CN1149238C - Bifunctional polymers - Google Patents
Bifunctional polymers Download PDFInfo
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- CN1149238C CN1149238C CNB998165980A CN99816598A CN1149238C CN 1149238 C CN1149238 C CN 1149238C CN B998165980 A CNB998165980 A CN B998165980A CN 99816598 A CN99816598 A CN 99816598A CN 1149238 C CN1149238 C CN 1149238C
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- alkylidene group
- carbonylamino
- group
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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
- D21H17/20—Macromolecular organic compounds
- D21H17/33—Synthetic macromolecular compounds
- D21H17/34—Synthetic macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H21/00—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties
- D21H21/14—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties characterised by function or properties in or on the paper
- D21H21/18—Reinforcing agents
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Paper (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Polyamides (AREA)
Abstract
Novel polymers are provided having phosphonated and sulphonated substituent groups such that the polymer is multifunctional in its use. Optional amide substituents are used to reduce electrostatic charge density or for hydrogen bonding. An advantage of the polymer is the flexibility of using it for multiple purposes. A particular application is for bonding paper fillers and paper fiber together.
Description
Invention field
The present invention relates to contain new polymers and its using method of acid amides, sulfonate and/or phosphate group, include but not limited to paper process, particularly as retention aid or intensity auxiliary agent.
Background technology
Recently, the amount of filler in the paper is restricted, and part is that the intensity of paper can reduce owing to the increase along with amount of filler.Minimum requirement of strength impels paper manufacturers to add more filler, because filler is generally cheap than lumber fibre, so usually wish to add mass filler with the replacing wood fiber.Add more filler and replace more valuable timber, the manufacturer is reduced production costs.In order to reach higher amount of filler, paper manufacturers need to strengthen paper intensity filler, additive or handle.Historically, paper manufacturers used methods such as filler modified, wet net additive and fibre modification to increase the intensity of paper.Filler modifiedly comprised change filler type, changed packing material size and filler has been carried out surface treatment.Wet net additive has comprised synthetic and natural polymer, as polyacrylamide and starch.Fibre modification has comprised change fiber type and fiber process method.
In a word, paper industry is tending to increase amount of filler to reduce cost, and the result is seeking the method for improving paper intensity always, and for this reason, the intensity auxiliary agent that a generation is new is that paper industry is needed.
At United States Patent (USP) 3,709, disclose in 780 by in the cellulose paper dispersion, adding 2-acrylamide-2-methyl propane sulfonic acid (AMPS) and be grafted on the chitin compound on the chitosan matrix, to improve intensive property.
At United States Patent (USP) 3,692, the polymkeric substance of acrylamide sulfonic acid and its salt is disclosed in 673, can be as the flocculation agent of aqueous system.
At United States Patent (USP) 4,555, water miscible AMPS, N are disclosed, the ter-polymers of N DMAA and vinyl cyanide in 558.It was reported that these ter-polymers can be used for the high temperature fluid loss additive and the rheology stablizer of the salt solution clay drilling fluid of high calcium-containing.
At United States Patent (USP) 3,926, disclose in 718 to use and had from the block of water-soluble monomer with from the water-soluble block polymer of N-vinyl pyrrolidone block.It is reported that at this moment these polymkeric substance can, be added to this polymkeric substance in the paper pulp as the discharge opeing and the retention aid of gauze.
At United States Patent (USP) 5,075, in 401, the graft copolymer of being made by radical reaction mechanism is disclosed, this polymkeric substance uses the polymer unit of acrylamide, vinylformic acid and/or AMPS.
Summary of the invention
The object of the invention provides the various substituent polymkeric substance with various functions or purposes.A special purpose provides a kind of polymkeric substance, is used for mineral filler is bonded in, particularly on the polysaccharide material, as paper pulp etc.Another object of the present invention provides and is used for the polymkeric substance that non-paper is used the tackiness agent of (as rubber, sealing agent, plastics, properties-correcting agent, medicine etc.).These and other objects can have phosphonic acidsization and sulfonated substituting group reaches with of the present invention, thereby this polymkeric substance is multi-functional in application.Optional amide substituents is used to reduce electrostatic charge density or increases hydrogen bond.The advantage of this polymkeric substance is to have handiness when being used for multiple purpose.Other advantage can be will appreciate that when reading this specification sheets by the people who is familiar with this art.
The invention discloses following content:
1. strengthen the method for paper intensity, be included in to add in the paper batching and comprise polymer core, be used for one or more sulfonated substituting groups of one or more phosphonic acids substituting groups of bonding no material effectively and effective bonding polysaccharide material and be used to one or more optional positively charged ions of reducing the electrostatic charge density of composition and increasing hydrogen bond or the polymer composition of the amide substituents of neutral charge
Wherein the substituent general formula of phosphonic acidsization is-A-P (=O) (OD
1) (OD
2), wherein " P " is phosphorus; " O " is oxygen, and " A " is selected from C or is selected from replacement or unsubstituted (C
1-C
6) alkylidene group, wherein substituting group is selected from (C with being independent of each other
1-C
3) alkyl and halogen or be selected from carbonyl, carbonylamino, alkylidene group carbonylamino, carbonylamino alkylidene group or alkylidene group carbonylamino alkylidene group, and " D " be hydrogen proton or the salt part that is selected from aluminium, calcium, iron, lithium, magnesium, potassium, sodium, titanium and zine ion,
Wherein sulfonated substituent general formula is-A-S (=O)
2(OD
1), wherein " S " is sulphur, " O " is oxygen, and " A " is selected from carbon-sulfide linkage or is selected from replacement or unsubstituted (C
1-C
6) alkylidene group, wherein substituting group is selected from (C with being independent of each other
1-C
3) alkyl and halogen or be selected from carbonyl, carbonylamino, alkylidene group carbonylamino, carbonylamino alkylidene group or alkylidene group carbonylamino alkylidene group, and " D " be hydrogen proton or the salt part that is selected from aluminium, calcium, iron, lithium, magnesium, potassium, sodium, titanium and zine ion,
Wherein the general formula of the amide substituents of positively charged ion or neutral charge is-A
1-C (=O)-N (B) R
1R
2, wherein " C " is carbon; " O " is oxygen, and " N " is nitrogen, " A
1" be to replace or unsubstituted (C
1-C
6) alkylidene group, wherein substituting group is selected from (C with being independent of each other
1-C
3) alkyl and halogen, " B " is hydrogen, hydroxyl or ether, " R
1" or " R
2" be hydrogen, halogen or (C with being independent of each other
1-C
3) alkyl,
Described paper batching randomly contains filler, and the consumption that wherein joins the polymer composition in the paper batching is 0.4536 kilogram on a paper per ton-4.5360 kilograms (1-10 pound).
