CN101805438A - Preparation method and applications of cationic waterborne polyurethane surface sizing agent - Google Patents
Preparation method and applications of cationic waterborne polyurethane surface sizing agent Download PDFInfo
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Abstract
The invention discloses a preparation method of cationic waterborne polyurethane, belonging to the field of organic adhesives. The technologic route implemented according to the following steps is divided into three stages: the first stage: prepolymerization, namely polyol, small molecular hydroxyl monomer, isocyanate and modified monomer are subject to stepwise polymerization and free radical polymerization to generate modified polyurethane prepolymer; the second stage: chain extension, namely the prepolymer is dropwise added with hydrophilic chain extending monomer (monomer containing hydrophilic groups), and ionizing groups are introduced in; and the third stage: neutralization and emulsification. Aiming at the above defects of the waterborne polyurethane surface sizing agent, polyurethane is modified by hydrophobic monomer in the method, and the modified polyurethane emulsion has excellent water resistance and stability. Paper subject to the sizing of the product according to the invention has obviously enhanced using performance.
Description
Technical field
The invention belongs to the organic binder bond field, relate to a kind of preparation method of cationic waterborne polyurethane surface sizing agent.
Background technology
Applying glue is the important step in the paper-making process, and it can give paper product certain liquid-repellency energy, and increases its intensity.The applying glue process is to utilize the hydrophobic nature material to be covered in the paper fiber surface to form one deck hydrophobic film, reduces the fiber surface free energy, thereby resists water or other liquid in the diffusion of fiber surface, wetting or infiltration, and the material that possesses this performance is referred to as sizing agent.Applying glue has two kinds of methods, and a kind of is that when batching (making beating or) makes an addition to sizing agent and be called plasm-glue-blending in the paper pulp before paper sheet formation, and another kind is to cover with paint, lacquer, colour wash, etc. in paper surface to be called top sizing behind paper sheet formation.Top sizing can improve the printing performance of paper and cardboard, improves anti-oil, anti-water, durable and wear resistance, improves physical strength, and the two sides of minimizing even elimination paper is poor.
Surface Size can be divided into natural polymer Surface Size and polymer Surface Sizing Agent.Last century the nineties, starch based natural polymer Surface Size consumption accounts for more than 90% of Surface Size total amount, but native starch class Surface Size film-forming properties is poor, the gelatinization flowability is not satisfactory, the variable muddy gel that forms during cooling, this has limited the application of native starch class Surface Size.Since during acid papermaking is converted in a large number/alkaline paper-making, during the synthetic surface sizing agent can overcome or remedy/some shortcoming of alkaline paper-making,, applying glue reverse slow as slaking, frictional coefficient are lower etc., and can conveniently change paper surface properties economically, but production high added value paper kind, thereby obtain more and more widely application.Aqueous polyurethane (WPU) is the class in the synthetic surface sizing agent, it with water as dispersion medium, it is good to have film forming properties, the cohesive strength height, characteristics such as wear-resisting, cold-resistant, pliable and tough, and nonpoisonous and tasteless, meet the environmental regulation requirement of increasingly stringent, in plastics, coating, building, weaving etc. are multi-field, be widely used, in paper industry, also become the research focus gradually.
Have on the cation aqueous polyurethane polymer molecular chain-NH-COO-base and cation group, it has some unique character, can directly combine with the negative charge of fiber after the positive charge applying glue of cation type polyurethane, form glued membrane and reach sizing efficiency preferably at fiber surface.Companies such as Germany BK, Bayer, BASF have released one after another based on cationic aqueous polyurethane product, and at present, cationic waterborne polyurethane surface sizing agent has become a research focus in the papermaking chemical product.But its resistance to elevated temperatures is not good, poor water resistance.
