CN110003813B - Biomass modified pressure-sensitive adhesive and preparation method thereof - Google Patents

Biomass modified pressure-sensitive adhesive and preparation method thereof Download PDF

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CN110003813B
CN110003813B CN201910265014.9A CN201910265014A CN110003813B CN 110003813 B CN110003813 B CN 110003813B CN 201910265014 A CN201910265014 A CN 201910265014A CN 110003813 B CN110003813 B CN 110003813B
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parts
sensitive adhesive
pressure
emulsion
biomass
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CN110003813A (en
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马丕明
于清清
钮德宇
余鳗漫
东为富
陈明清
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Jiangnan University
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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
    • C08F220/16—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
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    • 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
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    • 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
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    • 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
    • C09J133/068—Copolymers with monomers not covered by C09J133/06 containing glycidyl groups
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    • 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
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/20—Adhesives in the form of films or foils characterised by their carriers
    • C09J7/22—Plastics; Metallised plastics
    • C09J7/25—Plastics; Metallised plastics based on macromolecular compounds obtained otherwise than by reactions involving only carbon-to-carbon unsaturated bonds
    • C09J7/255—Polyesters
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    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
    • C09J7/38—Pressure-sensitive adhesives [PSA]
    • C09J7/381—Pressure-sensitive adhesives [PSA] based on macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
    • C09J7/385—Acrylic polymers
    • 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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    • C09J2301/00—Additional features of adhesives in the form of films or foils
    • C09J2301/30—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier
    • C09J2301/302—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier the adhesive being pressure-sensitive, i.e. tacky at temperatures inferior to 30°C
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    • C09J2301/00—Additional features of adhesives in the form of films or foils
    • C09J2301/30—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier
    • C09J2301/312—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier parameters being the characterizing feature
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    • C09J2301/00—Additional features of adhesives in the form of films or foils
    • C09J2301/40—Additional features of adhesives in the form of films or foils characterized by the presence of essential components
    • C09J2301/408—Additional features of adhesives in the form of films or foils characterized by the presence of essential components additives as essential feature of the adhesive layer
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    • C09J2301/00—Additional features of adhesives in the form of films or foils
    • C09J2301/40—Additional features of adhesives in the form of films or foils characterized by the presence of essential components
    • C09J2301/414—Additional features of adhesives in the form of films or foils characterized by the presence of essential components presence of a copolymer
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    • C09J2401/00—Presence of cellulose
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  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
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  • Polymers & Plastics (AREA)
  • Adhesives Or Adhesive Processes (AREA)

Abstract

The invention discloses a biomass modified pressure-sensitive adhesive and a preparation method thereof, belonging to the field of adhesives. The material comprises 40-98 parts of soft monomers, 2-15 parts of hard monomers, 0.1-5 parts of functional monomers, 0.5-5 parts of emulsifiers, 0.01-2 parts of initiators, 1-5 parts of biomass and 30-80 parts of deionized water. The water-based acrylate pressure-sensitive adhesive prepared by modifying the biomass material has excellent initial adhesion and peel strength, and can be widely applied to the fields of adhesive tapes, notepaper, electronic packaging and medical plasters.

Description

Biomass modified pressure-sensitive adhesive and preparation method thereof
Technical Field
The invention relates to a biomass modified pressure-sensitive adhesive and a preparation method thereof, belonging to the field of adhesives.
Background
Pressure-sensitive adhesives are a special adhesive, and can be bonded with the surface of an adherend in a short time only by applying proper pressure to generate bonding effect. Pressure-sensitive adhesives are mainly classified into rubber type and resin type. The rubber type can be divided into natural rubber and synthetic rubber; the resin type mainly comprises acrylic esters, organic silicon and polyurethane. The most widely used and more environment-friendly water-based acrylate pressure-sensitive adhesive is currently available.
The water-based acrylate pressure-sensitive adhesive is obtained by free radical copolymerization of various acrylate monomers, has the advantages of simple preparation process, low cost, no organic solvent, high solid content and no environmental pollution, and is widely applied to the fields of sealing tapes, labels, electronics, medicines and the like. However, the acrylate polymer is thermoplastic, linear molecules lack crosslinking points, and a three-dimensional network structure is difficult to form, so that the acrylate pressure-sensitive adhesive has the defects of poor water resistance, weather resistance, peeling strength and the like, and is difficult to replace solvent type acrylate pressure-sensitive adhesives in some special fields. Therefore, the improvement of the performance of the water-based acrylate pressure-sensitive adhesive by modification is always the research focus of the current adhesive industry.
At present, a plurality of methods for modifying the water-based acrylate pressure-sensitive adhesive are available, and common methods comprise blending modification, tackifying resin modification, reactive emulsifier modification and crosslinking modification, but the operation is complex and the production cost is high. Meanwhile, compared with the modification of inorganic nano particles such as silicon dioxide, titanium dioxide and the like, the thermal modification of the inorganic nano particles is not achieved, but because the nano particles are easy to agglomerate in the polymerization process, the superiority of the size of the nano particles is not brought into play. Therefore, it is very significant to find a water-based acrylate pressure-sensitive adhesive which is simple, green and efficient in preparation method and has excellent performance.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide a biomass modified water-based acrylate pressure-sensitive adhesive with excellent performance and a preparation method thereof. Adding biomass material nano cellulose or starch into an acrylate monomer through modification or non-modification for in-situ emulsion polymerization to prepare the high-performance biomass modified water-based acrylate pressure-sensitive adhesive.
