CN108504313A - A kind of nucleocapsid acrylate powder glue and preparation method thereof - Google Patents

A kind of nucleocapsid acrylate powder glue and preparation method thereof Download PDF

Info

Publication number
CN108504313A
CN108504313A CN201810236590.6A CN201810236590A CN108504313A CN 108504313 A CN108504313 A CN 108504313A CN 201810236590 A CN201810236590 A CN 201810236590A CN 108504313 A CN108504313 A CN 108504313A
Authority
CN
China
Prior art keywords
monomer
acrylate
nucleocapsid
preparation
emulsion
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
CN201810236590.6A
Other languages
Chinese (zh)
Other versions
CN108504313B (en
Inventor
傅和青
沈丽香
王盛
钟细明
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
South China University of Technology SCUT
Original Assignee
South China University of Technology SCUT
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by South China University of Technology SCUT filed Critical South China University of Technology SCUT
Priority to CN201810236590.6A priority Critical patent/CN108504313B/en
Publication of CN108504313A publication Critical patent/CN108504313A/en
Application granted granted Critical
Publication of CN108504313B publication Critical patent/CN108504313B/en
Expired - Fee Related legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
    • C09J133/04—Homopolymers or copolymers of esters
    • C09J133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
    • C09J133/062—Copolymers with monomers not covered by C09J133/06
    • C09J133/066—Copolymers with monomers not covered by C09J133/06 containing -OH groups
    • 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
    • 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
    • C08F2/30—Emulsion polymerisation with the aid of emulsifying agents non-ionic
    • 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
    • C08F2/38—Polymerisation using regulators, e.g. chain terminating agents, e.g. telomerisation
    • 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
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/02—Non-macromolecular additives
    • C09J11/04—Non-macromolecular additives inorganic
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/02—Non-macromolecular additives
    • C09J11/06—Non-macromolecular additives organic
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/08—Macromolecular additives
    • 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
    • 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
    • C08F220/1808—C8-(meth)acrylate, e.g. isooctyl (meth)acrylate or 2-ethylhexyl (meth)acrylate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/24—Acids; Salts thereof
    • C08K3/26—Carbonates; Bicarbonates
    • C08K2003/265—Calcium, strontium or barium carbonate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00—Specific properties of additives
    • C08K2201/011—Nanostructured additives

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Inorganic Chemistry (AREA)
  • Adhesives Or Adhesive Processes (AREA)
  • Polymerisation Methods In General (AREA)
  • Graft Or Block Polymers (AREA)

Abstract

The invention discloses a kind of nucleocapsid water-and acrylate plastic powders and preparation method thereof.Emulsifier is first added to the water by the preparation method, adds soft monomer, hard monomer, functional monomer and is uniformly mixed, magnetic agitation forms pre-emulsion.75~80 DEG C are warming up to, buffer solution is added in the reactor, in N2In atmosphere, the initiator of the pre-emulsion and 1/2~3/4 mass of 20~50% mass is added dropwise, is stirred to react and prepares colostric fluid；After heat preservation, remaining initiator and pre-emulsion is added dropwise, chain-transferring agent is added, after completion of dropwise addition, keeps the temperature 1~2h, cooling discharge；Coupling agent, nano-calcium carbonate or SiO is added2, polyvinyl alcohol water solution, after dispersion room temperature be ultrasonically treated, spray drying.Plastic powder of the present invention is environment-protecting and non-poisonous, both ensure that adhesive property, it may have good water resistance can use under conditions of complex precise, and production cost is low, easy to operate, and required time is short.

