CN1377436A

CN1377436A - Cationically modified polysaccharides

Info

Publication number: CN1377436A
Application number: CN00813784A
Authority: CN
Inventors: 迈克尔·D·弗尔班纳克; 谢里·L·汤姆森
Original assignee: Weyerhaeuser Co
Current assignee: Weyerhaeuser Co
Priority date: 1999-10-19
Filing date: 2000-09-07
Publication date: 2002-10-30
Also published as: US20040031579A1; US20020139501A1; AU7122100A; MXPA02003881A; JP2003512541A; SE0201183D0; SE0201183L; SE521309C2; WO2001029313A1; KR20020060204A; CA2386403A1

Abstract

A modified polysaccharide having enhanced surface charge. The polysaccharide is modified to include a cationic polymer, preferably a polyquaternary amine, and has a surface charge from about +5 to about +20 mV. The modified polysaccharide can be advantageous incorporated into a papermaking furnish with enhanced retention.

Description

Cation-modified polysaccharide

Invention field

The present invention relates to modification of polysaccharides, more specifically, relate to the modification of polysaccharides that surface charge strengthens as paper products and paperboard products filler and reinforcing aids.

Background of invention

A target of papermaking is the amount of filler that increases in the finished product, to reduce the amount of relatively costly composition-fiber.Increasing the amount of filler must be not have a negative impact to starching and other necessary performance of paper.In filler, starch is low-cost and validity and attractive with it.Usually the ative starch of non-modified can not be retained in the papermaking batching well, and reason is the effective interaction of shortage and fiber and retention agent.Although there is this kind shortcoming, in papermaking, use the method for starch as filler but designed.

In the production process of most of paper and cardboard, the abundant boiling of starch quilt also is used in the size press step.The starch that size press is used can contain gives paper or cardboard ideal performance, the additive of for example improved printing performance, hardness, caking property, dust removal performance, surperficial tearing performance (surface pick) and other performances.Cationic starch adds at the wet end of paper machine usually, can improve the strength character of paper and the retention rate of fine particle.Other charged synthetic polymer can combine with cationic starch and improve the retention rate of total fine particle.

Because the retention property of boiling and unmodified living amylum grain is not low to moderate unacceptablely, thereby it can not be added to the wet end of paper machine.When giving birth to starch in water during pulping, its particle surface electric charge is near zero.Lacking surface charge makes the interaction of living starch and charged retention agent and/or fiber very weak.Do not have strong interaction (as, chemistry connects), starch just can not be retained in the paper manufacturing systems well.Amylum grain is carried out mechanical infiltration partial starch is retained in the fiber web, but such reservation needs the flow box structure of specific type.

But, add surface charges by giving living amylum grain, just might increase the retention rate of starch in net significantly.So the starch that increases keeps by using the retention agent that the formation bridged bond connects between charged amylum grain and fiber surface to realize.In the past, by making some functional group, for example quaternary amines and starch are covalently bound carried out chemical modification to starch, thereby added electric charge for living starch.During papermaking, the common fully starch of these chemical modifications of boiling is added to it wet end of paper machine then.A kind of chemical modification method so obviously increases the cost of starch, and this method can not make electric charge enough on the starch band, thereby can not make the retention property of uncooked starch be higher than unmodified farinose retention property significantly.

Therefore, exist the demand to the economical and practical filler that is used for papermaking process, this filler can increase the retention rate of particle and can not have a negative impact to starching.Also exist the demand that retention property is strengthened and can increase the filler of paper products intensity.The present invention manages to satisfy these demands and other associated advantages is provided.

Summary of the invention

On the one hand, the invention provides the modification of polysaccharides that a kind of surface charge strengthens.Polysaccharide of the present invention is a kind of being modified and contain a kind of polysaccharide of cationic polymer.The modified starch of making according to the present invention has from about+5 to pact+20mV surface charge.It is favourable that the modification of polysaccharides that this retention property strengthens adds in the papermaking batching.

On the other hand, the invention provides the paper products of the modification of polysaccharides that contains the surface charge enhancing.The strength ratio that contains the paper products of modification of polysaccharides does not contain the intensity height of paper products of the similar composition of modification of polysaccharides.In one embodiment, paper products contain cellulose fiber peacekeeping modification of polysaccharides.In another embodiment, except that cellulose fiber peacekeeping modification of polysaccharides, paper products also contain the retention agent of a kind of fortifying fibre to the retention rate of modification of polysaccharides.Described retention agent can be the retention agent or the electronegative retention agent of positively charged.

Other aspect of the present invention provides the method for the formation modification of polysaccharides that surface charge strengthens, and by adding modification of polysaccharides, makes the method for filler retention raising, strengthened paper products.

Brief description of drawings

Also can make the present invention clearer in conjunction with the accompanying drawings by the reference following detailed description, aforementioned aspect of the present invention and some bonus will be more readily understood, wherein:

Fig. 1 is the schematic diagram according to a kind of typical modification of polysaccharides of the present invention's formation.

DESCRIPTION OF THE PREFERRED

On the one hand, the invention provides the polysaccharide that surface charge strengthens.This glycocalix modification and contain a kind of cationic additive that makes the polysaccharide surface have positive charge.Term used herein " polysaccharide " and " starch " are interchangeable, and term " modified starch " and " modification of polysaccharides " are meant the polysaccharide of the surface charge enhancing that forms according to the present invention.

Suitable cationic additive comprises and can irreversibly and/or consumingly combine with starch, and when combining with starch, strengthens the material of starch surface charge.Cationic additive comprises CATION organic polymer electrolyte and polymer.The preferred cationic additive comprises that cationic polymer is as poly-quaternary amine.In a preferred embodiment, cationic additive is low relatively, the strong electropositive poly-quaternary amine of molecular weight, and its molecular weight ranges is about 1-5 hundred myriagram/moles, about 3 milliequivalents quaternary amine/gram.A kind of poly-quaternary amine like this can be buied from the Nalco Chemical Co. of Illinois Naperville, and commodity are called Nalco 7527.The amount of the cationic additive that adds in the starch is about 15 pounds of/ton dried starch of about 1-, preferred about 5 pounds of/ton starch.

Comprise cationic polyacrylamide, aluminum sulfate, chitosan, polyamines, polyamidoamines, polyaziridine, polyamide-chloropropylene oxide (PAE), polyalkylene polyamine-chloropropylene oxide (PAPAE) and amine polymer-chloropropylene oxide (APE) to forming other useful cationic additive of modified starch of the present invention.

Measure by the zeta potential mensuration, the surface charge scope of the modified starch that forms according to the present invention be from pact+1mV pact+100mV extremely, preferably from pact+5mv pact+20mv extremely.

