CN101161931A - Surface sizing agent and method for preparing same - Google Patents
Surface sizing agent and method for preparing same Download PDFInfo
- Publication number
- CN101161931A CN101161931A CNA2007100505631A CN200710050563A CN101161931A CN 101161931 A CN101161931 A CN 101161931A CN A2007100505631 A CNA2007100505631 A CN A2007100505631A CN 200710050563 A CN200710050563 A CN 200710050563A CN 101161931 A CN101161931 A CN 101161931A
- Authority
- CN
- China
- Prior art keywords
- parts
- preparation
- cypres
- initator
- maleic anhydride
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Images
Landscapes
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Paper (AREA)
Abstract
The invention discloses a surface sizing agent which is soap-free emulsion of polymers with the following general formula I: (general formula I) wherein, R is selected from a saturated fatty alcohol group with carbon numbers of 1-18; X is selected from any one in Na<+>, K<+>, NH4<+>, etc; n is 10-1000. The sizing agent is a novel synthetic polymer surface sizing agent for paper, so surface sizing capability of paper can be greatly improved, binding fastness of paper and ink can be improved, surface strength of paper can be improved, etc.; besides, the invention also has the advantages that: few crust is provided during using process, cleaning is convenient, folding resistance of finished product is increased, wet strength is high, etc. The invention also discloses a preparation method of the sizing agent.
Description
Technical field
The invention belongs to pulp technology for making paper, particularly a kind of paper grade (stock) polymer Surface Sizing Agent.
Background technology
The paper grade (stock) sizing agent is meant in order to improve paper and paperboard surface intensity and to prevent the diffusion of water quality liquid (as writing ink) and infiltration and the chemical assistant that adds.It is a kind of large usage quantity, the important paper grade (stock) chemicals that application surface is wider.
According to the difference of its addition manner in paper-making process, the paper grade (stock) sizing agent can be divided into two big classes: (1) makes an addition to sizing agent the internal sizing agent that is called in the paper pulp before paper sheet formation; (2) behind paper sheet formation, cover with paint, lacquer, colour wash, etc. the Cypres that is called in paperboard surface.
Because internal sizing agent is subjected to the influence of working condition factors such as (as water quality, pH value, temperature and pumping time) shearings easily; While has proposed requirements at the higher level along with the application of improvement, high speed printing and the high viscosity inks of printing technology to surface strength of paper, depends merely on plasm-glue-blending and is difficult to reach, and must carry out top sizing to reach instructions for use to paper.
At present the Cypres that adopted of China's paper industry mainly contains starch and modified starch, PVA (polyvinyl alcohol), CMC (carboxymethyl cellulose) etc.The starch based cost is lower, but its cementitiousness is relatively poor, when printing easy hair and powder dropping, cause the scumming phenomenon; And the glossiness behind the one-tenth paper is lower; The CMC film strength is big, grease resistance good, but viscosity is too high, and WATER RESISTANCE is also relatively poor.
PVA is the most frequently used Cypres of present paper industry, and it is a kind of very important water soluble polymer.The PVA molecule is made up of hydrophobic backbone and hydrophilic side-chains, thereby has certain surface-activity, has fabulous surface strength owing to forming dense film, and the high PVA of the degree of polymerization especially is as 1799,2099 etc.; The PVA that uses in bank-note paper at present is 1099, and promptly the degree of polymerization is 1000, and pure solubility is 99%, and its aqueous solution viscosity is bigger, and intermolecular by hydrogen bonded formation PVA dense film, the bonding reaction formula is as follows:
But PVA is used as Cypres, especially has following shortcoming as the bank-note paper Cypres:
(1), the PVA dense film in the bank-note paper superficial layer, influence the strong bonded of ink molecules (particle) and paper fiber, finally cause sharply reduction of certain materialization grade (being the binding ability of paper and printing ink);
(2), the PVA molecule has certain surface-activity, be easy in the absorption of aqueous solution surface; Along with the volatilization of superficial layer moisture and increasing of hydrogen bonded point, the PVA molecule forms polymer film, i.e. skinning on the size tub surface;
(3), the viscosity of the PVA aqueous solution is bigger, residual a large amount of applying glue liquid on knobbling rolls, so on application roll conjunctiva, be difficult to clean;
(4), by the PVA film that rigid hydrogen bond forms, its fragility is bigger, finally causes the paper folding strength not high;
(5), to improving the almost not effect of paper wet strength.
