CN103554348A - Polymer and preparation method and application thereof - Google Patents
Polymer and preparation method and application thereof Download PDFInfo
- Publication number
- CN103554348A CN103554348A CN201310504533.9A CN201310504533A CN103554348A CN 103554348 A CN103554348 A CN 103554348A CN 201310504533 A CN201310504533 A CN 201310504533A CN 103554348 A CN103554348 A CN 103554348A
- Authority
- CN
- China
- Prior art keywords
- acid
- monomer
- ammonium
- sodium
- vinyl
- 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
Links
Abstract
The invention discloses a copolymer. The copolymer is prepared through copolymerizing monomers (a, b and c), wherein the monomers a are mixed monomers of one or more than two kinds of slightly-water-soluble or water-insoluble polymerizable monomers of a1) alkenes or derivatives thereof, a2) esters or derivatives thereof and a3) nitriles or derivatives thereof; the monomers b are mixed monomers of one or more than two kinds of polymerizable monomers of alkenyl silanes, acryloxy silanes and acrylamide silanes; the monomers c are mixed monomers of one or more than two kinds of polymerizable monomers with cationic groups and polymerizable monomers with anionic groups. Compared with the traditional organosilane group modified copolymers, the copolymer disclosed by the invention has the advantages that the silicon content is high, the storability of organosilane groups is good, and the storage is stable; polymers are modified by ionic groups, so that the copolymer has water solubility.
Description
Technical field
The present invention relates to high molecular polymer, relate in particular to the composition that there is silane-modified co-polymer and contain this co-polymer.
Background technology
Polyester emulsion tackiness agent, is one of the most salable aqueous adhesive kind in the market, is widely used in the industries such as paper conversion, weaving, building materials, coating, packing.But its glued membrane water resistance is poor, and particularly aqueous polyvinyl acetate emulsion is commonly called as white glue with vinyl, its glued membrane water resistance is poorer; While using as binding agent, its cohesive strength is lower.For solving poor water resistance and low this problem of cohesive strength of polyester emulsion tackiness agent, a kind of known method is, with the group with silane structure, traditional polyester emulsion is carried out to modification.
Publication number is in the Chinese invention patent of CN1500818, has disclosed a kind of aqueous polyvinyl acetate emulsion that carrys out modification with organo-siloxane, and its viscosity and water tolerance obviously improve.
Publication number is in the Chinese invention patent of CN1321716, has disclosed a kind of ethylene/vinyl acetate copolymer emulsion that carrys out graft modification with organo-siloxane, the also corresponding raising of its centrifugal stability, and particle does not produce.
Although upper two patents are prepared organic-silicon-modified polyvinyl acetate (PVA) and copolymer emulsion thereof, because silicone content is low, be difficult to fully demonstrate the excellent specific property after organic-silicon-modified, can not meet the top grade demand of taking second place; And, due to the facile hydrolysis of organosilane, its emulsion in preparation process and in storing stability be a greater impact, therefore limited the widespread use of organosilane-modified polyester and copolymer emulsion thereof.
Because the organosilane-modified polyester of traditional introducing and copolymer emulsion thereof are all generally to adopt to carry out letex polymerization by free radical mode and obtain, and due to the facile hydrolysis of organosilane, therefore, have not yet to see the modified poly ester of high silicon content and the example of co-polymer thereof.
Summary of the invention
The object of this invention is to provide a kind of novel co-polymer, this co-polymer has possessed crosslinking reaction, and tool water-soluble.The present invention also provides the Preparation method and use of this kind of co-polymer simultaneously.
In order to realize foregoing invention object, the present invention has adopted following technical scheme:
, it is characterized in that: co-polymer is to form by monomer a, b, c copolymerization, wherein:
Described monomer a is the monomer with one or more mixing in slightly water-soluble class polymerisable monomer or water-insoluble class polymerisable monomer, and monomer whose total addition level is 45～99.8% of polymerisable monomer total mass mark.
Described monomer b is the monomer with one or more mixing in siloxane groups polymerisable monomer or chlorosilane group polymerisable monomer, and monomer whose total addition level is 0.1%～40% of polymerisable monomer total mass mark
Described monomer c is the monomer that has cationic group polymerisable monomer or have one or more mixing in anionic property group polymerisable monomer, and monomer whose total addition level is 0.1%～15% of polymerisable monomer total mass mark.
Specifically, described in, having slightly water-soluble polymerisable monomer or water-insoluble polymerisable monomer is a1) alkene class or derivatives thereof or a2) ester class or derivatives thereof or a3) monomer of one or more mixing in nitrile or derivatives thereof class polymerisable monomer.Described alkene class or derivatives thereof class polymerisable monomer is selected from ethene, propylene, butylene, vinylbenzene, isopropenylbenzene etc., described ester class or derivatives thereof class polymerisable monomer is selected from methyl acrylate, ethyl propenoate, propyl acrylate, butyl acrylate, vinylformic acid hydroxyl methyl esters, Hydroxyethyl acrylate, Propylene glycol monoacrylate, vinylformic acid hydroxy butyl ester, methyl methacrylate, β-dimethyl-aminoethylmethacrylate, propyl methacrylate, butyl methacrylate, hydroxy methyl methacrylate, hydroxyethyl methylacrylate, Rocryl 410, methacrylic acid hydroxy butyl ester, formic acid vinyl acetate, vinyl acetate, propionate, valeric acid vinyl acetate, vinyl laurate, stearic acid vinyl ester, M-nitro benzoic acid vinyl acetate etc., described nitrile or derivatives thereof class polymerisable monomer is selected from vinyl cyanide, methacrylonitrile etc.
Specifically, described in, having siloxane groups polymerisable monomer or chlorosilane group polymerisable monomer is the monomer of one or more mixing in thiazolinyl silicane or acryloxy silicane or acrylamido silicane polymerisable monomer.Be selected from vinyltrimethoxy silane, vinyl methyl dimethoxysilane, vinyl-dimethyl methoxylsilane, vinyltriethoxysilane, vinyl methyldiethoxysilane, vinyl phenyl Trimethoxy silane, 3-(methyl) acrylamide-propyl trimethoxy silicane, 3-(methyl) acrylamide-propyl-triethoxysilicane, vinyl trichloro silane, vinyl dimethyl dichlorosilane (DMCS), vinyl-dimethyl base chlorosilane, 3-(methyl) acrylamide-propyltrichlorosilan, methacryloxypropyl triethoxyl silane etc.Preferred vinyl triethoxyl silane, 3-(methyl) acrylamide-propyl-triethoxysilicane etc., methacryloxypropyl triethoxyl silane, methacryloxypropyl trimethoxy silane etc.