2. the method for heading 1, wherein the phosphonic acids substituting group is selected from-PO
3H
2,-PO
3(CH
3)
2,-PO
3(H) (CH
3) ,-CH
2PO
3H
2,-CH
2PO
3(CH
3)
2,-CH
2PO
3(H) (CH
3) ,-C (=O) NHCH
2PO
3H
2, sulfonated substituting group is selected from-C (=O) NHC (CH
3)
2CH
2SO
3H ,-C (=O) NHCH
2SO
3H ,-CH
2C (=O) NHC (CH
3)
2,-CH
2SO
3H and-CH
2C (=O) N (CH
3) C (CH
3)
2CH
2SO
3H, amide substituents be selected from-C (=O) NH
2, CH
2C (=O) NH
2-C (=O) NHCH
3With-C (=O) N
+(CH
3)
3
3. the method for heading 2, wherein the phosphonic acids substituting group is-PO
3H
2, sulfonated substituting group is-C (=O) NHC (CH
3)
2CH
2SO
3H, amide substituents be-C (=O) NH
2
4. the arbitrary method among the heading 1-3, wherein the weight-average molecular weight of said composition is 100,000-20,000,000.
5. the arbitrary method among the heading 1-3, wherein degree of crosslinking is lower than 15% weight.
6. the arbitrary method among the heading 1-3, wherein degree of crosslinking is lower than 1% weight.
7. the arbitrary method among the heading 1-3, wherein batching also contains one or more fillers.
8. method that strengthens paper intensity, be included in the polymer composition that adds a kind of heading 1 definition in the paper batching, described paper batching randomly contains filler, and the consumption that wherein joins the described polymer composition in the described paper batching is a paper 0.4536-2.2680 kilogram per ton (1-5 pound).
9. the method for heading 8 further is included in the paper batching and adds starch.
10. the method for heading 9, wherein this starch is ethylating or the starch of oxidation or potato base or W-Gum.
11. the method for heading 9, wherein the consumption of starch is a paper 2.268-22.68 kilogram per ton (5-50 pound).
12. paper composition, comprise (a) paper grade (stock) cellulose fiber peacekeeping mineral filler, described cellulosic fibre exists with the consumption that is suitable for papermaking, and (b) a kind of composition as heading 1 definition, and wherein the phosphonic acids substituting group is 99/1-1/99 with the ratio of sulfonated substituting group.
13. the paper composition of heading 12 further comprises starch.
14. the paper composition of heading 13, wherein this starch is ethylating or the starch of oxidation or potato base or W-Gum.
15. the paper composition of heading 14, wherein this starch is effective mixture of composition in starch and the heading 1, the paper wood when wherein this mixture can be produced intensity effectively far above independent use starch or polymer composition.
16. a paper wood comprises the composition of heading 15, the intensity when wherein effectively the strength ratio of the paper wood produced of mixture is used starch or polymer composition separately significantly increases.
Detailed description of the invention
The polymer composition of a specific embodiments of the present invention has polymer core, one or more are used for the phosphine acidifying substituting group of effective bonding inorganic materials and the Sulfonated substituting group of one or more effective bonding polysaccharide materials.
Polymer core preferably includes one or more polymer units (obtaining as condensation or free radical method) that are selected from polymerisable monomeric unit, and these monomeric units are preferably selected from allyl group unit, epoxidation materialization thing unit and vinyl units.Polymer core can by various ratios or the order replacement or the unitary allyl group of unsubstituted monomer (or polymeric), epoxide unit and vinyl units form.Not every allyl group unit, epoxidation materialization thing unit or vinyl units need identical with other each allyl group unit, epoxide unit or vinyl units, but they can be identical.This difference can be from hydrolysis reaction, wherein regardless of being intentionally or being not intended to.Before polymerization or after the polymerization, these allyl groups, epoxide or vinyl units can have one or more phosphonic acids or Sulfonated substituting group to be connected.These unit of core can repeat with the order that can indicate or repeat randomly.
The allyl group unit can be from having CH
3CH
2The compound of=CH-part.Preferred allyl group unit is the polyacrylamide amine unit.The epoxide unit can be from the compound with lower part:
Vinyl units can be derived from having CH
2The compound of=CH-part.Preferred vinyl units is the vinyl phosphonic hydrochlorate.Any one or more hydrogen atoms can be substituted before polymerization, in the polymerization or after the polymerization.The ratio of allyl group unit, epoxide unit and vinyl units can differ widely, and perhaps polymkeric substance can only be made up of a kind of unit or the mixing of their different ratios.No matter polymkeric substance is to have only a kind of allyl group unit, have only a kind of epoxide unit or a kind of vinyl units or their different mixtures to make, and every class unit is because the substituting group relation can be identical or different.In a preferred embodiment, other components in proportions of polyacrylamide amine unit or epoxide unit and polymer composition or amount can reduce the electrostatic charge density of polymer composition effectively or increase the hydrogen bonding of polysaccharide material or be more preferably the both effective.
That polysaccharide material comprises is fine plain, starch and other similar natural and synthetic polysaccharide that sugar is connected of joining.Preferred polysaccharide is Mierocrystalline cellulose, more preferably lumber fibre and bagasse; The cellulosic fibre that more preferably is used for papermaking.
In one embodiment, polymer composition of the present invention comprises and connects monomeric unit, acid amides or and the various mixtures of epoxide monomer unit, phosphine acidifying monomeric unit and Sulfonated monomeric unit.
The preferred monomeric unit that connects can be represented with following formula :-CH-CH (R
1)-, be R wherein
1Be hydrogen, halogen or low alkyl group.
Amide monomer unit cationic or neutral charge can be represented with following general formula:
Wherein " C " is carbon, and " O " is oxygen, and " N " is nitrogen, and " A " is that replace or unsubstituted (C
1-C
6) alkylidene group or hydrogen, wherein substituting group is selected from (C with being independent of each other
1-C
3) alkyl and halogen, " B " is hydrogen, hydroxyl or ether, preferably hydrogen.Nitrogen N can be a quaternary nitrogen also, includes but not limited to the mixture of above-mentioned group, " R
1" and " R
2" be hydrogen, halogen or (C with being independent of each other
1-C
3) alkyl." A " then is (C if not hydrogen
1-C
6) alkylidene group, for example methylene radical, ethylidene, propylidene, butylidene, pentylidene or hexylidene.These alkylidene groups can have (C
1-C
3) alkyl substituent, for example methyl, ethyl or propyl group.The substituting group halogen is to be selected from bromine, chlorine and fluorine atom on alkyl or the alkylidene chain herein.For R
1And R
2, (C
1-C
3) alkyl is methyl, ethyl and just-propyl group.
Preferred epoxide monomer unit can be used-CHR-O-CH
2Expression.Wherein R is hydrogen or low alkyl group or alkylidene group, for example has an alkylidene group to six carbon atom.
