CN115304757B - Block type ink resin and preparation method thereof - Google Patents

Block type ink resin and preparation method thereof Download PDF

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Publication number
CN115304757B
CN115304757B CN202210853019.5A CN202210853019A CN115304757B CN 115304757 B CN115304757 B CN 115304757B CN 202210853019 A CN202210853019 A CN 202210853019A CN 115304757 B CN115304757 B CN 115304757B
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acrylate
meth
acid
butyl
ink resin
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CN115304757A (en
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王强
王旭朋
付勇
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Chengdu Exhibition Of New Materials Ltd By Share Ltd
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Chengdu Exhibition Of New Materials Ltd By Share Ltd
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/68—Polyesters containing atoms other than carbon, hydrogen and oxygen
    • C08G63/685—Polyesters containing atoms other than carbon, hydrogen and oxygen containing nitrogen
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/78—Preparation processes
    • 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
    • C09D11/02—Printing inks
    • C09D11/10—Printing inks based on artificial resins
    • C09D11/102—Printing inks based on artificial resins containing macromolecular compounds obtained by reactions other than those only involving unsaturated carbon-to-carbon bonds
    • C09D11/104—Polyesters

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)

Abstract

The invention discloses a block type ink resin and a preparation method thereof. The block ink resin is obtained by esterification reaction of dibasic acid (anhydride), dihydric alcohol, hydroxyl-terminated polyacrylate, modified rosin resin and the like. Because the polyester, polyacrylate and modified rosin resin structures are introduced into the ink resin, the block type ink resin has wide applicability to various plastic film substrates.

Description

Block type ink resin and preparation method thereof
Technical Field
The invention relates to the field of polymer chemistry, in particular to a block type ink resin.
Background
In recent years, the improvement of the living standard of people drives the rapid growth of the packaging industry, and the gravure printing plays an important role in the printing of domestic plastic films, so that the continuous development of the composite ink technology and the market for the gravure printing is promoted. At present, the ink resin for plastic gravure printing mainly comprises a polyurethane system, a vinyl chloride-vinyl acetate system, a polyamide system, a polyvinyl butyral system, a nitrocotton system and the like, but single resin is difficult to meet the requirements of various aspects of printing ink, so that the modification of the existing ink resin is always an important aspect of the development of the ink resin.
The composite ink prepared by taking polyacrylate as an ink binder is mainly suitable for printing of BOPP film base materials, so that in order to expand the application range of the ink resin, a plurality of enterprises and scientific research institutes actively develop research work in related aspects. Patent CN102653595a discloses a preparation method of polyester modified hydroxyl polyacrylate and a coating containing the polyester modified hydroxyl polyacrylate. The method prepares the resin through esterification reaction of hydroxyl polyester and hydroxyl polyacrylate containing anhydride. Patent CN101029122a discloses a preparation method and application of an acrylic ester modified polyester resin. The method comprises the steps of firstly preparing acrylic ester prepolymer with carboxyl, and then esterifying the prepolymer with dibasic acid and dihydric alcohol to prepare the resin.
Disclosure of Invention
The invention aims to provide a block type ink resin.
The technical scheme provided by the invention is as follows:
firstly, preparing hydroxyl-terminated polyacrylate, and then esterifying the hydroxyl-terminated polyacrylate with dibasic acid (anhydride), dihydric alcohol, modified rosin resin and the like to synthesize the block type ink resin.