The starch in multiple source all can be modified and prepare the starch that surface charge strengthens.Suitable starch can derive from corn, potato, cassava, pea and wheat and other sources.

Modified starch of the present invention can be formed by the slurry that uncooked living starch and cationic additive are made in water.In one embodiment, it is in 10 the water that uncooked living starch is added to pH, obtains solid content and is about 7% slurry.Starch is swelling in alkaline solution, is the pastel that is creamy white.Although swelling has taken place, starch still keeps the form of dispersed particle.But under higher pH, starch forms gel owing to sex change (for example, chemical steaming).Avoid the gelling in the modified starch forming process.Be not limited to following theory, this theory proposes the surface that cationic additive diffuses into the amylum grain of swelling, produces the particle of surface charging.Then, with the pH regulator of the starch slurry of treated cation during to about neutral pH, cationic additive is closed in amylum grain inside.After adding cationic additive, the form of starch becomes sand-like particle from the oyster white pastel.As selection, in another embodiment, add cationic additive in 7 the starch slurry and form modified starch by being about to pH.Although the swelling amount under neutral pH is lower than the swelling amount under alkaline pH, this swelling also is enough to produce the modified starch that surface charge strengthens.In a preferred embodiment, the polysaccharide of modification is granular polysaccharide.

Illustrating in Fig. 1 of the typical amylum grain that forms according to the present invention.With reference to Fig. 1, modified starch particle 10 comprises the cationic additive 12 that adheres on the amylum grain 14.

The preparation and the performance of the modified starch that typical surface charge strengthens are described in embodiment 1.The measurement of the surface charge of the amylum grain that the typical surface charge that forms according to the present invention strengthens is described in embodiment 2.

Modified starch of the present invention can advantageously add in the papermaking batching.As described below, modified starch is kept by the paper pulp height, thereby makes modified starch become a kind of paper products filler of economy.In addition, the intensity that comprises the paper products of modified starch paper pulp is improved.

Compare with uncooked living starch, the retention rate of modified starch in paper pulp improves.As described in embodiment 3, Britt Jar experimental results show that with conventional filler winnofil (PCC) and compares that modified starch can be kept by paper pulp on equal or higher degree.In general, for the fine paper batching, under the condition that keeps about 45%PCC, can keep about 70% modified starch of about 60-.

The paper pulp height keeps modified starch so that the paper pulp that can produce the paper products with high filler retention to be provided.As selection, except that modified starch, can in paper pulp, add other retention agent, further increase the retention rate of modified starch.Retention agent comprises retention agent and anion described below and the cationic retention aid agent that field of papermaking is known.

Can utilize a kind of anionic retention aids or additive to increase the retention rate of starch.Anionic retention aids comprises anion organic polymer electrolyte and polymer.The preferred anionic retention agent comprises anionic polymer, for example, and anionic polyacrylamide (APAM).In a preferred embodiment, anionic retention aids be molecular weight higher, with the polyacrylamide of a small amount of negative electrical charge.The molecular weight ranges of preferred polyacrylamide is the about 1,500 myriagram/moles of about 8-and is the copolymer of acrylic acid (30 moles of %) and acrylamide (70 moles of %).A kind of polyacrylamide like this can be from the New Jersey Cytec Industries Inc. of (NJ) West Patterson buy, commodity are called Accurac 171.Perhaps, can be from the State of Washington Northwest Specialty Chemicals of (WA) Vancouver buy this kind anionic polyacrylamide, commodity are called Nugen 24.The addition of anionic retention aids is about 0.1 to about 3.0 pounds of/ton fibers in cellulosic paper pulp, preferred about 0.5 pound of/ton fiber.

Other suitable anionic retention aids comprises the Flokal B of high molecular.

As described in embodiment 3, preferably the wet end at paper machine (for example, APAM) is added to typical anionic retention aids in the paper pulp, and can adds before adding modified starch, adds simultaneously with modified starch or add after adding modified starch.As shown in table 9, in paper pulp, add modified starch behind the adding APAM, obtain maximum retention rate (72 weight %).In paper pulp, add modified starch earlier and then add APAM, obtain second largest retention rate (58 weight %).This two set condition has all obtained the bigger retention rate than typical alkaline fine paper system (45 weight %).

Other additive also can advantageously increase the reservation of paper pulp to modified starch.For example, cationic retention aid agent and additive can the reservation of enhancing modified starch in paper pulp.The preferred cationic retention agent comprises cationic polymer, and for example, molecular weight is higher, the cationic polyacrylamide (CPAM) of band small positive charge.The molecular weight ranges of preferred polyacrylamide is the about 1,500 myriagram/moles of about 8-and is the copolymer of acrylamide (90 moles of %) and a kind of quaternary amine monomer (10 moles of %).A kind of polyacrylamide like this can be buied from the CytecIndustries Inc. of New Jersey West Patterson, and commodity are called Accurac 182RS.The amount of the cationic retention aid agent of adding in cellulosic paper pulp is about 0.1 to about 12 pounds of/ton fibers, is preferably about 0.4 to about 6 pounds of/ton fibers.The combination of anionic retention aids and cationic retention aid agent can be used to strengthen the retention property of paper pulp with modified starch.

Other suitable cationic retention aid agent comprises the cationic flocculant of high molecular, the cationic polyacrylamide that can buy from the Nalco Chemical Co. of Illinois Naperville for example, and commodity are called Nalco 7530 and 7520.

The paper pulp that contains the modified starch of high retention can be made into the paper products of the strength characteristic with favourable high filler retention and increase.Benefit from the paper products that add modified starch and comprise fine paper, newsprint, bleached paperboard, unimpregnated liner board, common cardboard and regeneration corrugated board (OCC) etc.

Contain modified starch and optionally the paper products of one or more above-mentioned retention agents can in intermittent pulp proportioning, add modified starch by wet end and retention agent (if desired) is made at paper machine.According to the desired properties of paper products, be benchmark with the gross weight of fiber, the amount that adds the modified starch in the intermittent pulp proportioning is about 0.5 to about 20 weight %, preferred about 3 to about 10 weight %.

The flow behavior of intermittent pulp proportioning comprises that batching can dehydrated ability be a key factor of high speed paper process and papermaking equipment.Although an advantage of the invention is that the modified starch retention rate of batching is very high, in intermittent pulp proportioning, add modified starch and can the flow behavior of batching not had a negative impact.In addition, when using the anionic retention aids pulp treatment, add modified starch and also can not have a negative impact batching according to the present invention.Add modified starch at the wet end of paper machine in the intermittent pulp proportioning of handling with anionic retention aids and can not produce gelatinous precipitate, gelatinous precipitate can have a negative impact to the quality of intermittent pulp proportioning and limit its application in high speed papermaking.Similarly, adding the cationic retention aid agent in the intermittent pulp proportioning that contains anionic retention aids and/or modified starch can not have a negative impact to intermittent pulp proportioning yet.