Specifically, described have cationic group polymerisable monomer for having quaternary ammonium type, tertiary amine-type, secondary amine type, primary amine type, dialdehyde type, the monomer of one or more mixing in solvay-type polymerisable monomer, be selected from DMAA, Diethyl Allylnime, dipropyl allyl amine, vinylformic acid dimethylin ethyl ester, Dimethylaminoethyl Methacrylate, methacrylic acid diethylin ethyl ester, methacrylic acid diethylin propyl ester, vinyloxy group ethyl dimethyl amine, vinyloxy group methyl diethylamide, dimethyl diallyl ammonium chloride, diethyl diallyl ammonium chloride, diethyl diallyl brometo de amonio, dimethyl diallyl ammonium iodide, MethacryloyloxyethylTrimethyl Trimethyl Ammonium Chloride, methylacryoyloxyethyl triethyl ammonium chloride, acrylyl oxy-ethyl-trimethyl salmiac, acrylyl oxy-ethyl triethyl ammonium chloride, 3-(methyl) acrylamide-oxypropyl trimethyl ammonium chloride, 3-(methyl) acrylamide-propyl group triethyl ammonium chloride etc.Because alkaline amine group has katalysis to the hydrolysis of siloxane groups and chlorosilane group, therefore, preferably from they corresponding quaternised salt, optional dimethyl diallyl ammonium chloride, diethyl diallyl ammonium chloride, diethyl diallyl brometo de amonio, dimethyl diallyl ammonium iodide, MethacryloyloxyethylTrimethyl Trimethyl Ammonium Chloride, methylacryoyloxyethyl triethyl ammonium chloride, acrylyl oxy-ethyl-trimethyl salmiac, acrylyl oxy-ethyl triethyl ammonium chloride, 3-(methyl) acrylamide-oxypropyl trimethyl ammonium chloride, 3-(methyl) acrylamide-propyl group triethyl ammonium chloride etc.
Specifically, described in, having anionic property group polymerisable monomer is the monomer with one or more mixing in hydroxy-acid group or its salt or sulfonic acid group or its salt or sulfate group or its salt or phosphate group or its esters polymerisable monomer.Be selected from vinylformic acid, methacrylic acid, methylene-succinic acid, toxilic acid, maleic anhydride, fumaric acid, equisetic acid, undecylenic acid, oleic acid, elaidic acid, erucic acid, sodium acrylate, sodium methacrylate, sodium itaconate, sodium maleate, sodium fumarate, equisetic acid sodium, undecylenic acid sodium, sodium oleate, elaidic acid sodium, erucic acid sodium, ammonium acrylate, ammonium methacrylate, methylene-succinic acid ammonium, toxilic acid ammonium, ammonium fumarate, equisetic acid ammonium, undecylenic acid ammonium, ammonium oleate, elaidic acid ammonium, erucic acid ammonium, potassium acrylate, methacrylic acid potassium, methylene-succinic acid potassium, maleic acid potassium, Potassium fumarate, equisetic acid potassium, potassium undecylenate, potassium oleate, elaidic acid potassium, erucic acid potassium, allyl sulphonic acid, vinyl sulfonic acid, ɑ-olefin sulfonic acid, allyloxy hydroxypropyl sulfonic acid, methacrylic sulfonic acid, vinylbenzenesulfonic acid, methylacryoyloxyethyl sulfonic acid, methacryloxypropyl sulfonic acid, methylacryoyloxyethyl sodium sulfonate, methylacryoyloxyethyl potassium sulfonate, methylacryoyloxyethyl ammonium sulphonate, 2-methacryloyl amido ethylsulfonic acid, 2-methacryloyl amido ethylsulfonic acid sodium, 2-methacryloyl amido ethylsulfonic acid potassium, 2-methacryloyl amido ethylsulfonic acid ammonium, sodium allyl sulfonate, sodium vinyl sulfonate, ɑ-sodium olefin sulfonate, allyloxy hydroxypropyl azochlorosulfonate acid sodium, methylpropene sodium sulfonate, vinylbenzenesulfonic acid sodium, allyl sulphonic acid potassium, vinyl sulfonic acid potassium, ɑ-olefin sulfonic acid potassium, allyloxy hydroxypropyl potassium sulfonate, methacrylic potassium sulfonate, vinylbenzenesulfonic acid potassium, allyl sulphonic acid ammonium, vinyl sulfonic acid ammonium, ɑ-olefin sulfonic acid ammonium, allyloxy hydroxypropyl ammonium sulphonate, methacrylic ammonium sulphonate, vinylbenzenesulfonic acid ammonium, vinyl sulfuric acid, vinyl sulfuric acid list sodium, vinyl sulfuric acid list potassium, vinyl sulfuric acid list ammonium, vinyl phosphoric acid, vinyl phosphoric acid list sodium, vinyl phosphoric acid list potassium, vinyl phosphoric acid list ammonium etc.Because acidic-group has katalysis to the hydrolysis of siloxane groups and chlorosilane group, therefore, preferably from they corresponding salt, optional sodium acrylate, sodium methacrylate, sodium itaconate, sodium maleate, sodium fumarate, equisetic acid sodium, undecylenic acid sodium, sodium oleate, elaidic acid sodium, erucic acid sodium, ammonium acrylate, ammonium methacrylate, methylene-succinic acid ammonium, toxilic acid ammonium, ammonium fumarate, equisetic acid ammonium, undecylenic acid ammonium, ammonium oleate, elaidic acid ammonium, erucic acid ammonium, potassium acrylate, methacrylic acid potassium, methylene-succinic acid potassium, maleic acid potassium, Potassium fumarate, equisetic acid potassium, potassium undecylenate, potassium oleate, elaidic acid potassium, erucic acid potassium, methylacryoyloxyethyl sodium sulfonate, methylacryoyloxyethyl potassium sulfonate, methylacryoyloxyethyl ammonium sulphonate, 2-methacryloyl amido ethylsulfonic acid sodium, 2-methacryloyl amido ethylsulfonic acid potassium, 2-methacryloyl amido ethylsulfonic acid ammonium, sodium allyl sulfonate, sodium vinyl sulfonate, ɑ-sodium olefin sulfonate, allyloxy hydroxypropyl azochlorosulfonate acid sodium, methylpropene sodium sulfonate, vinylbenzenesulfonic acid sodium, allyl sulphonic acid potassium, vinyl sulfonic acid potassium, ɑ-olefin sulfonic acid potassium, allyloxy hydroxypropyl potassium sulfonate, methacrylic potassium sulfonate, vinylbenzenesulfonic acid potassium, allyl sulphonic acid ammonium, vinyl sulfonic acid ammonium, ɑ-olefin sulfonic acid ammonium, allyloxy hydroxypropyl ammonium sulphonate, methacrylic ammonium sulphonate, vinylbenzenesulfonic acid ammonium, vinyl sulfuric acid list sodium, vinyl sulfuric acid list potassium, vinyl sulfuric acid list ammonium, vinyl phosphoric acid list sodium, vinyl phosphoric acid list potassium, vinyl phosphoric acid list ammonium etc.