Description

A kind of nucleocapsid acrylate powder glue and preparation method thereof
Technical field
The present invention relates to a kind of pressure sensitive adhesives, more particularly to a kind of nucleocapsid water-and acrylate plastic powder and its preparation Method；Belong to pressure-sensitive adhesive material manufacturing field.
Background technology
Water-and acrylate pressure-sensitive adhesive agent is quickly grown in recent years, is widely used in medical adhesive tape, label, conductive Glue, surface protection tape and pressure-sensitive label etc., compared with solvent-type acrylic ester pressure-sensitive, at low cost, peace Entirely, nuisanceless, synthetic operation is easy, the advantages that polymerization time is short, and rheology controllability is strong；With the raising of environmental consciousness, nontoxic, Free of contamination water-and acrylate adhesive is increasingly paid attention to, and demand and application range are all expanding, and becomes in lasting rise Gesture.But since water-and acrylate Performance of Pressure Sensitive Adhesive performance is stronger, it is difficult to apply to the space of some complex precises, such as The fixation for saying screw part, which has limited the uses of water soluble acrylic acid ester pressure-sensitive.
Invention content
The primary purpose of the present invention is that overcome the deficiencies of existing technologies, with the experimental program being simple and efficient, to acrylic acid Ester pressure-sensitive preparation is improved, and obtains a kind of preparation side of environmental protection low cost with nucleocapsid water-and acrylate plastic powder Method is conducive to product further exploitation and transition.
In order to achieve the above-mentioned object of the invention, present invention employs following technical schemes：
A kind of preparation method of nucleocapsid acrylate powder glue, includes the following steps：
1) emulsifier is added to the water, adds soft monomer, hard monomer, functional monomer and is uniformly mixed, magnetic agitation 10 ~30min forms pre-emulsion；The soft monomer, hard monomer, functional monomer constitute monomer；The emulsifier additive amount is monomer The 1~3% of gross mass；The water additive amount is the 20~40% of monomer gross mass；
The soft monomer is vinylacetate, ethyl methacrylate, Isooctyl acrylate monomer, the different certain herbaceous plants with big flowers of acrylic acid, acrylic acid It is one or more in hydroxyl ethyl ester, cyclohexyl acrylate, butyl acrylate；The soft monomer additive amount is the 65 of monomer gross mass ~82%；
The functional monomer is itaconic acid, acrylic acid, methacrylic acid, acrylamide, hydroxy-ethyl acrylate, methyl-prop It is one or more in olefin(e) acid hydroxyl ethyl ester, hydroxypropyl acrylate, hydroxy propyl methacrylate；The functional monomer additive amount is The 1~1.5% of monomer gross mass；
The hard monomer is one or more in methyl methacrylate, acrylonitrile, styrene, methyl acrylate；Institute State 12~17% that hard monomer additive amount is monomer gross mass；
2) 75~80 DEG C are warming up to, buffer solution is added in the reactor, in N2In atmosphere, while 20~50% matter are added dropwise The initiator of the pre-emulsion of amount and 1/2~3/4 mass, is stirred to react 30~60min, prepares initial latex；Keep the temperature 10~40min Afterwards, remaining initiator and pre-emulsion is added dropwise, chain-transferring agent is added, time for adding is 3~4h；
3) after completion of dropwise addition, 80~90 DEG C of heat preservation 1~2h cooling discharges form emulsion；
