CN103554348B - A kind of polymkeric substance, its preparation method and application - Google Patents

Abstract

The invention discloses a kind of co-polymer, this co-polymer is formed by monomer a, b, c copolymerization, and wherein said 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) monomers of one or more mixing in nitrile or derivatives thereof polymerisable monomer; Described monomer b is monomers of one or more mixing in alkenyl silanes class or acryloxy silane class or acrylamido silicane polymerisable monomer; Described monomer c has the polymerisable monomer of cation group or has the monomer of one or more mixing in the polymerisable monomer of anionic group.Compared with the co-polymer that co-polymer of the present invention is group modified with traditional organosilane, 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.

Description

A kind of polymer, its preparation method and application

technical field

The present invention relates to high molecular polymers, in particular to silane-modified interpolymers and compositions containing the interpolymers.

Background technique

Polyester emulsion adhesive is one of the most sold water-based adhesives in the market, and is widely used in paper processing, textiles, building materials, coatings, packaging and other industries. But its film water resistance is poor, especially polyvinyl acetate emulsion commonly known as white latex, its film water resistance is even worse; when used as a binder, its bond strength is low. In order to solve the problems of poor water resistance and low bond strength of polyester emulsion adhesives, a known method is to modify conventional polyester emulsions with groups having a silane structure.

In the Chinese invention patent with the publication number CN1500818, a polyvinyl acetate emulsion modified with organosiloxane is disclosed, and its viscosity and water resistance are obviously improved.

In the Chinese invention patent with the publication number CN1321716, an ethylene/vinyl acetate copolymer emulsion grafted and modified with organosiloxane is disclosed, and its centrifugal stability is correspondingly improved, and no particles are produced.

Although the above two patents have prepared organosilicon-modified polyvinyl acetate and its copolymer emulsion, due to the low content of organosilicon, it is difficult to fully reflect the excellent characteristics of organosilicon modification, and cannot meet the needs of high-grade; The easy hydrolysis of silanes greatly affects the stability of their emulsions during preparation and storage, thus limiting the wide application of organosilane-modified polyesters and their copolymer emulsions.

Since the traditional introduction of organosilane-modified polyester and its copolymer emulsion is generally obtained by emulsion polymerization by free radicals, and due to the easy hydrolysis of organosilane, there is no modified polyester with high silicon content. Examples of esters and their copolymers.

Contents of the invention

The object of the present invention is to provide a new type of copolymer, which has cross-linking reactivity and water solubility. The invention also provides the preparation method and application of the copolymer.

In order to realize the above-mentioned purpose of the invention, the present invention adopts the following technical solutions:

A kind of copolymer, it is characterized in that: copolymer is formed by the copolymerization of monomer a, b, c, wherein:

The monomer a is a monomer having one or more mixed monomers of slightly water-soluble polymerizable monomers or non-water-soluble polymerizable monomers, and the total amount of monomers added is the total mass of polymerizable monomers 45-99.8% of the score.

The monomer b is a monomer having a siloxane group polymerizable monomer or a chlorosilane group polymerizable monomer or a mixture of two or more monomers, and the total amount of the monomers added is the total amount of the polymerizable monomers 0.1%～40% of mass fraction

The monomer c is a monomer having a cationic group polymerizable monomer or an anionic group polymerizable monomer or a mixture of two or more monomers, and the total amount of the monomers added is the total amount of the polymerizable monomers 0.1% to 15% of the mass fraction.

Specifically, the polymerizable monomer having slight water solubility or non-water soluble polymerizable monomer is a1) alkenes or their derivatives or a2) esters or their derivatives or a3) nitriles or their derivatives One or two or more types of monomers that can be polymerized are mixed. The polymerizable monomers of the olefins or their derivatives are selected from ethylene, propylene, butylene, styrene, isopropenylbenzene, etc.; the polymerizable monomers of the esters or their derivatives are selected from methyl acrylate, Ethyl acrylate, Propyl acrylate, Butyl acrylate, Hydroxymethyl acrylate, Hydroxyethyl acrylate, Hydroxypropyl acrylate, Hydroxybutyl acrylate, Methyl methacrylate, Ethyl methacrylate, Propyl methacrylate, Butyl Methacrylate, Hydroxymethyl Methacrylate, Hydroxyethyl Methacrylate, Hydroxypropyl Methacrylate, Hydroxybutyl Methacrylate, Vinyl Formate, Vinyl Acetate, Vinyl Propionate, Valeric Acid Vinyl ester, vinyl laurate, vinyl stearate, vinyl benzoate, etc.; the polymerizable monomers of the nitriles or their derivatives are selected from acrylonitrile, methacrylonitrile, and the like.