For addressing this problem, the Liu Jianping of domestic Shaanxi Tech Univ, Yang Xiaomin are in " development of cation polyurethane sizing agent and application experiment " literary composition, with tolylene diisocyanate (TDI), glyceryl monostearate is a raw material, with the N methyldiethanol amine is chainextender, with acetone is solvent, reacts to obtain aqueous polyurethane emulsion in 6.5 hours.The influence to dairy industry stability of raw material NCO/OH value, temperature of reaction and time, chainextender consumption, solvent load has been discussed, and emulsion has been carried out structural characterization with TEM and FT-IR.The synthesis condition that has drawn urethane the best is: the NCO/OH value is at 1.05～1.15; The chainextender consumption accounts for 12.5%～15% of total amount; Total reaction time is 6.5 hours.What TEM and FT-IR microcosmic showed that it synthesizes is a kind of with amino PAUR emulsion.The preparation of this method be internal sizing agent, raw materials used more expensive, cost is higher, and internal sizing agent to use more now be cheap colophony type sizing agent, so its application is restricted.
Liu Jianfu, Xie Yiming is in " colophony type urethane synthetic sizing agent and the application in papermaking " literary composition, react 2.5 hours synthesis of polyurethane performed polymers with tolylene diisocyanate (TDI) and esterified rosin down at 70～80 ℃, utilize the methyldiethanolamine chain extension, (APAM) makes end-capping reagent with sodium bisulfite, and final emulsion obtains cation colophony type polyurethane emulsion.This kind sizing agent is applied to plasm-glue-blending, has studied the chainextender consumption, pH value and APAM consumption are to the influence of urethane sizability.Experiment shows, under the neutral and alkali condition, when the sizing agent consumption is 2%, the APAM consumption is 0.02% o'clock, and the degree of sizing of paper can reach 25s, and paper is had tangible enhancement.But this method is made end-blocking with S-WAT, the difficult control of reaction, and sizing efficiency is difficult to reach the requirement of the paper product that degree of sizing is had relatively high expectations.
Chinese patent CN 101440152A has reported a kind of preparation method of cation aqueous polyurethane emulsion and the application on top sizing thereof.This method is reacted 0.5～2 hour synthetic performed polymer by tolylene diisocyanate (TDI), the pure and mild polyoxyethylene glycol of polyester binary down at 45-55 ℃, 60～70 ℃ with 1,4-chain expansion of succinic acid 2-3 hour, with in the Glacial acetic acid and salify, under high-speed stirring, add emulsifying water, make cation aqueous polyurethane emulsion.Use but the emulsion that this preparation method makes needs with Tai-Ace S 150 or poly-aluminium is collaborative, do not meet the trend of paper industry plasm-glue-blending neutral and alkaliization, and degree of sizing is difficult to satisfy the requirement of cultural paper, still have with a certain distance from practical application.
Chinese patent CN 101654893A has reported the preparation method of a kind of cation polyurethane/positively charged ion styrene-acrylic composite emulsion Surface Size.This method is by isophorone diisocyanate, 1,4-butyleneglycol, polyoxyethylene react 1.5～3 hours synthetic performed polymers down at 60～65 ℃, under agitation drip the butanone solution of positively charged ion chainextender, dropwising the back reacted 3～4 hours down at 60～65 ℃, with in the neutralizing agent and salify, under high-speed stirring, add emulsifying water, make the cation polyurethane emulsion.The aqueous solution of drip styrene, acrylate, cationic monomer, acrylamide and water-soluble azo class initiator in the cation polyurethane emulsion reacted 2～4 hours again, promptly made cation polyurethane/positively charged ion phenylpropyl alcohol and met emulsion surface sizing agent.This method technology is complicated, and generated time is longer, and cation polyurethane/positively charged ion styrene-acrylic composite emulsion shelf-stable performance is not good, and the emulsion smell is bigger.
Summary of the invention
The object of the present invention is to provide a kind of preparation method of cation surface sizing agent, prepared cation aqueous polyurethane emulsion as the Surface Size of paper and cardboard, can improve surface strength, degree of sizing and other performance of paper and cardboard.
Operational path of the present invention is divided into three phases: the fs is prepolymerization, promptly passes through progressively polymerization and radical polymerization by polyvalent alcohol, micromolecular hydroxyl monomer, isocyanic ester and modified monomer, generates modified polyurethane prepolymer; Subordinate phase is a chain extension, promptly drips hydrophilic chain extension monomer (monomer that contains hydrophilic radical) in performed polymer, introduces ionogen; Phase III is neutralization and emulsification.
