CN105086322A - Glyoxal cross-linked polymer modified nano crystalline cellulose as well as preparation method and application thereof - Google Patents
Glyoxal cross-linked polymer modified nano crystalline cellulose as well as preparation method and application thereof Download PDFInfo
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Abstract
The invention discloses glyoxal cross-linked polymer modified nano crystalline cellulose. The glyoxal cross-linked polymer modified nano crystalline cellulose comprises two or more nano crystalline celluloses which are connected through a cross-linked polymer to form a nano crystalline cellulose cluster; the cross-linked polymer is formed by crosslinking a polymer formed through prepolymerization of nonionic monomers and a polymer formed through prepolymerization of cationic monomers via glyoxal; the nonionic monomers are selected from one or more of acrylamide, N,N-dimethyl acrylamide, N,N-diethyl acrylamide, N-vinylformamide and acrylonitrile; the cationic monomers are selected from one or more of methyl chloride or benzyl chloride quaternary ammonium salts of dimethyl diallyl ammonium chloride, dimethylaminoethyl acrylate and 2-(diethylamino)ethyl acrylate. The invention further provides application of glyoxal cross-linked polymer modified nano crystalline cellulose added into a paper machine's wet part as a papermaking additive.
Description
Technical field
The present invention relates to a kind of oxalic dialdehyde cross-linked polymer modified Nano crystalline cellulose and its preparation method and application, belong to polymer modification industrial additive and preparation and application technical field thereof.
Background technology
Paper industry take fiber as the chemical process industry of raw material, in slurrying, bleaches, manufactures paper with pulp and become each stage of this technique whole process of paper post-treatment, all be unable to do without the application of various chemical.They can not only give the various special high-performance of paper (as water resisting property, oil-proofness, wet tenacity, dry strength and force of cohesion strength property etc.), and the paper that the fibrous material making employing poor produces over-all properties higher becomes possibility; And can production process optimization be made, paper machine operation speed improves, and even significantly reduces environmental pollution, brings good economic and social benefit to paper industry.
The normally water-soluble or emulsification synthetic polymer of process and functional additive or resin petroleum derivation or modification obtain as starch, guar gum flour and derivatived cellulose as carboxymethyl cellulose is starched the natural product made by dissolving cellulos.The preparation method of the paper making additive such as disclosed in Chinese patent CN102121207A, CN102603977A, CN103254347A, CN103408702A and CN103726407A.Although these Study of Paper-Strengthening Agent Baseds can improve the intensity of dry paper, they really do not improve the intensity of wet web.High wet strength is the prerequisite ensureing that paper machine well runs.
A shortcoming of these additives of prior art causes to paper machine operation, especially on the impact of large high-speed paper motor speed owing to reducing the dehydration rate of wet web while the dry strength increasing paper.Another shortcoming of the additive of these technology is, for high conductivity and the anionic trash of high-content and the susceptibility of colloidalmaterial.Cause polymkeric substance can not active adsorption on the surface of fiber and fiber fines, because Polymer adsorption is poor under such plain boiled water condition, it is white water consistency increase that polymkeric substance greatly will be deposited in white-water system.
Summary of the invention
The present invention is just for the deficiency that prior art exists, a kind of oxalic dialdehyde cross-linked polymer modified Nano crystalline cellulose and preparation method thereof is provided, and provide oxalic dialdehyde cross-linked polymer modified Nano crystalline cellulose to add the application of wet end of machine to as paper making additive, thus improve dry strength, the wet tenacity of Paper or cardboard, and improve the dehydration rate of wet end of machine thus increase paper machine operation speed, improve initial journey retention rate in addition to lower white water consistency.
