CN112694561B - Preparation method and application of water-based acrylate adhesive cement - Google Patents
Preparation method and application of water-based acrylate adhesive cement Download PDFInfo
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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
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- 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
- C08F220/1802—C2-(meth)acrylate, e.g. ethyl (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
- C08F2/00—Processes of polymerisation
- C08F2/12—Polymerisation in non-solvents
- C08F2/16—Aqueous medium
- C08F2/22—Emulsion polymerisation
- C08F2/24—Emulsion polymerisation with the aid of emulsifying agents
- C08F2/26—Emulsion polymerisation with the aid of emulsifying agents anionic
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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
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- C08F2/12—Polymerisation in non-solvents
- C08F2/16—Aqueous medium
- C08F2/22—Emulsion polymerisation
- C08F2/24—Emulsion polymerisation with the aid of emulsifying agents
- C08F2/30—Emulsion polymerisation with the aid of emulsifying agents non-ionic
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
- D06P1/00—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed
- D06P1/44—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using insoluble pigments or auxiliary substances, e.g. binders
- D06P1/52—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using insoluble pigments or auxiliary substances, e.g. binders using compositions containing synthetic macromolecular substances
- D06P1/5207—Macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
- D06P1/525—Polymers of unsaturated carboxylic acids or functional derivatives thereof
- D06P1/5257—(Meth)acrylic acid
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Abstract
The invention discloses a preparation method and application of water-based acrylate adhesive cement. The water-based acrylate adhesive cement is prepared by polymerizing isomeric tridecyl fatty alcohol polyoxyethylene (40) ether, dioctyl sodium sulfosuccinate, itaconic acid, acetoacetoxyethyl methacrylate, hydroxyethyl methacrylate, ethyl acrylate, methyl methacrylate, styrene, ethyl isocyanate acrylate, an acrylic acid modified reactive slip agent, ammonium persulfate, a reducing agent FF6M, tert-butyl hydroperoxide and deionized water through a seed emulsion to form a polymerization emulsion; adding a proper amount of deionized water into the post-polymerization emulsion to adjust the solid content to 45 +/-1%; finally, the emulsion is prepared from a thickening agent FS-200E, glycerol, a defoaming agent and a polymerization emulsion with the solid content adjusted. The aqueous acrylate adhesive cement has soft and active hand feeling, good dryness, good elasticity and resilience, good weather resistance, no yellowing, no cracking and good fastness, and can be applied to the preparation of manual table printing, rotary screen printing and screen printing adhesive cement.
Description
Technical Field
The invention relates to the technical field of printing and dyeing, in particular to a preparation method of water-based acrylate adhesive cement and application of the water-based acrylate adhesive cement in preparation of adhesive cement for manual platen printing, rotary screen printing and screen printing by a flat screen machine.
Background
With the development of society, environmental protection is more and more emphasized by people, and in the textile pigment printing process, the mucilage is printed on the textile fabric through a silk screen to form character patterns with various colors. The silk-screen printing is a production process for printing on fabrics instead of dyes, and is a clean production process encouraged by the nation because wastewater generated by rinsing during dye printing is not generated. The mucilage printing is a form of screen printing, and because of its very good pattern coverage, the dark color clothes can be printed with any light color, and also has a certain glossiness and stereoscopic impression, so that the ready-made clothes look more high-grade, so that it can be quickly popularized.
The cements are generally classified into two categories, one being acrylates and the other being polyurethanes. The acrylic adhesive has strong bonding force, good fastness and wide application, but has the phenomena of easy embrittlement at low temperature and easy stickiness at high temperature, and has less lively hand feeling, and the using effect of the adhesive film is influenced by poor rebound resilience of the adhesive film. The polyurethane adhesive has good elasticity and excellent hand feeling, but has higher price, so that the wide use of the polyurethane adhesive is limited.
At present, for a physical blending system obtained by directly mixing polyurethane and acrylate, the problems of poor compatibility of two components, poor transparency after emulsion film forming and the like exist, so that the requirement of people on high quality of rubber cement printing is difficult to achieve.
Disclosure of Invention
Therefore, the invention aims to provide a preparation method of the water-based acrylate adhesive cement with soft and active hand feeling, dryness, good elasticity and rebound resilience, good weather resistance, no yellowing, no cracking and excellent fastness, and application of the water-based acrylate adhesive cement in preparation of manual table printing, rotary screen printing and flat screen machine printing adhesive cement.