The preparation method of cation aqueous polyurethane of the present invention is undertaken by following step:
1) preparation of base polyurethane prepolymer for use as: with polyvalent alcohol at 90 ℃, the 1h 0.08 dewater under～0.1Mpa the vacuum tightness, regulate 50～80 ℃ of pre-polymerization temperature, the isocyanate-monomer that adds metering, the micromolecular hydroxyl monomer, modified monomer and catalyzer di-n-butyltin dilaurate, control R value is 1.50～3.00 in the prepolymerization reaction process, the ratio of the mole number of total OH group in the R mole number that refers in the system total NCO group and the system wherein, the dosage of modified monomer can be regulated according to emulsion property and sizing efficiency, according to R adjustable size joint prepolymer molecular weight, make each material generation polycondensation and radical polymerization follow grafting simultaneously, IPN is regulated the viscosity of synthetic middle prepolymer by adding solvent;
Wherein said polyvalent alcohol comprises polyether glycol, polyester polyol, polyester polyethers polyol blend etc.; Be preferable over polyoxypropyleneglycol, polybutadiene diol, acrylate polyvalent alcohol, polyethylene glycol adipate glycol, poly-hexanodioic acid-1,6-hexylene glycol esterdiol, poly-tetrahydrochysene fluorine mutter glycol, poly-hexanodioic acid-1,4-butanediol ester glycol (PBA), poly-epsilon-caprolactone glycol, polycarbonate-1,6-hexylene glycol esterdiol; More preferably in polyoxypropyleneglycol, polyethylene glycol adipate glycol, poly-hexanodioic acid-1,4-butanediol ester glycol, most preferably in poly-hexanodioic acid-1,4-butanediol ester glycol or poly-hexanodioic acid-1, the mixture of 4-butanediol ester glycol and polyoxypropyleneglycol or polytetrahydrofuran diol;
Wherein said isocyanate-monomer is tolylene diisocyanate (TDI), ditan-4,4 '-vulcabond (MDI), liquefied mdi, poly methylene poly phenyl poly isocyanate (PAPI), 1, hexamethylene-diisocyanate (HDI), isophorone diisocyanate (IPDI), methylene radical-dicyclohexyl-4,4 '-vulcabond (H
12MDI), Methylcyclohexyl diisocyanate (HTDI), be preferable over tolylene diisocyanate (TDI), liquefied mdi, isophorone diisocyanate (IPDI);
Alcohol, amine that wherein said micromolecular hydroxyl monomer is two functionality or three-functionality-degree, be preferable over 1,4-butyleneglycol, ethylene glycol, glycol ether (glycol ether), 2,2-dimethylol propionic acid (DMPA), n-formyl sarcolysine base diethanolamine, N, N-dimethylethanolamine, trolamine, TriMethylolPropane(TMP) and quadrol etc.; More preferably in glycol ether, 1,4 one butyleneglycol, ethylene glycol, it accounts for 1%～5% of total solids quality;
Wherein said modified monomer is glyceride type, terminal hydroxy group silicane, end aminosilane class, modified rosin class, be preferable over esterified rosin, glyceryl monostearate, hydroxypropyl polydimethylsiloxane, gamma-amino propyl group triethylamine base silane, it accounts for 1%～10% of solid masses;
Wherein said solvent is 1-Methyl-2-Pyrrolidone (NMP), N, and dinethylformamide, butanone, acetone, toluene are preferable over 1-Methyl-2-Pyrrolidone or acetone, and wherein solvent accounts for 1～10% of solid total mass.
2) chain extension: on the basis of the first step, performed polymer is reduced to 30～60 ℃, at the uniform velocity in bottle, drip the hydrophilic chain extender of certain metering, wherein said hydrophilic chain extender is 20%～40% with solvent cut to massfraction, solvent for use is with step 1, after dripping off, when reaching theoretical value, the R value carries out the next step;
Wherein said hydrophilic chain extender is alcohol, the amine of two functionality or three-functionality-degree, be preferable over 1,4-butyleneglycol, ethylene glycol, glycol ether (glycol ether), n-formyl sarcolysine base diethanolamine, N, N-dimethylethanolamine, trolamine, TriMethylolPropane(TMP) and quadrol etc.; More preferably in n-formyl sarcolysine base diethanolamine, N, N-dimethylethanolamine and trolamine, it accounts for 4%～16% of total solids quality.