Except that above-mentioned Cypres commonly used, common Cypres also has phenylethylene-maleic anhydride polymer (SMA), styrene-propene acid polymer (SAA), cinnamic acrylic ester polymer emulsion (SAE), soluble polyurethane polymer surfaces sizing agents such as (PUD) on the overseas market.But above-mentioned polymer surfaces sizing agent all uses a large amount of solvents or emulsifying agent in preparation process, environment and effect etc. is had a negative impact; And these polymer surfaces sizing agents generally will use troublesome poeration in use with surface sizing starch (anion or nonionic).
Summary of the invention
The purpose of this invention is to provide a kind of novel paper grade (stock) polymer Surface Sizing Agent,, improve the fastness that combines of ink particle and Cypres and paper fiber to improve the Surface Sizing Properties of paper.
Another object of the present invention provides a kind of preparation method of above-mentioned Cypres.
The technical solution adopted for the present invention to solve the technical problems is:
A kind of Cypres, it is the soap-free emulsion of polymers with following general formula I:
General formula I
Wherein, to be selected from carbon number be 1～18 saturated fat alcohol groups to R; X is selected from Na
+, K
+, NH
4 +Deng in any one; N is 10～1000.
R preferably is 4～18 saturated fat alcohol groups from carbon number; X is preferably Na+.
Cypres of the present invention, be that above-mentioned soap-free emulsion of polymers with general formula I can make by following method: this method is dispersant with the polyvinyl alcohol, styrene, acrylate, acrylamide and four kinds of monomers of maleic anhydride are main raw material, initator (as persulfates such as potassium peroxydisulfate, ammonium persulfates), crosslinking agent (as glyoxal, glutaraldehyde, formaldehyde etc.) under the effect, make described polymer surfaces sizing agent by emulsifier-free emulsion polymerization.This preparation method mainly comprises the steps:
(1), the preparation of poly-vinyl alcohol solution: in the reactor of condensing unit is installed, add an amount of 90～95 ℃ hot water and solid polyethylene alcohol, the part by weight of hot water and polyvinyl alcohol is 90～95: 5～10, under agitation is incubated 1～1.5h, dissolves fully until polyvinyl alcohol;
(2), the alkali of maleic anhydride neutralization: in poly-vinyl alcohol solution, add the maleic anhydride of amount of calculation, under agitation the pH value of system is adjusted to 7.5～9.5 with alkali lye;
(3), the copolymerization of polymerization single polymerization monomer: styrene and acrylate are mixed evenly standby, it is 1～60% solution for standby that the initator water is dissolved into mass percent concentration; When in the alkali of maleic anhydride and after, temperature of reaction kettle is cooled to about 60 ℃ ± 5 ℃, with styrene and acrylate mixing liquid gross mass 1/3rd, acrylamide joins in the reactor and stirs; Add 1/2nd of initiator solution gross mass then, and continue to heat up; When temperature is raised to 80 ℃ ± 5 ℃, drip remaining styrene and acrylate mixing liquid and initiator solution simultaneously, add in 1.5 hours; Continue about 3～5 hours of reaction, after the adding crosslinking agent reacts about 0.5～1.5 hour again, be cooled to 40 ℃ ± 5 ℃ left and right sides dischargings and get final product.
Above-mentioned (2) are used in the step and the alkali lye of maleic anhydride can be selected from NaOH (NaOH), potassium hydroxide (KOH), ammoniacal liquor (NH
3H
2O) etc. any one in; NaOH more preferably.
Used initator can be selected from any one in the persulfates such as potassium peroxydisulfate, ammonium persulfate in above-mentioned (3) step; Potassium peroxydisulfate more preferably.
In above-mentioned (3) step used crosslinking agent can be selected from glyoxal, in the glutaraldehyde, formaldehyde etc. any one; Glyoxal more preferably.
Among the above-mentioned preparation method, the weight portion proportion optimization of dispersant, monomer, initator, crosslinking agent etc. is:
Dispersant (polyvinyl alcohol): 40～60 parts;
Monomer: styrene: 5～20 parts,
Acrylate: 10～25 parts,
Acrylamide: 5～15 parts,
Maleic anhydride: 1～15 part;
Initator: 1～8 part;
Crosslinking agent: 1～30 part.
The weight portion proportioning of above-mentioned dispersant, monomer, initator, crosslinking agent etc. is more preferably: dispersant (polyvinyl alcohol): 45～55 parts;
Monomer: styrene: 9～15 parts,
Acrylate: 15～21 parts,
Acrylamide: 8～12 parts,
Maleic anhydride: 6～10 parts;
Initator: 1～3 part;
Crosslinking agent: 10～20 parts.
