CN106543394A - Compound impregnating resin of novel aqueous polyurethane acroleic acid and preparation method thereof - Google Patents

Compound impregnating resin of novel aqueous polyurethane acroleic acid and preparation method thereof Download PDF

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Publication number
CN106543394A
CN106543394A CN201610974193.XA CN201610974193A CN106543394A CN 106543394 A CN106543394 A CN 106543394A CN 201610974193 A CN201610974193 A CN 201610974193A CN 106543394 A CN106543394 A CN 106543394A
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aqueous polyurethane
preparation
impregnating resin
novel aqueous
acid
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林孝州
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HANGZHOU TIANYUAN CHENGDA DECORATIVE MATERIAL CO Ltd
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HANGZHOU TIANYUAN CHENGDA DECORATIVE MATERIAL CO Ltd
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    • 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
    • C08G18/08—Processes
    • C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
    • C08G18/12—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step using two or more compounds having active hydrogen in the first polymerisation step
    • 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
    • C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
    • C08F283/006—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polymers provided for in C08G18/00
    • C08F283/008—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polymers provided for in C08G18/00 on to unsaturated polymers
    • 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
    • C08G18/48—Polyethers
    • C08G18/4804—Two or more polyethers of different physical or chemical nature
    • C08G18/4808—Mixtures of two or more polyetherdiols
    • 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
    • C08G18/48—Polyethers
    • C08G18/4825—Polyethers containing two hydroxy groups
    • 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
    • C08G18/48—Polyethers
    • C08G18/4854—Polyethers containing oxyalkylene groups having four carbon atoms in the alkylene group
    • 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
    • C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
    • C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
    • C08G18/6666—Compounds of group C08G18/48 or C08G18/52
    • C08G18/667—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38
    • C08G18/6674—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3203
    • 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
    • C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
    • C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
    • C08G18/6666—Compounds of group C08G18/48 or C08G18/52
    • C08G18/667—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38
    • C08G18/6674—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3203
    • C08G18/6677—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3203 having at least three hydroxy groups
    • 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
    • C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
    • C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
    • C08G18/6666—Compounds of group C08G18/48 or C08G18/52
    • C08G18/6692—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/34
    • 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
    • C08G18/67—Unsaturated compounds having active hydrogen
    • C08G18/671—Unsaturated compounds having only one group containing active hydrogen
    • C08G18/672—Esters of acrylic or alkyl acrylic acid having only one group containing active hydrogen

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

Abstract

The present invention relates to compound impregnating resin of novel aqueous polyurethane acroleic acid and preparation method thereof.Obtained in the method that purpose is to provide, resin should be able to organically combine the advantage of aqueous polyurethane and water soluble acrylic acid, become watersoluble polyurethane acrylic acid (PUA) composite resin of high comprehensive performance.Technical scheme is：Novel aqueous polyurethane acroleic acid is combined impregnating resin, including following component：Acrylate monomer, dihydromethyl propionic acid DMPA etc.；Its preparation method is as follows：(1) prepare base polyurethane prepolymer for use as；(2) prepare watersoluble polyurethane acrylic acid monomer mixed emulsion；(3), during be added to 20% in the middle of the mixed emulsion for preparing in reactor, the remaining deionized water of addition is warming up to 80 DEG C, adds oxidant potassium peroxydisulfate to be caused；Now note control temperature jump, after the general obvious blue light of emulsion, maintain reaction temperature constant, Deca remainder mixed emulsion and buffer agent sodium bicarbonate.

