CN113249063A - Water-based plastic substitute and preparation method thereof - Google Patents
Water-based plastic substitute and preparation method thereof Download PDFInfo
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- CN113249063A CN113249063A CN202110551621.9A CN202110551621A CN113249063A CN 113249063 A CN113249063 A CN 113249063A CN 202110551621 A CN202110551621 A CN 202110551621A CN 113249063 A CN113249063 A CN 113249063A
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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
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J133/00—Adhesives based on homopolymers or copolymers 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 only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
- C09J133/04—Homopolymers or copolymers of esters
- C09J133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
- C09J133/062—Copolymers with monomers not covered by C09J133/06
- C09J133/064—Copolymers with monomers not covered by C09J133/06 containing anhydride, COOH or COOM groups, with M being metal or onium-cation
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- 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
- C08F212/00—Copolymers 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 aromatic carbocyclic ring
- C08F212/02—Monomers containing only one unsaturated aliphatic radical
- C08F212/04—Monomers containing only one unsaturated aliphatic radical containing one ring
- C08F212/06—Hydrocarbons
- C08F212/08—Styrene
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- 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
- 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
- C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
- C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
- C08F220/1804—C4-(meth)acrylate, e.g. butyl (meth)acrylate, isobutyl (meth)acrylate or tert-butyl (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
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/02—Non-macromolecular additives
- C09J11/06—Non-macromolecular additives organic
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Abstract
The invention relates to the technical field of paper-plastic processing, in particular to a water-based plastic substitute and a preparation method thereof, which comprises the following steps: (1) synthesizing a first acrylic emulsion; (2) synthesizing a second acrylic acid emulsion; (3) and (3) preparing the water-based plastic substitute. The second acrylic emulsion adopted by the invention takes a small amount of methyl methacrylate as a hard monomer, so that emulsion particles are easy to form a film, and diacetone acrylamide is further added, and the film-forming property can be further improved by the crosslinking reaction of the diacetone acrylamide and adipic dihydrazide. According to the invention, the second acrylic emulsion with good film-forming property and the first acrylic emulsion with higher polarity are blended and modified in a specific ratio, and the colloidal particles of the second acrylic emulsion can be dispersed among the colloidal particles of the first acrylic emulsion, so that the first acrylic emulsion can be helpful for film formation, and the film layer has the performances of high hardness and high adhesive force.
Description
Technical Field
The invention relates to the technical field of paper-plastic processing, in particular to a water-based plastic substitute and a preparation method thereof.
Background
The traditional paper adopts a paper-plastic film-coated material, an adhesive is coated on a plastic film through a roller coating device, the plastic film is heated through a hot-pressing roller to soften the film, and then a printed product coated with a base material is pressed with the film to form a paper-plastic integrated film-coated product. But the phenomena of corrugation, foaming and finished product curling can occur in the production process, and the problems of white pollution, difficult circular pulping and the like are easily caused.
Disclosure of Invention
In order to overcome the defects in the prior art, the invention aims to provide a water-based plastic substitute and a preparation method thereof, and the water-based paint is adopted to replace the traditional glue film coating technology.
