CN111978474B - Preparation method of low-viscosity high-hydroxyl-value polymer surface reinforcing agent for paper - Google Patents

Preparation method of low-viscosity high-hydroxyl-value polymer surface reinforcing agent for paper Download PDF

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CN111978474B
CN111978474B CN202010864759.XA CN202010864759A CN111978474B CN 111978474 B CN111978474 B CN 111978474B CN 202010864759 A CN202010864759 A CN 202010864759A CN 111978474 B CN111978474 B CN 111978474B
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polymer
water
hydroxyl
parts
paper
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CN111978474A (en
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赵新民
邱旭峰
杨柳青
林俊辉
陈宪
王建军
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Zhejiang Hengchuan New Material Co ltd
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F265/00—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00
    • C08F265/04—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00 on to polymers of esters
    • C08F265/06—Polymerisation of acrylate or methacrylate esters on to polymers thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/63—Block or graft polymers obtained by polymerising compounds having carbon-to-carbon double bonds on to polymers
    • C08G18/633—Block or graft polymers obtained by polymerising compounds having carbon-to-carbon double bonds on to polymers onto polymers of compounds having carbon-to-carbon double bonds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/80—Masked polyisocyanates
    • C08G18/8061—Masked polyisocyanates masked with compounds having only one group containing active hydrogen
    • C08G18/8064—Masked polyisocyanates masked with compounds having only one group containing active hydrogen with monohydroxy compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/80—Masked polyisocyanates
    • C08G18/8061—Masked polyisocyanates masked with compounds having only one group containing active hydrogen
    • C08G18/807—Masked polyisocyanates masked with compounds having only one group containing active hydrogen with nitrogen containing compounds
    • C08G18/8077—Oximes
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H19/00—Coated paper; Coating material
    • D21H19/10—Coatings without pigments
    • D21H19/14—Coatings without pigments applied in a form other than the aqueous solution defined in group D21H19/12
    • D21H19/24—Coatings without pigments applied in a form other than the aqueous solution defined in group D21H19/12 comprising macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H21/00—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties
    • D21H21/14—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties characterised by function or properties in or on the paper
    • D21H21/16—Sizing or water-repelling agents
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H21/00—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties
    • D21H21/14—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties characterised by function or properties in or on the paper
    • D21H21/18—Reinforcing agents

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  • Chemical Kinetics & Catalysis (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Polyurethanes Or Polyureas (AREA)

Abstract

The invention discloses a preparation method of a polymer surface reinforcing agent with low viscosity and high hydroxyl value for paper. Firstly, taking diethylene glycol dimethyl ether as a dispersion medium, butyl acrylate, methyl methacrylate, hydroxypropyl acrylate, glycidyl methacrylate and isobornyl methacrylate as raw materials, and adopting a dibenzoyl peroxide and tert-butyl peroxybenzoate dual-initiation system to carry out free radical polymerization on a monomer to prepare an acrylate core; dripping acrylic acid, wherein carboxyl on a molecular chain can react with epoxy groups on glycidyl methacrylate to generate hydroxyl; then adding triethanolamine and dioctyl phthalate for neutralization to form quaternary ammonium salt, and preparing the ultrahigh hydroxyl acrylic resin by high-speed dispersion of water; and finally, constructing the polymer surface reinforcing agent for the paper by using the composite water-based blocked polyisocyanate crosslinking agent. The product of the invention has a multiple cross-linked network structure, and can also form a cross-linked network with a paper base material, thereby efficiently increasing the paper base performance.

Description

Preparation method of low-viscosity high-hydroxyl-value polymer surface reinforcing agent for paper
Technical Field
The invention belongs to a preparation method of a polymer surface reinforcing agent with low viscosity and high hydroxyl value for paper.
Background
The aqueous hydroxy acrylic resin is generally formed by uniformly mixing acrylic acid, acrylate monomers containing hydroxyl groups and functional acrylate monomers, and then adding a proper free radical polymerization initiator. After the reaction is finished, adding organic alcohol amine to neutralize carboxyl on the surface of the polymer, and then adding water to disperse under the condition of high-speed rotation to prepare the acrylic resin emulsion, which is also the most effective method for obtaining the high hydroxyl value aqueous acrylic resin emulsion. When the water-based high-hydroxyl-value acrylic resin and the curing agent are subjected to crosslinking reaction, the number of crosslinking sites is large, and the resin emulsion is easier to form a good compatible system with the curing agent, so that the application range of the composite system is wider; however, the resin has high viscosity, poor stability, difficult storage and insufficient crosslinking density due to too high hydroxyl content, which results in limited application.