For solving the problem, the technical solution used in the present invention is as follows:
A kind of oxalic dialdehyde cross-linked polymer modified Nano crystalline cellulose is provided, the polymkeric substance that the polymkeric substance comprising nanocrystal Mierocrystalline cellulose and formed for the formation of the non-ionic monomer prepolymerization of macromolecule carbon skeleton and the cationic monomer prepolymerization for introducing positive charge are formed, and the polymkeric substance that the polymkeric substance that formed of described nanocrystal Mierocrystalline cellulose, described non-ionic monomer prepolymerization and described cationic monomer prepolymerization are formed carries out by oxalic dialdehyde the nanocrystal Mierocrystalline cellulose bunch that crosslinking reaction forms block copolymerization;
Described non-ionic monomer is selected from acrylamide, N, one or more in N-DMAA, N, N-acrylamide, N-sec.-propyl propylene, N-vinyl formamide, NVP, 2-vinyl pyridine, 4-vinylpridine, vinyl cyanide, hydroxyethyl methylacrylate, Hydroxyethyl acrylate, Propylene glycol monoacrylate, Propylene glycol monoacrylate, hexadecyl metrhacrylate, octadecyl methyl acrylate, glycidyl methacrylate;
Described cationic monomer be selected from quaternary ammonium acrylate and methacrylic acid ester quat one or more.Described quaternary ammonium acrylate and methacrylic acid ester quat include but not limited to: dimethylamino ethyl acrylate methyl chloride ammonium salt, dimethylamino ethyl acrylate methylsulfuric acid ammonium salt, dimethylaminoethyl vinylformic acid benzyl chloride ammonium salt, dimethylamino ethyl acrylate vitriol, dimethyl amino ethyl acrylate hydrochloride, dimethylaminoethyl methacrylic ester methyl chloride ammonium salt, dimethylaminoethyl methyl methacrylate ammonium sulfate, dimethylaminoethyl methacrylic acid benzyl chloride ammonium salt, dimethylaminoethyl methacrylic ester vitriol, dimethylaminoethyl methacrylic acid ester hydrochloride, dimethylin acrylamide methviium ammonium sulfate, dimethylin acrylamide hydrochloride, Methacrylamide ammonium chlorine etc.
Specifically preferably, described non-ionic monomer is selected from one or more in acrylamide, N,N-DMAA, N, N-acrylamide, N-vinyl formamide, vinyl cyanide, described cationic monomer is selected from dimethyl diallyl ammonium chloride, the methyl chloride quaternary ammonium salt of dimethylamino ethyl acrylate, the methyl chloride quaternary ammonium salt of Dimethylaminoethyl Methacrylate, the methyl chloride quaternary ammonium salt of vinylformic acid Of, the methyl chloride quaternary ammonium salt of diethylaminoethyl base ethyl ester, the methyl chloride quaternary ammonium salt of dimethylamino propyl acrylamide, the methyl chloride quaternary ammonium salt of dimethylamino-propyl Methacrylamide, the benzyl chloride quaternary ammonium salt of dimethylamino ethyl acrylate, the benzyl chloride quaternary ammonium salt of Dimethylaminoethyl Methacrylate, the benzyl chloride quaternary ammonium salt of vinylformic acid Of, the benzyl chloride quaternary ammonium salt of diethylaminoethyl base ethyl ester, the benzyl chloride quaternary ammonium salt of dimethylamino propyl acrylamide, one or more in the benzyl chloride quaternary ammonium salt of dimethylamino-propyl Methacrylamide.
Specifically preferably, the cellulosic degree of crystallinity of described nanocrystal is not less than 90%, and length is not less than 100 microns, and diameter is not more than 100 nanometers.
Specifically preferably, the polymericular weight that described non-ionic monomer prepolymerization is formed is 1000 ~ 50000 dalton, the polymericular weight that described cationic monomer prepolymerization is formed is 1000 ~ 50000 dalton, and the molecular weight of described nanocrystal Mierocrystalline cellulose bunch is 10 ten thousand to 500 ten thousand dalton.
Invention also provides the preparation method of above-mentioned oxalic dialdehyde cross-linked polymer modified Nano crystalline cellulose, comprise the following steps:
Step one, be that (mixing of the ratio of 1 ~ 20) ︰ 100, is warmed up to 40 ~ 60 DEG C of stirring and dissolving, until after nanocrystal Mierocrystalline cellulose dissolves completely, be cooled to room temperature in mass ratio by nanocrystal Mierocrystalline cellulose and soft water;
Step 2, at room temperature, in the solution of step one, adds polymkeric substance that non-ionic monomer prepolymerization formed, polymkeric substance, oxalic dialdehyde and pH buffer reagent that cationic monomer prepolymerization is formed, carries out oxalic dialdehyde crosslinking reaction; In reaction process, in 7.5 ~ 9.5 scopes, control crosslinking reaction speed by pH buffer reagent adjust ph;
Described pH buffer reagent be selected from sulfuric acid, hydrochloric acid, phosphoric acid, acetic acid, sodium hydroxide, potassium hydroxide, strong acid weak base salt, strong base-weak acid salt one or more; Particularly, the consumption of described pH buffer reagent is determined according to actual needs, and the pH value of reaction mixture solution is adjusted between 7.5 ~ 9.5.