Specifically, the polymerizable monomer having a siloxane group or a polymerizable monomer with a chlorosilane group is one of the polymerizable monomers of alkenylsilanes, acryloyloxysilanes, or acrylamidosilanes. A mixture of two or more monomers. Selected from vinyltrimethoxysilane, vinylmethyldimethoxysilane, vinyldimethylmethoxysilane, vinyltriethoxysilane, vinylmethyldiethoxysilane, vinylphenyl Trimethoxysilane, 3-(meth)acrylamide-propyltrimethoxysilane, 3-(meth)acrylamide-propyltriethoxysilane, vinyltrichlorosilane, vinylmethyldichloride Silane, vinyldimethylchlorosilane, 3-(meth)acrylamide-propyltrichlorosilane, methacryloxypropyltriethoxysilane, etc. Preferred are vinyltriethoxysilane, 3-(meth)acrylamide-propyltriethoxysilane, etc., methacryloxypropyltriethoxysilane, methacryloxypropyltrimethoxysilane, etc. Oxysilane, etc.

Specifically, the cationic polymerizable monomer is one or both of quaternary ammonium type, tertiary amine type, secondary amine type, primary amine type, dialdehyde type, and complex type polymerizable monomer. More than one mixed monomer selected from dimethylallylamine, diethylallylamine, dipropylallylamine, dimethylaminoethyl acrylate, dimethylaminoethyl methacrylate , Diethylaminoethyl methacrylate, diethylaminopropyl methacrylate, vinyloxyethyldimethylamine, vinyloxymethyldiethylamine, dimethyldiallyl chloride Ammonium, diethyl diallyl ammonium chloride, diethyl diallyl ammonium bromide, dimethyl diallyl ammonium iodide, methacryloxyethyl trimethyl ammonium chloride, formazan Acryloyloxyethyltriethylammonium chloride, acryloyloxyethyltrimethylammonium chloride, acryloyloxyethyltriethylammonium chloride, 3-(meth)acrylamide-propyltrimethylammonium Ammonium chloride, 3-(meth)acrylamide-propyltriethylammonium chloride, etc. Since basic amine groups have a catalytic effect on the hydrolysis of siloxane groups and chlorosilane groups, they are preferably selected from their corresponding quaternized salts, optionally dimethyl diallyl ammonium chloride , Diethyl diallyl ammonium chloride, diethyl diallyl ammonium bromide, dimethyl diallyl ammonium iodide, methacryloxyethyl trimethyl ammonium chloride, methyl Acryloyloxyethyltriethylammonium chloride, acryloyloxyethyltrimethylammonium chloride, acryloyloxyethyltriethylammonium chloride, 3-(meth)acrylamide-propyltrimethylammonium Ammonium chloride, 3-(meth)acrylamide-propyltriethylammonium chloride, etc.