In order to achieve the above purpose, the invention provides the following technical scheme:
the invention provides a preparation method of water-based acrylate adhesive cement, which comprises the following steps of:
firstly, 5-6 parts of isomeric tridecane fatty alcohol polyoxyethylene (40) ether, 8-9.5 parts of dioctyl sodium sulfosuccinate, 2-3 parts of itaconic acid, 3.5-4.5 parts of acetoacetoxyethyl methacrylate, 0.5-1 part of hydroxyethyl methacrylate, 185 parts of ethyl acrylate 180-;
step two, 1-2 parts of isomeric tridecane fatty alcohol polyoxyethylene (40) ether, 1-1.5 parts of dioctyl sodium sulfosuccinate, 24-26 parts of methyl methacrylate, 23-25 parts of styrene, 0.5-0.8 part of isocyanate ethyl acrylate, 0.5-1 part of acrylic acid modified reactive slip agent and 29-38 parts of deionized water are fully stirred and emulsified to obtain pre-emulsion B;
step three, adding 110 parts of deionized water and 12-13.5 parts of pre-emulsion A into a reaction kettle, heating to 35-40 ℃, adding 4-6 parts of ammonium persulfate aqueous solution and 4-6 parts of reducing agent FF6M aqueous solution, and stirring to initiate reaction; when the emulsion has blue light and the temperature of the emulsion is 55-60 ℃, dropwise adding 16-19 parts of ammonium persulfate aqueous solution, 16-19 parts of reducing agent FF6M aqueous solution and the rest of pre-emulsion A while stirring, finishing dropwise adding for 2.5-3 hours, controlling the temperature to be 55-60 ℃ in the reaction process, continuously stirring after dropwise adding, and keeping the temperature for 1 hour;
step four, heating the reaction kettle to 70-75 ℃, keeping the temperature, dropwise adding the pre-emulsion B, 4-6 parts of ammonium persulfate aqueous solution and 4-6 parts of reducing agent FF6M aqueous solution while stirring, after dropwise adding is finished for 0.5-1 hour, continuously stirring after dropwise adding, and keeping the temperature for 1 hour;
step five, adding 0.1-0.15 part of tert-butyl hydroperoxide and 1.5-2.5 parts of FF6M aqueous solution into the reaction kettle, stirring for 10 minutes, adding 0.1-0.15 part of tert-butyl hydroperoxide and 1.5-2.5 parts of FF6M aqueous solution again, continuing stirring and keeping the temperature at 70-75 ℃ for 0.5 hour;
sixthly, cooling the reaction kettle to 30-40 ℃, adding triethylamine for neutralization, adjusting the pH value to 7-8, and adding deionized water for adjusting the solid content to obtain a polymerization emulsion;
and seventhly, taking 220 parts of the polymerization emulsion, adding a thickening agent, glycerol and a defoaming agent, and compounding to obtain the water-based environment-friendly modified acrylate adhesive cement.
And further, deionized water is added in the sixth step to adjust the solid content of the emulsion to be 45 +/-1%.
And further, in the seventh step, 5-7 parts of a thickener FS-200E, 6-10 parts of glycerol and 0.2-0.3 part of a defoaming agent.
And furthermore, in the third step, the ammonium persulfate aqueous solution is prepared by mixing 1.2-1.7 parts of ammonium persulfate and 24-31 parts of deionized water.
Furthermore, the reducing agent FF6M aqueous solution in the third step is prepared by mixing 1.4-2 parts of reducing agent FF6M 1.4 and 27-36 parts of deionized water.
Further, the compounding method of the seventh step is that the stirring is carried out for 15-30min at the rotating speed of 80-120 r/min.
Furthermore, the ionic property of the aqueous acrylate mucilage is negative.
On the other hand, the invention also discloses the application of the water-based acrylate adhesive cement prepared by the method in preparing the adhesive cement for manual platen printing, rotary screen printing and flat screen machine printing.
The invention has the following advantages:
the emulsifier applied in the invention has excellent wettability, carboxyl, hydroxyl and isocyanic acid radical in the formula are hydrophilic groups with strong hydrophilicity, and humectant glycerin is added during the glue paste compounding, and the conditions can not block the screen in the printing process, thus meeting the requirements of manual platen printing and rotary screen and flat screen machine printing.
The invention has soft and active hand feeling, dryness, good elasticity and rebound resilience, because the invention optimizes the proportion of soft and hard monomers, and makes the soft monomers in the core layer and most of the hard monomers distributed in the shell layer through process adjustment, and the polymerization temperature is controlled at 55-60 ℃, thus the polymer has larger grain diameter, and the compounded mucilage can form dry and comfortable film and has good elasticity.
Because the monomer acetoacetoxyethyl methacrylate applied in the polymerization reaction process has excellent elasticity and toughness, the elasticity of the polymer can be further improved by the reaction of carboxyl and hydroxyl in the formula. The polyurethane monomer ethyl acrylate and the organosilicon monomer acrylic acid modified reactive type slip agent are also introduced into the formula, the two monomers contain C ═ C which can be connected to a main chain, the reactive hand feeling, elasticity and rebound resilience of polymer film forming are obviously improved, and the isocyanic acid radical and the acetoacetoxy ethyl methacrylate can generate a crosslinking reaction, thereby playing a decisive role in the thick and reactive hand feeling of the polymer. Therefore, the compounded mucilage has active hand feeling, dryness, good elasticity and rebound resilience.
The invention has good weatherability and no yellowing, because the acrylate polymer has good weatherability, and the introduced siloxane has good stability to heat and chemicals and has outstanding aging resistance; the two selected emulsifiers have yellowing resistance, and hard monomers are distributed on a shell layer through process adjustment, so that the heat resistance and the weather resistance of the obtained polymer are effectively improved, and the polymer has good weather resistance and is not yellowed.
The adhesive cement disclosed by the invention is not cracked and has excellent fastness, and firstly, the weather resistance is good; secondly, the crosslinking monomers interact with each other to enhance the crosslinking density, thereby improving the tensile strength, the bonding force and the wear resistance; thirdly, the optimized proportion of the soft and hard monomers and the setting of the process improve the elasticity, the tensile strength and the bonding force of the polymer. Fourthly, the isocyanate ethyl acrylate and the acrylic acid modified reactive type slip agent modify the acrylate polymer, so that the elasticity, resilience, elongation, tensile strength and wear resistance of the polymer are obviously improved.