As optional mode, do not damaging under the front topic of effect of the present invention, as required, described co-polymer also available polymerisable monomer d carries out further modification to its polymkeric substance, described polymerisable monomer d is multi-group crosslink agent's monomer class with 2 or 2 above vinyl, alkadiene, Methacrylamide or derivatives thereof or acrylamide or derivatives thereof class, the vinyl ethers of vinyl ether or hydroxyl, allyl ether series, the monomer with oxyalkylene, ɑ-the olefin monomer with hydroxyl, the monomer of one or more mixing in the polymerisable monomers such as ketone, monomer whose total addition level is 0.1%～20% of polymerisable monomer total mass mark, preferably 0.1%～10%, more preferably 0.1%～5%.
For forming co-polymer of the present invention, monomer a, as co-polymer agent structure unit, plays skeleton function, is co-polymer main body composition.Monomer b is as crosslinking copolymers agent, give multipolymer tool coupling function, can be using this co-polymer when as tackiness agent or linking agent use by it, after organic siloxane group or the hydrolysis of chlorosilane group, generate silanol, silanol, by molecule or the intermolecular coupling or become firmly multipolymer rete with the group crosslinking curing of other component tool hydroxyl in tackiness agent of being cross-linked with each other, has improved water tolerance and the film strength of co-polymer or adhesive film.Monomer c is strong polar group, and tool is water-soluble, and it is given, and to have monomer a water-soluble at the co-polymer tool as agent structure, and convenience, operability and the feature of environmental protection used are provided.
A preparation method for co-polymer as above, it comprises the following steps successively:
A, polymerization: in reactor, add organic solvent, monomer a, b, c and radical initiator, and the chain-transfer agent can selectivity adding; And reactor is placed in to temperature control unit, after letting nitrogen in and deoxidizing, then heat up, and stir and carry out polyreaction at 50～80 ℃ of temperature; After stirring reaction 60～600min, finish polyreaction.
Described radical initiator is selected from one or more the mixture in azo-initiator or peroxidation class initiator, azo-initiator comprises Diisopropyl azodicarboxylate (AIBN), 2,2'-Azobis(2,4-dimethylvaleronitrile) (ABVN) etc., and peroxidation class initiator comprises dibenzoyl peroxide (BPO), di-isopropyl peroxydicarbonate etc.
Described chain-transfer agent is sulfur alcohol compound, preferably from lauryl mercaptan (DDT) or normal-butyl mercaptan one or more mixture wherein.
Described organic solvent is intensive polar solvent, preferably the mixture of one or more in methyl alcohol, ethanol, propyl alcohol, butanols, ether.
B, refining: after polyreaction finishes, first above-mentioned reaction solution is removed to unreacted monomer, then dry, obtain described co-polymer.
The preparation method of above-mentioned organosilane-modified co-polymer, for thering is the polymerization that slightly water-soluble class polymerisable monomer or water-insoluble class polymerisable monomer are principal monomer, can adopt mass polymerization, letex polymerization, the solution polymerization of suspension polymerization or organic solvent, but consider the facile hydrolysis wherein with siloxanes and chlorosilyl group in siloxane groups polymerisable monomer or chlorosilane group polymerisable monomer, more avoid reducing after the hydrolysis of siloxanes and chlorosilyl group and condensation the activity of co-polymer crosslinking reaction, and hydrolysis and the condensation of siloxanes and chlorosilyl group in process of production or in storage process, the gelatin phenomenon occurring and the stability that reduces, so adopted nonaqueous organic solvent solution polymerization methods in polyreaction.Simultaneously, because main monomer is non-water-soluble, for solving in use water miscible problem of co-polymer, in copolyreaction process, the ionic comonomer that has added strong polar group, this has just given slightly water-soluble class polymerisable monomer or water-insoluble class polymerisable monomer is water-soluble at the co-polymer tool as agent structure, and convenience, operability and the feature of environmental protection used are provided.
As preferred version, in above-mentioned steps A, the addition of each reactant is respectively: monomer a addition is 45～99.8% of polymerisable monomer total mass mark; Monomer b addition is 0.01～40% of polymerisable monomer total mass mark, preferably 0.1～40%, more preferably 0.5～25%; Monomer c addition is 0.01～15% of polymerisable monomer total mass mark, preferably 0.1～15%, more preferably 2～10%; Radical initiator---0.01～2% of relative polymerisable monomer total mass mark; Chain-transfer agent---relative 0.0～1 times of initiator mole number; Solvent---relative 0.1～6 times of polymerisable monomer total mass mark.
Due to the structural unit of introducing in molecular chain, as: the water-soluble that can improve its polymkeric substance in amides or ketone unit, the flexibility that introducing ethers unit can improve its polymkeric substance etc. introduced.So, purposes that also can be different according to it, monomer available d carries out further modification to its co-polymer.Therefore,, for above-mentioned co-polymer, in its polymerization process, also can add monomer d to carry out further modification.Described monomer d comprises one or more the mixed monomers in the polymerisable monomers such as vinyl ethers, the allyl ether series of multi-group crosslink agent's monomer class, alkadiene, Methacrylamide or derivatives thereof or acrylamide or derivatives thereof class, vinyl ether or the hydroxyl with 2 or 2 above vinyl, the monomer with oxyalkylene, the ɑ-olefin monomer with hydroxyl, ketone.
