CN106749844A - The preparation method of acrylate resin composition - Google Patents
The preparation method of acrylate resin composition Download PDFInfo
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- CN106749844A CN106749844A CN201510832305.3A CN201510832305A CN106749844A CN 106749844 A CN106749844 A CN 106749844A CN 201510832305 A CN201510832305 A CN 201510832305A CN 106749844 A CN106749844 A CN 106749844A
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- acrylate
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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
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/12—Esters of monohydric alcohols or phenols
- C08F220/14—Methyl esters, e.g. methyl (meth)acrylate
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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
- C09D11/02—Printing inks
- C09D11/10—Printing inks based on artificial resins
- C09D11/106—Printing inks based on artificial resins containing macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- C09D11/107—Printing inks based on artificial resins containing macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds from unsaturated acids or derivatives thereof
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- Wood Science & Technology (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
The invention discloses the preparation method of acrylate resin composition, including following operation：1）To methyl methacrylate, butyl acrylate, acrylic acid and hydroxy-ethyl acrylate is added in reactor, polymerization obtains mixed monomer solution；2）Primary solution is obtained to the stirring such as azodiisobutyronitrile and DAAM is added in mixed monomer solution；3）To propylene glycol methyl ether acetate and dimethylformamide is added in flask, solvent liquid is mixed to get, then to primary solution is at the uniform velocity added dropwise in solvent liquid, standing obtains crude product；4）It is well mixed to obtain acrylate resin composition to DMAE, distilled water and PH conditioning agents is added in crude product.In the present invention, from methyl methacrylate as hard monomer, its glass transition temperature is high, can so improve hardness, weatherability and water resistance of polymer etc..From butyl acrylate as soft monomer, the pliability of glued membrane can be improved, increase film adhesive.
Description
Technical field
The present invention relates to technical field of ink, more particularly, to the preparation method of acrylate resin composition.
Background technology
In the case of environmental protection consciousness is gradually enhanced, especially in food, toy for children and medical package field, water-based ink finally necessarily replaces solvent-based ink.But the aqueous solvent of water-based ink is polar material, it is generally difficult in the Plastic film surface such as PP, PE, OPP, PO wetting of low polarity.Adhesive force on a plastic film is improved, needs emphasis to consider the cohesive force size of link stuff and plastic sheeting when water-based ink is equipped with.Because waterborne acrylic paint has the advantages that color is shallow, transparency is high, good weatherability, it is widely used in field of product packaging.At present, waterborne acrylic paint generally improves the adhesive force of film using high-temperature cross-linking solidification, but easily curling deforms during PE/PP thin film high temperatures, and other performances on PE/PP films can not also meet demand.
The content of the invention
The purpose of the present invention is the defect for overcoming above-mentioned prior art, there is provided the preparation method of acrylate resin composition, and the resin as obtained in the present invention can improve film forming of the water-based ink on PE/PP films, adhesive force, glossiness and resistance to dry friction.
The purpose of the present invention is achieved through the following technical solutions：
The preparation method of acrylate resin composition, including following operation：
1）To methyl methacrylate, butyl acrylate, acrylic acid and hydroxy-ethyl acrylate is added in reactor, polymerization obtains mixed monomer solution, standby；
2）To operation 1）Azodiisobutyronitrile, DAAM, oxygen vinethene and polyoxyethylene glycol Arrcostab are added in the mixed monomer solution of gained, at a temperature of 25 DEG C, 20min is stirred by the rotating speed of 350 ~ 500r/min, obtain primary solution, it is standby；
3）A flask is taken, to propylene glycol methyl ether acetate and dimethylformamide is added in the flask, solvent liquid is mixed to get, 75 ~ 90 DEG C are heated to, then to the operation 2 is at the uniform velocity added dropwise in solvent liquid）The primary solution of gained, time for adding controls the reaction temperature control in 2h ~ 4h, dropwise addition that 80 ~ 90 DEG C are maintained the temperature at 75 ~ 90 DEG C, after completion of dropping, stands 2h ~ 4h, obtains crude product, standby；
4）Temperature is controlled at 40 ~ 50 DEG C, to operation 3）DMAE, distilled water and PH conditioning agents are added in the crude product of gained, regulation pH value is 8 ~ 9, adds adipic dihydrazide, well mixed to obtain acrylate resin composition；
The quality proportioning of each constituent of acrylate resin composition is：12 ~ 18 parts of methyl methacrylate, 12 ~ 18 parts of butyl acrylate, 4 ~ 8 parts of acrylic acid, 1.5 ~ 2.5 parts of hydroxy-ethyl acrylate, 0.5 ~ 1 part of DAAM, 33 ~ 46 parts of propylene glycol methyl ether acetate, 16 ~ 23 parts of dimethylformamide, 3 ~ 8 parts of oxygen vinethene, 2 ~ 6 parts of DMAE, 1 ~ 3 part of polyoxyethylene glycol Arrcostab, 0.5 ~ 1 part of azodiisobutyronitrile, 0.5 ~ 0.8 part of adipic dihydrazide, 80 ~ 160 parts of distilled water.