A block ink resin, the block ink resin being prepared by the steps of:
(1) Adding a solvent into a reaction kettle, heating to 75-90 ℃, dripping a mixed solution consisting of (methyl) acrylic ester, a styrene monomer, an active functional monomer, an initiator and a chain transfer agent into the reaction kettle at a constant speed within 2-5 hours, continuously stirring at the temperature for reacting for 5-8 hours after dripping, cooling to room temperature, and discharging to obtain hydroxyl-terminated polyacrylate;
(2) Adding dibasic acid (anhydride), dihydric alcohol and a catalyst into a reaction kettle, introducing nitrogen, heating to 140-150 ℃, starting stirring reaction after the raw materials are completely melted, heating to 180 ℃ within 2-5 hours, then heating to 220 ℃ at the speed of 10 ℃/hour, controlling the temperature at the top of a fractionating column to be 100+/-1 ℃, cooling to 120-130 ℃ when the acid value is 10-30 mgKOH/g in the heat preservation esterification reaction, adding hydroxyl-terminated polyacrylate and modified rosin resin into the reaction kettle, heating to 220 ℃ within 1-2 hours, stopping the reaction when the acid value is lower than 3mgKOH/g in the heat preservation esterification reaction, cooling to room temperature, and discharging to obtain the block type ink resin.
Further, in the step (1), the contents of the components in percentage by weight are as follows:
solvent 30-70 wt%
(meth) acrylic acid esters 10-35 wt%
15 to 30 percent wt percent of styrene monomer
1-15 wt% of active functional monomer;
the initiator is used in an amount of 0.5-10 wt% of the total weight of the styrene monomer and the active functional monomer, and the chain transfer agent is used in an amount of 10-50 wt% of the initiator.
Further, in the step (1), the solvent is any one or more of ethyl acetate, butyl acetate, cyclohexanone, methyl ethyl ketone and methyl amyl ketone.
Further, the (meth) acrylic acid ester in the step (1) is any one or more of methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, t-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, nonyl acrylate, decyl acrylate, dodecyl acrylate, cetyl (meth) acrylate, stearyl (meth) acrylate, phenyl (meth) acrylate, benzyl (meth) acrylate, cyclohexyl (meth) acrylate, trimethylcyclohexyl (meth) acrylate, t-butylcyclohexyl (meth) acrylate, isobornyl (meth) acrylate, methoxyethyl (meth) acrylate, ethoxymethyl acrylate, propoxyethyl acrylate, butoxyethyl acrylate, ethoxypropyl acrylate, 2- (2-methoxyethoxyethyl) ethyl acrylate, 2- (2-ethoxyethyl) acrylate, and 2-phenoxyethyl acrylate.
Further, the styrene monomer in the step (1) is any one or more of styrene, alpha-methylstyrene, p-methylstyrene, 4-acetoxystyrene, 3, 4-dimethylstyrene, 2,4, 6-trimethylstyrene, p-ethylstyrene, 2, 5-diethylstyrene, p-butylstyrene, m-tert-butylstyrene, p-benzylstyrene, o-methoxystyrene, p-methoxystyrene, 2, 6-dimethoxystyrene, 2-methoxy-5-isopropylstyrene.
Further, the reactive functional monomer in the step (1) is any one or more of (meth) acrylonitrile, N-methoxyethyl methacrylamide, N-butoxymethyl methacrylamide, dimethylaminomethyl (meth) acrylate, diethylaminomethyl (meth) acrylate, dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, dipropylaminoethyl methacrylate, dibutylamino ethyl methacrylate, dimethylaminopropyl (meth) acrylate, diethylaminopropyl (meth) acrylate.
Further, the initiator in the step (1) is any one or more of azobisisobutyronitrile, azobisisoheptonitrile, 2' -azobis (2, 4-dimethylvaleronitrile), dimethyl 2,2' -azobisisobutyrate, 4' -azobis (4-cyanovaleric acid), 2' -azobis (4-methoxy-2, 4-dimethylvaleronitrile), dimethyl 2,2' -azobis (2-methylpropionate), dibenzoyl peroxide, tert-butyl peroxybenzoate, diisopropyl peroxydicarbonate, tert-butyl peroxy2-ethylhexanoate, tert-butyl peroxyformate, tert-butyl hydroperoxide, tert-amyl hydroperoxide, cumene hydroperoxide, di-n-propyl peroxydicarbonate, di (2-ethoxy) ethyl peroxydicarbonate, tert-butyl peroxyneodecanoate, tert-butyl peroxypivalate, bis (3, 5-trimethylhexanoyl) peroxide, diacetyl peroxide.