The preparation of the hydroxyl acrylic acid aqueous solution dispersoid at home and abroad mainly adopts two methods of solution polymerization and emulsion polymerization. According to the emulsion polymerization method, the aqueous hydroxy acrylic resin emulsion with lower viscosity can be obtained, but the residual emulsifier can not be removed, so that the water resistance of the product is poor. Therefore, the method for preparing the aqueous hydroxy acrylic resin emulsion is usually a solution polymerization method. Cao inferior, etc. adopts propylene glycol methyl ether, ethylene glycol butyl ether, propylene glycol butyl ether, solvent gasoline and mixed solvent compounded by the same as synthetic solvent, and utilizes methyl methacrylate, butyl acrylate, hydroxyethyl methacrylate, acrylic acid and other acrylate monomers to successfully prepare different types of hydroxyacrylic acid aqueous dispersions. Wuchun et al add glycidyl versatate into a mixed solvent of dipropylene glycol butyl ether, propylene glycol butyl ether and propylene glycol methyl ether, divide a monomer mixed solution of hydroxyethyl methacrylate, methyl methacrylate, butyl acrylate, styrene, acrylic acid and isobornyl methacrylate into two parts with equal mass, gradually drop-add, and carry out free radical polymerization under the initiation of di-tert-amyl peroxide; in the process of dropwise adding the monomer mixed solution in the second step, acrylic acid grafted polyester polyol is introduced; and finally, preparing the high hydroxyl value acrylic resin through neutralization and water dispersion, and mixing the high hydroxyl value acrylic resin with a polyisocyanate curing agent Bayhydur to prepare the water-based anticorrosive paint for the surfaces of substrates such as metal, plastic and the like. The high hydroxyl value acrylic resin is directly compounded with the polyisocyanate, and the isocyanate can quickly react with hydroxyl or water in the water-based high hydroxyl value acrylic resin, so that the storage stability of a compound system is poor, and the compound system needs to be used as soon as possible after compounding. In addition, at present, the high hydroxyl value acrylic resin is mostly used for surface water-based coatings of metal, wood and the like, and reports of the high hydroxyl value acrylic resin for paper surface reinforcement are less. The surface of a substrate such as metal, wood and the like needs a high-hardness water-based coating, and the surface enhancement of paper needs a high-strength high-toughness water-based polymer surface enhancing agent. Therefore, the design concept of the polymer structure on the surface of hard substrates such as metal is different from that of soft substrates such as paper.
Disclosure of Invention
Aiming at the problems of poor stability, low crosslinking density and the like of the waterborne high-hydroxyl-value acrylic resin, the invention aims to provide a preparation method of a low-viscosity high-stability ultrahigh-hydroxyl polymer surface reinforcing agent for paper. The product of the invention can realize the unification of stability, crosslinking density and mechanical property, and solves the problems of poor stability, high viscosity and insufficient mechanical property of the waterborne high hydroxyl value acrylate. The product of the invention has a multiple cross-linked network structure, and can also form a cross-linked network with a paper base material, thereby efficiently increasing the paper base performance.
In order to achieve the purpose, the preparation scheme adopted by the invention is as follows:
a preparation method of a polymer surface reinforcing agent with low viscosity and high hydroxyl value for paper comprises the following steps:
taking diethylene glycol dimethyl ether as a dispersion medium, and taking a soft vinyl monomer, a hard vinyl monomer, a hydroxyl-containing vinyl monomer, glycidyl methacrylate and isobornyl methacrylate as raw materials, and mixing to obtain a monomer mixed solution;
the monomer mixed solution adopts a dibenzoyl peroxide and tert-butyl peroxybenzoate dual-initiation system to carry out free radical polymerization to prepare an acrylate core system;
adding an acrylic monomer, dibenzoyl peroxide and tert-butyl peroxybenzoate into the monomer mixed solution, uniformly mixing, and then dropwise adding into an acrylate core system to prepare a polymer with a cross-linking structure and carboxyl; adding triethanolamine and dioctyl phthalate into the polymer, and performing neutralization reaction to obtain a water-based ultrahigh hydroxyl value polymer with a cross-linked structure;
mixing polyisocyanate, cosolvent and dodecyl diglycol ether, dripping a catalyst, adding butanone oxime blocking agent after reaction, neutralizing after reaction, and adding deionized water for high-speed emulsification to prepare water-dispersible blocked polyisocyanate;
adding water-dispersible blocked polyisocyanate into the aqueous ultrahigh hydroxyl polymer for mixing to prepare a highly-crosslinked aqueous low-viscosity high-stability ultrahigh hydroxyl polymer surface reinforcing agent; the hydroxyl value of the modified polycarbonate resin can reach 145.4mgKOH/g at most, and the viscosity of the modified polycarbonate resin is 300-350 mPa.
As a further improvement of the invention, the specific steps for preparing and mixing the monomer mixed solution are as follows:
heating 25 parts by weight of diethylene glycol dimethyl ether dispersion medium to 120-140 ℃;
soft vinyl monomer, hard vinyl monomer, vinyl monomer containing hydroxyl, glycidyl methacrylate and isobornyl methacrylate are mixed according to the weight ratio of 20: 54: 14: 1: 3, mixing to obtain a monomer mixed solution.
As a further improvement of the invention, the preparation steps of the acrylate core system are as follows:
according to the weight portion, 69 portions of monomer mixed liquid is taken, 1.1 to 1.4 portions of dibenzoyl peroxide and 0.08 to 0.15 portion of tert-butyl peroxybenzoate dual initiator system are added, and the polymer core system is formed through heat preservation reaction.