Preferred phosphine acidifying monomeric unit can be represented with following general formula:
Wherein " P " is phosphorus, and " O " is that oxygen and " A " are selected from replacement or unsubstituted (C
0-C
6) alkylidene group, wherein substituting group is selected from (C with being independent of each other
1-C
3) alkyl is with regard to halogen, or be selected from carbonyl (CO-), carbonylamino (CO-NE-, " E " here is hydrogen, hydroxyl or ether), alkylidene group carbonylamino (for example-(CH
2)
x-CO-NE-, x herein is an integer), the carbonylamino alkylidene group (for example ,-CO-NE-(CH
2)
x-) or alkylidene group carbonylamino-alkylidene group (for example ,-(CH
2)
x-CO-NE (CH
2)
x-); " D " is hydrogen proton or the salt part that is selected from aluminium, calcium, iron, lithium, magnesium, potassium, sodium, titanium and zine ion.If in the salt part, these substituting groups cause substituent electronic equilibrium." A " is (C
0-C
6) alkylidene group, for example be assortedly pettyly do not have yet, be methylene radical, ethylidene, propylidene, butylidene, pentylidene or hexylidene.But these preferred alkylidene groups can have one or more (C
1-C
3) alkyl substituent, for example methyl, ethyl or propyl group.Be to be selected from bromine, chlorine and fluorine atom as substituent halogen on the alkyl chain herein.These halogens also can be the substituting groups on the alkylidene chain.When " A " be expressed as C (=O)-N (E)-time, then E is hydrogen, hydroxyl or ether, preferably hydrogen.Nitrogen N can be a quaternary nitrogen also, includes but not limited to the mixture of above-mentioned group.
When " D " is the hydrogen proton ,-PO
3-D can be expressed as-P (=O) (OH) (OH).When D is the salt part, then-PO
3-D can be by case representation:
-(PO
3)
-2(Na
+ 1)
2, when sodium is this part, or
-(PO
3)
-2(Ca
+ 2)
1, when calcium is this part.
" D " also can represent the paired of hydrogen and salt part, for example-and (PO
3) H
+ 1Na
+ 1
Inorganic materials is preferably as the paper of narration in the back or the mineral as filler material of non-paper product.Although consider these in the present invention, the present invention not necessarily is limited to these inorganic materials.In certain preferred aspects, inorganic materials is filler or other additive that is used for paper composition.In other embodiments, inorganic materials is filler or other additive that is used for non-paper composition (as plastics).Preferred inorganic materials from or with calcareous material manufacturing, as some clay or natural whiting.Another preferred inorganic materials is sedimentary lime carbonate.
Preferred sulfonated monomeric unit can be represented with following general formula:
Wherein " S " is sulphur, and " O " is oxygen, and " A " is selected from replacement or unsubstituted (C
0-C
6) alkylidene group, wherein, substituting group is selected from (C with being independent of each other
1-C
3) alkyl and halogen, or be selected from carbonyl (CO-), carbonylamino (CO-NE-, " E " herein is hydrogen, hydroxyl or ether), alkylidene group carbonylamino (for example-(CH
2)
x-CO-NE-, x herein is an integer), the carbonylamino alkylidene group (for example-CO-NE-(CH
2)
x-), or alkylidene group carbonylamino alkylidene group (for example, (CH
2)
x-CO-NE-(CH
2)
x-), and " D " is hydrogen proton or the salt part that is selected from aluminium, calcium, iron, lithium, magnesium, potassium, sodium, titanium and zine ion.If in the salt part, then these substituting groups cause substituent electronic equilibrium." A " is (C
0-C
6) alkylidene group, for example assortedly pettyly do not have yet, be methylene radical, ethylidene, propylidene, butylidene, pentylidene or hexylidene.But these alkylidene groups can have (C
1-C
3) alkyl substituent, for example methyl, ethyl or propyl group.Be to be selected from bromine, chlorine and fluorine atom as substituent halogen on the alkyl chain herein.These halogens also can be the substituting groups on the alkylidene chain.Be expressed as " A "-C (=O)-N (E)-time, then E is hydrogen, hydroxyl or ether, preferably hydrogen.Nitrogen N can be a quaternary nitrogen also, includes but not limited to the mixture of above-mentioned group.For example when D is sodium ,-SO
3-D can be expressed as-SO
3 -Na
+, when D is alkyl ,-SO
3-D can be expressed as-SO
3CH
3
Substituent limiting examples is:
1 phosphonic acids substituting group
-PO
3H
2 -PO
3(CH
3)
2 -PO
3(H)(CH
3)
-CH
2PO
3H
2 -CH
2PO
3CH
3)
2 -CH
2PO
3(H)(CH
3)
-C(＝O)NHCH
2PO
3H
2
The sulfonated substituting group of II
-C(＝O)NHCH
3SO
3H -C(＝O)NHC(CH
3)
2CH
2SO
3H
-CH
2C(＝O)NHC(CH
3)
2CH
2SO
3H -CH
2C(＝O)N(CH
3)C(CH
3)CH
2SO
3H
The amide substituents of III positively charged ion or neutral charge
-C(＝O)NH
2 -CH
2C(＝O)NH
2
-C(＝O)NHCH
3 -C(＝O)N
+(CH
3)
3
It is about 100 that molecular weight with above-mentioned core and substituent composition is preferably, 000-20,000,000.When the amide substituents that does not have optional positively charged ion or neutral charge was made, preferred molecular weight was about 500, and 000-about 5,000,000.When making with the amide substituents of optional positively charged ion or neutral charge, preferred molecular weight is about 500, and 000-about 5,000,000.
Composition of the present invention can be with various mole unit phosphonic acids substituting group ratio or ratio, Sulfonated substituting group and the optional positively charged ion or the amide substituents manufacturing of neutral charge.Phosphine acidifying substituting group and Sulfonated substituent mole unit ratio can be from about 99/1 to 1/99, but are preferably about 45/55-1/99, more preferably about 10/90-1/99.When having optional positively charged ion or neutral charge amide substituents in the polymkeric substance of making, these substituting groups account for main ratio when comparing with other substituting group, with respect to phosphine acidifying substituting group, be preferably 1/1, and more preferably 10/1 or higher.The mutual ratio of other two kinds of substituting groups can be as above-mentioned.Therefore, (positively charged ion or neutral charge amide substituents) and (Sulfonated substituting group) are (about 70[is preferably more than 85]-90) positively charged ion or neutral charge amide substituents with the unitary ratio of preferred mole of (phosphine acidifying substituting group): (0[preferably about 10]-30) sulfonated substituent mole unit: (about 0[preferably about 5]-10) mole unitary phosphonic acids substituting group unit.For example, the unitary mole of the amide substituents of positively charged ion or neutral charge/sulfonated unit/phosphonic acidsization unit ratio is 85/10/5,89/10/1 and 90/9/1.Other accurate ratio is also preferably in described scope.Although unitary order can be different according to using, general not preferably or requirement, the present invention here narrate without limits in any concrete order.Therefore, only otherwise can influence advantage of the present invention, the terminal units of polymkeric substance and other unit and substituting group can not be unit or the substituting groups of being discussed.Similarly, can there be the crosslinked of some degree, but preferably do not exist crosslinked basically.