The purpose of the invention is realized by the following technical scheme:
the preparation method of the water-based plastic substitute comprises the following steps:
(1) synthesis of the first acrylic emulsion: weighing the following raw materials in percentage by mass: 40-50% of styrene, 15-20% of butyl acrylate, 5-10% of acrylic acid, 0.5-1.5% of initiator, 1-2% of emulsifier and the balance of water, uniformly mixing the water, the emulsifier and part of the initiator, adding part of the styrene, part of the butyl acrylate and part of the acrylic acid, heating to 75-85 ℃, reacting for 20-30min, dropwise adding the rest of the styrene, the rest of the butyl acrylate, the rest of the acrylic acid and the rest of the initiator, continuing to perform heat preservation reaction for 2-3h after dropwise adding is completed, and then cooling to room temperature to obtain a first acrylic emulsion;
(2) synthesis of second acrylic emulsion: weighing the following raw materials in percentage by mass: 25-35% of methyl methacrylate, 30-35% of butyl acrylate, 5-10% of acrylic acid, 2-4% of diacetone acrylamide, 0.5-1.5% of initiator, 1-2% of emulsifier and the balance of water, uniformly mixing the water, the emulsifier and part of the initiator, adding part of the methyl methacrylate, part of the butyl acrylate, part of the acrylic acid and part of the diacetone acrylamide, heating to 75-85 ℃, reacting for 20-30min, dropwise adding the rest of the methyl methacrylate, the rest of the butyl acrylate, the rest of the acrylic acid, the rest of the diacetone acrylamide and the rest of the initiator, continuing the heat preservation reaction for 2-3h after the dropwise addition is finished, and then cooling to room temperature to obtain a second acrylic acid emulsion;
(3) preparing the water-based plastic substitute: and mixing the first acrylic emulsion and the second acrylic emulsion according to the mass ratio of 2-3:7-8, uniformly stirring, adding a neutralizing agent to adjust the pH value to 7-8, adding adipic dihydrazide, uniformly stirring, and filtering to obtain the water-based plastic substitute.
The water-based plastic substitute is emulsion type acrylic resin coating, in the emulsion type acrylic resin coating, the variety and the using amount of monomers determine various performances of emulsion and film forming, styrene and methyl methacrylate are hard monomers and endow the film with hardness and tensile strength, butyl acrylate is soft monomers and endow the film with adhesiveness and flexibility, acrylic acid is a functional monomer and provides a crosslinking point to promote polymerization reaction, diacetone acrylamide is a functional monomer and is matched with adipic dihydrazide for use, and the diacetone acrylamide and the adipic dihydrazide generate crosslinking reaction in the curing process to form a crosslinking network structure, so that the film forming temperature is reduced, and the water resistance and the hardness of the film are improved. Generally, the use of various monomers is formulated according to the performance requirements of an emulsion and a film layer, it is not necessary to use two kinds of polymerization emulsions for blending modification, emulsion particles need to be mutually permeated and dissolved in the curing process of the film layer, and two different polymers are easy to generate the phenomenon of phase separation, which is not favorable for the continuity of the film layer. The first acrylic emulsion adopted by the invention takes a large amount of styrene as a hard monomer, and the styrene has higher steric hindrance and lower Tg point relative to methyl methacrylate, so that a film layer formed by the part of emulsion particles has higher hardness, but has larger curing difficulty; the second acrylic emulsion adopted by the invention takes a small amount of methyl methacrylate as a hard monomer, so that the emulsion particles have a low Tg point, are easy to form a film and have good adhesiveness, and diacetone acrylamide is further added, and the film-forming property can be further improved by performing crosslinking reaction with adipic dihydrazide, and the crosslinking structure is also beneficial to improving the hardness of the film layer. According to the invention, the second acrylic emulsion with good film-forming property and the first acrylic emulsion with higher polarity are blended and modified in a specific ratio, and the colloidal particles of the second acrylic emulsion can be dispersed among the colloidal particles of the first acrylic emulsion, so that the first acrylic emulsion can be helpful for film formation, and the film layer has the performances of high hardness and high adhesive force. Based on cost control, the using amount of the diacetone acrylamide is less, the distribution of the diacetone acrylamide in a single emulsion prepared by directly adopting a moderate hard monomer, a soft monomer and the diacetone acrylamide is limited, the cross-linking property with the adipic dihydrazide is weaker, and the improvement degree of a film layer is not obvious.
Wherein the initiator is at least one of ammonium persulfate, potassium persulfate and dibenzoyl peroxide. Preferably, the initiator is ammonium persulfate, so that the cost is low.
Wherein the emulsifier consists of SDS and OP-10 according to the weight ratio of 2-3: 2. SDS is anionic surfactant, OP-10 is nonionic surfactant, the emulsifying capacity of anionic surfactant is better, but the emulsifying stability of nonionic surfactant is better, through the appropriate combination of the two, the storage stability of emulsion particles can be better improved.