4) coupling agent, nano-calcium carbonate or SiO are added into step 3)2, polyvinyl alcohol water solution, 40~50 DEG C dispersion 3 Room temperature is ultrasonically treated 10~30min after~15min；The coupling agent is gamma-aminopropyl-triethoxy-silane, 3- glycidol ethers Base hydroxypropyl methyl diethoxy silane, γ-(the third oxygen of 2,3- epoxies) propyl trimethoxy silicane, vinyltrimethoxysilane, It is one or more in γ-mercaptopropyl trimethoxysilane, γ-(methacryloxypropyl) propyl trimethoxy silicane；
5) nucleocapsid acrylate powder glue is obtained by step 4) products therefrom is spray-dried.
To further realize the object of the invention, it is preferable that the emulsifier is -10 (OP- of polyoxyethylene Zhong Xin phenolic ethers 10), lauryl sodium sulfate (SDS) nonylphenol polyoxyethylene ether (TX-10), ethoxylated nonylphenol sulfosuccinic acid semiester two It is one or more in sodium, neopelex (LAS) and polysorbas20 (Tween-20).
Preferably, the buffer solution is the NaHCO of 0.5wt~0.7wt%3Aqueous solution.
Preferably, the initiator is one kind or more of ammonium sulfate, potassium peroxydisulfate, sodium hydrogensulfite, azodiisobutyronitrile Kind.
Preferably, the initiator additive amount is the 0.1%~0.8% of monomer gross mass.
Preferably, the chain-transferring agent is lauryl mercaptan, and dosage is the 0.1~0.5% of monomer gross mass.
Preferably, the technological parameter of the spray drying be 150~180 DEG C of inlet temperature, 75~90 DEG C of outlet temperature, 3~10min of drying time.
Preferably, the coupling agent accounts for the 0.01~0.15% of emulsion quality；The nano-calcium carbonate or SiO2 Account for the 2~5% of emulsion quality；The polyvinyl alcohol water solution accounts for 10wt~30wt% of emulsion quality.
Preferably, the buffer solution total addition level is the 0.1~0.5% of monomer total amount；The initiator is total Additive amount is the 0.4~2.0% of monomer total amount；The chain-transferring agent additive amount is the 0.1%~0.8% of monomer total amount.
A kind of nucleocapsid acrylate powder glue being prepared by above-mentioned preparation method；The white powder of the pressure sensitive adhesive Shape, initial bonding strength reach 12-19#, peeling force 9.0-13.0N/25mm, holding power 200-350h；Water absorption rate is 1.2%- 15.0%, solid content 70%-85%.
Step 1) of the present invention, 2) the entire reaction process in carries out under stirring conditions, and stir speed (S.S.) is 150~ 350r/min。
Compared with prior art, the present invention has the following advantages：
1) the pioneering coupling agent of the present invention modifies acrylate polymer emulsion with dewatering nano material, makes to dredge using coupling agent Water nano SiO2Or calcium carbonate is uniformly firmly combined together with acrylate polymer, and utilize Nano-meter SiO_22Or carbonic acid It is strong in conjunction with the adhesive property of pressure sensitive adhesive can be greatly enhanced between calcium and coupling agent and base material.
2) the powder pressure sensitive adhesive of the invention made from spray drying is different from existing liquid adhesive, and product is solid , paper bag packing can be used as cement, be not required to metal bucket or plastic barrel packaging, cost can be not only greatly lowered, but also can reduce Volatile organic matter (VOC), is readily transported and long term storage.
3) present invention finally uses spray dried form, is rapidly and efficiently prepared for nucleocapsid acrylate powder glue, will Coupling agent and the uniform firm connection of nano-particle and adhesive together, while greatly shortening required preparation time.
