CN103524708A - Preparation method of closed water-based polyurethane modified PAE (polyarylether) wet strength agent - Google Patents
Preparation method of closed water-based polyurethane modified PAE (polyarylether) wet strength agent Download PDFInfo
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- CN103524708A CN103524708A CN201310485803.6A CN201310485803A CN103524708A CN 103524708 A CN103524708 A CN 103524708A CN 201310485803 A CN201310485803 A CN 201310485803A CN 103524708 A CN103524708 A CN 103524708A
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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
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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
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/2805—Compounds having only one group containing active hydrogen
-
- 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
- C08G18/2805—Compounds having only one group containing active hydrogen
- C08G18/285—Nitrogen containing compounds
- C08G18/286—Oximes
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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
- C08G18/28—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
- C08G18/60—Polyamides or polyester-amides
- C08G18/603—Polyamides
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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
- C08G18/28—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
- C08G18/6633—Compounds of group C08G18/42
- C08G18/6659—Compounds of group C08G18/42 with compounds of group C08G18/34
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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
- C08G18/28—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
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- 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
- D21H21/20—Wet strength 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
- D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
- D21H17/20—Macromolecular organic compounds
- D21H17/33—Synthetic macromolecular compounds
- D21H17/46—Synthetic macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- D21H17/54—Synthetic macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen
- D21H17/57—Polyureas; Polyurethanes
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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 invention provides a preparation method of a sealed water-based polyurethane modified PAE (polyarylether) wet strength agent, which comprises the following steps: carrying out vacuum dehydration on polyalcohol and carboxylic acid chain extender, adding organic solvent and polyisocyanate, reacting in a nitrogen atmosphere to obtain NCO-terminated polyurethane prepolymer, and adding a closing agent to react until the -NCO content is zero to obtain a closed polyurethane prepolymer; mixing polyethylene polyamine, dibasic acid and catalyst to carry out polycondensation reaction, removing the generated water by distillation, cooling to 120-140 DEG C, and adding hot water to obtain a polyamide-imide solution; and sequentially adding water and the closed polyurethane prepolymer into the polyamide-imide solution, dissolving by stirring, adding epoxy chloropropane to react, adding a terminator when the system viscosity reaches 40-100 cps, and regulating the pH value of the system to 3.0-5.0. Compared with the traditional PAE wet strength agent, after the wet strength agent provided by the invention is applied to paper, the dry tensile index, wet tensile index, wet strength retention and folding strength are enhanced.
Description
Technical field
The present invention relates to a kind of preparation method who seals waterborne polyurethane modified PAE Wet Strength Resin.
Background technology
Traditional Wet Strength Resin, mainly to take the neutral and alkali slaking Wet Strength Resin that the acid slaking Wet Strength Resin that urea-formaldehyde resin and melamine resin be representative and the daiamid epoxy chloropropane of take be representative, but can discharge a certain amount of formaldehyde in the use procedure of acid slaking Wet Strength Resin, contaminate environment, and need to slaking under lower ph value, broken is recycled certain difficulty; Daiamid epoxy chloropropane Wet Strength Resin water resisting property is not as terpolycyantoamino-formaldehyde resin, improving aspect paper industry dry strength effect not obvious, content of organic chloride is high, is considered to carcinogenic danger.
Isocyanic ester is the compound that contains isocyanate group (NCO) in molecule.It is upper that its chemically reactive is mainly manifested in its characteristic group-NCO, and this group has overlapping two strong unsaturated strong structure of height (N=C=O) of arranging, and its energy and the various compound that contains reactive hydrogen react, and chemical property is extremely active.
Polyisocyanates can with paper fiber in hydroxyl generation chemical reaction, generate polyurethane ester structure, the original hydrogen bonded of paper fiber is converted into chemical bonds, therefore can improve the physicals of paper.But isocyanic ester is easy and water reacts, and has limited its use in papermaking.