In an embodiment preferred of the present invention, the phosphine acidifying substituting group of discussion can have chemical structure-PO
3H; Sulfonated substituting group can have chemical structure-C (O) NHC (CH
3)
2CH
2SO
3H; The amide substituents of positively charged ion or neutral charge can have chemical structure-C (O) NH
2This polymkeric substance can be synthetic by vinyl phosphonic acid mono, 2-acrylamido-2-methyl propane sulfonic acid monomer and the acrylamide monomer polyreaction of various ratios.Below table 1 be the non-limitative illustration (molecular weight can be measured with the intrinsic viscosity method, as with Mark-Houwink-Sakurada constant method) of polymkeric substance and possible molecular weight.
Table 1
| Polymkeric substance is formed | Molecular weight |
| 99％AMPS 1％VPA | 75,000 |
| 125,000 | |
| 500,000 | |
| 89％ PAM 10％AMPS 1％VPA | 500,000 |
| 2,000,000 | |
| 5,000,000 | |
| 85％ PAM 10％ AMPS 5％VPA | 75,000 |
| 500,000 | |
| 2,000,000 | |
| 5,000,000 |
AMPS=2-acrylamido-2-methyl propane sulfonic acid monomer
VPA=vinyl phosphonic acid mono
PAM=polyacrylamide amine monomers
The limiting examples of one of polymkeric substance of the present invention can be represented with following polymer segment structure:
In preferred embodiments, the phosphonic acids substituting group is used for effective bonding mineral filler.These mineral fillers can be the fillers that generally is used for the papermaking purposes.The limiting examples of these fillers is clay, lime carbonate (as lime carbonate or the sedimentary lime carbonate that grinds) and talcum.As will be appreciated, used phosphonic acids substituting group with and effect will with the type of papermaking material (for example paper pulp with or/filler) different with creating conditions by (for example temperature, pressure and other chemical).Here said " bonding " can comprise that acid-alkali interacts and one of ionic bonding kind or both have, to set up adding or purposes that affinity is planned to be used for significant quantity between polymkeric substance and mineral filler.Therefore, bonding can be but be not necessarily indicated by secondary measurement, in retention or strength detection in the purposes of paper.
Sulfonated in preferred embodiments substituting group is effective to homopolysaccharide material bonding.These polysaccharide materials can be the materials that generally is used in the papermaking, as starch, fiber, thickening material etc.The limiting examples of these filamentary materials is timber, bamboo, bagasse or other cellulose biomass.The example of starch is positively charged ion or neutral waxy corn, potato, tapioca (flour), starch conversion or chemical modification, synthetic starch etc.Thickening material is the thickening material of carboxymethyl series etc.
In another embodiment, the phosphonic acids substituting group in the polymkeric substance of the present invention is effective to bonding and is used for non-paper and uses used mineral filler.In this application, mineral filler is used for also containing the composition with the sulfonated substituting group bonding of polymkeric substance.These non-paper are used can be including but not limited to relating to natural and synthetic rubber, sealing agent, plastics, paint (for example latex and emulsive), rheology modifier, tablet etc.These materials can comprise the non-paper material or the polymeric of the casting that contains micropore or extruding or be applicable to bonding sulfonated substituent polysaccharide material, as be used for the filler of volume or intensity purpose.
Be used to reduce electrostatic charge density and increase the optional positively charged ion of hydrogen bond or the consumption of the amide substituents of neutral charge and selection can owing to phosphonic acidsization with sulfonated substituent selection and different.
In another embodiment of the present invention, polymeric composition comprises the novel polymer of above-mentioned discussion.This polymeric composition can have the feature of the relevant molecular-weight average, molecular weight distribution, electric density and the monomeric unit type that differ widely.These features can be regulated according to the purposes difference.For example, in a desired application, molecular-weight average can be 1,000,000, and wherein 85% polymkeric substance can have molecular weight 1,000,000 ± 15%.In Another Application, another example is that 85% polymkeric substance can have molecular weight 1,000,000 ± 50%.
Polymkeric substance can be divided into straight-chain polymer and cross-linked polymer.Use known analytical procedure, can measure the degree (accounting for the % weight of total composition) of cross-linked polymer as NMR (Nuclear Magnetic Resonance) spectrum (NMR).In preferred embodiments, polymer composition of the present invention has the crosslinked of minuent, and about 15% weight of content more preferably is lower than 5% weight, particularly preferably is lower than the cross-linked polymer of 1% weight.
In another embodiment of the present invention, the phosphonic acids substituting group that need not have said structure, what composition of the present invention was used is the derivative that comprises condensed phosphate, for example poly-phosphate, pyrophosphate salt or ortho-phosphoric acid (for example tetra-sodium, metaphosphoric acid, peroxophosphoric acid or ortho-phosphoric acid).
On the other hand, specific embodiments of the present invention is to improve the method for the intensity of paper, comprise that some polymer composition with above-mentioned polymkeric substance joins in the optional paper batching that contains filler, preferred polymkeric substance is to comprise acrylamide monomer and phosphonic acids monomer or sulfonated monomeric multipolymer, or comprises acrylamide monomer, phosphonic acids monomer and sulfonated monomeric ter-polymers.Polymer composition can join before the head box of paper machine in dense or rare paper stock.Can use and separately or repeatedly add point and other strategy.The amount that adds can and be produced the purposes of paper and different with the character of papermaking batching, still generally should be batching adding about 0.4536-2.2680 kilogram (1 pound-5 pounds) polymer composition per ton.
Unexpected is that polymkeric substance of the present invention can make collaborative the increasing of intensity of product paper with the mixture of starch.On the one hand, synergistic effect can be by following fact proved: when independent use, do not add any additional polymkeric substance and starch and can obtain polymkeric substance and starch-mixed result.Used starch is the starch that generally is used for papermaking.This starch can be synthetic, form as ethylating or oxidation, or organically, as based on potato, be preferably the positively charged ion potato starch or based on corn, as positively charged ion wax W-Gum, when polymer composition and starch all were added in the paper batching, every kind adding point can be the each point in the head box upstream.Polymkeric substance preferably is added in the dense paper stock, and preferably adds before adding starch.Every kind of adding can be carried out separately and add.Use these polymkeric substance separately and mix use, the intensity of the paper that generates with polymkeric substance is improved with starch.With known method such as length of fracture, paper intensity is broken and method such as Scott bonding can be measured the improvement of this intensity easily.
Therefore, one embodiment of the invention are the methods of producing paper, this method comprises starch and polymer composition mixed, and polymer composition comprises that one or more are by acrylamide polymer, with the acrylamide polymer that contains pendant sulfonic acid group or phosphonyl group monomer copolymerization with the polymeric groups of acrylamide ter-polymers that contains the sulfonic acid group monomer of side chain and contain the phosphonyl group monomer copolymerization of side chain.Thisly be blended in when the preparation batching is provided before the paper machine of preparing burden or carry out before.Mixed order can the time be before or after starch and polymkeric substance are added to batching kind, be preferably before.When respectively polymer composition and starch being added to batching, preferred order is to add starch earlier.Polymer composition is discussed above.
