example is shown in FIG. 1, and the attribution of each peak is as labeled.
Example 2
The self-made hyperbranched polyvinyl acetate is used as a high molecular resin additive to prepare black writing ink.
(1) Heating 60 g of ethylene glycol phenyl ether solvent to 80-95 ℃, gradually adding 20 g of black dye solvent black No. 209 into the ethylene glycol phenyl ether solvent, uniformly stirring the mixture until the mixture is completely dissolved, slightly cooling the mixture, adding 1 g of Tween stabilizer into the mixture, and uniformly stirring the mixture to prepare the dye compound liquid A.
(2) And mixing 45 g of deionized water and 20 g of diethylene glycol ethyl ether, heating and uniformly stirring to obtain a solvent compound liquid B.
(3) Slowly adding the solvent complex liquid B into the dye complex liquid A while stirring, controlling the stirring speed at 600 plus 900 revolutions per minute, stirring for 30 minutes, continuously accelerating the stirring for 60-80 minutes after all the solvent complex liquid B is added, keeping the rotation speed at 3000 revolutions per minute, and keeping the system temperature at 60 ℃ to prepare an emulsified alcohol solution C.
(4) Taking 18 g of hyperbranched polyvinyl acetate, 45 g of water and 1 g of emulsifier OP, mixing, heating to 110-130 ℃, stirring for 1 hour, and completely dissolving to form the polymer resin compound liquid D.
(5) Taking out the corresponding emulsified alcohol solution C, adding the dissolved polymer resin compound solution D, finally adding 1 g of an auxiliary agent (mainly comprising a thickening agent of hydroxyethyl cellulose and a preservative of sodium benzoate), and fully stirring and uniformly mixing to obtain the black writing ink.
Example 3
Self-made hyperbranched polyvinyl acetate is taken as an important polymer resin additive to prepare blue writing ink.
(1) 60 g of phenethyl alcohol and ethylene glycol phenyl ether solvent (35 g of phenethyl alcohol and 25 g of ethylene glycol phenyl ether) are heated to 80-95 ℃, 18 g of blue dye solvent blue 38 is gradually added into the mixture and stirred evenly until the mixture is completely dissolved, and after the temperature is slightly reduced, 1 g of Tween is added into the mixture and stirred evenly, thus obtaining the dye compound liquid A.
(2)45 g of deionized water and 22 g of diethylene glycol ethyl ether are mixed, heated and uniformly stirred to obtain a solvent compound liquid B.
(3) Slowly adding the solvent compound liquid B into the dye compound liquid A, adding while stirring, controlling the stirring speed at 600-900 revolutions per minute, stirring for 30 minutes, continuously accelerating the stirring for 60-80 minutes after all the solvent compound liquid B is added, keeping the system temperature at 60 ℃ at 3000 revolutions per minute, and preparing the emulsified alcohol solution C.
(4) 20 g of hyperbranched polyvinyl acetate, 43 g of water and 1 g of emulsifier OP are mixed and heated to 110 ℃ and 130 ℃, and stirred for 1 hour to be completely dissolved, so as to form the polymer resin compound liquid D.
(5) Taking out the corresponding emulsified alcohol solution C, adding the dissolved polymer resin compound solution D, finally adding 1 g of auxiliary agent (mainly comprising thickening agent hydroxyethyl cellulose and preservative sodium benzoate), fully stirring and uniformly mixing to obtain the blue writing ink.
The writing inks prepared in examples 1 and 2 were filled into a pen core, and a writing performance test was performed to meet the industrial standards.
And (3) placing the writing ink in an electric heating constant-temperature incubator at 50 ℃ for 35 days (the rapid aging standard is that the ordinary test only needs to be placed for 30 days, which is equivalent to the normal-temperature placement for 18 months, and the writing ink is placed for 35 days, which is equivalent to the normal-temperature placement for 21 months, which is much higher than the ink industry standard), then filling the pen core again, and performing the writing performance test, wherein the test also reaches the standard. Specific test data are shown in table 1:
table 1: ink Performance test results of the invention
As is clear from Table 1, the writing ink of the present invention can be kept stable for a long period of time (18 months or more), and the writing performance and index are superior to those of the conventional emulsion ink. The produced emulsified ink meets the national standard of writing ink. The finished product of the refill made of the emulsified ink has the advantages of over 320m of marked lines, no obvious phenomena of broken lines and light traces, water resistance: not less than 1.5h, the stitch remains visible, the light resistance: and the stitch is kept visible for more than or equal to 72 hours.
Therefore, the invention realizes the synthesis of the polyvinyl acetate with the hyperbranched structure and provides a plurality of choices for the application of the polyvinyl acetate in the ink production. The prepared hyperbranched polymer is used as important emulsifier resin, the formula of the writing emulsion ink is optimized, the dosage of an organic solvent is greatly reduced, and the stability, the writing performance and the index of the pilot-made writing ink are superior to those of the common commercial emulsion ink.
The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention, and it should be noted that, for those skilled in the art, many modifications and variations can be made without departing from the technical principle of the present invention, and these modifications and variations should also be regarded as the protection scope of the present invention.