Wherein the neutralizing agent is diluted ammonia water and/or triethanolamine.
And (3) adding an auxiliary agent before adding the neutralizing agent, wherein the auxiliary agent is at least one of a flatting agent, a brightening agent, an abrasion-resistant auxiliary agent and a rheological agent.
Wherein, the specific operation of synthesizing the first acrylic emulsion in the step (1) is as follows: weighing the following raw materials in percentage by mass: 40-50% of styrene, 15-20% of butyl acrylate, 5-10% of acrylic acid, 0.5-1.5% of initiator, 1-2% of emulsifier and the balance of water, uniformly mixing the water, the emulsifier and the initiator 1/2 which accounts for the total mass of the initiator, adding 1/4% of styrene which accounts for the total mass of styrene, 1/4% of butyl acrylate which accounts for the total mass of butyl acrylate and 1/4% of acrylic acid which accounts for the total mass of acrylic acid under the stirring condition of keeping 300-350r/min, heating to 75-85 ℃, reacting for 20-30min, dropwise adding the rest of styrene, the rest of butyl acrylate, the rest of acrylic acid and the rest of initiator, continuing to perform heat preservation reaction for 2-3h after dropwise adding is finished, and then cooling to room temperature to obtain the first acrylic emulsion.
Wherein the specific operation of the (2) second acrylic emulsion synthesis comprises the following steps: weighing the following raw materials in percentage by mass: 25-35% of methyl methacrylate, 30-35% of butyl acrylate, 5-10% of acrylic acid, 2-4% of diacetone acrylamide, 0.5-1.5% of initiator, 1-2% of emulsifier and the balance of water, uniformly mixing the water, the emulsifier and 1/2 initiator accounting for the total mass of the initiator, adding 1/4% of methyl methacrylate, 1/4% of butyl acrylate, 1/4% of acrylic acid and 1/4% of diacetone acrylamide under the stirring condition of keeping 300-350r/min, heating to 75-85 ℃, reacting for 20-30min, and dropwise adding the rest of methyl methacrylate, the rest of butyl acrylate, the rest of diacetone acrylamide, And (3) continuously preserving the temperature and reacting for 2-3h after the residual acrylic acid, the residual diacetone acrylamide and the residual initiator are added dropwise, and then cooling to room temperature to obtain a second acrylic acid emulsion.
The polymerization reaction can be facilitated by controlling the stirring speed and controlling the amount of the monomer to be added in several portions.
Wherein, in the step (3), the adding molar quantity of the adipic dihydrazide is 0.8-1.2 times of the adding molar quantity of the diacetone acrylamide.
The invention has the beneficial effects that: the first acrylic emulsion adopted by the invention takes a large amount of styrene as a hard monomer, and the styrene has higher steric hindrance and lower Tg point relative to methyl methacrylate, so that a film layer formed by the part of emulsion particles has higher hardness, but has larger curing difficulty; the second acrylic emulsion adopted by the invention takes a small amount of methyl methacrylate as a hard monomer, so that the emulsion particles have a low Tg point, are easy to form a film and have good adhesiveness, and diacetone acrylamide is further added, and the film-forming property can be further improved by performing crosslinking reaction with adipic dihydrazide, and the crosslinking structure is also beneficial to improving the hardness of the film layer. According to the invention, the second acrylic emulsion with good film-forming property and the first acrylic emulsion with higher polarity are blended and modified in a specific ratio, and the colloidal particles of the second acrylic emulsion can be dispersed among the colloidal particles of the first acrylic emulsion, so that the first acrylic emulsion can be helpful for film formation, and the film layer has the performances of high hardness and high adhesive force. Based on cost control, the using amount of the diacetone acrylamide is less, the distribution of the diacetone acrylamide in a single emulsion prepared by directly adopting a moderate hard monomer, a soft monomer and the diacetone acrylamide is limited, the cross-linking property with the adipic dihydrazide is weaker, and the improvement degree of a film layer is not obvious.