Acrylate determines the performance of water-based ink substantially as link stuff, its performance, wherein, the water solubility of link stuff is not only related to the storage stability of water-based ink and printing applies membrane process, also affects the printing quality of ink.The water solubility of resin is mainly related to hydrophilic radical and content.Drying at room temperature film forming according to PE/PP film curing inks of the invention, while to reach excellent combination property, being polymerized from following component：, used as hard monomer, its glass transition temperature is high, can so improve hardness, weatherability and water resistance of polymer etc. for methyl methacrylate.Butyl acrylate can improve the pliability of glued membrane as soft monomer, increase film adhesive.Acrylic acid and hydroxy-ethyl acrylate, containing hydrophilic groups, hydroxyl etc., can improve the water solubility of polymer, and then cause that resin property is more stablized as hydrophilic monomer.DAAM is used as cross-linking monomer, adipic dihydrazide is used as crosslinking agent, DAAM can introduce the amino low-temperature self-crosslinking of reactive group ketone carbonyl and adipic dihydrazide, allow that resin occurs self-crosslinking reaction in low temperature, the performances such as adhesive force, hardness and the water resistance of film so can be not only improved, can be also applied on PE/PP films.
In Raolical polymerizable, polymerization speed depends primarily on the speed of trigger rate, and trigger rate is related to the species of initiator.From azodiisobutyronitrile as initiator, it can react the present invention at a lower polymerization temperature, and low viscosity, resin of light color can be obtained.In solution polymerization process, solvent can be produced a very large impact to polymerisation and polymerizate, and from propylene glycol methyl ether acetate as main solvent, existing ehter bond has carbonyl to the present invention again in its molecular structural formula, and carbonyl yet forms both the structure of ester group, also with alkyl；It is provided simultaneously with non-polar group and polar group, and this two parts group both mutually repelled by restriction, there is respective effect again, therefore, it can dissolve polarity and apolar substance.From dimethylformamide as cosolvent, it can be miscible with water, alcohols and alcohol ethers material.
The glass transition temperature appropriate to obtain resinous polymer, further, the total number of the methyl methacrylate, the butyl acrylate, the acrylic acid and the hydroxy-ethyl acrylate is a, the number of the methyl methacrylate is a*55%, and the number of the butyl acrylate is a*30%.Because the construction temperature of water-based ink can not be too high, thus the MFT of water-base resin is controlled on the premise of changing firmness requirements when ensureing to reach resin film forming.Balance by controlling the number of hard monomer and soft monomer to adjust the glass transformation temperature of resin to reach between hardness and MFT of the invention.
To reach good aqueous stability and film performance, further, acrylic acid number is a*9.2%, and the number of the hydroxy-ethyl acrylate is a*5.8%.Acrylic acid is mainly the adhesive force of the aqueous stability and film that improve resin；Hydroxy-ethyl acrylate is primarily introduced into reactive group hydroxyl, improves the aqueous stability of resin, improves the adhesive force and the degree of cross linking of film after reacting.
Further, the total number of the methyl methacrylate, the butyl acrylate, the acrylic acid, the hydroxy-ethyl acrylate and DAAM is b, and the number of the azodiisobutyronitrile is b*2%.In polymerisation, the concentration of azodiisobutyronitrile is inversely proportional to the molecular weight of polymer.Specifically, with the increase of dosage of azodiisobutyronitrile, the molecular weight low amplitude of resinous polymer diminishes, and especially when consumption increases to b*2% from b*1%, influences unobvious；And when dosage of azodiisobutyronitrile is too high, reacting the heat for producing is difficult to control, danger can be brought to a large amount of productions.Additionally, azodiisobutyronitrile is relatively costly, storage and transport are also fairly cumbersome, and consumption excessively can also increase product cost.Thus, the present invention is controlled the 2% of the total consumption of monomer the consumption of azodiisobutyronitrile under the conditions of the molecular weight for meeting resin application performance.