Step 3, in the reaction process of step 2, constantly sample viscosimetric, after at 25 DEG C, viscosity reaches 10 ~ 100mPas, adjust ph is stopped reaction below 3.0, finally adds soft water adjustment solid content to 10wt% ~ 20wt%, obtains described oxalic dialdehyde cross-linked polymer modified Nano crystalline cellulose.
Present invention also offers the application of described oxalic dialdehyde cross-linked polymer modified Nano crystalline cellulose as paper making intensifier.
Particularly, described oxalic dialdehyde cross-linked polymer modified Nano crystalline cellulose comprises the following steps as the application method of paper making intensifier: raw material carries out discongesting, pull an oar after, add the aqueous solution of described oxalic dialdehyde cross-linked polymer modified Nano crystalline cellulose, the consumption of described oxalic dialdehyde cross-linked polymer modified Nano crystalline cellulose is 0.2% ~ 0.8% of oven dry stock quality, Paper or cardboard of can manufacturing paper with pulp after fully stirring.
Described in american documentation literature US8398901 and US7497924: nanocrystal Mierocrystalline cellulose is natural to be present in vegetable fibre; Typical cellulosic fibre comprises noncrystalline cellulose and crystalline cellulose, and nanocrystal Mierocrystalline cellulose can be obtained from vegetable fibre by fractional crystallization Mierocrystalline cellulose.Nanocrystal Mierocrystalline cellulose makes crystalline cellulose high to sour hydrolysis due to its compact character, and nanocrystal Mierocrystalline cellulose is obtained by hydrolyzing plant fiber in acid condition usually.
Nanocrystal Mierocrystalline cellulose is the material that a kind of intensity is higher, but due to its small size constraints, it is very limited in the purposes of paper product as a kind of additive, because nanocrystal Mierocrystalline cellulose is the subset that of fiber is extremely short, they be general diameter much smaller than 1 micron, it not enough length assist the intensity quality requirements to long paper fiber; Do not have data information to show, these materials can be used for separately as toughener, to replace traditional paper making additive.Described in american documentation literature US6231657: in the preparation process of homogeneity, the cellulosic length of nanocrystal and long-width ratio are limited, just can not untie xylon and not cut down the intensity of fiber.
Described oxalic dialdehyde cross-linked polymer modified Nano crystalline cellulose provided by the invention added to paper making wet part and be distributed in the matrix of paper or cardboard uniformly, because nanocrystal Mierocrystalline cellulose bunch comprises a large amount of hydroxyls, the cellulosic long-width ratio of original nanocrystal can be changed together with non-ionic monomer and cationic monomer, thus improve density, rigidity and the supporting intensity of nanocrystal Mierocrystalline cellulose bunch, thus paper property can be significantly improved.The polymkeric substance that the present invention is formed by non-ionic monomer prepolymerization and the polymkeric substance that the cationic monomer prepolymerization introducing positive charge is formed, carry out with oxalic dialdehyde that chemical reaction is crosslinked obtains molecular weight at 10 ten thousand to 500 ten thousand daltonian macromolecule carbon skeletons as cross-linked polymer, then form nanocrystal Mierocrystalline cellulose bunch with the homopolymerization of nanocrystal Mierocrystalline cellulose block.