Detailed Description
The present invention will be further described with reference to the following examples for facilitating understanding of those skilled in the art, and the description of the embodiments is not intended to limit the present invention.
Example 1
The preparation method of the water-based plastic substitute comprises the following steps:
(1) synthesis of the first acrylic emulsion: weighing the following raw materials in percentage by mass: 45% of styrene, 17.5% of butyl acrylate, 7.5% of acrylic acid, 1% of initiator, 1.5% of emulsifier and the balance of water, uniformly mixing the water, the emulsifier and 1/2 initiator accounting for the total mass of the initiator, adding 1/4% of styrene accounting for the total mass of styrene, 1/4% of butyl acrylate accounting for the total mass of butyl acrylate and 1/4% of acrylic acid accounting for the total mass of acrylic acid under the stirring condition of keeping 320r/min, heating to 80 ℃, reacting for 25min, dropwise adding the rest of styrene, the rest of butyl acrylate, the rest of acrylic acid and the rest of initiator, continuing to perform heat preservation reaction for 2.5h after dropwise adding is finished, and then cooling to room temperature to obtain a first acrylic emulsion;
(2) synthesis of second acrylic emulsion: weighing the following raw materials in percentage by mass: 30% of methyl methacrylate, 32.5% of butyl acrylate, 7.5% of acrylic acid, 3% of diacetone acrylamide, 1% of initiator, 1.5% of emulsifier and the balance of water, uniformly mixing the water, the emulsifier and the initiator 1/2 which accounts for the total mass of the initiator, adding 1/4% of methyl methacrylate which accounts for the total mass of methyl methacrylate, 1/4% of butyl acrylate which accounts for the total mass of butyl acrylate, 1/4% of acrylic acid which accounts for the total mass of acrylic acid and 1/4% of diacetone acrylamide which accounts for the total mass of diacetone acrylamide under the stirring condition of keeping 320r/min, heating to 80 ℃, dropwise adding the rest of methyl methacrylate, the rest of butyl acrylate, the rest of acrylic acid, the rest of diacetone acrylamide and the rest of initiator after reacting for 25min, continuing the heat preservation reaction for 2.5h after dropwise adding is completed, then cooling to room temperature to obtain a second acrylic acid emulsion;
(3) preparing the water-based plastic substitute: and mixing the first acrylic emulsion and the second acrylic emulsion according to the mass ratio of 2.5:7.5, uniformly stirring, adding a neutralizing agent to adjust the pH value to 7, adding adipic dihydrazide, uniformly stirring, and filtering to obtain the water-based plastic substitute.
Wherein the initiator is ammonium persulfate.
Wherein the emulsifier consists of SDS and OP-10 according to the weight ratio of 2.5: 2.
Wherein the neutralizer is diluted ammonia water.
Wherein, in the step (3), the adding molar quantity of the adipic dihydrazide is 1 time of that of the diacetone acrylamide.