The first purpose of the invention is to provide a biomass modified water-based acrylate pressure-sensitive adhesive, which comprises the following components in parts by weight: 40-98 parts of soft monomer, 2-15 parts of hard monomer, 0.1-5 parts of functional monomer, 0.5-5 parts of emulsifier, 0.01-2 parts of initiator, 1-5 parts of biomass and 30-80 parts of water.
In one embodiment of the invention, the biomass comprises one or both of nanocellulose and starch.
In one embodiment of the present invention, the biomass may also be modified biomass, including one or both of modified nanocellulose and modified starch.
In one embodiment of the present invention, the method for preparing modified biomass comprises: mixing biomass, a solvent and a silane coupling agent in a weight ratio of 1: (4-17): (1-2), reacting for 8-24 hours at 30-80 ℃, and purifying to obtain the modified biomass.
In one embodiment of the present invention, the silane coupling agent is at least one of gamma-glycidoxypropyltrimethoxysilane (KH560), gamma-methacryloxypropyltrimethoxysilane (KH570), and gamma-aminopropyltriethoxysilane (KH 550).
In one embodiment of the present invention, the solvent is at least one of water, ethanol, and methanol.
In one embodiment of the present invention, the diameter of the nanocellulose is not more than 100 nm, and the length is 100 to 500 nm.
In one embodiment of the present invention, the soft monomer is at least one of ethyl acrylate, butyl acrylate, n-octyl acrylate, and 2-ethylhexyl acrylate.
In one embodiment of the present invention, the hard monomer is at least one of methyl acrylate, methyl methacrylate and vinyl acetate.
In one embodiment of the present invention, the functional monomer is at least one of hydroxyethyl acrylate, acrylic acid, glycidyl methacrylate, N-methylolacrylamide, acrylamide, methacrylic acid, and hydroxypropyl acrylate.
In one embodiment of the present invention, the initiator is at least one of ammonium persulfate, potassium persulfate, and tert-butyl hydroperoxide.
In one embodiment of the invention, the emulsifier is one or two of ethoxylated ammonium alkylphenol sulfate (CO436), Sodium Dodecyl Sulfate (SDS), polyoxyethylene octylphenol ether-10 (OP-10), polyoxyethylene (10) stearate (SE-10), succinic acid monoester disodium sulfonate mixture (A501) and sodium dodecyl diphenyl ether disulfonate (2A 1).
In one embodiment of the invention, the pressure-sensitive adhesive further comprises 0.01-0.5 part of a buffering agent according to the weight part ratio.
In one embodiment of the invention, the buffer comprises sodium bicarbonate.
In one embodiment of the invention, the preparation method of the biomass modified water-based acrylate pressure-sensitive adhesive comprises the following steps:
(1) mixing a soft monomer, a hard monomer, a functional monomer, biomass, an emulsifier and water according to the weight part ratio, and emulsifying to obtain a pre-emulsion;
(2) and (2) uniformly mixing part of the pre-emulsion in the step (1) with water and a buffering agent, adding part of the initiator, reacting until the emulsion turns blue, and then continuously adding the rest of the pre-emulsion and the initiator to obtain the pressure-sensitive adhesive.
In one embodiment of the present invention, the temperature of emulsification in the step (1) is 30 to 50 ℃.
In one embodiment of the present invention, the reaction temperature in the step (2) is 70 to 85 ℃.
In one embodiment of the present invention, the remaining pre-emulsion and the initiator are added dropwise for 3 to 6 hours in the step (2).
In one embodiment of the present invention, the step (2) further comprises adjusting the pH to 6.5 to 7.5 after completion of the reaction.
In an embodiment of the invention, the preparation method of the biomass modified water-based acrylate pressure-sensitive adhesive specifically comprises the following steps:
(1) adding an emulsifier and a proper amount of water into a reaction kettle to dissolve the emulsifier; adding a plurality of monomers and biomass materials, and quickly emulsifying at the temperature of 30-50 ℃ to obtain a pre-emulsion;
(2) pouring a small amount of the pre-emulsion into another reaction kettle, adding a proper amount of water and sodium bicarbonate, stirring for dissolving, uniformly mixing, adding a part of initiator aqueous solution, heating to 70-85 ℃ for reaction, continuing to react for half an hour after the emulsion turns blue, continuing to dropwise add the rest pre-emulsion and the initiator for 3-6 hours, finally preserving the temperature for 0.5-1 hour, adjusting the pH value of the emulsion to 6.5-7.5 by using ammonia water, filtering by using a 200-mesh silk screen, and discharging to obtain the pressure-sensitive adhesive.
A second object of the present invention is to provide a pressure-sensitive adhesive tape comprising the above pressure-sensitive adhesive.