As a further improvement of the invention, the specific steps for obtaining the aqueous ultrahigh hydroxyl value polymer with the crosslinking structure are as follows:
taking 17-69 parts of monomer mixed solution by weight, adding 3 parts of acrylic acid monomer, 0.5-1.5 parts of dibenzoyl peroxide and 0.05-0.2 part of tert-butyl peroxybenzoate, uniformly mixing, adding into a polymer core system, and carrying out heat preservation reaction to obtain a polymer with a cross-linking structure and carboxyl;
and (2) cooling the temperature of the polymer system to 70-90 ℃, adding 6.2 parts of triethanolamine and 3-10 parts of dioctyl phthalate, performing neutralization reaction, adding 90-150 parts of water while stirring, and dispersing to prepare the water-based ultrahigh hydroxyl value polymer with a cross-linked structure.
As a further improvement of the invention, the specific steps for preparing the water dispersible blocked polyisocyanate are as follows:
mixing polyisocyanate, cosolvent and dodecyl diglycol ether according to the weight ratio of 10: 10-20: 2-6, heating to 60-80 ℃, dropwise adding 0.5-1% of catalyst, and reacting to obtain hydrophilic alkyl ether chain modified polyisocyanate; then adding a butanone oxime blocking agent, wherein the molar ratio of the butanone oxime to the polyisocyanate is 1.5-1: 1, reacting at 50-70 ℃ for 2-4 hours, cooling to room temperature, adding triethylamine neutralizer, performing neutralization reaction, adding deionized water, and performing high-speed emulsification and dispersion to obtain the water-dispersible blocked polyisocyanate.
As a further improvement of the invention, 10-30 parts of water-dispersible blocked polyisocyanate is added to 100 parts of water-based ultrahigh hydroxyl polymer.
As a further improvement of the invention, the hard vinyl monomer is one or a mixture of two of methyl methacrylate and styrene in any proportion;
the soft vinyl monomer is one or a mixture of more of butyl acrylate, butyl methacrylate and ethyl acrylate in any proportion;
the hydroxyl-containing vinyl monomer is one or a mixture of more of hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxyethyl methacrylate and hydroxypropyl methacrylate in any proportion.
As a further improvement of the invention, the acrylic monomer is one or a mixture of more of acrylic acid and methacrylic acid in any proportion.
As a further improvement of the invention, the polyisocyanate is one or a mixture of more than one of hexamethylene diisocyanate trimer, hexamethylene diisocyanate, isophorone diisocyanate trimer, phenyl methane diisocyanate, trimethyl hexamethylene diisocyanate, toluene diisocyanate, dodecyl diisocyanate, diphenyl methylene diisocyanate, tetramethyl phenylene diisocyanate, methyl cyclohexyl diisocyanate and dicyclohexyl methane diisocyanate in any proportion.
As a further improvement of the invention, the cosolvent is one or a mixture of more of N, N-dimethylformamide, N-methylpyrrolidone and N, N-dimethylacetamide in any proportion.
Compared with the prior art, the invention has the following advantages:
the invention adopts a diethylene glycol dimethyl ether single solvent system, uses glycidyl methacrylate and isobornyl methacrylate as functional monomers by a stepwise dripping method, and initiates the polymerization of the monomers under the action of a dual initiator system, thereby preparing the acrylic polymer resin with ultrahigh hydroxyl value. In addition, glycidyl methacrylate in the system can increase the interaction between molecular chains and improve the crosslinking density of the polymer; isobornyl methacrylate has nonpolar ester alkoxy, so that steric hindrance can be improved for polymer molecular chains, molecular acting force among the polymer molecular chains is weakened, and the viscosity of the polymer is reduced; and simultaneously, the water resistance and the chemical resistance of the polymer can be improved. The dibenzoyl peroxide and tert-butyl peroxybenzoate dual initiator system has synergistic effect, so that the monomer reaction rate is more stable, and the phenomena of monomer implosion, gelation and the like are avoided, thereby preparing the low-viscosity high-stability ultrahigh hydroxyl value acrylic resin. And finally, compounding the water-based ultrahigh hydroxyl value acrylic resin with water-dispersible blocked polyisocyanate to prepare the low-viscosity high-stability ultrahigh hydroxyl value polymer surface reinforcing agent for the paper. The long-term storage stability of the surface reinforcing agent can be ensured by introducing the water-dispersible blocked polyisocyanate into the waterborne ultrahigh hydroxyl value acrylic resin. In addition, the size of the waterborne high hydroxyl value acrylic resin emulsion particle is nano-scale, and the waterborne high hydroxyl value acrylic resin emulsion particle is easy to permeate into paper; in the paper making process, the blocked polyisocyanate is gradually deblocked, and active isocyanate groups are exposed, and the active isocyanate groups and hydroxyl groups on the high-hydroxyl-value acrylic resin and paper fibers are subjected to crosslinking curing reaction; thereby forming a three-dimensional high-strength cross-linked network structure and greatly improving the strength of the paper. The hydroxyl value of the product can reach 145.4mgKOH/g at most, the viscosity is kept between 300 and 350mPa, and the performance parameters can greatly expand the application range of the waterborne high-hydroxyl-value acrylic resin.