3) neutralization and emulsification: on the basis in second step, add in the neutralizing agent and salify, degree of neutralization is 80%～120%, after 30 minutes, the aqueous solution of metering is scattered in the modified polyurethane prepolymer behind the salify, the control solid content is 10%～45%, and high-speed stirring 30 minutes, obtains outward appearance and is yellowish or the translucent cationic waterborne polyurethane surface sizing agent of oyster white;
Wherein said neutralizing agent is a Glacial acetic acid, dilute hydrochloric acid, dilute sulphuric acid, methyl-sulfate etc.; Be preferable over Glacial acetic acid, dilute hydrochloric acid, wherein neutralizing agent accounts for 2%～7% of PU (PU is except water and the total material of solvent) quality of material.
The present invention is directed to the above shortcoming of water-based polyurethane Surface Size, with hydrophobic monomer urethane is carried out modification, the polyaminoester emulsion after the modification has excellent water tolerance and stability.Paper is after product applying glue of the present invention, and use properties obviously improves.
Embodiment
Following example is used to illustrate the present invention, but never limits the scope of the invention.
Comparative Examples: with the poly-hexanodioic acid-1 of 7.5g, 4-butanediol ester glycol (PBA) and 4.17g polyoxypropyleneglycol (N210) add in the there-necked flask, mix and stir, and thermostatically heating under 90 ℃ of water bath condition vacuumizes dehydration 1h, and vacuum tightness is 0.098Mpa.Be cooled to 70 ℃, add 5.68gTDI, 0.58g glycol ether (DEG), 2g 1-Methyl-2-Pyrrolidone (NMP) and catalyzer di-n-butyltin dilaurate 0.12g, nco value in system gets performed polymer when reaching theoretical value substantially, be cooled to 55 ℃ then, at the uniform velocity drip hydrophilic chain extender nitrogen-methyldiethanolamine (is 30% with acetone diluted to massfraction) 2.00g, after dripping off, treat that the R value reaches theoretical value, with acetone (about 2～4g) dilutions, reduce viscosity, slowly add 1.20g Glacial acetic acid neutralize ionsization (degree of neutralization is 120%, and degree of neutralization refers to the mol ratio of neutralizing agent and hydrophilic chain extender) reaction 0.5h; Under high-speed stirring, add 70.44g water at last, reaction 0.5h, getting theoretical solid content is 25%, milky emulsion.
Embodiment 1: under the operational condition of Comparative Examples, add 1.0g hydroxypropyl polydimethylsiloxane (8427) again in there-necked flask before vacuumizing, add 53.79g water at last, getting theoretical solid content is 30%, faint yellow translucent emulsion.
Embodiment 2: under the operational condition of Comparative Examples, add the 0.5g glyceryl monostearate again in there-necked flask before vacuumizing, add 44.53g water at last, getting theoretical solid content is 35%, the translucent emulsion of oyster white.
Embodiment 3: under the operational condition of embodiment 1, change 5.68gTDI into 7.25g IPDI, in and the time add 0.1mol/L dilute hydrochloric acid 1.28g (degree of neutralization is 80%), add 225.05g water at last, theoretical solid content be 10%, colourless translucent emulsion.
Embodiment 4: under the operational condition of embodiment 2, changes 5.68gTDI into 8.85g MDI, under high-speed stirring, adds 34.57g water at last, and reaction 0.5h, getting theoretical solid content is 40%, gets yellow translucent emulsion.
Embodiment 5: under the operational condition of embodiment 1, changes 0.58g DEG into 0.34g ethylene glycol, under high-speed stirring, adds 78g water at last, and reaction 0.5h, getting theoretical solid content is 23.5%, gets faint yellow translucent emulsion.
Embodiment 6: under the operational condition of embodiment 2, with the poly-hexanodioic acid-1 of 7.50g, 4-butanediol ester glycol (PBA) changes 7.56g poly-epsilon-caprolactone glycol (PCL220) into, the hydrophilic chain extender that at the uniform velocity drips is changed to the 2.3g trolamine, add 40.59g water at last, getting theoretical solid content is 37%, faint yellow look translucent emulsion.