In one embodiment of the invention, the pressure-sensitive adhesive tape is prepared by uniformly coating the pressure-sensitive adhesive on any one substrate of a polylactic acid film, a polypropylene film and a polyethylene terephthalate film, and drying at 60-90 ℃ for 3-20 minutes, wherein the thickness of the pressure-sensitive adhesive is 10-50 microns, and the substrate film is preferably a biaxially oriented film, such as biaxially oriented polypropylene (BOPP), biaxially oriented polylactic acid (BOPLA) and biaxially oriented polyethylene terephthalate (BOPET).
The third purpose of the invention is to provide the biomass modified pressure-sensitive adhesive or the application of the pressure-sensitive adhesive tape.
In one embodiment of the invention, the application comprises the application in the fields of adhesive tapes, notepaper, electronic packaging and medical plasters.
The invention has the beneficial effects that:
1. according to the invention, the biomass material is added into the water-based acrylate monomer for in-situ emulsion polymerization, so that the prepared pressure-sensitive adhesive has excellent initial adhesion and peel strength, and the adhesion performance far exceeds the adhesion performance specified in the national standard GB/T22378-2008 'Universal biaxially oriented polypropylene film pressure-sensitive adhesive tape'.
2. The invention takes water as a dispersion medium, is green and environment-friendly, has simple and efficient polymerization process and is easy to realize industrial production.
3. According to the invention, the biomass raw material is modified, the raw material source is wide, and the modified biomass can be better dispersed in the water-based acrylate emulsion, so that the emulsion is stabilized and the adhesive force is improved; and secondly, after the biomass is modified, the biomass has better compatibility with the monomer, and the viscoelasticity of the biomass and the monomer is improved.
Description of the drawings:
FIG. 1 is a schematic diagram of the mechanism of the synthesis of the modified acrylate emulsions of examples 1-4; a is a mechanism process of cellulose (CNC) modified acrylate pressure-sensitive adhesive; b is modified nano cellulose (mCNC) modified acrylate pressure-sensitive adhesive.
Detailed Description
The present invention will be described in detail below with reference to examples and comparative examples, but the examples should not be construed as limiting the scope of the present invention.
Method for measuring viscosity: the viscosity of the emulsion is measured according to GB/T2794-2013 and is measured by a rotary viscometer. Each sample was measured three times, and the average value was taken, and the measurement temperature was (23. + -. 0.5). degree.C.
Particle size test method: and a Zeta potential and nano-particle size analyzer is adopted for determination. The emulsion particles were dispersed in deionized water and diluted to clear (concentration 0.1 mg/mL). Each sample was measured three times, and the average value was taken, and the measurement temperature was (20. + -. 0.5). degree.C.
The molecular weight and the molecular weight distribution thereof are tested by the following methods: the sol molecular weight and molecular weight distribution of the synthesized modified acrylate pressure-sensitive adhesive are measured by a Gel Permeation Chromatography (GPC) instrument, a monodisperse polystyrene standard sample is used as a standard curve for correction, the mobile phase is tetrahydrofuran, and the flow rate is 1.0 mu L/min.
Glass transition temperature (T)g) The test method (2): and measuring the glass transition temperature of the modified acrylate pressure-sensitive adhesive by using a differential scanning calorimeter. And (3) placing the pressure-sensitive adhesive in an aluminum crucible, heating at the speed of 10 ℃/min in a nitrogen environment, and heating from-65 ℃ to 100 ℃ to obtain a DSC curve.
Example 1:
a biomass modified water-based acrylate pressure-sensitive adhesive comprises, by weight, 72 parts of Butyl Acrylate (BA), 21 parts of 2-ethylhexyl acrylate (2-EHA), 4 parts of Methyl Methacrylate (MMA), 2 parts of hydroxyethyl acrylate (HEA), 1 part of Acrylic Acid (AA), 0.5 part of nano-crystalline cellulose (CNC), 1 part of emulsifier (CO436), and 1 part of sodium bicarbonate (NaHCO)3)0.2 part of deionized water, 70 parts of deionized water and 0.45 part of initiator Ammonium Persulfate (APS).
The preparation method comprises the steps of adding an emulsifier and 34 parts of water into a reaction kettle to dissolve the emulsifier, adding a plurality of monomers and nano-cellulose, and quickly emulsifying at 45 ℃ to form a pre-emulsion; pouring one tenth of the pre-emulsion into another reaction kettle, adding 30 parts of water and sodium bicarbonate, stirring for dissolving, uniformly mixing, dissolving one third of the initiator into 3 parts of water, adding into the reaction kettle, heating to 85 ℃ for reaction, continuing to react for half an hour after the emulsion turns blue, continuing to dropwise add the rest pre-emulsion and the initiator aqueous solution for 3.5 hours, finally preserving the temperature for 1 hour, adjusting the pH value of the emulsion to 7 by using ammonia water, and filtering and discharging by using a 200-mesh silk screen; the above emulsion was uniformly coated onto a BOPLA film and dried at 85 ℃ for 8 minutes, with a pressure sensitive adhesive thickness of 25 microns.