The composition and the performance that contain the typical paper goods OCC of modified starch are described in embodiment 4.The strength character of typical OCC goods is summarised in the table 11.The result shows with the OCC goods that do not contain modified starch of similar composition and compares that the Mullen bursting strength that contains the OCC goods of 3 weight % modified starches increases about 20%.Also observe the raising of short distance compression STFI, tensile strength (tensile) and percentage elongation (stretch).Compare with the OCC goods of the similar composition that does not contain modified starch, it is about 5% that the short distance of these OCC goods compression STFI rises, and it is about 9% that tensile strength rises, and percentage elongation rises about 16%.

Can also be by changing the amount that (a) is used for preparing the cationic additive of modified starch, the type and the consumption that (b) add the amount of the modified starch in the intermittent pulp proportioning and (c) add the retention agent in the intermittent pulp proportioning are made typical OCC goods.The starch retention rate percentage of various typical OCC goods is summarized in the table 12.With reference to table 12, the result proves that modified starch is kept by the paper pulp height, can increase the retention rate of modified starch by using retention agent.The raising of the retention rate that anionic retention aids caused is bigger than cationic retention aid agent.

Embodiment

The starch that the typical surface charge of embodiment 1 preparation strengthens

This embodiment has described the preparation and the physical property of the starch of typical surface charge enhancing.The preparation of typical starch that contains a kind of cationic polymer, a kind of poly-quaternary amine (PQA) is as described in first group of step.The preparation of typical starch that contains a kind of poly-quaternary amine and further contain a kind of retention agent (APAM) is as described in second group of step.

First group.Is that (Accosize 80 for a kind of cationic potato starch of 3.85% with a laboratory with the solid content in the boiling vessel boiling 1000mL deionized water, can buy from the Cytec Industries Inc. of New Jersey WestPatterson) (44g, solid content are 86%).With a kind of typical cationic polymer (a kind of low molecular weight, strong electropositive poly-quaternary amine PQA, can buy from the Nalco Chemical Co. of Illinois Naperville, commodity are called Nalco 7527) 0.1% solution dilution to active component content be 0.1% (1.43g is diluted to 500mL).

Be that 10 cushioning liquid is diluted to 50mL and left standstill 30 minutes with the unmodified tapioca of 5.71g in beaker 1,2 and 3 (bone dry (O.D.) 5.0g) with pH respectively.In beaker 2, add the cationic potato starch (1.25g 3.78% solution) of 0.95% boiling and fully mixing.In beaker 3, add 5 pounds of/ton Nalco 7527 (12.5g 0.1% solution) and fully mixing.Before with microscopic examination, three equal balances of beaker 30 minutes.

With 1N sulfuric acid the pH of three beakers is transferred to 7 and use microscopic examination then.It is 0.5% 1.0g O.D. paper pulp (hardwood matter bleached kraft pulp that three kinds of starch samples (starch of 1mL solid content about 7%) of 10 weight % (is benchmark with O.D. paper pulp) are added to denseness respectively, HWBK, the poplar of pulverizing can be buied from Weyerhaeuser Co.) and mix.Use the microscopic examination starch sample.

Second group.A laboratory with boiling vessel in the boiling solid content be 4.5% cationic potato starch (Accosize 80) (69g, solid content 86% is in the 1340mL deionized water).With 0.1% solution dilution to the active component content of Nalco 7527 is 0.1% (1.43g is diluted to 500mL).With a kind of typical retention agent (a kind of high molecular, with the polyacrylamide of a small amount of negative electrical charge, APAM, can buy from the Cytec Industries Inc. of New Jersey West Patterson, commodity are called Accurac 171) 0.1% solution dilution to active component content be 0.01% (1.43g is diluted to 500mL and dilutes 10 times).

Be that 10 cushioning liquid was diluted to 50mL and balance 15 minutes with the unmodified tapioca in beaker 1,2 and 3 (bone dry (O.D.) 4.4g) with pH respectively.In beaker 2, add 1.3% cationic potato starch (Accosize 80) (1.25g 4.5% solution) and fully mixing.In beaker 3, add 5.7 pounds of/ton PQA (Nalco 7527) (12.5g 0.1% solution) and fully mixing.After adding chemical reagent, made solution equilibria 30 minutes.Respectively the pH of three beakers is transferred to 7 and left standstill 1 hour with 1N sulfuric acid then.

Pulp processing.Hardwood matter bleached kraft pulp (HWBK) is disperseed and is diluted to denseness with deionized water is 0.25%.In six beakers, add denseness respectively and be 0.25% 0.5g paper pulp.By adding three pulp sample of 0.5 pound of/ton APAM (1.25g 0.01% solution) preliminary treatment.Fully mixed pulp adds starch solution afterwards in pulp sample.In without pretreated pulp sample, add 0.5 pound of/ton APAM (1.25g 0.01% solution) and mixing then.With microscope six kinds of situations are carried out qualitative analysis.

First designed experiment is that the unmodified tapioca to cationic potato starch that adds boiling or the poly-quaternary amine (PQA) of a kind of cationic polymer carries out qualitative comparison.With all physical change of microscopic examination or with the reaction of other amylum grain or fiber.Microexamination the results are shown in table 1.

The qualitative microexamination of table 1.

Beaker	After adding chemical agent	After regulating pH	Reaction with fiber
Beaker	After adding chemical agent	After regulating pH	Reaction with fiber	1 (contrast)	There is not flocculation	There is not flocculation	Do not have and interact
2 (cationic starches)	Some flocculations are arranged	Some flocculations are arranged	Some interactions are arranged	1 (contrast)	There is not flocculation	There is not flocculation	Do not have and interact
2 (cationic starches)	Some flocculations are arranged	Some flocculations are arranged	Some interactions are arranged	????3(PQA)	There is not flocculation	There is not flocculation (high degree of dispersion)	Some interactions are arranged

After adding PQA and reducing pH, marked difference appears in the behavior of starch slurry.Amylum grain seems high degree of dispersion.Before regulating pH and afterwards, also there are some interactions between modified starch and the fiber.Some interactions appear in the starch of adding boiling and PQA when making amylum grain in being added to fiber.

Also determined the influence of use a kind of anionic polymer (APAM) post processing or pretreatment of fiber to the reaction of modified starch solution.A kind of situation is, adds APAM before adding starch slurry in fiber, and second kind of situation is to add APAM add starch in fiber after.Observed result is listed in table 2.