Specifically, the polymerizable monomer having an anionic group is a carboxylic acid group or a salt thereof, or a sulfonic acid group or a salt thereof, or a sulfuric acid group or a salt thereof, or a phosphoric acid group or a salt thereof One or two or more types of monomers that can be polymerized are mixed. Acrylic acid, methacrylic acid, itaconic acid, maleic acid, maleic anhydride, fumaric acid, aconitic acid, undecylenic acid, oleic acid, elaidic acid, erucic acid, sodium acrylate, sodium methacrylate , Sodium Itaconate, Sodium Maleate, Sodium Fumarate, Sodium Aconitate, Sodium Undecylenate, Sodium Oleate, Sodium Elaidate, Sodium Erucate, Ammonium Acrylate, Ammonium Methacrylate, Itacon Ammonium Acid, Ammonium Maleate, Ammonium Fumarate, Ammonium Aconitate, Ammonium Undecylenate, Ammonium Oleate, Ammonium Elaidate, Ammonium Erucate, Potassium Acrylate, Potassium Methacrylate, Potassium Itaconate, Potassium Maleate, Potassium Fumarate, Potassium Aconitate, Potassium Undecylenate, Potassium Oleate, Potassium Elainate, Potassium Erucate, Allylsulfonic Acid, Vinylsulfonic Acid, Alpha-Alkenylsulfonic Acid acid, allyloxyhydroxypropylsulfonic acid, methacrylsulfonic acid, vinylbenzenesulfonic acid, methacryloyloxyethylsulfonic acid, methacryloxypropylsulfonic acid, methacryloyloxyethylsulfonic acid Sodium sulfonate, potassium methacryloyloxyethylsulfonate, ammonium methacryloyloxyethylsulfonate, 2-methacrylamidoethylsulfonic acid, 2-methacrylamidoethylsulfonic acid Sodium, potassium 2-methacrylamidoethylsulfonate, ammonium 2-methacrylamidoethylsulfonate, sodium allylsulfonate, sodium vinylsulfonate, sodium ɑ-alkenylsulfonate, alkenyl Sodium Propoxy Hydroxypropyl Sulfonate, Sodium Methacryl Sulfonate, Sodium Vinylbenzene Sulfonate, Potassium Allyl Sulfonate, Potassium Vinyl Sulfonate, Potassium Alpha-Alkenyl Sulfonate, Allyloxy Hydroxypropyl Sulfonate Potassium Propyl Sulfonate, Potassium Methacryl Sulfonate, Potassium Vinylbenzene Sulfonate, Ammonium Allyl Sulfonate, Ammonium Vinyl Sulfonate, Ammonium Alpha-Alkenyl Sulfonate, Allyloxy Hydroxypropyl Sulfonate Ammonium, Ammonium Methacrylate, Ammonium Vinylbenzene Sulfonate, Vinyl Sulfate, Monosodium Vinyl Sulfate, Monopotassium Vinyl Sulfate, Monoammonium Vinyl Sulfate, Vinyl Phosphate, Monosodium Vinyl Phosphate, Vinyl Monopotassium phosphate, monoammonium vinyl phosphate, etc. Since the acidic group has a catalytic effect on the hydrolysis of siloxane groups and chlorosilane groups, it is preferably selected from their corresponding salts, optionally sodium acrylate, sodium methacrylate, sodium itaconate, sodium maleate, Sodium fumarate, sodium aconitate, sodium undecylenate, sodium oleate, sodium elaidate, sodium erucate, ammonium acrylate, ammonium methacrylate, ammonium itaconate, ammonium maleate, fumaric acid Ammonium, ammonium aconitate, ammonium undecylenate, ammonium oleate, ammonium elaidate, ammonium erucate, potassium acrylate, potassium methacrylate, potassium itaconate, potassium maleate, potassium fumarate, Potassium cephalic acid, potassium undecylenate, potassium oleate, potassium elaidic acid, potassium erucate, sodium methacryloyloxyethylsulfonate, potassium methacryloyloxyethylsulfonate, methacryloyloxyethylsulfonate Ammonium ethylsulfonate, sodium 2-methacrylamidoethylsulfonate, potassium 2-methacrylamidoethylsulfonate, ammonium 2-methacrylamidoethylsulfonate, allylsulfonic acid Sodium, Sodium Vinyl Sulfonate, Sodium Alpha-Alkenyl Sulfonate, Sodium Allyloxyhydroxypropyl Sulfonate, Sodium Methacrylate Sulfonate, Sodium Vinylbenzene Sulfonate, Potassium Allyl Sulfonate, Vinyl Potassium sulfonate, potassium α-alkene sulfonate, potassium allyloxyhydroxypropyl sulfonate, potassium methylpropene sulfonate, potassium vinylbenzene sulfonate, ammonium allyl sulfonate, ammonium vinyl sulfonate, Ammonium α-alkenylsulfonate, ammonium allyloxyhydroxypropylsulfonate, ammonium methylpropenesulfonate, ammonium vinylbenzenesulfonate, monosodium vinylsulfate, monopotassium vinylsulfate, monoammonium vinylsulfate , monosodium vinyl phosphate, monopotassium vinyl phosphate, monoammonium vinyl phosphate, etc.