Blocked polyisocyanates is the derivative of isocyanic ester, during use, through deblocking, can recover reactive behavior.Polyisocyanates and isocyanate-terminated prepolymer can form " bridge formation " structure between fiber, can significantly improve paper wet tenacity.
Summary of the invention
The object of this invention is to provide the waterborne polyurethane modified PAE(polyamide-imide epoxy chloropropane of a kind of sealing) preparation method of Wet Strength Resin, the above-mentioned defect existing to overcome prior art.
The present invention seals the preparation method of waterborne polyurethane modified PAE Wet Strength Resin, comprises the steps:
(1) after polyvalent alcohol and carboxylic acid type chainextender are dewatered under vacuum, add organic solvent and polyisocyanates, in nitrogen atmosphere, react in system-NCO group content reaches theoretical value, obtain holding the base polyurethane prepolymer for use as of NCO base, add encapsulant, reaction to its-NCO group content is zero, obtains enclosed polyurethane performed polymer;
(2) polyethylene polyamine, diprotic acid and catalyst mix are carried out to polycondensation, the moisture of generation heats up in a steamer after removal, is cooled to 120-140 ℃ and slowly adds 60-80 ℃ of hot water, and cooling discharging after stirring, obtains polyamide-imide liquor;
(3) water, enclosed polyurethane performed polymer are added to stirring and dissolving in polyamide-imide liquor in turn, be warming up to 60-75 ℃, add epoxy chloropropane, reaction 2-5 hour, when system viscosity reaches 40.0-100.0cps, add terminator, tune system pH is 3.0-5.0.
As preferred version, each step reaction condition is as follows:
(1) polyvalent alcohol and carboxylic acid type chainextender were dewatered after 1-3 hour under 60-100 ℃ of vacuum, add organic solvent and polyisocyanates, in nitrogen atmosphere, 70～100 ℃ react in system-NCO group content reaches theoretical value, obtain holding the polyurethane prepolymer of NCO base, add encapsulant, at 75-85 ℃ reaction to its-NCO group content is zero, obtains enclosed polyurethane performed polymer;
(2) by polyethylene polyamine, diprotic acid and catalyst mix, the automatically violent intensification heat release of system; Be warming up to 170-180 ℃ and carry out polycondensation 2-4 hour, and the moisture that reaction is generated distillates after system, be cooled to 120-140 ℃ and add appropriate hot water, cooling discharging after stirring, obtain polyamide-imide liquor, solid content is 40-60%, and viscosity is 200-300cps;
(3) water, sealing urethane are added to stirring and dissolving in polyamide-imide liquor in turn, be warming up to 60-75 ℃, slowly add epoxy chloropropane, and at this temperature, react after 2-5 hour, when system viscosity reaches 40.0-100.0cps, add terminator, tune system pH is 3.0-5.0, obtains the waterborne polyurethane modified PAE Wet Strength Resin of described sealing.
In step (1), each composition weight umber is as follows:
Described polyvalent alcohol is selected from least one in poly adipate succinic acid ester dibasic alcohol, polytetrahydrofuran diol, polyoxypropyleneglycol, poly-SA butanediol ester dibasic alcohol or polyneopentyl glycol adipate dibasic alcohol;
Described carboxylic acid type chainextender is dimethylol propionic acid or dicarboxyl half ester;
Described polyisocyanates is selected from least one of tolylene diisocyanate, '-diphenylmethane diisocyanate, six methylene diisocyanates or isophorone diisocyanate;
Described organic solvent is selected from least one of acetone, butanone, DMF or N-Methyl pyrrolidone;
Described encapsulant is methyl ethyl ketoxime or acetoxime;
In step (2), the mol ratio of described polyethylene polyamine and diprotic acid is: 1-1.05:1; Described catalyzer is water, and add-on is 30% of polyethylene polyamine molar mass.
Described polyethylene polyamine is selected from diethylenetriamine, triethylene tetramine or tetraethylene pentamine, preferably diethylenetriamine;
Described diprotic acid select oneself diacid, pimelic acid or suberic acid, preferably hexanodioic acid;
Described terminator is hydrochloric acid, sulfuric acid or Glacial acetic acid.