The qualitative microscopic examination result of table 2.

Beaker	Use the APAM pretreatment of fiber	With APAM post processing fiber
Beaker	Use the APAM pretreatment of fiber	With APAM post processing fiber	1 (contrast)	No fiber interaction	Amylum grain drops on the fiber equably
2 (cationic starches)	Some starch cohesion/fiber interactions are arranged	Some starch cohesion/fiber interactions are arranged	1 (contrast)	No fiber interaction	Amylum grain drops on the fiber equably
2 (cationic starches)	Some starch cohesion/fiber interactions are arranged	Some starch cohesion/fiber interactions are arranged	????3(PQA)	No fiber interaction	No fiber interaction

The processing of carrying out with APAM does not have obvious influence to the outward appearance of the fiber handled with the starch of cationic starch or PQA modification.

Embodiment 2 measures the surface charge of the amylum grain of typical surface charge enhancing

This embodiment has described the surface charge of the amylum grain of measuring typical surface charge enhancing.Measure surface charge by the zeta potential mensuration.

The the 1st and the 2nd group: contrast and modified starch.Unmodified tapioca is all used in each test.Adding 50mL pH is 10 cushioning liquid in each starch sample (5.0g), makes solution left standstill afterwards 1 hour.After leaving standstill 1 hour, in starch, add 5 pounds of/ton (is benchmark with the active component) PQA (Nalco 7527) and fully mixing, obtain " modification sample ".In in the same old way, do not adding polymer.Sample was left standstill 1 hour again, with 1N sulfuric acid pH is transferred to 7 then.Sample is left standstill 1 hour again, analyze then.

The 3rd group: by changing the modified starch that pH makes.By being to add the unmodified tapioca of 5.0g (as previously mentioned) in 10 the cushioning liquid to 50mL pH, left standstill 1 hour, add 5 pounds of/ton PQA (Nalco 7527) then and prepare the modification sample.After 1 hour, with 1N sulfuric acid pH is transferred to 7 and also left standstill at last 1 hour.By add pH in 5.0g former state tapioca is that 10 cushioning liquid leaves standstill then and prepares second sample.After 1 hour, add 5 pounds of/ton PQA (Nalco 7527), left standstill again 2 hours and no longer carry out pH regulator.Prepare the 3rd sample as previously mentioned, it is 7 cushioning liquid and no longer carry out pH regulator that difference is in starch to add pH.

Zeta potential is measured.Use a Delsa 440 (Coulter Electronics, Inc., Hialeah, Florida) to measure the zeta potential of all samples, measuring instrument is in the frequency range operation of+500Hz, and electric current equals 1/2 of sample conductivity value.Measuring samples under two pond height (Cell Height) (16 and 84).Owing to added PQA, sample keeps dispersity quite uniformly, and sample was left standstill 1 hour, analyzes afterwards.

The zeta potential of the 1st group of sample the results are shown in Table 3.For two ponds high 16 and 84, electric charge is the mean value of 8.6,17.1,25.6 and 34.2 ° of angles.(unmodified sample) in the same old way measured three times twice of the sample in measurement of modification.The result show with to comparing in the same old way, add cationic polyacrylamide the electric charge of the sample of modification significantly increased.

Table 3. starch zeta potential measurement result

Sample	PQA (pound/ton)	??pH	Electrical conductivity (milli Siemens (ms)/cm)	Mean value (mV)
Sample	PQA (pound/ton)	??pH	Electrical conductivity (milli Siemens (ms)/cm)	Mean value (mV)	To contrast sample in the same old way in the same old way	????0 ????0 ????0	???7 ???7 ???7	????6.1 ????9.5 ????9.8	????1.59 ????2.67 ????-2.95
Modification sample modification sample	????5 ????5	???7 ???7	????7.7 ????9.1	????17.35 ????18.22	To contrast sample in the same old way in the same old way	????0 ????0 ????0	???7 ???7 ???7	????6.1 ????9.5 ????9.8	????1.59 ????2.67 ????-2.95

The zeta potential of the 2nd group of sample the results are shown in Table 4.Because the sedimentation meeting changes stationary plane (stationary plane) in a zeta potential pond, the sample of different denseness is tested to determine the influence of denseness to charge analysis.Change denseness by changing the sedimentation time of analyzing preceding starch slurry.Prepare identical sample according to first group of methods, comprise one in the same old way with a modification sample.Also use deionized water rinsing modification sample to determine electric charge and be on the particle surface or only faintly to be connected with the surface.

Table 4. starch zeta potential measurement result

Starch	PQA (pound/ton)	??pH	Condition	Electrical conductivity (ms/cm)	Sedimentation time (minute)	Mean value (mV)
Starch	PQA (pound/ton)	??pH	Condition	Electrical conductivity (ms/cm)	Sedimentation time (minute)	Mean value (mV)	To contrast sample in the same old way in the same old way	????0 ????0 ????0	???7 ???7 ???7	Not not flushing of flushing of flushing	????6.96 ????9.75 ????9.82	????0 ????9 ????15	??-2.08 ??-2.19 ??-2.47
Modification sample modification sample modification sample	????5 ????5 ????5	???7 ???7 ???7	Flushing was not washed	????6.86 ????7.95 ????8.40	????0 ????9 ????9	??10.72 ??15.24 ??10.10	To contrast sample in the same old way in the same old way	????0 ????0 ????0	???7 ???7 ???7	Not not flushing of flushing of flushing	????6.96 ????9.75 ????9.82	????0 ????9 ????15	??-2.08 ??-2.19 ??-2.47

The result shows that the sedimentation time is measured not influence to zeta potential.This result shows that further electric charge is present in the surface of particle and is not and surperficial faint the connection, and the flushing amylum grain is measured not obviously influence to zeta potential.

For measuring the influence of pH, three samples (preparing the 3rd group of sample as stated above) have been compared to the formation of modified starch and total particle charging.The results are shown in Table 5.

Table 5.pH regulates the influence to electric charge

Starch	7527 (pound/tons)	Initial pH	Final pH	Electrical conductivity (ms/cm)	Sedimentation time (minute)	Mean value (mV)
Starch	7527 (pound/tons)	Initial pH	Final pH	Electrical conductivity (ms/cm)	Sedimentation time (minute)	Mean value (mV)	Modification	????5	????7	????7	??6.79	????60	??17.25
Modification	????5	????10	????10	??8.00	????60	??15.86	Modification	????5	????7	????7	??6.79	????60	??17.25
Modification	????5	????10	????10	??8.00	????60	??15.86	Modification	????5	????10	????7	??8.05	????60	??18.29

The sample of all modifications all has approximate cationic charge.This shows that pH regulator has no significant effect the modifying process surface charge.