As an optional way, under the premise of not impairing the effect of the present invention, the copolymer can further modify its polymer with polymerizable monomer d according to needs, and the polymerizable monomer d is a multifunctional crosslinking agent monomer with 2 or more vinyl groups, dienes, methacrylamide or its derivatives or acrylamide or its derivatives, vinyl ether or hydroxyl-containing vinyl One or a mixture of two or more polymerizable monomers such as base ethers, allyl ethers, monomers with alkylene groups, α-olefin monomers with hydroxyl groups, ketones, etc. The total amount of monomers added is 0.1%-20% of the total mass fraction of the polymerizable monomers, preferably 0.1%-10%, more preferably 0.1%-5%.

For the copolymer constituting the present invention, the monomer a acts as a main structural unit of the copolymer, plays a role as a skeleton, and is the main component of the copolymer. Monomer b is used as a copolymer crosslinking agent to endow the copolymer with a coupling function, through which the copolymer can be generated after hydrolysis of the organosiloxane group or chlorosilane group when it is used as an adhesive or crosslinking agent Silanol, silanol through intramolecular or intermolecular cross-linking coupling or cross-linking and curing with other components in the adhesive with hydroxyl groups to form a strong copolymer film layer, which improves the water resistance of the copolymer or adhesive film and film strength. Monomer c is a strong polar group and has water solubility, which endows the copolymer having monomer a as the main structure with water solubility, and provides convenience, operability and environmental protection.

A kind of preparation method of above-mentioned copolymer, it comprises the following steps in sequence:

A. Polymerization: In the reactor, add organic solvent, monomer a, b, c and free radical initiator, and chain transfer agent that can be added optionally; After deoxygenation, the temperature is then raised, and the polymerization reaction is carried out with stirring at a temperature of 50-80° C.; the polymerization reaction is terminated after the stirring reaction for 60-600 minutes.

The free radical initiator is selected from one or more mixtures of azo initiators or peroxide initiators, and the azo initiators include azobisisobutyronitrile (AIBN), azobisisobutyronitrile Heptyl nitrile (ABVN), etc., peroxidation initiators include dibenzoyl peroxide (BPO), diisopropyl peroxydicarbonate, etc.

The chain transfer agent is a mercaptan compound, preferably one or a mixture of two or more of dodecyl mercaptan (DDT) or n-butyl mercaptan.

The organic solvent is a strong polar solvent, preferably one or a mixture of two or more selected from methanol, ethanol, propanol, butanol and ether.

B. Refining: After the polymerization reaction is completed, the above reaction solution is removed to remove unreacted monomers, and then dried to obtain the copolymer.

The preparation method of the above-mentioned organosilane-modified copolymer can adopt bulk polymerization, emulsion polymerization, suspension polymerization or organic The solution polymerization of the solvent, but considering the easy hydrolysis of the siloxane group and the chlorosilane group in the polymerizable monomer with a siloxane group or the polymerizable monomer with a chlorosilane group, the siloxane group and the chlorosilane group are more avoided. The hydrolysis and condensation of the chlorosilane group will reduce the activity of the crosslinking reaction of the copolymer, and the hydrolysis and condensation of the siloxane group and the chlorosilane group during the production process or the storage process will reduce the stability of the gel phenomenon. Therefore, a non-aqueous organic solvent solution polymerization method is used in the polymerization reaction. At the same time, since the main monomer is water-insoluble, in order to solve the problem of water solubility of the copolymer during use, an ionic monomer with a strong polar group is added during the copolymerization reaction, which endows the slightly water-soluble The polymerizable monomer or the non-water-soluble polymerizable monomer is water-soluble in the copolymer as the main structure, which provides convenience, operability and environmental protection.

As a preferred solution, the addition amount of each reactant in the above step A is respectively: the addition amount of monomer a is 45% to 99.8% of the total mass fraction of polymerizable monomers; the addition amount of monomer b is 45% to 99.8% of the total mass fraction of polymerizable monomers 0.01-40%, preferably 0.1-40%, more preferably 0.5-25%; the amount of monomer c added is 0.01-15% of the total mass fraction of polymerizable monomers, preferably 0.1-15%, more preferably 2 ~10%; free radical initiator—0.01~2% relative to the total mass fraction of polymerizable monomers; chain transfer agent——0.0~1 times relative to the molar number of initiator; solvent—relative to the total mass of polymerizable monomers 0.1 to 6 times the score.

