CN106758501A - Surface-crosslinked modified winnofil of fenugreek gum borax and preparation method thereof, using and a kind of paper - Google Patents

Surface-crosslinked modified winnofil of fenugreek gum borax and preparation method thereof, using and a kind of paper Download PDF

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CN106758501A
CN106758501A CN201710020032.1A CN201710020032A CN106758501A CN 106758501 A CN106758501 A CN 106758501A CN 201710020032 A CN201710020032 A CN 201710020032A CN 106758501 A CN106758501 A CN 106758501A
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paper
pcc
winnofil
fenugreek gum
borax
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CN106758501B (en
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谢玮
刘振华
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Wuzhou University
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Wuzhou University
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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
    • D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
    • D21H17/63—Inorganic compounds
    • D21H17/67—Water-insoluble compounds, e.g. fillers, pigments
    • D21H17/69—Water-insoluble compounds, e.g. fillers, pigments modified, e.g. by association with other compositions prior to incorporation in the pulp or paper
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
    • C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
    • C09C1/02—Compounds of alkaline earth metals or magnesium
    • C09C1/021—Calcium carbonates
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
    • C09C3/00—Treatment in general of inorganic materials, other than fibrous fillers, to enhance their pigmenting or filling properties
    • C09C3/10—Treatment with macromolecular organic compounds

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
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Abstract

The invention provides a kind of surface-crosslinked modified winnofil of fenugreek gum borax, the surface of described modified winnofil is crosslinked with fenugreek gum by borax, the present invention is intended to provide one kind is when it is applied to Fillers in Paper, can significantly improve tensile index, burst index, the tear index of paper, and filler first-past retention modified winnofil；Preparation method simultaneously present invention also offers the modified winnofil, application；Additionally, present invention also offers a kind of paper containing above-mentioned modified winnofil.

Description

Surface-crosslinked modified winnofil of fenugreek gum borax and preparation method thereof, using and A kind of paper
Technical field
The present invention relates to the modified surface-crosslinked modified winnofil of field, especially fenugreek gum borax of papermaking filler and its Preparation method, using and a kind of paper.
Background technology
Current the most frequently used filler of paper industry is calcium carbonate (grinding calcium carbonate, winnofil), kaolin and talcum powder, This three classes filler accounts for the 80%~90% of the total usage amount of filler, and based on kaolin, Europe is with carbonic acid for its Middle and North America paper industry Based on calcium, Asia is based on talcum powder.In addition titanium dioxide, zinc sulphide, calcium sulfate, diatomite, barium sulfate, silicon are also included Aluminate, calcium silicates and some organic fillers etc..Since 20 century 70s, as the production of high-grade paper is acid to neutral or alkali Sex reversal, pearl filler also gradually instead of kaolin and talcum powder.The consumption of domestic pearl filler in 2002 Exceed talcum powder first.
The surface electrical behavior of calcium carbonate with its as the retention of papermaking filler and be filled with paper relationship between quality it is close.Carbonic acid The concentration of calcium and the purity of water determine the surface electrical behavior of its particle, and the crystal of calcium carbonate particle is decomposed and recrystallization process in water Influence its surface electrical behavior.Calcium ion and carbanion determine that calcium carbonate is electrical in water, and calcium ion is more than in water Carbanion, therefore it is generally acknowledged that calcium carbonate particle carries positive charge in pure water.But PCC institutes are electrically charged very weak, in water Poor dispersion, cause its performance for being filled with paper to be affected, the optical property of paper is also affected；And filled paper The pore structure opened also is influenceed by filler grain degree of scatter.Contain dispersant, thus particle table in GCC prepared by wet method Face carries negative electrical charge, and preferably, cohesion tendency is smaller for stability.And dispersant is not contained in PCC particles, the cohesion between particle is inclined To just larger.In order to improve the application performance of pearl filler, reapplied after treatment can be modified to it.
The research being modified to pearl filler in papermaking now is more, and modification technology is also more ripe in theory, and carbon modified Application effect of the sour calcium in papermaking is also preferable, but the technology being applied in industrial production is few.Main bottleneck is still It is cost, there is inferior position in modified calcium carbonate filler price, whether it can balances its inferior position to the contribution that paper quality is improved, Or the production method of exploitation reduces cost, it will it is the main path of modified calcium carbonate future application development.
It is the more active field of a research that papermaking filler is modified, and wherein PCC is modified to be got the attention.Most It is filler modified mainly to lean on material modified physics or Hydrogenbond and calcium carbonate between in several research, due to this combination It is not very firmly, to reduce its application effect.Fenugreek gum is linked to winnofil by the present invention using borax crosslinkers Surface prepares modified winnofil (MPCC), and the fenugreek gum of crosslinking is difficult for drop-off in water than stronger.The present invention can be opened up Range of application of the calcium carbonate wide in papermaking, it will for the preparation and application of modified calcium carbonate provide new thinking, and improve and change The correlation theory that property winnofil is acted in paper making wet part, with important application value and Research Significance.