Drawings
FIG. 1 is a comparative scanning electron micrograph of the surface of a product prepared in the example, wherein the surface of an unsized paper (left) and a sized paper (right) is seen by scanning electron micrograph.
Detailed Description
The invention provides a preparation method of a polymer surface reinforcing agent with low viscosity and high hydroxyl value for paper, which comprises the following steps:
1) adding 25 parts by weight of diethylene glycol dimethyl ether dispersion medium into a reactor, and heating to 120-140 ℃.
2) Mixing soft vinyl monomer, hard vinyl monomer, vinyl monomer containing hydroxyl, glycidyl methacrylate and isobornyl methacrylate according to the weight ratio of 20: 54: 14: 1: 3 to obtain a monomer mixed solution A.
3) Weighing 69 parts of monomer mixed solution A, adding 1.1-1.4 parts of dibenzoyl peroxide and 0.08-0.15 part of tert-butyl peroxybenzoate dual-initiator system, uniformly mixing, slowly dropwise adding the dual-initiator system for 2-4 hours, and then continuously carrying out heat preservation reaction for 60-90 minutes to form a polymer core.
4) Weighing 17-69 parts of monomer mixed solution A, adding 3 parts of acrylic monomer, 0.5-1.5 parts of dibenzoyl peroxide and 0.05-0.2 parts of tert-butyl peroxybenzoate, and uniformly mixing to obtain monomer mixed solution B.
5) Gradually dripping the monomer mixed solution B into the polymer core for 40-90 minutes, and then continuing to perform heat preservation reaction for 60-90 minutes to prepare a polymer C with a cross-linking structure and carboxyl.
6) And (3) cooling the temperature of the polymer C system to 70-90 ℃, adding 6.2 parts of triethanolamine and 3-10 parts of dioctyl phthalate, neutralizing for 10-30 minutes, and adding 90-150 parts of water under high-speed stirring for dispersing to prepare the water-based ultrahigh hydroxyl value polymer D with the cross-linked structure.
7) Mixing polyisocyanate, cosolvent and dodecyl diglycol ether according to the weight ratio of 10: 10-20: 2-6, heating to 60-80 ℃, dropwise adding 0.5-1% of catalyst, and reacting for 60-120 minutes to obtain hydrophilic alkyl ether chain modified polyisocyanate; then adding a butanone oxime blocking agent, wherein the molar ratio of the butanone oxime to the polyisocyanate is 1.5-1: 1, reacting at 50-70 ℃ for 2-4 hours, cooling to room temperature, adding triethylamine neutralizer, performing neutralization reaction for 30 minutes, adding deionized water, emulsifying and dispersing at high speed for 30 minutes, and preparing the water-dispersible blocked polyisocyanate.
8) And adding 10-30 parts of water-dispersed blocked polyisocyanate to 100 parts of the water-based ultrahigh hydroxyl polymer D for mixing to prepare the water-based low-viscosity high-stability ultrahigh hydroxyl polymer surface reinforcing agent with high crosslinking degree.
Wherein the hard vinyl monomer is one or a mixture of two of methyl methacrylate and styrene in any proportion.
Wherein the soft vinyl monomer is one or a mixture of more of butyl acrylate, butyl methacrylate and ethyl acrylate in any proportion.
Wherein, the vinyl monomer containing hydroxyl is one or a mixture of more of hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxyethyl methacrylate and hydroxypropyl methacrylate in any proportion.
Wherein, the acrylic acid monomer is one or a mixture of more of acrylic acid and methacrylic acid in any proportion.
The polyisocyanate is one or a mixture of more of hexamethylene diisocyanate trimer, hexamethylene diisocyanate, isophorone diisocyanate trimer, phenyl methane diisocyanate, trimethyl hexamethylene diisocyanate, toluene diisocyanate, dodecyl diisocyanate, diphenyl methylene diisocyanate, tetramethyl phenylene diisocyanate, methyl cyclohexyl diisocyanate and dicyclohexyl methane diisocyanate in any proportion.
Wherein the cosolvent is one or a mixture of more of N, N-dimethylformamide, N-methylpyrrolidone and N, N-dimethylacetamide in any proportion.
Example 1:
1) 25 parts by weight of a diethylene glycol dimethyl ether dispersion medium was charged into the reactor and heated to 120 ℃.
2) Mixing soft vinyl monomer butyl acrylate, hard vinyl monomer methyl methacrylate, hydroxyl-containing vinyl monomer hydroxypropyl acrylate, glycidyl methacrylate and isobornyl methacrylate according to the weight ratio of 20: 54: 14: 1: 3 to obtain a monomer mixed solution A.
3) Weighing 69 parts of monomer mixed solution A, adding 1.1 parts of dibenzoyl peroxide and 0.8 part of tert-butyl peroxybenzoate diinitiator system, uniformly mixing, slowly dropwise adding the diinitiator system for 2 hours, and then continuously carrying out heat preservation reaction for 60 minutes to form a polymer core.
4) Weighing 17 parts of monomer mixed solution A, adding 3 parts of acrylic monomer, 0.5 part of dibenzoyl peroxide and 0.05 part of tert-butyl peroxybenzoate, and uniformly mixing to obtain monomer mixed solution B.