Embodiment 3 paper pulp are to the reservation of the starch of typical surface charge enhancing

This embodiment has described the reservation of paper pulp to the starch of typical surface charge enhancing.For measuring under high shear condition whether can keep modified starch, use Britt Jar to carry out retention rate research.

Preparation paper pulp.Use following condition: 3.0% denseness, 1.0 W-s/m are than edge load, 1250 rev/mins (rpm), 0.583km/s length of cut and 60 degree bar angles (bar angle), with an Escher Wyss conical refiner (Bird Escher Wyss, Manfield, MA) PrinceAlbert hardwood being milled to CSF (Canadian Standard Freeness) is 400 mL.Also except that being to use Escher Wyss that Prince Albert cork is milled to 600mL CSF under the condition identical the 3.0W-s/m than edge load.The net power specific energy that is used for hardwood is 48.6kW-h/t, and cork is 1.75kW-h/t.The pulp mixture for preparing 60% hardwood and 40% cork.Use one 200 order screening washer to remove chip.The final freedom value that does not contain the pulp mixture of chip is 695mL, denseness 2.2%.

Britt Jar condition.The Britt Jar that use has one 100 order taper screen cloth measures retention rate.Paper pulp is added among the vane type Britt Jar, and the jam-pack stopper mixes with starch with different speed.After sample time, open stopper, with filtrate collection in the aluminum pot (about 100 mL) of a taring.When taring, use immediately fourth gear balance (four-place balance) go up the weighing aluminum pot.Place 105 ℃ stove to spend the night aluminum pot.The preceding sample with drying of the aluminum pot of weighing once more places drier.The denseness of the slurry of Bao Liuing is not calculated by equation (1).

The percentage residual rate of paper pulp slurry is calculated by equation (2).

For measuring correct degree of shear or mixing velocity, carry out Primary Study with a kind of typical alkaline fine paper batching.The retention rate of the starch of making according to the present invention and the retention rate of winnofil compare.

Chemical reagent.It is 0.65% that the paper pulp that as above prepares is diluted to denseness with deionized water.Winnofil (PCC) obtains from the Specialty Minerals Inc. of Pennsylvania Bethlehem, and solid content is 31.6%.(APAM, Accurac 171) is diluted to 500mL with deionized water with the 1.43g anionic polyacrylamide, prepares anionic polyacrylamide solution highly charged, high molecular.This solution was mixed 15 seconds with Braun hand blender, obtains 0.1% APAM solution, then with deionized water with 10 times of the solution dilutions of 50mL 0.1% to 500mL, obtain 0.01% solution.69.9g cationic potato starch (Accosize 80, solid content 86%) is mixed with the 1340mL deionized water, and the preparation solid content is 4.5% cationic potato starch solution.

Britt Jar process.Paper pulp (2.5g, the 385g denseness is 0.65% paper pulp) is added among the BrittJar.Table 6 has been listed the chemical addition agent that is added in the pulp sample and the amount of adding, and the incorporation time behind each the interpolation.

The interpolation order and the incorporation time of table 6. chemical addition agent

Chemical addition agent	Incorporation time (second)
Chemical addition agent	Incorporation time (second)	17 pounds of/ton cationic starch (0.47g, solid content is 4.5%) 20%PCC (1.58g, solid content is 31.6%) 0.5 pound of/ton APAM (6.25g, concentration is 0.01%%)	????15 ????15 ????30

Carry out above-mentioned condition under three different blended sum velocity 500,1000 and 1500rpm, final purpose is to obtain actual filler retention.The retention rate of filler is generally 50-55% in the fine paper paper machine.Table 7 has been listed the mixing velocity result.

Table 7.Britt Jar filler retention: change mixing velocity

Mixing velocity (rpm)	The percentage filler retention
Mixing velocity (rpm)	The percentage filler retention	????500 ????1000 ????1500	????50.4 ????8.95 ????4.5

As seen from Table 7, the data group of 500rpm produces effectively and keeps, and the result of higher mixing velocity condition is the retention rate deficiency.The reservation of modified starch

Reservation and a kind of alkaline fine paper batching that typically contains PCC of modified starch of the present invention are compared.The preparation method of APAM and cationic starch solution is the same.In addition, the 1.43g raw material is diluted to 500mL with deionized water, preparation PQA solution (Nalco 7527).The active component content of PQA solution is 0.1%, mixes 15 seconds with the Braun hand blender.PCC as mentioned above.With deionized water paper pulp being diluted to denseness is 0.42%.

By being that 10 cushioning liquid is diluted to 50ml with the unmodified tapioca of 5.0g (solid content is 12.5%) and prepares modified starch with pH.Left standstill 1 hour after starch fully mixed.Adding 12.5mL 0.1%PQA (Nalco 7527) also mixes.Solution was left standstill 1 hour again.Use 1N sulfuric acid (about 2.7mL) that the pH value is transferred to 7 then.The final denseness of this starch solution is 6.7%.

By being that 10 cushioning liquid is diluted to 50mL with the unmodified tapioca of 5.0g (solid content is 12.5%) and prepares control starch with pH.Left standstill 1 hour after starch fully mixed.Adding 12.5mL deionized water also mixes.Again with solution left standstill 1 hour.Use 1N sulfuric acid (about 2.7mL) that the pH value is transferred to 7 then.The final denseness of this starch solution is 6.7%.

Britt Jar process.Each Britt Jar experiment is all added 2.5g paper pulp (595g, denseness is 0.42%), mix with the speed of 500rpm.For control starch and modified starch, adding 6.5g denseness is 6.7% starch (17.4%).For APAM, add 6.25mL0.01% solution (0.5 pound/ton) and reach for cationic potato starch, adding 0.5g solid content is 4.5% starch (17 pounds/ton).For PCC, add the solution (20%) of 1.6g 31.6%.Terms and conditions is listed in the table 8.Every kind of condition is all carried out three times, all tests to randomness (except that alkaline fine paper batching is finished earlier three times).

Table 8.Britt Jar electrochemical conditions

Add for the first time	Incorporation time (s)	Add for the second time	Incorporation time (s)
Add for the first time	Incorporation time (s)	Add for the second time	Incorporation time (s)	17.4% modified starch	????30	Do not have	????30
17.4% modified starch	????30	0.5 pound/ton APAM	????30	17.4% modified starch	????30	Do not have	????30
17.4% modified starch	????30	0.5 pound/ton APAM	????30	0.5 pound/ton APAM	????30	17.4% modified starch	????30
17.4% control starch	????30	Do not have	????30	0.5 pound/ton APAM	????30	17.4% modified starch	????30
17.4% control starch	????30	Do not have	????30	17.4% control starch	????30	0.5 pound/ton APAM	????30
0.5 pound/ton APAM	????30	17.4% control starch	????30	17.4% control starch	????30	0.5 pound/ton APAM	????30
0.5 pound/ton APAM	????30	17.4% control starch	????30	17 pounds of/ton cationic starch/20%PCC	????15/15	0.5 pound/ton APAM	????30

Table 9 has been listed the retention rate of filler (modified starch or PCC).