Therefore, the rubber cement has soft and active hand feeling, good dryness, good elasticity and rebound resilience, good weather resistance, no yellowing, no cracking and good fastness, and is suitable for various manual platen printing, rotary screen printing and flat screen machine printing.
Detailed Description
The present invention is described in terms of specific embodiments, and other advantages and benefits of the present invention will become apparent to those skilled in the art from the following disclosure. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
SPS produced by Beijing Baiyuan chemical company Limited of acrylic acid modified reaction type slip agent;
reductant FF6M CAS No. 283110;
the number in parentheses of isomeric tridecane alcohol polyoxyethylene (40) ether represents the number of addition of ethylene oxide in the molecule, and 40 represents that the isomeric tridecane alcohol polyoxyethylene ether is an isomeric tridecane alcohol polyoxyethylene ether added with 40 ethylene oxides.
Example 1
The invention provides a preparation method of water-based acrylate adhesive cement, which comprises the following specific operations:
step one, 5kg of isomeric tridecane fatty alcohol polyoxyethylene (40) ether, 8kg of dioctyl sodium sulfosuccinate, 2kg of itaconic acid, 3.5kg of acetoacetoxy ethyl methacrylate, 0.5kg of hydroxyethyl methacrylate, 180kg of ethyl acrylate, 4kg of methyl methacrylate, 5kg of styrene, 1kg of isocyanate ethyl acrylate, 1kg of acrylic acid modified reaction type slip agent, 100kg of deionized water, fully stirring for 40min at the speed of 100r/min, and emulsifying to obtain a pre-emulsion A;
step two, 1kg of isomeric tridecane fatty alcohol polyoxyethylene (40) ether, 1kg of dioctyl sodium sulfosuccinate, 24kg of methyl methacrylate, 23kg of styrene, 0.5kg of isocyanate ethyl acrylate, 0.5kg of acrylic acid modified reaction type slip agent, 29kg of deionized water, fully stirring for 40min at the speed of 100r/min, and emulsifying to obtain pre-emulsion B;
step three, mixing 1.2kg of ammonium persulfate and 24kg of deionized water to obtain an ammonium persulfate aqueous solution; 1.4kg of reducing agent FF6M 1.4 and 27kg of deionized water are mixed to obtain an aqueous solution of reducing agent FF 6M;
step four, adding 100kg of deionized water and 12kg of pre-emulsion A into a reaction kettle, heating to 35-40 ℃, adding 4kg of ammonium persulfate aqueous solution and 4kg of reducing agent FF6M aqueous solution, and stirring at 100r/min to initiate reaction; when the emulsion generates blue light and the temperature is 55-60 ℃, dropwise adding 16kg of ammonium persulfate aqueous solution, 16kg of reducing agent FF6M aqueous solution and the rest of pre-emulsion A, stirring while dropwise adding, controlling the temperature to be 55-60 ℃ in the reaction process, continuously stirring after dropwise adding and keeping the temperature for 1 hour, wherein the rotating speed is 120r/min, and the dropwise adding is finished within 2.5-3 hours;
step five, heating the reaction kettle to 70-75 ℃ and keeping the temperature, dropwise adding 4kg of pre-emulsion B, 4kg of ammonium persulfate aqueous solution and 4kg of reducing agent FF6M aqueous solution, stirring while dropwise adding, rotating speed of 120r/min, finishing dropwise adding within 0.5-1 hour, controlling the temperature to 70-75 ℃ in the reaction process, continuously stirring after dropwise adding, and keeping the temperature for 1 hour;
sixthly, adding 0.1kg of tert-butyl hydroperoxide and 1.5kg of FF6M aqueous solution into the reaction kettle, stirring for 10 minutes at 100r/min, adding 0.1kg of tert-butyl hydroperoxide and 1.5kg of FF6M aqueous solution again, stirring, and keeping the temperature at 70-75 ℃ for 0.5 hour;
seventhly, cooling the reaction kettle to 30-40 ℃, adding triethylamine for neutralization, adjusting the pH value to 7-8, and adding deionized water to adjust the solid content to 45 +/-1% to obtain a polymerization emulsion;
step eight, taking 200kg of the polymerized emulsion, 5kg of a thickening agent FS-200E, 6kg of glycerol and 0.2kg of a defoaming agent, and stirring at 100r/min for 30min to obtain the aqueous environment-friendly modified acrylate adhesive cement A.