The mol ratio of sealing base polyurethane prepolymer for use as and described polyamide-imide (not moisture) and epoxy chloropropane described in step (3) is: sealing urethane: polyamide-imide: epoxy chloropropane=1:7-8:2.5-4; The add-on of water is that to make the solid content of the finished product be 20-30wt%.
The present invention first reacts with polyisocyanates with polyvalent alcohol, carboxylic acid type chainextender in organic solvent, make the base polyurethane prepolymer for use as of isocyanate terminated base, then use encapsulant end-blocking, part substitutes epoxy chloropropane and reacts with polyamide-imide (PPC), be prepared into the polyurethane-modified PAE Wet Strength Resin of sealing, compare with traditional PAE Wet Strength Resin, there is good storage stability, because wet end adds, the dry tensile index of paper, wet tensile index, wet strength retention and folding endurance all have raising in various degree.
Embodiment
Embodiment 1
(1), the preparation of sealing base polyurethane prepolymer for use as: by 100g poly adipate succinic acid ester dibasic alcohol (molecular weight is 1000) and 8g2; 2 '-dimethylol propionic acid is put into the four-hole boiling flask with stirring and heating unit; after 100 ℃ of vacuum hydro-extraction 1h; add N methyl-2-pyrrolidone that 180g is dry and 41.8g tolylene diisocyanate ([NCO]/[OH]=1.5) in 80 ℃ under nitrogen protection reaction to its NCO content reach theoretical value, obtain holding the polyurethane prepolymer of NCO base.Then it is zero adding 7g methyl ethyl ketoxime at 80 ℃, to react to its NCO content, obtains blocked polyurethane prepolymer;
(2), the preparation of PPC: in the four-hole boiling flask of stirring, prolong is housed, add 103 grams of diethylenetriamines and 31 grams of deionized waters, open and stir, under agitation slowly add 146 grams of hexanodioic acids, make system temperature not over 130 ℃, after adding, stir 20 minutes, then with heating jacket, be heated to 170 ℃, collect water of condensation simultaneously, react after three hours, stop heating, when system temperature is down to 140 ℃, add 213 grams of deionized waters, be cooled to room temperature, the solid content PPC(glassy yellow transparent liquid that is 50%), viscosity is 300cps;
(3), in the four-hole boiling flask of stirring, prolong and dropwise adding pipeline is housed; add 336 grams of deionized waters, sealing base polyurethane prepolymer for use as 83 grams (0.025mol), 50% PPC74.5 gram (PPC0.175mol); open and stir; be warming up to 60 ℃; and at this temperature, slowly drip 4.20 grams of epoxy chloropropane (0.05mol); time for adding is 5 minutes; after dropwising; at this temperature, react after 5.0 hours; add 2.5 grams, 50% sulfuric acid, obtain product MPAE(emulsion form), its solid content is 25.0%; viscosity is 76cps, and pH extremely value is 3.96;
Embodiment 2
(1) by 100g polytetrahydrofuran diol (molecular weight is 1000) and 9.4g2; 2 '-dimethylol propionic acid is put into the four-hole boiling flask with stirring and heating unit; after 100 ℃ of vacuum hydro-extraction 1h; add N methyl-2-pyrrolidone and the 55g '-diphenylmethane diisocyanate ([NCO]/[OH]=1.3) that 180g is dry to react until its NCO content reaches theoretical value under nitrogen protection in 80 ℃, obtain holding the polyurethane prepolymer of NCO base.Then add 4.5g methyl ethyl ketoxime to react at 80 ℃, until its NCO content is zero, obtain blocked polyurethane prepolymer;
(2) preparation of PPC: in the four-hole boiling flask of stirring, prolong is housed, add 108 grams of diethylenetriamines and 31 grams of deionized waters, open and stir, under agitation slowly add 146 grams of hexanodioic acids, make system temperature not over 130 ℃, after adding, stir 20 minutes, then with heating jacket, be heated to 180 ℃, collect water of condensation simultaneously, react after 2 hours, stop heating, when system temperature is down to 140 ℃, add 218 grams of deionized waters, be cooled to room temperature, the solid content PPC(glassy yellow transparent liquid that is 50%), viscosity is 230cps;