Example 2:
the biomass modified water-based acrylate pressure-sensitive adhesive comprises, by weight, 72 parts of butyl acrylate, 21 parts of 2-ethylhexyl acrylate, 4 parts of methyl methacrylate, 2 parts of hydroxyethyl acrylate, 1 part of acrylic acid, 1 part of nanocellulose, 1 part of emulsifier (CO436), 0.2 part of sodium bicarbonate, 70 parts of deionized water and 0.45 part of initiator ammonium persulfate.
The preparation method comprises the steps of adding an emulsifier and 34 parts of water into a reaction kettle to dissolve the emulsifier, adding a plurality of monomers and nano-cellulose, and quickly emulsifying at 45 ℃ to form a pre-emulsion; pouring one tenth of the pre-emulsion into another reaction kettle, adding 30 parts of water and sodium bicarbonate, stirring for dissolving, uniformly mixing, dissolving one third of the initiator into 3 parts of water, adding into the reaction kettle, heating to 85 ℃ for reaction, continuing to react for half an hour after the emulsion turns blue, continuing to dropwise add the rest pre-emulsion and the initiator aqueous solution for 3.5 hours, finally preserving the temperature for 1 hour, adjusting the pH value of the emulsion to 7 by using ammonia water, and filtering and discharging by using a 200-mesh silk screen; the above emulsion was uniformly coated onto a BOPLA film and dried at 85 ℃ for 8 minutes, with a pressure sensitive adhesive thickness of 25 microns.
Example 3
A biomass modified waterborne acrylate pressure-sensitive adhesive comprises, by weight, 72 parts of Butyl Acrylate (BA) monomers, 21 parts of 2-ethylhexyl acrylate (2-EHA), 4 parts of Methyl Methacrylate (MMA), 2 parts of hydroxyethyl acrylate (HEA), 1 part of Acrylic Acid (AA), and modified acrylic acid0.5 part of nano-cellulose (mCNC), 1 part of emulsifier (CO436) and sodium bicarbonate (NaHCO)3)0.2 part of deionized water, 70 parts of deionized water and 0.45 part of initiator Ammonium Persulfate (APS).
The preparation method comprises the steps of adding an emulsifier and 34 parts of water into a reaction kettle, dissolving the emulsifier, adding a plurality of monomers and modified nano-cellulose, and quickly emulsifying at 45 ℃ to form a pre-emulsion; pouring one tenth of the pre-emulsion into another reaction kettle, adding 30 parts of water and sodium bicarbonate, stirring for dissolving, uniformly mixing, dissolving one third of the initiator into 3 parts of water, adding into the reaction kettle, heating to 85 ℃ for reaction, continuing to react for half an hour after the emulsion turns blue, continuing to dropwise add the rest pre-emulsion and the initiator aqueous solution for 3.5 hours, finally preserving the temperature for 1 hour, adjusting the pH value of the emulsion to 7 by using ammonia water, and filtering and discharging by using a 200-mesh silk screen; the above emulsion was uniformly coated onto a BOPLA film and dried at 85 ℃ for 8 minutes, with a pressure sensitive adhesive thickness of 25 microns.
The preparation method of the modified nano-cellulose comprises the following steps: mixing nano-cellulose, ethanol and a silane coupling agent KH570 according to the weight ratio of 1:13:1, reacting at 70 ℃ for 24 hours, and purifying to obtain the modified nano-cellulose.
Example 4
The biomass modified water-based acrylate pressure-sensitive adhesive comprises, by weight, 72 parts of butyl acrylate, 21 parts of 2-ethylhexyl acrylate, 4 parts of methyl methacrylate, 2 parts of hydroxyethyl acrylate, 1 part of acrylic acid, 1 part of modified nanocellulose, 1 part of emulsifier (CO436), 0.2 part of sodium bicarbonate, 70 parts of deionized water and 0.45 part of initiator ammonium persulfate.
The preparation method comprises the steps of adding an emulsifier and 34 parts of water into a reaction kettle, dissolving the emulsifier, adding a plurality of monomers and modified nano-cellulose, and quickly emulsifying at 45 ℃ to form a pre-emulsion; pouring one tenth of the pre-emulsion into another reaction kettle, adding 30 parts of water and sodium bicarbonate, stirring for dissolving, uniformly mixing, dissolving one third of the initiator into 3 parts of water, adding into the reaction kettle, heating to 85 ℃ for reaction, continuing to react for half an hour after the emulsion turns blue, continuing to dropwise add the rest pre-emulsion and the initiator aqueous solution for 3.5 hours, finally preserving the temperature for 1 hour, adjusting the pH value of the emulsion to 7 by using ammonia water, and filtering and discharging by using a 200-mesh silk screen; the above emulsion was uniformly coated onto a BOPLA film and dried at 85 ℃ for 8 minutes, with a pressure sensitive adhesive thickness of 25 microns.
The preparation method of the modified nano-cellulose is the same as that of the embodiment 3
Aiming at examples 1-4 and comparative example 2, the modified acrylate pressure-sensitive adhesive is prepared by changing the addition amount of biomass and keeping other conditions unchanged, and the influence of the biomass on the performance of the acrylate emulsion and the pressure-sensitive adhesive is analyzed.