Preferable methods comprises mixes starch and polymer composition effectively, and the strength ratio of the cardboard that obtains does not reckon with when using starch or polymer composition separately that ground is high, and is preferably high at least by 15%, more preferably high at least by 50%, and particularly preferably high at least 100%.
On the other hand, the method of embodiment of the present invention comprises mixes starch and polymer composition effectively, when using starch and polymkeric substance separately, the paper board strength ratio that obtains do not work in coordination with increase with reckoning with, this " collaborative increase " intensity when will do not existed with polymer composition with starch by the intensity that starch and mixed with polymers obtain is compared, and all not have use to compare with the interpolation total amount that increases respectively of the intensity of using separately with starch and polymer composition and starch and polymer composition and compares.Represent with equation then to be
SI＝[(SC-SA)/(SA)]-[(SS-SA)/(SA)+(SP-SA)/(SA)]，
Wherein SI is collaborative increment, the intensity of paper when SC is to use starch and polymeric blends, and SA is the intensity that does not have the paper of starch or polymer composition, SS and SP are respectively the intensity of paper when using starch and use polymer composition separately.The significant value of SI exists (for example surpass test artifact) to be considered to the result, and to be better than additive effect be great and unexpected expression.Collaborative in preferred embodiments increasing is not have independent adding polymkeric substance or starch will obtain the identical intensity [for inorganic (for example, filler) material of given % weight] that is obtained by polymkeric substance of the present invention and starch mixture when Individual existence.
The consumption of starch will be different with the paper of concrete batching and manufacturing.These consumptions generally can add 2.2680-22.68 kilogram (5 pounds-50 pounds) for paper per ton.Equally, the consumption of polymer composition is generally paper 1-10 pound per ton.
The following examples are explanation the present invention, rather than restriction the present invention, because other method also is possible.
Embodiment 1
Preparation of Polyacrylamide
In 4083 milliliters distilled water and 500 gram acrylamide (the purity 97% weight) flasks of packing into, material is stirred and is blown into nitrogen (commercial grade) 5 minutes.Flask contents is heated to 70 ℃, continues to be blown into nitrogen, and add potassium persulfate solution (0.083 gram Potassium Persulphate and 83.3 ml distilled waters).Content in the flask remain on 70 ℃ 1 hour, temperature is elevated to 80 ℃ then, thicken up to beginning.Temperature is reduced to 75 ℃.After 30 minutes, with temperature be raised to 80 ℃ 1 hour.Add second part of potassium persulfate solution (0.333 gram Potassium Persulphate and 83.3 ml distilled waters).After 3-4 minute, add sodium metabisulfite solution (0.167 gram sodium metabisulfite and 83.3 ml waters).The temperature of flask is kept 80 ℃ and add distilled water (4167 milliliters) and thicken avoiding, and flask remains on 80 ℃ and added entry about 1 hour, at this moment, takes a sample to check whether residual monomer is arranged.If residual monomer is too many, then continues to remain on 80 ℃ and can accept up to amount of monomer.Add remainder water (4167 milliliters) and thorough mixing then, cooling and recovery.
Embodiment 2
The preparation of polyacrylamide/AMPS (2-acrylamido-2-methyl propane sulfonic acid)
With 4080 milliliters distilled water, 368 gram acrylamides (purity 97% weight) and 60 gram AMPS sodium solutions (50%AMPS) are packed in the flask, with the material stirring and be blown into nitrogen (commercial grade) 5 minutes.Flask contents is heated to 70 ℃, continues to be blown into nitrogen, and add potassium persulfate solution (0.083 gram Potassium Persulphate and 83.3 milliliters distilled water).Content in the flask kept 30 minutes at 70 ℃, or up to the reaction beginning.If not reaction in 30 minutes then rises to temperature 80 ℃ and begin to add material solution [203.2 gram AMPS sodium (50%) and 291.4 ml distilled waters] with the speed of per minute 11 grams.Along with thickening takes place, adding reaches 3747 milliliters distilled water, behind the adding material solution, observes the temperature under the heat release condition.Add second part of potassium persulfate solution (0.333 gram Potassium Persulphate and 83.3 ml distilled waters).After 3-4 minute, add sodium metabisulfite solution (0.167 gram sodium metabisulphite and 83.3 ml distilled waters).The flask temperature is remained on 80 ℃ add distilled water (4167 milliliters) simultaneously to avoid thickening.The flask temperature is remained on 80 ℃ and added entry about 1 hour.At this moment, take a sample to check whether residual monomer is arranged.If residual monomer is too many, then continues to remain on 80 ℃ and can accept up to amount of monomer.Add remainder water (3747 milliliters) then, if desired.Then add other water (500 milliliters at the most), and thorough mixing, cooling and recovery.
Embodiment 3
The preparation of AMPS/PAM/VPA ter-polymers
In flask, add 145.0 milliliters distilled water, 21.75 gram acrylamides and 4.0 gram 2-acrylamido-2-methyl propane sulfonic acid sodium monomers (50%) and under nitrogen, be heated to 70 ℃.Add about 1 gram solid sodium hydroxide, pH regulator is arrived about 7.Add then and be dissolved in the gram Potassium Persulphate of 0.005 in 5 ml distilled waters and temperature is risen to 80 ℃.Along with the mixture retrogradation adds 5 ml distilled waters.In about 1 hour, add 25.0 distilled water, 11.78 gram 2-acrylamido-2-methyl propane sulfonic acid sodium monomers (50%) and the monomeric charging of 0.40 gram vinyl phosphoric acid, the sodium hydroxide solution that adds 2.4 grams 10% simultaneously arrives about 7 with the pH regulator of mixture.Along with the mixture retrogradation, add distilled water (in total adding phase, adding about 90 milliliters).Added after the charging 15 minutes, and added 15 ml distilled waters.After about 30 minutes, add 0.2 gram Potassium Persulphate and 5 ml distilled waters.After 3-4 minute, add 0.1 gram sodium metabisulfite and 5 ml distilled waters.The temperature of mixture is remained on 80 ℃.Add the cold distilled water of 200.0 grams.Continuing to be heated to 80 ℃ also continues to mix about 3 hours.Reclaim sample analysis: 5.88% solid, 0.069% residual monomer; 3.4027 intrinsic viscosity (for example Mark-Houwink-Sakurada constant), molecular weight 999,024.65.