The content of the invention
The present invention provides a kind of surface-crosslinked modified winnofil of fenugreek gum borax and preparation method thereof, application, when it When being applied to Fillers in Paper, tensile index, burst index, the tear index of paper, and filler one way can be significantly improved Retention；Present invention also offers a kind of paper containing above-mentioned modified winnofil.
In order to realize above-mentioned technique effect, the technical scheme that the present invention is provided is such：A kind of fenugreek gum borax surface Cross-linking modified winnofil, the surface of described modified winnofil is crosslinked with fenugreek gum by borax.
Contain 38 kinds of compounds, 17 kinds of amino acid, 53 kinds of trace elements in tonka-bean seed.Contain various biologies in its compound Alkali.Contain protein 27% in seed, wherein accounting for 55% based on nucleoprotein, fat oil 7% is mainly galactomannan and gathers in total reducing sugar Sugar.Its mean molecule quantity, close to 250000, is the glutinous polysaccharide of a neutrality.
Its molecular structure is as shown in figure 26.Mannosyl units constitute main chain, and galactose units constitute side chain, every 6 on main chain Individual mannosyl units have 5 galactolipin side chains.Main chain is the connected β-D- pyranoid form mannoses of 1,4-, and side chain is 1,6 connected D- galactofuranosylceramides, gala and mannosan composition ratio are 1 in molecule:1.2.C6, C4 and C2 on side chain through base Reactivity is respectively provided with, from the point of view of steric hindrance, the hydroxyl activity of C6 is more stronger；Hydroxyl in main chain sugar ring is likely to participate in Reaction.
In galactomannans macromolecular chain each monosaccharide residue has two cis hydroxyl groups, and this will cause and dissociates Borate ion is reacted, and hydration occurs and thickens, and crosslinking schematic diagram refers to Fig. 1, and reaction is carried out in acid condition.Work as glue During solution alkaline and the dissociation borate ion that has q.s then causes gelatification.
It should be noted that the weight of described fenugreek gum is the 0.25~2% of winnofil weight.
Preferably, the weight of described fenugreek gum is the 0.5~1.5% of winnofil weight.
It should be noted that the weight of described borax is the 1~10% of winnofil weight.
Preferably, the weight of described fenugreek gum is the 1~3% of winnofil weight.
A kind of preparation method of the surface-crosslinked modified winnofil of fenugreek gum borax as described above, including following step Suddenly：
Step 1：Fenugreek gum is added into the reactor containing water, intensification dispersed with stirring is subsequently adding winnofil；
Step 2：To adding borax, stirring reaction in reactor；
Step 3：Collecting reaction product.
It should be noted that the weight of described fenugreek gum is the 0.25~2% of winnofil weight, described borax Weight for winnofil weight 1~10%.
It should be noted that the weight of the water in described step 1 is 9~15 times of winnofil weight.
It should be noted that the reaction temperature in described step 2 is 20~80 DEG C, the reaction time is 20~90min.
In general, cross-linking reaction temperature can select to be normal temperature between 90 DEG C, be found through experiments that, as long as temperature is not Too high or too low, as long as suitable temperature range is that cross-linking reaction is smoothed out, its performance change is less notable.During reaction Between be preferably 10-30min.
In general the consumption of water will not produce conclusive influence to properties of product, its be mainly useful for fenugreek gum and PCC can effectively disperse, you can reach effect of the invention and purpose.
Meanwhile, the present invention also provides a kind of answering for surface-crosslinked modified winnofil of fenugreek gum borax as described above With the surface-crosslinked modified winnofil of described fenugreek gum borax is used as the filler of paper.
A kind of paper, the quantification of 40~70gm of described paper2。
It should be noted that be filled with modified winnofil as described above in described paper, the amount of being filled with is 20~ 40%.
The present invention compared with conventional method, with advantages below：
1. tensile index, burst index, tear index of the paper of modified winnofil etc. is with the addition of to obtain substantially Improve, and filler first-past retention is also significantly improved；
2. the winnofil that is modified is more suitable for preparing high intensity, high-filling amount and light basis weight than unmodified winnofil Paper；
3. the application performance of modified winnofil is better than directly addition winnofil and a great deal of fenugreek gum, better than straight Connect addition winnofil and a great deal of borax；
4. the paper surface that with the addition of modified winnofil is opposed flattened, fiber is combined more closely, the precipitation that is modified carbonic acid Calcium is more evenly distributed in fiber surface.