Example 2
The invention provides a preparation method of water-based acrylate adhesive cement, which comprises the following specific operations:
firstly, 5.2kg of isomeric tridecane fatty alcohol polyoxyethylene (40) ether, 8.4kg of dioctyl sodium sulfosuccinate, 2.2kg of itaconic acid, 3.7kg of acetoacetoxyethyl methacrylate, 0.6kg of hydroxyethyl methacrylate, 181kg of ethyl acrylate, 4.4kg of methyl methacrylate, 5.4kg of styrene, 1.05kg of isocyanate ethyl acrylate, 1.1kg of acrylic acid modified reaction type slip agent, 102kg of deionized water and 100r/min are fully stirred for 40min, and a pre-emulsion A is obtained after emulsification;
step two, 1.2kg of isomeric tridecane fatty alcohol polyoxyethylene (40) ether, 1.1kg of dioctyl sodium sulfosuccinate, 24.4kg of methyl methacrylate, 23.4kg of styrene, 0.55kg of isocyanate ethyl acrylate, 0.6kg of acrylic acid modified reaction type slip agent, 31kg of deionized water, fully stirring for 40min at 100r/min, and emulsifying to obtain pre-emulsion B;
step three, mixing 1.3kg of ammonium persulfate and 26kg of deionized water to obtain an ammonium persulfate aqueous solution, and mixing 1.5kg of reducing agent FF6M 1.5 and 29kg of deionized water to obtain a reducing agent FF6M aqueous solution;
step four, adding 101kg of deionized water and 12.4kg of pre-emulsion A into a reaction kettle, heating to 35-40 ℃, adding 4.4kg of ammonium persulfate aqueous solution and 4.4kg of reducing agent FF6M aqueous solution, and stirring at 200r/min to initiate reaction; when the emulsion generates blue light and the temperature is 55-60 ℃, dropwise adding 16.8kg of ammonium persulfate aqueous solution, 16.8kg of reducing agent FF6M aqueous solution and the rest of pre-emulsion A, stirring while dropwise adding, controlling the temperature to be 55-60 ℃ in the reaction process, continuously stirring after dropwise adding, and keeping the temperature for 1 hour after dropwise adding is finished and the rotating speed is 120r/min, wherein dropwise adding is finished for 2.5-3 hours;
step five, heating the reaction kettle to 70-75 ℃ and keeping the temperature, dropwise adding the pre-emulsion B, 4.4kg of ammonium persulfate aqueous solution and 4.4kg of reducing agent FF6M aqueous solution while stirring at a rotating speed of 120r/min, completing the dropwise adding within 0.5-1 hour, controlling the temperature within 70-75 ℃ in the reaction process, continuing to stir after the dropwise adding is completed, and keeping the temperature for 1 hour;
sixthly, adding 0.11kg of tert-butyl hydroperoxide and 1.7kg of FF6M aqueous solution into the reaction kettle, stirring at 200r/min for 10 minutes, adding 0.11kg of tert-butyl hydroperoxide and 1.7kg of FF6M aqueous solution again, stirring, and keeping the temperature at 70-75 ℃ for 0.5 hour;
seventhly, cooling the reaction kettle to 30-40 ℃, adding triethylamine for neutralization, adjusting the pH value to 7-8, and adding deionized water to adjust the solid content to 45 +/-1% to obtain a polymerization emulsion;
step eight, taking 204kg of the polymerized emulsion, 5.4kg of a thickener FS-200E, 6.8kg of glycerol and 0.22kg of a defoaming agent, and stirring at 100r/min for 15min to obtain the water-based environment-friendly modified acrylate adhesive cement B.
Example 3
The invention provides a preparation method of water-based acrylate adhesive cement, which comprises the following specific operations:
step one, 5.4kg of isomeric tridecane fatty alcohol polyoxyethylene (40) ether, 8.8kg of dioctyl sodium sulfosuccinate, 2.4kg of itaconic acid, 3.9kg of acetoacetoxyethyl methacrylate, 0.7kg of hydroxyethyl methacrylate, 182kg of ethyl acrylate, 4.8kg of methyl methacrylate, 5.8kg of styrene, 1.1kg of isocyanate ethyl acrylate, 1.2kg of acrylic acid modified reaction type slip agent, 104kg of deionized water, fully stirring for 30min at a speed of 100r/min, and emulsifying to obtain a pre-emulsion A;
step two, 1.4kg of isomeric tridecane fatty alcohol polyoxyethylene (40) ether, 1.2kg of dioctyl sodium sulfosuccinate, 24.8kg of methyl methacrylate, 23.8kg of styrene, 0.6kg of isocyanate ethyl acrylate, 0.7kg of acrylic acid modified reaction type slip agent, 33kg of deionized water, fully stirring for 30min at 100r/min, and emulsifying to obtain pre-emulsion B;
step three, mixing 1.4kg of ammonium persulfate and 28kg of deionized water to obtain an ammonium persulfate aqueous solution, mixing 1.6kg of reducing agent FF6M 1.6 and 31kg of deionized water, and mixing a reducing agent FF6M aqueous solution;
step four, adding 102kg of deionized water and 12.8kg of pre-emulsion into a reaction kettle, heating to 35-40 ℃, adding 4.8kg of ammonium persulfate aqueous solution and 4.8kg of reducing agent FF6M aqueous solution, and stirring at 100r/min to initiate reaction; when the emulsion generates blue light and the temperature is 55-60 ℃, dropwise adding 17.6kg of ammonium persulfate aqueous solution, 17.6kg of reducing agent FF6M aqueous solution and the rest of pre-emulsion A, stirring while dropwise adding, controlling the temperature to be 55-60 ℃ in the reaction process, continuously stirring after dropwise adding, and keeping the temperature for 1 hour after dropwise adding is finished and finishing dropwise adding for 2.5-3 hours;
step five, heating the reaction kettle to 70-75 ℃ and keeping the temperature, dropwise adding the pre-emulsion B, 4.8kg of ammonium persulfate aqueous solution and 4.8kg of reducing agent FF6M aqueous solution while stirring at a rotating speed of 120r/min, finishing dropwise adding within 0.5-1 hour, controlling the temperature to be 70-75 ℃ in the reaction process, continuing stirring after dropwise adding, and keeping the temperature for 1 hour;
sixthly, adding 0.12kg of tert-butyl hydroperoxide and 1.9kg of FF6M aqueous solution into the reaction kettle, stirring for 10 minutes at 100r/min, adding 0.12kg of tert-butyl hydroperoxide and 1.9kg of FF6M aqueous solution again, stirring and keeping the temperature at 70-75 ℃ for 0.5 hour;
seventhly, cooling the reaction kettle to 30-40 ℃, adding triethylamine for neutralization, adjusting the pH value to 7-8, and adding deionized water to adjust the solid content to 45 +/-1% to obtain a polymerization emulsion;
step eight, mixing 208kg of the polymerized emulsion, 5.8kg of a thickener FS-200E, 7.6kg of glycerol and 0.24kg of a defoaming agent, and stirring at 100r/min for 30min to obtain the water-based environment-friendly modified acrylate adhesive cement C.