Example 2
The preparation method of the water-based plastic substitute comprises the following steps:
(1) synthesis of the first acrylic emulsion: weighing the following raw materials in percentage by mass: 40% of styrene, 20% of butyl acrylate, 5% of acrylic acid, 0.5% of initiator, 1% of emulsifier and the balance of water, wherein the water, the emulsifier and the initiator 1/2 of the total mass of the initiator are uniformly mixed, 1/4% of styrene of the total mass of styrene, 1/4% of butyl acrylate of the total mass of butyl acrylate and 1/4% of acrylic acid of the total mass of acrylic acid are added under the condition of stirring at 300r/min, then the temperature is raised to 75 ℃, after the reaction is carried out for 20min, the residual styrene, the residual butyl acrylate, the residual acrylic acid and the residual initiator are dropwise added, the heat preservation reaction is continued for 2h after the dropwise addition is finished, and then the temperature is reduced to the room temperature to obtain a first acrylic emulsion;
(2) synthesis of second acrylic emulsion: weighing the following raw materials in percentage by mass: 25% of methyl methacrylate, 35% of butyl acrylate, 5% of acrylic acid, 2% of diacetone acrylamide, 0.5% of initiator, 1% of emulsifier and the balance of water, uniformly mixing the water, the emulsifier and 1/2% of initiator which accounts for the total mass of the initiator, adding 1/4% of methyl methacrylate which accounts for the total mass of methyl methacrylate, 1/4% of butyl acrylate which accounts for the total mass of butyl acrylate, 1/4% of acrylic acid which accounts for the total mass of acrylic acid and 1/4% of diacetone acrylamide which accounts for the total mass of diacetone acrylamide under the condition of stirring at 300r/min, heating to 75 ℃, reacting for 20min, dropwise adding the residual methyl methacrylate, the residual butyl acrylate, the residual acrylic acid, the residual diacetone acrylamide and the residual initiator, and continuing to perform heat preservation reaction for 2h after dropwise adding is completed, then cooling to room temperature to obtain a second acrylic acid emulsion;
(3) preparing the water-based plastic substitute: and mixing the first acrylic emulsion and the second acrylic emulsion according to the mass ratio of 2:8, uniformly stirring, adding a neutralizing agent to adjust the pH value to 8, adding adipic dihydrazide, uniformly stirring, and filtering to obtain the water-based plastic substitute.
Wherein the initiator is potassium persulfate.
Wherein the emulsifier consists of SDS and OP-10 according to the weight ratio of 2: 2.
Wherein the neutralizing agent is triethanolamine.
And (3) adding an auxiliary agent before adding the neutralizing agent, wherein the auxiliary agent is at least one of a flatting agent, a brightening agent, an abrasion-resistant auxiliary agent and a rheological agent.
Wherein, in the step (3), the adding molar quantity of the adipic dihydrazide is 0.8 times of the adding molar quantity of the diacetone acrylamide.
Example 3
The preparation method of the water-based plastic substitute comprises the following steps:
(1) synthesis of the first acrylic emulsion: weighing the following raw materials in percentage by mass: 50% of styrene, 15% of butyl acrylate, 10% of acrylic acid, 1.5% of initiator, 2% of emulsifier and the balance of water, uniformly mixing the water, the emulsifier and 1/2% of initiator which accounts for the total mass of the initiator, adding 1/4% of styrene which accounts for the total mass of styrene, 1/4% of butyl acrylate which accounts for the total mass of butyl acrylate and 1/4% of acrylic acid which accounts for the total mass of acrylic acid under the stirring condition of keeping 350r/min, heating to 85 ℃, reacting for 30min, dropwise adding the residual styrene, the residual butyl acrylate, the residual acrylic acid and the residual initiator, continuing to perform heat preservation reaction for 3h after dropwise adding is completed, and then cooling to room temperature to obtain a first acrylic emulsion;
(2) synthesis of second acrylic emulsion: weighing the following raw materials in percentage by mass: 35% of methyl methacrylate, 30% of butyl acrylate, 10% of acrylic acid, 4% of diacetone acrylamide, 1.5% of initiator, 2% of emulsifier and the balance of water, uniformly mixing the water, the emulsifier and 1/2% of initiator which accounts for the total mass of the initiator, adding 1/4% of methyl methacrylate which accounts for the total mass of methyl methacrylate, 1/4% of butyl acrylate which accounts for the total mass of butyl acrylate, 1/4% of acrylic acid which accounts for the total mass of acrylic acid and 1/4% of diacetone acrylamide which accounts for the total mass of diacetone acrylamide under the stirring condition of keeping 350r/min, heating to 85 ℃, reacting for 30min, dropwise adding the residual methyl methacrylate, the residual butyl acrylate, the residual acrylic acid, the residual diacetone acrylamide and the residual initiator, and continuing to perform heat preservation reaction for 3h after dropwise adding is completed, then cooling to room temperature to obtain a second acrylic acid emulsion;
(3) preparing the water-based plastic substitute: and mixing the first acrylic emulsion and the second acrylic emulsion according to the mass ratio of 3:7, uniformly stirring, adding a neutralizing agent to adjust the pH value to 7.5, adding adipic dihydrazide, uniformly stirring, and filtering to obtain the water-based plastic substitute.