5) Gradually dripping the monomer mixed solution B into the polymer core for 40-90 minutes, and then continuing to perform heat preservation reaction for 60 minutes to obtain a polymer C with a cross-linked structure and carboxyl.
6) And (3) reducing the temperature of the polymer C system to 70 ℃, adding 6.2 parts of triethanolamine and 3 parts of dioctyl phthalate, neutralizing for 10 minutes, and then adding 90 parts of water under high-speed stirring for dispersion to prepare the water-based ultrahigh hydroxyl value polymer D with a cross-linked structure.
7) Mixing polyisocyanate, cosolvent and dodecyl diglycol ether according to the weight ratio of 10: 10: 2, heating to 60 ℃, dropwise adding 0.5% of catalyst, and reacting for 60 minutes to obtain hydrophilic alkyl ether chain modified polyisocyanate; then adding butanone oxime blocking agent, wherein the molar ratio of the butanone oxime to the polyisocyanate is 1.5: 1, reacting at 50 ℃ for 2 hours, cooling to room temperature, adding triethylamine neutralizer, carrying out neutralization reaction for 30 minutes, adding deionized water, emulsifying and dispersing at high speed for 30 minutes, and obtaining the water-dispersible blocked polyisocyanate.
8) And adding 10 parts of water-dispersible blocked polyisocyanate to 100 parts of the aqueous ultrahigh hydroxyl number polymer D for mixing to prepare the highly-crosslinked aqueous low-viscosity high-stability ultrahigh hydroxyl number polymer surface reinforcing agent.
FIG. 1 is a comparative scanning electron micrograph of the surface of a product prepared in the example, wherein the surface of an unsized paper (left) and a sized paper (right) is seen by scanning electron micrograph.
Example 2:
1) 25 parts by weight of a diethylene glycol dimethyl ether dispersion medium was charged into the reactor and heated to 125 ℃.
2) Mixing soft vinyl monomer butyl methacrylate, hard vinyl monomer methyl methacrylate, hydroxyl-containing vinyl monomer hydroxypropyl acrylate, glycidyl methacrylate and isobornyl methacrylate according to the weight ratio of 20: 54: 14: 1: 3 to obtain a monomer mixed solution A.
3) Weighing 69 parts of monomer mixed solution A, adding 1.2 parts of dibenzoyl peroxide and 0.09 part of tert-butyl peroxybenzoate diinitiator system, uniformly mixing, slowly dropwise adding the diinitiator system for 3 hours, and then continuously carrying out heat preservation reaction for 70 minutes to form a polymer core.
4) Weighing 21 parts of monomer mixed solution A, adding 3 parts of acrylic monomer, 0.8 part of dibenzoyl peroxide and 0.1 part of tert-butyl peroxybenzoate, and uniformly mixing to obtain monomer mixed solution B.
5) Gradually dripping the monomer mixed solution B into the polymer core for 50 minutes, and then continuing to react for 70 minutes under the condition of heat preservation to prepare a polymer C with a cross-linked structure and carboxyl.
6) And (3) reducing the temperature of the polymer C system to 70 ℃, adding 6.2 parts of triethanolamine and 5 parts of dioctyl phthalate, neutralizing for 15 minutes, and then adding 100 parts of water under high-speed stirring for dispersing to prepare the water-based ultrahigh hydroxyl value polymer D with the cross-linked structure.
7) Mixing polyisocyanate, cosolvent and dodecyl diglycol ether according to the weight ratio of 10: 15: 3, heating to 70 ℃, dropwise adding 0.6% of catalyst, and reacting for 80 minutes to obtain hydrophilic alkyl ether chain modified polyisocyanate; then adding butanone oxime blocking agent, wherein the molar ratio of the butanone oxime to the polyisocyanate is 1.2: 1, reacting at 60 ℃ for 3 hours, cooling to room temperature, adding triethylamine neutralizer, carrying out neutralization reaction for 30 minutes, adding deionized water, emulsifying and dispersing at high speed for 30 minutes, and obtaining the water-dispersible blocked polyisocyanate.
8) Adding 15 parts of water-dispersed blocked polyisocyanate into 100 parts of water-based ultrahigh hydroxyl value polymer D for mixing to prepare the surface reinforcement of the water-based low-viscosity high-stability ultrahigh hydroxyl value polymer with high crosslinking degree
Example 3:
1) 25 parts by weight of a diethylene glycol dimethyl ether dispersion medium was charged into the reactor and heated to 130 ℃.
2) Mixing soft vinyl monomer butyl acrylate, hard vinyl monomer methyl methacrylate, hydroxyl-containing vinyl monomer hydroxypropyl acrylate, glycidyl methacrylate and isobornyl methacrylate according to the weight ratio of 20: 54: 14: 1: 3 to obtain a monomer mixed solution A.
3) Weighing 69 parts of monomer mixed solution A, adding 1.3 parts of dibenzoyl peroxide and 0.1 part of tert-butyl peroxybenzoate diinitiator system, uniformly mixing, slowly dropwise adding the diinitiator system for 3 hours, and then continuously carrying out heat preservation reaction for 70 minutes to form a polymer core.