4) nucleocapsid acrylate powder glue of the invention, not only ensure that adhesive property, but also due to hydrophobic nano SiO2Or the presence of calcium carbonate so that plastic powder also has pressure-sensitive property, enhanced water resistance, can be in the sealing of complex precise equipment It uses, production cost is low, easy to operate, environmentally protective, and application prospect is extensive.
Specific implementation mode
To more fully understand the present invention, with reference to embodiment, the present invention is further illustrated, but the present invention claims The range of protection is not limited to the range of embodiment expression.
Embodiment 1
1) 2.0g OP-10 are added into conical flask, adds 50g deionized waters magnetic agitation to emulsifier and dissolves, successively Butyl acrylate 70g, Isooctyl acrylate monomer 70g, hydroxy-ethyl acrylate 8g, vinylacetate 15g, methyl methacrylate is added 20g, hydroxyethyl methacrylate 4g, stirring (mixing speed 300r/min) 30min form pre-emulsion.
2) to equipped with thermometer, condenser pipe, agitating device 500ml four-hole boiling flasks in 0.2g NaHCO are added3, add Deionized water 40ml, 80 DEG C of reaction temperature, stirring to dissolving；Pre-emulsion is divided into two parts, by the pre-emulsion of 30% mass and 15g ammonium persulfate aqueous solutions are added dropwise simultaneously, and 30min keeps the temperature 30min after dripping off；It is added dropwise simultaneously again containing 4 drop lauryl mercaptans Remaining pre-emulsion and 6g ammonium persulfate aqueous solutions, 3.5h are added dropwise.
3) reaction temperature rises to 90 DEG C, keeps the temperature 1h under agitation, obtains water soluble acrylic acid ester pressure-sensitive emulsion.
4) it is sequentially added into step 3) and accounts for the coupling agent gamma-aminopropyl-triethoxy-silane of emulsion quality 0.1%, accounts for The nano-calcium carbonate of emulsion quality 3%, the polyvinyl alcohol water solution for accounting for emulsion quality 15wt%, 40 DEG C with 5000r/min Room temperature ultrasound 20min after dispersion 10min.
5) white nucleocapsid acrylic powder end glue, spray drying are obtained by product that step 4) obtains is spray-dried Technological parameter is 150 DEG C of inlet temperature, 80 DEG C of outlet temperature, drying time 8min.
Embodiment 2
1) 2.0g lauryl sodium sulfate is added into conical flask, adds 45g deionized waters magnetic agitation to emulsifier Dissolving, sequentially adds butyl acrylate 60g, Isooctyl acrylate monomer 80g, hydroxy-ethyl acrylate 8g, vinylacetate 10g, methyl Methyl acrylate 25g, hydroxyethyl methacrylate 4g, stirring (mixing speed 300r/min) 20min form pre-emulsion.
2) to equipped with thermometer, condenser pipe, agitating device 500ml four-hole boiling flasks in 0.3g NaHCO are added3, add Deionized water 40ml, 80 DEG C of reaction temperature, stirring to dissolving；30% pre-emulsion and 15g ammonium persulfate aqueous solutions are added dropwise simultaneously, 30min keeps the temperature 30min after dripping off；Remaining pre-emulsion and 6g ammonium persulfate aqueous solutions is added dropwise simultaneously again, 3h is added dropwise.
3) reaction temperature rises to 90 DEG C, keeps the temperature 1.5h under agitation, obtains water soluble acrylic acid ester pressure-sensitive emulsion.