As preferred version, in described steps A, also can add monomer d to carry out copolyreaction, monomer whose total addition level is 0.1%～20% of comonomer total mass mark, preferably 0.1%～10%, more preferably 0.1%～5%.
, contain above-mentioned co-polymer.
, contain above-mentioned co-polymer.
An inner, external wall coating, contains above-mentioned co-polymer.
The present invention will have slightly water-soluble class polymerisable monomer or water-insoluble class polymerisable monomer and have organosilane group polymerisable monomer and have ionic group polymerisable monomer, a kind of co-polymer aggregating into.Co-polymer of the present invention, compares with the co-polymer that traditional organosilane is group modified, and its silicone content is high, and organosilane group keeping quality is good, stable storing.And because its polymkeric substance is by ionic group modification, its co-polymer tool water-soluble.Therefore, can make full use of its characteristic, specifically, can be used as: the coating that Paper Coating is used, paper surface sizing agent and internal paper strengthening agent are made paper, can be used as tackiness agent and make glued board, can be used as buildings inner, external wall coating etc.
Embodiment
The present invention is further elaborated by the following examples, but embodiment does not limit the scope of the invention.
Slightly water-soluble monomer of the present invention is relatively water-insoluble monomer (as vinyl monomer) and water-soluble monomer (as vinylformic acid or acrylamide monomers), such as ester class or derivatives thereof class monomer.
Embodiment 1
The manufacture embodiment that this example is co-polymer of the present invention.
A, polymerization
In the 300ml there-necked flask of agitator, logical nitrogen and reflux condensate device is housed, add successively ethanol 175g, ethyl propenoate 45g, methacryloxypropyl triethoxyl silane 22.5g, MethacryloyloxyethylTrimethyl Trimethyl Ammonium Chloride 7.5g, Diisopropyl azodicarboxylate (AIBN) 0.75g.There-necked flask is placed in to temperature control water bath, drum nitrogen deoxygenation 30min, warming while stirring to 55 ℃ finishes polyreaction after 55 ℃ of stirring reaction 180min.
B, refining
After polyreaction finishes, shift out logical nitrogen device, and import ethanol steam 30min in reaction solution, evict unreacted monomer from, evict unreacted monomer from and introduce retrieving arrangement recovery, subsequently, above-mentioned reaction solution is placed in to vacuum drier and is at room temperature dried, obtain described co-polymer.
Embodiment 2
Another that this example is co-polymer of the present invention manufactured embodiment.
A, polymerization
In the 300ml there-necked flask of agitator, logical nitrogen and reflux condensate device is housed, add successively methyl alcohol 180g, vinyl acetate 52.5g, vinyltriethoxysilane 16.5g, dimethyl diallyl ammonium chloride 6g, Diisopropyl azodicarboxylate (AIBN) 0.9g.There-necked flask is placed in to temperature control water bath, drum nitrogen deoxygenation 30min, warming while stirring to 60 ℃ finishes polyreaction after 60 ℃ of stirring reaction 270min.
B, refining
After polyreaction finishes, shift out logical nitrogen device, and import methanol vapor 25min in reaction solution, evict unreacted monomer from, evict unreacted monomer from and introduce retrieving arrangement recovery, subsequently, above-mentioned reaction solution is placed in to vacuum drier and is at room temperature dried, obtain described co-polymer.
Embodiment 3
Another that this example is co-polymer of the present invention manufactured embodiment.
A, polymerization
In the 300ml there-necked flask of agitator, logical nitrogen and reflux condensate device is housed, add successively ethanol 180g, methylene-bisacrylamide 1.06g, vinyl acetate 52.5g, vinyltriethoxysilane 16.5g, dimethyl diallyl ammonium chloride 6g, Diisopropyl azodicarboxylate (AIBN) 0.75g, is placed in temperature control water bath by there-necked flask, drum nitrogen deoxygenation 30min, warming while stirring to 60 ℃ finishes polyreaction after 60 ℃ of stirring reaction 270min.
B, refining
After polyreaction finishes, shift out logical nitrogen device, and import ethanol steam 25min in reaction solution, evict unreacted monomer from, evict unreacted monomer from and introduce retrieving arrangement recovery, subsequently, above-mentioned reaction solution is placed in to vacuum drier and is at room temperature dried, obtain and have the described co-polymer of branched structure.
Embodiment 4
Another that this example is co-polymer of the present invention manufactured embodiment.
A, polymerization
In the 300ml there-necked flask of agitator, logical nitrogen and reflux condensate device is housed, add successively ethanol 175g, ethyl propenoate 35g, vinylbenzene 10g, methacryloxypropyl triethoxyl silane 22.5g, MethacryloyloxyethylTrimethyl Trimethyl Ammonium Chloride 7.5g, Diisopropyl azodicarboxylate (AIBN) 0.35g.There-necked flask is placed in to temperature control water bath, drum nitrogen deoxygenation 30min, warming while stirring to 55 ℃ finishes polyreaction after 55 ℃ of stirring reaction 180min.
B, refining
After polyreaction finishes, shift out logical nitrogen device, and import ethanol steam 25min in reaction solution, evict unreacted monomer from, evict unreacted monomer from and introduce retrieving arrangement recovery, subsequently, above-mentioned reaction solution is placed in to vacuum drier and is at room temperature dried, obtain described co-polymer.
Embodiment 5
Another that this example is co-polymer of the present invention manufactured embodiment.
A, polymerization
In the 300ml there-necked flask of agitator, logical nitrogen and reflux condensate device is housed, add successively ethanol 175g, methyl acrylate 50g, vinyl cyanide 5g, Hydroxyethyl acrylate 5g, 3-(methyl) acrylamide-propyl-triethoxysilicane 10g, sodium acrylate 10g, 2,2'-Azobis(2,4-dimethylvaleronitrile) (ABVN) 0.75g.There-necked flask is placed in to temperature control water bath, drum nitrogen deoxygenation 30min, warming while stirring to 50 ℃ finishes polyreaction after 50 ℃ of stirring reaction 200min.