Due to the structural units introduced in the molecular chain, such as: the introduction of amide or ketone units can improve the water solubility of its polymers, and the introduction of ether units can improve the flexibility of its polymers. Therefore, according to its different uses, the copolymer can be further modified with monomer d. Therefore, for the above-mentioned copolymer, during the polymerization reaction, monomer d can also be added for further modification. The monomer d includes multifunctional crosslinking agent monomers, dienes, methacrylamide or its derivatives or acrylamide or its derivatives, vinyl ether or One or two or more of polymerizable monomers such as hydroxyl-containing vinyl ethers, allyl ethers, monomers with alkylene oxides, alpha-olefin monomers with hydroxyl groups, and ketones monomer.

As a preferred solution, in the step A, monomer d can also be added for copolymerization reaction, and the total amount of monomer added is 0.1% to 20% of the total mass fraction of comonomers, preferably 0.1% to 10%, more preferably at 0.1%~5%.

A paper comprising the above-mentioned copolymer.

A plywood comprising the above-mentioned copolymer.

An interior and exterior wall coating of a building contains the above-mentioned copolymer.

The present invention is a kind of copolymerization of polymerizable monomers with slightly water-soluble or non-water-soluble polymerizable monomers and polymerizable monomers with organosilane groups and polymerizable monomers with ionic groups. things. Compared with the traditional organosilane group-modified copolymer, the copolymer of the present invention has high silicon content, good preservation of the organosilane group and stable storage. And because its polymer is modified by ionic groups, its copolymer has water solubility. Therefore, it can make full use of its characteristics. Specifically, it can be used as a coating for paper coating, a paper surface sizing agent and a paper internal strengthening agent to make paper, it can be used as an adhesive to make plywood, and it can be used as a building material. Interior and exterior wall coatings, etc.

detailed description

The present invention is further illustrated by the following examples, but the examples do not limit the scope of the present invention.

The slightly water-soluble monomers of the present invention are relative to water-insoluble monomers (such as ethylenic monomers) and water-soluble monomers (such as acrylic acid or acrylamide monomers), such as esters or derivatives thereof. body.

Example 1

This example is a production example of the copolymer of the present invention.

A. Polymerization

In a 300ml three-necked flask equipped with a stirrer, nitrogen gas and reflux condensing device, add 175g of ethanol, 45g of ethyl acrylate, 22.5g of methacryloxypropyltriethoxysilane, methacryloyloxyethyl Trimethyl ammonium chloride 7.5g, azobisisobutyronitrile (AIBN) 0.75g. Place the three-necked flask in a temperature-controlled water bath, blow nitrogen and oxygen for 30 minutes, raise the temperature to 55°C while stirring, and stop the polymerization reaction after stirring at 55°C for 180 minutes.

B. Refined

After the polymerization reaction is over, remove the nitrogen device, and introduce ethanol vapor into the reaction solution for 30 minutes to drive out unreacted monomers, and then introduce the unreacted monomers into a recovery device for recovery, and then place the above reaction solution in a vacuum Dry in a desiccator at room temperature to obtain the copolymer.

Example 2

This example is another production example of the copolymer of the present invention.

A. Polymerization

In a 300ml three-necked flask equipped with a stirrer, nitrogen and reflux condensing device, add methanol 180g, vinyl acetate 52.5g, vinyltriethoxysilane 16.5g, dimethyl diallyl ammonium chloride 6g , azobisisobutyronitrile (AIBN) 0.9g. Place the three-neck flask in a temperature-controlled water bath, blow nitrogen and oxygen for 30 minutes, raise the temperature to 60°C while stirring, and stop the polymerization reaction after stirring at 60°C for 270 minutes.

B. Refined

After the polymerization reaction is over, remove the nitrogen device, and introduce methanol vapor into the reaction solution for 25 minutes to drive out unreacted monomers, and then introduce the unreacted monomers into a recovery device for recovery, and then put the above reaction solution in a vacuum Dry in a desiccator at room temperature to obtain the copolymer.

Example 3

This example is another production example of the copolymer of the present invention.

A. Polymerization

In a 300ml three-necked flask equipped with a stirrer, nitrogen gas and reflux condensing device, add 180g of ethanol, 1.06g of methylenebisacrylamide, 52.5g of vinyl acetate, 16.5g of vinyltriethoxysilane, dimethyl Diallyl ammonium chloride 6g, azobisisobutyronitrile (AIBN) 0.75g, put the three-necked bottle in a temperature-controlled water bath, blow nitrogen and oxygen for 30min, raise the temperature to 60°C while stirring, at 60°C The polymerization reaction was terminated after stirring for 270 minutes.