Brief description of the drawings
Fig. 1 is fenugreek gum glycan molecule-borax-PCC crosslinking schematic diagrames；
Fig. 2 is the FT-IR phenograms of PCC (a) and MPCC (b)；
Fig. 3 is the XRD phenograms of PCC (a) and MPCC (b)；
Fig. 4 is the XPS phenograms of PCC (a)；
Fig. 5 is the XPS phenograms of MPCC (b)；
Fig. 6 is the SEM phenograms of PCC and MPCC；
Fig. 7 is the SEM phenograms for adding PCC and MPCC handsheets；
Fig. 8 is the graph of a relation of the fenugreek gum consumption with paper tensile index of modified PCC；
Fig. 9 is the graph of a relation of the fenugreek gum consumption with paper burst index of modified PCC；
Figure 10 is the graph of a relation of the fenugreek gum consumption with tear index of modified PCC；
Figure 11 is the graph of a relation of the fenugreek gum consumption with filler first-past retention of modified PCC；
Figure 12 is the graph of a relation of the borax consumption with paper tensile index of modified PCC；
Figure 13 is the graph of a relation of the borax consumption with burst index of modified PCC；
Figure 14 is the graph of a relation of the borax consumption with tear index of modified PCC；
Figure 15 is the graph of a relation of the borax consumption with filler first-past retention of modified PCC；
Figure 16 is the relation of the cross-linking reaction time with paper tensile index of modified PCC；
Figure 17 is the graph of a relation of the cross-linking reaction time with paper burst index of modified PCC；
Figure 18 is the graph of a relation of the cross-linking reaction time with paper tear index of modified PCC；
Figure 19 is the graph of a relation of the cross-linking reaction time with filler first-past retention of modified PCC；
Figure 20 is the graph of a relation of the amount of being filled with and paper tensile index；
Figure 21 is the graph of a relation of the amount of being filled with and paper burst index；
Figure 22 is the graph of a relation of the amount of being filled with and paper tear index；
Figure 23 is the graph of a relation of Substance and paper tensile index；
Figure 24 is the graph of a relation of Substance and paper burst index；
Figure 25 is the graph of a relation of Substance and paper tear index；
Figure 26 is the structural formula figure of fenugreek gum.
Specific embodiment
Claim of the invention is described in further detail with reference to specific embodiment, but is not constituted to this Any limitation of invention, the modification of any limited number of time for being made within the scope of the invention as claimed, still in right of the invention In claimed scope.
Embodiment 1
Step 1：0.75% (relative to PCC consumptions) fenugreek gum is added into oblique three mouthfuls containing 90g water, 80 are warming up to DEG C, and dispersed with stirring under 400rpm, it is subsequently adding 10g PCC；
Step 2：To 2.5% (relative to PCC consumptions) borax of addition, stirring reaction 20min in reactor；
Step 3：By product being collected by centrifugation and being washed, dries；
Step 4：MPCC, PCC is finely ground with mortar, the copper mesh of 200 mesh is crossed, respectively with SEM, Fu Li Leaf infrared spectrometer, elemental analyser etc. are analyzed and sign to it.
The type Fourier transformation infrared spectrometers of Magna IR 560 produced using U.S. Buddhist nun high-tensile strength (Nicolet) company are entered Row is determined, and sweep limits is 400~4000cm-1, 40 times/min of sweep speed.Using KBr pressed disc method sample preparations, appropriate determinand is taken Powder mixes in agate mortar with KBr crystal and grinds to form superfine powder, is then placed in mould, is cold-pressed into tablet press machine thin Piece can test.
After sample carries out metal spraying treatment, using the type SEM of EVO 18 (German ZEISS companies), sample is entered Row observation and analysis.
Fenugreek gum glycan molecule-borax-PCC is crosslinked schematic diagram as shown in figure 1, wherein, A represents fenugreek gum.
Fig. 2 is the FT-IR phenograms of PCC (a) and MPCC (b), as shown in Fig. 2 the FTIR spectrum of PCC and MPCC There is characteristic absorption peak (the 712,872 and ca.1460cm of PCC in figure-1).MPCC is in 2850~3000cm-1New absworption peak comes From in the C-H stretching vibration absworption peaks of fenugreek gum, illustrate that PCC surfaces are covered by fenugreek gum.
Fig. 3 is the XRD phenograms of PCC (a) and MPCC (b), and its abscissa represents 2Theta (degree), and its ordinate represents strong Degree.Characteristic peak 2 θ=23.09 ο (012), 29.47 ο of calcite crystal can be seen in the XRD spectra of PCC and MPCC (104), 35.97 o (110), 39.41 o (113), 43.15 o (202), 47.59 o (018) and 48.53 ο (116), illustrate that surface changes Property does not change the crystal structure of PCC.