4) it is sequentially added into step 3) and accounts for emulsion quality 0.05% gamma-aminopropyl-triethoxy-silane and 0.05% 3- glycidyl ether hydroxypropyl methyl diethoxy silanes coupling agent, 5% nano-calcium carbonate, the polyvinyl alcohol of 15wt% are water-soluble Liquid, 40 DEG C with room temperature ultrasound 20min after 6000r/min dispersions 15min.
5) white nucleocapsid acrylic powder end glue, spray drying are obtained by product that step 4) obtains is spray-dried Technological parameter is 180 DEG C of inlet temperature, 80 DEG C of outlet temperature, drying time 10min.
Embodiment 3
1) 2.0g nonylphenol polyoxyethylene ether ammonium sulfate is added into conical flask, adds 50g deionized water magnetic agitations It is dissolved to emulsifier, sequentially adds butyl acrylate 70g, Isooctyl acrylate monomer 70g, hydroxy-ethyl acrylate 8g, vinylacetate 10g, methyl methacrylate 25g, hydroxyethyl methacrylate 4g, stirring (mixing speed 300r/min) 30min form pre- breast Liquid.
2) to equipped with thermometer, condenser pipe, agitating device 500ml four-hole boiling flasks in 0.2g NaHCO are added3, add Deionized water 50ml, 75 DEG C of reaction temperature, stirring to dissolving；30% pre-emulsion and 15g ammonium persulfate aqueous solutions are added dropwise simultaneously, 40min keeps the temperature 30min after dripping off；Remaining pre-emulsion and 6g ammonium persulfate aqueous solutions is added dropwise simultaneously again, 3.5h is added dropwise.
3) reaction temperature rises to 85 DEG C, keeps the temperature 1h under agitation, obtains water soluble acrylic acid ester pressure-sensitive emulsion.
4) it is added into step 3) and accounts for 0.1% coupling agent gamma-aminopropyl-triethoxy-silane of emulsion quality, accounts for emulsion Quality 3%SiO2, account for the polyvinyl alcohol water solution of emulsion quality 20wt%, 40 DEG C are disperseed room temperature after 15min with 4500r/min Ultrasonic 20min.
5) white nucleocapsid acrylic powder end glue, spray drying are obtained by product that step 4) obtains is spray-dried Technological parameter is 160 DEG C of inlet temperature, 80 DEG C of outlet temperature, drying time 5min.
Embodiment 4
1) 2.0g OP-10 are added into conical flask, adds 45g deionized waters magnetic agitation to emulsifier and dissolves, successively Be added butyl acrylate 70g, Isooctyl acrylate monomer 78g, vinylacetate 10g, methyl methacrylate 25g, methacrylic acid Hydroxyl ethyl ester 2g, acrylic acid 2g, stirring (mixing speed 300r/min) 25min form pre-emulsion.
2) to equipped with thermometer, condenser pipe, agitating device 500ml four-hole boiling flasks in 0.3g NaHCO are added3, add Deionized water 40ml, 80 DEG C of reaction temperature, stirring to dissolving；30% pre-emulsion and 15g ammonium persulfate aqueous solutions are added dropwise simultaneously, 30min keeps the temperature 30min after dripping off；Remaining pre-emulsion and 6g ammonium persulfate aqueous solutions is added dropwise simultaneously again, 3.5h is added dropwise.
3) reaction temperature rises to 90 DEG C, keeps the temperature 1h under agitation, obtains water soluble acrylic acid ester pressure-sensitive emulsion.
4) it is sequentially added into step 3) and accounts for 0.1% coupling agent gamma-aminopropyl-triethoxy-silane of emulsion quality, accounts for breast Change liquid quality 5%SiO2, account for the polyvinyl alcohol water solution of emulsion quality 25wt%, after 45 DEG C are disperseed 10min with 6000r/min Room temperature ultrasound 15min.
5) white nucleocapsid acrylic powder end glue, spray drying are obtained by product that step 4) obtains is spray-dried Technological parameter is 170 DEG C of inlet temperature, 85 DEG C of outlet temperature, drying time 7min.