Oxalic dialdehyde cross-linked polymer modified Nano crystalline cellulose prepared by the present invention, as toughener, due to the distinctive good dewatering of oxalic dialdehyde cross-linked polymer, can significantly improve the dehydration rate of paper on screen cloth at wet end of machine; Produce two effects thus and can reach the object improving paper machine speed:
One of them effect is the raising of dehydration rate and the tensile strength of the wet web increased; The mechanism that technical scheme provided by the present invention improves press part dehydration is: its Bound moisture can be made to become free-water with fiber-reactive, and then make press dewatering become easier; Combination simultaneously between fortifying fibre, reduces the rewetting of the rear paper web of squeezing, improves mass dryness fraction, thus increase wet web strength.The raising of wet web tensile strength as shown in Figure of description 1, can find out that press part mass dryness fraction often promotes the lifting that 1% corresponds to wet web strength 11% in the relation of its mass dryness fraction.
Another one effect is reduced in oven dry portion to the demand of drying steam; The speed of a motor vehicle of most boxboard paper machine is limited and confined by the steam supply in oven dry portion; To the paper machine locking into drying capacity, the potentiality that the raising of paper dewatering rate has the very large speed of a motor vehicle to improve, simultaneously can steam saving consumption.
In addition, the cation group on cationic polymeric molecule chain, amide group etc. can and nanocrystal cellulosic molecule on produce ionic bonding, hydrogen bond and chemical bonds between abundant hydroxyl, the nanocrystal Mierocrystalline cellulose bunch of stable suitable dimension can be formed.After these nanocrystal Mierocrystalline celluloses bunch fully mix with paper pulp after adding wet end of machine, aldehyde radical on oxalic dialdehyde can make paper fibre form stable chemical bonding, and on large fiber active adsorption fiber fines, significantly can improve initial journey retention rate and system retention, reach and reduce white water consistency and significantly improve strengthening for paper effect.
Compared with prior art, implementation result of the present invention is as follows in the present invention:
1, oxalic dialdehyde cross-linked polymer modified Nano crystalline cellulose of the present invention can improve dry strength and the wet tenacity of Paper or cardboard simultaneously as toughener; And existing Dry Strength Resin mainly improves the dry strength of paper cardboard alive and is not significantly improved to wet tenacity, existing Wet Strength Resin mainly improves the wet tenacity of Paper or cardboard and is not significantly improved to dry strength.
2, oxalic dialdehyde cross-linked polymer modified Nano crystalline cellulose of the present invention is applied to the force of cohesion that papermaking can significantly improve paper as toughener, has improve more significantly the physical strength such as anti-tensile pulling force, burst index, folding rate of Paper or cardboard.
3, oxalic dialdehyde cross-linked polymer modified Nano crystalline cellulose of the present invention not only has raising in essence to the paper product matter of papermaking enterprise as toughener, and the dehydration rate of wet web can be improved, increase the tensile strength of wet web, paper machine speed can be improved largely, optimize paper machine operation, reduce steam consumption, have papermaking enterprise reduction production energy consumption and raising production capacity and benefit greatly, significant economic benefit can be brought to papermaking enterprise.
4, oxalic dialdehyde cross-linked polymer modified Nano crystalline cellulose of the present invention also has very large benefiting as toughener to the energy-saving and emission-reduction of papermaking enterprise, can the white-water system of cleaning paper machine, paper plant can be helped better to carry out closed circulation to white-water system, the COD of a large amount of reduction plant effluent and quantity discharged, be conducive to the environmental stress that reduction papermaking enterprise faces.
Accompanying drawing explanation
Fig. 1 is the graphic representation of wet web tensile strength and mass dryness fraction relation.
Embodiment
Below in conjunction with specific embodiments content of the present invention is described.
Specific embodiment 1
The preparation method of a kind of oxalic dialdehyde cross-linked polymer modified Nano crystalline cellulose that the present embodiment provides, main raw material used and charging capacity see table:
Preparation method comprises the following steps:
Add soft water 1200g to in turbine agitator, RTD temperature sensor 2000 ml flasks, under agitator stirring velocity is 120RPM, add nanocrystal Mierocrystalline cellulose 90g, warming while stirring to 50 DEG C, wait after dissolving completely, cool to room temperature.
Polyacrylamide polymers (molecular weight 10,000 dalton) 135g, Poly Dimethyl Diallyl Ammonium Chloride polymkeric substance (molecular weight 10,000 dalton) 15g, ten hydration tetra-na diphosphate 30g, oxalic dialdehyde 30g, after stirring by appropriate sodium hydroxide and dilute sulphuric acid adjust ph to 8.5.