Fig. 4 is the XPS phenograms of PCC, and its abscissa represents that, with reference to energy, its ordinate represents counting, and Fig. 5 is MPCC XPS phenograms, its abscissa represent with reference to can, its ordinate represents countings, according to Fig. 4-5 make MPCC as shown in table 1 with Essential element content in PCC, it is known that the essential element in PCC and MPCC is C, O and Ca, and this illustrates that it is PCC.
Boron element is found that in MPCC, illustrates that boron ion take part in cross-linking reaction.
Essential element content in the MPCC of table 1 and PCC
Fig. 6 for PCC and MPCC SEM phenograms, Fig. 6 the first rows its represent respectively PCC amplify 1000 times, 2000 times, 5000 times, electron microscope under conditions of 50000 times, the rows of Fig. 4 second its represent respectively MPCC amplify 1000 times, 2000 times, 5000 Times, electron microscope under conditions of 50000 times, PCC and MPCC outward appearances are fusiform, and it is poly- that substantially wadding occurs because of its high surface energy.
MPCC surfaces are rounder and more smooth and particle diameter is more than unmodified PCC, it was demonstrated that its surface is covered by fenugreek gum.
Embodiment 2
Step 1：0.75% (relative to PCC consumptions) fenugreek gum is added into oblique three mouthfuls containing 90g water, 80 are warming up to DEG C, and dispersed with stirring under 400rpm, it is subsequently adding 10g PCC；
Step 2：To 2.5% (relative to PCC consumptions) borax of addition, stirring reaction 20min in reactor；
Step 3：By product being collected by centrifugation and being washed, dries；
Step 4：By the bleached kraft pulp of more than the 4h that is soaked in water, discongest device with standard and discongest, be beaten using beater To 37 ° of SR, MPCC, PCC are separately added into after appropriate dilution, the amount of being filled with is 20% (being based on oven dry stock amount)；With reference to GB/T3703- 1999 methods, in sheet forming apparatus copy paper；After squeezing 1min under hydraulic press pressure 0.4MPa, done in the drier at 97 DEG C Dry 5min, the quantification of 70g/m of handsheet2；
Step 5：After two kinds of handsheets of step 4 gained are dried, taking a small pieces carries out sample preparation, uses SEM It is analyzed and sign.
Fig. 7 is the SEM phenograms for adding PCC and MPCC handmade papers, and Fig. 7 the first rows are using the handmade paper surface of PCC 100 times, 1000 times, 3000 times, 5000 times of Electronic Speculum enlarged drawings, the rows of Fig. 7 second be using 100 times of handmade paper surface of MPCC, 1000 times, 3000 times, 5000 times of Electronic Speculum enlarged drawings, as shown in fig. 7, addition MPCC handsheets surface and the comparing phase for adding PCC Seemingly, but the former seems smoother compared with the latter.
Embodiment 3
Step 1：Fenugreek gum is added into oblique three mouthfuls containing 90g water, 80 DEG C, and stirring point under 400rpm is warming up to Dissipate, be subsequently adding 10g PCC；As shown in figures s-11, its consumption is respectively the consumption of fenugreek gum：0.25%th, 0.5%, 0.75%th, 1%, 1.25%, 1.5%, 2% (relative to PCC consumptions)；
Step 2：To 10% (relative to PCC consumptions) borax of addition, stirring reaction 10min in reactor；
Step 3：By product being collected by centrifugation and being washed, dries；
Step 4：By the bleached kraft pulp of more than the 4h that is soaked in water, discongest device with standard and discongest, be beaten using beater To 37 ° of SR, MPCC is added after appropriate dilution, the amount of being filled with is 20% (being based on oven dry stock amount)；With reference to GB/T3703-1999 methods, In sheet forming apparatus copy paper；After squeezing 1min under hydraulic press pressure 0.4MPa, 5min, hand are dried in the drier at 97 DEG C The quantification of 70g/m of handsheet2；
Step 5：The measure of the tensile strength, pop strength and tearing strength of paper presses GB/T12914-1991, GB/ respectively T12914-2002 and GB/T455-2002 standard tests；
Step 6：First-past retention, formula as follows are calculated by content of ashes in paper：
In formula:Filler retention in R-paper, %；
Content of ashes in A-bone-dry paper, %；
The content of ashes of B-over dry slurry, %；
Content of ashes in C-paper pulp fiber, %；
The calcination mass loss of D-calcium carbonate, %.