Table 9.Britt Jar filler retention: change charging sequence

Sample (the first/the second additive)	The percentage filler retention
Sample (the first/the second additive)	The percentage filler retention	Contrast/APAM	????5
Modification /APAM	????58	Contrast/APAM	????5
Modification /APAM	????58	Cationic starch/PCC/APAM	????45
The APAM/ contrast	????3	Cationic starch/PCC/APAM	????45
The APAM/ contrast	????3	The APAM/ modification	????72
Contrast/nothing	????1	The APAM/ modification	????72
Contrast/nothing	????1	Modification/do not have	????10

Earlier in paper pulp, add APAM, add modified starch then, obtained the highest retention rate.Earlier in paper pulp, add modified starch, add APAM then, obtained the second high retention rate.These two kinds of conditions all have higher filler retention than typical alkaline fine paper system.Regulate the influence of pH to the modified starch retention rate

The paper pulp of starch retention rate maximum is obtained by the paper pulp fiber of handling with APAM in advance.For estimating the influence of pH, under three kinds of different pH conditions, use the modified starch pulp treatment to the retention rate of modified starch in paper pulp.The preparation method of paper pulp, APAM and PQA solution as mentioned above.With deionized water original pulp mixture being diluted to denseness is 0.41%.For adding the paper pulp of 2.5g bone dry, every kind of condition is all used 605g 0.41% solution.By following three kinds of starch solutions of method preparation.

Modified starch pH10-7.Be that 10 cushioning liquid is diluted to 50mL with the unmodified tapioca of 5g (solid content is 12.5%) with pH.Left standstill 1 hour after starch fully mixed.Adding 12.5mL 0.1%Nalco 7527 also mixes.Again with solution left standstill 1 hour.Use 1N sulfuric acid (about 2.7mL) that the pH value is transferred to 7 then.Solution is balance 1 hour again.The final denseness of this starch solution is 6.7%.

Modified starch pH10-10.Be that 10 cushioning liquid is diluted to 50mL with the unmodified tapioca of 5g (solid content is 12.5%) with pH.Left standstill 1 hour after starch fully mixed.Adding 12.5mL 0.1%Nalco 7527 also mixes.With solution left standstill 2 hours.The final denseness of this starch solution is 6.7%.

Modified starch pH7-7.Be that 7 cushioning liquid is diluted to 50mL with the unmodified tapioca of 5g (solid content is 12.5%) with pH.Left standstill 1 hour after starch fully mixed.Adding 12.5mL 0.1%Nalco 7527 also mixes.With solution left standstill 2 hours.The final denseness of this starch solution is 6.7%.

Britt Jar process.APAM is added in the paper pulp among the Britt Jar back mixed 30 seconds, add starch slurry then.In each experimentation, all add 0.5 pound of/ton APAM (6.25mL0.01% solution) and 20% starch (7.4mL 6.74% solution).Experimentize randomly, every kind of condition is carried out three experiments.Change the table 10 that the results are shown in of pH.

Table 10.Britt Jar filler retention: change pH

The APAM/ modification	The percentage filler retention
The APAM/ modification	The percentage filler retention	????pH10/pH10	????69
????pH10/pH7	????75	????pH10/pH10	????69
????pH10/pH7	????75	????pH7/pH7	????77

All experiment conditions all obtain high starch retention rate, and wherein the retention rate that obtains with the pH7/pH7 method is higher slightly than pH10/pH10 condition.

Embodiment 4 contains preparation and the performance of the OCC of the starch that typical surface charge strengthens

This embodiment has described the preparation and the performance of the regeneration corrugated board (OCC) that contains modified starch.Measure the performance of typical OCC goods, compare with the performance of the OCC goods that do not contain modified starch.

The OCC goods are made by the fiber furnish that contains 100%OCC.As mentioned above, prepare modified starch by adding 5 pounds of PQA (Nalco 7527)/ton starch.Add the modified starch of 3 weight % of total weight of fiber, add 5 pounds of CPAM (Accurac 182RS)/ton fiber then with 0.5 pound of APAM (Accurac 171)/ton starch pulp treatment batching back.The intermittent pulp proportioning that will contain modified starch deposits on the foraminate support plate, and the dewatering of pulp of deposition is dry then, obtains the OCC goods.

Performance by the OCC goods of top method preparation is listed in the table 11.Sample 1 is not add modified starch and the OCC goods made in the table, and sample 2 is the OCC goods that contain the modified starch of the 3 weight % that account for total weight of fiber.SSC STFI and TEA refer to that respectively short distance compression STFI and anti-opening can absorb on the surface in the table.

Table 11. contains the performance of the OCC of modified starch

Sample	Basic weight pound/Msf	Thickness (Caliper) is counted	Density kg/m ³	Mullen bursting strength pound	Index	SSC STFI pound/inch (in.)	Index	Tensile strength pound/inch (in.)	Index	Percentage elongation %	TEA inchpound (inlb)/square inch (in ²)
Sample	Basic weight pound/Msf	Thickness (Caliper) is counted	Density kg/m ³	Mullen bursting strength pound	Index	SSC STFI pound/inch (in.)	Index	Tensile strength pound/inch (in.)	Index	Percentage elongation %	TEA inchpound (inlb)/square inch (in ²)	??1	??32.7	????13.3	????473.9	????54	????45.9	????12.35	??11.3	????21.9	????20.1	???2.746	????0.4379
??2	??32.2	????12.9	????481.1	????64	????59.6	????12.8	??11.9	????24.6	????22.9	???3.191	????0.5657	??1	??32.7	????13.3	????473.9	????54	????45.9	????12.35	??11.3	????21.9	????20.1	???2.746	????0.4379

With reference to table 11 as can be seen, the Mullen bursting strength of sample 1 and 2 OCC goods shows with the OCC that does not contain modified starch of similar composition to be compared, and the Mullen bursting strength of sample 1 rises about 20%.Find out that also short distance compression STFI, tensile strength and percentage elongation also have increase.Compare with the OCC goods that do not contain modified starch of similar composition, that the short distance compression STFI that contains the OCC goods of modified starch rises is about 5%, tensile strength rises is about 9%, percentage elongation rises about 16%.