Further, the chain transfer agent in the step (1) is any one or more of beta-mercaptoethanol, 3-mercaptopropanol, 3-mercapto-2-butanol, 3-mercapto-2-pentanol, 3-mercapto-2-methylpentanol and 6-mercapto hexanol.
Further, in the step (2), the contents of the components in percentage by weight are as follows:
15 to 35 percent wt percent of dibasic acid (anhydride)
10 to 30 percent of dihydric alcohol wt percent
10 to 35 percent wt percent of hydroxyl-terminated polyacrylate
5-30 wt% of modified rosin resin;
the catalyst is used in an amount of 0.01 to 0.5wt% based on the total weight of the reactants.
Further, the dibasic acid (anhydride) in the step (2) is any one or more of oxalic acid, succinic acid, glutaric acid, adipic acid, suberic acid, azelaic acid, sebacic acid, undecanedioic acid, terephthalic acid, phthalic acid (anhydride), tetrahydrophthalic anhydride, hexahydrophthalic anhydride, isophthalic acid, maleic acid (anhydride), fumaric acid, 3-dimethylglutaric acid.
Further, in the step (2), the dihydric alcohol is any one or more of ethylene glycol, 1, 2-propylene glycol, 1, 3-propylene glycol, diethylene glycol, dipropylene glycol, 1, 4-butanediol, 1, 6-hexanediol, 1, 8-octanediol, 1, 10-decanediol, 1, 12-dodecanediol, methyl propylene glycol, neopentyl glycol, 2-ethyl-2-butyl-1, 3-propanediol, 1, 2-cyclohexanedimethanol and 1, 4-cyclohexanedimethanol.
Further, the modified rosin resin in the step (2) is any one or more of dihydro rosin, tetrahydro rosin, acrylic pimaric acid, maleic pimaric acid and fumaropimaric acid.
Further, the catalyst in the step (2) is any one or more of dibutyl tin dilaurate, stannous octoate, dibutyl tin diacetate, tributyl tin oxide, dioctyl tin oxide, tributyl tin chloride, lead 2-ethyl hexanoate, lead benzoate, lead naphthenate, cobalt benzoate, cobalt 2-ethyl hexanoate, zinc naphthenate and iron octoate.
The block type ink resin of the invention can be effectively suitable for printing of various plastic film substrates due to the combination of the characteristics of polyester, polyacrylate and modified rosin resin.
Detailed Description
The present invention is specifically described below by way of examples, which are provided only for further explanation of the present invention and should not be construed as limiting the scope of the present invention. Various modifications and alterations of this invention will be apparent to those skilled in the art without departing from the scope and general inventive concept, and it is intended to cover all such modifications and alterations as fall within the true scope of this invention.
Example 1
Preparation of block ink resin:
(1) 45kg of ethyl acetate is added into a reaction kettle, the temperature is raised to 75 ℃, a mixed solution composed of 25kg of propyl methacrylate, 19kg of styrene, 8kg of N-butoxy methyl methacrylamide, 0.78kg of 2,2' -azo-bis (2, 4-dimethyl valeronitrile) and 0.156kg of 3-mercapto-2-butanol is dropwise added into the reaction kettle at a uniform speed within 2 hours, the reaction is continued to be carried out for 5 hours at the temperature after the dropwise addition, the temperature is reduced to room temperature, and the hydroxyl-terminated polyacrylate is obtained after discharging;
(2) Adding 18kg of adipic acid, 5kg of 1, 3-propanediol, 7kg of 1, 10-decanediol and 0.155kg of stannous octoate into a reaction kettle, introducing nitrogen, heating to 140 ℃, starting stirring reaction after all raw materials are melted, heating to 180 ℃ in 2 hours, then heating to 220 ℃ at the speed of 10 ℃/hour, controlling the temperature at the top of a fractionating column to be 100+/-1 ℃, carrying out heat preservation esterification reaction until the acid value is 15mgKOH/g, cooling to 120 ℃, adding 20kg of hydroxyl-terminated polyacrylate and 12kg of tetrahydrorosin into the reaction kettle, heating to 220 ℃ in 1 hour, carrying out heat preservation esterification until the acid value is 2.9mgKOH/g, stopping the reaction, cooling to room temperature, and discharging to obtain the block type ink resin.