Further, the propylene glycol methyl ether acetate and the mass ratio of the dimethylformamide are 2:1.From this mass ratio mixed solvent when, the water-soluble good of synthetic resin, good fluidity, transparency are high.
Further, the adipic dihydrazide and the mass ratio of the azodiisobutyronitrile are 4:5.The adipic dihydrazide can produce influence with the mass ratio of the azodiisobutyronitrile on the film degree of cross linking, water absorption rate and hardness.From the mass ratio, the excellent degree of cross linking and hardness and the water absorption rate compared with ground can be obtained.
The invention has the advantages that：The acrylate resin composition as obtained in the present invention can improve film forming of the water-based ink on PE/PP films, adhesive force, glossiness and resistance to dry friction.Wherein, from methyl methacrylate as hard monomer, its glass transition temperature is high, can so improve hardness, weatherability and water resistance of polymer etc..From butyl acrylate as soft monomer, the pliability of glued membrane can be improved, increase film adhesive.From acrylic acid and hydroxy-ethyl acrylate as hydrophilic monomer, containing hydrophilic groups, hydroxyl etc., the water solubility of polymer can be improved, and then cause that resin property is more stablized.From DAAM as cross-linking monomer, adipic dihydrazide is used as crosslinking agent, DAAM can introduce the amino low-temperature self-crosslinking of reactive group ketone carbonyl and adipic dihydrazide, allow that resin occurs self-crosslinking reaction in low temperature, the performances such as adhesive force, hardness and the water resistance of film so can be not only improved, can be also applied on PE/PP films.
Specific embodiment
With reference to embodiment, the present invention is described in further detail, but embodiments of the present invention not limited to this.
Embodiment 1
The preparation method of acrylate resin composition, including following operation：
1）To methyl methacrylate, butyl acrylate, acrylic acid and hydroxy-ethyl acrylate is added in reactor, polymerization obtains mixed monomer solution, standby；
2）To operation 1）Azodiisobutyronitrile, DAAM, oxygen vinethene and polyoxyethylene glycol Arrcostab are added in the mixed monomer solution of gained, at a temperature of 25 DEG C, 20min is stirred by the rotating speed of 350 ~ 500r/min, obtain primary solution, it is standby；
3）A flask is taken, to propylene glycol methyl ether acetate and dimethylformamide is added in the flask, solvent liquid is mixed to get, 75 ~ 90 DEG C are heated to, then to the operation 2 is at the uniform velocity added dropwise in solvent liquid）The primary solution of gained, time for adding controls the reaction temperature control in 2h ~ 4h, dropwise addition that 80 ~ 90 DEG C are maintained the temperature at 75 ~ 90 DEG C, after completion of dropping, stands 2h ~ 4h, obtains crude product, standby；
4）Temperature is controlled at 40 ~ 50 DEG C, to operation 3）DMAE, distilled water and PH conditioning agents are added in the crude product of gained, regulation pH value is 8 ~ 9, adds adipic dihydrazide, well mixed to obtain acrylate resin composition；
The quality proportioning of each constituent of acrylate resin composition is：12 ~ 18 parts of methyl methacrylate, 12 ~ 18 parts of butyl acrylate, 4 ~ 8 parts of acrylic acid, 1.5 ~ 2.5 parts of hydroxy-ethyl acrylate, 0.5 ~ 1 part of DAAM, 33 ~ 46 parts of propylene glycol methyl ether acetate, 16 ~ 23 parts of dimethylformamide, 3 ~ 8 parts of oxygen vinethene, 2 ~ 6 parts of DMAE, 1 ~ 3 part of polyoxyethylene glycol Arrcostab, 0.5 ~ 1 part of azodiisobutyronitrile, 0.5 ~ 0.8 part of adipic dihydrazide, 80 ~ 160 parts of distilled water.