B. Refined

After the polymerization reaction is over, remove the nitrogen device, and introduce ethanol vapor into the reaction liquid for 25 minutes to drive out the unreacted monomers, and then introduce the unreacted monomers into the recovery device for recovery, and then put the above reaction liquid in a vacuum drying in a desiccator at room temperature to obtain the copolymer having a branched structure.

Example 4

This example is another production example of the copolymer of the present invention.

A. Polymerization

In a 300ml three-necked flask equipped with a stirrer, nitrogen gas and reflux condensing device, add 175g of ethanol, 35g of ethyl acrylate, 10g of styrene, 22.5g of methacryloxypropyl triethoxysilane, methyl Acryloyloxyethyltrimethylammonium chloride 7.5g, azobisisobutyronitrile (AIBN) 0.35g. Place the three-necked flask in a temperature-controlled water bath, blow nitrogen and oxygen for 30 minutes, raise the temperature to 55°C while stirring, and stop the polymerization reaction after stirring at 55°C for 180 minutes.

B. Refined

After the polymerization reaction is over, remove the nitrogen device, and introduce ethanol vapor into the reaction liquid for 25 minutes to drive out the unreacted monomers, and then introduce the unreacted monomers into the recovery device for recovery, and then put the above reaction liquid in a vacuum Dry in a desiccator at room temperature to obtain the copolymer.

Example 5

This example is another production example of the copolymer of the present invention.

A. Polymerization

In a 300ml three-necked flask equipped with a stirrer, nitrogen gas and reflux condensing device, add 175g of ethanol, 50g of methyl acrylate, 5g of acrylonitrile, 5g of hydroxyethyl acrylate, 3-(meth)acrylamide-propyl tris Ethoxysilane 10g, sodium acrylate 10g, azobisisoheptanonitrile (ABVN) 0.75g. Place the three-neck flask in a temperature-controlled water bath, blow nitrogen and oxygen for 30 minutes, raise the temperature to 50°C while stirring, and stop the polymerization reaction after stirring at 50°C for 200 minutes.

B. Refined

After the polymerization reaction is over, remove the nitrogen device, and introduce ethanol vapor into the reaction solution for 35 minutes to drive out unreacted monomers, and then introduce the unreacted monomers into a recovery device for recovery, and then place the above reaction solution in a vacuum Dry in a desiccator at room temperature to obtain the copolymer.

Example 6

This example is another production example of the copolymer of the present invention.

A. Polymerization

In a 250ml magnetic coupling stirring autoclave equipped with nitrogen and ethylene devices, add methanol 150g, vinyl acetate 44.5g, vinyltriethoxysilane 3.0g, dimethyl diallyl ammonium chloride 3.5g g, azobisisobutyronitrile (AIBN) 0.12g, dodecylmercaptan (DDT) 0.01g. Put the reaction kettle in a temperature-controlled water bath, blow nitrogen and exhaust oxygen for 30 minutes, then close the nitrogen valve and exhaust valve, and then feed 9g of ethylene, then use high-pressure nitrogen to control the pressure at 5.8-6.2MPa, and raise the temperature to 60°C while stirring , The polymerization reaction was terminated after the reaction was stirred at 60° C. for 270 min.

B. Refined

After the polymerization reaction is over, remove the nitrogen device, open the exhaust valve, and introduce methanol vapor into the reaction solution for 25 minutes to drive out the unreacted monomers, and then introduce the unreacted monomers into the recovery device for recovery. Subsequently, the above-mentioned The reaction solution was placed in a vacuum desiccator to dry at room temperature to obtain the copolymer.

Above-mentioned embodiment 1～6 is the embodiment that copolymer is prepared. Wherein in 1～5, selected the scheme that initiator content is higher for use, can not need chain transfer agent, has generated the copolymer polymer of low molecular weight, and its product can be used as crosslinking agent or reinforcing agent; In embodiment 6 , selected the scheme with lower initiator content, can add an appropriate amount of chain transfer agent, generated the copolymer of medium and high molecular weight, its product can be used as adhesive agent; in embodiment 3, selected diene A cross-linking agent, which is added as the monomer d component, can generate the copolymer with a branched structure, and its product can be used as a cross-linking agent or a reinforcing agent.