(3), in the four-hole boiling flask of stirring, prolong and dropwise adding pipeline is housed, add 371 grams of deionized waters, sealing base polyurethane prepolymer for use as 86.1 grams (0.025mol), 50% PPC85.1 gram (PPC0.2mol), open and stir, be warming up to 70 ℃, and at this temperature, slowly drip 9.25 grams of epoxy chloropropane (0.1mol), time for adding is 10 minutes, after dropwising, at this temperature, react after 2.0 hours, add 2.64 grams, 50% sulfuric acid, obtain product MPAE(emulsion form), its solid content is 24.8%, viscosity is 45cps, and pH extremely value is 3.71;
Embodiment 3
(1) by 100g polyneopentyl glycol adipate dibasic alcohol (molecular weight is 2000) and 4.7g2; 2 '-dimethylol propionic acid is put into the four-hole boiling flask with stirring and heating unit; after 100 ℃ of vacuum hydro-extraction 1h; add 170g N methyl-2-pyrrolidone and 32g isophorone diisocyanate ([NCO]/[OH]=1.7) to react until its NCO content reaches theoretical value under nitrogen protection in 80 ℃, obtain holding the polyurethane prepolymer of NCO base.Then add 5.2g methyl ethyl ketoxime to react at 80 ℃, until its NCO content is zero, obtain blocked polyurethane prepolymer;
(2) preparation of PPC: in the four-hole boiling flask of stirring, prolong is housed, add 108 grams of diethylenetriamines and 31 grams of deionized waters, open and stir, under agitation slowly add 146 grams of hexanodioic acids, make system temperature not over 130 ℃, after adding, stir 20 minutes, then with heating jacket, be heated to 175 ℃, collect water of condensation simultaneously, react after 2.5 hours, stop heating, when system temperature is down to 140 ℃, add 218 grams of deionized waters, be cooled to room temperature, the solid content PPC(glassy yellow transparent liquid that is 50%), viscosity is 200cps;
(3), in the four-hole boiling flask of stirring, prolong and dropwise adding pipeline is housed, add 230 grams of deionized waters, sealing base polyurethane prepolymer for use as 61.2 grams (0.01mol), 50% PPC32 gram (PPC0.075mol), open and stir, be warming up to 65 ℃, and at this temperature, slowly drip 9.25 grams of epoxy chloropropane (0.1mol), time for adding is 80 minutes, after dropwising, at this temperature, react after 4.0 hours, add 2.33 grams, 50% sulfuric acid, obtain product MPAE(emulsion form), its solid content is 25.6%, viscosity is 96cps, and pH extremely value is 3.32;
Embodiment 4
Blank technique: slurry 28g/m
2+ PCC5g/m
2(sub-prosperous fine particle calcium carbonate)+CPAM(200ppm)
Adding technology: slurry 28g/m
2+ Wet Strength Resin+PCC5g/m
2(sub-prosperous fine particle calcium carbonate)+CPAM(200ppm)
Wet Strength Resin addition: 0.8 ‰, paper basis weight 30.0 ± 1.0g/m2,
Take appropriate slurry, add AKD, Wet Strength Resin to stir 1 minute, then add PCC to stir 1 minute, after red Bel's handshcet former handsheet is shaped, squeezing machine squeezing, natural air drying, then detects the indexs such as dry, wet tenacity of pattern for 15 minutes after equilibrium water content 105 ℃ of baking oven slakings.
The indices of paper is as following table:
Note: the sample of comparative sample for adopting CN1966855A method to prepare.
As can be seen from the above data, addition (dry/dry) in the situation that, compare with comparative sample, its wet tensile (strength), the dry anti-intensity that rises, wet/dry, the wet tensile index of the anti-intensity that rises and folding endurance etc. are all greatly improved.