Observation can obtain, and the nucleocapsid acrylate powder glue that embodiment 1-4 is obtained is white powdered.
Above-described embodiment products obtained therefrom is tested for the property, the results are shown in Table 1.
1 product of table is tested for the property
Solid content is calculated as follows in table 1：
X=m1/ m × 100%
In formula：X is solid content (wt%)；m1For monomer gross mass (g)；M is lotion gross mass (g)
Water absorption rate is calculated as follows：
A=(a2‐a1)/a1× 100%
In formula：A is water absorption rate (wt%)；a1Quality (g) before absorbing water for plastic powder；a2Quality after absorbing water for plastic powder (g)；
Initial bonding strength is tested：According to GB/T 4852-2002 standards, adhesive initial bonding strength is surveyed；
Peel test force：According to GB/T 2792-1998 standards, adhesive peeling force is surveyed；
Holding power is tested：According to GB/T 485-1998 standards, adhesive holding power is surveyed.
As shown in table 1, the nucleocapsid acrylate powder glue that the present invention obtains has good comprehensive performance, including first Viscous force is up to 12-16#, peeling force：9.6-12.4N/25mm, holding power：212-347h；Also there is lower water absorption rate： 7.7%-15.8% and high solids content：63%-70%.The 180 ゜ strippings overcome present in the pressure sensitive adhesive of the prior art are strong Low, holding power is small, and gluing knotting strength is not high, poor water resistance and when solid content is more than 55%, and viscosity can steeply rise, and cause The shortcomings that gel implode.
The present invention initiates coupling agent and modifies acrylate polymer emulsion with dewatering nano material, is made using coupling agent hydrophobic Property Nano-meter SiO_22Or calcium carbonate is uniformly firmly combined together with acrylate polymer, utilizes Nano-meter SiO_22Or calcium carbonate and It is strong in conjunction with the adhesive property of pressure sensitive adhesive can be greatly enhanced between coupling agent and base material.Meanwhile it being made by being spray-dried Powder pressure sensitive adhesive be different from existing liquid adhesive, it is solid, and paper bag packing can be used as cement, is not required to iron Bucket or plastic barrel packaging, can not only be greatly lowered cost, but also can reduce volatile organic matter (VOC), be readily transported and protect for a long time It hides.
The present invention finally uses spray dried form, is rapidly and efficiently prepared for nucleocapsid acrylate powder glue, will be even Join agent and nano-particle and the uniform firm connection of adhesive together, while greatly shortening required preparation time.
The nucleocapsid acrylate powder glue of the present invention, not only ensure that adhesive property, but also since coupling agent, hydrophobicity are received Rice SiO2Or the presence of calcium carbonate so that plastic powder also has pressure-sensitive property, enhanced water resistance, can be sealed in complex precise equipment Middle use, production cost is low, easy to operate, environmentally protective, and application prospect is extensive.
It is defined it should be noted that above-described embodiment is not the conception to the present invention and protection domain.It is not departing from Under the premise of the present invention conceives, the various modifications and improvement that ordinary people in the field makes technical scheme of the present invention should all Drop into protection scope of the present invention.