Example 2
Preparation of block ink resin:
(1) Adding 56kg of butyl acetate into a reaction kettle, heating to 80 ℃, dropwise adding a mixed solution consisting of 14kg of n-butyl acrylate, 16kg of nonyl acrylate, 24kg of 2, 5-diethyl styrene, 11kg of dimethylaminopropyl methacrylate, 1.56kg of dibenzoyl peroxide and 0.624kg of 3-mercapto-2-pentanol into the reaction kettle at a constant speed within 3 hours, continuously stirring at the temperature for reaction for 6 hours after the dropwise adding is completed, cooling to room temperature, and discharging to obtain hydroxyl-terminated polyacrylate;
(2) Adding 7kg of succinic acid, 18kg of sebacic acid, 16kg of dipropylene glycol, 6kg of 1, 4-butanediol and 0.115kg of dioctyl tin oxide into a reaction kettle, introducing nitrogen, heating to 145 ℃, starting stirring reaction after the raw materials are completely melted, heating to 180 ℃ within 3 hours, then heating to 220 ℃ at the speed of 10 ℃/hour, controlling the temperature at the top of a fractionating column to be 100+/-1 ℃, cooling to 125 ℃ when the temperature is kept for esterification until the acid value is 21mgKOH/g, adding 20kg of hydroxyl-terminated polyacrylate and 15kg of propylene pimaric acid into the reaction kettle, heating to 220 ℃ within 2 hours, stopping the reaction when the acid value is 1.8mgKOH/g when the temperature is kept for esterification, cooling to room temperature, and discharging to prepare the block ink resin.
Example 3
Preparation of block ink resin:
(1) Adding 41kg of methyl ethyl ketone into a reaction kettle, heating to 85 ℃, dropwise adding a mixed solution consisting of 10kg of methyl methacrylate, 9kg of tert-butyl acrylate, 22kg of o-methoxystyrene, 14kg of diethylaminopropyl acrylate, 1.76kg of tert-amyl hydroperoxide and 0.493kg of 6-mercapto hexanol into the reaction kettle at a constant speed within 4 hours, continuously stirring at the temperature for reaction for 7 hours after the dropwise adding is completed, cooling to room temperature, and discharging to obtain hydroxyl-terminated polyacrylate;
(2) 23kg of suberic acid, 8kg of isophthalic acid, 9kg of 1, 2-propanediol, 18kg of 1, 2-cyclohexanedimethanol and 0.41kg of tributyltin oxide are added into a reaction kettle, nitrogen is introduced, the temperature is raised to 143 ℃, stirring reaction is started after the raw materials are completely melted, the temperature is raised to 180 ℃ within 5 hours, then the temperature is raised to 220 ℃ at the speed of 10 ℃/hour, the temperature at the top of a fractionating column is controlled to be 100+/-1 ℃, when the acid value is 14mgKOH/g in the thermal insulation esterification reaction, the temperature is reduced to 126 ℃, 19kg of hydroxyl-terminated polyacrylate and 22kg of fumaropimaric acid are added into the reaction kettle, the temperature is raised to 220 ℃ within 1.5 hours, the reaction is stopped when the acid value is 2.7mgKOH/g in the thermal insulation esterification reaction, the reaction is cooled to the room temperature, and the block type ink resin is prepared after discharging.