B, refining
After polyreaction finishes, shift out logical nitrogen device, and import ethanol steam 35min in reaction solution, evict unreacted monomer from, evict unreacted monomer from and introduce retrieving arrangement recovery, subsequently, above-mentioned reaction solution is placed in to vacuum drier and is at room temperature dried, obtain described co-polymer.
Embodiment 6
Another that this example is co-polymer of the present invention manufactured embodiment.
A, polymerization
At the 250ml magnetic coupling that logical nitrogen and ethylene unit are housed, stir in autoclave, add successively methyl alcohol 150g, vinyl acetate 44.5g, vinyltriethoxysilane 3.0g, dimethyl diallyl ammonium chloride 3.5g, Diisopropyl azodicarboxylate (AIBN) 0.12g, lauryl mercaptan (DDT) 0.01g.Reactor is placed in to temperature control water bath, after drum nitrogen deoxygenation 30min, close logical nitrogen valve and vent valve, then pass into ethene 9g, use subsequently high pressure nitrogen control pressure 5.8～6.2MPa, warming while stirring to 60 ℃ finishes polyreaction after 60 ℃ of stirring reaction 270min.
B, refining
After polyreaction finishes, shift out logical nitrogen device, open vent valve, and import methanol vapor 25min in reaction solution, evict unreacted monomer from, evict unreacted monomer from and introduce retrieving arrangement recovery, subsequently, above-mentioned reaction solution is placed in to vacuum drier and is at room temperature dried, obtain described co-polymer.
Above-described embodiment 1～6th, embodiment prepared by multipolymer.Wherein, in 1～5, selected the scheme that initiator content is higher, can generate low-molecular-weight co-polymer without chain-transfer agent, its product can make linking agent or toughener is used; In executing example 6, selected the scheme that initiator content is lower, can add appropriate chain-transfer agent, generated the co-polymer of middle and high molecular weight, its product can be used as glue paste; In embodiment 3, selected alkadiene linking agent, the scheme adding as monomer d composition, can generate the described co-polymer with branched structure, and its product can make linking agent or toughener is used.
Embodiment 7
This example is for adopting the prepared co-polymer of above-described embodiment 1 to make one group of embodiment that Surface Size is made size press coated paper
By the prepared co-polymer of embodiment 1 be soaked in water, heating for dissolving and dilution, make mass concentration and be 20% the aqueous solution, and be added to containing mixing in the hot gelatinization aqueous solution of 35% Sumstar 190, with sodium hydroxide, regulate pH value to 9～10 again, make the weight ratio of the solids component benchmark of co-polymer/starch reach 1/50, and water to be modulated into solid content be 20% sizing material, make Surface Size.
At 80g/m
2on two collagen paper surface, use metal bar to carry out the above-mentioned sizing material of top sizing to it, press dry solid content and be coated with 1g/m
2, then warm air drying obtains the size press coated paper of enhanced water resistance, high surface strength, and surface galling speed reaches 320cm/s.Embodiment 8
This example is for adopting the prepared co-polymer of above-described embodiment 5 to make one group of embodiment of high-strength paper as internal paper strengthening agent
By the prepared co-polymer of embodiment 5 be soaked in water, heating for dissolving dilution, with sodium hydroxide, regulate pH value to 9～10, then water is modulated into 4% the aqueous solution and makes internal paper strengthening agent.
By litter decoration paper, be soaked in water after 20min, through standard fluffer, discongest 20000r, then adopt the making beating of PFI mill, its beating process condition is: beating consistency 9%, final beating degree reaches 20 ± 2
0after SR, by solid content, add 0.3%(to fiber quality percentage ratio) the aqueous solution of embodiment 1 prepared co-polymer make internal paper strengthening agent, and stir, the handsheet machine that then adopts machine works of Shaanxi Tech Univ to produce, copying into is quantitatively 100g/m
2handsheet dry, this handsheet, after the fixed temperature and humidity of 24 hours is processed, is measured its physical strength according to national standard, its ring crush index reaches 8.8N.m/g.
Embodiment 9
This example is for adopting the prepared co-polymer of above-described embodiment 1 to make one group of embodiment that paper coating is made White Board.
By the prepared co-polymer of embodiment 1 be soaked in water, heating for dissolving dilution, then regulate pH value to 9～10 with sodium hydroxide, water is modulated into 40% the aqueous solution.
By polyvinyl alcohol (model-2099) be soaked in water, heating for dissolving and dilution, make mass concentration and be 12% the aqueous solution, and to add the above-mentioned co-polymer aqueous solution, polyvinyl alcohol water solution and the cationic polymers (as: polydiene propyl-dimethyl ammonia chloride) that plays tint retention to mass percent be to mix in 22% silica aqueous dispersion, make the weight ratio of the solids component benchmark of silicon-dioxide/co-polymer/PVA/ cationic polymers reach 100/2/30/5.Finally, adding water, to be modulated into solid content be 15% coating.
At 80g/m
2on the surface of two collagen paper, use metal bar coating above-mentioned coating, press dry solid content and be coated with 10g/m
2, complete rear warm air drying obtains Alhue paper, and its printing precision can reach 1400dpi.
Embodiment 10
This example is for adopting the prepared co-polymer of above-described embodiment 6 to make one group of embodiment of coating for wall surface.
By the prepared co-polymer of embodiment 6 be soaked in water, heating for dissolving dilution, then regulate pH value to 9～10 with sodium hydroxide, water is modulated into 40% the aqueous solution.
By polyvinyl alcohol (model-2099) be soaked in water, heating for dissolving and dilution, make mass concentration and be 12% the aqueous solution, and to add the above-mentioned co-polymer aqueous solution, polyvinyl alcohol water solution to solid content be that the mixing water of 65% kaolin and water-ground limestone disperses, in liquid, to mix.Make the weight ratio of the solids component benchmark of kaolin/water-ground limestone/co-polymer/PVA reach 30/70/3/6, add necessary water, be modulated into solid content and be 45% coating.
With hairbrush spreader, above-mentioned coating is applied on building wall, presses dry solid content and be coated with 20g/m
2, after being dried, obtain the coating having excellent water-resistance.
Embodiment 11
This example is for adopting the prepared co-polymer of above-described embodiment 4 to make one group of embodiment that tackiness agent is made glued board
By the prepared co-polymer of embodiment 4 be soaked in water, heating for dissolving dilution, then regulate pH value to 9～10 with sodium hydroxide, water is modulated into 40% the aqueous solution.