After reaching expection viscosity, regulate pH termination reaction with the appropriate vitriol oil, obtaining solid content is 20%, and viscosity is 12mPas, and pH value is the oxalic dialdehyde cross-linked polymer modified Nano crystalline cellulose of 2.8.
After adopting bleached sulphate needle slurry to carry out discongesting as raw material, pulling an oar, add the mass ratio of the oxalic dialdehyde cross-linked polymer modified Nano crystalline cellulose aqueous solution 1% ~ 4%(obtained as stated above corresponding to oven dry stock), stir 5 minutes, with the machine-processed write by hand scraps of paper obtaining quantitative 50g/m2 of handsheet, after oven dry, under standard atmosphere condition, balance 24 hours, measure its dry tensile strength; Burst index, the write by hand scraps of paper measure instant wet tenacity after soaking for 10 seconds; The results are shown in table 1.
The intensity index of table 1. bleached sulphate needle caiquejee copy paper sheet
Specific embodiment 2
The preparation method of a kind of oxalic dialdehyde cross-linked polymer modified Nano crystalline cellulose that the present embodiment provides, main raw material used and charging capacity see table:
Preparation method comprises the following steps:
Add soft water 1230g to in turbine agitator, RTD temperature sensor 2000 ml flasks, under agitator stirring velocity is 120RPM, add nanocrystal Mierocrystalline cellulose 75g, warming while stirring to 50 DEG C, wait after dissolving completely, cool to room temperature.
Poly-N, N-DMAA polymkeric substance (molecular weight 1.2 ten thousand dalton) 120g, Poly Dimethyl Diallyl Ammonium Chloride polymkeric substance (molecular weight 10,000 dalton) 15g, ten hydration tetra-na diphosphate 30g, oxalic dialdehyde 30g, after stirring by appropriate sodium hydroxide and dilute sulphuric acid adjust ph to 8.5.
After reaching expection viscosity, regulate pH termination reaction with the appropriate vitriol oil, obtaining solid content is 18%, and viscosity is 15mPas, and pH value is the oxalic dialdehyde cross-linked polymer modified Nano crystalline cellulose of 2.8.
After adopting 50/50 mixed bleach needle slurry/broad-leaved slurry to carry out discongesting as raw material, pulling an oar, add the weight ratio of the oxalic dialdehyde cross-linked polymer modified Nano crystalline cellulose aqueous solution 1% ~ 4%(obtained as stated above corresponding to oven dry stock), stir 5 minutes, with the machine-processed handsheet obtaining quantitative 100g/m2 of handsheet, after oven dry, under standard atmosphere condition, balance 24 hours, measure its folding endurance, bursting strength and ring crush intensity; Experimental result lists in table 2.
Table 2. mixed bleach needle slurry/broad-leaved caiquejee's copy paper sheet intensity index and water filtering performance increase rate
Specific embodiment 3
The monomer of N,N-DMAA poly-in specific embodiment 2 is replaced with one or more non-ionic monomers be selected from acrylamide, N,N-DMAA, N, N-acrylamide, N-vinyl formamide, vinyl cyanide, the monomer of Poly Dimethyl Diallyl Ammonium Chloride in specific embodiment 2 is replaced with and is selected from dimethyl diallyl ammonium chloride, the methyl chloride quaternary ammonium salt of dimethylamino ethyl acrylate, the methyl chloride quaternary ammonium salt of Dimethylaminoethyl Methacrylate, the methyl chloride quaternary ammonium salt of vinylformic acid Of, the methyl chloride quaternary ammonium salt of diethylaminoethyl base ethyl ester, the methyl chloride quaternary ammonium salt of dimethylamino propyl acrylamide, the methyl chloride quaternary ammonium salt of dimethylamino-propyl Methacrylamide, the benzyl chloride quaternary ammonium salt of dimethylamino ethyl acrylate, the benzyl chloride quaternary ammonium salt of Dimethylaminoethyl Methacrylate, the benzyl chloride quaternary ammonium salt of vinylformic acid Of, the benzyl chloride quaternary ammonium salt of diethylaminoethyl base ethyl ester, the benzyl chloride quaternary ammonium salt of dimethylamino propyl acrylamide, one or more cationic monomers in the benzyl chloride quaternary ammonium salt of dimethylamino-propyl Methacrylamide, all the other steps of preparation method are with reference to specific embodiment 2.