Wherein the initiator is ammonium persulfate.
Wherein the emulsifier consists of SDS and OP-10 according to the weight ratio of 3: 2.
Wherein the neutralizer is diluted ammonia water.
And (3) adding an auxiliary agent before adding the neutralizing agent, wherein the auxiliary agent is at least one of a flatting agent, a brightening agent, an abrasion-resistant auxiliary agent and a rheological agent.
Wherein, in the step (3), the adding molar quantity of the adipic dihydrazide is 1.2 times of the adding molar quantity of the diacetone acrylamide.
Comparative example 1
The preparation method of the water-based plastic substitute comprises the following steps:
weighing the following raw materials in percentage by mass: uniformly mixing 35% of methyl methacrylate, 30% of butyl acrylate, 8% of acrylic acid, 1% of initiator, 1.5% of emulsifier and the balance of water, adding 1/4% of methyl methacrylate, 1/4% of butyl acrylate and 1/4% of acrylic acid in the total mass of methyl methacrylate, heating to 80 ℃, reacting for 25min, dropwise adding the rest of styrene, the rest of butyl acrylate, the rest of acrylic acid and the rest of initiator, continuing to perform heat preservation reaction for 2.5h after dropwise adding, and then cooling to room temperature to obtain the water-based plastic substitute plastic cement
Comparative example 2
The preparation method of the water-based plastic substitute comprises the following steps:
weighing the following raw materials in percentage by mass: 35% of methyl methacrylate, 30% of butyl acrylate, 5% of acrylic acid, 3% of diacetone acrylamide, 1% of initiator, 1.5% of emulsifier and the balance of water, uniformly mixing the water, the emulsifier and 1/2% of initiator which accounts for the total mass of the initiator, adding 1/4% of methyl methacrylate which accounts for the total mass of methyl methacrylate, 1/4% of butyl acrylate which accounts for the total mass of butyl acrylate, 1/4% of acrylic acid which accounts for the total mass of acrylic acid and 1/4% of diacetone acrylamide which accounts for the total mass of diacetone acrylamide under the stirring condition of keeping 320r/min, heating to 80 ℃, reacting for 25min, dropwise adding the residual methyl methacrylate, the residual butyl acrylate, the residual acrylic acid, the residual diacetone acrylamide and the residual initiator, and continuing to perform heat preservation reaction for 2.5h after dropwise adding is completed, and then cooling to room temperature, adding a neutralizing agent to adjust the pH value to 7, adding adipic dihydrazide, uniformly stirring, and filtering to obtain the water-based plastic substitute.