4) Weighing 21 parts of monomer mixed solution A, adding 3 parts of acrylic monomer, 1.0 part of dibenzoyl peroxide and 0.1 part of tert-butyl peroxybenzoate, and uniformly mixing to obtain monomer mixed solution B.
5) Gradually dripping the monomer mixed solution B into the polymer core for 60 minutes, and then continuing to perform heat preservation reaction for 60 minutes to prepare a polymer C with a cross-linked structure and carboxyl.
6) And (3) reducing the temperature of the polymer C system to 80 ℃, adding 6.2 parts of triethanolamine and 5 parts of dioctyl phthalate, neutralizing for 20 minutes, and then adding 100 parts of water under high-speed stirring for dispersion to prepare the water-based ultrahigh hydroxyl value polymer D with the cross-linked structure.
7) Mixing polyisocyanate, cosolvent and dodecyl diglycol ether according to the weight ratio of 10: 15: 4, heating to 70 ℃, dropwise adding 0.8% of catalyst, and reacting for 90 minutes to obtain hydrophilic alkyl ether chain modified polyisocyanate; then adding butanone oxime blocking agent, wherein the molar ratio of the butanone oxime to the polyisocyanate is 1.4: 1, reacting at 60 ℃ for 3 hours, cooling to room temperature, adding triethylamine neutralizer, carrying out neutralization reaction for 30 minutes, adding deionized water, emulsifying and dispersing at high speed for 30 minutes, and obtaining the water-dispersible blocked polyisocyanate.
8) And (3) adding 20 parts of water-dispersed blocked polyisocyanate to 100 parts of the aqueous ultrahigh hydroxyl number polymer D for mixing to prepare the aqueous low-viscosity high-stability ultrahigh hydroxyl number polymer surface reinforcing agent with high crosslinking degree.
Example 4:
1) 25 parts by weight of a diethylene glycol dimethyl ether dispersion medium was charged into the reactor and heated to 130 ℃.
2) Soft vinyl monomer ethyl acrylate, hard vinyl monomer styrene, hydroxyl-containing vinyl monomer hydroxyethyl methacrylate, glycidyl methacrylate and isobornyl methacrylate are mixed according to the weight ratio of 20: 54: 14: 1: 3 to obtain a monomer mixed solution A.
3) Weighing 69 parts of monomer mixed solution A, adding 1.3 parts of dibenzoyl peroxide and 0.12 part of tert-butyl peroxybenzoate diinitiator system, uniformly mixing, slowly dropwise adding the diinitiator system for 3 hours, and then continuously carrying out heat preservation reaction for 60 minutes to form a polymer core.
4) Weighing 45 parts of monomer mixed solution A, adding 3 parts of acrylic monomer, 1.0 part of dibenzoyl peroxide and 0.1 part of tert-butyl peroxybenzoate, and uniformly mixing to obtain monomer mixed solution B.
5) Gradually dripping the monomer mixed solution B into the polymer core for 70 minutes, and then continuing to perform heat preservation reaction for 60 minutes to prepare a polymer C with a cross-linked structure and carboxyl.
6) And (3) reducing the temperature of the polymer C system to 80 ℃, adding 6.2 parts of triethanolamine and 5 parts of dioctyl phthalate, neutralizing for 20 minutes, and then adding 120 parts of water under high-speed stirring for dispersion to prepare the water-based ultrahigh hydroxyl value polymer D with the cross-linked structure.
7) Mixing polyisocyanate, cosolvent and dodecyl diglycol ether according to the weight ratio of 10: 16: 5, heating to 80 ℃, dropwise adding 0.8% of catalyst, and reacting for 80 minutes to obtain hydrophilic alkyl ether chain modified polyisocyanate; then adding butanone oxime blocking agent, wherein the molar ratio of the butanone oxime to the polyisocyanate is 1.5: 1, reacting at 60 ℃ for 3 hours, cooling to room temperature, adding triethylamine neutralizer, carrying out neutralization reaction for 30 minutes, adding deionized water, emulsifying and dispersing at high speed for 30 minutes, and obtaining the water-dispersible blocked polyisocyanate.
8) 26 parts of water-dispersible blocked polyisocyanate is added to 100 parts of water-based ultrahigh hydroxyl value polymer D and mixed to prepare the water-based low-viscosity high-stability ultrahigh hydroxyl value polymer surface reinforcing agent with high crosslinking degree.
Example 5:
1) 25 parts by weight of a diethylene glycol dimethyl ether dispersion medium was charged into the reactor and heated to 140 ℃.
2) Mixing soft vinyl monomer butyl methacrylate, hard vinyl monomer methyl methacrylate, hydroxyl-containing vinyl monomer hydroxypropyl acrylate, glycidyl methacrylate and isobornyl methacrylate according to the weight ratio of 20: 54: 14: 1: 3 to obtain a monomer mixed solution A.
3) Weighing 69 parts of monomer mixed solution A, adding 1.4 parts of dibenzoyl peroxide and 0.15 part of tert-butyl peroxybenzoate diinitiator system, uniformly mixing, slowly dropwise adding the diinitiator system for 4 hours, and then continuously carrying out heat preservation reaction for 60 minutes to form a polymer core.