Example 4
The invention provides a preparation method of water-based acrylate adhesive cement, which comprises the following specific operations:
firstly, 5.6kg of isomeric tridecane fatty alcohol polyoxyethylene (40) ether, 9.2kg of dioctyl sodium sulfosuccinate, 2.6kg of itaconic acid, 4.1kg of acetoacetoxy ethyl methacrylate, 0.8kg of hydroxyethyl methacrylate, 183kg of ethyl acrylate, 5.2kg of methyl methacrylate, 6.2kg of styrene, 1.13kg of isocyanate ethyl acrylate, 1.3kg of acrylic acid modified reaction type slip agent, 106kg of deionized water and 100r/min are fully stirred for 30min, and a pre-emulsion A is obtained after emulsification;
step two, 1.6kg of isomeric tridecane fatty alcohol polyoxyethylene (40) ether, 1.3kg of dioctyl sodium sulfosuccinate, 25.2kg of methyl methacrylate, 24.2kg of styrene, 0.68kg of isocyanate ethyl acrylate, 0.8kg of acrylic acid modified reaction type slip agent, 35kg of deionized water, fully stirring for 30min at 100r/min, and emulsifying to obtain pre-emulsion B;
step three, mixing 1.5kg of ammonium persulfate and 29kg of deionized water to obtain an ammonium persulfate aqueous solution; mixing reducing agent FF6M 1.7.7 kg and deionized water 33kg to obtain reducing agent FF6M water solution;
step four, adding 103kg of deionized water and 13.1kg of pre-emulsion into a reaction kettle, heating to 35-40 ℃, adding 5.2kg of ammonium persulfate aqueous solution and 5.2kg of reducing agent FF6M aqueous solution, and stirring at 200r/min to initiate reaction; when the emulsion has blue light and the temperature is 55-60 ℃, dropwise adding 18.4kg of ammonium persulfate aqueous solution, 18.4kg of reducing agent FF6M aqueous solution and the rest of pre-emulsion A, stirring while dropwise adding, rotating speed of 120r/min, finishing dropwise adding within 2.5-3 hours, controlling the temperature to be 55-60 ℃ in the reaction process, continuously stirring after dropwise adding, and keeping the temperature for 1 hour;
step five, heating the reaction kettle to 70-75 ℃ and keeping the temperature, dropwise adding the pre-emulsion B, 5.2kg of ammonium persulfate aqueous solution and 5.2kg of reducing agent FF6M aqueous solution, stirring while dropwise adding, rotating speed of 120r/min, completing dropwise adding within 0.5-1 hour, controlling the temperature within 70-75 ℃ in the reaction process, completing dropwise adding within 0.5-1 hour, continuing stirring after dropwise adding, and keeping the temperature for 1 hour;
sixthly, adding 0.13kg of tert-butyl hydroperoxide and 2.1kg of FF6M aqueous solution into the reaction kettle, stirring for 10 minutes at 200r/min, adding 0.13kg of tert-butyl hydroperoxide and 2.1kg of FF6M aqueous solution again, stirring and preserving heat for 0.5 hour at 70-75 ℃;
seventhly, cooling the reaction kettle to 30-40 ℃, adding triethylamine for neutralization, adjusting the pH value to 7-8, and adding deionized water to adjust the solid content to 45 +/-1% to obtain a polymerization emulsion;
step eight, taking 212kg of the polymerized emulsion, 6.2kg of a thickening agent FS-200E, 8.4kg of glycerol and 0.26kg of a defoaming agent, and stirring at 900r/min for 20min to obtain the water-based environment-friendly modified acrylate adhesive cement D.