With reference to the test method of specific embodiment 2, the obtained oxalic dialdehyde cross-linked polymer modified Nano crystalline cellulose aqueous solution of specific embodiment 3 as toughener addition when 40kg/ ton oven dry stock, dry tensile strength increase rate is more than 60%, wet tensile strength increase rate is more than 50%, burst index increase rate is more than 50%, and water filtering performance increase rate is more than 25%.
Specific embodiment 4
By N poly-in specific embodiment 2, the monomer of N-DMAA replaces with and is selected from acrylamide, N, one or more non-ionic monomers in N-DMAA, N, N-acrylamide, N-sec.-propyl propylene, N-vinyl formamide, NVP, 2-vinyl pyridine, 4-vinylpridine, vinyl cyanide, hydroxyethyl methylacrylate, Hydroxyethyl acrylate, Propylene glycol monoacrylate, Propylene glycol monoacrylate, hexadecyl metrhacrylate, octadecyl methyl acrylate, glycidyl methacrylate;
The monomer of Poly Dimethyl Diallyl Ammonium Chloride in specific embodiment 2 is replaced with one or more cationic monomers be selected from quaternary ammonium acrylate and methacrylic acid ester quat, described quaternary ammonium acrylate and methacrylic acid ester quat include but not limited to: dimethylamino ethyl acrylate methyl chloride ammonium salt, dimethylamino ethyl acrylate methylsulfuric acid ammonium salt, dimethylaminoethyl vinylformic acid benzyl chloride ammonium salt, dimethylamino ethyl acrylate vitriol, dimethyl amino ethyl acrylate hydrochloride, dimethylaminoethyl methacrylic ester methyl chloride ammonium salt, dimethylaminoethyl methyl methacrylate ammonium sulfate, dimethylaminoethyl methacrylic acid benzyl chloride ammonium salt, dimethylaminoethyl methacrylic ester vitriol, dimethylaminoethyl methacrylic acid ester hydrochloride, dimethylin acrylamide methviium ammonium sulfate, dimethylin acrylamide hydrochloride, Methacrylamide ammonium chlorine etc., all the other steps of preparation method are with reference to specific embodiment 2.
With reference to the test method of specific embodiment 2, the obtained oxalic dialdehyde cross-linked polymer modified Nano crystalline cellulose aqueous solution of specific embodiment 4 as toughener addition when 40kg/ ton oven dry stock, dry tensile strength increase rate is more than 10%, wet tensile strength increase rate is more than 20%, burst index increase rate is more than 5%, and water filtering performance increase rate is more than 20%.
Above content is detailed description made for the present invention in conjunction with specific embodiments, can not assert that the present invention specifically implements to be only limitted to these explanations.For those skilled in the art, without departing from the inventive concept of the premise, some simple deduction or replace can also be made, all should be considered as belonging to the scope of protection of the invention.
Claims (7)
1. an oxalic dialdehyde cross-linked polymer modified Nano crystalline cellulose, it is characterized in that, the polymkeric substance that the polymkeric substance comprising nanocrystal Mierocrystalline cellulose and formed for the formation of the non-ionic monomer prepolymerization of macromolecule carbon skeleton and the cationic monomer prepolymerization for introducing positive charge are formed, and the polymkeric substance that the polymkeric substance that formed of described nanocrystal Mierocrystalline cellulose, described non-ionic monomer prepolymerization and described cationic monomer prepolymerization are formed carries out by oxalic dialdehyde the nanocrystal Mierocrystalline cellulose bunch that crosslinking reaction forms block copolymerization;
Described non-ionic monomer is selected from acrylamide, N, one or more in N-DMAA, N, N-acrylamide, N-sec.-propyl propylene, N-vinyl formamide, NVP, 2-vinyl pyridine, 4-vinylpridine, vinyl cyanide, hydroxyethyl methylacrylate, Hydroxyethyl acrylate, Propylene glycol monoacrylate, Propylene glycol monoacrylate, hexadecyl metrhacrylate, octadecyl methyl acrylate, glycidyl methacrylate;
Described cationic monomer be selected from quaternary ammonium acrylate and methacrylic acid ester quat one or more.