4) 69 parts of monomer mixed solution A is weighed, 3 parts of acrylic monomer, 1.5 parts of dibenzoyl peroxide and 0.2 part of tert-butyl peroxybenzoate are added, and monomer mixed solution B is prepared after uniform mixing.
5) Gradually dripping the monomer mixed solution B into the polymer core for 90 minutes, and then continuing to react for 90 minutes under the condition of heat preservation to prepare the polymer C with a cross-linked structure and carboxyl.
6) And (3) reducing the temperature of the polymer C system to 90 ℃, adding 6.2 parts of triethanolamine and 10 parts of dioctyl phthalate, neutralizing for 30 minutes, and then adding 150 parts of water under high-speed stirring for dispersion to prepare the water-based ultrahigh hydroxyl value polymer D with the cross-linked structure.
7) Mixing polyisocyanate, cosolvent and dodecyl diglycol ether according to the weight ratio of 10: 20: 6, heating to 80 ℃, dropwise adding 1% of catalyst, and reacting for 120 minutes to obtain hydrophilic alkyl ether chain modified polyisocyanate; then adding butanone oxime blocking agent, wherein the molar ratio of the butanone oxime to the polyisocyanate is 1.5: 1, reacting for 4 hours at 70 ℃, cooling to room temperature, adding triethylamine neutralizer, carrying out neutralization reaction for 30 minutes, adding deionized water, emulsifying and dispersing at high speed for 30 minutes, and obtaining the water-dispersible blocked polyisocyanate.
8) And (3) adding 30 parts of water-dispersed blocked polyisocyanate to 100 parts of the aqueous ultrahigh hydroxyl number polymer D for mixing to prepare the aqueous low-viscosity high-stability ultrahigh hydroxyl number polymer surface reinforcing agent with high crosslinking degree.
The five aqueous polymer surface reinforcing agents with low viscosity, high stability and ultrahigh hydroxyl value obtained in the examples 1 to 5 are used for surface sizing of cotton pulp fiber paper, and the sizing amount is 3 +/-0.21 g/m2The main properties of the unsized and sized paper were examined and the results are shown in table 1.
TABLE 1 Performance test results
Detecting items Example 1 Example 2 Example 3 Example 4 Example 5
Cobb value (g/m)2) 24.3 25.5 17.2 21.0 22.5
Dry tensile force (N.m.g)-1) 90.5 95.6 102.3 98.7 100.2
Wet tensile force (n.m.g)-1) 42.7 43.6 51.6 47.3 48.5
Folding endurance (second) 5213 5476 6523 4915 4134
Surface strength (m.s)-1) 2.8 3.1 3.9 3.5 3.8
In conclusion, the invention discloses a preparation method of a polymer surface reinforcing agent with low viscosity and high hydroxyl value for paper. By adopting a step-by-step dropwise adding method, firstly, diethylene glycol dimethyl ether is taken as a dispersion medium, butyl acrylate, methyl methacrylate, hydroxypropyl acrylate, glycidyl methacrylate and isobornyl methacrylate are taken as raw materials, and a dibenzoyl peroxide and tert-butyl peroxybenzoate dual initiation system is adopted to carry out free radical polymerization on monomers so as to prepare an acrylate core with higher glass transition temperature and higher rigidity; in the second step of reaction, dripping acrylic acid, wherein carboxyl on a molecular chain of the acrylic acid can react with epoxy groups on glycidyl methacrylate to generate hydroxyl; then triethanolamine and dioctyl phthalate are added to neutralize to form quaternary ammonium salt, so that the water dispersion performance of the polymer is improved, and the water-based low-viscosity high-stability ultrahigh-hydroxyl acrylic resin with a core-shell structure is prepared by high-speed water dispersion. And finally, constructing the polymer surface reinforcing agent for the paper by using the composite water-based blocked polyisocyanate crosslinking agent. The product of the invention has a multiple cross-linked network structure, and can also form a cross-linked network with a paper base material, thereby efficiently increasing the paper base performance.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that those skilled in the art can make various improvements and modifications without departing from the principle of the present invention, and these improvements and modifications should also be construed as the protection scope of the present invention.