Example 5
The invention provides a preparation method of water-based acrylate adhesive cement, which comprises the following specific operations:
firstly, 5.8kg of isomeric tridecane fatty alcohol polyoxyethylene (40) ether, 9.4kg of dioctyl sodium sulfosuccinate, 2.8kg of itaconic acid, 4.3kg of acetoacetoxy ethyl methacrylate, 0.9kg of hydroxyethyl methacrylate, 184kg of ethyl acrylate, 5.6kg of methyl methacrylate, 6.6kg of styrene, 1.17kg of isocyanate ethyl acrylate, 1.4kg of acrylic acid modified reaction type slip agent, 108kg of deionized water and 100r/min are fully stirred for 30min, and a pre-emulsion A is obtained after emulsification;
step two, 1.8kg of isomeric tridecane fatty alcohol polyoxyethylene (40) ether, 1.4kg of dioctyl sodium sulfosuccinate, 25.6kg of methyl methacrylate, 24.6kg of styrene, 0.76kg of isocyanate ethyl acrylate, 0.9kg of acrylic acid modified reaction type slip agent, 37kg of deionized water, fully stirring for 30min at 100r/min, and emulsifying to obtain pre-emulsion B;
step three, mixing 1.6kg of ammonium persulfate and 30kg of deionized water to obtain an ammonium persulfate aqueous solution, and mixing 1.8kg of reducing agent FF6M 1.8 and 35kg of deionized water to obtain a reducing agent FF6M aqueous solution;
adding 104kg of deionized water and 13.3kg of pre-emulsion A into a reaction kettle, heating to 35-40 ℃, adding 5.6kg of ammonium persulfate aqueous solution and 5.6kg of reducing agent FF6M aqueous solution, and stirring at 100r/min to initiate reaction; when the emulsion has blue light and the temperature is 55-60 ℃, dropwise adding 18.7kg of ammonium persulfate aqueous solution, 18.7kg of reducing agent FF6M aqueous solution and the rest of pre-emulsion A, stirring while dropwise adding, rotating speed of 120r/min, completing dropwise adding within 2.5-3 hours, controlling the temperature to be 55-60 ℃ in the reaction process, continuously stirring after dropwise adding, and keeping the temperature for 1 hour;
step five, heating the reaction kettle to 70-75 ℃ and keeping the temperature, dropwise adding 5.6kg of pre-emulsion B, 5.6kg of ammonium persulfate aqueous solution and 5.6kg of reducing agent FF6M aqueous solution, stirring while dropwise adding, rotating speed of 120r/min, finishing dropwise adding within 0.5-1 hour, controlling the temperature to be 70-75 ℃ in the reaction process, continuously stirring after dropwise adding, and keeping the temperature for 1 hour;
sixthly, adding 0.14kg of tert-butyl hydroperoxide and 2.3kg of FF6M aqueous solution into the reaction kettle, stirring for 10 minutes at 200r/min, adding 0.14kg of tert-butyl hydroperoxide and 2.3kg of FF6M aqueous solution again, stirring and preserving heat for 0.5 hour at 70-75 ℃;
seventhly, cooling the reaction kettle to 30-40 ℃, adding triethylamine for neutralization, adjusting the pH value to 7-8, and adding deionized water to adjust the solid content to 45 +/-1% to obtain a polymerization emulsion;
step eight, taking 216kg of the polymerized emulsion, 6.6kg of a thickener FS-200E, 9.2kg of glycerol and 0.28kg of a defoaming agent, and stirring for 100 min to obtain the water-based environment-friendly modified acrylate adhesive cement E.
Example 6
The invention provides a preparation method of water-based acrylate adhesive cement, which comprises the following specific operations:
firstly, 6kg of isomeric tridecane fatty alcohol polyoxyethylene (40) ether, 9.5kg of dioctyl sodium sulfosuccinate, 3kg of itaconic acid, 4.5kg of acetoacetoxyethyl methacrylate, 1kg of hydroxyethyl methacrylate, 185kg of ethyl acrylate, 6kg of methyl methacrylate, 7kg of styrene, 1.2kg of isocyanate ethyl acrylate, 1.5kg of acrylic acid modified reaction type slip agent, 115kg of deionized water, fully stirring for 35min at the speed of 100r/min, and emulsifying to obtain a pre-emulsion A;
step two, 2kg of isomeric tridecane fatty alcohol polyoxyethylene (40) ether, 1.5kg of dioctyl sodium sulfosuccinate, 26kg of methyl methacrylate, 25kg of styrene, 0.8kg of isocyanate ethyl acrylate, 1kg of acrylic acid modified reactive slip agent, 38kg of deionized water, fully stirring at 100r/min for 35min, and emulsifying to obtain a pre-emulsion B;
step three, mixing 1.7kg of ammonium persulfate and 31kg of deionized water to obtain an ammonium persulfate aqueous solution, and mixing 6M 2kg of reducing agent FF and 36kg of deionized water to obtain a reducing agent FF6M aqueous solution;
step four, adding 110kg of deionized water and 13.5kg of pre-emulsion A into a reaction kettle, heating to 35-40 ℃, adding 6kg of ammonium persulfate aqueous solution and 6kg of reducing agent FF6M aqueous solution, and stirring at 100r/min to initiate reaction; when the emulsion has blue light and the temperature is 55-60 ℃, dropwise adding 19kg of ammonium persulfate water-soluble, 19kg of reducing agent FF6M water-soluble and the rest of pre-emulsion A, stirring while dropwise adding, wherein the rotating speed is 120r/min, the dropwise adding is finished within 2.5-3 hours, the temperature is controlled to be 55-60 ℃ in the reaction process, and continuously stirring and preserving heat for 1 hour after the dropwise adding is finished;
step five, heating the reaction kettle to 70-75 ℃ and keeping the temperature, dropwise adding the pre-emulsion B, 6kg of ammonium persulfate aqueous solution and 6kg of reducing agent FF6M aqueous solution, stirring while dropwise adding, controlling the temperature to 70-75 ℃ in the reaction process, continuously stirring after dropwise adding, and keeping the temperature for 1 hour, wherein the rotating speed is 120r/min, and the dropwise adding is finished within 0.5-1 hour;
sixthly, adding 0.15kg of tert-butyl hydroperoxide and 2.5kg of FF6M aqueous solution into the reaction kettle, stirring for 10 minutes at 200r/min, adding 0.15kg of tert-butyl hydroperoxide and 2.5kg of FF6M aqueous solution again, stirring and keeping the temperature at 70-75 ℃ for 0.5 hour;
seventhly, cooling the reaction kettle to 30-40 ℃, adding triethylamine for neutralization, adjusting the pH value to 7-8, and adding deionized water to adjust the solid content to 45 +/-1% to obtain a polymerization emulsion;
step eight, taking 220kg of the polymerized emulsion, 7kg of a thickening agent FS-200E, 10kg of glycerol and 0.3kg of a defoaming agent, and stirring at 100r/min for 20min to obtain the aqueous environment-friendly modified acrylate adhesive cement F.