The mechanism of emulsifier-free emulsion polymerization mainly comprises following two reactions among the above-mentioned preparation method:
1. have maleic anhydride and the alkali generation neutralization reaction of following general formula V, the product of alkali neutralization reaction has following general formula VI, and this product is as one of monomer of next step free radical copolymerization;
The alkali that participates in above-mentioned alkali neutralization reaction can be selected from NaOH, KOH, NH
4Among the OH etc. any one; Thereby the X among the general formula VI can be selected from Na
+, K
+, NH
4 +Deng.
2. the product of alkali neutralization reaction and other three kinds of monomers (have following general formula I I styrene, have following general formula I II acrylate, have the acrylamide of following general formula I V) exist at initator and issue living free radical copolymerization;
General formula I I general formula III general formula I V
Wherein, to be selected from carbon number be 1～18 saturated fat alcohol groups to the R in the general formula III; This free radical copolymerization formula is as follows:
Wherein, to be selected from carbon number be 1～18 saturated fat alcohol groups to R; X is selected from Na
+, K
+, NH
4 +Deng.
The temperature of polymerization technique is no more than 95 ℃ in the above-mentioned whole preparation method, and steam or electrical heating all can; The polymerization water is an ordinary tap water, and about 7 hours of production cycle, this production technology is fit to the industrialization operation very much.
In the preparation process of above-mentioned Cypres, the PVA mechanism of action as shown in Figure 1, under high-speed stirred, PVA forms microballoon and is present in the polymerization system, the first polymerization single polymerization monomer of part can depend on this microballoon, forms active " seed ", and the PVA that does not form microballoon can form the interfacial film with certain intensity on these activity " seed " surface again, when interfacial film intensity was enough big, polymerisation was then carried out at this fixed space that this interfacial film wrapped up fully.
Because PVA can give paper surface of good intensity, so still kept a part of PVA in Cypres product of the present invention, this part PVA mainly contains the effect of two aspects: (1) is as the dispersant and the stabilizing agent of polymerisation; (2) satisfy the requirement of paper to surface strength.
In Cypres product of the present invention, the main effect with polymer of general formula I is the soft or hard degree of telomerized polymer film (material behind the product drying), i.e. vitrification point.
And, in the macromolecular chain of Cypres of the present invention, also there is the active site of a large amount of high responses.The effect of these active sites just, this product just have some specific function that hope obtains, and promptly improve the binding ability of paper and printing ink etc.
The introducing of these active sites is mainly by introducing as the hydroxyl on the polyvinyl alcohol (PVA) of dispersant, and the hydroxyl on the PVA can wait generation as shown in the formula cross-linking reaction described or similarly with crosslinking agent glyoxal (OHC-CHO):
Cypres of the present invention improves the mechanism of action schematic diagram of paper and printing ink binding ability and sees Fig. 2.Active site in the sizing agent molecule can be combined into key with paper fiber and ink molecules (particle) respectively, reaches the purpose that improves paper and printing ink binding ability.Intermolecular bonding mode mainly is covalent bond, ionic bond, coordinate bond etc., and wherein ionic bond and coordinate bond can weaken along with the change of medium or disappear, and have only covalent bond to have nonvolatil, high bond strength in conventional media.And Cypres of the present invention is the macromolecule with a plurality of active sites, and each active site can both form covalent bond with paper fiber or ink molecules (particle); Be that part active site in the sizing agent molecule combines with the paper fiber, and other a part of active site combines with ink lay, finally forms firm combination, thereby improve the binding ability of paper and printing ink significantly.
Compared with prior art, the invention has the beneficial effects as follows:
Cypres of the present invention is the new type of polymer Cypres, and it has following main feature:
At first, in the macromolecular chain of Cypres of the present invention, there is the active site of a large amount of high responses; These active sites can be combined into firm covalent bond with paper fiber or ink molecules (particle) respectively, thereby improve the binding ability of paper and printing ink significantly.
Secondly, owing to kept a part of PVA in the Cypres product of the present invention, thereby the good characteristics of the film forming of PVA own had both been kept, can give necessary surface strength of paper and basic physical and chemical performance, again owing to can in PVA and acrylate copolymer, form lightly crosslinked network structure, make the paper for surface sizing layer of formation have better surface strength and folding quality simultaneously.
Once more, has the vitrification point that the polymer of general formula I can be regulated polymer film in the Cypres product of the present invention, to satisfy the needs of properties of product.