Example 4
Preparation of block ink resin:
(1) Adding 62kg of cyclohexanone into a reaction kettle, heating to 90 ℃, dropwise adding a mixed solution consisting of 5kg of ethyl methacrylate, 12kg of dodecyl acrylate, 17kg of 2,4, 6-trimethylstyrene, 6kg of dimethylaminoethyl methacrylate, 3kg of di-n-propyl peroxydicarbonate and 0.54kg of 3-mercaptopropanol into the reaction kettle at a constant speed within 5 hours, continuously stirring at the temperature for reaction for 8 hours after the dropwise adding is completed, cooling to room temperature, and discharging to obtain hydroxyl-terminated polyacrylate;
(2) Adding 14kg of azelaic acid, 9kg of 3, 3-dimethyl glutaric acid, 9kg of diethylene glycol, 15kg of methyl propylene glycol and 0.374kg of cobalt benzoate into a reaction kettle, introducing nitrogen, heating to 150 ℃, starting stirring reaction after the raw materials are completely melted, heating to 180 ℃ within 3.5 hours, then heating to 220 ℃ at the speed of 10 ℃/hour, controlling the temperature at the top of a fractionating column to be 100+/-1 ℃, cooling to 128 ℃ when the temperature is kept for esterification until the acid value is 24mgKOH/g, adding 15kg of hydroxyl-terminated polyacrylate and 25kg of maleopimaric acid into the reaction kettle, heating to 220 ℃ within 2 hours, keeping the temperature for esterification until the acid value is 1.1mgKOH/g, stopping the reaction, cooling to room temperature, and discharging to obtain the block ink resin.
Example 5
Preparation of block ink resin:
(1) Adding 58kg of pivalone into a reaction kettle, heating to 90 ℃, dropwise adding a mixed solution consisting of 12kg of methyl methacrylate, 14kg of benzyl acrylate, 26kg of 2, 6-dimethoxystyrene, 6kg of diethylaminoethyl methacrylate, 1.972kg of tert-butyl peroxyformate and 0.513kg of beta-mercaptoethanol into the reaction kettle at a constant speed within 5 hours, continuously stirring at the temperature for reaction for 7 hours after the dropwise adding is completed, cooling to room temperature, and discharging to obtain hydroxyl-terminated polyacrylate;
(2) Adding 10kg of glutaric acid, 17kg of fumaric acid, 8kg of ethylene glycol, 11kg of 1, 8-octanediol and 0.072kg of lead naphthenate into a reaction kettle, introducing nitrogen, heating to 142 ℃, starting stirring reaction after the raw materials are completely melted, heating to 180 ℃ within 4 hours, then heating to 220 ℃ at the speed of 10 ℃/hour, controlling the temperature at the top of a fractionating column to be 100+/-1 ℃, cooling to 126 ℃ when the temperature is kept for esterification until the acid value is 27mgKOH/g, adding 25kg of hydroxyl-terminated polyacrylate and 9kg of acrylic acid into the reaction kettle, heating to 220 ℃ within 1 hour, keeping the temperature for esterification until the acid value is 2.1mgKOH/g, stopping the reaction, cooling to room temperature, and discharging to obtain the block ink resin.
Example 6
Preparation of ink:
the block type ink resins prepared in examples 1,2, 3,4 and 5 were used to prepare composite inks for gravure printing, respectively, by the following processes: 33kg of the block type ink resin, 1.6kg of polyketone resin, 30kg of ethyl acetate, 6kg of butyl acetate, 29kg of titanium pigment, 2kg of BYK-191 dispersant, 1kg of polyethylene wax and 1.5kg of fumed silica are placed into a container, stirred for 30 minutes by a high-speed dispersing machine, the materials are taken out, sent into a sand mill for sand milling, discharged when the fineness is lower than 10 microns, and filtered to obtain the composite ink for intaglio printing. The detection indexes of the prepared composite ink for intaglio printing are shown in table 1.
Various detection indexes of the ink prepared in Table 1
。
The detection result is detected according to QB/T2024-2012 standard.
Comparative example 1
(1) 13kg of glutaric acid, 10kg of sebacic acid, 9kg of ethylene glycol, 15kg of neopentyl glycol and 0.12kg of tributyltin chloride are added into a reaction kettle, nitrogen is introduced, the temperature is raised to 150 ℃, stirring reaction is started after the raw materials are completely melted, the temperature is raised to 180 ℃ within 3.5 hours, then the temperature is raised to 220 ℃ at the speed of 10 ℃/hour, the top temperature of a fractionating column is controlled to be 100+/-1 ℃, the temperature is controlled, the temperature is reduced, and the material is discharged when the acid value is 2mgKOH/g after the esterification reaction is carried out.