Embodiment 4
Polymkeric substance is used for papermaking
Make handsheet with 75% hardwood/25% cork compound of the northern kraft pulp of bleaching, the terminal point that under 1.6% denseness, is refined to 400 canadian standard freeness jointly.Purified paper pulp is diluted to 0.3125% denseness with papermaking.Speed with 0.25% is added to Hercon75 kation alkyl ketene dimer emulsion in the batching, and the polymkeric substance of being made up of polyacrylamide, acrylamide and 2-acrylamido-2-methyl propane sulfonic acid (AMPS) multipolymer of functionalization not or PAM, AMPS and vinyl phosphoric acid (VPA) ter-polymers joins in the batching with 0.25% schedule speed.Organize handsheet with Albacar for each
The sedimentary lime carbonate of HO is added in the batching, regulates add-on and makes amount of filler be about 14,21 and 18%.The speed of Stalok 400 positively charged ion potato starches with 0.75% regulation is added in the batching, Reten 1523 anionic polyacrylamide retention aids are added in the batching with 0.025% schedule speed.Then every batch of batching is divided into the handsheets (60.6 gram/square metre) that quarter obtains 2.5 grams.At each handsheet at Forax (Noble﹠amp; Wood type) form on the template die type after, between stainless steel cylinder and rubber rollers,, between paper machine " wet felt " material piece, form sandwich goods simultaneously with 20 pounds/square inch exert pressure.These handsheets are dry on 115 ℃ of heated drums, under 23 ℃ of the TAPPI standard conditions and 50% relative humidity, to regulate and test then, test-results is shown in Fig. 1 and 2.
Embodiment 5
Second-order transition temperature
5 polymer composition sample undergo differential scanning calorimetry heat are analyzed to measure whether have unusual second-order transition temperature.The results are shown in the following table:
| Sample number | Molecular weight | AMPS | PAM | VPA | Second-order transition temperature |
| 1 | 2,100,000 | - | 100 | -- | 120.9 |
| 2 | 1,800,000 | 10 | 90 | -- | 110.93 |
| 3 | 1,000,000 | - | 90 | 10 | 78.78 |
| 4 | 500,000 | 10 | 85 | 5 | 83.63 |
| 5 | 1,000,000 | 10 | 89 | 1 | 96.87℃ |
Molecular weight is measured with the intrinsic viscosity method
The % weight of AMPS-2-acrylamido-2-methyl propane sulfonic acid
The % weight of PAM-polyacrylamide
The % weight of VPA-vinyl phosphonate.
Claims (16)
1. strengthen the method for paper intensity, be included in the paper batching and add a kind of polymkeric substance, this polymkeric substance comprises polymer core, is used for one or more phosphonic acids substituting groups and one or more the sulfonated substituting groups of effective bonding polysaccharide material and electrostatic charge density and non-essential one or more positively charged ions of increase hydrogen bond or the amide substituents of neutral charge that is used to reduce composition of bonding inorganic materials effectively
Wherein polymer core by various ratios or the order replacement or allyl group, epoxide and the vinyl units of unsubstituted monomeric unit form,
Wherein the substituent general formula of phosphonic acidsization is-A-P (=O) (OD
1) (OD
2), wherein " P " is phosphorus; " O " is oxygen, and " A " is selected from C or is selected from replacement or unsubstituted (C
1-C
6) alkylidene group, wherein substituting group is selected from (C with being independent of each other
1-C
3) alkyl and halogen or be selected from carbonyl, carbonylamino, alkylidene group carbonylamino, carbonylamino alkylidene group or alkylidene group carbonylamino alkylidene group, and " D " be hydrogen proton or the salt part that is selected from aluminium, calcium, iron, lithium, magnesium, potassium, sodium, titanium and zine ion,
Wherein sulfonated substituent general formula is-A-S (=O)
2(OD
1), wherein " S " is sulphur, " O " is oxygen, and " A " is selected from carbon-sulfide linkage or is selected from replacement or unsubstituted (C
1-C
6) alkylidene group, wherein substituting group is selected from (C with being independent of each other
1-C
3) alkyl and halogen or be selected from carbonyl, carbonylamino, alkylidene group carbonylamino, carbonylamino alkylidene group or alkylidene group carbonylamino alkylidene group, and " D " be hydrogen proton or the salt part that is selected from aluminium, calcium, iron, lithium, magnesium, potassium, sodium, titanium and zine ion,
Wherein the general formula of the amide substituents of positively charged ion or neutral charge is-A
1-C (=O)-N (B) R
1R
2, wherein " C " is carbon; " O " is oxygen, and " N " is nitrogen, " A
1" be to replace or unsubstituted (C
1-C
6) alkylidene group, wherein substituting group is selected from (C with being independent of each other
1-C
3) alkyl and halogen, " B " is hydrogen, hydroxyl or ether, " R
1" or " R
2" be hydrogen, halogen or (C with being independent of each other
1-C
3) alkyl,
Wherein the ratio of phosphonic acids substituting group and sulfonated substituting group is 99/1-1/99,
Described paper batching optionally contains filler, and the consumption that wherein joins the polymer composition in the paper batching is 0.4536 kilogram-4.5360 kilograms on a paper per ton.
2. the process of claim 1 wherein that the phosphonic acids substituting group is selected from-PO
3H
2,-PO
3(CH
3)
2,-PO
3(H) (CH
3) ,-CH
2PO
3H
2,-CH
2PO
3(CH
3)
2,-CH
2PO
3(H) (CH
3) ,-C (=O) NHCH
2PO
3H
2, sulfonated substituting group is selected from-C (=O) NHC (CH
3)
2CH
2SO
3H ,-C (=O) NH CH
2SO
3H ,-CH
2C (=O) NHC (CH
3)
2,-CH
2SO
3H and-CH
2C (=O) N (CH
3) C (CH
3)
2CH
2SO
3H, amide substituents be selected from-C (=O) NH
2, CH
2C (=O) NH
2-C (=O) NHCH
3With-C (=O) N
+(CH
3)
3
3. the method for claim 2, wherein the phosphonic acids substituting group is-PO
3H
2, sulfonated substituting group is-C (=O) NHC (CH
3)
2CH
2SO
3H, amide substituents be-C (=O) NH
2
4. the arbitrary method among the claim 1-3, wherein the weight-average molecular weight of this polymkeric substance is 100,000-20,000,000.
5. the arbitrary method among the claim 1-3, wherein this polymkeric substance is crosslinked, degree of crosslinking is lower than 15% weight.
6. the arbitrary method among the claim 1-3, wherein this polymkeric substance is crosslinked, degree of crosslinking is lower than 1% weight.
7. the arbitrary method among the claim 1-3, wherein batching also contains one or more fillers.