The sol molecular weight and the molecular weight distribution results of the modified acrylate pressure-sensitive adhesives with different CNC and mCNC contents are shown in Table 1. The viscosity and particle size of the modified acrylate emulsion with different CNC and mCNC contents are shown in table 2;
TABLE 1 Sol molecular weights and molecular weight distributions of modified acrylate pressure-sensitive adhesives of different CNC and mCNC contents
Figure BDA0002016506380000061
The sol molecular weights and the molecular weight distributions of the modified acrylate pressure-sensitive adhesives with different CNC (computer numerical control) and mCNC contents are respectively characterized by a gel permeation chromatograph, and the results are shown in Table 1. When the relative molecular weight of the pressure-sensitive adhesive is small, wetting of the adherend surface is facilitated to improve the initial adhesion of the pressure-sensitive adhesive, but when the relative molecular weight is too low, the cohesive strength is poor. When the relative molecular weight of the pressure-sensitive adhesive is larger, the cohesive strength is favorably improved, but the initial adhesion of the pressure-sensitive adhesive is favorably improved due to the overlarge relative molecular weight. Thus, good adhesive properties are only obtained when the relative molecular mass distribution of the pressure-sensitive adhesive is broad.
It can be seen from table 1 that the addition of nanocellulose or modified nanocellulose modified acrylate pressure-sensitive adhesive (examples 1-4) broadens the molecular weight distribution of the modified acrylate pressure-sensitive adhesive and the increase in the content of modified nanocellulose or nanocellulose broadens the molecular weight distribution of the modified acrylate pressure-sensitive adhesive, compared to pure acrylate pressure-sensitive adhesive (comparative example 2). Therefore, the initial adhesion and the cohesive strength of the acrylate pressure-sensitive adhesive can be improved simultaneously by modifying the nanocellulose and the modified nanocellulose.
TABLE 2 viscosity and particle size of modified acrylate emulsions with different cellulose (CNC) and modified cellulose (mCNC) contents
Figure BDA0002016506380000062
TABLE 3T of modified acrylate emulsions with different cellulose (CNC) and modified cellulose (mCNC) contentsg
Figure BDA0002016506380000063
The glass transition temperature of the modified acrylate pressure-sensitive adhesive was characterized, and Table 3 shows the glass transition temperature (T) of the modified acrylate pressure-sensitive adhesiveg) Data, TgIs one of the important factors affecting the adhesive performance of the pressure-sensitive adhesive. When T isgAt higher levels, the pressure sensitive adhesive generally exhibits rigidity and higher cohesive force; when T isgAt a lower level, fluidity is exhibited, wettability is better, and initial viscosity is higher. From Table 3, it can be seen that T of the pure acrylate pressure-sensitive adhesivegAbout-43.2 ℃ T when added to the nanoparticles CNC and mCNCgThe variation is not significant.
Example 5
The biomass modified water-based acrylate pressure-sensitive adhesive comprises, by weight, 72 parts of butyl acrylate, 21 parts of 2-ethylhexyl acrylate, 4 parts of methyl methacrylate, 2 parts of hydroxyethyl acrylate, 1 part of acrylic acid, 0.5 part of starch, 1 part of an emulsifier (CO436), 0.2 part of sodium bicarbonate, 70 parts of deionized water and 0.45 part of an initiator ammonium persulfate.
The preparation method comprises the steps of adding an emulsifier and 34 parts of water into a reaction kettle, dissolving the emulsifier, adding a plurality of monomers and starch, and quickly emulsifying at 45 ℃ to form a pre-emulsion; pouring one tenth of the pre-emulsion into another reaction kettle, adding 30 parts of water and sodium bicarbonate, stirring for dissolving, uniformly mixing, dissolving one third of the initiator into 3 parts of water, adding into the reaction kettle, heating to 85 ℃ for reaction, continuing to react for half an hour after the emulsion turns blue, continuing to dropwise add the rest pre-emulsion and the initiator aqueous solution for 3.5 hours, finally preserving the temperature for 1 hour, adjusting the pH value of the emulsion to 7 by using ammonia water, and filtering and discharging by using a 200-mesh silk screen; the above emulsion was uniformly coated onto a BOPLA film and dried at 85 ℃ for 8 minutes, with a pressure sensitive adhesive thickness of 25 microns.
Example 6
The biomass modified water-based acrylate pressure-sensitive adhesive comprises, by weight, 72 parts of butyl acrylate, 21 parts of 2-ethylhexyl acrylate, 4 parts of methyl methacrylate, 2 parts of hydroxyethyl acrylate, 1 part of acrylic acid, 1 part of starch, 1 part of an emulsifier (CO436), 0.2 part of sodium bicarbonate, 70 parts of deionized water and 0.45 part of initiator ammonium persulfate.