(2) 33kg of the prepared ink resin, 1.6kg of polyketone resin, 30kg of ethyl acetate, 6kg of butyl acetate, 29kg of titanium pigment, 2kg of BYK-191 dispersant, 1kg of polyethylene wax and 1.5kg of fumed silica are put into a container, stirred for 30 minutes by a high-speed dispersing machine, the materials are taken out, sent into a sand mill for sand milling, discharged when the fineness is lower than 10 microns, and filtered to obtain the composite ink for intaglio printing. The respective detection indexes of the composite ink for gravure printing are shown in table 2.
TABLE 2
。
The detection result is detected according to QB/T2024-2012 standard.
Finally, it should be noted that: the above embodiments are only for illustrating the technical solution of the present invention, and not for limiting the same; although the invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical scheme described in the foregoing embodiments can be modified or some or all of the technical features thereof can be replaced by equivalents; such modifications and substitutions do not depart from the spirit of the invention.

Claims (8)

1. A block ink resin, characterized in that the block ink resin is prepared by the steps of:
(1) Adding a solvent into a reaction kettle, heating to 75-90 ℃, dripping a mixed solution consisting of (methyl) acrylic ester, a styrene monomer, an active functional monomer, an initiator and a chain transfer agent into the reaction kettle at a constant speed within 2-5 hours, continuously stirring at the temperature for reacting for 5-8 hours after dripping, cooling to room temperature, and discharging to obtain hydroxyl-terminated polyacrylate;
(2) Adding dibasic acid and/or dibasic anhydride, dihydric alcohol and a catalyst into a reaction kettle, introducing nitrogen, heating to 140-150 ℃, starting stirring reaction after all raw materials are melted, heating to 180 ℃ within 2-5 hours, then heating to 220 ℃ at the speed of 10 ℃/hour, controlling the top temperature of a fractionating column to be 100+/-1 ℃, cooling to 120-130 ℃ when the acid value is 10-30 mgKOH/g in the heat preservation esterification reaction, adding hydroxyl-terminated polyacrylate and modified rosin resin into the reaction kettle, heating to 220 ℃ within 1-2 hours, stopping the reaction when the acid value is lower than 3mgKOH/g in the heat preservation esterification reaction, cooling to room temperature, and discharging to obtain the block type ink resin;
in the step (1), the contents of the components in percentage by weight are as follows:
solvent 30-70 wt%
(meth) acrylic acid esters 10-35 wt%
15 to 30 percent wt percent of styrene monomer
1-15 wt% of active functional monomer;
the initiator is 0.5-10wt% of the total weight of the styrene monomer and the active functional monomer, and the chain transfer agent is 10-50wt% of the initiator;
the active functional monomer is any one or more of (methyl) acrylonitrile, N-methoxyethyl methacrylamide, N-butoxy methyl methacrylamide, dimethyl amino methyl (meth) acrylate, diethyl amino methyl (meth) acrylate, dimethyl amino ethyl (meth) acrylate, diethyl amino ethyl (meth) acrylate, dipropyl amino ethyl methacrylate, dibutyl amino ethyl methacrylate, dimethyl amino propyl (meth) acrylate and diethyl amino propyl (meth) acrylate;
the chain transfer agent in the step (1) is any one or more of beta-mercaptoethanol, 3-mercaptopropanol, 3-mercapto-2-butanol, 3-mercapto-2-pentanol, 3-mercapto-2-methylpentanol and 6-mercapto hexanol;
in the step (2), the contents of the components in percentage by weight are as follows:
15 to 35 percent wt percent of dibasic acid and/or dibasic anhydride
10 to 30 percent of dihydric alcohol wt percent
10 to 35 percent wt percent of hydroxyl-terminated polyacrylate
5-30 wt% of modified rosin resin;
the dosage of the catalyst is 0.01 to 0.5 weight percent of the total weight of reactants;
the modified rosin resin is any one or more of dihydro rosin, tetrahydro rosin, acrylic pimaric acid, maleic pimaric acid and fumaropimaric acid.