Comparative example 3
The preparation method of the water-based plastic substitute comprises the following steps:
(1) synthesis of the first acrylic emulsion: weighing the following raw materials in percentage by mass: 45% of styrene, 17.5% of butyl acrylate, 7.5% of acrylic acid, 1% of initiator, 1.5% of emulsifier and the balance of water, uniformly mixing the water, the emulsifier and 1/2 initiator accounting for the total mass of the initiator, adding 1/4% of styrene accounting for the total mass of styrene, 1/4% of butyl acrylate accounting for the total mass of butyl acrylate and 1/4% of acrylic acid accounting for the total mass of acrylic acid under the stirring condition of keeping 320r/min, heating to 80 ℃, reacting for 25min, dropwise adding the rest of styrene, the rest of butyl acrylate, the rest of acrylic acid and the rest of initiator, continuing to perform heat preservation reaction for 2.5h after dropwise adding is finished, and then cooling to room temperature to obtain a first acrylic emulsion;
(2) synthesis of second acrylic emulsion: weighing the following raw materials in percentage by mass: 30% of methyl methacrylate, 32.5% of butyl acrylate, 10.5% of acrylic acid, 1% of initiator, 1.5% of emulsifier and the balance of water, uniformly mixing the water, the emulsifier and 1/2 initiator accounting for the total mass of the initiator, adding 1/4% of methyl methacrylate accounting for the total mass of the methyl methacrylate, 1/4% of butyl acrylate accounting for the total mass of the butyl acrylate and 1/4% of acrylic acid accounting for the total mass of the acrylic acid under the stirring condition of keeping 320r/min, heating to 80 ℃, dropwise adding the residual styrene, the residual butyl acrylate, the residual acrylic acid and the residual initiator after reacting for 25min, continuing to perform heat preservation reaction for 2.5h after dropwise adding is finished, and then cooling to room temperature to obtain a second acrylic acid emulsion;
(3) preparing the water-based plastic substitute: and mixing the first acrylic emulsion and the second acrylic emulsion according to the mass ratio of 2.5:7.5, uniformly stirring, and filtering to obtain the water-based plastic substitute.
The water-based plastic substitutes of example 1 and comparative examples 1 to 3 were tested for film hardness, film adhesion, film water resistance and film blocking resistance as follows:
film hardness: GB/T6739-2006;
film layer adhesiveness: after curing the water-based plastic substitute on the gray cardboard, adhering the cured water-based plastic substitute on the gray cardboard by using a 3M600 adhesive tape, peeling the adhesive tape at an angle of 90 degrees, and judging that the adhesive test is passed if the film layer does not fall off, lose gloss, lose color and the like;
and (3) water resistance of the film layer: curing the water-based plastic substitute on the gray card paper, soaking the gray card paper in water for 36 hours, removing and airing, and judging that the water resistance test is passed if the film layer does not fall off, bubble and the like;
the test results were as follows:
| example 1 | Comparative example 1 | Comparative example 2 | Comparative example 3 | |
| Hardness of film layer | 4H | 2H | 3H | 2H |
| Film adhesion | By passing | By passing | By passing | Do not pass through |
| Water resistance of film layer | By passing | Do not pass through | Do not pass through | Do not pass through |
The above-described embodiments are preferred implementations of the present invention, and the present invention may be implemented in other ways without departing from the spirit of the present invention.
Claims (9)
1. A preparation method of water-based plastic substitute is characterized by comprising the following steps: the method comprises the following steps:
(1) synthesis of the first acrylic emulsion: weighing the following raw materials in percentage by mass: 40-50% of styrene, 15-20% of butyl acrylate, 5-10% of acrylic acid, 0.5-1.5% of initiator, 1-2% of emulsifier and the balance of water, uniformly mixing the water, the emulsifier and part of the initiator, adding part of the styrene, part of the butyl acrylate and part of the acrylic acid, heating to 75-85 ℃, reacting for 20-30min, dropwise adding the rest of the styrene, the rest of the butyl acrylate, the rest of the acrylic acid and the rest of the initiator, continuing to perform heat preservation reaction for 2-3h after dropwise adding is completed, and then cooling to room temperature to obtain a first acrylic emulsion;
(2) synthesis of second acrylic emulsion: weighing the following raw materials in percentage by mass: 25-35% of methyl methacrylate, 30-35% of butyl acrylate, 5-10% of acrylic acid, 2-4% of diacetone acrylamide, 0.5-1.5% of initiator, 1-2% of emulsifier and the balance of water, uniformly mixing the water, the emulsifier and part of the initiator, adding part of the methyl methacrylate, part of the butyl acrylate, part of the acrylic acid and part of the diacetone acrylamide, heating to 75-85 ℃, reacting for 20-30min, dropwise adding the rest of the methyl methacrylate, the rest of the butyl acrylate, the rest of the acrylic acid, the rest of the diacetone acrylamide and the rest of the initiator, continuing the heat preservation reaction for 2-3h after the dropwise addition is finished, and then cooling to room temperature to obtain a second acrylic acid emulsion;
(3) preparing the water-based plastic substitute: and mixing the first acrylic emulsion and the second acrylic emulsion according to the mass ratio of 2-3:7-8, uniformly stirring, adding a neutralizing agent to adjust the pH value to 7-8, adding adipic dihydrazide, uniformly stirring, and filtering to obtain the water-based plastic substitute.