2. oxalic dialdehyde cross-linked polymer modified Nano crystalline cellulose as claimed in claim 1, it is characterized in that, described non-ionic monomer be selected from acrylamide, N,N-DMAA, N, N-acrylamide, N-vinyl formamide, vinyl cyanide one or more, described cationic monomer is selected from dimethyl diallyl ammonium chloride, the methyl chloride quaternary ammonium salt of dimethylamino ethyl acrylate, the methyl chloride quaternary ammonium salt of Dimethylaminoethyl Methacrylate, the methyl chloride quaternary ammonium salt of vinylformic acid Of, the methyl chloride quaternary ammonium salt of diethylaminoethyl base ethyl ester, the methyl chloride quaternary ammonium salt of dimethylamino propyl acrylamide, the methyl chloride quaternary ammonium salt of dimethylamino-propyl Methacrylamide, the benzyl chloride quaternary ammonium salt of dimethylamino ethyl acrylate, the benzyl chloride quaternary ammonium salt of Dimethylaminoethyl Methacrylate, the benzyl chloride quaternary ammonium salt of vinylformic acid Of, the benzyl chloride quaternary ammonium salt of diethylaminoethyl base ethyl ester, the benzyl chloride quaternary ammonium salt of dimethylamino propyl acrylamide, one or more in the benzyl chloride quaternary ammonium salt of dimethylamino-propyl Methacrylamide.
3. oxalic dialdehyde cross-linked polymer modified Nano crystalline cellulose as claimed in claim 1, it is characterized in that, the cellulosic degree of crystallinity of described nanocrystal is not less than 90%, and length is not less than 100 microns, and diameter is not more than 100 nanometers.
4. oxalic dialdehyde cross-linked polymer modified Nano crystalline cellulose as claimed in claim 1, it is characterized in that, the polymericular weight that described non-ionic monomer prepolymerization is formed is 1000 ~ 50000 dalton, the polymericular weight that described cationic monomer prepolymerization is formed is 1000 ~ 50000 dalton, and the molecular weight of described nanocrystal Mierocrystalline cellulose bunch is 10 ten thousand to 500 ten thousand dalton.
5. the preparation method of oxalic dialdehyde cross-linked polymer modified Nano crystalline cellulose as claimed in claim 1, is characterized in that, comprise the following steps:
Step one, be that (mixing of the ratio of 1 ~ 20) ︰ 100, is warmed up to 40 ~ 60 DEG C of stirring and dissolving, until after nanocrystal Mierocrystalline cellulose dissolves completely, be cooled to room temperature in mass ratio by nanocrystal Mierocrystalline cellulose and soft water;
Step 2, at room temperature, in the solution of step one, adds polymkeric substance that non-ionic monomer prepolymerization formed, polymkeric substance, oxalic dialdehyde and pH buffer reagent that cationic monomer prepolymerization is formed, carries out oxalic dialdehyde crosslinking reaction; In reaction process, in 7.5 ~ 9.5 scopes, control crosslinking reaction speed by pH buffer reagent adjust ph;
Described pH buffer reagent be selected from sulfuric acid, hydrochloric acid, phosphoric acid, acetic acid, sodium hydroxide, potassium hydroxide, strong acid weak base salt, strong base-weak acid salt one or more;
Step 3, in the reaction process of step 2, constantly sample viscosimetric, after at 25 DEG C, viscosity reaches 10 ~ 100mPas, adjust ph is stopped reaction below 3.0, finally adds soft water adjustment solid content to 10wt% ~ 20wt%, obtains described oxalic dialdehyde cross-linked polymer modified Nano crystalline cellulose.
6. oxalic dialdehyde cross-linked polymer modified Nano crystalline cellulose as claimed in claim 1 is as the application of paper making intensifier.