Example 7

This example is a group of examples of making surface sizing paper using the copolymer prepared in the above-mentioned embodiment 1 as a surface sizing agent

Soak the copolymer prepared in Example 1 in water, heat to dissolve and dilute to obtain an aqueous solution with a mass concentration of 20%, and add it to the hot gelatinized aqueous solution containing 35% oxidized starch and mix evenly, and then oxidize it with hydrogen Sodium adjusts the pH value to 9-10, so that the weight ratio of the solid content of the copolymer/starch reaches 1/50, and prepares a sizing material with a solid content of 20% with water as a surface sizing agent.

On the surface of 80g/m2 ^double -collagen paper, use a metal rod to sizing the above sizing material, apply 1g/ ^m2 according to the dry solid content, and then dry it with hot air to obtain surface sizing paper with high water resistance and high surface strength , The surface roughening speed is up to 320cm/s. Example 8

This example is a set of examples of making high-strength paper using the copolymer prepared in the above-mentioned Example 5 as a paper internal strengthening agent

Soak the copolymer prepared in Example 5 with water, heat to dissolve and dilute, adjust the pH value to 9-10 with sodium hydroxide, and then prepare a 4% aqueous solution with water as a paper internal strengthening agent.

After soaking the waste carton paper in water for 20 minutes, it was decomposed by a standard deflaker for ^20000r , and then it was beaten with a PFI mill. 0.3% (to the fiber mass percentage) the aqueous solution of the copolymer polymer that the embodiment 1 makes is made paper internal strengthening agent, and stirs evenly, adopts the sheet copying machine that Shaanxi University of Science and Technology Machinery Factory produces then, copies into quantitatively 100g/ ^m2 slices and dried, after the slices were subjected to constant temperature and humidity treatment for 24 hours, the physical strength was measured according to the national standard, and the ring pressure index reached 8.8Nm/g.

Example 9

This example is a set of examples for making coated paper by using the copolymer prepared in Example 1 above as paper coating.

Soak the copolymer prepared in Example 1 with water, heat to dissolve and dilute, then adjust the pH value to 9-10 with sodium hydroxide, and prepare a 40% aqueous solution with water.

Soak polyvinyl alcohol (model - 2099) in water, heat to dissolve and dilute to obtain an aqueous solution with a mass concentration of 12%, and mix the above-mentioned copolymer aqueous solution, polyvinyl alcohol aqueous solution and a cationic polymer (such as : polydiallyl dimethyl ammonium chloride) added to the 22% silica aqueous dispersion and mixed evenly, so that the solid content of silica/copolymer/PVA/cationic polymer is based on The weight ratio reaches 100/2/30/5. Finally, add water to prepare a coating with a solid content of 15%.

On the surface of 80g/m ² double-collagen paper, use a metal rod to coat the above-mentioned coating, and apply 10g/m ² according to the dry solid content, and then dry it with hot air to obtain inkjet printing paper, and the printing accuracy can reach 1400dpi.

Example 10

This example is a set of examples of using the copolymer prepared in Example 6 above as a wall coating.

Soak the copolymer prepared in Example 6 in water, heat to dissolve and dilute, then adjust the pH value to 9-10 with sodium hydroxide, and prepare a 40% aqueous solution with water.

Soak polyvinyl alcohol (model - 2099) in water, heat to dissolve and dilute to obtain an aqueous solution with a mass concentration of 12%, and add the above-mentioned copolymer aqueous solution and polyvinyl alcohol aqueous solution to kaolin with a solid content of 65% and heavy In the mixed water dispersion of calcium carbonate, mix well. Make the weight ratio of the solid content basis of kaolin/ground calcium carbonate/copolymer/PVA reach 30/70/3/6, add necessary water, and prepare a coating with a solid content of 45%.

Apply the above paint on the wall of the building with a brush applicator at a dry solid content of 20g/m ² , and obtain a coating with excellent water resistance after drying.

Example 11

This example is a group of examples of making plywood by using the copolymer prepared in the above-mentioned embodiment 4 as an adhesive

Soak the copolymer prepared in Example 4 in water, heat to dissolve and dilute, then adjust the pH value to 9-10 with sodium hydroxide, and prepare a 40% aqueous solution with water.