In addition, compare with traditional PVA sizing agent, Cypres of the present invention combines fastness, improves under the prerequisite of requirements such as surface strength of paper at the raising paper with printing ink, also have the following advantages:
(1) skinning seldom: sizing agent of the present invention has better surface-activity, and PVA is had better emulsification and dispersive property, and PVA can't be adsorbed on applying glue liquid surface like this; Simultaneously, be present between the sizing agent molecule of the present invention the hydrogen bond amount seldom, adsorbed sizing agent of the present invention can't form polymer film in the limited time, so skinning is seldom.
(2) be beneficial to cleaning: the PVA molecule has a large amount of hydroxyls, and strand exists with extended configuration in aqueous medium, forms a large amount of hydrogen bonds, and the system viscosity of causing is very big; And the hydroxyl on the sizing agent strand of the present invention seldom, exists with the state that curls in the aqueous solution, and is seldom residual on knobbling rolls so its viscosity is very little, and can not form polymer film in the limited time, and this smooth cleaning to equipment is extremely beneficial.
(3) folding strength increases: sizing agent of the present invention is the polymer surfaces sizing agent, and copolymer can obviously reduce the vitrification point of product, and promptly product fragility descends, and pliability increases, and finally can increase the folding strength of paper.
(4) improve wet strength: sizing agent of the present invention has multiple function, can satisfy every performance indications of paper, can also produce good synergy with wet strength agent.The service condition of PVA is generally faintly acid or neutrality, does not have facilitation for the wet strength agent of slaking under alkali condition; And the service condition of sizing agent of the present invention is an alkalescent, the slaking of present employed wet strength agent is had catalytic action, so can improve the wet strength of paper.
Description of drawings
Fig. 1 is the PVA mechanism of action schematic diagram of Cypres of the present invention in preparation process.
Fig. 2 is the mechanism of action schematic diagram that Cypres of the present invention improves paper and printing ink binding ability.
Among Fig. 2, the 1st, paper fibrage, the 2nd, sizing agent molecular layer, the 3rd, ink lay.
The specific embodiment
The present invention is described in further detail below in conjunction with the specific embodiment.
But this should be interpreted as that the scope of the above-mentioned theme of the present invention only limits to following embodiment.
Present embodiment is the soap-free emulsion of polymers Cypres with general formula I, wherein:
R is-CH
2(CH
2)
6CH
2OH, X are Na
+, n is 10～1000.
The present embodiment Cypres is to be dispersant with the polyvinyl alcohol, styrene, acrylate, acrylamide and four kinds of monomers of maleic anhydride are main raw material, under initiator potassium persulfate, the effect of crosslinking agent glyoxal, the polymer surfaces sizing agent that gets by emulsifier-free emulsion polymerization; Wherein, the weight proportion of dispersant, monomer, initator, crosslinking agent is:
Dispersant (polyvinyl alcohol): 50 parts;
Monomer: styrene: 12 parts,
Acrylate: 18 parts,
Acrylamide: 10 parts,
Maleic anhydride: 8 parts;
Initator (potassium peroxydisulfate): 2 parts;
Crosslinking agent (glyoxal): 15 parts.
Its preparation method mainly comprises the steps:
(1), the preparation of poly-vinyl alcohol solution: in the reactor of condensing unit is installed, add an amount of 95 ℃ hot water and solid polyethylene alcohol, the part by weight of hot water and polyvinyl alcohol is 90: 10, under agitation is incubated 1.5h, dissolves fully until polyvinyl alcohol;
(2), the alkali neutralization of maleic anhydride: in poly-vinyl alcohol solution, add the maleic anhydride of amount of calculation, under agitation be adjusted to about 8 with the pH value of NaOH solution with system;
(3), the copolymerization of polymerization single polymerization monomer: styrene and acrylate are mixed evenly standby, it is 40% solution for standby that initator (potassium peroxydisulfate) water is dissolved into mass percent concentration; When in the alkali of maleic anhydride and after, temperature of reaction kettle is cooled to about 60 ℃, with styrene and acrylate mixing liquid gross mass 1/3rd, acrylamide joins in the reactor and stirs; Add 1/2nd of initiator solution gross mass then, and continue to heat up; When temperature is raised to 80 ℃ of left and right sides, drip remaining styrene and acrylate mixing liquid and initiator solution simultaneously, add in about 1 hour; Continue about 4 hours of reaction, add crosslinking agent (glyoxal), react again and be cooled to 40 ℃ of left and right sides dischargings after about 1 hour and get final product.
Present embodiment is the soap-free emulsion of polymers Cypres with general formula I, wherein:
R is-CH
2(CH
2)
16CH
2OH, X are K
+, n is 10～1000.