Claims (10)
1. the preparation method of the waterborne polyurethane modified PAE Wet Strength Resin of sealing, is characterized in that, comprises the steps:
(1) after polyvalent alcohol and carboxylic acid type chainextender are dewatered under vacuum, add organic solvent and polyisocyanates, in nitrogen atmosphere, react in system-NCO group content reaches theoretical value, obtain holding the base polyurethane prepolymer for use as of NCO base, add encapsulant, reaction to its-NCO group content is zero, obtains enclosed polyurethane performed polymer;
(2) polyethylene polyamine, diprotic acid and catalyst mix are carried out to polycondensation, the moisture of generation heats up in a steamer after removal, is cooled to 120-140 ℃ and slowly adds 60-80 ℃ of hot water, and cooling discharging after stirring, obtains polyamide-imide liquor;
(3) water, enclosed polyurethane performed polymer are added to stirring and dissolving in polyamide-imide liquor in turn, be warming up to 60-75 ℃, add epoxy chloropropane, reaction 2-5 hour, when system viscosity reaches 40.0-100.0cps, add terminator, tune system pH is 3.0-5.0.
2. method according to claim 1, is characterized in that, in step (1), each component parts by weight are as follows:
3. method according to claim 1, it is characterized in that, described polyvalent alcohol is selected from least one in poly adipate succinic acid ester dibasic alcohol, polytetrahydrofuran diol, polyoxypropyleneglycol, poly-SA butanediol ester dibasic alcohol or polyneopentyl glycol adipate dibasic alcohol.
4. method according to claim 1, is characterized in that, described carboxylic acid type chainextender is dimethylol propionic acid or dicarboxyl half ester.
5. method according to claim 1, is characterized in that, described polyisocyanates is selected from least one of tolylene diisocyanate, '-diphenylmethane diisocyanate, six methylene diisocyanates or isophorone diisocyanate.
6. method according to claim 1, is characterized in that, described organic solvent is selected from least one of acetone, butanone, DMF or N-Methyl pyrrolidone; Described encapsulant is methyl ethyl ketoxime or acetoxime.
7. method according to claim 1, is characterized in that, in step (2), the mol ratio of described polyethylene polyamine and diprotic acid is: 1-1.05:1; Described catalyzer is water, and add-on is 30% of polyethylene polyamine molar mass.
8. method according to claim 1, is characterized in that, described polyethylene polyamine is selected from diethylenetriamine, triethylene tetramine or tetraethylene pentamine, preferably diethylenetriamine; Described diprotic acid select oneself diacid, pimelic acid or suberic acid, preferably hexanodioic acid; Described terminator is hydrochloric acid, sulfuric acid or Glacial acetic acid.
9. method according to claim 1, is characterized in that, the mol ratio of sealing base polyurethane prepolymer for use as and described polyamide-imide and epoxy chloropropane described in step (3) is: sealing urethane: polyamide-imide: epoxy chloropropane=1:7-8:2.5-4; The add-on of water is that to make the solid content of the finished product be 20-30wt%.
10. according to the method described in claim 1-9 any one, it is characterized in that, comprise the steps:
(1) polyvalent alcohol and carboxylic acid type chainextender were dewatered after 1-3 hour under 60-100 ℃ of vacuum, add organic solvent and polyisocyanates, in nitrogen atmosphere, 70～100 ℃ react in system-NCO group content reaches theoretical value, obtain holding the polyurethane prepolymer of NCO base, add encapsulant, at 75-85 ℃ reaction to its-NCO group content is zero, obtains enclosed polyurethane performed polymer;
(2) by polyethylene polyamine, diprotic acid and catalyst mix, the automatically violent intensification heat release of system; Be warming up to 170-180 ℃ and carry out polycondensation 2-4 hour, and the moisture that reaction is generated distillates after system, be cooled to 120-140 ℃ and add appropriate hot water, cooling discharging after stirring, obtain polyamide-imide liquor, solid content is 40-60%, and viscosity is 200-300cps;
(3) water, sealing urethane are added to stirring and dissolving in polyamide-imide liquor in turn, be warming up to 60-75 ℃, slowly add epoxy chloropropane, and at this temperature, react after 2-5 hour, when system viscosity reaches 40.0-100.0cps, add terminator, tune system pH is 3.0-5.0, obtains the waterborne polyurethane modified PAE Wet Strength Resin of described sealing.