Experimental comparative example
Elongation percentage: testing according to the national standard GB/T3923.1-2013 fabric tensile property
Rebound resilience: testing according to the trade standard FZT 70006-
Weather resistance: detection is carried out according to GB/T31899-2015 Standard for ultraviolet light exposure detection for textile weather resistance test
Washing fastness: measured according to the national standard GB/T8629-2001 household washing and drying program for textile testing.
Table 1 shows the comparison of the application of commercially available domestic adhesive cement T-90C and imported adhesive cement EL-555
The detection result shows that the indexes of softness, activity, dryness, elasticity, rebound resilience, weather resistance, yellowing and washing fastness of the product have obvious advantages compared with the commercially available product.
The emulsifiers used in the present invention have excellent wetting properties. Carboxyl, hydroxyl and isocyanic acid radicals in the formula are hydrophilic groups and have strong hydrophilicity, and humectant glycerol is added during the glue paste compounding, so that the product does not block a screen in the printing process, and the requirements of manual table printing and rotary screen and flat screen machine printing are met.
The invention has soft and active hand feeling, dryness, good elasticity and rebound resilience. The invention optimizes the proportion of the soft monomer and the hard monomer, leads the soft monomer to be in the nuclear layer and most of the hard monomer to be distributed in the shell layer through process adjustment, controls the polymerization reaction temperature to be between 55 and 60 ℃, and leads the particle size of the generated polymer to be larger, thus leading the compounded mucilage to form a dry film with good elasticity.
The invention has strong elasticity and toughness. The monomer acetoacetoxyethyl methacrylate applied in the polymerization reaction process has excellent elasticity and toughness, and can react with carboxyl and hydroxyl in the formula to further improve the elasticity of the polymer. The polyurethane monomer ethyl acrylate and the organosilicon monomer acrylic acid modified reactive type slip agent are also introduced into the formula, the two monomers contain C ═ C which can be connected to a main chain, the reactive hand feeling, elasticity and rebound resilience of polymer film forming are obviously improved, and the isocyanic acid radical and the acetoacetoxy ethyl methacrylate can generate a crosslinking reaction, thereby playing a decisive role in the thick and reactive hand feeling of the polymer. Therefore, the compounded mucilage has active hand feeling, dryness, good elasticity and rebound resilience.
The invention has good weather resistance and no yellowing. The acrylate polymer has good weather resistance, and simultaneously the introduced siloxane has good stability to heat and chemicals and has outstanding aging resistance; the two emulsifiers have yellowing resistance, and hard monomers of the emulsifiers are distributed in a shell layer through process adjustment, so that the heat resistance and the weather resistance of the obtained polymer are effectively improved. Therefore, the invention has good weather resistance and no yellowing.
The adhesive cement disclosed by the invention is free from cracking and excellent in fastness. Firstly, the invention has good weather resistance; secondly, the crosslinking monomers interact with each other to enhance the crosslinking density, thereby improving the tensile strength, the bonding force and the wear resistance; thirdly, the optimized proportion of the soft and hard monomers and the setting of the process improve the elasticity, the tensile strength and the bonding force of the polymer; and fourthly, modifying the acrylate polymer by isocyanate ethyl acrylate and acrylic acid modified reactive slip agent, so that the elasticity, resilience, elongation, tensile strength and wear resistance of the polymer are obviously improved.
Therefore, the adhesive cement has soft and active hand feeling, good dryness, good elasticity and resilience, good weather resistance, no yellowing, no cracking and good fastness, and can be used for preparing the adhesive cement for manual table printing, rotary screen printing and flat screen machine printing.
Although the invention has been described in detail above with reference to a general description and specific examples, it will be apparent to one skilled in the art that modifications or improvements may be made thereto based on the invention. Accordingly, such modifications and improvements are intended to be within the scope of the invention as claimed.