The present embodiment Cypres is to be dispersant with the polyvinyl alcohol, styrene, acrylate, acrylamide and four kinds of monomers of maleic anhydride are main raw material, under initiator ammonium persulfate, the effect of crosslinking agent glyoxal, the polymer surfaces sizing agent that gets by emulsifier-free emulsion polymerization; Wherein, the weight proportion of dispersant, monomer, initator, crosslinking agent is:
Dispersant (polyvinyl alcohol): 40 parts;
Monomer: styrene: 20 parts,
Acrylate: 15 parts,
Acrylamide: 12 parts,
Maleic anhydride: 1 part;
Initator (ammonium persulfate): 8 parts;
Crosslinking agent (glyoxal): 10 parts.
Its preparation method mainly comprises the steps:
(1), the preparation of poly-vinyl alcohol solution: in the reactor of condensing unit is installed, add an amount of 90 ℃ hot water and solid polyethylene alcohol, the part by weight of hot water and polyvinyl alcohol is 95: 5, under agitation is incubated 1h, dissolves fully until polyvinyl alcohol;
(2), the alkali neutralization of maleic anhydride: in poly-vinyl alcohol solution, add the maleic anhydride of amount of calculation, under agitation be adjusted to about 7.5 with the pH value of KOH solution with system;
(3), the copolymerization of polymerization single polymerization monomer: styrene and acrylate are mixed evenly standby, it is 10% solution for standby that initator (ammonium persulfate) water is dissolved into mass percent concentration; When in the alkali of maleic anhydride and after, temperature of reaction kettle is cooled to about 65 ℃, with styrene and acrylate mixing liquid gross mass 1/3rd, acrylamide joins in the reactor and stirs; Add 1/2nd of initiator solution gross mass then, and continue to heat up; When temperature is raised to 75 ℃ of left and right sides, drip remaining styrene and acrylate mixing liquid and initiator solution simultaneously, add in about 1.5 hours; Continue about 3 hours of reaction, add crosslinking agent (glyoxal), react again and be cooled to 45 ℃ of left and right sides dischargings after about 1.5 hours and get final product.
Present embodiment is the soap-free emulsion of polymers Cypres with general formula I, wherein:
R is-CH
2(CH
2)
2CH
2OH, X are NH
4 +, n is 10～1000.
The present embodiment Cypres is to be dispersant with the polyvinyl alcohol, styrene, acrylate, acrylamide and four kinds of monomers of maleic anhydride are main raw material, under initiator ammonium persulfate, the effect of crosslinking agent glutaraldehyde, the polymer surfaces sizing agent that gets by emulsifier-free emulsion polymerization; Wherein, the weight proportion of dispersant, monomer, initator, crosslinking agent is:
Dispersant (polyvinyl alcohol): 60 parts;
Monomer: styrene: 9 parts,
Acrylate: 21 parts,
Acrylamide: 5 parts,
Maleic anhydride: 15 parts;
Initator (ammonium persulfate): 1 part;
Crosslinking agent (glutaraldehyde): 20 parts.
Its preparation method mainly comprises the steps:
(1), the preparation of poly-vinyl alcohol solution: in the reactor of condensing unit is installed, add an amount of 92 ℃ hot water and solid polyethylene alcohol, the part by weight of hot water and polyvinyl alcohol is 92: 8, under agitation is incubated 1.5h, dissolves fully until polyvinyl alcohol;
(2), the alkali neutralization of maleic anhydride: in poly-vinyl alcohol solution, add the maleic anhydride of amount of calculation, under agitation be adjusted to about 8.5 with the pH value of ammoniacal liquor with system;
(3), the copolymerization of polymerization single polymerization monomer: styrene and acrylate are mixed evenly standby, it is 60% solution for standby that initator (ammonium persulfate) water is dissolved into mass percent concentration; When in the alkali of maleic anhydride and after, temperature of reaction kettle is cooled to about 55 ℃, with styrene and acrylate mixing liquid gross mass 1/3rd, acrylamide joins in the reactor and stirs; Add 1/2nd of initiator solution gross mass then, and continue to heat up; When temperature is raised to 85 ℃ of left and right sides, drip remaining styrene and acrylate mixing liquid and initiator solution simultaneously, add in about 1 hour; Continue about 3 hours of reaction, add crosslinking agent (glutaraldehyde), react again and be cooled to 35 ℃ of left and right sides dischargings after about 0.5 hour and get final product.
Embodiment 4
Present embodiment is the soap-free emulsion of polymers Cypres with general formula I, wherein:
R is-CH
2(CH
2)
10CH
2OH, X are Na
+, n is 10～1000.