Description

Compound impregnating resin of novel aqueous polyurethane acroleic acid and preparation method thereof
Technical field
The present invention relates to the impregnating resin of facing paper field, especially dipping decorative paper.
Background technology
As people are to clean manufacturing mode, the growing interest of environmental regulation, and the higher and higher environmental protection of terminal market Cry, has continued dipping woodgrained paper glue for many years, has also more and more been queried；Conventional woodgrained paper dipping glue is long-term Since be, with tripolycyanamide/ureaformaldehyde as major type of water-based glue (resin), this kind of pollution of formaldehyde can not to be prevented from principle Material, its process of manufacture are full of formaldehyde, equally also suffer from formaldehyde pollution in the production link of dipping woodgrained paper；Terminal man The products such as tool/floor, also can slow release formaldehyde, whole industrial chain hovers at the edge of environmental protection.
The content of the invention
It is an object of the invention to provide compound impregnating resin of a kind of watersoluble polyurethane acrylic acid and preparation method thereof, the method Obtained resin should be able to organically combine the advantage of aqueous polyurethane and water soluble acrylic acid, become the poly- ammonia of aqueouss of high comprehensive performance Ester acrylic acid (PUA) composite resin, for fine quality dipping paper product can be obtained after facing paper dipping production.
The present invention provide technical scheme be：
Novel aqueous polyurethane acroleic acid is combined impregnating resin, including following component and corresponding weight portion：
Acrylate monomer 55-65, Isosorbide-5-Nitrae one butanediol (BDO) 1-2, dihydromethyl propionic acid DMPA 2-5, trihydroxy methyl third Alkane 2-5, diethylenetriamine 0.5-1.5；
N, N- dihydroxy (diisopropyl) aniline (HPA) 1-3, diisocyanate (IPDI) 10-20, PTMG two Alcohol 10-15, its chlorinated polypropylene glycol (PPG) 20-30, dimethylethanolamine 2-6, acetone 30-50, dibutyltin dilaurate (DY-12)0.03；
Adipic dihydrazide (ADH) 5-7, N-[2-(2-methyl-4-oxopentyl) 10-15, sodium formaldehyde sulphoxylate 0.1-0.5, potassium peroxydisulfate 1-1.3, sodium bicarbonate 1-1.5, tert-butyl hydroperoxide 0.1-0.5, phenylpropyl alcohol isothiazolone 0.5-1, deionized water 350- 360。
Butyl acrylate, maleic acid two fourth of the acrylate monomer by 2-4 ﹕ 5-10 ﹕ 2-5 ﹕ 10-15 ﹕ 2-5 ﹕ 30-40 Ester, olefin(e) acid hydroxyl ethyl ester, 2-Propenoic acid, 2-methyl-, isooctyl ester, methacrylic acid and styrene composition.
The preparation method of the compound impregnating resin of novel aqueous polyurethane acroleic acid is as follows：
(1) preparation of base polyurethane prepolymer for use as
First by diisocyanate IPDI and PTMG, its chlorinated polypropylene glycol (PPG) reaction, Ran Houtian Plus dibutyltin dilaurate (DY-12), one butanediol of Isosorbide-5-Nitrae (BDO), trimethylolpropane, dihydromethyl propionic acid DMPA, N, N- dihydroxy (diisopropyl) aniline (HPA) and acetone, the slow high-temperature that rises react 15-30min, obtain polyurethane to 75 DEG C Performed polymer；Less than 50 DEG C are cooled to, and evacuation removes acetone；
(2) preparation of water-borne polyurethane-acrylate monomer mixed emulsion
Acrylate monomer, nertralizer dimethylethanolamine are added in base polyurethane prepolymer for use as, is stirred after mixing, plus Enter 300 parts of deionized water, N-[2-(2-methyl-4-oxopentyl) disperses 30 minutes at a high speed, adds diethylenetriamine, continue to stir, 50- In 60 DEG C, low temperature continuous reaction 40-90min, carries out chain growth；Obtain (pre- point of water-borne polyurethane-acrylate monomer mixed emulsion A prose style free from parallelism)；
(3), during be added to 20% in the middle of the mixed emulsion for preparing in reactor, the remaining deionized water of addition rises Temperature adds oxidant potassium peroxydisulfate to be caused to 80 DEG C；Now note control temperature jump, tie up after the general obvious blue light of emulsion Hold reaction temperature constant, Deca remainder mixed emulsion and buffer agent sodium bicarbonate.
Reaction adds tert-butyl hydroperoxide and sodium formaldehyde sulphoxylate to carry out post processing and reduces residual monomer after terminating Content.
Insulation adds phenylpropyl alcohol isothiazolone, adipic dihydrazide (ADH) to stir after terminating, fill after cooling.