Claims (10)

1. a kind of preparation method of nucleocapsid acrylate powder glue, it is characterised in that include the following steps：
1) emulsifier is added to the water, adds soft monomer, hard monomer, functional monomer and is uniformly mixed, magnetic agitation 10~ 30min forms pre-emulsion；The soft monomer, hard monomer, functional monomer constitute monomer；The emulsifier additive amount is that monomer is total The 1~3% of quality；The water additive amount is the 20~40% of monomer gross mass；
The soft monomer is vinylacetate, ethyl methacrylate, Isooctyl acrylate monomer, the different certain herbaceous plants with big flowers of acrylic acid, acrylic acid hydroxyl second It is one or more in ester, cyclohexyl acrylate, butyl acrylate；The soft monomer additive amount be monomer gross mass 65~ 82%；
The functional monomer is itaconic acid, acrylic acid, methacrylic acid, acrylamide, hydroxy-ethyl acrylate, methacrylic acid It is one or more in hydroxyl ethyl ester, hydroxypropyl acrylate, hydroxy propyl methacrylate；The functional monomer additive amount is monomer The 1~1.5% of gross mass；
The hard monomer is one or more in methyl methacrylate, acrylonitrile, styrene, methyl acrylate；It is described hard Monomer additive amount is the 12~17% of monomer gross mass；
2) 75~80 DEG C are warming up to, buffer solution is added in the reactor, in N2In atmosphere, while 20~50% mass are added dropwise The initiator of pre-emulsion and 1/2~3/4 mass, is stirred to react 30~60min, prepares initial latex；After keeping the temperature 10~40min, Remaining initiator and pre-emulsion is added dropwise, chain-transferring agent is added, time for adding is 3~4h；
3) after completion of dropwise addition, 80~90 DEG C of heat preservation 1~2h cooling discharges form emulsion；
4) coupling agent, nano-calcium carbonate or SiO are added into step 3)2, polyvinyl alcohol water solution, 40~50 DEG C dispersion 3~ Room temperature is ultrasonically treated 10~30min after 15min；The coupling agent is gamma-aminopropyl-triethoxy-silane, 3- glycidyl ethers Hydroxypropyl methyl diethoxy silane, γ-(the third oxygen of 2,3- epoxies) propyl trimethoxy silicane, vinyltrimethoxysilane, γ- It is one or more in mercaptopropyl trimethoxysilane, γ-(methacryloxypropyl) propyl trimethoxy silicane；
5) nucleocapsid acrylate powder glue is obtained by step 4) products therefrom is spray-dried.
2. the preparation method of nucleocapsid acrylate powder glue according to claim 1, it is characterised in that：The emulsification Agent is polyoxyethylene Zhong Xin phenolic ethers -10 (OP-10), lauryl sodium sulfate (SDS) nonylphenol polyoxyethylene ether (TX-10), second One in oxygroup nonyl phenol sulfosuccinic acid semiester disodium, neopelex (LAS) and polysorbas20 (Tween-20) Kind is a variety of.
3. the preparation method of nucleocapsid acrylate powder glue according to claim 1, it is characterised in that：The buffering Solution is the NaHCO of 0.5wt~0.7wt%3Aqueous solution.
4. the preparation method of nucleocapsid acrylate powder glue according to claim 1, it is characterised in that：The initiator For ammonium sulfate, potassium peroxydisulfate, sodium hydrogensulfite, azodiisobutyronitrile it is one or more.
5. the preparation method of nucleocapsid acrylate powder glue according to claim 1, it is characterised in that：The initiation Agent additive amount is the 0.1%~0.8% of monomer gross mass.
6. the preparation method of nucleocapsid acrylate powder glue according to claim 1, it is characterised in that：The chain turns Shifting agent is lauryl mercaptan, and dosage is the 0.1~0.5% of monomer gross mass.
7. the preparation method of nucleocapsid acrylate powder glue according to claim 1, it is characterised in that：The spraying Dry technological parameter is 150~180 DEG C of inlet temperature, 75~90 DEG C of outlet temperature, 3~10min of drying time.
8. the preparation method of nucleocapsid acrylate powder glue according to claim 1, it is characterised in that：The coupling Agent accounts for the 0.01~0.15% of emulsion quality；The nano-calcium carbonate or SiO2Account for the 2~5% of emulsion quality；It is described Polyvinyl alcohol water solution account for 10wt~30wt% of emulsion quality.
9. the preparation method of nucleocapsid acrylate powder glue according to claim 1, it is characterised in that：Described is described Buffer solution total addition level is the 0.1~0.5% of monomer total amount；The initiator total addition level be monomer total amount 0.4~ 2.0%；The chain-transferring agent additive amount is the 0.1%~0.8% of monomer total amount.
10. a kind of nucleocapsid acrylate powder glue being prepared by any one of claim 1~9 preparation method； The pressure sensitive adhesive is white powdered, and initial bonding strength reaches 12-19#, peeling force 9.0-13.0N/25mm, holding power 200-350h； Water absorption rate is 1.2%-15.0%, solid content 70%-85%.
CN201810236590.6A 2018-03-21 2018-03-21 Acrylate powder adhesive with core-shell structure and preparation method thereof Expired - Fee Related CN108504313B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201810236590.6A CN108504313B (en) 2018-03-21 2018-03-21 Acrylate powder adhesive with core-shell structure and preparation method thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201810236590.6A CN108504313B (en) 2018-03-21 2018-03-21 Acrylate powder adhesive with core-shell structure and preparation method thereof