Be retained in the result of mutual comparison of the percentage by weight of the starch in the typical OCC goods, and list among the table 12-15 with the comparative result that contains the OCC goods of unmodified starch.

By change be used for preparing the cationic additive of modified starch amount, add the amount of the modified starch in the intermittent pulp proportioning to and be added to the type and the consumption of the retention agent in the intermittent pulp proportioning, prepare several representational OCC goods.The percentage starch retention rate of various representational OCC goods is listed in table 12.In these goods, the cationic additive that is used to form modified starch is PQA (Nalco 7527), and anionic retention aids is APAM (Accurac 171), and the cationic retention aid agent is CPAM (Accurac 182).Used following term in the table 12:

Modified starch is meant the starch with 5 pounds of PQA (Nalco 7527)/ton starch conversion;

Variable PQA is meant with after 0.5 pound of APAM (Accurac 171)/ton fiber preliminary treatment, and the starch of using the PQA (Nalco 7527) by starch and different amounts to make is handled and the OCC goods made: A, B, C and D are meant the OCC goods that contain by the modified starch of 1,2,3,5 and 7 pound of PQA (Nalco7527)/ton starch preparation;

Variable APAM is meant with after APAM (Accurac 171) preliminary treatment of different amounts, uses by the modified starch of starch and 5 pounds of PQA (Nalco 7527)/ton starch preparation and handles and the OCC goods made: E, F and G are meant with 0.25,0.50 and 0.75 pound of APAP (Accurac171)/ton fiber pretreating paper pulp and prepare burden and the OCC goods made;

APAM/PQA/APAM uses the modified starch that is prepared by starch and 5 pounds of PQA (Nalco 7527)/ton starch to handle after being meant and using 0.25 pound of APAM (Accurac 171) pulp treatment batching in advance, uses 0.25 pound of APAM (Accurac 171)/ton fiber to handle and the OCC goods made again;

APAM/PQA/CPAM uses the modified starch that is prepared by starch and 5 pounds of PQA (Nalco 7527)/ton starch to handle after being meant and using 0.25 pound of APAM (Accurac 171) pulp treatment batching in advance, uses 2.0 pounds of CPAM (Accurac 182)/ton fiber to handle and the OCC goods made again;

Variable C PAM is meant after the modified starch pulp treatment batching of using by starch and 5 pounds of PQA (Nalco 7527)/ton starch preparation, and use CPAM (Accurac 182) the pulp treatment batching of different amounts again and the OCC goods made: H, I and J are meant the OCC goods made from 1.0,2.0 and 3.0 pounds of CPAM (Accurac 182)/ton fiber treatment intermittent pulp proportioning.

The comparison of table 12.OCC starch retention rate

The OCC filler	The percentage retention rate
The OCC filler	The percentage retention rate	Starch	????1.45
Modified starch	????20.82	Starch	????1.45
Modified starch	????20.82	Variable PQA A B C D	????79.19 ????95.63 ????94.52 ????88.20
Variable APAM E F G	????82.83 ????94.52 ????88.65	Variable PQA A B C D	????79.19 ????95.63 ????94.52 ????88.20
Variable APAM E F G	????82.83 ????94.52 ????88.65	????APAM/PQA/APAM	????81.29
????APAM/PQA/CPAM	????76.45	????APAM/PQA/APAM	????81.29
????APAM/PQA/CPAM	????76.45	Variable C PAM H I J	????37.50 ????42.31 ????45.42

The presentation of results modified starch height of table 12 is retained in the paper pulp, and by using retention agent can improve the modified starch retention rate.Anionic retention aids is bigger than cationic retention aid agent to the effect that retention rate improves.

Measured with 0.5 pound of anionic retention aids (APAM, Accruac171)/ton fiber preliminary treatment after, modified starch is retained in the percentage by weight in the typical OCC goods, and this percentage is the function of the consumption of starch cationic additive (PQA, Nalco 7527)/ton starch.The results are shown in the table 13.

Table 13.OCC starch retention rate: change PQA

PQA (pound/ton)	The percentage retention rate
PQA (pound/ton)	The percentage retention rate	????1 ????1	????84.5 ????73.9
????3 ????3	????87.7 ????103.6	????1 ????1	????84.5 ????73.9
????3 ????3	????87.7 ????103.6	????5 ????5	????94.5 ????94.6
????7 ????7	????88.8 ????87.6	????5 ????5	????94.5 ????94.6

Presentation of results has all obtained significant retention rate with 1-7 pound PQA/ ton starch, wherein uses about 5 pounds of PQA/ ton starch to obtain near best retention rate.

Measured anionic retention aids (APAM, Accurac 171) the preliminary treatment hand that uses different amounts, be retained in the percentage by weight of the modified starch (5 pounds of PQA/ ton starch) in the typical OCC goods, this percentage is the function of APAM consumption.The results are shown in the table 14.

Table 14.OCC starch retention rate: change APAM

APAM (pound/ton)	The percentage retention rate
APAM (pound/ton)	The percentage retention rate	????0.25 ????0.25	????79.5 ????86.1
????0.50 ????0.50	????94.5 ????94.6	????0.25 ????0.25	????79.5 ????86.1
????0.50 ????0.50	????94.5 ????94.6	????0.75 ????0.75	????89.0 ????88.3

Presentation of results obtains best retention rate with 0.50 pound of anionic retention aids/ton fiber preliminary treatment.

Measured with the cationic retention aid agent (CPAM, Accurac 182) of different amounts and handled hand, be retained in the percentage by weight of the modified starch (5 pounds of PQA/ ton starch) in the typical OCC goods, this percentage is the function of CPAM consumption.The results are shown in the table 15.

Table 15.OCC starch retention rate: change CPAM

CPAM (pound/ton)	The percentage retention rate
CPAM (pound/ton)	The percentage retention rate	????1 ????1	????27.1 ????47.9
????2 ????2	????42.5 ????42.2	????1 ????1	????27.1 ????47.9
????2 ????2	????42.5 ????42.2	????3 ????3	????44.4 ????46.5

Presentation of results uses 1-3 pound CPAM/ ton starch to obtain significant retention rate.

Although illustrate and described the preferred embodiments of the invention, can recognize under situation without departing from the spirit and scope of the present invention, can carry out multiple variation.

Claims

1. composition that contains polysaccharide particle and cationic additive, wherein cationic additive obtains having the polysaccharide particle of positive surface charge attached on the polysaccharide particle.

2. the desired composition of claim 1, wherein cationic additive comprises cationic polymer.

3. the desired composition of claim 2, wherein cationic polymer comprises poly-quaternary amine.

4. the desired composition of claim 3, wherein the molecular weight ranges of poly-quaternary amine is about 100 ten thousand to about 500 myriagram/moles.