Soak polyvinyl alcohol (model - 2099) in water, heat to dissolve and dilute to obtain an aqueous solution with a mass concentration of 12%. Then according to the ratio of 100 parts of urea-formaldehyde resin (U/F=1:1.3), 20 parts of filler, 1 part of ammonium chloride, 3 parts of copolymer, and 5 parts of polyvinyl alcohol (model—2099), add urea-formaldehyde resin, filler , ammonium chloride and stir evenly, and finally adjust the solid content to 50-52% with water to obtain urea-formaldehyde resin glue.

Use poplar-poplar-poplar group slab thickness/mm as 1.7-1.7-1.7 for the test, when the amount of glue applied is 275g/m ² (both sides), pre-press for 0.5h after glue coating; 1.0Mpa, temperature 110-120°C, hot pressing for 5 minutes to obtain plywood with high bonding strength.

Effect: The average bonding strength reaches 1.7Mpa after immersion in water at 63°C for 3 hours, and the wood damage rate reaches 100%.

Claims (10)

1. a preparation method for co-polymer, described multipolymer is formed 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) monomers 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 monomers of one or more mixing in alkenyl silanes class or acryloxy silane class or acrylamido silicane polymerisable monomer, and monomer whose total addition level is 0.1 ~ 40% of polymerisable monomer total mass mark,

Described monomer c has the polymerisable monomer of cation group or has monomers of 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 monomers 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,

The preparation method of described co-polymer comprises the following steps successively:

A, polymerization: in the reactor, add organic solvent, monomer and radical initiator; And reactor is placed in temperature control unit, after letting nitrogen in and deoxidizing, then heat up, and polyreaction is carried out in stirring at 50 ~ 80 DEG C of temperature; After stirring reaction 60 ~ 600min, terminate polyreaction,

B, refining: after polyreaction terminates, first above-mentioned reaction solution to be removed unreacted monomer, then dry, obtain described co-polymer.

2. the preparation method of 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, acrylate, Hydroxyethyl acrylate, Propylene glycol monoacrylate, hy-droxybutyl, methyl methacrylate, β-dimethyl-aminoethylmethacrylate, propyl methacrylate, butyl methacrylate, hydroxy methyl methacrylate, hydroxyethyl methylacrylate, Rocryl 410, methacrylate, formic acid vinyl acetate, vinyl acetate, propionate, vinyl valerate, 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. the preparation method of co-polymer according to claim 1, it is characterized in that: described alkenyl silanes class or acryloxy silane class or acrylamido silicane polymerisable monomer are selected from vinyltrimethoxy silane, vinyl methyl dimethoxysilane, vinyl-dimethyl methoxylsilane, vinyltriethoxysilane, vinyl methyl diethoxy silane, vinyl phenyl Trimethoxy silane, 3-(methyl) acrylamide-propyl trimethoxy silicane, 3-(methyl) acrylamide-propyl-triethoxysilicane, methacryloxypropyl, the monomer of one or more mixing in methacryloxypropyl trimethoxy silane.

4. the preparation method of co-polymer according to claim 1, it is characterized in that: described in there is quaternary ammonium type polymerisable monomer 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-hydroxypropyltrimonium chloride, the monomer of one or more mixing in 3-(methyl) 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 sulfonic acid potassium, methacrylic sulfonic acid potassium, vinylbenzenesulfonic acid potassium, allyl sulphonic acid ammonium, vinyl sulfonic acid ammonium, ɑ-olefin sulfonic acid ammonium, allyloxy hydroxypropyl sulfonic acid ammonium, methacrylic sulfonic acid ammonium, vinylbenzenesulfonic acid ammonium, vinylsulfuric acid list sodium, vinylsulfuric acid list potassium, vinylsulfuric 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. the preparation method of co-polymer according to claim 1, 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.

6. the preparation method of co-polymer according to claim 1, it is characterized in that: also comprise in described steps A and add chain-transfer agent, described chain-transfer agent is sulfur alcohol compound, is selected from lauryl mercaptan (DDT) or 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.

7. the co-polymer obtained by the arbitrary described preparation method of claim 1 ~ 6.

8. a paper, is characterized in that: containing the co-polymer obtained by claim arbitrary in claim 1 ~ 6.

9. a glued board, is characterized in that: containing the co-polymer obtained by claim arbitrary in claim 1 ~ 6.

10. a buildings inner, external wall coating, is characterized in that: containing the co-polymer obtained by claim arbitrary in claim 1 ~ 6.