The preparation method comprises the steps of adding an emulsifier and 34 parts of water into a reaction kettle, dissolving the emulsifier, adding a plurality of monomers and starch, and quickly emulsifying at 45 ℃ to form a pre-emulsion; pouring one tenth of the pre-emulsion into another reaction kettle, adding 30 parts of water and sodium bicarbonate, stirring for dissolving, uniformly mixing, dissolving one third of the initiator into 3 parts of water, adding into the reaction kettle, heating to 85 ℃ for reaction, continuing to react for half an hour after the emulsion turns blue, continuing to dropwise add the rest pre-emulsion and the initiator aqueous solution for 3.5 hours, finally preserving the temperature for 1 hour, adjusting the pH value of the emulsion to 7 by using ammonia water, and filtering and discharging by using a 200-mesh silk screen; the above emulsion was uniformly coated onto a BOPLA film and dried at 85 ℃ for 8 minutes, with a pressure sensitive adhesive thickness of 25 microns.
Example 7
The biomass modified water-based acrylate pressure-sensitive adhesive comprises, by weight, 72 parts of butyl acrylate, 21 parts of 2-ethylhexyl acrylate, 4 parts of methyl methacrylate, 2 parts of hydroxyethyl acrylate, 1 part of acrylic acid, 0.5 part of modified starch, 1 part of an emulsifier (CO436), 0.2 part of sodium bicarbonate, 70 parts of deionized water and 0.45 part of initiator ammonium persulfate.
The preparation method comprises the steps of adding an emulsifier and 34 parts of water into a reaction kettle, dissolving the emulsifier, adding a plurality of monomers and modified starch, and quickly emulsifying at 45 ℃ to form a pre-emulsion; pouring one tenth of the pre-emulsion into another reaction kettle, adding 30 parts of water and sodium bicarbonate, stirring for dissolving, uniformly mixing, dissolving one third of the initiator into 3 parts of water, adding into the reaction kettle, heating to 85 ℃ for reaction, continuing to react for half an hour after the emulsion turns blue, continuing to dropwise add the rest pre-emulsion and the initiator aqueous solution for 3.5 hours, finally preserving the temperature for 1 hour, adjusting the pH value of the emulsion to 7 by using ammonia water, and filtering and discharging by using a 200-mesh silk screen; the above emulsion was uniformly coated onto a BOPLA film and dried at 85 ℃ for 8 minutes, with a pressure sensitive adhesive thickness of 25 microns.
The preparation method of the modified starch comprises the following steps: mixing starch, ethanol and a silane coupling agent KH560 according to the weight ratio of 1:13:1, reacting at 70 ℃ for 24 hours, and purifying to obtain the modified starch.
Example 8
The biomass modified water-based acrylate pressure-sensitive adhesive comprises, by weight, 72 parts of butyl acrylate, 21 parts of 2-ethylhexyl acrylate, 4 parts of methyl methacrylate, 2 parts of hydroxyethyl acrylate, 1 part of acrylic acid, 1 part of modified starch, 1 part of an emulsifier (CO436), 0.2 part of sodium bicarbonate, 70 parts of deionized water and 0.45 part of initiator ammonium persulfate.
The preparation method comprises the steps of adding an emulsifier and 34 parts of water into a reaction kettle, dissolving the emulsifier, adding a plurality of monomers and modified starch, and quickly emulsifying at 45 ℃ to form a pre-emulsion; pouring one tenth of the pre-emulsion into another reaction kettle, adding 30 parts of water and sodium bicarbonate, stirring for dissolving, uniformly mixing, dissolving one third of the initiator into 3 parts of water, adding into the reaction kettle, heating to 85 ℃ for reaction, continuing to react for half an hour after the emulsion turns blue, continuing to dropwise add the rest pre-emulsion and the initiator aqueous solution for 3.5 hours, finally preserving the temperature for 1 hour, adjusting the pH value of the emulsion to 7 by using ammonia water, and filtering and discharging by using a 200-mesh silk screen; the above emulsion was uniformly coated onto a BOPLA film and dried at 85 ℃ for 8 minutes, with a pressure sensitive adhesive thickness of 25 microns.
The modified starch was prepared in the same manner as in example 7
Example 9
The biomass modified waterborne acrylate pressure-sensitive adhesive comprises, by weight, 80 parts of butyl acrylate, 10 parts of 2-ethylhexyl acrylate, 8 parts of methyl methacrylate, 1 part of hydroxyethyl acrylate, 1 part of acrylic acid, 1 part of modified nanocellulose, 1 part of a compound of an emulsifier (2A1) and an emulsifier (A501), 0.35 part of sodium bicarbonate, 80 parts of deionized water and 0.25 part of an initiator potassium persulfate.
The preparation method comprises the steps of adding an emulsifier and 34 parts of water into a reaction kettle, dissolving the emulsifier, adding a plurality of monomers and modified nano-cellulose, and quickly emulsifying at 30 ℃ to form a pre-emulsion; pouring one tenth of the pre-emulsion into another reaction kettle, adding 40 parts of water and sodium bicarbonate, stirring for dissolving, uniformly mixing, dissolving one third of the initiator into 3 parts of water, adding into the reaction kettle, heating to 80 ℃ for reaction, continuing to react for half an hour after the emulsion turns blue, continuing to dropwise add the rest pre-emulsion and the initiator aqueous solution for 5 hours, finally preserving the temperature for 1 hour, adjusting the pH value of the emulsion to 7 by using ammonia water, and filtering and discharging by using a 200-mesh silk screen; the above emulsion was uniformly coated onto a BOPP film and dried at 80 ℃ for 15 minutes, wherein the thickness of the pressure sensitive adhesive was 30 μm.