2. The preparation method of the water-based plastic substitute as claimed in claim 1, wherein the preparation method comprises the following steps: the initiator is at least one of ammonium persulfate, potassium persulfate and dibenzoyl peroxide.
3. The preparation method of the water-based plastic substitute as claimed in claim 1, wherein the preparation method comprises the following steps: the emulsifier is composed of SDS and OP-10 according to the weight ratio of 2-3: 2.
4. The preparation method of the water-based plastic substitute as claimed in claim 1, wherein the preparation method comprises the following steps: the neutralizing agent is diluted ammonia water and/or triethanolamine.
5. The preparation method of the water-based plastic substitute as claimed in claim 1, wherein the preparation method comprises the following steps: in the step (3), an auxiliary agent is added before the neutralizing agent is added, wherein the auxiliary agent is at least one of a leveling agent, a brightening agent, a wear-resistant auxiliary agent and a rheological agent.
6. The preparation method of the water-based plastic substitute as claimed in claim 1, wherein the preparation method comprises the following steps: the specific operation of synthesizing the first acrylic emulsion in the step (1) is as follows: weighing the following raw materials in percentage by mass: 40-50% of styrene, 15-20% of butyl acrylate, 5-10% of acrylic acid, 0.5-1.5% of initiator, 1-2% of emulsifier and the balance of water, uniformly mixing the water, the emulsifier and the initiator 1/2 which accounts for the total mass of the initiator, adding 1/4% of styrene which accounts for the total mass of styrene, 1/4% of butyl acrylate which accounts for the total mass of butyl acrylate and 1/4% of acrylic acid which accounts for the total mass of acrylic acid under the stirring condition of keeping 300-350r/min, heating to 75-85 ℃, reacting for 20-30min, dropwise adding the rest of styrene, the rest of butyl acrylate, the rest of acrylic acid and the rest of initiator, continuing to perform heat preservation reaction for 2-3h after dropwise adding is finished, and then cooling to room temperature to obtain the first acrylic emulsion.
7. The preparation method of the water-based plastic substitute as claimed in claim 1, wherein the preparation method comprises the following steps: the specific operation of (2) synthesizing the second acrylic emulsion is as follows: weighing the following raw materials in percentage by mass: 25-35% of methyl methacrylate, 30-35% of butyl acrylate, 5-10% of acrylic acid, 2-4% of diacetone acrylamide, 0.5-1.5% of initiator, 1-2% of emulsifier and the balance of water, uniformly mixing the water, the emulsifier and 1/2 initiator accounting for the total mass of the initiator, adding 1/4% of methyl methacrylate, 1/4% of butyl acrylate, 1/4% of acrylic acid and 1/4% of diacetone acrylamide under the stirring condition of keeping 300-350r/min, heating to 75-85 ℃, reacting for 20-30min, and dropwise adding the rest of methyl methacrylate, the rest of butyl acrylate, the rest of diacetone acrylamide, And (3) continuously preserving the temperature and reacting for 2-3h after the residual acrylic acid, the residual diacetone acrylamide and the residual initiator are added dropwise, and then cooling to room temperature to obtain a second acrylic acid emulsion.
8. The preparation method of the water-based plastic substitute as claimed in claim 1, wherein the preparation method comprises the following steps: in the step (3), the adding molar weight of the adipic dihydrazide is 0.8-1.2 times of that of the diacetone acrylamide.
9. The water-based plastic substitute is characterized in that: the water-based plastic substitute prepared by the preparation method of any one of claims 1 to 8.
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