By polyvinyl alcohol (model-2099) be soaked in water, heating for dissolving dilution, make mass concentration and be 12% the aqueous solution.Press again 100 parts of urea-formaldehyde resins (U/F=1:1.3), 20 parts of fillers, 1 part of ammonium chloride, 3 parts of co-polymers, the ratio that polyvinyl alcohol (model-2099) is 5 parts, adds urea-formaldehyde resin, filler, ammonium chloride also stirs, and it is 50～52% to obtain urea-formaldehyde resin adhesive that last water is adjusted to solid content.
With poplar-poplar-poplar assembly thickness of slab/mm, be that 1.7-1.7-1.7 tests, as resin added 275g/m
2(two-sided), precompressed 0.5h after gluing; Reusable heat pressure pressure 1.0Mpa, 110～120 ℃ of temperature, hot pressing 5min obtains the glued board of high bonding strength.
Effect: 63 ℃ of average bonding strengths of water logging 3h reach 1.7Mpa, and timber breakage rate reaches 100%.
Claims (10)
1. a co-polymer, is characterized in that: co-polymer is to form by monomer a, b, c copolymerization, wherein:
Described monomer a is slightly water-soluble or non-water-soluble a1) alkene class or derivatives thereof or a2) ester class or derivatives thereof or a3) monomer of one or more mixing in nitrile or derivatives thereof polymerisable monomer, monomer whose total addition level is 45～99.8% of polymerisable monomer total mass mark
Described monomer b is the monomer of one or more mixing in thiazolinyl silicane or acryloxy silicane or acrylamido silicane polymerisable monomer, and monomer whose total addition level is 0.1～40% of polymerisable monomer total mass mark,
Described monomer c is the monomer that has the polymerisable monomer of cation group or have one or more mixing in the polymerisable monomer of anionic group, described in there is cation group polymerisable monomer be quaternary ammonium type class polymerisable monomer; The described polymerisable monomer with anionic group is the monomer of one or more mixing in carboxylate salt or sulfonate or vitriol or phosphoric acid salt polymerisable monomer, and monomer whose total addition level is 0.1～15% of polymerisable monomer total mass mark.
2. co-polymer according to claim 1, is characterized in that: described alkene class or derivatives thereof class polymerisable monomer is selected from the monomer of one or more mixing in ethene, propylene, butylene, vinylbenzene, isopropenylbenzene, described ester class or derivatives thereof class polymerisable monomer is selected from methyl acrylate, ethyl propenoate, propyl acrylate, butyl acrylate, vinylformic acid hydroxyl methyl esters, Hydroxyethyl acrylate, Propylene glycol monoacrylate, vinylformic acid hydroxy butyl ester, methyl methacrylate, β-dimethyl-aminoethylmethacrylate, propyl methacrylate, butyl methacrylate, hydroxy methyl methacrylate, hydroxyethyl methylacrylate, Rocryl 410, methacrylic acid hydroxy butyl ester, formic acid vinyl acetate, vinyl acetate, propionate, valeric acid vinyl acetate, vinyl laurate, stearic acid vinyl ester, the monomer of one or more mixing in M-nitro benzoic acid vinyl acetate, described nitrile or derivatives thereof class polymerisable monomer is selected from the monomer of one or more mixing in vinyl cyanide, methacrylonitrile.
3. co-polymer according to claim 1, it is characterized in that: described thiazolinyl silicane or acryloxy silicane or acrylamido silicane polymerisable monomer are selected from vinyltrimethoxy silane, vinyl methyl dimethoxysilane, vinyl-dimethyl methoxylsilane, vinyltriethoxysilane, vinyl methyldiethoxysilane, vinyl phenyl Trimethoxy silane, 3-(methyl) acrylamide-propyl trimethoxy silicane, 3-(methyl) acrylamide-propyl-triethoxysilicane, methacryloxypropyl triethoxyl silane, the monomer of one or more mixing in methacryloxypropyl trimethoxy silane.
4. co-polymer according to claim 1, it is characterized in that: described in there is quaternary ammonium type polymerisable monomer and be selected from dimethyl diallyl ammonium chloride, diethyl diallyl ammonium chloride, diethyl diallyl brometo de amonio, dimethyl diallyl ammonium iodide, MethacryloyloxyethylTrimethyl Trimethyl Ammonium Chloride, methylacryoyloxyethyl triethyl ammonium chloride, acrylyl oxy-ethyl-trimethyl salmiac, acrylyl oxy-ethyl triethyl ammonium chloride, 3-(methyl) acrylamide-oxypropyl trimethyl ammonium chloride, 3-(methyl) monomer of one or more mixing in acrylamide-propyl group triethyl ammonium chloride, described have carboxylate salt or sulfonate or vitriol or phosphoric acid salt polymerisable monomer and be selected from sodium acrylate, sodium methacrylate, sodium itaconate, sodium maleate, sodium fumarate, equisetic acid sodium, undecylenic acid sodium, sodium oleate, elaidic acid sodium, erucic acid sodium, ammonium acrylate, ammonium methacrylate, methylene-succinic acid ammonium, toxilic acid ammonium, ammonium fumarate, equisetic acid ammonium, undecylenic acid ammonium, ammonium oleate, elaidic acid ammonium, erucic acid ammonium, potassium acrylate, methacrylic acid potassium, methylene-succinic acid potassium, maleic acid potassium, Potassium fumarate, equisetic acid potassium, potassium undecylenate, potassium oleate, elaidic acid potassium, erucic acid potassium, methylacryoyloxyethyl sodium sulfonate, methylacryoyloxyethyl potassium sulfonate, methylacryoyloxyethyl ammonium sulphonate, 2-methacryloyl amido ethylsulfonic acid sodium, 2-methacryloyl amido ethylsulfonic acid potassium, 2-methacryloyl amido ethylsulfonic acid ammonium, sodium allyl sulfonate, sodium vinyl sulfonate, ɑ-sodium olefin sulfonate, allyloxy hydroxypropyl azochlorosulfonate acid sodium, methylpropene sodium sulfonate, vinylbenzenesulfonic acid sodium, allyl sulphonic acid potassium, vinyl sulfonic acid potassium, ɑ-olefin sulfonic acid potassium, allyloxy hydroxypropyl potassium sulfonate, methacrylic potassium sulfonate, vinylbenzenesulfonic acid potassium, allyl sulphonic acid ammonium, vinyl sulfonic acid ammonium, ɑ-olefin sulfonic acid ammonium, allyloxy hydroxypropyl ammonium sulphonate, methacrylic ammonium sulphonate, vinylbenzenesulfonic acid ammonium, vinyl sulfuric acid list sodium, vinyl sulfuric acid list potassium, vinyl sulfuric acid list ammonium, vinyl phosphoric acid list sodium, vinyl phosphoric acid list potassium, the monomer of one or more mixing in vinyl phosphoric acid list ammonium.