Result shows：
As shown in Figure 8, as the fenugreek gum consumption of modified PCC increases, the tensile index of paper first increases, slow afterwards to reduce To continuing to have.Because before PCC particle surface fenugreek gum cross-linking amount reaches saturation, it is fragrant as fenugreek gum consumption increases Bean gum cross-linking amount is continuously increased, as shown in Fig. 2 addition is modified, the tensile index of PCC paper is continuously increased mechanism of crosslinking, but PCC Granule surface activity group-amount of hydroxyl groups is certain, and with the further increase of fenugreek gum consumption, they can be no longer with PCC cross-linking machines Increase, reach saturation, paper tensile index peaks；After reaching saturation, excessive fenugreek gum is in borax crosslinkers excess When, fenugreek gum that again can be surface-crosslinked with PCC is crosslinked, and mechanism of crosslinking is as shown in Fig. 2 dispersion so as to reduce modified PCC Property, cause the tensile index for adding modified PCC paper slowly to be reduced after reaching peak；The borax crosslinkers consumption of modified PCC It is excessive and certain, so the fenugreek gum amount for being linked to PCC surfaces finally keeps constant, the tensile index of the modified PCC paper of addition Finally keep constant.Therefore, when PCC is crosslinked with fenugreek gum, fenugreek gum consumption should not be too high, and this experiment is thought, when crosslinking agent boron When sand is excessive, the optimum amount of the PCC fenugreek gums that are modified is 0.75%, and the tensile index for adding MPCC paper is 26.7Nm/g, with The tensile index 22.1Nm/g for adding PCC paper is compared, and improves 20.81%.
As shown in Figure 9, as the fenugreek gum consumption of modified PCC increases, the burst index of paper is slowly reduced, and change is not Greatly, when the fenugreek gum consumption of modified PCC is 0.75%, compared with unmodified PCC is dosed, paper burst index from 1.6kPa.m2/ g increases to 2.6kPa.m2/ g, improves 60.47%.
As shown in Figure 10, as the fenugreek gum consumption of modified PCC increases, the tear index of paper slowly drops after first increasing Low, when the fenugreek gum consumption of modified PCC is 0.75%, compared with PCC paper is dosed, tear index is from 12.6mN.m2/ g increases It is added to 16.0mN.m2/ g, improves 26.98%.The fenugreek gum consumption of modified PCC is on the quality of paper, thickness and whiteness influence It is smaller.
As shown in Figure 11, as the fenugreek gum consumption of modified PCC increases, the PCC fillers first-past retention that is modified is first slow to be increased Plus rear slow reduction, when the fenugreek gum consumption of modified PCC is 0.75%, compared with unmodified PCC, be modified PCC filler one way Retention increases to 58.78% from 48.44%, improves 21.35%.
Embodiment 4
Step 1：0.75% (relative to PCC consumptions) fenugreek gum is added into oblique three mouthfuls containing 90g water, 80 are warming up to DEG C, and dispersed with stirring under 400rpm, it is subsequently adding 10gPCC；
Step 2：To adding borax of the amount (relative to PCC consumptions), stirring reaction as shown in figs. 12-15 in reactor 10min。
Step 3：By product being collected by centrifugation and being washed, dries；
Step 4：By the bleached kraft pulp of more than the 4h that is soaked in water, discongest device with standard and discongest, be beaten using beater To 37 ° of SR, MPCC is added after appropriate dilution, the amount of being filled with is 20% (being based on oven dry stock amount)；With reference to GB/T3703-1999 methods, In sheet forming apparatus copy paper；After squeezing 1min under hydraulic press pressure 0.4MPa, 5min, hand are dried in the drier at 97 DEG C The quantification of 70g/m of handsheet2；
Step 5：The measure of the tensile strength, pop strength and tearing strength of paper presses GB/T12914-1991, GB/ respectively T12914-2002 and GB/T455-2002 standard tests；
Step 6：First-past retention is calculated by content of ashes in paper, computing formula is as follows：
In formula:Filler retention in R-paper, %；
Content of ashes in A-bone-dry paper, %；
The content of ashes of B-over dry slurry, %；
Content of ashes in C-paper pulp fiber, %；
The calcination mass loss of D-calcium carbonate, %.
Result shows：
It can be recognized from fig. 12 that as the borax consumption of modified PCC increases, the tensile index of paper first increases, afterwards slowly It is reduced to and continues to have.Because before fenugreek gum consumption is certain, PCC surfaces fenugreek gum cross-linking amount reaches saturation, with boron The increase of sand dosage of crosslinking agent, the cross-linking amount of fenugreek gum is continuously increased, and mechanism of crosslinking is as shown in Fig. 2 the paper of the modified PCC of addition Tensile index be continuously increased, but PCC surface active groups amount of hydroxyl groups is certain, with the further increase of borax consumption, Fenugreek gum can not be further added by with PCC cross-linking machines, reach saturation, cause the tensile index for adding modified PCC paper not to be further added by.Cause This, considers that when PCC is crosslinked with fenugreek gum, borax consumption should not be too high, and this experiment is thought, works as perfume (or spice) from application effect and economy During bean gum consumption 0.75%, the optimum amount of the borax crosslinkers of the PCC that is modified is 2.5%, adds the tensile index of MPCC paper It is 27.7Nm/g, compared with the tensile index 22.1Nm/g of addition PCC paper, improves 25.34%.