Logical nitrogen protection is noted in course of reaction；Need to cool in time during reaction system very exothermic.
The invention has the beneficial effects as follows：The compound impregnating resin of watersoluble polyurethane acrylic acid obtained by the present invention, due to water The property special molecular structure of polyurethane and coherent condition, thus with excellent erosion resistant, pliability, adhesive force, chemicals-resistant and The advantages of soft or hard varies with temperature little, also with good resistance to water, weatherability and physical and mechanical propertiess；Entered using the resin The dipping production of row woodgrained paper, is obtained fine quality dipping paper product；Especially：The present invention does not have formaldehyde components, thus complete Meet full environmental requirement.(dipping papery ground is obtained flexible, can be used for coating and overlay, contrast PVC covering materials have preferably Homochromatism and texture)
Specific embodiment
Further illustrate with reference to embodiments.
Embodiment 1
Novel aqueous polyurethane acroleic acid is combined impregnating resin, including following component and corresponding weight portion：
Acrylate monomer 55, one butanediol of Isosorbide-5-Nitrae (BDO) 1, dihydromethyl propionic acid DMPA 5, trimethylolpropane 2, two Ethylene triamine 1.5；
N, N- dihydroxy (diisopropyl) aniline (HPA) 1, diisocyanate (IPDI) 20, PTMG 15, Its chlorinated polypropylene glycol (PPG) 20, dimethylethanolamine 6, acetone 30, dibutyltin dilaurate (DY-12) 0.04；
Adipic dihydrazide (ADH) 5, N-[2-(2-methyl-4-oxopentyl) 15, sodium formaldehyde sulphoxylate 0.1, potassium peroxydisulfate 1.3, carbonic acid Hydrogen sodium 1, tert-butyl hydroperoxide 0.5, phenylpropyl alcohol isothiazolone 0.5, deionized water 350.
The acrylate monomer by the butyl acrylate of 2 ﹕, 10 ﹕, 2 ﹕, 15 ﹕, 2 ﹕ 40, dibutyl maleate, olefin(e) acid hydroxyl ethyl ester, 2-Propenoic acid, 2-methyl-, isooctyl ester, methacrylic acid and styrene composition.
Preparation method is as follows：
(1) first by diisocyanate IPDI and PTMG, its chlorinated polypropylene glycol (PPG) reacts, so Add dibutyltin dilaurate (DY-12), 1,4 1 butanediols (BDO), trimethylolpropane, dihydromethyl propionic acid afterwards DMPA, N, N- dihydroxy (diisopropyl) aniline (HPA) and acetone, the slow high-temperature that rises react 30min, are gathered to 75 DEG C Urethane performed polymer；Less than 50 DEG C are cooled to, and evacuation removes acetone；
(2) acrylate monomer, dimethyl ethanol amine neutralizer are added in base polyurethane prepolymer for use as, is stirred after mixing equal It is even, add 300 parts of deionized water, N-[2-(2-methyl-4-oxopentyl) to disperse 30 minutes at a high speed, add diethylenetriamine, continue stirring equal Even, in 50 DEG C, low temperature continuous reaction 90min, carries out chain growth；Obtain water-borne polyurethane-acrylate monomer mixed emulsion；
During in the middle of the mixed emulsion for preparing 20% is added in reactor, the remaining deionized water of addition heats up To 80 DEG C, oxidant potassium peroxydisulfate is added to be caused；Now note control temperature jump, maintain after the general obvious blue light of emulsion Reaction temperature is constant, Deca remainder mixed emulsion and buffer agent sodium bicarbonate.
Reaction adds tert-butyl hydroperoxide and sodium formaldehyde sulphoxylate to carry out post processing after terminating, and reduces residual monomer Content.Insulation adds phenylpropyl alcohol isothiazolone, adipic dihydrazide (ADH) to stir after terminating, fill after cooling.
Embodiment 2
Novel aqueous polyurethane acroleic acid is combined impregnating resin, including following component and corresponding weight portion：
Acrylate monomer 65, one butanediol of Isosorbide-5-Nitrae (BDO) 2, dihydromethyl propionic acid DMPA 2, trimethylolpropane 5, two Ethylene triamine 0.5；
N, N- dihydroxy (diisopropyl) aniline (HPA) 3, diisocyanate (IPDI) 10, PTMG 10, Its chlorinated polypropylene glycol (PPG) 30, dimethylethanolamine 2, acetone 50, dibutyltin dilaurate (DY-12) 0.02；
Adipic dihydrazide (ADH) 7, N-[2-(2-methyl-4-oxopentyl) 10, sodium formaldehyde sulphoxylate 0.5, potassium peroxydisulfate 1, bicarbonate Sodium 1.5, tert-butyl hydroperoxide 0.1, phenylpropyl alcohol isothiazolone -1, deionized water 360.
The acrylate monomer by the butyl acrylate of 3 ﹕, 8 ﹕, 4 ﹕, 13 ﹕, 3 ﹕ 35, dibutyl maleate, olefin(e) acid hydroxyl ethyl ester, 2-Propenoic acid, 2-methyl-, isooctyl ester, methacrylic acid and styrene composition.