Claims (6)
1. The writing ink is characterized by comprising the following components in parts by weight:
10.0-30.0 parts of dye, 10.0-30.0 parts of organic solvent I, 25.0-50.0 parts of water, 10-30 parts of hyperbranched polyvinyl acetate and 0.5-1.0 part of auxiliary agent;
the dye is selected from solvent black No. 209 or solvent blue No. 38;
the auxiliary agents are a stabilizer, a thickening agent, a preservative and an emulsifier;
the emulsifier is OP; the thickening agent is hydroxyethyl cellulose; the stabilizer is tween;
the preparation method of the hyperbranched polyvinyl acetate comprises the following steps:
under the protection of inert atmosphere, carrying out reversible addition-fragmentation chain transfer polymerization on vinyl acetate in an organic solvent II at 40-70 ℃ under the action of a thermal initiator and an RAFT reagent to obtain the hyperbranched polyvinyl acetate; the RAFT agent has the following structural formula:
the preparation method of the writing ink comprises the following steps:
(1) Dissolving a dye in an organic solvent I at the temperature of 80-90 ℃ to obtain a dye compound solution A;
(2) heating water and an organic solvent and uniformly stirring to obtain a solvent complex liquid B;
(3) adding the solvent compound liquid B into the dye compound liquid A while stirring, controlling the stirring speed at 600 plus 900 revolutions per minute, stirring for 30 minutes, continuously accelerating the stirring for 60-80 minutes after all the solvent compound liquid B is added, keeping the rotation speed at 3000 revolutions per minute, and keeping the system temperature at 60 ℃ to obtain an emulsified alcohol dye mixed liquid;
(4) uniformly stirring hyperbranched polyvinyl acetate, water and an emulsifier at the temperature of 60 ℃ at the rotating speed of 500 plus 700 r/min until the hyperbranched polyvinyl acetate, the water and the emulsifier are completely dissolved to obtain a hyperbranched polyvinyl acetate emulsifier;
(5) adding the emulsified alcohol dye mixed solution into a hyperbranched polyvinyl acetate emulsifier, adding an auxiliary agent, and uniformly stirring at 500-600 revolutions per minute to obtain the writing ink.
2. A writing ink according to claim 1, wherein: the thermal initiator is one or more of azobisisobutyronitrile, dimethyl azobisisobutyrate and azobisisoheptonitrile.
3. A writing ink according to claim 1, wherein: the reaction time of the reversible addition fragmentation chain transfer polymerization is 5-8 hours.
4. A writing ink according to claim 1, wherein: the molar ratio of the vinyl acetate to the thermal initiator is 1-2: 1, the molar ratio of the vinyl acetate to the RAFT agent is 10-80: 1.
5. a writing ink according to claim 1, wherein: the organic solvent II is 1, 4-dioxane and/or tetrahydrofuran.
6. A writing ink according to claim 1, wherein: the organic solvent I is selected from one or more of phenethyl alcohol, ethylene glycol phenyl ether, ethylene glycol butyl ether, diethylene glycol ethyl ether and diethylene glycol methyl ether.
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Citations (8)
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| CN101891843A (en) * | 2010-07-09 | 2010-11-24 | 苏州大学 | A kind of preparation method of hyperbranched polyvinyl acetate |
| CN102361889A (en) * | 2009-01-23 | 2012-02-22 | 联邦科学与工业研究组织 | RAFT aggregation |
| CN102558966A (en) * | 2011-12-26 | 2012-07-11 | 上海乐美文具有限公司 | Dye-based emulsion ink and producing method thereof |
| CN102666611A (en) * | 2009-09-08 | 2012-09-12 | 联合利华有限公司 | Use of polymers |
| CN102741342A (en) * | 2009-09-08 | 2012-10-17 | 联合利华有限公司 | Use of branched copolymers in polymer blends |
| CN103214606A (en) * | 2013-04-28 | 2013-07-24 | 苏州大学 | Preparation method of cyclic polyvinyl acetate |
| CN107446081A (en) * | 2017-08-04 | 2017-12-08 | 苏州大学 | The preparation method of block copolymer |
| CN108623736A (en) * | 2017-03-17 | 2018-10-09 | 巨石集团有限公司 | A kind of self-cross linking type polyvinyl acetate film forming agent and its preparation method and application |
-
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- 2019-12-31 CN CN201911416872.5A patent/CN111138578B/en active Active
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| CN102361889A (en) * | 2009-01-23 | 2012-02-22 | 联邦科学与工业研究组织 | RAFT aggregation |
| CN102666611A (en) * | 2009-09-08 | 2012-09-12 | 联合利华有限公司 | Use of polymers |
| CN102741342A (en) * | 2009-09-08 | 2012-10-17 | 联合利华有限公司 | Use of branched copolymers in polymer blends |
| CN101891843A (en) * | 2010-07-09 | 2010-11-24 | 苏州大学 | A kind of preparation method of hyperbranched polyvinyl acetate |
| CN102558966A (en) * | 2011-12-26 | 2012-07-11 | 上海乐美文具有限公司 | Dye-based emulsion ink and producing method thereof |
| CN103214606A (en) * | 2013-04-28 | 2013-07-24 | 苏州大学 | Preparation method of cyclic polyvinyl acetate |
| CN108623736A (en) * | 2017-03-17 | 2018-10-09 | 巨石集团有限公司 | A kind of self-cross linking type polyvinyl acetate film forming agent and its preparation method and application |
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| 《Visible Light-Induced Living Radical Polymerization of Butyl Acrylate: Photocatalyst-Free, Ultrafast, and Oxygen Tolerance》;Li jiajia et al.;《MACROMOLECULAR RAPID COMMUNICATIONS》;20170731;第38卷(第13期);1600482：1-8 * |
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