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Cited By (11)
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| CN103866631A (en) * | 2014-02-25 | 2014-06-18 | 苏州恒康新材料有限公司 | Wet strength agent rich in fumaric acid and preparation method thereof |
| CN103866629A (en) * | 2014-02-28 | 2014-06-18 | 苏州恒康新材料有限公司 | Papermaking processing aid and preparation method thereof |
| CN103981760A (en) * | 2014-04-21 | 2014-08-13 | 苏州恒康新材料有限公司 | Modified polyamine epichlorohydrin wet strength agent and preparation method thereof |
| CN103993503A (en) * | 2014-04-21 | 2014-08-20 | 苏州恒康新材料有限公司 | Water-soluble paper wet strength agent and preparation method thereof |
| CN105445446A (en) * | 2015-12-25 | 2016-03-30 | 广东华凯科技股份有限公司 | Wet strength agent immersion detection method |
| CN105672033A (en) * | 2016-02-01 | 2016-06-15 | 杭州杭化哈利玛化工有限公司 | Modified PAE (polyamide epichlorohydrin resin) coating waterproof agent and preparation method thereof |
| CN106832185A (en) * | 2017-01-04 | 2017-06-13 | 上海华峰材料科技研究院（有限合伙） | Epoxy-capped polyurethane resin of use for synthetic leather large arch dam and preparation method thereof |
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| CN103866631B (en) * | 2014-02-25 | 2016-04-06 | 徐海军 | A kind of wet strength agent containing fumaric acid and preparation method thereof |
| CN103866629A (en) * | 2014-02-28 | 2014-06-18 | 苏州恒康新材料有限公司 | Papermaking processing aid and preparation method thereof |
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| CN103993503B (en) * | 2014-04-21 | 2016-01-13 | 南通玖伍捌科技企业孵化器有限公司 | Water-soluble wet strengthening agents for papermaking and preparation method thereof |
| CN103981760A (en) * | 2014-04-21 | 2014-08-13 | 苏州恒康新材料有限公司 | Modified polyamine epichlorohydrin wet strength agent and preparation method thereof |
| CN105445446A (en) * | 2015-12-25 | 2016-03-30 | 广东华凯科技股份有限公司 | Wet strength agent immersion detection method |
| CN105672033A (en) * | 2016-02-01 | 2016-06-15 | 杭州杭化哈利玛化工有限公司 | Modified PAE (polyamide epichlorohydrin resin) coating waterproof agent and preparation method thereof |
| CN106832185A (en) * | 2017-01-04 | 2017-06-13 | 上海华峰材料科技研究院（有限合伙） | Epoxy-capped polyurethane resin of use for synthetic leather large arch dam and preparation method thereof |
| CN107012731A (en) * | 2017-04-17 | 2017-08-04 | 浙江恒川新材料有限公司 | A kind of preparation method of the cross-linking modified high wet strength agent of PAE papermaking of environment-friendly type |
| CN107012731B (en) * | 2017-04-17 | 2018-10-16 | 浙江恒川新材料有限公司 | A kind of preparation method of the cross-linking modified high wet strength agent of PAE papermaking of environment-friendly type |
| CN108999030A (en) * | 2018-07-11 | 2018-12-14 | 张培磊 | A kind of high tenacity decorating base paper and preparation method thereof |
| CN109575278A (en) * | 2018-11-22 | 2019-04-05 | 山东同创精细化工股份有限公司 | A kind of strong PAE of high humidity and preparation method thereof |
| CN110004767A (en) * | 2019-02-25 | 2019-07-12 | 吴义峰 | A kind of high intensity wet strength agent for papermaking and preparation method thereof |
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