As can be seen from Figure 13, as the borax consumption of modified PCC increases, paper burst index is slow after being first slowly increased Reduce, when the borax consumption of modified PCC is 2.5%, compared with PCC paper is dosed, burst index is from 1.6kPa.m2/ g increases To 2.6kPa.m2/ g, improves 62.5%.
It is seen from figure 14 that as the borax consumption of modified PCC increases, the tear index of paper is slow after being slowly increased Reduce, when the borax consumption of modified PCC is 2.5%, and dose PCC paper tear indexes 12.6mN.m2/ g is compared, addition The tear index of MPCC paper increases to 16.8mN.m2/ g, improves 33.33%.
It can be seen from fig. 15 that as the borax consumption of modified PCC increases, the PCC fillers first-past retention that is modified is first slow Reduced after increase, when the borax consumption of modified PCC is 2.5%, the first-past retention of MPCC fillers reaches 62.49%, compares PCC The first-past retention 48.44% of filler, improves 29.00%.
Embodiment 5
Step 1：0.75% (relative to PCC consumptions) fenugreek gum is added into oblique three mouthfuls containing 90g water, 80 are warming up to DEG C, and dispersed with stirring under 400rpm, it is subsequently adding 10gPCC；
Step 2：To 2.5% (relative to PCC consumptions) borax of addition, stirring reaction time such as Figure 16-19 institutes in reactor Show, the time is respectively：5min、10min、15min、20min、25min、30min、40min；
Step 3：By product being collected by centrifugation and being washed, dries；
Step 4：By the bleached kraft pulp of more than the 4h that is soaked in water, discongest device with standard and discongest, reuse beater and beat Slurry adds MPCC to 37 ° of SR after appropriate dilution, the amount of being filled with is 20% (being based on oven dry stock amount)；With reference to GB/T3703-1999 side Method, in sheet forming apparatus copy paper；After squeezing 1min under hydraulic press pressure 0.4MPa, dried in the drier at 97 DEG C 5min, the quantification of 70g/m of handsheet2；
Step 5：The measure of the tensile strength, pop strength and tearing strength of paper presses GB/T12914-1991, GB/ respectively T12914-2002 and GB/T455-2002 standard tests；
Step 6：First-past retention is calculated by content of ashes in paper, computing formula is as follows：
In formula:Filler retention in R-paper, %；
Content of ashes in A-bone-dry paper, %；
The content of ashes of B-over dry slurry, %；
Content of ashes in C-paper pulp fiber, %；
The calcination mass loss of D-calcium carbonate, %.
Result shows：
As shown in Figure 16, Figure 17, Figure 18, with the increase of the cross-linking reaction time that PCC is modified, the anti-of MPCC paper is added Tensile index is slowly reduced after being first slowly increased after slow reduction, burst index first increase, tear index is slowly increased rear slow drop It is low.As can be seen from Figure 19, as the cross-linking reaction time of modified PCC increases, MPCC filler first-past retentions first increase and drop afterwards It is low.Meanwhile, the change of the quality of paper, thickness and whiteness is smaller.This experiment obtains the modified preferable cross-linking reaction times of PCC 20min。
As shown in figure 16, when reacted between for 20min when, compared with PCC paper is dosed, add MPCC paper anti-tensile refer to Number is 33.3Nm/g, compared with the tensile index 22.1Nm/g of addition PCC paper, improves 50.68%.
As can be seen from Figure 17, when reacted between for 20min when, compared with PCC paper is dosed, addition MPCC paper it is resistance to Break index from 1.6kPa.m2/ g increases to 2.9kPa.m2/ g, improves 81.25%.
As shown in figure 18, when reacted between for 20min when, and dose PCC paper tear indexes 12.6mN.m2/ g is compared, The tear index for adding MPCC paper increases to 17.9mN.m2/ g, improves 42.06%.
As can be seen from Figure 19, when reacted between for 20min when, the first-past retention of filler for adding MPCC paper reaches 56.39%, than the first-past retention 48.44% of PCC filler, improve 16.41%.