Claims (8)

1. A preparation method of a polymer surface reinforcing agent with low viscosity and high hydroxyl value for paper is characterized by comprising the following steps:
taking diethylene glycol dimethyl ether as a dispersion medium, and taking a soft vinyl monomer, a hard vinyl monomer, a hydroxyl-containing vinyl monomer, glycidyl methacrylate and isobornyl methacrylate as raw materials, and mixing to obtain a monomer mixed solution;
the monomer mixed solution adopts a dibenzoyl peroxide and tert-butyl peroxybenzoate dual-initiation system to carry out free radical polymerization to prepare an acrylate core system;
adding an acrylic monomer, dibenzoyl peroxide and tert-butyl peroxybenzoate into the monomer mixed solution, uniformly mixing, and then dropwise adding into an acrylate core system to prepare a polymer with a cross-linking structure and carboxyl; adding triethanolamine and dioctyl phthalate into the polymer, and performing neutralization reaction to obtain a water-based ultrahigh hydroxyl value polymer with a cross-linked structure;
mixing polyisocyanate, cosolvent and dodecyl diglycol ether, dripping a catalyst, adding butanone oxime blocking agent after reaction, neutralizing after reaction, and adding deionized water for high-speed emulsification to prepare water-dispersible blocked polyisocyanate;
adding water-dispersible blocked polyisocyanate into the aqueous ultrahigh hydroxyl polymer for mixing to prepare a highly-crosslinked aqueous low-viscosity high-stability ultrahigh hydroxyl polymer surface reinforcing agent; the highest hydroxyl value is 145.4mgKOH/g, and the viscosity is 300-350 mPa & s;
the preparation method of the monomer mixed solution comprises the following specific steps:
heating 25 parts by weight of diethylene glycol dimethyl ether dispersion medium to 120-140 ℃;
soft vinyl monomer, hard vinyl monomer, vinyl monomer containing hydroxyl, glycidyl methacrylate and isobornyl methacrylate are mixed according to the weight ratio of 20: 54: 14: 1: 3, mixing to obtain a monomer mixed solution;
the method for obtaining the water-based ultrahigh hydroxyl value polymer with the cross-linked structure comprises the following specific steps:
taking 17-69 parts of monomer mixed solution by weight, adding 3 parts of acrylic acid monomer, 0.5-1.5 parts of dibenzoyl peroxide and 0.05-0.2 part of tert-butyl peroxybenzoate, uniformly mixing, adding into a polymer core system, and carrying out heat preservation reaction to obtain a polymer with a cross-linking structure and carboxyl;
and (2) cooling the temperature of the polymer system to 70-90 ℃, adding 6.2 parts of triethanolamine and 3-10 parts of dioctyl phthalate, performing neutralization reaction, adding 90-150 parts of water while stirring, and dispersing to prepare the water-based ultrahigh hydroxyl value polymer with a cross-linked structure.
2. The method for preparing a low viscosity high hydroxyl number polymer surface enhancer for paper as claimed in claim 1, wherein: the preparation method of the acrylate core system comprises the following steps:
according to the weight portion, 69 portions of monomer mixed liquid is taken, 1.1 to 1.4 portions of dibenzoyl peroxide and 0.08 to 0.15 portion of tert-butyl peroxybenzoate dual initiator system are added, and the polymer core system is formed through heat preservation reaction.
3. The method for preparing a low viscosity high hydroxyl number polymer surface enhancer for paper as claimed in claim 1, wherein: the specific steps for preparing the water-dispersible blocked polyisocyanate are as follows:
mixing polyisocyanate, cosolvent and dodecyl diglycol ether according to the weight ratio of 10: 10-20: 2-6, heating to 60-80 ℃, dropwise adding 0.5-1% of catalyst, and reacting to obtain hydrophilic alkyl ether chain modified polyisocyanate; then adding a butanone oxime blocking agent, wherein the molar ratio of the butanone oxime to the polyisocyanate is 1.5-1: 1, reacting at 50-70 ℃ for 2-4 hours, cooling to room temperature, adding triethylamine neutralizer, performing neutralization reaction, adding deionized water, and performing high-speed emulsification and dispersion to obtain the water-dispersible blocked polyisocyanate.
4. The method for preparing a low viscosity high hydroxyl number polymer surface enhancer for paper as claimed in claim 1, wherein: 100 parts of water-based ultrahigh hydroxyl polymer is added with 10-30 parts of water-dispersed blocked polyisocyanate.
5. The method for preparing a low viscosity high hydroxyl number polymer surface enhancer for paper as claimed in claim 1, wherein: the hard vinyl monomer is one or a mixture of methyl methacrylate and styrene in any proportion;
the soft vinyl monomer is one or a mixture of more of butyl acrylate, butyl methacrylate and ethyl acrylate in any proportion;
the hydroxyl-containing vinyl monomer is one or a mixture of more of hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxyethyl methacrylate and hydroxypropyl methacrylate in any proportion.
6. The method for preparing a low viscosity high hydroxyl number polymer surface enhancer for paper as claimed in claim 1, wherein: the acrylic acid monomer is one or a mixture of more of acrylic acid and methacrylic acid in any proportion.
7. The method for preparing a low viscosity high hydroxyl number polymer surface enhancer for paper as claimed in claim 1, wherein: the polyisocyanate is one or a mixture of more of hexamethylene diisocyanate tripolymer, hexamethylene diisocyanate, isophorone diisocyanate tripolymer, phenyl methane diisocyanate, trimethyl hexamethylene diisocyanate, toluene diisocyanate, dodecyl diisocyanate, diphenyl methylene diisocyanate, tetramethyl xylylene diisocyanate, methyl cyclohexyl diisocyanate and dicyclohexyl methane diisocyanate in any proportion.
8. The method for preparing a low viscosity high hydroxyl number polymer surface enhancer for paper as claimed in claim 1, wherein: the cosolvent is one or a mixture of more of N, N-dimethylformamide, N-methylpyrrolidone and N, N-dimethylacetamide in any proportion.
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