Acrylate determines the performance of water-based ink substantially as link stuff, its performance, wherein, the water solubility of link stuff is not only related to the storage stability of water-based ink and printing applies membrane process, also affects the printing quality of ink.The water solubility of resin is mainly related to hydrophilic radical and content.Drying at room temperature film forming according to PE/PP film curing inks of the invention, while to reach excellent combination property, being polymerized from following component：, used as hard monomer, its glass transition temperature is high, can so improve hardness, weatherability and water resistance of polymer etc. for methyl methacrylate.Butyl acrylate can improve the pliability of glued membrane as soft monomer, increase film adhesive.Acrylic acid and hydroxy-ethyl acrylate, containing hydrophilic groups, hydroxyl etc., can improve the water solubility of polymer, and then cause that resin property is more stablized as hydrophilic monomer.DAAM is used as cross-linking monomer, adipic dihydrazide is used as crosslinking agent, DAAM can introduce the amino low-temperature self-crosslinking of reactive group ketone carbonyl and adipic dihydrazide, allow that resin occurs self-crosslinking reaction in low temperature, the performances such as adhesive force, hardness and the water resistance of film so can be not only improved, can be also applied on PE/PP films.
In Raolical polymerizable, polymerization speed depends primarily on the speed of trigger rate, and trigger rate is related to the species of initiator.From azodiisobutyronitrile as initiator, it can react the present invention at a lower polymerization temperature, and low viscosity, resin of light color can be obtained.In solution polymerization process, solvent can be produced a very large impact to polymerisation and polymerizate, and from propylene glycol methyl ether acetate as main solvent, existing ehter bond has carbonyl to the present invention again in its molecular structural formula, and carbonyl yet forms both the structure of ester group, also with alkyl；It is provided simultaneously with non-polar group and polar group, and this two parts group both mutually repelled by restriction, there is respective effect again, therefore, it can dissolve polarity and apolar substance.From dimethylformamide as cosolvent, it can be miscible with water, alcohols and alcohol ethers material.
The glass transition temperature appropriate to obtain resinous polymer, preferably, the total number of the methyl methacrylate, the butyl acrylate, the acrylic acid and the hydroxy-ethyl acrylate is a, and the number of the methyl methacrylate is a*55%, and the number of the butyl acrylate is a*30%.Because the construction temperature of water-based ink can not be too high, thus the MFT of water-base resin is controlled on the premise of changing firmness requirements when ensureing to reach resin film forming.Balance by controlling the number of hard monomer and soft monomer to adjust the glass transformation temperature of resin to reach between hardness and MFT of the invention.
To reach good aqueous stability and film performance, it is preferable that acrylic acid number is a*9.2%, and the number of the hydroxy-ethyl acrylate is a*5.8%.Acrylic acid is mainly the adhesive force of the aqueous stability and film that improve resin；Hydroxy-ethyl acrylate is primarily introduced into reactive group hydroxyl, improves the aqueous stability of resin, improves the adhesive force and the degree of cross linking of film after reacting.
Preferably, the total number of the methyl methacrylate, the butyl acrylate, the acrylic acid, the hydroxy-ethyl acrylate and DAAM is b, and the number of the azodiisobutyronitrile is b*2%.In polymerisation, the concentration of azodiisobutyronitrile is inversely proportional to the molecular weight of polymer.Specifically, with the increase of dosage of azodiisobutyronitrile, the molecular weight low amplitude of resinous polymer diminishes, and especially when consumption increases to b*2% from b*1%, influences unobvious；And when dosage of azodiisobutyronitrile is too high, reacting the heat for producing is difficult to control, danger can be brought to a large amount of productions.Additionally, azodiisobutyronitrile is relatively costly, storage and transport are also fairly cumbersome, and consumption excessively can also increase product cost.Thus, the present invention is controlled the 2% of the total consumption of monomer the consumption of azodiisobutyronitrile under the conditions of the molecular weight for meeting resin application performance.
Preferably, the propylene glycol methyl ether acetate and the mass ratio of the dimethylformamide are 2:1.From this mass ratio mixed solvent when, the water-soluble good of synthetic resin, good fluidity, transparency are high.
Preferably, the adipic dihydrazide and the mass ratio of the azodiisobutyronitrile are 4:5.The adipic dihydrazide can produce influence with the mass ratio of the azodiisobutyronitrile on the film degree of cross linking, water absorption rate and hardness.From the mass ratio, the excellent degree of cross linking and hardness and the water absorption rate compared with ground can be obtained.
Above content is to combine the further description that specific preferred embodiment is made to the present invention, it is impossible to assert that specific embodiment of the invention is confined to these explanations.For general technical staff of the technical field of the invention, the other embodiment drawn in the case where technical scheme is not departed from should be included within the scope of the present invention.