5. the desired polymer of claim 3 wherein gathers quaternary amine and contains the 3 milliequivalents quaternary amine/gram of having an appointment.

6. the desired composition of claim 1, wherein the content of cationic additive in composition is about 1 to about 15 pounds of/ton polysaccharide.

7. the desired composition of claim 1, wherein surface charge at pact+1mV to the scope of pact+100mV.

8. the desired composition of claim 1, wherein polysaccharide is selected from the group of being made up of cornstarch, farina, tapioca, pea starch and wheaten starch.

9. intermittent pulp proportioning that contains the polysaccharide particle of being with positive surface charge, the polysaccharide particle that wherein has positive surface charge contains attached to the cationic additive on the polysaccharide particle.

10. the desired batching of claim 9, wherein cationic additive comprises cationic polymer.

11. the desired batching of claim 10, wherein cationic polymer comprises poly-quaternary amine.

12. the desired batching of claim 9, wherein the polysaccharide particle has the surface charge from pact+1mV to pact+100mV scope.

13. the desired batching of claim 9, it further contains a kind of anionic retention aids.

14. the desired batching of claim 9, it further contains a kind of cationic retention aid agent.

15. the desired batching of claim 13, it further contains a kind of cationic retention aid agent.

16. the desired batching of claim 13, wherein anionic retention aids comprises anionic polyacrylamide.

17. the desired batching of claim 16, wherein anionic polyacrylamide comprises the copolymer of acrylic acid and acrylamide.

18. the desired batching of claim 17, wherein copolymer contains have an appointment 30 moles of % acrylic acid and about 70 moles of % acrylamides.

19. the desired batching of claim 17, wherein the molecular weight ranges of copolymer is about 8 to about 1,500 myriagram/moles.

20. the desired batching of claim 13, wherein the amount of anionic retention aids in batching is about 0.1 to about 3.0 pounds of/ton fibers.

21. the desired batching of claim 14, wherein the cationic retention aid agent comprises cationic polyacrylamide.

22. the desired batching of claim 21, wherein cationic polyacrylamide comprises the copolymer of acrylamide and quaternary amine monomer.

23. the desired batching of claim 22, wherein copolymer contains have an appointment 90 moles of % acrylamides and about 10 moles of % quaternary amine monomers.

24. the desired batching of claim 22, wherein the molecular weight ranges of copolymer is about 8 to about 1,500 myriagram/moles.

25. the desired batching of claim 14, wherein the amount of cationic retention aid agent in batching is about 0.1 to about 12 pounds of/ton fibers.

26. paper products that contain the polysaccharide particle of being with positive surface charge, wherein the polysaccharide particle with positive surface charge contains attached to the cationic additive on the polysaccharide particle.

27. the desired paper products of claim 26, wherein cationic additive comprises cationic polymer.

28. the desired paper products of claim 27, wherein cationic polymer comprises poly-quaternary amine.

29. the desired paper products of claim 26, wherein the polysaccharide particle has the surface charge from pact+1mV to pact+100mV scope.

30. the desired paper products of claim 26, it further contains a kind of anionic retention aids.

31. the desired paper products of claim 26, it further contains a kind of cationic retention aid agent.

32. the desired paper products of claim 30, it further contains a kind of cationic retention aid agent.

33. the desired paper products of claim 30, wherein anionic retention aids comprises anionic polyacrylamide.

34. the desired paper products of claim 31, wherein the cationic retention aid agent comprises cationic polyacrylamide.

35. the desired paper products of claim 26, wherein paper products are selected from the group of being made up of fine paper, newsprint, bleached paperboard, unimpregnated liner board, common cardboard and regeneration corrugated board.

36. a method of making paper products, it comprises:

The polysaccharide particle of band positive surface charge is added to and obtains second intermittent pulp proportioning in first intermittent pulp proportioning, and wherein the polysaccharide particle with positive surface charge contains the cationic additive that is attached on the polysaccharide particle;

Second intermittent pulp proportioning is deposited on the foraminate support plate, obtain a wet fiber web; With

Wet fiber net is dewatered and dried, obtain paper products.

37. the desired method of claim 36, wherein cationic additive comprises cationic polymer.

38. the desired method of claim 37, wherein cationic polymer comprises poly-quaternary amine.

39. the desired method of claim 36, wherein amylum grain has the surface charge from pact+1mV to pact+100mV scope.

40. the desired method of claim 36, it further comprises a kind of anionic retention aids is added in first intermittent pulp proportioning.

41. the desired method of claim 36, it further comprises a kind of cationic retention aid agent is added in first intermittent pulp proportioning.

42. the desired method of claim 40, it further comprises a kind of cationic retention aid agent is added in first intermittent pulp proportioning.

43. the desired method of claim 40, wherein anionic retention aids comprises anionic polyacrylamide.

44. the desired method of claim 41, wherein the cationic retention aid agent comprises cationic polyacrylamide.

45. the desired method of claim 36, wherein paper products are selected from the group of being made up of fine paper, newsprint, bleached paperboard, unimpregnated liner board, common cardboard and regeneration corrugated board.

46. a method that increases paper products intensity, it comprises:

A kind of polysaccharide particle that has positive surface charge added to obtaining second intermittent pulp proportioning in first intermittent pulp proportioning, the polysaccharide particle that wherein has positive surface charge contains the cationic additive that is attached on the polysaccharide particle;

Second intermittent pulp proportioning deposited to obtain a wet fiber web on the foraminate support plate; With

Wet fiber net is dewatered and dried, and the paper products that the paper products that obtain are compared the polysaccharide particle of being with positive surface charge not containing of similar composition have the intensity of raising.

47. the desired method of claim 46, wherein cationic additive comprises cationic polymer.

48. the desired method of claim 47, wherein cationic polymer comprises poly-quaternary amine.

49. the desired method of claim 47, wherein the polysaccharide particle has the surface charge from pact+1mV to pact+100mV scope.

50. the desired method of claim 47, it further comprises a kind of anionic retention aids is added in first intermittent pulp proportioning.

51. the desired method of claim 47, it further comprises a kind of cationic retention aid agent is added in first intermittent pulp proportioning.

52. the desired method of claim 50, it further comprises a kind of cationic retention aid agent is added in first intermittent pulp proportioning.

53. the desired method of claim 50, wherein anionic retention aids comprises anionic polyacrylamide.

54. the desired method of claim 52, wherein the cationic retention aid agent comprises cationic polyacrylamide.

55. the desired method of claim 46, wherein paper products are selected from the group of being made up of fine paper, newsprint, bleached paperboard, unimpregnated liner board, common cardboard and regeneration corrugated board.