Preparation method is as follows：
(1) first by diisocyanate IPDI and PTMG, its chlorinated polypropylene glycol (PPG) reacts, so Add dibutyltin dilaurate (DY-12), 1,4 1 butanediols (BDO), trimethylolpropane, dihydromethyl propionic acid afterwards DMPA, N, N- dihydroxy (diisopropyl) aniline (HPA) and acetone, the slow high-temperature that rises react 15min, are gathered to 75 DEG C Urethane performed polymer；Less than 50 DEG C are cooled to, and evacuation removes acetone；
(2) acrylate monomer, dimethyl ethanol amine neutralizer are added in base polyurethane prepolymer for use as, is stirred after mixing equal It is even, add 300 parts of deionized water, N-[2-(2-methyl-4-oxopentyl) to disperse 30 minutes at a high speed, add diethylenetriamine, continue stirring equal Even, 60 DEG C of sustained responses 40min carry out chain growth；Obtain water-borne polyurethane-acrylate monomer mixed emulsion；
During in the middle of the mixed emulsion for preparing 20% is added in reactor, the remaining deionized water of addition heats up To 80 DEG C, oxidant potassium peroxydisulfate is added to be caused；Now note control temperature jump, maintain after the general obvious blue light of emulsion Reaction temperature is constant, Deca remainder mixed emulsion and oxidant and remaining initiator and buffer agent sodium bicarbonate.
Reaction adds tert-butyl hydroperoxide and sodium formaldehyde sulphoxylate to carry out post processing after terminating, and reduces residual monomer Content.Insulation adds phenylpropyl alcohol isothiazolone, adipic dihydrazide (ADH) to stir after terminating, fill after cooling.
Embodiment 3
Novel aqueous polyurethane acroleic acid is combined impregnating resin, including following component and corresponding weight portion：
Acrylate monomer 60, one butanediol of Isosorbide-5-Nitrae (BDO) 1.5, dihydromethyl propionic acid DMPA 3, trimethylolpropane 4, Diethylenetriamine 1；
N, N- dihydroxy (diisopropyl) aniline (HPA) 2, diisocyanate (IPDI) 15, PTMG 13, Its chlorinated polypropylene glycol (PPG) 25, dimethylethanolamine 4, acetone 40, dibutyltin dilaurate (DY-12) 0.03；
Adipic dihydrazide (ADH) 6, N-[2-(2-methyl-4-oxopentyl) 13, sodium formaldehyde sulphoxylate 0.3, potassium peroxydisulfate 1.2, carbonic acid Hydrogen sodium 1.3, tert-butyl hydroperoxide 0.3, phenylpropyl alcohol isothiazolone 0.8, deionized water 350.
The acrylate monomer by the butyl acrylate of 4 ﹕, 5 ﹕, 5 ﹕, 10 ﹕, 5 ﹕ 30, dibutyl maleate, olefin(e) acid hydroxyl ethyl ester, 2-Propenoic acid, 2-methyl-, isooctyl ester, methacrylic acid and styrene composition.
Preparation method is as follows：
(1) first by diisocyanate IPDI and PTMG, its chlorinated polypropylene glycol (PPG) reacts, so Add dibutyltin dilaurate (DY-12), 1,4 1 butanediols (BDO), trimethylolpropane, dihydromethyl propionic acid afterwards DMPA, N, N- dihydroxy (diisopropyl) aniline (HPA) and acetone, the slow high-temperature that rises react 22min, are gathered to 75 DEG C Urethane performed polymer；Less than 50 DEG C are cooled to, and evacuation removes acetone；
(2) acrylate monomer, dimethyl ethanol amine neutralizer are added in base polyurethane prepolymer for use as, is stirred after mixing equal It is even, add 300 parts of deionized water, N-[2-(2-methyl-4-oxopentyl) to disperse 30 minutes at a high speed, add diethylenetriamine, continue stirring equal Even, 55 DEG C of sustained responses 70min carry out chain growth；Obtain water-borne polyurethane-acrylate monomer mixed emulsion；
During in the middle of the mixed emulsion for preparing 20% is added in reactor, the remaining deionized water of addition heats up To 80 DEG C, oxidant potassium peroxydisulfate is added to be caused；Now note control temperature jump, maintain after the general obvious blue light of emulsion Reaction temperature is constant, Deca remainder mixed emulsion and buffer agent sodium bicarbonate.
Reaction adds tert-butyl hydroperoxide and sodium formaldehyde sulphoxylate to carry out post processing after terminating, and reduces residual monomer Content.Insulation adds phenylpropyl alcohol isothiazolone, adipic dihydrazide (ADH) to stir after terminating, fill after cooling.
Overall merit of the compound impregnating resin of aqueous polyurethane acrylate (PUA) as dipping glue
After testing, the watersoluble polyurethane acrylic acid PUA composite resins that the present invention is provided, have good applying to graining paper Work performance, and obtained dipping paper, have good performance and widely application；Contrast is as follows：