2. The block ink resin according to claim 1, wherein the solvent in step (1) is any one or more of ethyl acetate, butyl acetate, cyclohexanone, methyl ethyl ketone, and methyl amyl ketone.
3. The block ink resin according to claim 1, wherein the (meth) acrylate in the step (1) is any one or more of methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, t-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, nonyl acrylate, decyl acrylate, dodecyl acrylate, sixteen (meth) acrylate, stearyl (meth) acrylate, phenyl (meth) acrylate, benzyl (meth) acrylate, cyclohexyl (meth) acrylate, trimethylcyclohexyl (meth) acrylate, t-butylcyclohexyl (meth) acrylate, isobornyl (meth) acrylate, methoxyethyl acrylate, ethoxymethyl acrylate, propoxyethyl acrylate, butoxyethyl acrylate, ethoxypropyl acrylate, 2- (2-methoxyethyl) ethyl acrylate, 2- (2-ethoxyethyl) acrylate, and 2-phenoxyethyl acrylate.
4. The block ink resin according to claim 1, wherein the styrene monomer in the step (1) is any one or more of styrene, α -methylstyrene, p-methylstyrene, 4-acetoxystyrene, 3, 4-dimethylstyrene, 2,4, 6-trimethylstyrene, p-ethylstyrene, 2, 5-diethylstyrene, p-butylstyrene, m-t-butylstyrene, p-benzylstyrene, o-methoxystyrene, p-methoxystyrene, 2, 6-dimethoxystyrene, 2-methoxy-5-isopropylstyrene.
5. The block ink resin according to claim 1, wherein the initiator in step (1) is any one or more of azobisisobutyronitrile, azobisisoheptonitrile, 2' -azobis (2, 4-dimethylpentanenitrile), dimethyl 2,2' -azobisisobutyrate, 4' -azobis (4-cyanovaleric acid), dimethyl 2,2' -azobis (4-methoxy-2, 4-dimethylpentanenitrile), dimethyl 2,2' -azobis (2-methylpropionate), dibenzoyl peroxide, t-butyl peroxybenzoate, diisopropyl peroxydicarbonate, t-butyl peroxy2-ethylhexanoate, t-butyl peroxyformate, t-butyl hydroperoxide, t-amyl hydroperoxide, cumene hydroperoxide, di-n-propyl peroxydicarbonate, di-2-ethoxy ethyl peroxydicarbonate, t-butyl peroxyneodecanoate, t-butyl peroxypivalate, bis (3, 5-trimethylhexanoyl) and diacetyl peroxide.
6. The block ink resin according to claim 1, wherein the dibasic acid and/or dibasic anhydride in the step (2) is any one or more of oxalic acid, succinic acid, glutaric acid, adipic acid, suberic acid, azelaic acid, sebacic acid, undecanedioic acid, terephthalic acid, phthalic acid and/or phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, isophthalic acid, maleic acid and/or maleic anhydride, fumaric acid, 3-dimethylglutaric acid.
7. The block ink resin according to claim 1, wherein the diol in the step (2) is any one or more of ethylene glycol, 1, 2-propylene glycol, 1, 3-propylene glycol, diethylene glycol, dipropylene glycol, 1, 4-butanediol, 1, 6-hexanediol, 1, 8-octanediol, 1, 10-decanediol, 1, 12-dodecanediol, methylpropanediol, neopentyl glycol, 2-ethyl-2-butyl-1, 3-propanediol, 1, 2-cyclohexanedimethanol, and 1, 4-cyclohexanedimethanol.
8. The block ink resin of claim 1, wherein the catalyst in step (2) is any one or more of dibutyltin dilaurate, stannous octoate, dibutyltin diacetate, tributyltin oxide, dioctyltin oxide, tributyltin chloride, lead 2-ethylhexanoate, lead benzoate, lead naphthenate, cobalt benzoate, cobalt 2-ethylhexanoate, zinc naphthenate, and iron octoate.
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