Embodiment 6
Step 1：0.75% (relative to PCC consumptions) fenugreek gum is added into oblique three mouthfuls containing 90g water, 80 are warming up to DEG C, and dispersed with stirring under 400rpm, it is subsequently adding 10g PCC；
Step 2：To 2.5% (relative to PCC consumptions) borax of addition, stirring reaction 20min in reactor；
Step 3：By product being collected by centrifugation and being washed, dries；
Step 4：By the bleached kraft pulp of more than the 4h that is soaked in water, discongest device with standard and discongest, reuse beater and beat Slurry adds MPCC to 37 ° of SR after appropriate dilution, the amount of being filled with as illustrated in figs 20-22, respectively 20%, 30%, 35%, 40%, 45%th, 50% (being based on oven dry stock amount)；With reference to GB/T3703-1999 methods, in sheet forming apparatus copy paper；In hydraulic press pressure After squeezing 1min under 0.4MPa, 5min, the quantification of 70g/m of handsheet are dried in the drier at 97 DEG C2；
Step 5：The measure of the tensile strength, pop strength and tearing strength of paper presses GB/T12914-1991, GB/ respectively T12914-2002 and GB/T455-2002 standard tests.
Result shows：
As illustrated in figs 20-22, compared with PCC, the MPCC amounts of being filled with are tensile index, resistance to index and the tear of 30% paper Index has been respectively increased 13.06%, 32.71% and 44.33%；The amount of being filled with is the tensile index of 40% paper, burst index 12.25%, 39.53% and 39.53% has been respectively increased with tear index；The amount of being filled with is the anti-tensile of 50% paper, resistance to break, tears Split index and be respectively increased 10.11%, 39.24% and 2.50%.
Therefore, it can prepare high-filling amount paper with MPCC.
Embodiment 7
Step 1：0.75% (relative to PCC consumptions) fenugreek gum is added into oblique three mouthfuls containing 90g water, 80 are warming up to DEG C, and dispersed with stirring under 400rpm, 10gPCC is subsequently adding, the amount of being filled with of MPCC is 20%；
Step 2：To 2.5% (relative to PCC consumptions) borax of addition, stirring reaction 20min in reactor；
Step 3：By product being collected by centrifugation and being washed, dries；
Step 4：By the bleached kraft pulp of more than the 4h that is soaked in water, discongest device with standard and discongest, be beaten using beater To 37 ° of SR, MPCC is added after appropriate dilution, with reference to GB/T3703-1999 methods, in sheet forming apparatus copy paper；In hydraulic press pressure After squeezing 1min under power 0.4MPa, 5min, the quantification of 40g/m of handsheet are dried in the drier at 97 DEG C2、50g/m2、 60g/m2、70g/m2、80g/m2；
Step 5：The measure of the tensile strength, pop strength and tearing strength of paper presses GB/T12914-1991, GB/ respectively T12914-2002 and GB/T455-2002 standard tests.
Result shows：
From Figure 23-25 as can be seen that compared with PCC is added, the Substance for adding MPCC is 80gm-2、70g·m-2、 60g·m-2And 50gm-2When, paper tensile index, resistance to index and tear index are dramatically increased；Particularly quantification of 60g m-2And 50gm-2Paper tensile index, burst index and tear index it is also of a relatively high.
Therefore, it can prepare high intensity, low quantitative paper sheets with MPCC.
Comparative example 1
Step 1：By the bleached kraft pulp of more than the 4h that is soaked in water, discongest device with standard and discongest, reuse beater and beat Slurry adds the PCC that the amount of being filled with is 20% (being based on oven dry stock amount) to 37 ° of SR after appropriate dilution；
Step 2：With reference to GB/T3703-1999 methods, in sheet forming apparatus copy paper；Squeezed under hydraulic press pressure 0.4MPa After 1min, 5min, the quantification of 70g/m of handsheet are dried in the drier at 97 DEG C2；
Step 3：The tensile strength of paper presses GB/T12914-1991 standard tests.
Comparative example 2
Step 1：By the bleached kraft pulp of more than the 4h that is soaked in water, discongest device with standard and discongest, reuse beater and beat Slurry adds PCC, 0.75% (relative to PCC consumptions) that the amount of being filled with is 20% (being based on oven dry stock amount) to 37 ° of SR after appropriate dilution Fenugreek gum；
Step 2：With reference to GB/T3703-1999 methods, in sheet forming apparatus copy paper；Squeezed under hydraulic press pressure 0.4MPa After 1min, 5min, the quantification of 70g/m of handsheet are dried in the drier at 97 DEG C2；
Step 3：The tensile strength of paper presses GB/T12914-1991 standard tests.
Comparative example 3
Step 1：By the bleached kraft pulp of more than the 4h that is soaked in water, discongest device with standard and discongest, reuse beater and beat Slurry adds PCC, 2.5% (relative to PCC consumptions) that the amount of being filled with is 20% (being based on oven dry stock amount) to 37 ° of SR after appropriate dilution Borax；
Step 2：With reference to GB/T3703-1999 methods, in sheet forming apparatus copy paper；Squeezed under hydraulic press pressure 0.4MPa After 1min, 5min, the quantification of 70g/m of handsheet are dried in the drier at 97 DEG C2；
Step 3：The tensile strength of paper presses GB/T12914-1991 standard tests.