Embodiment 7: under the operational condition of embodiment 1, change 4.17g polyoxypropyleneglycol (N210) into the poly-tetrahydrochysene fluorine of the 3.72g glycol (PTMGl000) of muttering, at the uniform velocity drip hydrophilic chain extender nitrogen-methyldiethanolamine (is 30% with acetone diluted to massfraction) 2.4g, add 168.21g water at last, getting theoretical solid content is 12.5%, colourless translucent emulsion.
Embodiment 8: under the operational condition of embodiment 1, will gather hexanodioic acid-1,4-butanediol ester glycol (PBA) changes 12.5g into by 7.5g, and polyoxypropyleneglycol (N210) changes 1.39g into by 4.17g, and getting theoretical solid content is 26.7%, faint yellow translucent emulsion.
Embodiment 9: under the operational condition of embodiment 7, change the preparation temperature of performed polymer into 55 ℃, change the chain extension temperature into 40 ℃, theoretical solid content be 20%, colourless translucent emulsion.
The test of cation aqueous polyurethane sizing agent sizing efficiency:
With massfraction be 2.5% cationic starch solution 90 ℃ of following gelatinizations 15～30 minutes, get a certain amount of sample emulsion, both are that 90: 10 mixed is even with the over dry ratio, make sizing emulsions.With this sizing emulsions to being 85g/m quantitatively
2Double gummed paper carry out top sizing, the hand sizing method is adopted in the applying glue of double gummed paper experiment.Earlier an end of body paper is fixed, get a certain amount of sizing agent and be uniformly coated on fixed one end, with glass stick uniform roll on paper, sizing agent is evenly smeared on paper, paper after the applying glue put on the photograph dryer dry, at last the sample after the applying glue was placed 24 hours under the fixed temperature and humidity condition, carried out physicals then and detect.
The cationic waterborne polyurethane surface sizing agent of preparation has good sizing efficiency, and when the consumption of sizing agent was 0.1%, the degree of sizing of the scraps of paper reached 61 seconds.Its top sizing effect sees the following form.
The sizing efficiency test:
| Example | Outward appearance | Degree of sizing/s | Whiteness | ??Cobb60/g/m 2 |
| Comparative Examples | Milky white | ??19 | ??85.9％ | ??67.5 |
| Embodiment 1 | Yellowish translucent | ??61 | ??81.6％ | ??45.01 |
| Embodiment 2 | Milky white translucent | ??62 | ??82.4％ | ??48.58 |
| Embodiment 3 | Colourless translucent | ??49 | ??84.8％ | ??51.21 |
| Embodiment 4 | Yellow translucent | ??57 | ??80.7％ | ??39.21 |
| Embodiment 5 | Faint yellow translucent | ??60 | ??82.8％ | ??40.39 |
| Embodiment 6 | Faint yellow translucent | ??58 | ??81.2％ | ??41.10 |
| Embodiment 7 | Colourless translucent | ??56 | ??86.4％ | ??42.46 |
| Embodiment 8 | Yellow translucent | ??59 | ??80.4％ | ??40.01 |
| Embodiment 9 | Colourless translucent | ??50 | ??85.2％ | ??43.11 |
Claims (6)
1. the preparation method of cation aqueous polyurethane is characterized in that being undertaken by following step:
1) preparation of base polyurethane prepolymer for use as: with the polyvalent alcohol 1h that under 90 ℃, 0.08～0.1Mpa vacuum tightness, dewaters, regulate 50～80 ℃ of pre-polymerization temperature, the isocyanate-monomer, micromolecular hydroxyl monomer, modified monomer and the catalyzer di-n-butyltin dilaurate that add metering, control R value is 1.50～3.00 in the prepolymerization reaction process;
Wherein said polyvalent alcohol comprises polyether glycol, polyester polyol, polyester polyethers polyol blend;
Wherein said isocyanate-monomer is tolylene diisocyanate (TDI), ditan-4,4 ' vulcabond (MDI), liquefied mdi, poly methylene poly phenyl poly isocyanate (PAPI), 1, hexamethylene-diisocyanate (HDI), isophorone diisocyanate (IPDI), methylene radical-dicyclohexyl-4,4 '-vulcabond (H
12MDI), Methylcyclohexyl diisocyanate (HTDI),
Alcohol, amine that wherein said micromolecular hydroxyl monomer is two functionality or three-functionality-degree, it accounts for 1%～5% of total solids quality;