The present embodiment Cypres is to be dispersant with the polyvinyl alcohol, styrene, acrylate, acrylamide and four kinds of monomers of maleic anhydride are main raw material, under initator sodium peroxydisulfate, the effect of crosslinking agent glyoxal, the polymer surfaces sizing agent that gets by emulsifier-free emulsion polymerization; Wherein, the weight proportion of dispersant, monomer, initator, crosslinking agent is:
Dispersant (polyvinyl alcohol): 45 parts;
Monomer: styrene: 15 parts,
Acrylate: 10 parts,
Acrylamide: 15 parts,
Maleic anhydride: 6 parts;
Initator (sodium peroxydisulfate): 3 parts;
Crosslinking agent (glyoxal): 1 part.
Its preparation method mainly comprises the steps:
(1), the preparation of poly-vinyl alcohol solution: in the reactor of condensing unit is installed, add an amount of 93 ℃ hot water and solid polyethylene alcohol, the part by weight of hot water and polyvinyl alcohol is 91: 9, under agitation is incubated 1h, dissolves fully until polyvinyl alcohol;
(2), the alkali neutralization of maleic anhydride: in poly-vinyl alcohol solution, add the maleic anhydride of amount of calculation, under agitation be adjusted to about 9.5 with the pH value of NaOH solution with system;
(3), the copolymerization of polymerization single polymerization monomer: styrene and acrylate are mixed evenly standby, it is 25% solution for standby that initator (sodium peroxydisulfate) water is dissolved into mass percent concentration; When in the alkali of maleic anhydride and after, temperature of reaction kettle is cooled to about 58 ℃, with styrene and acrylate mixing liquid gross mass 1/3rd, acrylamide joins in the reactor and stirs; Add 1/2nd of initiator solution gross mass then, and continue to heat up; When temperature is raised to 78 ℃ of left and right sides, drip remaining styrene and acrylate mixing liquid and initiator solution simultaneously, add in about 1 hour; Continue about 4 hours of reaction, add crosslinking agent (glyoxal), react again and be cooled to 42 ℃ of left and right sides dischargings after about 1 hour and get final product.
Embodiment 5
Present embodiment is the soap-free emulsion of polymers Cypres with general formula I, wherein:
R is for being-CH
2OH, X are Na
+, n is 10～1000.
The present embodiment Cypres is to be dispersant with the polyvinyl alcohol, styrene, acrylate, acrylamide and four kinds of monomers of maleic anhydride are main raw material, under initiator potassium persulfate, the effect of crosslinking agent formaldehyde, the polymer surfaces sizing agent that gets by emulsifier-free emulsion polymerization; Wherein, the weight proportion of dispersant, monomer, initator, crosslinking agent is:
Dispersant (polyvinyl alcohol): 5 parts;
Monomer: styrene: 5 parts,
Acrylate: 25 parts,
Acrylamide: 8 parts,
Maleic anhydride: 10 parts;
Initator (potassium peroxydisulfate): 1 part;
Crosslinking agent (formaldehyde): 30 parts.
Its preparation method mainly comprises the steps:
(1), the preparation of poly-vinyl alcohol solution: in the reactor of condensing unit is installed, add an amount of 95 ℃ hot water and solid polyethylene alcohol, the part by weight of hot water and polyvinyl alcohol is 94: 6, under agitation is incubated 1.5h, dissolves fully until polyvinyl alcohol;
(2), the alkali neutralization of maleic anhydride: in poly-vinyl alcohol solution, add the maleic anhydride of amount of calculation, under agitation be adjusted to about 9 with the pH value of NaOH solution with system;
(3), the copolymerization of polymerization single polymerization monomer: styrene and acrylate are mixed evenly standby, it is 1% solution for standby that initator (potassium peroxydisulfate) water is dissolved into mass percent concentration; When in the alkali of maleic anhydride and after, temperature of reaction kettle is cooled to about 60 ℃, with styrene and acrylate mixing liquid gross mass 1/3rd, acrylamide joins in the reactor and stirs; Add 1/2nd of initiator solution gross mass then, and continue to heat up; When temperature is raised to 82 ℃ of left and right sides, drip remaining styrene and acrylate mixing liquid and initiator solution simultaneously, add in about 1 hour; Continue about 4.5 hours of reaction, add crosslinking agent (formaldehyde), react again and be cooled to 40 ℃ of left and right sides dischargings after about 1 hour and get final product.
Claims (12)
1. Cypres, it is the soap-free emulsion of polymers with following general formula I:
Wherein, to be selected from carbon number be 1～18 saturated fat alcohol groups to R; X is selected from Na
+, K
+, NH
4 +N is 10～1000.