Claims (6)
1. the preparation method of acrylate resin composition, it is characterised in that：
Including following operation：
1）To methyl methacrylate, butyl acrylate, acrylic acid and hydroxy-ethyl acrylate is added in reactor, polymerization obtains mixed monomer solution, standby；
2）To operation 1）Azodiisobutyronitrile, DAAM, oxygen vinethene and polyoxyethylene glycol Arrcostab are added in the mixed monomer solution of gained, at a temperature of 25 DEG C, 20min is stirred by the rotating speed of 350 ~ 500r/min, obtain primary solution, it is standby；
3）A flask is taken, to propylene glycol methyl ether acetate and dimethylformamide is added in the flask, solvent liquid is mixed to get, 75 ~ 90 DEG C are heated to, then to the operation 2 is at the uniform velocity added dropwise in solvent liquid）The primary solution of gained, time for adding controls the reaction temperature control in 2h ~ 4h, dropwise addition that 80 ~ 90 DEG C are maintained the temperature at 75 ~ 90 DEG C, after completion of dropping, stands 2h ~ 4h, obtains crude product, standby；
4）Temperature is controlled at 40 ~ 50 DEG C, to operation 3）DMAE, distilled water and PH conditioning agents are added in the crude product of gained, regulation pH value is 8 ~ 9, adds adipic dihydrazide, well mixed to obtain acrylate resin composition；
The quality proportioning of each constituent of acrylate resin composition is：12 ~ 18 parts of methyl methacrylate, 12 ~ 18 parts of butyl acrylate, 4 ~ 8 parts of acrylic acid, 1.5 ~ 2.5 parts of hydroxy-ethyl acrylate, 0.5 ~ 1 part of DAAM, 33 ~ 46 parts of propylene glycol methyl ether acetate, 16 ~ 23 parts of dimethylformamide, 3 ~ 8 parts of oxygen vinethene, 2 ~ 6 parts of DMAE, 1 ~ 3 part of polyoxyethylene glycol Arrcostab, 0.5 ~ 1 part of azodiisobutyronitrile, 0.5 ~ 0.8 part of adipic dihydrazide, 80 ~ 160 parts of distilled water.
2. the preparation method of acrylate resin composition according to claim 1, it is characterised in that：The total number of the methyl methacrylate, the butyl acrylate, the acrylic acid and the hydroxy-ethyl acrylate is a, and the number of the methyl methacrylate is a*55%, and the number of the butyl acrylate is a*30%.
3. the preparation method of acrylate resin composition according to claim 2, it is characterised in that：Acrylic acid number is a*9.2%, and the number of the hydroxy-ethyl acrylate is a*5.8%.
4. the preparation method of acrylate resin composition according to claim 3, it is characterised in that：The total number of the methyl methacrylate, the butyl acrylate, the acrylic acid, the hydroxy-ethyl acrylate and DAAM is b, and the number of the azodiisobutyronitrile is b*2%.
5. the preparation method of the acrylate resin composition according to any one in claim 1 ~ 4, it is characterised in that：The propylene glycol methyl ether acetate is 2 with the mass ratio of the dimethylformamide:1.
6. the preparation method of acrylate resin composition according to claim 5, it is characterised in that：The adipic dihydrazide is 4 with the mass ratio of the azodiisobutyronitrile:5.
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| CN201510832305.3A CN106749844A (en) | 2015-11-25 | 2015-11-25 | The preparation method of acrylate resin composition |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111122557A (en) * | 2018-11-01 | 2020-05-08 | 武汉武药科技有限公司 | Method for measuring azo diisobutyronitrile free radical initiation efficiency |
| CN115637012A (en) * | 2022-10-21 | 2023-01-24 | 苏州双象光学材料有限公司 | Polymethyl methacrylate alloy resin composition and preparation method thereof |
-
2015
- 2015-11-25 CN CN201510832305.3A patent/CN106749844A/en active Pending
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111122557A (en) * | 2018-11-01 | 2020-05-08 | 武汉武药科技有限公司 | Method for measuring azo diisobutyronitrile free radical initiation efficiency |
| CN111122557B (en) * | 2018-11-01 | 2022-07-12 | 武汉武药科技有限公司 | Method for measuring azo diisobutyronitrile free radical initiation efficiency |
| CN115637012A (en) * | 2022-10-21 | 2023-01-24 | 苏州双象光学材料有限公司 | Polymethyl methacrylate alloy resin composition and preparation method thereof |
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