5. a preparation method for the co-polymer as described in arbitrary claim in claim 1～4, it comprises the following steps successively:
A, polymerization: in reactor, add organic solvent, monomer and radical initiator; And reactor is placed in to temperature control unit, after letting nitrogen in and deoxidizing, then heat up, and stir and carry out polyreaction at 50～80 ℃ of temperature; After stirring reaction 60～600min, finish polyreaction,
B, refining: after polyreaction finishes, first above-mentioned reaction solution is removed to unreacted monomer, then dry, obtain described co-polymer.
6. the preparation method of co-polymer according to claim 5, is characterized in that: described radical initiator is selected from one or more the mixture in azo-initiator or peroxidation class initiator; Azo-initiator is selected from Diisopropyl azodicarboxylate, 2,2'-Azobis(2,4-dimethylvaleronitrile), and peroxidation class initiator is selected from oxidation dibenzoyl, di-isopropyl peroxydicarbonate.
7. the preparation method of co-polymer according to claim 5, it is characterized in that: in described steps A, also comprise and add chain-transfer agent, described chain-transfer agent is sulfur alcohol compound, is selected from lauryl mercaptan (DDT) or normal-butyl mercaptan one or more mixture wherein; Described organic solvent is intensive polar solvent, is selected from one or more the mixture in methyl alcohol, ethanol, propyl alcohol, butanols, ether.
8. a paper, is characterized in that: contain the co-polymer described in arbitrary claim in claim 1～4.
9. a glued board, is characterized in that: contain the co-polymer described in arbitrary claim in claim 1～4.
10. a buildings inner, external wall coating, is characterized in that: contain the co-polymer described in arbitrary claim in claim 1～4.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310504533.9A CN103554348B (en) | 2013-10-23 | 2013-10-23 | A kind of polymkeric substance, its preparation method and application |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310504533.9A CN103554348B (en) | 2013-10-23 | 2013-10-23 | A kind of polymkeric substance, its preparation method and application |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103554348A true CN103554348A (en) | 2014-02-05 |
| CN103554348B CN103554348B (en) | 2016-03-30 |
Family
ID=50008730
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201310504533.9A Expired - Fee Related CN103554348B (en) | 2013-10-23 | 2013-10-23 | A kind of polymkeric substance, its preparation method and application |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103554348B (en) |
Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104341914A (en) * | 2014-10-14 | 2015-02-11 | 凤阳徽亨商贸有限公司 | Dirt-resistant mold-resistant paint for glass doors and preparation method thereof |
| WO2015197624A1 (en) * | 2014-06-23 | 2015-12-30 | Henkel Ag & Co. Kgaa | Vinyl acetate (co)polymers |
| CN105384884A (en) * | 2015-12-04 | 2016-03-09 | 湖北航天化学技术研究所 | Synthetic method for accelerator used for accelerating curing of chemically degradable propellant |
| CN107474776A (en) * | 2017-09-19 | 2017-12-15 | 常州市宝平不绣钢制品有限公司 | A kind of ultraviolet photo-curing cementing agent |
| CN108004695A (en) * | 2017-12-30 | 2018-05-08 | 绍兴恒钧环保科技有限公司 | Wash the viscous blended yarn weaved fabric short route dyeing and finishing technology of brocade |
| TWI626220B (en) * | 2017-03-06 | 2018-06-11 | Cationic flocculating agent and its application | |
| CN108483980A (en) * | 2018-04-12 | 2018-09-04 | 清华大学 | The preparation method of nano-carbon material-polymer-silicate composite micro-nano particle nucleation agent |
| CN109265123A (en) * | 2018-11-27 | 2019-01-25 | 襄阳华壁新型建材有限公司 | A kind of coal ash autoclaved air-entrained concrete building block and its production method |
| CN113845625A (en) * | 2021-10-25 | 2021-12-28 | 河北匠工新型建筑材料有限公司 | Environment-friendly modified white latex and preparation method thereof |
| CN114014969A (en) * | 2021-11-15 | 2022-02-08 | 上海华峰新材料研发科技有限公司 | Water-soluble polymer and preparation method and application thereof |
| CN115260860A (en) * | 2022-08-23 | 2022-11-01 | 广州大学 | Organic silicon coating and preparation method and application thereof |
| CN117143545A (en) * | 2023-10-31 | 2023-12-01 | 宁德时代新能源科技股份有限公司 | Adhesive and preparation method thereof, negative electrode plate, battery and power utilization device |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1321716A (en) * | 2001-03-22 | 2001-11-14 | 华南农业大学 | Preparation of vinyl acetate/ethylene copolymer emulsion contg organic siloxane group |
| CN1887921A (en) * | 2006-06-08 | 2007-01-03 | 武汉大学 | High performance organo-silicon modified vinyl acetate emulsion and its prepn |
| CN101928534A (en) * | 2010-08-24 | 2010-12-29 | 华南理工大学 | Single-component low temperature self-crossing emulsion adhesive for paper and plastic compounds and preparing method thereof |
-
2013
- 2013-10-23 CN CN201310504533.9A patent/CN103554348B/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1321716A (en) * | 2001-03-22 | 2001-11-14 | 华南农业大学 | Preparation of vinyl acetate/ethylene copolymer emulsion contg organic siloxane group |
| CN1887921A (en) * | 2006-06-08 | 2007-01-03 | 武汉大学 | High performance organo-silicon modified vinyl acetate emulsion and its prepn |
| CN101928534A (en) * | 2010-08-24 | 2010-12-29 | 华南理工大学 | Single-component low temperature self-crossing emulsion adhesive for paper and plastic compounds and preparing method thereof |
Cited By (18)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2015197624A1 (en) * | 2014-06-23 | 2015-12-30 | Henkel Ag & Co. Kgaa | Vinyl acetate (co)polymers |
| CN104341914A (en) * | 2014-10-14 | 2015-02-11 | 凤阳徽亨商贸有限公司 | Dirt-resistant mold-resistant paint for glass doors and preparation method thereof |