2. Cypres according to claim 1 is characterized in that: it is 4～18 saturated fat alcohol groups that the R in the described general formula I is selected from carbon number; X is Na
+
3. the preparation method of claim 1 or 2 described Cypres, this preparation method is to be dispersant with the polyvinyl alcohol, styrene, acrylate, acrylamide and four kinds of monomers of maleic anhydride are main raw material, under the effect of initator, crosslinking agent, make described polymer surfaces sizing agent by emulsifier-free emulsion polymerization, mainly comprise the steps:
(1), the preparation of poly-vinyl alcohol solution: in the reactor of condensing unit is installed, add an amount of 90～95 ℃ hot water and solid polyethylene alcohol, the part by weight of hot water and polyvinyl alcohol is 90～95: 5～10, under agitation is incubated 1～1.5h, dissolves fully until polyvinyl alcohol;
(2), the alkali of maleic anhydride neutralization: in poly-vinyl alcohol solution, add the maleic anhydride of amount of calculation, under agitation the pH value of system is adjusted to 7.5～9.5 with alkali lye;
(3), the copolymerization of polymerization single polymerization monomer: styrene and acrylate are mixed evenly standby, it is 1～60% solution for standby that the initator water is dissolved into mass percent concentration; When in the alkali of maleic anhydride and after, temperature of reaction kettle is cooled to 60 ℃ ± 5 ℃, with styrene and acrylate mixing liquid gross mass 1/3rd, acrylamide joins in the reactor and stirs; Add 1/2nd of initiator solution gross mass then, and continue to heat up; When temperature is raised to 80 ℃ ± 5 ℃, drip remaining styrene and acrylate mixing liquid and initiator solution simultaneously, add in 1.5 hours; Continue reaction 3～5 hours, after the adding crosslinking agent reacts 0.5～1.5 hour again, be cooled to 40 ℃ ± 5 ℃ dischargings and get final product.
4. the preparation method of Cypres according to claim 3 is characterized in that:
Described (2) are used in the step and the alkali lye of maleic anhydride is selected from NaOH, potassium hydroxide, the ammoniacal liquor any one.
5. the preparation method of Cypres according to claim 4, it is characterized in that: described alkali lye is NaOH.
6. the preparation method of Cypres according to claim 3, it is characterized in that: described initator is a persulfate.
7. the preparation method of Cypres according to claim 6, it is characterized in that: described initator is potassium peroxydisulfate or ammonium persulfate.
8. the preparation method of Cypres according to claim 7, it is characterized in that: described initator is a potassium peroxydisulfate.
9. the preparation method of Cypres according to claim 3 is characterized in that: described crosslinking agent be selected from glyoxal, in the glutaraldehyde, formaldehyde any one.
10. Cypres according to claim 7 is characterized in that: described crosslinking agent is a glyoxal.
11. the preparation method of Cypres according to claim 3 is characterized in that: the weight proportion of described dispersant, monomer, initator, crosslinking agent is:
Dispersant: 40～60 parts;
Monomer: styrene: 5～20 parts,
Acrylate: 10～25 parts,
Acrylamide: 5～15 parts,
Maleic anhydride: 1～15 part;
Initator: 1～8 part;
Crosslinking agent: 1～30 part.