Claims (8)
1. A preparation method of water-based acrylate adhesive cement is characterized in that,
the method comprises the following steps of:
step one, fully stirring and emulsifying 5-6 parts of isomeric tridecane fatty alcohol polyoxyethylene (40) ether, 8-9.5 parts of dioctyl sodium sulfosuccinate, 2-3 parts of itaconic acid, 3.5-4.5 parts of acetoacetoxyethyl methacrylate, 0.5-1 part of hydroxyethyl methacrylate, 185 parts of ethyl acrylate 180-containing materials, 4-6 parts of methyl methacrylate, 5-7 parts of styrene, 1-1.2 parts of isocyanate ethyl acrylate, 1-1.5 parts of acrylic acid modified reaction type slip agent and 115 parts of deionized water 100-containing materials to obtain a pre-emulsion A;
step two, fully stirring and emulsifying 1-2 parts of isomeric tridecyl fatty alcohol polyoxyethylene (40) ether, 1-1.5 parts of dioctyl sodium sulfosuccinate, 24-26 parts of methyl methacrylate, 23-25 parts of styrene, 0.5-0.8 part of isocyanate ethyl acrylate, 0.5-1 part of acrylic acid modified reactive slip agent and 29-38 parts of deionized water to obtain a pre-emulsion B;
step three, adding 110 parts of deionized water and 110 parts of pre-emulsion A12-13.5 parts into a reaction kettle, heating to 35-40 ℃, adding 4-6 parts of ammonium persulfate aqueous solution and 4-6 parts of reducing agent FF6M aqueous solution, and stirring to initiate reaction; when the emulsion generates blue light and the temperature of the emulsion is 55-60 ℃, dropwise adding 16-19 parts of ammonium persulfate aqueous solution, 16-19 parts of reducing agent FF6M aqueous solution and the rest pre-emulsion A while stirring, finishing dropwise adding for 2.5-3 hours, controlling the temperature to be 55-60 ℃ in the reaction process, continuing stirring after dropwise adding, and keeping the temperature for 1 hour;
step four, heating the reaction kettle to 70-75 ℃, keeping the temperature, dropwise adding the pre-emulsion B, 4-6 parts of ammonium persulfate aqueous solution and 4-6 parts of reducing agent FF6M aqueous solution while stirring, after dropwise adding is finished for 0.5-1 hour, continuously stirring after dropwise adding, and keeping the temperature for 1 hour;
step five, adding 0.1-0.15 part of tert-butyl hydroperoxide and 1.5-2.5 parts of FF6M aqueous solution into the reaction kettle, stirring for 10 minutes, adding 0.1-0.15 part of tert-butyl hydroperoxide and 1.5-2.5 parts of FF6M aqueous solution again, continuing stirring and keeping the temperature at 70-75 ℃ for 0.5 hour;
sixthly, cooling the reaction kettle to 30-40 ℃, adding triethylamine for neutralization, adjusting the pH value to 7-8, and adding deionized water to adjust the solid content to obtain a polymerization emulsion;
and step seven, taking 200 portions of the polymerization emulsion and 220 portions of the polymerization emulsion, adding a thickening agent, glycerol and a defoaming agent, and compounding to obtain the water-based acrylate adhesive cement.
2. The method for preparing the water-based acrylate cement according to claim 1,
and step six, adding deionized water to adjust the solid content of the emulsion to be 45 +/-1%.
3. The method for preparing the water-based acrylate cement according to claim 1,
in the seventh step, the amount of each component is as follows: 200-220 parts of polymerized emulsion, 5-7 parts of thickener FS-200E, 6-10 parts of glycerol and 0.2-0.3 part of defoamer.
4. The method for preparing the water-based acrylate adhesive cement according to claim 1,
in the third step, the ammonium persulfate aqueous solution is prepared by mixing 1.2-1.7 parts of ammonium persulfate and 24-31 parts of deionized water.
5. The method for preparing the water-based acrylate cement according to claim 1,
in the third step, the reducing agent FF6M aqueous solution is prepared by mixing 1.4-2 parts of reducing agent FF6M 1.4 and 27-36 parts of deionized water.
6. The method for preparing the water-based acrylate cement according to claim 1,
in the seventh step, the compounding method is that the rotating speed is 80-150r/min, and the stirring time is 15-30 min.
7. The method for preparing the water-based acrylate cement according to claim 1,
the ionic property of the aqueous acrylate mucilage is negative.
8. Use of an aqueous acrylate size prepared by the process according to any one of claims 1 to 7 for the preparation of a size for manual platen printing, rotary screen printing and screen machine printing.
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| CN109232794A (en) * | 2018-09-05 | 2019-01-18 | 辽宁恒星精细化工有限公司 | A kind of anti-pitting bores suede acrylate coatings lotion, coating adhesive and preparation method thereof |
| WO2019090469A1 (en) * | 2017-11-07 | 2019-05-16 | 和友纺织股份有限公司 | Method for preparing super-soft aqueous shell/core copolymer of polyacrylate and polyurethane by means of solvent-free process |
| CN111363078A (en) * | 2020-04-20 | 2020-07-03 | 广东花果山环保科技有限公司 | Double-crosslinking high-hardness macromolecular emulsifier, high-hardness aqueous single-component acrylic resin and preparation method thereof |
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| CN103741517A (en) * | 2013-12-30 | 2014-04-23 | 辽宁恒星精细化工有限公司 | Printing paste used for gold powder printing of stone wall paper and preparation method |
| WO2019090469A1 (en) * | 2017-11-07 | 2019-05-16 | 和友纺织股份有限公司 | Method for preparing super-soft aqueous shell/core copolymer of polyacrylate and polyurethane by means of solvent-free process |
| CN109232794A (en) * | 2018-09-05 | 2019-01-18 | 辽宁恒星精细化工有限公司 | A kind of anti-pitting bores suede acrylate coatings lotion, coating adhesive and preparation method thereof |
| CN111363078A (en) * | 2020-04-20 | 2020-07-03 | 广东花果山环保科技有限公司 | Double-crosslinking high-hardness macromolecular emulsifier, high-hardness aqueous single-component acrylic resin and preparation method thereof |
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