The measurement result of comparative example 1-4 is as shown in table 2,
The MPCC of table 2 compares with directly addition PCC and fenugreek gum or borax paper physical property
Result shows：The tensile index for adding MPCC paper reaches 33.3Nm/g, higher than the 22.1Nm/ of addition PCC paper G, tests as a comparison, and when 20%PCC and 0.75% (relative to PCC) fenugreek gum is directly added into, the tensile index of paper is 27.8Nm/g, higher than the paper of addition PCC, and is less than the paper for adding MPCC, therefore, changed with the fenugreek gum that borax is crosslinking agent The PCC of property can significantly improve the mechanical property of handsheet.Mechanical property raising because the tonka-bean glue gel on PCC surfaces with Hydrogenbond is generated between string.
Influence in view of borax to handsheet strength character, when the PCC amounts of being filled with are 20%, is directly added into 2.5% borax When, the tensile index of handsheet is 22.5Nm/g, closely adds the 22.1Nm/g of the handsheet of PCC, this independent boron of explanation Sand does not influence on the strength character of handsheet, and the Main Function of borax is, by tonka-bean gellation and mechanism of crosslinking, to help Fenugreek gum is linked to PCC surfaces.
It is above-described be only presently preferred embodiments of the present invention, it is all made in the range of the spirit and principles in the present invention appoint What modification, equivalent and improvement etc., should be included within the scope of the present invention.

Claims (10)

1. the surface-crosslinked modified winnofil of a kind of fenugreek gum borax, it is characterised in that described modified winnofil Surface is crosslinked with fenugreek gum by borax.
2. the surface-crosslinked modified winnofil of fenugreek gum borax according to claim 1, it is characterised in that described perfume (or spice) The weight of bean gum is the 0.25~2% of winnofil weight.
3. the surface-crosslinked modified winnofil of fenugreek gum borax according to claim 1, it is characterised in that described boron The weight of sand is the 1~10% of winnofil weight.
4. a kind of preparation method of the surface-crosslinked modified winnofil of fenugreek gum borax as claimed in claim 1, its feature It is to comprise the following steps：
Step 1：Fenugreek gum is added into the reactor containing water, intensification dispersed with stirring is subsequently adding winnofil；
Step 2：To adding borax, stirring reaction in reactor；
Step 3：Collecting reaction product.
5. the preparation method of the surface-crosslinked modified winnofil of fenugreek gum borax according to claim 4, its feature exists In the weight of described fenugreek gum is the 0.25~2% of winnofil weight, and the weight of described borax is winnofil The 1~10% of weight.
6. the preparation method of the surface-crosslinked modified winnofil of fenugreek gum borax according to claim 4, its feature exists In the weight of the water in described step 1 is 9~15 times of winnofil weight.
7. the preparation method of the surface-crosslinked modified winnofil of fenugreek gum borax according to claim 4, its feature exists In the reaction temperature in described step 2 is 20~80 DEG C, and the reaction time is 5~40min.
8. the application of the surface-crosslinked modified winnofil of a kind of fenugreek gum borax as described in claims 1 to 3 is any, it is special Levy and be, the surface-crosslinked modified winnofil of described fenugreek gum borax is used as the filler of paper.
9. a kind of paper, it is characterised in that the quantification of 40~70gm of described paper2。
10. a kind of paper according to claim 9, it is characterised in that be filled with described paper just like claim 1~ 3 any described modified winnofils, the amount of being filled with is 20~40%.
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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2010094937A1 (en) * 2009-02-20 2010-08-26 M-I Drilling Fluids Uk Limited Wellbore fluid and methods of treating an earthen formation
CN101857734A (en) * 2010-06-23 2010-10-13 牡丹江恒丰纸业股份有限公司 Composition and method for preparing modified calcium carbonate
CN102268845A (en) * 2011-07-27 2011-12-07 岳阳林纸股份有限公司 Food packing paper and production method thereof
CN105814168A (en) * 2013-12-12 2016-07-27 Omya国际股份公司 Improved gel stability

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2010094937A1 (en) * 2009-02-20 2010-08-26 M-I Drilling Fluids Uk Limited Wellbore fluid and methods of treating an earthen formation
CN101857734A (en) * 2010-06-23 2010-10-13 牡丹江恒丰纸业股份有限公司 Composition and method for preparing modified calcium carbonate
CN102268845A (en) * 2011-07-27 2011-12-07 岳阳林纸股份有限公司 Food packing paper and production method thereof
CN105814168A (en) * 2013-12-12 2016-07-27 Omya国际股份公司 Improved gel stability

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