The preparation method of the modified nano-cellulose comprises the following steps: mixing nano-cellulose, ethanol and a silane coupling agent KH560 according to the weight ratio of 1:14:1.5, reacting at 80 ℃ for 18 hours, and purifying to obtain the modified nano-cellulose.
Example 10
The biomass modified water-based acrylate pressure-sensitive adhesive comprises, by weight, 55 parts of ethyl acrylate, 30 parts of 2-ethylhexyl acrylate, 10 parts of vinyl acetate, 3 parts of hydroxyethyl acrylate, 2 parts of glycidyl methacrylate, 4 parts of modified starch, 3 parts of an emulsifier (CO436), 0.2 part of sodium bicarbonate, 70 parts of deionized water and 0.35 part of initiator ammonium persulfate.
The preparation method comprises the steps of adding an emulsifier and 34 parts of water into a reaction kettle, dissolving the emulsifier, adding a plurality of monomers and modified starch, and quickly emulsifying at 40 ℃ to form a pre-emulsion; pouring one tenth of the pre-emulsion into another reaction kettle, adding 30 parts of water and sodium bicarbonate, stirring for dissolving, uniformly mixing, dissolving one third of the initiator into 3 parts of water, adding into the reaction kettle, heating to 82 ℃ for reaction, continuing to react for half an hour after the emulsion turns blue, continuing to dropwise add the rest pre-emulsion and the initiator aqueous solution for 4.5 hours, finally preserving the temperature for 45 minutes, adjusting the pH value of the emulsion to 7.5 by using ammonia water, and filtering and discharging by using a 200-mesh silk screen; the emulsion was uniformly coated onto a BOPET film and dried at 90 ℃ for 5 minutes, wherein the thickness of the pressure sensitive adhesive was 20 microns.
The preparation method of the modified starch comprises the following steps: mixing starch, ethanol and a silane coupling agent KH570 according to the weight ratio of 1:15:2, reacting at 75 ℃ for 20 hours, and purifying to obtain the modified starch.
Comparative example 1:
referring to example 2, the biomass modified waterborne acrylate pressure-sensitive adhesive is prepared without adding functional monomers, and comprises 72 parts of butyl acrylate, 21 parts of 2-ethylhexyl acrylate, 4 parts of methyl methacrylate, 1 part of nano-cellulose, 1 part of emulsifier (CO436), 0.2 part of sodium bicarbonate, 70 parts of deionized water and 0.45 part of initiator ammonium persulfate according to the weight part ratio.
The preparation method comprises the steps of adding an emulsifier and 34 parts of water into a reaction kettle to dissolve the emulsifier, adding a plurality of monomers and nano-cellulose, and quickly emulsifying at 45 ℃ to form a pre-emulsion; pouring one tenth of the pre-emulsion into another reaction kettle, adding 30 parts of water and sodium bicarbonate, stirring for dissolving, uniformly mixing, dissolving one third of the initiator into 3 parts of water, adding into the reaction kettle, heating to 85 ℃ for reaction, continuing to react for half an hour after the emulsion turns blue, continuing to dropwise add the rest pre-emulsion and the initiator aqueous solution for 3.5 hours, finally preserving the temperature for 1 hour, adjusting the pH value of the emulsion to 7 by using ammonia water, and filtering and discharging by using a 200-mesh silk screen; the above emulsion was uniformly coated onto a BOPLA film and dried at 85 ℃ for 8 minutes, with a pressure sensitive adhesive thickness of 25 microns.
Comparative example 2
The pure water acrylate pressure-sensitive adhesive consists of butyl acrylate 72 weight portions, 2-ethylhexyl acrylate 21 weight portions, methyl methacrylate 4 weight portions, hydroxyethyl acrylate 2 weight portions, acrylic acid 1 weight portion, emulsifier CO 4361 weight portions, sodium bicarbonate 0.2 weight portions, deionized water 70 weight portions, and initiator ammonium persulfate 0.45 weight portions.
The preparation method comprises the steps of adding an emulsifier and 34 parts of water into a reaction kettle, dissolving the emulsifier, adding a plurality of monomers, and quickly emulsifying at 45 ℃ to form a pre-emulsion; pouring one tenth of the pre-emulsion into another reaction kettle, adding 30 parts of water and sodium bicarbonate, stirring for dissolving, uniformly mixing, dissolving one third of the initiator into 3 parts of water, adding into the reaction kettle, heating to 85 ℃ for reaction, continuing to react for half an hour after the emulsion turns blue, continuing to dropwise add the rest pre-emulsion and the initiator aqueous solution for 3.5 hours, finally preserving the temperature for 1 hour, adjusting the pH value of the emulsion to 7 by using ammonia water, and filtering and discharging by using a 200-mesh silk screen; the above emulsion was uniformly coated onto a BOPLA film and dried at 85 ℃ for 8 minutes, with a pressure sensitive adhesive thickness of 25 microns.