8. the method for claim 1, be included in the paper batching and add a kind of polymer composition, this polymkeric substance comprises polymer core, is used for one or more phosphonic acids substituting groups and one or more the sulfonated substituting groups of effective bonding polysaccharide material and electrostatic charge density and non-essential one or more positively charged ions of increase hydrogen bond or the amide substituents of neutral charge that is used to reduce composition of bonding inorganic materials effectively
Wherein polymer core by various ratios or the order replacement or allyl group, epoxide and the vinyl units of unsubstituted monomeric unit form,
Wherein the substituent general formula of phosphonic acidsization is-A-P (=O) (OD
1) (OD
2), wherein " P " is phosphorus; " O " is oxygen, and " A " is selected from C or is selected from replacement or unsubstituted (C
1-C
6) alkylidene group, wherein substituting group is selected from (C with being independent of each other
1-C
3) alkyl and halogen or be selected from carbonyl, carbonylamino, alkylidene group carbonylamino, carbonylamino alkylidene group or alkylidene group carbonylamino alkylidene group, and " D " be hydrogen proton or the salt part that is selected from aluminium, calcium, iron, lithium, magnesium, potassium, sodium, titanium and zine ion,
Wherein sulfonated substituent general formula is-A-S (=O)
2(OD
1), wherein " S " is sulphur, " O " is oxygen, and " A " is selected from carbon-sulfide linkage or is selected from replacement or unsubstituted (C
1-C
6) alkylidene group, wherein substituting group is selected from (C with being independent of each other
1-C
3) alkyl and halogen or be selected from carbonyl, carbonylamino, alkylidene group carbonylamino, carbonylamino alkylidene group or alkylidene group carbonylamino alkylidene group, and " D " be hydrogen proton or the salt part that is selected from aluminium, calcium, iron, lithium, magnesium, potassium, sodium, titanium and zine ion,
Wherein the general formula of the amide substituents of positively charged ion or neutral charge is-A
1-C (=O)-N (B) R
1R
2, wherein " C " is carbon; " O " is oxygen, and " N " is nitrogen, " A
1" be to replace or unsubstituted (C
1-C
6) alkylidene group, wherein substituting group is selected from (C with being independent of each other
1-C
3) alkyl and halogen, " B " is hydrogen, hydroxyl or ether, " R
1" or " R
2" be hydrogen, halogen or (C with being independent of each other
1-C
3) alkyl, described paper batching optionally contains filler, and the consumption that wherein joins the described polymer composition in the described paper batching is a paper 0.4536-2.2680 kilogram per ton.
9. the method for claim 8 further is included in the paper batching and adds starch.
10. the method for claim 9, wherein this starch is ethylating or the starch of oxidation or potato base or W-Gum.
11. the method for claim 9, wherein the consumption of starch is a paper 2.268-22.68 kilogram per ton.
12. paper composition; Comprise (a) paper grade (stock) cellulose fiber peacekeeping mineral filler; Described cellulose fibre exists with the consumption that is suitable for papermaking; And (b) a kind of polymer composition; This polymer comprises polymer core, be used for one or more sulfonated substituting groups of one or more phosphonic acids substituting groups of bonding inorganic material effectively and effective bonding polysaccharide material and for reducing the electrostatic charge density of composition with increase non-essential one or more cations of hydrogen bond or the amide substituents of neutral charge
Wherein polymer core by various ratios or the order replacement or allyl group, epoxide and the vinyl units of unsubstituted monomeric unit form,
Wherein the substituent general formula of phosphonic acidsization is-A-P (=O) (OD
1) (OD
2), wherein " P " is phosphorus; " O " is oxygen, and " A " is selected from C or is selected from replacement or unsubstituted (C
1-C
6) alkylidene group, wherein substituting group is selected from (C with being independent of each other
1-C
3) alkyl and halogen or be selected from carbonyl, carbonylamino, alkylidene group carbonylamino, carbonylamino alkylidene group or alkylidene group carbonylamino alkylidene group, and " D " be hydrogen proton or the salt part that is selected from aluminium, calcium, iron, lithium, magnesium, potassium, sodium, titanium and zine ion,
Wherein sulfonated substituent general formula is-A-S (=O)
2(OD
1), wherein " S " is sulphur, " O " is oxygen, and " A " is selected from carbon-sulfide linkage or is selected from replacement or unsubstituted (C
1-C
6) alkylidene group, wherein substituting group is selected from (C with being independent of each other
1-C
3) alkyl and halogen or be selected from carbonyl, carbonylamino, alkylidene group carbonylamino, carbonylamino alkylidene group or alkylidene group carbonylamino alkylidene group, and " D " be hydrogen proton or the salt part that is selected from aluminium, calcium, iron, lithium, magnesium, potassium, sodium, titanium and zine ion,
Wherein the general formula of the amide substituents of positively charged ion or neutral charge is-A
1-C (=O)-N (B) R
1R
2, wherein " C " is carbon; " O " is oxygen, and " N " is nitrogen, " A
1" be to replace or unsubstituted (C
1-C
6) alkylidene group, wherein substituting group is selected from (C with being independent of each other
1-C
3) alkyl and halogen, " B " is hydrogen, hydroxyl or ether, " R
1" or " R
2" be hydrogen, halogen or (C with being independent of each other
1-C
3) alkyl, wherein the phosphonic acids substituting group is 99/1-1/99 with the ratio of sulfonated substituting group.
13. the paper composition of claim 12 further comprises starch.
14. the paper composition of claim 13, wherein this starch is ethylating or the starch of oxidation or potato base or W-Gum.
15. the paper composition of claim 14, wherein this starch is effective mixture of starch and polymer composition, this polymkeric substance comprises polymer core, is used for one or more phosphonic acids substituting groups and one or more the sulfonated substituting groups of effective bonding polysaccharide material and electrostatic charge density and non-essential one or more positively charged ions of increase hydrogen bond or the amide substituents of neutral charge that is used to reduce composition of bonding inorganic materials effectively
Wherein polymer core by various ratios or the order replacement or allyl group, epoxide and the vinyl units of unsubstituted monomeric unit form,
Wherein the substituent general formula of phosphonic acidsization is-A-P (=O) (OD
1) (OD
2), wherein " P " is phosphorus; " O " is oxygen, and " A " is selected from C or is selected from replacement or unsubstituted (C
1-C
6) alkylidene group, wherein substituting group is selected from (C with being independent of each other
1-C
3) alkyl and halogen or be selected from carbonyl, carbonylamino, alkylidene group carbonylamino, carbonylamino alkylidene group or alkylidene group carbonylamino alkylidene group, and " D " be hydrogen proton or the salt part that is selected from aluminium, calcium, iron, lithium, magnesium, potassium, sodium, titanium and zine ion,
Wherein sulfonated substituent general formula is-A-S (=O)
2(OD
1), wherein " S " is sulphur, " O " is oxygen, and " A " is selected from carbon-sulfide linkage or is selected from replacement or unsubstituted (C
1-C
6) alkylidene group, wherein substituting group is selected from (C with being independent of each other
1-C
3) alkyl and halogen or be selected from carbonyl, carbonylamino, alkylidene group carbonylamino, carbonylamino alkylidene group or alkylidene group carbonylamino alkylidene group, and " D " be hydrogen proton or the salt part that is selected from aluminium, calcium, iron, lithium, magnesium, potassium, sodium, titanium and zine ion,
Wherein the general formula of the amide substituents of positively charged ion or neutral charge is-A
1-C (=O)-N (B) R
1R
2, wherein " C " is carbon; " O " is oxygen, and " N " is nitrogen, " A
1" be to replace or unsubstituted (C
1-C
6) alkylidene group, wherein substituting group is selected from (C with being independent of each other
1-C
3) alkyl and halogen, " B " is hydrogen, hydroxyl or ether, " R
1" or " R
2" be hydrogen, halogen or (C with being independent of each other
1-C
3) alkyl, the paper wood when wherein this mixture can be produced intensity effectively far above independent use starch or polymer composition.