Wherein said modified monomer is glyceride type, terminal hydroxy group silicane, end aminosilane class, modified rosin class, and it accounts for 1%～10% of solid masses;
Wherein said solvent is 1-Methyl-2-Pyrrolidone (NMP), N, dinethylformamide, butanone, acetone, toluene, and wherein solvent accounts for 1～10% of solid total mass;
2) chain extension: on the basis of the first step, performed polymer is reduced to 30～60 ℃, at the uniform velocity in bottle, drip the hydrophilic chain extender of certain metering, wherein said hydrophilic chain extender is 20%～40% with solvent cut to massfraction, solvent for use is with step 1, after dripping off, when reaching theoretical value, the R value carries out the next step;
Wherein said hydrophilic chain extender is alcohol, the amine of two functionality or three-functionality-degree, and it accounts for 4%～16% of total solids quality;
3) neutralization and emulsification: on the basis in second step, add in the neutralizing agent and salify, degree of neutralization is 80%～120%, after 30 minutes, the aqueous solution of metering is scattered in the modified polyurethane prepolymer behind the salify, the control solid content is 10%～45%, and high-speed stirring 30 minutes, obtains outward appearance and is yellowish or the translucent cationic waterborne polyurethane surface sizing agent of oyster white;
Wherein said neutralizing agent is a Glacial acetic acid, dilute hydrochloric acid, dilute sulphuric acid, methyl-sulfate; Wherein neutralizing agent accounts for 2%～7% of PU quality of material.
2. the preparation method of cation aqueous polyurethane according to claim 1, the wherein said polyvalent alcohol of its feature comprises polyoxypropyleneglycol, polybutadiene diol, acrylate polyvalent alcohol, polyethylene glycol adipate glycol, poly-hexanodioic acid-1,6-hexylene glycol esterdiol, poly-tetrahydrochysene fluorine mutter glycol, poly-hexanodioic acid-1,4-butanediol ester glycol (PBA), poly-epsilon-caprolactone glycol, polycarbonate-1,6-hexylene glycol esterdiol; Wherein said isocyanate-monomer is tolylene diisocyanate (TDI), liquefied mdi, isophorone diisocyanate (IPDI); Wherein said micromolecular hydroxyl monomer is 1,4-butyleneglycol, ethylene glycol, glycol ether (glycol ether), 2,2-dimethylol propionic acid (DMPA), n-formyl sarcolysine base diethanolamine, N, N-dimethylethanolamine, trolamine, TriMethylolPropane(TMP) and quadrol; Wherein said modified monomer is esterified rosin, glyceryl monostearate, hydroxypropyl polydimethylsiloxane, gamma-amino propyl group triethylamine base silane; Wherein said solvent is 1-Methyl-2-Pyrrolidone or acetone.
3. the preparation method of cation aqueous polyurethane according to claim 1, the wherein said hydrophilic chain extender of its feature is 1,4-butyleneglycol, ethylene glycol, glycol ether (glycol ether), n-formyl sarcolysine base diethanolamine, N, N-dimethylethanolamine, trolamine, TriMethylolPropane(TMP) and quadrol; Wherein said neutralizing agent is a Glacial acetic acid, dilute hydrochloric acid.Wherein said polyvalent alcohol comprises.
4. the preparation method of cation aqueous polyurethane according to claim 2, it is characterized in that wherein said polyvalent alcohol comprises polyoxypropyleneglycol, polyethylene glycol adipate glycol, poly-hexanodioic acid-1,4-butanediol ester glycol, wherein said micromolecular hydroxyl monomer is a glycol ether, 1,4 one butyleneglycol, ethylene glycol.
5. the preparation method of cation aqueous polyurethane according to claim 3, the wherein said hydrophilic chain extender of its feature is n-formyl sarcolysine base diethanolamine, N, N-dimethylethanolamine or trolamine.
6. the preparation method of cation aqueous polyurethane according to claim 4, it is characterized in that wherein said polyvalent alcohol is poly-hexanodioic acid-1,4-butanediol ester glycol or poly-hexanodioic acid-1, the mixture of 4-butanediol ester glycol and polyoxypropyleneglycol or polytetrahydrofuran diol.
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