12. the preparation method of Cypres according to claim 11 is characterized in that: the weight proportion of described dispersant, monomer, initator, crosslinking agent is:
Dispersant: 45～55 parts;
Monomer: styrene: 9～15 parts,
Acrylate: 15～21 parts,
Acrylamide: 8～12 parts,
Maleic anhydride: 6～10 parts;
Initator: 1～3 part;
Crosslinking agent: 10～20 parts.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2007100505631A CN101161931B (en) | 2007-11-21 | 2007-11-21 | Surface sizing agent and method for preparing same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2007100505631A CN101161931B (en) | 2007-11-21 | 2007-11-21 | Surface sizing agent and method for preparing same |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101161931A true CN101161931A (en) | 2008-04-16 |
| CN101161931B CN101161931B (en) | 2010-04-14 |
Family
ID=39296910
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2007100505631A Active CN101161931B (en) | 2007-11-21 | 2007-11-21 | Surface sizing agent and method for preparing same |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN101161931B (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103410051A (en) * | 2013-07-09 | 2013-11-27 | 上海东升新材料有限公司 | Surface sizing agent emulsion and preparation method for same |
| CN104294708A (en) * | 2013-09-30 | 2015-01-21 | 昆山市巴城镇顺拓工程机械配件厂 | Styrene-acrylic emulsion surface sizing agent |
| CN106432758A (en) * | 2016-09-21 | 2017-02-22 | 厦门市禾合科技有限公司 | Method for preparing crosslinking waterborne acrylic emulsion |
| CN110894256A (en) * | 2018-09-12 | 2020-03-20 | 上海昶法新材料有限公司 | Styrene derivative copolymer sizing agent and preparation method thereof |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100500995C (en) * | 2006-10-11 | 2009-06-17 | 上海东升新材料有限公司 | Sizing agent for treating paper surface and its preparing method and use |
-
2007
- 2007-11-21 CN CN2007100505631A patent/CN101161931B/en active Active
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103410051A (en) * | 2013-07-09 | 2013-11-27 | 上海东升新材料有限公司 | Surface sizing agent emulsion and preparation method for same |
| CN104294708A (en) * | 2013-09-30 | 2015-01-21 | 昆山市巴城镇顺拓工程机械配件厂 | Styrene-acrylic emulsion surface sizing agent |
| CN106432758A (en) * | 2016-09-21 | 2017-02-22 | 厦门市禾合科技有限公司 | Method for preparing crosslinking waterborne acrylic emulsion |
| CN106432758B (en) * | 2016-09-21 | 2019-03-19 | 厦门市禾合科技有限公司 | A kind of preparation method of cross-linking aqueous acrylic emulsion |
| CN110894256A (en) * | 2018-09-12 | 2020-03-20 | 上海昶法新材料有限公司 | Styrene derivative copolymer sizing agent and preparation method thereof |
| CN110894256B (en) * | 2018-09-12 | 2022-03-18 | 上海昶法新材料有限公司 | Styrene derivative copolymer sizing agent and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN101161931B (en) | 2010-04-14 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN100451037C (en) | Method of using hollow sphere polymers | |
| CN102140768A (en) | Novel cationic surface sizing agent and preparation method thereof | |
| CN101161931B (en) | Surface sizing agent and method for preparing same | |
| CN101848945A (en) | Glyoxalated N-vinylamine | |
| CN102086614A (en) | Surface sizing agent as well as preparation method and application thereof | |
| CN105531292A (en) | Vinyl alcohol polymer, thickener, stabilizer for emulsion polymerization, stabilizer for suspension polymerization, coating agent, coating, sizing agent for fibers, and method for producing sized yarn and textile | |
| CN101397353A (en) | Method for preparing high molecule emulsifying agent for ASA | |
| CN108341912A (en) | A kind of preparation method of gluing reinforcing agent | |
| CN106930141A (en) | A kind of starch base compounded mix and its preparation method and application | |
| CN106381759A (en) | Corrugated paper surface solid sizing reinforcing agent composition and production method thereof | |
| CN102432731B (en) | Cationic styrene acrylate emulsion as well as preparation method and application thereof | |
| CN113512906A (en) | Coating composition for pyrograph transfer paper, pyrograph transfer paper and preparation method thereof | |
| CN102757522A (en) | Synthetic method of anionic surface sizing agent | |
| CN102230301B (en) | Preparation method of cationic styrene acrylic surface sizing agent | |
| CN104177532A (en) | Modified vinyl alcohol-series polymer and its preparation method and use | |
| CN102517992B (en) | Compound surface reinforcing agent for packaging paperboard and method for preparing same | |
| CN103696321A (en) | Preparation method of composite surface sizing agent | |
| CN105985497A (en) | Acetic acrylic emulsion and preparing method thereof | |
| CA2401101A1 (en) | Ink receptive coating compositions containing poly(vinyl alcohol) grafted with amine functional groups | |
| US7144946B2 (en) | Cationic polyvinyl alcohol-containing compositions | |
| CN101851877A (en) | Surface coating liquid for papermaking and paper | |
| CN101519859B (en) | Synthetic method for cationic surface sizing agent | |
| CN103993502B (en) | A kind of environment-friendly type cationic polyacrylate and preparation method thereof and application | |
| CN105237648A (en) | Highly-branched starch modified by glyoxal crosslinked polymer, preparation method and application thereof | |
| CN101134860A (en) | Aqueous flexographic printing finish fat liquor and method for making same |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CP01 | Change in the name or title of a patent holder | ||
| CP01 | Change in the name or title of a patent holder |
Address after: 611130 No. 189, Golden Road, Wenjiang District, Sichuan, Chengdu Patentee after: China Banknote Printing and Minting Group Co.,Ltd. Address before: 611130 No. 189, Golden Road, Wenjiang District, Sichuan, Chengdu Patentee before: CHINA BANKNOTE PRINTING AND MINTING Corp. |