16. a paper wood comprises the composition of claim 15, the intensity when wherein effectively the strength ratio of the paper wood produced of mixture is used starch or polymer composition separately significantly increases.
Applications Claiming Priority (5)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US09/286,745 US6287423B1 (en) | 1999-04-06 | 1999-04-06 | Paper composition for improved sheet properties |
| US09/286,742 US6090242A (en) | 1999-04-06 | 1999-04-06 | Method of improvement strength of papers |
| US09/286,742 | 1999-04-06 | ||
| US09/286,745 | 1999-04-06 | ||
| US09/286745 | 1999-04-06 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1348473A CN1348473A (en) | 2002-05-08 |
| CN1149238C true CN1149238C (en) | 2004-05-12 |
Family
ID=26964044
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB998165980A Expired - Fee Related CN1149238C (en) | 1999-04-06 | 1999-12-22 | Bifunctional polymers |
Country Status (12)
| Country | Link |
|---|---|
| EP (1) | EP1171492B1 (en) |
| JP (1) | JP2002541276A (en) |
| CN (1) | CN1149238C (en) |
| AT (1) | ATE248867T1 (en) |
| AU (1) | AU2455300A (en) |
| BR (1) | BR9917249A (en) |
| CA (1) | CA2366474A1 (en) |
| DE (1) | DE69911073T2 (en) |
| HK (1) | HK1045534B (en) |
| NO (1) | NO20014814L (en) |
| PT (1) | PT1171492E (en) |
| WO (1) | WO2000059965A1 (en) |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE10334133A1 (en) * | 2003-07-25 | 2005-02-24 | Basf Ag | Aqueous composition and its use for papermaking |
| US8778140B2 (en) | 2007-09-12 | 2014-07-15 | Nalco Company | Preflocculation of fillers used in papermaking |
| US8747617B2 (en) | 2007-09-12 | 2014-06-10 | Nalco Company | Controllable filler prefloculation using a dual polymer system |
| US9752283B2 (en) | 2007-09-12 | 2017-09-05 | Ecolab Usa Inc. | Anionic preflocculation of fillers used in papermaking |
| US8088250B2 (en) | 2008-11-26 | 2012-01-03 | Nalco Company | Method of increasing filler content in papermaking |
| FR3001236B1 (en) | 2013-01-22 | 2015-06-26 | Emin Leydier | AQUEOUS COMPOSITION FOR THE PRODUCTION OF FIBROUS SHEET CARRIERS WITH IMPROVED MECHANICAL STRENGTH PROPERTIES, PROCESS, USE, FIBROUS CARRIERS AND MANUFACTURED ARTICLES THEREOF |
Family Cites Families (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3926718A (en) * | 1974-04-30 | 1975-12-16 | Calgon Corp | Process of improving water drainage from paper webs by addition of a water soluble block polymer to a cellulosic pulp slurry |
| DE3379330D1 (en) * | 1982-12-09 | 1989-04-13 | Cassella Farbwerke Mainkur Ag | Water soluble polymers, their preparation and their use |
| DE3248019A1 (en) * | 1982-12-24 | 1984-06-28 | Cassella Ag, 6000 Frankfurt | WATER-SOLUBLE COPOLYMERS, THEIR PRODUCTION AND THEIR USE |
| US5336316A (en) * | 1993-05-06 | 1994-08-09 | Bj Services Company | Cementing composition and method using phosphonated polymers to improve cement slurry properties |
| DE4330699A1 (en) * | 1993-09-10 | 1995-03-16 | Hoechst Ag | Vinylsulfonic acid polymers |
| DE4343993A1 (en) * | 1993-12-22 | 1995-06-29 | Stockhausen Chem Fab Gmbh | Graft copolymers of unsaturated monomers and polyhydroxy compounds, process for their preparation and their use |
| JPH08134792A (en) * | 1994-11-11 | 1996-05-28 | Nippon P M C Kk | Additive for papermaking and papermaking method |
| DE19508936A1 (en) * | 1995-03-13 | 1996-09-19 | Basf Ag | Complexing agent for the paper industry |
| AU3913197A (en) * | 1996-08-15 | 1998-03-06 | Hercules Incorporated | Amphoteric polyacrylamides as dry strength additives for paper |
-
1999
- 1999-12-22 EP EP99967997A patent/EP1171492B1/en not_active Expired - Lifetime
- 1999-12-22 WO PCT/IB1999/002101 patent/WO2000059965A1/en active IP Right Grant
- 1999-12-22 PT PT99967997T patent/PT1171492E/en unknown
- 1999-12-22 AT AT99967997T patent/ATE248867T1/en not_active IP Right Cessation
- 1999-12-22 CA CA002366474A patent/CA2366474A1/en not_active Abandoned
- 1999-12-22 AU AU24553/00A patent/AU2455300A/en not_active Abandoned
- 1999-12-22 DE DE69911073T patent/DE69911073T2/en not_active Expired - Fee Related
- 1999-12-22 CN CNB998165980A patent/CN1149238C/en not_active Expired - Fee Related
- 1999-12-22 BR BR9917249-6A patent/BR9917249A/en not_active Application Discontinuation
- 1999-12-22 JP JP2000609471A patent/JP2002541276A/en not_active Withdrawn
-
2001
- 2001-10-03 NO NO20014814A patent/NO20014814L/en not_active Application Discontinuation
-
2002
- 2002-09-26 HK HK02107083.1A patent/HK1045534B/en not_active IP Right Cessation
Also Published As
| Publication number | Publication date |
|---|---|
| HK1045534B (en) | 2005-02-18 |
| WO2000059965A1 (en) | 2000-10-12 |
| PT1171492E (en) | 2004-01-30 |
| EP1171492A1 (en) | 2002-01-16 |
| DE69911073T2 (en) | 2004-04-01 |
| NO20014814D0 (en) | 2001-10-03 |
| CN1348473A (en) | 2002-05-08 |
| ATE248867T1 (en) | 2003-09-15 |
| AU2455300A (en) | 2000-10-23 |
| CA2366474A1 (en) | 2000-10-12 |
| DE69911073D1 (en) | 2003-10-09 |
| EP1171492B1 (en) | 2003-09-03 |
| NO20014814L (en) | 2001-10-03 |
| BR9917249A (en) | 2002-01-08 |
| HK1045534A1 (en) | 2002-11-29 |
| JP2002541276A (en) | 2002-12-03 |
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