Publications (2)

Publication Number Publication Date
CN108504313A true CN108504313A (en) 2018-09-07
CN108504313B CN108504313B (en) 2020-02-18

Family

ID=63377919

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201810236590.6A Expired - Fee Related CN108504313B (en) 2018-03-21 2018-03-21 Acrylate powder adhesive with core-shell structure and preparation method thereof

Country Status (1)

Country Link
CN (1) CN108504313B (en)

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101423735A (en) * 2008-12-05 2009-05-06 武汉科技学院 Method for preparing environment-friendly type organosilicon modified acrylic ester binding agent
CN102766241A (en) * 2011-05-06 2012-11-07 北京化工大学 Core-shell structured nano-silica/polyacrylate emulsion and its preparation method
WO2017222979A1 (en) * 2016-06-20 2017-12-28 Arkema Inc. Hydrolysis resistant vinyl ester containing latexes
CN107629736A (en) * 2017-09-07 2018-01-26 滁州市光威化工有限公司 A kind of nano-silicon dioxide modified fire-retardant the High-speed Cigarette Adhesives for Filter Tipping of hud typed acrylate and vinyl acetate emulsion and preparation method

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101423735A (en) * 2008-12-05 2009-05-06 武汉科技学院 Method for preparing environment-friendly type organosilicon modified acrylic ester binding agent
CN102766241A (en) * 2011-05-06 2012-11-07 北京化工大学 Core-shell structured nano-silica/polyacrylate emulsion and its preparation method
WO2017222979A1 (en) * 2016-06-20 2017-12-28 Arkema Inc. Hydrolysis resistant vinyl ester containing latexes
CN107629736A (en) * 2017-09-07 2018-01-26 滁州市光威化工有限公司 A kind of nano-silicon dioxide modified fire-retardant the High-speed Cigarette Adhesives for Filter Tipping of hud typed acrylate and vinyl acetate emulsion and preparation method

Also Published As

Publication number Publication date
CN108504313B (en) 2020-02-18

Similar Documents

Publication Publication Date Title
CN104497920B (en) Water-based laminating adhesive and preparation method
CN107573469A (en) A kind of preparation method of the Acrylate pressure-sensitive adhesive emulsion of block structure
CN102532403B (en) Shell-structure acrylic emulsion for dispersible glue powder and preparation method of shell-structure acrylic emulsion
CN103849331B (en) A kind of high-peeling strength viscosity controlled water soluble aluminum foil adhesive composition and preparation method
CN106221623A (en) Flexible package aqueous moulds composite glue and preparation method thereof
CN104341547B (en) A kind of polyacrylate closing emulsion and preparation method thereof
CN103601404B (en) A kind of curing compound and preparation method thereof
CN106590477A (en) Acrylate tile back glue emulsion and preparation method thereof
CN105176457A (en) Environmentally-friendly aqueous binder
CN103865439A (en) Double-component aqueous neoprene spray glue
CN108003816A (en) A kind of compound special-purpose aqueous glue of aluminizer and preparation method thereof
CN110218275A (en) A kind of acrylic emulsion that anti-inner corner trim cracks and the aqueous damping coating comprising the lotion
CN102533181B (en) Sealing adhesive and preparation method thereof
CN106753079A (en) The preparation method of nanometer ferroferric oxide modification water-and acrylate magnetic pressure sensitive adhesive
CN106189950B (en) A kind of aqueous, environmental protective high intensity sticker adhesive and preparation method thereof
CN109321171A (en) Aqueous medical dialyzing paper heat-seal adhesive of one kind and preparation method thereof
CN108034018A (en) A kind of water-based sealing latex solution and preparation method thereof
CN106479407B (en) A kind of paper-plastic stick adhesive and preparation method thereof
CN107722882A (en) A kind of acrylate emulsion and preparation method thereof
CN103275260A (en) Preparation method of acrylic plastic-plastic composite latex
CN109777327A (en) A kind of preparation method of high-solid-content and low-viscosity acrylate adhesive lotion
CN108504313A (en) A kind of nucleocapsid acrylate powder glue and preparation method thereof
CN107936880A (en) A kind of non-woven fabric compounded special-purpose aqueous glue and preparation method thereof
CN108250991A (en) One kind can be used for decoration environment-friendly type amylan and preparation method thereof
CN106366255A (en) Preparation method of self-defoaming acrylic emulsion

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant
CF01 Termination of patent right due to non-payment of annual fee
CF01 Termination of patent right due to non-payment of annual fee

Granted publication date: 20200218