Claims (6)

1. novel aqueous polyurethane acroleic acid is combined impregnating resin, including following component and corresponding weight portion；
Acrylate monomer 55-60, one butanediol 1-2 of Isosorbide-5-Nitrae, dihydromethyl propionic acid 2-5, trimethylolpropane 2-5, divinyl three Amine 0.5-1.5；
N, N- dihydroxy (diisopropyl) aniline 1-3, diisocyanate 10-20, PTMG 10-15, oxidation are poly- Propylene glycol 20-30；
Dimethylethanolamine 2-6, acetone 30-50, dibutyltin dilaurate (DY-12) 0.03, adipic dihydrazide 5-7, double third Ketone acrylamide 10-15, sodium formaldehyde sulphoxylate 0.1-0.5, potassium peroxydisulfate 1-1.3, sodium bicarbonate 1-1.5, tert-butyl group mistake Hydrogen oxide 0.1-0.5, phenylpropyl alcohol isothiazolone 0.5-1, deionized water 350-370.
2. novel aqueous polyurethane acroleic acid according to claim 1 is combined impregnating resin, it is characterised in that：The propylene Acid ester monomer is by the butyl acrylate of 2-4 ﹕ 5-10 ﹕ 2-5 ﹕ 10-15 ﹕ 2-5 ﹕ 30-40, dibutyl maleate, olefin(e) acid hydroxyl ethyl ester, first Base Isooctyl acrylate monomer, methacrylic acid and styrene composition.
3. the preparation method of the compound impregnating resin of novel aqueous polyurethane acroleic acid described in claim 1 is as follows：
(1) preparation of base polyurethane prepolymer for use as
First by diisocyanate and PTMG, then the reaction of its chlorinated polypropylene glycol adds dibutyl tin two Laurate, one butanediol of Isosorbide-5-Nitrae, trimethylolpropane, dihydromethyl propionic acid, N, N- dihydroxy (diisopropyl) aniline, acetone, The slow high-temperature that rises reacts 15-30min, obtains base polyurethane prepolymer for use as, be cooled to less than 50 DEG C to 75 DEG C, and evacuation is removed Acetone；
(2) prepared by water-borne polyurethane-acrylate monomer mixed emulsion
Acrylate monomer, dimethyl ethanol amine neutralizer are added in base polyurethane prepolymer for use as, is stirred after mixing, addition is gone 300 parts of mass parts ionized waters, N-[2-(2-methyl-4-oxopentyl)s, dispersion 30 minutes, add diethylenetriamine, continue to stir at a high speed, In 50-60 DEG C, low temperature continuous reaction 40-90min, carries out chain growth；Obtain water-borne polyurethane-acrylate monomer mixed emulsion；
(3), during be added to 20% in the middle of the mixed emulsion for preparing in reactor, add deionized water, be warming up to 80 DEG C, add oxidant potassium peroxydisulfate to be caused；After the general obvious blue light of emulsion, maintain reaction temperature constant, the remaining mixing of Deca Emulsion and oxidant and remaining initiator and buffer agent sodium bicarbonate.
4. described novel aqueous polyurethane acroleic acid according to claim 3 is combined the preparation method of impregnating resin, its It is characterised by：Reaction adds tert-butyl hydroperoxide and sodium formaldehyde sulphoxylate to carry out post processing and reduces residual monomer after terminating Content.
5. described novel aqueous polyurethane acroleic acid according to claim 4 is combined the preparation method of impregnating resin, its It is characterised by：Insulation adds phenylpropyl alcohol isothiazolone, adipic dihydrazide after terminating, and stirs, fill after cooling.
6. described novel aqueous polyurethane acroleic acid according to claim 5 is combined the preparation method of impregnating resin, its It is characterised by：Logical nitrogen protection is noted in course of reaction；Need to cool in time during reaction system very exothermic.
CN201610974193.XA 2016-11-07 2016-11-07 Compound impregnating resin of novel aqueous polyurethane acroleic acid and preparation method thereof Pending CN106543394A (en)

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CN112921707A (en) * 2021-03-03 2021-06-08 东莞市贝辉装饰材料有限公司 Formaldehyde-free impregnated bond paper and preparation method thereof

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Application publication date: 20170329