The adhesive properties of the modified acrylate pressure-sensitive adhesives of examples 1 to 10 and comparative examples 1 to 2 are shown in Table 4.
TABLE 4 adhesive Properties of modified acrylate pressure-sensitive adhesives of examples 1-10 and comparative examples 1-2
Examples Initial viscosity number (#) Peel strength (N/10mm)
Example 1 22±0.8 2.3±0.4
Example 2 24±1.0 2.6±0.7
Example 3 24±0.7 3.4±0.8
Example 4 27±1.4 5.4±0.9
Example 5 23±0.6 2.8±0.4
Example 6 25±0.6 3.2±0.3
Example 7 25±0.5 3.1±0.6
Example 8 28±0.3 4.6±0.7
Example 9 28±0.5 5.5±0.3
Example 10 27±1.0 5.6±0.2
Comparative example 1 24±0.3 1.0±0.6
Comparative example 2 20±0.2 1.8±0.4
The initial tack and peel strength of examples 1-10 and comparative examples 1-2 were tested in accordance with GB/T-4852-.
As is clear from the data in Table 4, the pressure-sensitive adhesive (comparative example 2) for pure water-based acrylic ester has a low initial tack and a poor peel strength of less than 2N/10 mm. The peel strength of the modified acrylate pressure-sensitive adhesive (comparative example 1) with nanocellulose and no added functional monomer was also lower. After the nanocellulose and the functional monomer are added into the acrylate monomer, the peel strength of the modified acrylate pressure-sensitive adhesive is obviously improved along with the increase of the content of the nanocellulose (examples 1 to 4); after the nanocellulose is modified, the initial adhesion and the peel strength of the modified acrylate pressure-sensitive adhesive are improved more obviously.
After the starch is added into the acrylate monomer (examples 5-6), the initial adhesion is obviously improved, because the initial adhesion and the peel strength of the water-based acrylate pressure-sensitive adhesive are improved after the starch is gelatinized at high temperature. After the starch is modified (examples 7-8), the initial adhesion and the peel strength of the modified acrylate pressure-sensitive adhesive are improved more obviously. The biomass is modified, so that the biomass has better compatibility with the monomer, and can better perform in-situ emulsion polymerization with the monomer, thereby further improving the initial adhesion and the peel strength of the pressure-sensitive adhesive. In addition, in the embodiment, the pressure-sensitive adhesive can be prepared from any one of the base materials of the BOPLA film, the BOPP film and the BOPET film, the pressure-sensitive adhesive can be well adhered to the base material, the degumming phenomenon is avoided, and the prepared pressure-sensitive adhesive has excellent adhesion performance. Therefore, the water-based acrylate pressure-sensitive adhesive modified by the biomass has excellent initial adhesion and peel strength, and can be widely applied to the fields of adhesive tapes, notepaper, electronic packaging and medical plasters.
Those of ordinary skill in the art will understand that: the discussion of any embodiment above is meant to be exemplary only, and is not intended to intimate that the scope of the disclosure, including the claims, is limited to these examples; within the idea of the invention, also technical features in the above embodiments or in different embodiments may be combined and there are many other variations of the different aspects of the invention as described above, which are not provided in detail for the sake of brevity. Therefore, any omissions, modifications, substitutions, improvements and the like that may be made without departing from the spirit and principles of the invention are intended to be included within the scope of the invention.

Claims (6)

1. The biomass modified water-based acrylate pressure-sensitive adhesive is characterized by comprising the following components in parts by weight: 40-98 parts of soft monomer, 2-15 parts of hard monomer, 0.1-5 parts of functional monomer, 0.5-5 parts of emulsifier, 0.01-2 parts of initiator, 1-5 parts of biomass and 30-80 parts of water;
the biomass is modified biomass and comprises one or two of modified nano-cellulose and modified starch;
the preparation method of the modified biomass comprises the following steps: mixing biomass, a solvent and a silane coupling agent in a weight ratio of 1: (4-17): (1-2) mixing, and reacting at 30-80 ℃ to obtain modified biomass;
the preparation method of the pressure-sensitive adhesive comprises the following steps:
(1) mixing a soft monomer, a hard monomer, a functional monomer, biomass and an emulsifier according to the weight part ratio, and emulsifying to obtain a pre-emulsion;
(2) and (2) uniformly mixing part of the pre-emulsion in the step (1) with water and a buffering agent, adding part of the initiator, reacting until the emulsion turns blue, and then continuously adding the rest of the pre-emulsion and the initiator to obtain the pressure-sensitive adhesive.
2. The adhesive according to claim 1, wherein the silane coupling agent is at least one of KH560, KH570, and KH 550.
3. The pressure-sensitive adhesive according to claim 1, further comprising 0.01 to 0.5 parts of a buffer agent by weight.
4. The adhesive of claim 3, wherein the buffer comprises sodium bicarbonate.
5. A pressure-sensitive adhesive tape, characterized in that it comprises the pressure-sensitive adhesive according to any one of claims 1 to 4.
6. Use of a pressure-sensitive adhesive according to any of claims 1 to 4, or a pressure-sensitive adhesive tape according to claim 5 in the field of notepaper, electronic packaging, medical plasters.
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