7. oxalic dialdehyde cross-linked polymer modified Nano crystalline cellulose as claimed in claim 6 is as the application of paper making intensifier, it is characterized in that, method comprises the following steps: raw material carries out discongesting, pull an oar after, add the aqueous solution of described oxalic dialdehyde cross-linked polymer modified Nano crystalline cellulose, the consumption of described oxalic dialdehyde cross-linked polymer modified Nano crystalline cellulose is 0.2% ~ 0.8% of oven dry stock quality, Paper or cardboard of can manufacturing paper with pulp after fully stirring.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108221462A (en) * | 2018-01-03 | 2018-06-29 | 华南理工大学 | A kind of method using hydroformylation hemicellulose enhancing secondary stock base paper performance |
| CN113412104A (en) * | 2019-01-25 | 2021-09-17 | 雷诺尼尔性能纤维有限责任公司 | Improved absorption properties by cross-linking cellulose with glyoxal |
| CN115516031A (en) * | 2020-03-18 | 2022-12-23 | 凯米拉公司 | GPAM compositions and methods |
| CN116065424A (en) * | 2023-02-16 | 2023-05-05 | 华邦古楼新材料有限公司 | Nanocellulose reinforced food packaging paper and preparation method thereof |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4217425A (en) * | 1978-11-06 | 1980-08-12 | Nalco Chemical Company | Paper fiber additive containing polyacrylamide blended with glyoxal and polymeric diallyldimethyl ammonium chloride as a cationic regulator |
| CN101048548A (en) * | 2004-07-08 | 2007-10-03 | 朗盛公司 | High-performance strength resins in papermaking industries |
| CN102121207A (en) * | 2010-12-03 | 2011-07-13 | 江门市高力依科技实业有限公司 | Papermaking dry-strengthening agent |
| CN103408702A (en) * | 2013-07-09 | 2013-11-27 | 上海东升新材料有限公司 | Preparation method of graft-polymer cationic dry strength agent |
| WO2014154937A1 (en) * | 2013-03-26 | 2014-10-02 | Kemira Oyj | Process for production of paper or board |
-
2015
- 2015-09-29 CN CN201510631328.8A patent/CN105086322A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4217425A (en) * | 1978-11-06 | 1980-08-12 | Nalco Chemical Company | Paper fiber additive containing polyacrylamide blended with glyoxal and polymeric diallyldimethyl ammonium chloride as a cationic regulator |
| CN101048548A (en) * | 2004-07-08 | 2007-10-03 | 朗盛公司 | High-performance strength resins in papermaking industries |
| CN102121207A (en) * | 2010-12-03 | 2011-07-13 | 江门市高力依科技实业有限公司 | Papermaking dry-strengthening agent |
| WO2014154937A1 (en) * | 2013-03-26 | 2014-10-02 | Kemira Oyj | Process for production of paper or board |
| CN103408702A (en) * | 2013-07-09 | 2013-11-27 | 上海东升新材料有限公司 | Preparation method of graft-polymer cationic dry strength agent |
Non-Patent Citations (3)
| Title |
|---|
| 吴开丽等: "纳米纤维素晶体的制备方法及其在制浆造纸中的应用前景", 《造纸科学与技术》 * |
| 杨艳等: "PAE/NCC二元体系对纸张的增强作用", 《中国造纸学报》 * |
| 霍淑媛等: "不同尺寸纳米结晶纤维素对纸张性能的影响", 《中华纸业》 * |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108221462A (en) * | 2018-01-03 | 2018-06-29 | 华南理工大学 | A kind of method using hydroformylation hemicellulose enhancing secondary stock base paper performance |
| CN108221462B (en) * | 2018-01-03 | 2020-09-22 | 华南理工大学 | Method for enhancing performance of waste paper pulp base paper by adopting hydroformylation hemicellulose |
| CN113412104A (en) * | 2019-01-25 | 2021-09-17 | 雷诺尼尔性能纤维有限责任公司 | Improved absorption properties by cross-linking cellulose with glyoxal |
| CN115516031A (en) * | 2020-03-18 | 2022-12-23 | 凯米拉公司 | GPAM compositions and methods |
| CN116065424A (en) * | 2023-02-16 | 2023-05-05 | 华邦古楼新材料有限公司 | Nanocellulose reinforced food packaging paper and preparation method thereof |
| CN116065424B (en) * | 2023-02-16 | 2023-07-18 | 华邦古楼新材料有限公司 | Nanocellulose reinforced food packaging paper and preparation method thereof |
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