| CN105384884A (en) * | 2015-12-04 | 2016-03-09 | 湖北航天化学技术研究所 | Synthetic method for accelerator used for accelerating curing of chemically degradable propellant |
| TWI626220B (en) * | 2017-03-06 | 2018-06-11 | Cationic flocculating agent and its application | |
| CN107474776A (en) * | 2017-09-19 | 2017-12-15 | 常州市宝平不绣钢制品有限公司 | A kind of ultraviolet photo-curing cementing agent |
| CN108004695A (en) * | 2017-12-30 | 2018-05-08 | 绍兴恒钧环保科技有限公司 | Wash the viscous blended yarn weaved fabric short route dyeing and finishing technology of brocade |
| CN108483980B (en) * | 2018-04-12 | 2021-01-26 | 清华大学 | Preparation method of nano carbon material-polymer-silicate composite micro-nano particle nucleating agent |
| CN108483980A (en) * | 2018-04-12 | 2018-09-04 | 清华大学 | The preparation method of nano-carbon material-polymer-silicate composite micro-nano particle nucleation agent |
| CN109265123A (en) * | 2018-11-27 | 2019-01-25 | 襄阳华壁新型建材有限公司 | A kind of coal ash autoclaved air-entrained concrete building block and its production method |
| CN109265123B (en) * | 2018-11-27 | 2021-03-30 | 襄阳华壁新型建材有限公司 | Fly ash autoclaved aerated concrete block and production method thereof |
| CN113845625A (en) * | 2021-10-25 | 2021-12-28 | 河北匠工新型建筑材料有限公司 | Environment-friendly modified white latex and preparation method thereof |
| CN113845625B (en) * | 2021-10-25 | 2023-08-22 | 河北匠工新型建筑材料有限公司 | Environment-friendly modified white latex and preparation method thereof |
| CN114014969A (en) * | 2021-11-15 | 2022-02-08 | 上海华峰新材料研发科技有限公司 | Water-soluble polymer and preparation method and application thereof |
| CN114014969B (en) * | 2021-11-15 | 2023-08-11 | 上海华峰新材料研发科技有限公司 | Water-soluble polymer and preparation method and application thereof |
| CN115260860A (en) * | 2022-08-23 | 2022-11-01 | 广州大学 | Organic silicon coating and preparation method and application thereof |
| CN115260860B (en) * | 2022-08-23 | 2023-08-29 | 广州大学 | Organosilicon coating and preparation method and application thereof |
| CN117143545A (en) * | 2023-10-31 | 2023-12-01 | 宁德时代新能源科技股份有限公司 | Adhesive and preparation method thereof, negative electrode plate, battery and power utilization device |
| CN117143545B (en) * | 2023-10-31 | 2024-03-29 | 宁德时代新能源科技股份有限公司 | Adhesive and preparation method thereof, negative electrode plate, battery and power utilization device |
Also Published As
| Publication number | Publication date |
|---|---|
| CN103554348B (en) | 2016-03-30 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103554348B (en) | A kind of polymkeric substance, its preparation method and application | |
| CN104311716B (en) | Organic silicon modified styrene-acrylate microemulsion reinforcing agent as well as preparation method and application thereof | |
| KR101777888B1 (en) | Surface application of polymers and polymer mixtures to improve paper strength | |
| US5518585A (en) | Neutral sizing agent for base paper stuff with the use of cationic plastics dispersions | |
| CN103333352B (en) | A kind of preparation method of cross-linked graft modified polyvinyl alcohol surface reinforcing agent | |
| KR101836210B1 (en) | Surface application of polymers to improve paper strength | |
| CN104119480B (en) | High-branch type polyvinyl alcohol-acrylamide graft copolymer, preparing method thereof and applications of the copolymer | |
| CN103374854B (en) | A kind of papermaking filler special and the paper containing this filler | |
| CN104254545B (en) | The aqueous polymer dispersion that can be obtained by the emulsion polymerization that free radical in the presence of lignosulphonates causes | |
| CN102958954A (en) | Alkyl-modified vinyl alcohol polymer, and composition, thickener, coating material for paper, coated paper, adhesive and film that contain same | |
| CN108341912A (en) | A kind of preparation method of gluing reinforcing agent | |
| CN101848945A (en) | Glyoxalated N-vinylamine | |
| CN104086709A (en) | High-branch-chain water-soluble cellulose-acrylamide grafted copolymer and preparation method and application thereof | |
| MX2011001884A (en) | Polymer dispersion. | |
| CN101778976B (en) | Internal sizing agent for papermaking and use thereof | |
| CN104628946A (en) | Dry strength agent for coated paper and preparation method of dry strength agent | |
| CN106930141A (en) | A kind of starch base compounded mix and its preparation method and application | |
| JPH0213078B2 (en) | ||
| FI85739C (en) | KOBINDEMEDEL FOER BELAEGGNINGSMASSOR. | |
| CN104177532A (en) | Modified vinyl alcohol-series polymer and its preparation method and use | |
| CN103215825A (en) | Printing adhesive of stone paper wallpaper and preparation method of printing adhesive | |
| CN104592444A (en) | Dry strength agent for packaging paperboard and preparation method thereof | |
| US20170362776A1 (en) | Production of paper and board | |
| CN105693938B (en) | A kind of preparation method of imidizate SMA modified cation styrene-acrylic emulsions | |
| CN103554345A (en) | Preparation method for negative ion organosilicon modified polyacrylate paper reinforcing agent |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| TR01 | Transfer of patent right | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20181206 Address after: Room 105, Office Building of Management Committee of Sha-aquatic Industry Transfer Industrial Park, Shixing County, Shaoguan City, Guangdong Province Patentee after: Shaoguan Aida Paper Co., Ltd. Address before: 510000 No. 152 Xingang West Road, Guangzhou, Guangdong Province Patentee before: Guangdong Industry Technical College |
|
| 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: 20160330 Termination date: 20191023 |